FINAL DEMONSTRATION PLAN
FOR THE EVALUATION OF FIELD
PORTABLE
X-RAY FLUORESCENCE
TECHNOLOGIES
SUPERFUND INNOVATIVE TECHNOLOGY
EVALUATION PROGRAM
Sponsored by:
U.S. Environmental Protection Agency
Environmental Monitoring Systems Laboratory
Las Vegas, Nevada
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SUPERFUND INNOVATIVE TECHNOLOGY
EVALUATION PROGRAM
FINAL DEMONSTRATION PLAN
FOR THE EVALUATION OF FIELD PORTABLE
X-RAY FLUORESCENCE TECHNOLOGIES
Prepared for:
U.S. ENVIRONMENTAL PROTECTION AGENCY
Environmental Monitoring Systems Laboratory
Las Vegas, Nevada 89193
Work Assignment Number
Date Prepared
EPA Contract Number
PRC Project Number
PRC Project Manager
Telephone Number
EPA Project Manager
Telephone Number
0-65
March 1. 1995
68-CO-0047
047-6504
Eric Hess
(913) 573-1822
Steve Billets
(702) 798-2232
U.S. EPA Region III
Regional Center for Environmental
Information
1950 Arch Street (3PM52)
Philadelphia, PA 19103
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APPROVAL SIGNATURES
The purpose of this demonstration is to evaluate field portable x-ray fluorescence technologies in ho\
well they identify and quantify concentrations of metals in soils at hazardous waste sites. The
demonstration will take place under the Monitoring and Measurement Technologies Program of the
U.S. Environmental Protection Agency's Superfund Innovative Technology Evaluation Program.
This document is intended to ensure that all aspects of the demonstration are documented,
scientifically sound, and that operational procedures are conducted within quality assurance and
quality control specifications and health and safety regulations.
The signatures of the individuals below indicate concurrence with, and agreement to operate in
compliance with, procedures specified in this document.
FINAL DEMONSTRATION PLAN
> \ I
Eric Hess, PRC Date
Project Manager
(
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APPROVAL SIGNATURES
The signatures of the developers below indicate that they have reviewed the experimental design of
the demonstration plan and agree that the design will fairly represent and evaluate the performance of
their technologies.
FINAL DEMONSTRATION PLAN
Alan Seelos Date
Enviro-Recoverv Consultants. Inc.
John Moore Date
HNU Svstems. Inc.
James Pasmore Date
Metorex, Inc.
Stephen Shefsky Date
Niton Corporation
Bill Boyce Date
Scitec Corporation
Margo Myers Date
TN Spectrace
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DISCLAIMER NOTICE
This document was prepared for the U.S. Environmental Protection Agency's Environmental
Monitoring Systems Laboratory by PRC Environmental Management Inc., in partial fulfillment of
Contract No. 68-CO-0047, Work Assignment No. 0-65. The opinions, findings, and conclusions
expressed herein are those of the contractor and not necessarily those of the Environmental Protection
Agency or other cooperating agencies. Mention of company or product names should not be
construed as an endorsement by the agency.
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CONTENTS
Chapter Paee
APPROVAL SIGNATURES
DISCLAIMER NOTICE
LIST OF ACRONYMS x
EXECUTIVE SUMMARY ES-1
1 INTRODUCTION 1-1
1.1 SITE PROGRAM OVERVIEW 1-1
1.1.1 Selecting Technologies 1-1
1.1.2 Demonstrating Technologies 1-2
1.1.3 Evaluating Technologies 1-3
1.2 DEMONSTRATION PURPOSE 1-3
13 DEMONSTRATION TECHNOLOGIES AND DEVELOPERS 1-4
1.4 DEMONSTRATION PARTICIPANTS 1-4
15 DEMONSTRATION SITES 1-4
16 DEMONSTRATION SCHEDULE 1-5
2 DEMONSTRATION RESPONSIBILITIES AND COMMUNICATION 2-1
2.1 DEMONSTRATION PARTICIPANTS AND ROLES 2-1
2.2 SPECIFIC RESPONSIBILITIES 2-2
2.3 COMMUNICATION 2-3
3 PREDEMONSTRATION ACTIVITIES 3-1
3.1 IDENTIFYING DEVELOPERS 3-1
3.2 SELECTING SITES 3-1
3.3 CONFIRMATORY LABORATORY AND ANALYTICAL METHODS 3-3
3.4 PREDEMONSTRATION SAMPLING AND ANALYSIS 3-3
4 TECHNOLOGY DESCRIPTIONS 4-1
4.1 TN SPECTRACE 9000 4-4
4.1.1 Background Information 4-4
4.1.2 Equipment and Accessories 4-5
4.1.3 General Operating Procedures 4-8
4.1.4 Training and Maintenance 4-12
4.1.5 Testing Time and Cost 4-12
i
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CONTENTS (Continued)
Chapter
Page
4 2 X-MET 920
4-13
4.2 1 Background Information 4
4.2.2 Equipment and Accessories ^ ^
4.2.3 General Operating Procedures ^
4.2.4 Training and Maintenance 4 17
4.2.5 Testing Time and Cost ^ ^
4.3 MAP SPECTRUM ANALYZER ...
4-iy
4.3.1 Background Information 4
4.3.2 Equipment and Accessories 4 ^
4.3.3 General Operating Procedures 4 2q
4.3.4 Training and Maintenance 4 22
4.3.5 Testing Time and Cost 4 ^
4.4 SEFA-P ANALYZER 4_24
4.4.1 Background Information 4_2
4.4.2 Equipment and Accessories ^ 24
4.4.3 General Operating Procedures 4_2g
4.4.4 Training and Maintenance 4_2g
4.4.5 Testing Time and Cost 4 2g
4.5 XL SPECTRUM ANALYZER 4 29
4.5.1 Background Information
4.5.2 Equipment and Accessories 4_29
4.5.3 General Operating Procedures 4_3q
4.5.4 Training and Maintenance 4
4.5.5 Testing Time and Cost ' 4"32
4.6 TN SPECTRACE LEAD ANALYZER 4.32
4.6.1 Background Information 4 32
4.6.2 Equipment and Accessories
4.6.3 General Operating Procedures 4.35
4.6.4 Training and Maintenance
4.6.5 Testing Time and Cost 4_37
4.7 ATX-100
4-38
4.7.1 Background Information
4.7.2 Equipment and Accessories 4-38
4-38
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CONTENTS (Continued)
Chapter Page
4.7.3 General Operating Procedures 4-39
4.7.4 Training and Maintenance 4-40
4.7.5 Testing Time and Cost 4-40
4.8 SEFA-Px ANALYZER 4-40
4.8.1 Background Information 4-40
4.8.2 Equipment and Accessories 4-40
4.8.3 General Operating Procedures 4-42
4.8.4 Training and Maintenance 4-43
4.8.5 Testing Time and Cost 4-43
5 DEMONSTRATION SITE DESCRIPTIONS 5-1
5.1 ASARCO SITE 5-1
5.1.1 Site History 5-1
5.1.2 Site Characteristics 5-1
5.2 RV HOPKINS SITE 5-2
5.2.1 Site History 5-3
5.2.2 Site Characteristics 5-3
6 SAMPLING PLAN 6-1
6.1 SAMPLING AND FIELD ANALYSIS OPERATIONS 6-1
6.2 COMMUNICATIONS, DOCUMENTATION, AND EQUIPMENT . . : 6-6
6.3 QUALITY ASSURANCE/QUALITY CONTROL REQUIREMENTS 6-6
6.4 HEALTH AND SAFETY PROCEDURES 6-8
6.5 SAMPLE COLLECTION PROCEDURES 6-8
6.5.1 Sampling Locations 6-8
6.5.2 Soil Sampling Procedures 6-9
6.5.3 Sample Storage, Packaging, and Shipping 6-10
6.5.4 Decontamination 6-11
6.5.5 Schedule 6-11
7 EXPERIMENTAL DESIGN 7"1
7.1 OBJECTIVES 7"1
7.2 FACTORS TO BE CONSIDERED 7*1
7.2.1 Qualitative Factors 7-1
iii
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CONTENTS (Continued)
Chapter
7.2.2 Quantitative Factors
7.3
7.4
SAMPLING DESIGN . . .
STATISTICAL ANALYSIS
7.4.1 lntramethod Comparisons
7.4.2 Intermethod Comparisons
7.4.3 Matrix and Sample Preparation Studies ....
7.4.4 Software
QUALITY ASSURANCE PROJECT PLAN
8.1
8.2
8.3
8.4
8.6
8.7
PURPOSE AND SCOPE
QUALITY ASSURANCE RESPONSIBILITIES
DATA QUALITY PARAMETERS
8.3.1 Precision
8.3.2 Accuracy
8.3.3 Representativeness
8.3.4 Completeness . .
8.3.5 Comparability .
CALIBRATION PROCEDURES, QUALITY CONTROL CHECKS AND
CORRECTIVE ACTION . AND
8.4.1
8.4.2
8.4.3
8.4.4
8.4.5
8.4.6
8.4.7
Pagg
7-2
7-7
7-8
7-9
7-1]
7-15
7-16
8-1
8-1
8-2
8-3
8-3
8-5
8-6
8-6
8-6
8-7
8-9
8-10
8-11
Initial Calibration Procedures
Continuing Calibration Procedures
Method Blanks
Laboratory Control Samples g_I2
Matrix Spike Samples g
Performance Evaluation Samples
Duplicate Samples g_^
8.5 DATA REDUCTION, VALIDATION, AND REPORTING 8-16
8.5.1 Data Reduction
8.5.2 Data Validation
8.5.3 Data Reporting
CALCULATION OF DATA QUALITY INDICATORS
PERFORMANCE AND SYSTEM AUDITS
8.7.1 Performance Audit .
8.7.2 On-Site System Audits
8-16
8-17
8-17
8-18
8-19
8-19
8-20
IV
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CONTENTS (Continued)
Chapter Page
8.7.3 Secondary QC Laboratory 8-20
8.8 QUALITY ASSURANCE REPORTS TO MANAGEMENT 8-21
8.8.1 Monthly Reports 8-21
8.8.2 Audit Reports 8-21
9 DATA MANAGEMENT AND ANALYSIS 9-1
9.1 LABORATORY DATA MANAGEMENT ACTIVITIES 9-1
9.1.1 Moisture Content Data Management 9-1
9.1.2 Qualitative and Quantitative Analyses and Evaluations 9-2
9.1.3 Technology Data Management 9-2
10 HEALTH AND SAFETY PLAN 10-1
10.1 HEALTH AND SAFETY PLAN ENFORCEMENT 10-1
10.1.1 Project Manager and Field Site Supervisor 10-1
10.1.2 Health and Safety Director 10-2
10.1.3 Site Health and Safety Officer 10-2
10.2 VISITORS 10-2
10.3 DEMONSTRATION-SPECIFIC HAZARD EVALUATION 10-3
10.4 EXPOSURE PATHWAYS 10-4
10.4.1 Inhalation 10-4
10.4.2 Dermal Contact 10-5
10.4.3 Ingestion 10-5
10.5 HEALTH EFFECTS 10-5
10.6 PHYSICAL HAZARDS 10-6
10.7 TRAINING REQUIREMENTS 10-6
10.8 PERSONAL PROTECTION REQUIREMENTS 10-8
10.8.1 Levels of Protection 10-8
10.8.2 Protective Equipment and Clothing 10-9
10.8.3 Limitations of Protective Clothing 10-10
10.8.4 Duration of Work Tasks 10-11
10.8.5 Respirator Selection, Use, and Maintenance 10-11
10.9 MEDICAL SURVEILLANCE 10-13
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CONTENTS (Continued)
Chapter
10.9.1 Health Monitoring Requirements
10.9.2 Documentation and Recordkeeping Requirements
10.9.3 Medical Support and Follow-up Requirements
10.10 ENVIRONMENTAL SURVEILLANCE
10.10.1 Initial Air Monitoring . .
10.10.2 Periodic Air Monitoring
10.10.3 Monitoring Parameters .
10 11 USE AND MAINTENANCE OF SURVEY EQUIPMENT
10 12 COLD STRESS MONITORING
10.13 SITE CONTROL
10.13.1 Site Control Zones
10.13.2 Safe Work Practices
10.13.3 Health and Safety Plan Enforcement
10.13.4 Complaints
10 14 DECONTAMINATION
10.14.1 Personnel Decontamination
10.14.2 Equipment Decontamination
10 15 EMERGENCY CONTINGENCY PLANNING
10.15.1 Injury in the Exclusion or Contamination Reduction Zones
10.15.2 Injury in the Support Zone
10.15.3 Fire or Explosion
10.15.4 Protective Equipment Failure
10.15.5 Emergency Information Telephone Numbers
10.15.6 Hospital Route Directions
£igS
11 DELIVERABLES ll.l
11.1 DEMONSTRATION WORK PLAN u .
11.2 DEMONSTRATION PLAN Ul
113 TECHNOLOGY EVALUATION REPORT u_2
11.4 INNOVATIVE TECHNOLOGY EVALUATION REPORT u-3
11.5 TECHNOLOGY BRIEFS n,
11.6 OTHER REPORTS u_3
VI
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CONTENTS (Continued)
Chapter Page
REFERENCES R-l
Appendix
A COMMENTS FROM DEMONSTRATION PARTICIPANTS ON THE DRAFT
DEMONSTRATION PLAN AND PRC'S RESPONSES
vii
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FIGURES
Figure Page
2-1 ORGANIZATIONAL CHART 2-4
5-1 ASARCO SITE LOCATION MAP 5-5
5-2 RV HOPKINS SITE LOCATION MAP 5-6
6-1 SAMPLE PREPARATION AND ANALYSIS FLOW CHART 6-12
8-1 SAMPLE ANALYSIS RECORDING FORM FOR FPXRF IN SITU
TECHNOLOGIES 8-22
8-2 SAMPLE ANALYSIS RECORDING FORM FOR PRECISION FPXRF IN SITU
TECHNOLOGIES 8-23
8-3 SAMPLE ANALYSIS RECORDING FORM FOR FPXRF INTRUSIVE
TECHNOLOGIES 8-24
8-4 SAMPLE ANALYSIS RECORDING FORM FOR PRECISION FPXRF INTRUSIVE
TECHNOLOGIES 8-25
8-5 SAMPLE PREPARATION TRACKING FORM 8-26
8-6 CONFIRMATORY LABORATORY SAMPLE PACKAGING TRACKING FORM . . . 8-27
10-1 RV HOPKINS SITE HOSPITAL ROUTE MAP 10-30
10-2 ASARCO SITE HOSPITAL ROUTE MAP 10-31
viii
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TABLES
Table Page
1-1 TECHNOLOGY CAPABILITIES 1-6
1-2 DEMONSTRATION PARTICIPANTS 1-7
3-1 SURVEY OF POTENTIAL DEMONSTRATION SITES 3-5
4-1 RADIOISOTOPE SOURCE SUMMARY 4-44
4-2 TECHNOLOGY SPECIFICATIONS 4-45
5-1 MAXIMUM CONCENTRATION OF CONTAMINANTS IN SURFACE SOIL
SAMPLES COLLECTED DURING PREDEMONSTRATION SAMPLING
ACTIVITIES Asarco Site 5-7
5-2 MAXIMUM CONCENTRATION OF CONTAMINANTS IN SURFACE SOIL
SAMPLES COLLECTED DURING PREDEMONSTRATION SAMPLING
ACTIVITIES RV Hopkins Site 5-8
6-1 SAMPLE COLLECTION AND ANALYSIS STRATEGY 6-13
6-2 LIST OF FIELD EQUIPMENT NEEDED 6-15
7-1 CRITERIA FOR DATA QUALITY CHARACTERIZATION 7-18
8-1 SW-846 METHOD 6010A SOIL SAMPLE DETECTION LIMITS 8-28
8-2 SW-846 METHOD 6010A CALIBRATION PROCEDURES, METHOD-SPECIFIC
QC REQUIREMENTS, AND CORRECTIVE ACTION 8-29
10-1 HAZARDOUS MATERIALS POTENTIALLY PRESENT AT THE
DEMONSTRATION SITES 10-32
10-2 WORK TASK HAZARD ANALYSIS 10-34
ix
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LIST OF ACRONYMS
AC
Alternating Current
ACES
Automated Contaminant Evaluation Software
Am241
Americium-241
ASTM
American Society for Testing Materials
CCS
Continuing Calibration Standard
Cd109
Cadmium-109
CFR
Code of Federal Regulations
cm
Centimeter
cmJ
Cubic Centimeters
cm/s
Centimeter per Second
Co57
Cobalt 57
CRZ
Contamination Reduction Zone
Cm244
Curium-244
DQO
Data Quality Objective
eV
Electron Volt
EMSL-LV
Environmental Monitoring Systems Laboratory - Las Vegas
EPA
Environmental Protection Agency
ERC
Enviro-Recovery Consultants
Fe-55
Iron-55
FPXRF
Field Portable X-ray Fluorescence
HASP
Health and Safety Plan
Hgl2
Mercuric Iodide
HSD
Health and Safety Director
ICS
Interference Check Standard
ICV
Initial Calibration Verification
IDW
Investigation-Derived Waste
IOLM
International Organization of Legal Metrology
ITER
Innovative Technology Evaluation Report
keV
Kiloelectron Volt
Kg
Kilogram
LCD
Liquid Crystal Display
LCS
Laboratory Control Samples
MCA
Multichannel Analyzer
mCi
millicuries
MDL
Method Detection Limit
MDNR
Missouri Department of Natural Resources
M g/L
Microgram per Liter
Micrometers
mg/cm2
Milligram per Square Centimeter
mg/kg
Milligram per Kilogram
mg/m3
Milligram per Cubic Meter
mL
Milliliter
mm
Millimeter
MMTP
Monitoring and Measurement Technologies Program
MRI
Midwest Research Institute
x
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LIST OF ACRONYMS (Continued)
NEMA
National Electrical Manufacturers Association
MIOSH
National Institute of Occupational Safety and Health
MIST
National Institute of Standards and Technology
NPL
National Priorities List
ODEQ
Oklahoma Department of Environmental Quality
OSHA
Occupational Safety and Health Administration
OSW
Office of Solid Waste
%D
Percent Difference
PAL
Pacific Activities Limited
PARCC
Precision, Accuracy, Completeness, and Comparability
PC
Personal Computer
PE
Performance Evaluation
PM
Program Manager
PPE
Personal Protective Equipment
ppm
Parts per million
PRC
PRC Environmental Management. Inc.
PSI
Pounds Per Square Inch
QA
Quality Assurance
QAPP
Quality Assurance Project Plan.
QC
Quality Control
RCRA
Resource Conservation and Recovery Act
RPD
Relative Percent Difference
RSD
Relative Standard Deviation
SHSO
Site Health and Safety Officer
Si(Li)
Silicon (Lithium)
SITE
Superfund Innovative Technology Evaluation
SOP
Standard Operating Procedure
SRM
Standard Reference Materials
SSC
Site-Specific Calibration
TER
Technology Evaluation Report
TPM
Technical Project Manager
VGA
Video Graphics Array
XPCS
X-MET Personal Computer System
XRF
X-ray Fluorescence
xi
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EXECUTIVE SUMMARY
This demonstration was developed under the U.S. Environmental Protection Agency's (EPA)
Superfimd Innovative Technology Evaluation (SITE) Program. The purpose of this document is to
provide the information needed to fairly and thoroughly evaluate how well field portable x-ray
fluorescence (FPXRF) technologies identify and quantitate concentrations of metals in soils.
The developers involved in this demonstration are as follows: Enviro-Recovery Consultants, Inc.;
HNU Systems. Inc.; Metorex, Inc.; Niton Corporation; Scitec Corporation; and TN Spectrace. The
FPXRF technologies being demonstrated are either in situ or intrusive, or capable of both modes of
operation. Together these developers are supplying nine different instruments for evaluation. The
FPXRF in situ technologies analyze undisturbed soil samples. The FPXRF intrusive technologies
analyze soils that have been removed from their natural matrix and, in some cases, have undergone
sample preparation. Some of the developers manufacture both types of FPXRF technologies. After
reviewing information on each technology, PRC Environmental Management, Inc. (PRC), and the
EPA Environmental Monitoring Systems Laboratory (EMSL) determined that the FPXRF technologies
manufactured by these developers were suitable for this demonstration.
These technologies were developed to provide rapid, real-time, relatively low cost analysis of the
metals content of soil samples at hazardous waste sites. They are designed to quickly distinguish
contaminated areas from noncontaminated areas to allow investigation and remediation decisions to be
made more efficiently on site, and to reduce the number of samples that need to be submitted for
costly confirmatory analyses.
The primary objectives of this demonstration are (1) to determine how well each technology performs
in comparison to conventional analytical methods, (2) to identify the effects of sample matrix
variations on the performance of each technology, (3) to determine the logistical and economic
resources needed to operate each technology, and (4) to produce an SW-846 method for the use of
intrusive and in situ FPXRF technologies. Secondary objectives for this demonstration are to evaluate
FPXRF technologies for their (1) reliability, ruggedness, cost, and range of usefulness, (2) data
quality, and (3) ease of operation. The performances of the FPXRF technologies will not be
compared against each other. Instead, their performances will be compared to the performances of
ES-1
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conventional analytical methods used in performing site characterization activities. The calibration
and operational procedures for each technology will follow the developer's recommendations.
Two sites.have been selected for this demonstration: the RV Hopkins site and the Asarco Tacoma
Smelter site (Asarco). RV Hopkins is an active steel drum recycling facility and the location of a
former battery recycling operation. It is located in Davenport, Iowa. The Asarco site is the locatio
of a former copper and lead smelter and is located in Tacoma, Washington. These sites represent
different manufacturing processes that commonly generate heavy metals waste. The soils at the two
sites range in texture from sand to silty clay.
After completing the demonstration, a technical evaluation report (TER) will be prepared The TEI
will present objective results of the demonstration and provide supporting documentation. In additi<
an innovative technology evaluation report (ITER) will be prepared and published that summarizes I
findings presented in the TER. A separate ITER will be published for each developer. These repo
will help data users and technology reviewers assess the performance of each technology for possib
use on future site characterization or remediation projects at hazardous waste sites.
The November 1994 draft demonstration plan was made available to the demonstration participants
for review and comment. Comments received from the demonstration participants were addressed
and are reflected in the final demonstration plan. Appendix A contains the comments from the
demonstration participants and PRC's responses to those comments.
ES-2
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CHAPTER 1
INTRODUCTION
This chapter provides an overview of the Superfund Innovative Technology Evaluation (SITE)
Program and introduces elements of the field portable x-ray fluorescence technologies (FPXRF)
demonstration, such as the purpose of the demonstration, the technologies to be demonstrated, the
developers of the technologies, and where and when the demonstration will take place.
1.1 SITE PROGRAM OVERVIEW
The SITE Program evolved in response to the Superfund Amendments and Reauthorization Act of
1986, which recognized the need for a program to explore alternative or innovative technologies for
treating hazardous waste at Superfund sites. The two primary goals of the SITE Program are to
develop and implement (1) treatment technologies for hazardous waste remediation, and
(2) monitoring and measurement technologies for evaluating the nature and extent of hazardous waste
contamination.
The SITE Program consists of four related programs: Demonstration, Emerging Technologies,
Monitoring and Measurement Technologies, and Technology Transfer. This demonstration will be
conducted under the supervision and guidance of the Monitoring and Measurement Technologies
Program (MMTP). The goal of MMTP is to encourage the development, demonstration, and use of
innovative monitoring, measurement, and characterization technologies at Superfund sites. The
MMTP focuses on new technologies that can provide more cost effective, faster, and safer ways to
assess the nature and extent of contamination than current technologies. The EPA Environmental
Monitoring Systems Laboratory (EMSL) in Las Vegas, Nevada, implements the MMTP portion of the
SITE Program. The EPA Office of Solid Waste (OSW) provides technical support and method
validation for all SW-846 analytical methods.
1.1.1 Selecting Technologies
Technologies are selected by the U.S. Environmental Protection Agency (EPA) based on their
1-1
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potential use at Superfund sites, as well as EPA regional interest in a technology. Each technology is
evaluated for its ability to meet one or more of the following criteria:
• Capable of being used in the field or in a mobile laboratory
• Applicable to a variety of Superfund sites
• High potential for resolving problems for which current methods are not satisfactory
• Costs are significantly less than current methods
• Performance is significantly better than current methods in areas such as data quality
sample preparation, or analysis time
• Uses techniques that are easier and safer to perform than current methods
1.1.2 Demonstrating Technologies
After a technology has been accepted into the SITE Program, a cooperative agreement between EPA
and the developer is made. The purpose of the agreement is to specify responsibilities for conducting
the demonstration and evaluating the technology. The following issues are settled at this time:
• Assessing the maturity of the technology
• Estimating the potential benefits and limitations of the technology
• Identifying demonstration sites that will provide the appropriate analytes in the desired
environmental sample media or matrices (contaminants must be present in
concentrations amenable to the technology being evaluated)
• Identifying and defining the roles of appropriate demonstration participants, observers
and reviewers
• Arranging analytical support for comparative testing (for example, confirmatory
analysis)
• Supplying standard operating procedures (SOP), analysis methodologies, and other
relevant protocols
• Preparing a demonstration plan that addresses the experimental design, sampling
design, quality assurance/quality control (QA/QC), health and safety considerations,
scheduling of field and laboratory operations, data analysis procedures, and data
output format
• Determining logistical requirements and support (for example, field equipment, power
and water sources, mobile laboratory, communications network)
• Anticipating possible corrective actions that may be required during the actual
demonstration and providing this information to the demonstration participants
1-2
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1.1.3 Evaluating Technologies
Innovative technologies are evaluated independently and, when possible, against conventional
technologies. Data resulting from this demonstration will be used to evaluate the capabilities,
limitations, and field applications of each technology. Following the demonstration, a detailed
evaluation of the results will be presented in a technology evaluation report (TER) and in
technology-specific innovative technology evaluation reports (ITER). These reports will be reviewed
by EPA and technology developers for technical quality.
1.2 DEMONSTRATION PURPOSE
The purpose of this demonstration is to provide the information needed to fairly and thoroughly
demonstrate and evaluate how well FPXRF in situ and intrusive technologies identify and quantify
concentrations of metals in soils.
These two types of FPXRF technologies, in situ and intrusive, were developed to provide real time,
relatively low cost analyses of metals contamination. They were designed to provide information that
will allow investigation and remediation decisions to be made more efficiently on site, and provide
information that will reduce the number of samples that need to be submitted for confirmatory
analyses.
The primary objectives of this demonstration are (1) to determine how well each of the technologies
perform in comparison to conventional analytical methods, (2) to identify the effects, if any, of
sample matrix variations on each technology's performance, (3) to create an SW-846 method for the
use of in situ and intrusive FPXRF technologies, and (4) to identify the logistical and economic
resources needed to operate each technology.
Secondary objectives for this demonstration are to evaluate the FPXRF technologies for their (1)
reliability, ruggedness, cost, and range of usefulness, (2) data quality, and (3) ease of operation. The
performances of the FPXRF technologies will not be compared against each other. Their
performances will be compared to the performances of conventional analytical methods used in
performing site characterization activities. PRC also will examine the potential for loss of metals
1-3
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from soil samples by volatization during the drying of samples using a microwave. The conventional
analytical methods will be referred to as confirmatory methods throughout this demonstration plan.
The data they produce will be referred to as confirmatory data.
j 3 demonstration technologies and developers
To determine which technologies to include in this demonstration, PRC and the SITE Program
referred to the International Organization of Legal Metrology (IOLM) 1993 document "Portable and
Transportable X-ray Fluorescence Spectrometers for Field Measurements of Hazardous Elemental
Pollutants. " IOLM defines an FPXRF in situ technology as being self contained, as capable of
battery operation for at least 4 hours, and as weighing less than 23 pounds. IOLM defines FPXRF
intrusive technologies as being self contained, as capable of battery operation for at least 4 hours, and
as weighing between 23 and 68 pounds. In general, in situ technologies take measurements on the
soil surface or below the ground surface, and intrusive technologies take measurements from samples
removed from their natural setting.
A total of nine technologies will be demonstrated. Eight of these technologies have the dual
capability of analyzing both in situ and intrusively; each capability will be demonstrated. Table 1-1
shows the nine technologies, their capabilities, and who developed them.
1>4 demonstration participants
Participants in this demonstration are listed in Table 1-2. Participants include contacts from EPA
n i 7 and 10, several PRC offices, the confirmatory laboratory, the developers, and
offices in Regions 3, an«
the site contacts The specific responsibilities of each demonstration participant are outlined in greater
detail in Chapter 2.
1.5 demonstraTION sites
This demonstration will W cot*** at two sites: me RV Hopkins site in Davenport. Iowa, and th.
Asarco Tacotna Smelter (As*»> sitt to Washington.
1-4
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These sites were chosen because they exhibit different climates, modes of waste deposition, soil
textures, and because they are contaminated with a variety of heavy metals, including lead,
chromium, cadmium, arsenic, copper, and zinc. These metals will be the primary target analytes for
this demonstration because they are frequently detected at hazardous waste sites. Detailed
descriptions of each site are provided in Chapter 5.
1.6 DEMONSTRATION SCHEDULE
Predemonstration sampling for this demonstration was conducted between December 5 and 14, 1994.
PRC analyzed 100 samples during the predemonstration sampling activities. Thirty-nine samples
collected during this activity were submitted to the confirmatory laboratory for analysis. These 39
samples included nine field duplicates and one performance evaluation (PE) sample. The 29 soil
samples (excluding duplicates and the PE sample) were used by the developers to test and possibly
recalibrate their technologies using the site-specific soils. PRC used this data to select specific
sampling areas for the demonstration and to verify the magnitude and distribution of contaminants at
each site. The field duplicate sample analyses by the confirmatory laboratory were conducted to
evaluate the sample homogenization procedures planned for the demonstration. Specifics of the
predemonstration sampling and other predemonstration activities are discussed further in Chapter 3.
Demonstration activities, including sampling and analysis, are scheduled to occur in April 1995.
Details of the planned demonstration activities are provided in subsequent chapters.
1-5
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TABLE 1-1
TECHNOLOGY CAPABILITIES
Field Portable X-Ray Fluorescence Technologies
SITE Demonstration
Technology
In Situ
Intrusive
Developer
ATX-100
Yes
Yes
Enviro-Recovery Consultants
SEFA-P Analyzer
No
Yes
HNU Systems. Inc.
SEFA-Px Analyzer
Yes
Yes
HNU Systems, Inc.
X-MET 920 (Si(Li) detector)
Yes
Yes
Metorex, Inc.
X-MET 920 (gas-filled proportional
detector
Yes
Yes
Metorex, Inc.
XL Spectrum Analyzer
Yes
Yes
Niton Corporation
MAP Spectrum Analyzer
Yes
No
Scitec Corporation
TN Spectrace 9000
Yes
Yes
TN Spectrace
TN Spectrace Lead Analyzer
Yes
Yes
TN Spectrace
1-6
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TABLE 1-2
DEMONSTRATION PARTICIPANTS
Field Portable X-Ray Fluorescence Technologies
SITE Demonstration
Agency/Company
Point of Contact
Asarco
North 51st and Baltimore St.
Tacoma, WA 98407
- Tom Aldridge, Environmental Director
(206) 756-0203 (phone)
(206) 756-0250 (fax)
Enviro-Recovery Consultants, Inc.
150 South 600 East, Suite 5B
Salt Lake City, UT 84102
- Alan Seelos, President
(801) 328-3659 (phone)
(801) 328-3672 (fax)
EPA
Environmental Monitoring Systems
Laboratory
944 East Harmon
Las Vegas, NV 89193
~ Steve Billets, Program Manager/Technical Project
Manager
(702) 798-2232 (phone)
(702) 798-2261 (fax)
EPA
Office of Solid Waste
401 M St. SW
Washington. DC 20460
-- Oliver Fordham, Technical Advisor
(202) 260-4778 (phone)
(202) 260-0225 (fax)
EPA Region 7
Resource Conservation and Recovery
Act (RCRA) Iowa Section
726 Minnesota Ave.
Kansas City, KS 66101
-- Brian Mitchell, EPA Contact for RV Hopkins
(913) 551-7633 (phone)
(913) 551-7525 (fax)
EPA Region 10
Superfund Section
1200 Sixth Avenue
Seattle, WA 98101
-- Piper Peterson, Project Manager
(206) 553-4951 (phone)
HNU Systems, Inc.
160 Charlemont Street
Newton Highlands, MA 02161-9987
- John Moore, Director of Marketing
(617) 964-6690, Ext. 106 (phone)
(617) 558-0056 (fax)
Metorex, Inc.
1900 N.E. Division St., Suite 204
Bend, OR 97701
- James R. Pasmore, Director of Sales and Marketing
(800) 229-9209 (phone)
(503) 385-6750 (fax)
Midwest Research Institute
425 Volker Blvd.
Kansas City, Missouri 64110
- Gary Wester, Staff Chemist
(816) 753-7600 ext. 1713 (phone)
(816) 753-5359 (fax)
1-7
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TABLE 1-2 (Continued)
DEMONSTRATION PARTICIPANTS
Field Portable X-Ray Fluorescence Technologies
SITE Demonstration
Agency/Company
Point of Contact
Niton Corporation
74 Loomis Street, P.O. Box 368
Bedford, MA 01730-0368
-- Stephen Shefsky, Physicist
(617) 275-9275 (phone)
(617) 275-2397 (fax)
PRC
233 N. Michigan Avenue, Suite 1621
Chicago, IL 60601
— Harry Ellis, Lead Statistician
(312) 856-8700 (phone) |
(312) 938-0118 (fax) 1
-- Rob Foster, SITE Program Manager
(312) 856-8700 (phone)
(312) 938-0118 (fax)
— Kurt Sorensen, Health and Safety Director
(312) 856-8700 (phone)
(312) 938-0118 (fax)
PRC
650 Minnesota Avenue
Kansas City, KS 66101
- Eric Hess, Project Manager
(913) 573-1822 (phone)
(913) 281-5383 (fax)
- Patrick Splichal, Lead Chemist
(913) 573-1826 (phone)
(913) 281-5383 (fax)
- Kathleen Homer, QC Manager
(913) 573-1836 (phone)
(913) 281-5383 (fax)
RV Hopkins
743 Schmidt Rd.
Davenport, LA 52808
- Harold Abdo, President
(319) 323-5419 (phone)
Scitec Corporation
415 N. Quay
Kennewick, WA 99336-7735
- Bill Boyce, Vice President of Research &
development
466"5323 (phone)
(509) 735-9696 (fax)
TN Spectrace
2555 N. IH 35 P.O. Box 800
Round Rock, TX 78680-0800
~~ Myen. Product Manager
, , 388-9100 (phone)
1 (512) 388-9200 (fax)
1-8
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CHAPTER 2
DEMONSTRATION RESPONSIBILITIES AND COMMUNICATION
This chapter identifies the participants involved in this demonstration and describes the primary roles
of each participant. It also describes the methods and frequencies of communication that will be used
in coordinating the dem stration.
2.1 DEMONSTRATION PARTICIPANTS AND ROLES
All demonstration participants are shown in Table 1-2. Roles for each participant are briefly
discussed in the following paragraphs.
This demonstration is being conducted by PRC under contract to the EPA EMSL. EMSL's role is to
administer the MMTP portion of the SITE Program. PRC's role is to provide technical and
administrative leadership and support in conducting the demonstration. This support will include
subcontracting analytical services for the demonstration. The EPA EMSL program manager and
technical program manager for this demonstration is Mr. Steve Billets.
The EPA OSW will provide technical support on the experimental design of the demonstration and
the guidance necessary to produce a demonstration that can result in the submittal and validation of an
SW-846 method for in situ and intrusive FPXRF technologies. The EPA OSW technical advisor for
this demonstration is Mr. Oliver Fordham.
The developers selected for this demonstration include: Enviro-Recovery Consultants, HNU Systems,
Inc., Metorex, Inc., Niton Corporation, Scitec Corporation, and TN Spectrace. The developers will
participate in the review and development of the demonstration plan, operator training, and other
technical support as required.
Other participants in this demonstration include the EPA Region 7 Iowa Section, which has regulatory
authority over the RV Hopkins site, and the EPA Region 10 Superfund Section, which has regulatory
authority over the Asarco site. The EPA Region 7 point of contact for the RV Hopkins site is Mr.
Brian Mitchell. The EPA Region 10 point of contact for the Asarco site is Ms. Piper Peterson.
2-1
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2.2 SPECIFIC RESPONSIBILITIES
PRC, in consultation with the EPA EMSL program manager/technical project manager (TPM) and the
OSW technical advisor is responsible for the following elements of this demonstration:
• Designing, preparing, overseeing, and implementing all elements of this
demonstration plan
• Providing needed logistical support, establishing a communication network, and
scheduling and coordinating the activities of all demonstration participants
• Ensuring that an appropriate site and appropriate analytes and matrices are selected
for use in the demonstration
• Performing on-site sampling activities including collecting and homogenizing samples
dividing them into replicates, and bottling, labeling, and shipping them as necessary
• Providing monitoring, oversight, or operation of the technologies during the
demonstration and documenting the experimental methodology and operation of each
technology
• Developing a quality assurance project plan (QAPP) and a health and safety plan
(HASP) for the demonstration activities
• Acquiring the necessary confirmatory analysis data
• Managing, evaluating, interpreting, and reporting on data generated by the
demonstration
• Evaluating and reporting on the performance of the technologies
• Other tasks as assigned by the EPA EMSL program manager/TPM
Each developer is responsible for providing the following:
• Detailed protocols for using their respective technologies
• Complete, fteld-ready systems for demonstration
• Operation of the technologies during the demonstration or training on the operation of
the technologies. Operation of the technologies will only be necessary if a
developer's instrument is not marketed as equipment to be purchased and operated by
private individuals or organizations
• Data reduction and interpretation support, as required
• Logistical, troubleshooting, and other support, as required
2-2
-------
The site owners and the EPA contacts for each site will provide the following support:
Site access
Site characterization information on the site
Health and safety information on the site
Other logistical information and support needed for PRC to coordinate access to the
site for the field portion of the demonstration
PRC has subcontracted the analytical support for confirmatory chemical analyses. The subcontract
was issued to Midwest Research Institute (MRI) and it was solicited and issued under the
requirements of the Federal Acquisition Regulations. PRC will oversee confirmatory analyses and
provide independent QA/QC checks of the confirmatory laboratory.
2.3 COMMUNICATION
PRC will communicate regularly with all participants involved in the demonstration to coordinate
activities and to resolve any logistical, technical, or QA issues that arise as the demonstration
progresses. Communication will take place through the points of contact for each organization listed
in Table 1-2 in Chapter 1. The organizational structure for the demonstration showing lines of
communication is provided on Figure 2-1.
2-3
-------
DATE: 02/17/94 BCM DN
I II E IJAMf : K. \CAD\w4 <>M)4\GRG CM 12 DWG
Slave Billets
PM/TPM
EPA EMSL
Oliver Ford dam
Technical Advisor
EPA OSW
Brian Mitchell
Iowa RCRA
Region 7 EPA
Horold Abdo
RV Hopkins
Piper Peterson I
Supertund |
Region 10 EPAI
Alan S*«los
Enviro-Recovery
Consultants
Eric Hess
Pro|ect Manager
PRC
Tom Aldrldge
Asarco Site Contact J
Asarco
Harry Ellis
Lead Statistician
PRC
John Moore
HNU
Systems
Patrick Splichal
Lead Chemist
PRC
Gary Wester
MRI
Confirmatory Laboratory
Kathy- Homer
OC Manager
PRC
James Pasmorel
Metorex, Inc.
Stephen ShefskyJ
Niton, Corp
Bill Boyca
Scitec, Corp.
Margo Myers
TN Spectroce
I
FPXRF
SITE DEMONSTRATION
FIGURE 2-1
ORGANIZATIONAL
CHART
• AMA.nrMrMT »kj o
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CHAPTER 3
PREDEMONSTRATION ACTIVITIES
Several activities have been conducted by EPA EMSL, EPA OSW, PRC, and other demonstration
participants prior to the demonstration. These activities included identifying developers, selecting
demonstration sites, selecting a confirmatory laboratory and analytical methods, and performing
predemonstration sampling and analysis. This chapter summarizes these activities.
3.1 IDENTIFYING DEVELOPERS
At EPA EMSL's request, PRC began a search for developers of FPXRF technologies capable of
identifying and quantifying concentrations of heavy metals in soils. This search was conducted from
September 1994 to November 1994. PRC contacted research and academic institutions and
manufacturers of analytical and environmental equipment, followed leads from EPA EMSL and EPA
regional offices, and reviewed available literature on FPXRF technologies.
PRC initially identified ASOMA Instruments; Enviro-Recovery Consultants, Inc. (ERC); HNU
Systems, Inc.; Metorex, Inc.; Niton Corporation; Scitec Corporation; Oxford Instruments, Inc.; and
TN Spectrace, as potential demonstration participants. After reviewing information on each of their
technologies, EPA EMSL, EPA OSW, and PRC determined that they were suitable for this
demonstration. The decision process used by EPA EMSL, EPA OSW, and PRC to accept these
technologies for evaluation is briefly described in Chapter 1. Prior to the predemonstration activities,
both ASOMA Instruments and Oxford Instruments, Inc., withdrew from the demonstration.
3.2 SELECTING SITES
PRC conducted a search for suitable sites between September 1994 and November 1994. The
following criteria were used to select appropriate sites;
• The site owner had to agree to allow access for the demonstration.
• The site had to have soil contaminated with some or all of the target heavy metals.
(Slag, ash, and other mineralized metals deposits will not be assessed during this
demonstration.)
3-1
-------
• The site had to be accessible to two-wheei drive vehicles.
• The site had to exhibit one or more of the following soil textures: sand, clay, or
loam.
• The site had to exhibit surface soil contamination.
• The sites had to be situated in different climatological environments.
PRC used EPA EMSL, regional EPA offices, state environmental agencies, and metals fabrication
and smelting contacts to create an initial list of potential demonstration sites. PRC received
considerable assistance from EPA RCRA and Superfund Branches in Regions 4, 6, 7, 8. 9, and 10.
PRC also contacted the Montana Department of Health and Environment, the Nevada Bureau of
Mines and Geology, the Oklahoma Department of Environmental Quality, the Arizona Department of
Environmental Quality, the Missouri Department of Natural Resources, the Arizona Bureau of
Geology, and the New Mexico Bureau of Mines and Mineral Resources. PRC surveyed its offices in
Kansas City, Kansas; Atlanta, Georgia; Denver, Colorado; Dallas, Texas; Albuquerque, New
Mexico; Helena, Montana; Chicago, Illinois; Seattle, Washington; and San Francisco, California, for
information regarding potential sites. These PRC offices have existing RCRA, Superfund. or Navy
environmental contracts that allow access to regional state and federal site information. PRC also
used the Record of Decision Scan data base to search for appropriate sites. Table 3-1 contains a
listing of the candidate sites that PRC identified.
Based on the site-selection criteria listed above and the assistance of the various state and federal
agencies and others listed above, EPA EMSL, EPA OSW, and PRC selected the RV Hopkins and
Asarco sites as the demonstration sites.
These sites are contaminated with a variety of heavy metals. The RV Hopkins site is contaminated
primarily with chromium and lead. The Asarco site is contaminated primarily with lead, arsenic, and
copper.
These sites also exhibit a variety of soil textures and methods of waste deposition, and they exist in
vastly different climatological regions. The surface soil at the RV Hopkins site consists of silty and
clayey loams. The surface soil at the Asarco site consists of sands, loams, and isolated areas of silt.
3-2
-------
The variety of heavy metal contaminants, climatological regions, modes of waste deposition, and soil
matrices will allow a fair and thorough evaluation of how well each technology performs relative to
conventional analytical methods. This diversity also meets the EPA OSW requirements for sample
matrices for potential method validation.
3.3 CONFIRMATORY LABORATORY AND ANALYTICAL METHODS
To assess the performance of the FPXRF technologies, the data obtained using the technologies will
be compared to data obtained using conventional analytical methods. PRC has subcontracted
confirmatory laboratory services. This subcontracting has been carried out under the guidance of the
Federal Acquisition Regulations. MRI has been awarded the subcontract for analytical services for
this demonstration. MRI will abide by the requirements of the QAPP presented in Chapter 8.
All samples collected for confirmatory analysis will be analyzed for heavy metals using SW-846
Methods 3050A and 601 OA. PRC anticipates that approximately 400 samples will be analyzed by
these methods. This estimate includes field and laboratory QA/QC samples. Thirty percent of these
samples also will be extracted using SW-846 Draft Method 3052 (Microwave Assisted Acid Digestion
of Ash and Other Siliceous Wastes - January 1995) and analyzed by SW-846 Method 6010A.
Confirmatory data will meet Level 3 (Definitive) data quality requirements as defined in Chapter 7.
In addition, a quantitative determination of soil moisture content will be achieved by using American
Society for Testing and Materials (ASTM) Method D 2216-92 (Test Method for Laboratory
Determination of Water [Moisture] Content of Soil and Rock) or a similar method. This determination
will be made during the field sampling and analysis activities.
3.4 PREDEMONSTRATION SAMPLING AND ANALYSIS
In November 1994, PRC prepared a predemonstration sampling plan for this demonstration. This
plan defined the sampling rationale to be used at the two demonstration sites. The predemonstration
sampling at both sites was conducted between December 5 and 14, 1994. PRC analyzed 100 soil
samples during the predemonstration sampling activities. All of the samples were initially analyzed
on site with an FPXRF. Thirty-nine samples were submitted for confirmatory analysis during this
3-3
-------
activity. All 39 soil samples were submitted to MRI for confirmatory analysis by SW-846 Methods
3050A and 6010A. Tea percent of the samples were also analyzed by SW-846 draft Method 3052
and SW-846 Method 6010A.
These samples were collected from a wide range of concentrations and soil textures. PRC collected
surface soil samples (0 to L inch) using hand trowels. Samples were homogenized using the procedure
described in Chapter 7. Twenty-seven of these samples were split and sent to the developers. Nine
field duplicates were collected and submitted for confirmatory analysis to assess PRC's sample
homogenization procedures. One performance evaluation (PE) sample was submitted to the
confirmatory laboratory to provide an initial check of accuracy. This predemonstration sampling had.
the following objectives.
• To provide or verify data on the extent of surface contamination at each site and to
locate sampling areas for the demonstration
• To allow the developers to analyze samples from the demonstration sites in advance
and, if necessary, refine and recalibrate their technologies and revise their operatins*
instructions *
• To allow an evaluation of any unanticipated matrix effects or interferences that may
occur during the demonstration
• To check the QA/QC procedures of the confirmatory laboratory
3-4
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TABLE 3-1
SURVEY OF POTENTIAL DEMONSTRATION SITES
Field Portable X-Ray Fluorescence Technologies
SITE Demonstration
Site Name and Location
Contact
Status and Comments
St. Charles Metal Finishing
Company
St. Charles, Missouri
Ruben McCullers-EPA
Region 7 (913) 551-7455
Plating facility, already characterized,
moist climate; lead, chromium, zinc,
cadmium; access not granted
Asarco Lead Smelter
El Paso, Texas
Traci Fambrou-EPA
Region 6 (214) 665-2246
Lead, arsenic, some characterization, dry
climate, middle of Consent Order
negotiations; EPA does not want site used
Asarco Lead Smelter
Tacoma, Washington
Piper Peterson-EPA
Region 10 (206) 553-4951
National Priorities List (NPL) site,
arsenic, lead, copper, already
characterized, moist climate: access
granted
RV Hopkins Site
Davenport, Iowa
Brian Mitchell-EPA
Region 7 (913) 551-7633
Active drum recycling facility, partially
characterized, high lead and chromium
contamination; access granted
Pacific Activities Limited
(PAL) Site
Davenport, Iowa
Jeff Weatherford-EPA
Region 7 (913) 551-7695
Abandoned nickel-alloy pig manufacturer,
partially characterized, high concentrations
of all target analytes except arsenic; access
denied
Smeltertown
Salida, Colorado
Victor Ketellaper-EPA
Region 8 (303) 294-7146
Mining and smelting site, some
characterization, elevation above 7,000
feet, dry climate, lead, arsenic, zinc,
copper, barium; access granted; likely
snow covered for demo
East Helena Superfund Site
Helena, Montana
Scott Brown-EPA Region 8
(406) 449-5720
Asarco smelter, lead, arsenic, cadmium,
zinc, copper; EPA does not want
demonstration at this site
Silver Bow Creek
Butte, Montana
Neil Marsh-Montana
Department of Health and
Environment (406) 444-1420
Well characterized, mine tailings along a
creek and river, ARCO facility, tailings
generally saturated
Wicks Smelter Site
Helena, Montana
Dave Donahue-PRC
(406) 442-5588
Lead smelter, some characterization, lead,
arsenic, zinc, and copper; Bureau of
Mines site; likely snow covered for demo
West Dallas Lead Site
Dallas, Texas
Stan Hitt-EPA Region 6
(214) 665-6735
Lead smelter, some characterization,
primarily residential contamination, mostly
remediated
Border Steel
El Paso, Texas
Traci Fambrou-EPA
Region 6 (214) 665-2246
Lead smelter, facility going bankrupt, only
known contamination associated with an
on-site landfill; access denied
3-5
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TABLE 3-1 (Continued)
SURVEY OF POTENTIAL DEMONSTRATION SITES
Field Portable X-Ray Fluorescence Technologies
SITE Demonstration
Site Name and Location
Contact
Status and Comments ||
Kennecott Remediation
Salt Lake City, Utah
Eva Hoffman-EPA Region 8
(303) 293-1534
Many subsites, old cobalt refinery, already
characterized, lead, arsenic, cadmium,
copper, cobalt, cold and dry climate;
access granted; likely snow covered during
demo
Tri-siate Mining
Jasper County, Missouri
Mark Doolan-EPA Region 7
(913) 551-7169
Some characterization, lead, moist
environment; access granted; too limited
contaminant constituents
Tucson International Airport
Tucson, Arizona
Dennis Gott-U.S. Air Force
(513) 255-0258
Former plating operation, chrome waste in
unlined pond, wastes have been capped,
dry environment
Oracle Ridge Mining Partners
Arizona
Susan Johnson-EPA
Region 9 (415)744-2361
Only copper and zinc contamination; site
has been remediated
Portland Cement
Utah
No contact
Some characterization, too low metals
concentrations
Apache Powder
Arizona
Andrea Benncr-EPA
Region 9 (415) 744-2361
Well characterized, too low metals
concentrations; access could be a problem 1
Phelps-Dodge Reduction
Works
Bisby, Arizona
Caroline Douglas-EPA
Region 9 (415) 744-2343
NPL site; site has been remediated
ILCO Lead Smelter
Alabama
Kim Lantermac-EPA
Region 4
Lead and arsenic, NPL site, wet climate;
access denied
Sherwin Williams
Coffeyville, Kansas
Mark Matthews-EPA
Region 7 (913) 551-7635
Lead, zinc, barium, residential
contamination, moist environment, limits
area of gross contamination
Cleveland Mill
Silver City, New Mexico
Kathleen Aisling-EPA
Region 6 (214) 665-8500
EPA does not want a demonstration at this
site
Reeves Southeastern
Corporation
Tampa, Florida
Anita Davis-EPA Region 4
(404) 347-5054
Electroplating operation, contamination in
lagoons that have not been drained
Yakima Plating
Yakima, Washington
Joe Mollusky-PRC
(206) 624-2692
Site has been remediated
Goldere Junkyard
Morristown, New Jersey
Dennis Santella-EPA
Region 2 (212) 264-8677
Site does not have target analytes in high
enough concentrations for this
demonstration
3-6
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TABLE 3-1 (Continued)
SURVEY OF POTENTIAL DEMONSTRATION SITES
Field Portable X-Ray Fluorescence Technologies
SITE Demonstration
Site Name and Location
Contact
Status and Comments
NAVBASE Charleston
Charleston, North Carolina
Todd Haverkast-EnSafe
(803) 747-7937
Site includes a former abrasives blasting
area; contamination in this area is too low
for the demonstration
Tar Creek Site
Oklahoma
Nowell Bennet-EPA
Region 6 (214) 665-8514
This mining area is contaminated with lead
and zinc; access is granted; not sufficient
constituent variety
Eagle Picher Smelter
Joplin, Missouri
Mark Doolan-EPA Region 7
(913) 551-7169
This is pan of the Tri-state mining site,
the contaminants are lead and zinc; access
is granted; not sufficient constituent
variety
Peerless Plating
Muskegon, Minnesota
Mike Johnson-PRC
(312) 856-8700
Well characterized, sandy soil, lead,
chromium, zinc; access is possible; snow
covered during demo
Asarco Lead Smelter
Glover, Missouri
Kathy Flippin-MDNR
(314) 751-3176
High lead, copper, and zinc
concentrations, some characterization,
moist site; access MDNR was not
interested in demo
Eagle Picher Smelter
Henryetta, Oklahoma
Dennis Datin-ODEQ
(405) 271-7097
Arsenic, lead, cadmium, and zinc
contamination, some characterization,
moist site; access is possible; site now
owned by City of Henryetta; ODEQ was
not interested in demo
National Zinc
Bartlesville, Oklahoma
Scott Thompson-ODEQ
(405) 271-7213
Zinc, lead, and cadmium contamination,
wet site, remediation in progress, probably
finished by Spring 1995
Harbor Island
Tacoma, Washington
Keith Rose-EPA Region 10
(206) 553-7721
Privately-owned, lead, arsenic, cadmium,
chromium contamination, 400 acres,
record of decision (ROD) completed;
access may be problematic, wet site,
remedial action end of next year
Bunkerville Mining District
Southeastern Nevada
Paul Lechler-Nevada
Bureau of Mines-Geology
(702) 784-6691
Copper, chromium, nickel, no soil data
only data for ores and rocks, dry site
Boss Mine
Clark County, Nevada
Paul Lechler-Nevada
Bureau of Mines-Geology
(702) 784-6691
Copper, lead, zinc, gold, silver, platinum,
only data for ores and rocks, no soil data,
dry site
Weldon Springs, Missouri
Cecilia Tapia-EPA Region 7
(913) 551-7733
Limited constituent variety; only lead
present; wet site
3-7
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TABLE 3-1 (Continued)
SURVEY OF POTENTIAL DEMONSTRATION SITES
Field Portable X-Ray Fluorescence Technologies
SITE Demonstration
Site Name and Location
Contact
Status and Comments ||
Mare Island Naval
Shipyard-IR04
Vallejo, California
Cur: Enos-PRC
(913) 573-1827
Primarily chromium contamination, some H
copper, lead, nickel, and zinc. H
contamination in "green sands," well H
characterized, wet site; access possible; |
too low of contaminant concentrations for |
demo |
Hanover Whitewater Mine
Mevu Mexico
Ben Gorrod-EPA Region 6
(214) 665-6779
No response to request for information |
Helvetia Mining District Rick Trapp-Artzona Bureau
Arizona of Geology
AnZ (602) 882-4795
Lead, zinc, copper, possibly cadmium, 1
smelter on site, arid site, south of Tucson, 1
no analytical data: access may be a H
problem |
Phelps Dodge Smeller R«* Trapp-Arizona Bureau
Ajo. Arizona 1
Copper mine, arid location, no analytical 1
data; little known about site fl
Smelter Site *** Trapp-Arizona Bureau
Cortland G.eaaon. Arizona ^
Lead and zinc smelter, good access, arid g
site, no analytical data; little known about
site
Combined Metals No contact
Twilla. Utah
No information
Midvail Superfund Site No contact
Suburb of Salt Lake City, j
11 rah 1
No information
Indian Reservation ?
-------
CHAPTER 4
TECHNOLOGY DESCRIPTIONS
This chapter describes the FPXRF technologies manufactured by each deveioper. The descriptions
are based on the information provided by the developers and on information PRC obtained from
reports and journal articles written about the FPXRF technologies. The descriptions include
background information and a description of the equipment. General operating procedures, training
and maintenance requirements, and the cost of each technology also are discussed. References to
XRF technologies below refer to both field portable technologies and laboratory-grade technologies.
FPXRF technologies operate on the concept of energy dispersive x-ray fluorescence spectrometry.
Energy dispersive x-ray fluorescence spectrometry is a nondestructive qualitative and quantitative
analytical technique used to determine the metals composition, of samples. The field portable XRF
technologies described in this chapter use sealed radioisotope sources to irradiate samples with x-rays.
Laboratory-grade XRF technologies use an x-ray tube to irradiate the samples with x-rays. Both the
field portable and laboratory-grade technologies produce x-rays of known energies. By exposing a
sample to an x-ray excitation source having energy close to, but greater than, the binding energy of
the inner shell electrons of the metals, an inner shell electron is discharged. The electron vacancies
that result are filled by electrons cascading in from outer electron shells. Electrons in outer shells
have higher energy states than inner shell electrons, therefore, to fill the vacancies, the outer shell
electrons give off energy as they cascade down into the inner shell vacancies. There are three
electron shells generally involved in the emission of x-rays during the FPXRF analysis of
environmental samples: K, M, and L shell electrons. The emission of x-rays is termed x-ray
fluorescence. Each metal gives off x-rays of different energy levels. The specific type or energy of
the emitted x-ray is unique to a given metal and is called a "characteristic" x-ray. By measuring the
different energies of x-rays emitted by a sample exposed to an x-ray source, it is possible to identify
and sometimes quantify the metals composition of a sample. A qualitative analysis of the samples can
be made by observing the characteristic x-rays produced by the sample. The quantity or intensity of
each energy of x-rays emitted is proportional to the concentration of the target analytes.
The x-ray fluorescence from excited metals span a range of measurable energies. This energy is
measured in kiloelectron volts (keV). A typical emission pattern, also called an emission spectrum,
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from a given metal will have multiple intensity peaks generated from the emission of K. L, or M shell
electrons. Most metals contaminants have characteristic K and L electron shell emissions, however
only metals with an atomic number greater than 57 have measurable M emissions. These
characteristic electron shell emissions generally consist of at least two unique intensity peaks
identified as alpha and beta. These peaks are commonly described as lines and each metal produces a
unique fluorescence energy at each of these lines. For example, lead has the following characteristic
lines that can be detected in an emission spectra for lead: L-aipha (10.549 keVi, L-beta
(12.611 keV), K-alpha (74.957 keV), K-beta (84.922 keV), M-alpha (2.346 keV), and M-beta
(2.443 keV).
The energy of each intensity peak is characteristic of the excited metal. The magnitude of the
intensity peaks is related to the concentration of the metal. The magnitude of these peaks is measured
in "counts," and this unit of measure relates to the number of x-rays emitted per unit of time. For
most metals, the K and L emissions are used for identification and quantification.
Along with the K, L, and M electron shell emissions, the x-ray excitation source emits characteristic
x-rays of a set energy level. This emission energy can be measured along with the K. L, and M shell
emissions during XRF analysis. The emission peak of the excitation source is called the Compton
Peak. By selecting an excitation source with a Compton Peak energy close to either the K, L, or fcf
shell emissions of a target metal, the detection sensitivity of the XRF analysis is increased. XRF
technologies with x-ray tube sources can nine their excitation emissions to optimize the relationship
between the source's characteristic energy (Compton Peak energy) and the characteristic fluorescence
energy of the metals. Radioisotope sources, on the other hand, only emit x-rays at one characteristic
energy. Because of this, different radioisotope sources may be needed to provide adequate detection
sensitivity for a wide range of target anaiytes. For example, using an Iron-55 (Fe55) radioisotope
source would be appropriate for titanium analysis, however, the Compton Peak from this source is
too close to chromium to allow accurate or precise quantitation. When the Compton Peak is too close
to the characteristic emission energies for a target analyte, it interferes with the resolution of the
target analyte's emission peaks. For chromium analysis, a cadmium-109 (Cd109) radioisotope would
be more appropriate. The Cd109 Compton Peak energy is far enough away from the characteristic
energies of chromium, but close enough to allow good resolution and relatively low detection limits
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Another way to increase the sensitivity and precision of an XRF technology is to increase a samples
exposure time to an excitation source. This is commonly referred to as increasing count times. The
measurement of the x-ray emissions occurs concurrently with the excitation of a sample. By
increasing a sample's exposure time, more time is available for measuring the emission counts from
the sample. This generally increases the data gathered for a sample, and allows the averaging out of
natural variation in emissions, therefore, increasing precision and accuracy.
XRF technologies consist of a source for sample excitation, a detector, a sample chamber, and an
emission or fluorescence energy analyzer, such as a multichannel analyzer (MCA). The excitation
source types are either x-ray tubes coupled with primary radiation filters or sealed radioisotope
sources. The x-ray tube is an evacuated glass envelope comprised of a filament with adjustable
current control, a pure metal anode, which is typically rhodium, tungsten, or silver, and a beryllium
window through which the x-rays radiate toward the sample. . Common radioisotope sources used in
source-excited XRF analysis are Fe55, Cobalt-57 (Co57), Cd109, Americium-241 (Am241), and
Curium-244 (Cm244). The relative strength of the radioisotope sources is measured in units of
millicuries (mCi). The stronger the source, the greater its sensitivity and precision. XRF
radioisotope sources undergo constant decay. In fact, it is the process of decay that emits the
characteristic x-rays used to excite samples for XRF analysis. The decay of radioisotopes is measured
in "half lives. " The half-life of a radioisotope is defined as the length of time required to reduce its
strength or activity by 50 percent. Developers of XRF technologies recommend source replacement
at regular intervals, based on a source's half life. Table 4-1 provides a summary of the
characteristics of the radioisotope sources.
The detectors in the XRF technologies can either be solid-state detectors or gas-filled, proportional
counter detectors. Common solid-state detectors include lithium drifted silicon Si(Li) or mercuric
iodide (Hgl2). The Hgl2 detector can be operated at room temperature. The Si(Li) detector must be
cooled to at least -90 °C for operation. This can be done with liquid nitrogen or by thermoelectric
cooling via the Peltier effect. Proportional counters are rugged and lightweight, which are important
features of a field portable detector. However, the resolution of a proportional counter is not as good
as that of a solid-state detector.
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The MCA is used to collect and manipulate the data. The MCA receives pulses from the detector
separates every pulse by energy level. The MCA counts pulses per second to determine the height of
the peak in a spectrum, which is indicative of the target analyte's concentration. Most XRF
technologies are menu-driven from software built into the detector or from a personal computer (PC)
XRF technologies can be calibrated using the following methods, internally using fundamental
parameters determined by the developer, empirically based on calibration standards, or based on
Compton Peak ratios. XRF technologies can generally be calibrated by multiple methods.
Technology-specific calibration is described in the following subsections.
Table 4-2 summarizes general operational characteristics for the technologies involved in this
demonstration.
4.1 TN SPECTRACE 9000
This section presents information on the background, apparatus, general operating procedures,
training and maintenance requirements, and cost of the TN Spectrace 9000.
4.1.1 Background Information
TN Technologies introduced field portable XRF technology in 1966. In 1988, it released the first
field portable XRF technologies for mining, chemical plant, and refinery applications. Since then
TN Technologies and Spectrace Instruments together (as TN Spectrace) have been producing field
portable and laboratory-grade XRF technologies for a broad range of applications. The TN Spectra^
9000 was released in 1992 for environmental applications.
The Hgl2 detector, also referred to as a spectrometer, uses an Hgl2 semi-conductor x-ray detector
achieves a manganese K-alpha x-ray resolution of 270 electron volts (eV) while operating near
ambient temperature.
The TN Spectrace 9000 uses energy dispersive x-ray fluorescence spectrometry to determine
elemental composition of soils, sludges, aqueous solutions, oils, and other waste materials. It
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three radioactive isotopes, Fe55, Cd109, and Am241 to produce x-rays, which excite a corresponding
range of metals in a sample (Table 4-1). The TN Spectrace 9000 can identify and quantify the target
metals sulfur through uranium in a sample. When more than one source can excite metals, the
appropriate source is selected according to its excitation efficiency for the target metals.
The sample is positioned in front of the source-detector beryllium window and sample measurement is
initiated. This exposes the sample to primary radiation from the source. Fluorescent and
backscattered x-rays from the sample enter through the source-detector beryllium window and are
counted in a high resolution Hgl2 detector. The surface probe of the Hgl2 detector provides for both
in situ soil analysis and intrusive soil analysis with the probe in the upright position and the safety
shield attached.
Contaminant concentrations are computed using a fundamental parameter backscatter algorithm. The
TN Spectrace uses fundamental parameters to calibrate its FPXRF technology. The fundamental
parameters are based on the physics of the excitation and emission of x-rays. The menu-driven
software in the TN Spectrace 9000 supports multiple XRF calibrations called "applications." Each
application is a complete analysis configuration including target metals to be measured, interfering
target metals in the sample, and a set of fundamental parameter calibration coefficients. The
fundamental parameters method does not require site-specific calibration samples.
4.1.2 Equipment and Accessories
The TN Spectrace 9000 comes with all of the equipment necessary for in situ and intrusive operation.
A hard-shell carrying case is provided for transportation and storage.
Two main components make up the analytical system: a probe and an electronics unit. The main
components are discussed in the following paragraphs. A list of all primary and secondary
components follow die discussion.
The probe contains three radioisotope sources: Fe55 (50 mCi), Cd109 (5 mCi), and Am241 (5 mCi)
for sample excitation. The sources are encapsulated and housed in a metal turret with additional lead
shielding inside the probe. These sources can sequentially expose the sample to excitation radiation
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through a sealed 1-inch-diameter polypropylene window (probe window) in the face of the probe.
The x-ray induced fluorescence from the sample passes back through the window and is intercepted
by the Hgl2 detector. This detector quantitates the energy of each X-ray and builds a spectrum of
element peaks on a 2048-channel MCA.
Spectral data is communicated to the electronics unit through a flexible cable of 6. 12. or 20 feet in
length. Metal peaks are integrated and parts per million or percentage values are calculated. The
electronics unit will store and display both numerical results and spectra from a measurement. A
maximum of 300 sets of numerical results and 120 spectra can be stored before downloading to a PC
via a RS-232 cable.
The TN Spectrace 9000 is supplied with four factory-installed fundamental parameter-based
applications. The "Soils" application is for analysis of soils in which most of the sample is silica.
The TN Spectrace 9000 is programmed for three other applications, Fine-Mesh Soils," "Thin Film."
and "Lead in Paint," which will not be evaluated in this demonstration. TN Spectrace also will
develop calibrations to meet new user application requirements, such as adding target analytes to the
present "Soil Samples" application.
The TN Spectrace 9000 can be powered from a 115-volt or 220-volt wall outlet or from its 4-hour
capacity battery. It can be operated in temperatures ranging from 0 to 49 °C. Furthermore, the
probe and electronic unit can be exposed to light rain. However, additional protection is provided
when the system is contained in the optional water repellant carrying case.
The probe and electronics unit are comply sealed with rubber gaskets and can be decontaminated
with soap and water.
Equipment/Optional AcceMorte/Imtnnwit SptcUlcattom
Equipment
The standard TN Spectrace 9000 system i*1 udes.
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• Electronics unit for data acquisition, processing, storage, and display
Nickel and cadmium battery pack (4 to 5 hours of continuous use)
• Hand-held probe including:
Hgl2 detector
Three excitation sources (Fe55, Cd109, Am241)
Safety Cover
• Uniblock for table top use (the uniblock is a probe labstand that conveniently allows
the operator to analyze samples in cups and thin films, and to perform the check
procedure for the Lead in Paint application.)
Sample shield
Positioning ring for standard 31-millimeter (mm) x-ray sample cups
• Interconnecting probe cable (6-foot cable is standard)
• Pure element check samples kit
• Two blank samples for background setup and check out
• Battery charger
• RS-232 serial input/output interface cable
• System carrying/shipping case
• Operators manual, factory applications, and results management software
• Training video (22 minutes)
• Ten 31-mm-diameter sample cups
• 1 roll 6.0 micrometers (nm) Mylar XRF film (300 feet)
• Spare window assembly
Optional Accessories
• Field pack with shoulder straps ($245)
• Spare battery pack, charger, and adapter ($750)
• Battery eliminator for continuous use ($600)
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• "Applications Generator" software program
• National Institute of Standards and Technology (NIST) Soil Standard Kit (NIST
No. 2579)
• Micromatter Lead Thin Film Standards Kit (for lead in paint measurements)
• Dust wipe kit
Instrument Specifications
« Probe Dimensions Weight: 12.7 centimeters (cm) x 7.6 cm x 21.6 cm;
1.9 kilograms (kg)
• Cable: standard 6-foot length, optional 12 or 20-foot lengths
. Electronics rr"if Dimensions and Weight: 32 cm x 30 cm x 10 cm; 6.7 kg
• Power: operates from a nickel cadmium battery for 4 to 5 hours of continuous use.
Alsocan use 110 or 220 volt, 50 to 60 Hertz Alternating Current (AC) electricity.
• Operating tpmpp.raturev 0 to 49 °C (32 to 120 F)
• Storage Temperature:. -40 to 40 °C (-40 to 104 CF)
4.1.3 General Operating Procedures
To operate the TN Spectrace 9000, the nickel cadmium battery is plugged in, and the probe cable is
connected. The detector is turned on by pressing the "On" button. A message on the screen will ask
the operator for the date and time and then proceed to the MAIN MENU. It is important to set the
date correctly, otherwise errors in source-decay compensation can result.
The TN Spectrace 9000 software is menu driven. From the MAIN MENU, the operator selects a
predefined "Application," which is a complete analysis setup that defines the elements of interest, the
radioisotope sources to be used, and the matrix type that is being analyzed (soil, water, oil, sludge,
metal, and so on). The TN Spectrace 9000 comes with the following four applications installed:
1 Soils Application (an^yzes 25 elements in soil with each measurement)
2 Fine-Mesh Soils (for finely ground and cupped soils, 100 mesh or smaller)
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3. Thin Samples (25 elements on air fillers, wipes, platings, or coatings)
4. Lead in Paint (makes in situ measurements of lead in paint, substrate independent)
A PC-based software program called the "Applications Generator" allows the operator to develop
additional XRF applications for use in the electronics unit.
Once the application is selected, each analysis is completely automated by the TN Spectrace 9000
software. To begin measuring samples, the operator selects MEASURE to get to the "Ready
Screen. " From here the operator initiates an analysis by pressing either the probe trigger or the
"Continue" button on the electronics unit. Distinct sounds signal the beginning and end of a
measurement to alert the operator to take the next measurement. Results with standard deviations are
displayed at the end of each measurement. If desired, results and spectra can be automatically stored
on the electronics unit after each measurement. Transferring the results and spectra to a PC allows
printing, archiving, spreadsheet, and report generation
The TN Spectrace 9000 should be allowed to warm up for 30 minutes before performing analysis.
This time allows for detector cool down and instrument stabilization. Automatic gain compensation is
a feature of the "Soil Samples" application, which allows operation of the technology over a wide
range of ambient temperatures and from one day to another without standardization. If the automatic
gain control fails or is out of range, an error message will appear on the screen. If the error message
continues to appear after repeat analyses, then the Cd109 measurement time should be checked or an
energy calibration should be performed.
The "Set Store/Send Modes" option is located in the "more" screen, which can be accessed from the
main menu. Data or spectrum storage must be enabled for automatic on-board storing to occur.
Sufficient memory is available to store up to 300 sets of analytical results and up to 120 spectra. This
is adequate for 40 sample analyses since each sample is exposed to all three radiation sources, which
results in three spectra for each sample. When the available memory is Ml, the respective spectra or
results storage mode is automatically disabled. The spectra or results memory must be cleared and
the respective store mode enabled before results of spectra can be stored again.
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The main menu selection displays the application name, revision date, exposure time for each son
and accesses other options. Routine operation for soil sample analysis proceeds with the selection of
"Soils Analysis" from the main menu, which leads to a set up of the sample source exposure times
per source and initialization of the probe controls for measurement. Source exposure times can
v*ry i
Source exposure times for soil samples typically vary from 60 to 300 seconds. Generally the metal
detection limit is reduced by 50 percent for every four-fold increase in source exposure time Thjs
does not consider metal interferences and matrix interferences. Although counting statistics improve
as measurement time increases, the practical limit for typical applications is 600 to 800 seconds
The exposure time of a source is concluded with an audible signal followed by an on-screen report of
the analyzed metals. Results are labeled by metal symbol and include both element concentrations
and an indication of the computed standard deviations. The TN Spectrace 9000 can analyze soil
samples for 26 elements with the sequential use of all three excitation sources.
After analysis of a sample is complete, it is possible to retrieve and review stored results and sneet
The stored results and spectra may be reviewed, deleted, or downloaded to a PC. Selecting the
"Measure" option will immediately begin another analysis cycle.
There are several preoperational check samples that should be analyzed prior to sample analysis
The samples include an energy calibration check, a resolution check, a blank sample check, and a
target metals response check. An energy calibration should be performed after a technology is
shipped and periodically during storage (approximately every 2 weeks) to ensure proper energy
calibration. The energy calibration check is performed in the field daily and after an energy
calibration to verify proper energy calibration.
The resolution check examines the detector s ability to resolve x-ray energies. This should be
performed once at the beginning of the day. This is done by measuring a sample of iron using a
minimum acquisition time of 60 seconds for the Cd109 source.
The blank sample check is performed to monitor the technology's zero drift in the selected
application. This monitors baseline resp0®® of the technology, which affects quantitation and
detection. The blank sample check sh0u^ ^ conducted at the beginning of each day, after an energy
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calibration, after loading an application, and whenever the technology exhibits a persistent drift on a
blank or low-level sample. The blank sample check consists of the analysis of a quartz or Teflon
blank provided with the technology using a minimum source exposure time of 60 seconds for each
source.
The purpose of the target metals response check is to ensure that the technology and the selected
application are working properly prior to performing sample analysis. This check should be
performed at the beginning of each day. The check samples are generally standards or PE samples,
such as standard reference materials (SRM), both with known concentrations for some or all of the
target metals to be checked. The samples should be measured using the same source exposure times
that will be used for sample analysis.
No site-specific standards are needed with the TN Spectrace 9000. The technology is calibrated at the
factory using pure elements and calculates results of a soil sample using a matrix correcting
Fundamental Parameters algorithm. Two types of matrix effects are inherent with x-ray fluorescence
spectrometry: absorption and enhancement matrix effects. The absorption affects lower XRF data,
while the enhancement affects increase the XRF data relative to true value concentrations. The
Fundamental Parameters algorithm makes the appropriate matrix corrections for analysis of 25
elements in soil.
If desired, the TN Spectrace 9000 software can provide for a site-specific calibration to model a given
suite of standards.
For data QA, TN Spectrace recommends that a certified reference sample be run periodically. This
will provide valuable accuracy and precision data. Running a certified reference sample can also alert
the operator that either the probe window is contaminated or the technology is not operating properly.
The probe window can be cleaned with a towel and the condition of the detector can be checked using
the Standard Operational Check, which requires running a pure iron sample and the pure Teflon
sample to verify sensitivity and background, respectively.
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4.1.4
Training and Maintenance
The TN Spectrace 9000 comes with a 22-minute training video which discusses the theory of XRF,
operation, and general care of the technology. In cases where personalized training is requested, TN
Spectrace offers a 2-day, in-house training course. A 2-day on-site training course is another option
at Si.000 per day plus travel expenses.
TN Spectrace must be notified immediately of any conditions or concerns relative to the probe's
structural integrity, source shielding, source switching operation, or operability. The appropriate
state agency or the Nuclear Regulatory Commission must be notified immediately of any damage to
the i .iJioactive source, or any loss or theft of the device. The sources in the probe must be
leak-tested every 6 months as described in the TN Spectrace 9000 Operating Instructions. The leak
certificates must be kept on file, and a copy must accompany the technology at all times. If the probe
window becomes damaged or punctured, it should be replaced as soon as possible to prevent dust and
moisture from entering the probe. Replacement window assemblies can be ordered from TN
Spectrace. General service contracts are available from TN Spectrace with the purchase of a TN
Spectrace 9000.
The TN Spectrace 9000 can be cleaned with soap and water and is designed to be used in the field
where conditions may be wet, dirty and rugged. Given proper care, the technology should only
require the scheduled periodic maintenance of source replacement.
Due to the inherent safety design features and associated low levels of radiation and small quantities
of radioactive materials, the technology is supplied under a general license for radioisotope regulatory
purposes, which greatly simplifies its transportation and use.
4.1.5 Testing Time and Cost
The standard deviation for each measurement is reported with the data output. This information
allows the operator to optimize the source exposure times for the task at hand, balancing the standard
deviation (error) with the analysis t0 meeI ProJ«ct data quality objectives (DQO), as well as
project schedules. When analyzing s°iIs ^ m in «eas of high contaminant concentrations at a site,
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the developer recommends short source exposure times of 1 or 2 minutes. As the concentration nears
the action levels, the developer suggests a longer count time should be employed to increase the
precision (decrease the standard deviation of a measurement) at the action level. The developer
suggests that typical source exposure times for these conditions is 3 to 7 minutes. Since the
measurement is automated by the TN Spectrace 9000 software, the operator can prepare the next
sample or sampling area while the technology is running the previous one. An operator should be
able to analyze at least 50 samples per day.
The TN Spectrace 9000 costs $55,000 to purchase. This includes all of the equipment necessary for
operation of the technology. Purchased technologies are warranted for a full year with an optional
extended warranty. The TN Spectrace 9000 can be rented through several rental companies for
approximately $6,000 per month. Weekly rates are also available. Periodic maintenance includes
replacement of the Cd109 source every 2 to 3 years at a cost of $3,500 to $3,800. The Fe55 source
should be replaced every 4 to 5 years. The cost of replacement of the Cd109 and Fe55 sources
together is $6,800. The Am241 source has a half life of 433 years so it does not need replacing.
4.2 X-MET 920
This section presents information on the background, apparatus, general operating procedures,
training and maintenance requirements, and cost of the X-MET 920. This technology has two
detector configurations, a Si(Li) detector and a gas-filled proportional detector. Both detectors will
provide different levels of data quality and for the purpose of this demonstration they will be
evaluated separately.
4.2.1 Background Information
Metorex is an international supplier of advanced equipment for metal detection, materials testing, and
chemical analysis. It offers a wide range of products from field portable and laboratory-grade metals
and alloy analyzers to on-line systems. It has more than 20 years experience in developing x-ray
detection technologies. Metorex developed the X-MET 920 to perform elemental analysis in the
petroleum and petrochemical industry, the mining and minerals industry, and the environmental field.
The X-MET 920 is a light-weight portable technology that can be operated in situ or intrusively. It is
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offered with a gas-filled proportional detector or a Si(Li) detector. The Si(Li> detector is considered
the high resolution detector.
The X-MET 920 was designed as a modular system so that users can configure the technology with
the precise hardware and software for their analytical needs.
4.2,2 Equipment and Accessories
The basic configuration of the X-MET 920 includes: a disk operating system-based PC. software.
X-MET PC System (XPCS), and an analysis probe. The XPCS card contains a 2,048-channel MCA
that is used to collect, analyze, and display the spectrum. The MCA portion of the technology is
contained on a single electronic board that is plugged into one of two expansion slots of the PC.
The high resolution probe is a hand-held, compact unit that contains a Si(Li) detector. The detector
achieves a manganese K-alpha x-ray resolution of 170 eV. The detector is cooled by a 0.5-liter liquid
nitrogen dewar built into the probe, which allows for 8 to 12 hours of field use. A dewar is similar
to a Thermos except that it is used to store super cooled liquids. It can be used as a surface probe to
perform in situ analyses, or with the attachment of a sample cover, the probe can analyze soil sample*
intrusively from a sample cup. The probe dewar can be filled with liquid nitrogen before each
measurement session or can stay connected to the "mother" dewar (30-liter capacity) and removed
only for a few measurements. The •mother" dewar lasts, under normal conditions, for up to 30 days.
The other probe is also a hand-held, compact unit, but it contains a gas-filled proportional detector.
The detector achieves a manganese K-alpha x-ray resolution of 750 eV. The detector operates at
ambient temperatures (-13 to 140 degrees Fahrenheit, requiring no artificial cooling. It can be used
as a surface probe to perform in situ analyses, or with the attachment of a sample cover, the probe
can analyze soil samples intrusively from a sample cup.
Either detector will accommodate simultaneously two radioisotope sources to cover the elemental
range from potassium to uranium- The developer offers the following radioisotopes: Fe55, Cd109
and Am241. These isotopes are »n *** fo*m of an 8-mm-diameter by 5-mm-thick capsule. The
suggested dual source configurat*"5 «» Fe» and Cd'®, or Cd"» art Am™. The .taeoor U
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environmentally sealed by a 25-mm-diameter window of Kapton® film. The sources are driven into
the measurement position with nitrogen gas, which is evolved from the liquid nitrogen to create a
pressure in the dewar of 10 pounds per square inch (psi). The detector is equipped with interlock
mechanisms to prevent operator exposure to the radioactive sources or instrument exposure to high
voltage.
Instrument Specifications
• Computer: Disk operating system-based PC with the minimum configuration:
Central Processing Unit 80386 DX 33 megahertz with math coprocessor
2 megabytes random acceSs memory
80-megabyte hard disk
Video graphics array (VGA) grapnics
XPCS (One unit for each probe)
• Physical Dimensions:
Size: 38 cm x 35 cm x 7.5 cm
Weight: 5.5 kg with standard battery pack
Environmental Protection: National Electrical Manufacturers Association
(NEMA) No. 4 enclosure rating
• Si(Li) Detector Physical Dimensions;
Size: 20 cm x 10 cm x 25 cm
— Weight: 3.7 kg without liquid nitrogen; 4.1 kg with liquid nitrogen
• Gas-Filled Proportional Detector Physical Dimensions:
Size: 20 cm x 10 cm x 25 cm
Weight: 3.7 kg
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4.2.3
General Operating Procedures
The operating procedures for the two detector options are similar except for the liquid nitrogen
requirements for the Si(Li) detector. The liquid nitrogen dewar in the Si(Li) detector first has to be
filled. It takes approximately 15 minutes for the detector to achieve a stable operating temperature.
This step is not required for the gas-filled proportional detector.
Once the technology is turned on, all the software is menu driven. The technology can be calibrated
either empirically using external soil standards, or internally using instrument backscauer and
fundamental parameters related to instrument backscatter. The latter of the two is a sundardless
calibration that uses theoretical equations to describe the functional relationship between metals
concentrations and x-ray intensities. The technology uses regression analysis to establish a calibration
curve for empirical calibrations. The calibration curve can contain up to six linear and nonlinear
terms. Metorex points out that empirical calibration with a proper set of samples will always yield
better results than the fundamental parameters-based calibrations because of particle size effects and
errors in predicting the composition of the sample matrix rather than directly measuring it.
Once the technology is calibrated, the sample is placed in contact with the detector window. The
measurement is initiated by pressing the start button located in the detector handle. The measurement
is terminated automatically after the preset count time has expired. The detector automatically
exposes either one or two excitation sources sequentially, according to its programmable calibration
scheme. The operator can interrupt the measurement cycle at any time by pressing the reset button In
the detector handle.
When the analysis is completed, the results are automatically displayed on the computer screen along
with the standard deviation associa"*1 with each measurement result. Analysis can be based on either
a single measurement or the average of multiple measurements. The X-MET 920 also can display net
and raw count intensities for all m^^ents. The operator can store all analysis output to the hard
disk by opening the log file. The X-^y emission spectrum from unknown samples also can be
displayed. The horizontal axis of *e ***** is calibrated in keV and the vertical axis is the
intensity of the peak measured in counls- A peak has to fall within a specific keV range to be
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identified as a specific element. This range is predetermined by the developer or based on real time
calibration.
The primary limitation of the gas-filled proportional detector is its resolution. This detector may
produce anomalous data for compounds or matrices that are affected when L-lines overlap K-lines.
This can affect metals such as cobalt, nickel, and copper in the presence of rare earth elements such
as erbium, thulium, ytterbium, lutecium, hafnium, and tantalium. In addition, this type of detector
will only allow empirical calibration.
4.2.4 Training and Maintenance
Metorex offers a 3-day training course for X-MET 920 operators at its facility or on site. The
training course covers theory, operation, calibration, and routine maintenance.
All X-MET 920 technologies are warranted against defects in materials and workmanship for a period
of 1 year. Repair or replacement will be made without charge during the warranty period. The
X-MET 920 is marketed as fairly maintenance free. There is an "Instrument Maintenance Options"
menu in the software used in conjunction with the technology. It allows the operator to check the
gain initialization, perform a gain test, perform a test measurement, test initial resolution, perform a
probe and internal XPCS test, check probe parameters, and set the date, time, and colors on the
computer screen. The primary hardware maintenance is replacement of the 20 mCi Cd109 source
approximately every 1.5 to 2 years. This replacement schedule is recommended by the developer.
Since the detector contains a nuclear radiation source, it must not be opened except by authorized
personnel. If the detector becomes damaged, it should be stored in a secure area and a Metorex
representative should be contacted. The detector should not be stored in moist conditions because
moisture can corrode the beryllium window in the detector. The X-MET 920 is sold with a general
license for its radioactive sources meaning that it can be transported from state to state and used by
another operator without requirements to receive a specific license.
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4,2.5 Testing Time and Cost
The developer suites that « is possible to analyze one soil sample in 1 to 5 minutes w„h the X-MET
920 equipped with the Si(Li) detector. This time includes the time required for any sample
preparatton such as homogenization. drying, or grinding that may be needed. The developer s,at«
that these sample preparation tasks can be conducted by the operator while analyses are being
conducted. With the daily QC procedures that are conducted, the developer states that it is possible
to analyze 50 soU samples in at, 8- to 10-hour working day. The developer claims that sample
throughput for the use of the gas-filled proportional detector can reach 200 to 400 samples ,n an 8- to
10-hour working day. This is based on 10 to 100 second count times and minimal sample
preparation.
The X-MET 920, equipped with a Si(Li) detector and two radioisotope sources sells for $47,470,
which includes a portable computer. The computer is battery operated and contained in an industrua
grade, rugged, sealed, splash-proof case. The system also includes "Automated Contaminant
Evaluation- software (ACES) with the computer. The two sources in the X-MET 920 are a 20 mCi
Cd'09 and 3o mCi Am141 source. This price includes 3 days of training for two people at the
Metorex facility. Travel and accommodation costs are not included.
The X-MET 920 can be rented from Metorex. There is a 1 month minimum rental. The cost Is
15 percent of the purchase price per month, plus all shipping costs payable monthly in advance.
Metorex mandates that the renters be trained on the X-Met 920. Renters have a choice of training
ThJ flrst is a 3-day training class offered at Metorex's facility at $685 per person plus travel
ITlodging expenses. On-site training classes also are available. Metorex must be conacttd for
details on the on-site training classes.
spare batteries are available for $425 and spare battery chargers are available for $340. The
developer recommends replacement of the Cd'M source every 1.5 to 2 years. This costs $4,500
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4.3
MAP SPECTRUM ANALYZER
This section presents information on the background, apparatus, general operating procedures,
training and maintenance requirements, and cost of the MAP Spectrum Analyzer.
The MAP Spectrum Analyzer was originally developed by Scitec to detect lead in paint. It is a
lightweight, portable technology that collects in situ readings. Scitec is now marketing the MAP
Spectrum Analyzer as detecting lead in soil, as well as other metals in soil.
The primary components of the MAP Spectrum Analyzer are the control console and the ambient
scanner. The control console is connected to the ambient scanner with a 10-foot cable. The basic
MAP system also includes a carry pack, rechargeable batteries, operator's manual, target metal
standard, and a shipping case.
The control console is a 256-channel, miniature, rugged, MCA. It has a storage capacity of
1 megabyte of information or 325 spectra and analyses. It is constructed of high-impact plastic. It
has a liquid crystal display (LCD) that can provide readouts of operation menus, measurement values,
calibration menus, count rate, time clock, analysis identification number, number of the analyses
stored in each identification area, and a graphic spectrum display. The keyboard is weatherproof and
has a 14-key keypad.
Control Console Specifications
• Size: 19.3 cm long x 20 cm wide x 7.6 cm high
• Weight: 7 pounds with battery pack
• Environmental: Splash proof at 100 percent humidity, operates at any angle
• Operating Temperature: -6 °C to 43 °C
• Connectors: Breech-lok™ connects to battery charger or sensor
4.3.1
Background Information
4.3.2
Equipment and Accessories
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Power Supply: 2 Gel-Cell type, 12-volt direct current rechargeable batteries. Each
set is capable of 10 hours continuous use without recharging. Each Gel-Cell has an
approximate useful life of 12 to 18 months or 150 recharges. Weighs 1.2 kg. The
power supply operates at any orientation at a temperature range of -6° Centigrade (O)
or higher.
The ambient scanner is an in situ detector that allows for the source to be placed in direct contact
with the sample. It is shaped liked a pistol and contains the excitation source and the detector. It is
capable of holding only one source.
Ambient Scanner Specifications
Size: 33.7 cm
Weight: 1.6 kg
Environmental: Splash proof at 100 percent humidity
Operating Temperature: -6 °C to 43 °C
Electronics: Solid state amplifier; custom high gain, low noise
Detector: Solid state silicon; resolution 170 keV; size 5 mm x 5 mm active
area 25 mm- '
Source Shutter: Heavy tungsten and designed to house:
(1) Co37 - 40 miUicuries
(2) Am241 - 150 miUicuries
(3) Cd109 - 80 miUicuries
Safety: Removable oti-off key for source shutter
Connector: Breech-lok™
Grip: Rubber-cushioned P'stoi type
Construction: 6061
Front Face Plate: Alui™num 0.5-ram thick
Beryllium Window: O-5-mm thick
4.3.3
General Operating
procedures
a. oalyzer Consists of placing the ambient scanner in direct contact
Analysis with the MAP Spectrum An»
a n»nif)£ a sfnttter with a key. The opening of the shutter exposes the
with the sampling medium and openiw
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sample to the radioisotope source. Emission x-rays are counted (measured) over an operator-specified
period of time (source exposure time) by a counting circuit. This data is recorded by an MCA to
produce a spectrum characteristic of the metals in the sample. Net intensities for each target metal
are calculated by software deconvolution of the characteristic spectra and converted to concentration
values by means of a calibration model. This model is derived empirically by measuring the net
intensities of the target metals in a set of calibration standards, and fitting a linear function that relates
net intensity to concentration by a multiple regression procedure.
The MAP Spectrum Analyzer measures an area of about 20 mm in diameter. Only the near surface
(approximately 2 mm) depth is measured in samples by L-shell x-ray fluorescence, while K-shell
emissions for many metals may emerge from greater depths.
Calibration of the Map Spectrum Analyzer is performed by the developer. Calibration involves
measurement of known analyte concentrations (reference standards) and incorporation of data from
resultant spectra into a mathematical function. This function, which is a component or proprietary
software, is used to calculate concentrations of the target metals in measured field samples. The use
of a wide range of matrix conditions and target metal concentrations for calibration is the method
which allows accurate readings on most samples.
Two types of calibrations are performed by the developer: site-typical calibrations and site-specific
calibrations. A site-typical calibration curve is based on samples similar in composition, but not
necessarily matrix matched. Scitec cautions that a site-typical calibration curve should only be used
in preliminary screening and characterization. Scitec states that to minimize enhancement or
absorption and spectral interference errors, calibration standards should be collected from the specific
site in question. The site-specific calibration (SSC) standards should closely match the matrix of the
routine samples. The SSC standards are prepared as loose soils (screened through 2-mm sieve, but
unpulverized) so that panicle size bias of the routine samples is included in the instrument calibration.
Scitec recommends that characterization of the SSC standards be done using a total digestion
procedure rather than a partial extraction because x-ray fluorescence is most closely related to a total
extraction or digestion type analysis.
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The in situ analysis with the MAP Spectrum Analyzer does not require that a physical sample be
removed from the ground. The probe is placed on the ground and the analysis mode is activated by
turning on a key. Acquisition time can be preset at any desired length: "Screen," "Test, '' or
"Confirm," are the most common. The measurement times for the three options are 15 seconds,
60 seconds, and 240 seconds, respectively. Scitec points out that the precision of the analysis will
improve as the measurement time increases.
Scitec recommends that all routine samples be analyzed in triplicate and the means are the reported
values. The three in situ measurements should be made in a 6- by 6- by 6-inch triangular pattern
around the sample location marker. Scitec recommends that when few sample locations are to be
measured, "Confirm" measurements will optimize the data precision. Large-scale, high-density
sampling conducted in the "Test'' mode will result in briefer measurements, but greater sampling
density which may maintain optimum overall precision. Scitec recommends that one confirmatory
sample be selected from each group of 25 to 40 routine samples.
QC procedures for the MAP Spectrum Analyzer include a blank check and a calibration check
sample. The blank check is an instrumental blank that is a 0 milligrams per kilogram (mg/kg)
sample. It is analyzed to determine if there is contamination or a malfunction of the technology.
Each technology is provided with a calibration check sample. It is used to assess the accuracy of the
technology. The calibration check standard should be measured by attaching the standard to the face
of the excitation and detector unit with a rubber band and making measurements "air backed" (with
the unit separated from the nearest surface by at least 2 feet). A calibration check should be
performed every day prior to samp'e analysis and once each hour during the day. All values should
be averaged and compared to the developer-provided value. Average values that are inconsistent with
the true value should be reported to Scitec.
4.3.4 Training and Ma**1**11*11**
A license or permit to possess, or operate a technology that uses ionizing radiation produced from the
radioactive decay of a source is re3uired to possess or operate the MAP Spectrum Analyzer. Each
state is responsible for issuing sucfa ^ CI*ses. An operator must be trained by Scitec in the principle
of radiation and in the safe operat»°° of *he MAP Spectrum Analyzer to secure a license, Scitec
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provides approved training on a regular basis. The training is a 6-hour, audio-visual program that is
available at Scitec's factory or at a customer's facilities.
The operator of the technology should prevent it from being exposed to dirt or dust. Any dirt or dust
on the technology should be wiped off with a damp cloth or brushed off. If the rubber boot at the
front of the ambient scanner becomes contaminated, it may need to be replaced. Scitec offers an
annual service agreement that allows for the return of the MAP Spectrum Analyzer any time, for an
unlimited number of times, for cleaning and servicing. Each 1-year contract includes one Co57
source replacement, hardware and software enhancements, minor repair and service work, extra pans,
and a loaner system while the technology is having its source replaced.
4.3.5 Testing Time and Cost
As mentioned in Section 4.3.3. analysis times are on the order of 15 to 240 seconds. It is
recommended that each sample be analyzed in triplicate. Since this is an in situ technology, there is
little sample preparation required with the exception of removing any vegetation or debris from the
soil surface to be measured. It is possible to analyze 50 to 100 samples in one 8- to 10-hour working
day.
The standard Scitec MAP Spectrum Analyzer package sells for $15,590. The standard package
includes the control console, the ambient scanner, a 40-millicuries Co57 isotope source, auto source
decay time correction, carry pack, rechargeable batteries, spectrum display software, 256-kilobyte
memory, battery charger, operator's manual, shipping case, a 10-foot cable, and a lead-check
standard.
Scitec also provides other options and accessories with the technology. A lead in soil calibration
costs $1,390. Upgraded memory to 768 kilobytes can be purchased for $1,175. AcuTransfer*
Software, which is a data communications software utilities package that allows data to be
downloaded and manipulated from the console directly to a PC, costs $495. A special shipping
container with a lead shield and NIST standard reference materials can be purchased for $475 and
$260, respectively.
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A replacement of the Co57 source costs $3,695. An annual service agreement with the source
replacement costs $3,895. A basic radiation safety and operator training course is offered by Scitec
for $245 per person.
4.4 SEFA-P ANALYZER
This section presents information on the background, apparatus, general operating procedures,
training and maintenance requirements, and cost of SEFA-P Analyzer.
4.4.1 Background Information
HNU developed the SEFA-P Analyzer to be an intrusive, portable technology that could determine
metals concentrations in soils and other media at hazardous waste sites or at industrial locations. The
SEFA-P Analyzer has been on the market for approximately 4 years.
4.4.2 Equipment and Accessories
The basic SEFA-P Analyzer consists of one main cabinet that encloses the sample chamber, the
radioactive sources, a liquid nitrogen cooled Si(Li) detector, preamplifier, spectrometer electronics,
MCA, and a battery charger. It is approximately 21 inches long, 12 inches wide, 16 inches tall, and
weighs less than 50 pounds. The SEFA-P Analyzer operates at relative humidities between 20 and 95
percent. The ambient temperature limits of operation are between 0 and 42 °C.
A mechanical interlock on the door to the sample chamber protects the operator from being
accidentally exposed to radiation from any of the internal radiation sources. Access to the sample
chamber involves rotating the source knob to the safety position. This allows the operator to slide the
chamber door open. Each installed source is identified by a label on the source knob. The knob
cannot be turned to any of the source selections while the chamber is open. When the chamber is
closed, the knob can be rotated to expose the contents of the chamber to the selected radiation source.
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Three excitation sources are offered with the SEFA-P Analyzer. They are Fe55, Cd109, and Am241.
The maximum activity for each of the sources is 50 millicuries, 10 millicuries, and 25 millicuries,
respectively.
The SEFA-P Analyzer contains a Si(Li) detector. The detector has a manganese K-alpha line
resolution of 170 eV. It is 10 mm in diameter and has an active area of 45 mm2. The Si{Li) detector
is cooled with liquid nitrogen. The internal liquid nitrogen dewar has a capacity of 0.85 liters and
can last up to 24 hours.
A preamplifier in the technology collects the electronic signal from the detector, amplifies it, and
sends it to the MCA. The MCA sorts the signals coming from the preamplifier by energy level and
counts the number of x-rays that strike the detector. This data can be displayed on a cathode ray
tube, printed, or stored on a computer disk. The internal battery can power the MCA for 8 hours.
The battery charger is equipped for either 110 or 220 volt alternating current, and has a two-position
setting for either battery charging or continuous operation. It is recommended that the internal
battery be fully charged before operation.
The MCA has an RS232C interface that allows for external control of the SEFA-P Analyzer via a PC
or laptop computer. HNU has SEFA-P software that allows the detector to be operated from a PC.
All data can be downloaded and stored on the PC. The resulting spectra from the analysis of samples
can be viewed on the PC screen and can be printed to obtain a hard copy. Quantitative results also
are displayed on the PC screen.
Other supplies needed to operate the SEFA-P Analyzer incLude 30-mm-diameter polyethylene sample
cups, Mylar™ window film to cover the cups, and a 22-liter external liquid nitrogen dewar. If sample
preparation techniques are employed, the analysis also may require sieves, a mortar and pestle to
grind the soil samples, plastic weigh boats, and a drying oven (either standard convection oven,
toaster oven, or microwave oven). Lastly, SEFA-P Analyzer operation will require calibration
standards either commercially available from such sources as NIST or site-specific calibration
samples.
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4.4.3
General Operating Procedures
Prior to analysis of samples, the internal liquid nitrogen dewar should be recharged from the external
liquid nitrogen dewar. The SEFA-P Analyzer will not allow the operator to analyze samples until the
St(Li) detector is cool. This may require 20 to 30 minutes of cool down time after the initial charge
with liquid nitrogen.
Once the SEFA-P Analyzer has Been turned on, the battery voltage should be checked. If the battery
voltage is low. "low battery voltage" will be indicated on the LCD of the MCA. If the battery
voitage is acceptable, the amplifier gain and detector voltage can be set. The value of the amplifier
gain influences the energy calibration of the MCA. The optimal gain setting is usually 1105. but
should be verified periodically by analyzing a copper foil check standard. The range for the detector
voltage is commonly 500 to 1.000 or more volts. Optimum operating conditions generally occur at
501 volts.
This unit can be operated from the cathode ray tube and key pad built into the unit. When operated
to this mode, a mini-cassette tape is used to record numerical and spectral data. The data from
approximately 10 samples can be saved on one mini-cassette tape. A PC can also be used to operate
the unit HNU markets SEFA-PC. a menu-driven software that can be used to operate the analyzer,
^e' rnjor SEFA-PC menus include: Acquire. Setup. Qualitative. Quantitative, and Utilities. Within
the Setup menu, the acquisition setup selects which sources will be used for a selected job and which
qualitative and quantitative programs will be automatically executed after data is acquired from the
Acquire menu. The Report item Setup menu allows the operator the modify the report
format, as well as create a hud «*» di!k «« °f ^
the ooerator to enter the sample name and set the source exposure tune for
The Acquire menu allows ine t
i i r fmir camoles acquisition times for up to three sources can be entered. Thi*
each sample. Up to rour sampi^-
. CCPA p Ajiaiyzer' actiuires and stores spectral data, prompts the user to select the
routine sets up the SEFA-F aimu t A .
, . and automatically runs the programs which were selected in Acquire
appropriate sample and source, r .
. eS (source exposure times) of 300 to 500 seconds are typical for sou
menu. Quantitative analysis time r
„ ,-aice sure that the proper source and sample are in the correct position
analysis. The operator must ma* H ^ „
• , to analysis • The F2 function key is pressed on the PC to initiate the
in the sample chamber prior to a*
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analysis. At the end of each sample analysis, the computer will beep to alert the operator that the
analysis is complete. The operator can then turn the four-position sample chamber to the next sample
to begin another analysis.
The Qualitative menu allows the operator to reexamine previously acquired data. This includes
viewing complete sample spectra and magnifying selected portions of the spectra. This menu will
provide the gross and net fluorescence intensities of each element, and concentrations based on
calibration curves determined prior to sample analysts.
Prior to sample analysis, the SEFA-P Analyzer must be calibrated. Two types of calibrations can be
used with this technology: empirical or Compton ratio calibration. In the case of empirical
calibration, the SEFA-P Analyzer is calibrated with a minimum of three external standards. These
external standards contain known concentrations of the target metals. Generally, the concentration
range of the standards is 100 to 1,000 mg/kg. The other method of calibrating the SEFA-P Analyzer
is the Compton ratio method. This method involves a one standard calibration. In this case, the unit
is calibrated to one standard instead of generating a calibration curve for each target metal. The
Compton peak is the peak created by x-ray emissions from the radioisotope source used to excite the
sample. The Compton peak is present in the spectrum of every sample. The Compton peak intensity
will change with differing matrices. It is possible for the internal software of the x-ray program to
compute a Compton ratio by comparing the Compton peak intensity determined from the analysis of
the single standard to the intensity of the Compton peak measured during the analysis of a sample.
Calibration by the Compton peak can help reduce potential matrix effects between samples.
The Quantitative menu allows the operator to enter the target metals' ranges of characteristic x-ray
emissions, select the correction method to be used for the empirical calibration, enter the multi- and
single-standard calibration information, and calibrate the technology on both the empirical and
Compton ratio, and run the analysis. The ranges of characteristic ranges of x-ray emissions is used to
identify target metals and to determine gross and net metal emission peak areas for concentration
quantitation.
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The Utilities menu allows the operator to delete samples, display the file directory, format a disc
send a report file to a printer, display system information, display the disc space, backup or restore a
job and create a new job.
QC procedures include daily source emission energy checks and calibration, with a copper foil check
sample; continuing calibrations; method blanks; laboratory duplicates; and laboratory control samples
(LCS). The LCSs are often SRMs produced by NIST.
4.4.4 Training and Maintenance
The SEFA-P Analyzer is sold with a general license, meaning that the operator does not have to be
specifically licensed in each state that it is used in. The SEFA-P Analyzer is engineered to minimize
the possibility of operator exposure to ionizing radiation. The specimen chamber cover is interlock-^
mechanically to prevent exposing the radiation sources. The radioisotope sources should be
leak-tested every 6 months. It is necessary to replace the Cd109 source about every 2 years. HNU
will provide a 2-day training course on XRF principles and operation of the SEFA-P Analyzer
in-house or at a customer's facility.
4.4.5 Testing Time and Cost
The average time of analysis for a sample is 3 to 7 minutes. This does not include time for any
sample preparation, however, sample preparation can be conducted during the analysis of a different
sample. With calibration of the technology, analysis of QC samples, and sample preparation, it is
possible to analyze 30 to 50 samples in one 8- to 10-hour working day.
Currently, the SEFA-P Analyzer retails for approximately $45,000 depending on the options. This
does include one in-house XRF training course (not including travel expenses). A separate 2-day
training course is offered for $750 per person. Other supplies needed for the operation of this
instrument include an external dewar and PC (optional). These items vary in cost depending on the
place of purchase. The Cd109 source replacement costs about $4,000.
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4.5 XL SPECTRUM ANALYZER
This section presents information on the background, apparatus, general operating procedures,
training and maintenance requirements, and cost of XL Spectrum Analyzer.
4.5.1 Background Information
Niton was given two grants by the EPA through the Small Business Innovative Research Program to
develop a lead detector that was the least expensive, most portable, safest, and easiest to use on the
commercial market. Niton saw problems with other XRF technologies that used a Co57 source. The
XL Spectrum Analyzer uses a Cd109 source. Niton found the advantages of the Cd109 source over the
Co57 source to be lower cost, longer half life, less background interference problems, and safer to
use.
Niton developed the XL Spectrum Analyzer to be a hand-held, in situ, lead-in-paint detector.
However, Niton believes the capabilities of the XL Spectrum Analyzer allow it to be used to
determine lead and other metals in soil. The technology can not analyze for cadmium or any other
elements whose electrons cannot be discharged by the x-ray energy of the Cd109 source. This is
because it has only a cadmium source. Niton is currently developing methodology and accessories for
lead-in-soil technologies that it expects to be ready for demonstration some time in 1995.
4.5.2 Equipment and Accessories
The XL Spectrum Analyzer is a hand-held, portable, lead detector, designed to make fast, accurate,
nondestructive measurements of lead concentrations. The technology is 8.25 inches long by 3 inches
wide by 1.875 inches thick. It weighs slightly over 2.5 pounds with batteries. The radioactive
source is Cd109. The detector is a high resolution Silicon Pin-diode detector that is cooled via the
thermoelectric Peltier effect. Its operating temperature is 5 to 41 °C and operating humidity is 0 to
95 percent. The MCA has 1,024 channels with 100 channels displayed. The XL Spectrum Analyzer
has an RS232 port for computer hook-up to transfer and print data. The internal memory is capable
of storing 500 readings. The XL Spectrum Analyzer samples an area 1 cm by 2 cm. The technology
comes with a waterproof, unbreakable plastic carrying case.
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A battery pack can be installed on the bottom of the technology. The battery pack consists of 8
wrapped nickel metal hydride batteries. Fully charged, they will give 8 hours of use. For every
minute of recharging, they will give 4 minutes of use. A 2.5-hour charge will fully charge a spent
battery pack, but the 2.5-hour charge works only if the XL Spectrum Analyzer has been used
recently. The batteries can be recharged from a 110-voit outlet or car cigarette lighter. The battery
charger is included with the technology.
On the front of the XL Spectrum Analyzer is an LCD that shows spectra and numerical results, a
three-button control panel (2 scroll keys and one clear/enter key) and a plunger to show when the
technology is pressed up against the measuring surface. On the right side of the technology is a
safety slide and a shutter release to allow the radioactive source window to open. The radioactive
source window is in the back of the technology. At the bottom of the technology is the RS232 port
for downloading data, the on/off switch, and clamp screws for the battery pack. Although the
technology is currently configured to perform only in situ analysis, Niton has informed PRC that it is
making adaptations to the XL Spectrum Analyzer to perform intrusive sampling.
4.5.3 General Operating Procedures
Operation of the XL Spectrum Analyzer can be summarized in 9 steps:
1. Turn on the technology.
2. Press "Clear/Enter" to begin self calibration.
3. When the XL Spectrum Analyzer beeps, calibration is complete. Press "Clear/Enter."
Quickly check the logging screen.
The technology is ready for measurements. The first test will change the logging screen to measuring
screen, which will remain until the XL Spectrum Analyzer is turned off.
4. Fasten the wrist strap to hold the technology.
5. Pull out the safety slide that locks the shutter release.
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6. Begin the test by flicking a light pen across the template bar code. This is a software
developed for lead in paint to record the locations and descriptive information for each
measurement taken. This option may not be necessary for soil measurements.
7. Place the XL Spectrum Analyzer on the surface to be measured, push in the shutter
release, and firmly press the XL Spectrum Analyzer flat against the surface.
8. The XL Spectrum Analyzer's timed beeps will help the operator decide when the test
has reached the desired level of accuracy. For lead-in-paint analysis, results can be
obtained in 15 to 30 seconds. Niton has informed PRC that it expects analysis times
to be closer to 1 minute for multiple elements in soil.
9. The XL Spectrum Analyzer is lifted from the surface to end the test.
A measurement begins every time the XL Spectrum Analyzer is pressed flat against a surface,
depressing the plunger fully. The test is ended when the XL Spectrum Analyzer is lifted and the
plunger pops back out. The LCD screen will show a spectrum of the analysis. It also will show the
quantitative lead results for the lead K-Lines and L-Lines. It is probable that the steps outlined above
will be modified when using the XL Spectrum Analyzer to determine multiple metals concentrations
in soil. Currently, Niton has not developed the exact procedures for conducting this type of analysis.
4,5.4 Training and Maintenance
Niton requires a 2-day radiation safety and technology training to use the XL Spectrum Analyzer.
This training is performed by a company called Star Environmental Services.
All service, repair, maintenance, and source changing is handled by Niton. Niton requests that the
operator not attempt any adjustments or repairs to the technology. The operator's manual provides a
detailed discussion of general radiation safety and how to use the XL Spectrum Analyzer safely.
Operator servicing invalidates the warranty. Niton's warranty includes 2 years standard parts and
labor. The Cd109 source has a half life of 15 months and should be replaced every 2 years.
Niton manufactures the XL Spectrum Analyzer under a specific license with the State of Rhode
Island. Each operator has to be licensed to possess and operate a technology that uses ionizing
radiation produced from the radioactive decay of internal sources. Generally, such a license is
required in the particular state where the technology is to be operated. It is required under Niton's
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license that a leak test be performed every 6 months. Leak tests are performed on sealed radioisotope
sources to determine if any radioactive materials are being released from the sealed source. Leak-test
kits, with full instructions, are available from Suntrac. The leak-test sample should be mailed to
Suntrac's laboratory.
4.5.5 Testing Time and Cost
This technology would allow for 100 measurements to be taken in a day.
The XL Spectrum Analyzer with its standard package costs Si 1,990. The package includes the
battery pack and charger, cigarette lighter adapter, cable for RS232 downloading, waterproof carrying
case, operating and safety manual, paint standards, and a basic computer software. An extra battery
pack costs $300, while a wrist support costs $15. Shipping, handling, and insurance costs $80. The
radiation safety and operator's training runs $350 per person. A Cd109 source replacement costs
$2,200, which includes old source disposal, the leak test, and the certificate. Cd109 source
replacement plus routine maintenance is another available option that costs $2,600. An expanded
15-month warranty can be purchased for $1,200. Niton now offers a "Quick View Element Scanner"
software for $2,900. This program allows the operator to view the full spectrum for other elements
in addition to lead. Niton hopes to offer an upgrade to the program in the future that will provide
quantitative results for each element in mg/kg. Currently, the results are displayed as milligrams per
square centimeter for paint analysis.
4.6 TN SPECTRACE LEAD ANALYZER
This section presents information on the background, apparatus, general operating procedures,
training and maintenance requirements, and cost of the TN Spectrace Lead Analyzer (Lead Analyzer).
4.6.1 Background Information
The Lead Analyzer was developed by TN Technologies for specifically analyzing lead in a variety of
matrices. The Department of Housing and Urban Development, Occupational Safety and Health
Administration, and EPA have developed guidelines for protecting the public from lead poisoning.
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The operator can use the Lead Analyzer to address each one of those guidelines by selecting the
appropriate application on the analyzer. The factory installed and calibrated applications are: lead in
soil, lead in paint, lead in surface dust, lead on air filters, and lead in paint chips.
The Lead Analyzer is manufactured in Austin, Texas, by TN Technologies and contains a Hgl2
detector in the analysis probe. The probe also houses one Cd109 radioisotope source for sample
excitation. The Cd109 source is able to produce both lead K-shell emissions and the lead L-shell
emissions from a sample. The K-shell emissions are monitored during the analysis of underlying
layers of lead-based paint. The Lead Analyzer with a 30 mCi Cd109 source and Hgl2 detector is
optimized for the analysis of lead in paint.
4.6.2 Equipment and Accessories
The Lead Analyzer comes with all of the equipment necessary for in situ and intrusive operation. A
hard-shell carrying case is provided for transportation and storage.
Two main components make up the analysis system: a probe and an electronics unit. The main
components are discussed in the following paragraphs. A list of all primary and secondary
components follow the discussion.
The probe contains one radioisotope source, Cd109 (30 mCi), for efficient excitation of lead K and L
shell electrons. The source is ruggedly encapsulated and housed in a metal turret with additional lead
shielding inside the probe. This source is exposed to a sample through a sealed 1-inch-diameter
polypropylene window in the face of the probe (probe window). The fluorescence from the sample
passes back through the window and is intercepted by the Hgl2 detector. This detector quantitates the
energy of each x-ray and builds a spectrum of characteristic x-ray emission peaks on a 2048-channel
MCA.
Spectral data is communicated to the electronics unit through a flexible cable of 6. 12, or 20 feet in
length. Metals peaks are integrated and either milligram per square centimeter (mg/cm2), mg/kg, or
percent values are calculated. The electronics unit will store and display both results and spectra
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from a measurement. A maximum of 600 sets of results and iOO spectra can be stored before
downloading to a personal computer (PC) via an RS-232 cable.
Equipment/Optional Accessories/Instrument Specifications
Equipment
The standard Lead Analyzer system includes:
• Electronics unit for data acquisition, processing, storage and display
Nickel cadmium battery pack (4 to 5 hours of continuous use)
• Hand-held probe including:
Hgl2 detector
One excitation sources (Cd109)
Safety Cover
• Uniblock allows the operator to measure sample cups, thin films and to perform the
check procedure for the lead-in-paint application.
Sample shield
Positioning ring for standard 31-mm x-ray sample cups
• Interconnecting probe cable (6-foot cable is standard)
• Pure element check samples kit
• Two blank samples for background setup and check out
• Battery charger
• RS-232 serial input/output interface cable
• System carrying/shipping case
• Operators manual, factory applications and results management software
• Training video (22 minutes)
• Ten 31-mm-diameter sample cups
4-34
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• 1 roll 6.0 nm Mylar XRF film (300 feet)
• Spare window assembly
Ontional Accessories
• Field pack with shoulder straps ($245)
• Spare battery pack, charger, and adapter ($750)
• Battery eliminator for continuous use (S600)
• "Applications Generator" software
• NIST Soil Standard Kit (NIST No. 2579)
• Micromatter Lead Thin Film Standards Kit (for lead in paint measurements)
• Dust wipe kit
Instrument Specifications
• Probe Dimensions and Weight: 12.7 centimeters (cm) x 7.6 cm x 21.6 cm; 1.9
kilograms (kg)
• Cable: standard 6-foot length, optional 12- or 20-foot lengths
• Electronics Unit Dimensions and Weight: 32 cm x 30 cm x 10 cm; 6.7 kg
• Power: operates from a nickel cadmium battery for 4 to 5 hours of continuous use.
Also can use 110 or 220 volt, 50 to 60 Hertz AC electricity.
• Operating Temperature: 0 to 49 °C (32 to 120 °F)
• Storage Temperature: -40 to 40 °C (-40 to 104 °F)
4,6.3 General Operating Procedures
To operate the Lead Analyzer, the nickel cadmium battery is plugged in and the probe cable is
connected. The spectrometer is turned on by pressing the "On" button. A message on the screen
will ask the operator for the data and time and then proceed to the MAIN MENU.
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The Lead Analyzer software is menu driven. From the MAIN MENU, the operator selects a
predefined "Application." The Lead Analyzer comes with the following applications installed:
1 Soils Application (measures lead, arsenic, chromium, iron, copper, zinc, and
manganese in soils)
2. Lead in paint (makes in situ measurements of lead in paint, substrate independent
result in (mg/cm2)
3. Lead in Surface Dust
4. Lead in Air Filters
5. Lead in Paint Chips
Once the application is selected, the analysts is automated by the Lead Analyzer software. To begin
measuring samples, the operator selects MEASURE to get to the "Ready Screen." From here the
operator initiates an analysis by pressing either the probe trigger or the "Continue" button on the
electronics unit. Distinct sounds signal the beginning and end of a measurement to alert the operator
to take the next measurement. Results with standard deviations are displayed at the end of each
measurement. If desired, results and spectra can be automatically stored on the electronics unit after
each measurement. Transferring the results and spectra to a PC allows printing, archiving,
spreadsheet and report generation.
No site-specific calibrations standards are needed for instrument operation. The technology is
calibrated at the factory using pure elements, and calculates results of a soil sample using a matrix
correcting fundamental parameters algorithm. Two types of matrix effects are inherent with X-ray
fluorescence spectrometry: absorption and enhancement matrix effects. The fundamental panmetm
algorithm makes the appropriate matrix corrections for an accurate analysis of six elements in soil.
All applications except the lead in paint use a fundamental parameters algorithm. The lead in paint
application is calibrated using NIST standards.
If desired, the Lead Analyaer soft«r. can provide for a she-specific calibration to model a given
suite of standards.
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For data QA, TN Technologies recommends that a certified reference sample be run periodically.
This will provide valuable accuracy and precision data. Running a certified reference sample can also
alert the operator that either the probe window is contaminated or the technology is not operating
properly. The probe window can be cleaned with a towel and the condition of the spectrometer can
be checked using the Standard Operational Check, which requires running a pure lead sample and the
pure quartz sample to verify sensitivity and background, respectively.
4.6.4 Training and Maintenance
An operator can learn to use the Lead Analyzer by reading the Operators Manual. If personalized
training is desired, TN Technologies offers a 2-day in-house training course. The only expense to the
customer is travel. A 2-day on-site training course is also an option at $1,000 per day plus travel
expenses.
The Lead Analyzer can be cleaned with soap and water and is designed to be used in the field. Given
proper care, the developer claims that the technology should only require the scheduled periodic
maintenance of source replacement.
Due to the inherent safety design features and associated low levels of radiation, the instrument is
supplied under a general license for radioisotope regulatory purposes which greatly simplifies its
transportation and use.
4.6.5 Testing Time and Cost
The standard deviation of the x-ray emission data is reported with each measurement. This
information allows the operator to optimize the measurement time to meet project data quality
objectives and project scheduling. When screening soils that are in areas of high concentration at the
site, the developer recommends short source exposure times of 30 to 60 seconds. As the
concentration nears the action level, the developer recommends a longer source exposure times of 2 to
4 minutes. This decreases the standard deviation of the measurement and thus, increases precision.
Since the measurement is automated by the Lead Analyzer software, the operator can prepare the next
4-37
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sample or sampling site while the technology is running the previous one. The developer claims that
an operator should be able to analyze at least 100 samples per day.
The Lead Analyzer costs $39,500 to purchase. This includes all of the equipment necessary for
operation of the instrument. Spare parts and accessories are available as described in Section 4 6 2
Purchased technologies are warranted for a full year with an optional extended warranty. The Lead
Analyzer can be rented through TN Technologies for approximately $5,000 per month or $3 000 for
2 weeks. Periodic maintenance includes replacement of the Cd109 source every 2 to 3 years at a cost
of $3,500 to $3,800. The Cd109 source should also be "deshimmed" every 6 to 10 months at a cost
of $1,500.
4.7 ATX-100
This section presents information on the background, apparatus, general operating procedures,
training and maintenance requirements, and cost of ATX-100. Much of the information below is
incomplete and will be updated in the ITER.
4.7.1 Background Information
ERC conducts research and development in the area of x-ray fluorescence analysis. The company
manufactures, repairs, and operates the ATX-100. This technology is not marketed for sale to the
public, rather, it is marketed as an on-site x-ray fluorescence analysis service provided by ERC.
4.7.2 Equipment and Accessories
The ATX-100 is designed to make rapid, nondestructive measurements of more than 60 elements.
This technology takes in situ and intrusive measurements. The technology weighs 18 pounds and is
powered by eight D-size batteries. The technology is fitted with two radioactive sources: an Fe55
source and a Cd109 source. The detector-records spectral data on 512 channels sorted by emission
energy. The ATX-100 has an RS232 port for computer hook-up to transfer and print data. ERC has
computer software that interprets the spectral data, and identifies and quantifies contaminants.
Summary reports for batches of samples can be printed for up to seven target metals at a time.
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4.7.3
General Operating Procedures
Operation of the ATX-100 can be summarized in five steps:
1 Cover the environmental sample or sampling location with a protective cover, such as
plastic sheeting. The thickness and composition of the covering must remain constant
throughout a project.
2. Place the probe window over the sample location being analyzed.
3. Open the probe window and expose the sample or location to either the Fe55 or Cd109
source. Generally, the exposure time is set between 100 and 300 seconds.
4. Examine the resulting spectrum. Using the ERC software, identify and quantify
contaminants present.
5. Clean the probe window and move to the next sample or location.
ERC provides an internal calibration for this technology. If desired, site-specific calibrations can be
performed to increase the accuracy of the analysis.
When examining a sample's spectrum with the ATX-100, individual target metals are identified by
marking spectral peaks with the technology's cursor and entering the appropriate commands for the
software to conduct its target metal identification and quantitation routine. Cursor calibration is
necessary and often associated with duplicate sample analysis. The cursor adjustment is the only field
adjustment that can be made on the ATX-100. To check the cursor alignment, lead or copper foil is
analyzed. Cursor adjustment is necessary when the lead or copper spectral peaks are not properly
identified when the cursor marks their spectral peaks. This adjustment is made by turning the set
screws on the underside of the detection head.
ERC recommends that field duplicates and replicate samples be analyzed during use of the ATX-100.
The replicate sample analysis is used to monitor technology precision; the field duplicate analysis is
used to monitor sample heterogeneity.
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4.7.4
Training and Maintenance
ERC provides the ATX-100 as a service, thuSi jt does have a ^
employees. In addition. ERC conducts all technology maintenance.
4.7.5 Testing Time and Cost
ERC has provided no data on sample throughput for the ATX-100
The cost of the ATX-100 operator is billed at an hourly or daily rate, $85 nr «7
-------
The MCA is 10.5 inches long, 10.75 inches wide, 5 inches tall, and weighs 11 pounds. The
SEFA-Px Analyzer operates at relative humidities between 10 and 95 percent. The ambient
temperature limits of operation are between 0 and 40 °C.
A trigger activated interlocked safety shutter on the probe and software prompts help prevent operator
exposure to the radioisotope source. One excitation source is offered with the SEFA-Px Analyzer. It
is low energy 10 mCi Co57 source.
The SEFA-Px Analyzer contains a Si(Li) detector. The detector has a manganese K-alpha line
resolution of 180 eV. It is 10 mm in diameter and has an active area of 45 mm2. The Si(Li) detector
is cooled with liquid nitrogen. The internal liquid nitrogen dewar has a capacity which allows up to 8
hours of operation.
A preamplifier in the technology collects the electronic signal from the detector, amplifies it, and
sends it to the MCA. The MCA sorts the signals coming from the preamplifier by energy level and
counts the number of x-rays that strike the detector. This information is converted to lead
concentrations based on internal or external calibration. The unit has two factory calibrations, one for
NIST paint and one for NIST soil. In addition, the technology can accept user-defined calibrations
for paint and soil. The MCA can store up to 325 spectra and data points. The numerical
concentration data is displayed on a LCD screen on the back of the detector. The internal battery can
power the MCA for 8 to 10 hours.
The MCA has a readout module that includes an LCD text display and an instrument control key pad.
HNU provides software that allows the downloading of the stored data to a PC via a RS232C
interface. The resulting spectra from the analysis of samples can be viewed on the PC screen and can
be printed to obtain a hard copy. Quantitative results can also be displayed on the PC screen.
Other supplies needed to operate the SEFA-Px Analyzer include 30-mm-diameter polyethylene sample
cups, Mylar™ window film to cover the cups, and an external liquid nitrogen dewar. If sample
preparation techniques are employed, the analysis also may require sieves, a mortar and pestle to
grind the soil samples, plastic weigh boats, and a drying oven (either standard convection oven,
toaster oven, or microwave oven). Lastly, SEFA-Px Analyzer operation will require calibration
4-41
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standards either commercially available from such sources as NIST or site-specific calibration samples
if the pre-set factory calibration is not used.
4.8.3 General Operating Procedures
Prior to analysis of samples, the internal liquid nitrogen dewar should be recharged from the external
liquid nitrogen dewar. The SEFA-Px Analyzer will not allow the operator to analyze samples until
the Si(Li) detector is cool. This may require 20 to 30 minutes of cool down time after the initial
charge with liquid nitrogen.
Once the SEFA-Px Analyzer has been turned on, the battery voltage should be checked. If the
battery voltage is low, "low battery voltage" will be indicated on the LCD of the MCA.
Once the MCA has warmed up, the operator can select either preprogrammed parameter settings for
analysis or custom parameters can be imputed into the analysis program. Readings are taken by
activating the trigger cJn the probe. This initiates and runs the analysis program which determines
calibration parameters and source exposure times. Source exposure times can vary from 5 to 300
seconds. At the end of each sample analysis, the MCA will beep to alert the operator that the
analysis is complete.
Prior to sample analysis, the SEFA-Px Analyzer must be calibrated. Two types of calibrations can be
used with this instrument: empirical or factory set calibration. In the case of empirical calibration
the SEFA-Px Analyzer is calibrated with external lead standards. The matrix of these standards
should match the matrix being analyzed. The other method of calibrating the SEFA-Px Analyzer is
by using the factory pre-set calibrations for soil or paint.
QC procedures can include daily source emission energy checks, with a copper foil check sample;
continuing calibrations; method blanks; laboratory duplicates; and LCSs. The LCSs are often SRMs
produced by NIST.
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4.8.4
Training and Maintenance
The SEFA-Px Analyzer is sold with a general license, meaning that the operator does not have to be
specifically licensed in each state that it is used in. The SEFA-Px Analyzer is engineered to minimize
the possibility of operator exposure to ionizing radiation. The radioisotope source is isolated by a
shutter system that is interlocked mechanically to the probe trigger. The radioisotope source should
be leak-tested every 6 months. It may be necessary to replace the Co57 source about every 1 to 2
years. HNU will provide a 2-day training course on XRF principles and operation of the SEFA-Px
Analyzer in-house or at a customer's facility.
4.8.5 Testing Time and Cost
The average time of analysis for a sample is 5 to 300 seconds. This does not include time for any
sample preparation, however, sample preparation can be conducted during the analysis of a different
sample. With calibration of the technology, analysis of QC samples, and sample preparation, it may
be possible to analyze 100 or more samples in one 8- to 10-hour working day.
The retail cost of the SEFA-Px Analyzer is $25,000. The cost may include one in-house XRF
training course (not including travel expenses). A separate 2-day training course is offered for $750
per person. The developer recommends the Co57 source be replaced annually at a cost of $2,500.
Other supplies needed for the operation of this technology include an external dewar and PC
(optional). These items vary in cost depending on the place of purchase.
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TABLE 4-1
RADIOISOTOPE source SUMMARY
Field Portable X-Ray Fluorescence Technologies
SITE Demonstration
Source
Activity
(mCi)
Half Life
(Years)
Excitation Energy
(keV)
Elemental Analysis Range
Fe55
20 - 50
2.7
5.9
Sulfur to chromium k Lines
Molybdenum to barium L Lines
Co57
40
0.75
121.9 and 136
Cobalt to cerium k Lin^
Barium to lead L LinS
Cd109
5 - 30
1.3
22.1 and 87.9
Calcium to rhodium k Lines
Tantalum to lead k Lines
Barium to uranium l Lines
Am-41
5 - 30
458
26.4 and 59.6.
Copper to thulium k Lines
Tungsten to uranium L Lines
Cm244
60- 100
17.8
14.2
Titanium to selenium K Lines
Lanthanum to lead l Lines
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TABLE 4-2
TECHNOLOGY SPECIFICATIONS
Field Portable X-Ray Fluorescence Technologies
SITE Demonstration
Technology
Detector
Sources j
ATX-100
No information
Fe55, Cd109
SEFA-P Analyzer
Si(Li)
Fe55, Cd109, Am241
SEFA-Px Analyzer
Si(Li)
Cd109
X-MET 920 (Si(Li) Detector)
Si(Li)
Fe55, Cd109, Am241
X-MET 920 (gas-filled
proportaional detector)
Gas Filled Proportional
Fe55, Cd109. Am241
XL Spectrum Analyzer
Silicon Pin-Diode
Cd109
MAP Spectrum Analyzer
Si(Li)
Co57, Am241,Cd109
TN Spectrace 9000
Hgl2
Fe55, Cd109, Am241
TN Spectrace Lead Analyzer
Hgl2
Cd109
4-45
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CHAPTER 5
DEMONSTRATION SITE DESCRIPTIONS
This chapter discusses the history and characteristics of the two demonstration sites.
5.1 ASARCO SITE
The Asarco site is the location of a former lead and copper smelter situated on the shore of
Commencement Bay in Tacoma, Washington (Figure 5-1).
5.1.1 Site History
Prior to 1890, sawmills were operated at the location of the Asarco site. Lead smelting and refining
operations began at this site in 1890 and continued until 1912. In 1905, Asarco purchased the
property and continued the smelting operations. In 1912, Asarco converted the operation to a copper
refining and smelting operation. Asarco further refined the by-products of the smelting operation into
arsenic, sulfuric acid, liquid sulfur dioxide, and slag. All smelting-related operations were
discontinued at this site in 1985.
The Asarco site is part of the Commencement Bay Nearshore/Tideflats Superfund site in Tacoma,
Washington. The Commencement Bay site was placed on the NPL in September 1983. In September
1986, Asarco and EPA Region 10 entered into an Administrative Order on Consent in which Asarco
agreed to conduct a remedial investigation and feasibility study. The remedial investigation was
completed in 1992; the feasibility study was completed in 1994.
5.1.2 Site Characteristics
The Asarco site is located on the Point of Defiance peninsula in the municipalities of Ruston and
Tacoma, Washington. The site consists of 67 acres of land adjacent to Commencement Bay. The site
is marked by steep slopes leading into the bay, slag fill that was used to extend the original shoreline,
a cooling water pond, and the various buildings associated with the smelting process. Partial facility
demolition was conducted in 1987. Most of the buildings were demolished between 1993 and 1994.
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The only buildings remaining are the Fine Ore Building, the Administrative Building, and a
Maintenance Garage.
Soil sampling has targeted four general areas of the site: the plant administration area, the former
cooling pond, the 1987 demolition area, and the off-site residential areas adjacent to the smelter stack
Sampling has shown surficial soils to be more contaminated than subsurface soils. Arsenic, copper
and lead are the predominant contaminants in the local soils. The highest arsenic concentrations were
found in the soils around the former arsenic kitchen, along with cadmium and mercury. The soils
around the former cooling pond contained the highest copper concentrations, and high levels of silver
selenium, barium, and chromium. Lead concentrations are highest northeast of the arsenic plant A
brief summary of the confirmatory analytical data for this site is presented in Table 5-1.
The majority of the smelter site is covered with artificial fill material of varying thickness and
composition. Two general types of fill are found on site: granular fill and massive slag fill. The
composition of the granular fill material ranges from sand to silty, sandy gravel with demolition
debris and slag debris intermixed throughout. The massive slag fill is a solid, fractured media
restricted to the plant site.
The surface soil in the plant administration area has a layer of slag particles on top, ranging from 1 to
3 inches thick. Surficial material in the parking lot area and southwest of the stack is mostly of
glacial origin and composed of various mixtures of sand, gravel, and cobbles. The soils around the
former cooling pond are fine-grained lacustrine silts and clays. Alluvium in the drainage upgradient
of the former cooling pond has been almost entirely covered with granular fill material. Generally
soils in the arsenic kitchen and stack hill areas are sand mixed with gravel or sandy clay mixed with
cobbles.
5.2 RV Hopkins Site
The RV Hopkins site is located in the west end of Davenport, Iowa, (Figure 5-2). The facility
occupies approximately 6.68 acres in a heavy industrial/commercial zoned area.
5-2
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5.2.1
Site History
Industrial activities in the area of the RV Hopkins property included the manufacture of railroad
locomotive engines during the mid-1800s. The RV Hopkins property was a rock quarry during the
late 1800s. Scott County, Iowa, acquired the property in 1921; it then passed to People's Light and
Power Company in 1929; W. J. Vale and Vale, Inc. (Mr. Hopkins' uncle), in 1940; and to the Frank
BeTry Trust in 1957. Mr. Hopkins purchased the property in 1964 and the adjoining property,
formerly Sludgemaster, Inc., in 1978.
Aerial surveys beginning in 1929 show that the rock quarry occupied the majority of the site initially,
gradually decreasing until being completely filled by 1982. Mr. Vale reportedly used the site to
dispose of demolition debris, automotive, and scrap metal. The site also has been used by a company
that recycled lead acid batteries.
RV Hopkins began operating as a drum reconditioner in 1951 across the street from its current
location. After acquiring the current property in 1964, Mr. Hopkins reportedly covered the former
quarry area of the site with foundry sand. RV Hopkins receives between 400 to 600 drums per day
for reconditioning, accepting only drums which meet the Resource Conservation and Recovery Act
(RCRA) definition of "empty" according to 40 Code of Federal Regulations (CFR) 261.7. (2). Most
of the drums received at the facility come from the paint, oil, and chemical industries.
5,2.2 Site Characteristics
The area is reported to be underlain by Devonian-aged Wapsipinicon Limestone, and grey-green
shale, lime mud, and sand stringers dating back to the Pennsylvanian age.
The RV Hopkins property is composed of five buildings: the office and warehouse, a warehouse
used to store drums of hazardous waste and a waste pile, a manufacturing building, a drum
reclamation furnace, and a cutting shed. The office and the warehouse are located on the southwest
corner of the site. Areas investigated on site include the furnace area, the old and new baghouses, the
former drum storage area on the north end of the facility, the former landfill, and a drainage ditch.
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Major contaminants include barium, lead, chromium, and zinc, as well as lesser concentrations of
other metals, such as copper and nickel, pesticides, and volatile organic compounds.
The most highly concentrated contaminants in the furnace area are chromium, lead, and zinc. The
highest concentrations of chromium, lead, and zinc are at the furnace entrance, as opposed to the
furnace exit. The concentrations of lead are higher in the old baghouse than in the new, while the
new baghouse exhibits a higher concentration of chromium, as well as high iron, lead, and barium
concentrations. The former landfill has concentrations of barium, chromium, lead, nickel, and sine
greater than 1,000 mg/kg. Lead is the most prevalent contaminant in the former drum storage area
with lesser concentrations of barium, chromium, and zinc. In addition, polychlorinated biphenyls
(PCB) and chlordane were prevalent in the areas. Table 5-2 gives a brief summary of the
predemonstration confirmatory analytical data for this site.
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5-5
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POWER
POLS
POWER
POLS
legend
MONITORING WBLL
so 1(
APPROX. SCAUT Iff
FPXRF
SITE DEMONSTRATION
FIGURE 5-2
RV HOPKINS SITE LOCATION uao
tortronmiptml
5-6
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TABLE 5-1
MAXIMUM CONCENTRATION OF CONTAMINANTS IN SURFACE SOIL SAMPLES
COLLECTED DURING PREDEMONSTRATION SAMPLING ACTIVITIES
Asarco Site
Tacoma, Washington
Contaminant
Minimum
Concentration
of Contaminant
(rag/kg)
Maximum
Concentration
of Contaminant
(mg/kg)
Antimony
ND
2,300
Arsenic
31.8
24.800
Barium
38.1
2,630
Cadmium
ND
279
Chromium
11.0
51.9
Copper
118
44,200
Iron
9,150
41,700
Lead
27.2
15,600
Manganese
138
659
Mercury
ND
582
Nickel
ND
65.5
Silver
ND
65.4
Zinc
45.9
3,910
Notes:
Confirmatory analyses were performed by Midwest Research Institute.
ND Not detected
mg/kg Milligrams per kilogram
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TABLE 5-2
MAXIMUM CONCENTRATION OF CONTAMINANTS IN SURFACE SOIL SAMPLES
COLLECTED DURING PREDEMONSTRATION SAMPLING ACTIVITIES
RV Hopkins Site
Davenport, Iowa
Contaminant
Minimum
Concentration of
Contaminant
(mg/kg)
Maximum
Concentration
of Contaminant
(mg/kg)
Antimony
ND
68.0
Arsenic
ND
17.9
Barium
73.8
6,340
Cadmium
1.4
13.4
Chromium
24.8
1,450
Copper
21.1
155
Iron
9,100
68.500
Lead
159
10,400
Manganese
306
906
Mercury
ND
0.29
Nickel
32.8
151
Silver
ND
ND
Zinc
73.0
2,410
Notes:
Confirmatory analyses were performed by Midwest Research Institute.
ND Not detected
mg/kg Milligrams per kilogram
5-8
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CHAPTER 6
SAMPLING PLAN
The sampling plan for this demonstration specifies procedures that will be used to ensure the
consistency and integrity of samples, and control within sample variation. In addition, this plan
outlines the sample collection procedures necessary to meet the demonstration purpose and objectives.
Careful adherence to these procedures will ensure that samples analyzed using the FPXRF
technologies are comparable to samples analyzed by the confirmatory laboratory using conventional
analytical methods. Figure 6-1 and Table 6-1 summarize the sampling and analysis strategy for each
technology.
In addition to the standard objectives of a SITE demonstration, EPA has requested that an SW-846
method for FPXRF use be submitted to the EPA OSW for validation at the conclusion of the
demonstration. To meet this objective, EPA OSW has required that a wide range of environmentally
threatening metals be examined. The primary target metals discussed below are intended to meet this
criteria. Also, EPA OSW has required that the performance of the FPXRF technologies be tested
over a variety of soil textures. EPA OSW defined the critical soil textures as being fine grained (silts
and clays), organic (loams), and coarse grained (sands).
6.1 SAMPLING AND FIELD ANALYSIS OPERATIONS
The sites for this demonstration are the RV Hopkins site and the Asarco site. These sites exist in
different climatological regions of the United States; they contain surficial soils meeting the textural
requirements of the demonstration; and they exhibit a wide range of concentrations for all the target
metals. The differences in soil texture will allow analysis of the affects of matrix on technology
performance. The RV Hopkins site is located in a humid continental climate characterized by hot
summers. The Asarco site is located in a marine climate characterized by mild winters. The
selection of sites in these two different climates will permit analysis of the affects of soil moisture on
technology performance. The primary target metals for this demonstration are arsenic, barium,
chromium, copper, lead, and zinc. Nickel, iron, cadmium, and antimony are secondary target
metals. Several of these secondary target metals will allow analysis of a technology's response to
metals interferences.
6-i
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Approximately iOO soil samples wil! be collected from each of the three target soil textures: clays
loams, and sands. During the predemonstration sampling activities, PRC identified sandy and loamy
textured soils at the Asarco site and silty clay soils at the RV Hopkins site. Because two of the target
soil textures were found at the Asarco site and only one target soil texture at the RV Hopkins Site it
is expected that twice as many soil samples will be collected at the Asarco site.
Each type of FPXRF technology, in situ and intrusive, will involve slightly different sampling
procedures. The following discusses the sampling and analysis that will take place at each soil
sampling location at each site. First, an area 4 inches by 4 inches square will be cleared of all
vegetation, debris, and gravel larger than 2 mm in diameter. Each of the FPXRF in situ technologies
will take one measurement in the sample area. This data will represent FPXRF in situ technology
measurements for unprepared soils. At 10 percent of the locations selected for this type of sampling
each FPXRF in situ technology will take 10 replicate measurements (without moving the probe) to
assess instrument precision.
After ail the FPXRF in situ technologies have completed their analysis of a location, the soil within
the 4-inch by 4-inch square will be removed to a depth of 1 inch and homogenized in a labeled plastic
bag. This will produce a soil sample of approximately 375 grams or 250 cm3. The 1-inch-depth
interval was selected as the thinnest layer of soil that could be reliably removed under normal field
conditions. This interval also produces 80 to 90 percent of the signal used by the FPXRF in situ
technologies to identify and quantify metals contamination.
Sample homogenization will be monitored by adding sodium fluorescein salt to the sample
homogenization bag. During the predemonstration, it was determined that sodium fluorescein salts
will not affect the FPXRF or confirmatory analysis. This procedure is discussed in detail in
Section 6.3. The sample will be kneaded for 2 minutes. At this time, the sample preparation
technician will examine the sample under ultraviolet light to assess the distribution of sodium
fluorescein salt throughout the sample. The sodium fluorescein salt fluoresces when it is exposed to
ultraviolet light. If the sodium fluorescein salt is not evenly distributed throughout the sample, the
homogenization and checking process will be repeated until the sodium fluorescein salt is evenly
distributed throughout the sample. This monitoring process assumes that even distribution of sodium
6-2
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fluorescein salt is indicative of good sample homogenization. Field duplicate samples will be
collected to monitor the effectiveness of the homogenization procedure.
During the predemonstration sampling, field duplicates were collected and analyzed by the
confirmatory laboratory to assess the demonstration's homogenization procedure. Nine duplicate
samples were collected. These samples were collected from each soil texture and for each target
concentration range. The mean RPD for individual metals for the field duplicates was 13.17 percent.
Applying a 99 percent confidence interval around this mean yields an RPD range of 8.59 to
17.75 percent. In other words, if the same homogenization technique is used in the demonstration,
99 percent of the samples should produce RPDs from 8.59 to 17.75 percent if split analyses are run.
This is below the acceptance limit of less than or equal to 20 percent RPD defined in the QAPP for
pre-digestion laboratory duplicates. Based on this, PRC considers the homogenization technique
adequate. In fact, it is likely that the RPD range for field duplicates will be reduced during the
demonstration since sample volumes will be reduced by 100 to 150 percent relative to the
predemonstration samples.
This homogenized sample will then be spread out inside a 4- by 4- by 1-inch frame. At this point,
the FPXRF in situ technologies will analyze the homogenized sample material. Each FPXRF in situ
technology will take one measurement from this homogenized material. This will represent prepared
sample analysis for in situ technologies. Instrument precision measurements will also be collected
from 10 percent of this sample material. The instrument precision data will be collected from the
same soils used for unprepared soil precision measurements. This data will represent FPXRF in situ
technology measurements with sample preparation.
Once the homogenized sample has been analyzed by all the FPXRF in situ technologies, the sample
material will be passed through a No. 10 mesh sieve and returned to its labeled sample bag.
Approximately 10 grams of this material will be placed in sample cups for analysis by the FPXRF
intrusive technologies. Ten replicate measurements will be collected on 10 percent of these samples
by each technology to provide a measure of instrument precision. The samples used for replicate
analysis will be those collected from locations corresponding to the locations where the instrument
precision measurements were taken for the FPXRF in situ technologies. Wherever possible the same
sample, including the same sample cup, will be used for each of the FPXRF intrusive technologies to
6-3
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obtain measurements of metal concentrations. This data will represent FPXRF intrusive technology
measurements on soils with no sample preparation. After a sample has been analyzed by all the
FPXRF intrusive technologies, it will be returned to the labeled sample bag.
After the FPXRF intrusive technologies have completed their analysis of a sample, the material in the
sample cup or cups will be placed back into their respective labeled sample bags. Aliquots of this
material will be placed in two labeled polyethylene bottles. One bottle will be delivered to the
confirmatory laboratory and the second bottle will be archived for QA/QC analysis by a second
confirmatory laboratory, if necessary. The confirmatory laboratory requires a minimum of 20 grams
of sample for extraction and analysis by SW-846 Methods 3050A and 6010A, and for QA/QC
samples.
The homogenized sample in the labeled sample bag then will.be dried and ground with a mortar and
pestle to a uniform fine particle size. Initially the sample will be weighed to acquire a wet weight it
will then be dried in a convection oven at 150 °C for 2 hours. The dried sample will be weighed to
determine a dry weight. The dried material will then be ground with a mortar and pestle for
3 minutes. The ground material will then be passed through a No. 40 stainless-steel sieve (0.425 mm
openings). This size sieve passes fine sands and smaller particles, as defined in the Unified Soil
Classification System. Sample grinding will continue until at least 90 percent of the original sample
passes the No. 40 sieve. This drying and grinding represents a standard field sample preparation to
minimize variance in particle size for the FPXRF intrusive technologies. An aliquot of the ground
soil will be placed in a sample cup for measurement by the FPXRF intrusive technologies. Ten
percent of these samples will undergo 10 replicate measurements by each FPXRF intrusive technology
to evaluate precision. These samples will be collected from locations corresponding to the locations
where the precision measurements were taken for the FPXRF in situ technologies. Wherever
possible, the same aliquot and sample cup will be used for all the FPXRF intrusive technologies.
This data will allow an assessment of the effects of sample drying and grinding on the results from
the FPXRF intrusive technologies.
Thirty percent of the samples will also be identified for extraction and analysis by SW-846 Methods
3052 and 6010A. The minimum 20 grams of sample described above should provide sufficient
sample volume for this analysis also. PRC will attempt to evenly distribute these samples over the
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target soil textures and concentration ranges. PRC will note the additional analytical procedures on
sample labels and field sheets. This analysis will be used to produce confirmatory data based on total
digestion, more closely related to the type of measurement made by FPXRF technologies. The
standard method for metals analysis (SW-846 Methods 3050A and 6010A) does not use a total sample
digestion extraction.
Ten percent of the sample material also will be split and further dried by microwaving on high for
5 minutes. PRC will attempt to evenly distribute these samples across the target soil textures and
concentration ranges. The microwave dried samples will be submitted to the confirmatory laboratory
for analysis by SW-846 Methods 3050A and 6010A. In addition, matching aliquots (same sample
location) of unprepared samples, packaged at the beginning of the FPXRF intrusive technology
analysis, will be submitted for confirmatory analysis. This data will assess the potential loss of metals
due to volatization from either convection oven drying or microwave drying. PRC does not anticipate
the loss of any metals other than mercury (not a target metal for this demonstration) during the
convection oven drying process. Arsenic is the most volatile target metal, sublimating at 188 °C.
Figure 6-1 presents a sample collection, packaging, and analysis flow chart for this demonstration.
Instrument drift and potential temperature effects will be monitored during this demonstration. At
each site, each technology will analyze the same PE sample at 2-hour intervals during at least one day
of field operation. Whenever these measurements are collected, the ambient air temperature will be
recorded.
Sampling will be conducted in areas of each site that, based on data from the predemonstration
sampling, exhibit wide ranges of metal concentrations. This will allow the FPXRF technologies to be
evaluated on their effectiveness in analyzing a broad range of metal concentrations. Sampling
personnel will collect samples using the equipment and procedures described in Section 6.2.
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6.2
COMMUNICATIONS, DOCUMENTATION, AND EQUIPMENT
PRC will communicate regularly with the demonstration participants to coordinate all field activities
associated with this demonstration and to resolve any logistical, technical, or QA issues thai may arise
as the demonstration progresses. The successful implementation of the demonstration will require
detailed coordination and constant communication between all demonstration participants.
All PRC field activities will be thoroughly documented. Field documentation will include field
logbooks, photographs, field data sheets, and chain-of-custody forms. FPXRF data reporting forms
and sample packaging forms are discussed and presented in Chapter 8. The PRC field team leader
will be responsible for maintaining all field documentation. Field notes will be kept in a bound
logbook. Each page will be sequentially numbered and labeled with the project name and number
Completed pages will be signed and dated by the individual responsible for the entries. Errors will
have one line drawn through them and this line will be initialed and dated.
All photographs will be logged in the field logbook. These entries will include the time, date,
direction, subject of the photograph, and the identity of the photographer. Specific notes about each
sample collected will be written on sample field sheets, as well as in the field logbook. Any
deviations from the approved final demonstration plan will be thoroughly documented in the field
logbook and communicated to the EPA TPM and other parties that may be affected by the change
Original field sheets and chain-of-custody forms will accompany all samples that are shipped to the
confirmatory laboratory. Copies of field sheets and chain-of-custody forms for all samples will be
maintained in the project file.
PRC will obtain all equipment needed for field work associated with this demonstration. A list of
field equipment expected to be used for this demonstration is piovided in Table 6-2.
6.3 QUALITY ASSURANCE/QUALITY CONTROL REQUIREMENTS
A key issue in ensuring the effectiveness of this demonstration is ensuring that environmental ''nrpi^
analyzed by the confirmatory laboratory and by each of the FPXRF technologies are subsamples from
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a homogenous sample. To address this issue, sampling personnel will exercise particular care
throughout the field work to ensure that samples are thoroughly homogenized before they are split
into replicate samples. Homogenization will be conducted by kneading the soil in a plastic bag for a
minimum of 2 minutes. If after this time the samples do not appear to be well homogenized, they
will be kneaded for an additional 2 minutes. This will continue until the samples appear to be well
homogenized. In the case of the FPXRF in situ technologies, this is not as critical because these
technologies will analyze the entire sample and produce a concentration based on the mean
concentration throughout the sample. For the FPXRF intrusive technologies, however, only a small
aliquot of the homogenized sample will be used, therefore, homogenization is critical.
PRC will use sodium fluorescein as an indicator of thorough homogenization. If the samples are dry,
past experience has shown that sodium fluorescence will not work as an indicator of thorough
homogenization. If the samples are moist, approximately one-quarter teaspoon of dry sodium
fluorescein powder will be added to the sample prior to homogenization. The sample will be
homogenized for the specified time. After homogenization is completed, the sample will be examined
under an ultraviolet light to assess the distribution of sodium fluorescein throughout the sample. If
the fluorescent dye is evenly dispersed in the sample, homogenization will be considered complete. If
the dye is not evenly distributed throughout the sample, the homogenization mixing will be continued
and repeatedly checked until the dye is evenly distributed throughout the sample. PRC anticipates
that the homogenization process should take approximately 2 to 4 minutes per sample.
Field duplicates will be collected during the demonstration and submitted for confirmatory analysis.
These samples will be submitted for analysis at a rate of at least one duplicate for every 10 samples
submitted. These samples will be collected by splitting a single homogenized sample in the field.
Duplicate samples will be submitted for analysis to the confirmatory laboratory and to each of the
FPXRF technologies. These samples will be used to evaluate the precision (reproducibility) of sample
collection, homogenization, processing, and analysis. Multiple duplicate samples from each
concentration range will be collected.
Additional QA/QC information, including procedures for analytical work associated with this
demonstration, is provided in the QAPP in Chapter 8. All field activities for this demonstration will
be conducted according to the requirements of the sampling plan and the QAPP.
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6.4
HEALTH AND SAFETY PROCEDURES
Health and safety procedures that will be used during demonstration field work are detailed in the
HASP in Chapter 10.
6.5 SAMPLE COLLECTION PROCEDURES
Sampling personnel will collect and homogenize samples using the procedures described below /vil
field activities will conform with requirements of the HASP and with all requirements in this
demonstration plan.
Sampling personnel will maintain communication with the EPA TPM and the EPA regional site
contacts during field activities. If unanticipated or unusual situations are encountered that may alter
the sampling design, sampling location, or data quality, the situation will be discussed with the EPa.
TPM and the EPA regional site contacts before changes to the approved demonstration plan are mad*.
Any deviations from the approved demonstration plan will be thoroughly documented as discussed in
Section 6.2.
6.5.1 Sampling Locations
Soil samples will be collected from areas at the sites known to exhibit metal concentrations ranging
from less than 100 milligrams per kilogram (mg/kg) to concentrations greater than 1,000 mg/kg
(based on the target metals listed in Section 6.1). PRC is anticipating that the detection limit for mr**
metals using the FPXRF technologies will be in the range of 50 to 100 mg/kg.
Approximately 25 soil samples will be collected from the less than 100 mg/kg concentration range
each of the three target soil textures. These samples will be used to evaluate the low detection limits
of each FPXRF technology. Approximately 50 soil samples will be collected from areas with metal
concentrations ranging from 100 to 1,000 mg/kg, for all three target soil textures. There are more
soil samples in this range because action levels for metals in soil, such as lead and chromium, are
often in this concentration range, and PRC believes that this is within the linear range of
technologies. The additional sampling is required to increase the statistical power of this range of
6-8
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evaluation. Evaluating the performance of each FPXRF technology near action levels also will
determine their potential usefulness for site screening to determine the action or no action status of
sites. The remaining 25 soil samples will be collected from areas containing metals at concentrations
greater than 1,000 mg/kg, for each target soil texture. The results from the high concentration soil
samples will be used to evaluate data trends, such as linearity, at high concentrations.
Every effort will be made to collect the samples necessary to evaluate the FPXRF technologies over
the three concentration ranges, relative to all the target metals. If the some of the primary target
metals do not provide sufficient distribution to allow evaluation over these concentration ranges, the
data evaluation concerning these metals will be less thorough, however, PRC anticipates no problem
in obtaining the desired sample distribution in the 100 to 1,000 mg/kg range. This range contains
most of the FPXRF technology detection levels and environmental action levels for the target metals.
If secondary target metals are not present at the desired concentrations or distributions, then these
compounds may not be assessed.
Exact sample locations for the demonstration will be determined by the PRC field team leader in the
field. These locations will not be permanently marked or recorded. Locations will be selected based
on data and sampling maps obtained from previously written reports for both sites and from
predemonstration sampling data. The PRC field team leader will ensure that the appropriate number
of samples from each concentration range are collected. Since the confirmatory data will not be
available to guide the sampling, the field team leader will use the FPXRF technology data to track the
progress of sampling and the approximate concentration of the samples.
6.5.2 Soil Sampling Procedures
PRC will place plastic or fiberboard 4-inch by 4-inch squares at each sampling point at each site.
These squares will be numbered and secured to the ground surface with wire anchors. Each square
will also have an area for FPXRF operator sign-off to indicate that an operator's measurements have
been completed at a given square. The ground surface within each square will be cleared of all living
and dead organic matter and all rocks. The soil surface will then be smoothed to a level plane using
a metal masonry trowel. At this point, the square sample location will be ready for the initial FPXRF
in situ technology measurements. Once these measurements are complete at a sampling point, PRC
6-9
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win remove surface soil samples in the square areas to a M *pO. The surface sotl samples will
be removed and collected by using a hand trowe. or puny kntfe Co scrape .he soil surface. Satnpitag
personnel will comply with all health and safety requirements in the HASP (Chapter 10). All sou
sampling will be conducted according to the soil sampling procedures discussed in PRC SOP No. 5
¦Soil Sampling at Hazardous Waste Sites. ¦ This material will be placed into a numbered plastic
ziD lock bag Before soils are homogenized, rocks, pebbles, stick,, organic matter, and foreign
^ fmm the sanrole bag. Once the sample is placed in the sample bag, it will be
debris will be removed from the sample mb
handled as described in Section 6.1.
6S3 Sample Storage, Packaging, and Shipping
After collection and until analysts, all sampies will be stored in coolers. Custcrfy of sample, wil, be
maintained a, discussed in Section 6.2 «l according to the tenements of applicable section, o,
PRC SOP No. 18 "Sample Custody.
Samnles to be Shipped to the confirmatory laboratory will be packaged and shipped according to U*
II packaging and shipment requ— of PRC SOP No. 19 "Packaging a*i Shipping
1 K - xLhnical requirements for holding times for soil samples being analyzed for metal,
cling to SW-846 methods have no. been established. Th. recommended holding time prior u>
extraction and analysis is 6 mon^s. For me purpose of this demo— A. sample, be
elcted and amlyzed 30 ^ " "" '"r^
. wil, be stored for 90 days pending data reduction. H any samples are identified as omh«,.
H samples will be reana^zed by a second conf.rmau.ry Uboratory (QA laboratory). OuUier. wu,
TLifL by statistical analysis (Chapter 7, or by failure to meet QA/QC requirements
(Chanter 8 ) The QA laboratory will be different from the original confirmatory iaboratory, and U
nl identified prior to the implementation of this demonstration plan. Analytic* data produced by
rrm *-————«- qa—' — -
the QA/QC conditions specified in the QAPP.
6-10
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6.5.4 Decontamination
Disposable clothing or sampling equipment coming into contact with grossly contaminated material
will be double-bagged and handled as investigation-derived waste (IDW). IDW will be properly
disposed of according to the requirements in the EPA "IDW Management Guidance Manual - Second
Draft" (1990). EPA will be considered the generator of any IDW produced during this
demonstration.
Only material that has come into contact with grossly contaminated material will be treated as IDW.
Contamination avoidance practices will be used whenever possible to minimize the volume of IDW
generated. Waste not coming into contact with grossly contaminated material will be disposed of in a
local sanitary landfill.
Health and safety monitoring equipment will be bagged to prevent instrument contamination. The
only open areas on the monitoring equipment will be at sample entry points.
Nondisposable sampling equipment will be decontaminated by scrubbing with an Alconox solution and
water with a final water rinse. The sieves will undergo a dry brushing prior to the wet wash. Sieves
will be oven dried before they are used again. If the wet decontamination method is not adequate to
remove soil particles, a high-pressure hot water cleaning unit may be used for decontamination. All
decontamination water will be contained in 30-gallon steel drums pending confirmatory analysis.
Depending on the concentration of metals in the decontamination water, the water will either be
disposed of at a local publicly owned treatment works or by a licensed hazardous waste disposal
contractor.
6.5.5 Schedule
Demonstration activities are scheduled to start at the Asarco site on April 2. 1995. Demonstration
activities will begin on April 17, 1995, at the RV Hopkins site. This demonstration should require 7
to 12 field days at each site.
6-11
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INSfTU MEASLREM&JT
(4X4 INCH GRID)
, ^ CONDUCT v Ye
| ^PRECISION MEASUREMENTS —
10* OF
LOCATIONS /
"COLLECT
10 RBHJCATE
wruovr
COLLECT 10-20 GRAM
SUBSAMPLEFOR
WATER CONTENT
DETERM NATION
COLLECT SOtL FROM
- Tno J
1
CONDUCT
insttu
MEASUREMENT
^Was SAMP1_E\
PREVIOUSLY USED"
f, FOR PRECISON
\oereRMiNATioN?^
,oiua»ucAT«
HSS*
(A
2]
s
FPXRF
SITE DEMONSTRATION
FIGURE 6-1
SAMPLE PREPARATION
AND ANALYSIS FLOW CHART
.on |
rnc ENVIRONMENTAL MANAGEMENT
6-12
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TABLE 6-1
SAMPLE COLLECTION AND ANALYSIS STRATEGY
Field Portable X-Ray Fluorescence Technologies
SITE Demonstration
Step
Sample Preparation
FPXRF Analysis
1.
Mark a 4-inch by 4-inch square area
with a plastic or fiberboard square.
Clear loose rocks and organic matter
from the soil surface.
Conduct 10 replicate measurements at
10 percent of these areas.2
Conduct measurements over the entire
square with the FPXRF in situ
technologies. The data generated by
each technology will be averaged to
produce one measurement
representative of the entire square.
2.
Remove the upper I inch of the soil
within the square. Homogenize this
material and verify degree of
homogenization with fluorescein dye.
Evenly distribute this material onto a
1-inch-deep, 4- by 4-inch square frame
lined with wax paper,
Conduct 10 replicate measures on the
homogenized materials corresponding
to the areas where replicate
measurements were collected in
Step l.a
Conduct measurements over the entire
square with the FPXRF in situ
technologies. The data generated by
•each technology will be averaged to
produce one measurement
representative of the entire square.
3.
Place approximately 10 grams of the
material described in Step 2 into a
plastic analysis cup.
Collect a sample aliquot for moisture
content determination.
Package approximately 20 grams of
this material in a labeled polyethylene
sample bottle.b Store this material
until the microwave drying in Step 4.
Conduct 10 replicate measures on the
homogenized materials corresponding
to the areas where replicate
measurements were collected in Step 1
above.3
Analyze this material with each
FPXRF intrusive technology. Attempt
to use the same sample cup for each
analysis.
6-13
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TABLE 6-1 (Continued)
SAMPLE COLLECTION AND ANALYSIS STRATEGY
Field Portable X-Ray Fluorescence Technologies
SITE Demonstration
Step
Sample Preparation
FPXRF Analysis
4.
Dry the sample in a convection oven at
150 °C for 2 hours. Then grind this
material until 90 percent passes
through a No. 40 sieve.
Conduct 10 replicate measures on the
homogenized materials corresponding
to the areas where replicate
measurements were collected in Step 1
above."
Collect field duplicates at a 1:10
ratio.c
Drv splits from 10 percent of the
sample material in a microwave oven
on high for 5 minutes.b
Analyze 10 to 12 PE samples for
method accuracy check.
Analyze this material with each
FPXRF intrusive technology. Attempt
to use the same sample cup tor each
analysis.
Submit approximately 20 grams of
every sample to the confirmatory
laboratory for extraction and analysis
by SW-846 Methods 3050A and
601 OA. Twenty percent of these
samples also will be extracted and
analyzed by SW-846 Methods 3052
and 6010A. The field duplicates also
will be submitted for these
confirmatory analysis.0
Submit the microwave dried samples
for confirmatory analysis by SW-846
Methods 3050A and 6010A. Submit
samples (unprepared) from the same
locations already packaged in Step 2
above.b
Submit all PE samples, double blind,
for confirmatory analysis by SW-846
Methods 3050A and 601 OA, and 3052
and 6010A.
Archive approximately 20 grams of
every sample for potential submittal to
the QA laboratory.
5.
Analyze PE samples.d
Analyze these samples every 2 hours
during at least one day with all the
technologies. Record the ambient air
temperature when these samples are
analyzed.d
Notes:
a Precision determination data.
b Metals volatization check
c Homogenization check data.
d Calibration check and drift monitoring data.
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TABLE 6-2
LIST OF FIELD EQUIPMENT NEEDED
Field Portable X-Rav Fluorescence Technologies
SITE Demonstration
Equipment
NIST SRMs
PE Samples
Stainless-steel garden trowels
Stainless-steel spoons
Polyethylene sample bottles (2 ounce)
Field forms
Clipboard
ASTM Type II water
Stainless-steel sprayers
Plastic bins
Disposable aluminum pans
Plastic sheeting
Aluminum foil
Tap water
Alconox
Plastic bags (Ziploc bags)
Permanent markers
Kimwipes
Field logbook
Sample labels
Wash tubs
Brushes
Sieves
Mortars and pestles
Microwave ovens
Wax Paper
Plastic frames
Fluorescein dye
Black light
No. 40 Stainless-Steel Sieve
Sieve Decontamination Station
Convection Oven
Shipping Equipment
Cooler chests
Tape (duct, packing, and Teflon)
Shipping forms
Shipping labels
Bubble wrap
Health and Safety Equipment
Disposable latex gloves
Disposable nitrile gloves
Tyvek coveralls
Cloth coveralls
Hard hats
Air-purifying respirators
AEP3 HEPA combination cartridge filters
Safety glasses
Steel-toe shoes
First aid kit
Disposable overboots
Miniram Model PDM-3
Photographic Equipment
35-ram camera
Film
Miscellaneous
Barricade tape (yellow, caution)
Paper towels
Garbage bags
6-15
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CHAPTER 7
EXPERIMENTAL DESIGN
This chapter discusses the objectives of this demonstration, factors that must be considered to meet
the DQOs, and the statistical and other means that PRC will use to evaluate the results of the
demonstration.
7.1 OBJECTIVES
The primary objectives of this demonstration are to evaluate FPXRF technologies in the following
areas: (1) their performance relative to conventional analytical methods, (2) the impacts of sample
matrix variations (texture, moisture, and chemical composition) on their performance, (3) the
logistical and economic resources necessary to operate these technologies, and (4) to submit an
FPXRF analytical method for validation and inclusion in SW-846. Secondary objectives for this
demonstration are to evaluate FPXRF technologies for their (1) reliability, ruggedness, cost, and
range of usefulness, (2) data quality, and (3) ease of operation. The performances of the FPXRF
technologies will not be compared against each other. Their performances will be compared to the
performances of conventional analytical methods used in performing site characterization activities.
7.2 FACTORS TO BE CONSIDERED
This section discusses factors which will be considered in the design and implementation of the
demonstration. These factors include comparability, precision, portability, ease of operation,
ruggedness and instrument reliability, health and safety issues, sample throughput, and sample matrix
effects. This section discusses the importance of these factors and ways of measuring their effects,
when warranted.
7.2.1 Qualitative Factors
Some factors, while important, are difficult or impossible to quantify. These are considered
qualitative factors. One such factor is the ease of learning to use the different FPXRF technologies
and applying them in the field. To assess this factor, PRC field personnel will be trained by a
7-1
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developer representative on how to operate each FPXRF technology. The developers will train th
PRC operators using their respective operator training manuals. Based on this training and field
experience, the operators will prepare a subjective evaluation detailing the training and operation
experiences during the demonstration.
Other important factors which cannot easily be quantified are the portability of a technology anfj
logistical requirements necessary for using it. The weight and size of each technology will be
documented. An evaluation of the logistical requirements will include an assessment of the
technology's power source, licensing requirements, and the need for other equipment or supplies
such as liquid nitrogen to cool the detector or a computer to operate the technology. Each operator
will record notes in a field logbook on the logistical requirements for each technology.
Demonstration procedures will simulate routine field conditions as much as possible. For this rri| |(J
operators will be trained just prior to the demonstration and will not have prior experience on the
specific FPXRF technologies they will use in the demonstration.
7.2.2 Quantitative Factors
Many factors in this demonstration can be quantified by various means. These are quantitative
factors. Some can be measured while others, such as the presence of interferants, cannot be
controlled. These quantitative factors are discussed below.
One quantitative factor is instrument reliability or the susceptibility of each FPXRF technology |q
environmental conditions. One critical environmental factor is change in temperature. TnipLlu(^
change effects will be assessed by conducting repeated measures of one or more soil samples o
course of each day at each demonstration site. PRC will use PE samples for this study. This
produce data that can be used to identify trends in the effect of changing temperature on tedmolr*—.
drift.
Many standard applications of FPXRF technologies involve the drying of samples with a
oven. Sample temperatures during this procedure can be high enough to melt some mineral
in the sample or combust organic matter. Several metals that present environmental hazards
7-2
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volatize at elevated temperatures. Mercury is volatile at standard temperature and pressure. This
compound will volatize whenever any accelerated drying is attempted. Since this compound is not a
target metal for this demonstration, its high degree of volatility will not be addressed. Arsenic, on
the other hand, sublimates at 188 °C, well within the potential sample temperatures achieved during
microwave drying, but below the temperatures achieved through the convection oven drying that will
be used during this demonstration. To assess this potential affect, 10 percent of the samples dried by
convection oven will be subsampled. One subsample will be of unprepared material, and the second
subsample will be heated in a microwave oven on high for 5 minutes. These subsamples will then be
submitted for confirmatory analysis. This data will be compared to its corresponding data produced
from the convection oven dried sample.
Another quantitative factor is the count time used to acquire data. During the formal sample
quantitation and precision measurement phase of the demonstration, the count times will be set by the
developers and remain constant throughout the demonstration. To assess the affect of count times,
where possible, the soil samples used for the instrument drift assessment also will be analyzed in
replicate using different (relative to developer instructions) count times to assess the effects on
technology performance.
An important health and safety issue is the effectiveness of radioactivity shielding of each FPXRF
technology. PRC will take occasional radiation readings with either a gamma ray or an x-ray specific
detector near each technology to assess the potential exposure to radiation.
The cost of using each FPXRF technology is another important factor. Cost includes expendable
supplies such as liquid nitrogen, nonexpendable equipment, labor, licensing agreements for the
radioactive sources, operator training costs, and IDW disposal. These costs will be tracked during
the demonstration. A cost per sample will then be computed. Sample throughput will also be
documented, and will have an effect on cost per sample. Since sample throughput can be affected by
adjusting count times, PRC operators will maintain constant count times throughout the
demonstration. The selected count times will be determined by the developer.
Technology performance relative to the confirmatory laboratory and the associated secondary sample
quantitation objectives are the most important quantitative factors. These factors will be statistically
7-3
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evaluated. Instrument performance near method detection limits and action levels is of great interest
to potential users. To evaluate performance, all samples collected for the demonstration will be split
between the FPXRF technologies and the confirmatory laboratory for analysis. Results from the
confirmatory laboratory will be considered the actual concentrations of metals in each sample. Where
duplicate samples exist, the concentrations for the duplicates will be averaged and the average
concentration will represent the true value for the sample pair. If one or both samples in a pair
exhibit a nondetect for a particular compound, that pair of data will not be used in the statistical
evaluation for that compound.
Many analytical methods can have significant "operator effects," in which individual differences in
operator technique have a significant effect on the numerical results. For the FPXRF technologies
being demonstrated, the primary anticipated operator effect will be variation in sample preparation
and measurement techniques. Variation in measurement techniques is expected to have a relatively
minor effect on the final results obtained with each FPXRF technology. Based on general laboratory
practices, the error introduced through measurement technique variation is expected to be less thqn
± 5 percent, much less than the expected variation in results from the FPXRF technologies
themselves. The potential exists for this type of operator effect also to occur in the confirmatory
laboratory. To reduce the potential impact of measurement technique variation, PRC will use a single
operator to operate each FPXRF technology, and accept that this error source will be confounded
with the inherent variation in technology readings. This policy will approximate ordinary field
conditions being simulated, in which only one FPXRF technology is typically used. To control this
effect for the confirmatory laboratory, only one laboratory will be used to analyze the samples. This
does not include the second confirmatory laboratoiy, which may be used to reanalyze samples where
original sample results were determined to be statistical outliers. To control the potential sample
preparation variation effect, PRC will use the same personnel to prepare samples throughout the
demonstration.
All analytical methods have a specific usable range with lower and upper limits. The usable range for
each FPXRF technology will be determined by comparing results from each FPXRF technology to
results obtained from the confirmatory laboratory. Statistical analysis of the results will identify the
region in which results from each technology's results are linear to the confirmatory laboratory's
result, as well as their lower detection limits.
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The most potentially variable factors are interferences with the analysis and matrix effects. Some
types of interferences and matrix effects and ways they will be controlled or evaluated during this
demonstration are summarized below:
• Heterogeneity : As noted in the sampling plan (Chapter 6), every sample will be
thoroughly homogenized after the initial FPXRF in situ technologies have collected
data. In keeping with standard field sampling procedures, rocks and gross organic
matter such as twigs will be removed before mixing. At least 10 percent of the
homogenized samples will be duplicated for confirmatory analysis to determine the
effectiveness of the homogenization techniques. These samples are the field duplicates
described in Chapter 6.
• Particle Size: After the FPXRF intrusive technologies have collected data on the
homogenized samples, the samples will be ground to a uniform particle size as
described in Chapter 6. The soil samples will then be reanalyzed by the FPXRF
intrusive technologies to determine the effects of particle size on the results. The sites
chosen for this demonstration have different soil textures. The performance of each
FPXRF technology in different soil textures should provide an assessment of particle
size influences on the FPXRF technologies.
• Moisture Content: Moisture content of the soil sample may have an effect on the
analytical results from the FPXRF technologies. Results will be obtained from moist
and dried soil samples with the FPXRF intrusive technologies to evaluate the effects
of moisture content as discussed in Chapter 6.
• Overlapping Spectra of Elements: Interferences result from overlapping spectra of
metals that emit x-rays with similar energy levels. An example is the interference of
arsenic (K-alpha at 10.54 keV) with the lead (L-alpha at 10.55 keV) x-ray spectra.
This interference will not be controlled, however, the confirmatory analysis will
provide data on the concentration of potential interferants in each sample. This data
may be used to explain FPXRF technology data outliers or data quality trends
observed during this demonstration.
The results from each technology will be dependent on the quality of data generated. Many factors
could affect the data quality generated. The following factors will be used in determining each
technology's data quality.
Method blanks will be used to evaluate technology-induced contamination, which may cause false
positive results. An example of this contamination is the build up of dust in a sample chamber or
source window, or detector saturation from highly contaminated samples. Method blanks to be
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analyzed each day will consist of lithium carbonate that has been taken through all the sample
collection and preparation steps. Method blank results will be tabulated and discussed in the TER
Calibration check samples will be analyzed to assess instrument drift.
Intramethod accuracy and precision are critical factors in an evaluation of data quality for each
FPXRF technology. Precision will be assessed by conducting 10 replicate analyses on 10 percent of
the soil samples collected at each site. In the case of the FPXRF in situ technologies, replicate
measurements will be taken on the unhomogenized and homogenized soil samples to assess the effect
of homogenization on precision. These replicate analyses will be obtained without moving the
technology between replicate measurements. For the FPXRF intrusive technologies, precision will be
assessed at each step of sample preparation. This will provide data that will allow PRC to evaluate
the effect of sample preparation on FPXRF technology precision.
Accuracy will be assessed by analyzing 10 to 12 PE samples that contain known concentrations of
metals. The PE samples for this demonstration will be SRMs purchased from the NIST (Nos. 2710
2711, and 2704) and PE samples purchased from other certified sources. PRC took two
predemonstration samples from each site, one low and one high concentration, and will have
analyzed by at least four independent laboratories before the demonstration to create site-specific pg
samples. These samples will be analyzed by a laboratory-grade XRF. The data generated by the
laboratory-grade XRF will be used to define mean concentrations and 99 percent confidence intervals
for use in evaluating the accuracy of the FPXRFs. For these SRMs and the ones purchased from
NIST, PRC will define the acceptance limits as 80 to 120 percent of the true value concentration of a
target metal.
Between 10 and 12 PE samples will be analyzed blindly by each FPXRF technology during the
demonstration. The PE samples will contain a wide range of metals concentrations. The PE sample,
will also be submitted blindly to the confirmatory laboratory for both methods of extraction and
analysis by SW-846 Method 601 OA.
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7.3
SAMPLING DESIGN
As described in the sampling plan (Chapter 6), the basis for the experimental design of the
demonstration is to control within-sample variation for soil. This will be achieved for the FPXRF
in situ technologies because they will analyze the 4-inch by 4-inch square representing the entire soil
sample. This will be achieved for the FPXRF intrusive technologies by using a thoroughly
homogenized sample, and wherever possible, by using the same soil sample for each intrusive
technology analysis. This variation also will be controlled for the confirmatory analysis. The
confirmatory samples will be composed of the same sample material analyzed by the FPXRF intrusive
technologies.
As discussed in Chapter 6, soil samples for this demonstration will be collected as follows:
(1) 25 samples from areas containing less than 100 mg/kg of metals; (2) 50 samples from areas
containing 100 to 1,000 mg/kg of metals; and (3) the remaining 25 samples from areas of greater than
1,000 mg/kg of metals. These three concentration ranges have been chosen for the following reasons.
Most FPXRF technologies have detection limits in the range of 50 to 100 mg/kg for many of the
target metals for this demonstration. Samples in the low concentration range will be used to evaluate
the low detection limits for each FPXRF technology. The largest number of samples will be collected
in the 100 to 1,000 mg/kg concentration range because action levels for metals in soil, such as lead
and chromium, are often set in this concentration range. It is important to evaluate how effective the
FPXRF technologies are at concentrations near action levels. At concentrations greater than 1,000
mg/kg, it is expected that the FPXRF technology results and those from the confirmatory laboratory
will begin to diverge because of the differences in the methods of extraction and analysis. Results in
this concentration range will be used to evaluate this potential trend.
PRC will collect 100 samples from each of the three soil-textures: clays, loams, and sands. Within
earh of these groups of samples, PRC will attempt to collect samples representative of the
concentration distribution discussed above. This data will allow examination of an overall soil texture
effect.
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7.4
STATISTICAL ANALYSIS
This demonstration will require comparisons of various groups of data. Each data group will be
analyzed in a similar fashion. For each FPXRF technology, there will be one data set from each of
the three soil textures. This grouping will be intended to assess potential soil textural effects. Within
each of these three data sets, three data subsets will be created for the FPXRF intrusive technologies-
one for soil samples with no sample preparation, one for samples that have been ground into a fine
powder and dried, and one for confirmatory samples subjected to both a total digestion extraction
(SW-846 draft Method 3052) and a standard or partial digestion extraction (SW-846 Method 3050A)
For the FPXRF in situ technologies, three data sets will be created, one for each soil texture. Two
data sets will be created within each of these three main data sets: one for undisturbed soil
measurements and one for homogenized soil measurements.
Data also will be separated by grouping the texture-specific data sets into results within the three
concentration ranges established above. This grouping is intended to assess potential concentration
effects on the data analysis and assess the linear range of the technology.
Additional data sets will be created for the field duplicate data, the FPXRF technology precision
measurements, and the metals volatility. The field duplicate data set will be used to assess sample
homogenization. The FPXRF precision measurements will be used to assess the precision of ca^
FPXRF. The metals volatility data will be used to assess the potential impact of high temperature
drying on metals concentrations in soil samples.
After data from the FPXRF technologies and the confirmatory laboratory are received, PRC will
evaluate the results using the statistical methods discussed in the following sections. For this
demonstration, the determination of significance for inferential statistics will be set at a 5 percent
probability of making a Type I error, accepting a false null hypothesis.
When averaging duplicate samples or when comparing the results of an FPXRF technology to those
from the confirmatory laboratory, sample pairs that contain a nondetect will be removed from the riatB
sets. While other statistical methods can be used when nondetects are encountered, PRC feels thai the
variance introduced by eliminating these data pairs would be less than, or no more than equal to, the
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variance produced by giving nondetected results an arbitrary value. Predemonstration sampling has
reduced the potential for collecting samples without detectable metals contamination relative to
confirmatory analysis.
7,4,1 Intramethod Comparisons
Sample results from each technology will be compared to replicate sample measurement results and to
other QA/QC sample results. These comparisons are called intramethod comparisons and they will be
conducted independently for each target metal. These comparisons will be components in determining
the data quality of each FPXRF technology. Three data quality levels will be considered during this
evaluation. The two highest data quality levels are screening data and definitive data as described in
EPA's "Data Quality Objectives Process for Superfund - Interim Final Guidance" (1993). The
definition for the lowest data quality level is qualitative screening data and was created specifically for
fhis demonstration. These definitions are as follows:
Level 3 Data: Definitive Data
Definitive data are generated using rigorous analytical methods, such as approved EPA
reference methods. Data are analyte-specific, with confirmation of analyte identity and
concentration. Methods produce tangible raw data (e.g., chromatograms, spectra, digital
values) in the form of paper printouts or computer-generated electronic files. Data may be
generated at the site or at an off-site location, as long as the methods' QA/QC requirements
are satisfied. For the data to be definitive, either analytical or total measurement error must
be determined.
Level 2 Data: Screening Data
Screening data are generated by rapid, less precise methods of analysis with less rigorous
sample preparation. Sample preparation steps may be restricted to simple procedures such as
dilution with a solvent, instead of elaborate extraction/digestion and cleanup. Screening data
provide analyte identification and quantification, although the quantification may be relatively
imprecise. At least 10 percent of the screening data or all critical samples are confirmed
using analytical methods and QA/QC procedures and criteria associated with definitive data.
Screening data without associated confirmation data are not considered to be of known
quality.
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Level 1 Data: Qualitative Screening Data
Qualitative screening data are generated by rapid, less precise methods of analysis with little
to no sample preparation. This level of data provide identification of the presence or absence
of contaminants in a sample matrix. This data may be compound-specific or specific to
classes of contaminants. This data will identify the presence or absence of target analytes
however, it may have no relationship to true concentrations of those analytes.
Since the FPXRF is a new and innovative analytical method, approved EPA methods do not exist
For the purpose of this demonstration, the lack of approved EPA methods will not preclude a
technology from being considered a Level 3 technology. The main criteria for data quality level
assignment will be based on the comparability of an FPXRF technology's data to confirmatory
laboratory data. The confirmatory data is produced using an EPA-approved Level 3 analytical
method. Therefore, if a technology is statistically similar to the confirmatory method, it will be
considered capable of producing Level 3 data. As the statistical significance of the comparability
decreases, a technology will be considered to produce data of a correspondingly lower quality
Table 7-1 defines the criteria that must be met for a technology to be considered Level 1, 2, or 3 for
this demonstration. PRC could find no references that provided quantitative control limits for rfa»a
quality. The control limits presented in Table 7-1 were produced by PRC in consultation with EPA
EMSL and EPA OSW.
Intramethod accuracy will be measured by assessing each FPXRF technology's performance in
analyzing PE samples. If the method produces results within the acceptance range for the target
metals of the PE samples, the technology will be considered to have intramethod accuracy meeting the
requirements of Level 3 data. If the technology produces data outside the acceptance ranges for the
PE sample, it will be considered inaccurate. Assessment of the technologies comparability to
confirmatory data, discussed later in this chapter, can be used as an indicator of performance and to
identify the technology's data quality classification.
Intramethod precision will be assessed through the calculation of percent relative standard deviations
(RSD) or the percent coefficient of variation on replicate analyses of the same sample. The pcrrn^
RSD is calculated by dividing the standard deviation by the mean of the replicate measurement
meet Level 3 data quality, an FPXRF technology will require a ± 10 percent precision. Level 2 riata
quality will require a ±20 percent precision (EPA 1991). PRC also will use replicate data analyse
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to calculate technology-specific precision control limits using SW-846 protocols. The collection of
the precision data is detailed in Section 7.2.2.
7.4,2 Intermethod Comparisons
The data sets from the two types of FPXRF technologies, intrusive and in situ, will be statistically
compared to the results from the confirmatory laboratory. This type of comparison is called an
intermethod comparison and will be used to determine instrument performance. In this case, the
results from the confirmatory laboratory are considered to be accurate and precise. The statistical
methods used to evaluate this performance are linear regression analysis and either a paired t-test or
the Wilcoxon Signed Ranks Test. The determination of significance, also referred to as the
probability of making a Type I error, will be set at 0.05 for the inferential statistics used for this
demonstration.
Confirmatory laboratory results will be validated following EPA guidelines, [f any confirmatory
laboratory results are rejected, the corresponding technology results also will be rejected. If less than
5 percent of the confirmatory laboratory results are reported as estimates, they may be rejected. The
QC concerns that caused these data to be estimated will be reviewed. If the QC issues are determined
not to be directly tied to the quantitation of the result (such as low level blank contamination), the
data will be used.
If more than 5 percent of the confirmatory laboratory's results are estimated, all estimated values will
be retained. Although this will increase the apparent variation between technology and confirmatory
laboratory results, major decreases in the number of samples would have the same effect.
If duplicate or replicate analyses are performed by the confirmatory laboratory or the FPXRF
technologies, the mean value for that sample will be used as the sample result in all statistical
analyses.
The distribution of both the FPXRF technologies' and confirmatory laboratory's data sets will be
evaluated. PRC will use a chi-square test and probability plots to assess whether the data sets are
normally distributed. If these tests indicate the data are not normally distributed, a
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Kolmograv-Smirnov test will be run to verify this determination. If the data sets are normally
distributed, PRC will use parametric statistics (paired t-test) to produce inferential statistics. If the
data sets are not normally distributed, PRC will use nonparametric tests (Wilcoxon Signed Ranks
Test) to produce inferential statistics. Nonparametric tests require no assumption regarding the
population distribution of the two sets of data being evaluated other than that the distributions will
occur identically. In other words, when one data point deviates, its respective point in the other set
of data will deviate similarly. Because the only deviation expected during the demonstration is a
difference in the concentrations reported by each FPXRF technology, the two sets of data are
expected to deviate in the same way. The distribution of the data will not strongly affect the linear
regression analysis. Only extreme departures from normality will cause spurious results (Kleinbaum
and Kupper 1978).
In linear regression analysis, the correlation coefficient (r) serves as a measure of both comparability
and precision. The square of r (r2) is the fraction of variation in the technology result, which is
explained by the variation in the confirmatory laboratory results (Havlick and Crain 1988). The t2 is
also known as the coefficient of determination. It is mathematically equivalent to the square of r, the
correlation coefficient. If one or both of the paired analytical results (confirmatory and technology)
are "not detected," then that sample cannot be used in the linear regression.
Following the linear regression analysis, PRC will use post-hoc techniques to further evaluate the test
results. This will allow the identification of data outliers. The primary technique that will be used is
"residual examination" (Draper and Smith 1981), an empirical procedure for determining which
factors contribute most to unexplained variation (residual error) in the results. Two uses of this
technique are to remove data points that exhibit disproportionate influence on the regression and da»n
points that are outliers from the general distribution. Both of these approaches generally improve
correlation and regression. Another use of this technique is determining the linear range of a
statistical analysis. For example, if trimming some points off one end of the regression curve will
result in a major improvement in the regression coefficient, then the eliminated region represents a
nonlinear response of the technology. If this response represents a major effect, PRC may cornier
using data transformations to further improve the statistical analysis (Natrella 1963). In consultation
with the EPA TPM, PRC also may conduct additional post-hoc analyses to further evaluate
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demonstration data. One such analysis may involve the use of the multiple linear regression data
discussed in Section 7.4.3 to help identify general factors that bias the results.
PRC will calculate linear regression by the method of least squares. Calculating linear regression in
this way makes it possible to determine whether two sets of data are reasonably related, and if so,
how closely. The linear regression will determine the correlation between the FPXRF data and the
confirmatory data, and the coefficient of determination for this relationship. If the correlation
coefficient is greater than or equal to 0.84 (this is equivalent to an r2 of 0.70), the relationship will be
considered good enough to proceed with linear regression and attempt to produce a mathematical
model defining the relationship. PRC will use the slope and y-mtercept of the regression model to
create the mathematical model, and determine the similarity of the FPXRF data to the confirmatory
data. PRC will evaluate correlation before and after post-hoc data reduction.
Calculating linear regression results in an equation that can be visually expressed as a line Pour
factors are defined during calculations of linMr ,egress,These factors are the y-intercept. the
slope of the line, and the correlation coefficient (r), and the coefficient of determination (r2). All of
these factors will be considered when making an assessment of the level of data quality produced bv
the FPXRF technologies (Table 7-1).
The correlation coefficient expresses the mathematical relationship between two data sets. If the
correlation coefficient is 1 or -1. the dependent variable is a linear transform of the independent
variable, and thus the two da« sets are directly related. A positive correlation coefficient
,hal as one variable increases the second variable also increases. A negative correlation
indicates an inverse relationship, as one variable increases the other variable decreases. Because of
,he heterogeneous nature of environmental samples, correlation coefficients with absolute values
between 0.84 (this is equivalent to an r* of 0.70) and 1 will be considered necessary to continue datt
evaluation through linear regression. Correlation coefficients with absolute values below 0 84 wui
no. result in regression analysis and the variables will not be considered comparable, w „
best, Level 1 data may be produced.
b, linear regression the coefficient of determine <"« « explained by the regression
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relationship between dependent and independent variables. An r of 1.0 indicates that the regression
model explains all the variation between the FPXRF and confirmatory data. As the r deviates from
1.0, there is more unexplained variation. For the purposes of this demonstration, an r2 less than 0 70
will indicate that enough unexplained variation exists to preclude the formulation of a linear model to
allow data prediction or correction.
If the regression analysis results in an r2 between 0.85 and 1, then the regression line's y-intercept
and slope will be examined to determine how closely the two data sets match. A slope of one and a
y-intercept of zero would mean that the results of the FPXRF technology match those of the
confirmatory laboratory perfectly. Theoretically, the greater the slope and y-intercept differ from
these expected values, the less accurate the FPXRF technology. Still, a slope or y-intercept can differ
slightly from their expected values without that difference being statistically significant. To determine
whether such differences are statistically significant, PRC will use the normal deviate test statistic
This test statistic results in a value that is compared to a table. The value at the 95 percent
confidence level will be used for the comparison (5 percent chance of a Type 1 error). To meet data
quality Level 3 requirements, both the slope and y-intercept have to be statistically the same as their
ideal values. Data falling into this category will be considered statistically equivalent to the
confirmatory data, and not requiring bias correction.
If the r2 is between 0.70 and 1, and one or both of the other two regression parameters are not
statistically equivalent to their ideal, the technology will be considered to produce Level 2 quality
data. Results in this case could be mathematically corrected if 10 to 20 percent of the samples were
sent to a confirmatory laboratory. Analysis of a percentage of the samples by a confirmatory
laboratory would provide a basis for determining a correction factor. Only in cases where the r2, the
y-intercept, and the slope are all found to be acceptable will PRC determine that the technology is
accurate, meeting Level 3 data quality requirements.
Data placed in the Level 1 category has r2 values less than 0.70, data not statistically similar to the
confirmatory data based on parametric or non-parametric testing, or results that do not meet the
developer's performance specifications. However, the technology must indicate the presence (not
concentration) or lack of contamination, above its detection limit, with at least a 95 percent accuracy
rate.
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The second statistical method used to assess the intermethod accuracy of the data from each FPXRF
technology will be either the paired t-test or the Wilcoxon Signed Ranks Test. These tests compare
matched pairs of data. They can be used to evaluate whether two sets of data are significantly
different.
The paired t-test compares the means of two data sets, which are composed of matched pairs of data.
The significance of the relationship between two matched-pairs sets of data can be determined by
comparing the calculated t-statistic with the critical t-value determined from a standard t-distribution
table at the desired level of significance and degrees of freedom. The Wilcoxon Signed Ranks Test
also compares two data sets composed of matched pairs of data. Unlike the paired t-test, the
Wilcoxon Signed Ranks Test compares the number of samples analyzed and a ranking of the
difference between the result obtained from an FPXRF technology and the corresponding result from
the confirmatory laboratory. The rankings can be compared to predetermined values on a standard
Wilcoxon distribution table which indicates whether, overall, the two methods have produced similar
results-
7.4.3 Matrix and Sample Preparation Studies
As noted in Chapter 6, two sites with different soil types will be used during this demonstration.
PRC will regress the entire data set from each soil type against the data from the confirmatory
laboratory to determine comparability between methods. PRC will use the regression techniques
(described in Section 7.4.2 to determine if one data set is more comparable than the others, therefore,
indicating the presence of a matrix effect.
Within ?arh of the three data sets, PRC will evaluate the potential effects of sample preparation on
gjje ppXRF technology results. PRC will use multiple linear regression techniques on the data sets
from the prepared and unprepared soil samples versus the confirmatory laboratory results to
jffgrmine if there was a sample preparation effect. A step-wise linear regression will be used to
the impact of each sample preparation data set on the overall correlation. In other words, this
statistical test will identify the sample preparation techniques that have the greatest influence on the
correlation between the FPXRF technology data and the confirmatory laboratory data. This
will be based on a review of the resultant r2 for each step-wise linear regression.
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PRC also will use a paired t-test to determine if the two data sets (prepared versus unprepared) are
significantly different. PRC may conduct this test on log-transformed data. The log transformation
will reduce the skewing effects that may be introduced by high concentration samples on the linear
regression.
At each site, PRC will choose approximately 10 percent of the soil sample locations that span the
concentration range for metals to test the potential effect of sample preparation on precision. Each of
the FPXRF technologies will perform 10 replicate analyses on each of the soil samples (prepared and
unprepared). As discussed in Section 7.4.1, from these measurements a percent RSD or coefficient
of variation will be calculated for the unprepared and prepared samples to determine precision A
paired t-test or a Wilcoxon Signed Ranks Test will be performed to determine if the precision results
are significantly different.
The FPXRF data will also be compared to the confirmatory data produced from the total digestion
analysis (SW-846 draft Method 3052 and Method 6010A). This comparison will be carried out as
described above.
PRC will evaluate the loss of metals due to high temperature drying (microwave) by comparing
matched pairs of convection oven dried and microwave oven dried sample data to their corresponding
confirmatory data. Correlation and regression analysis will be used to determine the relationship and
attempt to define a linear model that can be used to correct microwave data, if necessary. In
addition, the inferential statistics described above will be used to test the statistical similarity between
the two data sets.
7.4.4 Software
The primary software PRC will use for data analysis will be SYSTAT, which was developed by
Systat, Inc. (1990). System capabilities include:
• Data entry (from keyboard and text files) and editing
• Data transformations
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• Multivariate regression (including step-by-step selection of variable)
• Nonlinear regressions
« Post-hoc analyses
• Graph and table production
One particularly useful feature of this software is that "not detected" results can be entered as missing
data so the calculations automatically skip over data points including such entries. This system
appears adequate for the intended calculations, including data transformation, as well as the more
complex manipulations discussed in Sections 7.4.1 and 7.4.2.
Before using this software. PRC will confirm its usefulness by repeating known calculations drawn
from standard references, such as Draper and Smith (1981), Havlick and Crain (1988), and
Natrella (1963).
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TABLE 7-1
CRITERIA FOR DATA QUALITY CHARACTERIZATION
Field Portable X-Ray Fluorescence Technologies
SITE Demonstration
Data
Quality
Level
Statistical Parameters
3
r2 = 0.85 to L.0, and the slope and y-intercept are statistically similar to 1.0 and
0.0 respectively, the precision (RSD) is less than or equal to 10 percent and
inferential statistics indicate the two data sets are statistically similar.
2
r2 = 0.70 to 1.0, the precision (RSD) is between 10 and 20 percent, the technology
meets its developer's performance specifications, normal deviate test statistics on the
two regression parameters indicate the two data sets are statistically not similar; or 1
in the case where the regression analysis indicates the data is of Level 3 quality, but I
the inferential statistics indicate the data sets are statistically different. ' |
1
r2 = < 0.70, or the precision (RSD) is >20 percent, the technology has less than a!
10 percent false negative rate when identifying the absence of contaminants, or the I
technology does not meet its developer's performance specifications. j
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CHAPTER 8
QUALITY ASSURANCE PROJECT PLAN
The QAPP for this demonstration specifies procedures that will be used to ensure data quality and
integrity. Careful adherence to these procedures will ensure that data generated from the
confirmatory laboratory will meet the desired DQOs and will provide sound analytical results that can
be used for a comparison with the data from the FPXRF technologies.
g.l PURPOSE AND SCOPE
The primary purpose of this QAPP is to outline steps that will be taken by the confirmatory
laboratory and by operators of the FPXRF technologies to ensure that data resulting from this
demonstration is of known quality and that a sufficient number of critical measurements are taken.
This QAPP also details the QA/QC criteria that will be used to validate the confirmatory laboratory
results. According to the EPA EMSL statement of work for this demonstration, the demonstration is
classified as a Category II project. This chapter of the demonstration plan addresses the key elements
that are required for Category II projects prepared according to guidelines in the EPA guidance
documents "Preparing Perfect Project Plans" (1989) and the "Interim Guidelines and Specifications
for Preparing Quality Assurance Project Plans" (Stanley and Verner 1983).
The scope of the QAPP includes a comparison of FPXRF technology results to results generated by a
confirmatory laboratory using EPA-approved methods. Each FPXRF operator will use a method
specified by the developer. These methods may include written instructions and verbal directions.
The confirmatory laboratory will use EPA SW-846 Method 6010A "Inductively Coupled
plasma-Atomic Emission Spectroscopy" for sample analysis. All samples will be extracted by EPA
SW-846 Method 3050A "Acid Digestion of Sediments, Sludges, and Soils" prior to analysis by
SW-846 Method 6010A. Thirty percent of the samples also will be extracted by SW-846 draft
Method 3052 "Microwave Assisted Acid Digestion of Ash and Solid Waste."
Data generated by each FPXRF technology will be evaluated to determine the level of data quality it
is capable of generating. Each FPXRF technology is expected to produce Level 1 or Level 2 data
quality- which is expected to generally parallel, if not match, the results from SW-846 Method
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601 OA. Extraction methods SW-846 Method 3050A, draft Method 3052. and Method 6010A can
provide Level 3 data quality. Adherence to the QA/QC requirements of this QAPP will ensure that
definitive level data quality is generated by the confirmatory laboratory.
QUALITY ASSURANCE RESPONSIBILITIES
The PRC project manager is responsible for coordinating the preparation of a QAPP for this
demonstration and its approval by the EPA TPM and the developers. The PRC project manager will
ensure that the QAPP is implemented during all demonstration activities. The PRC analytical QA
manager for the demonstration will review and approve the QAPP and will provide independent QA
oversight of all demonstration activities.
Samples will be collected and analyzed on site by the FPXRF technologies and off site by the
confirmatory laboratory using EPA-approved methods. Many individuals will be responsible for
sampling and analysis QA/QC throughout the demonstration. Primary responsibility for ensuring that
sampling activities comply with the requirements of the sampling plan (Chapter 6} will rest with the
PRC field team leader.
FPXRF operators will be responsible for following written and verbal directions given by the
developer, for supplying information required for the preparation of the draft SW-846 method,
recording observations in logbooks, and recording FPXRF data on the forms exhibited on Figures 8-1
to 8-4. QA/QC activities for each FPXRF technology will at least follow the recommendations of the
developers. If PRC adds QA/QC measurements not required by the developers, PRC will document
these measurements and the rationale for their addition. At this time, PRC anticipates aHHjng
additional QA/QC measurements, such as matrix blanks, precision determination measurements, and
PE sample measurements, all of which are generally not included in a developer's instructions. The
purpose for each of these additions is discussed in Chapters 6 and 7.
QA/QC activities for the confirmatory laboratory analysis of samples will be the responsibility of the
confirmatory laboratory analysts, supervisors, and manager. If problems arise or any data appear
unusual, they will be thoroughly documented and corrective actions will be implemented as specified
in the confirmatory laboratory's QAPP and this demonstration QAPP. Many of the QA/QC
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measurements made by the confirmatory laboratory are dictated by the analytical methods being used.
This QAPP includes additional QA/QC guidance which must be followed during the analysis of
FPXRF demonstration samples.
8.3 DATA QUALITY PARAMETERS
The data obtained during the demonstration must be of sound quality for conclusions to be drawn on
the FPXRF technologies, and to support the submission of a draft SW-846 method for FPXRF
technologies. For all measurement and monitoring activities conducted for EPA, the agency requires
that data quality parameters be established based on the proposed end uses of the data. Data quality
parameters include five indicators of data quality referred to as the PARCC parameters: precision,
accuracy, representativeness, completeness, and comparability.
High quality, well documented confirmatory laboratory results are essential for meeting the purpose
and objectives of this demonstration. Therefore, the PARCC parameters, which will be used as
indicators of data quality, will be closely evaluated to determine the quality of data generated by the
confirmatory laboratory. In addition, the PARCC parameters will be utilized to evaluate the quality
of data generated by each of the FPXRF technologies.
The following subsections detail each of the PARCC parameters and include specific QA/QC samples
which will be used to evaluate the quality of data generated by the confirmatory laboratory and each
FPXRF technology.
g31 Precision
precision refers to the degree of mutual agreement among individual measurements and provides an
estimate of random error. Precision for this demonstration will be expressed in terms of the percent
IISD between replicate sample measurements and the RPD of laboratory and field duplicate samples.
precision for each FPXRF technology will be assessed with field duplicate samples and the analysis of
replicate sample measurements, and through the use of PE samples. The field duplicate samples will
provide precision data for the sample collection, field preparation, handling, and transportation
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procedures, as well as the FPXRF analysis precision. Replicate sample measurements will provide
data for FPXRF analysis precision.
PE samples also will be used to determine FPXRF technology precision through the use of means
standard deviations, and RSDs for percent recoveries of each target metal in the PE samples. It is
expected that between 10 to 12 PE samples will be submitted for analysis for each FPXRF technology
during the course of the demonstration.
Precision for SW-846 Method 6010A will be assessed through field duplicate and laboratory duplicate
samples. Laboratory duplicate samples will include pre- and post-digestion sample duplicate analyses
Pre-digestion laboratory duplicate samples will provide precision data for sample extraction and
analysis activities. Post-digestion laboratory duplicate samples will provide precision data for analysis
activities.
Method precision for each FPXRF technology and SW-846 Method 6010A will be evaluated.
Instrumental precision data for each FPXRF technology will be evaluated through a RSD calculation
for replicate sample measurements. Instrumental precision for SW-846 Method 6010A will be
evaluated through post-digestion laboratory duplicate samples. Extraction and analysis precision of
SW-846 Method 6010A will be evaluated through pre-digestion laboratory duplicate samples.
A comparison of the FPXRF precision to the SW-846 Method 6010A precision will be performed
through the evaluation of field duplicate samples. Field duplicate sample RPDs will be statistically
evaluated through determination of the RPD mean and through a one-sided student's T-test using the
95 percent confidence interval. The student's T-test will provide an upper controi limit for RPD of
demonstration Field duplicate samples and will identify any outlier duplicate sample results. The field
duplicate RPD upper control limit for each FPXRF technology can be compared to the field duplicate
RPD upper control limit of the confirmatory laboratory for a comparison of precision. An additional
statistical comparison of the FPXRF to the confirmatory laboratory precision can be performed
through the use of a matched pair student's T-test, which compares the mean RPDs of the FPXRF
field duplicate samples to SW-846 Method 6010A field duplicate samples. This statistical comparison
can determine if there is a significant difference between the two means. If a significant different
does exist, an inference can be made which is that the lower mean value provides better precision.
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PE samples also will be used to determine SW-846 Method 6010A precision through the use of
means, standard deviations, and RSDs for percent recoveries of each target metal in the PE samples.
It is expected that between 10 to 12 PE samples will be submitted for analysis using both SW-846
Methods 3050A and 3052 extraction procedures for SW-846 Method 6010A analysis during the
course of the demonstration.
8.3.2 Accuracy
Accuracy refers to the difference between a sample result and the reference or true value for the
sample. Bias, a measure of the departure from the complete accuracy, can be caused by such
processes as errors in standard preparations, technology calibrations, incomplete extraction of the
target analyte. loss of target analyte in the extraction process, interferences, and systematic or
carryover contamination from one sample to the next.
Accuracy and bias will be assessed for the FPXRF technologies using data on method blank results
and PE samples. Data quality parameters for accuracy of the FPXRF technologies in this
demonstration will be method blank results which contain no target compounds above the method
detection limits. Accuracy will also be evaluated through the use of PE samples. PE samples used
during this demonstration will provide the best estimate of accuracy because they will represent the
best estimate of target analyte concentrations in any of the samples analyzed during the demonstration.
Accuracy for the PE sample results will be evaluated through the comparison of percent recoveries
for each target analyte.
Accuracy and bias will be assessed for SW-846 Method 6010A using data on method blanks,
instrument check standards, pre- and post-digestion matrix spike samples, and PE samples. Data
quality parameters for accuracy in this demonstration will be method blank results which contain no
target compounds above the method reporting limits, instrument check standard results which are
within 10 percent of the expected recoveries, pre- and post-digestion spike recoveries which fall
within accepted limits listed in SW-846 Method 6010A, and PE sample results which fall within
aCCeptance limits as published in SW-846 Method 601 OA or those generated through interlaboratory
analyses which have been published by EPA or by PE sample suppliers.
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8.3.3 Representativeness
Representativeness refers to the degree to which the data accurately and precisely represents the
conditions or characteristics of the parameter represented by the data. In this demonstration,
representativeness will be ensured by executing consistent sample collection procedures, including
sample locations, sampling procedures, sample storage, sample packaging, sample shipping, sample
equipment decontamination, and proper laboratory subsampling (Chapter 6). Representativeness also
will be ensured by using each method at its optimum capability to provide results that represent the
most accurate and precise measurement it is capable of achieving. QC samples which will be used to
evaluate representativeness during this demonstration include method blank samples, field duplicate
samples and PE samples. These QC samples will be used for both the FPXRF technologies and
SW-846 Method 6010A.
8.3.4 Completeness
Completeness refers to the amount of data collected from a measurement process compared to the
amount that was expected to be obtained. For this demonstration, completeness refers to the
proportion of valid, acceptable data generated using each method. The completeness objective for
data generated during this demonstration is 95 percent.
8.3.5 Comparability
Comparability refers to the confidence with which one data set can be compared to another. A
primary objective of this demonstration is to evaluate how well the FPXRF technologies perform in
comparison to conventional analytical methods used by a confirmatory laboratory based on the
experimental design discussed in Chapter 7. Additional QC for comparability will be achieved by
analyzing QC samples and method blanks as discussed in Chapter 6 and by adhering to methods and
SOPs for sample preparation and instrument operation. This will be performed through a Wilcoxon
signed rank test of each FPXRF technology result to the SW-846 Method 6010A result. An
evaluation of the detection limit achieved for the target metals by each FPXRF technology will be
compared to the lower reporting limits (LRL) achieved by SW-846 Method 6010A for an additional
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check of comparability. Expected SW-846 Me,hod 60,OA LRLs for target metals identified durins
the demonstration activities is presented in Table 8-1
soil sample drying and homogenization will be performed prior to FPXRF technology and SW 846
Method 6020A analysts. Samples win he reported on an "as received" basis by both the FPXRF
technology and SW-846 Method 6010A.
8 4 ™l;I„BRAT,ON PROCEDURES, QUALITY CONTROL CHECKS Avn
CORRECTIVE ACTION CHECKS, AND
Calibration procedures, method-spec.fic QC requirements, and corrective action associated with
nonconformance QC for the FPXRF technologies and the SW-846 Method 6010A are described in the
following subsections. Table 8-2 lists calibration procedures, method-specific QC requirements a*i
corrective action for SW-846 Method 601 OA.
QC Criteria for FPXRF technologies will be specified by each developer and are no, available for
tabulation, but wtll be noted by each technology operator and included in the TER ITER and the
dr3ft SW"846 f0r FPXRF -get metals tha, wiiI be to£rrnined _
FPXRF ,echn0l08ics and SW"84« W10A include: arsenic, barium, chromium copper
lead, and z,nc. Secondary target metals for SW-846 Method 60!0A include: nickel, cadmium,
antimony, and ,ron. Other metals may also be reported by both the FPXRF technologies and SW-846
Method 6010A.
Some of the metals which may be reported by SW-846 Method 60I0A can be affected by the
extraction and analysis methods used. Antimony (a secondary target metal) and silver form insoluble
precipes when mixed with the hydrochloric acid used for the SW-846 Methods 3050A and 3052
extraction techniques. Mercury may also form insoluble precipitant when ™xed with hydrochloric
acid, and due to us volatility may be lost during sample extraction procedures. Antimony silver a»l
DierCUtT reSulB pr0vided * »»"« Method 6010A using extraction Methods 3050A and'3052 may
not meet all QA/QC criteria and can be coded and reported as estimated values
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QC requirements listed in Table 8-2 for initial and continuing calibrations, calibration verification
standards, calibration blank standards, method blank samples, and LCSs must be met bv the
confirmatory laboratory. Corrective actions required for these QC requirements are listed in
Table 8-2. Other QC requirements included in Table 8-2 pertain only to the primary target metais
These include pre- and post-digestion spike samples and pre- and post-laboratory duplicate samples
Corrective action required by the confirmatory laboratory when pre- and post-digestion spike and
duplicate samples fall outside of the control limits for the primary target metals include:
(I) reanalysis of the QC sample, (2) reextraction and reanalysis of the QC sample, and if the
reextraction and reanalysis of the QC sample produces results which fall within the control limits,
then (3) reextraction and reanalysis of the QC sample and the batch of samples associated with the
QC sample.
When reextraction and reanalysis of the QC sample produces results which fall outside control limits
the QC sample and the batch of samples associated with the QC sample will be set aside and options
for corrective action will be discussed and balanced with project needs, after all samples have been
initially analyzed. When this occurs, the confirmatory laboratory QC manager must contact the PRC
project manager. The PRC project manager will advise the EPA TPM of the situation and will
coordinate with the EPA TPM and the confirmatory laboratory QC manager to determine specific
options which may be employed to correct the problem.
The control limits for secondary target metals can be relaxed to those listed in SW-846 Method
601 OA. If the QC control limits are exceeded for secondary target metals, corrective action must be
taken one time. If this does not resolve the problem, the data from the two runs will be averaged for
the secondary target metals in question and reported with data qualifiers identifying the data as
estimated values.
It is expected that QC samples will be designated by PRC. Instructions for samples which require
pre- and post-digestion spike samples and pre-and post-digestion laboratory duplicate samples will be
included on sample chain-of-custody forms submitted to the confirmatory laboratory along with the
samples. Pre- and post-digestion spike samples and pre- and post-digestion laboratory duplicate
samples will all be performed on the same sample.
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All QC samples and control limits listed in Table 8-2 and detailed in the following subsections will be
used for all samples extracted with SW-846 Method 3050A and 3052.
g 41 Initial Calibration Procedures
Initial calibration for each FPXRF technology will be performed according to the developer's
recommendation. The types of standards used and the acceptance criteria for the initial calibration or
calibration curve also will be those recommended by the developer. These recommendations will be
thoroughly documented by each observer and included in the TER, ITER, and the draft SW-846
method prepared for the FPXRF technologies.
The initial calibration for SW-846 Method 6010A consists of the analysis of three concentration levels
of each target metal and a calibration blank. The low-level calibration standard will be at a
concentration which defines the LRLs of the method. The remaining calibration standard levels will
be used to define the linear range of the instrument. The initial calibration is used to establish
calibration curves for each target analyte.
Accuracy of the initial calibration are verified through the use of a calibration blank, an initial
calibration verification (ICV) standard, the reanalysis of the high level calibration standard, and the
analysis of an interference check standard (ICS).
A calibration blank is used to establish technology responses to the reagents used for standard and
sainple preparation. An analysis of the calibration blank must show that no target metals are present
at concentrations above the low-level standard, or above the result of multiplying the low-level
standard by the ratio of the final volume of the sample extractant divided by the mass of the soil
sample extracted. This blank also must show that interfering spectral lines are not present in the
analytical system that may interfere with the quantitation of any target analyte in the standards or
samples. Corrective action, which can be taken if the above criteria can not be met includes:
(1) cleaning the analytical system according to developer's recommendations, (2) reanalyzing the
calibration blank and calibration standards, and (3) repreparation of calibration standards until the
a^ove criteria is met.
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The validity of the initial calibration used for SW-846 Method 6010A is verified through the use of
the ICY standards. The 1CV is performed with each initial calibration performed. The ICV standard
is obtained from a different source than the initial calibration standards, and is prepared at a
concentration near the mid-level concentration of the initial calibration. The results of the ICV
standard must be within 10 percent of the expected value. When results are greater than 10 percent
of the expected value, the analysis must be halted and the source of the problem must be identified
and corrected. Corrective action which must be taken if the above criteria cannot be met includes-
(1) reanalysis of the initial calibration, (2) reanalysis of the ICV standard, and (3) repreparation of the
initial calibration and ICV standards.
Before sample analysis begins the high-level standard is again analyzed. Concentration values for this
standard should not deviate by more than 5 percent of the expected value as determined from the
initial calibration. If the deviation is greater than 5 percent, corrective action is required to find the
source of the problem and to correct it. Corrective action which must be taken if the above criteria
cannot be met includes: (I) reanalysis of the high-level calibration standard, (2) reanalysis of the
initial calibration standards, and (3) follow manufacturer's recommendations for correction of the
problem. A new initial calibration must then be analyzed along with the high-level standard check to
ensure response deviations of less than 5 percent.
An ICS is analyzed to verify the accuracy of background correction used for spectral interferences.
The ICS is analyzed along with each initial calibration and is used to evaluate appropriate correction
factors used by SW-846 Method 6010A. The ICS includes known concentrations of interfering
elements along with target compounds. QC criteria of the ICS is 80 percent recovery of each target
compound in the ICS, Corrective action which must if the above criteria cannot be met includes: (1)
reanalysis of the ICS, (2) reanalysis of the initial calibration, (3) repreparation of the calibration
standards.
8.4.2 Continuing Calibration Procedures
Continuing calibration checks for each FPXRF technology will be performed according to the
developer's recommendation. The standard levels used and the acceptance criteria for continuing
calibrations also will be those recommended by the developer. These recommendations will be
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thoroughly documented by each observer and included in the TER, ITER, and the draft SW-846
method prepared for the FPXRF technologies.
The validity of the initial calibration used for SW-846 Method 6010A is verified after the analysis of
every 10 samples through a continuing calibration. The continuing calibration is performed with a
calibration blank and a continuing calibration standard (CCS), which is the mid-level initial calibration
standard. Requirements for the continuing calibration blank are the same as those of the initial
calibration blank sample. The results of the CCS must be within 10 percent of the expected value.
When results are greater than 10 percent of the expected value, the analysis must be halted and the
source of the problem found and corrected. Corrective action which must be taken if the above
criteria cannot be met includes: (1) reanalysis of the CCS, (2) reanalysis of the initial calibration
standards, and (3) reanalysis of the ten samples analyzed prior to the CCS.
/^n ICS sample is analyzed after the analysis of 20 samples and is an ongoing check of instrumental
interference. QC requirements of this ICS are the same as those listed in the initial calibration ICS.
8.4.3 Method Blanks
The analysis of method blanks by the FPXRF technologies will be performed as directed by the
developers. If a developer does not require method blanks, PRC will add method blanks analysis to
the field, use of the technology. If PRC adds method blanks analysis to an FPXRF technology's
operating procedure, the resulting data will not be used for corrective action, rather it will be used in
the TER and ITER to explain strengths or weaknesses of a particular FPXRF technology.
Method blanks will be analyzed for SW-846 Method 6010A. Method blanks monitor
laboratory-induced contaminants or interferences. Method blanks are analyzed with each batch of
samples analyzed. A batch is defined as up to 20 samples of a similar matrix extracted and analyzed
together. To be acceptable, a method blank must not contain any target compound above the LRLs.
Corrective action that must be taken if the above criteria cannot be met includes: (1) reanalysis of the
jnethod blank sample, (2) repreparation of the method blank and all associated samples extracted with
the method blank, and (3) reanalysis of the method blank and all associated samples.
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8.4.4
Laboratory Control Samples
LCSs will noi be used for the FPXRF technology unless .heir use is recommended by the developer.
However, if the developer does recommend LCSs. their use w.ll be performed following the
developer's recommendations.
LCSs will be used for SW-846 Method 6010A. LCSs are a clean soil matrix to which a known
concentrate of target metals is added. The source of the target metals used for spiking must be
from a different source than those used for calibration standards. LCSs are be prepared and analyzed
in exactly the same manner as all other samples, and are prepared with each batch of up to 20
samples and are used to evaluate the precision of the analytical method. Control limits for LCSs are
from 80 to 120 percent recovery. Corrective aeon that must be taken if the above criteria cannot be
met include: (1) reanalysis of the LCS. (2) repreparation of the LCS and all samples extracted along
with the LCS, and (3) reanalys.s of the LCS and all associated samples.
8.4.5 Matrix Spike Samples
Matrix spike samples wtll not be used for the FPXRF technolog.es unless their use is -commended
by the developer. However, if the deve!oper does recommend matrix samples, their use will be
performed following the developer's recommendations.
Matrix spUce samples will be performed for SW-846 Method 60!0A and will be performed through
the use of pre- and post-digestion spike samples. Pre- and post-digest,on spike samples will be
analyzed to assess the accuracy of SW-846 Method 6010A and to evaluate matrix effects of samples.
Pre digestion spike samples are samples to which a known concentration of target analytes are added
prior to sample extraction. The pre-digestion spike sample are prepared and analyzed in exactly the
same manner as all other samples, and can be used to evaluate the accuracy of the extraction and
analysis process of the method. Post-digestion spike samples are samples which have been extracted
•„ ,he same manner as other samples, but to which a known amount of targe, analytes have been
added to the sample extractam. These samples are analyzed in the same manner as other samples and
used to evaluate the accuracy of the method without the losses incurred through the extraction
process Control limits for both pre- and post-digestion spike samples are from 80 to 120 percent
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recovery. Corrective action that must be taken if the above criteria cannot be met include:
(1) reanalysis of the spiked sample. (2) reextraction and reanalysis of the spiked sample, and if the
reextraction and reanalysis of the spiked sample produces results which fall within the control limits,
then (3) reextraction and reanalysis of the spiked sample and the batch of samples associated with the
spiked sample. However, when reextraction and reanalysis of the spiked sample produces results
which fall outside of the control limits, the spiked sample and the batch of samples associated with the
spiked sample will be set aside. The PRC project manager will then be contacted and advised of the
situation. Final decisions on corrective action regarding samples outside the QA/QC control limits
due to matrix efforts will be delayed until all samples have undergone initial analysis. These
decisions will be based on project needs.
g.4.6 Performance Evaluation Samples
Between 10 and 12 PE samples will be purchased and submitted for analysis by both the FPXRF
technologies and by SW-846 Method 6010A. These samples are very important to the demonstration
because they will provide the only absolute check of method accuracy during the demonstration. PE
samples which will be used during the demonstration will be SRMs supplied by NIST, the U.S.
Geological Survey, or the Canadian Geological Survey. The PE samples are generally supplied with
true value results and a statistical error range. PE samples will be submitted as double blind samples
for both FPXRF technologies and for SW-846 Method 6010A. This means that the operator will not
know that the sample is a PE sample and will not know the concentrations of target analytes in the
samples.
PPXRF results of the PE samples will be compared to the published true value for each PE sample.
The accuracy of each FPXRF technology will be assessed through a determination of the percent
recovery for each target metal in each of the PE samples. Statistical evaluations of mean recoveries,
standard deviations, and relative standard deviations will be utilized for each target metal to assess
ppXRF accuracy.
gW-846 Method 6010A will be expected to provide percent recoveries of all target metals within the
raJtgc of 80 to 120 percent recovery. Accuracy for SW-846 Method 6010A will be assessed through
a determination of the percent recovery for each target metal in each of the PE samples. Statistical
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evaluations of mean recoveries, standard deviations, and relative standard deviations will be utilized
for each target metal to assess SW-846 Method 6010A accuracy and precision. PE samples for
SW-846 Method 6010A will be prepared for both extraction methods. SW-846 Methods 3050A and
3052. This will provide an absolute accuracy assessment of both extraction methods.
Because PE samples will be submitted as double blind samples, the corrective actions will not be
initiated by the confirmatory laboratory. When confirmatory laboratory results are received for the
PE samples, PRC will compare the results to the true values and acceptance ranges of each PE
sample. When the SW-846 Method 6010A results fall outside of the acceptance ranees. PRC will
request that the confirmatory laboratory reextract and reanalyze the PE samples. This will be the
only corrective action required.
8.4.7 Duplicate Samples
Two types of duplicate samples will be used during this demonstration to provide an evaluation of
precision: field duplicate samples and laboratory duplicate samples. Field duplicate samples are the
same sample which are collected in the field, but are submitted for analysis in separate sample
containers. Field duplicate samples are used to provide an evaluation for the precision of sample
collection, handling, transportation, as well as laboratory precision. One field duplicate samples will
be submitted with each set of ten samples submitted for analysis. Laboratory duplicate samples are
the duplicate analysis of the same sample. Laboratory duplicate samples are used to provide an
evaluation of laboratory precision. One laboratory duplicate sample will be prepared and analyzed
with each set of 20 samples submitted for analysis.
Field duplicate samples will be used by the FPXRF technologies to assess precision. Precision for
field duplicate samples will be assessed through an RPD calculation of the original sample result
compared to the field duplicate samples result. An additional precision measurement will be
performed for each FPXRF technology through the use of replicate measurements. One replica^
measurement will be performed for each ten samples submitted for analysis. A replicate measurement
will be performed ten times on the same sample, and the mean, standard deviation, and relative
standard deviation will be calculated. The replicate measurements will provide data on instrumental
precision for each FPXRF technology.
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Duplicate samples which will be used by the SW-846 Method 6010A to assess precision include field
and laboratory duplicate samples. Precision for field duplicate samples will be assessed through an
RPD calculation of the original sample result compared to the field duplicate samples result. Field
duplicate samples will be used to measure total precision and will also be used to evaluate the
adequacy of soil sample homogenization. The data generated from the analysis of field duplicate
samples will be used to determine total precision and will be used to generate precision control limits
for total precision.
Two types of laboratory duplicate analyses will be performed by SW-846 Method 6010A: pre- and
post-digestion laboratory duplicate samples. Pre-digestion laboratory duplicate samples are two
samples from the same sample jar that are extracted and analyzed, separately. Post-digestion
laboratory duplicate samples are two analyses performed on the same sample extractant. Both, pre-
and post-digestion laboratory duplicate samples will be evaluated through an RPD calculation.
Control limits for both pre- and post-digestion laboratory duplicate samples will only be enforceable
when both original and laboratory duplicate results are greater than or equal to 5 times the LRLs for
each primary target metal. If matrix interferences make this control limit impractical, PRC may raise
the lower level control limit to 10 times the LRLs. Control limits for RPD of pre-digestion
laboratory duplicate samples are RPD values less than or equal to 20 percent. Control limits for RPD
of post-digestion laboratory duplicate samples are less than or equal to 10 percent. Corrective action
which must be taken when these control limits are not met include: (1) reanalysis of the duplicate
sample, (2) reextraction and reanalysis of the laboratory duplicate sample, and if the reextraction and
reanalysis of the laboratory duplicate produces results which fall within the control limits, then
(3) reextraction and reanalysis of the laboratory duplicate sample and the batch of samples associated
with the laboratory duplicate sample. However, when reextraction and reanalysis of the laboratory
duplicate sample produces results which fall outside of the control limits, the laboratory duplicate
sample and the batch of samples associated with the laboratory duplicate sample will be set aside.
The PRC project manager will then be contacted and advised of the situation. Decisions regarding
corrective action for these samples will be delayed until all samples have undergone initial analysis.
Final decisions on corrective action for these samples will be based on project needs.
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8.5
DATA REDUCTION, VALIDATION, AND REPORTING
To maintain good data quality, specific procedures will be followed during data reduction, validation,
and reporting. These procedures are detailed below. These procedures will be implemented for
FPXRF technology and confirmatory laboratory data.
Data reduction will be performed by the operator performing the analyses. The FPXRF technologies
and the confirmatory laboratory will produce data in field logbooks, hard copy spectrograms and
reports, hard copy spreadsheet reports, and floppy disks or computer cassettes containing both
spectroscopic data and spreadsheet data. This data will be reduced to produce a report detailing the
analytical results. Data reduction will be performed following the formats and requirements of
pertinent SOPs or the laboratory QA plan. This will include qualifying data that failed one or more
of the QC checks and providing definitions for each code used.
The FPXRF technologies will produce results for individual target metals based on internal or
external calibrations. The developers' procedures for calibration will be used during this
demonstration. After calibration, the FPXRF technologies will produce direct readouts of analyte
concentrations. No data conversions are necessary.
SW-846 Method 6010A will provide results for individual target metals. The results will be reported
in units of milligrams per liter as determined from the calibration curve and any dilution factor
employed. A general calculation to convert the solution concentration to the sample concentration for
each target metal is shown below.
8.5.1
Data Reduction
C x V
Concentration (as received) (mg/kg) =
(8-1)
W
where
C = concentration from regression equation based on initial calibration (mg/L)
V = final volume after sample preparation (L)
W = weight of sample as received (Kg)
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This equation allows the t'inal data to be reported in units of rag/kg (as received).
g,5.2 Data Validation
The operator will verify the completion of the appropriate data forms and the completeness and
correctness of data acquisition and reduction. The confirmatory laboratory or field team leader will
review calculations and inspect laboratory logbooks and data sheets to verify accuracy, completeness,
and adherence to the specific analytical method protocols. Calibration and QC data will be examined
by the technology operators and the confirmatory laboratory supervisor. Laboratory project managers
and QA managers will verify that all instrument systems are in control and that QA objectives for
accuracy, precision, completeness, and method detection limits on LRLs have been met.
Analytical outlier data are defined as those QC data lying outside a specific QC objective window for
precision and accuracy for a given analytical method. Should QC data be outside of control limits,
the confirmatory laboratory or field team leader will investigate the cause of the problem. If the
problem involves an analytical problem, the sample will be reanalyzed. If the problem can be
attributed to the sample matrix, the result will be flagged with a data qualifier. This data qualifier
will be included and explained in the final analytical report submitted by the confirmatory laboratory.
8.5.3 Data Reporting
SW-846 Method 6010A analytical data will be reported using the confirmatory laboratory's standard
report forms. At a minimum, the forms will list the results for each sample and include
detection limits, reporting units, sample numbers, results, and data qualifiers.
PRC also will request that all QC forms and raw analytical data be included in the final analytical
report submitted by the confirmatory laboratory. This data will enable PRC to evaluate and
determine the margin of error associated with SW-846 Method 6010A analytical data to obtain a fair
comparison to the data produced by each FPXRF technology. The FPXRF technology data will be
recorded on the appropriate forms shown on Figures 8-1 to 8-4. The preparation and packaging of
samples will be logged on the forms shown on Figures 8-5 and 8-6.
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8.6
CALCULATION OF DATA QUALITY INDICATORS
The following calculation will be used by all methods for determining precision for the confirmatory
laboratory. This calculation is used to determine the precision between sample results and duplicate
sample results.
RPD = [(A - B) / {(A + B)/2}] x 100 _
V.o-2
where
RPD = absolute relative percent difference
A = sample result
B = duplicate sample result
In the case of the FPXRF technologies, an RSD will be calculated to assess precision. The following
equation is used to calculate an RSD.
RSD = (SD / mean concentration) x 100 ^ ^
where
RSD = relative standard deviation
SD = standard deviation
Mean concentration = average concentration of analyte in replicate sample measurements
Standard deviation is determined through the following calculation.
SD = [{E (x5 - avg x)2} / (n-1)]*
where
SD = standard deviation
£ = sum of
Xj = concentration of analyte in specific replicate sample
avg x = average concentration of analyte in all replicate samples
n = total number of replicate sample measurements
8-18
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The following calculation is used to determine percent recovery which can be used to assess the
accuracy of the analytical method. This calculation can be used to calculate post digestion spike
recovery.
% Rec = [(amt. tound in Sp - amt. found in sample) / amt. spiked] x 100 (8-5
where
% Rec = percent recovery
amt. found in Sp = amount of analyte found in the spiked sample
amt. found in sample = amount of analyte found in the original sample
amt. spiked = amount of analyte added to the spiked sample
The following calculation is used to determine the LCS and PE recovery, which can be used to assess
the accuracy of the analytical method.
% Rec = (conc. found / true value) x 100 (8_6
where
% Rec = percent recovery
conc. found = concentration found in sample
true value = the true certified value as provided in the LCS documentation
8.7 PERFORMANCE AND SYSTEM AUDITS
The following audits will be performed during this demonstration. These audits will determine if this
demonstration plan is being implemented as intended.
8.7.1 Performance Audit
A performance audit will be performed during this demonstration. PE samples will be ordered from
a QC sample supplier and will be submitted to the confirmatory laboratory and to the FPXRF
technologies for analysis. The control limits for the PE samples will be used to evaluate the FPXRF
technology and confirmatory laboratory's method performance.
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PE samples come with statistics about each sample, which have been derived from the analysis of the
sample by a number of laboratories using EPA-approved methods. These statistics include a true
value of the PE sample, a mean of the laboratory results obtained from the analysis of the PE sample
and an acceptance range for sample values. The confirmatory laboratory is expected to provide
results from the analysis of the PE sample that fall within the QC sample supplier-generated
acceptance limits. However, if the PE sample does not have acceptance ranges, then the acceptance
ranges will be 80 to 120 percent of the true value concentration for each target analyte.
The FPXRF technologies will analyze the PE samples periodically during the demonstration. These
samples will act as technology accuracy check samples. If the replicate measures on the check
samples vary by more than recommended by the developer, the technologies will be recalibrated and
the samples analyzed between the recaiibrations will be reanalyzed.
8.7.2 On-Site System Audits
On-site system audits for sampling activities, field operations, and laboratories will be conducted as
requested by the EPA TPM. These audits will be scheduled through the EPA TPM and separate
audit reports will be completed by PRC after the audits.
8.7.3 Secondary QC Laboratory
This demonstration may use a secondary laboratory to check confirmatory laboratory results, only for
SW-846 Methods 3050A and 6010A analyses that deviate significantly from results obtained with the
FPXRF technologies. The secondary QC laboratory will analyze samples from the demonstration
when all of the FPXRF technologies' results vary from the confirmatory laboratory's results by more
than a factor of 10.
The secondary QC laboratory will use SW-846 Methods 3050A and 6010A for sample analysis. The
samples sent to the secondary QC laboratory will be split samples collected concurrently with the
initial confirmatory sample, and archived by PRC. The analytical result obtained from the secondary
QC laboratory will be compared to the confirmatory laboratory result through an RPD calculation. It
is expected that the confirmatory laboratory and the secondary QC laboratory results will not vary by
8-20
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more than a factor of 2. or an RPD value of 67 percent. When this occurs, the confirmatory
laboratory result will be used for comparison to the FPXRF technology. When the confirmatory
laboratory and the secondary QC laboratory resuits vary by more than 67 percent RPD, the secondary
QC laboratory results will be used for comparison to the FPXRF technologies.
The secondary QC laboratory also will be required to analyze PE samples to establish its accuracy
and will analyze field and laboratory duplicate samples to establish its precision. The secondary
laboratory is required to comply with all QC parameters listed in Section 8.4.
8.8 QUALITY ASSURANCE REPORTS TO MANAGEMENT
QA reports provide management with the necessary information to monitor data quality effectively. It
is anticipated that the following types of QA reports will be prepared as part of this demonstration
project.
8.8.1 Monthly Reports
The PRC project manager will prepare monthly reports for the EPA TPM. These reports will discuss
project progress, problems and associated corrective actions, and future scheduled activities associated
with the demonstration. When problems occur, the PRC project manager will discuss them with the
EPA TPM, estimate the type and degree of impact, and describe the corrective actions taken to
mitigate the impact and to prevent a recurrence of the problems.
8.8.2 Audit Reports
Any QA audits or inspections that take place in the field or at the confirmatory laboratory while the
demonstration is being conducted will be formally reported by the auditors to the PRC analytical QC
manager and the PRC project manager who will forward them to the EPA TPM.
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FIGURE 8-1
SAMPLE ANALYSIS RECORDING FORM FOR
FPXRF IN SITU TECHNOLOGIES
Technology Name:
Circle One: Unprepared or Prepared
Q Sample No.
Analyte Concentration (mg/kg)
Antimony
Arsenic
Barium
Cadmium
Chromium
Copper
Iron
Lead
Nickel
Zinc
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FIGURE 8-2
SAMPLE ANALYSIS RECORDING FORM FOR PRECISION
FPXRF IN SITU TECHNOLOGIES
Technology Name: , Sample Number:
Circle One: Unprepared or Prepared
Analyte Concentration (mg/kg)
Antimony
Arsenic
Barium
Cadmium
Chromium
Copper
Iron
Lead
Nickel
Zinc
Reading 1
Reading 2
Reading 3
Reading 4
Reading 5
Reading 6
Reading 7
Reading 8
Reading 9
Reading 10
Mean
Standard
Deviation
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FIGURE 8-3
SAMPLE ANALYSIS RECORDING FORM FOR
FPXRF INTRUSIVE TECHNOLOGIES
Technology Name:
Circle One: Unprepared or Prepared
Sample
Number
Analyte Concentration (mg/kg)
Antimony
Arsenic
Barium
Cadmium
Chromium
Copper
Iron
Lead
Nickel
Zinc
-------
FIGURE 8-4
SAMPLE ANALYSIS RECORDING FORM FOR PRECISION
FPXRF INTRUSIVE TECHNOLOGIES
Technology Name: Sample No.:
Circle One: Unprepared or Prepared
Analyte Concentration (mg/kg)
Antimony
Arsenic
Barium
Cadmium
Chromium
Copper
Iron
Lead
Nickel
Zinc
Reading 1
Reading 2
Reading 3
Reading 4
Reading 5
Reading 6
Reading 7
Reading 8
Reading 9
Reading 10
Mean
Standard
1 Deviation
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FIGURE 8-5
SAMPLE PREPARATION TRACKING FORM
Sample
No.
Grid
Sample
Homog.
all
Samples
Field
Duplicate
20%
In Situ
Analysis (or
all Samples
Intrusive
Analysis for
all Samples
Package 20
grams of all
Samples for C.L.
Del. Water
Content for
all Samples
Microwatt
10% of
Samples
Convection
Oven Drying
of all Samples
Del. Wafer
Content for
all Samples
Grind and
Sieve all
Samples
Notes:
Homog Homogenized
C.L. Confirmatory Utboratoiy
Dct Determination
-------
FIGURE 8-6
CONFIRMATORY LABORATORY SAMPLE PACKAGING TRACKING FORM
Sample
Number
Date Packaged
10% of the
Homogenized
Sample9
All of the
Prepared
Sample
Field Duplicate
Sample1*
10% of the
Microwave
Dried
30% Labeled for
Both SW-846
Methods 3050A and
3052
Other Samples
(i.e., PE Samples)
Notes:
These 10 percent must be from the same original sample.
These samples must be collected at the rate of 1:10 and they must be evenly divided among soil texture and concentration ranges.
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TABLE 8-1
SW-846 METHOD 6010A
SOIL SAMPLE DETECTION LIMITS
Primary and Secondary
Target Metals
Lower Reporting Limita
(mg/kg)
Antimony
6.4
Arsenic*
10.6
Barium*
5.0
Cadmium
0.80
Chromium*
2.0
Copper*
1.2
Iron
600
Lead*
8.4
Nickel
3.0
Zinc*
2.0
Notes:
a Lower reporting limit for extraction Methods 3050A and 3052 are expected to be similar.
* Primary target metal
8-28
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TABLE 8-2
SW-846 METHOD 6010A
CALIBRATION PROCEDURES,
METHOD-SPECIFIC QC REQUIREMENTS, AND CORRECTIVE ACTION
QC Parameter
Frequency
Control Limits
Corrective Action
Initial Calibration
Verification (ICV)
Standard
With each initial
calibration
±10 percent
of expected value
1. Reanalyze initial calibration
2. Reprepare ICV standards
3. Reprepare initial calibration standards
Continuing Calibration
Standard (CCS)
After analysis of every
10 samples and at the
end of analytical run
± 10 percent
of expected value
1. Reanalyze CCS
2. Reanalyze initial calibration standards
3. Reprepare initial calibration standards
Calibration Blank
With each continuing
calibration, after
analysis of every 10
samples, and at the
end of analytical run
No target analytes
above method detection
limit
1. Reanalyze calibration blank
2. Reanalyze calibration standards
3. Reprepare initial calibration standards and
calibration blank
Interference Check Standards
(ICS)
With every initial
calibration and after
analysis of 20 samples
80 percent recovery
, 1. Reanalyze ICS
2. Reanalyze initial calibration and ICS
3. Evaluate instrument for possible problems
High Level Calibration
Check Standard
With every initial
calibration
± 5 percent
expected value
1. Reanalyze high level standard
2. Reanalyze initial calibration
3. Follow technology developers
recommendations for correction
Method Blanks
With each batch of
samples of a similar
matrix
No target analytes
above method detection
limit
1. Reanalyze method blank
2. Reprepare method blank
3. Reprepare all associated samples
Laboratory Control Samples
(LCS)
With each batch of
samples of a similar
matrix
80 to 120 percent
recovery4
1. Reanalyze LCS
2. Reprepare LCS and all associated samples
3. Perform new initial calibration
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TABLE 8-2 (Continued)
SW-846 METHOD 6010A
CALIBRATION PROCEDURES,
METHOD-SPECIFIC QC REQUIREMENTS, AND CORRECTIVE ACTION
QC Parameter
Frequency
Control Limits
Corrective Action
Pre-Digestion Matrix Spike
Samples
With each batch of
samples of a similar
matrix
80 to 120 percent
recovery3
1. Reanalyze pre-digestion matrix spike sample
2. Reprepare pre-digestion matrix spike sample
3. Reprepare all associated samples
Post-Digestion Matrix Spike
Samples
With each batch of
samples of a similar
matrix
80 to 120 percent
recovery3
1. Reanalyze post-digestion matrix spike sample
2. Reprepare post-digestion matrix spike sample
3. Reprepare all associated samples
Performance Evaluation (PE)
Samples
As submitted during
demonstration
80 to 120 percent
recovery*
1. Reprepare and reanalyze PE sample
Pre-Digestion Laboratory
Duplicate Samples
With each batch of
samples of a similar
matrix
20 percent
relative percent
difference (RPD)b
1. Reanalyze sample and duplicate
2. Reprepare sample and duplicate
3. Reprepare all associated samples
Post-Digestion Laboratory
Duplicate Samples
With each batch of
samples of a similar
matrix
10 percent
relative percent
difference (RPD)b
1. Reanalyze sample and duplicate
2. Reprepare sample and duplicate
3. Reprepare all associated samples
Notes:
Stated control limits pertain only to primary target metals. Control limits for secondary target metals identified and quantified in
SW-846 Method 6010A should fall within published control limits listed in SW-846 Method 6010A. If these control limits are not
met, qualification of the data for these analytes may be performed.
RPD control limits only pertain to original and laboratory duplicate sample results which are greater than or equal to 5 times the
LRL.
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CHAPTER 9
DATA MANAGEMENT AND ANALYSIS
As part of this demonstration, PRC will establish a data management system that will include
computerized data files and hard copy documentation, such as field and laboratory sheets and
hardbound logbooks. This data management system will be used to store analytical data obtained
from each technology and the confirmatory laboratory. This data management system will be used to
conduct statistical analyses of the data as described in Chapter 7 and to verify that the data meets the
data quality parameters established in Chapter 8.
This chapter describes the procedures that will be used for obtaining and entering data into this
system and for analyzing the data after it has been entered.
9.1 LABORATORY DATA MANAGEMENT ACTIVITIES
All soil samples will be collected and documented as described in Chapter 6. Each sample will be
labeled with a unique sample number assigned in the field. The sample number will include a
three-digit, alpha-numeric code that will identify the sample number, as well as the site from which it
was collected. Each sample will be submitted for analysis accompanied by a field sheet containing
additional information about the sample. Once a sample has been submitted for analysis, data
associated with the sample will be managed as described below.
9.1.1 Moisture Content Data Management
Samples collected for soil moisture analysis will be analyzed on site. A project-specific logbook will
be used to document sample receipt for each sample submitted for analysis. Laboratory tracking will
be performed by the operator responsible for sample analysis. Samples will be analyzed and the data
obtained will be reduced, validated, and reported as described in Chapter 8. Sample result tables will
then be transferred from the report forms generated by the operators to the computerized data
management system by computer file transfer or by data entry transcription. In either case, all data
transferred to the data management system will be checked for transcription errors before the actual
statistical evaluation is performed.
9-1
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9.1.2
Qualitative and Quantitative Analyses and Evaluations
Samples subdued for chemical analysis will be analyzed by a confirmatory laboratory. Each
shipment of samples sen, to the laboratory will be accompanted by a chain-of-custody form, which
will be completed by the laboratory's sample custodian and returned to the PRC project manager.
Samples will be entered into the laboratory's Laboratory .nformattott Managemer System. This
system tracks the progress of sample analysis within the laboratory and provides a reporting form*
tor sample results. After samples are analyzed, the data will be reduced, val,dated, and repotted as
described in Chapter 8.
Validated sample results will be sent to PRC for entry into its data management system. In addition
,o sample results, PRC will request QA/QC summary forms for the confirmatory analysis. These
forms wtll enable PRC to verify the quality of data genera,ed by these methods. PRC w„l then
transfer this data into its data management system. AH data transcribed will be double-chKked for
accuracy in PRC's data management system.
9 13 Technology Data Management
The sample analysis methods for each technology differ from those used by the contamory
laboratory.
. . tn each technology will record the technology sample number and
The PRC operator assigned to eacn tecnn
corresponding confirmatory sample numbers. The PRC operators w,ll he response for obtatntng.
reducing, interpreting, va.ida.ing, and reponing data associated with their technology s perforn^e.
.... rMiuired to provide the PRC field team supervisor wtth copies of the results
Fach operator will be requirea to pruviu-
obtain* from each sampling point, as wel, as any g^ca. data used for fe d*-*, of sue
contamination. PRC wHl compare this da* to the data generated by the conftrmatory analyst,
The PRC operator, also will be responsible for obuintag inform***. about the assigned technology.
This information will include a general description of the technology and how tt ts used tn the
Ea h PRC observe, will take notes on specif, aspects of the technology Tb«e noteswtlibe as*
nt checHist created for each technology before the demonstration aatvtttes beg,, The cheats,
-------
will provide information that will be used in the TER and ITER. In general, the checklists will
contain the following items:
• Description of equipment used
• Logistical considerations including size and weight of technologies, power
requirements, and other accessories needed, but not provided by the developer
• Historical uses and applications of the technology
• Estimated cost of the equipment or the cost of using the equipment
• Number of people required to operate equipment
• Qualifications of technology operator
• Training required for technology operator
• Description of data each technology can produce and a description of the operational
mode required for producing this data
• Analytes which the technology can detect
• Approximate detection levels of each analyte
• Initial calibration criteria
• Calibration check criteria
• Corrective action used for unacceptable calibrations
• Specific QC procedures followed
• QC samples used
• Corrective action for QC samples
• Description of the number of samples that can be analyzed in one work day
• Description of the amount of time required for data interpretation
• Description of the reports and graphics that each technology will produce
• Specific problems or breakdowns occurring during the demonstration
• Matrix interferences found during the demonstration
9-3
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The PRC operators will be responsible for reading the approved demonstration plan, as well as any
other information submitted to PRC by the developers. A copy of the completed checklists will be
included in the TER. Notes taken by each PRC operator will be documented in a hardbound logbook
and will be used as a reference when preparing the TER and ITER.
9-4
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CHAPTER 10
HEALTH AND SAFETY PLAN
This chapter describes specific health and safety procedures PRC will use during the field work to be
performed at the demonstration sites. The demonstration sites include the RV Hopkins site and the
Asarco site.
The purpose of the HASP is to define the requirements and designate the protocols to be followed
during the field work specified under Occupational Health and Safety Administration (OSHA) 29
CFR 1910.120(b) Final Rule. All PRC personnel, subcontractors, and visitors on site must be
informed of site emergency response procedures and any potential fire, explosion, health, or safety
hazards related to demonstration activities. A copy of the HASP will be provided to all PRC
personnel, subcontractors, and site visitors who may be exposed to dangerous conditions during the
demonstration.
This HASP must be reviewed and approved by the PRC health and safety director (HSD), the PRC
project manager, and the EPA TPM. A HASP compliance agreement form must be signed by all
field personnel before they enter site. Any revisions to this plan must be approved by the EPA TPM
and the PRC HSD.
10.1 HEALTH AND SAFETY PLAN ENFORCEMENT
The PRC project manager, field site supervisor, HSD, and site health and safety officer (SHSO) will
be responsible for implementing and enforcing the health and safety provisions of this HASP. Their
duties are described in the following subsections.
10.1.1 Project Manager and Field Site Supervisor
The PRC project manager will ultimately be responsible for ensuring that all demonstration
participants abide by the requirements of this HASP. The PRC field site supervisor will oversee and
direct field activities, including subcontractor activities, and also is responsible for ensuring
compliance with this HASP.
10-1
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10.1.2 Health and Safety Director
The PRC HSD will be responsible for coordinating the technical aspects of the health and safety
program. The HSD will act in an advisory capacity to the PRC SHSO and will report to the PRC
project manager. Liaison with EPA representatives on matters relating to health and safety will be
handled by the HSD or SHSO. The HSD will be responsible for maintaining up-to-date records of
HASP-related documentation and HASP participants. HASP-related documentation will be maintained
at PRC's Chicago office. This documentation will include the following:
• Documentation of the physician's examination of each employee (Section 10.10,
Medical Surveillance)
• The training record for each employee who has completed the training necessary to
perform his or her job
• Documentation of a fit test for each employee required to wear respiratory protection
equipment meeting the requirements of OSHA 29 CFR 1910.134 and American
National Standards Institute Z88.2-1980
• Task-specific air monitoring information (regarding drilling, drumming of waste, and
other activities)
Any employee who does not meet HASP requirements will not be allowed to conduct field work.
10.1.3 Site Health and Safety Officer
The PRC SHSO will be responsible for implementing and enforcing the requirements of this HASP in
the field. The SHSO will have advanced field work experience and will be familiar with health and
safety requirements specific to the demonstration. The SHSO will ensure that a Safety Meeting
Sign-off Sheet is signed by all employees who are to perform field work, and that each employee
complete a Daily Site Log before leaving the site.
10.2 VISITORS
All visitors to PRC operations at the site will be required to read the HASP and sign a compliant
agreement form. Visitors will be expected to comply with relevant OSHA requirements. Visitors
10-2
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will also be expected to provide their own personal protection equipment (PPE) as required by the
HASP.
Any visitors who do not adhere to the provisions of the HASP will be ordered to leave the work area.
Visitors who have not met OSHA training and medical surveillance requirements will not be permitted
to enter areas where exposure to hazardous materials is possible. Exceptions will be strongly
discouraged, but they can be made on a case-by-case basis under the following conditions:
(1) respirators are not required, (2) visitors' time on site is limited, (3) visitors are given a pre-entry
briefing, (4) visitors are accompanied by trained personnel at all times, and (5) PRC SHSO approval
is obtained.
10.3 DEMONSTRATION-SPECIFIC HAZARD EVALUATION
The hazards associated with this demonstration include worker exposure to heavy metals, exposure to
weather extremes, physical hazards associated with work on active or abandoned industrial facilities,
and exposure to x-rays associated with the FPXRF in situ technologies.
The hazardous materials expected to be present at the sites and a work task hazard analysis are
provided in Tables 10-1 and 10-2. These elements are heavy metal contaminants in the surface soils.
Therefore, the primary exposure pathway will be inhalation of contaminated dusts.
This demonstration will occur in early spring; therefore, the possibility for cold weather exists,
particularly at the RV Hopkins site. In addition to cold exposure, it is possible that the demonstration
tf?m will be working during precipitation events. This coupled with the cold temperatures of the
season present the possibility of workers experiencing hypothermia.
general hazards associated with active or abandoned industrial facilities include trip and fall hazards,
surficial debris, unmaintained structures, and manufacturing processes themselves.
The primary hazard associated with the use of FPXRF technologies involves exposure to ionizing
radiation. The FPXRF intrusive technologies have shielded radioactive sources; those sources remain
shielded during sample analysis. This virtually eliminates the potential for operator exposure to
10-3
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ionizing radiation. The FPXRF in situ technologies have sources that are shielded until measurements
are taken. During the measurement process, ionizing radiation is directed through the probe and into
the matrix being analyzed. If an operator's body comes between the detector and the sample matrix
during measurement, the operator will be exposed to ionizing radiation. This also will occur if the
sample matrix is too thin to absorb all the ionizing radiation, and a portion of the radiation passes
through the opposite side of a sample matrix. This is most likely to occur if the technologies are used
on vertical surfaces, such as walls. In this case, an operator on the other side of the sample matrix
has the potential for exposure to ionizing radiation. To eliminate this exposure potential, all
measurements will be on horizontal surfaces. If the horizontal surface is above the ground surface
physical barriers will put in place to prevent operator contact with any ionizing radiation passing
through the sample matrix.
10.4 EXPOSURE PATHWAYS
Exposure to heavy metal contaminants during field activities may occur through inhalation or
ingestion of airborne contaminated dust, or dermal contact. Descriptions of these exposure pathways
are provided below.
10.4.1 Inhalation
One possible exposure pathway for heavy metals contaminants during this demonstration will be
through inhalation of airborne dust.
PRC personnel will monitor the concentrations of airborne dust in real-time with a dust monitoring
instrument, such as a Miniram Model PDM-3.
Level D personal protection will generally be used, but when the monitoring instruments indirar*
potential problems, personal protection will be upgraded to Level C.
10-4
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10.4.2 Dermal Contact
Dermal contact with contaminated soil may occur at both sites during demonstration activities.
Dermal contact will be prevented with the use of PPE, such as inner and outer gloves. Safe personal
protection procedures are described in Section 10.9.
10.4.3 Ingestion
Ingestion of heavy metals, although unlikely, may occur if personnel demonstrate a lack of proper
hygiene or decontamination. Section 10.14.2 discusses safe work practices that may prevent ingestion
of contaminated material.
10.5 HEALTH EFFECTS
This section describes the possible health effects of exposure to heavy metals. Health effect
information has been determined by the National Institute for Occupational Safety and Health
(NIOSH). Low, medium, or high levels of heavy metals may be encountered during sampling
activities at the demonstration sites.
Acute symptoms of exposure to the heavy metals detected at the demonstration sites are listed in
Table 10-1. Chronic symptoms of exposure to heavy metals such as lead, chromium, and cadmium
include: histologic fibrosis of lungs, pulmonary edema, diarrhea, emphysema, anemia, and cancer.
Exposure to heavy metals in soil will be controlled through proper use of PPE and real-time air
monitoring for airborne particles. The need for respiratory protection (air purifying respirators) will
be based on real-time air monitoring results. If the concentration of airborne particles exceeds
0.3 milligrams per cubic meter (mg/m3) as measured with a dust-monitoring instrument, the level of
protection will be upgraded from Level D to Level C.
The OSHA permissible exposure limit for lead, the most toxic of the heavy metal constituents
potentially present, is 0.03 mg/m3. Given a worst-case scenario of 3 percent (30,000 mg/kg) lead in
10-5
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soil, the permissible exposure limit could be increased to 1 mg/m3. Adding a safety factor of 2
PRC's action level for upgrading to Level C personal protection is 0.5 mg/m3 total dust.
10.6 PHYSICAL HAZARDS
Physical hazards associated with sampling and other field activities present a potential threat to on-site
personnel. Dangers are posed by utility and power lines, unseen obstacles, noise, cold, and poor
illumination.
Injuries may result from the following:
• Accidents due to slipping, tripping, or falling
• Improper lifting techniques
• Moving or rotating equipment
• Equipment mobilization and operation (for example, electrocution from contact with
overhead or underground power lines)
• Improperly maintained equipment
Injuries resulting from physical hazards can be avoided by adopting safe work practices and by using
caution when working with machinery. Safe work practices to be used during all field activities are
described in Section 10.14.2. To ensure a safe work place, the PRC SHSO will conduct and
document regular safety meetings to make sure that all personnel are informed of any potential
physical hazards related to the site.
10.7 TRAINING REQUIREMENTS
All PRC personnel, subcontractors, and site visitors who may be exposed to hazardous on-site
conditions at the demonstration sites will be required to meet the training requirements outlined in
OSHA 29 CFR 1910.120, which covers hazardous waste operations and emergency response. All
PRC personnel, subcontractors, and visitors entering the site will be required to read this HASP and
sign the compliance agreement form. All site workers will be required to sign a Safety Meeting
Sign-off Sheet as well.
10-6
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Before field activities begin, a briefing will be presented by the SHSO for all personnel who will
participate in field activities. The following topics will be addressed during the briefing:
• Names of the PRC SHSO and the designated alternate
• Site history
• Hazardous chemicals that may be encountered during on-site activities
• Physical hazards that may be encountered on site
• Training requirements
• Levels of protection to be used for specific work tasks
• Work tasks
• Environmental surveillance equipment use and maintenance
• Action levels (Section 10.11.3, Monitoring Parameters) and identification of situations
requiring an upgrade or downgrade in levels of protection
• Site control measures, including site control zones, communications, and safe work
practices (Section 10.14)
• Emergency communication signals and codes
• Decontamination procedures
• Environmental accident emergency procedures (in case contamination spreads outside
the exclusion zone)
• Personnel exposure and accident emergency procedures (in case of exposure to
hazardous substances, falls, and other hazardous situations)
• Fire and explosion emergency procedures
• Emergency telephone numbers
• Emergency routes
Any other health- and safety-related topics that may arise before field activities begin also will be
discussed at the briefing.
Issues that arise during implementation of field activities will be addressed during "tailgate" safety
meetings to be held daily before the shift begins. Any changes in procedures or site-specific health-
and safety-related matters will be addressed during these meetings.
10-7
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10.8 PERSONAL PROTECTION REQUIREMENTS
PPE wil] be worn to protect personnel from known or suspected physical hazards, and air and soil
contamination. The levels of personal protection to be used for work tasks have been selected based
on known or anticipated physical hazards and concentrations of contaminants that may be encountered
on site, and their chemical properties, toxicity, exposure routes, and contaminant matrices. The
following sections describe levels of protection, protective equipment and clothing, limitations of
protective clothing, duration of work tasks, and respirator selection, use, and maintenance.
10.8.1 Levels of Protection
Personnel will wear protective equipment when field activities involve known or suspected
atmospheric contamination, when dust particles may be generated by field activities, or when direct
contact with skin-affecting substances may occur. Full-face respirators will protect lungs, the
gastrointestinal tract, and eyes against airborne contaminants. Chemical-resistant clothing will protect
the skin from contact with skin-destructive and absorbable chemicals.
For this demonstration, the levels of protection and necessary components for each are classified
under two categories according to the degrees of protection afforded:
Level D: This level provides minimal protection against chemical hazards. Worn only
as a work uniform; not to be worn in areas posing respiratory or skin hazards
Level C: Worn when the criteria described for Level C protection in Section 10.11.3
for using air-purifying respirators are met, and a lesser level of skin protection
is needed.
Field activities for this demonstration will be conducted in Level D. The demonstration team will
monitor the ambient air for airborne particles. If the concentration of airborne particles exceeds
0.3 mg/m3, personnel will upgrade their level of protection to Level C.
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10.8.2 Protective Equipment and Clothing
The following general levels of protection and the associated PPE ensembles have been selected for
use by personnel during sampling and field screening activities (see Table 10-2, Work Task Hazard
Analysis). Because the anticipated hazard level is low, field work will be performed using Level D
protection. If site conditions or the results of air monitoring performed during field activities warrant
Level C protection, all personnel will upgrade to Level C protection. Descriptions of equipment and
clothing required for Levels D and C protection are provided below.
• Level D
Coveralls or work clothes, if applicable
Steel-toed boots with shanks
Hard hat (face shield optional)
Disposable outer gloves (polyvinyl chloride or nitrile), if applicable
Safety glasses or goggles
Chemical-resistant clothing (Tyvek® or Saranex®), if applicable
Disposable boot covers (when entering wet or muddy areas with known
elevated contamination levels, such as previously excavated waste areas)
Hearing protection (for areas with a noise level exceeding 85 decibels on the
A-weighted scale)
• Level C
Coveralls or work clothes, if applicable
Chemical-resistant clothing (Tyvek® or Saranex®)
- Outer gloves (neoprene or nitrile)
Inner gloves (nitrile or polyvinyl chloride)
Steel-toed boots with shanks
Disposable boot covers or chemical-resistant outer boots
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Full- or half-face, air-purifying respirator with NIOSH- or OSHA-approved
cartridges to protect against organic vapors, dust, fumes, and mists (cartridges
will be changed at the end of each shift or at breakthrough, whichever occurs
first)
Safety glasses or goggles (with half-face respirator only)
Hard hat (face shield optional)
Hearing protection (for areas with a noise level exceeding 85 decibels on the
A-weighted scale)
10.8.3 Limitations of Protective Clothing
PPE clothing ensembles designated for use during field activities have been selected to provide
protection against contaminants at known or anticipated concentrations in soil. However, no
protective garment, glove, or boot is entirely chemical-resistant, nor does any protective clothing
provide protection against all types of chemicals. Permeation of a given chemical through PPE
depends on contaminant concentrations, environmental conditions, the physical condition of the
protective garment, and the resistance of the garment to the specific contaminant. Chemical
permeation may continue even after the source of contamination has been removed from the garment.
To obtain optimum use from PPE, the following procedures will be followed by all personnel:
• When using Tyvek® or Saranex® coveralls, 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-
Imperfect seams
Nonuniform coatings
Tears
Poorly functioning closures
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• Inspect reusable garments, boots, and gloves both before and during use for visible
signs of chemical permeation such as the following:
Swelling
Discoloration
Stiffness
Brittleness
Cracks
Any sign of puncture
Any sign of abrasion
Reusable gloves, boots, or coveralls exhibiting any of the characteristics listed above must be
discarded. PPE clothing used in areas with known or suspected elevated concentrations of
contaminants should not be reused. Reusable PPE will be decontaminated according to the
procedures described in Section 10.15 and will be neatly stored in the support zone away from work
zones.
10.8.4 Duration of Work Tasks
The duration of field activities involving use of PPE will be established by the PRC SHSO or a
designee and will be based on ambient temperature and weather conditions, the capacity of personnel
to work in the designated level of PPE (taking into account such conditions as hypothermia), and the
limitations of the PPE. All rest breaks will be taken in the support zone after decontamination and
removal of PPE.
10.8.5 Respirator Selection, Use, and Maintenance
All PRC personnel and subcontractors taking part in field activities must fulfill worker provisions
outlined in OSHA 29 CFR 1910.120. PRC and subcontractor personnel will be informed of the
proper use, maintenance, and limitations of air-purifying respirators during the daily safety briefing,
if applicable. All personnel must complete a qualitative fit test for the respirator to be used on site.
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Respirator use is not anticipated at the demonstration sites. However, if respirator use becomes
necessary, a full-face air-purifying respirator equipped with NIOSH- or OSHA-approved cartridges
will be selected for use to protect against dust. Respirators will be selected by the PRC SHSO based
on knowledge of the substances that may be present at the sites and the concentrations of compounds
previously encountered at the sites. Air-purifying respirators will be used only when they can provide
protection against the substances encountered at the sites.
Respirators will be inspected daily and any necessary repairs will be made during the time of
inspection. Damaged respirators will be properly disposed of. Respirators issued to personnel will
be cleaned and disinfected in the support zone at least weekly. When a respirator is used by more
than one person, the respirator will be cleaned and disinfected after each use. After being cleaned,
respirators will be placed in clean plastic bags and stored in the support zone. The following
respirator inspection and cleaning procedures will be followed whenever respirator protection is used:
• Daily inspection and checkout procedures:
Visually inspect the entire unit for obvious damage and deteriorated rubber.
Inspect the face-piece harness for damage.
Inspect the lens for damage and make sure the face piece has the proper seal.
Pull the plastic cover off the exhalation valve and check the valve for debris
and tears in the neoprene that could cause leakage.
Unscrew the cartridges of both inhalation valves and visually inspect the
neoprene valves for tears. Make sure the inhalation valves and cartridge
receptacle gaskets are in place.
Make sure a protective cover is attached to the lens.
Make sure the speaking diaphragm retainer ring is hand-tight.
Don the respirator, and perform a negative pressure test.
• Weekly cleaning procedures:
Disassemble the respirator in the support zone by removing the cartridges,
damaging them to prevent accidental reuse, and discarding them. To clean th<
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respirator thoroughly, remove the inhalation and exhalation valves, speaking
diaphragm, and any hoses.
To clean the respirator, dissolve cleaning and disinfecting solution (usually
provided by the manufacturer) in warm water in an appropriate tub. With
gloved hands, swirl the respirator in the tub for at least 1 minute. A soft
brush may be used to facilitate cleaning.
Rinse the cleaned and disinfected respirator thoroughly with potable water to
remove all traces of detergent and disinfectant. This step is very important in
preventing dermatitis.
Air dry the respirator on a clean surface. The respirator may also be hung
upside down, but care must be taken not to damage or distort the face piece.
Reassemble the clean, dry, respirator and inspect it in an area separate from
the disassembly area to avoid contamination. Inspect the respirator carefully
for detergent or soap residue left by inadequate rinsing. Residue appears most
often under the seat of the exhalation valve and can cause valve leakage or
sticking.
• Procedures to follow after routine use in the exclusion zone:
Wash and rinse the respirator in the support zone with soap and warm water.
At a minimum, wipe the respirator with disinfectant wipes that have been
soaked in benzoalkaloid or isopropyl alcohol. Allow the respirator to air dry
in the support zone.
The effectiveness of the respiratory protection program will be continuously monitored by the PRC
SHSO or designee. Monitoring of worker stress levels during activities that require respiratory
protection will also be performed by the SHSO or designee.
10.9 MEDICAL SURVEILLANCE
The following sections describe PRC's medical surveillance program, including health monitoring,
documentation and recordkeeping, and medical support and follow-up requirements. This program
will be followed for all field activities during this demonstration.
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10.9.1
Health Monitoring Requirements
All PRC and subcontractor personnel involved in field activities at the demonstration sites must
participate in a health monitoring program, as required by OSHA 29 CFR 1910.120(f). PRC has
established a health monitoring program with Environmental Medicine Resources, Inc., of Atlanta,
Georgia. Under this program, PRC personnel receive annual or biennial physical examinations
consisting of the following:
• A baseline medical examination that includes the following:
Completion of a personal, family, and environmental history questionnaire
Physical examination
Vision screening
Laboratory tests
Audiometric screening
Pulmonary function test
Resting electrocardiogram
Chest x-ray (required once every 3 years)
• A complete blood count that includes the following:
White blood count
Red blood count
Hemoglobin test
Hematocrit test
Liver function test
Kidney function test
Lipid metabolism test
Carbohydrate metabolism test
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• A urinalysis that includes the following:
Sugar content test
Albumin content test
Specific gravity test
• Laboratory chemistries for the following:
Cholinesterase
Coproporphyrin and uroporphyrin
Arsenic
Cadmium
Iron
PRC receives a copy of the examining physician's written opinion after post-examination laboratory
tests have been completed. PRC employees also receive a copy of the written opinion. This written
opinion includes the following information (according to 29 CFR 1910.120(f)(7)):
• The results of the medical examination and tests.
• The physician's opinion on whether or not the employee has any medical conditions
that might place the employee at an increased risk of health impairment from work in
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 under conditions expected on site (for example, temperature extremes).
• A statement that the employee has been informed by the physician of the medical
examination results and of any medical conditions that require further examination or
treatment.
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10.9.2 Documentation and Recordkeeping Requirements
PRC's Chicago office will maintain medical surveillance records for each PRC employee performing
hazardous waste site activities. These records will be in compliance with OSHA
29 CFR 1910.120(f). The records also will be maintained at Environmental Medicine Resources in
Atlanta, Georgia. Any visitor or observer at the site will be required to provide records in
compliance with OSHA 29 CFR 1910.120(f) before entering the site. PRC will be responsible for
recording and reporting accidents, illnesses, and injuries involving PRC employees in accordance with
OSHA 29 CFR 1910 and 1926 and EPA requirements. A copy of this information will be added to
PRC's medical surveillance records in the event of a reportable accident, illness, or injury.
10.9.3 Medical Support and Follow-up Requirements
PRC personnel will be required to seek medical attention and physical testing in the event of injury or
possible exposure above established exposure limits. Depending on the type of injury or exposure,
follow-up testing, if required, must be performed within 24 to 48 hours of this incident. The type of
test to be performed to monitor exposure effects will be based on the circumstances involved and will
be selected by a qualified health professional from Environmental Medicine Resources.
10.10 ENVIRONMENTAL SURVEILLANCE
Air monitoring will be performed during designated sampling and other field activities to protect
personnel against exposure to airborne hazardous substances and to determine appropriate levels of
PPE for work tasks. The following sections discuss initial air monitoring, periodic air monitoring,
monitoring parameters, use and maintenance of survey equipment, and cold stress monitoring.
10.10.1 Initial Air Monitoring
Initial air monitoring of the work area will be performed before beginning site activities. This
monitoring will be performed using real-time field survey instrumentation, such as a Miniram Model
PDM-3, to determine the concentrations of airborne dust particles. Airborne dust concentrations also
will be monitored at the beginning of each work day to identify background contaminant
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concentrations and to detect any potentially hazardous situation that might have developed during
off-shift periods.
10.10.2 Periodic Air Monitoring
Periodic air monitoring will be performed during all site activities. This type of monitoring will be
performed as a minimum requirement when the following situations arise:
• Work begins on a different portion of the site
• Workers experience physical difficulties
Required survey instrumentation, sampling procedures, and monitoring procedures are specified in
Section 10.11.3. Sampling methods will be subject to review by the PRC SHSO.
10.10.3 Monitoring Parameters
Air monitoring for dust particles will be performed at shoulder height (in the breathing zone) on
personnel most likely to be exposed to potentially hazardous concentrations of contaminants. The
following instrument and monitoring frequency may be used to monitor for dust particles during site
activities.
• Instrument: Miniram Model PDM-3
• Activity: Direct Real-Time Air Monitoring
• Monitoring Frequency: Monitoring will occur continuously during field
activities. Miniram readings will initially be recorded
in the field logbook every hour. If continued
monitoring does not indicate the presence of dust at or
above 5 mg/m3, readings may be recorded every
2 hours or longer based on the PRC SHSO's review of
the monitoring data collected.
The OSHA permissible exposure limit for lead is 0.03 mg/m3. Given a worst-case scenario of 3
percent (30,000 mg/kg) lead in the airborne particulates, the permissible exposure limit could be
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increased to 1 mg/m3. Adding a protection factor of 2, the action level drops to 0.5 mg/m3 total
dust.
General action levels
Situation:
Action:
Situation:
Action:
Concentration of dust below 0.5 mg/m3
Continue investigation at Level D without respiratory
protection and continue monitoring
Concentration of dust at or above 0.5 mg/m3
Notify PRC SHSO; upgrade to Level C protection and
continue work unless otherwise specified
10.11
USE AND MAINTENANCE OF SURVEY EQUIPMENT
All personnel using field survey equipment will be briefed on its operation, limitations, and
maintenance by the PRC SHSO. Maintenance and calibration will be performed according to
manufacturer guidelines by a designated individual familiar with the devices. Repairs, maintenance
and routine calibration of this equipment will be recorded in an equipment maintenance logbook that
will be signed by the trained service technician. The equipment maintenance logbook for each piece
of equipment will be kept in the carrying case for that equipment.
Air monitoring equipment, such as the Miniram, will be calibrated before work begins. Only routine
maintenance (such as changing batteries and cleaning the optical chamber) will be performed by field
personnel. Any additional maintenance will be performed by a trained service technician.
10.12 COLD STRESS MONITORING
Cold stress may be of particular concern when a wind chill-adjusted temperature of 10 °F or less is
expected. The following guidelines describe different forms of cold stress, conditions under which
cold stress may occur, and preventative measures:
• Personnel working outdoors in temperatures at or below freezing may be frostbitten.
Working in extreme cold even for a short time may cause severe injury to the surface
of the body or may result in profound generalized cooling, causing hypothermia and
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possibly deaih. Areas of the body that have a high surface area-to-volume ratio, such
as ears, fingers, and toes are most susceptible to frostbite.
• Local injury from cold is included in the generic term "frostbite. '' Frostbite
symptoms can be categorized according to the following degrees of severity:
Frostbite nip or initial frostbite is characterized by sudden blanching or
whitening of the skin.
Superficial frostbite causes the skin to have a waxy appearance and to be firm
to the touch while the tissue underneath is resilient.
Deep frostbite causes tissues to be cold, pale, and solid. This degree of
frostbite is extremely serious.
• Systemic hypothermia manifests itself in five stages of symptoms: (1) shivering;
(2) apathy, listlessness, sleepiness, and sometimes rapid cooling of the body to less
than 95 °F; (3) unconsciousness, glassy eyes, and slow respiration and pulse;
(4) freezing of the extremities; and (5) death. .
• Trench foot or immersion foot occurs when feet are kept cold and wet for an extended
period of time. Feet become pale, cold, and possibly pulseless. During recovery,
feet become red, hot, and swollen from excessive blood flow.
• Ambient temperatures and wind velocity influence the development of a cold injury.
Wind chill (the chilling effect of moving air) should be taken into consideration along
with the air temperature when determining whether or not outdoor work is safe.
• When chemical-resistant equipment is removed and the clothing underneath is
perspiration-soaked, the body cools very rapidly. Workers should therefore avoid
removing equipment until they are in a warm area.
• Thermal socks, long cotton or thermal underwear, hard-hat liners, and other
cold-weather gear can help prevent hypothermia.
• Blankets, warm drinks (other than caffeinated coffee), and warm rest areas are
essential.
The following chart contains general guidelines that can be used to monitor cold weather field work:
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Cooling Power of Wind on Exposed Flesh Expressed as Equivalent Temperature
. Actual Temperature Reading (°F)
Wind Speed 50 40 30 20 10 0 -10 -20 -30 -40 -50 -60
(in miles per hour - mph)
Equivalent Chill Temperature (°F)
CALM
50
40
30
20
10
0
-10
-20
-30
-40
-50
-60
5
48
37
27
16
6
-5
-15
-26
-36
-47
-57
-68
10
40
28
16
4
-9
-24
-33
-46
-58
-70
-83
-95
15
36
22
9
-5
-18
-32
-45
-58
-72
-85
-99
-112
20
32
18
4
-10
-25
-39
-53
-67
-82
-96
-110
-121
25
30
16
0
15
-29
-44
-59
-74
-88
-104
-118
-133
30
28
13
-2
18
-33
-48
-63
-79
-94
-109
-125
-140
35
27
11
-4
20
-35
-51
-67
-82
-98
-113
-129
-145
40
26
10
-6
21
-37
-53
-69
-85
-100
-116
-132
-148
(Wind speeds greater
than 40 mph have little
additional effect.)
LITTLE DANGER
in less than 1 hour with
dry skin; maximum
danger from false sense
of security
INCREASING DANGER
from freezing of exposed
flesh within 1 minute
GREAT DANGER
that flesh may freeze
within 30 seconds
Trench foot may occur at any point on this chart.
SOURCE: MODIFIED FROM AMERICAN CONFERENCE OF GOVERNMENTAL INDUSTRIAL
HYGIENISTS 1993-1994
In addition to cold stress preventative measures, personnel will be briefed on the dangers of cold
stress and frostbite. Personnel will be monitored by the PRC SHSO during all rest periods and site
activities for signs of hypothermia or frostbite. Self-monitoring and peer monitoring will be
encouraged.
10.13 SITE CONTROL
Work areas on or near the demonstration sites will, depending on results of environmental
monitoring, be divided into three zones: an exclusion zone, a contamination reduction zone (CRZ),
also known as decontamination zone, and a support zone. Generally, the exclusion zone will be
designated by barricade tape or traffic cones. Access to a contaminated exclusion zone will be
through the CRZ, and it will be restricted to authorized personnel. The support zone will be the area
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where supplies are staged and samples are packaged. A daily roster with the date of each person's
entrance into the contaminated zone; the person's name, signature, and organization; the time of
entry; and the time of exit will be kept for all personnel working in such an area. Any visitors to the
area must present proper identification and be authorized to be on site. Visitors must comply with all
provisions of this HASP. The PRC SHSO will identify work areas that visitors or personnel are
authorized to enter and will enforce site control measures. The following subsections discuss site
control zones, safe work practices. HASP enforcement, and complaints.
10.13.1 Site Control Zones
The PRC SHSO will establish site control zones after initial monitoring of site conditions. Should the
conditions change during field activities, the SHSO will reevaluate the current site control zones and
establish new zones, if necessary.
10.13.2 Safe Work Practices
Safe work practice requirements for field activities will include the following;
• All personnel will enter a designated exclusion zone only through the contamination
reduction corridor. All personnel leaving an exclusion zone must exit through the
contamination reduction corridor and undergo the CRZ decontamination procedure.
• Only equipment necessary to complete sampling will be permitted within an exclusion
zone. All nonessential equipment will remain within the support zone.
• All personnel will avoid contact with potentially contaminated substances. Walking
through puddles or mud and kneeling on the ground will be avoided whenever
possible.
• Equipment will not be placed on potentially contaminated surfaces.
• Food and beverages will not be permitted in the exclusion zone or CRZ. Possession
or use of tobacco products and application of cosmetics also are prohibited in these
areas.
• Matches and lighters will not be permitted in the exclusion or CRZ zones.
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• During rest periods, all personnel will be required to observe each other for signs of
toxic exposure and heat stress. Indications of adverse effects include, but are not
limited to, the following:
Changes in complexion and skin discoloration
Changes in coordination
Changes in demeanor
Excessive salivation and pupillary response
Changes in speech patterns
• Personnel will inform each other of nonvisual effects of illness, such as the following
Headache
Dizziness
Nausea
Blurred vision
Cramps
Irritation of eyes, skin, or the respiratory tract
The following paragraphs describe safe work practices regarding avoidance of trip and fall hazards,
performance of activities near utility and power lines, avoidance of excessive noise exposure,
illumination, sanitation, working near bodies of water, and site housekeeping.
A vmHnnrp nf Trip and Fq||
Personnel will be informed of any potential trip and fall hazards during regular health and safety
meetings. Whenever possible, trip and fall hazards will be eliminated or clearly identified with
yellow caution tape.
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Field Activities Near Utility and Power Lines
Field activities will proceed with caution in any area where historical data or instrument surveys
indicate the presence of utility lines (such as gas, telephone, water, and other lines). All field activity
locations will be coordinated by the PRC project manager.
The demonstration sites have overhead power lines in certain areas of the sites. The PRC project
manager and PRC SHSO will be responsible for ensuring that field activities, especially drilling or
probing, will not place equipment or personnel near power lines. However, if site activities near
power lines are required, necessary arrangements to turn off the power will be coordinated by the
PRC project supervisor.
Outdoor work will not be performed after sunset or when a lack of natural illumination makes
outdoor work difficult.
^Sanitation
potable water, drinking cups, nonpotable water, toilet facilities, washing facilities, and other
sanitation requirements will be provided in compliance with specifications of OSHA
29 CFR 19l0.120(n).
Si^e Housekeeping
Potentially hazardous wastes generated during field activities will be drummed, if necessary, and
handled in accordance with RCRA requirements. Nonhazardous waste and debris will be disposed of
as standard municipal waste.
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10.13.3 Health and Safety Plan Enforcement
The PRC SHSO will be responsible for enforcement of the HASP during field sampling activities
Personnel who fail to follow HASP procedures will face disciplinary action that may, at a maximum
include dismissal from the site.
At least one copy of this HASP will be available to all personnel at all times. Any necessary changes
in HASP procedures will be made at the beginning of each work day by the SHSO.
10.13.4 Complaints
Personnel will be encouraged to report to the PRC SHSO any conditions or practices that they
consider detrimental to their health or safety or that they believe are in violation of applicable health
and safety standards. Such complaints may be made orally or in writing. Personnel who believe that
an imminent danger threatens human health or the environment will be encouraged to bring the matter
to the immediate attention of the SHSO for resolution.
10.14 DECONTAMINATION
Decontamination is the process of removing or neutralizing contaminants from personnel or
equipment. When properly conducted, decontamination procedures protect personnel from
contaminants that may have accumulated on PPE, tools, and other equipment. Proper
decontamination also prevents transport of potentially harmful materials to unaffected areas.
Personnel and equipment decontamination procedures are described in the following subsections.
10.14.1 Personnel Decontamination
Minimal personnel decontamination is anticipated at the demonstration sites because disposable PPE
will be used. If necessary, personnel decontamination will be completed according to the guidance
given in the "Occupational Safety and Health Guidance Manual for Hazardous Waste Site Activities"
(Department of Health and Human Services 1985). Personnel and PPE will be decontaminated with
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potable water or a mixture of detergent and water. Liquid and solid wastes produced during
decontamination will be collected and drummed.
The following decontamination procedures will be conducted if personnel decontamination is required:
• 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 the Tyvek® or Saranex® suit 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. The filter may be changed daily or at longer intervals, depending on the
use and application. Clean and disinfect the respirator with towelettes or a
non-phosphate cleaning solution. Place, it in a plastic bag for storage.
• Remove inner gloves and place them in a plastic bag for disposal.
• Thoroughly wash hands and face with water and soap.
Used, disposable PPE will be collected in plastic bags and placed in fiberboard drums and disposed of
as municipal waste, unless otherwise specified. Further personnel decontamination procedures may
be established as needed.
10.14.2 Equipment Decontamination
Decontamination of all nondisposable sampling and field monitoring equipment used during field
activities will be required. The equipment decontamination procedures described in the following
paragraphs are based on guidelines appropriate for low-level contamination. When appropriate,
Liquinox® or Alconox® cleaning solutions and deionized water rinses will be used to decontaminate
equipment. Wastewater from equipment decontamination activities will be placed in a 55-gallon
drum. A representative sample will be collected from the wastewater and analyzed for contaminants
of concern before a decision regarding its disposal is made.
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Sampling Equipment
Sampling equipment, such as stainless-steel spades, spoons, and stainless-steei or aluminum pans, will
be decontaminated before and after each use. Potable water will be used for the following sampling
equipment decontamination procedures:
• Scrub the equipment with a brush in a bucket containing Liquinox®, or Alconox®
solution and potable water.
• Triple-rinse the equipment with water, and allow it to air dry.
• Reassemble the equipment and place it in a clean area on plastic.
Field Monitoring Equipment
A Miniram Model PDM-3 will be used for monitoring concentrations of dust in the atmosphere. This
equipment will be cleaned daily by wiping it with isopropyl alcohol. Also, the equipment will be kept
in a bag to minimize the exposure to the dust.
10.15 EMERGENCY CONTINGENCY PLANNING
The PRC SHSO will be notified of any on-site emergencies and will be responsible for ensuring that
appropriate emergency procedures are followed. Standard emergency procedures to be used by
personnel are described in the following subsections. All subcontractors, developers, and visitors will
be informed about emergency procedures and the location of the nearest hospital. A copy of this
HASP will be available to all personnel before field work begins.
10.15.1 Injury in the Exclusion or Contamination Reduction Zones
In the event of an injury in the exclusion or CRZ zones, all personnel will exit the exclusion zone and
assemble at the decontamination line, and the PRC SHSO will be immediately notified if necessary.
The SHSO will contact the PRC HSD, and together they will evaluate the nature and extent of the
injury. The affected person will be decontaminated to the extent practical before being moved to the
support zone. Appropriate first aid procedures will be performed, an immediate request for an
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ambulance will be made (if necessary), and the designated medical facility will be notified (if
necessary). Emergency numbers for each site are provided in Section 10.16.5. No personnel will
re-enter the exclusion zone until the cause of injury or illness is determined and re-entry is considered
safe. In case of severe injury, the PRC SHSO will implement procedures to minimize the possibility
of further injury. If the need to transport the patient to a medical facility supersedes the need to
decontaminate the patient, the medical facility will be notified that the patient has not been
decontaminated before the patient arrives. Documentation requirements are outlined in
Section 10.10.2.
10.15.2 Injury in the Support Zone
If an injury occurs in the support zone, the PRC SHSO will be notified immediately. Appropriate
first aid will be administered and, if necessary, the injured individual will be transported to the
designated medical facility. If the injury does not affect, the safety or performance of site personnel,
operations will continue. Documentation requirements are outlined in Section 10.10.2.
10.15.3 Fire or Explosion
In the event of a fire or explosion at the site, the local fire department will be contacted as soon as
possible, and an evacuation of the site will begin immediately.
10.15.4 Protective Equipment Failure
If personnel in the exclusion zone experience a failure of protective equipment that affects his or her
personal protection, all personnel will immediately leave the exclusion zone. Re-entry to the
exclusion zone will not be permitted until the protective equipment has been repaired or replaced and
the cause of equipment failure has been determined and is no longer considered a threat.
10.15.5 Emergency Information Telephone Numbers
PRC will have a cellular telephone on site that can be used for any emergency situations. Emergency
telephone numbers for each of the demonstration sites are listed below. Emergency telephone
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numbers not presented below can be obtained, during working hours, by calling Ms. Kathy Schuessler
of PRC at (312) 856-8700.
RV Hopkins Site
Asarco Site
Emergency Service
Local Police Department:
Local Fire Department:
Local Hospital: Mercy Hospital
Local Ambulance Service:
Emergency Service
Local Police Department:
Local Fire Department:
Local Hospital: St. Joseph Hospital
Local Ambulance Service:
Telephone Number
911
911
(319) 383-1100
911
Telephone Number
911
911
911
911
The following emergency contacts are applicable to all demonstration sites:
Poison Control Center:
National Response Center:
CHEMTREC Chemical Transportation
Emergency Center:
PRC (Kansas City office):
Eric Hess, PRC Project Manager:
Kurt Sorensen, PRC HSD:
Steve Billets, EPA PM and TPM:
1 (800) 822-3232
1 (800) 424-8802
1 (800) 424-9300
(913) 281-2277
(913) 573-1822
(312) 856-8763
(702) 798-2232
10-28
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The following numbers can be used to contact the demonstration team at the sites on PRC's mobile
telephone. To access the mobile telephone, dial the first number, wait for a tone, and then dial the
second number:
RV Hopkins Site: (319) 349-ROAM, (816) 536-0944
Asarco Site: (206) 972-ROAM, (816) 536-0944
10.15.6 Hospital Route Directions
Before performing any field activities, PRC personnel will conduct a pre-emergency hospital run from
each site to the hospital. Maps showing the hospital routes from each site are provided in
Figures 10-1 and 10-2.
10-29
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TRINITY _UTHE3AN
MERCY HOSPITAL
•RV HOPKINS
FPXRF
SITE DEMONSTRATION
LEGEND
FIGURE 10-1
RV HOPKINS SITE
HOSPITAL ROUTE
HOSPITAL ROUTE MAP
NOT TO SCALE
PRC ENVIRONMENTAL MANAGEMENT iisir
10-30
-------
LINg
POINT
j fGENQ N0T T0 SCALE
mmmm, HOSPITAL ROUTE
FPXRF
SITE DEMONSTRATION
FIGURE 10-2
ASARCO SITE
HOSPITAL ROUTE MAP
jmC ENVIRONMENTAL MANAGEMENT, INC.
10-31
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TABLE 10-1
HAZARDOUS MATERIALS POTENTIALLY PRESENT
AT THE
DEMONSTRATION SITES
Field Portable X-Ray Fluorescence Technologies
SITE Demonstration
9
u>
K)
Chemicals Present
at the Site
ll%hm Observed
Concentration in Soil
(ug/kg)
Airborne Exposure
Limits
IDLII
Symptoms and Effects of Acute Exposure
Antimony
and compounds (as Sb)
No Data
0.5 mg/m3
80 mg/m3
Irritated nose, throat, mouth, cough; dizziness; headache, nausea, vommng,
diarThea, cramps; insomnia; anoreua; irntaicd skin; unable [(! smell; cardiac
Barium
soluble compounds
(as Ba)
2.640
0.5 mg/m3
250 mg/mJ
Upper respiratory irritation, gastrointestinal; muscle spasms; slow pulse,
extrasystoles; hypokalemia, irritated eyes; skin burns
Beryllium
and compounds (as Be)
No Data
2.0 fig/a13
Ca
Respiratory symptoms; weakness, fatigue; weight loss, carcinogen
Cadmium dust
(asCd)
500
0.2 mg/m3
Ca
Pulmonary edema, dyspnea, cough, tight chest, substernal pain, headache,
chills, muscle aches; nausea, diarrhea; anosmia, emphysema; proteinuria;
anemia; carcinogen
Calcium arsenate
(as As)
403.100
10 ugltf?
Ca
Weakness; gastrointestinal, peripheral neuropathy, hyperpigmentation,
palmar planter hyperkeratoses; dermatitis; carcinogen
Chromic acid
and chromates (as C1O3)
22,100
0.1 mg/m3
30 mg/m3
Respiratory, nasal septum irritation; leukocytosis, leukopenia, monocytosis,
eosinophils, eye injury, conjunctivitis; skin ulcer, sensitization dermatitis
Chromium
metal and insoluble salts
(as Cr)
22.100
1 mg/m3
500 mg/m3
Histologic fibrosis of lungs; Chromium (VI): carcinogen
Cobalt
metal, fume, and dust
(as Co)
No Data
0.1 mg/m1
20 mg/m3
Cough, dyspnea, decreased pulmonary function, weight loss; dermatitis;
diffuse nodular fibrosis, respiratory hypersensitivity
Copper
dust and mist (as Cu)
341.000
1 mg/m3
NA
Irritated mucus membrane, pharynx; nasal perforation; eye initation; metal
taste; dermatitis
Lead
Inorganic fumes and dusts
(as Pb)
33,750
0.03 mg/m3
NA
Lassitude; insomnia; pallor, eye grounds; anorexia, weigh! loss,
malnutrition; constipation, abdominal pain, colic; hypotenuse; anemia;
gingival lead line; trembling, paralyzed wnst
Manganese
and compounds (as Mn)
22,000
5 mg/m3
10,000 mg/m3
Parkinson's disease; asthenia, insomnia, mental; metal fume fever; dry
throat, cough, right chest, dyspnea, rales; low back pain; vomiting,
malnutrition; fatigue
Mercury
and inorganic compounds
(asHg)
700
0.1 mg/m3
28 mg/m3
Cough, dyspnea, bronchial pneumonia; tremor, insomnia; irritability,
indecision; headache; fatigue, weakness; stomatitis; salivation;
gastroinlenstinal, anorexia, loss of weight; proteinuria; irritated eyes, skin
-------
TABLE 10-1 (Continued)
HAZARDOUS MATERIALS POTENTIALLY PRESENT
AT THE
DEMONSTRATION SITES
Field Portable X-Ray Fluorescence Instruments
SITE Demonstration
Chemicals Present
al the Silt
Highest Observed
Concentration in Soil
(tag/kg)
Airborne Exposure
1 Jmi«<
IDL11
Symptoms and Effects of Acute Exposure
Molybdenum
insoluble compounds
(as Mo)
No Data
15 mg/m3
NA
In animals: irritated eyes, nose, throat, weight loss
Nickel
metal and soluble
compounds (as Ni)
519
1 mg/m3
Ca
Sensitization dermatitis: allergic asthma; nasal cavities, pneumonitis,
carcinogen
Selenium compounds
(asSe)
No Data
0 2 mg/m3
100 mg/m3
Irritated eyes, nose, throat; disturbed vision; headache; chills, fever;
dyspnea, bronchitis, metal taste, garlic breath: gastrointestinal; dermatitis;
blurry eyes; skin
Silica
(crystalline)
No Data
10 mg/m3
NA
Cough, dyspnea, wheeze; impaired pulmonary functions; progressive
symptoms
Thallium
soluble compounds (as Tl)
1.080
0.1 mg/m3
20 mg/m3
Nausea, diarrhea, abdominal pain; ptosis, strabismus; peripheral neuritis
tremors, paresthesia legs, retster chest pain, pulmonary edema; seizure
chorea psychialopecia
Tin
inorganic compounds
except oxides (as Sn)
No Data
2 mg/m?
400 mg/m3
Irritated eyes, skin
Notes:
NA Not applicable
Ca Carcinogen
-------
TABLE 10-2
WORK TASK HAZARD ANALYSIS
Field Portable X-Ray Fluorescence Technologies
SITE Demonstration
Task
Potential Hazard
Anticipated Level
of Protection
Upgraded Level
of Protection
Task 1
Sampling
Chemical
Physical
Level D
LevelC
Task 2
Chemical
Field Screening
Radiological
Level D
Level C
Note:
Levels of protection are discussed in detail in Section 10.9.2.
10-34
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CHAPTER 11
DELIVERABLES
Several documents and reports will be produced as part of this demonstration. Anticipated
deliverables include a work plan, a demonstration plan, a TER, an ITER, and technology briefs.
Other reports may be submitted as requested by the EPA TPM. Each of these reports is discussed
below.
11.1 DEMONSTRATION WORK PLAN
The work plan was submitted to EPA EMSL on September 29, 1994. The work plan described the
tasks PRC will complete for this demonstration. Tasks listed in the work plan include: work plan
preparation and project coordination, technical support, predemonstration sampling and analysis,
preparation of a demonstration plan, field method development, demonstration activities, and
preparation of draft and final TERs, ITERs, and technology briefs. The work plan describes each of
these tasks and discusses the steps PRC will take to complete each task.
11.2 DEMONSTRATION PLAN
This demonstration plan has been prepared to provide a detailed description of all activities that will
take place as part of this demonstration. This plan includes the following elements:
• Test Plan. The test plan includes an overview of the demonstration process
(Chapter 1), a description of the roles and responsibilities of involved parties
(Chapter 2), a discussion of the sampling protocols (Chapter 6), a discussion of the
experimental design for the demonstration (Chapter 7), and an explanation of the
methodology for evaluating the performances of the technologies (Chapter 7).
• OAPP. This document was prepared according to EPA guidelines listed in the
statement of work. The QAPP includes a project description, delineation of QA/QC
responsibilities, QA objectives for critical measurements, sampling and analytical
procedures, data reduction, validation, and reporting procedures, plans for system and
performance audits, and descriptions of internal QC checks, calculation of data quality
indicators, plans for corrective actions, and QC reports to management. The QAPP is
provided in Chapter 8.
11-1
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HASP. The HASP identifies the key personnel who will be involved with
demonstration activities and the minimum training requirements for field personnel,
evaluates anticipated hazards associated with field work, and discusses site entry,
personal protection equipment, communication, and decontamination procedures to be
followed during field work. The HASP is provided in Chapter 10.
Sampling Plan. The sampling plan describes the objectives of the sampling proposed
for the demonstration and identifies specific sampling methods and analytical
procedures to be followed. The sampling plan is provided in Chapter 6. Analytical
procedures for the confirmatory laboratory are outlined in Chapter 8.
11.3 TECHNOLOGY EVALUATION REPORT
The main product of a completed demonstration under the SITE Program is a TER. This report
documents the results of the demonstration and reports on the performances of the technologies. The
TER will include descriptions of analytical and instrument procedures, data collection and
management procedures, and associated QA/QC requirements.
The report for this demonstration project will include the following specific elements:
• A demonstration summary prepared according to directions from the EPA TPM
• A description of the technologies that were demonstrated including diagrams,
operating instructions, and a brief discussion of the theoretical concepts under which
the technologies operate
• One generic method for using FPXRF technologies in a format comparable to EPA
SW-846 methods
• A description of any deviations in the experimental design for the demonstration
including method protocols, sampling and analysis procedures and methods, QA/QC
procedures and records, descriptions of the demonstration sites, and any other
pertinent information about the demonstration
• An interpretation and assessment of the technologies comparing their analytical results
to those obtained using conventional analytical methods
• Analytical performance data and data interpretation for each technology including an
evaluation of data quality parameters (precision, accuracy, comparability,
completeness, representativeness), and a description of the methods used to assess this
data
• Conclusions about the advantages and limitations of each technology on its own merit
compared to conventional EPA sample analysis
11-2
-------
• Recommendations for the potential use of the technologies for site characterization and
regulatory activities, as well as recommendations for improvements or further testing,
if appropriate
11.4 INNOVATIVE TECHNOLOGY EVALUATION REPORT
The vehicle used to publish the results of a completed demonstration under the SITE Program is an
ITER. This report condenses the data presented in a TER. focusing primarily on application-related
data and observations. This report will be similar to the TER except all appendices will be eliminated
and detailed data analysis discussions will be eliminated.
11.5 TECHNOLOGY BRIEFS
The technology briefs are one-page summaries of the gross findings presented in the ITER. A
technology brief will be produced for each technology demonstrated. These documents are intended
to be technology transfer fact sheets.
11.6 OTHER REPORTS
PRC will prepare other reports or documents as directed by the EPA TPM. Examples of other
reports which may be required include memorandum trip reports following field activities or visits to
developer facilities. In addition, the EPA TPM may require development of technology transfer
documents including technology mailers, bulletins, journal articles, or other publications.
11-3
-------
REFERENCES
American Conference of Governmental Industrial Hygienists (ACGIH). 1993-1994. "Threshold
Limit Values for Chemical Substances and Physical Agents and Biological Exposure Indices."
American Society for Testing and Materials (ASTM). 1992. "Standard Test Method for Laboratory
Determination of Water (Moisture) Content of Soil and Rock." ASTM Method D 2216-92.
1994. "Standard Practice for Microwave Digestion of Industrial Furnace Feedstreams for
Trace Element Analysis." ASTM Method 5513.94.
Draper, N. R., and H. Smith. 1981. Applied Regression Analyses. John Wiley & Sons, Inc.
New York. 2nd ed.
Freeze, R., and John A. Cherry. 1979. Groundwater. Prentice Hall, Inc..
Havlick, Larry L., and Ronald D. Crain. 1988. Practical Statistics for the Physical Sciences.
American Chemical Society. Washington, D.C.
International Organization of Legal Metrology. 1993. "Portable and Transportable X-ray
Fluorescence Spectrometers for Field Measurements of Hazardous Elemental Pollutants."
Kleinbaum, David G., and Lawrence L. Kupper. 1978. Applied Regression Analysis and Other
Multivariable Methods. Duxbury Press. Boston, Massachusetts.
National Institute for Occupational Safety and Health (NIOSH). 198S. "Pocket Guide to Chemical
Hazards." U.S. Department of Health and Human Services. U.S. Government Printing
Office. Washington. D C.
Natrella, Mary Gibbons. 1963. "Experimental Statistics." National Bureau of Standards
Handbook 91. U.S. Government Printing Office. Washington, D.C.
Stanley, T. W., and S. S. Veraer. 1983. "Interim Guidelines and Specifications for Preparing
Quality Assurance Project Plans." U.S. Environmental Protection Agency, Washington D.C.
EPA/600/4-83/004.
Systat, Inc. 1990. SYSTAT/SYGRAPH Software for DOS. Evanston, Illinois.
U.S. Department of Health and Human Services. 1985. "Occupational Safety and Health Guidance
Manual for Hazardous Waste Site Activities." Public Health Service.
U.S. Environmental Protection Agency. March 1986. "Handbook for Preparing Office of Research
and Development Reports." Center for Environmental Research Information. Cincinnati,
Ohio. EPA/600/9-83/006. March.
. 1989. "Preparing Perfect Project Plans." Risk Reduction Engineering Laboratory.
Cincinnati, OH. EPA/600/9-89/087.
R-l
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1990. "IDW Management Guidance Manual-Second Draft." May 25.
1991. Quality Assurance Technical Information Bulletin-Field Portable X-ray Fluorescence.
Office of Solid Waste and Emergency Response. Volume 1, Number 4. May.
1993. "Data Quality Objectives Process for Superfund-Interim Final Guidance." Office of
Solid Waste and Emergency Response. Washington, DC.. EPA/540/R-93/071.
R-2
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APPENDIX A
DEMONSTRATION PARTICIPANT COMMENTS ON THE
DRAFT DEMONSTRATION PLAN
-------
DEMONSTRATION PARTICIPANT COMMENTS ON THE
DRAFT DEMONSTRATION PLAN
This demonstration was originally submitted in draft form to the U.S. Environmental Protection
Agency (EPA) on November 1, 1994. Copies of the draft demonstration plan also were provided to
the technology developers at that time. EPA and the developers submitted comments to PRC on the
draft demonstration plan.
All comments on the draft demonstration plan submitted by EPA and the developers have been
addressed in this final version of the plan.
Reviewers submitted numerous specific and general comments on the draft demonstration plan. Each
unedited comment is presented and addressed in the following pages with a discussion of PRC's
response and rationale for its response. The reviewers' comments are presented in italics. PRC's
response to each comment is presented in standard type.
A-l
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COMMENTS BY EPA OSW
OLLIE FORD HAM, TECHNICAL ADVISOR
1. Recoveries of 80 to 120 percent are necessary for confirmatory sample analyses in order to
use them as reference standards to compare XRF technologies against. Of course. NIST
SRMs are the best samples to compare the XRF technology against, since their certified values
have been carefully established.
PRC revised the recoveries for pre- and post-digestion spikes. These control limits were
tightened lo 80 to 120 percent. In addition, these control limits also were applied to
performance evaluation samples without defined acceptance limits, and to matrix spike
samples.
2. Homogeneity of the samples will be very important especially for confirmatory analysis. On
Page 6-5 the samples should really be ground and riffle split. Keep the ground and split
samples for future demos. They could be very valuable. On Page 6-4, the use of stainless
steel sieves should be considered. As long as they are properly cleaned, they will not cause
contamination at the high analyte levels being looked at in this study.
The predemonstration sampling showed that the planned homogenization procedure was highly
effective. Mean relative percent differences between the field duplicates was below 9 percent.
This effective homogenization eliminates the need for riffle splitting the samples.
3. Use SW-846 draft Method 3052, Microwave Assisted Digestion of Silicious Materials, instead
of ASTM Method D5513-94.
Draft SW-846 Method 3052 will be used to conduct the total digestion extractions. In
addition, the percentage of samples extracted by this method has been increased from 20 to
30 percent.
4. QC criteria for sample matrix: use three different soil types, a sandy soil (high silica), a clay
soil (high alumino-silicates and exchange capacity), and a loam (high organic content).
The following three distinct soil textures have been targeted by this demonstration: silty clays,
sands, and loam soils. The silty clays are located at the RV Hopkins site; the loams and
sands are found at the Asarco site.
5. QC criteria for analyte concentration levels: use three different levels for example, low 0 to
100 ppm, medium 100 to 1,000 ppm, and high 0.1 to 10 percent.
These target concentration ranges are identified in the demonstration plan.
6. QC criteria in the XRF method will be critical. Performance of the method must be proven at
a level to meet the DQOs of the study, site assessment, or regulation. As an example, for
toxicity characteristic testing of soils using total analysis in lieu ofTCLP, the regulatory limit
A-2
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COMMENTS BY EPA OSW (Continued)
OLLIE FORDHAM, TECHNICAL ADVISOR
is the TC limit times 20 (the dilution factor in TCLP). In order for XRF to be valid for this
type of analysis, its practical quantitation limit should be at or below the regulatory limit.
The practical quantitation limits will be determined for each of the FPXRF technologies. This
is stated in the project objectives.
7. You might consider factor analysis along with the other statistics mentioned on Page 7-11 as
an excellent tool to determine the major causes of variance in this study.
A step-wise multiple regression may be used to identify specific factors and their influence on
the statistical evaluation.
8. The final product needed by OSW is a well validated, generic, field portable XRF screening
method (see Page 11-2) in SW-846 and/or EEMC format (I need to check with Barry Lesnik
on format). The method should not be written specifically for any instrument manufacturer's
equipment but should be applicable to all vendors' instrumentation.
The creation of a generic draft SW-846 method is a specific objective of this demonstration.
A-3
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COMMENTS FROM CONSORTIUM FOR SITE CHARACTERIZATION TECHNOLOGY
GRACE BUJEWSKI, SANDIA NATIONAL LABORATORIES
1. A typo on Page 4-1: Cesium-244 should be Curium-244.
This typographical error has been corrected.
2. Will the final plan have more predemonstration sampling details and, therefore, more final
demonstration sampling details ? This is how I imagined a demonstration plan would be
finalized, taking into account the lessons learned in the field during the predemo sampling,
would like to know the locations that are chosen for the sampling at each site.
Predemonstration sampling details have been included in the final demonstration plan. The
predemonstration sampling identified general areas for the demonstration sampling. The
creation of a detailed sampling location map is not considered pertinent to this demonstration.
In fact, access has been granted on the condition that the demonstration sampling locations not
be recorded.
3. It would be easier to follow if there was a table in Chapter 4 to summarize the technologies.
Specifically, I had a hard time remembering which were ex situ and which were in situ. I
wanted to keep track of these as I was reading to figure out how long a stop at a sampling
location might take. Also, will all instruments be used at all three demo sites?
Instrument-specific information tables have been added to the final demonstration plan,
specifically in Chapters 1 and 4. All instruments will be used at each demonstration site.
4. It would be easier to follow if there ivai a flow chart depicting the steps of sampling/analysis
described in Chapter 6.
A sample preparation and analysis flow chart has been added to Chapter 6.
A-4
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COMMENTS FROM OTHER EPA REVIEWERS
STEVEN CHANG, OFFICE OF EMERGENCY AND REMEDIAL RESPONSE
1. The statistical sampling method is not described in detail in Chapter 6. The issue is that EPA
needs to convince the public that the sample is a representation of the true population. Many
types of sampling can be employed, including simple random sampling, stratified random
sampling, cluster sampling, and systematic sampling. Please document the sampling
method(s) in the final report so that the appropriate statistical analyses can be used.
Random sampling would be appropriate if the objective of the demonstration was to describe
the spatial distribution of contamination at both sites. However, since the purpose of the
demonstration is to evaluate the performance of FPXRF technologies, it is necessary to apply
these instruments to a biased sampling that will rigorously test the instruments below, at, and
above common action levels. The sampling design is described in detail in Chapter 6.
2. The sample size needs to be calculated depending on the confidence level specified. Since the
sample size already is predetermined as 300 total, this may or may not give the 90 percent
confidence level as specified in the draft.
This comment applies to the use of the data to define the spatial distribution of contamination
at the site. Therefore, the comment is not addressed in the final demonstration plan. The
sample size will be used to evaluate the statistical power of the evaluation at the end of the
demonstration, when the data has been validated and the sample population's variance is
known.
3a. I am concerned about the use of linear regression as I had expressed at our September
meeting in Las Vegas. The current plan suggests using a step-wise multiple linear regression.
I interpret that as plotting a linear regression equation to compare confirmatory data with
XRF data for each type of soil, each type of sample preparation, and so on. The apparent
assumption is that, within a linear range, the accuracy of data based on the XRF method is
comparable to that from the laboratory analyses.
My initial questions are that, if one XRF instrument has a linear correlation with the
laboratory data using one soil type (e.g., clays), but has nonlinear correlation using a second
soil type (e.g., sands), does it mean that under mixed soil type conditions the instrument
would be unreliable? Does it mean that EPA would have to carry multiple instruments to a
site investigation and switch instruments for different soil types?
The demonstration and subsequent data evaluation is intended to evaluate these possibilities.
If performance is matrix dependent, then this is important information to distribute to users of
FPXRF technologies.
3b. More importantly, I question the assumption in Section 7.4.2 that'the results from the
confirmatory laboratory are considered to be accurate and precise." Based on my very
limited experience, the confirmatory (e.g., CLP) data are not always accurate and precise.
The draft also alluded to the fact that data couid be estimated values. The issue is that the
confirmatory data may be dependent variables that are not controlled or determined by the
researcher.
A-5
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COMMENTS FROM OTHER EPA REVIEWERS (Continued)
STEVEN CHANG, OFFICE OF EMERGENCY AND REMEDIAL RESPONSE
The basic premise of the SITE Program, relative to monitoring technologies, is to compare
innovative technologies to commonly used standard methods. The demonstration plan takes
the position that the confirmatory data is accurate and precise in order to evaluate the FPXRF
technologies. The QAPP has been designed to provide the highest quality of data possible for
this comparison and for the validation of an FPXRF method. In addition, the confirmatory
data can be considered an independent variable, with the FPXRF data being the dependent
variables. The demonstration plan has not been changed relative to this comment.
3c. If the confirmatory data were dependent variables, then the use of linear regression may be
inappropriate. The reason is that the assumption of a Model I linear regression is that the
dependent variables (XRF data) is a function of the independent variables (confirmatory data).
If both are dependent variables, then the use of correlation technique, such as a simple linear
correlation, may be more appropriate.
In correlation, by contrast, one is concerned largely whether two variables are interdependent
or covary—that is, vary together. We do not express: one as a function of the other, and a
more typical assumption is that the two variables are both effects of a common cause (e.g.,
soil type). When one wishes to establish the degree of association between the pairs of
variables in a population sample, correlation analysis is the proper approach.
Further, calculating a coefficient of determination (r2) depends on meeting the requirement
that the data are collected at random on variables from the bivariate normal distribution.
Otherwise, a nonparametric method should be used (e.g., Spearman's Rank Correlation).
In summary, the linear regression is not the appropriate test to use in this case, because we
cannot control the accuracy of the confirmatory data. Instead, calculating a coefficient of
determination, and using a test of statistical significance (hypotheses testing using a t-test),
would suffice. If the data are not normally distributed, either a data transformation or a
nonparametric test should be used.
PRC does not agree with the interpretations presented in this comment. The confirmatory
data is an independent variable and the QAPP controls the accuracy of the confirmatory data.
The demonstration plan has been altered to place a greater emphasis on the correlation
coefficient to define the quality of the relationship between the confirmatory data and the
FPXRF data.
4. The draft discusses the blocking effects for soil texture, sample preparation, concentration,
and so on. The draft, however, does not detail how the effects will be eliminated all together.
If one is concerned about all the effects, perhaps a step-wise multivariate regression should be
used, if appropriate. Each effect could be added to the step-wise process to re-calculate the
coefficient of determination.
Another suggestion is to employ the analysis of variance (ANOVA) such as a randomized block
design. / realize that the requirements for using ANOVA, including random sampling,
A-6
-------
COMMENTS FROM OTHER EPA REVIEWERS (Continued)
STEVEN CHANG, OFFICE OF EMERGENCY AND REMEDIAL RESPONSE
normality, homogeneity of variances, and independence, must be met. The alternative, again,
is using a nonparametric test.
The demonstration plan calls for the use of a step-wise multiple regression in the evaluation of
the effects of soil texture and sample preparation.
5. Please cite the reference for Table 7-1. Obviously, I am unfamiliar with the correlation
coefficient values in relationship to the data quality level.
This reference has been added to the final demonstration plan.
A-7
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COMMENTS FROM METOREX
JAMES PASMORE, DEVELOPER
1. P 4-1 Curium-244, not Cesium-244
The final demonstration plan has been corrected.
2. P 4-2 Published specs of the Spectrace 9000 indicate analysis of "26 elements from S-U".
(See attached copy of Spectrace 9000 brochure from 6/15/94)—not "all elements from
Al-U," as indicated.
Spectrace-generated data has been used to correct this portion of the final demonstration plan.
3. P 4-3 Since both the Spectrace and Metorex use backscatter fundamental parameters, both
descriptions should include this terminology. The Spectrace 9000 does not use a true
fundamental parameter program as it does not measure all elements (i.e., it cannot
measure C, O, Si, Al, etc.). It uses backscatter signal to estimate these elements, as
does Metorex's fundamental parameter program, ACES.
The final demonstration plan has been modified to reflect this information.
4. Since resolution is mentioned in regard to the Metorex Si (Li) detector, it is important to
provide similar data for the Spectrace 9000 Hgl2 detector.
This data has been added to the final demonstration plan.
5. P 4-6 The Spectrace cannot simultaneously analyze using all the sources. They must be
used in sequence for each applicable range of elements.
The final demonstration plan has been corrected based on data provided by Spectrace.
6. P 4-9 Both the proportional and Si (Li) probes are being used. They should both be
mentioned.
The final demonstration plan has been modified to present data on both detectors.
7. P 4-10 Includes additional info on the proportional detector.
No alterations to the final demonstration plan were made based on this comment.
A-8
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COMMENTS FROM TN SPECTRACE
MARGO MEYERS, DEVELOPER
Ms. Meyers submitted a rewrite of the descriptions of the TN Spectrace technologies. PRC
incorporated these revisions in the final demonstration plan.
A-9
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