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: 0-65
Date Prepared : March 1, 1995
EPA Contract Number: 68-CO-0047
PRC Project Number: 047-6504
PRC Project Manager: Eric Hess
Telephone Number: (913) 573-1822
EPA Project Manager: Steve Billets
Telephone Number: (702) 798-2232
CONTENTS
APPROVAL SIGNATURES
DISCLAIMER NOTICE
LIST OF ACRONYMS
EXECUTIVE SUMMARY
1 INTRODUCTION
1.1 SITE PROGRAM OVERVIEW
1.1.1 Selecting Technologies
1.1.2 Demonstrating Technologies
1.1.3 Evaluating
1.2 DEMONSTRATION PURPOSE
1.3 DEMONSTRATION TECHNOLOGIES AND DEVELOPERS
1.4 DEMONSTRATION PARTICIPANTS
1.5 DEMONSTRATION SITES
1.6 DEMONSTRATION SCHEDULE
2 DEMONSTRATION RESPONSIBILITIES AND COMMUNICATION
2.1 DEMONSTRATION PARTICIPANTS AND ROLES
2.2 SPECIFIC RESPONSIBILITIES
2.3 COMMUNICATION
3 PREDEMONSTRATION ACTIVITIES
3.1 IDENTIFYING DEVELOPERS
3.2 SELECTING SITES
3.3 CONFIRMATORY LABORATORY AND ANALYTICAL METHODS
3.4 PREDEMONSTRATION SAMPLING AND ANALYSIS
4 TECHNOLOGY DESCRIPTIONS
4.1 TN SPECTRACE 9000
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4.1.1 Background Information
4.1.2 Equipment and Accessories
4.1.3 General Operating Procedures
4.1.4 Training and Maintenance
4.1.5 Testing Time and Cost
4.2 X-MET 920
4.2.1 Background Information
4.2.2 Equipment and Accessories
4.2.3 General Operating Procedures
4.2.4 Training and Maintenance
4.2.5 Testing Time and Cost
4.3 MAP SPECTRUM
4.3.1 Background Information
4.3.2 Equipment and Accessories
4.3.3 General Operating Procedures
4.3.4 Training and Maintenance
4.3.5 Testing Time and Cost
4.4 SEFA-P ANALYZER
4.4.1 Background Information
4.4.2 Equipment and Accessories
4.4.3 General Operating Procedures
4.4.4 Training and Maintenance
4.4.5 Testing Time and Cost
4.5 XL SPECTRUM ANALYZER
4.5.1 Background Information
4.5.2 Equipment and Accessories
4.5.3 General Operating Procedures
4.5.4 Training and Maintenance
4.5.5 Testing Time and Cost
4.6 TN SPECTRACE LEAD ANALYZER
4.6.1 Background Information
4.6.2 Equipment and Accessories
4.6.3 General Operating Procedures
4.6.4 Training and Maintenance
4.6.5 Testing Time and Cost
4.7 ATX-100
4.7.1 Background Information
4.7.2 Equipment and Accessories
4.7.3 General Operating Procedures
4.7.4 Training and Maintenance
4.7.5 Testing Time and Cost
4.8 SEFA-Px ANALYZER
4.8.1 Background Information
4.8.2 Equipment and Accessories
4.8.3 General Operating Procedures
4.8.4 Training and Maintenance
4.8.5 Testing Time and Cost
5 DEMONSTRATION SITE DESCRIPTIONS
5.1 ASARCO SITE
5.1.1 Site History
5.1.2 Site Characteristics
5.2 RV HOPKINS SITE
5.2.1 Site History
5.2.2 Site Characteristics
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6 SAMPLING PLAN
6.1 SAMPLING AND FIELD ANALYSIS OPERATIONS
6.2 COMMUNICATIONS, DOCUMENTATION, AND EQUIPMENT
6.3 QUALITY ASSURANCE/QUALITY CONTROL REQUIREMENTS
6.4 HEALTH AND SAFETY PROCEDURES
6.5 SAMPLE COLLECTION PROCEDURES
6.5.1 Sampling Locations
6.5.2 Soil Sampling Procedures
6.5.3 Sample Storage, Packaging, and Shipping
6.5.4 Decontamination
6.5.5 Schedule
7 EXPERIMENTAL DESIGN
7.1 OBJECTIVES
7.2 FACTORS TO BE CONSIDERED
7.2.1 Qualitative Factors
7.2.2 Quantitative Factors
7.3 SAMPLING DESIGN
7.4 STATISTICAL ANALYSIS
7.4.1 Intramethod Comparisons
7.4.2 Intermethod Comparisonsl
7.4.3 Matrix and Sample Preparation Studies
7.4.4 Software
8 QUALITY ASSURANCE PROJECT PLAN
8.1 PURPOSE AND SCOPE
8.2 QUALITY ASSURANCE RESPONSIBILITIES
8.3 DATA QUALITY PARAMETERS
8.3.1 Precision
8.3.2 Accuracy
8.3.3 Representativeness
8.3.4 Completeness
8.3.5 Comparability
8.4 CALIBRATION PROCEDURES, QUALITY CONTROL CHECKS, AND CORRECTIVE ACTION
8.4.1 Initial Calibration Procedures
8.4.2 Continuing Calibration Procedures
8.4.3 Method Blanks
8.4.4 Laboratory Control Samples
8.4.5 Matrix Spike Samples
8.4.6 Performance Evaluation Samples
8.4.7 Duplicate Samples
8.5 DATA REDUCTION, VALIDATION, AND REPORTING
8.5.1 Data Reduction
8.5.2 Data Validation
8.5.3 Data Reporting
8.6 CALCULATION OF DATA QUALITY INDICATORS
8.7 PERFORMANCE AND SYSTEM AUDITS
8.7.1 Performance Audit
8.7.2 On-Site System Audits
8.7.3 Secondary QC Laboratory
8.8 QUALITY ASSURANCE REPORTS TO MANAGEMENT
8.8.1 Monthly Reports
8.8.2 Audit Reports
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9 DATA MANAGEMENT AND ANALYSIS
9.1 LABORATORY DATA MANAGEMENT ACTIVITIES
9.1.1 Moisture Content Data Management
9.1.2 Qualitative and Quantitative Analyses and Evaluations
9.1.3 Technology Data Management
10 HEALTH AND SAFETY PLAN
10.1 HEALTH AND SAFETY PLAN ENFORCEMENT
10.1.1 Project Manager and Field Site Supervisor
10.1.2 Health and Safety Director
10.1.3 Site Health and Safety Officer
10.2 VISITORS
10.3 DEMONSTRATION-SPECIFIC HAZARD EVALUATION
10.4 EXPOSURE PATHWAYS
10.4.1 Inhalation
10.4.2 Dermal Contact
10.4.3 Ingestion
10.5 HEALTH EFFECTS
10.6 PHYSICAL HAZARDS
10.7 TRAINING REQUIREMENTS
10.8 PERSONAL PROTECTION REQUIREMENTS
10.8.1 Levels of Protection
10.8.2 Protective Equipment and Clothing
10.8.3 Limitations of Protective Clothing
10.8.4 Duration of Work Tasks
10.8.5 Respirator Selection, Use, and Maintenance
10.9 MEDICAL SURVEILLANCE
10.9.1 Health Monitoring Requirements
10.9.2 Documentation and Record keeping 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
11 DELIVERABLES
11.1 DEMONSTRATION WORK PLAN
11.2 DEMONSTRATION PLAN
11.3 TECHNOLOGY EVALUATION REPORT
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11.4 INNOVATIVE TECHNOLOGY EVALUATION REPORT
11.5 TECHNOLOGY BRIEFS
11.6 OTHER REPORTS
REFERENCES
Appendix A
COMMENTS FROM DEMONSTRATION PARTICIPANTS ON THE DRAFT DEMONSTRATION PLAN
AND PRC'S RESPONSES
FIGURES
2-1 ORGANIZATIONAL CHART
5-1 ASARCO SITE LOCATION MAP
5-2 RV HOPKINS SITE LOCATION MAP
6-1 SAMPLE PREPARATION AND ANALYSIS FLOWCHART
8-1 SAMPLE ANALYSIS RECORDING FORM FOR FPXRF IN SITU TECHNOLOGIES
8-2 SAMPLE ANALYSIS RECORDING FORM FOR PRECISION FPXRF IN SITU TECHNOLOGIES
8-3 SAMPLE ANALYSIS RECORDING FORM FOR FPXRF INTRUSIVE TECHNOLOGIES
8-4 SAMPLE ANALYSIS RECORDING FORM FOR PRECISION FPXRF INTRUSIVE TECHNOLOGIES
8-5 SAMPLE PREPARATION TRACKING FORM
8-6 CONFIRMATORY LABORATORY SAMPLE PACKAGING TRACKING FORM 97
10-1 RV HOPKINS SITE HOSPITAL ROUTE MAP
10-2 ASARCO SITE HOSPITAL ROUTE MAP
TABLES
1-1 TECHNOLOGY CAPABILITIES
1-2 DEMONSTRATION PARTICIPANTS
3-1 SURVEY OF POTENTIAL DEMONSTRATION SITES
4-1 RADIOISOTOPE SOURCE SUMMARY
4-2 TECHNOLOGY SPECIFICATIONS
5-1 MAXIMUM CONCENTRATION OF CONTAMINANTS IN SURFACE
DURING PREDEMONSTRATION SAMPLING ACTIVITIES Asarco Site
5-2 MAXIMUM CONCENTRATION OF CONTAMINANTS IN SURFACE
DURING PREDEMONSTRATION SAMPLING ACTIVITIES RV Hopkins
6-1 SAMPLE COLLECTION AND ANALYSIS STRATEGY
6-2 LIST OF FIELD EQUIPMENT NEEDED
7-1 CRITERIA FOR DATA QUALITY CHARACTERIZATION
8-1 SW-846 METHOD 601 OA SOIL SAMPLE DETECTION LIMITS
8-2 SW-846 METHOD 601 OA CALIBRATION PROCEDURES, METHOD-SPECIFIC QC
REQUIREMENTS, AND CORRECTIVE ACTION
10-1 HAZARDOUS MATERIALS POTENTIALLY PRESENT AT THE DEMONSTRATION SITES
10-2 WORK TASK HAZARD ANALYSIS
APPROVAL SIGNATURES
The purpose of this demonstration is to evaluate field portable x-ray fluorescence technologies in how
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.
SOIL SAMPLES COLLECTED
SOIL SAMPLES COLLECTED
Site
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FINAL DEMONSTRATION PLAN
Eric Hess, PRC Date
Project Manager
Patrick Splichal, PRC Date
Lead Chemist
Harry Ellis, PRC Date
Statistician
Kathleen Homer, PRC Date
Quality Control Manager
Steve Billets, EPA EMSL Date
Program Manager/Technical Project Manager
Oliver Fordham, EPA OSW Date
Technical Advisor
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-Recovery Consultants, Inc.
John Moore Date
HNU Systems, Inc.
James Pasmore Date
Metorex, Inc.
Stephen Shefsky Date
Niton Corporation
Bill Boyce Date
Scitec Corporation
Margo Myers Date
TN Spectrace
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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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
cm3 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 lron-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
g/L Microgram per Liter
m 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
NEMA National Electrical Manufacturers Association
NIOSH National Institute of Occupational Safety and Health
NIST 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
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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
EXECUTIVE SUMMARY
This demonstration was developed under the U.S. Environmental Protection Agency's (EPA) Superfund
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
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operation. The performances of the FPXRF technologies will not be compared against each other.
Instead, their performances will be compared to the performances of 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 location 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 TER will
present objective results of the demonstration and provide supporting documentation. In addition, an
innovative technology evaluation report (ITER) will be prepared and published that summarizes the
findings presented in the TER. A separate ITER will be published for each developer. These reports will
help data users and technology reviewers assess the performance of each technology for possible use on
future site characterization or remediation projects at hazardous waste sites.
The November 1994 draft demonstration plan was made available to the demonstrates 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.
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XRF Chapter 1
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
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)
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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
1.1.3 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 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.
1.3 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.
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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 offices in
Regions 3, 7, and 10, several PRC offices, the confirmatory laboratory, the developers, and 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 be conducted at two sites: the RV Hopkins site in Davenport, Iowa, and the
Asarco Tacoma Smelter (Asarco) site in Tacoma, Washington.
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.
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TABLE 1-1
TECHNOLOGY CAPABILITIES
Technology In
Situ
ATX-100 Yes
SEFA-P Analyzer No
SEFA-Px Analyzer Yes
X-MET 920 (Si(Li) detector) Yes
X-MET 920 (gas-filled Yes
proportional
detector
XL Spectrum Analyzer Yes
MAP Spectrum Analyzer Yes
TN Spectrace 9000 Yes
TN Spectrace Lead Analyzer Yes
Intrusive
Yes
Yes
Yes
Yes
Yes
Yes
No
Yes
Yes
Developer
Enviro-Recovery
Consultants
HNU Systems, Inc.
HNU Systems, Inc.
Metorex, Inc.
Metorex, Inc.
Niton Corporation
Scitec Corporation
TN Spectrace
TN Spectrace
TABLE 1-2
DEMONSTRATION PARTICIPANTS
Agency/Company
Asarco
North 51st and Baltimore St.
Tacoma, WA 98407
(Enviro-Recovery Consultants, Inc.
H 50 South 600 East, Suite 5B
Salt Lake City, UT 84102
EPA Environmental Monitoring
Systems
(Laboratory
944 East Harmon
Las Vegas, NV 89193
EPA Office of Solid Waste
(401 M St. SW
'Washington, DC 20460
EPA Region 7
[Resource Conservation and
[Recovery Act (RCRA) Iowa Section
[726 Minnesota Ave.
Kansas City, KS 66101
EPA Region 10
Superfund Section
h 200 Sixth Avenue
Point of Contact
-- Tom Aldridge, Environmental
Director
(206) 756-0203 (phone)
(206) 756-0250 (fax)
,-- Alan Seelos, President
1(801) 328-3659 (phone)
(801) 328-3672 (fax)
- Steve Billets, Program
Manager/Technical Project
(Manager
'(702) 798-2232 (phone)
(702) 798-2261 (fax)
-- Oliver Fordham, Technical
(Advisor
'(202) 260-4778 (phone)
(202) 260-0225 (fax)
- Brian Mitchell, EPA Contact for
RV Hopkins
1(913) 551-7633 (phone)
| (913) 551-7525 (fax)
-- Piper Peterson, Project Manager
(206) 553-4951 (phone)
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Seattle, WA 98101
HNU Systems, Inc.
160 Charlemont Street
[Newton Highlands, MA 02161-9987
Metorex, Inc.
1900 N.E. Division St., Suite 204
Bend, OR 97701
.Midwest Research Institute
(425 Volker Blvd.
Kansas City, Missouri 64110
Niton Corporation
74 Loomis Street, P.O. Box 368
Bedford, MA 01730-0368
PRC
(233 N. Michigan Avenue, Suite 1621
[Chicago, IL 60601
PRC
(650 Minnesota Avenue
[Kansas City, KS 66101
RV Hopkins
743 Schmidt Rd.
Davenport, IA 52808
Scitec Corporation
415 N. Quay
Kennewick, WA 99336-7735
TN Spectrace
2555 N. IH 35 P.O. Box 800
'Round Rock, TX 78680-0800
- John Moore, Director of
Marketing
617) 964-6690, Ext. 106 (phone)
617) 558-0056 (fax)
- James R. Pasmore, Director of
Sales and Marketing
800) 229-9209 (phone)
503) 385-6750 (fax)
Gary Wester, Staff Chemist
816) 753-7600 ext. 1713 (phone)
816) 753-5359 (fax)
Stephen Shefsky, Physicist
617) 275-9275 (phone)
617) 275-2397 (fax)
Harry Ellis, Lead Statistician
312) 856-8700 (phone)
312) 938-0118 (fax)
- 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)
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)
Harold Abdo, President
319) 323-5419 (phone)
- Bill Boyce, Vice President of
Research & Development
800) 466-5323 (phone)
509) 735-9696 (fax)
Margo Myers, Product Manager
512) 388-9'l 00 (phone)
512) 388-9200 (fax)
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XRF 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 demonstration.
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 OSWwill 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.
2.2 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
Performing 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, field-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
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.
FIGURE 2-1 ORGANIZATIONAL CHART
(not available)
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XRF 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.)
The site had to be accessible to two-wheel 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.
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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. 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
601 OA. 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 activity. All 39 soil samples were submitted to MRI for confirmatory analysis by
SW-846 Methods 3050A and 601 OA. Ten percent of the samples were also analyzed by SW-846
draft Method 3052 and SW-846 Method 601 OA.
These samples were collected from a wide range of concentrations and soil textures. PRC collected
surface soil samples (0 to 1 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:
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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 operating 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
TABLE 3-1
SURVEY OF POTENTIAL DEMONSTRATION SITES
Site Name and
Location
St. Charles Metal
Finishing Company
St. Charles,
Missouri
Asarco Lead
Smelter
El Paso, Texas
Asarco Lead
Smelter
Tacoma,
Washington
RV Hopkins Site
Davenport, Iowa
Pacific Activities
Limited (PAL) Site
Davenport, Iowa
Smeltertown
Salida, Colorado
East Helena
Superfund Site
Helena, Montana
Silver Bow Creek
Butte, Montana
Wicks Smelter Site
Helena, Montana
West Dallas Lead
Site
Dallas, Texas
Border Steel
El Paso, Texas
Contact
Status and Comments
Ruben McCullers-EPA Plating facility, already characterized, moist
Region 7 (913) 551-
7455
Traci Fambrou-EPA
Region 6 (214) 665-
2246
Piper Peterson-EPA
Region 10 (206) 553-
4951
Brian Mitchell-EPA
Region 7 (913) 551-
7633
Jeff Weatherford-EPA
Region 7 (913) 551-
7695
Victor Ketellaper-EPA
Region 8 (303) 294-
7146
Scott Brown-EPA
Region 8 (406) 449-
5720
Neil Marsh-Montana
Department of Health
and Environment
(406) 444-1420
Dave Donahue-PRC
(406) 442-5588
Stan Hitt-EPA Region
6 (214) 665-6735
Traci Fambrou-EPA
Region 6 (214) 665-
climate; lead, chromium, zinc, cadmium;
access not granted
Lead, arsenic, some characterization, dry
climate, middle of Consent Order
negotiations; EPA does not want site used
National Priorities List (NPL) site, arsenic,
lead, copper, already characterized, moist
climate; access granted
Active drum recycling facility, partially
characterized, high lead and chromium
contamination; access granted
Abandoned nickel-alloy pig manufacturer,
partially characterized, high concentrations
of all target analytes except arsenic; access
denied
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
Asarco smelter, lead, arsenic, cadmium,
zinc, copper; EPA does not want
demonstration at this site
Well characterized, mine tailings along a
creek and river, ARCO facility, tailings
generally saturated
Lead smelter, some characterization, lead,
arsenic, zinc, and copper; Bureau of Mines
site; likely snow covered for demo
Lead smelter, some characterization,
primarily residential contamination, mostly
remediated
Lead smelter, facility going bankrupt, only
known contamination associated with an
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2246
Kennecott Eva Hoffman-EPA
Remediation Region 8 (303) 293-
Salt Lake City, Utah 1534
Tri-state Mining
Jasper County,
Missouri
Tucson
International Airport
Tucson, Arizona
Oracle Ridge
Mining Partners
Arizona
Portland Cement
Utah
Apache Powder
Arizona
Phelps-Dodge
Reduction Works
Bisby, Arizona
ILCO Lead Smelter
Alabama
Sherwin Williams
Coffeyville, Kansas
Cleveland Mill
Silver City, New
Mexico
Reeves
Southeastern
Corporation
Tampa, Florida
Yakima Plating
Yakima,
Washington
Goldere Junkyard
Morristown, New
Jersey
NAVBASE
Charleston
Charleston, North
Carolina
Tar Creek Site
Oklahoma
Eagle Picher
Smelter
Joplin, Missouri
Peerless Plating
Mark Doolan-EPA
Region 7 (913) 551-
7169
Dennis Gott-U.S. Air
Force (513) 255-0258
Susan Johnson-EPA
Region 9 (415) 744-
2361
No contact
Andrea Benner-EPA
Region 9 (415) 744-
2361
Caroline Douglas-EPA
Region 9 (415) 744-
2343
Kim Lanterman-EPA
Region 4
Mark Matthews-EPA
Region 7 (913) 551-
7635
Kathleen Aisling-EPA
Region 6 (214) 665-
8500
Anita Davis-EPA
Region 4 (404) 347-
5054
Joe Mollusky-PRC
(206) 624-2692
on-site landfill; access denied
Many subsites, old cobalt refinery, already
characterized, lead, arsenic, cadmium,
copper, cobalt, cold and dry climate; access
granted; likely snow covered during demo
Some characterization, lead, moist
environment; access granted; too limited
contaminant constituents
Former plating operation, chrome waste in
unlined pond, wastes have been capped,
dry environment
Only copper and zinc contamination; site
has been remediated
Some characterization, too low metals
concentrations
Well characterized, too low metals
concentrations; access could be a problem
NPL site; site has been remediated
Lead and arsenic, NPL site, wet climate;
access denied
Lead, zinc, barium, residential
contamination, moist environment, limited
area of gross contamination
EPA does not want a demonstration at this
site
Electroplating operation, contamination in
lagoons that have not been drained
Site has been remediated
Dennis Santella-EPA Site does not have target analytes in high
Region 2 (212) 264-
8677
Todd Haverkast-
EnSafe (803) 747-
7937
Nowell Bennet-EPA
Region 6 (214) 665-
8514
Mark Doolan-EPA
Region 7 (913) 551 -
7169
Mike Johnson-PRC
enough concentrations for this
demonstration
Site includes a former abrasives blasting
area; contamination in this area is too low
for the demonstration
This mining area is contaminated with lead
and zinc; access is granted; not sufficient
constituent variety
This is part of the Tri-state mining site, the
contaminants are lead and zinc; access is
granted; not sufficient constituent variety
Well characterized, sandy soil, lead,
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Muskegon,
Minnesota
Asarco Lead
Smelter
Glover, Missouri
Eagle Picher
Smelter
Henryetta,
Oklahoma
National Zinc
Bartlesville,
Oklahoma
Harbor Island
Tacoma,
Washington
Bunkerville Mining
District
Southeastern
Nevada
Boss Mine
Clark County,
Nevada
Weldon Springs,
Missouri
Mare Island Naval
Shipyard-IR04
Vallejo, California
Hanover
Whitewater Mine
New Mexico
Helvetia Mining
District
Arizona
Phelps Dodge
Smelter
Ajo, Arizona
Smelter Site
Cortland Gleason,
Arizona
Combined Metals
Twilla, Utah
Midvail Superfund
Site
Suburb of Salt Lake
(312) 856-8700
Kathy Flippin-MDNR
(314) 751-3176
Dennis Datin-ODEQ
(405) 271-7097
Scott Thompson-
ODEQ
(405) 271-7213
Keith Rose-EPA
Region 10
(206) 553-7721
Paul Lechler-Nevada
Bureau of Mines-
Geology
(702) 784-6691
Paul Lechler-Nevada
Bureau of Mines-
Geology
(702) 784-6691
Cecilia Tapia-EPA
Region 7
(913) 551-7733
Curt Enos-PRC
(913) 573-1827
Bert Gorrod-EPA
Region 6
(214) 665-6779
Rick Trapp-Arizona
Bureau of Geology
(602) 882-4795
Rick Trapp-Arizona
Bureau of Geology
(602) 882-4795
Rick Trapp-Arizona
Bureau of Geology
(602) 882-4795
No contact
No contact
chromium, zinc; access is possible; snow
covered during demo
High lead, copper, and zinc concentrations,
some characterization, moist site; access
MDNR was not interested in demo
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
Zinc, lead, and cadmium contamination, wet
site, remediation in progress, probably
finished by Spring 1995
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
Copper, chromium, nickel, no soil data only
data for ores and rocks, dry site
Copper, lead, zinc, gold, silver, platinum,
only data for ores and rocks, no soil data,
dry site
Limited constituent variety; only lead
present; wet site
Primarily chromium contamination, some
copper, lead, nickel, and zinc,
contamination in "green sands," well
characterized, wet site; access possible; too
low of contaminant concentrations for demo
No response to request for information
Lead, zinc, copper, possibly cadmium,
smelter on site, arid site, south of Tucson,
no analytical data; access may be a
problem
Coppermine, arid location, no analytical
data; little known about site
Lead and zinc smelter, good access, arid
site, no analytical data; little known about
site
No information
No information
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City, Utah
Indian Reservation
Santa Clara, New
Mexico
General Electric
Facility
Albuquerque, New
Mexico
Flagstaff Smelter
South of Salt Lake
City, Utah
Big River
Desloge-St.
Francois Co.
Missouri
Barb Everett-PRC
(505) 246-9192
Vince Malloy-EPA
Region 6
(214) 665-8313
Joel Hebdon-SAIC
(801) 539-0500
Paul Doherty-EPA
Region 7
(913) 551-7924
Metals concentrations too low; access may
be a problem
Lead contamination, soil sampling during
excavation, no information received on this
site
State lead, Superfund site, less than 20
acres, lead, arsenic, copper, zinc; dry, likely
snow covered during demo
Mine tailings, lead and zinc contamination,
NPL site; tailings stay wet, too limited
constituent variety
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XRF Chapter 4
TECHNOLOGY DESCRIPTIONS
This chapter describes the FPXRF technologies manufactured by each developer. 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). Atypical emission pattern, also called an emission spectrum,
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-alpha (10.549 keV), 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 M
-------
shell emissions of a target metal, the detection sensitivity of the XRF analysis is increased. XRF
technologies with x-ray tube sources can tune 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 analytes. For example, using an lron-55
(Fe5) 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.
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.
The MCA is used to collect and manipulate the data. The MCA receives pulses from the detector
and 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.
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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
Spectrace 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
that 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 uses
three radioactive isotopes, Fe55, Cd 09, 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 the 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 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
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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 completely sealed with rubber gaskets and can be
decontaminated with soap and water.
Equipment/Optional Accessories/Instrument Specifications
Equipment
The standard TN Spectrace 9000 system includes:
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
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1 roll 6.0 micrometers (m) 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)
"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 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 Alternating Current (AC) electricity.
Operating Temperature: 0 to 49 C (32 to 120 F)
Storage Temperature: -40 to 40 C (-40 to 104 F)
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 (analyzes 25 elements in soil with each measurement)
2. Fine-Mesh Soils (for finely ground and cupped soils, 100 mesh or smaller)
3. Thin Samples (25 elements on air filters, 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
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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 full, 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.
The main menu selection displays the application name, revision date, exposure time for each
source, 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 vary. Source exposure times for soil samples typically vary from 60 to 300
seconds. Generally, the metals detection limit is reduced by 50 percent for every four-fold increase
in source exposure time. This 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
spectra. 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 pre-operational 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 response of the technology, which affects quantitation and
detection. The blank sample check should be conducted at the beginning of each day, after an
energy 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
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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.
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 $1,000 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 radioactive 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.
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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 time to meet project data quality objectives (DQO), as
well as project schedules. When analyzing soils that are in areas of high contaminant
concentrations at a site, 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 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
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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. 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
Am These isotopes are in the form of an 8-mm-diameter by 5-mm-thick capsule. The suggested
dual source configurations are Fe55 and Cd109, or Cd109 and Am241. The detector is environmentally
sealed by a 25-mm-diameter window of Kaptonฎ 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 co-processor
- 2 megabytes random access memory
- 80-megabyte hard disk
- Video graphics array (VGA) graphics
- 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 backscatter and
fundamental parameters related to instrument backscatter. The latter of the two is a standardless
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 associated 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 measurements. The operator can store all analysis
output to the hard disk by opening the log file. The x-ray emission spectrum from unknown samples
also can be displayed. The horizontal axis of the spectrum is calibrated in keV and the vertical axis
is the intensity of the peak measured in counts. A peak has to fall within a specific keV range to be
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.
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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.
4.2.5 Testing Time and Cost
The developer states that it is possible to analyze one soil sample in 1 to 5 minutes with the X-MET
920 equipped with the Si(Li) detector. This time includes the time required for any sample
preparation, such as homogenization, drying, or grinding that may be needed. The developer states
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 soil samples in an 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 in 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
industrial 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 Cd109 and 30 mCi Am 41 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
options. The first is a 3-day training class offered at Metorex's facility at $685 per person plus travel
and lodging expenses. On-site training classes also are available. Metorex must be contacted 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 Cd109 source every 1.5 to 2 years. This costs $4,500
with a $500 disposal fee for the old source.
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.
4.3.1 Background Information
The MAP Spectrum Analyzer was originally developed by Scitecto 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.
4.3.2 Equipment and Accessories
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.
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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
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 (C) 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 mm2
Source Shutter: Heavy tungsten and designed to house:
(1) Co57 - 40 millicuries
(2) Am241 - 150 millicuries
(3) Cd109 - 80 millicuries
Safety: Removable on-off key for source shutter
Connector: Breech-lok
Grip: Rubber-cushioned pistol type
Construction: 6061 aluminum
Front Face Plate: Aluminum 0.5-mm thick
Beryllium Window: 0.5-mm thick
4.3.3 General Operating Procedures
Analysis with the MAP Spectrum Analyzer consists of placing the ambient scanner in direct contact
with the sampling medium and opening a shutter with a key. The opening of the shutter exposes the
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.
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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 particle 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.
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 sample 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 Maintenance
A license or permit to possess, or operate a technology that uses ionizing radiation produced from
the radioactive decay of a source is required to possess or operate the MAP Spectrum Analyzer.
Each state is responsible for issuing such licenses. An operator must be trained by Scitec in the
principles of radiation and in the safe operation of the MAP Spectrum Analyzer to secure a license.
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Scitec 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
parts, 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. AcuTransferฎ
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.
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.
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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.
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.
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 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-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
voltage 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
in this mode, a mini-cassette tape is used to record numerical and spectral data. The data from
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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. The major 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 within the Setup menu allows the operator
the modify the report format, as well as create a hard copy and disk file of the report.
The Acquire menu allows the operator to enter the sample name and set the source exposure time
for each sample. Up to four samples with acquisition times for up to three sources can be entered.
This routine sets up the SEFA-P Analyzer, acquires and stores spectral data, prompts the user to
select the appropriate sample and source, and automatically runs the programs which were
selected in Acquire menu. Quantitative analysis times (source exposure times) of 300 to 500
seconds are typical for soil analysis. The operator must make sure that the proper source and
sample are in the correct position in the sample chamber prior to analysis. The F2 function key is
pressed on the PC to initiate the 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 analysis.
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.
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.
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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
interlocked 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.
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 Cd 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-volt 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.
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.
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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
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 $11,990. 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.
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 Cd1 9 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
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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
from a measurement. A maximum of 600 sets of results and 100 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
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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 m 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)
"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.
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)
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3. Lead in Surface Dust
4. Lead in Air Filters
5. Lead in Paint Chips
Once the application is selected, the analysis 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
parameters 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 Analyzer software can provide for a site-specific calibration to model a given
suite of standards.
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
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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 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.
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.
cc ฆi nq
3. Open the probe window and expose the sample or location to either the Fe or Cd 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.
4.7.4 Training and Maintenance
ERC provides the ATX-100 as a service, and thus, it does not have a training program for non-ERC
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 or $750, respectively. The
cost for using the ATX-100 is billed at a weekly or monthly rate, $1,500 or $4,500, respectively.
Equipment and personnel mobilization is billed at $0.45 per mile. Per diem for the operator is billed
at $75 per day. Other sample preparation equipment, such as stainless steel-sieves, mortar and
pestles, sample grinders, sample cups, microwave ovens, and generators can be rented or
purchased from ERC.
4.8 SEFA-Px Analyzer
This section presents information on the background, apparatus, general operating procedures,
training and maintenance requirements, and cost of the SEFA-Px Analyzer.
4.8.1 Background Information
HNU developed the SEFA-Px Analyzer to provide simple and rapid in situ or intrusive analysis of
lead in paint, dust, or soil. The SEFA-Px Analyzer was introduced into the market in February 1995.
4.8.2 Equipment and Accessories
The basic SEFA-Px Analyzer consists of an analysis probe for in situ and intrusive measurements,
a single radioisotope sources, a liquid nitrogen cooled Si(Li) detector, preamplifier, a MCA, and a
battery charger. The probe is 13 inches long, 4.5 inches wide, 10 inches tall, and weighs 7 pounds.
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
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 on 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.
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 dewarand PC
(optional). These items vary in cost depending on the place of purchase.
TABLE 4-1
RADIOISOTOPE SOURCE SUMMARY
Source
Activity
(mCi) I
Half Life
(Years)
Excitation Energy
(keV)
Elemental Analysis Range
Fe55
20-50
2.7
5.9
Sulfur to
chromium
Molybdenum
to barium
K Lines
| L Lines
Co57
40 ,
0.75
121.9 and 136
Cobalt to
cerium
Barium to lead
I K Lines
| L Lines
Cd109
5-30
1.3
22.1 and 87.9
Calcium to
rhodium
Tantalum to
lead
Barium to
uranium
K Lines
| K Lines
| L Lines
Am241
5-30
458
26.4 and 59.6
Copper to
thulium
Tungsten to
uranium
K Lines
, L Lines
Cm244
60-100
17.8
14.2
Titanium to
selenium
Lanthanum to
lead
K Lines
| L Lines
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TABLE 4-2
TECHNOLOGY SPECIFICATIONS
Technology
ATX-100
SEFA-P Analyzer
SEFA-Px Analyzer
X-MET 920 (Si(Li) Detector)
X-MET 920 (gas-filled
proportional detector)
XL Spectrum Analyzer
MAP Spectrum Analyzer
TN Spectrace 9000
TN Spectrace Lead Analyzer
Detector
No information
Si(Li)
Si(Li)
Si(Li)
Sources
109
Feฐฐ, Cd
Fe55, Cd109, Am241
Cd109
Fe55, Cd109, Am241
Gas Filled Proportional Feฐ5, Cd109, Am241
Silicon Pin-Diode Cd
Si(Li)
Hgl2
Hgl2 Cd
109
Co57, Am241,Cd109
Fe55, Cd109, Am241
109
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XRF 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. 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.
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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.
5.2.1 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
Berry 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. 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 zinc
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.
FIGURE 5-1 ASARCO SITE LOCATION MAP
(not available)
FIGURE 5-2 RV HOPKINS SITE LOCATION MAP
(not available)
TABLE 5-1
MAXIMUM CONCENTRATION OF CONTAMINANTS IN SURFACE SOIL SAMPLES
COLLECTED DURING PREDEMONSTRATION SAMPLING ACTIVITIES
Asarco Site
Tacoma, Washington
Minimum ( Maximum
Concentration ( Concentration
of | of Contaminant (
Contaminant | (mg/kg)
(mg/kg) |
Contaminant
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
Minimum Maximum
j Concentration of | Concentration j
Contaminant ( of Contaminant i
Contaminant
(mg/kg)
(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
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SAMPLING PLAN
XRF Chapter 6
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 OSWfor validation at the conclusion of the
demonstration. To meet this objective, EPA OSWhas 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.
Approximately 100 soil samples will 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 all 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 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 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 601 OA, 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 601 OA. 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 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 601 OA) 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 601 OA. 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.
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 that 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 provided 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 samples
analyzed by the confirmatory laboratory and by each of the FPXRF technologies are subsamples from a
homogeneous 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.
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.
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6.5 SAMPLE COLLECTION PROCEDURES
Sampling personnel will collect and homogenize samples using the procedures described below. All 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 made. 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 most 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 for
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 these technologies. The
additional sampling is required to increase the statistical power of this range of 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 orfiberboard 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
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technology measurements. Once these measurements are complete at a sampling point, PRC will
remove surface soil samples in the square areas to a 1-inch depth. The surface soil samples will be
removed and collected by using a hand trowel or putty knife to scrape the soil surface. Sampling
personnel will comply with all health and safety requirements in the HASP (Chapter 10). All soil 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 zip-lock bag. Before soils
are homogenized, rocks, pebbles, sticks, organic matter, and foreign debris will be removed from the
sample bag. Once the sample is placed in the sample bag, it will be handled as described in Section 6.1.
6.5.3 Sample Storage, Packaging, and Shipping
After collection and until analysis, all samples will be stored in coolers. Custody of samples will be
maintained as discussed in Section 6.2 and according to the requirements of applicable sections of PRC
SOP No. 18 "Sample Custody."
Samples to be shipped to the confirmatory laboratory will be packaged and shipped according to the
sample packaging and shipment requirements of PRC SOP No. 19 "Packaging and Shipping Samples."
Technical requirements for holding times for soil samples being analyzed for metals according to SW-846
methods have not been established. The recommended holding time prior to extraction and analysis is 6
months. For the purpose of this demonstration, the samples will be extracted and analyzed within 30 days
of their receipt by the confirmatory laboratory. Analyzed samples will be stored for 90 days pending data
reduction. If any samples are identified as outliers, those samples will be reanalyzed by a second
confirmatory laboratory (QA laboratory). Outliers will be identified by statistical analysis (Chapter 7) or by
failure to meet QA/QC requirements (Chapter 8.) The QA laboratory will be different from the original
confirmatory laboratory, and it will be identified prior to the implementation of this demonstration plan.
Analytical data produced by the QA laboratory will replace original confirmatory laboratory results if the
QA laboratory meets all the QA/QC conditions specified in the QAPP.
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). IDWwill 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.
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TABLE 6-1
SAMPLE COLLECTION AND ANALYSIS STRATEGY
Step Sample Preparation
1. j 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.3
2. Remove the upper 1 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
1.a
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.
FPXRF Analysis
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.
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.
Analyze this material with each FPXRF
intrusive technology. Attempt to use the
same sample cup for each analysis.
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
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
Analyze this material with each FPXRF
intrusive technology. Attempt to use the
same sample cup for 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
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measurements were collected in Step 1
above.3
Collect field duplicates at a 1:10 ratio.0
Dry 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.
percent of these samples also will be
extracted and analyzed by SW-846
Methods 3052 and 601 OA. 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 601 OA. 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 601 OA.
5. j Analyze PE samples.01
Archive approximately 20 grams of every
sample for potential submittal to the QA
laboratory.
j 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."
Notes:
a Precision determination data.
b Metals volatization check
0 Homogenization check data.
d Calibration check and drift monitoring data.
TABLE 6-2
LIST OF FIELD EQUIPMENT NEEDED
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
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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-mm camera
Film
Miscellaneous
Barricade tape (yellow, caution)
Paper towels
Garbage bags
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XRF Chapter 7
EXPERIMENTAL DESIGN
7.0 EXPERIMENTAL DESIGN
This section discusses the objectives of the demonstration, the factors that must be considered to meet
the performance objectives, and the statistical and other means that SNL will use to evaluate the results
of the demonstration.
The primary objectives of this demonstration are to evaluate developer claims for the use of field
transportable GC/MS technologies for use in the analysis of VOCs.
The following areas will be evaluated:
Their performance relative to conventional analytical methods (e.g., confirmatory laboratory)
accuracy and precision
The logistical and economic resources necessary to operate these technologies in a field
environment
To obtain verified performance data on the GC/MS technologies that may be provided to potential
technology users
Verify performance claims
Secondary objectives for this demonstration are evaluating:
Data quality
Field portable GC/MS technologies for their reliability
Ruggedness
Cost
Range of usefulness
Ease of operation
7.1 Vendor Claims
7.1.1 Bruker-Franzen Analytical
1. Air and water samples-analysis time 8-10 minutes per sample; throughput time of 6 samples per hour
Accuracy-35% of the confirmatory laboratory value
Precision-30% RPD (Relative Percent Differences)
Completeness-96%
2. Soil samples-analysis time 7-9 minutes headspace; throughput time of 7-8 samples per hour
Accuracy-35% of the confirmatory laboratory value
Precision-35% RPD
Completeness-96%
3. Set-up time of instrument 60 minutes.
4. Shut-down time of instrument 5 minutes
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5. Data presented after each sample run
7.1.2 Teledyne Electronic Technologies
1. Compact, lightweight, and easily transportable mass spectrometer. Low power consumption (will
operate under battery power). No cooling water or other utilities required for field use.
2. Set up time for Ion Trap mass spectrometer system 30 min. or less.
3. Direct sampling inlet system is time and cost effective by elimination the need for extensive sample
handling and pretreatment, the use of trapping sorbents, and expensive, bulky, gas chromatographic
equipment.
4. Samples analyzed by Direct Sampling techniques at the rate of 1 sample every 10 min. or less.
5. MS Windows PC based data acquisition and storage system will produce stored sample data within 1
min. after sample run and quantitative results within 5 min. after sample run.
7.1.3 Viking Instruments Corporation
1. Precision-RPD < 25%
2. Accuracy-within 30% of confirmatory laboratory value
3. Completeness-95% of known target compounds detected.
4. Sample-throughput which depends on methodology. Samples requiring concentration may run for 30
minutes apiece. Direct injections average 10-15 min. apiece. Direct membrane analyses can be
performed several times per minute.
5. Calibration-the instrument will be initially calibrated before arriving at the demonstration site and daily
calibration samples will be analyzed.
6. Data-quantitative results will be submitted at the end of the demonstration. The data analysis software
is also capable of full, detailed reports which include ion chromatograms, spectra, library searches, and
calibration reports. Detailed data may be submitted when time permits.
7. Deployment-the Viking SpectraTrak can be set up and ready to run within 30 minutes.
7.2 Objectives
The primary objectives of this demonstration are to evaluate GC/MS technology in the following areas: (1)
how well it performs relative to conventional analytical methods, (2) verify each developer's performance
claims, and (3) the logistical and economic resources necessary to operate the technology. Secondary
objectives for this demonstration are to evaluate GC/MS technology for its: (1) reliability, ruggedness,
cost, and range of usefulness, and (2) data quality, and ease of operation. The performance will be
compared to the performance of conventional analytical methods used in performing site characterization
activities.
7.3 Factors to Be Considered
This section discusses factors that were 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. The
importance of these factors and ways of measuring their effects are discussed when warranted.
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7.3.1 Qualitative Factors
Some factors, while important, are difficult or impossible to quantify. These are considered qualitative
factors. Important factors that cannot easily be quantified are the portability of a technology and the
logistical requirements necessary for using it. The weight and size of each technology will be documented
per developer's specifications. An evaluation of the logistical requirements will include an assessment of
the technology's power source, operator's level of training, routine instrument maintenance, and the need
for other equipment or supplies, such as a computer to operate the technology. Each operator will record
notes in a field logbook on the logistical requirements for the technology.
Demonstration procedures will simulate routine field conditions as much as possible. For the purpose of
this demonstration, vendors will supply their own personnel to set up and operate the field equipment.
Operators will have prior experience with the GC/MS technologies they will use in the demonstrations.
7.3.2 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 susceptibility to environmental conditions. One
environmental factor is change in temperature. Temperature change effects will be monitored by
conducting repeated measures of one or more media over the course of each day at the demonstration
site. Air temperature will be recorded hourly during operation. SNL will use PE samples for this
demonstration. This will produce data that can be used to identify trends in the effect of changing
temperature on technology drift.
The cost of using GC/MS technology is another important factor. Cost includes expendable supplies such
as helium, non-expendable equipment, labor, licensing agreements, operator training costs, and waste
disposal costs. These costs will be tracked during the demonstration. The cost per sample will then be
computed. Sample throughout will also be documented and will have an effect on cost per sample.
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
evaluated. Instrument performance near 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
GC/MS technologies and the confirmatory laboratory for analysis. Results from the confirmatory
laboratory will be considered the reference values of the analytes in each sample. Where the duplicate
samples exist, the concentrations for the duplicates will be averaged unless the QA/QC indicates a
problem with one of the samples. 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 of that compound.
Many analytical methods can have significant "operator effects" in which individual differences in operator
technique have a significant effect on the numerical result. For the GC/MS technologies being
demonstrated, the primary anticipated operator effect will be the variation in sample presentation to the
developers and sample introduction which is instrument dependent. The potential also exists for this type
of operator effect to occur in the confirmatory laboratory. To reduce the potential impact of measurement
technique variation, SNL will use site specific personnel to conduct the sampling. Each technology will be
operated by developer personnel.
The results from the technologies will be dependent on the quality of the data generated. Many factors
could affect the quality of the data generated. The following factors will be used in determining GC/MS
technologies' data qualities.
Method blanks will be used to evaluate technologies-induced contamination. An example of this
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contamination is residual build-up of VOCs in the capillary column, or detector saturation from highly
contaminated samples. Method blanks to be analyzed each day will consist of 99.9% nitrogen, soil
blanks, and water blanks. Method blank results will be tabulated and discussed in the TER.
Calibration check samples will be analyzed to assess instrument drift. Accuracy will be assessed by
analyzing two PE samples per media that contain known concentrations of VOCs. The PE samples for
these samples are PE samples generated for the EPA Superfund Analytical Program. The soil gas
samples will be NIST certified VOC standards. These samples will be analyzed by GEL at SRS and TA at
WAFB using GC/MS SW-846 Method 8260. The data generated by the laboratory or established
acceptance windows will be used to define mean concentrations and 95% confidence intervals for use in
evaluating the accuracy of the GC/MS technology.
7.4 Sampling Design
As described in the sampling plan (Section 6), the basis for the experimental design of the demonstration
is to validate/verify the performance of field transportable GC/MS technology. Two demonstration sites
were chosen to accurately assess the GC/MS technology. Descriptions and site geology is described in
Section 4.
The number of samples to be analyzed were determined using the following criteria:
Number of samples needed to make a meaningful decision regarding the validity of the performance
claims
Cost for confirmatory laboratory analysis
Time frame to conduct demonstration
Through-put time needed per sample
Personnel available to conduct demonstration
Number of samples to be analyzed at SRS is found in Table 3-1. Number of samples and concentration
levels for WAFB is in Table 3-2.
7.5 Statistical Analysis
Guidance for Data Quality Assessment EPA QA/G-9 will be used. A specific protocol of statistical
techniques to be used in the analysis of the demonstration data (Protocol II) is underdevelopment.
Statistical analysis will be performed on the data generated from the demonstrations. Basic statistical
approaches to be used in this demonstration are comparison tests, variability, comparability, accuracy,
and precision. Statistical calculations to be used for data analysis are found in Section 8.6.
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XRF 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.
8.1 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 601 OA "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 601 OA. 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 601 OA. Extraction methods SW-846 Method 3050A, draft Method 3052, and Method 601 OA, 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.
8.2 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.
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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 adding
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 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.
8.3.1 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 RSD between replicate sample measurements and the RPD of laboratory and field
duplicate samples.
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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 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 601 OA 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 601 OA 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 601 OA will
be evaluated through post-digestion laboratory duplicate samples. Extraction and analysis precision of SW-846 Method 601 OA will be evaluated
through pre-digestion laboratory duplicate samples.
A comparison of the FPXRF precision to the SW-846 Method 601 OA 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 control 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 601 OA field duplicate samples. This statistical comparison can determine if there is a significant
difference between the two means. If a significant difference does exist, an inference can be made which is that the lower mean value provides
better precision.
PE samples also will be used to determine SW-846 Method 601 OA 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 601 OA 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.
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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 601 OA 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 601 OA, and PE sample results which fall within
acceptance limits as published in SW-846 Method 601 OA or those generated through inter-laboratory analyses which have been published by
EPA or by PE sample suppliers.
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 601 OA.
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
Wlcoxon signed rank test of each FPXRF technology result to the SW-846 Method 601 OA 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 601 OA for an
additional check of comparability. Expected SW-846 Method 601 OA LRLs for target metals identified during the demonstration activities is
presented in Table 8-1.
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Soil sample drying and homogenization will be performed prior to FPXRF technology and SW-846 Method 601 OA analysis. Samples will be
reported on an "as received" basis by both the FPXRF technology and SW-846 Method 601 OA.
8.4 CALIBRATION PROCEDURES, QUALITY CONTROL CHECKS, AND CORRECTIVE ACTION
Calibration procedures, method-specific QC requirements, and corrective action associated with non-conformance QC for the FPXRF
technologies and the SW-846 Method 601 OA are described in the following subsections. Table 8-2 lists calibration procedures, method-specific
QC requirements, and corrective action for SW-846 Method 601 OA.
QC criteria for FPXRF technologies will be specified by each developer and are not available for tabulation, but will be noted by each technology
operator and included in the TER, ITER, and the draft SW-846 method for FPXRF technologies. Primary target metals that will be determined
using the FPXRF technologies and SW-846 Method 601 OA include: arsenic, barium, chromium, copper, lead, and zinc. Secondary target metals
for SW-846 Method 601 OA include: nickel, cadmium, antimony, and iron. Other metals may also be reported by both the FPXRF technologies and
SW-846 Method 601 OA.
Some of the metals which may be reported by SW-846 Method 601 OA can be affected by the extraction and analysis methods used. Antimony (a
secondary target metal) and silver form insoluble precipitants when mixed with the hydrochloric acid used for the SW-846 Methods 3050A and
3052 extraction techniques. Mercury may also form insoluble precipitants when mixed with hydrochloric acid, and due to its volatility may be lost
during sample extraction procedures. Antimony, silver, and mercury results provided by SW-846 Method 601 OA using extraction Methods 3050A
and 3052 may not meet all QA/QC criteria and can be coded and reported as estimated values.
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 by 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 metals. 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: (1) reanalysis of the QC sample, (2) re-extraction and
reanalysis of the QC sample, and if the re-extraction and reanalysis of the QC sample produces results which fall within the control limits, then (3)
re-extraction and reanalysis of the QC sample and the batch of samples associated with the QC sample.
When re-extraction 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.
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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.
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.
8.4.1 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 601 OA 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 sample 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) re-preparation of calibration
standards until the above criteria is met.
The validity of the initial calibration used for SW-846 Method 601 OA is verified through the use of the ICV standards. The ICV 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) re-preparation 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: (1) reanalysis
of the high-level calibration standard, (2) reanalysis of the initial calibration standards, and (3) follow manufacturer's recommendations for
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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 601 OA. 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) re-preparation 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
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 601 OA 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.
An 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 601 OA. 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 method blank sample, (2) re-preparation 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 not be used for the FPXRF technologies unless their use is recommended by the developer. However, if the developer does recommend
LCSs, their use will be performed following the developer's recommendations.
LCSs will be used for SW-846 Method 6010A. LCSs are a clean soil matrixto which a known concentration 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 action that must be taken if the above
criteria cannot be met include: (1) reanalysis of the LCS, (2) re-preparation of the LCS and all samples extracted along with the LCS, and (3)
reanalysis of the LCS and all associated samples.
8.4.5 Matrix Spike Samples
Matrix spike samples will not be used for the FPXRF technologies unless their use is recommended by the developer. However, if the developer
does recommend matrix samples, their use will be performed following the developer's recommendations.
Matrix spike samples will be performed for SW-846 Method 601 OA and will be performed through the use of pre- and post-digestion spike
samples. Pre- and post-digestion spike samples will be analyzed to assess the accuracy of SW-846 Method 601 OA 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 in the same
manner as other samples, but to which a known amount of target analytes have been added to the sample extractant. These samples are
analyzed in the same manner as other samples and are 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 recovery. Corrective action that must
be taken if the above criteria cannot be met include: (1) reanalysis of the spiked sample, (2) re-extraction and reanalysis of the spiked sample, and
if the re-extraction and reanalysis of the spiked sample produces results which fall within the control limits, then (3) re-extraction and reanalysis of
the spiked sample and the batch of samples associated with the spiked sample. However, when re-extraction 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.
8.4.6 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 601 OA.
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
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submitted as double blind samples for both FPXRF technologies and for SW-846 Method 601 OA. 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.
FPXRF 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 FPXRF accuracy.
SW-846 Method 601 OA will be expected to provide percent recoveries of all target metals within the range of 80 to 120 percent recovery. Accuracy
for SW-846 Method 601 OA 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
SW-846 Method 601 OA accuracy and precision. PE samples for SW-846 Method 601 OA 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 601 OA results fall outside of the acceptance ranges, PRC will request that the confirmatory laboratory re-
extract 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 often 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 replicate 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.
Duplicate samples which will be used by the SW-846 Method 601 OA 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.
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Two types of laboratory duplicate analyses will be performed by SW-846 Method 601 OA: 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) re-extraction and reanalysis of the laboratory duplicate sample, and if the re-extraction and reanalysis of the
laboratory duplicate produces results which fall within the control limits, then (3) re-extraction and reanalysis of the laboratory duplicate sample
and the batch of samples associated with the laboratory duplicate sample. However, when re-extraction 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.
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.
8.5.1 Data Reduction
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 601 OA 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.
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Concentration (as received) (mg/kg) = (C x V)/W (8-1)
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)
This equation allows the final data to be reported in units of mg/kg (as received).
8.5.2 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 601 OA analytical data will be reported using the confirmatory laboratory's standard data 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 601 OA 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.
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.
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RPD = [(A - B) / {(A + B)/2}] x 100 (8-2)
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 (8-3)
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 = [{(x, - avg x)2} / (n-1)] (8-4)
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
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. found 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
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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.
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 recalibrations 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 601 OA
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 601 OA 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 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 results vary by more than 67 percent RPD, the secondary QC laboratory results will be used for comparison to the FPXRF
technologies.
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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.
FIGURE 8-1
SAMPLE ANALYSIS RECORDING FORM FOR FPXRF IN SITU TECHNOLOGIES
Technology Name:
Circle One: Unprepared or Prepared
Sample Analyte Concentration (mg/kg)
Number
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:
Circle One: Unprepared or Prepared
Sample Analyte Concentration (mg/kg)
Number
Antimony Arsenic Barium Cadmium Chromium Copper Iron Lead Nickel Zinc
FIGURE 8-3
SAMPLE ANALYSIS RECORDING FORM FOR FPXRF INTRUSIVE TECHNOLOGIES
Technology Name:
Circle One: Unprepared or Prepared
Sample Analyte Concentration (mg/kg)
Number
Antimony Arsenic Barium Cadmium Chromium Copper Iron Lead Nickel Zinc
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FIGURE 8-4
SAMPLE ANALYSIS RECORDING FORM FOR PRECISION 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
Reading 1
|
Reading 2
Reading 3
Reading 4
Reading 5
Reading 6
|
Reading 7
|
Reading 8
|
Reading 9
j
Reading 10
|
Mean
I
Std. Deviation
I
|
I
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FIGURE 8-5
SAMPLE PREPARATION TRACKING FORM
Sample
No.
Grid
Sample
Homog. All
Samples
Field
Duplicate
20 %
In Situ
Analysis
for All
Samples
Notes:
Homog. Homogenized
C.L. Confirmatory Laboratory
Det. Determination
Intrusive
Analysis
for All
Samples
Package
20 grams
of All
Samples
for C.L.
Det. Water
Content for
All
Samples
Microwave
10% of
Samples
Convect.
Oven
Drying of
All
Samples
FIGURE 8-6
CONFIRMATORY LABORATORY SAMPLE PACKAGING TRACKING FORM
Det. Water Grind and
Content for | Sieve All
All ! Samples
Samples
Sample
Number
Date Packaged
10% of the
Homogenized
Sample9
All of the
Prepared
Sample
Field Duplicate
Sampleb
10% of the Microwave Dried
30% Labeled for Both SW-846
Methods 3050A and 3052
Other Samples
(e.g., PE Samples)
Notes:
a These 10 percent must be from the same original sample.
b 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 601 OA SOI
Primary and Secondary Target
Metals
L SAMPLE DETECTION LIMITS
Lower Reporting Limit3
(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
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TABLE 8-2
SW-846 METHOD 601 OA CALIBRATION PROCEDURES, METHOD-SPECIFIC QC REQUIREMENTS, AND CORRECTIVE ACTION
QC Parameter
Initial Calibration Verification
(ICV) Standard
Continuing Calibration Standard
(CCS)
Calibration Blank
Interference Check Standards
(ICS)
High Level Calibration Check
Standard
Method Blanks
Frequency
With each initial calibration
After analysis of every 10
samples and at the end of
analytical run
With each continuing calibration,
after analysis of every 10
samples, and at the end of
analytical run
With every initial calibration and
after analysis of 20 samples
With every initial calibration
With each batch of samples of a
similar matrix
Control Limits
10 percent of expected value
10 percent
of expected value
No target analytes above method
detection limit
80 percent recovery
5 percent expected value
No target analytes above method
detection limit
Corrective Action
1. Reanalyze initial calibration
2. Re-prepare ICV standards
3. Re-prepare initial calibration
standards
1. Reanalyze CCS
2. Reanalyze initial calibration
standards
3. Re-prepare initial calibration
standards
1. Reanalyze calibration blank
2. Reanalyze calibration
standards
3. Re-prepare initial calibration
standards and calibration blank
1. Reanalyze ICS
2. Reanalyze initial calibration
and ICS
3. Evaluate instrument for
possible problems
1. Reanalyze high level standard
2. Reanalyze initial calibration
3. Follow technology developers
recommendations for correction
1. Reanalyze method blank
2. Re-prepare method blank
3. Re-prepare all associated
samples
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Laboratory Control Samples
(ICS)
With each batch of samples of a
similar matrix
80 to 120 percent recovery3
1. Reanalyze LCS
2. Re-prepare LCS and all
associated samples
3. Perform new initial calibration
Pre-Digestion Matrix Spike
Samples
Post-Digestion Matrix Spike
Samples
With each batch of samples of a
similar matrix
With each batch of samples of a
similar matrix
80 to 120 percent recovery3
80 to 120 percent recovery3
1. Reanalyze pre-digestion matrix
spike sample sample
3. Re-prepare all associated
samples
1. Reanalyze post-digestion
matrix spike sample
2. Re-prepare post-digestion
matrix spike sample
3. Re-prepare all associated
samples
1. Re-prepare and reanalyze PE
sample
1. Reanalyze sample and
duplicate
2. Re-prepare sample and
duplicate
3. Re-prepare all associated
samples
1. Reanalyze sample and
duplicate
2. Re-prepare sample and
duplicate
3. Re-prepare all associated
samples
Notes:
3 Stated control limits pertain only to primary target metals. Control limits for secondary target metals identified and quantified in SW-846 Method
601 OA should fall within published control limits listed in SW-846 Method 601 OA. If these control limits are not met, qualification of the data for
these analytes may be performed.
b RPD control limits only pertain to original and laboratory duplicate sample results which are greater than or equal to 5 times the LRL.
Performance Evaluation (PE)
Samples
Pre-Digestion Laboratory
Duplicate Samples
As submitted during
demonstration
With each batch of samples of a
similar matrix
80 to 120 percent recovery3
20 percent relative percent
difference (RPD)b
Post-Digestion Laboratory
Duplicate Samples
With each batch of samples of a
similar matrix
10 percent relative percent
difference (RPD)b
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XRF 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.
9.1.2 Qualitative and Quantitative Analyses and Evaluations
Samples submitted for chemical analysis will be analyzed by a confirmatory laboratory. Each shipment of
samples sent to the laboratory will be accompanied 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 Information Management System. This system tracks the progress of
sample analysis within the laboratory and provides a reporting format for sample results. After samples
are analyzed, the data will be reduced, validated, and reported as described in Chapter 8.
Validated sample results will be sent to PRC for entry into its data management system. In addition to
sample results, PRC will request QA/QC summary forms for the confirmatory analysis. These forms will
enable PRC to verify the quality of data generated by these methods. PRC will then transfer this data into
its data management system. All data transcribed will be double-checked for accuracy in PRC's data
management system.
9.1.3 Technology Data Management
The sample analysis methods for each technology differ from those used by the confirmatory laboratory.
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The PRC operator assigned to each technology will record the technology sample number and
corresponding confirmatory sample numbers. The PRC operators will be responsible for obtaining,
reducing, interpreting, validating, and reporting data associated with their technology's performance. Each
operator will be required to provide the PRC field team supervisor with copies of the results obtained from
each sampling point, as well as any graphical data used for the delineation of site contamination. PRC will
compare this data to the data generated by the confirmatory analysis.
The PRC operators also will be responsible for obtaining information about the assigned technology. This
information will include a general description of the technology and how it is used in the field. Each PRC
observer will take notes on specific aspects of the technology. These notes will be based on a checklist
created for each technology before the demonstration activities begin. The checklist 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 workday
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
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.
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XRF 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.
10.1.2 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.
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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 compliance
agreement form. Visitors will be expected to comply with relevant OSHA requirements. Visitors 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 team 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 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.
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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 indicate potential
problems, personal protection will be upgraded to Level C.
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 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.
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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.
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.
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10.8 PERSONAL PROTECTION REQUIREMENTS
PPE will 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.
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 (Tyvekฎ or Saranexฎ), 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 (Tyvekฎ or Saranexฎ)
Outer gloves (neoprene or nitrile)
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Inner gloves (nitrile or polyvinyl chloride)
Steel-toed boots with shanks
Disposable boot covers or chemical-resistant outer boots
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 Tyvekฎ or Saranexฎ 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
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,
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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.
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 the 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.
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10.9 MEDICAL SURVEILLANCE
The following sections describe PRC's medical surveillance program, including health monitoring,
documentation and record keeping, and medical support and follow-up requirements. This program will
be followed for all field activities during this demonstration.
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
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.
-------
10.9.2 Documentation and Record keeping 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 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 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: Concentration of dust below 0.5 mg/m3
Action: Continue investigation at Level D without respiratory protection and continue monitoring
- Situation: Concentration of dust at or above 0.5 mg/m3
Action: 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 possibly death. 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 pulse less. 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 captivated coffee), and warm rest areas are essential.
The following chart contains general guidelines that can be used to monitor cold weather field work:
Cooling Power of Wind on Exposed Flesh Expressed as Equivalent Temperature
Estimated Wind Speed (in miles per hour [mphj)
Actual Temperature Reading (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 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.
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.
Avoidance of Trip and Fall Hazards
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.
Illumination
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 OSHA29 CFR 1910.120(n).
Site 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.
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.
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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 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 Liquinoxฎ or Alconoxฎ 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 Liquinoxฎ or Alconoxฎ solution and rinse them in water. Remove outer gloves
and place them in a plastic bag for disposal.
Remove the Tyvekฎ or Saranexฎ 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, Liquinoxฎ or Alconoxฎ
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.
Sampling Equipment
Sampling equipment, such as stainless-steel spades, spoons, and stainless-steel 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 Liquinoxฎ, or Alconoxฎ 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.
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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 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 numbers
not presented below can be obtained, during working hours, by calling Ms. Kathy Schuessler of PRC at
(312) 856-8700.
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RV Hopkins Site
Emergency Service
Local Police Department
Local Fire Department
Local Hospital (Mercy Hospital)
Local Ambulance Service
Telephone Number
911
911
(319) 383-1100
911
Asarco Site
Emergency Service
Local Police Department
Local Fire Department
Local Hospital (St. Joseph Hospital)
Local Ambulance Service
Telephone Number
911
911
911
911
The following emergency contacts are applicable to all demonstration sites:
Poison Control Center: 1 (800) 822-3232
National Response Center: 1 (800) 424-8802
CHEMTREC Chemical Transportation
Emergency Center: 1 (800) 424-9300
PRC (Kansas City office): (913) 281-2277
Eric Hess, PRC Project Manager: (913) 573-1822
Kurt Sorensen, PRC HSD: (312) 856-8763
Steve Billets, EPA PM and TPM: (702) 798-2232
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.
FIGURE 10-1 RV HOPKINS SITE HOSPITAL ROUTE MAP
(not available)
FIGURE 10-2 ASARCO SITE HOSPITAL ROUTE MAP
(not available)
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TABLE 10-1
HAZARDOUS MATERIALS POTENTIALLY PRESENT AT THE
DEMONSTRATION SITES
Chemicals Present Highest
at the Site j Observed
( Concentration in
Soil (mg/kg)
Antimony
and compounds (as
Sb)
No Data
Barium
soluble compounds
(as Ba)
Beryllium
and compounds (as
Be)
Cadmium dust
(as Cd)
Calcium arsenate
(as As)
Chromic acid
and chromates (as
Cr03)
2,640
No Data
500
403,100
22,100
Airborne
Exposure
Limits
0.5 mg/m
IDLH Symptoms and Effects
I of Acute Exposure
80 mg/m Irritated nose, throat,
| mouth; cough; dizziness;
| headache;nausea,
| vomiting, diarrhea;
| cramps; insomnia;
1 anorexia; irritated skin;
unable to smell; cardiac
0.5 mg/m j 250 mg/m j Upper respiratory
| | irritation;
| | gastrointestinal; muscle
| | spasms; slow pulse,
| | extrasystoles;
| | hypokalemia; irritated
' ' eyes; skin burns
2.0 g/m3 Ca Respiratory symptoms;
weakness, fatigue;
weight loss; carcinogen
0.2 mg/m3 , Ca , Pulmonary edema,
| I dyspnea, cough, tight
| I chest, substernal pain;
| I headache; chills, muscle
| I aches; nausea, diarrhea;
| I anosmia, emphysema;
i ! proteinuria; anemia;
carcinogen
10 g/m3 Ca , Weakness;
gastrointestinal;
peripheral neuropathy;
hyperpigmentation,
palmar planter
hyperkeratoses;
dermatitis; carcinogen
0.1 mg/m3 30 mg/m3 Respiratory, nasal
septum irritation;
leukocytosis,
leukopenia,
monocytosis,
eosinophilia; eye injury,
conjunctivitis; skin ulcer,
-------
sensitization dermatitis
Chromium
metal and insoluble
salts
(as Cr)
Cobalt
metal, fume, and
dust
(as Co)
Copper
dust and mist (as
Cu)
22,100 1 mg/m 500 mg/m Histologic fibrosis of
| | I lungs; Chromium (VI):
' 1 ' carcinogen
No Data j 0.1 mg/m ( 20 mg/m Cough, dyspnea,
decreased pulmonary
function; weight loss;
dermatitis; diffuse
nodular fibrosis,
respiratory
hypersensitivity
341,000 1 mg/m3 NA Irritated mucus
, , , membrane, pharynx;
| | | nasal perforation; eye
| irritation; metal taste;
I dermatitis
Lead
Inorganic fumes and
dusts
(as Pb)
33,750
Manganese
and compounds (as
Mn)
22,000
Mercury
and inorganic
compounds
(as Hg)
Molybdenum
insoluble
compounds
0.03 mg/m NA Lassitude; insomnia;
, pallor, eye grounds;
j | anorexia, weight loss,
j | malnutrition;
j | constipation, abdominal
j | pain, colic; hypotenuse;
j | anemia; gingival lead
i ! line; trembling,
paralyzed wrist
5 mg/m3 ; 10,000 mg/m3 ( Parkinson's disease;
| asthenia, insomnia,
| mental; metal fume
| fever; dry throat, cough,
| tight chest, dyspnea,
| rales; low back pain;
| vomiting, malnutrition;
| fatigue
0.1 mg/m3 28 mg/m3 Cough, dyspnea,
bronchial pneumonia;
tremor, insomnia;
irritability, indecision;
headache; fatigue,
weakness; stomatitis;
salivation;
gastrointenstinal,
anorexia, loss of weight;
proteinuria; irritated
eyes, skin
No Data 15 mg/m NA In animals: irritated
| | | eyes, nose, throat;
' ' ' weight loss
700
-------
(as Mo) | |
Nickel
metal and soluble
compounds (as Ni)
519
1 mg/m3
Ca
Sensitization dermatitis;
allergic asthma; nasal
cavities; pneumonitis;
carcinogen
j Selenium
| compounds
| (as Se)
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
No Data
2 mg/m3
400 mg/m3
Irritated eyes, skin
| compounds j | |
' except oxides (as ' 1 1
Sn)
Notes:
NA Not applicable
Ca Carcinogen
TABLE 10-2
WORK TASK HAZARD ANALYSIS
Task
Potential Hazard
Task 1
Sampling
Task 2
Field Screening
Chemical
Physical
Chemical
Radiological
Anticipated Level of
Protection
Upgraded Level of
Protection
Level D
Level C
Level D
Level C
Note:
Levels of protection are discussed in detail in Section 10.9.2.
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XRF 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).
QAPP. 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.
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:
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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
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.
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