November 1998
Environmental Technology
Verification Report
Field-Portable Gas Chromatograph/
Mass Spectrometer
Inficon, Inc., HAPSITE
U.S. Environmental Protection Agency
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EPA/600/R-98/142
November 1998
Environmental Technology Verification
Report
Field-Portable Gas Chromatograph/
Mass Spectrometer
Inficon, Inc., HAPSITE
by
Wayne Einfeld
Sandia National Laboratories
Albuquerque, New Mexico 87185-0755
IAGDW89936700-01-0
Project Officer
Stephen Billets
National Exposure Research Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Las Vegas, Nevada 89193
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Notice
The U.S. Environmental Protection Agency (EPA), through its Office of Research and Development (ORD), funded
and managed, under Interagency Agreement No. DW89936700-01-0 with the U.S. Department of Energy's Sandia
National Laboratory, the verification effort described in this document. This report has received both technical peer
and administrative policy reviews and has been approved for publication as an EPA document. Mention of
corporate names, trade names, or commercial products does not constitute endorsement or recommendation for use.
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UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
Office of Research and Development
Washington, D.C. 20460
ENVIRONMENTAL TECHNOLOGY VERIFICATION PROGRAM
VERIFICATION STATEMENT
TECHNOLOGY TYPE:
APPLICATION:
TECHNOLOGY NAME:
COMPANY
ADDRESS:
PHONE:
FIELD-PORTABLE GAS CHROMATOGRAPH/
MASS SPECTROMETER
MEASUREMENT OF CHLORINATED VOLATILE ORGANIC
COMPOUNDS IN WATER
HAPSITE with Headspace Sampling Accessory
Inficon, Inc.
Two Technology Place
East Syracuse, NY 13057
(315)434-1100
PROGRAM DESCRIPTION
The U.S. Environmental Protection Agency (EPA) created the Environmental Technology Verification Program
(ETV) to facilitate the deployment of innovative environmental technologies through performance verification and
information dissemination. The goal of the ETV Program is to further environmental protection by substantially
accelerating the acceptance and use of improved and cost-effective technologies. The ETV Program is intended to
assist and inform those involved in the design, distribution, permitting, and purchase of environmental technologies.
Under this program, in partnership with recognized testing organizations, and with the full participation of the
technology developer, the EPA evaluates the performance of innovative technologies by developing demonstration
plans, conducting field tests, collecting and analyzing the demonstration results, and preparing reports. The testing
is conducted in accordance with rigorous quality assurance protocols to ensure that data of known and adequate
quality are generated and that the results are defensible. The EPA National Exposure Research Laboratory, in
cooperation with Sandia National Laboratories, the testing organization, evaluated field-portable systems for
monitoring chlorinated volatile organic compounds (VOCs) in water. This verification statement provides a
summary of the demonstration and results for the Inficon HAPSITE field-portable gas chromatograph/mass
spectrometer (GC/MS) system.
DEMONSTRATION DESCRIPTION
The field demonstration of the HAPSITE portable GC/MS was held in September 1997. The demonstration was
designed to assess the instrument's ability to detect and measure chlorinated volatile organic compounds in
groundwater at two contaminated sites: the Department of Energy's Savannah River Site, near Aiken, South
Carolina, and the McClellan Air Force Base, near Sacramento, California. Groundwater samples from each site
were supplemented with performance evaluation (PE) samples of known composition. Both sample types were used
to assess instrument accuracy, precision, sample throughput, and comparability to reference laboratory results. The
primary target compounds at the Savannah River Site were trichloroethene and tetrachloroethene. At McClellan Air
EPA-VS-SCM-25
The accompanying notice is an integral part of this verification statement
iii
November 1998
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Force Base, the target compounds were trichloroethene, tetrachloroethene, 1,2-dichloroethane, 1,1,2-
trichloroethane, 1,2-dichloropropane, and ?ra«s-l,3-dichloropropene. These sites were chosen because they contain
varied concentrations of chlorinated VOCs and exhibit different climatic and geologic conditions. The conditions at
these sites are typical, but not inclusive, of those under which this technology would be expected to operate. A
complete description of the demonstration, including a data summary and discussion of results, may be found in the
report entitled Environmental Technology Verification Report, Field-Portable Gas Chromatograph/Mass
Spectrometer, Inflcon, Inc., HAPSITE. (EPA/600/R-98/142).
TECHNOLOGY DESCRIPTION
GC/MS is a proven laboratory analytical technology that has been used for environmental characterization and
monitoring for many years. The combination of gas chromatography and mass spectrometry allows the rapid
separation and identification of compounds in complex mixtures. The gas chromatograph separates the sample into
individual components. These components are introduced into the electron impact source module of the
spectrometer, where the molecules are fragmented into ions by an electron beam. The ion fragments are further
separated by mass and detected by an electron multiplier. The resulting mass spectrum is characteristic of a
particular compound and can be used to identify each component in the sample extract through comparison with a
reference spectral library. Quantitation is achieved by comparing the abundance of ions which are characteristic of a
specific compound with the detector response from the analysis of a standard mixture. Field-portable GC/MS is a
versatile technique that can be used to provide rapid screening data or laboratory-quality analyses. As with many
field analytical studies, it may be necessary to send a portion of the samples to an independent laboratory for
confirmatory analyses.
The Inficon HAPSITE with a headspace sampling accessory is a commercially available GC/MS system that
provides laboratory-grade performance in a field-transportable package. The instrument, including the on-board
computer, is designed for field use and is encapsulated in a weather-resistant case. The GC/MS unit weighs about 35
pounds and the headspace sampling accessory weighs about 15 pounds. Both units can be easily transported and
operated in the rear compartment of a minivan or station wagon. The instrument utilizes an equilibrium headspace
technique for the analysis of VOCs in water. Instrument detection limits for most chlorinated VOCs in water are in
the range of 5 to 10 ng/L. At the time of the demonstration, the cost of the HAPSITE with headspace accessory was
in the range of $75,000 to $95,000, depending upon instrument options. Operational costs, which include
consumable supplies but not labor costs, are on the order of $150 per 8-hour day.
VERIFICATION OF PERFORMANCE
The following performance characteristics of the HAPSITE were observed:
Sample Throughput: Throughput was approximately two to three water samples per hour. This rate includes the
periodic analysis of blanks and calibration check samples.
Completeness: The HAPSITE reported results for all but one of the 166 PE and groundwater samples provided for
analysis at the two demonstration sites. One sample was dropped during preparation.
Analytical Versatility: The HAPSITE detected all of the compounds in the PE samples for which it was calibrated.
Its calibration included 84% (27 of 32) of all chlorinated and nonchlorinated volatile hydrocarbon compounds
included in the PE samples at the demonstration. Additional compounds could have been detected with a longer
GC/MS run time and a reduced sample throughput. The HAPSITE detected all (59 of 59) of the groundwater
contaminants in excess of 5 ng/L reported by the reference laboratory at both sites. A total of 68 contaminants, at
concentration levels of 1 ng/L or higher, were detected by the reference laboratory in all groundwater samples.
Precision: Precision was determined by analyzing sets of four replicate samples from a variety of PE mixtures
containing known concentrations of chlorinated VOCs. The results are reported as relative standard deviations
(RSD). The RSDs compiled for all reported PE compounds from both sites had a median value of 12% and a 95th
percentile value of 29%. By comparison, the compiled RSDs from the reference laboratory had a median value of
EPA-VS-SCM-25 The accompanying notice is an integral part of this verification statement November 1998
iv
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7% and a 95th percentile value of 25%. The ranges of HAPSITE RSD values for specific target compounds were as
follows: trichloroethene 7 to 18%, tetrachloroethene, 6 to 22%; 1,2-dichloroethane, 2 to 12%; 1,1,2-trichloroethane,
8 to 28%; 1,2-dichloropropane, 7 to 21%; and ?ra«s-l,3-dichloropropene, 7 to 17%.
Accuracy: Instrument accuracy was evaluated by comparing HAPSITE results with the known concentrations of
chlorinated organic compounds in PE mixtures. Absolute percent difference (APD) values from both sites were
calculated for all analytes in the PE mixtures. The APDs for all reported compounds from both sites had a median
value of 8% and a 95th percentile value of 27%. By comparison, the compiled APDs from the reference laboratory
had a median value of 7% and a 95th percentile value of 24%. The ranges of HAPSITE APD values for target
compounds were as follows: trichloroethene, 1 to 20%; tetrachloroethene, 6 to 33%; 1,2-dichloroethane, 2 to 20%;
1,1,2-trichloroethane 1 to 21%; 1,2-dichloropropane, 3 to 21%; and ?ra«s-l,3-dichloropropene, 1 to 15%.
Comparability: A comparison of HAPSITE and reference laboratory data was based on 33 groundwater samples
analyzed at each site. The correlation coefficients (r) for all compounds detected by both the HAPSITE and
laboratory at or below 100 |j,g/L concentration levels were 0.983 at Savannah River and 0.978 at McClellan. The r
values for compounds detected at concentration levels in excess of 100 ng/L were 0.996 for Savannah River and
1.000 for McClellan. These correlation coefficients reveal a highly linear relationship between HAPSITE and
laboratory data. The median absolute percent difference between groundwater compounds mutually detected by the
HAPSITE and reference laboratory was 13%, with a 95th percentile value of 60%.
Deployment: The system was ready to analyze samples within 30 minutes of arrival at the site. At both sites, the
instrument was transported in a minivan and was operated in its rear luggage compartment. The instrument was
powered by self-contained batteries or from line ac power. The recommended training interval for routine sample
processing is about 3 days for a chemist with limited GC/MS experience. Method development and analysis of very
complex samples requires a higher level of operator training and experience in GC/MS data interpretation.
The results of this demonstration show that the HAPSITE can provide useful, cost-effective data for environmental
site screening and routine monitoring. This instrument could be employed in a variety of applications, ranging from
producing rapid analytical results in screening investigations, to producing accurate and precise data that are directly
comparable with that obtained from an off-site laboratory. These data could be used to develop risk assessment
information, support a remediation process, or fulfill monitoring requirements. In the selection of a technology for
deployment at a site, the user must determine what is appropriate through consideration of instrument performance
and the project's data quality objectives.
Gary J. Foley, Ph. D.
Director
National Exposure Research Laboratory
Office of Research and Development
Samuel G. Varnado
Director
Energy and Critical Infrastructure Center
Sandia National Laboratories
NOTICE: EPA verifications are based on an evaluation of technology performance under specific, predetermined criteria
and the appropriate quality assurance procedures. EPA makes no expressed or implied warranties as to the performance of
the technology and does not certify that a technology will always, under circumstances other than those tested, operate at
the levels verified. The end user is solely responsible for complying with any and all applicable federal, state and local
requirements.
EPA-VS-SCM-25
The accompanying notice is an integral part of this verification statement
V
November 1998
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Foreword
The U.S. Environmental Protection Agency (EPA) is charged by Congress with protecting the nation's natural
resources. The National Exposure Research Laboratory (NERL) is the EPA center for the investigation of technical
and management approaches for identifying and quantifying risks to human health and the environment. The
NERL research goals are to (1) develop and evaluate technologies for the characterization and monitoring of air,
soil, and water; (2) support regulatory and policy decisions; and (3) provide the science support needed to ensure
effective implementation of environmental regulations and strategies.
The EPA created the Environmental Technology Verification (ETV) Program to facilitate the deployment of
innovative technologies through verification of performance and dissemination of information. The goal of the ETV
Program is to further environmental protection by substantially accelerating the acceptance and use of improved
and cost-effective technologies. It is intended to assist and inform those involved in the design, distribution,
permitting, and purchase of environmental technologies.
Candidate technologies for this program originate from the private sector and must be market ready. Through the
ETV Program, developers are given the opportunity to conduct rigorous demonstrations of their technologies under
realistic field conditions. By completing the evaluation and distributing the results, the EPA establishes a baseline
for acceptance and use of these technologies.
Gary J. Foley, Ph. D.
Director
National Exposure Research Laboratory
Office of Research and Development
VI
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Executive Summary
The U.S. Environmental Protection Agency, through the Environmental Technology Verification Program, is
working to accelerate the acceptance and use of innovative technologies that improve the way the United States
manages its environmental problems. As part of this program, the Consortium for Site Characterization
Technology was established as a pilot program to test and verify field monitoring and site characterization
technologies. The Consortium is a partnership involving the U.S. Environmental Protection Agency, the
Department of Defense, and the Department of Energy. In 1997 the Consortium conducted a demonstration of five
systems designed for the analysis of chlorinated volatile organic compounds in groundwater (GW). The developers
participating in this demonstration were Electronic Sensor Technology, Perkin-Elmer Photovac, and Sentex
Systems, Inc. (field-portable gas chromatographs); Inficon, Inc. (field-portable gas chromatograph/mass
spectrometer, GC/MS); and Innova AirTech Instruments (photoacoustic infrared analyzer). This report documents
demonstration activities, presents demonstration data, and verifies the performance of the Inficon HAPSITE field-
portable GC/MS. Reports documenting the performance of the other technologies have been published separately.
The demonstration was conducted at two geologically and climatologically different sites: the U.S. Department of
Energy's Savannah River Site, near Aiken, South Carolina, and McClellan Air Force Base, near Sacramento,
California. Both sites have groundwater resources that are significantly contaminated with a variety of chlorinated
volatile organic compounds. The demonstrations to evaluate the capabilities of each field-portable system were
conducted in September 1997 and were coordinated by Sandia National Laboratories.
The demonstration provided adequate analytical and operational data with which to evaluate the performance of the
Inficon HAPSITE GC/MS system. Instrument precision and accuracy were determined from analyses of replicate
samples from 16 multicomponent standard mixtures of known composition. The relative standard deviations
obtained from analyses of 4 replicate samples from each of the 16 standard mixtures were used as measures of
precision. The distribution of relative standard deviations from all compounds had a median value of 12% and a
95th percentile value of 29%. Accuracy was expressed as the absolute percent difference between the HAPSITE
measured value and the true value of the component in the standard mixtures. The distribution of absolute percent
difference values for all compounds in all standard mixtures had a median value of 8% and a 95th percentile value
of 27%. A comparison of HAPSITE and reference laboratory results from groundwater samples at each site re-
sulted in a median absolute percent difference of 13%, with a 95th percentile value of 60%. A correlation analysis
between HAPSITE and laboratory results indicates a high degree of linear correlation (r >0.98) at both low (<100
Hg/L) and high (>100 |o,g/L) contaminant concentrations. The sample throughput rate of the HAPSITE was
determined to be two to three samples per hour.
The HAPSITE detected all of the groundwater contaminants reported by the reference laboratory at both sites
which were present at concentration levels in excess of 5 |o,g/L. The results of the demonstration show that the
Inficon HAPSITE field-portable GC/MS with its headspace sampling accessory can provide useful, cost-effective
data for environmental site characterization and routine monitoring. As with any technology selection, the user
must determine whether the technology is appropriate for the application by taking into account instrument
performance parameters and the project's data quality objectives.
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Vlll
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Contents
Notice ii
Verification Statement iii
Foreword vi
Executive Summary vii
Figures xiii
Tables xiv
Acronyms and Abbreviations xv
Acknowledgments xvii
Chapter 1 Introduction 1
Site Characterization Technology Challenge 1
Technology Verification Process 2
Identification of Needs and Selection of Technology 2
Planning and Implementation of Demonstration 2
Preparation of Report 3
Distribution of Information 3
The Wellhead VOC Monitoring Demonstration 3
Chapter 2 Technology Description 5
Technology Overview 5
Principle of Operation 6
History of the Technology 6
Applications 6
Advantages 7
Limitations 7
Performance Characteristics 7
Practical Quantitation Limits and Method Detection Limits 7
Accuracy 7
Precision 7
IX
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Instrument Working Range 9
Comparison with Reference Laboratory Analyses 9
Data Completeness 9
Other Analytical Performance Characteristics and Requirements 9
Other Field Performance Characteristics 9
Instrument Setup and Disassembly Time 9
Instrument Calibration Frequency During Field Use 9
Ancillary Equipment Requirements 10
Field Maintenance Requirements 10
Sample Throughput Rate 10
Operator Training Requirements and Ease of Operation 10
Chapter 3 Demonstration Design and Description 11
Introduction 11
Overview of Demonstration Design 11
Quantitative Factors 11
Qualitative Factors 12
Site Selection and Description 13
Savannah River Site 13
McClellan Air Force Base 15
Sample Set Descriptions 17
PE Samples and Preparation Methods 20
Groundwater Samples and Collection Methods 22
Sample Handling and Distribution 22
Field Demonstration Schedule and Operations 23
Site Operations and Environmental Conditions 23
Field Audits 24
Data Collection and Analysis 25
Demonstration Plan Deviations 25
Chapter 4 Laboratory Data Results and Evaluation 26
Introduction 26
Reference Laboratory 26
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Laboratory Selection Criteria 26
Summary of Analytical Work by DataChem Laboratories 27
Summary of Method 8260A 27
Method 8260A Quality Control Requirements 27
Summary of Laboratory QC Performance 27
Target Compound List and Method Detection Limits 28
Sample Holding Conditions and Times 28
System Calibration 28
Daily Instrument Performance Checks 30
Batch-Specific Instrument QC Checks 30
Sample-Specific QC Checks 30
Summary of Analytical and QC Deviations 32
Other Data Quality Indicators 32
PE Sample Precision 33
PE Sample Accuracy 33
Groundwater Sample Precision 38
Summary of Reference Laboratory Data Quality 39
Chapters Demonstration Results 40
HAPSITE Calibrated and Reported Compounds 40
Preanalysis Sample Information 40
Sample Completion 41
Blank Sample Results 41
Performance at Instrument Detection Limit 41
PE Sample Precision 42
PE Sample Accuracy 45
Comparison with Laboratory Results 45
Sample Throughput 51
Performance Summary 51
Chapter 6 Field Observations and Cost Summary 53
Introduction 53
XI
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Method Summary 53
Equipment 53
Sample Preparation and Handling 54
Consumables 54
Historical Use 55
Equipment Cost 55
Operators and Training 55
Data Processing and Output 55
Compounds Detected 56
Initial and Daily Calibration 56
QC Procedures and Corrective Actions 56
Sample Throughput 56
Problems Observed During Audit 56
Data Availability and Changes 56
Applications Assessment 56
Chapter 7 Technology Update 58
Review of Demonstration and Results 58
Observed False Positive Results 58
Observed False Negative Results 58
Comparison of HAPSITE and Laboratory Groundwater Sample Results 59
Number of Compounds Detected 59
Chapter 8 Other Deployments 60
References 61
xn
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Figures
3-1. The general location of the Savannah River Site in the southeast United States 13
3-2. A map of the A/M area at the Savannah River Site showing the subsurface TCE plume 14
3 -3. A map of Sacramento and vicinity showing the location of McClellan Air Force Base 16
3 -4. Subsurface TCE plumes at McClellan Air Force Base in the shallowest (A) aquifer layer 18
4-1. Laboratory control standard recovery values for SRS analyses 31
4-2. Laboratory control standard recovery values for MAFB analyses 31
4-3. Laboratory precision on SRS PE samples containing mix 1 34
4-4. Laboratory precision on SRS PE samples containing mix 2 34
4-5. Laboratory precision on MAFB PE samples containing mix 2 35
4-6. Laboratory precision on MAFB PE samples containing mix 3 35
4-7. Laboratory mean recoveries for SRS PE samples containing mix 1 36
4-8. Laboratory mean recoveries for SRS PE samples containing mix 2 36
4-9. Laboratory mean recoveries for MAFB PE samples containing mix 2 37
4-10. Laboratory mean recoveries for MAFB PE samples containing mix 3 37
5-1. HAPSITE precision on PE mix 1 at the SRS 43
5-2. HAPSITE precision on PE mix 2 at the SRS 43
5-3. HAPSITE precision on PE mix 2 at MAFB 44
5-4. HAPSITE precision on PE mix 3 at MAFB 44
5-5. HAPSITE recovery on PE mix 1 at the SRS 46
5-6. HAPSITE recovery on PE mix 2 at the SRS 46
5-7. HAPSITE recovery on PE mix 2 at MAFB 47
5-8. HAPSITE recovery on PE mix 3 at MAFB 47
5-9. HAPSITE groundwater results at the SRS relative to laboratory results 50
5-10. HAPSITE groundwater results at MAFB relative to laboratory results 50
6-1. The HAPSITE GC/MS 54
xin
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Tables
2-1. Inficon HAPSITE GC/MS Analyte List 8
3-1. Quarterly Monitoring Results for SRS Wells Sampled in the Demonstration 15
3-2. Groundwater Contaminants at MAFB 19
3-3. Quarterly Monitoring Results for MAFB Wells Sampled in the Demonstration 19
3-4. Composition of PE Source Materials 21
3-5. PE Sample Composition and Count for SRS Demonstration 21
3-6. PE Sample Composition and Count for MAFB Demonstration 22
3-7. Weather Summary for SRS and MAFB During Demonstration Periods 24
4-1. Method 8260A Quality Control Summary 28
4-2. Reference Laboratory Method Detection Limits for Target Compounds 29
4-3. Summary of Reference Laboratory Quality Control and Analytical Deviations 32
4-4. Sources of Uncertainty in PE Sample Preparation 33
4-5. Summary of SRS Groundwater Analysis Precision 38
4-6. Summary of MAFB Groundwater Analysis Precision 38
5-1. HAPSITE Calibrated and Reported Compounds 40
5-2. False Positive Rates from Blank Sample Analysis 41
5-3. False Negative Rates from Very Low-Level PE Sample Analysis 41
5-4. Target Compound Precision for PE Samples at Both Sites 42
5 -5. Summary of PE Sample Precision and Percent Difference Statistics for SRS and MAFB 42
5-6. Target PE Compound Recovery at Both Sites 45
5-7. HAPSITE and Reference Laboratory Results for SRS Groundwater Samples 48
5-8. HAPSITE and Reference Laboratory Results for MAFB Groundwater Samples 49
5 -9. HAPSITE Absolute Percent Difference Summary for Pooled Groundwater Results 51
5-10. Correlation Coefficients for Laboratory andHAPSITE Groundwater Analyses 51
5-11. Summary of HAPSITE GC/MS Performance 52
6-1. HAPSITE GC/MS Cost Summary 55
xiv
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Acronyms and Abbreviations
ac
amu
APD
BNZN
°C
ccc
CCL4
CLFRM
dc
11DCA
12DCA
DCE
11DCE
c!2DCE
112DCE
DCL
DOE
EPA
ETV
eV
GC
GW
GC/MS
hp
Hz
i.d.
L
m
mg
mg/L
mL
mm
MAFB
MCL
MDL
MS
NERL
NIST
alternating current
atomic mass unit
absolute percent difference
benzene
degrees centigrade
calibration check compounds
carbon tetrachloride
chloroform
direct current
1,1 -dichloroethane
1,2-dichloroethane
dichloroethene
1,1-dichloroethene
cis-1,2-dichloroethene
trans-1,2-dichloroethene
DataChem Laboratories
Department of Energy
Environmental Protection Agency
Environmental Technology Verification Program
electron-volt
gas chromatograph
groundwater
gas chromatograph/mass spectrometer
horsepower
hertz, cycles per second
inside diameter
liter
meter
milligram
milligram per liter
milliliter
millimeter
McClellan Air Force Base
maximum concentration level
method detection limit
mass spectroscopy
National Exposure Research Laboratory
National Institute of Standards and Technology
xv
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NR
PC
PCE
PE
ppb
ppm
PQL
PVC
QA
QC
r
RPD
RSD
SPCC
SRS
TCA
111TCA
TCE
V
Vac
VGA
VOC
XYL
MS
not reported
personal computer
tetrachloroethene (perchloroethene)
performance evaluation
parts per billion
parts per million
practical quantitation limit
poly (vinyl chloride)
quality assurance
quality control
correlation coefficient
relative percent difference
relative standard deviation
system performance check compounds
Savannah River Site
trichloroethane
1,1,1 -trichloroethane
trichloroethene
volts
volts alternating current
volatile organics analysis
volatile organic compound
xylene
microgram
microgram per liter
microliter
xvi
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Acknowledgments
The author wishes to acknowledge the support of all those who helped to plan and conduct the demonstrations,
analyze the data, and prepare this report. In particular, the technical expertise of Gary Brown, Robert Helgesen,
Michael Hightower, and Dr. Brian Rutherford of Sandia National Laboratories in the planning and conduct of the
study are recognized. The assistance of Dr. Timothy Jarosch and Joseph Rossabi of Westinghouse Savannah River
Co. in planning the demonstration and field activities at both Savannah River and McClellan is also recognized.
The willingness of Phillip Mook and Timothy Chapman of the Environmental Directorate at McClellan Air Force
Base to host the McClellan phase of the study is also greatly appreciated. The availability of funding from the
Department of Defense's Strategic Environmental Research and Development Program helped to make the
McClellan phase of the study possible. The guidance and contributions of project technical leaders Dr. Stephen
Billets and Eric Koglin of the EPA National Exposure Research Laboratory, Environmental Sciences Division, in
Las Vegas, Nevada, during all phases of the project are also recognized.
The participation of personnel from Inficon, Inc. in this technology demonstration is also acknowledged. Chuck
Sadowski and co-workers operated the instrument during the demonstrations.
For more information on the wellhead monitoring demonstration, contact:
Stephen Billets, Project Technical Leader, U.S. Environmental Protection Agency
National Exposure Research Laboratory, Environmental Sciences Division
P.O. Box 93478, Las Vegas, Nevada 89193-3478
(702) 798-2232
For more information on the Inficon HAPSITE gas chromotograph/mass spectrometer technology, contact:
Bill Worthington, Technical Marketing Manager, Inficon, Inc.
Two Technology Place, East Syracuse, NY 13057
(315)434-1100
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XV111
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Chapter 1
Introduction
Site Characterization Technology Challenge
The U.S. Environmental Protection Agency (EPA) created the Environmental Technology Verification (ETV)
Program to facilitate the deployment of innovative environmental technologies through verification of performance
and dissemination of information. The goal of the ETV Program is to further environmental protection by
substantially accelerating the acceptance and use of improved and cost-effective technologies. It is intended to
assist and inform those involved in the design, distribution, permitting, purchase, and use of environmental
technologies. The ETV Program capitalizes on and applies the lessons that were learned in the implementation of
the Superfund Innovative Technology Evaluation Program to twelve pilot programs: Drinking Water Systems,
Pollution Prevention for Waste Treatment, Pollution Prevention for Innovative Coatings and Coatings Equipment,
Indoor Air Products, Advanced Monitoring Systems, EvTEC (an independent, private-sector approach), Wet
Weather Flows Technologies, Pollution Prevention for Metal Finishing, Source Water Protection Technologies, Site
Characterization and Monitoring Technology, Climate Change Technologies, and Air Pollution Control.
For each pilot, the EPA utilizes the expertise of partner "verification organizations" to design efficient procedures
for performance tests of the technologies. The EPA selects its partners from both public and private sectors,
including federal laboratories, states, and private sector entities. Verification organizations oversee and report
activities based on testing and quality assurance protocols developed with input from all major stakeholder and
customer groups associated with the technology area. The U.S. Department of Energy's (DOE's) Sandia National
Laboratories in Albuquerque, New Mexico, served as the verification organization for the demonstration described
in this report.
The performance verification reported here is based on data collected during a demonstration of technologies for the
characterization and monitoring of chlorinated volatile organic compounds (VOCs) in groundwater. Rapid,
reliable, and cost-effective field screening and analysis technologies are needed to assist in the complex task of
characterizing and monitoring hazardous and chemical waste sites. Environmental regulators and site managers are
often reluctant to use new technologies that have not been validated in an objective EPA-sanctioned testing program
or other similar process. Until the field performance of a technology can be verified through objective evaluations,
users will remain skeptical of innovative technologies, despite the promise of better, less expensive, and faster
environmental analyses. This demonstration was administered by the Site Characterization and Monitoring
Technology Pilot Program, which is also known as the Consortium for Site Characterization Technology. The
mission of the Consortium is to identify, demonstrate, and verify the performance of innovative site characterization
and monitoring technologies. The Consortium also disseminates information about technology performance to
developers, environmental remediation site managers, consulting engineers, and regulators.
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Technology Verification Process
The technology verification process consists of the four key steps shown here and discussed in more detail in the
following paragraphs:
1. identification of needs and selection of technology;
2. planning and implementation of demonstration;
3. preparation of report; and
4. distribution of information.
Identification of Needs and Selection of Technology
The first aspect of the verification process is to determine the technology needs of the EPA and the regulated
community. The EPA, the U.S. Department of Energy, the U.S. Department of Defense, industry, and state
agencies are asked to identify technology needs for site characterization and monitoring. Once a need is recognized,
a search is conducted to identify suitable technologies that will address this need. This search and identification
process consists of reviewing responses to Commerce Business Daily announcements, searching industry and trade
publications, attending related conferences, and following up on suggestions from technology developers and
experts in the field. Candidate characterization and monitoring technologies are evaluated against the following
criteria:
• may be used in the field or in a mobile laboratory;
• has a regulatory application;
• is applicable to a variety of environmentally affected sites;
• has a high potential for resolving problems for which current methods are unsatisfactory;
• has costs that are competitive with current methods;
• has performance as good or better than current methods in areas such as data quality, sample preparation, and/or
analytical turnaround time;
• uses techniques that are easier and safer than current methods; and
• is a commercially available, field-ready technology.
Planning and Implementation of Demonstration
After a technology has been selected, the EPA, the verification organization, and the developer(s) agree on a
strategy for conducting the demonstration and evaluating the technology. A conceptual plan for designing a
demonstration for a site characterization technology has been published by the Site Characterization and
Monitoring Technology Pilot Program (EPA, 1996a). During the planning process, the following steps are carried
out:
• identification of at least two demonstration sites that will provide the appropriate physical or chemical attributes
in the desired environmental media;
• identification and definition of the roles of demonstration participants, observers, and reviewers;
• determination of logistical and support requirements (for example, field equipment, power and water sources,
mobile laboratory, communications network);
• arranging for field sampling and reference analytical laboratory support; and
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• preparation and implementation of a demonstration plan that addresses the experimental design, sampling design,
quality assurance and quality control (QA/QC), health and safety considerations, scheduling of field and
laboratory operations, data analysis procedures, and reporting requirements.
Preparation of Report
Each of the innovative technologies is evaluated independently and, when possible, against a reference technology.
The technologies are operated in the field by the developers in the presence of independent observers who are
provided by the EPA or the verification organization. Demonstration data are used to evaluate the capabilities,
limitations, and field applications of each technology. Following the demonstration, all raw and reduced data used
to evaluate each technology are compiled in a technology evaluation report, which is a record of the demonstration.
A data summary and detailed evaluation of each technology are published in an environmental technology
verification report. The report includes a verification statement, which is a concise summary of the instrument's
performance during the demonstration.
Distribution of Information
The goal of the information distribution strategy is to ensure that environmental technology verification reports and
accompanying verification statements are readily available to interested parties through traditional data distribution
pathways, such as printed documents. Related documents and updates are also available on the World Wide Web
through the ETV Web site (http://www.epa.gov/etv) and through a Web site supported by the EPA Office of Solid
Waste and Emergency Response Technology Innovation Office (http://clu-in.com). Additional information at the
ETV Web site includes a summary of the demonstration plan, test protocols (where applicable), demonstration
schedule and participants, and in some cases a brief narrative and pictorial summary of the demonstrations.
The Wellhead VOC Monitoring Demonstration
In August 1996, the selection of a technology for monitoring chlorinated VOCs in water was initiated by
publication in the Commerce Business Daily of a solicitation and notice of intent to conduct such a technology
demonstration. Potential participants were also solicited through manufacturer and technical literature references.
The original demonstration scope was limited to market-ready in situ technologies; however, only a limited response
was obtained, so the demonstration scope was expanded to include technologies that could be used to measure
groundwater (GW) at or near the wellhead. The final selection of technologies was based on the readiness of the
technologies for field demonstration and their applicability to the measurement of chlorinated VOCs in groundwater
at environmentally affected sites.
For this demonstration, five instrument systems were selected. Three of them were field-portable gas
chromatographs with various detection systems: one with a surface acoustic wave detector from Electronic Sensor
Technology, one with dual electron capture and photoionization detectors from Perkin-Elmer Photovac, and one
with an argon ion/electron capture detector from Sentex Systems. The fourth instrument was a field-portable gas
chromatograph/mass spectrometer (GC/MS) from Inficon, and the fifth was a photoacoustic infrared spectrometer
from Innova AirTech Instruments. This report documents demonstration activities, presents demonstration data,
and verifies the performance of the Inficon, Inc., HAPSITE field-portable gas chromatograph/mass spectrometer.
Reports documenting the performance of the other four technologies have been published separately.
The demonstration was conducted in September 1997 at the DOE Savannah River Site (SRS) near Aiken, Georgia,
and at McClellan Air Force Base (MAFB), near Sacramento, California. Both sites have subsurface plumes of
-------
chlorinated VOCs and extensive networks of ground-water monitoring wells. The demonstrations were coordinated
by Sandia National Laboratories with the assistance of personnel from the Savannah River Site.
The primary objective of this demonstration was to evaluate and verify the performance of field-portable
characterization and monitoring technologies for analysis of chlorinated VOCs in groundwater. Specific
demonstration objectives were to:
• verify instrument performance characteristics that can be directly quantified (such factors include response to
blank samples, measurement accuracy and precision, sample throughput, and data completeness);
• verify instrument characteristics and performance in various qualitative categories such as ease of operation,
required logistical support, operator training requirements, transportability, versatility, and other related
characteristics; and
• compare instrument performance with results from standard laboratory analytical techniques currently used to
analyze groundwater for chlorinated VOCs.
The goal of this and other ETV demonstrations is to verify the performance of each instrument as a separate entity.
Technologies are not compared with each other in this program. The demonstration results are summarized for
each technology independent of other participating technologies. In this demonstration, the capabilities of the five
instruments varied and in many cases were not directly comparable. Some of the instruments are best suited for
routine monitoring where compounds of concern are known and there is a maximum contaminant concentration
requirement for routine monitoring to determine regulatory compliance. Other instruments are best suited for
characterization or field-screening activities where groundwater samples of unknown composition can be analyzed
in the field to develop an improved understanding of the type of contamination at a particular site. This field
demonstration was designed so that both monitoring and characterization technologies could be verified.
-------
Chapter 2
Technology Description
This chapter was provided by the developer and was edited for format and relevance. The data presented include
performance claims that may not have been verified as part of the demonstration. Chapters 5 and 6 report
instrument features and performance observed in this demonstration. Publication of this material does not
represent EPA approval or endorsement.
Technology Overview
The Inficon HAPSITE is a field-portable gas chromatograph/mass spectrometer that can be operated from battery
or ac line power. The basic instrument was originally designed to analyze gas samples in the parts per billion (ppb)
to parts per million (ppm) range. Sample components are separated by gas chromatography, and are detected with
a conventional quadrupole mass spectrometer. The mass spectrometer is capable of scanning from 1 to 300 atomic
mass units (amu) and employs a continuous dynode electron multiplier detector system. The primary application of
the HAPSITE is for direct air measurements. The HAPSITE provides an MS-only mode of operation in which an
air sample can be directly introduced into the mass spectrometer via a membrane interface without GC separation.
An equilibrium headspace sample accessory can be used to concentrate volatile sample components from water,
soil, or sludge matrices in the gas phase above the sample. The accessory automatically introduces a portion of the
headspace gas into the GC/MS.
The HAPSITE GC/MS can be operated in a field-portable or transportable mode. In the transportable mode, a
suitable working environment, such as a trailer or van equipped with 110 V ac line power, is required for operation.
The HAPSITE GC/MS is mounted on a service module that contains a turbomolecular and roughing pump. The
combined weight of the system in the transportable mode is 75 pounds.
In the field-portable mode, the HAPSITE utilizes a proprietary chemical getter pumping system to maintain the
vacuum in the mass spectrometer. The pumping system, which contains no moving parts, provides a vacuum for
30 days, at 8 hours use per day, after which it must be replaced. In the field-portable mode, the weight of the
GC/MS is 35 pounds. The unit is rugged and water resistant and is designed to be operated in the typical
environment found in a manufacturing or chemical plant or at a hazardous waste site. It can withstand the normal
shocks and bumps encountered during field use. Battery life in the field-portable mode is 2 to 3 hours. The system
uses a self-contained carrier gas, and internal standard gases are used to tune and calibrate the mass spectrometer.
The internal standards can also be coinjected with air samples. The carrier gas supply is sufficient for 8 hours of
operation, and the internal standard gas supply will last 3 days at 8 hours per day of use. The headspace sampling
accessory can be operated via battery or ac line power, weighs 15 pounds, and will equilibrate up to four samples
simultaneously. A separate carrier gas supply is required for the headspace accessory.
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The HAPSITE consists of an inlet system (heated transfer line, sample pump, gas sampling valve); gas
chromatograph (isothermal oven and 27-m x 32-mm i.d. capillary column with Supelco SPB-1, l-|om film coating,
and 3-m precolumn for backflush), and mass spectrometer (membrane interface, quadrupole mass spectrometer,
internal computer, and hard disk). An external notebook personal computer (PC) is included with the system and
can be used for system control as well as to display and analyze data in real time. The external PC is not required
for operation once methods have been developed and stored on the HAPSITE internal PC.
Principle of Operation
The headspace sampling accessory uses a temperature-controlled environment to equilibrate a water, soil, or sludge
sample in a sealed vial. The volatile components in the sample matrix reach an equilibrium distribution between the
water sample and the vapor headspace above the sample. A portion of the headspace gas is transferred to the gas
sampling loop of the HAPSITE sample introduction system via a pump and carrier gas. The fixed volume of the
loop is then injected onto the GC precolumn. The principle of headspace equilibration and subsequent headspace
sampling is similar to SW-846 Method 3810 (EPA, 1986). The GC is operated isothermally at 60 °C and the
analytes are separated during an 11-minute run. Compounds that would elute after 11 minutes are backflushed
from the precolumn. Components elute from the GC column and enter the mass spectrometer ionizer assembly
through a poly(dimethylsilicone) membrane interface, which excludes most of the nitrogen carrier gas. The
membrane is maintained at 60 °C.
The separated compounds produce a characteristic 70-eV electron impact spectrum. When tuned to the
manufacturer's specifications, the spectrometer will produce consistent, National Institute of Standards and
Technology (NIST), library-searchable spectra for compounds in the low parts-per-billion to parts-per-million
range. The mass spectrometer can be operated in a full scan or selected ion mode. In this demonstration, the unit
was operated in full scan mode. Target compounds are identified by their GC retention time and comparison of
their mass spectra with a target compound library of spectra collected during calibration. Spectra of unknown
compounds can be compared with spectra in the NIST mass spectral library for tentative identification.
Quantification is accomplished by applying a relative response factor from a daily calibration standard. For the
headspace method, internal standards and surrogates are used to identify and compensate for matrix effects.
Internal and surrogate standards used in this demonstration were toluene-ds, chlorobenzene-d5, fluorobenzene, 4-
bromofluorobenzene, l,2-dichloroethane-d4, dibromofluoromethane, and dichlorobenzene-d4.
History of the Technology
Inficon, Inc. is one of the world's largest manufacturers of quadrupole mass spectrometers for application in a
variety of manufacturing processes. The mass spectrometer in the HAPSITE is an adaptation of this industrial
spectrometer product line. The HAPSITE GC/MS was originally designed to meet the requirements for source
emission testing as specified in the 1990 Clean Air Act amendments. The EPA has provisionally approved a
Method-301 validation for use of the HAPSITE in source-emission testing. The method has been approved for
source measurements of mineral calciners and is pending extension as a general source-testing method for gaseous
organic compounds.
Applications
The HAPSITE GC/MS and headspace sampling accessory are designed to measure the presence and concentration
of volatile organic compounds in water, soil, and sludge. The technology is applicable to site investigation and
characterization and to periodic monitoring to determine the migration of volatiles at remediation sites. Site
-------
engineers charged with definition of site contamination and monitoring the effectiveness of remediation techniques
comprise the largest group of potential users.
Advantages
The primary advantage of the HAPSITE is its ability to provide on-site results of a quality comparable to
conventional laboratory GC/MS. Decisions can be made in a cost-effective manner in regard to the need for further
sampling or the use of high-cost field equipment, such as drilling rigs. The initial cost is comparable to a
laboratory GC/MS equipped with a purge-and-trap accessory. Field-portable gas chromatographs with nonspecific
detectors are less costly but lack the ability of the GC/MS to identify and quantitate the organic components in
complicated sample matrices.
Limitations
The major limitation of the HAPSITE is the isothermal GC oven. Standard chromatographic run times of 10
minutes must be extended to 20 minutes in order to detect the dichlorobenzenes. The last five analytes from the
EPA Method 8260A list of compounds—l,2-dibromo-3-chloropropane, 1,2,4-trichlorobenzene, naphthalene,
hexachlorobutadiene, and 1,2,3-trichlorobenzene—are not compatible with this instrument. The technique is
limited to the determination of those compounds with sufficient volatility to be removed from the sample in
detectable concentrations using the equilibrium headspace technique.
Performance Characteristics
The HAPSITE/headspace GC/MS method is applicable to a wide range of organic compounds that have
sufficiently high volatility to be effectively removed from water, soil, or sludge samples via equilibrium headspace.
The chemical compounds shown in Table 2-1 have been evaluated by Inficon personnel during method development
and are suitable for analysis with the HAPSITE.
Practical Quantitation Limits and Method Detection Limits
The practical quantitation limits (PQLs) for chemical analytes in water are also listed in Table 2-1. The practical
quantitation limit is the lower bound of the calibration range and represents a peak-to-peak signal-to-noise ratio of
10:1. This signal level provides acceptable and reproducible (±20%) signal integration with the HAPSITE
software. The method detection limit (MDL) is estimated at one half the PQL.
Accuracy
The HAPSITE GC/MS headspace system is expected to perform at an accuracy level of ±25% or better over the
calibration range 95% of the time.
Precision
The precision, as represented by the relative standard deviation (RSD) on replicate measurements, is expected to be
<20% over the working range of the instrument.1
1 The relative standard deviation is the sample standard deviation divided by the mean value and multiplied by 100.
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Table 2-1. Inficon HAPSITE GC/MS Analyte List
Compound
Benzene
Bromobenzene
Bromochloromethane
Bromodichloromethane
Bromoform
Bromomethane
Carbon tetrachloride
Chlorobenzene
Chloroethane
Chloroform
Chloromethane
Dibromochloromethane
1 ,2-Dibromoethane
Dibromomethane
Dichlorodifluoromethane
1,1-Dichloroethane
1 ,2-Dichloroethane
1,1-Dichloroethene
c/s-1 ,2-Dichloroethene
frans-1 ,2-Dichloroethene
1 ,2-Dichloropropane
2,2-Dichloropropane
1,1-Dichloropropene
c/s-1 ,3-Dichloropropene
frans-1 ,3-Dichloropropene
Ethyl benzene
Isopropyl benzene
Methylene chloride
Styrene
1 ,1 ,1 ,2-Tetrachloroethane
1 ,1 ,2,2-Tetrachloroethane
Tetrachloroethene
Toluene
1,1,1-Trichloroethane
1,1,2-Trichloroethane
Trichloroethene
Trichlorofluoromethane
1 ,2,3-Trichloropropane
Vinyl chloride
orfrto-Xylene
mefa-Xylene
para-Xylene
CASa Number
71-43-2
108-86-1
74-97-5
75-27-4
75-25-2
74-83-9
56-23-5
108-90-7
75-00-3
67-66-3
74-87-3
124-48-1
106-93-4
95-50-1
75-71-8
75-35-3
107-06-2
75-35-4
156-59-2
156-60-5
78-87-5
594-20-7
563-58-6
10061-01-5
10061-02-6
100-41-4
98-82-8
75-09-2
100-42-5
630-20-6
79-34-5
127-18-4
108-88-3
71-55-6
79-00-5
79-01-6
75-69-4
96-18-4
75-01-4
95-47-6
108-38-3
106-42-3
PQI_b(ng/L)
5
10
15
5
15
5
5
5
10
5
5
5
5
5
10
5
5
5
5
5
10
10
10
10
10
5
10
5
5
20
20
5
5
5
5
5
5
15
5
5
5
5
Quant. Mass0
78
77
49
83
173
94
117
112
64
83
50
129
107
174
85
63
62
61
61
61
63
77
75
75
75
91
105
49
104
131
83
166
91
97
97
130
101
75
62
91
91
91
Notes: This table was provided by the instrument developer.
a CAS = Chemical Abstracts Service.
b PQL = practical quantitation limit.
0 Quant, mass = quantification mass.
The PQL is defined as a peak-to-peak signal-to-noise ratio of 10:1.
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Instrument Working Range
The HAPSITE can measure the volatile organics listed in Table 2-1 over a dynamic range of 104. For
tetrachloroethene, this would represent a working range of 5 |o,g/L to 50 mg/L. The working range of the instrument
can be adjusted from the lower limit upward by controlling the injection volume. For a sample containing
tetrachloroethene in the 10- to 100-mg/L range, the injection volume could be reduced by 50% to allow
measurement within the linear dynamic range of the instrument.
Comparison with Reference Laboratory Analyses
The FiAPSITE GC/MS analytical results for VOCs in water are expected to differ from reference laboratory
measurements, using Method 8260A (EPA, 1986b), by no more than ±35%, 95% of the time.
Data Completeness
Analysis and valid results will be reported for 90% or more of the samples presented for analysis during the
demonstration.
Other Analytical Performance Characteristics and Requirements
An MS tune check is performed every 12 hours to manufacturer's specification using the tuning compounds 1,3,5
tris-(trifluoromethyl) benzene and bromopentafluorobenzene. This tune check verifies the stability of the
instrument. The system must pass the tune check prior to sample analysis. In addition, the initial calibration curve
for all target analytes must generate a relative standard deviation of 30% or less for each compound in the
calibration. A GC/MS calibration check is performed at least once during every 12 hours of operation. Specific
analytes from the initial calibration curve are designated as calibration check compounds (CCCs). All CCC sample
results must be within 25% of initial calibration results. System blanks must also be run prior to field sample
analysis. Instrument carryover from a high concentration sample to a low concentration sample will be less than
0.25% of the high sample. For example, a 5-mg/L sample of tetrachloroethene should generate a result of less than
12.5 |o,g/L in a blank sample immediately following the high-level sample.
Other Field Performance Characteristics
The following performance parameters are provided by the instrument developer.
Instrument Setup and Disassembly Time
The HAPSITE GC/MS requires 30 minutes for setup and disassembly. The FIAPSITE and headspace accessory
can be shipped or carried as checked baggage. The carrier and internal standard gas canisters must be shipped as
hazardous materials.
Instrument Calibration Frequency During Field Use
An MS tune check is required at startup and after every 12 hours of operation. A daily calibration check is also
required at startup and after every 12 hours of operation.
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Ancillary Equipment Requirements
A power source of 110-V 60-Hz ac is desirable for initial startup of the instrument. Approximately 40% of the
battery life is expended in startup. Normal operation is to start the instrument on ac power prior to taking it to the
field. During field use, the instrument is powered by battery. Carrier gas and tuning gases are required. A 20-mL
Luer lock syringe, 40-mL volatile organic analysis (VOA) vials, and 10-|aL syringes for internal standards and
surrogates are also required.
Field Maintenance Requirements
Battery life is 3 hours; carrier gas must be replaced every 8 hours. Operation in the field requires a nonevaporative
getter or chemical pump. The usable life on the pump is 30 days at 8 hours of operation per day.
Sample Throughput Rate
Initial headspace analysis equilibration time for the first sample is 30 minutes. Analysis time is 15 minutes per
sample. Up to four samples can be equilibrated simultaneously while an analysis is being carried out on a fifth
sample.
Operator Training Requirements and Ease of Operation
The HAPSITE GC/MS requires 3 days of training for technical personnel familiar with GC/MS operation. This
training includes setup and maintenance of the instrument and methods. Training for field operation of the
instrument (sample preparation and injection only) requires 1 day.
10
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Chapter 3
Demonstration Design and Description
Introduction
This chapter summarizes the demonstration objectives and describes related field activities. The material is
condensed from the Demonstration Plan for Wellhead Monitoring Technology Demonstration (Sandia, 1997),
which was reviewed and approved by all participants prior to the field demonstration.
Overview of Demonstration Design
The primary objective was to test and verify the performance of field-portable characterization and monitoring
technologies for the analysis of chlorinated VOCs in groundwater. Specific demonstration objectives are listed
below:
• verify instrument performance characteristics that can be directly quantified; such factors include response to
blank samples, measurement accuracy and precision, data completeness, sample throughput, etc.;
• verify instrument characteristics and performance in various qualitative categories such as ease of operation,
required logistical support, operator training requirements, transportability, versatility, and other considerations;
and
• compare instrument results with data from standard laboratory analytical methods currently used to analyze
groundwater for chlorinated VOCs.
The experimental design included a consideration of both quantitative and qualitative performance factors for each
participating technology.
Quantitative Factors
The primary quantitative performance factors that were verified included such instrument parameters as precision
and accuracy, blank sample response, instrument performance at sample concentrations near its limit of detection,
sample throughput, and comparability with reference methods. An overview of the procedures used to determine
quantitative evaluation factors is given below.
Precision
Measurement uncertainty was assessed over the instrument's working range by the use of blind replicate samples
from a number of performance evaluation (PE) mixtures. Eight PE mixtures containing chlorinated VOCs at
concentrations ranging from 50 |o,g/L to over 1000 |o,g/L were prepared and distributed at each site. The mixtures
were prepared from certified standard mixes with accompanying documentation giving mixture content and purity.
The relative standard deviation was computed for each compound contained in each set of replicate PE samples and
was used as a measure of instrument precision.
11
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Accuracy
Instrument accuracy was also evaluated by using results from the PE samples. A mean recovery was computed for
each reported compound in each PE mixture. The average instrument result for each compound, based on four
blind replicate sample analyses, was compared against the known concentration in the PE mixture and reported as
the average percent recovery and the absolute percent difference.
Blank Sample Response
At least two blank groundwater samples were analyzed with each instrument system per demonstration day. These
were distributed as blind samples in the daily set of samples provided to each instrument operator. The results from
these samples were used to assess the degree to which instrument contamination and sample-to-sample carryover
resulted in a false positive.
Low-Level Sample Response
The scope of this demonstration did not include an exhaustive determination of instrument detection limits.
However, 10 replicate spiked samples at concentrations near typical regulatory action limits were provided for
analysis at each site to validate the instrument performance at these low concentration levels. The results from
these analyses were compiled as detects and nondetects and were used to calculate the percentage of correct
determinations and false negatives.
Sample Throughput
Sample throughput takes into account all aspects of sample processing, including sample preparation, instrument
calibration, sample analysis, and data reduction. The multiday demonstration design permitted the determination of
sample throughput rates over an extended period. Thus the throughput rates are representative of those likely to be
observed in routine field use of the instrument.
Laboratory-Field Comparability
The degree to which the field measurements agree with reference laboratory measurements is a useful parameter in
instrument evaluation. In this demonstration, comparisons were made on groundwater samples by computing the
absolute percent difference between laboratory and field technology results for all groundwater contaminants
detected. Linear regression of the two data sets was also carried out to determine the strength of the linear
correlation between the two data sets.
Qualitative Factors
Key qualitative instrument performance factors observed during the demonstration were instrument portability,
logistical support requirements, operator training requirements, and ease of operation. Logistical requirements
include the technology's power requirements, setup time, routine maintenance, and the need for other equipment or
supplies, such as a computers, reagent solutions, or gas mixtures. Qualitative factors were assessed during the
demonstration by review of vendor information and on-site audits. Vendors provided information concerning these
factors during preparation of the demonstration plan. Vendor claims regarding these specifications and
requirements are included in Chapter 2. During the field demonstration phase, auditors from the verification
organization observed instrument operation and documented the degree of compliance with the instrument
specifications and methodology. Audit results are included in Chapter 6.
12
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Site Selection and Description
Two sites—the DOE Savannah River Site near Aiken, South Carolina, and McClellan Air Force Base near
Sacramento, California—were chosen for this demonstration. This section provides a brief history of each site, a
discussion of important geological features, and an outline of the nature and extent of contamination at each site.
The sites chosen met the following selection criteria:
• presence of chlorinated VOCs in groundwater;
• multiple wells at the site with a variety of contaminants and depths;
• documented well-sampling history with characterization and monitoring data;
• convenient access; and
• support facilities and services at the site.
Savannah River Site
The Savannah River Site is operated under contract by the Westinghouse Savannah River Company. The complex
covers 310 square miles in western South Carolina, adjacent to the Savannah River, as shown in Figure 3-1. The
SRS was constructed during the early 1950s to produce the basic materials used in the fabrication of nuclear
weapons, primarily tritium and plutonium-239. Production of weapons material at the SRS also produced unusable
byproducts such as intensely radioactive waste. In addition to these high-level wastes, other wastes at the site
include low-level solid and liquid radioactive wastes, transuranic waste, hazardous chemical waste, and mixed
waste.
South Carolina
// 1 Savannah
'%/. '•'"'" /
Athens^! .Ajke
\ Atlanta O
Georgia
Figure 3-1. The general location of the Savannah River Site in
the southeast United States.
Geological Characteristics
The SRS is located on the upper Atlantic Coastal Plain. The site is underlain by a thick wedge (approximately
1000 feet) of unconsolidated Tertiary and Cretaceous sediments that overlie Precambrian and Paleozoic
metamorphic rocks and consolidated Triassic sediments (siltstone and sandstone). The younger sedimentary section
consists predominantly of sand and sandy clay. The depth to the water table from the surface ranges from 50 to
170 feet for the wells used in this demonstration.
13
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Groundwater and Monitoring Wells
The wells selected for sampling in this demonstration were in the A/M area, located in the northwest section of the
site. This area encompasses an abandoned process transfer line that, beginning in 1958, carried wastewater for 27
years from M-area processing facilities to a settling basin. Site characterization data indicate that several leaks
occurred in the transfer line, which is buried about 20 feet below the surface, producing localized contamination.
Past industrial operations resulted in the release of chlorinated solvents, primarily trichloroethene (TCE),
tetrachloroethene (PCE), and 1,1,1-trichloroethane, to the subsurface.
The A/M area monitoring-well network, shown in Figure 3-2, consists of approximately 400 wells. The dark
squares in the figure indicate soil borings and the light squares indicate monitoring wells. The largest group of
wells, comprising approximately 70% of the total, are associated with the plume originating from the process
transfer lines and the settling basin. The majority of these wells are constructed of 4-inch poly(vinyl chloride)
(PVC) casing with wire-wrapped screens varying in length from 5 to 30 feet. The wells are screened either in the
water-table aquifer (M-area aquifer, well depths ranging from 30 to 170 feet), the underlying tertiary aquifer (Lost
Lake aquifer, well depths ranging from 170 feet to 205 feet), or a narrow permeable zone within the confining unit
above the cretaceous aquifer (Crouch Branch Middle Sand, well depths ranging from 215 to 260 feet). The wells
are all completed with approximately 2.5 feet of standpipe above ground and a protective housing. Most wells are
equipped with a dedicated single-speed centrifugal pump (1/2 hp Grundfos Model 10S05-9) that can be operated
with a control box and generator. Wellhead pump connections also contain a flow meter and totalizer for
monitoring pumped volumes.
All the wells are measured quarterly for water levels. On a semiannual basis, all point-of-compliance wells (41),
plume definition wells (236), and background wells (6) are sampled to assess compliance with groundwater
protection standards. Other water quality parameters such as conductivity, turbidity, temperature, and pH are
Light Gray = High TCE Concentrations
Dark Gray = Lower TCE Concentrations
Each Grid Square = 1000 Feet
The 10 wells used in the demonstration were located in the plume shown.
The demonstration setup area was located very near the center of the figure.
Figure 3-2. A map of the A/M area at the Savannah
River Site showing the subsurface TCE plume.
14
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also measured. As a part of the monitoring program, VOCs are measured using EPA Method 8260A at an off-site
contract laboratory. The most recent (winter of 1996) quarterly water analysis results for the 10 wells used in this
demonstration are shown in Table 3-1. Well cluster numbers shown in the table include a letter designation (A
through D) that indicates the relative screening depth and aquifer zone. The A wells are the deepest of a cluster,
while the D wells mark the shallowest.
Table 3-1. Quarterly Monitoring Results for SRS Wells Sampled in the Demonstration
Sample Description
Very low 1
Very low 2
Low 1
Low 2
Mid 1
Mid 2
Very high 1
Very high 2
Very high 1
Very high 2
Well Number
MSB 33B
MSB 33C
MSB 18B
MSB 37B
MSB4D
MSB 64C
MSB4B
MSB 70C
MSB 14A
MSB8C
Compound
Trichloroethene
Tetrachloroethene
Trichloroethene
Tetrachloroethene
Trichloroethene
Tetrachloroethene
1,1-Dichloroethene
Trichloroethene
Tetrachloroethene
Carbon tetrachloride
Trichloroethene
Tetrachloroethene
Trichloroethene
Tetrachloroethene
1,1-Dichloroethene
Trichloroethene
Tetrachloroethene
Trichloroethene
Tetrachloroethene
1,1-Dichloroethane
1,1,1-Trichloroethane
Trichloroethene
Tetrachloroethene
Trichloroethene
Tetrachloroethene
Qtrly. Results3 (ng/L)
10
5
5
12
12
12
3
28
2
2
219
178
51
337
13
830
43
1290
413
61
17
3240
2440
3620
2890
a Winter 1996.
McClellan Air Force Base
McClellan Air Force Base is located 7 miles northeast of downtown Sacramento, California, as shown in
Figure 3-3. The installation consists of about 3000 acres bounded by the city of Sacramento on the west and
southwest, the city of Antelope on the north, the unincorporated areas of Rio Linda on the northwest, and North
Highlands on the east.
McClellan has been an active industrial facility since its dedication in 1936, when it was called the Sacramento Air
Depot. Operations have changed from maintenance of bombers during World War II and the Korean War, to
maintenance of jet aircraft in the 1960s, and now include the maintenance and repair of communications equipment
and electronics. McClellan currently operates as an installation of the Air Force Materiel Command and employs
approximately 13,400 military and civilian personnel.
15
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Elverta Road
Antelope
N
1 2
— —
Scale in Miles
Figure 3-3. A map of Sacramento and vicinity showing the
location of McClellan Air Force Base.
Currently, most of the industrial facilities are located in the southeastern portion of the base. The southwestern
portion has both industrial and storage areas. In the far western part are vernal pools and wetland areas. Between
these wetlands and the engine test cells along the taxiways is an open area that was used for disposal pits.
McClellan Air Force Base is listed on the EPA Superfund National Priorities List of hazardous waste sites. The
most important environmental problem at MAFB is groundwater contamination caused by the disposal of
hazardous wastes, such as solvents and oils, into unlined pits. Approximately 990 acres beneath McClellan are
contaminated with volatile organic compounds. Remediation activities at MAFB include an extensive groundwater
pump-and-treat network, as well as soil-vapor extraction systems.
McClellan has been designated a Chlorinated Hydrocarbons Remedial Demonstration Site as part of the National
Environmental Technology Test Sites program. The Strategic Environmental Research and Development Program
is the parent organization that provides support staff for the environmental technologies undergoing development
and testing at MAFB.
16
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Geological Characteristics
Surface features at MAFB include open grassland, creeks and drainages, and vernal pools, as well as industrial,
residential, and runway areas. The land surface is a relatively flat plain that slopes gently to the west. Surface
elevations range from about 75 feet above mean sea level on the eastern side of the base to about 50 feet above
mean sea level on the western side.
Surface soils at MAFB are variable, but are generally sediments that have formed from stream erosion of granite
rocks in the Sierra Nevada. Soil in the vadose zone—the unsaturated region between the surface and the
groundwater table—is composed of interbedded layers of sands, silts, and clays. The vadose zone ranges from 90
to 105 feet. Clays and hardpan layers in this zone slow, but do not halt, infiltration of liquids into the underlying
aquifer.
The groundwater beneath MAFB behaves as one hydrogeologic unit. This single aquifer has been divided into five
groundwater monitoring zones, designated A, B, C, D, and E, from shallowest to deepest.
Groundwater and Monitoring Wells
An estimated 14 billion gallons of contaminated water underlie MAFB. Trichloroethene is the most frequently
detected contaminant in the subsurface groundwater. Over 90% of the contaminant mass is located in the A zone,
the shallowest portion of the aquifer. An estimated surface area of approximately 664 acres is underlain by a
plume in the A zone that exceeds the 5-(jg/L maximum contaminant level for TCE, as shown in Figure 3-4.
Groundwater contaminants consistently detected above federal maximum concentration limits (MCLs) are shown in
Table 3-2.
Other detected compounds that are either below regulatory levels or are not currently regulated are also shown in
the table.
Monitoring wells at McClellan range from 2 to 8 inches in diameter. Well casings are Schedule 5 stainless steel
(304) and the well screen is Johnson stainless steel (304) with a 0.01- or 0.02-inch screen slot size. The screen is
surrounded by either 16 x 40 or 8 x 20 mesh gravel pack to a level about 3 feet above the screen. An
approximately 3-foot sand bridge and 3-foot bentonite seal are placed above the gravel pack. A concrete sanitary
seal containing about 3% bentonite powder is used to seal the well casing between the bentonite seal and the ground
surface.
For this demonstration, monitoring wells that penetrate both A and B aquifer zones in operational units A and B
were selected for sample collection. Quarterly monitoring data exist for 354 wells at the A and B zone aquifer
levels in these operational units. Monitoring results for TCE were used to select ten wells. Groundwater TCE
concentrations in the selected wells ranged from very low (-10 |og/L) to very high (>5000 |o,g/L) levels.
Wells that had multiple contaminants or nonchlorinated contaminants were given selection preference over those
with only a few chlorinated hydrocarbons. The most recent (winter of 1996) monitoring results for the wells chosen
for this demonstration are shown in Table 3-3.
Sample Set Descriptions
The experimental design of the demonstration specified the preparation and collection of an approximately equal
number of PE samples and groundwater samples for distribution to the participants and reference laboratory.
Descriptions of the PE and groundwater samples and their preparation are given below.
17
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N
0
Figure 3-4. Subsurface TCE plumes at McClellan Air Force Base in the
shallowest (A) aquifer layer. The circular lines enclose plume concentrations in
excess of 5 ng/L TCE. OU refers to operational units. Monitoring wells used in
the demonstration were primarily in OUs A and B. The demonstration setup area
was very near OU D (upper left in the figure).
18
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Table 3-2. Groundwater Contaminants at MAFB
Detected above MCLa
Benzene
Carbon tetrachloride
Chloroform
1 ,2-Dichlorobenzene
1,2-Dichloroethane
1,1-Dichloroethene
1 ,2-Dichloroethene (cis and trans)
Tetrachloroethene
1,1,1-Trichloroethane
Trichloroethene
Vinyl chloride
Detected below MCL
Bromodichloromethane
Trichlorofluoromethane
Detected - Not Regulated
Acetone
2-Butanone
1,1-Dichloroethane
4-Methyl-2-pentanone
Toluene
MCL = maximum concentration limit.
Table 3-3. Quarterly Monitoring Results for MAFB Wells Sampled in the Demonstration
Sample Description
Very low 1
Very low 2
Low 1
Low 2
Midi
Mid 2
Highl
High 2
Well Number
EW-86
MW-349
MW-331
MW-352
EW-87
MW-341
MW-209
MW-330
Compound
Trichloroethene
1,1-Dichloroethene
Trichloroethene
Tetrachloroethene
Chloroform
Acetone
1,1-Dichloroethane
Carbon tetrachloride
Chloroform
Trichloroethene
c/s-1 ,2-Dichloroethene
1,1-Dichloroethane
Tetrachloroethene
Freon11
1,1,1-Trichloroethane
1,1-Dichloroethene
Trichloroethene
c/s-1 ,2-Dichloroethene
Trichloroethene
c/s-1 ,2-Dichloroethene
Chloroform
Trichloroethene
c/s-1 ,2-Dichloroethene
frans-1 ,2-Dichloroethene
Chloroform
Trichloroethene
c/s-1 ,2-Dichloroethene
frans-1 ,2-Dichloroethene
Qtrly. Results3 (ng/L)
8
13
9
5
8
9
16
5
7
19
41
6
5
115
17
334
220
5
350
18
53
586
80
13
44
437
64
9
19
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Table 3-3. Quarterly Monitoring Results for MAFB Wells Sampled in the Demonstration
(Continued)
Sample Description
Very high 1
Very high 2
Well Number
MW-334
MW-369
Compound
1,1-Dichloroethene
Benzene
Carbon tetrachloride
Chloroform
Dichloromethane
Trichloroethene
c/s-1 ,2-Dichloroethene
Xylene
1,2-Dichloroethane
Carbon tetrachloride
Chloroform
Tetrachloroethene
Trichloroethene
c/s-1 ,2-Dichloroethene
Qtrly. Results3 (ng/L)
1000
705
728
654
139
20,500
328
59
13
91
84
6
10,200
246
Winter 1996.
PE Samples and Preparation Methods
Three different commercially available (Supelco, Bellefonte, Pennsylvania) standard solutions of chlorinated VOCs
in methanol were used to prepare the PE mixtures. The standard solutions were supplied with quality control
documentation giving the purity and weight of the compounds in the mixture. The contents of the three mixtures,
termed mix 1, mix 2, and mix 3, are given in Table 3-4. VOC concentration levels in these standard solutions were
either 200 |o,g/L or 2000 |o,g/L. The PE mixtures were prepared by dilution of these standard solutions.
The number of replicate samples and the compound concentrations from each of the nine PE mixtures prepared at
each site are given in Table 3-5 for the SRS and Table 3-6 for MAFB. Ten replicates of the mixture with the
lowest concentration level were prepared so technology performance statistics near typical regulatory action levels
could be determined. Four replicates were prepared for each technology and the reference laboratory from the other
eight PE mixtures. The highest-level PE mixture, denoted "spike/low" in the tables, consisted of high-level (>1000
Hg/L) concentrations of TCE and PCE (and other compounds at MAFB as noted in the table) in the presence of a
low-level (50 or 100 ng/L) PE mixture background. Eight blank samples were also provided to each technology at
each site. The blank samples were prepared from the same batch of deionized, carbon-filtered water used to
prepare the PE mixtures.
Performance evaluation mixtures were prepared in either 8-L or 10-L glass carboys equipped with bottom
spigots. Stock PE solutions were dispensed with microsyringes into a known volume of deionized, carbon-
filtered water in the carboy. The mixture was gently stirred for 5 minutes with a Teflon-coated stir bar prior to
dispensing samples from the bottom of the carboy. A twofold excess volume of PE mixture was prepared in
order to ensure a sample volume well in excess of the required volume. The mixture was not stirred during
sample dispensing to minimize headspace losses in the lower half of the carboy. Headspace losses that did occur
during dispensing were limited to the top portion of the mixture, which was discarded after the samples were
dispensed. Samples were dispensed into bottles specified by participants (40 mL, 250 mL, and 1 L) with zero
20
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Table 3-4. Composition of PE Source Materials
PE Mix 1 - Purgeable A
Supelco Cat. No. 4-8059
Lot LA68271
Trichlorofluoromethane
1,1-Dichloroethane
Dichloromethane
1,1-Dichloroethene
Chloroform
Carbon tetrachloride
Trichloroethene
1,2-Dichloropropane
1 ,1 ,2-Trichloroethane
Tetrachloroethene
Dibromochloromethane
Chlorobenzene
1 ,2-Dichlorobenzene
2-Chloroethyl vinyl ether
PE Mix 2 - VOC 3
Supelco Cat. No. 4-8779
Lot LA64701
1,1-Dichloropropene
1,2-Dichloroethane
Trichloroethene
1 ,2-Dichloropropane
1,1,2-Trichloroethane
1,3-Dichloropropane
1 ,2-Dibromoethane
1 ,1 ,1 ,2-Tetrachloroethane
1 ,1 ,2,2-Tetrachloroethane
1 ,2,3-Trichloropropane
1 ,2-Dibromo-3-chloropropane
c/s-1 ,3-Dichloropropene
frans-1 ,3-Dichloropropene
Hexachlorobutadiene
PE Mix 3 - Purgeable B
Supelco Cat. No. 4-8058
Lot LA 63978
1,2-Dichloroethane
1 ,1 ,2,2-Tetrachloroethane
c/s-1 ,3-Dichloropropene
frans-1 ,3-Dichloropropene
frans-1 ,2-Dichloroethene
1,1,1-Trichloroethane
Benzene
Bromodichloromethane
Toluene
Ethyl benzene
Bromoform
Table 3-5. PE Sample Composition and Count for SRS Demonstration
Sample Concentration Level
Very low level
Low level
Mid level
High level
Spike / low
Total number of samples
PE Mixture - Mixture Concentration3
VOC Mix 1 -10|ig/L
VOC Mix 1 - 50 jjg/L
VOC Mix 2- 100|ig/L
VOC Mix 1 - 200 jjg/L
VOC Mix 2- 200|ig/L
VOC Mix 1 - 600 jjg/L
VOC Mix 2- 800|ig/L
1 .02 mg/L TCE spike + 50 ng/L mix 1
1 .28 mg/L TCE and 1 .23 mg/L PCE
spike + 1 00 ng/L mix 2
No. of Replicates
10
4
4
4
4
4
4
4
4
42
a TCE = trichloroethene; PCE = tetrachloroethene.
headspace. The samples for field analysis were not preserved with chemical additives since sterile, nutrient-free
water was used in their preparation.
Reference laboratory samples were preserved by acidification as specified in Method 8260A. Following
preparation, all samples were kept under refrigeration until they were distributed to participants. All PE mixtures
were prepared and dispensed on the weekend before the demonstration week.
21
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Table 3-6. PE Sample Composition and Count for MAFB Demonstration
Sample Concentration Level
Very low level
Low level
Mid level
High level
Spike / low
Total number of samples
PE Mixture - Mixture Concentration3
VOC Mix 3- 10|ig/L
VOC Mix 3 - 50 jjg/L
VOCMix2- 100|ig/L
VOC Mix 3 - 200 jjg/L
VOC Mix 2- 300|ig/L
VOC Mix 1 - 600 jjg/L
VOC Mix 2- 800|ig/L
1 .22 mg/L TCE, 1 .00 mg/L PCE, 0.50 mg/L 1 1 DCA,
and 0.50 mg/L BNZN spike + 1 00 ug/L mix 3
1 .04 mg/L 1 1 DCA, 0.86 mg/L BNZN, 0.57 mg/L
TCE, and 0.51 mg/L PCE spike + 50 ug/L mix 2
No. of Replicates
10
4
4
4
4
4
4
4
4
42
TCE = trichloroethene; PCE = tetrachloroethene; 11 DCA = 1,1 -dichloroethane; BNZN = benzene.
Groundwater Samples and Collection Methods
A total of 33 groundwater samples were provided to each participant and reference laboratory at each
demonstration site. These samples were collected from 10 wells selected to cover TCE concentrations ranging from
10 ug/L to >1000 ug/L. The presence of other groundwater contaminants was also considered in well selection, as
noted previously. Samples from each well were prepared in either triplicate or quadruplicate to allow statistical
evaluation of instrument precision and accuracy relative to the reference laboratory results.
Groundwater at both sites was sampled by the same contract personnel who conduct sampling for quarterly well
monitoring. Site-specific standard operational procedures, published in the demonstration plan, were followed at
both sites. The sampling procedure is briefly summarized in the next paragraph.
The wells were purged with three well volumes using a submersible pump. During the purge, pH, temperature, and
conductivity were monitored. Following well purge, pump flow was reduced and the purge line was used to fill a
10-L glass carboy. This initial carboy volume of groundwater was discarded. The carboy was filled to between 9
and 10 L a second time at a fill rate of 2 to 3 L/minute with the water stream directed down the side of the carboy
for minimal agitation. The filled carboy was gently mixed with a Teflon stir bar for 5 minutes. Zero-headspace
samples were immediately dispensed from the carboy while it was at the wellhead in the same manner as PE
samples. Either three or four replicate samples were prepared for each technology and the reference laboratory.
Following dispensing, the sample bottles were placed in a cooler and held under refrigeration until they were
distributed to the participants. Groundwater sampling was completed during the first 2 days of each demonstration.
Lists of the sampled wells and quarterly monitoring results are given in Tables 3-1 and 3-3 for the SRS and MAFB,
respectively.
Sample Handling and Distribution
The distribution and status of all samples were tracked with chain-of-custody forms. Samples were dispensed to
participants in small coolers containing a supply of blue ice. Normally, two sets of either 10 or 11 samples were
distributed to participants each day during the 4 days of the demonstration, for a total of 83 samples, including
blanks, at each site.
22
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Some of the participants required information concerning the content of the samples prior to carrying out an
analysis. This information was noted on the chain-of-custody form for each PE and groundwater sample, and was
made available to the participants. Recorded information included:
• number of contaminants in the sample;
• list of contaminants in the sample;
• boiling point range of sample constituents; and
• approximate concentration range of contaminants in sample (low, mid, high).
The type of information provided during this demonstration would be required by the technology as a part of its
normal operational procedure and did not compromise the results of the test. The information provided to each of
the participants is documented in Chapter 5.
Field Demonstration Schedule and Operations
The following schedule was followed at both sites. The field team arrived on the Thursday prior to the
demonstration week. Performance evaluation samples were prepared on Friday, Saturday, and Sunday.
Technology participants arrived at the site on Monday morning and immediately began instrument setup. The first
set of PE samples was normally distributed to all participants by midday Monday. The groundwater sampling
crew, consisting of at least two on-site contractors and at least one ETV field-team member, carried out sampling of
the 10 wells on Monday and Tuesday. The first groundwater samples were distributed on Wednesday. Thursday
was reserved as a visitor day during which local and regional regulatory personnel and other potential instrument
users were invited to hear presentations about instrument capabilities as well as to view the instruments in
operation. Sample analysis was also performed on Thursday. On Friday, the final day of the demonstration,
participants finished sample analysis, packed up, and departed by midafternoon.
Site Operations and Environmental Conditions
Instruments were deployed in parking lots or open fields adjacent to the well networks sampled during each
demonstration. All participants came to the site self-equipped with power and shelter. Some came with field-
portable generators and staged under tent canopies; others operated their instruments inside vehicles and used dc-to-
ac power inverters connected to the vehicle's battery. Tables were provided for those participants who required a
work space. Each team provided its own instrument operators. Specifics regarding instrument setup and the
qualifications, training, and experience of the instrument operators are given in Chapter 6.
The SRS demonstration took place on September 8 through 12, 1997, and the MAFB demonstration on
September 22 through 26, 1997. The verification organization team staged its operations out of a tent at the SRS
and out of a mobile laboratory at MAFB. The PE mixtures at the SRS were prepared at a nearby SRS laboratory
facility and in the mobile laboratory at MAFB. Refrigerators at on-site facilities of the groundwater sampling
contractors were used to store the samples at both sites prior to their distribution.
Environmental conditions at both sites are summarized in Table 3-7. Conditions at SRS were generally hot and
humid. Sporadic rain showers were encountered on one of the test days, but did not impede demonstration
activities. Conditions at MAFB were initially hot and progressed to unseasonably hot. Moderately high winds
were also encountered during the last 2 days at MAFB.
23
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Table 3-7. Weather Summary for SRS and MAFB During Demonstration Periods
Site/Parameters
Mon
Tue
Wed
Thu
Fri
SRS
Temperature range (°C)
Relative humidity range (%)
20-34
25-68
21 -33
28-67
21 -28
51 -71
18-30
40-70
19-33
26-70
MAFB
Temperature range (°C)
Relative humidity range (%)
Wind speed range (knots)
17-33
17-72
0-7
18-36
25-47
3-6
18-37
15-59
1 -6
24-35
17-67
4-13
24-35
31 -83
2-11
Note: Ranges are given for the 7 a.m. to 7 p.m. time interval.
Field Audits
Field auditors were used to observe and record specific features of technology operations. The demonstration goal
was to have at least two auditors observe each technology over the course of the two field demonstrations. Audit
results are documented in Chapter 6. The following checklist was used by the audit team as a guideline for
gathering information during the audit:
• description of equipment used;
• logistical considerations, including size and weight, shipping and power requirements, other required accessories;
• historical uses and applications of the technology;
• estimated cost of the equipment and its field operation;
• number of operators required;
• required operator qualifications;
• description of data produced;
• compounds that the equipment can detect;
• approximate detection limits for each compound, if available;
• initial calibration criteria;
• calibration check criteria;
• corrective actions for unacceptable calibrations;
• specific QC procedures followed;
• QC samples used;
• corrective action for QC samples;
• sample throughput rate;
• time requirements for data analysis and interpretation;
• data output format and description;
• specific problems or breakdowns occurring during the demonstration;
• possible sample matrix interference; and
• other auditor comments and observations.
24
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Data Collection and Analysis
The analytical results were collected in hardcopy format at the end of each day. These results were used to
document sample completion and throughput. The participants also provided a compilation of their results on
computer disks at the conclusion of each demonstration week. No feedback on analytical results or performance
was given to the participants during the course of either demonstration week. Following the SRS demonstration,
and only after all results were submitted, was qualitative verbal feedback given to each participant concerning their
accuracy and precision on SRS PE sample results. This was reasonable since a well-defined monitoring plan would
use preliminary samples to determine control limits and to make system modifications or refinements prior to
advancing to the next phase of sampling and analysis. Three weeks following the MAFB demonstration, copies of
all submitted data were entered into spreadsheets by the verification organization and transmitted to participants for
final review. This gave each participant the opportunity to detect and change calculation or transcription errors. If
other more substantive changes were proposed, they were submitted to the verification organization, along with
documentation outlining the rationale for the change. Following this final data review opportunity, no other data
changes were permitted. The extent and nature of any changes are discussed in Chapter 6.
Demonstration Plan Deviations
The following deviations from the written demonstration plan were recorded during the field demonstration. The
impact of each deviation on the overall verification effort, if any, is also included.
• Five blank samples were submitted to the reference laboratory from the SRS demonstration instead of the
8 samples specified in the demonstration plan. The impact on the verification effort was minimal since a total of
13 blanks (8% of the total field sample count) were analyzed by the reference laboratory.
• During groundwater sampling of SRS well MSB 14A, two 250-mL sample bottles were not filled. Omission of
this sample resulted in a double replicate sample set instead of a triple replicate for Electronic Sensor Technology
and Sentex. The impact on the study was insignificant since this omission accounted for only 1 sample out of a
total groundwater sample count of 33.
• The demonstration plan specified that only two VOC mixtures would be used at each demonstration site. In fact,
three mixtures were used at the MAFB demonstration (Table 3-6) to add complexity to the sampling. This
change caused some minor confusion with one of the developers, who was not expecting this particular set of
compounds at MAFB. The most significant impact of this change was a loss of time for the affected developer as
a result of extended data review of the unanticipated mixture. The misunderstanding was verbally clarified and
no further problems were encountered. The results from the high-level VOC mix 1 were not used in the statistical
analyses.
25
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Chapter 4
Laboratory Data Results and Evaluation
Introduction
A reference laboratory was used to verify PE sample concentrations and to generate analytical results for all
groundwater samples using EPA Method 8260A. This chapter includes a brief description of the reference
laboratory and its data quality control program; the methodology and accompanying quality control procedures
employed during sample analysis; and laboratory results and associated measures of data quality for both
demonstration sites.
Reference Laboratory
DataChem Laboratories (DCL) in Salt Lake City, Utah, was chosen as the reference laboratory for both phases of
this demonstration. This is a full-service analytical laboratory with locations in Salt Lake City and Cincinnati,
Ohio. It provides analytical services in support of environmental, radiological, mixed-waste, and industrial hygiene
programs. DataChem's qualifications include U.S. EPA Contract Laboratory Program participation in both
inorganic and organic analysis and American Industrial Hygiene Association accreditation, as well as U.S. Army
Environmental Center and U.S. Army Corps of Engineers (Missouri River Division) certification. State-specific
certifications for environmental analytical services include Utah, California, Washington, New Jersey, New York,
Florida, and others.
Laboratory Selection Criteria
Selection criteria for the reference laboratory included the following: relevant laboratory analytical experience,
adequacy of QC documentation, turnaround time for results, preselection audit results, and cost. Early discussions
with DCL revealed that the laboratory conducts a high number of water analyses using Method 8260A. Prior to
laboratory selection, a copy of the DataChem Quality Assurance Program Plan (DataChem, 1997) was carefully
reviewed. This document outlines the overall quality assurance program for the laboratory and provides specific
quality control measures for all the standard analytical methods used by the laboratory. Laboratory analysis and
reporting time for sample analysis was 21 days, with a per-sample cost of $95.
In June 1997, Sandia sent several PE water samples to DCL for evaluation. Laboratory performance on these
samples was reviewed during an audit in June 1997. The laboratory detected all compounds contained in the PE
mixtures. Reported concentration levels for all compounds in the mixtures were within acceptable error margins.
The audit also indicated that the laboratory conducted its operations in accordance with its QA plan. The results of
this preliminary investigation justified the selection of DCL as the reference laboratory and provided ample
evidence of the laboratory's ability to correctly use Method 8260A for the analysis of demonstration samples.
26
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Summary of Analytical Work by DataChem Laboratories
In addition to the preselection audit samples noted above, DCL also analyzed predemonstration groundwater
samples collected at SRS in August 1997. During the demonstration phase, DCL was sent split samples of all PE
and groundwater samples given to the demonstration participants from both the Savannah River and McClellan
sites. A total of 90 and 91 samples from the SRS and MAFB demonstrations, respectively, were received and
analyzed by the laboratory. Over the course of 1 month, demonstration samples were run in 9 batches of
approximately 20 samples per batch. The results were provided in both hardcopy and electronic format. The hard
copy included all paperwork associated with the analysis, including the mass spectral information for each
compound detected and complete quality control documentation. The electronic copy was provided in spreadsheet
format and included only the computed result for each target compound in each sample.
Preselection evaluation of DCL established their competence in the use of Method 8260A. In light of these findings
and in an effort to expedite laboratory analysis of demonstration samples, an estimate of the concentration levels of
target compounds in both PE and groundwater samples was provided to the laboratory with each batch of samples.
With a knowledge of the approximate concentration range of the target compounds, the analyst was able to dilute
the sample appropriately, thereby eliminating the need to do multiple dilutions in order to obtain a suitable result
within the calibrated range of the instrument.
Summary of Method 8260A
Method 8260A, which is included in the EPA SW-846 compendium of methods, is used to measure volatile organic
compounds in a variety of solid waste matrices, including groundwater (EPA, 1996b). The method can be used to
quantify most volatile organic compounds with boiling points below 200 °C that are either insoluble or only slightly
soluble in water. The method employs a chromatography/mass spectrometric procedure with purge-and-trap
sample introduction. An inert gas is bubbled through a vessel containing the water sample. The volatile organic
compounds partition into the gas phase and are carried to a sorbent trap, where they are adsorbed. Following the
purge cycle, the sorbent trap is heated and the volatile compounds are swept into the GC column, where they are
separated according to their boiling points. The gas chromatograph is interfaced directly to a mass spectrometer
that bombards the compounds with electrons as they sequentially exit the GC column. The resulting fragments,
which possess charge and mass characteristics that are unique for each compound, are detected by the
spectrometer's mass detector. The signal from the mass detector is used to build a compound mass spectrum that is
used to identify the compound. The detector signal intensities for selected ions unique to each target compound are
used to quantify the amount of the compound in the sample.
Method 8260A Quality Control Requirements
Method 8260A specifies a number of quality control activities to be carried out in conjunction with routine sample
analysis. These activities are incorporated into DCL QA documentation and are summarized in Table 4-1
(DataChem, 1997). Corrective actions are specified in the event of failure to meet QC criteria; however, for the
sake of brevity they are not given in the table. In most cases the first corrective action is a calculation check. Other
corrective actions include system recalibration, sample rerun, batch rerun, or flag data.
Summary of Laboratory QC Performance
The following sections summarize the QC activities and results that accompanied the analysis of each sample batch.
27
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Table 4-1. Method 8260A Quality Control Summary
Activity
Spectrometer tune check
System performance
check
System calibration check
Lab method blank
Field blank
Laboratory control
standard
Matrix spike
Matrix spike duplicate
Surrogate standards
Internal standards
Frequency
Bromofluorobenzene
standard every 12 hours
SPCCa sample every 12
hours
CCCb sample every 1 2
hours
One or more per batch
(approx. 20 samples)
One or more per batch
One or more per batch
One or more per batch
One or more per batch
Included in every sample
Included in every sample
Data Acceptance Criteria
Relative abundance; range of characteristic mass
fragments meets specifications.
Compound relative response factors must exceed
required minimums.
Response factor of CCC varies by no more than +25%
from initial calibration.
Internal standard retention time within 30 seconds of last
check.
Internal standard area response within -50 to 1 00% of
last check.
< 3x Detection limit.
< 3x Detection limit.
Compound recovery within established limits.0
Spike recovery within established limits. c
Relative percent difference of check compounds <50%.
Recovery within established limits. c
Recovery within established limits. c
SPCC = system performance check compounds.
b CCC = calibration check compounds.
0 The laboratory generates control limits that are based on 100 or more analyses of designated compounds. The upper and lower acceptable recovery limits
are based on a 3-standard-deviation-interval about the mean recovery from the multiple analyses. The result from a single analysis must fall within these
control limits in order to be considered valid.
Target Compound List and Method Detection Limits
The method detection limits and practical quantitation limits for the 34 target compounds used in this demonstration
are given in Table 4-2. The PQL marks the lower end of the calibrated working range of the instrument and
indicates the point at which detection and reported results carry a 99% certainty. Detects reported between the
MDL and PQL carry less certainty and are flagged accordingly in the tabulated results.
Sample Holding Conditions and Times
Method 8260A specifies a maximum 14-day holding time for refrigerated water samples. All samples prepared in
the field were kept under refrigeration before and during shipment to the laboratory. Upon receipt at the laboratory,
they were held under refrigeration until analysis. All samples were analyzed within the 14-day time period
following their preparation or collection.
System Calibration
Method 8260A stipulates that a five-point calibration be carried out using standard solutions for all target
compounds across the working range of the instrument. Each mix of compounds is run five times at each of the
five points in the instrument range. For an acceptable calibration, precision from these multiple analyses, as
28
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Table 4-2. Reference Laboratory Method Detection Limits for Target Compounds
Target Compound
Trichlorofluoromethane
1,1-Dichloroethane
Methylene chloride
1,1-Dichloroethene
Chloroform
Carbon tetrachloride
1,1-Dichloropropene
1,2-Dichloroethane
Trichloroethene
1 ,2-Dichloropropane
1,1,2-Trichloroethane
Tetrachloroethene
1 ,3-Dichloropropane
Dibromochloromethane
1 ,2-Dibromoethane
Chlorobenzene
1,1,1 ,2-Tetrachloroethane
1 ,1 ,2,2-Tetrachloroethane
1 ,2,3-Trichloropropane
1 ,2-Dibromo-3-chloropropane
Hexachlorobutadiene
c/s-1 ,3-Dichloropropene
frans-1 ,3-Dichloropropene
1 ,2-Dichlorobenzene
frans-1 ,2-Dichloroethene
1,1,1-Trichloroethane
Benzene
Bromodichloromethane
Toluene
Ethyl benzene
Bromoform
c/s-1 ,2-Dichloroethene
orfrto-Xylene
Acetone
Method Detection Limit
(vail.)
0.15
0.08
0.10
0.08
0.07
0.10
0.10
0.04
0.14
0.04
0.09
0.10
0.06
0.08
0.09
0.06
0.05
0.07
0.50
0.62
0.10
0.17
0.08
0.17
0.17
0.26
0.12
0.11
0.15
0.14
0.10
0.14
0.11
2.9
Practical Quantitation
Limit (ng/L)
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
5
Notes: Detection limits are given for an undiluted 5-mL sample volume. Detection limits are determined annually using the
method outlined in 40 CFR Part 136 Appendix B (seven replicates of deionized water spiked at 1 jxg/L concentration
level). Dilutions of the original sample raise the MDL and PQL values accordingly. Surrogate standards used in the
analyses were 1,2-dichloroethane-d4, toluene-d8, and 4-bromofluorobenzene. Internal standards were fluorobenzene,
chlorobenzene-ds, and 1,4-dichlorobenzene-d4.
29
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given by the relative standard deviation, must be 30% or less. A minimum instrument response factor1 is also
prescribed by the method for a designated subset of compounds termed system performance check compounds
(SPCC). The five-point calibration curve from the most recent instrument calibration met the specified precision
criteria. The system performance check compound response factors also met method criteria.
Daily Instrument Performance Checks
Daily mass spectrometer tune checks as well as other system performance and calibration checks noted in Table 4-1
were carried out for each of the nine sample batches and met Method 8260A on quality control criteria.
Batch-Specific Instrument QC Checks
Method Blanks
All method blank analyses met established criteria (Table 4-1), with one exception. Hexachlorobutadiene, one of
the demonstration target compounds, was detected in two of the method blanks at levels in excess of 3 times the
MDL. This compound was a component in one of the standard mixes used in preparing the PE samples because
reference laboratory data for this compound were not used in the study. Only one of the participating technologies
was calibrated to detect this particular compound. Occasional detection of this compound as a minor instrument
contaminant does not adversely affect the analytical results for other target compounds.
Laboratory Control Standard
At least one laboratory control standard was run with each of the nine batches of samples. Recovery values for
each component in the mixture are given in Figure 4-1 for SRS analyses and Figure 4-2 for MAFB analyses.
Recovery values were all within the laboratory-specific control criteria.
Matrix Spike and Matrix Spike Duplicate
The compounds in the matrix spike were the same as those in the laboratory control standard. Computed matrix
spike and matrix spike duplicate recoveries were all within the recovery ranges noted in Table 4-1. The relative
percent differences (RPDs)2 calculated for the matrix spike and matrix spike duplicate samples also met the
laboratory criteria of <50%. All RPD values from matrix spike analyses were less than 10% for the SRS samples
and less than 13% for MAFB samples.
Sample-Specific QC Checks
Internal Standard
All samples met internal standard acceptance criteria except one. All three internal standards in sample SP31 failed
to meet area response criteria and results from that sample were not included in the reference data set.
1 The response factor is the ratio of instrument response for a particular target compound to the instrument response for an
internal standard.
2 The relative percent difference between two samples is the absolute value of their difference divided by their mean and
multiplied by 100.
30
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DCL Laboratory Control Standard Recoveries
Savannah River Data Set
120
110
^
>
o
u
100
Batch 1
Batch 2 Batch 3
Analysis Batch No.
Batch 4
Batch 5
Figure 4-1. Laboratory control standard recovery values for SRS analyses.
DCL Laboratory Control Standard Recoveries
McClellan Data Set
120
Batch 1 Batch 2 Batch 3 Batch 4
Analysis Batch No.
Batch 5
Figure 4-2. Laboratory control standard recovery values for MAFB analyses.
31
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Surrogate Standard
With the following exceptions, surrogate standard recoveries met the criteria established by the laboratory, as noted
in Table 4-1. Six samples (SP12, SP16, SP26, SP29, SP33, and SP65) failed surrogate recovery criteria for 1,2-
dichloroethane-d4 and passed recovery criteria for 4-bromofluorobenzene and toluene-ds. The actions taken are
noted in Table 4-3.
Summary of Analytical and QC Deviations
A summary of QC deviations as well as other analytical errors or omissions is given in Table 4-3. The actions
taken with regard to the affected data and the reference data set are also tabulated, along with a brief rationale.
Table 4-3. Summary of Reference Laboratory Quality Control and Analytical Deviations
Deviation or QC Criteria Failure
Required dilution not made on two samples (SP20 and
SP21). Some compounds were present above
instrument linear range.
Three field blanks were not sent to DCL from SRS
demonstration.
Calculation error in original DCL report. Dilution factors
applied incorrectly in two samples (SP55 and SP57).
Sample SP31 failed internal standard recovery limits.
The following samples failed one or more surrogate
standard recovery limits: SP12, SP16, SP26, SP29,
SP33, and SP65.
Hexachlorobutadiene detected as a contaminant in
selected blanks and samples.
Chloroethyl vinyl ether was not detected in PE samples
known to contain this compound.
Three sample results (MG20, MG51 , and MG59) are
from a second withdrawal from the original zero-
headspace sample vial.
Action
Data Included: Data values for affected samples fall in
the range of the other three replicate samples.
No Action: Five field blanks and 10 method blanks were
run, yielding an adequate data set.
Data Corrected and Included: The correct dilution
factors were applied following a teleconference with the
DCL analyst.
Data Not Included.
Data Not Included: SP12; results clearly fall outside of
the range of other three replicate samples.
Data Included: All others; nearly all target compounds
fall within the range of concentration reported for the
other three replicate samples.
No Action: This compound was not a target compound
for any of the technologies. Its presence as a low-level
contaminant does not affect the results of other target
compounds.
No Action: The GC/MS was not calibrated for this
compound. None of the technologies included this
compound in their target compound lists.
Data Included: The original volume withdrawn from the
vial was 0.05 mL, resulting in an insignificant headspace
volume and no expected impact on the composition of
the second sample.
Other Data Quality Indicators
The demonstration design incorporated nine PE mixtures of various target compounds at each site that were
prepared in the field and submitted in quadruplicate to each technology as well as to the laboratory. Laboratory
accuracy and precision checks on these samples were assessed. Precision on replicate analysis of groundwater
samples was also evaluated. The results of these assessments are summarized in the following sections.
32
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PE Sample Precision
The relative standard deviation from quadruplicate laboratory analyses of each PE mixture prepared in the field
was computed for each target compound in the mixture. As noted in Chapter 3, care was taken to ensure the
preparation and distribution of homogeneous samples from each PE mixture. The RSD values represent an overall
estimate of precision that takes into account field handling, shipping, storage, and analysis of samples.
The precision data are shown in Figures 4-3 and 4-4 for SRS and Figures 4-5 and 4-6 for MAFB. (See Tables
3-5 and 3-6 for the composition and concentration level of each PE mixture.) The compiled RSDs for all PE
sample results had a median value of 7% and a 95th percentile value of 25%. In selected instances, precision in
excess of Method 8260A specifications (<30% RSD) is observed for tetrachloroethene, trichloroethene, c/s-1,3-
dichloropropene, 1,2,3-trichloropropane, and 1,1,2,2-tetrachloroethane. Precision well in excess of method
specifications is observed for l,2-dibromo-3-chloropropane, fra«s-l,3-dichloropropene, and 1,1-dichloropropene.
The implications of these results with respect to evaluation of the technology performance are discussed, when
applicable, in Chapters 5 or 7.
PE Sample Accuracy
An error propagation analysis was carried out to estimate the degree of uncertainty in the stated "true"
concentration level of the PE samples prepared in the field. The sources of uncertainty and their magnitude
encountered during PE sample preparation are listed in Table 4-4. These errors are combined using the
methodology described by Bevington (1969) to arrive at a combined uncertainty in the PE sample value of ±5%.
Thus, for a 100-u.g/L PE mix, the true value is known with 99% certainty to be within the range of 95 to 105 u.g/L.
Table 4-4. Sources of Uncertainty in PE Sample Preparation
Type of Uncertainty
Weight of component in PE mix
ampule.
Volume of methanol solvent used
to dilute neat compounds.
Volume of PE solution (from
ampule) used in final PE solution.
Volume of water diluent in final
PE solution.
Magnitude
O.Smg in 1200 mg
0.2 ml in 600 ml
+5% of microsyringe volume;
e.g., 25 uL for a 500-|j,L syringe
5ml in 10 L
Source of Estimate
Gravimetric balance uncertainty included
in PE mix certification documents
Published tolerances for volumetric flasks
(Fisher Catalog)
Published tolerances in certificates
shipped with microsyringes
Published tolerances for volumetric flasks
(Fisher Catalog)
The laboratory results for PE samples are compared with the "true" value of the mixture to provide an additional
measure of laboratory performance. A mean recovery3 was computed for each PE compound in each of the four
sample splits analyzed from each mixture. The SRS recovery values are shown in Figures 4-7 and 4-8, and MAFB
recoveries are shown in Figures 4-9 and 4-10. Acceptable mean percent recovery values, specified in Method
8260A, fall within the range of 70 to 130% with exceptions for a few compounds that pose analytical difficulties.
With the following exceptions, all PE compounds at all concentration ranges met the Method 8260A recovery
criteria. The exceptions are 1,2,3-trichloropropane, 1,1-dichloropropene, l,2-dibromo-3-chloropropane,
Recovery is the ratio of the mean concentration level from analysis of the four sample splits to the reference or "true"
concentration levels of the target compounds in each PE mix.
33
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Target Compound
1,2-Dichlorobenzene
Chlorobenzene
Dibromochloromethane
Tetrachloroethene
1,1,2-Trichloroethane
1,2-Dichloropropane
Trichloroethene
Carbon Tetrachloride
Chloroform
1,1-Dichloroethene
Methylene Chloride
1,1-Dichloroethane
Trichlorofluoromethane
DataChem PE Sample Precision
Site: Savannah River Mix 1
20 30
Relative Standard Deviation, %
Figure 4-3. Laboratory precision on SRS PE samples containing mix 1.
Trichloroethene was spiked into the spike/low samples.
DataChem PE Sample Precision
Target Compound Slte: Savannah River Mix 2
Tetrachloroethene
trans- 1 ,3-Dichloropropene
cis-1,3-Dichloropropene
1 ,2-Dibromo-3-Chloro pro pane
1 ,2,3-Trichloropropane
1,1,2, 2-Tetrach loroethane
1,1, 1 , 2-Tetrach loroethane
1 ,2-Dibromoethane
1,3-Dichloropropane
1,1,2-Trichloroethane
1 ,2-Dichloropropane
Trichloroethene
1 ,2-Dichloroethane
1 ,1-Dichloropropene
=• '
==-"
P '
' '
= — :— '
1
= '
= '
= — '
= — '
i
EEF^
1
1
8
6
• bpiKe/Low
DHigh
DMid
n i ™\/
5
6
85
/66
10 20 30
Relative Standard Deviation, %
40
50
Figure 4-4. Laboratory precision on SRS PE samples containing mix 2.
Tetrachloroethene was spiked into the mix 2 samples. Trichloroethene and
tetrachloroethene were spiked into the spike/low samples.
34
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Target Compound
Benzene
trans-1,3-Dichloropropene
cis-1,3-Dichloropropene
1,2-Dibromo-3-Chloropropane
1,2,3-Trichloropropane
1,1,2,2-Tetrachloroethane
1,1,1,2-Tetrachloroethane
1,2-Dibromoethane
1,3-Dichloropropane
Tetrachloroethene
1,1,2-Trichloroethane
1,2-Dichloropropane
Trichloroethene
1,2-Dichloroethane
1,1-Dichloropropene
1,1-Dichloroethane
DataChem PE Sample Precision
Site: McClellan Mix 2
20 30
Relative Standard Deviation, %
Figure 4-5. Laboratory precision on MAFB PE samples containing mix 2.
Trichloroethene, tetrachloroethene, 1,1-dichloroethane, and benzene were
spiked into the spike/low samples.
Target Compound
Bromoform
Ethyl benzene
Toluene
Bromodichloromethane
Benzene
1,1,1-Trichloroethane
trans-1,2-Dichloroethene
trans-1,3-Dichloropropene
cis-1,3-Dichloropropene
1,1,2,2-Tetrachloroethane
Tetrachloroethene
Trichloroethene
1,2-Dichloroethane
1,1-Dichloroethane
DataChem PE Sample Precision
Site: McClellan Mix 3
20
30
Relative Standard Deviation, %
Figure 4-6. Laboratory precision on MAFB PE samples containing mix 3.
Trichloroethene, tetrachloroethene, 1,1-dichloroethane, and benzene were
spiked into the spike/low samples.
35
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Target Compound
1,2-Dichlorobenzene
Chlorobenzene
Dibromochloro methane
Tetrachloroethene
1,1,2-Trichloroethane
1,2-Dichloropropane
Trichloroethene
Carbon Tetrachloride
Chloroform
1,1-Dichloroethene
Methylene Chloride
1,1-Dichloroethane
Trichlorofluoro methane
DataChem PE Sample Recovery
Site: Savannah River Mix 1
50
) 90 100 110 120
Average Percent Recovery
Figure 4-7. Laboratory mean recoveries for SRS PE samples containing mix 1.
Trichloroethane was spiked into the spike/low samples.
Target Compound
trans-1,3-Dichloropropene
cis-1,3-Dichloropropene
1,2-Dibromo-3-Chloropropane
1,2,3-Trichloropropane
1,1,2,2-Tetrachloroethane
1,1,1,2-Tetrachloroethane
1,2-Dibromoethane
1,3-Dichloropropane
Tetrachloroethene
1,1,2-Trichloroethane
1,2-Dichloropropane
Trichloroethene
1,2-Dichloroethane
1,1-Dichloropropene
DataChem PE Sample Recovery
Site: Savannah River Mix 2
50
80 90 100 110 120
Average Percent Recovery
Figure 4-8. Laboratory mean recoveries for SRS PE samples containing mix
2. Trichloroethane and tetrachloroethene were spiked into the spike/low
samples.
36
-------
Target Compound
Benzene
trans-1,3-Dichloropropene
cis-1,3-Dichloropropene
1,2-Dibromo-3-Chloropropane
1,2,3-Trichloropropane
1,1,2,2-Tetrachloroethane
1,1,1,2-Tetrachloroethane
1,2-Dibromoethane
1,3-Dichloropropane
Tetrachloroethene
1,1,2-Trichloroethane
1,2-Dichloropropane
Trichloroethene
1,2-Dichloroethane
1,1-Dichloropropene
1,1-Dichloroethane
DataChem PE Sample Recovery
Site: McClellan Mix 2
50
80 90 100 110 120
Average Percent Recovery
Figure 4-9. Laboratory mean recoveries for MAFB PE samples containing
mix 2. Trichloroethene, tetrachloroethene, 1,1-dichloroethane, and benzene
were spiked into the spike/low samples.
Target Compound
Bromoform
Ethylbenzene
Toluene
Bromodichloro methane
Benzene
1,1,1-Trichloroethane
trans-1,2-Dichloroethene
trans-1,3-Dichloropropene
cis-1,3-Dichloropropene
1,1,2,2-Tetrachloroethane
Tetrachloroethene
Trichloroethene
1,2-Dichloroethane
1,1-Dichloroethane
DataChem PE Sample Recovery
Site: McClellan Mix 3
D Spike/Low
DMid
DLow
• VLow
50
80 90 100 110 120
Average Percent Recovery
Figure 4-10. Laboratory mean recoveries for MAFB PE samples containing mix
3. Trichloroethene, tetrachloroethene, 1,1-dichloroethane, and benzene were
spiked into the spike/low samples.
37
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and 1,2-dichlorobenzene at selected concentration levels. The implications of these exceptions for the technology
evaluation are further discussed, if applicable, in Chapter 5. The compiled absolute percent differences (APDs)4
for all PE sample results had a median value of 7% and a 95th percentile value of 25%.
Groundwater Sample Precision
Relative standard deviations are given in Table 4-5 for compound concentrations in excess of 1 ng/L in
ground-water samples from the SRS demonstration. Trichloroethene and tetrachloroethene were the only
contaminants detected in SRS groundwater samples. A similar compilation of RSD values from the MAFB
groundwater samples is included in Table 4-6. These values are based on analytical results from either three or four
replicate samples. With three exceptions, all tabulated values are less than 20%.
Table 4-5. Summary of SRS Groundwater Analysis Precision
Sample Description
Very low 1
Very low 2
Low 1
Low 2
Midi
Mid 2
Highl
High 2
Very high 1
Very high 2
Relative Standard Deviation (%)
TCE
10.6
34.4
5.4
7.1
9.4
7.3
0.8
11.8
8.4
6.2
PCE
14.3
12.4
5.7
8.7
11.6
4.2
1.8
7.9
5.7
6.3
Table 4-6. Summary of MAFB Groundwater Analysis Precision
Sample
Description
Very low 1
Very low 2
Low 1
Low 2
Midi
Mid 2
Highl
High 2
Very high 1
Very high 2
Relative Standard Deviation (%)
11DCE
9.1
2.6
6.8
11.5
12.0
2.5
TCE
5.0
<0.1
3.7
5.2
10.5
3.6
2.4
5.3
5.4
8.0
CLFRM
1.3
2.0
4.9
20.9
5.3
5.2
6.4
CCL4
4.2
1.9
4.0
4.9
PCE
5.7
22.3
13.9
11DCA
<0.1
4.1
9.4
C12DCE
3.8
12.6
3.8
4.1
5.1
6.5
10.1
t12DCE
3.8
BNZN
4.9
Notes: 11DCE = 1,1 -dichloroethene; TCE = trichloroethene; CLFRM = chloroform; CCL4 = carbon tetrachloride; PCE = tetrachloroethene; 11DCA =
1,1 -dichloroethane; c12DCE = c/s-1,2-dichloroethene; (12DCE = frans-1,2-dichloroethene; BNZN = benzene.
Blank cells indicate that the compound was not present.
The absolute percent difference is the absolute value of the percent difference between a measured value and a true value.
38
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Summary of Reference Laboratory Data Quality
With the exceptions noted below, a review of DCL analytical data showed that all Method 8260A QC criteria were
met. Internal standard recovery limits were not met for one sample. The results for this sample were markedly
different from the other three samples in the replicate set and the sample was omitted from the data set. Six
samples failed one or more surrogate standard recovery criteria. These sample results were compared with
replicate sample results. Five of the six samples were comparable and were included in the reference data set.
The data for the remaining sample were not comparable and were omitted from the reference data set. Other
quality control deviations, which are summarized in Table 4-3, did not significantly affect the quality of the
laboratory data.
A review of DCL precision and accuracy on field-prepared PE mixtures corroborates laboratory internal QC
results. A similar precision evaluation on groundwater samples from both sites further supports these observations.
Overall, the internal and external QC data reveal appropriate application and use of Method 8260A by DataChem
Laboratories. The laboratory results for groundwater samples from both sites are considered suitable for use as a
reference data set.
39
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Chapter 5
Demonstration Results
HAPSITE Calibrated and Reported Compounds
Prior to the field demonstration, the participants were given a list of all compounds that were to be used in the PE
mixtures to facilitate preparations for predemonstration instrument calibration. The HAPSITE GC/MS was
calibrated for 32 compounds at SRS, and 6 more were added prior to the MAFB demonstration (Table 5-1). Note
that some calibrated compounds were not demonstration PE mixture compounds. A total of 32 chlorinated and
nonchlorinated hydrocarbon compounds were included in the PE mixtures noted in Table 3-4. The HAPSITE
reported results for 27 of these compounds. It did not report results for 5 PE compounds since it was not calibrated
for them. These were dibromochloromethane, 1,2-dichlorobenzene, 2-chloroethyl vinyl ether, l,2-dibromo-3-
chloropropane, and hexachlorobutadiene. Trichlorofluoromethane, another PE compound, was not reported at the
SRS but was reported at MAFB.
Preanalysis Sample Information
Groundwater (GW) and PE samples were provided to the HAPSITE team without additional information on the
number of compounds in the sample or compound concentration levels.
Table 5-1. HAPSITE Calibrated and Reported Compounds
Calibrated Compounds at Both Demonstrations
1,1-Dichloroethene
Methylene chloride
trans-1 ,2-Dichloroethene
1,1-Dichloroethane
Bromochloromethane
Chloroform
1 ,2-Dichloroethane
1,1,1-Trichloroethane
1,1-Dichloropropene
Benzene
Carbon tetrachloride
Dibromomethane
1 ,2-Dichloropropane
Bromodichloromethane
Trichloroethene
c/s-1 ,3-Dichloropropene
trans-1 ,3-Dichloropropene
1 ,1 ,2-Trichloroethane
1 ,3-Dichloropropane
Toluene
Dibromochloromethane
1 ,2-Dibromoethane
Tetrachloroethene
1,1,1 ,2-Tetrachloroethane
Chlorobenzene
Ethyl benzene
meta- and para-Xylene
Bromoform
Styrene
orffto-Xylene
1 ,1 ,2,2-Tetrachloroethane
1 ,2,3-Trichloropropane
Additional Calibrated Compounds at MAFB
Chloromethane
Vinyl chloride
Bromoethane
Chloroethane
Trichlorofluoromethane
c/s-1 ,2-Dichloroethene
40
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Sample Completion
All but one of the 166 PE and groundwater samples submitted for analysis to the HAPSITE team were completed
at both demonstration sites. The HAPSITE team at the SRS lost a PE sample from the spike/low category of PE
mix 1 during sample preparation.
Blank Sample Results
Eight blank samples were provided for analysis at each demonstration site. False positive detects were counted
only for compounds reported at concentration levels greater than the HAPSITE MDL for most target compounds
(typically 3 u,g/L). A listing of false positive detects is given for both sites in Table 5-2.
Table 5-2. False Positive Rates from Blank Sample Analysis
SRS Blank Sam
Compound
Dichloromethane
Trichloroethene
Chlorobenzene
pies
False Positive
1 of 8 (13%)
3 of 8 (38%)
1 of 8 (13%)
MAFB Blank Samples
Compound
1,2-Dichloroethane
Trichloroethene
c/s-1 ,3-Dichloropropene
frans-1 ,3-Dichloropropene
1 ,2-Dibromoethane
False Positive
1 of 8 (13%)
1 of 8 (13%)
1 of 8 (13%)
1 of 8 (13%)
1 of 8 (13%)
Performance at Instrument Detection Limit
Ten replicate samples of a PE mixture at a concentration level of 10 u.g/L (the "very low" concentration level) were
provided for analysis at each site. Reported nondetects were compiled and are given as percent false negatives in
Table 5-3. Vendor-provided compound detection limits are also shown in the table for comparison.
Table 5-3. False Negative Rates from Very Low-Level PE Sample Analysis
SRSPEMixl (10ng/L)
Compound
1,1-Dichloroethene(3)
Dichloromethane (3)
1,1-Dichloroethane (3)
Chloroform (3)
Carbon tetrachloride (3)
1 ,2-Dichloropropane (3)
Trichloroethene (3)
1 ,1 ,2-Trichloroethane (3)
Dibromochloromethane (3)
Tetrachloroethene (3)
Chlorobenzene (3)
2-Chloroethyl vinyl ether
Trichlorofluoromethane
1 ,2-Dichlorobenzene
False Negative
Oof 10
Oof 10
Oof 10
Oof 10
1 of 10(10%)
Oof 10
Oof 10
4 of 10(40%)
2 of 10(20%)
4 of 10(40%)
1 of 10(10%)
No calibration
No calibration
No calibration
MAFB PE Mix 3 (10
Compound
frans-1,2-Dichloroethene (3)
1,2-Dichloroethane (3)
1,1,1-Trichloroethane (3)
Benzene (3)
Bromodichloromethane (5)
c/s-1 ,3-Dichloropropene (5)
frans-1 ,3-Dichloropropene (5)
Toluene (3)
Ethyl benzene (3)
Bromoform (8)
1,1,2,2-Tetrachloroethane (10)
og/L)
False Negative
Oof 10
Oof 10
Oof 10
Oof 10
Oof 10
Oof 10
Oof 10
Oof 10
Oof 10
9 of 10(90%)
3 of 10(30%)
Notes: Vendor-provided detection limits (in jxg/L) are shown in parentheses after each compound.
41
-------
PE Sample Precision
Precision results from each of the four replicate sample sets provided from eight PE mixtures at SRS and the seven
mixtures at MAFB are shown in Figures 5-1 and 5-2 for SRS and Figures 5-3 and 5-4 for MAFB. The figures
show the relative standard deviation for each compound in the PE mixtures at the four concentration levels used in
the study.1 (The composition and concentrations of each of these mixtures were given in Table 3-5 for SRS and
Table 3-6 for MAFB.) Note that precision and accuracy were not determined for the very low concentration level.
Instrument precision data for six target compounds which are all regulated under the Safe Drinking Water Act are
shown in Table 5-4. The relative standard deviations are given for each target compound at each of the four
concentration levels used in the study. The RSD range for each target compound is given in the last column of the
table.
Overall instrument precision is summarized in Table 5-5 for PE mixtures used at each site. For this summary,
RSD values from all PE sample analyses for all compounds at each site were pooled and the median and 95th
percentile values of the distribution were computed.
Table 5-4. Target Compound Precision for PE Samples at Both Sites
Target Compound
Trichloroethene
1 ,2-Dichloroethane
1,1,2-Trichloroethane
1 ,2-Dichloropropane
Tetrachloroethene
frans-1 ,3-Dichloropropene
Site
SRS
MAFB
SRS
MAFB
SRS
MAFB
SRS
MAFB
SRS
MAFB
SRS
MAFB
Relative Standard Deviation (%)
Low
7
13
6
12
10
19
21
11
22
11
16
Mid
18
7
8
9
8
15
17
7
19
7
17
High
15
13
10
8
9
21
8
12
16
6
18
17
Spike/Low
16
15
2
5
28
28
18
17
14
8
16
10
Range
7-18
2-12
8-28
7-21
6-22
7-17
Note: Blank cells indicate that no data were reported.
Table 5-5. Summary of PE Sample Precision and Percent Difference Statistics for SRS and
MAFB
Parameter
RSD, %
Absolute percent
difference
Percentile
50th
95th
Number in pool
50th
95th
Number in pool
SRS
PE Mix 1
12
24
45
11
33
44
PE Mix 2
12
31
49
13
36
49
MAFB
PE Mix 2
14
30
52
5
26
51
PE Mix 3
8
19
37
4
17
36
Combined Sites
Combined Mixes
12
29
183
8
27
180
Precision data for the PE mix 1 sample set at MAFB are not shown in a figure. Precision results from this mixture were
comparable to those obtained from the same mixture at the SRS.
42
-------
Compound
Chlorobenzene
Tetrachloroethene
Dibromochloro methane
1,1,2-Trichloroethane
Trichloroethene
1,2-Dichloropropane
Carbon tetrachloride
Chloroform
1,1-Dichloroethane
Methylene Chloride
1,1-Dichloroethene
Inficon HAPSITE PE Sample Precision
Site: Savannah River Mix 1
10 20 30
Relative Standard Deviation, %
40
50
Figure 5-1. HAPSITE precision on PE mix 1 at the SRS. Trichloroethene
was spiked into the spike/low samples.
Inficon HAPSITE PE Sample Precision
Site: Savannah River Mix 2
Compound
1,2,3-Trichloropropane
1,1,2,2-Tetrachloroethane
1,1,1,2-tetrachloroethane
1,2-Dibromoethane
1,3-Dichloropropane
1,1,2-Trichloroethane
trans-1,3-Dichlopropene
cis-1,3-Dichloropropene
Trichloroethene
1,2-Dichloropropane
1,1-Dichloropropene
1,2-Dichloroethane
75
53
20 30
Relative Standard Deviation, %
Figure 5-2. HAPSITE precision on PE mix 2 at the SRS. Trichloroethene
and tetrachloroethene were spiked into the spike/low samples.
43
-------
Compound
1,2,3-Trichloropropane
1,1,2,2-Tetrachloroethane
1,1,1,2-Tetrachloroethane
Tetrachloroethene
1,2-Dibromoethane
1,3-Dichloropropane
1,1,2-Trichloroethane
trans-1,3-Dichlopropene
cis-1,3-Dichloropropene
Trichloroethene
1,2-Dichloropropane
Benzene
1,1-Dichloropropene
1,2-Dichloroethane
1,1-Dichloroethane
Inficon HAPSITE PE Sample Precision
Site: McClellanAFB Mix 2
• Spike/Low
DHigh
• Mid
DLow
50
10 20 30
Relative Standard Deviation, %
Figure 5-3. HAPSITE precision on PE mix 2 at MAFB. Trichloroethene,
tetrachloroethene, 1,1-dichloroethane, and benzene were spiked into the
spike/low samples.
Compound
1,1,2,2-Tetrachloroethane
Bromoform
Ethyl benzene
Tetrachloroethene
Toluene
trans-1,3-Dichlopropene
cis-1,3-Dichloropropene
Trichloroethene
Bromodichloromethane
Benzene
1,1,1 -Trichloroethane
1,2-Dichloroethane
1,1-Dichloroethane
trans-1,2-Dichloroethene
Inficon - HAPSITE PE Sample Precision
Site: McClellanAFB Mix 3
20 30
Relative Standard Deviaton, %
40
50
Figure 5-4. HAPSITE precision on PE mix 3 at MAFB. Trichloroethene,
tetrachloroethene, 1,1-dichloroethane, and benzene were spiked into the
spike/low samples.
44
-------
PE Sample Accuracy
The HAPSITE accuracy on PE samples was determined by comparing the average value from each of the four-
sample replicate sets with the known concentration of the PE mixture (Tables 3-5 and 3-6 for SRS and MAFB,
respectively). These comparisons are shown as percent recoveries2 in Figures 5-5 and 5-6 for SRS and Figures 5-7
and 5-8 for MAFB.3 To assist in assessment of the sign of the difference, the percent recovery data are plotted as
either a positive or negative deviation from the 100% recovery line.
Instrument recovery performance for the six target compounds is shown in Table 5-6, which contains the average
percent recoveries and associated ranges for each compound.
Table 5-5 contains a summary of overall FfAPSITE differences relative to PE mixture true values for both sites,
along with the precision summary. For this summary, percent recoveries were expressed as percent difference (for
example, a 90% recovery is equivalent to a -10% difference; 120% recovery is equivalent to a +20% difference)
and all data from PE mixtures were pooled. The median and 95th percentiles of the absolute values of these pooled
values were computed and are reported under the absolute percent difference (APD) category in Table 5-5.
Table 5-6. Target PE Compound Recovery at Both Sites
Target Compound
Trichloroethene
1,2-Dichloroethane
1,1,2-Trichloroethane
1 ,2-Dichloropropane
Tetrachloroethene
frans-1 ,3-Dichloropropene
Site
SRS
MAFB
SRS
MAFB
SRS
MAFB
SRS
MAFB
SRS
MAFB
SRS
MAFB
Average Recovery (%)
Low
83
113
96
102
120
107
79
95
86
90
101
Mid
103
108
93
98
99
103
97
95
94
85
95
High
112
114
91
103
108
101
103
113
89
93
85
96
Spike/Low
80
101
92
80
84
79
113
91
67
86
85
88
Range
80-114
91-103
79-120
79-113
67-93
85-101
Note: Blank cells indicate that no data were reported.
Comparison with Laboratory Results
For each demonstration site, a total of 33 samples collected from 10 wells were provided to the participants and
to the reference laboratory. Replicate sample sets were composed of either 3 or 4 samples from each well.
Average laboratory results from each replicate set were used as the reference values for comparison with
technology results. A side-by-side comparison of laboratory and FfAPSITE results for all groundwater samples
Percent recovery is the HAPSITE value divided by the true value, multiplied by 100.
Percent recovery data for the single PE mix 1 sample set at MAFB are not shown in a figure. Recovery results from this
mixture were comparable to those obtained from the same mixture at the SRS.
45
-------
Inficon HAPSITE PE Sample Recovery
Compound
Chloro benzene
Tetrachloroethene
Dibromochloromethane
1,1,2-Trichloroethane
Trichloroethene
1,2-Dichloro propane
Carbon tetrachloride
Chloroform
1,1-Dichloroethane
Methylene Chloride
1,1-Dichloroethene
Savannah River -
l=^
I
C!EE
r^
^E
^^
r^
I
[
E
I .
I
•
^^
Mix 1
• High
• Mid
— I DLow
Er^
i
i
^m
H
P
20
D 80 100 120 140
Average Percent Recovery
Figure 5-5. HAPSITE recovery on PE mix 1 at the SRS. Trichloroethene
was spiked into the spike/low samples.
Compound
1,2,3-Trichloropropane
1,1,2,2-Tetrachloroethane
1,1,1,2-tetrachloroethane
1,2-Dibromoethane
1,3-Dichloropropane
1,1,2-Trichloroethane
trans-1,3-Dichlopropene
cis-1,3-Dichloropropene
Trichloroethene
1,2-Dichloropropane
1,1-Dichloropropene
1,2-Dichloroethane
Inficon HAPSITE PE Sample Recovery
Savannah River — Mix 2
20
60 80 100 120 140
Average Percent Recovery
160 180
200
Figure 5-6. HAPSITE recovery on PE mix 2 at the SRS. Trichloroethene
and tetrachloroethene were spiked into the spike/low samples.
46
-------
Compound
1,2,3-Trichloropropane
1,1,2,2-Tetrachloroethane
1,1,1,2-Tetrachloroethane
Tetrachloroethene
1,2-Dibromoethane
1,3-Dichloropropane
1,1,2-Trichloroethane
trans-1,3-Dichlopropene
cis-1,3-Dichloropropene
Trichloroethene
1,2-Dichloropropane
Benzene
1,1-Dichloropropene
1,2-Dichloroethane
1,1-Dichloroethane
Inficon - HAPSITE PE Sample Recovery
McClellanAFB - Mix 2
• Spike/Low
DHigh
DMid
DLow
60 80 100 120 140
Average Percent Recovery
Figure 5-7. HAPSITE recovery on PE mix 2 at MAFB. Trichloroethene,
tetrachloroethene, 1,1-dichloroethane, and benzene were spiked into the
spike/low samples.
Compound
1,1,2,2-Tetrachloroethane
Bromoform
Ethyl benzene
Tetrachloroethene
Toluene
trans-1,3-Dichlopropene
cis-1,3-Dichloropropene
Trichloroethene
Bromodichloromethane
Benzene
1,1,1 -Trichloroethane
1,2-Dichloroethane
1,1-Dichloroethane
trans-1,2-Dichloroethene
Inficon HAPSITE PE Sample Recovery
McClellanAFB-Mix 3
80 100 120
Average Percent Recovery
Figure 5-8. HAPSITE recovery on PE mix 3 at MAFB. Trichloroethene,
tetrachloroethene, 1,1-dichloroethane, and benzene were spiked into the
spike/low samples.
47
-------
is given in Table 5-7 for the SRS and Table 5-8 for MAFB. The RSD values and their statistical summaries are
included in the table. Well designation (very low, low, mid, high, and very high) is based on TCE concentration
levels; however, other compounds were present in the groundwater samples at concentration levels noted in the
tables. The precision of the HAPSITE on replicate groundwater sample sets is shown as RSDs in the last column
of the table.
Table 5-7. HAPSITE and Reference Laboratory Results for SRS Groundwater Samples
Sample
Description
Very low 1
Very low 2
Low 1
Low 2
Midi
Mid 2
Highl
High 2
Very high 1
Very high 2
Well
Number
MSB 33B
MSB 33C
MSB18B
MSB 37B
MSB4D
MSB 64C
MSB4B
MSB 70C
MSB14A
MSB8C
Compound
Trichloroethene
Tetrachloroethene
Trichloroethene
Trichloroethene
Tetrachloroethene
Trichloroethene
Tetrachloroethene
Chloroform
Carbon tetrachloride
Trichloroethene
Tetrachloroethene
Trichloroethene
Tetrachloroethene
1,1-Dichloroethene
Trichloroethene
Tetrachloroethene
Trichloroethene
Tetrachloroethene
1,1-Dichloroethene
Trichloroethene
Tetrachloroethene
Trichloroethene
Tetrachloroethene
Replicates
3
3
3
4
4
3
3
4
3
3
Lab.
Avg.
(H9/L)
9.0
3.5
2.4
11
27
27
22
1.3
1.0
150
87
35
240
12
747
33
1875
520
32
1367
800
4933
3668
Range
Median
95th Percentile
Lab.
RSD
(%)
11
14
34
5
6
7
9
0
15
9
12
7
4
8
1
2
12
8
8
8
6
6
6
0-34
8
15
HAPSITE
aAvg.
(H9/L)
8.8
2.5
1.9
13
28
27
19
NR
NR
126
68
29
186
7.3
726
37
1703
454
26
1460
898
4783
3197
HAPSITE
a
RSD
(%)
43
89
32
11
19
12
17
NR
NR
7
12
19
15
19
8
11
8
23
42
6
12
3
12
3-89
12
43
NR = not reported.
The average percent difference between average HAPSITE and laboratory results for the compounds detected in
each set of groundwater samples is shown in Figures 5-9 and 5-10 for SRS and MAFB, respectively. Average
laboratory results for groundwater contaminants reported at levels less than 1 |o,g/L are not included in the
comparison. The SRS groundwater comparison in Figure 5-9 includes only TCE and PCE. Two well samples at
the SRS were also contaminated with 1,1-dichloroethene and other compounds, as noted in Table 5-7. The
groundwater samples at MAFB were more complex, as indicated by the additional compounds shown in Table 5-8
and Figure 5-10. (See the vendor comment in Chapter 7 concerning laboratory results for c/'s-l,2-dichloroethene at
MAFB.)
48
-------
Table 5-8. HAPSITE and Reference Laboratory Results for MAFB Groundwater Samples
Sample
Description
Very low 1
Very low 2
Low 1
Low 2
Midi
Mid 2
Highl
High 2
Very high 1
Very high 2
Well
Number
EW-86
MW-349
MW-331
MW-351
EW-87
MW-341
MW-209
MW-330
MW-334
MW-369
Replicates
3
3
4
3
4
3
3
4
3
3
Compound
Trichloroethene
1,1-Dichloroethene
Trichloroethene
Tetrachloroethene
Chloroform
1,1-Dichloroethene
Carbon tetrachloride
1,1-Dichloroethene
1,1-Dichloroethane
Carbon tetrachloride
Chloroform
Trichloroethene
Freon11
1,1-Dichloroethene
1,1-Dichloroethane
c/s-1 ,2-Dichloroethene
Carbon tetrachloride
Trichloroethene
1,1-Dichloroethene
1,1-Dichloroethane
c/s-1 ,2-Dichloroethene
1,1,1-Trichloroethane
Trichloroethene
Tetrachloroethene
c/s-1 ,2-Dichloroethene
Chloroform
Trichloroethene
c/s-1 ,2-Dichloroethene
Chloroform
Trichloroethene
frans-1 ,2-Dichloroethene
c/s-1 ,2-Dichloroethene
Chloroform
1 ,2-Dibromochloropropane
Trichloroethene
1,1-Dichloroethene
c/s-1 ,2-dichloroethene
Chloroform
Benzene
Trichloroethene
Carbon tetrachloride
c/s-1 ,2-Dichloroethene
Chloroform
Carbon tetrachloride
Trichloroethene
Lab.
Avg.
(W/L)
4.6
7.7
13
2.0
9.0
3.8
137
2.5
15
7.5
4.8
16
20
1.5
5.1
1.5
1.4
22
180
3.0
3.3
6.8
114
1.2
15
3.5
280
38
6.9
238
7.7
66
42
6.1
380
690
237
397
283
10,667
350
207
63
51
6167
Range
Median
95th Percentile
Lab.
RSD
(%)
5
9
0
6
1
3
4
7
0
2
2
4
6
12
4
4
4
5
12
9
13
12
11
14
4
5
4
4
21
2
4
5
5
6
5
3
7
5
5
5
5
10
6
5
8
0-21
5
14
HAPSITE3
Avg.
(W/L)
12.8
6.3
15
NR
9.0
2.9
140
NR
13
6.0
4.5
17
NR
NR
4.0
1.9
NR
25.1
189
NR
4.0
5.3
111
NR
24
3.1
264
56
6.4
240
7.1
97
45
4.7
398
1032
426
418
265
11,714
565
299
67
60
6821
HAPSITE3
RSD
(%)
93
7
15
NR
12
20
22
NR
15
30
4
27
NR
NR
23
34
NR
11
23
NR
12
34
12
NR
8
16
3
11
5
11
10
12
5
19
9
33
9
8
12
13
44
16
3
23
15
3-93
13
36
NR = not reported.
49
-------
Compound
Inficon HAPSITE GW Sample Difference
Site: SRS Ref: Laboratory
Tetrachloroethene
Trichloroethene
• VHigh2
nVHighl
• High2
DHighl
• Mid2
DMidl
DLow2
DLowl
DVLow2
DVLowl
-100 -80 -60 -40 -20 0 20 40 60 80 100
Average Percent Difference
Figure 5-9. HAPSITE groundwater results at the SRS relative to laboratory
results.
Compound
cis-1,2-Dichloroethene
Chloroform
Carbon tetrachloride
1,1-Dichloroethane
1,1-Dichloroethene
Trichloroethene
Inficon HAPSITE GW Sample Difference
Site: MAFB Ref: Laboratory
• VHigh2
DVHighl
• High2
DHighl
DMid2
DMidl
DLow2
DLowl
DVLow2
DVLowl
176
-40 -20 0 20 40
Average Percent Difference
80 100
Figure 5-10. HAPSITE groundwater results at MAFB relative to laboratory
results.
50
-------
The median and 95th percentile of the distribution of absolute percent differences between HAPSITE and laboratory
results for all groundwater samples are given in Table 5-9.
Table 5-9. HAPSITE Absolute Percent Difference Summary for
Pooled Groundwater Results
Percentile
50th
95th
Number of samples in pool
SRS
13
29
21
MAFB
13
64
38
Combined Sites
12
43
59
To assess the degree of linear correlation between the HAPSITE and laboratory groundwater data pairs shown in
Tables 5-7 and 5-8, correlation coefficients (r) were computed. The data pairs were divided into two subsets for
each site to reduce the likelihood of spuriously high r values caused by large differences in the data (e.g.,
concentrations ranging from 1 u.g/L to those in excess of 1000 u.g/L) (Havlicek and Grain, 1988). One subset
contained all data pairs with laboratory results less than or equal to 100 u.g/L and the other subset included all data
pairs with laboratory values greater than 100 u.g/L. The computed correlation coefficients are shown in
Table 5-10.
Table 5-10. Correlation Coefficients for Laboratory and HAPSITE
Groundwater Analyses
Data Set
SRS Laboratory (1 through 100 |ag/L)
SRS Laboratory (> 1 00 |ag/L)
MAFB Laboratory (1 through 1 00 |ag/L)
MAFB Laboratory (> 1 00 |ag/L)
Correlation
Coefficient
0.983
0.996
0.978
1.000
Number of
Data Pairs
13
9
24
14
Sample Throughput
HAPSITE sample throughput rates ranged from two to three samples per hour. Throughput rates were assessed by
using the time lapsed between sample checkout in the morning and delivery of hardcopy results in the afternoon,
and the number of samples completed. HAPSITE GC run times were slightly longer at the MAFB demonstration
as a result of the additional five compounds in the system calibration file. Sample throughput rates were not
significantly influenced by the sample complexity since more complex PE and less complex groundwater samples
were run through the same analysis sequence and had the same GC run times.
Performance Summary
Table 5-11 contains a summary of HAPSITE performance characteristics, including important instrument
performance parameters and operational features verified in this demonstration. For groundwater samples, the
results from the reference laboratory are given alongside HAPSITE performance results to facilitate comparison of
the two methodologies.
51
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Table 5-11. Summary of HAPSITE GC/MS Performance
Instrument
Feature/Parameter
Blank sample
Detection limit sample
PE sample precision
PE sample accuracy
HAPSITE comparison with
laboratory results for
groundwater samples
Analytical versatility
Sample throughput
Support requirements
Operator requirements
Total system weight
Portability
Total system cost
Shipping requirements
Performance Summary
False positives detected at low (13 to 38%) rates for 8 compounds
False negatives reported at rates between 10 and 90% for 7 of 22 compounds, at
concentration levels of 10 |j,g/L, for which the instrument was calibrated
Target compounds, RSD range: 2 to 28%
All compounds, HAPSITE median RSD: 12%; 95th percentile RSD: 29%
All compounds, laboratory median RSD: 7%; 95th percentile RSD: 25%
(Target compounds: TCE, 1 ,2-dichloroethane, 1,1,1-trichloroethane, 1,2-
dichloropropane, PCE, and frans-1 ,3-dichloropropene)
Target compounds, absolute percent difference range: 1 to 33%
All compounds, HAPSITE median APD: 8%; 95th percentile APD: 27%
All compounds, laboratory median APD: 7%; 95th percentile APD: 24%
(Target compounds same as those for sample precision)
HAPSITE median RSD: 12% Laboratory median RSD: 6%
HAPSITE 95th percentile RSD: 43% Laboratory 95th percentile RSD: 1 4%
HAPSITE laboratory median APD: 13%; 95th percentile APD: 60%
HAPSITE laboratory correlation:
SRS low cone. (<100 |ag/L) r= 0.983
SRS high cone. (>100|ag/L) r= 0.996
MAFB low cone. (<100 |ag/L) r= 0.978
MAFB high cone. (>100 |ag/L) r = 1 .000
PE samples: calibrated for 27 of 32 PE compounds (84%)
GW samples: HAPSITE reported 59 of 59 compounds detected by the laboratory in all
GW samples at or above the 5 (og/L concentration level. A total of 68 compounds at
concentration levels > 1 ^g/L were detected by the reference laboratory in all
groundwater samples.
2.5 samples per hour
Self-contained carrier gas, batteries, optional printer
Internal and surrogate standard solutions and syringes
Sample processing: technician with 3-day training
Data processing and review: B.S. chemist or equivalent
60 pounds
Transportable — best suited for use in vehicle at the wellhead
$95,000
Airfreight, hand carry, luggage check
Carrier and internal standard gases shipped as hazardous material
52
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Chapter 6
Field Observations and Cost Summary
Introduction
The following subsections summarize the audit findings obtained while observing instrument operation at both field
sites. The purpose of the audits was to observe the instrument in operation as well as to verify that the analytical
procedures used during the demonstration were consistent with the written procedures submitted to the verification
organization prior to the field demonstration. An instrument cost summary and an applications assessment is
provided.
Method Summary
The HAPSITE uses a static (equilibrium) headspace method with temperature control. The headspace vapors from
a temperature-equilibrated sample are transferred to a gas sampling loop and automatically injected into the
GC/MS. Compounds are identified by library spectral matching and quantified by integrating the peak area of a
selected quantification ion. Internal and surrogate standards are also incorporated into the method.
Equipment
Without the service module, the HAPSITE GC/MS is 18 inches x 17 inches x 7 inches and weighs 35 pounds. The
headspace sampling accessory is 16 inches x 14 inches x 7 inches and weighs 15 pounds; the notebook computer is
8 pounds and the printer weighs 5 pounds. Configured for water sample analysis, the system is transportable and
easily fits in the rear luggage storage area of a minivan or station wagon. Equipment weights include batteries and
gas cartridges. Nickel-cadmium battery lifetimes are about 2 to 3 hours for the HAPSITE and 4 to 6 hours for the
headspace sampling accessory. The system can be connected to a 24-V marine battery for extended remote
operation. The system was run with both batteries and ac power during the demonstration. The system is also
equipped with a service module with dimensions of 18 inches x 17 inches x 8.5 inches and a weight of 45 pounds.
The module is used to pump an initial vacuum on the spectrometer and normally is not taken to the field.
Additional required equipment includes 40-mL screw-cap septa vials (Supelco, graduated with diameter to fit the
headspace sampling accessory heater block); 1-mL (with MIN-inert valve) and 2-mL vials for calibration;
microliter syringe(s); 50-mL Teflon Luer lock syringes for sample transfer; and commercially available (Supelco or
equivalent) internal and surrogate standard mixtures.
The equipment was transported to the SRS by vehicle and to the MAFB site as carry-on luggage. It can also be
checked as baggage in its shipping case.
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Figure 6-1. The HAPSITE GC/MS.
Sample Preparation and Handling
Sample preparation begins by pouring a cold, zero-headspace, 40-mL volatile organics analysis vial sample into an
open 50-mL gas-tight syringe. The syringe plunger is inserted, the syringe inverted, and excess air expelled.
Twenty milliliters are ejected as waste. The remaining 20-mL sample is transferred to a headspace vial and capped
with a Teflon-lined silicone septum and screw cap. A 5-|oL volume of internal or surrogate standard mixture is
injected through the septum with a microliter syringe. All samples were prepared in this manner immediately after a
sample batch was received. Following preparation, all vials were then stored on ice. Calibration standards were
prepared directly in headspace vials. Since the standards were not carried through the sample transfer process,
there was little risk for the loss of compounds that may occur during routine sample handling and transfer.
Consumables
Disposable gas bottles are used for the nitrogen carrier gas, the internal standard mixture, and the headspace
sampling accessory purge-and-sweep gas. These bottles can be changed out quickly in the field. Standard gas
cylinders can also be used for nitrogen carrier and headspace sampling accessory purge and sweep. The system has
a chemical getter pump that maintains the system vacuum during operation. The getter pump must be replaced
after 240 hours of use.
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Historical Use
This is the first demonstration of the HAPSITE GC/MS and the headspace sampling accessory for the analysis of
volatile organics in water. The HAPSITE unit alone has been used extensively for vapor analysis applications
(exhaust, stack, and soil gas analysis).
Equipment Cost
The HAPSITE and headspace sampling accessory have a combined cost that ranges from $75,000 to $95,000,
depending upon options selected. The instrument can be purchased without a service module for $75,000. With
this configuration, the instrument must be sent back to the maintenance facility in Syracuse, New York, for periodic
replacement of the getter pump. Purchase of the service module allows the user to replace the getter pump in the
field. With either option, a notebook computer is included in the package for data processing and instrument
control. Daily operating costs are about $150 and include gases, battery packs, and replacement getter pumps (all
via maintenance agreement). Instrument costs are summarized in Table 6-1. Laboratory costs were $95 per
sample plus overnight Express Mail costs, which were about $30 per batch of 12 samples. HAPSITE sample
throughput is in the range of 2 to 3 samples per hour.
Table 6-1. HAPSITE GC/MS Cost Summary
Instrument/Accessory
Instrument
(HAPSITE / headspace sampling accessory /
service module (option), notebook computer and
startup kit)
Instrument accessories (field-portable printer)
Sample handling accessories (syringes, vials,
standards)
Maintenance costs
Carrier gas, internal standard gas, and getter pump
replacement
Cost
$75,000 (without service module)
$95,000 (with service module)
$300 - $500
$500 per 100 samples
$4500 per 240 hours of use
$500 service charge for pump replacement at
factory
Operators and Training
One operator is required for GC/MS operation. An additional person is helpful when the headspace sampling
accessory is used with a high volume of samples, such as in this demonstration. For wellhead monitoring
operations where instrument use would follow a well-sampling team, one operator is probably sufficient since only
one or two samples would be provided per hour. The GC/MS operator should be a well-trained technician,
preferably with a B.S. in chemistry. Sampling preparation and injection into the instrument could be carried out by
a field technician with minimal training; however, instrument response and results would have to be checked daily
by a qualified analyst.
Data Processing and Output
The instrument produces a typical GC/MS report with internal and surrogate standard checks directly from
operating software. The software operates in a multitasking environment so that a sample analysis can be in
progress while the results of completed samples are being reviewed. Data reports were checked and printed within
minutes of run completion. The operator's objective of reporting valid results for 90% or more of 20 samples by
the end of the day was easily met. The unit can also be operated without the laptop, by use of a liquid crystal
display screen and keypad on the instrument. Data collected in this manner can be downloaded to a laptop and
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reviewed at the end of the day. Total ion chromatograms can be reprocessed (reintegrated) with other parameters
and/or calibration responses. Data can be downloaded to a spreadsheet for further evaluation or graphical
reporting.
Compounds Detected
With the relatively low column temperature (< 80 °C) in isothermal operation, hexachlorobutadiene and three other
higher boiling point compounds (1,2-dichlorobenzene, 2-chloroethyl vinyl ether, and 1,2-dibromochloropropane)
listed in the demonstration plan were not included in the GC/MS method. The instrument can detect
dichlorobenzenes with a longer run time, but the choice was made to go with shorter run times for this
demonstration to increase the sample throughput rate.
Initial and Daily Calibration
Calibration was done as specified in Method 8260A and in the written field method. Linear regression with a
forced zero intercept was used to derive a single response factor for each target compound. A full calibration was
performed before bringing the instrument to the SRS demonstration. The calibration runs used to generate the
method calibration table can be selected by the operator. A continuing calibration check sample was typically run
two times per day. These daily calibration checks can be used to update calibration response factors if necessary.
QC Procedures and Corrective Actions
Mass calibration checks and updates were run after 4 hours of operation to account for ambient temperature
changes. This procedure is specified in the field method and is required when temperature changes of 10 °C or
more are encountered during instrument operation. In addition to periodic calibration checks, internal and surrogate
standards were run with nearly every sample. These standards give additional measures of instrument data quality.
Blanks were also run at the start of the day. Corrective actions such as calibration rechecks, or sample reruns were
taken when surrogate standard recoveries were <60 or >140% of a typical response. See Chapter 7 for additional
vendor comments on the use of blank samples following high-concentration samples.
Sample Throughput
Maximum sample throughput is about 25 samples per 10-hour day.
Problems Observed During Audit
No problems were observed during the audit.
Data Availability and Changes
Data from the HAPSITE were obtained at the end of each demonstration day in hardcopy format. Data were
provided in spreadsheet format at the conclusion of each demonstration week. Several typographical errors were
corrected at the final data review; however, no substantive data changes were made.
Applications Assessment
This demonstration was intended to provide an assessment of the instrument's suitability for analytical tasks in site
characterization and routine site monitoring. Site characterization refers to those instances where subsurface
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contamination is suspected but information on specific compounds and their concentration levels is not available.
The instrument best suited for this application is one that can screen a wide array of compounds in a timely and
cost-effective manner. Analytical precision and accuracy requirements may be relaxed in these instances since a
general description of the site characteristics is adequate for remediation planning. At the other end of the spectrum
is a monitoring application where contaminant compounds and their subsurface concentrations are known with
some certainty. Periodic monitoring requirements imposed by local regulatory agencies may specify the
performance of analyses for specific contaminant compounds known to be present in the water. Quarterly well-
monitoring programs fall into this category.
Based on its performance in this demonstration, the HAPSITE is suitable for both characterization and monitoring
applications. Since it is a GC/MS system utilizing data-processing software that includes a mass-spectral library
and search routines, it is particularly well suited to characterization applications that require identification of
unknowns. The existence of two compound characteristics, GC column retention time and mass spectral data,
allows unknown compounds to be identified with a high degree of certainty. The precision and accuracy of the
HAPSITE indicate that it is also suited for routine monitoring applications; the results obtained on groundwater
samples with the HAPSITE were comparable to those obtained from a reference laboratory.
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Chapter 7
Technology Update
Note: The following comments were submitted by the technology developer. They have been edited for format
consistency with the rest of the report. The technical content in the following comments has not been verified by
the verification organization.
Review of Demonstration and Results
The ETV Program offered an excellent opportunity to test the performance of the HAPSITE with an equilibrium
headspace accessory for the determination of VOCs in water. As a developer of new technology, we recognize the
benefit of independent verification of system performance as an important step in the acceptance of innovative
technologies. The data contained in the report represent a thorough evaluation of important performance attributes,
precision, accuracy, and operational parameters of the HAPSITE for field work. We appreciate the commitment of
the EPA and the resources contributed by the Agency to make this evaluation possible.
The demonstration has shown that the HAPSITE produces analytical results in the field that are directly
comparable to reference laboratory results. The data represented in this report support the use of the instrument in
all phases of site investigation and remediation work, including the generation of data for regulatory compliance.
Evaluation of the results has resulted in further improvements in the design of the system and analytical method.
The following comments address these changes and some minor discrepancies between the HAPSITE and reference
laboratory results.
Observed False Positive Results
The initial system design specified a carryover of <0.25% from sample to sample. The false positives listed in
Table 5-2 indicate that the components are the result of carryover from high-level samples run prior to the blanks.
While the carryover was less than the specification of 0.25%, changes have been made to the instrument design to
further reduce this specification to <0.15%.
Observed False Negative Results
Eight of the 12 false negatives (Table 5-3) from the SRS site were generated on the first day of testing. After the
first day, a change was made in the flow rate that transfers the sample from the headspace unit to the GC/MS. This
flow rate affects system sensitivity. After the flow rate was reset, only four additional false negatives were
generated. These compounds could be seen by manual review of the GC/MS data, but had not been found by the
peak detection software. Software settings were modified to correct this. The improved flow rate and software
settings were incorporated prior to MAFB testing and resulted in improved performance. The two compounds
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that did cause false negatives at MAFB (1,1,2,2-tetrachloroethane and bromoform) were tested near the system
MDL for these compounds. The performance for bromoform indicates that the reported method detection limit
should be raised.
Comparison of HAPSITE and Laboratory Groundwater Sample Results
A comparison of HAPSITE and reference laboratory groundwater results demonstrates a highly linear relationship.
The HAPSITE produces results that match laboratory results, within ± 35%, 95% of the time. The absolute
percent difference for pooled groundwater samples from the SRS was 29% for the 95th percentile. However, the
MAFB absolute percent difference for pooled groundwater samples was 64% for the 95th percentile. We believe
this number is unduly high and is a result of an error in the reference laboratory results. Figure 5-10 shows a
consistently high percent difference between the HAPSITE and reference laboratory results for the compound cis-
1,2-dichloroethene. It is our opinion that this systematic bias for c/'s-l,2-dichloroethene is due to an error at the
reference laboratory. In the groundwater samples MG-30, MG16, MG17, and MG24 from MAFB, cis-1,2-
dichloroethene was detected by the HAPSITE at an average value of 42 |o,g/L with an RSD of 9% for the replicates.
The laboratory detected c/s-l,2-dichloroethene in only one of the replicates at 27 |og/L, resulting in the compound
being reported as a nondetect for the average. Manual review of the HAPSITE results confirmed the presence of
c/5-l,2-dichloroethene by retention time and mass spectrum. The last quarterly monitoring result from MAFB
supports the HAPSITE data, with c/s-l,2-dichloroethene present at 41 |o,g/L for the low, No. 1 sample set
(Table 3-3).
Number of Compounds Detected
The HAPSITE detected 59 out of 68 compounds reported by the reference laboratory in the groundwater samples at
concentration levels greater than 1 |o,g/L. Of the 9 compounds not detected, 8 were reported by the reference
laboratory at or below the MDL of the HAPSITE for that compound. Trichlorofluoromethane (Freonl 1) was
reported at 20 |o,g/L by the reference laboratory. The HAPSITE report listed the compound as detected, but no
concentration was reported. The concentration was not reported because the standard for the gases failed internal
instrument QA/QC.
The HAPSITE detected a number of compounds not reported by the laboratory in the very high-level samples. This
is a result of the ability of the HAPSITE to analyze these samples undiluted. The laboratory was informed which
samples were expected at a high level and diluted these samples prior to analysis to prevent contamination of the
purge-and-trap and stay within the linear range of the system. The dilution caused a number of compounds to go
undetected because they were then below the detection limits of the system. The ability to analyze samples without
dilution and to run samples of unknown concentration without fear of system contamination is a major advantage
when using equilibrium headspace for site work.
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Chapter 8
Other Deployments
Monterey Airport (April 1998)
Monterey, CA
Groundwater Investigation
Contractor: U.S. Army Corp of Engineers
Contacts: Pat Cantrell - USAGE, Sacramento District
Pam Wehrmann- USAGE, Sacramento District
Field-Portable Analytical was contracted by the U.S. Army Corp of Engineers to perform a groundwater plume
investigation for benzene, toluene, ethyl benzene, and xylenes. The HAPSITE GC/MS and headspace sampling
systems were used to analyze samples during the site investigation. The results were used to decide if further
sampling was needed and where the next sample would be located. Immediate, definitive data were required to
make these decisions. Results from the HAPSITE were reported within 30 minutes of sample collection.
Field-Portable Analytical, Inc.
6054 Garden Towne Way, Suite G
Orangevale, CA 95662
(916) 989-6200
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References
Bevington, P. R, 1969, Data Reduction and Error Analysis for the Physical Sciences, pp. 52-60. McGraw-Hill,
New York.
DataChem, 1997, "DataChem Laboratories Environmental Chemistry/Radiochemistry Quality Assurance Program
Plan," 1997 Revision, DataChem Laboratories, Salt Lake City, UT.
EPA, 1986, "Test Methods for Evaluating Solid Waste," 3rd ed., Vol. 1A (Test Method 3810). Office of Solid
Waste and Emergency Response, Washington, DC.
EPA, 1996a, "A Guidance Manual for the Preparation of Site Characterization and Monitoring Technology
Demonstration Plans," Office of Research and Development, National Exposure Research Laboratory, Las Vegas,
NV. [Available at the ETV Web Site (www.epa.gov/etv) in pdf format.]
EPA, 1996b, "Test Methods for Evaluating Solid Waste: Physical/Chemical Methods; Third Edition; Final Update
III," Report No. EPA SW-846.3-3, Government Printing Office Order No. 955-001-00000-1, Office of Solid
Waste and Emergency Response, Washington, DC.
Havlicek, L. L., and R. D. Grain, 1988, Practical Statistics for the Physical Sciences, pp. 80-93. American
Chemical Society, Washington, DC.
Sandia, 1997, "Demonstration Plan for Wellhead Monitoring Technology Demonstration; Sandia National
Laboratories," Albuquerque, NM. [Available at the ETV Web Site (www.epa.gov/etv) in pdf format.]
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