United States
Environmental Protection
Agency
Office of Research and
Development
Washington, D.C. 20460
EPA/600/R-98/144
November 1998
Environmental Technology
Verification Report
Field-Portable Gas Chromatograph
Perkin-Elmer Photovac
Voyager
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EPA/600/R-98/144
November 1998
Environmental Technology Verification
Report
Field-Portable Gas Chromatograph
Perkin-Elmer Photovac, Voyager
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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t
u
a
UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
Office of Research and Development
Washington, D.C. 20460
E
ENVIRONMENTAL TECHNOLOGY VERIFICATION PROGRAM
VERIFICATION STATEMENT
TECHNOLOGY TYPE:
APPLICATION:
TECHNOLOGY NAME:
COMPANY
ADDRESS:
PHONE:
FIELD-PORTABLE GAS CHROMATOGRAPH
MEASUREMENT OF CHLORINATED VOLATILE ORGANIC
COMPOUNDS IN WATER
Voyager
Perkin-Elmer Corporation - Photovac Monitoring Instruments
50 Danbury Road
Wilton, CT 06897
(203) 761-2557
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 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. 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 Perkin-Elmer Photovac, Voyager field-portable gas
chromatograph (GC).
DEMONSTRATION DESCRIPTION
The field demonstration of the Voyager portable GC was held in September 1997. The demonstration was designed
to assess the instrument's ability to detect and measure chlorinated VOCs 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 Force Base, the target compounds were
EPA-VS-SCM-24
The accompanying notice is an integral part of this verification statement
iii
November 1998
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trichloroethene, tetrachloroethene, 1,2-dichloroethane, 1,1,2-trichloroethane, 1,2-dichloropropane, and trans-\,3-
dichloropropene. These sites were chosen because they contain varied concentrations of chlorinated VOCs and
exhibit different climatic and geological 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, Perkin-Elmer Photovac, Voyager. (EPA/600/R-
98/144).
TECHNOLOGY DESCRIPTION
Gas chromatography with electron capture detection is a proven analytical technology that has been used in
environmental laboratories for many years. The gas chromatographic column separates the sample into individual
components. The electron capture detector measures a change in electron current from a sealed radioactive source as
compounds exit the chromatographic column, move through the detector, and capture electrons. The electron
capture detector is particularly sensitive to chlorinated compounds. Compounds are identified by matching the
column retention time of sample components, run under controlled temperature conditions, to those of standard
mixtures run under similar conditions. Quantitation is achieved by comparing the detector response intensity of the
sample component and the standard. A GC offers some potential for identification of unknown components in a
mixture; however, a confirmational analysis by an alternative method is often advisable. Portable GC is a versatile
technique that can be used to provide rapid screening data or routine monitoring of groundwater samples. In many
GC systems, the instrument configuration can also be quickly changed to accommodate different sample matrices
such as soil, soil gas, water, or air. As with all field analytical studies, it may be necessary to send a portion of the
samples to an independent laboratory for confirmatory analyses.
The Voyager includes an on-board processor and is encapsulated in a weather-resistant case. The GC unit weighs
about 15 pounds and the accessories for water analysis weigh about 33 pounds. Both units can be easily transported
and operated in the rear compartment of a minivan. The instrument utilizes an equilibrium headspace technique for
the analysis of VOCs in water. Instrument detection limits for many chlorinated VOCs in water are in the range of 5
to 10 ng/L. Sample processing and analysis can be accomplished by a chemical technician with 1 day of training;
however, instrument method development and initial calibration may require additional experience and training. At
the time of the demonstration, the baseline cost of the Voyager and headspace sampling accessories was $24,000.
Operational costs, which take into account consumable supplies, are on the order of $25 per 8-hour day.
VERIFICATION OF PERFORMANCE
The following performance characteristics of the Voyager were observed:
Sample Throughput: Throughput was one to three samples per hour. This rate includes the periodic analysis of
blanks and calibration check samples. The sample throughput rate is influenced by the complexity of the sample,
with less complex samples yielding higher throughput rates.
Completeness: The Voyager reported results for all 166 PE evaluation and groundwater samples provided for
analysis at the two demonstration sites.
Analytical Versatility: The Voyager was calibrated for and detected 75% (24 of 32) of the PE sample VOCs
provided for analysis at the demonstration. Three pairs of coeluting compounds were encountered in the GC
methods used during this demonstration. For the groundwater contaminant compounds for which it was calibrated,
the Voyager detected 39 of the 44 compounds reported by the reference laboratory at concentration levels in excess
of 1 ng/L. A total of 68 compounds 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 in terms of relative standard
deviations (RSD). The RSDs compiled for all reported compounds from both sites had a median value of 20% and
a 95th percentile value of 69%. By comparison, the compiled RSDs from the reference laboratory had a median
EPA-VS-SCM-24 The accompanying notice is an integral part of this verification statement November 1998
iv
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value of 7% and a 95th percentile value of 25%. The range of Voyager RSD values for specific target compounds
was as follows: trichloroethene, 7 to 71%; tetrachloroethene, <30% (limited dataonly one value was available);
1,2-dichloroethane and 1,2-dichloropropane (coeluting pair), 4 to 44%; 1,1,2-trichloroethane, 11 to 103%; and
?ra«s-l,3-dichloropropene, 8 to 46%.
Accuracy: Instrument accuracy was evaluated by comparing Voyager results with the known concentrations of
chlorinated organic compounds in PE mixtures. Absolute percent difference (APD) values from both sites were
calculated for all reported compounds in the PE mixtures. The APDs from both sites had a median value of 41%
and a 95th percentile value of 170%. By comparison, the compiled APDs from the reference laboratory had a
median value of 7% and a 95th percentile value of 24%. The range of Voyager APD values for target compounds
was as follows: trichloroethene, 8 to 244%; tetrachloroethene, 24 to 99%; 1,2-dichloroethane and 1,2-
dichloropropane (coeluting pair), 14 to 70%; 1,1,2-trichloroethane, 16 to 50%; and fra«5-l,3-dichloropropene, 3 to
62%.
Comparability: A comparison of Voyager and reference laboratory data was based on 33 groundwater samples
analyzed at each site. The correlation coefficient (r) for all compounds detected by both the Voyager and the
laboratory at or below the 100 ng/L concentration level was 0.890 at Savannah River and 0.660 at McClellan. The
r values for compounds detected at concentration levels in excess of 100 ng/L were 0.830 for Savannah River and
0.999 for McClellan. These correlation coefficients reveal a moderately linear relationship between Voyager and
laboratory data. The median absolute percent difference between groundwater compounds mutually detected by the
Voyager and reference laboratory was 74%, with a 95th percentile value of 453%.
Deployment: The system was ready to analyze samples within 60 minutes of arrival at the site. At both sites, the
instrument was transported in and operated from the rear luggage compartment of a minivan. The instrument was
powered by self-contained batteries or from a small dc-to-ac inverter connected to the vehicle's battery.
The results of the demonstration revealed that sample handling methodologies may have adversely affected the
observed precision and accuracy of the instrument. Perkin-Elmer Photovac has developed an improved field method
for sample preparation and handling that includes the use of an internal standard. The new method is expected to
result in improved instrument precision and accuracy. The Voyager may be suitable for both field screening and
routine analysis applications. In the selection of a technology for use at a particular 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-24
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. 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 Perkin-Elmer Photovac
Voyager field-portable gas chromatograph. 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 designed to evaluate the capabilities of each field-transportable
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
Voyager gas chromatograph. 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
analysis 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 20% and a 95th percentile value
of 69%. Accuracy was expressed as the absolute percent difference between the Voyager 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 41% and a 95th percentile value of 170%. A comparison
of Voyager and reference laboratory results from 33 groundwater samples at each site resulted in a median absolute
percent difference of 74%, with a 95th percentile value of 453%. A correlation analysis between Voyager and
laboratory groundwater yields correlation coefficients (r) greater than 0.66 at low (<100 |o,g/L) contaminant
concentrations and greater than 0.83 at high (>100 |o,g/L) concentrations. The sample throughput rate of the Voyager
was determined to be between 1 and 3 samples per hour.
The results of this study suggest that the sample handling methodology used in this demonstration may have
adversely affected instrument precision and accuracy. A refinement of sample handling methods may improve
overall instrument performance. Under appropriate applications, the Voyager gas chromatograph can provide
useful, cost-effective data for environmental site characterization and routine monitoring. As with any technology
selection, the user must determine what is appropriate by taking into account instrument performance 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
Analytical Methods 6
Advantages 6
Limitations 7
Applications 7
Operator Training 7
Performance Characteristics 7
Method Detection Limits and Practical Quantitation Limit 7
Accuracy 7
IX
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Precision 8
Comparison with Reference Laboratory Analyses 8
Data Completeness 9
Specificity 9
Other Field Performance Characteristics 9
Instrument Setup and Disassembly Time 9
Instrument Calibration Frequency During Field Use 9
Ancillary Equipment Requirements 11
Field Maintenance Requirements 11
Sample Throughput Rate 11
Ease of Operation 11
Chapter 3 Demonstration Design and Description 12
Introduction 12
Overview of Demonstration Design 12
Quantitative Factors 12
Qualitative Factors 13
Site Selection and Description 14
Savannah River Site 14
McClellan Air Force Base 16
Sample Set Descriptions 18
PE Samples and Preparation Methods 21
Groundwater Samples and Collection Methods 23
Sample Handling and Distribution 23
Field Demonstration Schedule and Operations 24
Site Operations and Environmental Conditions 24
Field Audits 25
Data Collection and Analysis 26
Demonstration Plan Deviations 26
Chapter 4 Laboratory Data Results and Evaluation 27
Introduction 27
Reference Laboratory 27
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Laboratory Selection Criteria 27
Summary of Analytical Work by DataChem Laboratories 28
Summary of Method 8260A 28
Method 8260A Quality Control Requirements 28
Summary of Laboratory QC Performance 28
Target Compound List and Method Detection Limits 29
Sample Holding Conditions and Times 29
System Calibration 29
Daily Instrument Performance Checks 31
Batch-Specific Instrument QC Checks 31
Sample-Specific QC Checks 31
Summary of Analytical and QC Deviations 33
Other Data Quality Indicators 33
PE Sample Precision 34
PE Sample Accuracy 34
Groundwater Sample Precision 39
Summary of Reference Laboratory Data Quality 40
Chapter 5 Demonstration Results 41
Voyager Calibrated and Reported Compounds 41
Preanalysis Sample Information 41
Sample Completion 42
Blank Sample Results 42
Performance at Instrument Detection Limit 42
PE Sample Precision 43
PE Sample Accuracy 43
Comparison with Laboratory Results 49
Sample Throughput 49
Performance Summary 49
Chapter 6 Field Observations and Cost Summary 55
Introduction 55
XI
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Method Summary 55
Equipment 55
Sample Preparation and Handling 55
Consumables 56
Historical Use 56
Equipment Cost 57
Operators and Training 57
Data Processing and Output 57
Compounds Detected 58
Initial and Daily Calibration 58
QC Procedures and Corrective Actions 58
Sample Throughput 58
Problems Observed During Audit 58
Data Availability and Changes 58
Instrument Transport 59
Applications Assessment 59
Chapter 7 Technology Update 60
Introduction 60
Additional Performance Testing 60
Voyager Configuration and Method Improvements 60
Sample Preparation and Handling 61
Reference Laboratory 61
Test Results 61
Calculation of Concentrations 61
Precision and Accuracy 61
Chapter 8 Previous Deployments 65
References 66
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Figures
2-1. A schematic diagram of the Voyager GC 5
3-1. The general location of the Savannah River Site in the southeast United States 14
3-2. A map of the A/M area at the Savannah River Site showing the subsurface TCE plume 15
3 -3. A map of Sacramento and vicinity showing the location of McClellan Air Force Base 17
3 -4. Subsurface TCE plumes at McClellan Air Force Base in the shallowest (A) aquifer layer 19
4-1. Laboratory control standard recovery values for SRS analyses 32
4-2. Laboratory control standard recovery values for MAFB analyses 32
4-3. Laboratory precision on SRS PE samples containing mix 1 35
4-4. Laboratory precision on SRS PE samples containing mix 2 35
4-5. Laboratory precision on MAFB PE samples containing mix 2 36
4-6. Laboratory precision on MAFB PE samples containing mix 3 36
4-7. Laboratory mean recoveries for SRS PE samples containing mix 1 37
4-8. Laboratory mean recoveries for SRS PE samples containing mix 2 37
4-9. Laboratory mean recoveries for MAFB PE samples containing mix 2 38
4-10. Laboratory mean recoveries for MAFB PE samples containing mix 3 38
5-1. Voyager precision on PE mix 1 at the SRS 44
5-2. Voyager precision on PE mix 2 at the SRS 44
5-3. Voyager precision on PE mix 2 at MAFB 45
5-4. Voyager precision on PE mix 3 at MAFB 45
5-5. Voyager recovery on PE mix 1 at the SRS 46
5-6. Voyager recovery on PE mix 2 at the SRS 46
5-7. Voyager recovery on PE mix 2 at MAFB 48
5-8. Voyager recovery on PE mix 3 at MAFB 48
5-9. Voyager groundwater results at the SRS relative to laboratory results 52
5-10. Voyager groundwater results at MAFB relative to laboratory results 52
6-1. The Voyager GC 56
xin
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Tables
2-1. Voyager Specifications for MDL, PQL, and Upper Range for Selected Chlorinated Hydrocarbons 8
2-2. Voyager Retention Times and Resolution Factors 10
3-1. Quarterly Monitoring Results for SRS Wells Sampled in the Demonstration 16
3-2. Groundwater Contaminants at MAFB 20
3-3. Quarterly Monitoring Results for MAFB Wells Sampled in the Demonstration 20
3-4. Composition of PE Source Materials 22
3-5. PE Sample Composition and Count for SRS Demonstration 22
3-6. PE Sample Composition and Count for MAFB Demonstration 23
3-7. Weather Summary for SRS and MAFB During Demonstration Periods 25
4-1. Method 8260A Quality Control Summary 29
4-2. Reference Laboratory Method Detection Limits for Target Compounds 30
4-3. Summary of Reference Laboratory Quality Control and Analytical Deviations 33
4-4. Sources of Uncertainty in PE Sample Preparation 34
4-5. Summary of SRS Groundwater Analysis Precision 39
4-6. Summary of MAFB Groundwater Analysis Precision 39
5-1. Voyager Calibrated and Reported Compounds 41
5-2. False Positive Rates from Blank Sample Analysis 42
5-3. False Negative Rates from Very Low-Level PE Sample Analysis 42
5-4. Target Compound Precision at Both Sites 43
5 -5. Summary of PE Sample Precision and Percent Difference Statistics for the SRS and MAFB 47
5-6. Target Compound Recovery for PE Mix 2 at Both Sites 47
5-7. Voyager and Reference Laboratory Results for SRS Groundwater Samples 50
5-8. Voyager and Reference Laboratory Results for MAFB Groundwater Samples 51
5 -9. Voyager Absolute Percent Difference Summary for Pooled Groundwater Results 53
5-10. Correlation Coefficients for Laboratory and Voyager Groundwater Analyses 53
5-11. Summary of Voyager Performance 53
6-1. Voyager GC Cost Summary 57
7-1. Blank Sample Results 62
7-2. Very Low-Level Sample (7 |o,g/L) Results 62
7-3. Low-Level Sample (30 |o,g/L) Results 63
7-4. Midlevel Sample (700 |^g/L) Results 63
7-5. Mid- to High-Level Sample (300 and 5000 |^g/L) Results 64
7-6. Very High-Level Sample (3000 |^g/L) Results 64
7-7. Summary Mean Percent Recoveries 64
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Acronyms and Abbreviations
ac
APD
BNZN
BTEX
°C
ccc
CCL4
CLFRM
dc
11DCA
12DCA
DCE
11DCE
c!2DCE
t!2DCE
DCL
DOE
BCD
EPA
ETV
eV
GC
GW
GC/MS
Hz
L
m
mg
mg/L
mL
mm
MAFB
MCL
MDL
MS
NA
alternating current
absolute percent difference
benzene
xylene
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
electron capture detector
Environmental Protection Agency
Environmental Technology Verification Program
electron-volt
gas chromatograph
groundwater
gas chromatograph/mass spectrometer
hertz, cycles per second
liter
meter
milligram
milligrams per liter
milliliter
millimeter
McClellan Air Force Base
maximum concentration level
method detection limit
mass spectroscopy
not analyzed
xv
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ND not detected
NERL National Exposure Research Laboratory
ng/L nanograms per liter
NR not reported
PC personal computer
PCE tetrachloroethene (perchloroethene)
PE performance evaluation
PID photoionization detector
ppb parts per billion
ppm parts per million
ppt parts per trillion
PQL practical quantitation limit
PVC poly (vinyl chloride)
QA quality assurance
QC quality control
r correlation coefficient
RPD relative percent difference
RSD relative standard deviation
SPCC system performance check compounds
SRS Savannah River Site
TCE trichloroethene
V volts
V ac volts alternating current
VOA volatile organics analysis
VOC volatile organic compound
|o,g microgram
|o,g/L micrograms per liter
|oL microliter
jam micrometer
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 Perkin-Elmer Photovac in this technology demonstration is also acknowledged.
Susan Johnke and Suzanne Moller 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 Perkin Elmer - Photovac, Voyager gas chromatograph, contact:
Dr. Mark Collins, Product Manager
Perkin-Elmer Corporation - Photovac Monitoring Instruments
50 Danbury Road, Wilton, CT 06897
(203) 761-2557
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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 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 Perkin-Elmer Photovac Voyager gas chromatograph. 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
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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.
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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 the EPA 's approval or endorsement.
Technology Overview
The Voyager is a field-portable, computer-controlled, gas chromatograph that incorporates three columns and dual
detectors to achieve broadened analytical capabilities. The instrument's triple column and dual detector
configuration is shown schematically in Figure 2-1.
Voyager GC Assay # 1
Column Arrangement
Carrier column A
Gas (N2)
Make-Up I
Carrier Gas
Precolumn: 4m x 0.53mm x 2.0 um SPB-35
Column A (HEAVY|: 8m x 0.25mm BLANK Fused Silica
Column B (MID-RANGE): 20m x 0.32mm x 1.0 um Supelcowaxl 0 (PEG)
Column C (LIGHT): 15m x 0.32mm x 12 um Quadrex 007-1
Figure 2-1. A schematic diagram of the Voyager GC.
The Voyager has dimensions of 15.4 inches x 10.6 inches x 5.4 inches and weighs 15 pounds. It incorporates a
high-sensitivity photoionization detector (PID) and a miniature electron capture detector (BCD). The instrument is
the fourth generation in the evolutionary design of field-portable GCs from the Photo vac division of the Perkin-
Elmer Corporation. The Voyager was developed with consideration of ergonomic and analytical performance
demands in field environments. Previous generations of Perkin-Elmer Photovac field-portable GCs, such as the
10S50 and 10S70 GC, have been utilized by the EPA Emergency Response Team based in Edison, New Jersey.
This team has generated standard operating procedures for using these instruments to analyze water, soil, ambient
air, and soil gas.
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A unique internal analytical engine includes a specially designed miniature stainless steel valve array to provide fast
sample delivery and minimize sample carryover (and contamination) caused by high VOC concentrations. The
instrument also incorporates a unique triple-column arrangement, with precolumn and backflush, and a syringe
injection port for headspace sampling of aqueous and soil extract media. The two detectors are configured in
parallel. Gas flow from the three internal columns is split to the detectors, with 80% going to the PID and 20%
going to the BCD. Columns A, B, and C, whose configurations are shown in Figure 2-1, are for heavy (C7 to Ci2),
midrange (C4 to C7), and light (d to C3) hydrocarbon compounds, respectively. The internal sampling train,
sample loop, GC columns, valves, and injection port are heated isothermally at temperatures from 55 to 80 °C. The
Voyager is also unique in that it is the only GC of its kind in the world that is classified as intrinsically safe (Class
1, Division I, Groups A, B, C, and D), rendering it useful in hazardous locations.
The instrument is powered by field-rechargeable and replaceable batteries that allow up to 9 hours of field use with
a 5-hour charge time. Alternatively, the Voyager can be operated from an external 10 to 18-V dc power supply
such as a vehicle battery using a cigarette lighter receptacle. The instrument can also be operated on ac power.
The Voyager can be effectively used to monitor many of the volatile organic compounds listed in EPA Method
8240A (EPA, 1996b), including chlorinated and aromatic hydrocarbons. Sample matrices of applicability include
soil, soil gas, water, and ambient air. Method detection limits (MDLs) for VOCs range from parts per trillion (ppt)
in water (ng/L) to about 500 parts per million (ppm) in ambient air, depending upon the type of compound and
detector used.
Analytical results are displayed on the built-in liquid crystal display and include a list of compounds detected, with
concentrations as well as chromatograms. Built-in data logging allows storage of up to 40 10-minute
chromatograms or 400 analyses obtained during operation in a total-VOC screening mode.
Analytical Methods
The Voyager GC can be configured with one analytical method (assay) at a time. The assay includes the
compound library, column temperature, carrier gas pressure (flow rate), and sampling method (internal variable
volume loop or syringe injection). The preferred method of setting up a new analytical method is by using a PC
interface and downloading files. A laptop computer is required for on-site operation if various types of samples are
to be analyzed that require the installation of different methods. The PC does not have to be connected
continuously to the instrument; however, for accurate quantification of trace concentrations of target compounds, it
is recommended that correct integration of chromatogram peak areas be visually verified on the computer screen.
Advantages
The instrument is lightweight and small. The triple-column configuration and dual PID and ECD give this
instrument sensitivity and selectivity (through confirmational analysis) for a wide cross-section of VOCs on site.
Furthermore, the ability to use the internal pump to draw air samples or to perform syringe injections from
headspace samples of soil and groundwater adds further analytical flexibility for different monitoring tasks. The
Voyager has the added advantage of multiple columns and dual detector systems, which can aid in identifying
unknown compounds.
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Limitations
The instrument contains radioactive components in the electron capture detector and normally requires state-
specific licensing and periodic inventory. As a gas chromatograph, the instrument is also somewhat limited in its
ability to identify unknown compounds. Column retention time is used as an indicator; however, as with most GC
systems, an additional data dimension such as mass spectra, provided by GC/MS systems, is not available.
The Voyager utilizes an equilibrium headspace method to determine VOCs in water. Thus it is only able to analyze
those compounds with solubilities and vapor pressures that promote the formation of a detectable equilibrium
headspace concentration.
Applications
The Voyager GC will detect chlorinated solvents such as trichloroethene (TCE) and tetrachloroethene (sometimes
identified as perchloroethene, PCE) at sub-parts-per-billion (ppb or |o,g/L) levels in aqueous media using the PID
and BCD. Benzene, toluene, ethyl benzene, and xylene isomers are also detected at these trace levels using the PID.
Operator Training
One full day of operator training is adequate. The training covers instrument operation, calibration, automatic
(pump) sampling, headspace syringe injection, data storage and retrieval, and method customization and
development, as well as routine maintenance and troubleshooting.
Performance Characteristics
Method Detection Limits and Practical Quantitation Limit
Voyager, in the Assay No. 1 configuration, which includes a PID and BCD and uses a 500-|oL headspace injection,
will give the method detection limits for the chlorinated hydrocarbons shown in Table 2-1 with 95% confidence.
Assay No. 1 covers 40 of the compounds listed in EPA Methods 8260A (EPA, 1996b) and TO-14 (EPA, 1988).
Method detection limits are estimated by determining the Voyager's average sensitivity for a particular compound
(e.g., parts per billion per millivolt x seconds) in its working range, and then multiplying this sensitivity factor by
the minimum detectable peak area (also in units of millivolts x seconds). The Voyager with the Assay No. 1
column-PID/ECD configuration will give a practical quantitation limit (PQL) at a level 5 to 10 times the standard
deviation of the instrument noise signal. Table 2-1 gives the MDLs, PQLs, and upper ranges for various
chlorinated hydrocarbons, including TCE and PCE.
Accuracy
Voyager will provide an accuracy within ±20% for each target compound, over its working range, 95% of the time
through the use of a three-point calibration.
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Table 2-1. Voyager Specifications for MDL, PQL, and Upper Range for Selected
Chlorinated Hydrocarbons
Compounds
MDL
(ng/L)
PID | ECD
PQL
(ng/L)
PID | ECD
Upper Range
(ug/L) PQL x 500
PID
ECD
Column A (C7 - C12)
Bromoform
1 ,1 ,2,2-Tetrachloroethane
1 ,3-Dichlorobenzene
1 ,4-Dichlorobenzene
1 ,2-Dichlorobenzene
20.00
180.00
0.80
0.60
1.60
10.00
30.00
60.00
540.00
2.40
1.80
4.80
30
90
30,000
270,000
1200
900
2400
15,000
45,000
Column B (C4 - C7)
Trichloroethene
1 ,2-Dichloropropane
Tetrachloroethene
2-Chloroethyl vinyl ether
c/s-1 ,3-Dichloropropene
Bromodichloromethane
trans-1 ,3-Dichloropropene
Chlorobenzene
1 ,1 ,2-Trichloroethane
Dibromochloromethane
0.08
6.00
0.06
10.00
0.60
32.00
1.40
0.12
280.00
6.00
0.03
0.10
1200
0.24
18.00
0.18
30
1.80
96.00
4.20
0.36
840
18.00
0.10
0.30
3600
120
9000
90
15,000
900
48,000
2100
180
420,000
9000
48
150
Column C (C1 - C3)
Bromomethane
1,1-Dichloroethene
Methylene chloride
frans-1 ,2-Dichloroethene
Vinyl acetate
c/s-1 ,2-Dichloroethene
Chloroform
1 ,2-Dichloroethane
1,1,1-Trichloroethane
Carbon tetrachloride
0.12
0.08
1.80
0.04
10.00
0.60
40.00
12.00
0.06
1.20
80.00
0.18
0.40
0.36
0.24
5.40
0.12
30
1.80
120
36.00
0.18
3.60
240
0.54
1.20
180
120
2700
60
15,000
900
60,000
18,000
90
1800
120,000
270
600
Note: Blank cells indicate no determination.
Precision
The precision of the Voyager, as represented by the relative standard deviation (RSD)1 on six replicate
measurements, will be < 20% over the working range of the instrument for each compound.
Comparison with Reference Laboratory Analyses
To date, comparison checks that follow EPA protocols have not been carried out on the Voyager against reference
analytical methods for chlorinated species in water.
The relative standard deviation is the sample standard deviation divided by the mean value and multiplied by 100.
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Data Completeness
A complete analysis for TCE; PCE; and benzene, toluene, ethyl benzene, and xylene (BTEX) may take up to 20
minutes. Under these conditions, throughput will be approximately 20 samples and 1 calibration in an 8-hour day.
If there are only 2 analytes (e.g., TCE and PCE), the analysis time will be greatly reduced and sample throughput
will be significantly increased.
Specificity
Specificity is defined in this performance statement as the degree of separation in a mixture of analytes as indicated
by the chromatographic resolution (R)2 The Voyager's resolution is provided in Table 2-2 and is within 20%
reproducibility 95% of the time. Compounds with R < 1 coelute with those immediately above or immediately
below them in the table.
Other Field Performance Characteristics
Instrument Setup and Disassembly Time
The daily operational procedure consists of the following steps:
1. Fill the built-in carrier gas cylinder with nitrogen (assuming portable field operation).
2. Turn the instrument on.
3. Allow stabilization for 60 minutes.
4. Download desired method (assuming a different method is to be used than in the previous day's work).
5. Prepare standards and calibrate for the target compounds at a specified concentration.
6. Analyze samples.
If the carrier gas pressure drops below 200 pounds per square inch, as indicated on the Voyager's internal cylinder
gauge, the cylinder can be recharged from an external supply cylinder. If the "battery voltage low" message is
displayed on the instrument's display panel, the Voyager can be switched off and the battery replaced with a fully
charged one (assuming field operation). After the battery is replaced, the Voyager should be recalibrated in order to
meet specifications. If the Voyager was not connected to a computer before being switched off on the previous day,
the instrument should be connected to a PC running the Windows-based SiteChart software so that any logged data
files may be downloaded. Shutdown time for the Voyager is less than 5 minutes.
Instrument Calibration Frequency During Field Use
Multipoint calibration curves can be prepared for target compounds prior to field deployment. Accuracy
specifications assume that such curves have been established for each compound under headspace conditions. This
will increase sample throughput rather than utilizing a "generic environmental assay." The Voyager requires daily
calibration checks with target analytes.
2 Chromatographic resolution, R, is defined as the time between the maximum values of two adjacent peaks divided by 4
times the standard deviation of the peak. The standard deviation of the peak is half the peak width at its inflection point.
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Table 2-2. Voyager Retention Times and Resolution Factors
Compound
Retention Time
(seconds)
Chromatographic
Resolution (R)
Column A
orffto-Xylene
Styrene
Bromoform
1 ,1 ,2,2-Tetrachloroethane
1 ,3-Dichlorobenzene
1 ,4-Dichlorobenzene
1 ,2-Dichlorobenzene
472.8
506
638.6
715.3
1199.5
1313.5
1629
0.73
2.55
1.27
5.86
1.07
2.55
Column B
Benzene
Trichloroethene
Methyl isobutyl ketone
1 ,2-Dichloropropane
Toluene
Tetrachloroethene
2-Hexanone
2-Chloroethyl vinyl ether
c/s-1 ,3-Dichloropropene
Bromodichloromethane
Ethyl benzene
mefa-Xylene
para-Xylene
frans-1 ,3-Dichloropropene
orffto-Xylene
Chlorobenzene
1 ,1 ,2-Trichloroethane
Dibromochloromethane
267.5
329.6
381.3
413.7
468.8
484.4
571.7
632
668.6
708.7
833.9
872.8
872.8
1010
1144
1162
1367
1673
1.38
3.15
1.84
2.94
0.79
4.14
2.61
1.50
1.57
4.53
1.30
0
4.25
3.73
0.47
5.00
6.39
Column C
Chloromethane
Vinyl chloride
Bromomethane
Chloroethane
Acetone
1,1-Dichloroethene
Dichloromethane
Carbon disulfide
trans-1 ,2-Dichloroethene
Vinyl acetate
Methyl ethyl ketone
c/s-1 ,2-Dichloroethene
1 ,2-Dichloroethene
1,1,1-Trichloroethane
Benzene
Carbon tetrachloride
105.7
118.4
147.2
156.6
190.2
241.1
252.8
283.7
316.3
339
370.3
416.8
552.1
573.3
645.2
675.8
1.02
2.08
0.62
2.03
2.63
0.54
1.35
1.31
0.84
1.09
1.49
3.63
0.49
1.57
0.62
Note: Blank cells indicate no determination.
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Ancillary Equipment Requirements
If the Voyager is used in a stationary (indoor) location, ac or dc power will be required for on-going analyses.
Sample handling accessories include such items as 40-mL volatile organics analysis (VOA) vials, gas-tight syringes
for headspace sampling, spare septa for the syringe injection port, and a small water bath for sample equilibration.
A cylinder of zero-grade nitrogen should be available with a two-stage regulator to run the Voyager in a stationary
location or to refill the internal carrier gas cylinder during field use.
Field Maintenance Requirements
Periodic refilling of the internal carrier gas cylinder is required. The Voyager's on-board battery pack can be
replaced in the field as required. The 10.6-eV light source in the PID can also be cleaned or replaced in the field if
necessary.
Sample Throughput Rate
Depending upon the number and molecular weights of the analytes to be monitored, a typical GC column run for
TCE, PCE, and BTEX may take about 20 minutes in a complex sample background. Additional time is required
for sample preparation and headspace equilibration. For an 8-hour workday and a daily calibration (not including
blanks), the sample throughput would be about 20 per day. If only TCE and PCE are being monitored, the daily
sample throughput will be significantly higher.
Ease of Operation
Once the analytical method has been installed in the Voyager, the instrument can be disconnected from the PC for
field use and the start/stop key can be used to begin and end analyses as required. All Voyager data, including
chromatograms, are logged on an internal data logger and are automatically downloaded when a PC connection is
made.
The Voyager's mode of operation in the field can also be set to a "user only" mode. In this mode, the field
operator can only access the method parameters by entering a password established during method development. In
this manner, the Voyager is used as a simple "point-and-press" instrument with no access to method parameters in
the field.
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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.
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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.
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Site Selection and Description
Two sitesthe DOE Savannah River Site near Aiken, South Carolina, and McClellan Air Force Base near
Sacramento, Californiawere 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.
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.
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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.
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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.
16
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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.
17
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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 zonethe unsaturated region between the surface and the
groundwater tableis 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.
18
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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).
19
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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
20
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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
21
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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 |ig/L
VOC Mix 2- 100|ig/L
VOC Mix 1 - 200 |ig/L
VOC Mix 2- 200|ig/L
VOC Mix 1 - 600 |ig/L
VOC Mix 2- 800|ig/L
1 .02 mg/L TCE spike + 50 |ig/L mix 1
1 .28 mg/L TCE and 1 .23 mg/L PCE
spike + 1 00 |ig/L mix 2
No. of Replicates
10
4
4
4
4
4
4
4
4
42
a TCE = trichloroethene; PCE = tetrachloroethene.
bottles specified by participants (40 mL, 250 mL, and 1 L) with zero 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.
22
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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.
23
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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.
24
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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.
25
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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.
26
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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.
27
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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.
28
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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
29
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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.
30
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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.
31
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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
110
^
>
o
I
100
90
80
Batch 1 Batch 2 Batch 3 Batch 4
Analysis Batch No.
Batch 5
Figure 4-2. Laboratory control standard recovery values for MAFB analyses.
32
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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.
33
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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.
34
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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 ^A/
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.
35
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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.
36
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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
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.
37
-------
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.
38
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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
Mid 1
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.
39
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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.
40
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Chapter 5
Demonstration Results
Voyager 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 Voyager system was calibrated
for 24 compounds at the SRS and 17 compounds at the MAFB site (Table 5-1). The number of target analytes was
reduced at MAFB in order to increase sample throughput. A total of 32 chlorinated and nonchlorinated
hydrocarbon compounds were included in the PE mixtures noted in Table 3-4. The Voyager was also calibrated at
both sites for c/s-1,2-dichloroethene, which was not a PE compound. Three pairs of compounds were reported as
coeluting pairs, as also noted in Table 5-1. The Voyager was not calibrated for the following nine PE compounds
at either site: trichlorofluoromethane, 1,1-dichloroethane, 1,2-dichlorobenzene, 2-chloroethyl vinyl ether, 1,1,2,2-
tetrachloroethane, 1,2,3-trichloropropane, l,2-dibromo-3-chloropropane, hexachlorobutadiene, and bromoform.
Table 5-1. Voyager Calibrated and Reported Compounds
Calibrated Compounds at Both Sites
1 ,3-Dichloropropane
1,2-Dichloroethane(a)
1 ,2-Dichloropropane(a)
1,1-Dichloropropene
Benzene
Bromodichloromethane
Trichloroethene
c/s-1 ,3-Dichloropropene
c/s-1 ,2-Dichloroethene
1,1,2-Trichloroethane(c)
1 ,2-Dibromoethane(c)
Toluene
Dibromochloromethane
Tetrachloroethene
1,1,1 ,2-Tetrachloroethane
Chlorobenzene
Ethyl benzene
Additional Calibrated Compounds at SRS
1,1-Dichloroethene(b)
Methylene chloride(b)
Chloroform
frans-1 ,3-Dichloropropene
Carbon tetrachloride
frans-1 ,2-Dichloroethene
1,1,1-Trichloroethane
Note: Superscripts denote coeluting compound pairs.
Preanalysis Sample Information
Samples were provided to the Voyager team without additional information on the number of compounds in the
sample or compound concentration levels.
41
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Sample Completion
All 166 PE and groundwater samples submitted for analysis to the Voyager team were completed at both
demonstration sites. All Voyager PE and groundwater results are included in Appendix B.
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 1 u,g/L. A list 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 Samples
Compound
Trichloroethene
c/s-1 ,3-Dichloropropene
Chlorobenzene
False Positive
2 of 8 (25%)
1 of 8 (13%)
1 Of 8 (13%)
MAFB Blank Samples
Compound
1,1-Dichloropropene
Trichloroethene
Tetrachloroethene
frans-1 ,3-Dichloropropene
False Positive
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 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, where available, are also shown in the table for comparison.
Table 5-3. False Negative Rates from Very Low-Level PE Sample Analysis
SRS PEMixl (10(ig/L)
Compound
1,1-Dichloroethene (0.06)
Dichloromethane (NA)
Chloroform (11)
Carbon tetrachloride (1)
1 ,2-Dichloropropane (NA)
Trichloroethene (1)
1 ,1 ,2-Trichloroethane (NA)
Dibromochloromethane (1)
Tetrachloroethene (3)
Chlorobenzene (3)
2-Chloroethyl vinyl ether
Trichlorofluoromethane
1,1-Dichloroethane
1 ,2-Dichlorobenzene
False Negative
OoflO
OoflO
10 of 10 (100%)
OoflO
8 of 10 (80%)
OoflO
10 of 10 (100%)
9 of 10 (90%)
OoflO
OoflO
No calibration
No calibration
No calibration
No calibration
MAFB PEMix3(10(ig/L)
Compound
frans-1 ,2-Dichloroethene (1)
1 ,2-Dichloroethane (80)
Benzene (1)
Bromodichloromethane (1)
c/s-1 ,3-Dichloropropene (1)
frans-1 ,3-Dichloropropene (3)
Toluene (1)
Ethyl benzene (1)
Bromoform
1 ,1 ,2,2-Tetrachloroethane
1,1,1-Trichloroethane
False Negative
10 of 10 (100%)
10of10
OoflO
5 of 10 (50%)
OoflO
OoflO
1 of 10 (10%)
6 of 10 (60%)
No calibration
No calibration
No calibration
Notes: Vendor-provided detection limits (in jxg/L) are shown in parentheses after each compound.
NA = not available; the vendor provided no MDL for these compounds.
42
-------
PE Sample Precision
Precision results from each of the four replicate sample sets provided to the participant from eight PE mixtures at
the SRS and seven mixtures at MAFB are shown in Figures 5-1 and 5-2 for the SRS and Figures 5-3 and 5-4 for
MAFB. In instances where no data are reported, no compound names or graph bars are shown. 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 compositions and concentrations of each of these mixtures were given in Table 3-5 for the SRS and
Table 3-6 for MAFB. Note that precision and accuracy were not determined for the "very low" concentration
level.) Relative standard deviations for coeluting compound pairs are also shown in the figures. 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 also given in the last column of the table.
Table 5-4. Target Compound Precision at Both Sites
Target Compound
Trichloroethene
1,2-Dichloroethane(a)
1 ,2-Dichloropropane(a)
1,1,2-Trichloroethane
Tetrachloroethene
frans-1 ,3-Dichloropropene
Site
SRS
MAFB
SRS
MAFB
SRS
MAFB
SRS
MAFB
SRS
MAFB
SRS
MAFB
Relative Standard Deviation (%)
Low
32
7
37
31
37
31
ND
19
ND
ND
14
46
Mid
15
71
19
21
19
21
ND
30
ND
ND
8
30
High
7
14
25
44
25
44
ND
11
ND
ND
33
37
Spike/Low
15
3
4
ND
4
ND
ND
103
29
ND
23
18
Range
7-71
4-44
4-44
11-103
<29
8-46
Notes: 1,2-Dichloroethane and 1,2-dichloropropane are reported as a coeluting compound pair (a); the same results are reported for each
compound of the pair.
ND = not detected.
A summary of overall instrument precision is given in Table 5-5 for the PE mixtures used at both sites. For this
summary, RSD values from all PE sample analyses for all compounds at each site were pooled, and the median and
percentile values of the distribution were computed.
95th
PE Sample Accuracy
The Voyager accuracy for PE sample analyses 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 the SRS and
MAFB, respectively). These comparisons are shown as percent recoveries2 in Figures 5-5 and 5-6 for the SRS
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 SRS.
2 Percent recovery is the Voyager value divided by the true value, multiplied by 100.
43
-------
PE-Photovac Voyager PE Sample Precision
Compound
Trichloroethene
1 ,2-Dichloropropane+ 1 ,2-
Dichloroethane
Tetrachlorethene
Chlorobenzene
Dibromochloromethane
1,1-Dichloroethene+
Dichloromethane
Chloroform
Carbon tetrachloride
1
I
|
i
1
1
1
I ni «
1 DMid
DHiar
| DKpik
1
1
1
1
1
~|
T
1
]
1
1
1 1
1
I
e/Low
0 10 20 30 40 50 60 70 80 90 100
Relative Standard Deviation, %
Figure 5-1. Voyager precision on PE mix 1 at the SRS.
PE-Photovac PE Sample Precision
Compound
Trichloroethene
1 ,2-Dichloropropane+ 1 ,2-
Dichloroethane
Tetrachlorethene
4 Q ry i_i
c ,o LJicmoropropene
. _ _.. i_i
,o LJicmoropropane
..__.. . -
.._....
ot\o - re mix £.
1
| Blow
| nfipikp/l nw
1 ' '
1
1
1
1
i
i
I
i
|
1
0 10 20 30 40 50 60 70
Relative Standard Deviation, %
90 100
Figure 5-2. Voyager precision on PE mix 2 at the SRS.
44
-------
PE-Photovac Voyager PE Sample Precision
MAFB - PE Mix 2
Compound
1,1-Dichloropropene
Benzene
Trichloroethene
1 ,2-Dichloropropane+ 1 ,2-
Dichloroethane
c-1 ,3-Dichloropropene
t-1 ,3-Dichloropropene
1 ,1 ,2-Trichloroethane+ 1 ,2-
Dibromoethane
1,1,1 ,2-Tetrachloroethane
1
i
1
Mid
|
1
1
I
, 1
1
1
1
1
I
1
103
10 20 30 40 50 60 70 80 90 100
Relative Standard Devation, %
Figure 5-3. Voyager precision on PE mix 2 at MAFB.
PE-Photovac Voyager PE Sample Precision
Compound MAFB - PE Mlx 3
Benzene
Trichloroethene
Toluene
Tetrachlorethene
Bromodichloromethane
Ethyl Benzene
t-1 ,3-Dichloropropene
I
| BLOW
Mid
DSpik
I
I
I
! J
1
1
|
1
1
e/Low
0 10 20
30 40 50 60 70
Relative Standard Deviation, %
80 90 100
Figure 5-4. Voyager precision on PE mix 3 at MAFB.
45
-------
PE-Photovac Voyager PE Sample Recovery
Compound
1,2-Dichloropropane+ 1,2-
Dichloroethane
rvK M ih
1 , 1 -Dichloroethene+
Chloroform
r> K ii M 'A
SF
I
c
I
I
B*l
JS - PE MIX 1
1,
1 Blow
DMid
! 1 BHigh
1 DSpike/Low
1
1
1
I
^
^
| 1
~|
_l
50
100 150 200
Average Percent Recovery
Figure 5-5. Voyager recovery on PE mix 1 at the SRS.
PE-Photovac Voyager PE Sample Recovery
50 100 150 200
Average Percent Recovery
250
300
Compound
_ . . . .
1,2-Dichloropropane+ 1,2-
Dichloroethane
Tetrachlorethene
. _ _. . .
1 ">. rv HI
. _ _. . .
-i -i rv hi
SK
1
1
1
1
a - rt ivnx ^
1
1 1
1 BLnw
BMid
BHigh
DSpike/Low
1
rn
i
"
p
i
i 1
i
i
I
250
300
Figure 5-6. Voyager recovery on PE mix 2 at the SRS.
46
-------
and Figures 5-7 and 5-8 for MAFB.3 In instances where no data were reported, no compound names or graph bars
are shown. To assist in assessing 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 (in PE mix 2 at both sites) is shown in Table 5-6, which contains the average percent recoveries and
associated ranges for each compound.
A summary of overall Voyager recovery differences relative to PE mixture true values is given for both sites,
alongside the precision summary in Table 5-5. For this summary, percent recoveries were expressed as percent
difference (e.g., a 90% recovery is equivalent to a -10% difference; a 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 5-5.4
Table 5-5. Summary of PE Sample Precision and Percent Difference Statistics for the SRS
and MAFB
Parameter
RSD, %
Absolute percent
difference
Percentile
50th
95th
Number in pool
50th
95th
Number in pool
SRS
PE Mix 1
24
77
29
20
47
29
PE Mix 2
20
59
28
48
156
28
MAFB
PE Mix 2
19
61
29
50
219
29
PE Mix 3
19
56
25
77
170
25
Combined Sites
Combined Mixes
20
69
111
41
170
111
Table 5-6. Target Compound Recovery for PE Mix 2 at Both Sites
Target Compound
Trichloroethene
1,2-Dichloroethane(a)
1 ,2-Dichloropropane(a)
1 , 1 ,2-Trichloroethane
Tetrachloroethene
frans-1 ,3-Dichloropropene
Site
SRS
MAFB
SRS
MAFB
SRS
MAFB
SRS
MAFB
SRS
MAFB
SRS
MAFB
Average Recovery (%)
Low
92
231
55
82
55
82
ND
116
ND
ND
106
95
Mid
137
246
86
133
86
133
ND
54
ND
ND
154
97
High
164
333
85
170
85
170
ND
50
1
ND
162
143
Spike/Low
116
344
34
ND
34
ND
ND
116
124
ND
122
72
Range
92 - 344
34-170
34-170
50-116
1-124
72-162
Notes: 1,2-Dichloroethane and 1,2-dichloropropane are reported as a coeluting compound pair (a); the same results are reported for each
compound of the pair.
ND = not detected.
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.
The absolute percent difference is the absolute value of the percent difference between a field and reference (in this case
the reference laboratory) measurement. As an example, the percent difference between a field measurement of 85 and a
laboratory measurement of 110 is -22.7% and the absolute percent difference is 22.7%.
47
-------
PE-Photovac Voyager PE Sample Recovery
Compound
4 4 rv M
Benzene
Trichloroethene
4 n rv u
A A A r\ -f L Ul *U
IVIA
Mid
High
D Spike/Low
1
|
1
1 1
I
'
-B - Kt MIX i
\
1
1 1
|
1 vn
1
344
1
1
I
1
1
1
m
i
i
i
50 100 150 200
Average Percent Recovery
Figure 5-7. Voyager recovery on PE mix 2 at MAFB.
PE-Photovac Voyager PE Sample Recovery
50
100 150 200
Average Percent Recovery
250
300
Compound
Benzene
Trichloroethene
Toluene
Tetrachlorethene
Bromodichloromethane
Ethyl Benzene
t-1 ,3-Dichloropropene
Low
Mid
DSpike/Low
1
MAFB - PE Mix 3
1
I
367
1
1
5^
| 1
1
1
250
300
Figure 5-8. Voyager recovery on PE mix 3 at MAFB.
48
-------
Comparison with Laboratory Results
At 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 Voyager results for all groundwater samples 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 Voyager on replicate groundwater samples is also shown in the last column of the table.
The average percent difference between average Voyager and laboratory results for the compounds detected in each
set of groundwater samples is shown in Figures 5-9 and 5-10 for the 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
were also contaminated with 1,1-dichloroethene (11DCE) and one well contained chloroform (CLFRM) and carbon
tetrachloride (CCL4), as noted in Table 5-7. The groundwater samples at MAFB were by choice more complex, as
indicated by the additional compounds shown in Table 5-8 and Figure 5-10.
The median and 95th percentiles of the distribution of absolute percent differences between Voyager and laboratory
results for all groundwater samples are given in Table 5-9.
To assess the degree of linear correlation between the Voyager 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 |o,g/L to those in excess of 1000 |o,g/L) (Havlicek and Grain, 1988). One subset
contained all data pairs with laboratory results less than or equal to 100 |o,g/L and the other subset included all data
pairs with laboratory values greater than 100 |o,g/L. The computed correlation coefficients are shown in Table 5-
10.
Sample Throughput
Voyager throughput rates ranged from one 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. Voyager GC run times were influenced to some extent by sample complexity.
Groundwater samples with fewer and known components could be run relatively quickly, whereas multicomponent
PE mixtures required longer run times.
Performance Summary
Table 5-11 contains a summary of Voyager 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 Voyager performance results to facilitate comparison of
the two methodologies.
49
-------
Table 5-7. Voyager and Reference Laboratory Results for SRS Groundwater Samples
Sample
Description
Very low 1
Very low 2
Low 1
Low 2
Mid 1
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
MSB 14A
MSB8C
Compound
Trichloroethene
Tetrachloroethene
Trichloroethene
Tetrachloroethene
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.
(ng/U
9.0
3.5
2.4
0.7
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
12
5
6
7
9
0
15
9
12
7
4
8
1
2
12
8
8
8
6
6
6
0-34
8
15
Voyager3
Avg.
(ng/U
18
18
7.0
5.3
71
148
46
40
NR
NR
242
261
55
427
NR
968
67
1321
1016
NR
1378
1585
2231
3356
Voyager3
RSD
(%)
22
28
100
93
79
120
5
6
NR
NR
9
75
19
15
NR
29
88
13
22
NR
27
6
13
10
5-120
22
101
NR = Not reported.
50
-------
Table 5-8. Voyager and Reference Laboratory Results for MAFB Groundwater Samples
Sample
Description
Very low 1
Very low 2
Low1
Low 2
Midi
Mid 2
Highl
High 2
Very high 1
Very high 2
Well
Number
EW-86
MW-349
MW-331
MW-352
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
c/s-1 ,2,dichloroethene
Carbon tetrachloride
Chloroform
Trichloroethene
Freonl 1
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.
(H9/L)
4.6
7.7
13
2.0
9.0
3.8
137
2.5
15
NR
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
NR
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
13
Voyager3
Avg.
(H9/L)
3.3
NR
16
6
NR
NR
NR
NR
NR
45
NR
NR
25
NR
NR
NR
1.3
NR
43
NR
NR
2.8
NR
214
5.0
16
NR
463
46
NR
497
NR
86
NR
NR
946
NR
404
NR
468
27,300
NR
261
NR
NR
17,433
Voyager3
RSD
(%)
17
NR
9
0
NR
NR
NR
NR
NR
3
NR
NR
4
NR
NR
NR
43
NR
15
NR
NR
18
NR
4
0
16
NR
59
1
NR
26
NR
5
NR
NR
5
NR
4
NR
9
0
NR
15
NR
NR
7
0-59
7
43
NR = not reported.
51
-------
Compound
PE-Photovac Voyager GW Sample Difference
Site: SRS Ref: Laboratory
Trichloroethene
Tetrachlorethene
DVLowl
VLow2
DLowl
DLow2
Midi
Mid2
DHighl
High2
IVHighl
IVHigh2
-500 -400 -300 -200 -100 0 100 200 300 400 500
Average Difference, %
Figure 5-9. Voyager groundwater results at the SRS relative to laboratory results.
Compound
Benzene
PE-Photovac Voyager GW Sample Difference
Site: MAFB Ref: Laboratory
c-1,2-Dichloroethene
Trichloroethene
Tetrachlorethene
VLowl
VLow2
DLowl
DLow2
DMidl
Mid2
DHighl
DHigh2
DVHigh!
VHigh2
-200 -150 -100 -50 0 50 100 150 200 250
Average Difference, %
Figure 5-10. Voyager groundwater results at MAFB relative to laboratory results.
52
-------
Table 5-9. Voyager Absolute Percent Difference Summary for
Pooled Groundwater Results
Percentile
50the
95th
Number of samples in pool
SRS
89
551
20
MAFB
65
206
20
Combined Sites
74
453
40
Table 5-10. Correlation Coefficients for Laboratory and Voyager
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
0.890
0.830
0.660
0.999
Number of
Data Pairs
10
9
15
9
Table 5-11. Summary of Voyager Performance
Instrument
Feature/Parameter
Performance Summary
Blank sample
False positives detected at low (13 to 25%) rates for 6 of 24 reported compounds.
Detection limit sample
False negatives reported at rates between 10 and 100% for 8 of 18 compounds at
concentration levels of 10 |j.g/L.
PE sample precision
Target compounds, RSD range: 4 to 103%
All compounds, Voyager median RSD: 20%; 95th percentile RSD: 69%
All compounds, laboratory median RSD: 7%; 95th percentile RSD: 25%
(Target compounds: TCE, 1,2-dichloroethane, 1,1,2-trichloroethane,
1,2-dichloropropane, PCE, and frans-1,3-dichloropropene)
PE sample accuracy
Target compounds: absolute percent difference range: 8 to 244%
All compounds, Voyager median APD: 41 %; 95th percentile APD: 170%
All compounds, laboratory median APD: 7%; 95th percentile APD: 24%;
(Target compounds same as those for sample precision)
Voyager comparison
with laboratory results
forgroundwater
samples
Voyager median RSD: 15%
Voyager 95th percentile RSD: 93%
Laboratory median RSD: 6%
Laboratory 95th percentile RSD: 14%
Voyager: laboratory median APD: 74%; 95 percentile APD: 453%
Voyager: laboratory correlation:
SRS low cone. (< 100 |ag/L) r = 0.890
SRS high cone. (> 100 |ag/L) r= 0.830
MAFB low cone. (< 100 |ag/L) r= 0.660
MAFB high cone. (>100|ag/L) r= 0.999
53
-------
Table 5-11. Summary of Voyager Performance (Continued)
Instrument
Feature/Parameter
Analytical versatility
Sample throughput
Support requirements
Operator requirements
Total system weight
Portability
Total system cost
Shipping requirements
Performance Summary
PE samples: calibrated for 24 of 32 PE compounds (75%)
Three pairs of coeluting compounds were reported.
GW samples: For the compounds for which it was calibrated, Voyager reported
of 44 compounds detected by the laboratory in all GW samples at or above the
1 |j,g/L concentration level. A total of 68 compounds were detected by the
laboratory in all groundwater samples.
39
1 to 3 samples per hour
Water bath
Radioactive detector permit/license
Sample processing: field technician with 1-day training
Data processing and review: B. S. chemist or equivalent
48 pounds
GC is field-portable; accessories (water bath) are transportable
$24,000 (with notebook computer and printer)
Air freight, hand carry, luggage check (no compressed gas via commercial flight)
Recharge carrier gas cylinder requires drop shipment
54
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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 analytical
procedures used during the demonstration were consistent with written procedures submitted to the verification
organization prior to the field demonstration. An instrument cost summary and an applications assessment are
provided.
Method Summary
The Voyager uses a static equilibrium headspace method with temperature control. The headspace vapors from a
temperature-equilibrated sample are manually withdrawn with a gas-tight syringe and injected into the Voyager.
The instrument is a three-column GC with dual (photoionization and electron capture) detectors. Compounds are
identified by retention time and quantified by integrating the peak area of the compound and comparing it with that
of calibration standards. Internal and surrogate standards are not used. (See Chapter 7 for discussion of a revised
method that incorporates internal standards.)
Equipment
The Voyager dimensions are 15 inches x 11 inches x 5 inches and it weighs 15 pounds. A notebook computer
(8 pounds) and field-portable printer (10 pounds) were also used during the demonstration for data download,
review, and printing. Equipment weights include batteries and self-contained carrier gas. A small, ac-powered
water bath (15 pounds) was used for temperature equilibration of the sample vials. The system was deployed on
the folded-down middle seat of a minivan. The Voyager is field-portable and could be easily carried to a wellhead
(Figure 6-1); however, the accessory water bath requires ac power. The entire system is best regarded as
transportable in a vehicle to a site. A small cylinder of compressed nitrogen was used for periodic recharge of the
internal carrier gas cylinder. Battery lifetime is normally about 9 hours; however, for this demonstration, the
instrument and computer were powered by a dc-to-ac inverter that was connected to the vehicle's battery.
Additional equipment used at the demonstration included 40-mL, screw-cap sample vials with septa; chemical
standards; 20-mL syringes and vent needles for sample transfer; and 500-jaL gas-tight syringes for sample injection
into the GC.
Sample Preparation and Handling
For sample handling at the SRS, a zero-headspace, 40-mL sample vial was inverted and placed in a 30 °C water
bath. Following a 15-minute equilibration, the vial was uncapped and a 20-mL quantity poured into a second
40-mL vial and capped. The second vial was vigorously shaken for 2 minutes and then returned to the water bath
55
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Figure 6-1. The Voyager GC.
and held for 5 minutes. The vial was removed from the bath and a 500-|oL, gas-tight syringe was used to withdraw
a headspace sample from the vial through the cap septum. This syringe sample was then manually injected into the
Voyager.
The sampling procedures at MAFB were modified as follows: The zero-headspace, 40-mL sample vial was inverted
and placed into a 30 °C water bath. Following a 15-minute equilibration, the vial was removed from the bath for
withdrawal of a portion of the sample. The needle of a 20-mL syringe was inserted, along with a second vent
needle, through the septum and a 20-mL portion of the water sample was withdrawn. The withdrawn portion was
discarded and the original vial was returned to the water bath for an additional 5 minutes. A headspace vapor
sample was then withdrawn with a gas-tight syringe and injected into the Voyager, in the same manner as carried
out at the SRS.
Consumables
An internal gas bottle contains nitrogen carrier gas. An external cylinder is used to periodically refill the internal
cylinder.
Historical Use
This is the first demonstration of the Voyager GC for VOC analysis in water. The instrument and its predecessors
have been used extensively for air and soil gas analysis.
56
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Equipment Cost
The Voyager, as equipped at the demonstration, has a purchase price of $20,000. This includes the proprietary
SiteChart software but does not include a notebook computer for data processing and instrument control. Ancillary
equipment costs are about $4000. 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. Voyager sample
throughput is in the range of 1 to 3 samples per hour.
Table 6-1. Voyager GC Cost Summary
Instrument/Accessory
Instrument
(Voyager three-column GC and dual PID, ECD;
SiteChart software)
Instrument accessories
(notebook computer, field-portable printer)
Shipping case (option)
Thermally insulated soft case (option)
Water bath
Sample handling accessories
(carrier gas, syringes, vials, standards)
Maintenance costs: periodic PID window cleaning,
column replacement, etc.
Cost
$20,000
$3000 (notebook computer)
$500 (printer)
$200
$500 per 100 samples
One-year parts and labor warranty
Service maintenance agreement ~$2000 per year
Operators and Training
The Voyager was operated by two sales and application technicians at the demonstration. Both of them had
bachelors'-level training in chemistry. Only one person is needed to operate the instrument. With 1 hour of
training, an experienced chemical technician could operate the system. A novice technician operator would require
1 day of training. Experience with GC data processing is required to do method development and analysis of
complex mixtures.
Data Processing and Output
A real-time chromatogram is displayed on the Voyager's display panel and on the PC's SiteChart software, if
connected. Hardcopy output is available immediately after analysis. The analysis report, available as a monitor
display or hard copy, includes the following:
chromatogram;
analysis parameters;
analysis method;
integration method; and
peak report (compounds identified, compound concentration, peak area and height, retention time, and status).
57
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Compounds Detected
The system was calibrated for 24 compounds at the SRS site and utilized two different methods and two columns.
To reduce analysis time and increase sample throughput, at the MAFB site the system was calibrated for 17
compounds on a single column. The calibrated compounds are given in Table 5-1.
Initial and Daily Calibration
A three-point calibration for each target compound was completed at Photovac facilities prior to the demonstration
period. The software will accommodate up to a five-point calibration, with the lowest point being a blank sample.
The user can choose a linear calibration curve or a quadratic fit curve. The linear curve selection produces a point-
to-point line based on the calibration data. A standard mixture of target compounds at an intermediate
concentration (100 |o,g/L) was analyzed at the beginning of each demonstration day to update compound retention
times and detector response factors in the calibration file.
QC Procedures and Corrective Actions
Standard mixtures of chlorinated VOCs in methanol were used in a single daily calibration run. Injection syringes
were decontaminated between uses by heating them in sunlight. Carrier gas flow was controlled by an automatic
pressure regulator to permit analysis at varying atmospheric pressures with no mathematical data manipulation.
No internal standards or surrogate standards were used to monitor sample matrix effects.
Sample Throughput
Chromatographic analysis run time was observed to be approximately 60 minutes for a multicomponent PE sample,
and 10 minutes for a groundwater sample containing only TCE and PCE. Preliminary hardcopy data were
available at the end of the day and final data in spreadsheet format were available the following day. Typical
throughput rates were one to three samples per hour.
Problems Observed During Audit
The auditors observed that sample handling procedures used by the Voyager team at the SRS may have contributed
to imprecise or inaccurate results. The PE and groundwater samples were heated to 30 °C and then uncapped and
poured. Handling warm samples in this manner could result in volatile losses of target compounds, with resulting
degraded instrument recovery and precision. The method was changed at MAFB so that warm samples were never
opened. The precision data presented in Chapter 5 reveal improvement at MAFB compared with the SRS,
particularly for groundwater samples (see Tables 5-7 and 5-8). A moderate improvement in Voyager accuracy at
MAFB for groundwater samples was also noted (see Table 5-9).
The Voyager team encountered problems with the laptop computer during the latter portion of the MAFB
demonstration. This delayed delivery of hardcopy data until the computer could be repaired. The Voyager GC
performed acceptably throughout the demonstrations at both sites.
Data Availability and Changes
Preliminary data from the Voyager 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 and
transcription errors were corrected at the final data review. The concentration levels of several compounds were
58
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reevaluated and changed after the final demonstration period when it was discovered that incorrect compound
response factors in the original calibration file were applied to several compounds. A software change has since
been made to remedy this situation in future use.
Instrument Transport
The Voyager can either be carried on or checked as luggage on airline flights provided that the internal carrier gas
cylinder is emptied. The GC is equipped with a purge valve so that the cylinder can be easily discharged. Drop
shipment is the preferred method for transporting the external carrier gas cylinder since carrying compressed gases
on commercial flights is not permitted. A hard-sided shipping case is available as an instrument option. When
shipping a Voyager equipped with an BCD, no special shipping papers are required since the radiation level of the
detector falls within the International Air Transportation Association level for exempt packages. A 2-week prior
notification is required to bring the Voyager to a particular state in the United States. There is usually no fee
associated with this notification and typically it is valid for 1 year.
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
contamination is suspected but information on specific compounds and their concentration level 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 that analyses
be carried out 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 Voyager is most applicable to routine monitoring applications
where sample composition is known. It could also be successfully used in sample screening situations where the
contaminants and their approximate concentration in the water are known. Chromatographic methods utilized with
the Voyager may require specific tailoring for a given routine monitoring application.
The Voyager team has observed that their method of sample preparation could be improved. One suggested
improvement is to inject an internal standard in the water sample prior to temperature equilibration and withdrawal
of the headspace gas sample. The internal standard would yield a QC check on every sample and would reveal
such conditions as a plugged syringe or sample matrix effects. A low or high recovery of the internal standard
would prompt the analyst to flag the data and further investigate or reanalyze the sample. See Chapter 7 for a
vendor discussion of a modified method that incorporates an internal standard.
59
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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.
Introduction
Perkin-Elmer Photovac personnel reviewed the Environmental Technology Verification Report and found the
document to be written in a well-organized and objective manner. Since our participation in the ETV
demonstration, we have improved the method of sample preparation and handling. The revised method specifies the
injection of an internal standard into the water sample prior to temperature equilibration, headspace sampling, and
analysis with the Voyager GC. In addition, a heater block is now used instead of a water bath to provide more
uniform warming of the samples. In accordance with the applications assessment section in Chapter 6, the revised
data review process now includes a QC check based upon analytical results using an internal standard. These
results will help to identify abnormal conditions such as a plugged syringe or unusual sample matrix effects.
Additional Performance Testing
A summary of accuracy and precision results from limited additional testing using the improved methodology is
included in this chapter. This testing was carried out by Perkin-Elmer Photovac without verification organization
oversight and followed a design similar to that used during the field demonstrations.
Voyager Configuration and Method Improvements
Optimum separation of eight chlorinated and nonchlorinated VOC analytes examined in this test was achieved
utilizing two of the three columns in the Voyager's analytical engine. The columns are described below:
Column B: 20 m x 0.32 mm x 1 jam Supelcowax 20 (PEG)
Column C: 25 m x 0.32 mm x 12 jam Quadrex 007-1
Improvements in the analytical protocol include:
a modified headspace equilibration system using a heater block to ensure precise, uniform heating of samples at
30 °C;
use of dibromomethane as an internal standard for both the PK) and ECD; and
60
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a five-point calibration curve stored in the Voyager's built-in assay library instead of the previous two-point (zero
and upscale value) calibration protocol.
Sample Preparation and Handling
For the postdemonstration test, standard solutions of the following compounds were prepared from certified stock
solutions at concentration levels of 7, 30, 700, and 3000 |o,g/L: benzene, toluene, ethyl benzene, raeto-xylene,
trichloroethene, tetrachloroethene, bromodichloromethane, and dibromochloromethane. A two-level mixture was
also prepared with TCE and PCE at 5000 |o,g/L levels and the other compounds at 300 |o,g/L levels.
The standard samples were prepared by serial addition into organic-free water. Each solution was then transferred
to a 40-mL volatile organics analysis (VOA) vial with zero headspace. Twelve replicate vials of each concentration
were prepared in this manner. Four vials of each concentration were stored upside down in a refrigerator at 4 °C
for Voyager analysis. The remaining eight replicates (four samples of each concentration plus four extras in case
of breakage) were placed in a cooler with ice packs and shipped to Phoenix Environmental Laboratories, Inc., in
Manchester, Connecticut, for analysis using EPA Method 8260A. The sample preparation and handling procedures
were essentially the same as those used during the field demonstration.
Sample handling during Voyager analysis was conducted by withdrawing a 20-mL portion of the water sample
from the 40-mL VOA through the septum using a syringe. The withdrawn sample aliquot was discarded. A
100-|oL volume of the dibromomethane internal standard was then injected through the septum to produce a final
solution concentration of 1000 |o,g/L. The vial was gently agitated for 30 seconds and placed in a heater block at
30 °C for 15 minutes. The vial was then removed from the heater block and a lOO-joL volume of headspace gas
was manually withdrawn from the vial and injected into the Voyager with a gas-tight syringe.
Reference Laboratory
For consistency with the field demonstration design plan, Phoenix Environmental Laboratories was used as a
reference laboratory for verification of sample concentrations using EPA Method 8260A. A total of 24 samples (4
replicates of 5 different mixtures and 4 blanks) were analyzed by the reference laboratory for verification of
mixture composition and concentration.
Test Results
Calculation of Concentrations
Analytical results obtained using chromatograph column B were manually calculated from response factors derived
from peak area and weight ratios of earlier calibration runs of the dibromomethane internal standard and 500 |o,g/L
standards of each target analyte. The results for toluene and PCE on chromatograph column C were calculated
using Voyager internal software and a five-point calibration curve. The dibromomethane internal standard was not
used for these two compounds since it coelutes with toluene on this particular column.
Precision and Accuracy
Relative standard deviations for the nine compounds and six (five and a blank) concentration levels investigated in
this study are provided in Tables 7-1 to 7-6. The RSD values were computed from four replicate samples analyzed
at each concentration level. The average percent recovery of each compound, also computed from the replicate
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samples, is also shown in Tables 7-1 to 7-6. In each table, three different recovery values are given: (1) the
percent ratio of the Voyager result to the laboratory result; (2) the percent ratio of the Voyager result to the "true"
value; and (3) the percent ratio of the laboratory value to the "true" value. The mean percent recoveries for each
target compound over all concentration ranges are given in Table 7-7.
Table 7-1. Blank Sample Results
Compound
Benzene
Trichloroethene
Toluene
Tetrachloroethene
Dibromomethane
Ethyl benzene
mefa-Xylene
Dibromochloromethane
Bromodichloromethane
Voyager Avg.
(ng/U
No detect
No detect
No detect
13
1007
No detect
No detect
No detect
No detect
Voyager RSD
(%)
84.8
6.7
True Cone.
(ng/U
<0.5
<0.5
<0.5
<0.5
1000
<0.5
<0.5
<0.5
<0.5
Lab. Avg.
(ng/U
No detect
No detect
No detect
No detect
NA
No detect
No detect
No detect
No detect
Notes: In this table and the following five tables, average and RSD values are computed from four replicate samples.
NA = not analyzed.
Table 7-2. Very Low-Level Sample (7 u,g/L) Results
Compound
Benzene
Trichloroethene
Toluene
Tetrachloroethene
Dibromomethane
Ethyl benzene
mefa-Xylene
Dibromochloromethane
Bromodichloromethane
Voyager
Avg.
(ng/U
6.0
6.0
10.0
10.0
980
1.0
1.0
9.0
6.5
Voyager
RSD
(%)
32.9
27.3
46.2
47.5
18.6
66.7
66.7
200.0
115.5
True
Cone.
(ng/U
7
7
7
7
1000
7
7
7
7
Lab.
Avg.
(ng/U
15
12
13
10
NA
19
11
14
16
Percent Recovery
Voyager
to Lab.
38
52
75
95
NA
4
7
61
41
Voyager
to True
82
89
139
136
98
11
11
121
93
Lab. to
True
214
171
186
143
NA
271
157
200
229
Note: NA = not analyzed.
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Table 7-3. Low-Level Sample (30 u,g/L) Results
Compound
Benzene
Trichloroethene
Toluene
Tetrachloroethene
Dibromomethane
Ethyl benzene
mefa-Xylene
Dibromochloromethane
Bromodichloromethane
Voyager
Avg.
(ng/U
42
44
35
17
846
47
47
23
62
Voyager
RSD
(%)
10.2
4.8
23.8
58.2
10.9
10.0
7.4
72.8
3.8
True
Cone.
(ng/U
30
30
30
30
1000
30
30
30
30
Lab.
Avg.
(ng/U
40
44
40
39
NA
42
42
46
41
Percent Recovery
Voyager
to Lab.
104
99
86
43
NA
111
112
49
151
Voyager
to True
139
145
115
56
85
155
157
75
206
Lab. to
True
133
147
133
130
NA
140
140
153
137
Note: NA = not analyzed.
Table 7-4. Midlevel Sample (700 u,g/L) Results
Compound
Benzene
Trichloroethene
Toluene
Tetrachloroethene
Dibromomethane
Ethyl benzene
mefa-Xylene
Dibromochloromethane
Bromodichloromethane
Voyager
Avg.
(ng/U
787
717
743
808
1058
686
520
705
680
Voyager
RSD
(%)
4.1
1.0
7.1
11.3
3.6
6.3
2.2
10.1
7.5
True
Cone.
(ng/U
700
700
700
700
1000
700
700
700
700
Lab.
Avg.
(ng/U
585
633
528
628
NA
648
403
733
655
Percent Recovery
Voyager
to Lab.
134
113
141
129
NA
106
129
96
104
Voyager
to True
112
102
106
115
106
98
74
101
97
Lab. to
True
84
90
75
90
NA
93
58
105
94
Note: NA = not analyzed.
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Table 7-5. Mid- to High-Level Sample (300 and 5000 u,g/L) Results
Compound
Benzene
Trichloroethene
Toluene
Tetrachloroethene
Dibromomethane
Ethyl benzene
mefa-Xylene
Dibromochloromethane
Bromodichloromethane
Voyager
Avg.
(ng/U
197
3300
254
4749
597
182
157
238
219
Voyager
RSD
(%)
12.6
12.9
11.4
12.2
8.9
13.0
19.9
18.1
13.1
True
Cone.
(ng/U
300
5000
300
5000
1000
300
300
300
300
Lab.
Avg.
(ng/U
135
3025
95
2850
NA
123
135
98
125
Percent Recovery
Voyager
to Lab.
146
109
267
167
NA
148
117
243
175
Voyager
to True
66
66
85
95
60
61
52
79
73
Lab. to
True
45
61
32
57
NA
41
45
33
42
Note: NA = not analyzed.
Table 7-6. Very High-Level Sample (3000 u,g/L) Results
Compound
Benzene
Trichloroethene
Toluene
Tetrachloroethene
Dibromomethane
Ethyl benzene
mefa-Xylene
Dibromochloromethane
Bromodichloromethane
Voyager
Avg.
(ng/U
2825
2675
2765
2948
748
2775
2800
3050
3050
Voyager
RSD
(%)
6.0
16.3
16.1
16.3
31.5
16.5
15.4
1.9
4.2
True
Cone.
(ng/U
3000
3000
3000
3000
1000
3000
3000
3000
3000
Lab.
Avg.
(ng/U
2200
1625
2175
1375
NA
1950
1950
2375
2325
Percent Recovery
Voyager
to Lab.
128
165
127
214
NA
142
144
128
131
Voyager
to True
94
89
92
98
75
93
93
102
102
Lab. to
True
73
54
73
46
NA
65
65
79
78
Note: NA = not analyzed.
Table 7-7. Summary Mean Percent Recoveries
Compound
Benzene
Toluene
Ethyl benzene
mefa-Xylene
Trichloroethene
Tetrachloroethene
Dibromochloromethane
Bromodichloromethane
Mean Percent Recovery at Concentration Level (M.Q/L)
7
82
139
11
11
89
136
121
93
30
139
115
155
157
145
56
75
206
700
112
106
98
74
102
115
101
97
3000
94
92
93
93
89
98
102
102
300/5000
66
85
60
52
66
95
79
73
Overall Mean
Percent Recovery
99
107
83
77
98
100
96
114
64
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Chapter 8
Previous Deployments
Note from vendor: The names and companies listed below are current Perkin-Elmer Photovac Voyager users.
The individuals and/or companies are not endorsing the Voyager or its use for a specific application. Questions
about the Voyager and its use or application should be addressed to the Perkin-Elmer Photovac Applications group
at (203) 761-5040.
Vicky Bliss
Mobil Oil
Joliet, IL
(815)423-7397
Application: Assay 2 - Petrochemical
Paulette Lane
PSE&G of New Jersey
(201)761-1188
Application: Assay 2 - Petrochemical
Hilary Eustace
City of Somerville
Somerville, MA
(617) 625-6600
Application: Assay 1 - Environmental
Jan McChesney
Bayer Rubber
Sarnia, Ontario
(519)337-8251
Application: Assay 4 - ABS Rubber
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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, 1988, "Compendium of Methods for the Determination of Toxic Organic Compounds in Ambient Air,"
Report No. EPA/600/4-89/017, Office of Research and Development, U.S. Environmental Protection Agency,
Research Triangle Park, NC.
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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