EPA/600/R-98/142

November 1998

Environmental Technology Verification

Report

Field-Portable Gas Chromatograph/

Mass Spectrometer

Inficon, Inc., HAPSITE

by

Wayne Einfeld

Sandia National Laboratories

Albuquerque, New Mexico 87185-0755

IAG DW89936700-01-0

Project Officer

Stephen Billets

National Exposure Research Laboratory

Office of Research and Development

U.S. Environmental Protection Agency

Las Vegas, Nevada 89193
ii

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.
UNITED STATES ENVIRONMENTAL PROTECTION AGENCY

Office of Research and Development

Washington, D.C. 20460

EPA-VS-SCM-25 The accompanying notice is an integral part of this verification statement November 1998

iii

ENVIRONMENTAL TECHNOLOGY VERIFICATION PROGRAM

VERIFICATION STATEMENT

PROGRAM DESCRIPTION

The U.S. Environmental Protection Agency (EPA) created the Environmental Technology Verification Program

(ETV) to facilitate the deployment of innovative environmental technologies through performance verification and

information dissemination. The goal of the ETV Program is to further environmental protection by substantially

accelerating the acceptance and use of improved and cost-effective technologies. The ETV Program is intended to

assist and inform those involved in the design, distribution, permitting, and purchase of environmental technologies.

Under this program, in partnership with recognized testing organizations, and with the full participation of the

technology developer, the EPA evaluates the performance of innovative technologies by developing demonstration

plans, conducting field tests, collecting and analyzing the demonstration results, and preparing reports. The testing

is conducted in accordance with rigorous quality assurance protocols to ensure that data of known and adequate

quality are generated and that the results are defensible. The EPA National Exposure Research Laboratory, in

cooperation with Sandia National Laboratories, the testing organization, evaluated field-portable systems for

monitoring chlorinated volatile organic compounds (VOCs) in water. This verification statement provides a

summary of the demonstration and results for the Inficon HAPSITE field-portable gas chromatograph/mass

spectrometer (GC/MS) system.

DEMONSTRATION DESCRIPTION

The field demonstration of the HAPSITE portable GC/MS was held in September 1997. The demonstration was

designed to assess the instrument’s ability to detect and measure chlorinated volatile organic compounds in

groundwater at two contaminated sites: the Department of Energy’s Savannah River Site, near Aiken, South

Carolina, and the McClellan Air Force Base, near Sacramento, California. Groundwater samples from each site

were supplemented with performance evaluation (PE) samples of known composition. Both sample types were used

to assess instrument accuracy, precision, sample throughput, and comparability to reference laboratory results. The

primary target compounds at the Savannah River Site were trichloroethene and tetrachloroethene. At McClellan Air

 TECHNOLOGY TYPE: FIELD-PORTABLE GAS CHROMATOGRAPH/

MASS SPECTROMETER

 APPLICATION: MEASUREMENT OF CHLORINATED VOLATILE ORGANIC

COMPOUNDS IN WATER

 TECHNOLOGY NAME: HAPSITE with Headspace Sampling Accessory

 COMPANY Inficon, Inc.

 ADDRESS: Two Technology Place

East Syracuse, NY 13057

 PHONE: (315) 434-1100
EPA-VS-SCM-25 The accompanying notice is an integral part of this verification statement November 1998

iv

Force Base, the target compounds were trichloroethene, tetrachloroethene, 1,2-dichloroethane, 1,1,2-

trichloroethane, 1,2-dichloropropane, and trans-1,3-dichloropropene. These sites were chosen because they contain

varied concentrations of chlorinated VOCs and exhibit different climatic and geologic conditions. The conditions at

these sites are typical, but not inclusive, of those under which this technology would be expected to operate. A

complete description of the demonstration, including a data summary and discussion of results, may be found in the

report entitled Environmental Technology Verification Report, Field-Portable Gas Chromatograph/Mass

Spectrometer, Inficon, Inc., HAPSITE. (EPA/600/R-98/142).

TECHNOLOGY DESCRIPTION

GC/MS is a proven laboratory analytical technology that has been used for environmental characterization and

monitoring for many years. The combination of gas chromatography and mass spectrometry allows the rapid

separation and identification of compounds in complex mixtures. The gas chromatograph separates the sample into

individual components. These components are introduced into the electron impact source module of the

spectrometer, where the molecules are fragmented into ions by an electron beam. The ion fragments are further

separated by mass and detected by an electron multiplier. The resulting mass spectrum is characteristic of a

particular compound and can be used to identify each component in the sample extract through comparison with a

reference spectral library. Quantitation is achieved by comparing the abundance of ions which are characteristic of a

specific compound with the detector response from the analysis of a standard mixture. Field-portable GC/MS is a

versatile technique that can be used to provide rapid screening data or laboratory-quality analyses. As with many

field analytical studies, it may be necessary to send a portion of the samples to an independent laboratory for

confirmatory analyses.

The Inficon HAPSITE with a headspace sampling accessory is a commercially available GC/MS system that

provides laboratory-grade performance in a field-transportable package. The instrument, including the on-board

computer, is designed for field use and is encapsulated in a weather-resistant case. The GC/MS unit weighs about 35

pounds and the headspace sampling accessory weighs about 15 pounds. Both units can be easily transported and

operated in the rear compartment of a minivan or station wagon. The instrument utilizes an equilibrium headspace

technique for the analysis of VOCs in water. Instrument detection limits for most chlorinated VOCs in water are in

the range of 5 to 10 μg/L. At the time of the demonstration, the cost of the HAPSITE with headspace accessory was

in the range of $75,000 to $95,000, depending upon instrument options. Operational costs, which include

consumable supplies but not labor costs, are on the order of $150 per 8-hour day. 

VERIFICATION OF PERFORMANCE

The following performance characteristics of the HAPSITE were observed:

Sample Throughput: Throughput was approximately two to three water samples per hour. This rate includes the

periodic analysis of blanks and calibration check samples.

Completeness: The HAPSITE reported results for all but one of the 166 PE and groundwater samples provided for

analysis at the two demonstration sites. One sample was dropped during preparation. 

Analytical Versatility: The HAPSITE detected all of the compounds in the PE samples for which it was calibrated.

 Its calibration included 84% (27 of 32) of all chlorinated and nonchlorinated volatile hydrocarbon compounds

included in the PE samples at the demonstration. Additional compounds could have been detected with a longer

GC/MS run time and a reduced sample throughput. The HAPSITE detected all (59 of 59) of the groundwater

contaminants in excess of 5 μg/L reported by the reference laboratory at both sites. A total of 68 contaminants, at

concentration levels of 1 μg/L or higher, were detected by the reference laboratory in all groundwater samples. 

Precision: Precision was determined by analyzing sets of four replicate samples from a variety of PE mixtures

containing known concentrations of chlorinated VOCs. The results are reported as relative standard deviations

(RSD). The RSDs compiled for all reported PE compounds from both sites had a median value of 12% and a 95th

percentile value of 29%. By comparison, the compiled RSDs from the reference laboratory had a median value of
EPA-VS-SCM-25 The accompanying notice is an integral part of this verification statement November 1998

v

7% and a 95th percentile value of 25%. The ranges of HAPSITE RSD values for specific target compounds were as

follows: trichloroethene 7 to 18%, tetrachloroethene, 6 to 22%; 1,2-dichloroethane, 2 to 12%; 1,1,2-trichloroethane,

8 to 28%; 1,2-dichloropropane, 7 to 21%; and trans-1,3-dichloropropene, 7 to 17%.

Accuracy: Instrument accuracy was evaluated by comparing HAPSITE results with the known concentrations of

chlorinated organic compounds in PE mixtures. Absolute percent difference (APD) values from both sites were

calculated for all analytes in the PE mixtures. The APDs for all reported compounds from both sites had a median

value of 8% and a 95th percentile value of 27%. By comparison, the compiled APDs from the reference laboratory

had a median value of 7% and a 95th percentile value of 24%. The ranges of HAPSITE APD values for target

compounds were as follows: trichloroethene, 1 to 20%; tetrachloroethene, 6 to 33%; 1,2-dichloroethane, 2 to 20%;

1,1,2-trichloroethane 1 to 21%; 1,2-dichloropropane, 3 to 21%; and trans-1,3-dichloropropene, 1 to 15%.

Comparability: A comparison of HAPSITE and reference laboratory data was based on 33 groundwater samples

analyzed at each site. The correlation coefficients (r) for all compounds detected by both the HAPSITE and

laboratory at or below 100 μg/L concentration levels were 0.983 at Savannah River and 0.978 at McClellan. The r

values for compounds detected at concentration levels in excess of 100 μg/L were 0.996 for Savannah River and

1.000 for McClellan. These correlation coefficients reveal a highly linear relationship between HAPSITE and

laboratory data. The median absolute percent difference between groundwater compounds mutually detected by the

HAPSITE and reference laboratory was 13%, with a 95th percentile value of 60%.

Deployment: The system was ready to analyze samples within 30 minutes of arrival at the site. At both sites, the

instrument was transported in a minivan and was operated in its rear luggage compartment. The instrument was

powered by self-contained batteries or from line ac power. The recommended training interval for routine sample

processing is about 3 days for a chemist with limited GC/MS experience. Method development and analysis of very

complex samples requires a higher level of operator training and experience in GC/MS data interpretation. 

The results of this demonstration show that the HAPSITE can provide useful, cost-effective data for environmental

site screening and routine monitoring. This instrument could be employed in a variety of applications, ranging from

producing rapid analytical results in screening investigations, to producing accurate and precise data that are directly

comparable with that obtained from an off-site laboratory. These data could be used to develop risk assessment

information, support a remediation process, or fulfill monitoring requirements. In the selection of a technology for

deployment at a site, the user must determine what is appropriate through consideration of instrument performance

and the project’s data quality objectives.

Gary J. Foley, Ph. D. Samuel G. Varnado

Director Director

National Exposure Research Laboratory Energy and Critical Infrastructure Center

Office of Research and Development 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.
vi

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
vii

Executive Summary

The U.S. Environmental Protection Agency, through the Environmental Technology Verification Program, is

working to accelerate the acceptance and use of innovative technologies that improve the way the United States

manages its environmental problems. As part of this program, the Consortium for Site Characterization

Technology was established as a pilot program to test and verify field monitoring and site characterization

technologies. The Consortium is a partnership involving the U.S. Environmental Protection Agency, the

Department of Defense, and the Department of Energy. In 1997 the Consortium conducted a demonstration of five

systems designed for the analysis of chlorinated volatile organic compounds in groundwater (GW). The developers

participating in this demonstration were Electronic Sensor Technology, Perkin-Elmer Photovac, and Sentex

Systems, Inc. (field-portable gas chromatographs); Inficon, Inc. (field-portable gas chromatograph/mass

spectrometer, GC/MS); and Innova AirTech Instruments (photoacoustic infrared analyzer). This report documents

demonstration activities, presents demonstration data, and verifies the performance of the Inficon HAPSITE fieldportable GC/MS. Reports documenting the performance of the other technologies have been published separately.

The demonstration was conducted at two geologically and climatologically different sites: the U.S. Department of

Energy’s Savannah River Site, near Aiken, South Carolina, and McClellan Air Force Base, near Sacramento,

California. Both sites have groundwater resources that are significantly contaminated with a variety of chlorinated

volatile organic compounds. The demonstrations to evaluate the capabilities of each field-portable system were

conducted in September 1997 and were coordinated by Sandia National Laboratories.

The demonstration provided adequate analytical and operational data with which to evaluate the performance of the

Inficon HAPSITE GC/MS system. Instrument precision and accuracy were determined from analyses of replicate

samples from 16 multicomponent standard mixtures of known composition. The relative standard deviations

obtained from analyses of 4 replicate samples from each of the 16 standard mixtures were used as measures of

precision. The distribution of relative standard deviations from all compounds had a median value of 12% and a

95th percentile value of 29%. Accuracy was expressed as the absolute percent difference between the HAPSITE

measured value and the true value of the component in the standard mixtures. The distribution of absolute percent

difference values for all compounds in all standard mixtures had a median value of 8% and a 95th percentile value

of 27%. A comparison of HAPSITE and reference laboratory results from groundwater samples at each site resulted in a median absolute percent difference of 13%, with a 95th percentile value of 60%. A correlation analysis

between HAPSITE and laboratory results indicates a high degree of linear correlation (r >0.98) at both low (≤100 

μg/L) and high (>100 μg/L) contaminant concentrations. The sample throughput rate of the HAPSITE was

determined to be two to three samples per hour.

The HAPSITE detected all of the groundwater contaminants reported by the reference laboratory at both sites

which were present at concentration levels in excess of 5 μg/L. The results of the demonstration show that the

Inficon HAPSITE field-portable GC/MS with its headspace sampling accessory can provide useful, cost-effective

data for environmental site characterization and routine monitoring. As with any technology selection, the user

must determine whether the technology is appropriate for the application by taking into account instrument

performance parameters and the project’s data quality objectives.
viii
ix

Contents

Notice .................................................................................................................................................................. ii

Verification Statement......................................................................................................................................... iii

Foreword ............................................................................................................................................................ vi

Executive Summary ........................................................................................................................................... vii

Figures.............................................................................................................................................................. xiii

Tables............................................................................................................................................................... xiv

Acronyms and Abbreviations.............................................................................................................................. xv

Acknowledgments ............................................................................................................................................ xvii

Chapter 1 Introduction.......................................................................................................................................... 1

Site Characterization Technology Challenge....................................................................................... 1

Technology Verification Process........................................................................................................ 2

Identification of Needs and Selection of Technology..................................................................... 2

Planning and Implementation of Demonstration............................................................................ 2

Preparation of Report.................................................................................................................. 3

Distribution of Information.......................................................................................................... 3

The Wellhead VOC Monitoring Demonstration.................................................................................. 3

Chapter 2 Technology Description........................................................................................................................ 5

Technology Overview........................................................................................................................ 5

Principle of Operation........................................................................................................................ 6

History of the Technology.................................................................................................................. 6

Applications...................................................................................................................................... 6

Advantages........................................................................................................................................ 7

Limitations........................................................................................................................................ 7

Performance Characteristics .............................................................................................................. 7

Practical Quantitation Limits and Method Detection Limits.......................................................... 7

Accuracy..................................................................................................................................... 7

Precision ..................................................................................................................................... 7
x

Instrument Working Range.......................................................................................................... 9

Comparison with Reference Laboratory Analyses ........................................................................ 9

Data Completeness...................................................................................................................... 9

Other Analytical Performance Characteristics and Requirements........................................................ 9

Other Field Performance Characteristics............................................................................................ 9

Instrument Setup and Disassembly Time...................................................................................... 9

Instrument Calibration Frequency During Field Use..................................................................... 9

Ancillary Equipment Requirements............................................................................................ 10

Field Maintenance Requirements ............................................................................................... 10

Sample Throughput Rate........................................................................................................... 10

Operator Training Requirements and Ease of Operation............................................................. 10

Chapter 3 Demonstration Design and Description ............................................................................................... 11

Introduction..................................................................................................................................... 11

Overview of Demonstration Design.................................................................................................. 11

Quantitative Factors.................................................................................................................. 11

Qualitative Factors.................................................................................................................... 12

Site Selection and Description.......................................................................................................... 13

Savannah River Site .................................................................................................................. 13

McClellan Air Force Base ......................................................................................................... 15

Sample Set Descriptions.................................................................................................................. 17

PE Samples and Preparation Methods........................................................................................ 20

Groundwater Samples and Collection Methods .......................................................................... 22

Sample Handling and Distribution.................................................................................................... 22

Field Demonstration Schedule and Operations.................................................................................. 23

Site Operations and Environmental Conditions................................................................................. 23

Field Audits..................................................................................................................................... 24

Data Collection and Analysis........................................................................................................... 25

Demonstration Plan Deviations........................................................................................................ 25

Chapter 4 Laboratory Data Results and Evaluation............................................................................................. 26

Introduction..................................................................................................................................... 26

Reference Laboratory ...................................................................................................................... 26
xi

Laboratory Selection Criteria........................................................................................................... 26

Summary of Analytical Work by DataChem Laboratories................................................................ 27

Summary of Method 8260A............................................................................................................. 27

Method 8260A Quality Control Requirements.................................................................................. 27

Summary of Laboratory QC Performance ........................................................................................ 27

Target Compound List and Method Detection Limits ................................................................. 28

Sample Holding Conditions and Times....................................................................................... 28

System Calibration.................................................................................................................... 28

Daily Instrument Performance Checks....................................................................................... 30

Batch-Specific Instrument QC Checks....................................................................................... 30

Sample-Specific QC Checks...................................................................................................... 30

Summary of Analytical and QC Deviations................................................................................ 32

Other Data Quality Indicators.......................................................................................................... 32

PE Sample Precision ................................................................................................................. 33

PE Sample Accuracy................................................................................................................. 33

Groundwater Sample Precision.................................................................................................. 38

Summary of Reference Laboratory Data Quality.............................................................................. 39

Chapter 5 Demonstration Results........................................................................................................................ 40

HAPSITE Calibrated and Reported Compounds .............................................................................. 40

Preanalysis Sample Information....................................................................................................... 40

Sample Completion.......................................................................................................................... 41

Blank Sample Results...................................................................................................................... 41

Performance at Instrument Detection Limit ...................................................................................... 41

PE Sample Precision........................................................................................................................ 42

PE Sample Accuracy....................................................................................................................... 45

Comparison with Laboratory Results............................................................................................... 45

Sample Throughput ......................................................................................................................... 51

Performance Summary .................................................................................................................... 51

Chapter 6 Field Observations and Cost Summary ............................................................................................... 53

Introduction..................................................................................................................................... 53
xii

Method Summary...................................................................................................................... 53

Equipment................................................................................................................................. 53

Sample Preparation and Handling.............................................................................................. 54

Consumables............................................................................................................................. 54

Historical Use ........................................................................................................................... 55

Equipment Cost......................................................................................................................... 55

Operators and Training.............................................................................................................. 55

Data Processing and Output ...................................................................................................... 55

Compounds Detected................................................................................................................. 56

Initial and Daily Calibration ...................................................................................................... 56

QC Procedures and Corrective Actions...................................................................................... 56

Sample Throughput................................................................................................................... 56

Problems Observed During Audit .............................................................................................. 56

Data Availability and Changes................................................................................................... 56

Applications Assessment.................................................................................................................. 56

Chapter 7 Technology Update............................................................................................................................. 58

Review of Demonstration and Results.............................................................................................. 58

Observed False Positive Results....................................................................................................... 58

Observed False Negative Results ..................................................................................................... 58

Comparison of HAPSITE and Laboratory Groundwater Sample Results.......................................... 59

Number of Compounds Detected...................................................................................................... 59

Chapter 8 Other Deployments............................................................................................................................. 60

References.......................................................................................................................................................... 61
xiii

Figures

3-1. The general location of the Savannah River Site in the southeast United States........................................ 13

3-2. A map of the A/M area at the Savannah River Site showing the subsurface TCE plume.......................... 14

3-3. A map of Sacramento and vicinity showing the location of McClellan Air Force Base............................. 16

3-4. Subsurface TCE plumes at McClellan Air Force Base in the shallowest (A) aquifer layer ....................... 18

4-1. Laboratory control standard recovery values for SRS analyses. .............................................................. 31

4-2. Laboratory control standard recovery values for MAFB analyses............................................................ 31

4-3. Laboratory precision on SRS PE samples containing mix 1 .................................................................... 34

4-4. Laboratory precision on SRS PE samples containing mix 2. ................................................................... 34

4-5. Laboratory precision on MAFB PE samples containing mix 2................................................................. 35

4-6. Laboratory precision on MAFB PE samples containing mix 3................................................................. 35

4-7. Laboratory mean recoveries for SRS PE samples containing mix 1......................................................... 36

4-8. Laboratory mean recoveries for SRS PE samples containing mix 2......................................................... 36

4-9. Laboratory mean recoveries for MAFB PE samples containing mix 2 ..................................................... 37

4-10. Laboratory mean recoveries for MAFB PE samples containing mix 3 ..................................................... 37

5-1. HAPSITE precision on PE mix 1 at the SRS.......................................................................................... 43

5-2. HAPSITE precision on PE mix 2 at the SRS.......................................................................................... 43

5-3. HAPSITE precision on PE mix 2 at MAFB............................................................................................ 44

5-4. HAPSITE precision on PE mix 3 at MAFB............................................................................................ 44

5-5. HAPSITE recovery on PE mix 1 at the SRS........................................................................................... 46

5-6. HAPSITE recovery on PE mix 2 at the SRS........................................................................................... 46

5-7. HAPSITE recovery on PE mix 2 at MAFB ............................................................................................ 47

5-8. HAPSITE recovery on PE mix 3 at MAFB ............................................................................................ 47

5-9. HAPSITE groundwater results at the SRS relative to laboratory results.................................................. 50

5-10. HAPSITE groundwater results at MAFB relative to laboratory results.................................................... 50

6-1. The HAPSITE GC/MS.......................................................................................................................... 54
xiv

Tables

2-1. Inficon HAPSITE GC/MS Analyte List ................................................................................................... 8

3-1. Quarterly Monitoring Results for SRS Wells Sampled in the Demonstration ........................................... 15

3-2. Groundwater Contaminants at MAFB.................................................................................................... 19

3-3. Quarterly Monitoring Results for MAFB Wells Sampled in the Demonstration ....................................... 19

3-4. Composition of PE Source Materials...................................................................................................... 21

3-5. PE Sample Composition and Count for SRS Demonstration ................................................................... 21

3-6. PE Sample Composition and Count for MAFB Demonstration ............................................................... 22

3-7. Weather Summary for SRS and MAFB During Demonstration Periods .................................................. 24

4-1. Method 8260A Quality Control Summary .............................................................................................. 28

4-2. Reference Laboratory Method Detection Limits for Target Compounds.................................................. 29

4-3. Summary of Reference Laboratory Quality Control and Analytical Deviations........................................ 32

4-4. Sources of Uncertainty in PE Sample Preparation................................................................................... 33

4-5. Summary of SRS Groundwater Analysis Precision................................................................................. 38

4-6. Summary of MAFB Groundwater Analysis Precision ............................................................................. 38

5-1. HAPSITE Calibrated and Reported Compounds..................................................................................... 40

5-2. False Positive Rates from Blank Sample Analysis................................................................................... 41

5-3. False Negative Rates from Very Low-Level PE Sample Analysis............................................................ 41

5-4. Target Compound Precision for PE Samples at Both Sites...................................................................... 42

5-5. Summary of PE Sample Precision and Percent Difference Statistics for SRS and MAFB ........................ 42

5-6. Target PE Compound Recovery at Both Sites......................................................................................... 45

5-7. HAPSITE and Reference Laboratory Results for SRS Groundwater Samples......................................... 48

5-8. HAPSITE and Reference Laboratory Results for MAFB Groundwater Samples ..................................... 49

5-9. HAPSITE Absolute Percent Difference Summary for Pooled Groundwater Results................................. 51

5-10. Correlation Coefficients for Laboratory and HAPSITE Groundwater Analyses....................................... 51

5-11. Summary of HAPSITE GC/MS Performance......................................................................................... 52

6-1. HAPSITE GC/MS Cost Summary ......................................................................................................... 55
xv

Acronyms and Abbreviations

ac alternating current

amu atomic mass unit

APD absolute percent difference

BNZN benzene

°C degrees centigrade

CCC calibration check compounds

CCL4 carbon tetrachloride

CLFRM chloroform

dc direct current

11DCA 1,1-dichloroethane

12DCA 1,2-dichloroethane

DCE dichloroethene

11DCE 1,1-dichloroethene

c12DCE cis-1,2-dichloroethene

t12DCE trans-1,2-dichloroethene

DCL DataChem Laboratories

DOE Department of Energy

EPA Environmental Protection Agency

ETV Environmental Technology Verification Program

eV electron-volt

GC gas chromatograph

GW groundwater

GC/MS gas chromatograph/mass spectrometer

hp horsepower

Hz hertz, cycles per second

i.d. inside diameter

L liter

m meter

mg milligram

mg/L milligram per liter

mL milliliter

mm millimeter

MAFB McClellan Air Force Base

MCL maximum concentration level

MDL method detection limit

MS mass spectroscopy

NERL National Exposure Research Laboratory

NIST National Institute of Standards and Technology
xvi

NR not reported

PC personal computer

PCE tetrachloroethene (perchloroethene)

PE performance evaluation

ppb parts per billion

ppm parts per million

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

TCA trichloroethane

111TCA 1,1,1-trichloroethane

TCE trichloroethene

V volts

V ac volts alternating current

VOA volatile organics analysis

VOC volatile organic compound

XYL xylene

μg microgram

μg/L microgram per liter

μL microliter
xvii

Acknowledgments

The author wishes to acknowledge the support of all those who helped to plan and conduct the demonstrations,

analyze the data, and prepare this report. In particular, the technical expertise of Gary Brown, Robert Helgesen,

Michael Hightower, and Dr. Brian Rutherford of Sandia National Laboratories in the planning and conduct of the

study are recognized. The assistance of Dr. Timothy Jarosch and Joseph Rossabi of Westinghouse Savannah River

Co. in planning the demonstration and field activities at both Savannah River and McClellan is also recognized.

The willingness of Phillip Mook and Timothy Chapman of the Environmental Directorate at McClellan Air Force

Base to host the McClellan phase of the study is also greatly appreciated. The availability of funding from the

Department of Defense’s Strategic Environmental Research and Development Program helped to make the

McClellan phase of the study possible. The guidance and contributions of project technical leaders Dr. Stephen

Billets and Eric Koglin of the EPA National Exposure Research Laboratory, Environmental Sciences Division, in

Las Vegas, Nevada, during all phases of the project are also recognized.

The participation of personnel from Inficon, Inc. in this technology demonstration is also acknowledged. Chuck

Sadowski and co-workers operated the instrument during the demonstrations.

For more information on the wellhead monitoring demonstration, contact:

Stephen Billets, Project Technical Leader, U.S. Environmental Protection Agency

National Exposure Research Laboratory, Environmental Sciences Division

P.O. Box 93478, Las Vegas, Nevada 89193-3478

(702) 798-2232

For more information on the Inficon HAPSITE gas chromotograph/mass spectrometer technology, contact:

Bill Worthington, Technical Marketing Manager, Inficon, Inc.

Two Technology Place, East Syracuse, NY 13057

(315) 434-1100
xviii
1

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.
2

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
3

• preparation and implementation of a demonstration plan that addresses the experimental design, sampling design,

quality assurance and quality control (QA/QC), health and safety considerations, scheduling of field and

laboratory operations, data analysis procedures, and reporting requirements.

Preparation of Report

Each of the innovative technologies is evaluated independently and, when possible, against a reference technology.

The technologies are operated in the field by the developers in the presence of independent observers who are

provided by the EPA or the verification organization. Demonstration data are used to evaluate the capabilities,

limitations, and field applications of each technology. Following the demonstration, all raw and reduced data used

to evaluate each technology are compiled in a technology evaluation report, which is a record of the demonstration.

A data summary and detailed evaluation of each technology are published in an environmental technology

verification report. The report includes a verification statement, which is a concise summary of the instrument’s

performance during the demonstration.

Distribution of Information

The goal of the information distribution strategy is to ensure that environmental technology verification reports and

accompanying verification statements are readily available to interested parties through traditional data distribution

pathways, such as printed documents. Related documents and updates are also available on the World Wide Web

through the ETV Web site (http://www.epa.gov/etv) and through a Web site supported by the EPA Office of Solid

Waste and Emergency Response Technology Innovation Office (http://clu-in.com). Additional information at the

ETV Web site includes a summary of the demonstration plan, test protocols (where applicable), demonstration

schedule and participants, and in some cases a brief narrative and pictorial summary of the demonstrations.

The Wellhead VOC Monitoring Demonstration

In August 1996, the selection of a technology for monitoring chlorinated VOCs in water was initiated by

publication in the Commerce Business Daily of a solicitation and notice of intent to conduct such a technology

demonstration. Potential participants were also solicited through manufacturer and technical literature references.

The original demonstration scope was limited to market-ready in situ technologies; however, only a limited response

was obtained, so the demonstration scope was expanded to include technologies that could be used to measure

groundwater (GW) at or near the wellhead. The final selection of technologies was based on the readiness of the

technologies for field demonstration and their applicability to the measurement of chlorinated VOCs in groundwater

at environmentally affected sites.

For this demonstration, five instrument systems were selected. Three of them were field-portable gas

chromatographs with various detection systems: one with a surface acoustic wave detector from Electronic Sensor

Technology, one with dual electron capture and photoionization detectors from Perkin-Elmer Photovac, and one

with an argon ion/electron capture detector from Sentex Systems. The fourth instrument was a field-portable gas

chromatograph/mass spectrometer (GC/MS) from Inficon, and the fifth was a photoacoustic infrared spectrometer

from Innova AirTech Instruments. This report documents demonstration activities, presents demonstration data,

and verifies the performance of the Inficon, Inc., HAPSITE field-portable gas chromatograph/mass spectrometer.

Reports documenting the performance of the other four technologies have been published separately.

The demonstration was conducted in September 1997 at the DOE Savannah River Site (SRS) near Aiken, Georgia,

and at McClellan Air Force Base (MAFB), near Sacramento, California. Both sites have subsurface plumes of
4

chlorinated VOCs and extensive networks of groundwater 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.
5

Chapter 2 

Technology Description

This chapter was provided by the developer and was edited for format and relevance. The data presented include

performance claims that may not have been verified as part of the demonstration. Chapters 5 and 6 report

instrument features and performance observed in this demonstration. Publication of this material does not

represent EPA approval or endorsement.

Technology Overview

The Inficon HAPSITE is a field-portable gas chromatograph/mass spectrometer that can be operated from battery

or ac line power. The basic instrument was originally designed to analyze gas samples in the parts per billion (ppb)

to parts per million (ppm) range. Sample components are separated by gas chromatography, and are detected with

a conventional quadrupole mass spectrometer. The mass spectrometer is capable of scanning from 1 to 300 atomic

mass units (amu) and employs a continuous dynode electron multiplier detector system. The primary application of

the HAPSITE is for direct air measurements. The HAPSITE provides an MS-only mode of operation in which an

air sample can be directly introduced into the mass spectrometer via a membrane interface without GC separation.

An equilibrium headspace sample accessory can be used to concentrate volatile sample components from water,

soil, or sludge matrices in the gas phase above the sample. The accessory automatically introduces a portion of the

headspace gas into the GC/MS.

The HAPSITE GC/MS can be operated in a field-portable or transportable mode. In the transportable mode, a

suitable working environment, such as a trailer or van equipped with 110 V ac line power, is required for operation.

The HAPSITE GC/MS is mounted on a service module that contains a turbomolecular and roughing pump. The

combined weight of the system in the transportable mode is 75 pounds.

In the field-portable mode, the HAPSITE utilizes a proprietary chemical getter pumping system to maintain the

vacuum in the mass spectrometer. The pumping system, which contains no moving parts, provides a vacuum for

30 days, at 8 hours use per day, after which it must be replaced. In the field-portable mode, the weight of the

GC/MS is 35 pounds. The unit is rugged and water resistant and is designed to be operated in the typical

environment found in a manufacturing or chemical plant or at a hazardous waste site. It can withstand the normal

shocks and bumps encountered during field use. Battery life in the field-portable mode is 2 to 3 hours. The system

uses a self-contained carrier gas, and internal standard gases are used to tune and calibrate the mass spectrometer.

The internal standards can also be coinjected with air samples. The carrier gas supply is suffficient for 8 hours of

operation, and the internal standard gas supply will last 3 days at 8 hours per day of use. The headspace sampling

accessory can be operated via battery or ac line power, weighs 15 pounds, and will equilibrate up to four samples

simultaneously. A separate carrier gas supply is required for the headspace accessory.
6

The HAPSITE consists of an inlet system (heated transfer line, sample pump, gas sampling valve); gas

chromatograph (isothermal oven and 27-m × 32-mm i.d. capillary column with Supelco SPB-1, 1-μm film coating,

and 3-m precolumn for backflush), and mass spectrometer (membrane interface, quadrupole mass spectrometer,

internal computer, and hard disk). An external notebook personal computer (PC) is included with the system and

can be used for system control as well as to display and analyze data in real time. The external PC is not required

for operation once methods have been developed and stored on the HAPSITE internal PC.

Principle of Operation

The headspace sampling accessory uses a temperature-controlled environment to equilibrate a water, soil, or sludge

sample in a sealed vial. The volatile components in the sample matrix reach an equilibrium distribution between the

water sample and the vapor headspace above the sample. A portion of the headspace gas is transferred to the gas

sampling loop of the HAPSITE sample introduction system via a pump and carrier gas. The fixed volume of the

loop is then injected onto the GC precolumn. The principle of headspace equilibration and subsequent headspace

sampling is similar to SW-846 Method 3810 (EPA, 1986). The GC is operated isothermally at 60 °C and the

analytes are separated during an 11-minute run. Compounds that would elute after 11 minutes are backflushed

from the precolumn. Components elute from the GC column and enter the mass spectrometer ionizer assembly

through a poly(dimethylsilicone) membrane interface, which excludes most of the nitrogen carrier gas. The

membrane is maintained at 60 °C.

The separated compounds produce a characteristic 70-eV electron impact spectrum. When tuned to the

manufacturer’s specifications, the spectrometer will produce consistent, National Institute of Standards and

Technology (NIST), library-searchable spectra for compounds in the low parts-per-billion to parts-per-million

range. The mass spectrometer can be operated in a full scan or selected ion mode. In this demonstration, the unit

was operated in full scan mode. Target compounds are identified by their GC retention time and comparison of

their mass spectra with a target compound library of spectra collected during calibration. Spectra of unknown

compounds can be compared with spectra in the NIST mass spectral library for tentative identification.

Quantification is accomplished by applying a relative response factor from a daily calibration standard. For the

headspace method, internal standards and surrogates are used to identify and compensate for matrix effects.

Internal and surrogate standards used in this demonstration were toluene-d8, chlorobenzene-d5, fluorobenzene, 4-

bromofluorobenzene, 1,2-dichloroethane-d4, dibromofluoromethane, and dichlorobenzene-d4.

History of the Technology

Inficon, Inc. is one of the world’s largest manufacturers of quadrupole mass spectrometers for application in a

variety of manufacturing processes. The mass spectrometer in the HAPSITE is an adaptation of this industrial

spectrometer product line. The HAPSITE GC/MS was originally designed to meet the requirements for source

emission testing as specified in the 1990 Clean Air Act amendments. The EPA has provisionally approved a

Method-301 validation for use of the HAPSITE in source-emission testing. The method has been approved for

source measurements of mineral calciners and is pending extension as a general source-testing method for gaseous

organic compounds.

Applications

The HAPSITE GC/MS and headspace sampling accessory are designed to measure the presence and concentration

of volatile organic compounds in water, soil, and sludge. The technology is applicable to site investigation and

characterization and to periodic monitoring to determine the migration of volatiles at remediation sites. Site
7

engineers charged with definition of site contamination and monitoring the effectiveness of remediation techniques

comprise the largest group of potential users.

Advantages

The primary advantage of the HAPSITE is its ability to provide on-site results of a quality comparable to

conventional laboratory GC/MS. Decisions can be made in a cost-effective manner in regard to the need for further

sampling or the use of high-cost field equipment, such as drilling rigs. The initial cost is comparable to a

laboratory GC/MS equipped with a purge-and-trap accessory. Field-portable gas chromatographs with nonspecific

detectors are less costly but lack the ability of the GC/MS to identify and quantitate the organic components in

complicated sample matrices.

Limitations

The major limitation of the HAPSITE is the isothermal GC oven. Standard chromatographic run times of 10

minutes must be extended to 20 minutes in order to detect the dichlorobenzenes. The last five analytes from the

EPA Method 8260A list of compounds—1,2-dibromo-3-chloropropane, 1,2,4-trichlorobenzene, naphthalene,

hexachlorobutadiene, and 1,2,3-trichlorobenzene—are not compatible with this instrument. The technique is

limited to the determination of those compounds with sufficient volatility to be removed from the sample in

detectable concentrations using the equilibrium headspace technique.

Performance Characteristics

The HAPSITE/headspace GC/MS method is applicable to a wide range of organic compounds that have

sufficiently high volatility to be effectively removed from water, soil, or sludge samples via equilibrium headspace.

The chemical compounds shown in Table 2-1 have been evaluated by Inficon personnel during method development

and are suitable for analysis with the HAPSITE.

Practical Quantitation Limits and Method Detection Limits

The practical quantitation limits (PQLs) for chemical analytes in water are also listed in Table 2-1. The practical

quantitation limit is the lower bound of the calibration range and represents a peak-to-peak signal-to-noise ratio of

10:1. This signal level provides acceptable and reproducible (±20%) signal integration with the HAPSITE

software. The method detection limit (MDL) is estimated at one half the PQL.

Accuracy

The HAPSITE GC/MS headspace system is expected to perform at an accuracy level of ±25% or better over the

calibration range 95% of the time.

Precision

The precision, as represented by the relative standard deviation (RSD) on replicate measurements, is expected to be

≤20% over the working range of the instrument.1

 

1 The relative standard deviation is the sample standard deviation divided by the mean value and multiplied by 100.
8

Table 2-1. Inficon HAPSITE GC/MS Analyte List

Compound CASa Number PQLb (μg/L) Quant. Massc

Benzene 71-43-2 5 78

Bromobenzene 108-86-1 10 77

Bromochloromethane 74-97-5 15 49

Bromodichloromethane 75-27-4 5 83

Bromoform 75-25-2 15 173

Bromomethane 74-83-9 5 94

Carbon tetrachloride 56-23-5 5 117

Chlorobenzene 108-90-7 5 112

Chloroethane 75-00-3 10 64

Chloroform 67-66-3 5 83

Chloromethane 74-87-3 5 50

Dibromochloromethane 124-48-1 5 129

1,2-Dibromoethane 106-93-4 5 107

Dibromomethane 95-50-1 5 174

Dichlorodifluoromethane 75-71-8 10 85

1,1-Dichloroethane 75-35-3 5 63

1,2-Dichloroethane 107-06-2 5 62

1,1-Dichloroethene 75-35-4 5 61

cis-1,2-Dichloroethene 156-59-2 5 61

trans-1,2-Dichloroethene 156-60-5 5 61

1,2-Dichloropropane 78-87-5 10 63

2,2-Dichloropropane 594-20-7 10 77

1,1-Dichloropropene 563-58-6 10 75

cis-1,3-Dichloropropene 10061-01-5 10 75

trans-1,3-Dichloropropene 10061-02-6 10 75

Ethyl benzene 100-41-4 5 91

Isopropyl benzene 98-82-8 10 105

Methylene chloride 75-09-2 5 49

Styrene 100-42-5 5 104

1,1,1,2-Tetrachloroethane 630-20-6 20 131

1,1,2,2-Tetrachloroethane 79-34-5 20 83

Tetrachloroethene 127-18-4 5 166

Toluene 108-88-3 5 91

1,1,1-Trichloroethane 71-55-6 5 97

1,1,2-Trichloroethane 79-00-5 5 97

Trichloroethene 79-01-6 5 130

Trichlorofluoromethane 75-69-4 5 101

1,2,3-Trichloropropane 96-18-4 15 75

Vinyl chloride 75-01-4 5 62

ortho-Xylene 95-47-6 5 91

meta-Xylene 108-38-3 5 91

para-Xylene 106-42-3 5 91

Notes: This table was provided by the instrument developer. The PQL is defined as a peak-to-peak signal-to-noise ratio of 10:1.

a CAS = Chemical Abstracts Service.

b

PQL = practical quantitation limit.

c Quant. mass = quantification mass.
9

Instrument Working Range

The HAPSITE can measure the volatile organics listed in Table 2-1 over a dynamic range of 104. For

tetrachloroethene, this would represent a working range of 5 μg/L to 50 mg/L. The working range of the instrument

can be adjusted from the lower limit upward by controlling the injection volume. For a sample containing

tetrachloroethene in the 10- to 100-mg/L range, the injection volume could be reduced by 50% to allow

measurement within the linear dynamic range of the instrument.

Comparison with Reference Laboratory Analyses

The HAPSITE GC/MS analytical results for VOCs in water are expected to differ from reference laboratory

measurements, using Method 8260A (EPA, 1986b), by no more than ±35%, 95% of the time.

Data Completeness

Analysis and valid results will be reported for 90% or more of the samples presented for analysis during the

demonstration.

Other Analytical Performance Characteristics and Requirements

An MS tune check is performed every 12 hours to manufacturer’s specification using the tuning compounds 1,3,5

tris-(trifluoromethyl) benzene and bromopentafluorobenzene. This tune check verifies the stability of the

instrument. The system must pass the tune check prior to sample analysis. In addition, the initial calibration curve

for all target analytes must generate a relative standard deviation of 30% or less for each compound in the

calibration. A GC/MS calibration check is performed at least once during every 12 hours of operation. Specific

analytes from the initial calibration curve are designated as calibration check compounds (CCCs). All CCC sample

results must be within 25% of initial calibration results. System blanks must also be run prior to field sample

analysis. Instrument carryover from a high concentration sample to a low concentration sample will be less than

0.25% of the high sample. For example, a 5-mg/L sample of tetrachloroethene should generate a result of less than

12.5 μg/L in a blank sample immediately following the high-level sample.

Other Field Performance Characteristics

The following performance parameters are provided by the instrument developer.

Instrument Setup and Disassembly Time

The HAPSITE GC/MS requires 30 minutes for setup and disassembly. The HAPSITE and headspace accessory

can be shipped or carried as checked baggage. The carrier and internal standard gas canisters must be shipped as

hazardous materials.

Instrument Calibration Frequency During Field Use

An MS tune check is required at startup and after every 12 hours of operation. A daily calibration check is also

required at startup and after every 12 hours of operation.
10

Ancillary Equipment Requirements

A power source of 110-V 60-Hz ac is desirable for initial startup of the instrument. Approximately 40% of the

battery life is expended in startup. Normal operation is to start the instrument on ac power prior to taking it to the

field. During field use, the instrument is powered by battery. Carrier gas and tuning gases are required. A 20-mL

Luer lock syringe, 40-mL volatile organic analysis (VOA) vials, and 10-μL syringes for internal standards and

surrogates are also required.

Field Maintenance Requirements

Battery life is 3 hours; carrier gas must be replaced every 8 hours. Operation in the field requires a nonevaporative

getter or chemical pump. The usable life on the pump is 30 days at 8 hours of operation per day.

Sample Throughput Rate

Initial headspace analysis equilibration time for the first sample is 30 minutes. Analysis time is 15 minutes per

sample. Up to four samples can be equilibrated simultaneously while an analysis is being carried out on a fifth

sample.

Operator Training Requirements and Ease of Operation

The HAPSITE GC/MS requires 3 days of training for technical personnel familiar with GC/MS operation. This

training includes setup and maintenance of the instrument and methods. Training for field operation of the

instrument (sample preparation and injection only) requires 1 day.
11

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 μg/L to over 1000 μg/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.
12

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.
13

Site Selection and Description

Two sites—the DOE Savannah River Site near Aiken, South Carolina, and McClellan Air Force Base near

Sacramento, California—were chosen for this demonstration. This section provides a brief history of each site, a

discussion of important geological features, and an outline of the nature and extent of contamination at each site.

The sites chosen met the following selection criteria:

• presence of chlorinated VOCs in groundwater;

• multiple wells at the site with a variety of contaminants and depths;

• documented well-sampling history with characterization and monitoring data;

• convenient access; and

• support facilities and services at the site.

Savannah River Site

The Savannah River Site is operated under contract by the Westinghouse Savannah River Company. The complex

covers 310 square miles in western South Carolina, adjacent to the Savannah River, as shown in Figure 3-1. The

SRS was constructed during the early 1950s to produce the basic materials used in the fabrication of nuclear

weapons, primarily tritium and plutonium-239. Production of weapons material at the SRS also produced unusable

byproducts such as intensely radioactive waste. In addition to these high-level wastes, other wastes at the site

include low-level solid and liquid radioactive wastes, transuranic waste, hazardous chemical waste, and mixed

waste.

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.
14

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

Figure 3-2. A map of the A/M area at the Savannah

River Site showing the subsurface TCE plume.
15

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 Well Number Compound Qtrly. Resultsa(μg/L)

Very low 1 MSB 33B Trichloroethene

Tetrachloroethene

10

5

Very low 2 MSB 33C Trichloroethene

Tetrachloroethene

5

12

Low 1 MSB 18B Trichloroethene

Tetrachloroethene

1,1-Dichloroethene

12

12

3

Low 2 MSB 37B Trichloroethene

Tetrachloroethene

Carbon tetrachloride

28

2

2

Mid 1 MSB 4D Trichloroethene

Tetrachloroethene

219

178

Mid 2 MSB 64C Trichloroethene

Tetrachloroethene

1,1-Dichloroethene

51

337

13

Very high 1 MSB 4B Trichloroethene

Tetrachloroethene

830

43

Very high 2 MSB 70C Trichloroethene

Tetrachloroethene

1,1-Dichloroethane

1,1,1-Trichloroethane

1290

413

61

17

Very high 1 MSB 14A Trichloroethene

Tetrachloroethene

3240

2440

Very high 2 MSB 8C Trichloroethene

Tetrachloroethene

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

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

Geological Characteristics

Surface features at MAFB include open grassland, creeks and drainages, and vernal pools, as well as industrial,

residential, and runway areas. The land surface is a relatively flat plain that slopes gently to the west. Surface

elevations range from about 75 feet above mean sea level on the eastern side of the base to about 50 feet above

mean sea level on the western side.

Surface soils at MAFB are variable, but are generally sediments that have formed from stream erosion of granite

rocks in the Sierra Nevada. Soil in the vadose zone—the unsaturated region between the surface and the

groundwater table—is composed of interbedded layers of sands, silts, and clays. The vadose zone ranges from 90

to 105 feet. Clays and hardpan layers in this zone slow, but do not halt, infiltration of liquids into the underlying

aquifer.

The groundwater beneath MAFB behaves as one hydrogeologic unit. This single aquifer has been divided into five

groundwater monitoring zones, designated A, B, C, D, and E, from shallowest to deepest.

Groundwater and Monitoring Wells

An estimated 14 billion gallons of contaminated water underlie MAFB. Trichloroethene is the most frequently

detected contaminant in the subsurface groundwater. Over 90% of the contaminant mass is located in the A zone,

the shallowest portion of the aquifer. An estimated surface area of approximately 664 acres is underlain by a

plume in the A zone that exceeds the 5-μg/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 × 40 or 8 × 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 μg/L) to very high (>5000 μg/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

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 μg/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

Table 3-2. Groundwater Contaminants at MAFB

Detected above MCLa Detected below MCL Detected – Not Regulated

Benzene Bromodichloromethane Acetone

Carbon tetrachloride Trichlorofluoromethane 2-Butanone

Chloroform 1,1-Dichloroethane

1,2-Dichlorobenzene 4-Methyl-2-pentanone

1,2-Dichloroethane Toluene

1,1-Dichloroethene

1,2-Dichloroethene (cis and trans)

Tetrachloroethene

1,1,1-Trichloroethane

Trichloroethene

Vinyl chloride

a

 MCL = maximum concentration limit.

Table 3-3. Quarterly Monitoring Results for MAFB Wells Sampled in the Demonstration

Sample Description Well Number Compound Qtrly. Resultsa

 (μg/L)

Very low 1 EW-86 Trichloroethene

1,1-Dichloroethene

8

13

Very low 2 MW-349 Trichloroethene

Tetrachloroethene

Chloroform

Acetone

9

5

8

9

Low 1 MW-331 1,1-Dichloroethane

Carbon tetrachloride

Chloroform

Trichloroethene

cis-1,2-Dichloroethene

16

5

7

19

41

Low 2 MW-352 1,1-Dichloroethane

Tetrachloroethene

Freon11

6

5

115

Mid 1 EW-87 1,1,1-Trichloroethane

1,1-Dichloroethene

Trichloroethene

cis-1,2-Dichloroethene

17

334

220

5

Mid 2 MW-341 Trichloroethene

cis-1,2-Dichloroethene

350

18

High 1 MW-209 Chloroform

Trichloroethene

cis-1,2-Dichloroethene

trans-1,2-Dichloroethene

53

586

80

13

High 2 MW-330 Chloroform

Trichloroethene

cis-1,2-Dichloroethene

trans-1,2-Dichloroethene

44

437

64

9
20

Table 3-3. Quarterly Monitoring Results for MAFB Wells Sampled in the Demonstration

(Continued)

Sample Description Well Number Compound Qtrly. Resultsa

 (μg/L)

Very high 1 MW-334 1,1-Dichloroethene

Benzene

Carbon tetrachloride

Chloroform

Dichloromethane

Trichloroethene

cis-1,2-Dichloroethene

Xylene

1000

705

728

654

139

20,500

328

59

Very high 2 MW-369 1,2-Dichloroethane

Carbon tetrachloride

Chloroform

Tetrachloroethene

Trichloroethene

cis-1,2-Dichloroethene

13

91

84

6

10,200

246

a

 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 μg/L or 2000 μg/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 

μg/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 μg/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, carbonfiltered water in the carboy. The mixture was gently stirred for 5 minutes with a Teflon-coated stir bar prior to

dispensing samples from the bottom of the carboy. A twofold excess volume of PE mixture was prepared in

order to ensure a sample volume well in excess of the required volume. The mixture was not stirred during

sample dispensing to minimize headspace losses in the lower half of the carboy. Headspace losses that did occur

during dispensing were limited to the top portion of the mixture, which was discarded after the samples were

dispensed. Samples were dispensed into bottles specified by participants (40 mL, 250 mL, and 1 L) with zero
21

Table 3-4. Composition of PE Source Materials

PE Mix 1 - Purgeable A

Supelco Cat. No. 4-8059

Lot LA68271

PE Mix 2 - VOC 3

Supelco Cat. No. 4-8779

Lot LA64701

PE Mix 3 - Purgeable B

Supelco Cat. No. 4-8058

Lot LA 63978

Trichlorofluoromethane 1,1-Dichloropropene 1,2-Dichloroethane

1,1-Dichloroethane 1,2-Dichloroethane 1,1,2,2-Tetrachloroethane

Dichloromethane Trichloroethene cis-1,3-Dichloropropene

1,1-Dichloroethene 1,2-Dichloropropane trans-1,3-Dichloropropene

Chloroform 1,1,2-Trichloroethane trans-1,2-Dichloroethene

Carbon tetrachloride 1,3-Dichloropropane 1,1,1-Trichloroethane

Trichloroethene 1,2-Dibromoethane Benzene

1,2-Dichloropropane 1,1,1,2-Tetrachloroethane Bromodichloromethane

1,1,2-Trichloroethane 1,1,2,2-Tetrachloroethane Toluene

Tetrachloroethene 1,2,3-Trichloropropane Ethyl benzene

Dibromochloromethane 1,2-Dibromo-3-chloropropane Bromoform

Chlorobenzene cis-1,3-Dichloropropene

1,2-Dichlorobenzene trans-1,3-Dichloropropene

2-Chloroethyl vinyl ether Hexachlorobutadiene

Table 3-5. PE Sample Composition and Count for SRS Demonstration

Sample Concentration Level PE Mixture - Mixture Concentrationa No. of Replicates

Very low level VOC Mix 1 - 10 μg/L 10

Low level VOC Mix 1 - 50 μg/L 4

VOC Mix 2 - 100 μg/L 4

Mid level VOC Mix 1 - 200 μg/L 4

VOC Mix 2 - 200 μg/L 4

High level VOC Mix 1 - 600 μg/L 4

VOC Mix 2 - 800 μg/L 4

Spike / low 1.02 mg/L TCE spike + 50 μg/L mix 1 4

1.28 mg/L TCE and 1.23 mg/L PCE

spike + 100 μg/L mix 2

4

Total number of samples 42

a

 TCE = trichloroethene; PCE = tetrachloroethene.

headspace. The samples for field analysis were not preserved with chemical additives since sterile, nutrient-free

water was used in their preparation.

Reference laboratory samples were preserved by acidification as specified in Method 8260A. Following

preparation, all samples were kept under refrigeration until they were distributed to participants. All PE mixtures

were prepared and dispensed on the weekend before the demonstration week.
22

Table 3-6. PE Sample Composition and Count for MAFB Demonstration

Sample Concentration Level PE Mixture - Mixture Concentrationa No. of Replicates

Very low level VOC Mix 3 - 10 μg/L 10

Low level VOC Mix 3 - 50 μg/L 4

VOC Mix 2 - 100 μg/L 4

Mid level VOC Mix 3 - 200 μg/L 4

VOC Mix 2 - 300 μg/L 4

High level VOC Mix 1 - 600 μg/L 4

VOC Mix 2 - 800 μg/L 4

Spike / low 1.22 mg/L TCE, 1.00 mg/L PCE, 0.50 mg/L 11DCA,

and 0.50 mg/L BNZN spike + 100 μg/L mix 3

4

1.04 mg/L 11DCA, 0.86 mg/L BNZN, 0.57 mg/L

TCE, and 0.51 mg/L PCE spike + 50 μg/L mix 2

4

Total number of samples 42

a

 TCE = trichloroethene; PCE = tetrachloroethene; 11DCA = 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 μg/L to >1000 μg/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

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 fieldportable generators and staged under tent canopies; others operated their instruments inside vehicles and used dc-toac 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

Table 3-7. Weather Summary for SRS and MAFB During Demonstration Periods

Site/Parameters Mon Tue Wed Thu Fri

SRS

Temperature range (°C) 20 – 34 21 – 33 21 – 28 18 – 30 19 – 33

Relative humidity range (%) 25 – 68 28 – 67 51 – 71 40 – 70 26 – 70

MAFB

Temperature range (°C) 17 – 33 18 – 36 18 – 37 24 – 35 24 – 35

Relative humidity range (%) 17 – 72 25 – 47 15 – 59 17 – 67 31 – 83

Wind speed range (knots) 0 – 7 3 – 6 1 – 6 4 – 13 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

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

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

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

Table 4-1. Method 8260A Quality Control Summary

Activity Frequency Data Acceptance Criteria

Spectrometer tune check Bromofluorobenzene

standard every 12 hours

Relative abundance; range of characteristic mass

fragments meets specifications.

System performance

check

SPCCa sample every 12

hours

Compound relative response factors must exceed

required minimums.

System calibration check CCCb sample every 12

hours

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 100% of

last check.

Lab method blank One or more per batch

(approx. 20 samples)

≤ 3× Detection limit.

Field blank One or more per batch ≤ 3× Detection limit.

Laboratory control

standard

One or more per batch Compound recovery within established limits.c

Matrix spike One or more per batch Spike recovery within established limits. c

Matrix spike duplicate One or more per batch Relative percent difference of check compounds ≤50%.

Surrogate standards Included in every sample Recovery within established limits. c

Internal standards Included in every sample Recovery within established limits. c

a

SPCC = system performance check compounds.

b CCC = calibration check compounds.

c

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

Table 4-2. Reference Laboratory Method Detection Limits for Target Compounds

Target Compound Method Detection Limit

(μg/L)

Practical Quantitation

Limit (μg/L)

Trichlorofluoromethane 0.15 1

1,1-Dichloroethane 0.08 1

Methylene chloride 0.10 1

1,1-Dichloroethene 0.08 1

Chloroform 0.07 1

Carbon tetrachloride 0.10 1

1,1-Dichloropropene 0.10 1

1,2-Dichloroethane 0.04 1

Trichloroethene 0.14 1

1,2-Dichloropropane 0.04 1

1,1,2-Trichloroethane 0.09 1

Tetrachloroethene 0.10 1

1,3-Dichloropropane 0.06 1

Dibromochloromethane 0.08 1

1,2-Dibromoethane 0.09 1

Chlorobenzene 0.06 1

1,1,1,2-Tetrachloroethane 0.05 1

1,1,2,2-Tetrachloroethane 0.07 1

1,2,3-Trichloropropane 0.50 1

1,2-Dibromo-3-chloropropane 0.62 1

Hexachlorobutadiene 0.10 1

cis-1,3-Dichloropropene 0.17 1

trans-1,3-Dichloropropene 0.08 1

1,2-Dichlorobenzene 0.17 1

trans-1,2-Dichloroethene 0.17 1

1,1,1-Trichloroethane 0.26 1

Benzene 0.12 1

Bromodichloromethane 0.11 1

Toluene 0.15 1

Ethyl benzene 0.14 1

Bromoform 0.10 1

cis-1,2-Dichloroethene 0.14 1

ortho-Xylene 0.11 1

Acetone 2.9 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 μg/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-d5, and 1,4-dichlorobenzene-d4.
30

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

DCL Laboratory Control Standard Recoveries

Savannah River Data Set

80

90

100

110

120

Batch 1 Batch 2 Batch 3 Batch 4 Batch 5

Analysis Batch No. 

Recovery, %

11DCE

Benzene

Cl Benzene

Toluene

TCE

Figure 4-1. Laboratory control standard recovery values for SRS analyses.

DCL Laboratory Control Standard Recoveries

McClellan Data Set

80

90

100

110

120

Batch 1 Batch 2 Batch 3 Batch 4 Batch 5

Analysis Batch No. 

Recovery, %

11DCE

Benzene

Cl Benzene

Toluene

TCE

Figure 4-2. Laboratory control standard recovery values for MAFB analyses.
32

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-d8. 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 Action

Required dilution not made on two samples (SP20 and

SP21). Some compounds were present above

instrument linear range.

Data Included: Data values for affected samples fall in

the range of the other three replicate samples.

Three field blanks were not sent to DCL from SRS

demonstration.

No Action: Five field blanks and 10 method blanks were

run, yielding an adequate data set.

Calculation error in original DCL report. Dilution factors

applied incorrectly in two samples (SP55 and SP57).

Data Corrected and Included: The correct dilution

factors were applied following a teleconference with the

DCL analyst.

Sample SP31 failed internal standard recovery limits. Data Not Included.

The following samples failed one or more surrogate

standard recovery limits: SP12, SP16, SP26, SP29,

SP33, and SP65.

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.

Hexachlorobutadiene detected as a contaminant in

selected blanks and 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.

Chloroethyl vinyl ether was not detected in PE samples

known to contain this compound.

No Action: The GC/MS was not calibrated for this

compound. None of the technologies included this

compound in their target compound lists.

Three sample results (MG20, MG51, and MG59) are

from a second withdrawal from the original zeroheadspace sample vial.

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

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, cis-1,3-

dichloropropene, 1,2,3-trichloropropane, and 1,1,2,2-tetrachloroethane. Precision well in excess of method

specifications is observed for 1,2-dibromo-3-chloropropane, trans-1,3-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-μg/L PE mix, the true value is known with 99% certainty to be within the range of 95 to 105 μg/L.

Table 4-4. Sources of Uncertainty in PE Sample Preparation

Type of Uncertainty Magnitude Source of Estimate

Weight of component in PE mix

ampule.

0.5 mg in 1200 mg Gravimetric balance uncertainty included

in PE mix certification documents

Volume of methanol solvent used

to dilute neat compounds.

0.2 mL in 600 mL Published tolerances for volumetric flasks

(Fisher Catalog)

Volume of PE solution (from

ampule) used in final PE solution.

±5% of microsyringe volume;

e.g., 25 μL for a 500-μL syringe

Published tolerances in certificates

shipped with microsyringes

Volume of water diluent in final

PE solution.

5 ml in 10 L 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, 1,2-dibromo-3-chloropropane,

 

3 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

DataChem PE Sample Precision

Site: Savannah River Mix 1

0 10 20 30 40 50

Trichlorofluoromethane

1,1-Dichloroethane

Methylene Chloride

1,1-Dichloroethene

Chloroform

Carbon Tetrachloride

Trichloroethene

1,2-Dichloropropane

1,1,2-Trichloroethane

Tetrachloroethene

Dibromochloromethane

Chlorobenzene

1,2-Dichlorobenzene

Target Compound

Relative Standard Deviation, %

Spike/Low

High

Mid

Low

Figure 4-3. Laboratory precision on SRS PE samples containing mix 1.

Trichloroethene was spiked into the spike/low samples.

DataChem PE Sample Precision

Site: Savannah River Mix 2

0 10 20 30 40 50

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

cis-1,3-Dichloropropene

trans-1,3-Dichloropropene

Tetrachloroethene

Target Compound

Relative Standard Deviation, %

Spike/Low

High 

Mid

Low

85

66

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.

85

66
35

DataChem PE Sample Precision

Site: McClellan Mix 2

0 10 20 30 40 50

1,1-Dichloroethane

1,1-Dichloropropene

1,2-Dichloroethane

Trichloroethene

1,2-Dichloropropane

1,1,2-Trichloroethane

Tetrachloroethene

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

cis-1,3-Dichloropropene

trans-1,3-Dichloropropene

Benzene

Target Compound

Relative Standard Deviation, %

Spike/Low

High

Mid

Low

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.

DataChem PE Sample Precision

Site: McClellan Mix 3

0 10 20 30 40 50

1,1-Dichloroethane

1,2-Dichloroethane

Trichloroethene

Tetrachloroethene

1,1,2,2-Tetrachloroethane

cis-1,3-Dichloropropene

trans-1,3-Dichloropropene

trans-1,2-Dichloroethene

1,1,1-Trichloroethane

Benzene

Bromodichloromethane

Toluene

Ethylbenzene

Bromoform

Target Compound

Relative Standard Deviation, %

Spike/Low

Mid

Low

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.

57
36

DataChem PE Sample Recovery

Site: Savannah River Mix 1

50 60 70 80 90 100 110 120 130 140 150

Trichlorofluoromethane

1,1-Dichloroethane

Methylene Chloride

1,1-Dichloroethene

Chloroform

Carbon Tetrachloride

Trichloroethene

1,2-Dichloropropane

1,1,2-Trichloroethane

Tetrachloroethene

Dibromochloromethane

Chlorobenzene

1,2-Dichlorobenzene

Target Compound

Average Percent Recovery

Spike/Low

High

Mid

Low

VLow

3

Figure 4-7. Laboratory mean recoveries for SRS PE samples containing mix 1.

Trichloroethane was spiked into the spike/low samples.

DataChem PE Sample Recovery

Site: Savannah River Mix 2

50 60 70 80 90 100 110 120 130 140 150

1,1-Dichloropropene

1,2-Dichloroethane

Trichloroethene

1,2-Dichloropropane

1,1,2-Trichloroethane

Tetrachloroethene

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

cis-1,3-Dichloropropene

trans-1,3-Dichloropropene

Target Compound

Average Percent Recovery

Spike/Low

High

Mid

Low

Figure 4-8. Laboratory mean recoveries for SRS PE samples containing mix

2. Trichloroethane and tetrachloroethene were spiked into the spike/low

samples.
37

DataChem PE Sample Recovery

Site: McClellan Mix 2

50 60 70 80 90 100 110 120 130 140 150

1,1-Dichloroethane

1,1-Dichloropropene

1,2-Dichloroethane

Trichloroethene

1,2-Dichloropropane

1,1,2-Trichloroethane

Tetrachloroethene

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

cis-1,3-Dichloropropene

trans-1,3-Dichloropropene

Benzene

Target Compound

Average Percent Recovery

Spike/Low

High

Mid

Low

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.

DataChem PE Sample Recovery

Site: McClellan Mix 3

50 60 70 80 90 100 110 120 130 140 150

1,1-Dichloroethane

1,2-Dichloroethane

Trichloroethene

Tetrachloroethene

1,1,2,2-Tetrachloroethane

cis-1,3-Dichloropropene

trans-1,3-Dichloropropene

trans-1,2-Dichloroethene

1,1,1-Trichloroethane

Benzene

Bromodichloromethane

Toluene

Ethylbenzene

Bromoform

Target Compound

Average Percent Recovery

Spike/Low

Mid

Low

VLow

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

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 μg/L in

groundwater 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 Relative Standard Deviation (%)

TCE PCE

Very low 1 10.6 14.3

Very low 2 34.4 12.4

Low 1 5.4 5.7

Low 2 7.1 8.7

Mid 1 9.4 11.6

Mid 2 7.3 4.2

High 1 0.8 1.8

High 2 11.8 7.9

Very high 1 8.4 5.7

Very high 2 6.2 6.3

Table 4-6. Summary of MAFB Groundwater Analysis Precision

Sample Relative Standard Deviation (%)

Description 11DCE TCE CLFRM CCL4 PCE 11DCA c12DCE t12DCE BNZN

Very low 1 9.1 5.0

Very low 2 2.6 <0.1 1.3 4.2 5.7

Low 1 6.8 3.7 2.0 1.9 <0.1

Low 2 11.5 5.2 4.0 22.3 4.1 3.8

Mid 1 12.0 10.5 13.9 9.4 12.6

Mid 2 3.6 4.9 3.8

High 1 2.4 20.9 4.1

High 2 5.3 5.3 5.1 3.8

Very high 1 2.5 5.4 5.2 6.5 4.9

Very high 2 8.0 6.4 4.9 10.1

Notes: 11DCE = 1,1-dichloroethene; TCE = trichloroethene; CLFRM = chloroform; CCL4 = carbon tetrachloride; PCE = tetrachloroethene; 11DCA =

1,1-dichloroethane; c12DCE = cis-1,2-dichloroethene; t12DCE = trans-1,2-dichloroethene; BNZN = benzene.

Blank cells indicate that the compound was not present.

 

4 The absolute percent difference is the absolute value of the percent difference between a measured value and a true value.
39

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

Chapter 5 

Demonstration Results

HAPSITE Calibrated and Reported Compounds

Prior to the field demonstration, the participants were given a list of all compounds that were to be used in the PE

mixtures to facilitate preparations for predemonstration instrument calibration. The HAPSITE GC/MS was

calibrated for 32 compounds at SRS, and 6 more were added prior to the MAFB demonstration (Table 5-1). Note

that some calibrated compounds were not demonstration PE mixture compounds. A total of 32 chlorinated and

nonchlorinated hydrocarbon compounds were included in the PE mixtures noted in Table 3-4. The HAPSITE

reported results for 27 of these compounds. It did not report results for 5 PE compounds since it was not calibrated

for them. These were dibromochloromethane, 1,2-dichlorobenzene, 2-chloroethyl vinyl ether, 1,2-dibromo-3-

chloropropane, and hexachlorobutadiene. Trichlorofluoromethane, another PE compound, was not reported at the

SRS but was reported at MAFB.

Preanalysis Sample Information

Groundwater (GW) and PE samples were provided to the HAPSITE team without additional information on the

number of compounds in the sample or compound concentration levels.

Table 5-1. HAPSITE Calibrated and Reported Compounds

Calibrated Compounds at Both Demonstrations

1,1-Dichloroethene trans-1,3-Dichloropropene

Methylene chloride 1,1,2-Trichloroethane

trans-1,2-Dichloroethene 1,3-Dichloropropane

1,1-Dichloroethane Toluene

Bromochloromethane Dibromochloromethane

Chloroform 1,2-Dibromoethane

1,2-Dichloroethane Tetrachloroethene

1,1,1-Trichloroethane 1,1,1,2-Tetrachloroethane

1,1-Dichloropropene Chlorobenzene

Benzene Ethyl benzene

Carbon tetrachloride meta- and para-Xylene

Dibromomethane Bromoform

1,2-Dichloropropane Styrene

Bromodichloromethane ortho-Xylene

Trichloroethene 1,1,2,2-Tetrachloroethane

cis-1,3-Dichloropropene 1,2,3-Trichloropropane

Additional Calibrated Compounds at MAFB

Chloromethane Chloroethane

Vinyl chloride Trichlorofluoromethane

Bromoethane cis-1,2-Dichloroethene
41

Sample Completion

All but one of the 166 PE and groundwater samples submitted for analysis to the HAPSITE team were completed

at both demonstration sites. The HAPSITE team at the SRS lost a PE sample from the spike/low category of PE

mix 1 during sample preparation.

Blank Sample Results

Eight blank samples were provided for analysis at each demonstration site. False positive detects were counted

only for compounds reported at concentration levels greater than the HAPSITE MDL for most target compounds

(typically 3 μg/L). A listing of false positive detects is given for both sites in Table 5-2.

Table 5-2. False Positive Rates from Blank Sample Analysis

SRS Blank Samples MAFB Blank Samples

Compound False Positive Compound False Positive

Dichloromethane 1 of 8 (13%) 1,2-Dichloroethane 1 of 8 (13%)

Trichloroethene 3 of 8 (38%) Trichloroethene 1 of 8 (13%)

Chlorobenzene 1 of 8 (13%) cis-1,3-Dichloropropene 1 of 8 (13%)

trans-1,3-Dichloropropene 1 of 8 (13%)

1,2-Dibromoethane 1 of 8 (13%)

Performance at Instrument Detection Limit

Ten replicate samples of a PE mixture at a concentration level of 10 μg/L (the “very low” concentration level) were

provided for analysis at each site. Reported nondetects were compiled and are given as percent false negatives in

Table 5-3. Vendor-provided compound detection limits are also shown in the table for comparison.

Table 5-3. False Negative Rates from Very Low-Level PE Sample Analysis

SRS PE Mix 1 (10 μg/L) MAFB PE Mix 3 (10 μg/L)

Compound False Negative Compound False Negative

1,1-Dichloroethene (3) 0 of 10 trans-1,2-Dichloroethene (3) 0 of 10

Dichloromethane (3) 0 of 10 1,2-Dichloroethane (3) 0 of 10

1,1-Dichloroethane (3) 0 of 10 1,1,1-Trichloroethane (3) 0 of 10

Chloroform (3) 0 of 10 Benzene (3) 0 of 10

Carbon tetrachloride (3) 1 of 10 (10%) Bromodichloromethane (5) 0 of 10

1,2-Dichloropropane (3) 0 of 10 cis-1,3-Dichloropropene (5) 0 of 10

Trichloroethene (3) 0 of 10 trans-1,3-Dichloropropene (5) 0 of 10

1,1,2-Trichloroethane (3) 4 of 10 (40%) Toluene (3) 0 of 10

Dibromochloromethane (3) 2 of 10 (20%) Ethyl benzene (3) 0 of 10

Tetrachloroethene (3) 4 of 10 (40%) Bromoform (8) 9 of 10 (90%)

Chlorobenzene (3) 1 of 10 (10%) 1,1,2,2-Tetrachloroethane (10) 3 of 10 (30%)

2-Chloroethyl vinyl ether No calibration

Trichlorofluoromethane No calibration

1,2-Dichlorobenzene No calibration

Notes: Vendor-provided detection limits (in μg/L) are shown in parentheses after each compound.
42

PE Sample Precision

Precision results from each of the four replicate sample sets provided from eight PE mixtures at SRS and the seven

mixtures at MAFB are shown in Figures 5-1 and 5-2 for SRS and Figures 5-3 and 5-4 for MAFB. The figures

show the relative standard deviation for each compound in the PE mixtures at the four concentration levels used in

the study.1 (The composition and concentrations of each of these mixtures were given in Table 3-5 for SRS and

Table 3-6 for MAFB.) Note that precision and accuracy were not determined for the very low concentration level.

Instrument precision data for six target compounds which are all regulated under the Safe Drinking Water Act are

shown in Table 5-4. The relative standard deviations are given for each target compound at each of the four

concentration levels used in the study. The RSD range for each target compound is given in the last column of the

table.

Overall instrument precision is summarized in Table 5-5 for PE mixtures used at each site. For this summary,

RSD values from all PE sample analyses for all compounds at each site were pooled and the median and 95th

percentile values of the distribution were computed.

Table 5-4. Target Compound Precision for PE Samples at Both Sites

Target Compound Site Relative Standard Deviation (%)

Low Mid High Spike/Low Range

Trichloroethene SRS 7 18 15 16 7 – 18

MAFB 13 7 13 15

1,2-Dichloroethane SRS 6 8 10 2 2 – 12

MAFB 12 9 8 5

1,1,2-Trichloroethane SRS 10 8 9 28 8 – 28

MAFB 19 15 21 28

1,2-Dichloropropane SRS 21 17 8 18 7 – 21

MAFB 11 7 12 17

Tetrachloroethene SRS 22 19 16 14 6 – 22

MAFB 6 8

trans-1,3-Dichloropropene SRS 11 7 18 16 7 – 17

MAFB 16 17 17 10

Note: Blank cells indicate that no data were reported.

Table 5-5. Summary of PE Sample Precision and Percent Difference Statistics for SRS and

MAFB

Parameter Percentile SRS MAFB Combined Sites

PE Mix 1 PE Mix 2 PE Mix 2 PE Mix 3 Combined Mixes

RSD, % 50th 12 12 14 8 12

95th 24 31 30 19 29

Number in pool 45 49 52 37 183

Absolute percent 50th 11 13 5 4 8

difference 95th 33 36 26 17 27

Number in pool 44 49 51 36 180

 

1

Precision data for the PE mix 1 sample set at MAFB are not shown in a figure. Precision results from this mixture were

comparable to those obtained from the same mixture at the SRS.
43

Inficon HAPSITE PE Sample Precision

Site: Savannah River Mix 1

0 10 20 30 40 50

 1,1-Dichloroethene

 Methylene Chloride

 1,1-Dichloroethane

 Chloroform

 Carbon tetrachloride

 1,2-Dichloropropane

 Trichloroethene

 1,1,2-Trichloroethane

 Dibromochloromethane

 Tetrachloroethene

 Chlorobenzene

Compound

Relative Standard Deviation, %

Spike/Low

High

Mid

Low

Figure 5-1. HAPSITE precision on PE mix 1 at the SRS. Trichloroethene

was spiked into the spike/low samples.

Inficon HAPSITE PE Sample Precision

Site: Savannah River Mix 2

0 10 20 30 40 50

 1,2-Dichloroethane

 1,1-Dichloropropene

 1,2-Dichloropropane

 Trichloroethene

 cis-1,3-Dichloropropene

 trans-1,3-Dichlopropene

 1,1,2-Trichloroethane

 1,3-Dichloropropane

 1,2-Dibromoethane

 1,1,1,2-tetrachloroethane

 1,1,2,2-Tetrachloroethane

 1,2,3-Trichloropropane

Compound

Relative Standard Deviation, %

Spike/Low

High

Mid

Low

Figure 5-2. HAPSITE precision on PE mix 2 at the SRS. Trichloroethene

and tetrachloroethene were spiked into the spike/low samples.

75

53
44

Inficon HAPSITE PE Sample Precision

Site: McClellan AFB Mix 2

0 10 20 30 40 50

 1,1-Dichloroethane

 1,2-Dichloroethane

 1,1-Dichloropropene

 Benzene

 1,2-Dichloropropane

 Trichloroethene

 cis-1,3-Dichloropropene

 trans-1,3-Dichlopropene

 1,1,2-Trichloroethane

 1,3-Dichloropropane

 1,2-Dibromoethane

 Tetrachloroethene

 1,1,1,2-Tetrachloroethane

 1,1,2,2-Tetrachloroethane

 1,2,3-Trichloropropane

Compound

Relative Standard Deviation, %

Spike/Low

High

Mid

Low

Figure 5-3. HAPSITE precision on PE mix 2 at MAFB. Trichloroethene,

tetrachloroethene, 1,1-dichloroethane, and benzene were spiked into the

spike/low samples.

Inficon - HAPSITE PE Sample Precision

Site: McClellan AFB Mix 3

0 10 20 30 40 50

 trans-1,2-Dichloroethene

 1,1-Dichloroethane

 1,2-Dichloroethane

 1,1,1-Trichloroethane

 Benzene

 Bromodichloromethane

 Trichloroethene

 cis-1,3-Dichloropropene

 trans-1,3-Dichlopropene

 Toluene

 Tetrachloroethene

 Ethyl benzene

 Bromoform

 1,1,2,2-Tetrachloroethane

Compound

Relative Standard Deviaton, %

Spike/Low

Mid

Low

Figure 5-4. HAPSITE precision on PE mix 3 at MAFB. Trichloroethene,

tetrachloroethene, 1,1-dichloroethane, and benzene were spiked into the

spike/low samples.

50
45

PE Sample Accuracy

The HAPSITE accuracy on PE samples was determined by comparing the average value from each of the foursample replicate sets with the known concentration of the PE mixture (Tables 3-5 and 3-6 for SRS and MAFB,

respectively). These comparisons are shown as percent recoveries2 in Figures 5-5 and 5-6 for SRS and Figures 5-7

and 5-8 for MAFB.3 To assist in assessment of the sign of the difference, the percent recovery data are plotted as

either a positive or negative deviation from the 100% recovery line.

Instrument recovery performance for the six target compounds is shown in Table 5-6, which contains the average

percent recoveries and associated ranges for each compound.

Table 5-5 contains a summary of overall HAPSITE differences relative to PE mixture true values for both sites,

along with the precision summary. For this summary, percent recoveries were expressed as percent difference (for

example, a 90% recovery is equivalent to a –10% difference; 120% recovery is equivalent to a +20% difference)

and all data from PE mixtures were pooled. The median and 95th percentiles of the absolute values of these pooled

values were computed and are reported under the absolute percent difference (APD) category in Table 5-5.

Table 5-6. Target PE Compound Recovery at Both Sites

Target Compound Site Average Recovery (%)

Low Mid High Spike/Low Range

Trichloroethene SRS 83 103 112 80 80 – 114

MAFB 113 108 114 101

1,2-Dichloroethane SRS 96 93 91 92 91 – 103

MAFB 102 98 103 80

1,1,2-Trichloroethane SRS 120 99 108 84 79 – 120

MAFB 107 103 101 79

1,2-Dichloropropane SRS 79 97 103 113 79 – 113

MAFB 95 95 113 91

Tetrachloroethene SRS 86 94 89 67 67 – 93

MAFB 93 86

trans-1,3-Dichloropropene SRS 90 85 85 85 85 – 101

MAFB 101 95 96 88

Note: Blank cells indicate that no data were reported.

Comparison with Laboratory Results

For each demonstration site, a total of 33 samples collected from 10 wells were provided to the participants and

to the reference laboratory. Replicate sample sets were composed of either 3 or 4 samples from each well.

Average laboratory results from each replicate set were used as the reference values for comparison with

technology results. A side-by-side comparison of laboratory and HAPSITE results for all groundwater samples

 

2

Percent recovery is the HAPSITE value divided by the true value, multiplied by 100.

3

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.
46

Inficon HAPSITE PE Sample Recovery

Savannah River -- Mix 1

0 20 40 60 80 100 120 140 160 180 200

 1,1-Dichloroethene

 Methylene Chloride

 1,1-Dichloroethane

 Chloroform

 Carbon tetrachloride

 1,2-Dichloropropane

 Trichloroethene

 1,1,2-Trichloroethane

 Dibromochloromethane

 Tetrachloroethene

 Chlorobenzene

Compound

Average Percent Recovery

Spike/Low

High

Mid

Low

Figure 5-5. HAPSITE recovery on PE mix 1 at the SRS. Trichloroethene

was spiked into the spike/low samples.

Inficon HAPSITE PE Sample Recovery

Savannah River -- Mix 2

0 20 40 60 80 100 120 140 160 180 200

 1,2-Dichloroethane

 1,1-Dichloropropene

 1,2-Dichloropropane

 Trichloroethene

 cis-1,3-Dichloropropene

 trans-1,3-Dichlopropene

 1,1,2-Trichloroethane

 1,3-Dichloropropane

 1,2-Dibromoethane

 1,1,1,2-tetrachloroethane

 1,1,2,2-Tetrachloroethane

 1,2,3-Trichloropropane

Compound

Average Percent Recovery

Spike/Low

High

Mid

Low

Figure 5-6. HAPSITE recovery on PE mix 2 at the SRS. Trichloroethene

and tetrachloroethene were spiked into the spike/low samples.
47

Inficon - HAPSITE PE Sample Recovery

McClellan AFB -- Mix 2

0 20 40 60 80 100 120 140 160 180 200

 1,1-Dichloroethane

 1,2-Dichloroethane

 1,1-Dichloropropene

 Benzene

 1,2-Dichloropropane

 Trichloroethene

 cis-1,3-Dichloropropene

 trans-1,3-Dichlopropene

 1,1,2-Trichloroethane

 1,3-Dichloropropane

 1,2-Dibromoethane

 Tetrachloroethene

 1,1,1,2-Tetrachloroethane

 1,1,2,2-Tetrachloroethane

 1,2,3-Trichloropropane

Compound

Average Percent Recovery

Spike/Low

High

Mid

Low

Figure 5-7. HAPSITE recovery on PE mix 2 at MAFB. Trichloroethene,

tetrachloroethene, 1,1-dichloroethane, and benzene were spiked into the

spike/low samples.

Inficon HAPSITE PE Sample Recovery

McClellan AFB -- Mix 3

0 20 40 60 80 100 120 140 160 180 200

 trans-1,2-Dichloroethene

 1,1-Dichloroethane

 1,2-Dichloroethane

 1,1,1-Trichloroethane

 Benzene

 Bromodichloromethane

 Trichloroethene

 cis-1,3-Dichloropropene

 trans-1,3-Dichlopropene

 Toluene

 Tetrachloroethene

 Ethyl benzene

 Bromoform

 1,1,2,2-Tetrachloroethane

Compound

Average Percent Recovery

Spike/Low

Mid

Low 

Figure 5-8. HAPSITE recovery on PE mix 3 at MAFB. Trichloroethene,

tetrachloroethene, 1,1-dichloroethane, and benzene were spiked into the

spike/low samples.
48

is given in Table 5-7 for the SRS and Table 5-8 for MAFB. The RSD values and their statistical summaries are

included in the table. Well designation (very low, low, mid, high, and very high) is based on TCE concentration

levels; however, other compounds were present in the groundwater samples at concentration levels noted in the

tables. The precision of the HAPSITE on replicate groundwater sample sets is shown as RSDs in the last column

of the table.

Table 5-7. HAPSITE and Reference Laboratory Results for SRS Groundwater Samples

Sample

Description

Well

Number

Compound Replicates Lab.

Avg.

(μg/L)

Lab.

RSD

(%)

HAPSITE

a

 Avg.

(μg/L)

HAPSITE

a

RSD

(%)

Very low 1 MSB 33B Trichloroethene

Tetrachloroethene

3 9.0

3.5

11

14

8.8

2.5

43

89

Very low 2 MSB 33C Trichloroethene 3 2.4 34 1.9 32

Low 1 MSB 18B Trichloroethene

Tetrachloroethene

3 11

27

5

6

13

28

11

19

Low 2 MSB 37B Trichloroethene

Tetrachloroethene

Chloroform

Carbon tetrachloride

4 27

22

1.3

1.0

7

9

0

15

27

19

NR

NR

12

17

NR

NR

Mid 1 MSB 4D Trichloroethene

Tetrachloroethene

4 150

87

9

12

126

68

7

12

Mid 2 MSB 64C Trichloroethene

Tetrachloroethene

1,1-Dichloroethene

3 35

240

12

7

4

8

29

186

7.3

19

15

19

High 1 MSB 4B Trichloroethene

Tetrachloroethene

3 747

33

1

2

726

37

8

11

High 2 MSB 70C Trichloroethene

Tetrachloroethene

1,1-Dichloroethene

4 1875

520

32

12

8

8

1703

454

26

8

23

42

Very high 1 MSB 14A Trichloroethene

Tetrachloroethene

3 1367

800

8

6

1460

898

6

12

Very high 2 MSB 8C Trichloroethene

Tetrachloroethene

3 4933

3668

6

6

4783

3197

3

12

Range 0 – 34 3 – 89

Median 8 12

95th Percentile 15 43

a NR = not reported.

The average percent difference between average HAPSITE and laboratory results for the compounds detected in

each set of groundwater samples is shown in Figures 5-9 and 5-10 for SRS and MAFB, respectively. Average

laboratory results for groundwater contaminants reported at levels less than 1 μg/L are not included in the

comparison. The SRS groundwater comparison in Figure 5-9 includes only TCE and PCE. Two well samples at

the SRS were also contaminated with 1,1-dichloroethene and other compounds, as noted in Table 5-7. The

groundwater samples at MAFB were more complex, as indicated by the additional compounds shown in Table 5-8

and Figure 5-10. (See the vendor comment in Chapter 7 concerning laboratory results for cis-1,2-dichloroethene at

MAFB.)
49

Table 5-8. HAPSITE and Reference Laboratory Results for MAFB Groundwater Samples

Sample

Description

Well

Number

Replicates Compound Lab.

Avg.

(μg/L)

Lab.

RSD

(%)

HAPSITEa

Avg.

(μg/L)

HAPSITEa

RSD

(%)

Very low 1 EW-86 3 Trichloroethene

1,1-Dichloroethene

4.6

7.7

5

9

12.8

6.3

93

7

Very low 2 MW-349 3 Trichloroethene

Tetrachloroethene

Chloroform

1,1-Dichloroethene

Carbon tetrachloride

13

2.0

9.0

3.8

137

0

6

1

3

4

15

NR

9.0

2.9

140

15

NR

12

20

22

Low 1 MW-331 4 1,1-Dichloroethene

1,1-Dichloroethane

Carbon tetrachloride

Chloroform

Trichloroethene

2.5

15

7.5

4.8

16

7

0

2

2

4

NR

13

6.0

4.5

17

NR

15

30

4

27

Low 2 MW-351 3 Freon11

1,1-Dichloroethene

1,1-Dichloroethane

cis-1,2-Dichloroethene

Carbon tetrachloride

Trichloroethene

20

1.5

5.1

1.5

1.4

22

6

12

4

4

4

5

NR

NR

4.0

1.9

NR

25.1

NR

NR

23

34

NR

11

Mid 1 EW-87 4 1,1-Dichloroethene

1,1-Dichloroethane

cis-1,2-Dichloroethene

1,1,1-Trichloroethane

Trichloroethene

Tetrachloroethene

180

3.0

3.3

6.8

114

1.2

12

9

13

12

11

14

189

NR

4.0

5.3

111

NR

23

NR

12

34

12

NR

Mid 2 MW-341 3 cis-1,2-Dichloroethene

Chloroform

Trichloroethene

15

3.5

280

4

5

4

24

3.1

264

8

16

3

High 1 MW-209 3 cis-1,2-Dichloroethene

Chloroform

Trichloroethene

38

6.9

238

4

21

2

56

6.4

240

11

5

11

High 2 MW-330 4 trans-1,2-Dichloroethene

cis-1,2-Dichloroethene

Chloroform

1,2-Dibromochloropropane

Trichloroethene

7.7

66

42

6.1

380

4

5

5

6

5

7.1

97

45

4.7

398

10

12

5

19

9

Very high 1 MW-334 3 1,1-Dichloroethene

cis-1,2-dichloroethene

Chloroform

Benzene

Trichloroethene

Carbon tetrachloride

690

237

397

283

10,667

350

3

7

5

5

5

5

1032

426

418

265

11,714

565

33

9

8

12

13

44

Very high 2 MW-369 3 cis-1,2-Dichloroethene

Chloroform

Carbon tetrachloride

Trichloroethene

207

63

51

6167

10

6

5

8

299

67

60

6821

16

3

23

15

Range 0 – 21 3 – 93

Median 5 13

95th Percentile 14 36

a

 NR = not reported.
50

Inficon HAPSITE GW Sample Difference

Site: SRS Ref: Laboratory

-100 -80 -60 -40 -20 0 20 40 60 80 100

Trichloroethene

Tetrachloroethene

Compound

Average Percent Difference

VHigh2

VHigh1

High2

High1

Mid2

Mid1

Low2

Low1

VLow2

VLow1

Figure 5-9. HAPSITE groundwater results at the SRS relative to laboratory

results.

Inficon HAPSITE GW Sample Difference

Site: MAFB Ref: Laboratory

-100 -80 -60 -40 -20 0 20 40 60 80 100

 Trichloroethene

 1,1-Dichloroethene

 1,1-Dichloroethane

 Carbon tetrachloride

 Chloroform

 cis-1,2-Dichloroethene

Compound

Average Percent Difference

VHigh2

VHigh1

High2

High1

Mid2

Mid1

Low2

Low1

VLow2

VLow1

176

Figure 5-10. HAPSITE groundwater results at MAFB relative to laboratory

results.
51

The median and 95th percentile of the distribution of absolute percent differences between HAPSITE and laboratory

results for all groundwater samples are given in Table 5-9.

Table 5-9. HAPSITE Absolute Percent Difference Summary for

Pooled Groundwater Results

Percentile SRS MAFB Combined Sites

50th 13 13 12

95th 29 64 43

Number of samples in pool 21 38 59

To assess the degree of linear correlation between the HAPSITE and laboratory groundwater data pairs shown in

Tables 5-7 and 5-8, correlation coefficients (r) were computed. The data pairs were divided into two subsets for

each site to reduce the likelihood of spuriously high r values caused by large differences in the data (e.g.,

concentrations ranging from 1 μg/L to those in excess of 1000 μg/L) (Havlicek and Crain, 1988). One subset

contained all data pairs with laboratory results less than or equal to 100 μg/L and the other subset included all data

pairs with laboratory values greater than 100 μg/L. The computed correlation coefficients are shown in

Table 5-10.

Table 5-10. Correlation Coefficients for Laboratory and HAPSITE

Groundwater Analyses

Data Set Correlation

Coefficient

Number of

Data Pairs

SRS Laboratory (1 through 100 μg/L) 0.983 13

SRS Laboratory (> 100 μg/L) 0.996 9

MAFB Laboratory (1 through 100 μg/L) 0.978 24

MAFB Laboratory (> 100 μg/L) 1.000 14

Sample Throughput

HAPSITE sample throughput rates ranged from two to three samples per hour. Throughput rates were assessed by

using the time lapsed between sample checkout in the morning and delivery of hardcopy results in the afternoon,

and the number of samples completed. HAPSITE GC run times were slightly longer at the MAFB demonstration

as a result of the additional five compounds in the system calibration file. Sample throughput rates were not

significantly influenced by the sample complexity since more complex PE and less complex groundwater samples

were run through the same analysis sequence and had the same GC run times.

Performance Summary

Table 5-11 contains a summary of HAPSITE performance characteristics, including important instrument

performance parameters and operational features verified in this demonstration. For groundwater samples, the

results from the reference laboratory are given alongside HAPSITE performance results to facilitate comparison of

the two methodologies.
52

Table 5-11. Summary of HAPSITE GC/MS Performance

Instrument

Feature/Parameter

Performance Summary

Blank sample False positives detected at low (13 to 38%) rates for 8 compounds

Detection limit sample False negatives reported at rates between 10 and 90% for 7 of 22 compounds, at

concentration levels of 10 μg/L, for which the instrument was calibrated

PE sample precision Target compounds, RSD range: 2 to 28%

All compounds, HAPSITE median RSD: 12%; 95th percentile RSD: 29%

All compounds, laboratory median RSD: 7%; 95th percentile RSD: 25%

(Target compounds: TCE, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,2-

dichloropropane, PCE, and trans-1,3-dichloropropene)

PE sample accuracy Target compounds, absolute percent difference range: 1 to 33%

All compounds, HAPSITE median APD: 8%; 95th percentile APD: 27%

All compounds, laboratory median APD: 7%; 95th percentile APD: 24%

(Target compounds same as those for sample precision)

HAPSITE comparison with

laboratory results for

groundwater samples

HAPSITE median RSD: 12% Laboratory median RSD: 6%

HAPSITE 95th percentile RSD: 43% Laboratory 95th percentile RSD: 14%

HAPSITE laboratory median APD: 13%; 95th percentile APD: 60%

HAPSITE laboratory correlation:

SRS low conc. (≤100 μg/L) r = 0.983

SRS high conc. (>100 μg/L) r = 0.996

MAFB low conc. (≤100 μg/L) r = 0.978

MAFB high conc. (>100 μg/L) r = 1.000

Analytical versatility PE samples: calibrated for 27 of 32 PE compounds (84%)

GW samples: HAPSITE reported 59 of 59 compounds detected by the laboratory in all

GW samples at or above the 5 μg/L concentration level. A total of 68 compounds at

concentration levels ≥ 1 μg/L were detected by the reference laboratory in all

groundwater samples.

Sample throughput 2.5 samples per hour

Support requirements Self-contained carrier gas, batteries, optional printer

Internal and surrogate standard solutions and syringes

Operator requirements Sample processing: technician with 3-day training

Data processing and review: B.S. chemist or equivalent

Total system weight 60 pounds

Portability Transportable—best suited for use in vehicle at the wellhead

Total system cost $95,000

Shipping requirements Air freight, hand carry, luggage check

Carrier and internal standard gases shipped as hazardous material
53

Chapter 6 

Field Observations and Cost Summary

Introduction

The following subsections summarize the audit findings obtained while observing instrument operation at both field

sites. The purpose of the audits was to observe the instrument in operation as well as to verify that the analytical

procedures used during the demonstration were consistent with the written procedures submitted to the verification

organization prior to the field demonstration. An instrument cost summary and an applications assessment is

provided.

Method Summary

The HAPSITE uses a static (equilibrium) headspace method with temperature control. The headspace vapors from

a temperature-equilibrated sample are transferred to a gas sampling loop and automatically injected into the

GC/MS. Compounds are identified by library spectral matching and quantified by integrating the peak area of a

selected quantification ion. Internal and surrogate standards are also incorporated into the method.

Equipment

Without the service module, the HAPSITE GC/MS is 18 inches × 17 inches × 7 inches and weighs 35 pounds. The

headspace sampling accessory is 16 inches × 14 inches × 7 inches and weighs 15 pounds; the notebook computer is

8 pounds and the printer weighs 5 pounds. Configured for water sample analysis, the system is transportable and

easily fits in the rear luggage storage area of a minivan or station wagon. Equipment weights include batteries and

gas cartridges. Nickel-cadmium battery lifetimes are about 2 to 3 hours for the HAPSITE and 4 to 6 hours for the

headspace sampling accessory. The system can be connected to a 24-V marine battery for extended remote

operation. The system was run with both batteries and ac power during the demonstration. The system is also

equipped with a service module with dimensions of 18 inches × 17 inches × 8.5 inches and a weight of 45 pounds.

The module is used to pump an initial vacuum on the spectrometer and normally is not taken to the field.

Additional required equipment includes 40-mL screw-cap septa vials (Supelco, graduated with diameter to fit the

headspace sampling accessory heater block); 1-mL (with MIN-inert valve) and 2-mL vials for calibration;

microliter syringe(s); 50-mL Teflon Luer lock syringes for sample transfer; and commercially available (Supelco or

equivalent) internal and surrogate standard mixtures.

The equipment was transported to the SRS by vehicle and to the MAFB site as carry-on luggage. It can also be

checked as baggage in its shipping case.
54

Figure 6-1. The HAPSITE GC/MS.

Sample Preparation and Handling

Sample preparation begins by pouring a cold, zero-headspace, 40-mL volatile organics analysis vial sample into an

open 50-mL gas-tight syringe. The syringe plunger is inserted, the syringe inverted, and excess air expelled.

Twenty milliliters are ejected as waste. The remaining 20-mL sample is transferred to a headspace vial and capped

with a Teflon-lined silicone septum and screw cap. A 5-μL volume of internal or surrogate standard mixture is

injected through the septum with a microliter syringe. All samples were prepared in this manner immediately after a

sample batch was received. Following preparation, all vials were then stored on ice. Calibration standards were

prepared directly in headspace vials. Since the standards were not carried through the sample transfer process,

there was little risk for the loss of compounds that may occur during routine sample handling and transfer.

Consumables

Disposable gas bottles are used for the nitrogen carrier gas, the internal standard mixture, and the headspace

sampling accessory purge-and-sweep gas. These bottles can be changed out quickly in the field. Standard gas

cylinders can also be used for nitrogen carrier and headspace sampling accessory purge and sweep. The system has

a chemical getter pump that maintains the system vacuum during operation. The getter pump must be replaced

after 240 hours of use.
55

Historical Use

This is the first demonstration of the HAPSITE GC/MS and the headspace sampling accessory for the analysis of

volatile organics in water. The HAPSITE unit alone has been used extensively for vapor analysis applications

(exhaust, stack, and soil gas analysis).

Equipment Cost

The HAPSITE and headspace sampling accessory have a combined cost that ranges from $75,000 to $95,000,

depending upon options selected. The instrument can be purchased without a service module for $75,000. With

this configuration, the instrument must be sent back to the maintenance facility in Syracuse, New York, for periodic

replacement of the getter pump. Purchase of the service module allows the user to replace the getter pump in the

field. With either option, a notebook computer is included in the package for data processing and instrument

control. Daily operating costs are about $150 and include gases, battery packs, and replacement getter pumps (all

via maintenance agreement). Instrument costs are summarized in Table 6-1. Laboratory costs were $95 per

sample plus overnight Express Mail costs, which were about $30 per batch of 12 samples. HAPSITE sample

throughput is in the range of 2 to 3 samples per hour.

Table 6-1. HAPSITE GC/MS Cost Summary

Instrument/Accessory Cost

Instrument

(HAPSITE / headspace sampling accessory /

service module (option), notebook computer and

startup kit)

$75,000 (without service module)

$95,000 (with service module)

Instrument accessories (field-portable printer) $300 – $500

Sample handling accessories (syringes, vials,

standards)

$500 per 100 samples

Maintenance costs $4500 per 240 hours of use

Carrier gas, internal standard gas, and getter pump

replacement

$500 service charge for pump replacement at

factory

Operators and Training

One operator is required for GC/MS operation. An additional person is helpful when the headspace sampling

accessory is used with a high volume of samples, such as in this demonstration. For wellhead monitoring

operations where instrument use would follow a well-sampling team, one operator is probably sufficient since only

one or two samples would be provided per hour. The GC/MS operator should be a well-trained technician,

preferably with a B.S. in chemistry. Sampling preparation and injection into the instrument could be carried out by

a field technician with minimal training; however, instrument response and results would have to be checked daily

by a qualified analyst.

Data Processing and Output

The instrument produces a typical GC/MS report with internal and surrogate standard checks directly from

operating software. The software operates in a multitasking environment so that a sample analysis can be in

progress while the results of completed samples are being reviewed. Data reports were checked and printed within

minutes of run completion. The operator’s objective of reporting valid results for 90% or more of 20 samples by

the end of the day was easily met. The unit can also be operated without the laptop, by use of a liquid crystal

display screen and keypad on the instrument. Data collected in this manner can be downloaded to a laptop and
56

reviewed at the end of the day. Total ion chromatograms can be reprocessed (reintegrated) with other parameters

and/or calibration responses. Data can be downloaded to a spreadsheet for further evaluation or graphical

reporting.

Compounds Detected

With the relatively low column temperature (< 80 °C) in isothermal operation, hexachlorobutadiene and three other

higher boiling point compounds (1,2-dichlorobenzene, 2-chloroethyl vinyl ether, and 1,2-dibromochloropropane)

listed in the demonstration plan were not included in the GC/MS method. The instrument can detect

dichlorobenzenes with a longer run time, but the choice was made to go with shorter run times for this

demonstration to increase the sample throughput rate.

Initial and Daily Calibration

Calibration was done as specified in Method 8260A and in the written field method. Linear regression with a

forced zero intercept was used to derive a single response factor for each target compound. A full calibration was

performed before bringing the instrument to the SRS demonstration. The calibration runs used to generate the

method calibration table can be selected by the operator. A continuing calibration check sample was typically run

two times per day. These daily calibration checks can be used to update calibration response factors if necessary.

QC Procedures and Corrective Actions

Mass calibration checks and updates were run after 4 hours of operation to account for ambient temperature

changes. This procedure is specified in the field method and is required when temperature changes of 10 °C or

more are encountered during instrument operation. In addition to periodic calibration checks, internal and surrogate

standards were run with nearly every sample. These standards give additional measures of instrument data quality.

Blanks were also run at the start of the day. Corrective actions such as calibration rechecks, or sample reruns were

taken when surrogate standard recoveries were <60 or >140% of a typical response. See Chapter 7 for additional

vendor comments on the use of blank samples following high-concentration samples.

Sample Throughput

Maximum sample throughput is about 25 samples per 10-hour day.

Problems Observed During Audit

No problems were observed during the audit.

Data Availability and Changes

Data from the HAPSITE were obtained at the end of each demonstration day in hardcopy format. Data were

provided in spreadsheet format at the conclusion of each demonstration week. Several typographical errors were

corrected at the final data review; however, no substantive data changes were made.

Applications Assessment

This demonstration was intended to provide an assessment of the instrument’s suitability for analytical tasks in site

characterization and routine site monitoring. Site characterization refers to those instances where subsurface
57

contamination is suspected but information on specific compounds and their concentration levels is not available.

The instrument best suited for this application is one that can screen a wide array of compounds in a timely and

cost-effective manner. Analytical precision and accuracy requirements may be relaxed in these instances since a

general description of the site characteristics is adequate for remediation planning. At the other end of the spectrum

is a monitoring application where contaminant compounds and their subsurface concentrations are known with

some certainty. Periodic monitoring requirements imposed by local regulatory agencies may specify the

performance of analyses for specific contaminant compounds known to be present in the water. Quarterly wellmonitoring programs fall into this category.

Based on its performance in this demonstration, the HAPSITE is suitable for both characterization and monitoring

applications. Since it is a GC/MS system utilizing data-processing software that includes a mass-spectral library

and search routines, it is particularly well suited to characterization applications that require identification of

unknowns. The existence of two compound characteristics, GC column retention time and mass spectral data,

allows unknown compounds to be identified with a high degree of certainty. The precision and accuracy of the

HAPSITE indicate that it is also suited for routine monitoring applications; the results obtained on groundwater

samples with the HAPSITE were comparable to those obtained from a reference laboratory.
58

Chapter 7 

Technology Update

Note: The following comments were submitted by the technology developer. They have been edited for format

consistency with the rest of the report. The technical content in the following comments has not been verified by

the verification organization.

Review of Demonstration and Results

The ETV Program offered an excellent opportunity to test the performance of the HAPSITE with an equilibrium

headspace accessory for the determination of VOCs in water. As a developer of new technology, we recognize the

benefit of independent verification of system performance as an important step in the acceptance of innovative

technologies. The data contained in the report represent a thorough evaluation of important performance attributes,

precision, accuracy, and operational parameters of the HAPSITE for field work. We appreciate the commitment of

the EPA and the resources contributed by the Agency to make this evaluation possible.

The demonstration has shown that the HAPSITE produces analytical results in the field that are directly

comparable to reference laboratory results. The data represented in this report support the use of the instrument in

all phases of site investigation and remediation work, including the generation of data for regulatory compliance.

Evaluation of the results has resulted in further improvements in the design of the system and analytical method.

The following comments address these changes and some minor discrepancies between the HAPSITEand reference

laboratory results.

Observed False Positive Results

The initial system design specified a carryover of ≤0.25% from sample to sample. The false positives listed in

Table 5-2 indicate that the components are the result of carryover from high-level samples run prior to the blanks.

While the carryover was less than the specification of 0.25%, changes have been made to the instrument design to

further reduce this specification to ≤0.15%.

Observed False Negative Results

Eight of the 12 false negatives (Table 5-3) from the SRS site were generated on the first day of testing. After the

first day, a change was made in the flow rate that transfers the sample from the headspace unit to the GC/MS. This

flow rate affects system sensitivity. After the flow rate was reset, only four additional false negatives were

generated. These compounds could be seen by manual review of the GC/MS data, but had not been found by the

peak detection software. Software settings were modified to correct this. The improved flow rate and software

settings were incorporated prior to MAFB testing and resulted in improved performance. The two compounds
59

that did cause false negatives at MAFB (1,1,2,2-tetrachloroethane and bromoform) were tested near the system

MDL for these compounds. The performance for bromoform indicates that the reported method detection limit

should be raised.

Comparison of HAPSITE and Laboratory Groundwater Sample Results

A comparison of HAPSITE and reference laboratory groundwater results demonstrates a highly linear relationship.

The HAPSITE produces results that match laboratory results, within ± 35%, 95% of the time. The absolute

percent difference for pooled groundwater samples from the SRS was 29% for the 95th percentile. However, the

MAFB absolute percent difference for pooled groundwater samples was 64% for the 95th percentile. We believe

this number is unduly high and is a result of an error in the reference laboratory results. Figure 5-10 shows a

consistently high percent difference between the HAPSITE and reference laboratory results for the compound cis1,2-dichloroethene. It is our opinion that this systematic bias for cis-1,2-dichloroethene is due to an error at the

reference laboratory. In the groundwater samples MG-30, MG16, MG17, and MG24 from MAFB, cis-1,2-

dichloroethene was detected by the HAPSITE at an average value of 42 μg/L with an RSD of 9% for the replicates.

The laboratory detected cis-1,2-dichloroethene in only one of the replicates at 27 μg/L, resulting in the compound

being reported as a nondetect for the average. Manual review of the HAPSITE results confirmed the presence of

cis-1,2-dichloroethene by retention time and mass spectrum. The last quarterly monitoring result from MAFB

supports the HAPSITE data, with cis-1,2-dichloroethene present at 41 μg/L for the low, No. 1 sample set

(Table 3-3).

Number of Compounds Detected

The HAPSITE detected 59 out of 68 compounds reported by the reference laboratory in the groundwater samples at

concentration levels greater than 1 μg/L. Of the 9 compounds not detected, 8 were reported by the reference

laboratory at or below the MDL of the HAPSITE for that compound. Trichlorofluoromethane (Freon11) was

reported at 20 μg/L by the reference laboratory. The HAPSITE report listed the compound as detected, but no

concentration was reported. The concentration was not reported because the standard for the gases failed internal

instrument QA/QC.

The HAPSITE detected a number of compounds not reported by the laboratory in the very high-level samples. This

is a result of the ability of the HAPSITE to analyze these samples undiluted. The laboratory was informed which

samples were expected at a high level and diluted these samples prior to analysis to prevent contamination of the

purge-and-trap and stay within the linear range of the system. The dilution caused a number of compounds to go

undetected because they were then below the detection limits of the system. The ability to analyze samples without

dilution and to run samples of unknown concentration without fear of system contamination is a major advantage

when using equilibrium headspace for site work.
60

Chapter 8 

Other Deployments

Monterey Airport (April 1998)

Monterey, CA

Groundwater Investigation

Contractor: U.S. Army Corp of Engineers

Contacts: Pat Cantrell – USACE, Sacramento District

Pam Wehrmann- USACE, Sacramento District

Field-Portable Analytical was contracted by the U.S. Army Corp of Engineers to perform a groundwater plume

investigation for benzene, toluene, ethyl benzene, and xylenes. The HAPSITE GC/MS and headspace sampling

systems were used to analyze samples during the site investigation. The results were used to decide if further

sampling was needed and where the next sample would be located. Immediate, definitive data were required to

make these decisions. Results from the HAPSITE were reported within 30 minutes of sample collection.

Field-Portable Analytical, Inc.

6054 Garden Towne Way, Suite G

Orangevale, CA 95662

(916) 989-6200
61

References

Bevington, P. R, 1969, Data Reduction and Error Analysis for the Physical Sciences, pp. 52–60. McGraw-Hill,

New York.

DataChem, 1997, “DataChem Laboratories Environmental Chemistry/Radiochemistry Quality Assurance Program

Plan,” 1997 Revision, DataChem Laboratories, Salt Lake City, UT.

EPA, 1986, “Test Methods for Evaluating Solid Waste,” 3rd ed., Vol. 1A (Test Method 3810). Office of Solid

Waste and Emergency Response, Washington, DC.

EPA, 1996a, “A Guidance Manual for the Preparation of Site Characterization and Monitoring Technology

Demonstration Plans,” Office of Research and Development, National Exposure Research Laboratory, Las Vegas,

NV. [Available at the ETV Web Site (www.epa.gov/etv) in pdf format.]

EPA, 1996b, “Test Methods for Evaluating Solid Waste: Physical/Chemical Methods; Third Edition; Final Update

III,” Report No. EPA SW-846.3-3, Government Printing Office Order No. 955-001-00000-1, Office of Solid

Waste and Emergency Response, Washington, DC.

Havlicek, L. L., and R. D. Crain, 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.]