United States
Environmental Protection
Agency
Office of Research and
Development
Washington, DC 20460
EPA/600/R-01/060
June 2000
&EPA Demonstration Plan
Field Measurement
Technologies for
Total Petroleum Hydrocarbons
in Soil
-------
EPA/600/R-01/060
June 2000
Demonstration Plan
Field Measurement Technologies for
Total Petroleum Hydrocarbons in Soil
Prepared by
Tetra Tech EM Inc.
Chicago, Illinois
Contract No. 68-C5-0037
Dr. Stephen Billets
Environmental Sciences Division
National Exposure Research Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Las Vegas, Nevada 89193-3478
-------
Concurrence Signatures
The primary purpose of the demonstration is to evaluate innovative field measurement technologies
for total petroleum hydrocarbons in soil based on their performance and cost as compared to a
conventional, off-site laboratory analytical method. The demonstration will take place under the
sponsorship of the U.S. Environmental Protection Agency (EPA) Superfund Innovative Technology
Evaluation Program.
This document is intended to ensure that all aspects of the demonstration are documented and
scientifically sound and that operational procedures are conducted in accordance with quality
assurance and quality control specifications and health and safety regulations.
The signatures of the individuals specified below indicate their concurrence and agreement to operate
in compliance with the procedures specified in this document.
StepherK&illets
EPA Project Manager
Date
George Brilis
Date
EPA National Exposure Research Laboratory
Quality Assurance Officer
I lenry Castaneda Date
CHEMetrics, Inc.
Technology Developer Project Manager
•• "J, •' : *~/) "7 ""•<, I -I
""' Sandy Rintoul • Date
Wilks Enterprise, Inc.
Technology Developer Project Manager
Jim Vance Date
Horiba Instruments, Incorporated
Technology Developer Project Manager
Tedl^PLynn Date
Dexsil* Corporation
..Technology DVeloper%Project Manager
George Hv
** i
EnvironmentaKSysSems Corporation
Technology Devejoger Project Manager
Date
Stephen Greason
siteEAB* Corporation
Technology Developer Project Manager
Date
11
-------
Joseph Dautlick Date
Strategic Diagnostics, Inc.
Technology Developer Project Manager
to*-
J*
Ernest Lory (
Navy Base Ventura County
Demonstration Site Representative
7
'ate
A /
4 ^vnt4sf*/^ •
Amy Whitley
Kelly Air Force Base
Demonstration Site Representative
Date
'to
Jay Simonds
Handex of Indiana
Denjflnstration Site Representative
Date
Susan Bell Date
Seve«i Trent Laboratories in Tampa, Florida
Andres Ronieu Date
Severn Trent Laboratories in Tampa, Florida
Quality Assurance Manager
Jeffrey Lovvry
Environmental Resource Associates
ProjeoOWanager
Date
Kirankumar Topudurti
Tetra Tech EM Inc.
Project Manager ,
Date
Greg Swan son
Tetra Tech EM Inc.
Quality Assurance Manager
Date
Judith Wagner
Tetra Tech EM Inc.
Health a/td Safety Representative
Date
(o
Date
catalyst Information Resources, L.L.C.
Project Technical Consultant
in
-------
Demonstration Plan Distribution List
Organization
U.S. Environmental Protection Agency
Navy Base Ventura County
Kelly Air Force Base
Handex of Indiana
CHEMetrics, Inc.
Wilks Enterprise, Inc.
Horiba Instruments, Incorporated
Dexsil® Corporation
Environmental Systems Corporation
site LAB® Corporation
Strategic Diagnostics, Inc.
Severn Trent Laboratories
Environmental Resource Associates
Tetra Tech EM Inc.
Catalyst Information Resources, L.L.C.
Mailing Address
National Exposure Research
Laboratory
944 East Harmon Avenue
Las Vegas, NV89114
NFESC
110023rd Avenue
Port Hueneme, CA 93043
SA-ALC/EMRR
307 Tinker Drive (Building 306)
Kelly Air Force Base, TX 78241
8579 Zionsville Road
Indianapolis, IN 46268
Route 28
Calverton, VA20138
345 Riverview Drive
Boulder Creek, CA 95006
17671 Armstrong Avenue
Irvine, CA 9261 4
One Hamden Park Drive
Hamden,CT06517
200 Tech Center Drive
Knoxville, TN37912
94 Highland Street
Portsmouth, NH 03801
1 1 1 Pencader Drive
Newark, DE 19702
5910 Breckenridge Parkway, Suite H
Tampa, FL 33610
5540 Marshall Street
Arvada, CO 80002
200 East Randolph Drive, Suite 4700
Chicago, IL 60601
591 Camino de la Reina, Suite 640
San Diego, CA92108
3550 Salt Creek Lane, Suite 105
Arlington Heights, IL 60004
625 Eden Park Drive, Suite 100
Cincinnati, OH 45202
1513 Bergen Parkway, #238
Evergreen, CO 80439
Recipient
Dr. Stephen Billets
Mr. George Brills
Mr. Ernest Lory
Ms. Amy Whitley
Mr. Jay Simonds
Mr. Henry Castaneda
Ms. Sandy Rintoul
Mr. Jim Vance
Dr. Ted B. Lynn
Dr. George Hyfantis
Mr. Stephen Greason
Mr. Joseph Dautlick
Ms. Susan Bell
Mr. Jeffrey Lowry
Dr. Kirankumar Topudurti
Mr. Eric Monschein
Ms. Sandy
Anagnostopoulos
Ms. Jill Ciraulo
Ms. Kelly Hirsch
Ms. Kim Huynh
Mr. Jeff Lifka
Mr. Kevin Schnoes
Ms. Suzette Tay
Dr. Greg Swanson
Ms. Judith Wagner
Mr. Carl Rhodes
Mr. Jerry Parr
No. of
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IV
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Notice
This document was prepared for the U.S. Environmental Protection Agency Superfund Innovative
Technology Evaluation Program under Contract No. 68-C5-0037. The document has been subjected
to the EPA's peer and administrative reviews and has been approved for publication. Mention of
corporation names, trade names, or commercial products does not constitute endorsement or
recommendation for use.
v
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Foreword
The U.S. Environmental Protection Agency (EPA) is charged by Congress with protecting the
nation's natural resources. Under the mandate of national environmental laws, the agency strives to
formulate and implement actions leading to a compatible balance between human activities and the
ability of natural systems to support and nurture life. To meet this mandate, the EPA's Office of
Research and Development provides data and scientific support that can be used to solve
environmental problems, build the scientific knowledge base needed to manage ecological resources
wisely, understand how pollutants affect public health, and prevent or reduce environmental risks.
The National Exposure Research Laboratory is the agency' s center for investigation of technical and
management approaches for identifying and quantifying risks to human health and the environment.
Goals of the laboratory' s research program are to (1) develop and evaluate methods and technologies
for characterizing and monitoring air, soil, and water; (2) support regulatory and policy decisions;
and (3) provide the scientific support needed to ensure effective implementation of environmental
regulations and strategies.
The EPA's Superfund Innovative Technology Evaluation (SITE) Program evaluates technologies
designed for characterization and remediation of contaminated Superfund and Resource Conservation
and Recovery Act sites. The SITE Program was created to provide reliable cost and performance
data in order to speed acceptance and use of innovative remediation, characterization, and monitoring
technologies by the regulatory and user community.
Effective monitoring and measurementtechnologies are needed to assess the degree of contamination
at a site, provide data that can be used to determine the risk to public health or the environment, and
monitor the success or failure of a remediation process. One component of the EPA SITE Program,
the Monitoring and Measurement Technology Program, demonstrates and evaluates innovative
technologies to meet these needs.
Candidate technologies can originate within the federal government or the private sector. Through
the SITE Program, developers are given the opportunity to conduct a rigorous demonstration of their
technologies under actual field conditions. By completing the demonstration and distributing the
results, the agency establishes a baseline for acceptance and use of these technologies. The
Monitoring and Measurement Technology Program is managed by the Office of Research and
Development's Environmental Sciences Division in Las Vegas, Nevada.
Gary Foley, Ph.D.
Director
National Exposure Research Laboratory
Office of Research and Development
VI
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Abstract
The demonstration of innovative field measurement devices for total petroleum hydrocarbons (TPH)
in soil is being conducted under the U.S. Environmental Protection Agency (EPA) Superfund
Innovative Technology Evaluation Program in June 2000 at the Navy Base Ventura County site in
PortHueneme, California. The primary purpose of the demonstration is to evaluate innovative field
measurement devices for TPH in soil based on their performance and cost as compared to a
conventional, off-site laboratory analytical method. The seven field measurement devices listed
below will be demonstrated.
• CHEMetrics, Inc.'s, RemediAid™ Total Petroleum Hydrocarbon Starter Kit
• Wilks Enterprise, Inc.' s, Infracal® TOG/TPH Analyzer, Models CVH and HATR-T
• Horiba Instruments, Incorporated's, OCMA-350 Oil Content Analyzer
• Dexsil® Corporation's PetroFLAG™ Hydrocarbon Test Kit for Soil
• Environmental Systems Corporation's Synchronous Scanning Luminoscope
• siteLAB® Corporation's Analytical Test Kit UVF-3100A
• Strategic Diagnostics, Inc.'s, EnSys Petro Test System
This demonstration plan describes the procedures that will be used to verify the performance and cost
of each field measurement device. The plan incorporates the quality assurance and quality control
elements needed to generate data of sufficient quality to document each device's performance and
cost. A separate innovative technology verification report (ITVR) will be prepared for each device.
The ITVRs will present the demonstration findings associated with the demonstration objectives.
vn
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Contents
Chapter Page
Concurrence Signatures ii
Demonstration Plan Distribution List iv
Notice v
Foreword vi
Abstract vii
Figures xv
Tables xvi
Abbreviations, Acronyms, and Symbols xviii
Acknowledgments xxi
Executive Summary xxii
1 Introduction 1
1.1 Description of SITE Program 2
1.2 Scope of Demonstration 5
1.3 Components and Definition of TPH 6
1.3.1 Composition of Petroleum and Its Products 7
1.3.
1.3.
1.3.
1.3.
1.3.
.1 Gasoline 8
.2 Naphthas 9
.3 Kerosene 9
.4 Jet Fuels 9
.5 Fuel Oils 10
1.3. .6 Diesel 10
1.3. .7 Lubricating Oils 11
1.3.2 Measurement of TPH 11
1.3.2.1 Historical Perspective 11
1.3.2.2 Current Options for TPH Measurement in Soil 13
1.3.2.3 Definition of TPH 14
Vlll
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Contents (Continued)
Chapter Page
2 Innovative Technology and Field Measurement Device Descriptions 17
2.1 Technology Descriptions 18
2.1.1 Friedel-Crafts Alkylation Reaction and Colorimetry 18
2.1.1.1 Friedel-Crafts Alkylation Reaction 20
2.1.1.2 Colorimetry 21
2.1.2 Infrared Analysis 22
2.1.3 Emulsion Turbidimetry 23
2.1.4 Ultraviolet Fluorescence Spectroscopy 24
2.1.5 Immunoassay and Colorimetry 25
2.1.5.1 Immunoassay 26
2.1.5.2 Colorimetry 30
2.2 Field Measurement Device Descriptions 30
2.2.1 RemediAid™ Starter Kit 31
2.2.1.1 Device Description 31
2.2.1.2 Operating Procedure 33
2.2.1.3 Advantages and Limitations 35
2.2.2 Infracal® TOG/TPH Analyzer, Models CVH and HATR-T 36
2.2.2.1 Device Description 36
2.2.2.2 Operating Procedure 39
2.2.2.3 Advantages and Limitations 40
2.2.3 OCMA-350 40
2.2.3.1 Device Description 41
2.2.3.2 Operating Procedure 43
2.2.3.3 Advantages and Limitations 44
2.2.4 PetroFLAG™ Test Kit 44
2.2.4.1 Device Description 45
2.2.4.2 Operating Procedure 47
2.2.4.3 Advantages and Limitations 48
2.2.5 Luminoscope 49
2.2.5.1 Device Description 49
2.2.5.2 Operating Procedure 51
2.2.5.3 Advantages and Limitations 52
2.2.6 UVF-3100A 52
2.2.6.1 Device Description 53
2.2.6.2 Operating Procedure 55
2.2.6.3 Advantages and Limitations 56
2.2.7 EnSys Petro Test System 57
2.2.7.1 Device Description 57
2.2.7.2 Operating Procedure 61
2.2.7.3 Advantages and Limitations 63
3 Demonstration Site Descriptions 64
3.1 Navy Base Ventura County Site 66
3.1.1 Fuel Farm Area 66
3.1.2 Naval Exchange Service Station Area 66
IX
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Contents (Continued)
Chapter Page
3.1.3 Phytoremediation Area 69
3.2 Kelly Air Force Base Site 70
3.3 Petroleum Company Site 70
4 Demonstration Approach 74
4.1 Demonstration Objectives 74
4.2 Demonstration Design 75
4.3 Data Analysis Procedures 85
4.3.1 Primary Objective PI: Method Detection Limit 86
4.3.2 Primary Objective P2: Accuracy and Precision 87
4.3.3 Primary Objective P3: Effect of Interferents 91
4.3.4 Primary Objective P4: Effect of Soil Mositure Content 91
4.3.5 Primary Objective P5: Time Required for TPH Measurement 92
4.3.6 Primary Objective P6: Costs Associated with TPH Measurement ..92
4.4 Demonstration Schedule 92
5 Confirmatory Process 97
5.1 Reference Method Selection 97
5.2 Reference Laboratory Selection 100
6 Demonstration Organization and Responsibilities 101
6.1 EPA Project Personnel 101
6.2 Tetra Tech Project Personnel 101
6.3 Developer Personnel 105
6.4 Demonstration Site Representatives 105
6.5 Laboratory Project Personnel 106
7 Field Sampling Procedures 110
7.1 Sampling Procedures Ill
7.1.1 Sample Collection 112
7.1.1.1 Navy Base Ventura County Site 114
7.1.1.1.1 Fuel Farm Area 123
7.1.1.1.2 Naval Exchange Service Station Area 123
7.1.1.1.3 Phytoremediation Area 124
7.1.1.2 Kelly Air Force Base Site 124
7.1.1.3 Petroleum Company Site 125
7.1.2 Sample Handling and Shipping 125
7.1.3 Sample Preparation 126
7.1.3.1 Environmental Samples 126
7.1.3.2 PE Samples 128
7.1.3.3 QC Samples 131
7.2 Sample Handling and Shipping Procedures 132
7.3 Sampling Equipment Decontamination and Investigation-Derived Waste
Disposal Procedures 136
7.4 Field Documentation Procedures 137
-------
Contents (Continued)
Chapter Page
8 Calibration Requirements and Sample Management Procedures for Innovative Field
Measurement Devices 138
8.1 Calibration Requirements 138
8.1.1 RemediAid™ Starter Kit 138
8.1.2 Infracal® TOG/TPH Analyzer, Models CVH and HATR-T 141
8.1.3 OCMA-350 144
8.1.4 PetroFLAG™ Test Kit 146
8.1.5 Luminoscope 147
8.1.6 UVF-3100A 147
8.1.7 EnSys Petro Test System 149
8.2 Sample Management Procedures 149
9 Laboratory Sample Preparation and Analytical Methods, Calibration Requirements, and
Sample Management Procedures 151
9.1 Laboratory Sample Preparation and Analytical Methods 151
9.2 Calibration Requirements 151
9.3 Sample Management Procedures 152
10 QA/QC Procedures 163
10.1 QA Objectives 163
10.1.1 Reporting Limits 163
10.1.2 Precision and Accuracy 166
10.1.3 Completeness 166
10.1.4 Representativeness 166
10.1.5 Comparability 170
10.2 Internal QC Checks 170
10.2.1 Reference Method QC Checks 170
10.2.1.1 Method and Instrument Blanks 171
10.2.1.2 Surrogates 171
10.2.1.3 MS/MSDs 171
10.2.1.4 Extract Duplicates 172
10.2.1.5 LCS/LCSDs 172
10.2.1.6 Laboratory Duplicate 173
10.2.2 Field Measurement Device QC Checks 173
10.2.3 Sample Collection QC Checks 173
10.3 Calculation of Data Quality Indicators 174
10.3.1 Precision 174
10.3.2 Accuracy 175
10.3.3 Completeness 176
10.3.4 Representativeness 176
10.4 QA Reports 176
10.5 Special QC Requirements 177
11 Audits and Corrective Actions 178
XI
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Contents (Continued)
Chapter Page
11.1 System Audits 179
11.2 Performance Audits 180
11.3 Corrective Action Procedures 181
12 Data Management 182
12.1 Data Reduction 182
12.2 Data Review 182
12.2.1 Data Review by Developers 183
12.2.2 Data Review by STL Tampa East 183
12.2.3 Data Review by Tetra Tech 185
12.3 Data Reporting 186
12.3.1 Developer Data Packages 186
12.3.2 STL Tampa East Data Packages 186
12.3.3 STL Tampa East Electronic Data Deliverables 189
123.4 Innovative Technology Verification Reports 189
12.3.5 Data Evaluation Report 190
12.4 Data Storage 190
13 Health and Safety Procedures 192
13.1 Health and Safety Personnel and Procedure Enforcement 193
13.1.1 Project Personnel 193
13.1.1.1 Project Manager and Field Manager 194
13.1.1.2 Site Safety Coordinator 195
13.1.1.3 Health and Safety Representative 195
13.1.1.4 Tetra Tech Employees 195
13.1.2 Subcontractors and Developers 195
13.1.3 Visitors 196
13.1.4 Health and Safety Procedure Enforcement 196
13.2 Site Background 196
13.2.1 Demonstration Site Descriptions 196
13.2.2 Planned Demonstration Activities 197
13.3 Site-Specific Hazard Evaluation 197
13.3.1 Chemical Hazards 197
13.3.1.1 Volatile Organic Compounds 198
13.3.1.2 Inorganic Compounds 198
13.3.2 Physical Hazards 198
13.4 Training Requirements 201
13.5 Personal Protection Requirements 202
13.5.1 Protective Equipment and Clothing 202
13.5.2 Reassessment of Protection Levels 204
13.5.3 Limitations of Protective Clothing 205
13.5.4 Respirator Selection, Use, and Maintenance 208
13.6 Medical Surveillance 209
13.6.1 Health Monitoring Requirements 210
13.6.2 Site-Specific Medical Monitoring 211
xn
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Contents (Continued)
Chapter Page
13.6.3 Medical Support and Follow-Up Requirements 211
13.7 Environmental Monitoring and Sampling 211
13.7.1 Initial and Background Air Monitoring 211
13.7.2 Personal Monitoring 212
13.7.3 Ambient Air Monitoring 212
13.7.4 Monitoring Parameters and Devices 213
13.7.4.1 Organic Vapors 213
13.7.4.2 Known Compounds 213
13.7.4.3 Combustible Atmospheres 213
13.7.4.4 Percent Oxygen 214
13.7.4.5 External Exposure to Radiation 214
13.7.4.6 Particulates 214
13.7.5 Use and Maintenance of Survey Equipment 215
13.7.6 Thermal Stress Monitoring 215
13.7.7 Noise Monitoring 215
13.8 Site Control 216
13.8.1 On-Site Communications 216
13.8.2 Site Control Zones 217
13.8.2.1 Zone 1: Exclusion Zone 217
13.8.2.2 Zone 2: Decontamination Zone 217
13.8.2.3 Zone 3: Support Zone 218
13.8.3 Site Access Control 218
13.8.4 Site Safety Inspections 218
13.8.5 Safe Work Practices 218
13.9 Decontamination 219
13.9.1 Personnel Decontamination 219
13.9.2 Equipment Decontamination 220
13.10 Emergency Response Planning 220
13.10.1 Pre-Emergency Planning 220
13.10.2 Personnel Roles and Lines of Authority 221
13.10.3 Emergency Recognition and Prevention 221
13.10.4 Evacuation Routes and Procedures 221
13.10.5 Emergency Contacts and Notifications 221
13.10.6 Hospital Route Directions 222
13.10.7 Emergency Medical Treatment Procedures 222
13.10.8 Protective Equipment Failure 222
13.10.9 Fire or Explosion 223
13.10.10 Weather-Related Emergencies 223
13.10.11 Spills or Leaks 223
13.10.12 Emergency Equipment and Facilities 224
13.10.13 Reporting 224
REVIEWS AND APPROVALS 225
14.0 References 226
Xlll
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Contents (Continued)
Chapter Page
Appendix A Review of Predemonstration Investigation Procedures and Results 228
Appendix B Emergency Information 235
Appendix C Tetra Tech, Inc., Forms 245
xiv
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Figures
Figure Page
1 -1. Distribution of various petroleum hydrocarbon types throughout boiling point range of
crude oil 8
2-1. Wavelength range used by each measurement device 19
2-2. Schematic of ultraviolet fluorescence spectroscopy 25
2-3. Immunoglobulin G antibody structure and locations of antigen-binding sites 27
2-4. Enzyme-linked immunosorbent assay 29
3-1. Navy Base Ventura County site map 67
3-2. Navy Base Ventura County site sampling locations 68
3-3. Kelly Air Force Base site map 71
3-4. Kelly Air Force Base site sampling locations 72
3-5. Petroleum company site sampling locations 73
5-1. Reference method selection process 98
6-1. Organizational chart 102
7-1. Chain-of-custody form 134
xv
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Tables
Table Page
1-1. Summary of Calibration Information for Infrared Analytical Method 12
1-2. Current Technologies for TPH Measurement 13
2-1. Summary of Technologies, Measurement Devices, and Device Developers 17
2-2. RemediAid™ Starter and Replenishment Kit Components 33
2-4. Infracal® TOG/TPH Analyzer, Models CVH and HATR-T Components 38
2-5. OCMA-350 Components 42
2-6. PetroFLAG™ Test Kit Method Detection Limits and Response Factors for Petroleum
Products Measured 45
2-7. PetroFLAG™ Test Kit Components 46
2-8. UVF-3100A Method Detection Limits 53
2-9. UVF-3100A Components 54
2-10. EnSys Petro Test System Method Detection Limits 59
2-11. EnSys Petro Test System Components 60
3-1. Summary of Site Characteristics 65
4-1. Demonstration Approach 76
4-2. Expected Method Detection Limits for Each Field Measurement Device 80
4-3. Action Levels to be Used to Evaluate Analytical Accuracy 81
4-4. Schedule for Innovative Total Petroleum Hydrocarbon Field Measurement Device
Demonstration Project 93
4-5. Field Activity Schedule for Demonstration 94
6-1. Demonstration Participants 108
7-1. Critical andNoncritical Measurements Ill
7-2. Sampling Depth Intervals, Sampling Parameters, and Associated Rationale 115
7-3. Environmental Samples 118
7-4. Performance Evaluation Samples 120
7-5. Sample Container, Preservation, and Holding Time Requirements 128
xvi
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Tables (Continued)
Table Page
8-1. Summary of Total Petroleum Hydrocarbon Field Measurement Device Calibration
Requirements 139
8-2. Response Factors for Common Hydrocarbons 141
8-3. Calibration Standards for Model HATR-T 143
8-4. Components of Calibration Standards 147
9-1. Laboratory Sample Preparation and Analytical Methods 152
9-2. Summary of Project-Specific Procedures for Gasoline Range Organic Analysis 153
9-3. Summary of Project-Specific Procedures for Extended Diesel Range Organic
Analysis 156
9-4. Summary of Laboratory Calibration Requirements 159
10-1. Reporting Limits for Reference Method, Field Measurement Device, and Sample
Collection Parameters 164
10-2. Internal Quality Control Checks, Frequencies, Acceptance Criteria, and Corrective
Actions for Reference Method, Field Measurement Device, and Sample Collection
Parameters 167
11-1. Activities to be Assessed During Field Sampling, Field Measurement, and Laboratory
Measurement Technical System Audits 179
12-1. Full Data Package Format for Gasoline Range Organic and Extended Diesel Range
Organic Analyses 188
13-1. Task Hazard Analysis 199
13-2. Demonstration Participant Responsibilities for Providing Material Safety Data Sheets 200
13-3. Site-Specific Air Monitoring Requirements and Action Levels 206
xvn
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Abbreviations, Acronyms, and Symbols
±
(im
%C
%R
AC
ACGIH
AEHS
AFB
AIHA
A1C13
API
ASTM
AZUR
bgs
BTEX
BVC
C
C6H6
Catalyst
ccv
CFC
CFR
CH2C12
CHEMetrics
CLP
cm
dBA
DC
DER
Dexsil®
DOT
Greater than
Greater than or equal to
Less than
Less than or equal to
Plus or minus
Wavelength
Microgram
Microliter
Micrometer
Percent completeness
Percent recovery
Alternating current
American Conference of Governmental Industrial Hygienists
Association for Environmental Health and Sciences
Air Force Base
American Industrial Hygiene Association
Aluminum chloride
American Petroleum Institute
American Society for Testing and Materials
AZUR Environmental Ltd
Below ground surface
Benzene, toluene, ethylbenzene, and xylene
Base Ventura County
Carbon
Benzene
Catalyst Information Resources, L.L.C.
Continuing calibration verification
Chlorofluorocarbon
Code of Federal Regulations
Dichloromethane
CHEMetrics, Inc.
Contract Laboratory Program
Centimeter
Decibel as measured on the A-weighted scale
Direct current
Data evaluation report
Dexsil® Corporation
U.S. Department of Transportation
xvin
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DRO
EDO
EDRO
ELISA
EPA
EPH
ERA
ESC
ESLI
FFA
FID
GC
GRO
HEPA
Horiba
HSR
IATA
ICV
ID
IDLH
IDW
Ig
ITVR
kg
L
LCS
LCSD
LEL
Luminoscope
m
MCAWW
MDL
mg
min
mL
mm
MMT
mRem/hr
MS
MSD
MSDS
MTBE
NA
NDIR
NERL
NEX
ng
NIOSH
NIST
nm
Diesel range organics
Electronic data deliverable
Extended diesel range organics
Enzyme-linked immunosorbent assay
U.S. Environmental Protection Agency
Extractable petroleum hydrocarbon
Environmental Resource Associates
Environmental Systems Corporation
End-of-service-life indicator
Fuel Farm Area
Flame ionization detector
Gas chromatograph
Gasoline range organics
High-efficiency particulate
Horiba Instruments, Incorporated
Health and safety representative
International Air Transport Association
Initial calibration verification
Inside diameter
Immediately dangerous to life or health
Investigation-derived waste
Immunoglobulin
Innovative technology verification report
Kilogram
Liter
Laboratory control sample
Laboratory control sample duplicate
Lower explosive limit
Synchronous Scanning Luminoscope
Meter
"Methods for Chemical Analysis of Water and Wastes"
Method detection limit
Milligram
Minute
Milliliter
Millimeter
Monitoring and Measurement Technology
Millirem per hour
Matrix spike
Matrix spike duplicate
Material safety data sheet
Methyl-tert-butyl ether
Not applicable
Nondispersive infrared
National Exposure Research Laboratory
Naval Exchange
Nanogram
National Institute for Occupational Safety and Health
National Institute for Standards and Technology
Nanometer
xix
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NRMRL
OCMA-350
ORD
OSHA
OSWER
PAH
PbSe
PC
PCB
PE
PEG
PEL
PetroFLAG™ test kit
PHC
PID
ppb
PPE
ppm
PRA
PRO
QA
QC
R2
RemediAid™ starter kit
RPD
RSD
SCBA
SDI
SFT
SITE
siteLAB®
ssc
STL Tampa East
SW-846
SWP
Tetra Tech
TLD
TLV
TMB
TPH
TSA
uses
UST
UVF-3100A
V
v/v
VGA
VOC
VPH
Wilks
National Risk Management Research Laboratory
OCMA-350 Oil Content Analyzer
Office of Research and Development
Occupational Safety and Health Administration
Office of Solid Waste and Emergency Response
Polynuclear aromatic hydrocarbon
Lead selenium
Petroleum company
Polychlorinated biphenyl
Performance evaluation
Polyethylene glycol
Permissible exposure limit
PetroFLAG™ Hydrocarbon Test Kit for Soil
Petroleum hydrocarbon
Photoionization detector
Part per billion
Personal protective equipment
Part per million
Phytoremediation Area
Petroleum range organics
Quality assurance
Quality control
Square of the correlation coefficient
RemediAid™ Total Petroleum Hydrocarbon Starter Kit
Relative percent difference
Relative standard deviation
Self-contained breathing apparatus
Strategic Diagnostics, Inc.
Slop Fill Tank
Superfund Innovative Technology Evaluation
siteLAB® Corporation
Site safety coordinator
Severn Trent Laboratories in Tampa, Florida
"Test Methods for Evaluating Solid Waste"
Safe work practice
Tetra Tech EM Inc.
Thermoluminescence detector
Threshold limit value
Tetramethylbenzidine
Total petroleum hydrocarbons
Technical system audit
Unified Soil Classification System
Underground storage tank
siteLAB® Analytical Test Kit UVF-3100A
Volume
Volume per volume
Volatile organic analysis
Volatile organic compound
Volatile petroleum hydrocarbon
Wilks Enterprise, Inc.
xx
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Acknowledgments
Tetra Tech EM Inc. acknowledges the support of the following individuals in preparing this
document: Dr. Stephen Billets and Mr. George Brilis of the U.S. Environmental Protection Agency's
(EPA) National Exposure Research Laboratory (NERL); Mr. Ernest Lory of Navy Base Ventura
County; Ms. Amy Whitley of Kelly Air Force Base; Mr. Jay Simonds of Handex of Indiana;
Mr. Henry Castaneda of CHEMetrics, Inc.; Ms. Sandy Rintoul of Wilks Enterprise, Inc.; Mr. Jim
Vance of Horiba Instruments, Incorporated; Dr. Ted B. Lynn of Dexsil® Corporation; Dr. George
Hyfantis of Environmental Systems Corporation; Mr. Stephen Greason of siteLAB® Corporation; and
Mr. Joseph Dautlick of Strategic Diagnostics, Inc.
This document was peer reviewed by Mr. John Glaser of the EPA National Risk Management
Research Laboratory, Mr. Gary Robertson of the EPA NERL, Dr. Roger Claff of the American
Petroleum Institute, Dr. Dominic DeAngelis of Exxon Mobil Corporation, Dr. Ileana Rhodes of
Equilon Enterprises, and Dr. Al Verstuyft of Chevron Research and Technology Company.
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Executive Summary
Performance verification of innovative environmental technologies is an integral part of the
regulatory and research mission of the U.S. Environmental Protection Agency (EPA). The Superfund
Innovative Technology Evaluation (SITE) Program was established by the EPA Office of Solid
Waste and Emergency Response and Office of Research and Development under the Superfund
Amendments and Reauthorization Act of 1986. The program is designed to meet three primary
objectives: (1) identify and remove obstacles to the development and commercial use of innovative
technologies, (2) demonstrate promising innovative technologies and gather reliable performance and
cost information to support site characterization and cleanup activities, and (3) develop procedures
and policies that encourage use of innovative technologies at Superfund sites as well as other waste
sites or commercial facilities. The intent of a SITE demonstration is to obtain representative, high-
quality performance and cost data on innovative technologies so that potential users can assess a
given technology's suitability for a specific application.
The demonstration of innovative field measurement devices for total petroleum hydrocarbons (TPH)
in soil is to be conducted under the SITE Program in June 2000 at the Navy Base Ventura County
site in Port Hueneme, California. The demonstration is being conducted under the Monitoring and
Measurement Technology Program, which is administered by the Environmental Sciences Division
of the EPA National Exposure Research Laboratory in Las Vegas, Nevada. The primary purpose of
the demonstration is to evaluate innovative field measurement devices for TPH in soil based
on comparison of their performance and cost to those of a conventional, off-site laboratory analytical
method.
The following seven field measurement devices will be demonstrated:
CHEMetrics, Inc.'s, RemediAid™ Total Petroleum Hydrocarbon Starter Kit
Wilks Enterprise, Inc.'s, Infracal® TOG/TPH Analyzer, Models CVH and HATR-T
• Horiba Instruments, Incorporated's, OCMA-350 Oil Content Analyzer
• Dexsil® Corporation's PetroFLAG™ Hydrocarbon Test Kit for Soil
• Environmental Systems Corporation's Synchronous Scanning Luminoscope
siteLAB® Corporation's Analytical Test Kit UVF-3100A
Strategic Diagnostics, Inc.'s, EnSys Petro Test System
The performance and cost of each device will be compared to those of a conventional, off-site
laboratory analytical method—that is, a reference method. The performance and cost of one device
will not be compared to those of another device. The reference method that will be used for the
demonstration is "Test Methods for Evaluating Solid Waste" (SW-846) Method 8015B (modified).
A separate innovative technology verification report (ITVR) will be prepared for each device.
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The demonstration has both primary and secondary objectives. The primary objectives are critical
to the technology evaluations and require use of quantitative results to draw conclusions regarding
technology performance. The secondary objectives pertain to information that is useful but do not
necessarily require use of quantitative results to draw conclusions regarding technology
performance. The primary objectives for the demonstration of the individual field measurement
devices are as follows:
PI. Determine the method detection limit
P2. Evaluate the accuracy and precision of TPH measurement for a variety of contaminated soil
samples
P3. Evaluate the effect of interferents on TPH measurement
P4. Evaluate the effect of soil moisture content on TPH measurement
P5. Measure the time required for TPH measurement
P6. Estimate costs associated with TPH measurement
The secondary objectives for the demonstration of the individual field measurement devices are as
follows:
S1. Document the skills and training required to properly operate the device
S2. Document health and safety concerns associated with operating the device
S3. Document the portability of the device
S4. Evaluate the device' s durability based on its materials of construction and engineering design
S5. Document the availability of the device and associated spare parts
To address the demonstration objectives, both environmental and performance evaluation (PE)
samples will be analyzed during the demonstration. The environmental samples will be collected
from five areas contaminated with gasoline, diesel, lubricating oil, or other petroleum products, and
the PE samples will be obtained from a commercial provider. Collectively, the environmental and
PE samples will have the range of physical (sand, silt, and clay) and chemical (petroleum
hydrocarbon type and concentration) characteristics necessary to properly evaluate the field
measurement devices.
Upon completion of the demonstration, field measurement device and reference method results will
be compared to evaluate the performance and associated cost of each device. The ITVRs for the
seven devices are scheduled for completion in October 2001.
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Chapter 1
Introduction
The U.S. Environmental Protection Agency (EPA) Office of Research and Development (ORD) National Exposure
Research Laboratory (NERL) has contracted with Tetra Tech EM Inc. (Tetra Tech) to conduct a demonstration of
innovative field measurement devices for total petroleum hydrocarbons (TPH) in soil. The demonstration is being
conducted as part of the EPA Superfund Innovative Technology Evaluation (SITE) Monitoring and Measurement
Technology (MMT) Program in June 2000 at Port Hueneme in California. The purpose of this demonstration is to
obtain reliable performance and cost data on the devices in order to provide (1) potential users with a better
understanding of the devices' performance and operating costs under well-defined field conditions and (2) the device
developers with documented results that will help them promote acceptance and use of their devices.
This demonstration plan describes the procedures that will be used to verify the performance and associated cost of
each field measurement device. The plan also incorporates the quality assurance and quality control (QA/QC)
elements needed to generate data of sufficient quality to document each device's performance and cost. This plan
has been prepared using the NERL's "A Guidance Manual for the Preparation of Site Characterization and Monitoring
Technology Demonstration Plans" (EPA 1996a) and in accordance with the EPA National Risk Management Research
Laboratory's (NRMRL) "Quality Assurance Project Plan Requirements for Applied Research Projects" (EPA 1998).
This demonstration plan describes the SITE Program, the scope of the demonstration, and the components and
definition of TPH (Chapter 1); the seven innovative TPH field measurement devices that will be demonstrated and
the technologies that they are based on (Chapter 2); the three demonstration sites (Chapter 3); the demonstration
approach (Chapter 4); the reference method and laboratory that will be used during the demonstration (Chapter 5);
the demonstration organization and responsibilities (Chapter 6); the field sampling procedures (Chapter 7); the
calibration requirements and sample management procedures for the devices (Chapter 8); the laboratory sample
preparation and analytical methods, calibration requirements, and sample management procedures (Chapter 9); the
QA/QC procedures (Chapter 10); the audits and associated corrective actions (Chapter 11); the data management
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procedures (Chapter 12); the health and safety procedures (Chapter 13); and the references used to prepare this
demonstration plan (Chapter 14).
1.1 Description of SITE Program
Performance verification of innovative environmental technologies is an integral part of the regulatory and research
mission of the EPA. The SITE Program was established by the EPA Office of Solid Waste and Emergency Response
(OSWER) and ORD under the Superfund Amendments and Reauthorization Act of 1986. The overall goal of the
SITE Program is to conduct performance verification studies and to promote the acceptance of innovative
technologies that may be used to achieve long-term protection of human health and the environment. The program
is designed to meet three primary objectives: (1) identify and remove obstacles to the development and commercial
use of innovative technologies, (2) demonstrate promising innovative technologies and gather reliable performance
and cost information to support site characterization and cleanup activities, and (3) develop procedures and policies
that encourage use of innovative technologies at Superfund sites as well as at other waste sites or commercial
facilities.
The intent of a SITE demonstration is to obtain representative, high-quality performance and cost data on one or more
innovative technologies so that potential users can assess a given technology's suitability for a specific application.
The SITE Program includes the following elements:
MMT Program—Evaluates technologies that sample, detect, monitor, or measure hazardous and toxic
substances. These technologies are expected to provide better, faster, or more cost-effective methods for
producing real-time data during site characterization and remediation studies than do conventional
technologies.
Remediation Technology Program—Conducts demonstrations of innovative treatment technologies to
provide reliable performance, cost, and applicability data for site cleanups.
Technology Transfer Program—Provides and disseminates technical information in the form of updates,
brochures, and other publications that promote the SITE Program and participating technologies. The
Technology Transfer Program also offers technical assistance, training, and workshops to support the
technologies. A significant number of these activities are performed by EPA's Technology Innovation
Office.
The TPH field measurement device demonstration is being conducted as part of the MMT Program, which provides
developers of innovative hazardous waste sampling, monitoring, and measurement technologies with an opportunity
to demonstrate their devices' performance under actual field conditions. These devices may be used to sample,
detect, monitor, or measure hazardous and toxic substances in water, soil, soil gas, and sediment. The technologies
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include chemical sensors for in situ (in place) measurements, groundwater samplers, soil and sediment samplers, soil
gas samplers, field-portable analytical equipment, and other systems that support field sampling or data acquisition
and analysis.
The MMT Program promotes acceptance of technologies that can be used to (1) accurately assess the degree of
contamination at a site, (2) provide data to evaluate potential effects on human health and the environment, (3) apply
data to assist in selecting the most appropriate cleanup action, and (4) monitor the effectiveness of a remediation
process. The program places a high priority on innovative technologies that provide more cost-effective, faster, or
safer methods for producing real-time or near-real-time data than do conventional, laboratory-based technologies.
These innovative technologies are demonstrated under field conditions, and the results are compiled, evaluated,
published, and disseminated by the ORD. The primary objectives of the MMT Program are as follows:
• Test and verify the performance of field sampling and analytical technologies that enhance sampling,
monitoring, and site characterization capabilities
Identify performance attributes of innovative technologies to address field sampling, monitoring, and
characterization problems in a more cost-effective and efficient manner
• Prepare protocols, guidelines, methods, and other technical publications that enhance acceptance of these
technologies for routine use
The MMT Program is administered by the Environmental Sciences Division of the NERL in Las Vegas, Nevada. The
NERL is the EPA's center for investigation of technical and management approaches for identifying and quantifying
risks to human health and the environment. The NERL's mission components include (1) developing and evaluating
methods and technologies for sampling, monitoring, and characterizing water, air, soil, and sediment; (2) supporting
regulatory and policy decisions; and (3) providing the technical support needed to ensure effective implementation
of environmental regulations and strategies. By demonstrating selected innovative field measurement devices for TPH
in soil, the MMT Program is supporting the development and evaluation of methods and technologies for field
measurement of TPH concentrations in a variety of soil types.
The MMT Program's technology verification process is designed to conduct demonstrations that will generate high-
quality data so that potential users have reliable information regarding the device performance and cost. Four steps
are inherent in the process: (1) needs identification and technology selection, (2) demonstration planning and
implementation, (3) report preparation, and (4) information distribution.
The first step of the technology verification process begins with identifying technology needs of the EPA and
regulated community. The EPA regional offices, the U.S. Department of Energy, the U.S. Department of Defense,
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industry, and state environmental regulatory agencies are asked to identify technology needs for sampling,
measurement, and monitoring of environmental media. Once a need is identified, a search is conducted to identify
suitable technologies that will address the need. The technology search and identification process consists of
examining industry and trade publications, attending related conferences, exploring leads from technology developers
and industry experts, and reviewing responses to Commerce Business Daily announcements. Selection of technologies
for field testing includes evaluation of the candidate technologies based on several criteria. A suitable technology
for field testing
• Is designed for use in the field
• Is applicable to a variety of environmentally contaminated sites
• Has potential for solving problems that current methods cannot satisfactorily address
• Has estimated costs that are lower than those of conventional methods
• Is likely to achieve better results than current methods in areas such as data quality and turnaround time
• Uses techniques that are easier or safer than current methods
• Is commercially available
Once candidate technologies are identified, their developers are asked to participate in a developer conference. This
conference gives the developers an opportunity to describe their technologies' performance and to learn about the
MMT Program.
The second step of the technology verification process is to plan and implement a demonstration that will generate
high-quality data to assist potential users in selecting a technology. Demonstration planning activities include a
predemonstration sampling and analysis investigation that assesses existing conditions at the proposed demonstration
site or sites. The objectives of the predemonstration investigation are to (1) confirm available information on
applicable physical, chemical, and biological characteristics of contaminated media at the sites to justify selection of
site areas for the demonstration; (2) provide the technology developers with an opportunity to evaluate the areas,
analyze representative samples, and identify logistical requirements; (3) assess the overall logistical requirements for
conducting the demonstration; and (4) provide the reference laboratory involved with an opportunity to identify any
matrix-specific analytical problems associated with the contaminated media and to propose appropriate solutions.
Information generated through the predemonstration investigation is used to develop the final demonstration design
and sampling and analysis procedures.
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Demonstration planning activities also include preparation of a demonstration plan that describes the procedures to
be used to verify the performance and cost of each innovative technology. The demonstration plan incorporates
information generated during the predemonstration investigation as well as input from technology developers,
demonstration site representatives, and technical peer reviewers. The demonstration plan also incorporates the
QA/QC elements needed to produce data of sufficient quality to document the performance and cost of each
technology.
During the demonstration, each innovative technology is evaluated independently and, when possible and appropriate,
is compared to a reference technology. The performance and cost of one innovative technology are not compared to
those of another technology evaluated in the demonstration. Rather, demonstration data are used to evaluate the
performance, cost, advantages, limitations, and field applicability of each technology.
As part of the third step of the technology verification process, the EPA publishes a verification statement and a
detailed evaluation of each technology in an innovative technology verification report (ITVR). To ensure its quality,
the ITVR is published only after comments from the technology developer and external peer reviewers are
satisfactorily addressed. All demonstration data used to evaluate each innovative technology are summarized in adata
evaluation report (DER) that constitutes a complete record of the demonstration. The DER is not published as an EPA
document, but an unpublished copy may be obtained from the EPA project manager.
The fourth step of the verification process is to distribute demonstration information. To benefit technology
developers and potential technology users, the EPA distributes demonstration bulletins and ITVRs through direct
mailings, at conferences, and on the Internet. ITVRs and additional information on the SITE Program are available
on the EPA ORD web site (http://www.epa.gov/ORD/SITE).
1.2 Scope of Demonstration
The purpose of the demonstration is to evaluate innovative field measurement devices for TPH in soil in order to
provide (1) potential users with a better understanding of each device's performance and cost under well-defined field
conditions and (2) developers with documented results that will assist them in promoting acceptance and use of their
devices.
Chapter 2 describes the field measurement devices that will be evaluated during the demonstration. Because TPH
is a "method-defined parameter," the performance results for each device will be compared to the results obtained
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using an off-site laboratory measurement method—that is, an approved reference method. Details on the selection
of the reference method and laboratory are provided in Chapter 5.
The demonstration has both primary and secondary objectives. Primary objectives are critical to the technology
verification and required use of quantitative results. Secondary objectives pertain to information that is useful but
will not necessarily require the use of quantitative results. Both the primary and secondary objectives are presented
in Chapter 4.
To meet the demonstration objectives, samples will be collected from five individual areas at three sites. The first
site is referred to as the Navy Base Ventura County (BVC) site; is located in Port Hueneme, California; and contains
three sampling areas. The Navy BVC site lies in EPA Region 9. The second site is referred to as the Kelly Air Force
Base (AFB) site; is located in San Antonio, Texas; and contains one sampling area. The Kelly AFB site lies in EPA
Region 6. The third site is referred to as the petroleum company (PC) site, is located in north-central Indiana, and
contains one sampling area. The PC site lies in EPA Region 5.
In preparation for the demonstration, a predemonstration sampling and analysis investigation was completed at the
three sites in January 2000. The purpose of this investigation was to assess whether the sites and sampling areas were
appropriate for evaluating the field measurement devices based on the demonstration objectives. Demonstration field
activities are scheduled to occur between June 5 and 18,2000. Draft ITVRs will be available for peer and developer
review in March 2001, and final ITVRs will be submitted to the EPA in October 2001.
1.3 Components and Definition of TPH
To understand the term "TPH," it is necessary to understand the composition of petroleum and its products. This
section briefly describes the composition of petroleum and its products and defines TPH from a measurement
standpoint. The organic compounds containing only hydrogen and carbon that are present in petroleum and its
derivatives are collectively referred to as petroleum hydrocarbons (PHC). Therefore, in this demonstration plan, the
term "PHC" is used to identify sample constituents, and the term "TPH" is used to identify analyses performed and
the associated results (for example, TPH concentrations).
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1.3.1 Composition of Petroleum and Its Products
Petroleum is essentially amixture of gaseous, liquid, and solid hydrocarbons that occur in sedimentary rock deposits.
On the molecular level, petroleum is a complex mixture of hydrocarbons; organic compounds of sulfur, nitrogen, and
oxygen; and compounds containing metallic constituents, particularly vanadium, nickel, iron, and copper. Based on
the limited data available, the elemental composition of petroleum appears to vary over a relatively narrow range: 83
to 87 percent carbon, 10 to 14 percent hydrogen, 0.05 to 6 percent sulfur, 0.1 to 2 percent nitrogen, and 0.05 to 1.5
percent oxygen. Metals are present in petroleum at concentrations of up to 0.1 percent (Speight 1991).
Petroleum in the crude state (crude oil) is a mineral resource, but when refined, it provides liquid fuels, solvents,
lubricants, and many other marketable products. The hydrocarbon components of crude oil include paraffmic,
naphthenic, and aromatic groups. Paraffins (alkanes) are saturated, aliphatic hydrocarbons with straight or branched
chains but without any ring structure. Naphthenes are saturated, aliphatic hydrocarbons containing one or more rings,
each of which may have one or more paraffmic side chains (alicyclic hydrocarbons). Aromatic hydrocarbons contain
one or more aromatic nuclei, such as benzene, naphthalene, and phenanthrene ring systems, that may be linked with
(substituted) naphthenic rings or paraffmic side chains. In crude oil, the relationship among the three primary groups
of hydrocarbon components is a result of hydrogen gain or loss between any two groups. Another class of compounds
that is present in petroleum products such as automobile gasoline but rarely in crude oil is known as olefins. Olefins
(alkenes) are unsaturated, aliphatic hydrocarbons with straight or branched chains but without any ring structure.
The distribution of paraffins, naphthenes, and aromatic hydrocarbons depends on the source of crude oil. For
example, Pennsylvania crude oil contains high levels of paraffins (about 50 percent), whereas Borneo crude oil
contains less than 1 percent paraffins. As shown in Figure 1-1, the proportion of straight or branched paraffins
decreases with increasing molecular weight or boiling point fraction for a given crude oil; however, this is not true
for naphthenes or aromatic hydrocarbons. The proportion of monocyclonaphthenes decreases with increasing
molecular weight or boiling point fraction, whereas the opposite is true for polycyclonaphthenes and polynuclear
aromatic hydrocarbons (PAH); the proportion of mononuclear aromatic hydrocarbons appears to be independent of
molecular weight or boiling point fraction.
Various petroleum products consisting of carbon and hydrogen are formed when crude oil is subjected to distillation
and other processes in a refinery. Processing of crude oil results in petroleum products with trace quantities of metals
and organic compounds that contain nitrogen, sulfur, and oxygen. These products include liquefied petroleum gas,
gasoline, naphthas, kerosene, fuel oils, lubricating oils, coke, waxes, and asphalt. Of these products, gasoline,
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0
Lighter oils
> Increasing nitrogen, oxygen, sulfur, and metal content
>• Heavier oils and residues
Polynuclear aromatic hydrocarbons
Mononuclear aromatic hydrocarbons
Monocyclonaphtnenes
Polycyclonaphthenes
Straight and branched paraffins
0
100
200 300
Boiling point, °C
Source: Speight 1991
Figure 1-1. Distribution of various petroleum hydrocarbon types throughout boiling point range of crude oil.
500
naphthas, kerosene, fuel oils, and lubricating oils are liquids and may be present at petroleum-contaminated sites.
Except for gasoline and some naphthas, these products are made primarily by collecting particular boiling point
fractions of crude oil from a distillation column. Because this classification of petroleum products is based on boiling
point and not on chemical composition, the composition of these products, including the ratio of aliphatic to aromatic
hydrocarbons, varies depending on the source of crude oil. In addition, specific information (such as boiling points
and carbon ranges) for different petroleum products, varies slightly depending on the source of the information.
Commonly encountered forms and blends of petroleum products are briefly described below. The descriptions are
primarily based on information in books written by Speight (1991) and Gary and Handwerk (1993). Additional
information is provided by Dryoff (1993).
1.3.1.1
Gasoline
Gasoline is a major exception to the boiling point classification described above because "straight-run gasoline"
(gasoline directly recovered from a distillation column) is only a small fraction of the blended gasoline that is
commercially available as fuel. Commercially available gasolines are complex mixtures of hydrocarbons that boil
below 180 °C or at most 200 °C and that contain hydrocarbons with 4 to 12 carbon atoms per molecule. Of the
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commercially available gasolines, aviation gasoline has a narrower boiling range (38 to 170 °C) than automobile
gasoline (-1 to 200 °C). In addition, aviation gasoline may contain high levels of paraffins (50 to 60 percent),
moderate levels of naphthenes (20 to 30 percent), a low level of aromatic hydrocarbons (10 percent), and no olefins,
whereas automobile gasoline may contain up to 30 percent olefins and up to 40 percent aromatic hydrocarbons.
Gasoline composition can vary widely depending on the source of crude oil. In addition, gasoline composition varies
from region to region because of consumer needs for gasoline with a high octane rating to prevent engine "knocking."
Moreover, EPA regulations regarding the vapor pressure of gasoline, the chemicals used to produce a high octane
rating, and cleaner-burning fuels have affected gasoline composition. For example, when use of tetraethyl lead to
produce gasoline with a high octane rating was banned by the EPA, oxygenated fuels came into existence. Production
of these fuels included addition of methyl-tert-butyl ether (MTBE), ethanol, and other oxygenates. Use of oxygenated
fuels also results in reduction of air pollutant emissions (for example, carbon monoxide and nitrogen oxides).
1.3.1.2 Naphthas
"Naphtha" is a generic term applied to petroleum solvents. Under standardized distillation conditions, at least
10 percent of naphthas should distill below 175 °C, and at least 95 percent of naphthas should distill below 240 °C.
Naphthas can be both aliphatic and aromatic and contain hydrocarbons with 6 to 12 carbon atoms per molecule.
Depending on the intended use of a naphtha, it may be free of aromatic hydrocarbons (to make it odor-free) and sulfur
(to make it less toxic). Many forms of naphthas are commercially available, including Varnish Makers' and Painters'
naphthas (Types I and II), mineral spirits (Types I through IV), and aromatic naphthas (Types I and II). Stoddard
solvent, a commonly used dry cleaning solvent, is an example of an aliphatic naphtha.
1.3.1.3 Kerosene
Kerosene is a straight-run petroleum fraction that has a boiling point range of 205 to 260 °C. Kerosene typically
contains hydrocarbons with 12 or more carbon atoms per molecule. Because of its use as an indoor fuel, kerosene
must be free of aromatic and unsaturated hydrocarbons as well as sulfur compounds.
1.3.1.4 Jet Fuels
Jet fuels, which are also known as aircraft turbine fuels, are manufactured by blending gasoline, naphtha, and
kerosene in varying proportions. Therefore, jet fuels may contain a carbon range that covers gasoline through
kerosene. Jet fuels are used in both military and commercial aircraft. Some examples of jet fuels include Type A,
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Type A-l, Type B, JP-4, JP-5, and JP-8. The aromatic hydrocarbon content of these fuels ranges from 20 to
25 percent. The military jet fuel JP-4 has a wide boiling point range (65 to 290 °C), whereas commercial jet fuels,
including JP-5 and Types A and A-l, have a narrower boiling point range (175 to 290 °C) because of safety
considerations. Increasing concerns over combat hazards associated with JP-4 jet fuel led to development of JP-8 jet
fuel, which has a flash point of 38 °C and a boiling point range of 165 to 275 °C. JP-8 jet fuel contains hydrocarbons
with 9 to 15 carbon atoms per molecule. Type B j et fuel has a boiling point range of 5 5 to 23 0 °C and a carbon range
of 5 to 13 atoms per molecule. A new specification is currently being developed by the American Society for Testing
and Materials (ASTM) for Type B jet fuel.
1.3.1.5 Fuel Oils
Fuel oils are divided into two classes: distillates and residuals. No. 1 and 2 fuel oils are distillates and include
kerosene, diesel, and home heating oil. No. 4, 5, and 6 fuel oils are residuals or black oils, and they all contain crude
distillation tower bottoms (tar) to which cutter stocks (semirefmed or refined distillates) have been added. No. 4 fuel
oil contains the most cutter stock, and No. 6 fuel oil contains the least.
Commonly available fuel oils include No. 1,2,4, 5, and 6. The boiling points, viscosities, and densities of these fuel
oils increase with increasing number designation. The boiling point ranges for No. 1, 2, and 4 fuel oils are about 180
to 320, 175 to 340, and 150 to 480 °C, respectively. No. 1 and 2 fuel oils contain hydrocarbons with 10 to 22 carbon
atoms per molecule; the carbon range for No. 4 fuel oil is 22 to 40 atoms per molecule. No. 5 and 6 fuel oils have
a boiling point range of 150 to 540 °C but differ in the amounts of residue they contain: No. 5 fuel oil contains a small
amount of residue, whereas No. 6 fuel oil contains a large amount. No. 5 and 6 fuel oils contain hydrocarbons with
28 to 90 carbon atoms per molecule. Fuel oils typically contain about 60 percent aliphatic hydrocarbons and 40
percent aromatic hydrocarbons.
1.3.1.6 Diesel
Diesel is primarily used to operate motor vehicle and railroad diesel engines. Automobile diesel is available in two
grades: No. 1 and 2. No. 1 diesel has a boiling point range of 180 to 320 °C and a cetane number above 50. The
cetane number is similar to the octane number of gasoline; a higher number corresponds to less knocking. No. 2
diesel is very similar to No. 2 fuel oil. No. 2 diesel has a boiling point range of 175 to 340 °C and a minimum cetane
number of 52. No. 1 diesel is used in high-speed engines such as truck and bus engines, whereas No. 2 diesel is used
in other diesel engines. Railroad diesel is similar to No. 2 diesel but has a higher boiling point (up to 370 °C) and
10
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lower cetane number (40 to 45). The ratio of aliphatic to aromatic hydrocarbons in diesel is about 5. The carbon
range for hydrocarbons present in diesel is 10 to 28 atoms per molecule.
1.3.1.7 Lubricating Oils
Lubricating oils can be distinguished from other crude oil fractions by their high boiling points (greater than 400 °C)
and viscosities. Materials suitable for production of lubricating oils are composed principally of hydrocarbons
containing 25 to 35 or even 40 carbon atoms per molecule, whereas residual stocks may contain hydrocarbons with
50 to 60 or more (up to 80 or so) carbon atoms per molecule. Because it is difficult to isolate hydrocarbons from the
lubricant fraction of petroleum, aliphatic to aromatic hydrocarbon ratios are not well documented for lubricating oils.
However, these ratios are expected to be comparable to those of the source crude oil.
1.3.2 Measurement of TPH
As described in Section 1.3.1, the composition of petroleum and its products is complex and variable, which
complicates TPH measurement. The measurement of TPH in soil is further complicated by weathering effects. When
a petroleum product is released to soil, the product's composition immediately begins to change. The components
with lower boiling points are volatilized, the more water-soluble components migrate to groundwater, and
biodegradation can affect many other components. Within a short period, the contamination remaining in soil may
have only some characteristics in common with the parent product.
This section provides a historical perspective on TPH measurement, reviews current options for TPH measurement
in soil, and discusses the definition of TPH that was used for the demonstration.
1.3.2.1 Historical Perspective
Most environmental measurements are focused on identifying and quantifying a particular trace element (such as
lead) or organic compound (such as benzene). However, for some "method-defined" parameters, the particular
substance being measured may yield different results depending on the measurement method used. Examples of such
parameters include oil and grease and surfactants. Perhaps the most problematic of the method-defined parameters
is TPH. TPH arose as a parameter for wastewater analyses in the 1960s because of petroleum industry concerns that
the original "oil and grease" analytical method, which is gravimetric in nature, might inaccurately characterize
petroleum industry wastewaters that contained naturally occurring vegetable oils and greases along with PHCs.
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These naturally occurring materials are typically long-chain fatty acids (for example, oleic acid, the major component
of olive oil).
Originally, TPH was defined as any material extracted with a particular solvent that is not adsorbed by the silica gel
used to remove fatty acids and that is not lost when the solvent is evaporated. Although this definition covers most
of the components of petroleum products, it includes many other organic compounds as well, including chlorinated
solvents, pesticides, and other synthetic organic chemicals. Furthermore, because of the evaporation step in the
gravimetric analytical method, the definition excludes most of the petroleum-derived compounds in gasoline that are
volatile in nature. For these reasons, an infrared analytical method was developed to measure TPH. In this method,
a calibration standard consisting of three components is analyzed at a wavelength of 3.41 micrometers ((im), which
corresponds to an aliphatic CH2 hydrocarbon stretch. As shown in Table 1-1, the calibration standard is designed to
mimic a petroleum product having a relative distribution of aliphatic and aromatic compounds as well as a certain
percentage of aliphatic CH2 hydrocarbons. The infrared analytical method indicates that any compound that is
extracted by the solvent, is not absorbed by silica gel, and contains a CH2 bond is a PHC. Both the gravimetric and
infrared analytical methods include a silica gel fractionation step to remove polar, biogenic compounds such as fatty
acids, but this cleanup step can also remove some petroleum degradation products that are polar in nature.
Table 1-1. Summary of Calibration Information for Infrared Analytical Method
Standard
Constituent
Hexadecane
Isooctane
Chlorobenzene
Constituent Type
Straight-chain aliphatic
Branched-chain aliphatic
Aromatic
Portion of Constituent
in Standard
(percent by volume)
37.5
37.5
25
Number of Carbon Atoms
Aliphatic
CH3
2
5
0
CH2
14
1
0
CH
0
1
0
Aromatic
CH
0
0
5
Average
Portion of Aliphatic CH2 in
Standard Constituent
(percent by weight)
91
14
0
35
In the 1980s, because of the change in focus from wastewater analyses to characterization of hazardous waste sites
that contained contaminated soil, many parties began to adapt the existing wastewater analytical methods for
application to soil. Unfortunately, the term "TPH" was in common use, as many states had adopted this term
(and the wastewater analytical methods) for cleanup activities at underground storage tank (UST) sites. Despite
efforts by the American Petroleum Institute (API) and others to establish new analyte names (for example, gasoline
range organics [GRO] and diesel range organics [DRO]), "TPH" is still present in many state regulations as a
somewhat ill-defined term, and most state programs still have cleanup criteria for TPH.
12
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1.3.2.2
Current Options for TPH Measurement in Soil
Three widely used technologies measure some form of TPH in soil to some degree. These technologies were used
as starting points in deciding how to define TPH for the demonstration. The three technologies and the analytes
measured are summarized in Table 1-2.
Table 1-2. Current Technologies for TPH Measurement
Technology
Gravimetry
Infrared
Gas chromatograph/flame ionization
detector
What Is Measured
All analytes removed from the sample by the
extraction solvent that are not volatilized
All analytes removed from the sample by the
extraction solvent that contain an aliphatic CH2 stretch
All analytes removed from the sample by the
extraction solvent that can be chromatographed and
that respond to the detector
What Is Not Measured
Volatiles; very polar organics
Benzene, naphthalene, and other aromatic
hydrocarbons with no aliphatic group attached;
very polar organics
Very polar organics; compounds with high
molecular weights or high boiling points
Of the three technologies, gravimetry and infrared are discussed in Section 1.3.2.1. The third technology, the gas
chromatograph/flame ionization detector (GC/FID), came into use because of the documented shortcomings of the
other two technologies. The GC/FID had long been used in the petroleum refining industry as a product QC tool to
determine the boiling point distribution of pure petroleum products. In the 1980s, environmental laboratories began
to apply this technology along with sample preparation methods developed for soil samples to measure PHCs at
environmental levels (Zilis, McDevitt, and Parr 1988). GC/FID methods measure all organic compounds that are
extracted by the solvent and that can be chromatographed. However, because of method limitations, the very volatile
portion of gasoline compounds containing four or five carbon atoms per molecule is not addressed by GC/FID
methods; therefore, 100 percent recovery cannot be achieved for pure gasoline. This omission is not considered
significant because these low-boiling-point aliphatic compounds (1) are not expected to be present in environmental
samples (because of volatilization) and (2) pose less environmental risk than the aromatic hydrocarbons in gasoline.
The primary limitation of GC/FID methods relates to the extraction solvent used. The solvent should not interfere
with the analysis, but to achieve environmental levels of detection (in the low milligram per kilogram [mg/kg] range)
for soil, some concentration of the extract is needed because the sensitivity of the FID is in the nanogram (ng) range.
This limitation has resulted in three basic approaches for GC/FID analyses for GRO, DRO, and PHCs.
For GRO analysis, a GC/FID method was developed as part of research sponsored by API and was the subject of an
interlaboratory validation study (API 1994); the method was first published in 1990. In this method, GRO is defined
as the sum of the organic compounds in the boiling point range of 60 to 170 °C, and the method uses a synthetic
13
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calibration standard as both a window-defining mix and a quantitation standard. The GRO method was specifically
incorporated into the EPA's "Test Methods for Evaluating Solid Waste" (SW-846) Method 8015B in 1996 (EPA
1996). The GRO method uses the purge-and-trap technique for sample preparation, effectively limiting the TPH
components to the volatile compounds only.
For DRO analysis, a GC/FID method was developed under the sponsorship of API as a companion to the GRO
method and was interlaboratory-validated in 1994. In the DRO method, DRO is defined as the sum of the organic
compounds in the boiling point range of 170 to 430 °C. As in the GRO method, a synthetic calibration standard is
used for quantitation. The DRO method was also incorporated into SW-846 Method 8015B in 1996. The technology
used in the DRO method can measure hydrocarbons with boiling points up to 540 °C. However, the hydrocarbons
with boiling points in the range of 430 to 540 °Care specifically excluded from SW-846 Method 8015B so as not to
include the higher-boiling-point petroleum products. The DRO method uses a solvent extraction and concentration
step, effectively limiting the method to nonvolatile hydrocarbons.
For PHC analysis, a GC/FID method was developed by Shell Oil Company (now Equilon Enterprises). This method
was interlaboratory-validated along with the GRO and DRO methods in an API study in 1994. The PHC method
originally defined PHCs as the sum of the compounds in the boiling point range of about 70 to 400 °C, but it now
defines PHCs as the sum of the compounds in the boiling point range of 70 to 490 °C. The method provides options
for instrument calibration, including use of synthetic standards, but it recommends use of products similar to the
contaminants present at the site of concern. The PHC method has not been specifically incorporated into SW-846;
however, the method has been used as the basis for the TPH methods in several states, including Massachusetts,
Washington, and Texas. The PHC method uses solvent microextraction and thus has a higher detection limit than
the GRO and DRO methods. The PHC method also begins peak integration after elution of the solvent peak for n-
pentane. Thus, this method probably cannot measure some volatile compounds (for example, 2-methyl pentane and
MTBE) that are measured using the GRO method.
1.3.2.3 Definition of TPH
It is not possible to establish a definition of TPH that would include crude oil and its refined products and exclude
other organic compounds. Rather, the TPH definition selected for the demonstration is intended to
Include compounds that are PHCs, such as paraffins, naphthenes, and aromatic hydrocarbons
Include, to the extent possible, the major petroleum products (gasoline, naphthas, kerosene, jet fuels, fuel
oils, diesel, and lubricating oils)
14
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• Have little inherent bias based on the composition of an individual manufacturer's product
• Have little inherent bias based on the relative concentrations of aliphatic and aromatic hydrocarbons present
• Include much of the volatile portion of gasoline, including all weathered gasoline
Include MTBE
• Exclude crude oil residuals beyond the extended diesel organic (EDRO) range
• Exclude nonpetroleum organic compounds (for example, chlorinated solvents, pesticides, polychlorinated
biphenyls [PCB], and naturally occurring oils and greases)
Allow TPH measurement using a widely accepted method
Reflect accepted TPH measurement practice in many states
Several states, including Massachusetts, Alaska, Louisiana, and North Carolina, have implemented or are planning
to implement a TPH contamination cleanup approach based on the aliphatic and aromatic hydrocarbon fractions of
TPH. The action levels for the aromatic hydrocarbon fraction are more stringent than those for the aliphatic
hydrocarbon fraction. The approach used in these states involves performing a sample fractionation procedure and
two analyses to determine the aliphatic and aromatic hydrocarbon concentrations in a sample. However, in most
applications of this approach, only a few samples are subjected to the determination of aliphatic and aromatic
hydrocarbon concentrations because of the cost associated with performing sample cleanup and two analyses.
For the demonstration, TPH is not defined based on the aliphatic and aromatic hydrocarbon fractions because
• Such a definition is used in only a few states.
• Variations exist among the sample fractionation and analysis procedures used in different states.
• The repeatability and versatility of sample fractionation and analysis procedures are not well documented.
• In some states, TPH-based action levels are still used.
• The associated analytical costs are high.
As stated in Section 1.3.2.2, analytical methods currently available for measurement of TPH each exclude some
portion of TPH and are unable to measure TPH alone while excluding all other organic compounds, thus making TPH
a method-defined parameter. After consideration of all the information presented above, the GRO and DRO
analytical methods were selected for TPH measurement for the demonstration. However, because of the general
interest in higher-boiling-point petroleum products, the integration range of the DRO method was extended to include
15
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compounds with boiling points up to 540 °C. Thus, for the demonstration, the TPH concentration is the sum of all
organic compounds that have boiling points between 60 and 540 °C and that can be chromatographed, or the sum of
the results obtained using the GRO and DRO methods. This approach accounts for most gasoline, including MTBE,
and virtually all other petroleum products and excludes a portion (25 to 50 percent) of the heavy lubricating oils.
Thus, TPH measurement for the demonstration includes PHCs as well as some organic compounds that are not PHCs.
More specifically, TPH measurement does not exclude nonpetroleum organic compounds such as chlorinated
solvents, other synthetic organic chemicals such as pesticides and PCBs, and naturally occurring oils and greases.
A silica gel fractionation step used to remove polar, biogenic compounds such as fatty acids in some GC/FID methods
is not included in the sample preparation step because, according to the State of California, this step can also remove
some petroleum degradation products that are also polar in nature (California Environmental Protection Agency
1999). The step-by-step approach used to select the reference method for the demonstration and the project-specific
procedures implemented for soil sample preparation and analysis using the reference method are detailed in
Chapter 5.
16
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Chapter 2
Innovative Technology and Field Measurement Device Descriptions
This chapter describes the seven innovative TPH field measurement devices that will be demonstrated and the
technologies upon which they are based. Table 2-1 identifies the technologies, devices, and device developers.
Table 2-1. Summary of Technologies, Measurement Devices, and Device Developers
Technology
Measurement Device
Measurement Device Developer
Friedel-Crafts alkylation reaction and
colorimetry
Infrared analysis
Emulsion turbidimetry
Ultraviolet fluorescence spectroscopy
Immunoassay and colorimetry
RemediAid™ Total Petroleum Hydrocarbon Starter Kit
Infracal® TOG/TPH Analyzer, Models CVH and HATR-T
OCMA-350 Oil Content Analyzer
PetroFLAG™ Hydrocarbon Test Kit for Soil
Synchronous Scanning Luminoscope
siteLAB® Analytical Test Kit UVF-3100A
EnSys Petro Test System
CHEMetrics, Inc., and
AZUR Environmental Ltd
Wilks Enterprise, Inc.
Horiba Instruments, Incorporated
Dexsil® Corporation
Environmental Systems Corporation
siteLABiB Corporation
Strategic Diagnostics, Inc.
The performance results generated during the demonstration of each device will be compared to the results obtained
using a modified, off-site laboratory measurement method—that is, a reference method. For the demonstration, the
reference method for measuring TPH is based on SW-846 Method 8015B (EPA 1996). First, soil samples will be
extracted using (1) SW-846 Methods 5030B and 5035 for GRO and (2) SW-846 Method 3540C for extended diesel
range organics (EDRO), as appropriate. The extracts will then be analyzed for GRO and EDRO using SW-846
Method 8015B (modified). The GRO and EDRO concentrations thus obtained will be summed to estimate the TPH
concentration. Chapter 9 further discusses the SW-846 methods that will be used for the demonstration.
Section 2.1 describes the technologies upon which the devices are based, and Section 2.2 describes the devices that
will be demonstrated. The technology and device descriptions presented in this chapter will be used to evaluate the
developers' field activities during the demonstration.
17
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2.1 Technology Descriptions
This section describes the technologies upon which the field measurement devices are based. In general, TPH
measurement by these devices involves extraction of PHCs in soil using an appropriate solvent followed by
measurement of the TPH concentration in the extract using an optical method. The extraction solvent is selected such
that it will not interfere with the optical measurement of TPH in the extract. Some of the devices use light in the
visible wavelength range, and others use light outside the visible wavelength range (for example, infrared). The
wavelength range that each device uses is illustrated in Figure 2-1. Use of visible light to measure TPH
concentrations requires development of a color whose intensity is a measure of TPH concentration. For
measurements that do not us visible light, color development is not required.
The optical measurements made by the devices involve absorbance, reflectance, or fluorescence. In general, the
optical measurement for a soil extract is compared to a calibration curve in order to determine the TPH concentration.
Calibration curves are developed by (1) using a series of calibration standards selected based on the type of PHCs
being measured at a site or (2) establishing a correlation between off-site laboratory measurements and field
measurements for selected, site-specific soil samples.
The technology descriptions presented below are not intended to provide complete operating procedures for
measuring TPH concentrations in soil using the devices. For example, soil sample extraction procedures are not
discussed in this section because the soil extraction step is common to all the devices, although different solvents may
be used for extraction. Detailed operating procedures for the devices, including soil extraction procedures, are
presented in Section 2.2.
2.1.1 Friedel- Crafts A Ikylation Reaction and Colorimetry
TPH measurement in soil using the RemediAid™ Total Petroleum Hydrocarbon Starter Kit (RemediAid™ starter
kit) is based on a combination of the Friedel-Crafts alkylation reaction and colorimetry. Collectively, these two
technologies are suitable for measuring aromatic hydrocarbons independent of their carbon range. These
technologies are described below.
18
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Wavelength range
Measurement device
106 --
105
104
I
o
c
OJ
B 103
®
I
102
10
Microwave
Infrared
'_ Visible
I Ultraviolet
I X-ray
None
lnfracal®TOG/TPH Analyzer, Models CVH and HATR-T
OCMA-350 Oil Content Analyzer
RemediAid™ Total Petroleum Hydrocarbon Starter Kit
PetroFLAG™ Hydrocarbon Test Kit for Soil
EnSys PetroTest System
Synchronous Scanning Luminoscope
siteLAB® Analytical Test Kit UVF-3100A
None
Figure 2-1. Wavelength range used by each measurement device.
19
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2.1.1.1
Friedel-Crafts Alkylation Reaction
The Friedel-Crafts alkylation reaction involves reaction of an alkyl halide, such as dichloromethane (CH2C12), with
an aromatic hydrocarbon, such as benzene (C6H6), in the presence of a solid-phase metal halide catalyst, such as
anhydrous aluminum chloride (A1C13) (Fox 1994).
The first step in the reaction is the metal halide, anhydrous A1C13, reacting with the alkyl halide, CH2C12, as shown
in Equation 2-1. An alkyl halide is a molecule that contains at least one carbon-chlorine bond. The metal halide
polarizes the carbon-chlorine bond or bonds of the alkyl halide, causing the positively charged carbocation (+CH2C1)
and negatively charged metal halide ions to separate. This separation results in an intermediate (+CH2C1), which is
a positively charged ion whose charge resides on the carbon atom.
CH2CI2 + AICI3 • •+CH2CI + AICI4-
(2-1)
In the second step of the reaction, the carbocation attaches to the aromatic hydrocarbon, C6H6, producing an
intermediate as shown in Equation 2-2.
+CH
,c: * /
(2-2)
Equation 2-2 shows one possible structure of the intermediate. The positive charge, like the aromatic double bonds,
may be on several of the ring carbon atoms. In the third step of the reaction, this sharing of the charge stabilizes the
intermediate and gives it time to react with an A1C14" ion as shown in Equation 2-3. This reaction regenerates the
catalyst (anhydrous A1C13) and forms a colored reaction product (a hydrocarbon derivative) that can absorb light in
the visible range of the electromagnetic spectrum. The colored reaction product remains bound to the solid-phase
metal halide and settles to the bottom of the reaction mixture.
CH2CI
+ AICL
CH9CI + HCI + AICL
(2-3)
The concentration of the aromatic hydrocarbon in the reaction mixture is determined by comparing the intensity of
the colored reaction product with photographs of standards (color charts) or by using a reflectance spectrophotometer
20
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that can measure the concentration of the colored reaction product in the visible range of the electromagnetic
spectrum. The intensity of the color produced is directly proportional to the concentration of the aromatic
hydrocarbon present.
The RemediAid™ starter kit is based on a modified version of the Friedel-Crafts alkylation reaction. The modified
version has the same reaction steps as the classical Friedel-Crafts alkylation reaction described above except that the
colored reaction product is not bound to the solid-phase metal halide but remains in the liquid phase of the reaction
mixture. This effect is achieved by using the alkyl halide in amounts exceeding the stoichiometry. The TPH
concentration in the reaction mixture is determined by comparing the intensity of the colored reaction product with
color charts or by using an absorbance spectrophotometer. Color measurement and concentration estimation are
further discussed in Section 2.1.1.2.
2.1.1.2 Colorimetry
Colorimetry is atechnique by which the intensity of color is assessed using visual or spectrophotometric means. Use
of a spectrophotometer is preferred over visual assessment of color charts because the spectrophotometer provides
a more accurate and precise measurement and does not rely on a person's skill in interpreting color charts. A
reflectance spectrophotometer measures the intensity of light reflected from solid particles in a reaction mixture, and
an absorbance spectrophotometer measures the intensity of light that passes through the liquid portion of a reaction
mixture. For the classical Friedel-Crafts alkylation reaction (Equations 2-1 through 2-3), a reflectance
spectrophotometer is used because the colored reaction product is bound to a solid-phase metal halide. The
RemediAid™ starter kit uses an absorbance spectrophotometer because the colored reaction product is present in the
liquid phase. Therefore, this section describes Colorimetry using an absorbance spectrophotometer.
When a spectrophotometer is used in the visible wavelength range, the reaction mixture is placed in a glass or quartz
cuvette that is then inserted into the spectrophotometer and covered with an opaque light shield. A beam of visible
light is then passed through the reaction mixture. The wavelength of the light entering the reaction mixture is initially
selected by performing a series of absorbance measurements over a range of wavelengths; the selected wavelength
generally provides maximum absorbance and allows target compound measurement over a wide concentration range.
Some of the light is absorbed by the chemicals in the reaction mixture, and the rest of the light passes through.
Absorbance, which is defined as the logarithm of the ratio of the radiant power of the light source to that of the light
that passes through the reaction mixture, is measured by a photoelectric detector in the spectrophotometer (Fritz and
Schenk 1987). Absorbance can be calculated using Equation 2-4.
21
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A = log (lo/l) (2-4)
where
A = Absorbance
I0 = Intensity of light source
I = Intensity of light that passes through the reaction mixture
Therefore, the intensity of the light that passes through the reaction mixture is inversely proportional to the
concentration of target compounds in the reaction mixture, or the intensity of the light absorbed by the reaction
mixture is directly proportional to the concentration of target compounds in the reaction mixture.
According to Beer-Lambert's law, Equation 2-4 may be expressed as shown in Equation 2-5.
A = • be (2-5)
where
A = Absorbance
• • = Molar absorptivity (centimeter per mole per liter)
b = Light path length (centimeter)
c = Concentration of absorbing species (mole per liter)
Thus, according to Beer-Lambert's law, the absorbance of a chemical species is directly proportional to the
concentration of the absorbing chemical species and the path length of the light passing through the reaction mixture.
In Equation 2-5, the molar absorptivity is a proportionality constant, which is a characteristic of the absorbing species
and changes as the wavelength changes. Therefore, Beer-Lambert's law applies only to monochromatic light (light
of one wavelength).
After the absorbance of the reaction mixture is measured, the TPH concentration is determined by comparing the
absorbance reading for the reaction mixture to absorbance values for a series of reference standards, which are plotted
on a calibration curve.
2.1.2 Infrared Analysis
TPH measurement in soil using the Infracal® TOG/TPH Analyzer and the OCMA-350 Oil Content Analyzer
(OCMA-350) is based on infrared analysis. This technology is suitable for measuring aromatic and aliphatic
hydrocarbons independent of their carbon range.
Each infrared field measurement device contains a nondispersive infrared (NDIR) spectrophotometer equipped with
an infrared radiation source and a filter to isolate the desired wavelength. The NDIR spectrophotometers offer
22
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several advantages over conventional, scanning infrared spectrophotometers. A scanning infrared spectrophotometer
takes about 1 to 3 minutes to scan a sample and has moderate sensitivity and stability, whereas an NDIR
spectrophotometer can achieve a stable reading in about 5 seconds and has greater sensitivity and stability.
The general procedure for infrared analysis of a sample extract for TPH involves the same principles as are described
in Section 2.1.1.2 except that light in the infrared wavelength range is used instead of visible light. Measurement of
PHCs using infrared analysis involves absorbance measurement because the carbon-hydrogen bonds in the
hydrocarbons absorb infrared light. During infrared analysis, absorbances associated with CH, CH2, and CH3
configurations are measured at a wavelength of about 3,400 nanometers (nm). Specifically, infrared devices that
operate in the 3,380- to 3,500-nm wavelength range should be able to measure CH (3,380 nm), CH2 (3,420 nm), and
CH3 (3,500 nm) configurations (Simard and others 1951). The absorbance of a sample extract thus measured is
directly proportional to the concentration of PHCs present in the extract in accordance with Beer-Lambert's law (see
Section 2.1.1.2).
2.1.3 Emulsion Turbidimetry
TPH measurement in soil using the PetroFLAG™ Hydrocarbon Test Kit for Soil (PetroFLAG™ test kit) is based on
emulsion turbidimetry. This technology is suitable for measuring aromatic and aliphatic hydrocarbons in the C8
through C36 carbon range.
Turbidimetry may be described as measurement of the attenuation, or loss in intensity, of a light beam as the beam
passes through a solution with particles large enough to scatter the light. Emulsion turbidimetry involves
measurement of attenuation of light by an emulsion (in an emulsion, one liquid is stably dispersed in a second,
immiscible liquid). A direct relationship that follows Beer-Lambert's law exists between the amount of light
attenuated and the concentration of the emulsion (McGraw-Hill 1984).
For emulsion turbidimetry, a sample extract is added to a vial containing an aqueous, polar developer solution. The
developer solution acts as an emulsifier, causing the aromatic and aliphatic hydrocarbons in solution to precipitate
out and form uniformly sized micelles. Micelles are electrically charged, colloidal particles composed of aggregates
of large molecules that are stable for some time. The vial containing the resulting emulsion is placed in aturbidimeter.
A turbidimeter is similar to the reflectance spectrophotometer described in Section 2.1.1.2 except that the
spectrophotometer measures the amount of light reflected by a solution and the turbidimeter measures the amount of
light scattered by an emulsion. In the turbidimeter, light at a wavelength of 585 nm is passed through the emulsion,
and the amount of light scattered by the emulsion at a 90-degree angle is measured. A wavelength of 585 nm is
23
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typically used because the maximum amount of light is scattered by the emulsion at this wavelength. The TPH
concentration in the emulsion is then determined by either comparing the turbidity reading for the emulsion to that
of a reference standard or a standard calibration curve.
2.1.4 Ultraviolet Fluorescence Spectroscopy
TPH measurement in soil using the Synchronous Scanning Luminoscope (Luminoscope) and the siteLAB® Analytical
Test Kit UVF-3100A (UVF-3100A) is based on ultraviolet fluorescence spectroscopy. This technology is suitable
for measuring aromatic hydrocarbons independent of their carbon range.
When a sample extract containing both aromatic and aliphatic hydrocarbons is exposed to ultraviolet light, only the
aromatic hydrocarbons are excited. The aromatic hydrocarbons then emit light at specific wavelengths that are longer
than the excitation wavelength. The intensity and wavelength of the light emitted can be measured, and correlated
to the aromatic hydrocarbon concentration in the sample extract. Figure 2-2 shows a schematic of the general process
of measurement using ultraviolet fluorescence spectroscopy. The excitation and emission optics may consist of
optical lenses that are used to focus light on an optical filter or monochromator. A monochromator is a series of
optical filters that reduce a multiple-wavelength light beam to a single-wavelength beam.
In ultraviolet fluorescence spectroscopy, a multiple-wavelength lamp that emits light in the ultraviolet range is used
as a light source. Figure 2-1 shows ultraviolet light in relation to the electromagnetic spectrum. The ultraviolet light
is directed through the excitation optics. The resulting focused light energy from the excitation optics is used to
irradiate the sample extract under analysis. Some of the light energy is absorbed by the molecules of the aromatic
hydrocarbons in the sample extract, resulting in excitation of those molecules.
When the excited molecules return to a stable state by losing energy, the energy emitted has longer wavelengths than
those of the energy absorbed by the molecules. The emission optics are placed at a 90-degree angle to the excitation
optics, and the longer-wavelength energy emitted by the molecules passes through the emission optics and is detected
by a photomultiplier tube. The photomultiplier tube detects and amplifies the energy and converts it into an electrical
signal that is used to determine the intensity of the light energy emitted. The emission optics and photomultiplier
tube are placed at a 90-degree angle to the light source in order to minimize the light source interference detected by
the photomultiplier tube.
24
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Light
source
Excitation
optics
Sample extract
in quartz cuvette
Emission
optics
ill
Photomultiplier
tube
Figure 2-2. Schematic of ultraviolet fluorescence spectroscopy.
A spectrum of fluorescence intensity versus emission wavelength is generated and evaluated to determine whether
any of the peaks correspond to known groups of hydrocarbons. To determine the relationship between the
fluorescence intensity and the aromatic hydrocarbon concentration of a sample extract, a calibration curve can be
generated using site-specific TPH, GRO, or EDRO concentrations or known standards selected based on the type of
PHCs being measured at a site.
2.1.5
Immunoassay and Colorimetry
TPH measurement in soil using the EnSys Petro Test System is based on a combination of immunoassay and
colorimetry. This combination of technologies is suitable for measuring a large portion of the aromatic hydrocarbons
and a few aliphatic hydrocarbons in the C6 through C22 carbon range. Immunoassay and colorimetry are described
below.
25
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2.1.5.1 Immunoassay
Immunoassay is a technique for measuring a target compound's concentration using biologically engineered
antibodies. Antibodies are a class of proteins known as immunoglobulins that are produced by the immune system
of animals in response to a foreign substance (an antigen). The antibodies produced can bind with the antigen that
stimulated their production. Specifically, antibodies are produced in response to localized, reactive sites called
antigenic determinants on the surface of the antigen. Antigenic determinants consist of amino acid sequences
(Rittenburg 1990). Because an antigen may possess more than one type of antigenic determinant, more than one type
of antibody may be produced by the immune system. In general, the antibodies produced are structured in such a way
that they selectively bind to the antigenic determinants on the antigen that stimulated their production, resulting in
formation of an antibody-antigen complex.
Five major classes of antibodies (immunoglobulin [Ig] A, IgD, IgE, IgG, and IgM) are produced by the immune
system. IgG is the most common type of antibody used in immunoassay (Rittenburg 1990). IgG is a Y-shaped
molecule consisting of two identical heavy polypeptide chains and two identical light polypeptide chains bound
together by disulfide bonds. Both the heavy and light chains have variable and constant regions. The variable regions
at the ends of the two arms of the Y-shaped antibody form areas called antigen-binding sites; therefore, two antigen-
binding sites are present on each antibody. The general structure of the IgG antibody is shown in Figure 2-3.
The dimensions and contours of antigen-binding sites are determined by the sequence of amino acids in the variable
regions of the antibody. On a single antibody molecule, the two binding sites have identical variable regions. As a
result, the two binding sites have identical specificity for a particular antigenic determinant (Rittenburg 1990).
However, the binding sites of antibodies produced in response to different antigenic determinants are not the same.
The binding affinity between an antibody and antigen is determined by (1) the sequence of amino acids in the variable
regions of the antibody, (2) the structure and location of the antigenic determinant on the antigen, and (3) the attractive
forces that stabilize the antibody-antigen complex. The attractive forces include a combination of hydrogen bonds,
hydrophobic bonds, coulombic interaction, and van der Waals forces (Rittenburg 1990). The closer the antigenic
determinant is to the antigen-binding site on the antibody, the higher the binding affinity.
Immunoassays employ either polyclonal or monoclonal antibodies. Because an antigen generally contains more than
one type of antigenic determinant, more than one type of antibody may be produced in the immune response.
Therefore, the antibodies produced are not identical and are called polyclonal antibodies. Because polyclonal
antibodies are not identical, they will, as a group, exhibit varied specificities and binding affinities for antigenic
26
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Antigen-binding
sites
Heavy
chains
~
CH
-s-s-
-s-s-
.1
_(
.1
.(
3 S-
3 S-
3 S-
3 S-
^
CH
Light
chain
Notes:
-S-S- = Disulfide bond
C = Constant region
H = Heavy polypeptide chain
L = Light polypeptide chain
V = Variable region
Figure 2-3. Immunoglobulin G antibody structure and locations of antigen-binding sites.
determinants. Monoclonal antibodies are produced by isolating those antibodies produced in response to one type
of antigenic determinant. As a result, monoclonal antibodies are structurally identical and exhibit the same
specificities and binding affinities for the antigenic determinant that stimulated their production.
27
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Although an antibody has a particular specificity and binding affinity for the antigenic determinant that produced the
antibody, cross-reactivity with other compounds may occur. For example, cross-reactivity may occur when the
antigenic determinant that stimulated the antibody's production is present in other compounds (SDI 2000). Cross-
reactivity may also occur with other compounds that possess structurally similar antigenic determinants (Rittenburg
1990).
Immunoassay effectiveness is primarily a function of (1) the specificities and binding affinities of the polyclonal or
monoclonal antibodies used and (2) whether one compound or a group of compounds is being measured. For
example, cross-reactivity will result in false positives when only one compound is being measured. However, cross-
reactivity is desirable when a group of compounds, such as PHCs, is being measured. Whether polyclonal or
monoclonal antibodies are better suited for measuring PHCs depends on the individual antibodies used; for example,
highly cross-reactive, monoclonal antibodies can be as effective as less cross-reactive, polyclonal antibodies.
The EnSys Petro Test System is based on a type of immunoassay called enzyme-linked immunosorbent assay
(ELISA). ELISA uses either polyclonal or monoclonal antibodies adsorbed to the inside wall of a test tube in order
to facilitate separation of target compounds from nontarget compounds during a washing step. In ELISA, an enzyme
conjugate solution is used to produce color whose intensity is inversely proportional to the total concentration of
PHCs in a sample extract. ELISA involves the following three steps: (1) enzyme conjugate and sample extract
addition, (2) washing, and (3) color development. These steps are described below and are illustrated in Figure 2-4.
The intensity of the color produced during color development is measured using standard colorimetric principles as
described in Section 2.1.5.2.
Enzyme Conjugate and Sample Extract Addition. As a first step, an enzyme conjugate solution is added to the
soil sample extract. An enzyme conjugate is an enzyme bound to a target compound. The antigen used to initiate
antibody production is also used as the target compound portion of the enzyme conjugate. The enzyme portion of
the enzyme conjugate plays its role in ELISA during the color development step; the enzyme typically used in ELISA
is horseradish peroxidase. The reaction mixture containing the sample extract and enzyme conjugate solution is
added to an antibody-coated test tube. Because both the sample extract target compound and the enzyme conjugate
can bind with the antibodies, the sample extract target compound and the enzyme conjugate compete for the antigen-
binding sites on the antibodies. The sample extract target compound and the enzyme conjugate bind to the antibodies
in direct proportion to their relative concentrations in the reaction mixture. For example, the greater the ratio of the
sample extract target compound concentration to the enzyme conjugate concentration, the greater the proportion of
antigen-binding sites that are occupied by the sample extract target compound.
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Step
Schematic
Description
Enzyme conjugate and sample extract
addition
A reaction mixture containing the sample
extract and enzyme conjugate solution is
added to an antibody-coated test tube. The
sample extract target compound and
enzyme conjugate compete for antigen-
binding sites.
Washing
The unbound sample extract target
compound and enzyme conjugate are
removed from the test tube.
Color development
A substrate and chromogen are added to
the test tube.
The substrate and chromogen react with
the enzyme in the enzyme conjugate to
produce color. The lower the color
intensity, the higher the sample extract
target compound concentration.
Notes:
Y Antibody
• • Sample extract target compound
• • Enzyme conjugate
^ Substrate
_,_ Chromogen
Figure 2-4. Enzyme-linked immunosorbent assay.
Washing. The sample extract target compound and the enzyme conjugate that are bound to the antibodies are
separated from the unbound sample extract target compound and enzyme conjugate by emptying the reaction mixture
from the test tube and washing the test tube with potable water.
Color Development. A substrate, such as hydrogen peroxide, and a chromogen, such as tetramethylbenzidine or
orthophenylenediamine, are then added to the test tube in order to produce color when they react with the enzyme
in the enzyme conjugate. For example, the enzyme horseradish peroxidase reacts with the hydrogen peroxide to
release a proton, which in turn reduces the tetramethylbenzidine or orthophenylenediamine to form the colored
product. After a specified period of time, color development in the test tube is terminated using a stopping solution
such as hydrochloric acid. The amount of color formed is directly proportional to the amount of enzyme conjugate
bound to the antibodies. Because the sample extract target compound competes with the enzyme conjugate for
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antigen-binding sites, ELISA results in formation of color in the test tube whose intensity is inversely proportional
to the concentration of the sample extract target compound; for example, less color indicates a higher concentration
of the sample extract target compound.
2.1.5.2 Colorimetry
After completion of color development, the concentration of PHCs in the sample extract is determined using
colorimetry. During colorimetry, the intensity of the color is assessed by measuring the absorbance of the colored
reaction mixture using a differential spectrophotometer. The differential spectrophotometer is a double-beam
instrument in which two equivalent beams of light are produced within the visible range of the electromagnetic
spectrum. One beam passes through the colored reaction mixture developed using the sample extract, while the other
beam passes through a colored reaction mixture developed using a reference standard. The spectrophotometer
measures the difference in absorbance between the two colored reaction mixtures. A positive reading on the
spectrophotometer indicates that the concentration of PHCs in the sample extract is less than that in the reference
standard. Similarly, a negative reading on the spectrophotometer indicates that the concentration of PHCs in
the sample extract is greater than that in the reference standard.
2.2 Field Measurement Device Descriptions
This section describes the seven innovative TPH field measurement devices that will be demonstrated. Field
measurement devices may be categorized as quantitative, semiquantitative, and qualitative. These categories are
explained below.
A quantitative measurement device measures TPH concentrations ranging from its reporting limit through
its linear range. The measurement result is reported as a single, numerical value that has an established
precision and accuracy.
• A semiquantitative measurement device measures TPH concentrations above its reporting limit. The
measurement result may be reported as a concentration range with lower and upper limits.
• A qualitative measurement device indicates the presence or absence of PHCs above or below a specified
value (for example, the reporting limit or an action level).
Each of the seven devices that will be demonstrated produces either quantitative or semiquantitative results. The
device descriptions presented in Sections 2.2.1 through 2.2.7 identify the type of results produced by each device.
Performance data included in the device descriptions were provided by the device developers.
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2.2.1 RemediAid1™ Starter Kit
The RemediAid™ starter kit, a quantitative test kit developed by CHEMetrics, Inc. (CHEMetrics), and AZUR
Environmental Ltd (AZUR) in conjunction with Shell Research Ltd. and manufactured by CHEMetrics, is based on
a combination of the Friedel-Crafts alkylation reaction and colorimetry discussed in Section 2.1.1. The kit has been
commercially available since 1998. This section describes the kit, presents its operating procedure, and discusses its
advantages and limitations.
2.2.1.1 Device Description
As stated in Section 2.1.1, the Friedel-Crafts alkylation reaction involves reaction of an alkyl halide with an aromatic
compound in the presence of a metal halide. The RemediAid™ starter kit uses CH2C12 as both the alkyl halide and
extraction solvent and uses anhydrous AlCl3as the metal halide. When excessive CH2C12 is used, the colored reaction
product to be measured remains in the liquid phase. According to the developers of the kit, because the presence of
chlorinated solvents in the sample extract may result in false positive results, a premeasured volume of CH2C12 is
included with the kit in a sealed, single-use, double-point ampule. A known volume of CH2C12 is used so that this
value can be incorporated into the sample extract concentration calculation as described in the kit operating procedure
(see Section 2.2.1.2). Anhydrous A1C13 is used because it is the most sensitive metal halide and it provided the most
accurate recoveries for various types of hydrocarbons during laboratory tests performed by CHEMetrics and AZUR.
As described in Section 2.1.1.2, the kit uses an absorbance LED-based photometer and measures sample extract
absorbance using visible light of a 430-nm wavelength.
According to CHEMetrics and AZUR, the RemediAid™ starter kit responds to all hydrocarbon products as long as
they contain aromatic hydrocarbons. The kit can respond to aromatic hydrocarbons independent of their carbon range.
For optimum performance, the spectrophotometer should be used in environments with a temperature range of 0 to
50 °C and with a maximum relative humidity of 95 percent, and it should not be stored at temperatures greater than
32 °C. The kit does not require any other special storage conditions because its chemicals are vacuum-sealed and are
therefore not susceptible to degradation.
According to CHEMetrics and AZUR, the method detection limit (MDL), precision, and accuracy that can be
achieved with the RemediAid™ starter kit vary depending on the reactivity of the hydrocarbons being measured. No
information is available on the MDL, precision, and accuracy for soil sample extracts. However, assuming that
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a sample extract does not require dilution before analysis, the following MDL, precision, and accuracy ranges
generally apply to the kit: MDLs ranging from 2.0 mg/L for weathered gasoline to 10 mg/L for heavy oil, precision
values ranging from 2.0 mg/L for weathered gasoline to plus or minus (±) 11.0 mg/L for heavy oil, and accuracy
values ranging from -4.8 mg/L for weathered gasoline to + 31.3 mg/L for heavy oil.
A kit user must first purchase the RemediAid™ starter kit and may then purchase replenishment kits thereafter.
Table 2-2 lists the components of the RemediAid™ starter kit and the replenishment kit. The RemediAid™ starter
kit includes enough supplies to perform 8 soil analyses, and the replenishment kit includes enough supplies to perform
16 more soil analyses.
The components of the RemediAid™ starter kit are packaged in a carrying case that is 13.75 inches long, 15.5 inches
wide, and 4.5 inches deep. The replenishment kit components are packaged in a box that is 9.25 inches long,
10.25 inches wide, and 4.5 inches deep. A kit user needs to provide disposable gloves, safety glasses, and a disposal
pipet or syringe capable of measuring 5 mL. The photometer operates on one 9-volt battery; weighs 0.43 pound; and
is 6.0 inches long, 2.4 inches wide, and 1.25 inches deep.
The RemediAid™ starter kit (Model No. TPH0001) can be purchased for $800, and the replenishment kit (Model
No. TPH0002) can be purchased for $240. Kit components may also be purchased individually from the developers.
The RemediAid™ starter and replenishment kits are not available for rental.
According to CHEMetrics, one technician can perform 16 analyses in about 1 hour using the kit. All kit reagents are
premeasured and contained in vacuum-sealed ampules. Only one technician is required to perform analyses using
the RemediAid™ starter kit. The kit is designed to be used by those with basic wet chemistry skills. CHEMetrics
provides technical support over the telephone at no additional cost.
According to the developers, the RemediAid™ starter kit is innovative because the colored reaction product remains
in the liquid phase, which allows measurement of color intensity using a portable absorbance spectrophotometer.
According to the developers, portable versions of reflectance spectrophotometers are not commercially available,
making interpretation of a solid colored reaction product impossible in the field. All chemicals supplied as part of
the RemediAid™ starter and replenishment kits are vacuum-sealed, which minimizes user contact with reagents and
eliminates the need for pipetting and measuring skills, thus minimizing the possibility of user error.
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Table 2-2. RemediAid™ Starter and Replenishment Kit Components
Starter Kit Components
Battery-powered balance (9-volt battery included)
Battery-powered timer (AAA battery included)
Battery-powered, portable photometer (9-volt battery included)
8 double-tipped ampules containing 20 milliliters each of dichloromethane
8 vacuum-sealed ampules containing anhydrous aluminum chloride and filtering columns
Anhydrous sodium sulfate (50 grams)
8 extraction cleanup tubes and caps containing Florisil
8 reaction tubes and caps containing sodium sulfate
8 small, silicone ampule caps
8 weighing boats
Tip-breaking tool
Light shield
Ampule rack that holds 36 ampules
Reaction tube plug/snapper
Spatula
Reagent blank ampule
Test procedure manual and simplified instruction card
Material Safety Data Sheets
Carrying case
Replenishment Kit Components
16 double-tipped ampules containing 20 milliliters each of dichloromethane
16 vacuum-sealed ampules containing anhydrous aluminum chloride and filtering columns
16 extraction cleanup tubes and caps containing Florisil
16 reaction tubes and caps containing sodium sulfate
16 weighing boats
2.2.1.2 Operating Procedure
Measuring TPH in soil using the RemediAid™ starter kit involves the following three steps: (1) extraction/extraction
clean-up, (2) color development, and (3) color measurement. These three steps are detailed below. Calibration
procedures and QC checks required for the device are presented in Chapter 8.
Step 1 - Extraction
1. Measure 5 grams of soil sample.
2. Transfer the soil sample to the reaction tube containing anhydrous sodium sulfate, a drying agent for
removing moisture from the soil sample. Cap the tube, and shake it briefly to obtain a uniform, free-flowing
mixture. If the sample still appears to be wet or does not form a granular, uniform mixture, add more
anhydrous sodium sulfate, and shake the tube vigorously until a uniform, free-flowing mixture is obtained.
If necessary, use a spatula to break up clumps of wet soil.
3. Hold the double-tipped ampule containing 20 milliliters (mL) of solvent (CH2C12) overthe reaction tube, and
snip off the top end of the ampule using the green, tip-breaking tool.
4. Carefully invert the ampule over the reaction tube. Snip off the other end of the ampule to allow the solvent
to flow freely into the reaction tube. Cap the reaction tube, and shake it vigorously for 3 minutes.
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5. Let the reaction tube stand undisturbed for 2 minutes, and allow the soil to settle to the bottom of the tube.
6. Decant the extract to an extraction clean-up tube containing 2.0 grams of Florisil, using care not to transfer
any soil to the extraction clean-up tube. Florisil is an activated magnesium silicate used as a polar adsorbent
to minimize interference from natural organic material (for example, humic substances). Cap this reaction
tube, and shake it for 1 minute. Allow the Florisil to settle for approximately 2 minutes.
7. Remove the cap from the reaction tube, and replace the cap with the reaction tube plug/snapper, a round,
white plug with a small hole in the center.
Step 2 - Color Development
1. Push a filtering column onto the tip of the vacuum-sealed ampule containing anhydrous A1C13 until the
column fits snugly.
2. Insert the column and ampule assembly through the hole in the reaction tube plug/snapper up to the blue line
on the ampule. While holding the reaction tube, gently pull the ampule to one side in order to snap the
ampule tip. The ampule will then slowly draw liquid from the reaction tube.
3. Withdraw the column and ampule assembly from the reaction tube, and invert the assembly. Remove the
column.
4. Firmly place a small, silicone ampule cap on the tip of the ampule, and invert the ampule every 2 minutes for
10 minutes. Then let the ampule stand undisturbed for 10 minutes. Depending on the concentration and type
of hydrocarbon present, the solvent in the ampule will turn a yellow to orange-brown color. If the ampule
appears to be cloudy after 10 minutes of standing, wait an additional 5 to 10 minutes for the cloudiness to
settle out. Do not let the ampule stand longer than 1 hour before placing it in the spectrophotometer, as this
may result in a small positive bias.
Step 3 - Color Measurement
1. Immediately after allowing the ampule to stand undisturbed for 10 minutes, or after waiting for any
cloudiness to settle out, insert the reagent blank ampule into the spectrophotometer to zero the instrument.
2. Remove the reagent blank, insert the test ampule into the spectrophotometer, and record the absorbance.
3. If the absorbance is less than 0.700, use Equation 2-6 to convert the absorbance value to mg/kg TPH in the
soil sample on a wet weight basis.
TPH concentration in soil sample (mg/kg) = ^A x S^''] x V (2-6)
where
A = Absorbance
S = Slope for a specific hydrocarbon mixture ([mg/L/A]; see the test procedure manual)
I = Intercept for a specific hydrocarbon mixture (mg/L; see the test procedure manual)
V = Volume of extract: 20 mL
W = Weight of soil sample: 5 grams
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Note: CHEMetrics and AZUR developed S and I values by plotting absorbance on the x-axis and
concentration on the y-axis, which is the opposite of conventional practice. Hence, S and I are
expressed in concentration units of mg/L.
4. If the absorbance is equal to or greater than 0.700, perform a five-times dilution by first placing 5 mL of the
extract supernatant from item 5 of the extraction step in a reaction tube. Add the contents of a double-tipped
ampule (20 mL of CH2C12) to the reaction tube, cap the tube, and shake it briefly. Then follow the color
development and color measurement steps described above. Use Equation 2-7 to convert the absorbance
value to mg/kg TPH in the soil sample on a wet weight basis.
TPH concentration in soil sample (mg/kg) = [(A x S) ^ x V x 5 (2-7)
2.2.1.3 Advantages and Limitations
An advantage of the RemediAid™ starter kit is that it is easy to operate, requiring one operator with minimal skills
in basic wet chemistry techniques. The kit provides premeasured amounts of chemicals in specially designed, single-
use ampules. The ampules are vacuum-sealed, and therefore the chemicals are not susceptible to degradation. The
single-use ampules eliminate the need for measuring and pipetting skills, minimize user contact with reagents, and
minimize the possibility of operator error. In addition, the spectrophotometer operates on a 9-volt battery, so an
alternating current (AC) power source is not required in the field.
The kit uses a drying agent (anhydrous sodium sulfate) to remove moisture from soil samples. As a result, no
correction associated with solvent dilution is required, which is necessary for wet soil samples. The kit also uses
Florisil to eliminate interferences from natural organic matter in soil. However, this practice results in removal of
polar compounds from the sample extract, including PHC degradation products (California Environmental Protection
Agency 1999).
Another advantage of the kit is that it can quantitatively measure all fuel types that contain an aromatic hydrocarbon
component. According to the developers, the kit is designed to measure aromatic hydrocarbons regardless of their
carbon range. If a site-specific calibration is performed, the kit can measure aliphatic hydrocarbons in the presence
of aromatic compounds, but a limitation of the kit is that it does not measure aliphatic hydrocarbons when aromatic
compounds are not present in the sample.
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2.2.2 Infracal® TOG/TPHAnalyzer, Models CVHandHATR-T
The Infracal® TOG/TPH Analyzer, a quantitative device developed by Wilks Enterprise, Inc. (Wilks), is based on
infrared analysis as discussed in Section 2.1.2. The Infracal® TOG/TPH Analyzer is identified according to the
sample stage used in the device. The device can be operated as either Model CVH or Model HATR-T simply by
switching the sample stages. Model CVH uses the CVH sample stage, which contains a quartz cuvette, while
Model HATR-T uses the cubic zirconia horizontal attenuated total reflection sample stage. Models CVH and
HATR-T have been commercially available since 1996 and 1997, respectively. Model CVH is used when a sample
contains either GRO or GRO and EDRO; Model HATR-T cannot measure GRO. This section describes both models
of the device, presents their operating procedure, and discusses their advantages and limitations.
2.2.2.1 Device Description
Models CVH and HATR-T include a single-beam, fixed-wavelength, NDIR filter-based spectrophotometer with a
dual detector system. As stated above, the only difference between the two models involves the sample stage used.
In Model CVH, infrared radiation from a tungsten lamp is captured using an elliptical source mirror and transmitted
through a quartz cuvette that contains a sample extract. The radiation that has passed through the extract enters a dual
detector system containing filters that isolate a reference wavelength of 2,500 nm and an analytical wavelength of
3,400 nm. The reference wavelength stabilizes device response and automatically corrects absorbance values for
fluctuations in ambient temperature and relative humidity.
Model CVH is suitable for analyzing sample extracts that have been extracted from soil using Freon 113 or other
solvents invisible in the measurement range. Model HATR-T, unlike Model CVH, is based on an evaporation
technique and measures residual hydrocarbons after volatile organics evaporate from the sample extract. Therefore,
analyses using Model HATR-T result in the loss of some volatiles in the GRO range. Vertrel® MCA, a
hydrochlorofluorocarbon extraction solvent manufactured by DuPont, is used with Model HATR-T. Although hexane
can be used as the extraction solvent with Model HATR-T, Vertrel® MCA is preferred because (1) it achieves
measurement stability more quickly than hexane (in 1.5 to 2 minutes instead of 3 to 5 minutes); (2) it has a lower
boiling point than hexane, which results in fewer light-end volatile organic compounds being lost in the evaporation
process; and (3) it is less flammable than hexane, resulting in fewer disposal concerns. In addition, Model HATR-T
does not require a cuvette to contain the sample extract. The extract is transferred directly to the sample stage.
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The Infracal® TOG/TPH Analyzer presents results in units selected by the user during calibration, such as mg/kg,
mg/L, or absorbance values. According to Wilks, both Models CVH and HATR-T can measure aromatic and aliphatic
hydrocarbons. However, Model CVH can measure both GRO and EDRO, but Model HATR-T can primarily measure
EDRO. Model CVH has (1) an MDL of 3 mg/kg and is linear up to 5,000 mg/kg in soil; (2) a measurement accuracy
of ± 1 percent; and (3) a measurement precision of ± 1 percent. Model HATR-T has an MDL of 20 mg/kg and is
linear up to 5,000 mg/kg in soil. The Infracal® TOG/TPH Analyzer uses a point-to-point calibration to correct for
non-linearity. The Infracal® TOG/TPH Analyzer can operate in a temperature range of 4 to 43 °C and a relative
humidity range of 10 to 60 percent. When the device is not in operation, it can be stored in a temperature range
of-18 to 52 °C.
Table 2-4 lists the components of the Infracal® TOG/TPH Analyzer. The device weighs 4.5 pounds and is 6.5 inches
long, 6.5 inches wide, and 5 inches deep. Wilks offers users a field sampling kit for TPH in soil, KIT-10410-S, the
components of which are also presented in Table 2-4. Additional supplies required for TPH analysis using the
Infracal® TOG/TPH analyzer are also listed in the table.
The Infracal® TOG/TPH Analyzer has a standard, nine-pin, female DB9 connector (RS232-C) for serial data
communication. Wilks offers an optional software package, InfraWin, that allows the user to connect a personal
computer to the device and automatically download, label, and save measurement results; remotely control
measurement parameters; generate and store multiple calibration tables; and report measurement results in various
numerical and graphical formats. The built-in microprocessor in the device can store up to 10 measurement results
for use with its averaging function or for local recall and display. Measurement results may be transferred via the
serial communication interface to a serial printer or to an external personal computer. The device may be connected
to an external battery pack or an automobile cigarette lighter. The device draws only about 8 watts (0.67 ampere) of
power.
Model CVH can be purchased for $4,675. Rental is available for 15 percent of the purchase price per month. The
HATR-T sample stage can be purchased for an additional $1,150. The serial printer can be purchased from Wilks
for $695. KIT-10410-S can be purchased for $865 and includes enough supplies to perform at least 75 soil analyses.
Additional required supplies that can be purchased from Wilks include a set of four 10-mm, quartz cuvettes with
Teflon™ stoppers ($575) and the InfraWin software package ($475). Additional required supplies that cannot be
purchased from Wilks are listed in Table 2-4.
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Table 2-4. Infracal® TOG/TPH Analyzer, Models CVH and HATR-T Components
Spectrophotometer and Accessories
Infrared Spectrophotometer
CVH or HATR-T sample stage
Dust cover
Power supply cable
Instruction manual
KIT-10410-S Components
Timer (batteries included)
Battery-powered balance (batteries included)
Silica gel (60-200 mesh) (500 grams)
Teflon™ wash bottle (125 milliliters)
Glass funnel
10-milliliter, graduated cylinder
100-milliliter, graduated cylinder with stopper
Air syringe
20-milliliter, glass beaker
Spatula
50-microliter pipette with pipette tips (pack of 50)
250-milliliter syringe
40-milliliter vials (box of 50)
Extraction reservoirs (box of 50)
Reservoir sealer
Extraction procedure instructions
Additional Required Supplies that Can Be Purchased from Wilks
10-millimeter, quartz cuvettes
50-millimeter, quartz cuvette and holder
Additional Required Supplies that Cannot be Purchased from Wilks
Extraction solvents (Freon 113 or Vertrel® MCA)
Seven standards (104; 208; 260; 389; 519; 778; and 1,038 milligrams per liter) of 3-IN-ONE oil in Freon 113 in sealed cuvettes for
Model CVH (standards for Model HATR-T will be prepared in Vertrel® MCA solvent on site)
100-microliter, glass syringe
One 3-ounce bottle of 3-IN-ONE oil
4-ounce, high-density polyethylene, disposable bottles
Disposable eye droppers
According to Wilks, the average sample extraction and analysis time for Models CVH and HATR-T is 10 to
15 minutes per sample. Both models are easy to use. Normal training for using each model involves reading the
instruction manual. Wilks also provides technical support over the telephone at no additional cost.
According to Wilks, Models CVH and HATR-T are innovative TPH field measurement devices because their
Spectrophotometer uses a pulsed, infrared light source instead of a "chopper," which mechanically "chops" the light
beam to turn the radiation signal on and off. The chopper, which is a primary component of most conventional
spectrophotometers, requires more maintenance to prevent drift than does the pulsed, infrared light source. In
addition, Model HATR-T does not use Freon 113, which is expensive and is being phased out of use.
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2.2.2.2 Operating Procedure
Measuring TPH in soil using Models CVH and HATR-T involves the following three steps: (1) extraction,
(2) measurement of TPH in the extract, and (3) calculation of the TPH concentration in soil. These steps are described
below for both models. In these steps, operating procedures specific to Model CVH are identified as "(a)" and to
Model HATR-T are identified as "(b)." Calibration procedures and QC checks required for the Infracal® TOG/TPH
Analyzer are presented in Chapter 8.
Step 1 - Extraction
1. Measure 20 grams of soil sample, and place the measured amount in a 40-mL vial.
2. Add 2 to 5 grams of 60-200 mesh silica gel to the vial, depending on the soil's moisture content. Cap and
shake the vial, and ensure that its contents are free-flowing.
3. Add 20 mL of (a) Freon 113 or (b) Vertrel® MCA to the vial.
4. Cap the vial, and shake it vigorously for 2 minutes. Then let the vial stand for up to 2 minutes in order to
allow the soil and sample extract to separate.
5. Decant the sample extract into an extraction reservoir with a filter frit (to capture large particles) and a silica
gel cartridge (to capture small particles and remove natural hydrocarbons). Leave as much of the soil in the
vial as possible.
6. Seal the extraction reservoir with a sealer, and insert the tip of the air syringe into the sealer.
7. Place the tip of the extraction reservoir over the vial, and push down on the air syringe plunger so that the
sample extract drips slowly into the vial.
8. Discard the first 1 mL (4 or 5 drops) of sample extract in the vial.
Step 2 - Measurement of TPH in Extract
1. (a) Place the tip of the extraction reservoir over a 10-mm, quartz cuvette, and allow the rest of the sample
extract to drip into the cuvette until the cuvette is full.
(b) Place the tip of the extraction reservoir over a beaker, and allow the rest of the sample extract to drip
into the beaker. Immediately collect 50 microliters (\\L) of the sample extract from the beaker using
a pipette.
2. (a) Insert the quartz cuvette into the CVH sample stage, and record the sample extract concentration in
mg/L.
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(b) Transfer the sample extract from the pipette onto the center of the HATR-T sample stage, allow the
sample extract to evaporate, and record the residual sample extract concentration in mg/L.
Step 3 - Calculation of TPH Concentration in Soil
Because the infrared spectrophotometer can measure the soil TPH concentration in mg/kg on a wet weight basis, no
additional calculations are required. However, any variations from the soil sample amount or reagent amount
specified in Step 1 or any sample dilutions should be factored into a calculation of the TPH concentration.
2.2.2.3 Advantages and Limitations
An advantage of the Infracal® TOG/TPH Analyzer is that it is easy to operate, requiring one person with basic wet
chemistry skills. It has no moving parts that require optical alignment or adjustment, and it uses a pulsed, infrared
light source instead of a chopper to prevent measurement fluctuations resulting from mechanical wear. The chopper,
which is a primary component of most conventional spectrophotometers, requires more maintenance than does the
pulsed, infrared light source. In addition, the devices can be operated using either a direct current (DC) power source
such as an automobile cigarette lighter or an external battery pack; an AC power source is not required in the field.
Model CVH can measure all TPH fuel types and is designed to measure both aromatic and aliphatic hydrocarbons
independent of their carbon range. Model HATR-T can also measure both aromatic and aliphatic hydrocarbons
primarily in the EDRO range.
Model CVH can use Freon 113, a chlorofluorocarbon (CFC), as the extraction solvent. CFCs that are discharged to
the atmosphere are primary contributors to depletion of the earth's stratospheric ozone layer. The United States, as
a party to the Montreal Protocol on Substances that Deplete the Ozone Layer and as required by law under the Clean
Air Act of 1990, is committed to controlling and eventually phasing out use of CFCs. As a result, Freon 113 will
become increasingly scarce and expensive. However, Model HATR-T allows use of Vertrel® MCA or hexane as the
extraction solvent instead of Freon 113.
2.2.3 OCMA-350
The OCMA-350, a quantitative device developed by Horiba Instruments, Incorporated (Horiba), is based on infrared
analysis as discussed in Section 2.1.2. The OCMA-350 has been commercially available since 1995. This section
describes the device, presents its operating procedure, and discusses its advantages and limitations.
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2.2.3.1 Device Description
The OCMA-350 includes a single-beam, fixed-wavelength, NDIR filter-based spectrophotometer. Infrared radiation
from a tungsten lamp is transmitted through a cylindrical, quartz cuvette containing a sample extract. The radiation
that has passed through the extract enters a detector containing a filter that isolates analytical wavelengths in the
3,400- to 3,500-nm range. The infrared spectrophotometer may be used to analyze soil samples that have been
extracted using Horiba' s proprietary S-316 extraction solvent, Freon 113, tetrachloroethylene, or carbon tetrachloride.
Horiba recommends its proprietary S-316 extraction solvent because it has ahigher boiling point (134 °C) and a lower
freezing point (-143 °C) than other extraction solvents. In addition, the S-316 extraction solvent is nonflammable,
nontoxic, and relatively nonvolatile because of its low vapor pressure.
According to Horiba, the infrared spectrophotometer can measure both aromatic and aliphatic hydrocarbons
independent of their carbon range. The spectrophotometer's response to aliphatic hydrocarbons is more sensitive than
its response to aromatic hydrocarbons. However, the calibration standards provided by Horiba include aromatic
hydrocarbons to compensate for the lower aromatic hydrocarbon response. The spectrophotometer presents results
in units selected by the user during calibration, such as mg/kg in soil or absorbance values.
The infrared spectrophotometer has an MDL of 1 mg/kg for TPH and is linear up to 1,000 mg/kg in soil. It can
achieve repeatability of ± 2 mg/kg from 0 to 99.9 mg/kg, ± 4 mg/kg from 100 to 200 mg/kg, and ±10 mg/kg from
201to l,000mg/kg. No information on the spectrophotometer's accuracy is available from Horiba. The OCMA-350
has an operating temperature range of 0 to 40 °C and an operating humidity range of 0 to 90 percent.
Components of the OCMA-350 are listed in Table 2-5. Also listed in the table are additional components available
from Horiba, including a Model SR-300 solvent reclaimer to reclaim S-316 extraction solvent and a Model GE-50
ultrasonic mixer to disperse the soil sample in the solvent. Additional components required for measuring TPH in
soil that are not available from Horiba are also listed in Table 2-5.
The infrared spectrophotometer weighs 11 pounds and is 7 inches long, 9.8 inches wide, and 11 inches deep. The
spectrophotometer can operate using a 110- or 220-volt AC power source. With the addition of a DC to AC
converter, the device can be powered by an automobile battery or cigarette lighter. The spectrophotometer is also
equipped with a parallel printer port and an RS232-C data port to allow transfer of data to a computer or other data
logger. The spectrophotometer keeps a record of the time and date of measurement along with each data set that it
records. Spectrophotometer printouts contain the time and date of each measurement along with the concentration
or absorbance value, which facilitates recordkeeping.
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Table 2-5. OCMA-350 Components
Spectrophotometer and Accessories
Infrared Spectrophotometer
Proprietary, 10-millimeter, quartz cuvette with cap
25-microliter microsyringe
10-milliliter syringe
10-milliliters of B-heavy oil for preparing span adjustment solution
3.15-ampere fuse
Power supply cable
Instruction manual and simplified operating instruction sheet
Additional Components Available from Horiba
S-316 extraction solvent
Model SR-300 solvent reclaimer
Model VC-50 ultrasonic mixer
Additional Components Not Available from Horiba
40-milliliter vials
100 milliliters of isooctane
100 milliliters of hexadecane
100 milliliters of chlorobenzene
Anhydrous sodium sulfate
Stainless-steel spatula
11 -centimeter-diameter, No. 40 Whatman filter paper
Glass funnel
Glass beaker
Balance
Currently, Horiba does not rent its measurement devices or components. The purchase cost for the infrared
Spectrophotometer and accessories listed in Table 2-5 is $6,500. Horiba offers the S-316 extraction solvent for $240
for a 1.5-kg bottle and $1,040 for a 7-kg bottle. The Model SR-300 solvent reclaimer is available from Horiba for
$1,650. Horiba offers the Model VC-50 ultrasonic mixer for $2,080. During the demonstration, Horiba will use the
Model GE-50 ultrasonic mixer, which is no longer available from the developer. According to Horiba, the
Model GE-50 and VC-50 ultrasonic mixers are functionally the same. To analyze samples using the OCMA-350, the
user must provide the additional components listed in Table 2-5 that are not available from Horiba.
According to Horiba, one person can use the OCMA-350 to perform up to 20 analyses in 1 hour. The device is
relatively easy to use. Normal training for using the device is limited to reading the instruction manual and simplified
operating instruction sheet. Horiba offers a 1-day training course to discuss operation, maintenance, and service of
the OCMA-350, but according to the developer, purchasers of the device rarely choose this option. Horiba also
provides technical support over the telephone at no additional charge.
Horiba considers the OCMA-350 to be an innovative TPH field measurement device for soil because previous devices
in the OCMA series have been used since the 1970s for measurement of oil in water, but the OCMA-350 allows the
user to determine hydrocarbon concentration in soil. The Model SR-300 solvent reclaimer is also considered to be
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innovative because it recycles the extraction solvent, which is difficult to dispose of, and thus can reduce costs by
up to 90 percent.
2.2.3.2 Operating Procedure
Measuring TPH in soil using the OCMA-350 involves the following three steps: (1) extraction, (2) measurement of
TPH in the extract, and (3) calculation of the TPH concentration in soil. These steps are described below. Calibration
procedures and QC checks required for the OCMA-350 are presented in Chapter 8.
Step 1 - Extraction
1. Measure 5 grams of the soil sample, and place the measured amount in a 40-mL vial.
2. Add 1 gram of anhydrous sodium sulfate to the vial in order to dry the soil. This is done to prevent water
damage to the quartz cuvette and clogging of the filter used below. Mix the soil and anhydrous sodium
sulfate with a stainless-steel spatula.
3. Add a carefully measured amount of S-316 extraction solvent (nominally 20 mL) to the vial.
4. Cap the vial, and mix the sample for 1 minute. During the demonstration, Horiba will use the Model GE-50
ultrasonic mixer to disperse the soil in the solvent.
5. Place the vial in its upright position, and wait at least 1 minute to allow soil particles to settle.
6. Place an 11-centimeter-diameter, No. 40 Whatman filter paper in a glass funnel.
7. Pour the extract through the filter and funnel into a clean beaker.
Step 2 - Measurement of TPH in Extract
1. Pre-rinse the quartz sample cuvette using 1 to 4 mL of the filtered sample extract.
2. Place about 6 mL of the filtered sample extract in an OCMA-350 quartz cuvette.
3. Insert the cuvette into the infrared spectrophotometer, and press Measure.
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Step 3 - Calculation of TPH Concentration in Soil
Because the infrared spectrophotometer can measure the soil TPH concentration in mg/kg on a wet weight basis, no
additional calculations are required. However, any variations from the soil sample amount or reagent amount
specified in Step 1 or any sample dilution should be factored into a calculation of the TPH concentration.
2.2.3.3 Advantages and Limitations
An advantage of the OCMA-350 is that it is easy to operate, requiring one person with basic wet chemistry skills.
In addition, the infrared spectrophotometer can be operated in the field using a 110- or 220-volt AC power source,
a gasoline-powered electric generator, or a DC to AC power converter to provide power from a battery.
The OCMA-350 can quantitatively measure all TPH fuel types. According to Horiba, the OCMA-350 can measure
both aromatic and aliphatic hydrocarbons independent of their carbon range.
Another advantage of the OCMA-350 is that the proprietary S-316 extraction solvent has desirable characteristics
relative to other, conventional solvents. According to Horiba, because of the S-316 extraction solvent's high boiling
point (134 °C) and low freezing point (-129 °C), measurements can be made in a wider temperature range than other
extraction solvents allow. The S-316 extraction solvent is nonflammable, nontoxic, and relatively nonvolatile.
The OCMA-350 uses a drying agent—anhydrous sodium sulfate as specified in "Methods for Chemical Analysis of
Water and Wastes" (MCAWW) Methods 413.2 and 418.1 (EPA 1983)—to remove moisture from soil samples. As
a result, no correction associated with solvent dilution is required, which is necessary for wet soil samples. In
addition, not all the supplies necessary to analyze samples using the device are available from Horiba; therefore, an
OCMA-350 user must obtain some supplies from another source.
2.2.4 PetroFLAGrM Test Kit
The PetroFLAG™ test kit, a quantitative device manufactured by Dexsil® Corporation (Dexsil®), is based on
emulsion turbidimetry as discussed in Section 2.1.3. The device has been commercially available since January 1995.
This section describes the device, presents its operating procedure, and discusses its advantages and limitations.
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2.2.4.1 Device Description
The PetroFLAG™ test kit uses a proprietary, nonpolar organic solvent mixture for extraction that is composed of
alcohols, primarily methanol. The device also uses a proprietary developer solution that is polar in nature and that
acts as the emulsifying agent. The developer solution also contains water and surfactants that stabilize the emulsion.
According to Dexsil®, the PetroFLAG™ test kit can measure the petroleum products listed in Table 2-6. The device
does not distinguish between aromatic and aliphatic hydrocarbons, and it responds to compounds in the C8 through
C36 carbon range. MDLs for the device are also listed in Table 2-6 and range from 10 mg/kg for hydraulic fluid to
1,000 mg/kg for weathered gasoline. Based on precision and accuracy tests conducted for diesel and motor oil, the
precision and accuracy of the device are estimated to be ± 10 and ± 20 percent, respectively. The device's response
factors are based on mineral oil. These response factors are listed in Table 2-6 and range from 2 for weathered
gasoline to 10 for transformer oil, indicating that the device is more sensitive to transformer oil than weathered
gasoline. If no information is available regarding the type of contamination in a sample, Dexsil® recommends using
an average response factor of 5. For accurate measurement of TPH in soil, Dexsil® recommends using its
FIYDROSCOUT® meter to measure the moisture content of samples so that an appropriate solvent dilution correction
may be applied to the TPH concentration.
Table 2-6. PetroFLAG™ Test Kit Method Detection Limits and Response Factors for Petroleum Products Measured
Petroleum Product
Mineral oil
Transformer oil
Grease
Hydraulic fluid
Transmission fluid
Motor oil
No. 2 fuel oil
No. 6 fuel oil
Diesel
Gear oil
Low-aromatic diesel
Pennsylvania crude oil
Kerosene
Jet A fuel
Weathered gasoline
Method Detection Limit (milligram per kilogram)
15
15
15
10
19
19
25
18
13
22
27
20
28
27
1,000
Response Factor
10
10
9
8
8
7
7
6
5
5
4
4
4
4
2
For optimum performance, the PetroFLAG™ test kit should be used in environments with a temperature range of
about 4 to 45 °C. The turbidimeter is equipped with a built-in temperature sensor. This sensor measures the ambient
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temperature while TPH measurements are being made. The turbidimeter then uses the sensor's temperature readings
to correct for measurement fluctuations caused by temperature variations. However, the temperature corrections are
valid only for ambient temperatures within 10 °C of the calibration temperature. Therefore, if the ambient temperature
deviates from the calibration temperature by more than 10 °C, an error condition results, and the turbidimeter has to
be recalibrated.
Table 2-7 lists the components of the PetroFLAG™ test kit. The device's components are packaged in the carrying
case, which is about 19 inches wide, 14.25 inches long, and 5.5 inches deep. All device reagents are premeasured
and sealed in glass ampules; additional reagents can be ordered in multiples of the supply requirements for
10 analyses. The turbidimeter weighs 0.6 pound and is 5.75 inches long, 3.5 inches wide, and 2 inches deep. The
complete device weighs less than 10 pounds. The turbidimeter operates on one 9-volt battery, which can last for about
18,000 readings.
Table 2-7. PetroFLAG™ Test Kit Components
Battery-powered, hand-held, digital turbidimeter (9-volt battery included)
Battery-powered balance (batteries included)
Battery-powered timer (batteries included)
10 plastic screw-capped, polypropylene tubes
10 filter-syringe assemblies
2 calibration standards
10 breaktop vials of extraction solvent
10 glass vials containing developer solution
Test procedure manual
Material Safety Data Sheets for all chemicals in kit
Carrying case
The PetroFLAG™ test kit can be purchased for $695 and includes enough supplies to perform 10 soil analyses.
Additional reagents can be purchased for $10 to $15 per analysis, depending on the total quantity purchased. The
FiYDROSCOUT® meter may be purchased for an additional $395. Neither the device components nor the
HYDROSCOUT® meter is available for rental from Dexsil®.
The PetroFLAG™ test kit enables the user to perform up to 16 analyses in 1 hour. Only one person is required to
perform analyses using the device. The device is designed to be used by those with basic wet chemistry skills. A free
training videotape for the device is available from Dexsil®, which also provides technical support over the telephone
at no additional cost.
According to the developer, the PetroFLAG™ test kit is innovative because it responds to a broad range of PHCs
regardless of the source or state of weathering. Also, the proprietary solvent mixture used in the device was selected
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to provide consistent extraction efficiencies for a range of soil types and conditions, including moisture content and
ionic strength.
2.2.4.2 Operating Procedure
Measuring TPH in soil using the PetroFLAG™ test kit involves the following three steps: (1) extraction, (2) filtration
and emulsion development, and (3) turbidity measurement and calculation of the TPH concentration. Calibration
procedures and QC checks required for the device are presented in Chapter 8.
Step 1 - Extraction
1. Measure 10 grams (±0.1 gram) of the soil sample, and place the measured amount in a polypropylene tube.
To extend the quantification range for samples containing EDRO, either a 1-gram sample can be analyzed
or a 10-gram sample can be analyzed using the High Range procedure.
2. Pour one breaktop vial of extraction solvent into the tube, and cap the tube.
3. Set the timer to 5 minutes, and shake the tube for 15 seconds or until the sample is fully wet.
4. Continue to shake the tube intermittently for a minimum of 4 minutes, then let it stand for 1 minute. Samples
containing EDRO contaminants can be extracted for up to 1 hour without significant loss.
Step 2 - Filtration and Emulsion Development
1. Remove the plunger from the filter-syringe assembly, and verify that the 0.2-(im filter disk is firmly attached
to the syringe barrel.
2. Remove the cap from a 6-mL, glass vial containing developer solution.
3. Remove the cap from the polypropylene tube containing the soil and extraction solvent, and pour the extract
supernatant into the syringe barrel. Do not allow soil to enter the syringe, as too much soil might plug the
filter.
4. Discard the first few drops of the extract from the filter into a waste container, and then filter the extract into
the vial containing developer solution. Add the extract into the vial one drop at atime until the meniscus just
enters the vial neck.
5. Cap the vial, and shake it for 10 seconds. Then set the timer to 10 minutes, and let the vial stand. During
the 10-minute period, an emulsion associated with the hydrocarbons in the extract is developed. Do not let
the vial stand longer than 20 minutes before placing it in the turbidimeter, as this might result in a low bias.
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Step 3 - Turbidity Measurement and Calculation ofTPH Concentration
1. After the 10-minute development period, place the vial in the turbidimeter, which should have been
calibrated using a blank and a single calibration standard.
2. If the primary contaminant in a sample is known or suspected, set the appropriate response factor shown in
Table 2-6 on the turbidimeter. If not, use a response factor of 5 as a default value.
3. When the vial is placed in the turbidimeter, a beam of light at a wavelength of 5 85 nm passes through the vial,
and the intensity of the light scattered at an angle of 90 degrees to the initial beam of light is measured. The
TPH reading of the sample extract is displayed on the turbidimeter as mg/kg TPH in soil on a wet weight
basis.
4. In certain circumstances, the water content of the soil and analyte carbon number range may require a
correction factor to account for soil-water content. To correct the TPH concentration in mg/kg on a wet
weight basis for solvent dilution associated with the moisture content of a given soil sample, use
Equation 2-8.
mg/kg TPH after correcting _ mg/kg TPH before correcting 100 + Percent Moisture
for solvent dilution for solvent dilution 100
2.2.4.3 Advantages and Limitations
An advantage of the PetroFLAG™ test kit is that it is easy to operate, requiring one person with basic wet chemistry
skills. In addition, the turbidimeter operates using a 9-volt battery; therefore, an AC power source is not required in
the field.
According to Dexsil®, another advantage of the PetroFLAG™ test kit is that a soil moisture content of up to 25
percent does not interfere with soil analysis. Therefore, no chemicals need to be added to a soil sample in order to
reduce its moisture content. In addition, the turbidimeter is able to correct for measurement fluctuations caused by
temperature variations.
A limitation of the PetroFLAG™ test kit is that it cannot quantitatively measure TPH in the C6 and C7, and the C37
through C40 carbon ranges. According to Dexsil®, the device can measure both aromatic and aliphatic hydrocarbons
in the C8 through C36 carbon range. In addition, the device is less sensitive to weathered gasoline than to other
petroleum products.
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2.2.5 Luminoscope
The Luminoscope was developed by the Oak Ridge National Laboratory under the sponsorship of the U.S.
Department of Energy and the EPA in collaboration with Environmental Systems Corporation (ESC). The device
produces quantitative results and is based on ultraviolet fluorescence spectroscopy as discussed in Section 2.1.4. The
Luminoscope has been commercially available since 1997. This section describes the device, presents its operating
procedure, and discusses its advantages and limitations.
2.2.5.1 Device Description
The Luminoscope is based on ultraviolet fluorescence spectroscopy and uses excitation and emission
monochromators. The components of the Luminoscope are structured to maintain a constant wavelength interval
(delta lambda) between the excitation and emission monochromators. This modification of classical fluorescence
technology is called synchronous fluorescence and takes advantage of the overlap between the excitation and emission
spectra for a sample to produce more sharply defined spectral peaks. According to ESC, this modification maximizes
the Luminoscope's capability to differentiate among various aromatic hydrocarbons that may be present in a sample
extract. For TPH analyses of soil samples, a delta lambda of 18 run is typically used.
The Luminoscope uses a high-pressure xenon lamp as its light source. The xenon lamp emits light of wavelengths
ranging from 200 to 650 nm. The Luminoscope has a spherical, concave mirror that collects back-emitted light and
directs it toward the excitation monochromator. A laptop computer with Grams/32 software developed by Galactic
Industries is used to control the Luminoscope and to manage data collected by the device. The Luminoscope allows
the user to generate emission spectra ranging from 200 to 650 nm.
Several solvents can be used to complete extraction of soil samples for Luminoscope analysis, including methanol,
CH2C12, and cyclohexane. According to ESC, the choice of solvent depends on (1) the carbon range of the
contaminant of concern and (2) the solvent that would typically be used to analyze for the contaminant under
conventional, laboratory methods. For the demonstration, methanol will be used to extract all soil samples.
The Luminoscope can be used to measure concentrations of PHCs in soil. Because aromatic hydrocarbons fluoresce
when they are excited by ultraviolet light, the Luminoscope responds to their concentrations in sample extracts.
Although aliphatic hydrocarbons do not fluoresce, off-site laboratory results for TPH analysis of a subset of samples
can be used to develop a site-specific calibration curve of luminescence intensity versus TPH concentration. Once
the Luminoscope has been used to measure the luminescence intensities of the remaining sample extracts, the
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calibration curve can be used to calculate the concentrations of TPH present. The Luminoscope can achieve an MDL
of 50 micrograms (|ig) per kg for TPH. No information is currently available from ESC regarding the accuracy and
precision of the device. Interpretation of the spectra generated by the Luminoscope allows the user to report data as
GRO and EDRO concentrations based on the carbon range selected. Additional extraction or analysis of the sample
extract is not required to report data as GRO and EDRO concentrations.
ESC does not specify an operating temperature range forthe Luminoscope; however, the device has been successfully
operated at ambient temperatures ranging from -7to38°C. ESC also does not specify a particular storage temperature
for the Luminoscope. In addition, according to ESC, humidity levels do not appear to affect the operation of the
Luminoscope.
The Luminoscope is 12 inches long, 16 inches wide, and 16 inches deep; weighs 34 pounds; and comes with a
carrying case. The Luminoscope can be operated using a standard automobile battery; an appropriate battery
converter may be purchased from ESC. To analyze samples using the Luminoscope, a user may also purchase quartz
cuvettes and a sampling kit from ESC. The sampling kit contains enough vials, pipettes, test tubes, and filters to
analyze 25 samples along with 1 L of extraction solvent. Grams/32, the computer software used to control the
Luminoscope and manage its data, is purchased separately. Additional equipment required to operate the
Luminoscope that is not provided by ESC includes a balance, centrifuge, test tube shaker, and laptop computer.
According to ESC, about 40 samples can be analyzed by one on-site technician using the Luminoscope over an 8-hour
period. Although it is not necessary for operation of the device, ESC recommends 3 days of training in fluorescence
theory, device operation, sample preparation, and data display. The cost of this training is included in the purchase
cost of the Luminoscope. ESC also provides technical support over the telephone at no additional cost.
The Luminoscope's purchase cost is $26,500. Quartz cuvettes cost an additional $110 each. Depending on auser's
requirements, ESC can prepare a sampling kit that contains enough support equipment to analyze 25 samples; such
a kit costs about $115. To analyze samples using the Luminoscope, the user must also provide a balance, centrifuge,
test tube shaker, and laptop computer that are not available for purchase from ESC. The software used to operate
the Luminoscope, Grams/32, costs an additional $2,400. The Luminoscope and Grams/32 software may also be
rented from ESC for $600 per day. This cost covers a technician to operate the device and enough support equipment
to analyze about 40 samples. The Luminoscope purchase and rental costs do not include travel and per diem costs
for the training instructor and technician, respectively.
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According to ESC, the Luminoscope is innovative when compared with conventional ultraviolet fluorescence
spectroscopes because the device uses synchronous fluorescence to take advantage of the overlap between the
absorption and emission spectra for a sample extract to generate more sharply defined spectral peaks. This feature
enhances the Luminoscope's capability to differentiate among various aromatic hydrocarbons that may be present in
a sample extract. The Luminoscope is also able to separately report TPH concentrations for GRO and EDRO without
additional extraction or analysis.
2.2.5.2 Operating Procedure
Measuring TPH in soil using the Luminoscope involves the following two steps: (1) extraction and (2) concentration
measurement. These steps are described below. Calibration procedures and QC checks required for the Luminoscope
are presented in Chapter 8.
Step 1 - Extraction
1. Measure 2 grams of soil sample, and place the measured amount in a test tube.
2. Add 10 mL of the appropriate solvent to the test tube.
3. Manually shake the test tube until, based on visual observation, more than 90 percent of the sample is
suspended in the solvent. If multiple test tubes need to be shaken, use a test tube shaker.
4. Spin the test tube in a centrifuge to separate the soil.
5. Pour the extract into a second test tube.
6. If any soil particles are visible, use a syringe with a detachable filter to transfer the extract to a cuvette. If soil
particles are not visible, transfer the extract directly to a cuvette.
Step 2 - Concentration Measurement
1. Analyze the sample over a predetermined wavelength range. For TPH analyses, a wavelength range of 250
to 400 nm is typically used.
2. Use the Grams/32 software to integrate the area under the peaks of the sample spectrum. To report results
as a TPH concentration, integrate the area under the curve from about 275 to 340 nm. To report results as
GRO and EDRO concentrations, integrate the areas under the curve from about 275 to 300 nm and 300 to
340 nm, respectively.
3. Use a calibration curve to convert area counts reported by the Luminoscope into a TPH, GRO, or EDRO
concentration.
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2.2.5.3 Advantages and Limitations
An advantage of the Luminoscope is that it is easy to operate, requiring one person with basic analytical chemistry
skills. In addition, the device is operated using a DC power source such as an automobile cigarette lighter; therefore,
an AC power source is not required in the field.
Another advantage of the Luminoscope is that it can quantitatively measure all fuel types in the (ig/kg range that
contain aromatic hydrocarbons. In addition, interpretation of the spectra generated by the Luminoscope allows the
user to report data as GRO and EDRO concentrations without additional sample extraction or analysis.
According to ESC, an advantage of the Luminoscope over conventional ultraviolet fluorescence spectroscopes is that
the device uses synchronous fluorescence to take advantage of the overlap between absorption and emission spectra
for a sample extract. This feature maximizes the Luminoscope's ability to differentiate among various aromatic
hydrocarbons that may be present in a sample extract.
A limitation of the Luminoscope is that it requires calibration and calculation of TPH concentrations using site-
specific soil sample concentrations measured by an off-site laboratory during a presampling or postsampling effort.
The presampling effort allows the Luminoscope user to determine on-site TPH concentrations while in the field but
increases the mobilization costs for a project. The postsampling effort does not increase mobilization costs, but the
Luminoscope user cannot determine TPH concentrations in the field; only luminescence intensity readings can be
taken. In addition, a laptop computer must be used to analyze samples and to report data generated using the
Luminoscope.
2.2.6 UVF-3100A
The UVF-3100A, a quantitative device developed by siteLAB® Corporation (siteLAB®), is based on ultraviolet
fluorescence spectroscopy as discussed in Section 2.1.4. The UVF-3100A is manufactured for siteLAB® by Turner
Designs and has been modified and distributed for environmental use by siteLAB®. The UVF-3100A has been
commercially available since October 1998. This section describes the device, presents its operating procedure, and
discusses its advantages and limitations.
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2.2.6.1 Device Description
The siteLAB® portable fluorometer is fitted with excitation and emission filters that are appropriate for TPH analysis
of soil samples. In addition, siteLAB® has developed and provides software that can be used to manage and present
data generated by the UVF-3100A.
The UVF-3100A uses a mercury vapor lamp with a predominant emission of 254-nm wavelength as its light source.
Light from the lamp is directed through an excitation filter of 254 nm before it irradiates a sample extract held in a
quartz cuvette. Depending on the analysis being conducted, the fluorometer is fitted with an appropriate emission
filter that corresponds to the wavelength at which the sample extract is expected to fluoresce. For GRO, an emission
filter with a bandwidth of 280 nm is used, and for EDRO, an emission filter with a bandwidth between 300 and 400
nm is used. These filters are used because GRO and EDRO aromatic hydrocarbons fluoresce within these wavelength
ranges. Both the excitation and emission filters are fitted into sleeves that fit into ports in the fluorometer. To analyze
soil samples using the UVF-3100A, methanol is used as the extraction solvent.
The UVF-3100A can be used to measure petroleum fuel products. Because aromatic hydrocarbons fluoresce when
they are excited by ultraviolet light, the fluorometer can measure their concentrations in sample extracts. Aliphatic
hydrocarbons do not fluoresce; therefore, the fluorometer cannot quantify aliphatic hydrocarbon concentrations.
However, siteLAB® software can estimate aliphatic hydrocarbon fractions and individual PAH or BTEX
concentrations by generating response factors based on aromatic and aliphatic hydrocarbon ratios for two to five site-
specific samples that are sent to an off-site laboratory for GC analysis. siteLAB® has determined MDLs for the
UVF-3100A by analyzing sand blanks. The resulting MDLs for petroleum fuel products in soil range from 0.08 to
6.9 mg/kg and are listed in Table 2-8.
Table 2-8. UVF-3100A Method Detection Limits
Petroleum Fuel Product Method Detection Limit for Soil (milligram per kilogram)
No. 2 fuel oil 0.50
No. 4 fuel oil 0.20
No. 6 fuel oil 0.08
Diesel 0.60
50 percent weathered diesel 0.34
Gasoline 6.9
50 percent weathered gasoline 3.9
Motor oil 1.0
Extended diesel range organics-polynuclear aromatic hydrocarbons 0.04
Gasoline range organics-benzene, toluene, ethylbenzene, and xylenes 0.10
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The operating temperature range for the UVF-3100A is 0 to 38 °C. The lowest operating temperature is based on
the possibility of the fluorometer's quartz crystal display freezing. According to siteLAB®, the UVF-3100A does
not have a storage temperature or operating humidity restriction.
The siteLAB® UVF-3100A Extraction System includes the fluorometer and support equipment listed in Table 2-9.
siteLAB® separately provides a 20 Sample Extraction Kit that contains the equipment listed in Table 2-9. Calibration
kits for a variety of TPH standards are also available from siteLAB®. Each calibration kit includes five linear
calibration standards and one reference standard.
Table 2-9. UVF-3100A Components
UVF-3100A Extraction System
Fluorometer
Alternating current power adapter
Direct current power converter
RS-232 cable
Quartz cuvettes (2)
Timer (batteries included)
Certified clean sand (500 grams)
High-performance liquid chromatography-grade methanol (1 liter)
Solvent dispenser bottle
5-millimeter volumetric flask
10-millimeter volumetric flask
Tissue wipes
2 stainless-steel spatulas
Adjustable pipette
Test tube rack
Battery-powered balance (9-volt battery included)
Markers
Shaker/mixer can
site LAB® software
Portable field case
Instruction manual and simplified instruction sheet
20 Sample Extraction Kit
20 extraction jars
20 weighing boats
20 pipette tips
20 syringes with detachable filters
40 10-milliliter test tubes
40 stainless-steel mixing balls
The UVF-3100A Extraction System and 20 Sample Extraction Kit fit in a portable field case that is 12 inches long,
36 inches wide, and 24 inches deep and weighs 55 pounds. The UVF-3100A may be operated using a using a DC
power source such as an automobile cigarette lighter; therefore, an AC power source is not required in the field.
Connecting the UVF-31OOA to a computer allows downloading and manipulation of calibration and sample data using
siteLAB® software, although a computer connection is not needed to collect or read data. To connect the device to
a computer, an RS-232 cable connection is used. At a minimum, the computer must support the Microsoft
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Windows 95 operating system and have Microsoft Excel software installed. If a computer that does not meet these
requirements is used, a special computer program and technical support can be provided by siteLAB® to assist the user
in manipulating data.
Using the UVF-3100A, 40 to 50 samples can be analyzed by one on-site technician in an 8-hour period. Each sample
takes about 5 to 10 minutes to process; analysis time is 5 to 10 seconds. Although it is not required for operation of
the UVF-31OOA, siteLAB® recommends 0.5 to 1 day of training by a siteLAB® instructor in device operation and data
management. The cost of this training is included in the purchase cost of the UVF-31 OOA. siteLAB® also provides
technical support over the telephone at no additional cost.
The UVF-31 OOA Extraction System has a purchase price of $11,999. siteLAB® also rents the UVF-31 OOA at a rate
of $1,250 per day. The rental cost covers a technician and all the support equipment required to operate the device.
siteLAB® does not rent the UVF-31 OOA without a technician. The purchase and rental costs do not include travel and
per diem costs for an instructor or technician. In the New England region, siteLAB® rents the device at a rate of $ 150
per hour for the UVF-31 OOA and a technician; a 4-hour rental minimum is required to obtain this rate, and travel costs
for the technician may also be applied. The 20 Sample Extraction Kit costs $299. In addition, calibration kits for a
variety of TPH standards cost $199 each. siteLAB® provides software upgrades at no cost.
siteLAB® considers the UVF-31 OOA to be innovative because the device adapts a laboratory technology for field use.
The device is able to separately report aromatic hydrocarbon concentrations for GRO and EDRO analyses.
2.2.6.2 Operating Procedure
Measuring TPH in soil using the UVF-3100A involves the following two steps: (1) extraction and (2) concentration
measurement. The UVF-3100A can measure both GRO and EDRO components of sample extracts. Both analyses
may be performed on one sample extract; however, the emission filter must be replaced and the device must be
recalibrated between the GRO and EDRO analyses. The two-step operating procedure for the device is described
below. Calibration procedures and QC checks required for the UVF-31 OOA are presented in Chapter 8.
Step 1 - Extraction
1. Measure 10 grams of soil sample, and place the measured amount in a high-density polypropylene sample
extraction jar.
2. Add two steel mixing balls to the jar. For clay soil, add three mixing balls to the jar.
55
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3. Add 10 mL of methanol to the j ar, and cap the j ar.
4. Manually shake the jar for 2 minutes. If multiple jars must be shaken, use the shaker/mixer can, which can
hold up to five jars.
5. If soil particles are visible in the jar, allow the soil to settle for 1 to 2 minutes.
6. Use a syringe with a detachable filter to transfer 3 mL of filtered extract into a test tube.
7. Cap the test tube, and let it stand until concentration measurement is performed.
Step 2 - Concentration Measurement
1. Decant the extract from the test tube into a quartz cuvette. Place the cuvette in the sample chamber of the
UVF-3100A.
2. The device displays concentrations in ng/L, (ig/L, mg/L, parts per trillion, parts per billion (ppb), ppm, or
fluorescence units. Device readings may be downloaded to a computer and compiled with other data as part
of a spreadsheet or may be manually recorded from the UVF-3100A display.
3. The concentration measured represents only the aromatic hydrocarbons present in the sample extract. The
aliphatic hydrocarbon concentration may be estimated using the UVF-3100A software.
2.2.6.3 Advantages and Limitations
An advantage of the UVF-3100A is that it is easy to operate, requiring one person with basic analytical chemistry
skills. In addition, the device is operated using a DC power source such as an automobile cigarette lighter; therefore,
an AC power source is not required in the field. After sample extraction, analysis takes less than 10 seconds.
Another advantage of the UVF-3100A is that it can quantitatively measure all TPH fuel types that contain aromatic
hydrocarbons. The device does not measure aliphatic hydrocarbons. However, the device's software can estimate
aliphatic hydrocarbon fractions based on response factors developed using off-site laboratory analytical results for
site-specific samples. The UVF-3100A can also measure both GRO and EDRO compounds of all fuel types
regardless of weathering. However, between GRO and EDRO analyses, the emission filter must be changed and the
device must be recalibrated; then the sample extract must be reanalyzed. The UVF-3100A uses reusable, certified
standards for calibration.
A limitation of the UVF-3100A is that response factors must be developed to measure aliphatic hydrocarbon
concentrations. These response factors are developed using site-specific soil sample concentrations measured by an
off-site laboratory during a presampling or postsampling effort. A presampling effort allows the UVF-3100A user
56
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to determine TPH concentrations while in the field but increases the mobilization costs of a project. A postsampling
effort does not increase the mobilization costs, but the UVF-3100A user cannot determine aliphatic hydrocarbon
concentrations in the field; only aromatic concentration readings can be taken.
2.2.7 EnSys Petro Test System
The EnSys Petro Test System, a semiquantitative device manufactured by Strategic Diagnostics, Inc. (SDI), is based
on a combination of immunoassay, specifically ELISA, and colorimetry as discussed in Section 2.1.5. The device
has been commercially available since 1992. The device conforms to SW-846 Method 4030 for screening PHCs using
immunoassay detection (EPA 1996). This section describes the device, presents its operating procedure, and discusses
its advantages and limitations.
2.2.7.1 Device Description
The EnSys Petro Test System includes the SDI Sample Extraction Kit, the EnSys Petro 12T Soil Test Kit, and the
EnSys/EnviroGard® Common Accessory Kit. The EnSys Petro Test System includes antibody-coated test tubes
containing monoclonal antibodies, which are produced using m-xylene as the antigen. The enzyme conjugate used
to produce color is composed of m-xylene as the target compound and horseradish peroxidase as the enzyme. The
washing step is performed with a dilute detergent solution. Color development is achieved using hydrogen peroxide
as the substrate and tetramethylbenzidine (TMB) as the chromogen. The stop solution added to terminate color
development is 0.5 percent sulfuric acid. A differential spectrophotometer that emits light in the visible range of the
electromagnetic spectrum at 450-nm wavelength is used to measure the absorbance of the sample extract and of a
reference standard containing 3 mg/L m-xylene during color measurement. The concentration of PHCs in the
sample extract is then determined by comparing the absorbance readings associated with the sample extract and
reference standard.
According to SDI, the EnSys Petro Test System can be used to measure the following petroleum products in soil:
gasoline, diesel, Jet A fuel, JP-4, kerosene, No. 2 fuel oil , No. 6 fuel oil, and mineral spirits. The device is not
designed to respond to every petroleum product component that may be present in a sample extract. The monoclonal
antibodies used in the device are specific to a subset of petroleum product components. According to SDI, the subset
includes a large portion of the aromatic hydrocarbons and a few aliphatic hydrocarbons in the C6 through C22 carbon
range.
57
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The MDLs of the EnSys Petro Test System for a variety of aromatic and aliphatic hydrocarbons are presented in
Table 2-10. Except for C6H6, which has an MDL of 400 mg/kg, the aromatic hydrocarbons listed in Table 2-10 have
MDLs that are less than 40 mg/kg, indicating a high degree of selectivity. A few aliphatic hydrocarbons, such as
2-methylpentane and isooctane, also have low MDLs. Table 2-10 also presents the MDLs for various petroleum fuel
products. These MDLs generally range from 10 mg/kg (gasoline) to 40 mg/kg (mineral spirits). The MDLs for
machine oil, brake fluid, motor oil, grease, and mineral oil are all greater than 1,000 mg/kg, indicating that the EnSys
Petro Test System is not as sensitive to these formulated petroleum products. Additional information on EnSys Petro
Test System performance is available in SW-846 Method 4030 (EPA 1996).
The operating temperature range for the EnSys Petro 12T Soil Test Kit is 16 to 38 °C. According to SDI, the test kit
does not have an operating humidity restriction. The test kit should be stored at less than 27 °C when not in use. The
shelf life of the test kit is typically 1 year after its date of manufacture; lot-specific expiration date information is
provided on the test kit packaging. The chromogen and substrate solutions should not be exposed to direct sunlight
during test kit operation or storage.
The components of the EnSys Petro Test System are listed in Table 2-11. The SDI Sample Extraction Kit contains
enough components to perform 12 soil sample extractions. The EnSys Petro 12T Soil Test Kit contains enough
components to process up to 12 samples (for example, 10 soil sample extracts and duplicate calibration standards).
The components of the EnSys/EnviroGard® Common Accessory Kit are multi-use items and do not require frequent
replacement. All components of the accessory kit are housed in a hard-plastic carrying case to prevent component
damage during kit transport. The components of the extraction kit and soil test kit are shipped in cardboard boxes.
The spectrophotometer (Artel DP™ Differential Photometer) included in the EnSys/EnviroGard® Common Accessory
Kit is designed to provide an immediate, direct comparison of the absorbance of two liquid samples (for example, a
soil sample extract and a reference standard) by means of a digital display; the display indicates the difference in
absorbance between the two samples. The spectrophotometer emits light at a factory-preset wavelength of 450 nm.
This spectrophotometer is 3.4 inches long, 5.3 inches wide, and 2.6 inches tall and weighs 0.8 pound. The power
supply for the spectrophotometer consists of four rechargeable nickel-cadmium batteries; the spectrophotometer
cannot be operated using an AC power source. The batteries require 8 to 10 hours to achieve a full recharge after
discharge and last for about 500 readings between recharges. The operating temperature range for the
spectrophotometer is 10 to 40 °C. According to SDI, the spectrophotometer does not have an operating humidity
restriction. The spectrophotometer should be stored at a temperature between -20 and 65 °F when not in use.
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Table 2-10. EnSys Petro Test System Method Detection Limits
Compound or Substance Method Detection Limit (milligram per kilogram)3
Petroleum fuel product
Gasoline
Diesel
Jet A fuel
JP-4
Kerosene
No. 2 fuel oil
No. 6 fuel oil
Formulated petroleum product
Mineral spirits
Machine oil
Brake fluid
Unused motor oil
Grease
Mineral oil
Aromatic hydrocarbon
Benzene
Toluene
Ethylbenzene
o-Xylene
m-Xylene
p-Xylene
Styrene
1,2-Dichlorobenzene
Hexachlorobenzene
Naphthalene
Acenaphthalene
Biphenyl
Creosote
Aliphatic hydrocarbon
2-Methylpentane
Hexanes (mixed)
Heptane
Isooctane
Undecane
Trichloroethylene
Methyl-tert-butyl-ether
10
15
15
15
15
15
25
> 1,000*
>1,000b
>1,000b
>1,000b
> 1,000
400
40
7
8.5
8
4.5
7
2.5
10
0.8
0.5
10
1.5
35
65
130
>1,000b
>1,000b
> 1,000
Notes:
> = Greater than
a Minimum soil concentration necessary to obtain a positive result more than 95 percent of the time
b Highest concentration tested; positive result not obtained at this concentration
Source: SDI 1999
The purchase cost for the SDI Sample Extraction Kit designed for the EnSys Petro Test System is $120. The
purchase cost for the EnSys Petro 12T Soil Test Kit is $366. The EnSys/EnviroGard® Common Accessory Kit can
be purchased for $1,999 or rented for $175 per day, $450 per week, or $800 per month. Individual kit components
may also be purchased separately from SDI.
According to SDI, 12 samples (including soil sample extracts and reference standards) can be analyzed as one batch
by one person using the EnSys Petro Test System in approximately 45 minutes. The device is easy to operate and
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Table 2-11. EnSys Petro Test System Components
SDI Sample Extraction Kit
12 extraction jars with screw caps (each jar contains 3 stainless-steel mixing balls)
12 filter units (tops and bottoms)
12 ampule crackers
12 dilution ampules (for EnSys Petro Test System only)
12 wooden spatulas
12 weigh canoes
12 disposable transfer pipettes
12 ampules containing 100 percent methanol solvent
User guide
EnSys Petro 12T Soil Test Kit
12 monoclonal antibody-coated tubes
16 conjugate tubes
1 80-milliliter bottle of phosphate buffer solution
1 15-milliliter bottle of chromogen (tetramethylbenzidine)
1 15-milliliter bottle of substrate (hydrogen peroxide)
1 15-milliliter bottle of stop solution (0.5 percent sulfuric acid)
3 15-milliliter vials of Petro standard (3 milligrams per liter m-xylene)
24 Microman® positive displacement pipettor tips
3 5-milliliter Combitips® for the repeater pipettor
1 12.5-milliliter Combitip® for the repeater pipettor
12 ampule crackers
3 amber vials (for storage of remnant solution from cracked ampules)
3 disposable transfer pipettes
1 480-milliliter bottle of dilute detergent solution
2 wash bottles
User guide
EnSys/EnviroGard® Common Accessory Kit
1 battery-powered Artel DP™ Differential Photometer
1 battery-powered ACCULAB® digital balance
1 battery-powered digital timer
1 Gilson M-25 Microman® positive displacement pipettor
1 Eppendorf™ repeater pipettor
1 5-milliliter Combitip® for the repeater pipettor
1 12.5-milliliter Combitip® for the repeater pipettor
1 50-milliliter Combitip® for the repeater pipettor
1 wash bottle
1 foam workstation
User guide
Carrying case
is designed to be used by those with basic wet chemistry skills. In addition to the user guide that accompanies each
kit of the device, SDI provides technical support over the telephone at no additional cost. SDI also offers a 1-day,
on-site training program for $999, which covers instructor travel, instructor per diem, and one EnSys Petro Test
System for training purposes.
According to SDI, the EnSys Petro Test System is innovative because the device uses biologically engineered
antibodies to measure PHCs in soil. The device measures most aromatic hydrocarbons and some aliphatic
hydrocarbons in the C6 through C22 carbon range.
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2.2.7.2 Operating Procedure
Measuring TPH in soil using the EnSys Petro Test System involves the following five steps: (1) extraction, (2) sample
and standard preparation, (3) washing, (4) color development, and (5) color measurement and estimation of TPH
concentration. These steps are described below. Calibration procedures and QC checks required for the device are
presented in Chapter 8.
Step 1 - Extraction
1. Measure 10 ± 0.1 grams of soil sample, and placed the measured amount in an extraction jar.
2. Pour the contents of one solvent ampule (containing 20 mL of 100 percent methanol) into the jar, and cap the
jar.
3. Shake the jar vigorously for 1 minute.
4. Allow the soil to settle for 1 minute or until a liquid solvent layer (supernatant) is observed above the soil.
If the supernatant is not observed within 15 minutes, decreasing the soil to solvent ratio may be required.
Also, when a clay soil sample is being extracted, the soil might absorb all the methanol, leaving little or no
excess liquid to filter. Under these circumstances, add another 10 mL of methanol to the jar, and shake the
jar vigorously for an additional 1 to 2 minutes. Factor this dilution into the calculations for interpreting the
photometric results during Step 5.
5. Transfer at least half a bulb pipette (about 1.5 mL) of supernatant into the bottom portion of the filter unit;
do not transfer more than one full bulb of supernatant.
6. Press the top portion of the filter unit (the piece with the cap and filter) into the bottom portion (containing
the sample extract) until the unit snaps together or until most of the liquid has passed upward through the
filter.
Step 2 - Sample and Standard Preparation
1. Add 1.25 mL of phosphate buffer solution to each conjugate tube. The phosphate buffer solution (1) hydrates
the enzyme conjugate (which is freeze-dried) and (2) helps maintain the pH in the antibody-coated tube (thus
preventing the antibodies from denaturing) when the enzyme conjugate is added to the antibody-coated tube.
2. Transfer 60 (iL of sample extract from the filter unit to each of the conjugate tubes designated for sample
extract.
3. Add 60 \\L of standard (3-mg/L m-xylene) to each of the two conjugate tubes designated for the reference
standard.
4. Fit an antibody-coated tube on top of each conjugate tube.
61
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5. Set the timer for 10 minutes.
6. Invert all the connected tube pairs so that the liquid is poured into the antibody-coated tubes.
7. Invert all the tube pairs several more times during the 10-minute period to mix the solutions. Make sure that
each tube pair is positioned with the antibody-coated tube on the bottom after each inversion.
8. Disconnect the conjugate tubes, and discard them.
Step 3 - Washing
1. Vigorously shake out each antibody-coated tube's contents into a sink or suitable container.
2. Fill each antibody-coated tube to overflowing with a vigorous stream of dilute detergent solution. Then
vigorously shake out the tube contents into a sink or suitable container. Repeat this washing activity three
more times. After the final wash, remove as much water as possible by tapping the inverted tube on absorbent
paper.
Step 4 - Color Development
1. Add 200 (iL of chromogen (TMB) to each antibody-coated tube.
2. Set the timer for 2.5 minutes.
3. Add 200 (iL of substrate (hydrogen peroxide) to each antibody-coated tube. Addition of the substrate turns
the reaction mixture blue.
4. At the end of 2.5 minutes, add 200 \\L of stop solution (0.5 percent sulfuric acid) to each antibody-coated
tube. Addition of the stop solution turns the reaction mixture yellow.
Step 5 - Color Measurement and Estimation of TPH Concentration
1. Place the two tubes that contain the reference standard in the differential photometer.
2. Switch the reference standard tubes until the photometer reading is negative or zero. If the reading is less
than -0.30, the results are outside QC limits. In this case, re-extract the soil samples, and repeat Steps 2
through 4.
3. Remove and discard the reference standard tube in the right well of the photometer; the reference standard
tube in the left well contains the lower standard concentration, which will result in a conservative estimate
of the sample extract concentration.
4. Place the sample extract tube in the right well of the photometer, and record the absorbance reading. If the
photometer reading is negative or zero, the TPH concentration in the sample extract is equal to or greater than
that in the reference standard (3-mg/L m-xylene). If the photometer reading is positive, the TPH
concentration in the sample extract is less than that in the reference standard (3-mg/L m-xylene).
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5. Convert the concentration of the reference standard to petroleum fuel product equivalents. For example, the
3-mg/L m-xylene standard is equivalent to 8 mg/kg m-xylene in soil on a wet weight basis. According to
Table 2-10, the gasoline fuel product equivalent to 8 mg/kg m-xylene in soil on a wet weight basis is
10 mg/kg gasoline in soil on a wet weight basis. Similarly, for diesel, the equivalent concentration is
15 mg/kg in soil on a wet weight basis. The petroleum fuel product equivalent is selected based on the
petroleum fuel product known to be present where the sample was collected. Therefore, if the absorbance
reading is negative and gasoline is believed to be present in the soil, the TPH concentration in the sample
would be estimated to be greater than 10 mg/kg gasoline; if the absorbance reading is positive or zero, the
TPH concentration in the sample would be estimated to be less than or equal to 10 mg/kg gasoline.
6. If the absorbance reading is negative, the analysis may be performed at multiple detection levels by diluting
the sample extract with methanol and assaying the sample extract again. Interpret the resulting photometer
reading as described in item 5; however, multiply the petroleum fuel product equivalent by the dilution factor
to determine the approximate soil sample concentration. Methanol dilutions must be conducted at least four
times apart to adequately discriminate between measurements.
2.2.7.3 Advantages and Limitations
An advantage of the EnSys Petro Test System is that it is easy to operate, requiring one person with basic wet
chemistry skills. In addition, the spectrophotometer is battery-operated; therefore, an AC power source is not required
in the field.
A limitation of the device is that it does not measure all TPH fuel types. According to SDI, the device is designed
to measure a large portion of the aromatic hydrocarbons but only a few of the aliphatic hydrocarbons in the C6 through
C22 carbon range. In addition, spectrophotometer results are not reported in terms of TPH. Instead, absorbance results
are converted to petroleum fuel product equivalents for only one type of fuel—for example, gasoline or diesel. The
device is not designed to account for more than one fuel type that may be present in a sample extract, and the
individual fuel types that can be measured are limited to those for which SDI has developed petroleum fuel product
equivalents (see Table 2-10).
Another limitation of the EnSys Petro Test System is that it does not generate quantitative results. The
semiquantitative results produced by the device can only indicate whether the PHC concentration in a sample extract
is above or below a particular level. The concentration range of the sample extract can be narrowed by increasing
the number of dilutions in a sample batch. However, increasing the number of dilutions increases the analytical time
and cost per sample.
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Chapter 3
Demonstration Site Descriptions
This chapter describes the three sites selected for conducting the demonstration. The first site is referred to as the
Navy BVC site; it is located in Port Hueneme, California, and contains three sampling areas. The second site is
referred to as the Kelly AFB site; it is located in San Antonio, Texas, and contains one sampling area. The third site
is referred to as the PC site; it is located in north-central Indiana and contains one sampling area. After review of the
information available on these and other candidate sites, the Navy BVC, Kelly AFB, and PC sites were selected based
on the following criteria:
• Site Diversity—Collectively, the three sites contain sampling areas with the different soil types and the
different levels and types of PHC contamination needed to evaluate the field measurement devices described
in Chapter 2.
Access and Cooperation—The site representatives are interested in supporting the demonstration by
providing site access for collection of soil samples required for the demonstration. In addition, because the
field measurement devices will be demonstrated at the Navy BVC site using soil samples from all three sites,
the Navy BVC site representatives will provide the site support facilities required for the demonstration and
will support a visitors' day during the demonstration. As a testing location for the Department of Defense
National Environmental Technology Test Site Program, the Navy BVC site is used to demonstrate
technologies and systems for characterizing or remediating soil, sediment, and groundwater contaminated
with fuel hydrocarbons or waste oil.
The site descriptions in Sections 3.1 through 3.3 are based on data collected in January 2000 during the
predemonstration investigation sampling activities as well as on the information provided by the site representatives.
The predemonstration investigation samples were analyzed for GRO and EDRO using SW-846 Method 8015B
(modified) by Tetra Tech's SITE team laboratory, Severn Trent Laboratories in Tampa, Florida (STL Tampa East).
Physical characterization of these samples was done in the field by a geologist. Some of the predemonstration
investigation samples were also analyzed by the measurement device developers at their facilities. Table 3-1
summarizes key site characteristics, including the contamination type, predemonstration investigation sampling depth
intervals, associated TPH concentrations, and soil type in each sampling area.
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Table 3-1. Summary of Site Characteristics
Site
Navy BVC
Kelly AFB
PC
Sampling Area
FFA
NEX Service
Station Area
PRA
B-38 Area
SFTArea
Type of Contamination
EDRO (weathered diesel
with carbon range from
C10 through C40)
GRO and EDRO (fairly
weathered gasoline with
carbon range from C7
through C14)
EDRO (heavy lubricating
oil with carbon range from
C14 through C40+)
GRO and EDRO (heavy
lubricating oil with carbon
range from C24 through
C30)
GRO and EDRO
(combination of slightly
weathered gasoline,
kerosene, JP-5, and
diesel with carbon range
from C6 through C32)
Approximate
Sampling Depth
Interval
(foot bgs)
Upper layer3
Lower layer3
5 to 6
6 to 7
7 to 8
8 to 9
9 to 10
10 to 11
1.5 to 2.5
13to17
29 to 30
2 to 4
4 to 6
6 to 8
8 to 10
TPH Concentration
Range (mg/kg)
38 to 470
7,700 to 1 1 ,000
21 to 22
15to18
25 to 60
23 to 65
40 to 1 ,600
24 to 300
1 ,500 to 2,700
9
9 to 18
27 to 1 ,300
200 to 1 ,300
46 to 600
49 to 260
Type of Soil
Silty sand
Silty sand
Silty sand with some clay
Clayey silt in upper depth interval
and sandy clay with significant
gravel in deeper depth interval
Sandy silt and clay with increasing
clay content in deeper depth
intervals
Notes:
AFB = Air Force Base
bgs = Below ground surface
BVC = Base Ventura County
C = Carbon
EDRO = Extended diesel range organic
FFA = Fuel farm area
GRO = Gasoline range organic
mg/kg = Milligram per kilogram
NEX = Naval Exchange
PC = Petroleum company
PRA = Phytoremediation area
SFT = Slop Fill Tank
TPH = Total petroleum hydrocarbons
Because of soil conditions encountered in the FFA, the sampling depth intervals could not be accurately determined. Sample collection was
initiated approximately 10 feet bgs, and attempts were made to collect 4-foot-long soil cores. This approach resulted in varying degrees of
core tube penetration up to 17 feet bgs. At each location in the area, the sample cores were divided into two samples based on visual
observations. The upper layer of the soil core, which consisted of yellowish-brown, silty sand, made up one sample, and the lower layer of
the soil core, which consisted of grayish-black, silty sand and smelled of hydrocarbons, made up the second sample.
The primary purpose of the predemonstration investigation was to assess existing conditions and confirm available
information on physical and chemical characteristics of soil in each demonstration area. The demonstration approach
presented in Chapter 4 is based on the predemonstration investigation results as well as available historical data.
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3.1 Navy Base Ventura County Site
The Navy BVC site in Port Hueneme, California, covers about 1,600 acres along the south California coast. Three
areas at the Navy BVC site were selected as sampling areas for the demonstration: (1) the Fuel Farm Area (FFA),
(2) the Naval Exchange (NEX) Service Station Area, and (3) the Phytoremediation Area (PRA). These areas are
briefly described below and are shown in Figure 3-1.
3.1.1 Fuel Farm Area
The FFA is a tank farm in the southwest corner of the Navy BVC site. The area contains five tanks and was
constructed to refuel ships and to supply heating fuel for the Navy BVC site. Tank No. 5114 along the south edge
of the FFA was used to store marine diesel. After Tank No .5114 was deactivated in 1991, corroded pipelines leading
into and out of the tank leaked and contaminated the surrounding soil with diesel.
Predemonstration investigation samples were collected at three locations in the FFA using a Geoprobe® (see
Figure 3-2). The horizontal area of contamination is estimated to be about 20 feet wide and 90 feet long. Samples
were collected at the three locations from east to west and about 5 feet apart. During the predemonstration
investigation, soil in the area was found to generally consist of silty sand, and the soil cores contained two distinct
layers. The upper layer consisted of yellowish-brown, silty sand with TPH concentrations ranging from 38 to
470 mg/kg. The lower layer consisted of grayish-black, silty sand with TPH concentrations ranging from 7,700 to
11,000 mg/kg. Gas chromatograms showed that FFA soil samples contained (1) weathered diesel, (2) hydrocarbons
in the C10 through C28 carbon range with the hydrocarbon hump maximizing at C17, and (3) hydrocarbons in the C12
through C40 carbon range with the hydrocarbon hump maximizing at C20.
3.1.2 Naval Exchange Service Station Area
The NEX Service Station Area lies in the northeast portion of the Navy BVC site. About 11,000 gallons of regular
and unleaded gasoline was released from UST lines in this area between September 1984 and March 1985. Although
the primary soil contaminant in this area is gasoline, EDRO is also of concern because (1) another spill north of the
area may have resulted in a commingled plume of gasoline and diesel and (2) a significant portion of weathered
gasoline is associated with EDRO.
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Naval
Exchange
Service
Station Area
Approximate scale:
1 inch = 1,200 feet
Figure 3-1. Navy Base Ventura County site map.
67
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Fuel Farm Area
Tank No.-]
5113
O
o
plank No.
5022
o
O""—Tank
No.
5021
t
x:
Sampling locations
Scale: 1 inch = 50 feet
Naval Exchange Service Station Areu
73nrt A von I ic.
Credit-.
Union
Building
1336
Sampling
locations
D
Scale: 1 inch = 200 feet
'Hi/toremediation Area
Track 14 Road
LEGEND
• Sampling location
Unvegetated
Mix 1 — grass and legume mix
Mix 2 - native grass mix
Sample
management
trailer -
100 feet
a
Scale: 1 inch = 150 feet
Figure 3-2. Navy Base Ventura County site sampling locations.
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Predemonstration investigation samples were collected at three locations in the NEX Service Station Area using a
Geoprobe® (see Figure 3-2). Samples were collected from 5 to 11 feet below ground surface (bgs) at 1-foot depth
intervals. The horizontal area of contamination is estimated to be about 450 feet wide and 750 feet long. Samples
were collected at the three locations from south to north and about 60 feet apart. During the predemonstration
investigation, soil in the area was found to generally consist of (1) brown, silty sand in the depth intervals above the
water table (which was about 9 feet bgs) and (2) black, silty sand in the depth intervals at and below the water table.
The highest TPH concentrations in the NEX Service Station Area were detected in the depth interval that contained
the water table (up to 1,600 mg/kg in the 9- to 10-foot bgs depth interval) at the middle and south sampling locations;
at the north sampling location, however, a relatively low concentration of TPH was detected in this depth interval
(40 mg/kg). The TPH concentrations in the (1) top four depth intervals ranged from 15 to 65 mg/kg and (2) bottom
depth interval (10 to 11 feet bgs) ranged from 24 to 3 00 mg/kg. Gas chromatograms showed that NEX Service Station
Area soil samples contained (1) fairly weathered gasoline with a high aromatic hydrocarbon content and
(2) hydrocarbons in the C7 through C14 carbon range. Benzene, toluene, ethylbenzene, and xylene (BTEX) analytical
results for the 9- to 10-foot bgs depth interval at the middle sampling location revealed a concentration of 347 mg/kg;
BTEX made up 39 percent of the total GRO and 27 percent of the TPH at this location.
3.1.3 Phytoremediation Area
The PRA lies north of the FFA and west of the NEX Service Station Area at the Navy BVC site. The PRA consists
of soil from a fuel tank removal project conducted at the Naval Weapons Station in Seal Beach, California. The area
is contained within concrete railings and is 60 feet wide, 100 feet long, and about 3 feet deep. It consists of 12 cells
of equal size (20 by 25 feet) that have three different types of cover: (1) unvegetated cover, (2) a grass and legume
mix (Mix 1), and (3) a native grass mix (Mix 2). There are four replicate cells of each cover type.
Predemonstration investigation samples were collected from the 1.5- to 2.5-foot bgs depth interval at six locations
in the PRA using a split-core sampler (see Figure 3-2). During the predemonstration investigation, soil in the area
was found to generally consist of silty sand with some clay. The TPH concentrations in the samples ranged from
1,500 to 2,700 mg/kg. Gas chromatograms showed that PRA soil samples contained (1) heavy lubricating oil and
(2) hydrocarbons in the C14 through C40 carbon range with the hydrocarbon hump maximizing at C32.
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3.2 Kelly Air Force Base Site
The Kelly AFB site covers approximately 4,660 acres and is about 7 miles from the center of San Antonio, Texas
(see Figure 3-3). One area at Kelly AFB, the B-38 Area, was selected as a sampling area for the demonstration. The
B-38 Area lies along the east boundary of Kelly AFB and is part of an active UST farm that serves the government
vehicle refueling station at the base. During UST removal and upgrading activities in December 1992, soil
contamination from leaking diesel and gasoline USTs was observed in the UST and associated piping excavations.
Predemonstration investigation samples were collected in the 13 - to 17- and 29- to 3 0-foot bgs depth intervals at four
locations in the B-38 Area using a Geoprobe® (see Figure 3-4). The B-38 Area is estimated to be about 150 square
feet in size. The water table in the area fluctuates between 16 and 24 feet bgs. During the predemonstration
investigation, soil in the area was found to generally consist of (1) clayey silt in the upper depth interval above the
water table interval with a TPH concentration of about 9 mg/kg and (2) sandy clay with significant gravel in the
deeper depth interval below the water table interval with TPH concentrations ranging from 9 to 18 mg/kg. Gas
chromatograms showed that B-38 Area soil samples contained (1) heavy lubricating oil and (2) hydrocarbons in the
C24 through C30 carbon range.
3.3 Petroleum Company Site
One area at the PC site in north-central Indiana, the Slop Fill Tank (SFT) Area, was selected as a sampling area for
the demonstration (see Figure 3-5). The SFT Area lies in the west-central portion of the PC site and is part of an
active fuel tank farm. Although the primary soil contaminant in this area is gasoline, EDRO is also of concern
because of a heating oil release that occurred north of the area.
Predemonstration investigation samples were collected at five locations in the SFT Area using a Geoprobe® (see
Figure 3-5). Samples were collected from 2 to 10 feet bgs at 2-foot depth intervals. The SFT Area is estimated to
be 20 feet long and 20 feet wide. Four of the sampling locations were spaced about 15 feet apart to form the corners
of a square, and the fifth sampling location was at the center of the square. During the predemonstration
investigation, soil in the area was found to generally consist of sandy silt and clay with increasing clay content in
deeper depth intervals. Soil in the top three depth intervals consisted of brown, sandy silt with clay that smelled
increasingly of hydrocarbons with depth and had TPH concentrations ranging from 27 to 1,300 mg/kg. Soil in the
deepest depth interval consisted of sandy clay with increasing clay content with depth, exhibited a moderate to strong
hydrocarbon odor, and had TPH concentrations ranging from 49 to 260 mg/kg.
70
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Figure 3-3. Kelly Air Force Base site map.
71
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B-38 Area
I—1
II I II
I L_Tank No. 10903 ^^-^^7
Scale: 1 inch = 30 feet
Figure 3-4. Kelly Air Force Base site sampling locations.
72
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Scale: 1 inch = 100 feet
Figure 3-5. Petroleum company site sampling locations.
Gas chromatograms showed that SFT Area soil samples contained (1) slightly weathered gasoline, kerosene, JP-5,
and diesel and (2) hydrocarbons in the C6 through C20 carbon range. There was also evidence of an unidentified
petroleum product containing hydrocarbons in the C24 through C32 carbon range. BTEX analytical results for the
deepest depth interval revealed concentrations of 26, 197, and 67 mg/kg at the northwest, center, and southwest
sampling locations, respectively. At the northwest location, BTEX made up 13 percent of the total GRO and
5 percent of the TPH. At the center location, BTEX made up 16 percent of the total GRO and 7 percent of the TPH.
At the southwest location, BTEX made up 23 percent of the total GRO and 18 percent of the TPH.
73
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Chapter 4
Demonstration Approach
This chapter presents the objectives, design, data analysis procedures, and schedule for the innovative TPH field
measurement device demonstration.
4.1 Demonstration Objectives
The primary goal of the SITE MMT Program is to develop reliable performance and cost data on innovative, field-
ready technologies. A SITE demonstration must provide detailed and reliable performance and cost data so that
potential technology users have adequate information to make sound judgments regarding an innovative technology' s
applicability to a specific site and to compare the technology to conventional technologies.
The demonstration has both primary and secondary objectives. Primary objectives are critical to the technology
evaluation and require the use of quantitative results to draw conclusions regarding a technology's performance.
Secondary objectives pertain to information that is useful but will not necessarily require the use of quantitative results
to draw conclusions regarding a technology's performance.
The primary objectives for the demonstration of the individual field measurement devices are as follows:
P1. Determine the MDL
P2. Evaluate the accuracy and precision of TPH measurement for a variety of contaminated soil samples
P3. Evaluate the effect of interferents on TPH measurement
P4. Evaluate the effect of soil moisture content on TPH measurement
P5. Measure the time required for TPH measurement
P6. Estimate costs associated with TPH measurement
74
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The secondary objectives for the demonstration of the individual field measurement devices are as follows:
S1. Document the skills and training required to properly operate the device
S2. Document health and safety concerns associated with operating the device
S3. Document the portability of the device
S4. Evaluate the device's durability based on its materials of construction and engineering design
S5. Document the availability of the device and associated spare parts
The objectives for the demonstration were developed based on input from MMT Program stakeholders, general user
expectations of field measurement devices, characteristics of the demonstration areas, the time available to complete
the demonstration, and device capabilities that the developers participating in the demonstration intend to highlight.
4.2 Demonstration Design
In January 2000, Tetra Tech conducted a predemonstration sampling and analysis investigation to assess existing
conditions and confirm available information on physical and chemical characteristics of soil in each demonstration
area. Based on information from the predemonstration investigation as well as available historical data, a
demonstration design was developed to address the demonstration objectives. Input regarding the demonstration
design was obtained from developers participating in the demonstration. Appendix A presents several findings of the
predemonstration investigation, developer review comments on the predemonstration investigation results, and Tetra
Tech responses to the developers' comments. Table 4-1 summarizes the demonstration area characteristics and
demonstration design.
Tetra Tech will collect core samples of soil from the demonstration areas at the Navy BVC, Kelly AFB, and PC sites
described in Chapter 3. The soil core samples collected at the Kelly AFB and PC sites will be shipped to the Navy
BVC site 6 days prior to the start of field analysis activities. Tetra Tech will homogenize the soil core sample
collected from a given depth interval at a given sampling location in a given area and will aliquot soil samples for each
of the developers and the reference laboratory. In addition, Tetra Tech will obtain performance evaluation (PE)
samples from Environmental Resource Associates (ERA) in Arvada, Colorado, for distribution to the developers and
the reference laboratory. Field analysis of all environmental and PE samples will be conducted at the Navy BVC site.
The environmental samples collected at the three demonstration sites will be used to address the demonstration
objectives. However, if environmental samples will not allow a given objective to be effectively addressed, PE
75
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samples will be used to supplement environmental samples as necessary. Each field measurement device will be
evaluated based primarily on how it compares with the reference method selected for the demonstration. PE samples
will be used to verify that the reference method's performance is acceptable. However, during the comparison with
the field measurement device results, the reference method results will not be adjusted based on the recoveries
observed during analysis of the PE samples. Any problems encountered when the reference method or a given field
measurement device is used to analyze the PE samples (for example, consistent high or low bias) will be
appropriately mentioned in the ITVRs.
To facilitate effective use of available information on both the environmental and PE samples, the developers and the
reference laboratory will be informed of (1) whether each sample is an environmental or PE sample, (2) the area
that each environmental sample was collected in, and (3) the expected contamination type and concentration range
of each sample. This information will be included in each sample identification number. Each sample will be
identified as having an expected low (less than 100 mg/kg), medium (100 to 1,000 mg/kg), or high (greater than
1,000 mg/kg) TPH concentration. The expected concentration ranges will be based on predemonstration investigation
results or the amount of TPH added during PE sample preparation. For each PE sample containing interferents, the
expected TPH concentration will be based on the expected analytical result for the sample and not on the
concentrations of the interferents added to the sample.
Some PE samples will also contain interferents specifically added to evaluate the effective of interferents on TPH
measurement; the interferent nature and concentration range will be identified; however, the specific compounds used
as interferents will not be identified. The expected concentration ranges are meant to be used only as a guide by the
developers and reference laboratory. Additional information regarding sample collection, preparation, and labeling
is included in Chapter 7. During the demonstration, each developer will operate its own field measurement device
or devices. Tetra Tech will make observations to evaluate each device as described in the demonstration design.
The performance and cost of each field measurement device will be compared only to those of the reference method;
the field measurement devices will not be compared to one another. Developers may choose not to analyze samples
collected in a particular area or a particular class of samples, depending on the intended use of their devices.
However, the developers must notify Tetra Tech if they choose not to analyze any of the demonstration samples.
The general approach for addressing each primary objective is discussed below. Specific procedures for addressing
each primary objective are presented in Section 4.3.
79
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To determine the MDL for each field measurement device (primary objective PI), low-level GRO and EDRO
PE samples will be analyzed. The low-level PE samples will be prepared using methanol or Freon 113 as a
carrier. Details on PE sample preparation are provided in Chapter 7. The target concentrations of the PE
samples will be set to meet the following criteria: (1) at the minimum acceptable recoveries, the samples will
contain measurable TPH concentrations, and (2) the sample TPH concentrations will generally be ten times
the MDLs claimed by the developers and the reference laboratory. Each developer and the reference
laboratory will analyze seven GRO and seven EDRO PE samples to statistically determine the MDLs for
GRO and EDRO soil samples. Table 4-2 presents the expected MDLs for each measurement device based
on data provided by the developers. The reference method's MDLs for GRO and EDRO soil samples are
0.43 and 6.3 mg/kg, respectively.
Table 4-2. Expected Method Detection Limits for Each Field Measurement Device
Method Detection Limit (milligram per kilogram)
Device Gasoline Range Organics Extended Diesel Range Organics
RemediAid™ starter kit 8a 40a
Model CVH 3 3b
Model HATR-T Not recommended 20
OCMA-350 1 1
PetroFLAG™ test kit 1,000 20
Luminoscope 0.050 0.050
UVF-3100A 3.9 0.080
EnSys Petro Test System 10 15
Notes:
a According to CHEMetrics, the method detection limits for liquid samples for gasoline range organicsand extended diesel range organicsare
2 and 10 milligrams per liter, respectively; Tetra Tech calculated the method detection limits for soil samples assuming 5 grams of soil are
extracted using 20 milliliters of solvent.
b During the demonstration, if a sample does not contain gasoline range organics, Wilks will use Model HATR-T; otherwise, Wilks will use
Model CVH. Model CVH can be converted into Model HATR-T simply by changing the sample stage, and the reverse is also true. Therefore,
the demonstration design does not include separate evaluation of Models CVH and HATR-T.
Because SDF s EnSys Petro Test System reports results relative to an action level or as a concentration range,
MDLs cannot be statistically determined for this device. SDI will be asked to report whether the GRO and
EDRO PE samples contain TPH concentrations above 10 and 15 mg/kg, respectively. These concentrations
are close to SDFs reported MDLs for the EnSys Petro Test System. In addition, Dexsil® has chosen not to
analyze the low-level GRO PE samples because the PetroFLAG™ test kit has an MDL of 1,000 mg/kg for
GRO.
To estimate the accuracy and precision of each field measurement device (primary objective P2), both
environmental and PE samples will be analyzed. To evaluate analytical precision, one set of blind field
triplicate environmental samples will be collected from each depth interval at one location in each
demonstration area. Blind triplicate low-, medium-, and high-level PE samples will also be used to address
P2 because TPH concentrations in environmental samples collected during the demonstration may differ
from the analytical results for predemonstration investigation samples. The low- and medium-level PE
samples will be prepared using methanol or Freon 113 as a carrier. Details on PE sample preparation are
provided in Chapter 7.
80
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Information regarding analytical precision will be collected by having the developers and the reference
laboratory analyze extract duplicates. For environmental samples, one sample from each depth interval will
be designated as an extract duplicate. Each sample selected as an extract duplicate will be collected from a
location where field triplicates are collected. For PE samples, one low-, one medium-, and one high-level
GRO sample and one low-, one medium-, and one high-level EDRO sample will be designated as extract
duplicates.
The evaluation of analytical accuracy will be based on the assumption that a field measurement device may
be used to (1) determine whether the TPH concentration in a given area exceeds an action level (a state or
other action level) or (2) perform a preliminary characterization of soil in a given area. To evaluate whether
the TPH concentration in a soil sample exceeds an action level, each developer and the reference laboratory
will be asked to determine whether TPH concentrations in a given area or PE sample type exceed the action
levels listed in Table 4-3. The action levels chosen for environmental samples are based on the
predemonstration investigation analytical results and state action levels. The action levels chosen for the PE
samples are based in part on ERA's acceptance limits for PE samples; therefore, each PE sample is expected
to have at least the TPH concentration indicated in Table 4-3.
Table 4-3. Action Levels to be Used to Evaluate Analytical Accuracy
Site
Navy BVC
Kelly AFB
PC
Area
FFA
NEX Service Station Area
PRA
B-38 Area
S FT Area
PE samples (GRO)
PE samples (EDRO)
Expected Concentration3
Lto H
Lto H
H
L
LtoH
L
M
H
L
M
H
Primary Objective P2 Action Level (mg/kg)
100
50
1,500
100
500
10
200
2,000
15
200
2,000
Notes:
< = Less than GRO
> = Greater than H
AFB = Air Force Base kg
BVC = Base Ventura County L
EDRO = Extended diesel range organics M
FFA = Fuel Farm Area mg
Gasoline range organics
High (>1,000 mg/kg)
Kilogram
Low(<100 mg/kg)
Medium (100 to 1,000 mg/kg)
Milligram
NEX = Naval Exchange
PC = Petroleum company
PE = Performance evaluation
PRA = Phytoremediation Area
SFT = Slop Fill Tank
The expected concentrations shown cover all the depth intervals in each area. Table 4-1 shows the depth intervals to be sampled in each
area and the expected concentration for each depth interval. The action level for each area will be used as the basis for evaluating sample
analytical results regardless of the expected concentrations for the various depth intervals.
To evaluate the effect of interferents on each field measurement device's ability to accurately measure TPH
(primary objective P3), high-level soil PE samples that contain GRO or EDRO with or without an interferent
will be analyzed. Six different interferents, I( 1) through 1(6), will be evaluated. The boiling points and vapor
pressures of (1) interferents 1(1) and 1(2) are similar to those of GRO, (2) interferents 1(3) and 1(4) are similar
to those of GRO and EDRO, and (3) interferents 1(5) and 1(6) are similar to those of EDRO. Separate PE
samples will be prepared for GRO and EDRO analyses with the following exceptions: PE samples
containing 1(1) and 1(2) will not be prepared with EDRO and PE samples containing 1(5) and 1(6) will not
81
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be prepared with GRO because these interferents are not expected to impact the analyses and because
practical difficulties such as solubility constraints are associated with preparation of such samples. Both
GRO and EDRO PE samples will be spiked with a high concentration of TPH (greater than 1,000 mg/kg).
Interferents will be added to the samples at two concentrations ranging from 50 to 500 percent of the TPH
concentrations.
Appropriate control samples will be prepared and analyzed to address P3. These samples include reference
soil, reference soil plus GRO or EDRO, reference soil plus interferent, and reference soil plus interferent plus
GRO or EDRO samples. When a soil sample containing only a given interferent cannot be prepared because
of solubility constraints, liquid samples containing the interferent will be prepared and used as quasi-control
samples to evaluate the effect of the interferent alone on the result obtained by each measurement device and
the reference method. Each PE sample will be prepared in triplicate. Average and variability information
for the triplicates will be used to interpret the effect of the interferent.
To evaluate the effect of soil moisture content on each field measurement device's ability to accurately
measure TPH (primary objective P4), high-level soil PE samples that contain GRO or EDRO will be
analyzed. For GRO, PE samples will be prepared at two moisture levels: (1) about 9 percent moisture
because this is the minimum level required to containerize PE samples in EnCores (these samples are already
accounted for under primary objective P2) and (2) about 18 percent because this is the saturation level of the
soil. For EDRO, PE samples will be prepared at two moisture levels: (1) negligible moisture (none added)
and (2) about 9 percent (these samples are already accounted for under P2). Each PE sample will be prepared
in triplicate. Average and variability information for the triplicates will be used to interpret the effect of
moisture.
The time required for TPH measurement (primary objective P5) or the sample throughput (the number of
TPH measurements made per unit of time) will be determined by measuring the time required for each
activity associated with TPH measurement, including field measurement device setup, sample extraction,
sample analysis, and data package preparation. Tetra Tech will provide each developer with investigative
samples stored in coolers. The developers will unpack the coolers and check the chain-of-custody forms to
verify that they have received the correct samples. Time measurement will begin when a developer begins
to set up the device. The total time required to complete analysis of all investigative samples will be
recorded. Analysis will be considered complete and the time measurement will stop when the developer
provides Tetra Tech with a summary table of results, a run log, and any supplementary information that the
developer chooses. The summary table must list all samples analyzed and their respective TPH
concentrations (and GRO and EDRO concentrations, if applicable) in mg/kg on a wet weight basis.
For the purposes of the demonstration, investigative samples will include environmental, field triplicate, and
PE samples provided to the developers by Tetra Tech as well as the extract duplicates specified by Tetra
Tech. The total number of samples recorded as being analyzed in a given period by a developer will be based
on the number of investigative samples analyzed. If a developer conducts multiple extractions, dilutions,
reanalyses, or QC checks, these will be noted by Tetra Tech but will not be included in the number of
investigative samples analyzed, and the total time expended will not be adjusted because any additional work
performed by the developer is considered to be required in order to provide data of adequate quality.
In addition to the total time expended to analyze the investigative samples, Tetra Tech will measure the time
required to analyze two "batches" of samples. A "batch" will be a group of samples that the developer
prepares or analyzes in one sequence. Tetra Tech will measure only the time expended for the first and last
batches of samples. Tetra Tech will note the elements that comprise each batch, such as environmental
samples, developer QC samples, multiple dilutions, re-extractions, and others. In addition to measuring the
time required to analyze the first and last batches of samples, Tetra Tech will confirm that each analytical
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step is completed by the developer as described in Chapter 2. For example, if a developer claims that part
of the device operating procedure is to shake a sample extract for 3 minutes, Tetra Tech will verify that the
sample was actually shaken for 3 minutes.
Each developer will be made aware of when the timing of each activity begins and ends. If the developer's
entire field team chooses to take a break, this time will not be counted as part of the analytical time. If a
device is not working or requires repair, this fact will be noted, but the resulting downtime will not be
counted as part of the analytical time.
For the reference laboratory, the total analytical time will begin to be measured when the laboratory receives
all investigative samples, and the time measurement will continue until Tetra Tech receives a complete data
package from the laboratory.
To estimate the costs associated with TPH measurement (primary objective P6), the following five cost
categories will be considered: capital, labor, supplies, investigation-derived waste (IDW), and support
equipment. A summary of the costs that will be estimated for each measurement device is provided below.
1. The capital cost will be estimated based on price lists for purchasing, renting, or leasing each field
measurement device. If the device has to be purchased, the capital cost will include no salvage value
for the device after work is completed.
2. The labor cost will be estimated based on the number of people required to analyze samples during
the demonstration for each field measurement device. The labor rate will be based on a standard
hourly rate for a technician. During the demonstration, the skill level required will be confirmed
based on input from the developer regarding operation of the device and Tetra Tech's observation
of the skills required to operate the device or to interpret data in order to calculate TPH
concentrations. In addition, the labor cost will be based on (1) the actual number of hours required
to complete analysis of all investigative samples as measured under primary objective P5 and (2) the
assumption that a technician who has worked for a portion of a day would be paid for an entire
8-hour day.
3. The cost of supplies will be estimated based on any supplies required to analyze all investigative
samples during the demonstration using each field measurement device but not included in the
capital cost category, such as a balance, extraction solvent, glassware, pipettes, spatulas, agitators,
and so on. Tetra Tech will note the type and quantity of all supplies brought to the field as well as
the quantity of supplies used by each developer to analyze all the investigative samples during the
demonstration.
If a developer typically provides all supplies to a user, the developer's costs will be used to estimate
the cost of supplies. If the supplies required to analyze a set number of samples are covered by the
purchase cost of a measurement device, this cost will not be broken out separately as part of the cost
of supplies. However, the cost of any additional supplies required to analyze all the investigative
samples will be included in the cost of supplies. If a developer provides supplies as part of a refill
kit, the cost for the number of kits required to analyze all the investigative samples will be included
in the cost of supplies. If a developer creates refill kits specific to a user's needs, the associated cost
of supplies will be based on the cost of the refill kits that the developer uses during the
demonstration. Unless a developer allows a user to return unused portions of a refill kit, the cost of
supplies will be estimated under the assumption that no salvage value is associated with unused refill
kit supplies. If unused supplies can be returned to a developer, the quantities of unused supplies will
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be noted during the demonstration, and the appropriate credit will be applied to the cost of supplies
minus any restocking charge.
If a developer typically does not provide all required supplies to a user, Tetra Tech will estimate the
cost of supplies using independent vendor quotes. Tetra Tech will note the identification numbers
and manufacturers of supplies used by the developer during the demonstration and will attempt to
obtain pricing information for these supplies. If the costs of these supplies are not available, Tetra
Tech will use the prices of comparable supplies to estimate the cost of supplies. If unused supplies
can be returned to a vendor or manufacturer, the quantities of unused supplies will be noted during
the demonstration and the appropriate credit will be applied to the cost of supplies minus any
restocking charge.
4. The IDW disposal cost will be estimated for each device. Each developer will be provided with two
20-gallon laboratory packs: one for flammable wastes and one for corrosive wastes, as necessary.
IDW generated may include decontamination fluids, decontamination equipment, spent solvents,
unused chemicals that a user cannot return to the developer or an independent vendor, used EnCores,
TPH-contaminated soil samples, and soil extracts. The cost for disposal of personal protective
equipment (PPE), glassware, and plastic utensils used during the demonstration will not be included
in the disposal cost because these wastes can be disposed of in a dumpster along with municipal
garbage. The cost for disposal of laboratory packs will be included in the overall analysis cost for
each developer. Each developer will provide containers to containerize individual wastes, and the
cost of these containers will not be included in the total analysis cost.
5. The support equipment cost will be estimated for each field measurement device based on
information provided by the developer and any support equipment such as tables, chairs, and a tent
observed to be required for the device during the demonstration. Tetra Tech will note the type and
quantity of all support equipment used by each developer during the demonstration.
The cost per analysis will not be estimated for the field measurement devices because the cost per analysis
would decrease as more samples were analyzed and because the initial capital cost would be distributed
across a greater number of samples. This decrease in cost per analysis cannot be fairly compared to the
reference laboratory's fixed cost per analysis.
Secondary objectives will be addressed based on observations made during the demonstration. Because of the
number of developers involved, several Tetra Tech personnel will be required to make simultaneous observations
during the demonstration. Two Tetra Tech personnel will be assigned to observe a pair of developers for the entire
demonstration. These personnel will make observations and take notes regarding TPH measurement activities. To
ensure observational consistency, Tetra Tech personnel will discuss and compare observations made and notes taken
regarding each device at the end of each day of the demonstration. Developers will also be given the opportunity to
review and comment on the notes taken by Tetra Tech regarding their devices at the end of each day of the
demonstration. Any issues that may arise will be resolved with the direction of the EPA, if necessary. The approach
for addressing each secondary objective is discussed below.
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• The skills and training required for proper device operation (secondary objective SI) will be addressed by
observing and noting the skills required to operate each device during the demonstration, assessing how easy
the device is to operate, and discussing any necessary user training with the developer.
• Health and safety concerns associated with device operation (secondary objective S2) will be addressed by
observing and noting possible health and safety concerns during the demonstration, such as the types of
hazardous substances that must be handled by a user of a device during analysis, the number of times that
hazardous substances must be transferred from one container to another during the analytical procedure, and
any direct user exposure to hazardous substances.
• The portability of a given device (secondary objective S3) will be addressed by observing and noting the
weight and size of the device and its required support equipment as well as how easily the device is set up
for use during the demonstration.
• The durability of a given device (secondary objective S4) will be addressed by noting the materials of
construction of the device and its required support equipment. Also, Tetra Tech will note any device failures
or any repairs that may be necessary during extended use of the device. Any downtime required to make
device repairs during the demonstration will be noted.
The availability of a given device and associated spare parts (secondary objective S5) will be addressed by
discussing the availability of the replacement device with the developer and determining whether spare parts
are available in retail stores or only from the developer. In addition, if the replacement device or spare parts
are required during the demonstration, their availability will be noted.
Demonstration field and laboratory data will be collected to address the demonstration objectives. The procedures
that will be used to analyze these data are presented in Section 4.3. Critical and noncritical measurement are
identified in Chapter 7. Specific procedures for collecting samples and making measurements to address the
objectives as well as the numbers of samples to be collected and the types of analyses to be completed are also
presented in Chapter 7.
4.3 Data Analysis Procedures
As discussed in Section 4.2, demonstration field and laboratory data will be used to meet the specific project
objectives discussed in Section 4.1. Section 4.3 presents and describes data analysis procedures that will be used to
address each primary objective as well as cost categories that will be assessed as part of the field measurement device
cost analysis. Depending on the primary objective involved, some data will be analyzed using statistical approaches
such as hypothesis testing, some data will be analyzed using simple descriptive parameters such as means and
standard deviations, and other data will be used without use of statistical procedures. Data analysis will be completed
separately for field measurement devices and the reference method unless otherwise noted below. A given field
measurement device's TPH results will be compared only to the reference method TPH results; one field
measurement device's TPH results will not be compared to another's. This section describes the data analysis
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procedures that will be used to address the primary objectives only. Secondary objectives are not discussed in this
section because these objectives do not involve quantitative data analysis.
The statistical hypothesis testing procedures described in this section are based on the assumption that the data will
be normally distributed. This assumption will be verified using the Wilk-Shapiro test. If the normality assumption
is not satisfied, a nonparametric test such as the Wilcoxon signed rank test will be used for data analysis. Statistical
software such as Staffs fix will be used to perform all statistical calculations for data analysis.
4.3.1
Primary Objective PI: Method Detection Limit
To determine the MDLs for GRO and EDRO for each field measurement device under primary objective PI, Tetra
Tech will use each device's TPH results for seven low-level GRO and seven low-level EDRO soil PE samples to
calculate the variance and standard deviation for the seven replicate samples using Equations 4-1 and 4-2.
S2=.
n-1
I I
y x2--
i=1
1=1
(4-1)
where
s2 =
n =
S =
s = vs
Variance of replicate TPH results
Number of sample replicates
TPH result in mg/kg on a wet weight basis for the ith sample
Standard deviation of replicate TPH results
(4-2)
The Student's t value and standard deviation will be used to calculate the MDL as shown in Equation 4-3.
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where
t(n-i 1—=099) = Student'st value appropriate for a 99 percent confidence level and a standard deviation
estimate with n-1 degrees of freedom (3.143 for n = 7)
Tetra Tech will follow the same procedure to determine the MDLs achieved by the reference laboratory for the
reference method. However, because all GRO samples will be analyzed for both GRO (C6 through C10) and EDRO
(C10 through C40) and the reference laboratory will report EDRO analytical results for the diesel range (C10 through
C28) and the extended diesel range (C28 through C40) separately, the TPH result for a given sample will be calculated
by summing the three values reported by the reference laboratory. After calculating the seven TPH results, Tetra
Tech will use Equations 4-1 through 4-3 to determine the MDL. For each sample that contains only EDRO, the TPH
result will be calculated using the two values reported by the reference laboratory (for Q 0 through C28 and C28 through
C40) instead of three values. To avoid potential confusion regarding which GRO value should be added to which
EDRO value, each replicate will be uniquely identified by the Tetra Tech field team.
The procedure described above is based on 40 Code of Federal Regulations (CFR) Part 136, Appendix B,
Revision 1.11. This procedure appears to be based on an assumption that the replicates used are homogeneous
enough to allow proper measurement of the analytical precision, which will be true for the demonstration because
of the PE sample preparation procedures that will be followed. If the replicates used are not subsamples of a
homogenous matrix, the resulting high sample variability may not allow proper measurement of TPH analytical
precision and subsequent determination of MDLs.
For field measurement devices that cannot provide quantitative measurements, such as SDFs EnSys Petro Test
System, MDLs cannot be determined using the statistical procedure described above. Therefore, SDI will be provided
with seven low-level GRO samples and asked to report how many samples contain TPH concentrations above
10 mg/kg, a value close to the MDL claimed by the developer. Similarly, SDI will be provided with seven low-level
EDRO samples and asked to report how many samples contain TPH concentrations above 15 mg/kg, a value close
to the MDL claimed by the developer.
4.3.2 Primary Objective P2: A ccuracy and Precision
To determine whether a field measurement device can accurately and precisely measure TPH under primary objective
P2, Tetra Tech will compare device TPH measurement results with reference method TPH results.
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The evaluation of a field measurement device's ability to accurately measure TPH will be based on the assumption
that a field measurement device may be used to (1) determine whether the TPH concentration in a given area exceeds
an action level (a state or other action level) or (2) perform a preliminary characterization of soil in a given area.
These scenarios are addressed below.
Sample TPH results obtained using the reference method and a given field measurement device will be compared to
the action levels presented in Table 4-3 in order to determine whether a particular sample's TPH concentration is
above the action level. The findings obtained using the reference method and the device will be compared to
determine how many times the device's findings agreed with those of the reference method for a particular area or
for all areas taken together.
To complete a preliminary characterization of soil in a given area using a field measurement device, the device user
may have to demonstrate to a regulatory agency that (1) no statistically significant difference exists between the
results of the laboratory method selected for the project (the reference method) and the device results, indicating that
the device may be used as a substitute for the laboratory method, or (2) a consistent correlation exists between device
results and laboratory method results, indicating that the device results can be adjusted using the established
correlation.
Tetra Tech will evaluate whether a statistically significant difference exists between a given field measurement
device's results and the reference method results by performing a two-tailed, paired, Student's t-test. The null
hypothesis will be that the mean difference between the device results and the reference method results equals zero.
Assuming that the data are normally distributed, Tetra Tech will perform the t-test with a 0.05 significance level using
Equation 4-4.
t = TTTT^ (4-4)
Sd/A/n
where
t = Critical t value
d = Mean difference between TPH results of a given field measurement device and the reference method
Sd = Standard deviation of d
n = Number of samples (for a particular area or for all areas taken together)
-------
Equations 4-5 and 4-6 will be used to calculate d and Sd, respectively.
n
d= l=1 ' (4-5)
M-1 (4"6)
where
n = Number of samples (for a particular area or for all areas taken together)
x2i = TPH concentration measured in the ith sample using the reference method
X1: = TPH concentration measured in the ith sample using a given field measurement device
d = Difference between TPH results of a given field measurement device and the reference method
In addition, the ratio of the TPH results of a given field measurement device to the TPH results of the reference
method will be calculated. The ratio will be used to develop a frequency distribution in order to determine how many
of the results of the device and the reference method are within 30 percent, within 50 percent, and outside the
50 percent window. A ratio of 0.7 to 1.3 would imply that a device result is within 30 percent of the reference method
result. Similarly, a ratio of 0.5 to 1.5 would imply that a device result is within 50 percent of the reference method
result. A ratio less than 0.5 or greater than 1.5 would imply that the device result is outside the 50 percent window.
To determine whether a consistent correlation exists between the TPH results of a given field measurement device
and the reference method, a linear regression will be performed to estimate the square of the correlation coefficient
(R2), the slope, and the intercept of each regression equation. Separate regression equations will be developed for
each demonstration area and for PE samples. The reliability of these regression equations will be tested using the
F-test; the regression equation probability from the F-test will be used to evaluate whether the correlation between
the TPH results of the device and the reference method is merely by chance. A low probability (5 percent or less)
would suggest that the correlation is unlikely to have occurred by chance and that the device is an acceptable
substitute for the reference method.
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To evaluate a given field measurement device's ability to precisely measure TPH, Tetra Tech will calculate the
relative standard deviation (RSD) of the reference method and device TPH results for the triplicate samples. The
RSD will be calculated using Equation 4-7.
RSD = Standard deviation x
Mean ( '
A low RSD indicates high precision. For a given set of replicate samples, the RSD of a given field measurement
device's TPH results will be compared with that of the reference method's TPH results to determine whether the
reference method is more precise than the device or vice versa. In addition, Tetra Tech will compare the action level
findings of the reference method and a given field measurement device to evaluate whether the findings are consistent
for a given set of replicates.
Using the TPH results for extract duplicates, Tetra Tech will calculate the analytical precision for a given field
measurement device and the reference method. The relative percent difference (RPD) of the TPH results will be
calculated for the device and the reference method using Equation 4-8.
_ Difference between TPH results for extract duplicates „ Hnn
— X IUU (4-8)
Average TPH result for extract duplicates
A low RPD indicates high precision. The RPD values for a given pair of extract duplicates will be compared to
determine whether the reference method has higher analytical precision than a given field measurement device or vice
versa.
For the field measurement device to be demonstrated by SDI, precision and accuracy will be evaluated only for the
action level scenarios. SDI will be asked to report its results using the tightest concentration range possible relative
to a given action level. To evaluate how broad the range is, the ratio of the upper limit to the lower limit of the range
will be calculated.
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4.3.3 Primary Objective P3: Effect of Interferents
To evaluate the effect of interferents on each field measurement device's ability to accurately measure TPH under
primary objective P3, Tetra Tech will calculate the means and standard deviations of the TPH results for the
following triplicate PE samples: reference soil, reference soil plus TPH (GRO or EDRO), reference soil plus TPH
(GRO or EDRO) plus interferent (level 1), and reference soil plus TPH (GRO or EDRO) plus interferent (level 2).
Tetra Tech will review the means for each group of samples to qualitatively evaluate whether the data show any
trend—that is, to evaluate whether an increase in the interferent concentration resulted in an increase or decrease in
the measured TPH concentration. Tetra Tech will also perform a one-way analysis of variance to determine whether
the group means are the same or different. If they are different, the analysis will also identify which means are
different from one another. This analysis will be performed at a significance level of 0.05.
Tetra Tech may be able to qualitatively evaluate SDFs field measurement device in order to address P3, but this
evaluation can occur only if SDI reports different TPH concentration ranges for the samples collected.
4.3.4 Primary Objective P4: Effect of Soil Moisture Content
To evaluate the effect of soil moisture content on each field measurement device's ability to accurately measure TPH
under primary objective P4, Tetra Tech will calculate the means and standard deviations of the TPH results for
triplicate PE samples containing GRO or EDRO at two moisture levels. Tetra Tech will compare the means to
determine whether the device and reference method results were impacted by moisture—that is, to determine whether
an increase in moisture resulted in an increase or decrease in the measured TPH concentration. During the
comparison, Tetra Tech will consider the variability associated with each mean. For example, if the mean
concentrations are within one standard deviation for a given field measurement device but are within two standard
deviations for the reference method, Tetra Tech may conclude that the effect of moisture is more significant for the
reference method.
Tetra Tech may be able to qualitatively evaluate SDI's field measurement device in order to address P4, but this
evaluation can occur only if SDI reports different TPH concentration ranges for the samples collected.
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4.3.5 Primary Objective P5: Time Required for TPH Measurement
Tetra Tech will measure the time required for each activity associated with field analysis to address primary objective
P5. Activities that will be timed include field measurement device setup, sample extraction, sample analysis, and data
package preparation. Sample homogenization and sample containerization will be conducted by Tetra Tech;
therefore, the time required for these activities will not be included in the sample analysis time required by the
developers. For the reference method, the time required for sample analysis will be the number of days that elapse
from the time that the reference laboratory receives the samples to the time that Tetra Tech receives the laboratory's
full data package.
4.3.6 Primary Objective P6: Costs Associated with TPH Measurement
Tetra Tech will estimate the costs associated with field analysis to address primary objective P6. The costs associated
with analyzing all the investigative samples will be estimated and documented separately for each field measurement
device except Wilks' Models CVH and HATR-T, for which costs will be estimated and documented jointly. The
elements to be included in the cost analysis are capital, labor, supply, IDW disposal, and support equipment costs;
these elements are discussed in detail in Section 4.2. The total cost to analyze all the investigative samples will be
estimated for each device. For the reference method, the cost associated with TPH measurement will be equal to the
analytical cost per sample multiplied by the number of samples analyzed by a given device.
4.4 Demonstration Schedule
This section discusses the overall project schedule and provides a detailed field activity schedule for the
demonstration. Table 4-4 presents the overall project schedule from work plan preparation to completion of the
ITVRs for the seven TPH field measurement devices and the DER. The predemonstration investigation field
activities were completed in January 2000. Demonstration field activities are scheduled to occur between June 5 and
18, 2000, as discussed below. Draft ITVRs will be available for peer and developer review on March 19, 2001, and
final ITVRs will be submitted to the EPA on October 1, 2001.
Table 4-5 presents the field activity schedule for the demonstration. Field mobilization activities are scheduled to
be conducted on June 5, 6, and 7,2000. Demonstration soil sampling activities are scheduled to be conducted at the
demonstration sites on June 7 and 8, 2000. Soil sample homogenization, preparation, and distribution will be
conducted from June 9 through 11, 2000. The developers will analyze practice samples and will meet individually
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Table 4-4. Schedule for Innovative Total Petroleum Hydrocarbon Field Measurement Device Demonstration Project
Task
Task 1. Project Management and Work Plan Preparation
Project management
Work plan preparation
Task 2. Technology Developer and Demonstration Site Selection
Task 3. Predemonstration Sampling and Analysis Investigation
Task 4. Demonstration Plan Preparation
EPA and developer review of draft demonstration plan
Response to comments
Final demonstration plan
Task 5. Field Demonstration
Navy BVC site preparation and mobilization
Soil sample collection at all sites
Field analysis activities
Visitors' day
Demobilization
Task 6. Laboratory Analysis
Pre-audit
Sample analysis
In-process audit
Task 7. ITVR Preparation
ITVR1
ITVR1, draft!
EPA project manager review of draft 1
Draft 2
Peer and developer review of draft 2
Draft 3
EPA project manager review of draft 3
Final ITVR 1
ITVRs 2 through 4
ITVRs 2 through 4, draft 1
EPA project manager review of draft 1
Draft 2
Peer and developer review of draft 2
Draft 3
EPA project manager review of draft 3
Final ITVRs 2 through 4
ITVRs 5 through 7
ITVRs 5 through 7, draft 1
EPA project manager review of draft 1
Draft 2
Peer and developer review of draft 2
Draft 3
EPA project manager review of draft 3
Final ITVRs 5 through 7
Start Date
07/06/99
07/06/99
07/06/99
07/19/99
10/01/99
05/01/00
05/01/00
05/16/00
05/16/00
06/05/00
06/05/00
06/07/00
06/1 3/00
06/15/00
06/17/00
06/13/00
01/25/00
06/13/00
07/18/00
06/26/00
06/26/00
06/26/00
11/01/00
11/09/00
03/19/01
04/17/01
07/26/01
08/09/01
06/26/00
06/26/00
1 2/26/00
01/05/01
03/19/01
04/17/01
07/26/01
08/09/01
06/26/00
06/26/00
02/14/01
02/22/01
03/19/01
04/17/01
07/26/01
08/09/01
Finish Date
07/28/01
07/28/01
08/06/99
09/30/99
02/02/00
06/05/00
05/15/00
05/30/00
06/05/00
06/18/00
06/07/00
06/08/00
06/1 6/00
06/15/00
06/18/00
07/31/00
01/26/00
07/31/00
07/19/00
10/01/01
10/01/01
10/31/00
11/08/00
11/23/00
04/16/01
07/25/01
08/08/01
10/01/01
10/01/01
12/22/00
01/04/01
01/19/01
04/16/01
07/25/01
08/08/01
10/01/01
10/01/01
02/13/01
02/21/01
03/16/01
04/16/01
07/25/01
08/08/01
10/01/01
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Table 4-4. Schedule for Innovative Total Petroleum Hydrocarbon Field Measurement Device Demonstration Project (Continued)
Task
Task 8. DER Preparation
DER, draft 1
EPA project manager review of draft 1
Draft 2
Peer and developer review of draft 2
Draft 3
EPA project manager review of draft 3
Final DER
Start Date
06/26/00
06/26/00
01/16/01
01/24/01
03/19/01
04/17/01
07/26/01
08/09/01
Finish Date
10/01/01
01/15/01
01/23/01
02/07/01
04/16/01
07/25/01
08/08/01
10/01/01
Notes:
BVC = Base Ventura County
DER = Data evaluation report
EPA = U.S. Environmental Protection Agency
ITVR = Innovative technology verification report
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Table 4-5. Field Activity Schedule for Demonstration
Date
June 5 and 6, 2000 (Monday
and Tuesday)
June 7, 2000 (Wednesday)
June 8, 2000 (Thursday)
June 9 through 11, 2000
(Friday through Sunday)
June 12, 2000a (Monday)
June 13, 2000a (Tuesday)
June 14, 2000a (Wednesday)
June 15, 2000a (Thursday)
June 16, 2000a (Friday)
June 17 and 18, 2000a
(Saturday and Sunday)
Activity
Morning
Afternoon
Tetra Tech conducts field mobilization activities.
Tetra Tech conducts field mobilization
activities.
Tetra Tech collects soil cores in the
PRA.
Tetra Tech collects soil cores in the B-38 and SFT Areas and ships the cores to the
Navy BVC site in Port Hueneme, California.
Tetra Tech collects soil cores in the FFA.
Tetra Tech collects soil cores in the NEX
Service Station Area.
Tetra Tech homogenizes samples collected from each area and prepares samples
for distribution to developers and STL Tampa East-Tampa.
Each developer analyzes practice samples. Tetra Tech and the EPA meet with each
developer for about 1 hour. During this meeting, Tetra Tech observes the developer
analyzing samples and answers any questions that arise. In addition, Tetra Tech
ships samples (except soil PE samples for GRO analysis) to STL Tampa East for
next-day delivery.
All samples except soil PE samples for GRO analysis are distributed to each
developer at 7:30 a.m., and field analysis activities begin.
Field analysis activities continue. At a minimum, all developers complete analyses of
all environmental samples that contain GRO. Tetra Tech ships the soil PE samples
for GRO analysis to STL Tampa East for next-day delivery.
Soil PE samples for GRO analysis are distributed to each developer at 7:30 a.m.
Visitors' day activities are conducted, and field analysis activities continue.
(Developer participation in the visitors' day activities is voluntary.)
Field analysis activities continue.
Field analysis activities are conducted only if, because of bad weather or other
unforeseen circumstances, sample analysis has not been completed on June 16,
2000. Tetra Tech conducts demobilization activities.
Site/Area
Navy BVC/PRA
Kelly AFB/B-38 Area
PC/SFT Area
Navy BVC/FFA and
NEX Service Station
Area
Navy BVC/PRA
Notes:
AFB =
BVC =
EPA =
FFA =
GRO =
NEX =
Air Force Base
Base Ventura County
U.S. Environmental Protection Agency
Fuel Farm Area
Gasoline range organics
Naval Exchange
PC
PE
PRA
SFT
Petroleum company
Performance evaluation
Phytoremediation Area
Slop Fill Tank
STL Tampa East = Severn Trent Laboratories in Tampa, Florida
Tetra Tech = Tetra Tech EM Inc.
The workday will begin at 7:30 a.m. and end at 5:30 p.m. to comply with Navy BVC site work guidelines.
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with Tetra Tech and the EPA on June 12, 2000. Field analysis activities will be conducted from June 13 through 16,
2000. Visitors' day activities will be conducted in the PRA on June 15, 2000. Demobilization activities will be
completed over a 2-day period immediately following completion of field analysis activities at the Navy BVC site.
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Chapter 5
Confirmatory Process
The performance results for each innovative TPH field measurement device will be compared to the performance
results for an off-site laboratory measurement method—that is, a reference method. This chapter describes the
rationale for the selection of the reference method (Section 5.1) and the reference laboratory (Section 5.2).
5.1 Reference Method Selection
During the demonstration, environmental and PE samples will be analyzed for TPH by the reference laboratory using
SW-846 Method 8015B (modified). This section describes the analytical methods considered for the demonstration
and provides a rationale for the reference method selected. Project-specific procedures for sample preparation and
analysis are summarized in Chapter 9.
The reference method to be used was selected based on the following criteria:
• It is not a field screening method.
• It is widely used and accepted.
• It measures light (gasoline) to heavy (lubricating oil) fuel types.
• It can provide separate measurements of GRO (C6 through C10) and EDRO (greater than C10 through C40)
fractions of TPH.
It meets project-specific reporting limit requirements.
The analytical methods considered for the demonstration and the reference method selected based on the above-listed
criteria are illustrated in a flow diagram in Figure 5-1. The reference method selection process is briefly discussed
below.
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The analytical methods considered for the demonstration were identified based on a review of SW-846, MCAWW,
American Society for Testing and Materials (ASTM), API, and state-specific methods and collectively represent six
different measurement technologies. Of the methods considered, those identified as field screening methods, such
as SW-846 Method 4030, were eliminated from further consideration in the reference method selection process.
A literature review was conducted to determine whether the remaining methods are widely used and accepted in the
United States (Association for Environmental Health and Sciences [AEHS] 1999). As a result of this review, state-
specific methods such as the Massachusetts Extractable Petroleum Hydrocarbon (EPH) and Volatile Petroleum
Hydrocarbon (VPH) Methods (Massachusetts Department of Environmental Protection 2000), the Florida Petroleum
Range Organic (PRO) Method (Florida Department of Environmental Protection 1996), and Texas Method 1005
(Texas Natural Resource Conservation Commission 2000) were eliminated from the selection process. Also
eliminated were the gravimetric and infrared methods except for MCAWW Method 418.1 (EPA 1983). The use and
acceptability of MCAWW Method 418.1 will likely decline because the extraction solvent used in this method is a
CFC (Freon 113), and use of CFCs will eventually be phased out under the Montreal Protocol. However, because
several states still accept the use of MCAWW Method 418.1 for measuring TPH, the method was retained for further
consideration in the selection process (AEHS 1999).
Of the remaining methods, MCAWW Method 418.1, the API PHC Method, and SW-846 Method 8015B can measure
light (gasoline) to heavy (lubricating oil) fuel types. However, GRO and EDRO fractions cannot be measured
separately using MCAWW Method 418.1. As a result, this method was eliminated from the selection process.
Both the API PHC Method and SW-846 Method 8015B can be used to separately measure the GRO (C6 through C10)
and DRO (greater than C10 through C28) fractions of TPH. These methods can also be modified to extend the DRO
range to EDRO (greater than C10 through C40) by using a calibration standard that includes even-numbered alkanes
in the EDRO range.
Based on a review of state-specific action levels for TPH, a TPH reporting limit of 10 mg/kg is considered to be
appropriate for the demonstration. Because the TPH reporting limit for the API PHC Method (50 to 100 mg/kg) is
greater than 10 mg/kg, this method was eliminated from the selection process (API 1994). SW-846 Method 8015B
(modified) can meet the reporting limit requirements for the demonstration. For GRO, SW-846 Method 8015B
(modified) has a reporting limit of 5 mg/kg, and for EDRO, this method has a reporting limit of 10 mg/kg. Therefore,
SW-846 Method 8015B (modified) satisfies all the criteria established for selecting the reference method. In
addition, this method provides a fingerprint (chromatograph) of TPH components.
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Several states, including Massachusetts, Alaska, Louisiana, and North Carolina, have implemented or are planning
to implement a TPH contamination fractionation approach based on the aliphatic and aromatic hydrocarbon fractions
of TPH. The approach used in these states involves performing a sample extract fractionation procedure and two
analyses to determine the aliphatic and aromatic hydrocarbon concentrations in a sample. However, the ability of
an analytical method to determine aliphatic and aromatic hydrocarbon concentrations was not considered in the
reference method selection process because
The approach is used in only a few states.
Variations exist among the sample extract fractionation and analysis procedures used in different states.
The repeatability and versatility of sample extract fractionation and analysis procedures are not well
documented.
• In some of the above-mentioned states, TPH-based action levels are still used.
5.2 Reference Laboratory Selection
This section provides the rationale for the selection of the reference laboratory. STL Tampa East was selected as the
reference laboratory because it (1) has been performing TPH analyses for many years, (2) has passed many external
audits by successfully implementing a variety of TPH analytical methods, and (3) agreed to implement project-
specific analytical requirements. In January 2000, a project-specific audit of the laboratory was conducted and
determined that STL Tampa East satisfactorily implemented the reference method during the predemonstration
investigation. In addition, STL Tampa East successfully analyzed double-blind PE samples and blind field triplicates
for GRO and EDRO during the predemonstration investigation. Furthermore, in 1998 STL Tampa East was one of
four recipients and in 1999 was one of six recipients of the Seal of Excellence Award issued by the American Council
of Independent Laboratories. In each instance, this award was issued based on the results of PE sample analyses and
client satisfaction surveys. Thus, the selection of the reference laboratory was based primarily on performance and
not cost.
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Chapter 6
Demonstration Organization and Responsibilities
This chapter identifies key project personnel and summarizes their demonstration responsibilities. Figure 6-1 is an
organizational chart that shows key project personnel and the lines of communication among them. Table 6-1 at the
end of this chapter presents the key demonstration participants.
During the demonstration, the organizations identified below may choose to follow the Tetra Tech health and safety
procedures identified in Chapter 13. However, each organization is directly and fully responsible for the health and
safety of its own employees; Tetra Tech assumes no such responsibility for non-Tetra Tech personnel.
6.1 EPA Project Personnel
The EPA project manager, Stephen Billets, has overall responsibility for the project. Dr. Billets will review and
concur with the project deliverables, including the demonstration plan, ITVRs, and DER. The EPA QA officer at
the EPA NERL, George Brilis, is also responsible for reviewing and concurring with the demonstration plan.
6.2 Tetra Tech Project Personnel
The Tetra Tech project manager, Kirankumar Topudurti, is responsible for conducting day-to-day management of
Tetra Tech project personnel, maintaining direct communication with the EPA and the developers, and ensuring that
all Tetra Tech personnel involved in the demonstration understand and comply with the demonstration plan. Dr.
Topudurti is also responsible for distributing the draft and final demonstration plans to all key project personnel and
for reviewing measurement and analytical data obtained during the demonstration. Tetra Tech project personnel will
assist Dr. Topudurti in preparing project deliverables and in performing day-to-day project activities. In consultation
with the EPA, Tetra Tech project personnel are responsible for the following elements of the demonstration:
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EPA project manager
Stephen Billets
EPA NERL
QA officer
George Brilis
Demonstration site
representatives
Ernest Lory
(Navy BVC site)
Amy Whitley
(Kelly AFB site)
Jay Simonds
(Petroleum company site)
Field measurement device developers
Henry Castaneda
(CHEMetrics, Inc.)
Sandy Rintoul
(Wilks Enterprise, Inc.)
George Hyfantis
(Environmental Systems Corporation)
Stephen Greason
(siteLAB® Corporation)
Jim Vance Joseph Dautlick
(Horiba Instruments, Incorporated) (Strategic Diagnostics, Inc.)
TedB. Lynn
(Dexsil® Corporation)
Tetra Tech SITE
program manager
Carl Rhodes
Tetra Tech
project manager
Kirankumar Topudurti
Project
technical consultant
Jerry Parr
(Catalyst Information Resources, L.L.C.)
Tetra Tech SITE
QA manager
Greg Swanson
ERA
project manager
Jeffrey Lowry
Tetra Tech
health and safety
director
Judith Wagner
STL-Tampa
project manager
Susan Bell
STL-Tampa
QA manager
Andres Romeu
Tetra Tech
field manager
Eric Monschein
Tetra Tech
project staff
Sandy Anagnostopoulos
Jill Ciraulo
Kelly Hirsch
Kim Huynh
JeffLifka
Kevin Schnoes
Suzette Tay
Notes:
AFB
BVC
EPA
ERA
NERL
Air Force Base QA
Base Ventura County SITE
U.S. Environmental Protection Agency STL Tampa East
Environmental Resource Associates Tetra Tech
National Exposure Research Laboratory
Quality assurance
Superfund Innovative Technology Evaluation
Severn Trent Laboratories in Tampa, Florida
Tetra Tech EM Inc.
Figure 6-1. Organizational chart.
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• Developing and implementing all elements of this demonstration plan
• Scheduling and coordinating the activities of all demonstration participants
• Performing on-site sample collection in the five demonstration areas
• Coordinating the PE sample preparation by ERA
• Performing sample preparation at the Navy BVC site for the developers and STL Tampa East
• Overseeing operation of the innovative TPH field measurement devices and documenting the operation of
each device during the demonstration
Coordinating meetings among the EPA, the developers, STL Tampa East, and the site representatives
Summarizing, evaluating, interpreting, and documenting demonstration data for inclusion in the ITVRs and
DER
• Evaluating and reporting on the performance and cost of each device
• Preparing draft, final, and camera-ready versions of seven ITVRs (one for each device)
• Preparing draft and final versions of the DER
The project technical consultant, Jerry Parr of Catalyst Information Resources, L.L.C. (Catalyst), will support the
Tetra Tech project manager and will provide technical assistance and guidance throughout all phases of the project.
Tetra Tech subcontracted Mr. Parr specifically for this project because of his extensive experience in the area of PHC
measurement technologies. Mr. Parr's specific responsibilities include the following:
• Providing technical assistance and guidance during development of the demonstration plan
• Auditing field and laboratory operations to determine whether the operations are properly performed
• Providing technical reviews of the demonstration plan, ITVRs, DER, and other project documents
• Providing technical assistance and guidance throughout all phases of the project
The Tetra Tech field manager, Eric Monschein, is responsible for day-to-day field operations and for reporting to the
Tetra Tech project manager. Mr. Monschein will monitor sample preparation and analysis activities to ensure that
procedures set forth in the demonstration plan are followed. Mr. Monschein will also ensure that chain-of-
custody procedures and applicable U.S. Department of Transportation (DOT) shipping regulations are followed for
sample shipment to STL Tampa East. Specific responsibilities of the Tetra Tech field manager include the following:
• Managing field staffing and mobilization activities
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• Overseeing and performing sample collection and preparation activities
• Overseeing sample analysis activities
• Overseeing the activities of project personnel in the field
• Overseeing operation of the innovative TPH field measurement devices and documenting the operation of
each device during the demonstration
Providing required planning, scheduling, cost control, documentation, and data management for field
activities
• Managing demobilization activities, including IDW disposal, as required by the demonstration site
representatives
Immediately communicating any deviation from the demonstration plan during field activities to the Tetra
Tech project manager and discussing appropriate resolutions of the deviation
Tetra Tech project personnel will assist Mr. Monschein in conducting day-to-day field activities during the
demonstration, including sample collection, sample preparation, measurement of time associated with TPH field
measurements, and oversight of TPH field measurements.
At the Navy BVC site, Mr. Monschein will oversee sample collection activities in the FFA and NEX Service Station
Area. In these areas, sample collection using a Geoprobe® will be conducted by Tetra Tech's subcontractor. In the
PRA at the Navy BVC site, Mr. Monschein or other Tetra Tech project personnel will perform split core sample
collection activities. The samples collected in the three areas at the Navy BVC site will be transferred by Mr.
Monschein to the sample management trailer in the PRA. At the Kelly AFB site, Jill Ciraulo of Tetra Tech will
oversee sample collection activities and perform sample shipment to the Navy BVC site. At the Kelly AFB site,
sample collection using a Geoprobe® will be conducted by Tetra Tech's subcontractor. At the PC site, Suzette Tay
of Tetra Tech will oversee sample collection activities and perform sample shipment to the Navy BVC site. At the
PC site, sample collection using a Geoprobe® will be conducted by a subcontractor to the demonstration site
representative.
Kevin Schnoes of Tetra Tech will cut open the soil sample core tube liners and perform soil classification activities
at the sample management trailer in the PRA. Tetra Tech's health and safety representative (HSR), Judith Wagner,
will review the site-specific health and safety procedures, and she or her designee will audit field procedures during
the demonstration to ensure compliance with the health and safety procedures presented in Chapter 13 of the
demonstration plan.
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Tetra Tech's SITE program manager, Carl Rhodes, is responsible for project review and for allocating Tetra Tech
resources. The Tetra Tech SITE QA manager, Greg Swanson, is responsible for overall project QA. Dr. Swanson
will be available to resolve any project-specific QA issues.
6.3 Developer Personnel
The developers of the seven field measurement devices are responsible for providing, mobilizing, operating, and
demobilizing their respective devices. The developer responsibilities include the following:
• Providing Tetra Tech with information on the devices
Reviewing and concurring with the demonstration plan pertaining to the devices
Notifying Tetra Tech in writing of device-specific requirements, such as the type of power supply and the
amount of work space needed, so that proper arrangements can be made for field demonstration of the
devices
Providing the personnel and all supplies needed for demonstration of the devices unless otherwise arranged
in advance with Tetra Tech
• Analyzing the samples specified in the demonstration plan
• Analyzing appropriate QC samples (for example, blanks or standards) in accordance with the developer
specifications
Providing device-specific demonstration results to Tetra Tech at the end of the demonstration
• Reviewing and commenting on the device-specific ITVRs
6.4 Demonstration Site Representatives
The representatives for the three demonstration sites are Ernest Lory for the Navy BVC site, Amy Whitley for the
Kelly AFB site, and Jay Simonds for the PC site. All work performed at each demonstration site will be scheduled,
coordinated, and conducted with the permission of the individual demonstration site representative, who will be the
primary contact for the Tetra Tech project manager. The demonstration site representatives are responsible for
obtaining the site access and permission necessary for performing sampling activities at the sites. The demonstration
site representatives are also responsible for reviewing and concurring with the demonstration plan.
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At the Navy BVC site, Mr. Lory's specific responsibilities include the following:
Providing Tetra Tech with background information on the three demonstration areas
Providing logistical support for conducting visitors' day activities, which will include providing a meeting
room and transporting visitors between the meeting room and PRA, if necessary
• Preparing the sample management trailer area and providing utilities, a power source when necessary, work
space with tables and chairs, distilled water for field blanks, and logistical support needed for the
demonstration
• Providing access to the sample management trailer in the PRA
At the Kelly AFB site, Ms. Whitley's specific responsibilities include the following:
• Providing Tetra Tech with background information the B-38 Area
• Providing Tetra Tech with access to the B-38 Area
At the PC site, Mr. Simonds' specific responsibilities include the following:
• Providing Tetra Tech with background information on the SFT Area
Procuring a Geoprobe® subcontractor to collect soil core samples
Providing Tetra Tech with the soil core samples
Providing Tetra Tech with access to the SFT Area
6.5 Laboratory Project Personnel
The reference laboratory for the project, STL Tampa East, will perform laboratory analyses of environmental and
PE samples provided by Tetra Tech during the demonstration. The STL Tampa East project manager, Susan Bell,
is responsible for overall planning, scheduling, budgeting, and reporting of laboratory activities. All STL Tampa East
work will be conducted under the direct supervision of Ms. Bell, who will be the primary contact for the Tetra Tech
project manager. Ms. Bell is also responsible for reviewing and concurring with the demonstration plan, and she will
immediately discuss appropriate resolutions of any deviation from the STL Tampa East activities specified in the plan
with the Tetra Tech project manager. STL Tampa East's QA manager, Andres Romeu, will assist Ms. Bell in
ensuring adherence to all QA/QC elements specified in the demonstration plan that pertain to the analyses performed
at their laboratory.
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ERA will prepare all soil and liquid PE samples requested by Tetra Tech and will ship them to the Navy BVC site.
The ERA project manager, Jeffrey Lowry, is responsible for all planning, scheduling, and budgeting of laboratory
activities and for preparation of PE samples. All PE sample preparation work will be conducted under the direct
supervision of Mr. Lowry, who will be the primary contact for the Tetra Tech project manager.
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Table 6-1. Demonstration Participants
Organization
Participant
Contact Information
U.S. Environmental Protection Agency
Tetra Tech EM Inc.
Catalyst Information Resources, L.L.C.
Navy Base Ventura County
Dr. Stephen Billets
Mr. George Brills
Dr. Kirankumar Topudurti
Mr. Eric Monschein
Ms. Sandy Anagnostopoulos
Ms. Jill Ciraulo
Ms. Kelly Hirsch
Ms. Kim Huynh
Mr. Jeff Lifka
Mr. Kevin Schnoes
Ms. Suzette Tay
Ms. Judith Wagner
Mr. Carl Rhodes
Dr. Greg Swanson
Mr. Jerry Parr
Mr. Ernest Lory
Kelly Air Force Base
Ms. Amy Whitley
Handex of Indiana
CHEMetrics
Mr. Jay Simonds
Mr. Henry Castaneda
National Exposure Research Laboratory
944 East Harmon Avenue
Las Vegas, NV 89119
Telephone: (702) 798-2232
Fax: (702) 798-2261
E-mail: billets.stephen@epamail.epa.gov
200 East Randolph Drive, Suite 4700
Chicago, IL 60601
Telephone: (312) 856-8700
Fax:(312)938-0118
E-mail: topuduk@ttemi.com
3550 Salt Creek Lane, Suite 105
Arlington Heights, IL 60005
Telephone: (847) 255-4166
Fax: (847) 255-8528
E-mail: wagnerj@ttemi.com
250 West Court Street, Suite 200 W
Cincinnati, OH 45202
Telephone: (513)241-0149
Fax:(513)241-0354
E-mail: rhodesc@ttemi.com
591 Camino de la Reina, Suite 640
San Diego, CA 92108
Telephone: (619)718-9676
Fax: (619)718-9698
E-mail: swansog@ttemi.com
1153 Bergen Parkway, # 238
Evergreen, CO 80439
Telephone: (303) 670-7823
Fax: (303) 670-2964
E-mail: catalyst@eazy.net
NFESC
1100 23rd Avenue
Port Hueneme, CA 93043
Telephone: (805) 982-1299
Fax: (805) 982-4304
e-mail: loryee@nfesc.navy.mil
SA-ALC/EMRR
307 Tinker Drive (Bldg. 306)
Kelly AFB, TX 78241
Telephone: (210) 925-3100 (Ext. 214)
Fax: (210)925-1814
e-mail: amy.whitley@kelly.af.mil
8579 Zionsville Road
Indianapolis, IN 46268
Telephone: (317) 228-6240
Fax:(317)228-6243
e-mail: jsimonds@handexmail.com
CHEMetrics, Inc.
Route 28
Calverton, VA20138
Telephone: (800) 356-3072
Fax: (540) 788-4856
E-mail: henryc@chemetrics.com
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Table 6-1. Demonstration Participants (Continued)
Organization
Participant
Contact Information
Wilks
Ms. Sandy Rintoul
Horiba
Mr. Jim Vance
Dexsil®
Dr. Ted B. Lynn
ESC
Dr. George Hyfantis
site LAB®
Mr. Stephen Greason
SDI
Mr. Joseph Dautlick
Severn Trent Laboratories
Environmental Resource Associates
Ms. Susan Bell
Mr. Andres Romeu
Mr. Jeffrey Lowry
Wilks Enterprise, Inc.
345 Riverview Drive
Boulder Creek, CA 95006
Telephone: (831) 338-7459
Fax: (831)338-3393
E-mail: srintoul@dellnet.com
Horiba Instruments, Incorporated
17671 Armstrong Avenue
Irvine, CA 92614
Telephone: (800) 4HORIBA, ext. 170
Fax: (949) 250-0924
E-mail: jim.vance@horiba.com
Dexsil® Corporation
One Hamden Park Drive
Hamden, CT06517
Telephone: (203) 288-3509
Fax: (203) 248-6523
E-mail: tblynn@dexsil.com
Environmental Systems Corporation
200 Tech Center Drive
Knoxville,TN37912
Telephone: (865) 688-7900
Fax: (865) 687-8977
E-mail: ghyfantis@envirosys.com
site LAB® Corporation
94 Highland Street
Portsmouth, NH 03801
Telephone: (877) SITELAB
Fax: (603) 436-9008
E-mail: sgreason@site-lab.com
Strategic Diagnostics, Inc.
111 Pencader Drive
Newark, DE 19702
Telephone: (800) 544-8881, ext. 222
Fax: (302) 456-6770
E-mail: jdautlick@sdix.com
5910 Breckenridge Parkway, Suite H
Tampa, FL 33610
Telephone: (813)621-0784
Fax: (813)623-6021
E-mail: bellsu@quanterra.com
5540 Marshall Street
Arvada, CO 80002
Telephone: (800) 372-0122
Fax:(303)421-0159
E-mail: jlowry@eraqc.com
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Chapter 7
Field Sampling Procedures
This chapter discusses the field sampling procedures to be used during the demonstration. Specifically, this chapter
addresses the sampling procedures (Section 7.1), sample handling and shipping procedures (Section 7.2), sampling
equipment decontamination and IDW disposal procedures (Section 7.3), and field documentation procedures
(Section 7.4) to be used during the demonstration.
The critical and noncritical measurements for the demonstration are summarized in Table 7-1. Critical measurements
will be used to address primary objectives. Although critical measurements generally involve a greater level of QC
than noncritical measurements, several critical measurements for the demonstration do not have significant QC
procedures. For example, noting the number of technicians required to operate an innovative TPH field measurement
device is considered to be a critical measurement because the number of technicians required is associated with
estimating the time and cost requirements for each field measurement activity (primary objectives P5 and P6).
However, the number of technicians will be noted only once for each device during the demonstration because the
number is not likely to change or to be subject to measurement error. Noncritical measurements will provide
additional information regarding the devices but are not critical to addressing the primary objectives. A number of
demonstration measurements, such as those for sampling locations and depth intervals, are classified as noncritical
because these measurements were made during the predemonstration investigation and because it is adequate if the
demonstration sampling locations and depth intervals are within 1 to 2 feet of the predemonstration investigation
sampling locations and depth intervals. The demonstration will take advantage of as much predemonstration
investigation data as possible. Because of the qualitative nature of the demonstration's secondary objectives,
measurement and sampling activities will not be conducted primarily to address secondary objectives.
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Table 7-1. Critical and Noncritical Measurements
Measurement
Critical or
Noncritical
Measurement
Rationale (Primary or Secondary Objective)
Measurements Made Specifically During Sample Collection
Sampling locations and depth intervals Noncritical
Water level measurements at Kelly AFB, B-38 Area Noncritical
Photoionization detector measurements at Kelly Noncritical
AFB, B-38 Area
Measurements Made During Demonstration as a Whole
Collect samples at locations and depth intervals close to those of
predemonstration investigation
Locate soil sampling depth intervals 2 feet above and 2 feet
below the water table
Characterize soil sample concentrations as nondetect, low,
medium, or high
STL Tampa East and developer TPH measurements
Percent moisture for soil samples
Number of technicians required
Time required for sample analysis activities
Volume of investigation-derived waste generated
Extra items required to perform analysis
Personal protective equipment required
Support facilities required
Time required for homogenization of environmental
samples
Physical soil classification using USCS
Critical
Critical
Critical
Critical
Critical
Critical
Noncritical
Noncritical
Noncritical
Noncritical
Evaluate method detection limits (P1), precision and accuracy
(P2), effect of interferents (P3), and effect of moisture (P4)
Document moisture content of samples (P4)
Estimate time and cost associated with each field measurement
activity (P5 and P6)
Estimate time and cost associated with each field measurement
activity (P5 and P6)
Estimate cost associated with each field measurement activity
(P6)
Estimate cost associated with each field measurement activity
(P6)
Document health and safety concerns associated with operating
each device (S2)
Document power sources and amount of work space required
(S5)
Document sample preparation procedures
Characterize environmental samples for physical parameters (for
example, sand, silt, and clay content)
Notes:
AFB = Air Force Base
STL Tampa East = Severn Trent Laboratories in Tampa, Florida
TPH = Total petroleum hydrocarbons
USCS = Unified Soil Classification System
7.1
Sampling Procedures
The demonstration will involve both environmental and PE samples. Environmental samples will be collected by
Tetra Tech or its subcontractor in core tube liners, sectioned as appropriate to represent approximate depth intervals
at each sampling location, homogenized, containerized, and labeled. Homogenous PE samples will be prepared,
containerized, and shipped to Tetra Tech at the Navy BVC site by ERA in Arvada, Colorado. Tetra Tech will not
open any of the PE sample containers but will assign them sample identification numbers and distribute them to STL
Tampa East and the developers.
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For the demonstration, environmental samples will be collected in the areas that were used for the January 2000
predemonstration investigation: (1) the FFA, NEX Service Station Area, and PRA at the Navy BVC site; (2) the B-38
Area at the Kelly AFB site; and (3) the SFT Area at the PC site. These areas are shown in Figures 3-2, 3-4, and 3-5
of Chapter 3. Samples will be collected in all areas except the PRA using a subcontractor-operated Geoprobe®; in
the PRA, samples will be collected by Tetra Tech personnel using a Split Core Sampler. Where a subcontractor-
operated Geoprobe® is used, Tetra Tech personnel will be present to supervise sample collection and to determine
whether enough sample material is collected in a given depth interval. Except in the PRA, after sampling is
completed at a location, the boring will be grouted with bentonite to the ground surface. In the PRA, planter soil will
be used to fill the borings.
All samples will be managed at the sample management trailer in the PRA at the Navy BVC site. Samples collected
at the Kelly AFB and PC sites will be shipped in core tube liners to the sample management trailer, where Tetra Tech
will section the core tube liners as needed, record soil characteristics using the Unified Soil Classification System
(USCS), homogenize the sample material collected from a given depth interval at a particular sampling location, and
prepare samples for shipment to STL Tampa East and for transfer to the developers on site. Sample collection,
handling, and shipping procedures to be used at each of the three demonstration sites are detailed in Sections 7.1.1
and 7.1.2. Sample preparation procedures are detailed in Section 7.1.3.
Tetra Tech is aware that some of the sample collection and homogenization procedures to be used may result in
significant loss of GRO from the samples. Specifically, the core tube liners used to transport samples to the Navy
BVC site and the homogenization techniques described in Section 7.1.3 may result in GRO losses of up to one order
of magnitude. Despite these losses, based on observations during the predemonstration investigation, the
demonstration samples are expected to contain adequate concentrations of GRO after homogenization. Moreover,
the homogenization procedures will ensure that STL Tampa East and the developers receive the same sample material
for analysis, which is necessary to perform a meaningful comparison of the reference method and device analytical
results.
7.1.1 Sample Collection
This section describes environmental sample collection activities to be performed at the three demonstration sites.
Homogenous PE samples will be prepared, containerized, and shipped to Tetra Tech at the Navy BVC site by ERA
in Arvada, Colorado. Tetra Tech will not open any of the PE sample containers but will assign them sample
identification numbers and distribute them to STL Tampa East and the developers.
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During the demonstration, Tetra Tech will collect samples from locations and depth intervals immediately adjacent
to the predemonstration investigation sampling locations and depth intervals with a few exceptions; based on
predemonstration investigation results, some of the sampling locations and depth intervals have been modified for
the demonstration. To allow later identification of the predemonstration investigation sampling locations at each site,
Tetra Tech marked them with either metal or plastic stakes. Also, Tetra Tech's field logbooks contain sketches of
the sampling locations and measurements of each location with respect to a permanent reference point; these
measurements were made using a measuring tape and compass.
During the predemonstration investigation, Tetra Tech found that in some sampling areas the TPH concentrations
were highest at or near the water table because of contamination floating on the groundwater surface. For example,
based on discussions between Tetra Tech and the demonstration site representative for Kelly AFB, the contamination
is expected to be highest at or near the water table. Four groundwater monitoring wells exist in the B-38 Area.
Therefore, Tetra Tech will use a water-level indicator to measure the depth to groundwater in each of the monitoring
wells before collecting soil samples. In addition, Tetra Tech will identify any monitoring wells or piezometers in
the other sampling areas and, where possible, will measure the depth to groundwater in the areas before collecting
soil samples. The measurements will be used to modify sampling depth intervals during sample collection, as
necessary.
During the predemonstration investigation, the diameter of the core tube liners used and the soil depth intervals
selected generally allowed collection of enough sample volume for analysis. In some cases, however, additional
sample volume was needed for collection of field triplicates. The additional sample volume was obtained by
advancing an additional Geoprobe® boring within 1 foot of the initial sampling location. Because all samples will
be distributed to both STL Tampa East and the developers during the demonstration, and because triplicates will be
collected at a frequency of one per depth interval, additional sample volume may be required. Therefore, during the
demonstration, additional Geoprobe® borings may be advanced immediately adj acent to the initial sampling locations
in order to obtain adequate sample volume.
When core tube liners containing samples arrived at the sample management trailer at the Navy BVC site during the
predemonstration investigation, the core tube liners were visually examined, and depth intervals were identified for
the liners. The depth intervals were identified based on Tetra Tech field logbook notes taken during sample
collection that documented (1) the length of the Geoprobe® rods in the ground when filling of the core tube liners
started and (2) visual observations of staining or differing soil types in various depth intervals. For a given sampling
location, the topmost portion of the entire length of the sample corresponded to the depth at which the core tube liner
was introduced for sample collection, and the soil recovered in each core tube liner was measured using that top depth
113
-------
as a reference point. For example, when Tetra Tech attempted to collect a sample from 2 to 4 feet bgs and only a
1-foot length of soil was recovered in the core tube liner, the soil sample's depth interval was identified as 2 to 3 feet
bgs. Tetra Tech used this approach because soil recoveries were sometimes less than the length of the core tube
liners. This approach did not account for soil compression or loss of soil during sample collection. Tetra Tech will
use a consistent method of identifying depth intervals for samples in each area during the demonstration.
Table 7-2 summarizes the proposed demonstration sampling depth intervals, the expected contamination types and
concentrations for each interval, and the rationale for the selection of intervals based on the objectives to be addressed
and the analyses to be performed by STL Tampa East. Table 7-3 summarizes the proposed demonstration sampling
depth intervals, expected contamination types and concentrations, objectives to be addressed, numbers of
environmental and QA/QC samples to be collected, and numbers of analyses to be performed for environmental
samples. The sampling depth intervals for the demonstration have been slightly modified from those used during the
predemonstration investigation in the FFA, NEX Service Station Area, and B-38 Area. An explanation of each
modification is provided in the following site-specific sections. Table 7-4 summarizes the expected contamination
types and concentrations, objectives to be addressed, numbers of samples and analyses, and numbers of sample
containers for the PE samples that will be prepared by ERA.
Contamination types and concentration ranges shown in Tables 7-2, 7-3, and 7-4 are based on predemonstration
investigation results in the case of environmental samples and discussions with ERA in the case of PE samples. In
these tables, a low (L) concentration corresponds to a TPH value of less than 100 mg/kg; a medium (M) concentration
corresponds to a TPH range of 100 to 1,000 mg/kg; and a high (H) concentration corresponds to a TPH value of more
than 1,000 mg/kg. The concentration information should be used only as a guide to determine appropriate dilutions
for sample analysis. Certain information, such as the specific compounds to be used as interferents in preparing the
PE samples required to address primary objective P3, is purposely not included in this demonstration plan.
7.1.1.1 Navy Base Ventura County Site
This section describes the sampling locations, depth intervals, and types of sampling equipment to be used in the three
demonstration areas at the Navy BVC site.
114
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121
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ontinued)
le 7-4. Performance Evaluation Samples (C
.Q
re
ig interferents 1(5) and 1(6) will not be prepared with GRO because these interferents are not expected
sd with preparing the 1(1) or l(2) + EDROand l(5) or l(6) + GRO PE samples will not allow use of these
erferents are based on expected analytical results for the samples and not on the concentrations of
.b ~ -K
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D analysis. Similarly, PE samples contai
I difficulties (solubility constraints) assoc
ncentrations for PE samples containing
interferents are not expected to impact EDR(
to impact GRO analysis. In addition, practica
samples in the demonstration. Expected coi
interferents to be added to the samples.
: interferent levels, L1 and L2.
C
0)
nterferents will be prepared at two differ
Performance evaluation samples containing i
ast; however, no additional sample volume will be required for these analyses.
LU
be analyzed for moisture by STL Tampa
All performance evaluation samples will also
ast = number of GRO analyses x 2
Number of 5-gram EnCores to STL Tampa E
= number of EDRO analyses
Number of 4-ounce jars to STL Tampa East :
?O samples with the methanol carrier because DexsiP will not demonstrate the PetroFLAG™ test kit
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Both models need to be used in order to provide enough control samples to address primary objective
i__!
Iks to use both Models CVH and HATR-'
This number includes enough samples for Wi
P3 (effects of interferents).
moisture cannot be containerized in EnCores.
"c
vials because soil with less than 9 perce
These samples will be containerized in VOA
pies as explained in footnote i.
E
because VOA vials will be used for 21 s;
The total number of EnCores is actually 595
122
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7.1.1.1.1 Fuel Farm Area
Soil samples will be collected by Tetra Tech in the FFA at three locations south of Tank No. 5114 (see Figure 3-2).
Specifically, the sampling locations will consist of the three locations sampled during the predemonstration
investigation and three of the four locations sampled by site representatives in September 1999. The three
demonstration sampling locations lie about 30 feet apart. Based on historical data regarding the extent of area
contamination and Tetra Tech's knowledge ofthe area gained during the predemonstration investigation, soil samples
will be collected in two depth intervals at the three sampling locations. During the predemonstration investigation,
Tetra Tech could not identify exact sampling depth intervals because ofthe soil types encountered and the recoveries
obtained. The two depth intervals were classified as the upper layer and lower layer, with the upper layer consisting
of yellowish-brown, silty sand and the lower layer consisting of grayish-black, silty sand with a hydrocarbon odor.
During the demonstration, based on visual observations, Tetra Tech will attempt to sample the same depth intervals
as were sampled during the predemonstration investigation. As stated in Chapter 3, hydrocarbon contamination in
the FFA is not homogeneous. To the extent possible, Tetra Tech will not mix soil types in a given soil sample. Based
on soil profiles, a field decision will be made regarding whether the sampling depth intervals should be modified to
achieve as much homogeneity as possible in each soil sample.
Tetra Tech's subcontractor will conduct sample collection activities using a Geoprobe® with push rods containing
approximately 1.7-inch-diameter, plastic liners that can be capped at both ends. Based on the history of
contamination in the FFA, soil samples collected in this area will be analyzed for EDRO by STL Tampa East.
7.1.1.1.2 Naval Exchange Service Station Area
Soil samples will be collected by Tetra Tech in the NEX Service Station Area at three locations between Building
1184 and Credit Union Building 1336 (see Figure 3-2). Specifically, the sampling locations will consist ofthe three
locations sampled during the predemonstration investigation and sampled by site representatives in September 1999.
The sampling locations are about 30 feet apart. Based on historical data regarding the extent of area contamination
and Tetra Tech's knowledge ofthe area gained during the predemonstration investigation, soil samples will be
collected in 1 -foot depth intervals from 7 to 11 feet bgs at the three sampling locations. These intervals were selected
based on soil contamination characteristics observed during predemonstration investigation sampling in the area.
The 5- to 6- and 6- to 7-foot bgs depth intervals sampled during the predemonstration investigation will not be
sampled during the demonstration because TPH concentrations in these intervals were negligible. To the extent
possible, Tetra Tech will not mix soil types in a given soil sample. Based on soil profiles, a field decision will be
123
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made regarding whether the sampling depth intervals should be modified to achieve as much homogeneity as possible
in each soil sample.
Sampling will be conducted using a Geoprobe® with push rods containing approximately 1.7-inch-diameter, plastic
liners that can be capped at both ends. Based on the history of contamination in the NEX Service Station Area and
Tetra Tech's knowledge of the area gained during the predemonstration investigation, soil samples collected in this
area will be analyzed for both GRO and EDRO by STL Tampa East.
7.1.1.1.3 Phytoremediation Area
Soil samples will be collected by Tetra Tech in the PRA at six locations using a Split Core Sampler containing a 2-
inch-diameter, plastic liner. Specifically, one soil sample will be collected from each of six cells; each cover type (that
is, unvegetated, native grass mix, and grass and legume mix) will be represented twice in the sampling (see
Figure 3-2). Samples will be collected from 1.5 to 2.5 feet bgs. Based on the results of previous investigations in the
PRA, the samples collected in this area will be analyzed for EDRO by STL Tampa East.
7.1.1.2 Kelly Air Force Base Site
At the Kelly AFB site, soil samples will be collected in the B-38 Area at the four locations sampled during the
predemonstration investigation (see Figure 3-4). The depth intervals sampled during the demonstration will be
different from those sampled during the predemonstration investigation because the latter contained low or nondetect
TPH concentrations. Based on discussions with the demonstration site representative after the predemonstration
investigation, it was determined that most of the contamination in the B-38 Area can be found at or near the water
table. Therefore, the depth intervals to be sampled during the demonstration will be located 2 feet above and 2 feet
below the water table. For the purposes of this demonstration plan, Tetra Tech assumes that the surface of the water
table will be about 20 feet bgs during the demonstration. This assumption is based on previous groundwater-level
data provided by the site representative. The exact depth to groundwater will be measured by Tetra Tech using a
water-level indicator in four nearby monitoring wells at the time of the demonstration. Tetra Tech will then calculate
an average depth to groundwater and will collect the soil samples 2 feet above and 2 feet below the average water
table depth. Therefore, soil samples will likely be collected in two depth intervals—18 to 20 and 20 to 22 feet
bgs—at the four sampling locations.
Sampling will be conducted using a Geoprobe® with push rods containing approximately 1.7-inch-diameter, plastic
liners that can be capped at both ends. Based on the history of contamination in the B-38 Area and Tetra Tech's
124
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knowledge of the area gained during the predemonstration investigation, soil samples collected in this area will be
analyzed for both GRO and EDRO by STL Tampa East.
7.1.1.3 Petroleum Company Site
At the PC site, soil samples will be collected in the SFT Area at five sampling locations. Specifically, samples will
be collected from the four corners and center of the square sampling area shown in Figure 3-5, which are the five
locations sampled during the predemonstration investigation. Based on the known extent of area contamination, soil
samples will be collected in 2-foot depth intervals from 2 to 10 feet bgs at the five sampling locations.
Sampling will be conducted using a Geoprobe® with push rods containing approximately 1.7-inch-diameter, plastic
liners that can be capped at both ends. Based on the history of contamination in the SFT Area and Tetra Tech's
knowledge of the area gained during the predemonstration investigation, soil samples collected in this area will be
analyzed for both GRO and EDRO by STL Tampa East.
7.1.2 Sample Handling and Shipping
Following its recovery, each soil sample collected using a lined Geoprobe® or Split Core Sampler will be removed
intact in the liner from the sampling equipment. If necessary, the liner will be cut to a length that will fit in a cooler.
After the liner is removed and cut, it will be immediately closed with plastic caps at both ends to minimize
volatilization of contaminants. The liner caps will be of two colors to designate the top and bottom of the soil sample.
To ensure that the caps will not be detached from the liner, the caps will be taped to the liner. The liner will then be
labeled. The label will contain information on the site, sampling area, sampling location, and depth interval from
which the sample was collected.
The samples collected at the Kelly AFB and PC sites will be placed in coolers containing ice and will be shipped by
overnight courier to the sample management trailer at the Navy BVC site. At this location, the soil samples collected
at all three demonstration sites will be profiled, homogenized, and prepared for shipment to STL Tampa East and for
transfer to the developers on site. PE samples will be shipped to Tetra Tech at the Navy BVC site by ERA in Arvada,
Colorado. Tetra Tech will not open any of the PE sample containers but will assign them sample identification
numbers and distribute them to STL Tampa East and the developers.
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7.1.3 Sample Preparation
This section describes environmental, PE, and QC sample preparation activities that will be conducted during the
demonstration.
7.1.3.1 Environmental Samples
After the liners containing environmental samples are transported to the sample management trailer at the Navy BVC
site, Tetra Tech will cut the liners longitudinally. Tetra Tech will then profile the samples to determine where the
soil cores have to be sectioned if their depth intervals are found to differ from the target depth intervals based on soil
characteristics. The soil samples will be characterized by a Tetra Tech geologist using the USCS.
Because the TPH concentrations encountered in the B-38 Area at Kelly AFB during the predemonstration
investigation were low or nondetects, photoionization detector (PID) readings will also be used to select the depth
intervals to be sampled for this area. The PID readings will be used qualitatively to determine whether contamination
is present at low, medium, or high levels or not at all. If the PID does not detect any measurable contamination, Tetra
Tech will make a field decision regarding whether to analyze samples from the B-38 Area.
Each core sample will be transferred to a stainless-steel bowl. The presence of any unrepresentative material such
as sticks, roots, and stones will be noted in a field logbook, and such material will be removed to the extent possible
using gloved hands. Any lump of clay in the sample that is greater than about 1/8 inch in diameter will be crushed
between gloved fingers before homogenization.
Tetra Tech will homogenize each soil sample by stirring the soil for at least 2 minutes using a stainless-steel spoon
or gloved hands until the sample is visibly homogeneous. During or immediately following homogenization, Tetra
Tech will pour off any free water from the stainless-steel bowl containing the soil sample into a container designated
for IDW. During the predemonstration investigation, nitrile gloves were used by the field sampling team for most
sample preparation; however, when the supply of nitrile gloves was depleted, locally available plastic gloves were
used. Use of plastic gloves resulted in phthalate contamination in the EDRO range in the predemonstration
investigation sample analytical results. Therefore, during the demonstration, only nitrile gloves will be used by the
field sampling team.
Tetra Tech will then place the samples in (1) EnCores for GRO and TPH analyses and (2) STL Tampa East-provided,
4-ounce, glass sample jars for EDRO analysis. The 4-ounce, glass sample jars will be filled after all the EnCores
126
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have been filled for a given sample. A sample that will be submitted for GRO analysis will be aliquoted from the
mixing bowl into an EnCore of approximately 5-gram capacity. Similarly, a sample that will be submitted for TPH
analysis will be aliquoted from the mixing bowl into an EnCore of approximately 25-gram capacity. A sample to be
submitted for EDRO analysis will be placed in 4-ounce, glass jars. Using a quartering technique, Tetra Tech will
fill each sample container by alternately spooning soil from one quadrant of the mixing bowl and then from the
opposite quadrant until the container is full. After a sample container is filled, it will be immediately closed to
minimize volatilization of contaminants. The top of each sample container will be carefully wiped with a clean,
disposable laboratory wipe to remove any soil particles that might be present. To minimize the time required for
sample homogenization and filling of sample containers, these activities will be conducted by two or three Tetra Tech
personnel simultaneously.
Some time will elapse between the filling of the first EnCore and the filling of the last EnCore for the developers.
Therefore, to distribute the EnCores to the developers in such a way that the order in which they were filled is not
critical, the following procedure will be used. The seven EnCores per sampling location for the developers will be
labeled 1 through 7 by Tetra Tech prior to the demonstration. When filling these EnCores, Tetra Tech will always
start with number 1 and fill them sequentially through number 7. When field triplicates are collected, 21 EnCores
will be filled for the developers. These samplers will be labeled as three batches of 1 through 7 and will be filled one
batch at a time in numerical sequence. The field triplicates can thus be used to check Tetra Tech's soil
homogenization procedures. The numbered EnCores that the developers receive will be varied so that all the
developers receive approximately the same distribution of EnCores of a given number. When a sample is prepared
for submittal to STL Tampa East for GRO analysis, the 5-gram EnCores for STL Tampa East will always be filled
after one-half of the 25-gram EnCores designated for a given depth interval and location have been filled.
Table 7-5 summarizes the sample container, preservation, and holding time requirements for (1) GRO, EDRO, and
percent moisture analyses to be performed by STL Tampa East and (2) TPH analyses to be performed by the
developers. STL Tampa East will receive two EnCores, each containing approximately 5 grams of soil, for GRO
analysis and two 4-ounce, glass jars filled to two-thirds of their capacity with soil to be analyzed for EDRO and
percent moisture. The 4-ounce j ars will be filled to two-thirds of their capacity so that STL Tampa East can mix each
sample before separating aliquots for EDRO and percent moisture analyses. Field triplicates will be collected at a
rate of one per depth interval per area. For GRO analysis, when matrix spike/matrix spike duplicate (MS/MSD) or
field triplicate samples are required, four additional 5-gram EnCores will be filled with soil and sent to STL Tampa
East. For EDRO analysis, only field triplicates require additional sample volume. For each environmental field
triplicate, four additional 4-ounce, glass jars will be filled with soil and sent to STL Tampa East. Each developer will
receive one EnCore sample containing about 25 grams of soil for TPH analysis. MS/MSDs and field triplicates
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Table 7-5. Sample Container, Preservation, and Holding Time Requirements
Holding Time (days)
Parameter3
GRO
EDRO
Percent moisture
Total petroleum hydrocarbons
GRO and EDRO
Medium
Soil
Soil
Soil
Soil
Liquid
Container
Two 5-gram EnCores
Two 4-ounce, glass jars with Teflon™-lined lids
Two 4-ounce, glass jars with Teflon™-lined lids
One 25-gram EnCore
One 2-milliliter ampule
Preservation
4±2°C
4±2°C
4±2°C
4±2°C
Not
applicable
Extraction Analysis
2b 14
14b 40
Not applicable 7
Performed on site0
See note d
Notes:
± = Plus or minus
EDRO = Extended diesel range organics
GRO = Gasoline range organics
a Severn Trent Laboratories in Tampa, Florida, will measure percent moisture using part of the soil sample from a container designated for
extended diesel range organic analysis.
b The extraction holding time will start on the day that samples are shipped.
0 If gasoline range organics are likely to be present, extraction will take place within 2 days. Otherwise, all extractions and analyses will be
completed on site within 7 days.
d Severn Trent Laboratories in Tampa, Florida, will crack open each ampule and will immediately add a specified aliquot of the sample to
methanol for GRO analysis and to methylene chloride for EDRO analysis in such a way that the final volumes of the extracts for GRO and
EDRO analyses are 5.0 and 1.0 milliliters, respectively. Once the extracts are prepared, the GRO and EDRO analyses will be performed
within 14 and 40 days, respectively.
will be designated by Tetra Tech for a given area based on the expected contaminant concentration range and visual
observations of soil characteristics. These samples will be selected in such a way that they reflect a variety of
concentration ranges and all the soil types in a given area. Unused soil will be collected as IDW and will be managed
in the manner described in Section 7.3.
7.1.3.2
PE Samples
All PE samples will be prepared by ERA and shipped to Tetra Tech at the sample management trailer at the Navy
BVC site. PE samples will consist of soil samples and liquid samples. ERA will prepare soil PE samples using two
reference soils. Reference soil 1 will consist of Ottawa sand and will be used to prepare low-level PE samples.
Reference soil 2 will consist of processed garden soil (sandy silt) and will be used to prepare the rest of the soil PE
samples. Reference soil 2 may contain native trace levels of GRO and low levels of EDRO. However, for medium-
and high-level PE samples, reference soil 2 will be used because the sandy silt will allow a more realistic evaluation
of contaminant recovery than Ottawa sand and because the trace levels of background contamination present in the
sandy silt will not impact the integrity of the samples. Each soil PE sample will be spiked with a known type of
contaminant at a known concentration as summarized in Table 7-4.
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To prepare the soil PE samples, ERA will spike the required volume of soil based on the number of PE samples and
the quantity of soil per PE sample requested by Tetra Tech. ERA will then homogenize the soil by manually mixing
it. ERA will use a GRO-range spiking material and an EDRO-range spiking material, and spiking will be done at
three levels: low, medium, and high. A low-level sample will correspond to a TPH value of less than 100 mg/kg; a
medium-level sample will correspond to a TPH range of 100 to 1,000 mg/kg; and a high-level sample will correspond
to a TPH value of more than 1,000 mg/kg. Some soil samples will also be spiked with interferents 1(1) through 1(6)
at two different levels, LI and L2. The interferent levels will range from 50 to 500 percent of the expected TPH
concentration in a given sample. Whenever possible, the interferents will be added at levels that best represent real-
world conditions.
To spike each low- and medium-level soil sample, ERA must use a "carrier" to distribute the contaminant evenly
throughout the sample. During the predemonstration investigation, methanol and Freon 113 were used as carriers
for low-level soil PE samples. After reviewing STL Tampa East data for these samples, Tetra Tech determined that
the samples prepared using methanol contained lower levels of TPH than those prepared using Freon 113 (up to
40 percent lower). According to the manufacturer of EnCores, using methanol as the carrier in an EnCore may have
caused the sampler to swell, opening the pores on the sampler's viton ring; as a result, some of the volatiles in the
sample may have escaped. To address this potential loss of volatiles, ERA will spike the low- and medium-level PE
samples prepared using methanol with slightly higher levels than those actually requested by Tetra Tech. The low-
and medium-level PE samples will be used to address primary objectives P1 and P2, but most of the PE samples will
be used to address primary objective P3. This objective will be addressed using these high-level PE samples because
these samples do not require a carrier. Tetra Tech is attempting to minimize the use of PE samples that require a
carrier because when carriers are used, two sets of PE samples must be sent to STL Tampa East, one prepared with
Freon 113 and one prepared with methanol. As a result, sample preparation and analysis costs increase.
The liquid PE samples will be prepared to address primary objective P3 and will each consist of one of five
interferents, 1(1) through 1(5), at two different levels. Neat materials will be used as liquid PE samples; no carrier will
be used. Each liquid PE sample will consist of approximately 2 mL of liquid in a flame-sealed, glass ampule.
ERA will prepare the samples in such a way that a minimum amount of liquid corresponds to 1 gram of soil. The
amount of liquid that corresponds to 1 gram of soil will range from 2.5 to 12.5 (iL depending on the interferent used.
During the demonstration, both STL Tampa East and the developers will be given a table informing them of the
amount of liquid sample to be used per gram of soil extracted. STL Tampa East or a given developer will analyze
the liquid PE samples using an amount of liquid that corresponds to the amount of soil that would normally be used
for analysis. For example, if a particular device requires 5 grams of soil for analysis, and if 5 (iL per gram is the
129
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amount of liquid sample corresponding to 1 gram of soil, 25 (iL of liquid sample would be used for the analysis.
Thus, the 1 mL of liquid in each PE sample will be adequate for conducting multiple analyses, if necessary.
ERA will provide Tetra Tech with a certified value and acceptance limits for each PE sample prepared. The certified
values will be derived differently for EDRO PE samples and GRO PE samples. For an EDRO PE sample, the
certified value will be equal to the concentration of spiking material used. For a GRO PE sample, the certified value
will be derived by analyzing a portion of the spiked, homogenized sample using a GC/FID method. After
homogenization of the soil spiked with GRO, ERA will collect and analyze three soil samples: one before filling any
EnCores, one after all the 5-gram EnCores are filled, and one after all the 25-gram EnCores are filled. ERA will then
report the average value as the certified value for that batch of PE samples. This method will be used to determine
the GRO PE sample certified values because a significant portion of the GRO spiking material could be lost during
homogenization due to the volatility of the spiking material.
The acceptance limits will be derived by ERA based on historical mean recovery values for similar types of samples.
The acceptance limits will be evenly distributed about the historical mean recovery values. However, these
acceptance limits will not be evenly distributed about the certified values because the certified values will not have
been corrected for the historical mean recovery values. Therefore, the acceptance limits may seem to be biased low
or high, depending on whether the certified values are higher or lower than the historical mean recovery values.
ERA will group like PE samples together in a resealable bag and will place all samples in a cooler containing ice for
overnight shipment to Tetra Tech at the Navy BVC site. When Tetra Tech receives the PE samples, Tetra Tech will
label them with the appropriate sample identification numbers and will place them in an appropriate cooler for
shipment to STL Tampa East or for transfer to the developers at the site. Detailed sample handling and shipping
procedures are provided in Section 7.2. PE samples spiked with GRO only will be sent to STL Tampa East for
analysis for both GRO and EDRO because the spiking material used by ERA for GRO PE samples may contain some
EDRO and because reference soil 2 may contain native low levels of EDRO. Therefore, for GRO PE samples, STL
Tampa East will receive two EnCores, each containing approximately 5 grams of soil sample, and one 4-ounce, glass
jar containing at least 100 grams of soil for EDRO analysis. Only one jar will be provided for EDRO PE samples
rather than two because of the significant costs associated with sample preparation by ERA. All PE samples will be
prepared in triplicate; therefore, for each PE triplicate, four additional 5-gram EnCores and two additional 4-ounce,
glass j ars will be sent to STL Tampa East. In the event that a PE sample cannot be used by STL Tampa East because
its container is broken during shipment, an aliquot from one of the other two remaining triplicates will be used for
extraction and analysis. However, the triplicates will be submitted to STL Tampa East as blind samples; therefore,
Tetra Tech will inform STL Tampa East of which triplicate should be used as a backup for an unusable sample.
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7.1.3.3 QC Samples
The following field QC samples will be collected during the demonstration: (1) MS/MSD samples, (2) field triplicate
samples, (3) extraction duplicates, (4) field blanks, and (5) temperature blanks. Table 7-3 identifies the planned
numbers of MS/MSD and field triplicate samples. MS/MSD samples will be collected for environmental samples at
a frequency of one per depth interval in each sampling area for analysis by STL Tampa East. This frequency
exceeds the typical frequency of one per analytical batch. MS/MSDs for PE samples will be analyzed by STL Tampa
East at a frequency of one per analytical batch. MS/MSD samples will not be analyzed by the developers.
Blind field triplicate samples will be prepared by Tetra Tech for environmental samples at a frequency of one per
depth interval in each sampling area. All PE samples will be prepared by ERA in triplicate as blind samples.
Tetra Tech will designate certain environmental samples as extraction duplicates, meaning that duplicate analyses
will be performed on the sample extracts by the developers and STL Tampa East. Extraction duplicate samples will
be used to address the analytical precision component of primary objective P2. These samples will be designated
at a rate of one per depth interval in each sampling area; each extraction duplicate will be one of the field triplicate
samples. Therefore, the developers and STL Tampa East will each receive 13 environmental samples designated as
extraction duplicates. Tetra Tech will designate an extraction duplicate by adding "ED" to the end of the sample
designation (see Section 7.2). If a device's operating procedure requires that all the sample extract be used for one
analysis, extraction duplicates will not be analyzed by that device.
Tetra Tech will designate certain soil PE samples as extraction duplicates, meaning that duplicate analyses will be
performed on the sample extracts by the developers and STL Tampa East. Extraction duplicate samples will be used
to address the analytical precision component of primary objective P2. Only PE samples that contain soil with GRO
or soil with EDRO at low, medium, or high levels and that do not contain interferents will be designated as extraction
duplicates. Therefore, each developer will receive 6 PE samples designated as extraction duplicates, and STL Tampa
East will receive 10 PE samples designated as extraction duplicates (because STL Tampa East will analyze low- and
medium-level PE samples containing methanol and Freon). If a device's operating procedure requires that all the
sample extract be used for one analysis, extraction duplicates will not be analyzed by that device. Tetra Tech will
designate an extraction duplicate by adding "ED" to the end of the sample designation (see Section 7.2).
Field blanks consisting of distilled water in beakers exposed to the atmosphere throughout the day will be available
to the developers at the Navy BVC site during the demonstration. If they choose to, the developers may analyze the
field blank samples to assess whether atmospheric conditions at the site may have impacted device measurements.
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Temperature blanks consisting of potable water in sealed containers will be prepared by Tetra Tech at a frequency
of one per cooler for both STL Tampa East and the developers.
The QA objectives for the demonstration are presented in Chapter 10.
7.2
Sample Handling and Shipping Procedures
Each environmental sample will have a unique sample designation and will be identified by sampling area, expected
type of contamination, expected concentration range, sampling location, sample number, and QC identification, as
appropriate. Each PE sample will also have a unique sample designation that identifies it as a PE sample. Each PE
sample designation will also identify the expected contamination type and range, whether the sample is soil or liquid,
and the sample number. PE sample numbers will be assigned for Tetra Tech's reference only. Each sample container
will be labeled with the unique sample designation, date, time, preservative, initials of Tetra Tech personnel filling
the container, and analysis to be performed. Examples of sample designations are listed below.
FFA/E/LM/A01
NEX/GE/L/B02/ED
PRA/E/H/C02
B38/GE/L/B01
SFT/GE/MH/D04/MSMSD
PE/E/M/S01
PE/GE/H/L02
FFA, EDRO analysis by STL Tampa East, low- to medium-concentration
range, location A, sample number 01
NEX Service Station Area, GRO and EDRO analyses by STL Tampa East,
low-concentration range, location B, sample number 02, extraction
duplicate
PRA, EDRO analysis by STL Tampa East, high-concentration range,
location C, sample number 02
B-38 Area, GRO and EDRO analyses by STL Tampa East, low-
concentration range, location B, sample number 01
SFT Area, GRO and EDRO analyses by STL Tampa East, medium- to
high-concentration range, location D, sample number 04, MS/MSD
analyses by STL Tampa East
PE sample, EDRO analysis by STL Tampa East, medium-concentration
range, soil sample number 01
PE sample, GRO and EDRO analyses by STL Tampa East, high-
concentration range, liquid sample number 02
Tetra Tech will maintain master data sheets that list each sample designation used during the demonstration and the
corresponding sampling area, location, and depth interval.
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Tetra Tech's sample custody will begin when samples are placed in iced coolers in the possession of the designated
field sample custodian. Samples for STL Tampa East analysis will be placed in coolers containing ice and will be
shipped by overnight courier to STL Tampa East. Chain-of-custody forms will be completed and will accompany
each sample shipment to STL Tampa East. Samples for the developers will be placed in coolers containing ice and
chain-of-custody forms and will be given directly to each developer at the Navy BVC site. Chain-of-custody forms
will be filled out and initialed by Tetra Tech personnel. As indicated in Figure 7-1, the following information will
be provided on each chain-of-custody form:
Project Name Demonstration of Field Measurement Devices for TPH in Soil
Project Number G0067-47140
Project Manager Kirankumar Topudurti
Telephone Number Tetra Tech project manager's telephone number: (312) 856-8700
Sampler Names.
Initials, and Signatures The sampling technicians' printed names, initials, and signatures
STL Tampa East or Developer Sample
Identification Number Unique sample identification number assigned by STL Tampa East or the
developer after receipt of samples
Matrix Sample matrix (S for soil and L for liquid)
Field Sample Identification Number Tetra Tech-assigned field sample identification number
Date Date of sample collection
Time Time of filling sample container
Initials Sampling technician's initials
Requested Analyses The number of sample containers for each requested analysis
When all appropriate line items are completed, Tetra Tech's field manager or his designee will confirm the
completeness of all descriptive information on the form and will sign and date the form. Each individual who
subsequently assumes responsibility for the samples will sign the chain-of-custody form. For samples shipped by
courier service, the courier service will not sign the chain-of-custody form; the airbill invoice will serve as part of
the chain-of-custody documentation. Use of the chain-of-custody form will end when STL Tampa East or the
developer receives the samples and enters the STL Tampa East or developer sample identification numbers on the
form. The Tetra Tech field manager will retain the pink copy of the chain-of-custody form for the project files.
133
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ield Measurement Devices for TPH in Soil
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All samples for STL Tampa East analysis will be packaged and labeled for shipment in compliance with current DOT
and International Air Transport Association (IATA) regulations for dangerous materials. Only plastic coolers will
be used for shipping samples. Each cooler shipped to STL Tampa East will be lined with two 6-mil, plastic bags.
Styrofoam or bubble wrap will be used in the coolers to absorb shocks. After the sample containers are packaged,
the inner 6-mil, plastic bag around the containers will be sealed to prevent leaks by twisting the top and securely
taping the bag closed. To meet preservation requirements, ice will be placed in the coolers along with the sample
containers. The white and yellow copies of the chain-of-custody forms will accompany each cooler. These forms
will be enclosed in a waterproof, plastic bag that will be taped to the underside of the cooler lid.
All samples for the developers will be packaged in the same manner as the samples for STL Tampa East. Coolers
containing samples for developers will be given directly to the developers by Tetra Tech personnel at the Navy BVC
site.
Each cooler prepared for shipment to STL Tampa East will be securely taped shut. Sample custody seals will be
placed on the front and back of each cooler to reveal any unauthorized tampering with samples before analysis. The
Tetra Tech field manager or his designee will sign and date the custody seals and will affix the seals at the time of
sample packaging. Reinforced or other suitable tape (such as duct tape) will be wrapped at least twice around the
cooler near each end where the hinges are located.
Each cooler to be shipped to STL Tampa East will be marked in accordance with DOT regulations for shipping
hazardous materials (49 CFR Part 172 and IATA Dangerous Goods Regulations, 31st Edition, January 1, 1987). In
addition to complete mailing addresses, each cooler will clearly display "This End Up" arrows on all four sides and
a label on the exterior lid indicating the originator's and recipient's addresses.
When selecting means of sample shipment to STL Tampa East, Tetra Tech field personnel will ensure that allowable
sample holding times will not be exceeded. When commercial common carriers are used to ship samples, all samples
will be shipped "Priority One/Overnight." If necessary, samples may be shipped using a reliable commercial carrier
such as Federal Express. If commercial carriers are used, airbills will be completed and attached to the exterior lids
of the coolers. Multiple-shipment labels will be used when more than one cooler is being shipped.
The STL Tampa East sample coordinator or a designee will receive samples and assume custody of them until they
have been properly logged in the laboratory and stored in secured areas. The laboratory sample management
procedures to be followed are presented in Section 8.2.
135
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Tetra Tech's field logbooks will contain the information entered by Tetra Tech on the chain-of-custody forms and
will be maintained by the field manager or his designee on site. The developers will have an opportunity to cross-
check all samples with the chain-of-custody forms before the demonstration officially begins. The demonstration
will officially end for a particular developer when all of the developer's sample analytical results are provided to
Tetra Tech on site.
7.3 Sampling Equipment Decontamination and Investigation-Derived Waste Disposal
Procedures
The Tetra Tech field team will take steps to minimize the volume of IDW generated. Nondisposable sampling
equipment will be decontaminated by scrubbing it with an Alconox® solution, washing it with potable water, and then
rinsing it with distilled water. Decontamination of nondisposable sampling equipment will be conducted prior to
sampling at each site as well as between sampling areas. All IDW generated, including unused sample material and
decontamination water that has come into contact with grossly contaminated material, will be managed and disposed
of in accordance with site-specific IDW management practices.
Solid wastes expected to be generated during the demonstration include disposable glassware, EnCores, unused or
extra soil samples, and PPE. Used, disposable, empty glassware and used, empty EnCores will be disposed of as
general refuse in a dumpster or garbage can provided by Tetra Tech at the Navy BVC site. Unused or extra soil
samples and used PPE such as gloves will be placed in an on-site drum designated for nonhazardous solid waste;
Tetra Tech will provide this drum.
Liquid wastes expected to be generated during the demonstration include decontamination water and spent or excess
chemicals from the devices. Decontamination water will be placed in an on-site drum designated for nonhazardous
liquid waste; Tetra Tech will provide this drum. Spent or excess chemicals from the field devices will be disposed
of in 20-gallon laboratory packs in accordance with 40 CFR 261.5 regulations pertaining to conditionally exempt
small-quantity generators (those generating less than 100 kilograms or 220 pounds of hazardous waste during a
calendar month). Spent or excess chemicals will be separated as either corrosive or flammable wastes and will be
placed in separate laboratory packs. Tetra Tech will provide each developer with one laboratory pack for corrosive
wastes and one for flammable wastes, as needed. The developers will be responsible for providing any secondary
containment necessary within the laboratory packs. If the developers choose to, they may retain their spent or excess
chemicals rather than dispose of them at the Navy BVC site. However, if they choose to retain such chemicals, and
if this option would not normally be available to users of their devices, then the amount of the chemicals will be
measured by Tetra Tech so that a disposal cost can be estimated. After the demonstration, the laboratory packs will
136
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be transported to either a waste storage area at the Navy BVC site or an off-site, state-approved hazardous waste
facility.
7.4 Field Documentation Procedures
Field documentation will include use of field logbooks, chain-of-custody forms, and photographs. Tetra Tech will
be responsible for all field documentation. Field logbooks will be labeled with the project name and number. Each
page of each field logbook will be sequentially numbered. Completed logbook pages will be signed and dated by the
individual responsible for the entries. An error in a field logbook or chain-of-custody form will have one line drawn
through it, and this line will be initialed and dated by the person making the correction. All photographs will be
logged in the field logbooks, and each such entry will include the date, time, orientation, and subject of the
photograph. Specific information regarding samples (such as profiling information, visual observations, or deviations
from this demonstration plan) will also be documented in the field logbooks. At the end of each day of the
demonstration, each developer will have the opportunity to review the field logbooks pertaining to the developer's
activities and to verify the accuracy and completeness of the observations recorded in the logbook.
137
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Chapter 8
Calibration Requirements and Sample Management Procedures
for Innovative Field Measurement Devices
This chapter identifies calibration requirements and describes sample management procedures for the seven
innovative TPH field measurement devices. IDW disposal and field documentation procedures to be used for the
demonstration are described in Chapter 7. The operating procedures for the devices are presented in Section 2.2.
8.1 Calibration Requirements
This section describes the calibration requirements for each TPH field measurement device. Table 8-1 summarizes
the calibration requirements for each device, including the frequency of continuing calibration verification, the
calibration acceptance criterion, and corrective action.
8.1.1 RemediAidIM Starter Kit
The RemediAid™ Starter Kit is calibrated using slope and intercept values (response factors) designated by the
developer for calibration curves for common hydrocarbons. These response factors are presented in the device user's
manual and in Table 8-2. When the hydrocarbon or hydrocarbons present in a sample are unknown, the slope and
intercept values for "unknown" hydrocarbons in Table 8-2 are used to determine TPH concentration in soil. These
values represent the averages of the slope and intercept values for the other hydrocarbons listed in the table.
Alternatively, the users may generate their own calibration curves using site-specific data following guidelines
presented in the user's manual. For the demonstration, predemonstration results will be used to determine the type
of hydrocarbons present in soil samples at a given site; therefore, CHEMetrics will use the response factors presented
in Table 8-2.
138
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Step 1 - Zero Calibration
Model CVH
1. Rinse a quartz cuvette with Freon 113 until the cuvette is clean.
2. Fill the cuvette with clean Freon 113.
3. Insert the cuvette in the TPH analyzer sample stage such that the frosted side of the cuvette is facing you.
4. Press and hold the ZERO button until bAL appears on the display. Then a reading will appear.
5. Press the RUN button. The display should read 00 ± 2. If it does not, repeat the five calibration steps.
Model HATR-T
1. Hold the HATR crystal plate vertically over a waste container, and squirt a small stream of Vertrel® MCA
from the wash bottle onto the HATR sample stage.
2. Shake the crystal plate to dry it, or use an antistatic wipe (for example, a Kimwipe) to wipe the crystal plate.
3. Place the crystal plate on the HATR sample stage.
4. Press and hold the ZERO button until the timer value is displayed. The timer will begin counting down to
zero. Press and release the RUN button to override the timer. bAL will appear on the display, and then a
reading will appear.
5. Press the RUN button. The timer will begin counting down to zero. Press the RUN button again to override
the timer. The display should read 00 ± 2. If it does not, repeat the five calibration steps.
Step 2 - Standard Calibration
Model CVH
1. Insert the sealed cuvette containing the lowest concentration standard in the TPH analyzer sample stage such
that the frosted side of the cuvette is facing you.
2. Record the absorbance reading of the standard.
3. Repeat Steps 1 and 2 for the remaining six standards.
4. After the absorbance readings for all calibration standards are recorded, press the CAL button once and then
press the RECALL button repeatedly until "Edit" appears on the display. Press the CAL button again.
5. When prompted for the number of calibration standards used, press the UP and DOWN Arrow buttons until
the display reads "7."
142
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6. Press the CAL button. When prompted for the absorbance and concentration of each standard, use the UP
and DOWN Arrow buttons to enter the appropriate pairs of values (absorbance and concentration), beginning
with the lowest concentration standard. Press the CAL button between each entry. Once all values have
been entered, the display will read "idLE."
Model HATR-T
1. Put 100 mL of Vertrel® MCA in a 100-mL graduated cylinder.
2. Pour 3-IN-ONE oil into a 40-mL vial and label the vial "Stock Oil."
3. Put the appropriate amount of stock oil (see Table 8-3), beginning with the highest concentration, in the
100-mL graduated cylinder using a 100-(iL glass syringe.
Table 8-3. Calibration Standards for Model HATR-T
Standard Concentration (milligram per liter)
Volume of Solvent (milliliter)
Volume of Stock Oil (microgram per liter)
4,000
2,000
1,000
500
250
100
100
100
100
100
400
200
100
50
25
4. Place a stopper on the graduated cylinder and shake for 1 minute.
5. Transfer the calibration standard into a 40-mL vial and label the vial with the date and concentration.
6. Repeat Steps 1 through 3 under Zero Calibration procedures for Model HATR-T.
7. Pour 6 to 8 mL of a calibration standard, beginning with the lowest concentration, into an extraction
reservoir.
8. Seal the extraction reservoir with a sealer, and insert the tip of the air syringe into the sealer.
9. Place the tip of the extraction reservoir over a waste container and push down on the air syringe plunger so
that about 1 mL of the standard drips into the container.
10. Place the tip of the extraction reservoir over a beaker and push down on the air syringe plunger so that about
1 or 2 mL of the standard drips into the beaker. Immediately collect 50 (iL of the standard from the beaker
using a pipette.
11. Transfer the standard from the pipette onto the center of the Model HATR-T sample stage, and record the
absorbance.
12. Repeat Steps 7 through 11 for each standard in order of increasing concentration.
13. Perform Steps 4 through 6 under Standard Calibration procedure for Model CVH. (Note: In Step 5, press
the UP and DOWN Arrow buttons until the display reads "5" instead of "7.")
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Once calibration is complete, the device is ready for sample analysis. The operating procedure for the Infracal®
TOG/TPH Analyzer is detailed in Section 2.2.2.2.
8.1.3 OCMA-350
The OCMA-350 requires two-point calibration involving a solvent blank and a calibration standard. The OCMA-350
can be calibrated using (1) the device default calibration settings for standard measurement conditions or (2) user-
specified calibration settings. The default calibration settings are listed below.
Zero calibration value: 0 mg/L
Standard calibration value: 200 mg/L
• Solvent volume: 1 mL
• Sample mass: 1 gram
The user can change these settings by using the panel buttons on the OCMA-350 to specify new values, as necessary.
Calibration of the OCMA-350 involves two steps: zero calibration and standard calibration. According to the
developer, the user must conduct zero calibration before sample analysis under one or more of the following
conditions:
1. The OCMA-350 quartz cuvette is replaced.
2. A different lot of solvent is being used.
3. The device is turned off for more than 1 week.
4. A new calibration standard is prepared.
5. The device is being used continuously. (Zero calibration is required every 4 hours.)
6. The device is moved.
7. The ambient temperature and humidity have significantly changed (more than 5 °C and more than 10 percent,
respectively).
The user must also conduct standard calibration before sample analysis under conditions 4, 5, 6, and 7. Horiba
recommends use of B-heavy oil, which is provided with the OCMA-350, as the default calibration standard when the
hydrocarbon content of the soil is unknown. Based on the results of the predemonstration investigation sampling,
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Horiba will use diesel as the calibration standard for the demonstration. According to the developer, the device user
should use one lot of S-316 extraction solvent both for zero and standard calibration and for measurement. The zero
and standard calibration steps are presented below.
Step 1 - Zero Calibration
1. Partially fill an OCMA-350 quartz cuvette with 1 to 4 mL of solvent.
2. Cap and shake the cuvette to pre-rinse it, and then pour out the solvent.
3. Put about 6 mL of solvent in the cuvette.
4. Insert the cuvette into the OCMA-350.
5. Press MEAS. and then ZERO CAL. on the OCMA-350. The device should read 0 mg/L.
Step 2 - Standard Calibration
1. Put 100 mL of solvent in a 250-mL volumetric flask.
2. Put 55.6 (iL of diesel calibration standard in the flask.
3. Swirl the contents of the flask just enough to dissolve the diesel in the solvent.
4. Add solvent to fill the flask to the 250-mL mark.
5. Close the flask with a stopper, and swirl the flask contents until they are well mixed.
6. Partially fill an OCMA-350 quartz cuvette with 1 to 4 mL of diesel.
7. Cap and shake the cuvette, and then pour out its contents.
8. Put about 6 mL of die sel in the cuvette.
9. Insert the cuvette into the OCMA-350.
10. Press MEAS. and then SPAN CAL. on the OCMA-350. The device should read 200 mg/L.
Once calibration is complete, the device is ready for sample analysis. The operating procedure for the OCMA-350
is detailed in Section 2.2.3.2.
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8.1.4 PetroFLAGrM Test Kit
The PetroFLAG™ Test Kit is factory-calibrated using default calibration settings for standard measurement
conditions before it is issued to the user. However, to maximize field measurement accuracy, the device can also be
calibrated in the field, where calibration standards provided by the developer are used to generate a two-point
calibration curve.
Calibration of the PetroFLAG™ Test Kit in the field involves two steps: zero calibration and standard calibration.
As part of the device, Dexsil® provides (1) an extra extraction solvent vial to be used as a blank for zero calibration
and (2) a calibration standard for standard calibration. The blank and calibration standard are intended for one-time
use. The zero calibration and standard calibration steps are presented below.
Step 1 - Zero Calibration
1. Add the contents of a break-top vial of extraction solvent provided by the developer to a soil extraction tube
labeled "blank."
2. Process the "blank" in accordance with the operating procedure for analyzing soil samples presented in
Section 2.2.4.2.
3. After 5 seconds, the device display should read "0."
Step 2 - Standard Calibration
1. Add the contents of the break-top vial containing the calibration standard (1,000 mg/L of mineral oil
dielectric fluid) provided by the developer to the soil extraction tube labeled "standard."
2. Process the "standard" in accordance with the operating procedure for analyzing soil samples presented in
Section 2.2.4.2.
3. After 5 seconds, the device display should read "1,000."
If the device is not calibrated properly or if the concentration is not correct, an error message will flash until NEXT
is pushed. The user will be prompted to recalibrate the device until a valid calibration is completed. Once calibration
is complete, the device is ready for sample analysis. The operating procedure for the PetroFLAG™ Test Kit is
detailed in Section 2.2.4.2.
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8.1.5
Luminoscope
The Luminoscope will be calibrated before the demonstration using off-site laboratory analytical results and device
readings for each demonstration area. The calibration curve will consist of absorbance values on the x-axis and
corresponding off-site laboratory sample analytical results on the y-axis; the TPH concentration in each sample will
be determined based on the sample's luminescence as read by the device. Calibration curves will be generated for
each demonstration area using the off-site laboratory sample analytical results and the Luminoscope results from the
predemonstration investigation. This section briefly discusses additional calibration that will be conducted in the
field.
A calibration check of the Luminoscope involves taking measurements in the field using a Starna quartz cuvette
containing anthracene and naphthalene standards (0.2 mg/L and 0.8 mg/L, respectively) at the beginning and end of
each day. According to the developer, calibration using a known contaminant should be performed to check the
device's ability to consistently analyze for a known contaminant. Once the calibration check is complete, the device
is ready for sample analysis. The operating procedure for the Luminoscope is detailed in Section 2.2.5.2.
8.1.6
UVF-3100A
The UVF-3100A requires six-point calibration involving five calibration standards and a calibration blank. Separate
calibration curves have been generated for GRO and EDRO. Specifically, the curves have been generated at
concentrations of 0.1, 0.5, 1.0, 5.0, and 10.0 mg/L for GRO and at concentrations of 0.05, 0.1, 0.5, 1.0, and 1.5 mg/L
for EDRO. GRO and EDRO will be measured separately by using a filter to change the device's wavelengths. The
components of each set of calibration standards provided by the developer are presented in Table 8-4.
Table 8-4. Components of Calibration Standards
Gasoline Range Organics
Benzene
Chlorobenzene
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
Ethylbenzene
Toluene
m-Xylene
o-Xylene
p-Xylene
Acenaphthene
Acenaphthylene
Anthracene
Benz(a)anthracene
Benzo(a)pyrene
Benzo(b)fluoranthene
Benzo(g,h,i)perylene
Benzo(k)fluoranthene
Chrysene
Dibenz(a,h)anthracene
Extended Diesel Range Organics
Fluoranthene
Fluorene
lndeno(1 ,2,3-cd)pyrene
2-Methylnaphthalene
Naphthalene
Phenanthrene
Pyrene
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Calibration of the UVF-3100A involves two steps: standard calibration and zero calibration. The calibration steps
are presented below.
Step 1 - Standard Calibration
1. Select the multioptional direct concentration mode for the UVF-3100A by pressing ENT at the HOME
screen, 1 for setup, and then 1 again for mode. Press ESC to return to the previous screen, and then press
2 to choose the calibration procedure. Use the — key to choose "Direct Cone" for the direct concentration
calibration procedure. Press ESC to return to the previous screen. To choose the unit of measure, press 3,
and then use the — key to choose the required unit. Press ESC twice to return to the Setup/Cal screen.
2. To access the calibration sequence, press 2 at the Setup/Cal screen. The direct concentration calibration
sequence will appear.
3. When the device prompts you for the "maximum range," press 9 to enter the range of expected concentration
values.
4. Enter 5 as the number of calibration standards that will be used, and press ENT.
5. When the device prompts you for the "Hi Std Cone," press 1 to accept the default value or press 9 to enter
a new value. Enter the actual concentration of the highest standard being used, and press ENT. The
developer recommends that the Hi Std be about 80 percent of the maximum range entered. Additionally, the
standards used should not be too close in concentration; the difference in concentration between any two
standards should not be less than 10 percent of the maximum range entered.
6. Fill a clean cuvette with the Hi Std, and insert the cuvette into the sample adapter in the sample chamber.
Press *. The device will adjust its sensitivity, which is displayed as the "SENS FACTOR," to the level
appropriate for the standard and will then analyze the standard.
7. Remove the Hi Std cuvette. The device will prompt you to enter the actual concentration of the second
standard. Repeat the process described in items 5 and 6 until all five standards have been analyzed. Press
* and then ENT when each standard has been analyzed.
Step 2 - Zero Calibration
1. When the five calibration standards have been analyzed, the UVF-3100A will prompt you to insert a
calibration blank. Insert the cuvette containing blank solvent into the sample adapter in the sample chamber,
and press ENT.
2. Wait for the blank reading to stabilize, and then press 0. The device will read the blank as having zero
concentration, and the display will automatically return to the HOME screen.
Once calibration is complete, the device is ready for sample analysis. The operating procedure for the UVF-3100A
is detailed in Section 2.2.6.2.
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8.1.7 EnSys Petro Test System
This section discusses calibration procedures for the EnSys Petro Test System. This device does not require
generation of a calibration curve because it provides semiquantitative results.
Calibration procedures for the EnSys Petro Test System involve conducting zero calibration of the spectrophotometer.
The procedures for zero calibration are presented below.
Zero Calibration
1. Prepare two calibration blanks by filling two conjugate tubes with potable water.
2. Insert the two tubes into the spectrophotometer. The reading on the display should be 0.00 ± 0.02. If the
reading is outside this range, reverse the positions of the tubes.
3. If the reading changes from positive to negative or from negative to positive when the tubes' positions are
reversed, there is a lack of equality between the two calibration blanks. In this case, prepare a new pair of
calibration blanks and conduct zero calibration.
If the reading remains about the same when the tubes' positions are reversed, the spectrophotometer zero
needs to be adjusted. In this case, with the two tubes still in the spectrophotometer, use a small screwdriver
to turn trimmer R-17 at the rear of the spectrophotometer until the display reads zero.
Once zero calibration is complete, the device is ready for sample analysis. The operating procedure for the EnSys
Petro Test System is detailed in Section 2.2.7.2.
8.2 Sample Management Procedures
Demonstration samples collected for the developers for TPH analysis will be presented to the developers by Tetra
Tech at the Navy BVC site. These samples will be in coolers and will be accompanied by chain-of-custody forms.
Each developer will be responsible for the samples it receives. When a developer receives a sample cooler, the
developer will open the cooler and carefully check its contents for evidence of breakage or leakage. The developer
will verify that all information on the sample container labels is correct and consistent with the chain-of-custody
forms.
149
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Any discrepancy between sample container labels and chain-of-custody forms, any broken or leaking sample
containers, or any other abnormal situation will be reported to the Tetra Tech field manager, who will implement
corrective action.
Tetra Tech will provide sample data sheets to the developers in order to ensure that TPH field measurement device
results are recorded in a consistent manner. The results generated by the devices will be entered on the appropriate
sample data sheets.
150
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Chapter 9
Laboratory Sample Preparation and Analytical Methods,
Calibration Requirements, and Sample Management Procedures
Soil samples collected during the demonstration will be analyzed for GRO, EDRO, and percent moisture by STL
Tampa East. STL Tampa East will also analyze liquid PE samples for GRO and EDRO.
This section describes the laboratory sample preparation and analytical methods, calibration requirements, and sample
management procedures proposed for the demonstration.
9.1 Laboratory Sample Preparation and Analytical Methods
The laboratory sample preparation and analytical methods proposed for the demonstration are summarized in
Table 9-1. Chapter 5 describes the rationale for the selection of the GRO and EDRO reference method. The SW-846
methods listed in Table 9-1 for GRO and EDRO analyses were tailored to meet the definition of TPH for the proj ect
(see Chapter 1). Project-specific procedures for soil sample preparation and analysis for GRO and EDRO are
summarized in Tables 9-2 and 9-3, respectively. To prepare the liquid PE samples, STL Tampa East will add an
aliquot of PE sample to the extraction solvent used for soil samples. A specified aliquot of the liquid PE sample will
be diluted in methanol for GRO analysis and in methylene chloride for EDRO analysis such that the final volume of
the solution for GRO and EDRO analyses is 5.0 and 1.0 mL, respectively. The solution will then be analyzed for
GRO and EDRO using the same procedures as are used for soil samples. For this reason, liquid sample analyses are
not separately discussed in this chapter.
9.2 Calibration Requirements
This section describes the calibration procedures, acceptance criteria, and corrective action procedures for GRO,
EDRO, and percent moisture laboratory analyses. For these analyses, calibration data will be recorded on
151
-------
Table 9-1. Laboratory Sample Preparation and Analytical Methods
Parameter Method Reference (Step) Method Title
Gasoline range Based on SW-846 Method 5035 (extraction) Closed-System Purge-and-Trap and Extraction for Volatile
organics Organics in Soil and Waste Samples
Based on SW-846 Method 5030B (purge and trap) Purge-and-Trap for Aqueous Samples
Based on SW-846 Method 8015B (analysis) Nonhalogenated Volatile Organics by Gas Chromatography
Extended diesel Based on SW-846 Method 3540C (extraction) Soxhlet Extraction
range organics Based on SW-846 Method 8015B (analysis) Nonhalogenated Volatile Organics by Gas Chromatography
Percent moisture Based on MCAWW Method 160.3a Residue, Total (Gravimetric, Dried at 103-105 °C)
Notes:
MCAWW = "Methods for Chemical Analysis of Water and Wastes"
SW-846 = "Test Methods for Evaluating Solid Waste"
a MCAWW Method 160.3 will be modified to include calculation and reporting of percent moisture in solid samples.
printouts from instrument data systems and calibration summary forms similar to the EPA Contract Laboratory
Program (CLP) forms. These records will be made a permanent part of the project files. The calibration records will
include tracking numbers for standards so that the source and method of preparation of each standard solution used
may be identified. The frequencies, acceptance criteria, and corrective actions required for calibration of laboratory
analytical measurement equipment are outlined in Table 9-4. All calibration standards for GRO and EDRO analyses
will be prepared using commercially available (Supelco or equivalent) standards or using standards verified against
independently prepared, separate source standards.
9.3 Sample Management Procedures
Demonstration samples collected for GRO, EDRO, and percent moisture analyses will be shipped to STL Tampa
East. The laboratory sample coordinator, Carol McNulty, or her designated alternate will receive the samples and
assume custody of them until they have been properly logged in the laboratory and stored in secured areas.
When a sample shipment is received at the laboratory, the cooler containing the samples will be inspected for warning
labels and security breaches before it is opened. The laboratory sample coordinator will open the cooler and carefully
check its contents for evidence of breakage or leakage. The interior of the cooler will also be inspected for the chain-
of-custody form and other information or instructions. The temperature of the temperature blank in the cooler will
be included in the sample receipt log along with the date and the signature of the person making the entry.
152
-------
Table 9-2. Summary of Project-Specific Procedures for Gasoline Range Organic Analysis
SW-846 Method Reference (Step)
Project-Specific Procedures
5035 (Extraction)
Low-level (0.5 to 200 |jg/kg) or high-level (>200 |jg/kg) samples may
be prepared.
Samples may be collected with or without use of a preservative
solution.
A variety of sample containers, including EnCores, may be used
when high-level samples are collected without use of a preservative.
Samples collected in EnCores should be transferred to vials
containing the extraction solvent as soon as possible or analyzed
within 48 hours.
For samples not preserved in the field, a solubility test should be
performed using methanol, PEG, and hexadecane to determine an
appropriate extraction solvent.
Removal of unrepresentative material from the sample is not
discussed.
Procedures for adding surrogates to the sample are inconsistently
presented. Section 2. 2.1 indicates that surrogates should be added
to an aliquot of the extract solution. Section 7.3.3 indicates that soil
should be added to a vial containing both the extraction solvent
(methanol) and surrogate spiking solution.
Nine ml of methanol should be added to a 5-gram (wet weight) soil
sample.
When practical, dispersing the sample to allow contact with the
methanol is recommended by shaking or using other mechanical
means for 2 minutes without opening the sample container. When
shaking is not practical, the sample should be dispersed with a
narrow, metal spatula, and the sample container should be
immediately resealed.
Because the project-specific reporting limit for GRO is 5 milligrams
per kilogram, all samples to be analyzed for GRO will be prepared
using procedures for high-level samples.
Samples will be collected without use of a preservative.
Samples will be containerized in EnCores.
Samples will be weighed and extracted within 2 calendar days of their
shipment. The holding time for analysis will be 1 4 days after
extraction. A full set of quality control samples (method blanks,
MS/MSDs, and LCS/LCSDs) will be prepared at this time.
Because the reference laboratory obtained acceptable results for PE
samples extracted with methanol during the predemonstration
investigation, samples will be extracted with methanol.
During sample homogenization, field sampling technicians will
attempt to remove unrepresentative material such as sticks, roots,
and stones if present in the sample; the reference laboratory will not
remove any remaining unrepresentative material.
The soil sample will be ejected into a volatile organic analysis vial, an
appropriate amount of surrogate solution will be added to the
sample, and then methanol will be quickly added.
Five ml of methanol will be added to the entire soil sample
contained in a 5-gram EnCore.
The sample will be dispersed using a stainless-steel spatula to allow
contact with the methanol. The volatile organic analysis vial will then
be capped and shaken vigorously until the soil is dispersed in
methanol, and the soil will be allowed to settle.
5030B (Purge and Trap)
Screening of samples before the purge and trap procedure is
recommended using one of the two following techniques:
Use of an automated headspace sampler (see SW-846
Method 5021) connected to a GC equipped with a photoionization
detector in series with an electrolytic conductivity detector
Extraction of the samples with hexadecane (see SW-846
Method 3820) and analysis of the extracts using a GC equipped with
a flame ionization detector or electron capture detector
SW-846 Method 5030B indicates that contamination by carryover can
occur whenever high-level and low-level samples are analyzed in
sequence. Where practical, analysis of samples with unusually high
concentrations of analytes should be followed by an analysis of
organic-free reagent water to check for cross-contamination.
Because the trap and other parts of the system are subject to
contamination, frequent bake-out and purging of the entire system
may be required.
The sample purge device used must demonstrate adequate
performance.
Samples will be screened with an automated headspace sampler
(see SW-846 Method 5021) connected to a GC equipped with a
flame ionization detector.
According to the reference laboratory, a sample extract concentration
equivalent to 1 0,000 ng on-column is the minimum concentration of
GRO that could result in carryover. Therefore, if a sample extract
has a concentration that exceeds the minimum concentration for
carryover, the next sample in the sequence will be evaluated as
follows: (1) if the sample is clean (has no chromatographic peaks),
no carryover has occurred; (2) if the sample has detectable analyte
concentrations (chromatographic peaks), it will be reanalyzed under
conditions in which carryover would not occur.
A Tekmar 201 6 autosampler and a Tekmar LSC 2000 concentrator
will be used. Based on quality control sample results, the reference
laboratory has demonstrated adequate performance using these
devices.
153
-------
Table 9-2. Summary of Project-Specific Procedures for Gasoline Range Organic Analysis (Continued)
SW-846 Method Reference (Step)
Project-Specific Procedures
5030B (Purge and Trap) (Continued)
Purge and trap conditions for high-level samples are not clearly
specified. According to SW-846, manufacturer recommendations for
the purge and trap devices should be considered when this method
is implemented. The following purge and trap general conditions are
recommended for samples that are water-miscible (methanol extract):
Purge gas: nitrogen or helium
Purge gas flow rate: 20 mL/min
Purge time: 15 ± 0.1 min
Purge temperature: 85 ± 2 °C
Desorb time: 1.5 min
Desorb temperature: 180 °C
Backflush inert gas flow rate: 20 to 60 mL/min
Bake time: not specified
Bake temperature: not specified
Multiport valve and transfer line temperatures: not specified
The purge and trap conditions that will be used are listed below.
These conditions are based on manufacturer recommendations for
the purge device specified above and the VOCARB 3000 trap.
Purge gas: helium
Purge gas flow rate: 35 mL/min
Purge time: 8 min with 2-min dry purge
Purge temperature: ambient temperature
Desorb time: 1 min
Desorb temperature: 250 °C
Backflush inert gas flow rate: 35 mL/min
Bake time: 7 min
Bake temperature: 270 °C
Multiport valve and transfer line temperatures: 1 1 5 and 1 20 °C
8015B (Analysis)
GC Conditions
The following GC conditions are recommended:
Column: 30-m x 0.53-mm-ID, fused-silica capillary column
chemically bonded with 5 percent methyl silicone,
1 .5-um field thickness
Carrier gas: helium
Carrier gas flow rate: 5 to 7 mL/min
Makeup gas: helium
Makeup gas flow rate: 30 mL/min
Injector temperature: 200 °C
Detector temperature: 340 °C
Temperature program:
Initial temperature: 45 °C
Hold time: 1 min
Program rate: 45 to 1 00 °C at 5 °C/min
Program rate: 100 to 275 °C at 8 °C/min
Hold time: 5 min
Overall time: 38.9 min
The HP 5890 Series II will be used as the GC. The following GC
conditions will be used based on manufacturer recommendations:
Column: 30-m x 0.53-mm-ID, fused-silica capillary column
chemically bonded with 5 percent methyl silicone,
1 .5-um field thickness
Carrier gas: helium
Carrier gas flow rate: 15 mL/min
Makeup gas: helium
Makeup gas flow rate: 1 5 mL/min
Injector temperature: 200 °C
Detector temperature: 200 °C
Temperature program:
Initial temperature: 25 °C
Hold time: 3 min
Program rate: 25 to 120 °C at 25 °C/min
Hold time: 4 min
Program rate: 120 to 245 °C at 25 °C/min
Hold time: 5 min
Overall time: 20.4 min
Calibration
The chromatographic system may be calibrated using either internal
or external standards.
Calibration should be performed using samples of the specific fuel
type contaminating the site. When such samples are not available,
recently purchased, commercially available fuel should be used.
ICV is not required.
CCV should be performed at the beginning of every 12-hour work
shift and at the end of an analytical sequence. CCV throughout the
12-hour shift is also recommended; however, the frequency is not
specified.
CCV should be performed using a fuel standard.
According to SW-846 Method 8000, CCV should be performed at the
same concentration as the midpoint concentration of the initial
calibration curve; however, the concentration of each calibration
point is not specified.
The chromatographic system will be calibrated using external
standards.
Calibration will be performed using a commercially available,
1 0-component GRO standard that contains 35 percent aliphatic
hydrocarbons and 65 percent aromatic hydrocarbons.
ICV will be performed using a second-source standard.
CCV will be performed at the beginning of each analytical batch,
after every tenth analysis, and at the end of the analytical batch.
CCV will be performed using a commercially available,
1 0-component GRO standard that contains 35 percent aliphatic
hydrocarbons and 65 percent aromatic hydrocarbons.
CCV will be performed at a concentration equivalent to 2,000 ng
on-column.
154
-------
Table 9-2. Summary of Project-Specific Procedures for Gasoline Range Organic Analysis (Continued)
SW-846 Method Reference (Step)
Project-Specific Procedures
8015B (Analysis) (Continued)
Calibration (Continued)
Method sensitivity check is not required.
The method sensitivity check will be performed daily using a
calibration standard at a concentration equivalent to 100 ng
on-column. See Table 9-4 for details.
Retention Time Windows
The retention time range (window) should be established using
2-methylpentane (C6) and 1 ,2,4-trimethylbenzene (C10) during initial
calibration. Three measurements should be made over a 72-hour
period; the results should be used to determine the average retention
time. As a minimum requirement, the retention time should be
verified using a midlevel calibration standard at the beginning of each
12-hour shift. Additional analysis of the standard throughout the 12-
hour shift is strongly recommended.
The retention time range will be established using the opening or first
CCV specific to each analytical batch. The first eluter, C6
(2-methylpentane), and last eluter, C10 (1 ,2,4-trimethylbenzene), of
the GRO standard will be used to establish each day's retention time
range.
Quantitation
Quantitation is performed by summing the areas of all
chromatographic peaks eluting within the retention time range
established using 2-methylpentane (C6) and 1 ,2,4-trimethylbenzene
(C10). Subtraction of the baseline rise for the method blank resulting
from column bleed is generally not required.
Quantitation will be performed by summing the areas of all
chromatographic peaks from C6 (2-methylpentane) through C10
(1 ,2,4-trimethylbenzene). This range includes C10 (n-decane).
Baseline rise subtraction will not be performed.
Quality Control
Spiking compounds for MS/MSDs and LCSs are not specified.
According to SW-846 Method 8000, spiking levels for MS/MSDs are
determined differently for compliance and noncompliance monitoring
applications. For noncompliance applications, the laboratory may
spike the sample (1 ) at the same concentration as the reference
sample (LCS), (2) at 20 times the estimated quantitation limit for the
matrix of interest, or (3) at a concentration near the middle of the
calibration range.
According to SW-846 Method 8000, in-house laboratory acceptance
criteria for MS/MSDs and LCSs should be established. As a general
rule, the recoveries of most compounds spiked into a sample should
fall within the range of 70 to 130 percent, and this range should be
used as a guide in evaluating in-house performance.
The LCS should consist of an aliquot of a clean (control) matrix that
is similar to the sample matrix.
No LCSD is required.
The surrogate compound and spiking concentration are not
specified. According to SW-846 Method 8000, establishing in-house
laboratory acceptance criteria for surrogate recoveries is
recommended.
The method blank matrix is not specified.
The extract duplicate is not specified.
Spiking compounds for MS/MSDs and LCSs are discussed in
Sections 10. 2. 1.3 and 10.2.1.5, respectively.
MS/MSD spiking levels will be targeted to be between 50 and
150 percent of the unspiked sample concentration. The reference
laboratory will use historical information to adjust the spike amounts
or to adjust sample amounts to a preset spike amount. The spiked
samples and unspiked samples will be prepared such that the
sample mass and extract volume used for analysis will be the same.
Reference laboratory acceptance criteria for MS/MSDs and LCSs are
specified in Table 10-2. The acceptance criteria are based on
laboratory historical data.
The LCS/LCSD matrix will be Ottawa sand.
LCSD spiking compounds, concentrations, and acceptance criteria
are discussed in Section 10.2.1 .5.
The surrogate compound will be 4-bromofluorobenzene. See
Section 1 0.2.1 .2 for details.
The method blank matrix will be Ottawa sand.
The extract duplicate will be performed. See Section 10. 2. 1.4 for
details.
Notes:
ug/kg
urn
C
CCV
GC
GRO
Plus or minus ICV
Greater than ID
Microgram per kilogram LCS
Micrometer LCSD
Carbon m
Continuing calibration verification min
Gas chromatograph mL
Gasoline range organics mm
Initial calibration verification
Inside diameter
Laboratory control sample
Laboratory control sample duplicate
Meter
Minute
Milliliter
Millimeter
MS = Matrix spike
MSD = Matrix spike duplicate
ng = Nanogram
PE = Performance evaluation
PEG = Polyethylene glycol
SW-846 = "Test Methods for Evaluating
Solid Waste"
155
-------
Table 9-3. Summary of Project-Specific Procedures for Extended Diesel Range Organic Analysis
SW-846 Method Reference (Step)
Project-Specific Procedures
3540C (Extraction)
Any free water present in the sample should be decanted and
discarded. The sample should then be thoroughly mixed, and any
unrepresentative material such as sticks, roots, and stones should be
discarded.
Ten grams of soil sample should be blended with 10 grams of
anhydrous sodium sulfate.
Extraction should be performed using 300 ml of extraction solvent.
Acetone and hexane (1 :1 v/v) or methylene chloride and acetone
(1:1 v/v) may be used as the extraction solvent.
Note: Methylene chloride and acetone do not constitute a constant-
boiling solvent and thus do not provide a suitable solvent for
SW-846 Method 3540C. Methylene chloride was used as an
extraction solvent for method validation of SW-846
Method 3540C.
The micro Snyder column technique or nitrogen blowdown technique
may be used to adjust (concentrate) the soil extract to the required
final volume.
Procedures for addressing contamination carryover are not specified.
During sample homogenization, field sampling technicians will
attempt to remove unrepresentative material such as sticks, roots,
and stones. In addition, the field sampling technicians will decant
any free water present in the sample. The reference laboratory will
not decant water or remove any unrepresentative material from the
sample. The reference laboratory will mix the sample with a wooden
tongue depressor.
Thirty grams of sample will be blended with at least 30 grams of
anhydrous sodium sulfate. For medium- and high-level samples, 6
and 2 grams of soil will be used for extraction, respectively, and
proportionate amounts of anhydrous sodium sulfate will be added.
The amount of anhydrous sodium sulfate used will not be measured
gravimetrically but will be sufficient to ensure that free moisture is
effectively removed from the sample.
Extraction will be performed using 200 ml of extraction solvent.
Methylene chloride will be used as the extraction solvent.
Kuderna Danish and nitrogen evaporation will be used as the
concentration techniques.
According to the reference laboratory, a sample extract concentration
of 100,000 ug/mL is the minimum concentration of EDRO that could
result in carryover. Therefore, if a sample extract has a
concentration that exceeds the minimum concentration for carryover,
the next sample in the sequence will be evaluated as follows: (1) if
the sample is clean (has no chromatographic peaks), no carryover
has occurred; (2) if the sample has detectable analyte concentrations
(chromatographic peaks), it will be reanalyzed under conditions in
which carryover would not occur.
8015B (Analysis)
GC Conditions
The following GC conditions are recommended:
Column: 30-m x 0.53-mm-ID, fused-silica capillary column
chemically bonded with 5 percent methyl silicone,
1 .5-um field thickness
Carrier gas: helium
Carrier gas flow rate: 5 to 7 mL/min
Makeup gas: helium
Makeup gas flow rate: 30 mL/min
Injector temperature: 200 °C
Detector temperature: 340 °C
Temperature program:
Initial temperature: 45 °C
Hold time: 3 min
Program rate: 45 to 275 °C at 12 °C/min
Hold time: 12 min
Overall time: 34.2 min
An HP 6890 GC will be used with the following conditions:
Column: 30-m x 0.53-mm-ID, fused-silica capillary column
chemically bonded with 5 percent methyl silicone,
1 .5-um field thickness
Carrier gas: hydrogen
Carrier gas flow rate: 1 .9 mL/min
Makeup gas: hydrogen
Makeup gas flow rate: 23 mL/min
Injector temperature: 250 °C
Detector temperature: 345 °C
Temperature program:
Initial temperature: 40 °C
Hold time: 2 min
Program rate: 40 to 345 °C at 30 °C/min
Hold time: 5 min
Overall time: 17.2 min
Calibration
The chromatographic system may be calibrated using either internal
or external standards.
The chromatographic system will be calibrated using external
standards.
156
-------
Table 9-3. Summary of Project-Specific Procedures for Extended Diesel Range Organic Analysis (Continued)
SW-846 Method Reference (Step)
Project-Specific Procedures
8015B (Analysis) (Continued)
Calibration (Continued)
Calibration should be performed using samples of the specific fuel
type contaminating the site. When such samples are not available,
recently purchased, commercially available fuel should be used.
ICV is not required.
CCV should be performed at the beginning of every 12-hour work
shift and at the end of an analytical sequence. CCV throughout the
12-hour shift is also recommended; however, the frequency is not
specified.
CCV should be performed using a fuel standard.
According to SW-846 Method 8000, CCV should be performed at the
same concentration as the midpoint concentration of the initial
calibration curve; however, the concentration of each calibration
point is not specified.
Method sensitivity check is not required.
Calibration will be performed using a commercially available standard
that contains even-numbered alkanes from C10 through C40.
ICV will be performed using a second-source standard that contains
even-numbered alkanes from C10 through C40.
CCV will be performed at the beginning of each analytical batch,
after every tenth analysis, and at the end of the analytical batch.
CCV will be performed using a standard that contains only even-
numbered alkanes from C10 through C40
CCV will be performed at a concentration equivalent to 3,750 ng
on-column.
The method sensitivity check will be performed daily using a
calibration standard at a concentration equivalent to 75 ng
on-column.
Retention Time Windows
The retention time range (window) should be established using
C10 and C28 alkanes during initial calibration. Three measurements
should be made over a 72-hour period; the results should be used to
determine the average retention time. As a minimum requirement,
the retention time should be verified using a midlevel calibration
standard at the beginning of each 1 2-hour shift. Additional analysis
of the standard throughout the 1 2-hour shift is strongly
recommended.
Two retention time ranges will be established using the opening CCV
for each analytical batch. The first range, labeled diesel range
organics, will be marked by the end of the C10 (n-decane) peak
through C28 (n-octacosane). The second range, labeled oil range
organics, will be marked by the end of the C28 (n-octacosane) peak
through C40 (tetracontane)
Quantitation
Quantitation is performed by summing the areas of all
chromatographic peaks eluting between C10 (n-decane) and C28
(n-octacosane).
Subtraction of the baseline rise for the method blank resulting from
column bleed is appropriate.
Because phthalate esters contaminate many types of products
commonly found in the laboratory, consistent quality control should
be practiced.
Quantitation will be performed by summing the areas of all
chromatographic peaks from greater than C10 (n-decane) through C28
(n-octacosane). A separate quantitation will also be performed to
sum the areas of all chromatographic peaks from greater than C28
(n-octacosane) through C40 (tetracontane). Separate average
response factors for each carbon range will be used for quantitation.
The quantitation results will then be summed to determine the total
EDRO concentration.
All calibrations, CCVs, ICVs, and associated batch quality control will
be controlled for the entire EDRO range (greater than C10 [n-decane]
through C40 [tetracontane]) using a single quantitation performed
over the entire EDRO range.
The reference laboratory will identify any occurrences of baseline
rise in the data package. The need to subtract baseline rise will be
evaluated during data validation.
Phthalate peaks, if present, will not be included in quantitation.
Quality Control
Spiking compounds for MS/MSDs and LCSs are not specified.
Spiking compounds for MS/MSDs and LCSs are discussed in
Sections 10.2. 1.3 and 10.2.1.5, respectively.
157
-------
Table 9-3. Summary of Project-Specific Procedures for Extended Diesel Range Organic Analysis (Continued)
SW-846 Method Reference (Step)
Project-Specific Procedures
8015B (Analysis) (Continued)
Quality Control (Continued)
According to SW-846 Method 8000, spiking levels for MS/MSDs are
determined differently for compliance and noncompliance monitoring
applications. For noncompliance applications, the laboratory may
spike the sample (1 ) at the same concentration as the reference
sample (LCS), (2) at 20 times the estimated quantitation limit for the
matrix of interest, or (3) at a concentration near the middle of the
calibration range.
According to SW-846 Method 8000, in-house laboratory acceptance
criteria for MS/MSDs and LCSs should be established. As a general
rule, the recoveries of most compounds spiked into a sample should
fall within the range of 70 to 130 percent, and this range should be
used as a guide in evaluating in-house performance.
The LCS should consist of an aliquot of a clean (control) matrix that is
similar to the sample matrix.
No LCSD is required.
The surrogate compound and spiking concentration are not
specified. According to SW-846 Method 8000, establishing in-house
laboratory acceptance criteria for surrogate recoveries is
recommended.
The method blank matrix is not specified.
The extract duplicate is not specified.
MS/MSD spiking levels will be targeted to be between 50 and
150 percent of the unspiked sample concentration. The reference
laboratory will use historical information to adjust the spike amounts
or to adjust sample amounts to a preset spike amount. The spiked
samples and unspiked samples will be prepared such that the
sample mass and extract volume used for analysis will be the same.
Reference laboratory acceptance criteria for MS/MSDs and LCSs are
specified in Table 10-2.
The LCS/LCSD matrix will be Ottawa sand.
LCSD spiking compounds, concentrations, and acceptance criteria
are discussed in Section 10.2.1 .5.
The surrogate compound will be o-terphenyl. See Section 10.2.1.2
for details.
The method blank matrix will be Ottawa sand.
The extract duplicate will be performed. See Section 10. 2. 1.4 for
details.
Notes:
urn =
C
CCV =
EDRO =
GC
ICV =
ID
LCS =
Microgram
Micrometer
Carbon
Continuing calibration verification
Extended diesel range organics
Gas chromatograph
Initial calibration verification
Inside diameter
Laboratory control sample
LCSD = Laboratory control sample duplicate
m = Meter
min = Minute
mL = Milliliter
mm = Millimeter
MS = Matrix spike
MSD = Matrix spike duplicate
SW-846 = "Test Methods for Evaluating Solid Waste"
v/v = Volume per volume
158
-------
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160
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The sample coordinator will verify that all information on the sample container labels is correct and consistent with
the information on the chain-of-custody form and will sign the receipt log. The yellow copy of the chain-of-custody
form will be retained in the laboratory's project files, and the white copy will be returned to Tetra Tech in order to
verify sample receipt.
Any discrepancy between the sample container labels and chain-of-custody form, any broken or leaking sample
containers, or any other abnormal situation will be reported to the laboratory project manager. The laboratory project
manager will inform the Tetra Tech project manager of any such problem, and corrective actions will be discussed
and implemented. The problem and its resolution will be noted in a nonconformance memorandum, which will be
initialed and dated (electronically) by the laboratory project manager.
Each shipment of samples received at STL Tampa East will be assigned a unique lot number. Each lot will be divided
into groups of 20 samples or less. In addition, each sample in the shipment will be assigned a sequential sample
number, and each sample container will be assigned a unique work order number. A laboratory sample label
specifying the lot number, sample number, and work order number will be attached to each sample container. A
worksheet will be prepared that specifies the samples to be analyzed, the analyses to be performed, the level of QC
for the project, and any other necessary information. The worksheet, accompanied by a copy of the chain-of-custody
form, will be given to the laboratory project manager for review and approval. Copies of the approved worksheet
will be given to the laboratory group leaders, who will schedule the extractions and analyses in accordance with
applicable sample holding times and project schedules. Bench sheets initiated at the first point of sample preparation
will accompany the samples throughout the analytical sequence.
Samples for GRO and EDRO analyses will be stored in designated refrigerators. Unless otherwise specified by Tetra
Tech, an aliquot from the samples for EDRO analysis will be used for percent moisture determination. A logbook
will be maintained for each refrigerator, and the refrigerator's temperature will be recorded each working day. All
samples will be stored at 4 ± 2 °C. A sample storage logbook or form will be used to document each instance when
a sample is removed from or replaced in a storage area.
All unused samples and associated extracts will be stored for 6 months after their receipt or generation at the
laboratory. If a longer storage period is needed based on Tetra Tech's review of the analytical data, the Tetra Tech
project manager will so notify the laboratory in writing prior to the end of the 6-month storage period. All unused
samples will be stored in their original containers, and all associated extracts will be stored in bottles or vials with
Teflon™-lined caps or septa. Unused samples and extracts will be stored at 4 ± 2 °C. The laboratory will contact
the Tetra Tech project manager before disposing of any unused samples or extracts.
161
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The laboratory will be responsible for properly disposing of all samples and extracts as well as all wastes associated
with sample analysis. However, if a sample, extract, or waste is expected to be incompatible with a laboratory waste
stream, the laboratory will notify the Tetra Tech project manager of this problem in writing, and the problem will
be resolved before the demonstration begins. However, based on the results of the predemonstration investigation,
no such problem is expected to occur.
162
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Chapter 10
QA/QC Procedures
The purpose of QA/QC is to ensure generation of high-quality, scientifically valid, and legally defensible data that
meet the demonstration objectives. QA objectives, internal QC checks, calculation of data quality indicators, QA
reports, and special QC requirements for the demonstration of the innovative TPH field measurement devices are
discussed below.
10.1 QA Objectives
The overall QA objective for the demonstration is to produce well-documented data of known quality. Data quality
will be measured in terms of the data's reporting limits, precision and accuracy, completeness, representativeness,
and comparability.
Depending on the measurement parameter involved, individual QA objectives or acceptance criteria were set based
on either demonstration objectives or STL Tampa East's and the technology developers' experience in analyzing the
predemonstration investigation samples and similar environmental samples. If analytical or measurement data fail
to meet the QA objectives described in this section, corrective actions will be taken. Corrective actions associated
with the reference method, field measurement device, and sample collection internal QC checks are discussed in
detail in Section 10.2. In the DER, Tetra Tech will explain why any QA objectives were not met (for example,
because of matrix interferences) and will describe the usefulness and limitations of all data.
10.1.1 Reporting Limits
The reporting limits for reference method, field measurement device, and sample collection parameters are presented
in Table 10-1. The project-required reporting limits for GRO and EDRO presented in Table 10-1 were identified
based on (1) a review of state action levels for TPH, (2) detection levels achieved by the field measurement devices
163
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Table 10-1. Reporting Limits for Reference Method, Field Measurement Device, and Sample Collection Parameters
Parameter
Reference Method
TPH measurement
GRO
EDRO
GRO
EDRO
Percent moisture
Analytical cost
Time required for sample analysis
Field Measurement Devices
TPH measurement
Number of developer technicians
Number of samples analyzed
Time required for sample analysis activities
Number of measurement kits required to
perform analyses
Items not included in measurement kit that
are required to perform analyses
Cost of measurement kits
Personal protective equipment items used
during sample analyses
Power source used during sample analyses
Work space used during sample analyses
Volume of IDW generated
Sample Collection
Sampling location
Groundwater level
Depth interval sampled
Photoionization detector measurement
Physical description of sample
Time required for sample homogenization
Cooler temperature
Notes:
Matrix
Soil
Soil
Liquid
Liquid
Soil
Not
applicable
Not
applicable
Soil and liquid
Not
applicable
Not
applicable
Not
applicable
Not
applicable
Not
applicable
Not
applicable
Not
applicable
Not
applicable
Not
applicable
Soil and liquid
Not
applicable
Groundwater
Soil
Air
Soil
Not
applicable
Water
EDRO = Extended diesel range organics
EPA = U.S. Environmental Protection Agency
GRO = Gasoline range organics
IDW = Investigation-derived waste
Method Reference3
SW-846 Method 801 5B (modified)
SW-846 Method 801 5B (modified)
SW-846 Method 801 5B (modified)
SW-846 Method 801 5B (modified)
MCAWW Method 160.3
Not applicable
Not applicable
See Note0
See Section 4.2 (P6)
See Section 4.1 (P5)
See Section 4.2 (P5)
See Section 4.2 (P6)
See Section 4.2 (P6)
See Section 4.2 (P6)
See Section 4.2 (S2)
None
None
See Section 4.2 (P6)
See Section 7.1.1
See Section 7.1.1.2
See Section 7.1.1
Manufacturer instructions
uses
See Section 7.1.3.1
See Section 7.1.3.3
Reporting Unit
mg/kg (wet weight basis)
mg/kg (wet weight basis)
mg/L in the extract
mg/L in the extract
Percent
Dollar
Day
mg/kg (wet weight basis)
Person
Sample
Minute
Kit
Variable
Dollar
Variable6
Variable6
Variable6
Laboratory pack
Foot
Inch
Inch
Part per million
See Note'
Minute
°C
Reporting
Limit
5b
10b
0.02b
0.075"
1
10
1
See Noted
1
1
1
1
1
10
1
1
1
1
0.5
1
1
5
Not applicable
1
1
mg/kg = Milligram per kilogram
mg/L = Milligram per liter
SW-846 = "Test Methods for Evaluating Solid Waste"
TPH = Total petroleum hydrocarbons
MCAWW = "Methods for Chemical Analysis of Water and Wastes"
USCS = Unified Soil Classification System
164
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Table 10-1. Reporting Limits for Reference Method, Field Measurement Device, and Sample Collection Parameters (Continued)
a SW-846 method reference: EPA 1996b; MCAVWV method reference: EPA 1983; manufacturer instruction reference: HNU Systems, Inc.
1985
b Reporting limits will be adjusted for dilutions made during sample preparation and analysis.
0 See Chapter 2 for a description of the operating procedure for each field measurement device.
d See Table 4-2 for developer-claimed method detection limits for each field measurement device.
e The personal protective equipment, power source, and work space used will vary depending on the field measurement device being
demonstrated.
f Tetra Tech EM Inc. will record qualitative observations regarding soil sample color, composition, and water content, as appropriate.
165
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(see Table 4-2), and (3) reporting limits achieved by STL Tampa East. These reporting limits are the concentrations
at or above which the objectives for precision and accuracy can be met. The general criterion applied by STL Tampa
East for evaluation of MDL data and their use to support reporting limit data is that the method detection limit for a
target parameter should be lower than the reporting limit by a factor of 2 to 5. STL Tampa East performs MDL
studies annually. STL Tampa East's last MDL study for (1) GRO in soil was done in September 1999 and (2) EDRO
in soil was done in March 2000. MDLs for the reference method and field measurement devices will be determined
under primary objective PI as discussed in Section 4.3.
10.1.2 Precision and Accuracy
QA objectives for precision and accuracy depend on the types of samples to be collected, the analyses to be
performed, and the ultimate use of the analytical data. Table 10-2 summarizes the precision (RPD) and accuracy
(percent recovery [%R]) acceptance criteria for the reference method, field measurement device, and sample
collection parameters. Specific QC samples that will be used to estimate precision and accuracy, such as MS/MSDs
and laboratory control sample/laboratory control sample duplicates, are discussed in Section 10.2. The equations
that will be used to estimate precision and accuracy are presented in Section 10.3.
10.1.3 Completeness
Completeness is determined by assessing the amount of valid data obtained from a measurement system compared
to the amount of data planned to be obtained. The percent completeness (%C) is calculated by dividing the number
of samples yielding valid data by the total number of samples planned for collection and multiplying by 100. The
project QA objective for completeness is 100 percent for each parameter. If completeness is less than 100 percent,
Tetra Tech will prepare documentation explaining why this objective was not met and what impact, if any, the lower
percentage will have on meeting the demonstration objectives. The equation that will be used to calculate %C is
presented in Section 10.3.
10.1.4 Representativeness
The QA objective for representativeness is to obtain samples and measurements that represent demonstration area
conditions. For example, predemonstration investigation results have been used to select demonstration sampling
locations and depth intervals that possess appropriate physical and chemical characteristics for assessing the
166
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performance of the field measurement devices. In addition, to ensure that each sample analyzed by the developers
and STL Tampa East is representative of the material collected during the demonstration, (1) all soil collected in a
specified depth interval at a given sampling location will be homogenized in the field, and (2) the PE samples
prepared by ERA will be homogenized by ERA. Also, sampling procedures will be implemented in the field to
minimize bias associated with TPH volatilization during filling of sample containers. These procedures are discussed
in Section 7.1.3.1.
10.1.5 Comparability
Tetra Tech will ensure data comparability by (1) using standard methods such as SW-846 (GRO and EDRO) and
MCAWW (percent moisture) methods, (2) consistently reporting results in the standard units shown in Table 10-1,
and (3) presenting data in tabular and graphic formats that allow effective comparisons.
10.2 Internal QC Checks
Internal QC will consist of checks used to ensure that QA objectives are met. These checks are also intended to
identify any need for corrective action. Internal QC checks apply to the reference method, field measurement devices,
and sample collection. A discussion of the internal QC checks to be used for the demonstration is provided below.
10.2.1 Reference Method QC Checks
With regard to reference method QC checks, QC checks will be used to (1) demonstrate the absence of interferents
and contamination from laboratory glassware and reagents, (2) verify that the measurement system is in control,
(3) evaluate the precision and accuracy of laboratory analyses, and (4) ensure the comparability of data. Reference
method QC checks for soil samples will consist of method blanks, surrogates, MS/MSDs, extract duplicates, and
LCS/LCSDs for GRO and EDRO analyses, and laboratory duplicates will be used as QC checks for percent moisture
analysis.
Reference method QC checks for liquid PE samples will consist of method blanks, surrogates, MS/MSDs, and
LCS/LCSDs for GRO analysis. Because EDRO analysis does not contain a preparation step, surrogates, MS/MSDs,
and LCS/LCSDs will not be performed for EDRO analysis. However, an instrument blank will be performed for
EDRO analyses as a method blank equivalent.
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The reference method QC checks for both environmental and PE samples are discussed below; the frequencies,
acceptance criteria, and corrective actions for the QC checks are presented in Table 10-2.
10.2.1.1 Method and Instrument Blanks
Method or instrument blanks will be used to verify that steps in the analytical procedures do not introduce
contaminants that affect analytical results, as applicable. Each method blank for soil samples will be prepared by
adding all reagents and surrogates, as appropriate, to Ottawa sand. Liquid PE sample method blanks for GRO
analysis will be prepared by adding 100 (iL of methanol and surrogates, as appropriate, to 5 mL of deionized water.
These blanks will then undergo all the procedures required for sample preparation. The method blanks will be
analyzed along with environmental and PE samples prepared under identical conditions. For liquid PE samples
analyzed for EDRO, instrument blanks that consist of the solvent (methylene chloride) without the surrogate will be
analyzed.
10.2.1.2 Surrogates
Surrogates will be spiked into each soil sample for GRO and EDRO analyses before extraction to determine whether
significant matrix effects exist within the samples and to measure the efficiency of analyte recovery during sample
preparation and analysis. Each surrogate spike will be prepared by adding a known amount of the surrogate to a
sample; the compound will be similar to the compounds that the sample will be analyzed for. The calculated %R of
the spike will be used as a measure of the accuracy of the total analytical method. STL Tampa East will use
4-bromofluorobenzene and o-terphenyl as the surrogate spiking compounds for GRO and EDRO analyses,
respectively. For GRO analysis, 0.25 mL of 40-mg/L 4-bromofluorobenzene will be added to each soil sample. For
EDRO analysis, 1.0 mL of 100-mg/L o-terphenyl will be added to each soil sample.
A surrogate will also be spiked into each liquid PE sample for GRO analysis. STL Tampa East will spike 5 (iL of
40-(ig/mL 4-bromofluorobenzene into 5 mL of deionized water.
10.2.1.3 MS/MSDs
MS/MSD results will be evaluated to determine the accuracy and precision of the analytical results with respect to
the effects of the sample matrix. The matrix spiking solutions for soil samples will be (1) the 10-component GRO
calibration standard for GRO analysis and (2) the EDRO standard that contains even-numbered alkanes from C10
through C40 for EDRO analysis. For GRO analysis, 0.25 mL of 400-mg/L spiking solution will be added to each soil
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sample designated as an MS/MSD. For EDRO analysis, 1.0 mL of 1,500-mg/L spiking solution will be added to each
soil sample designated as an MS/MSD. If the MS/MSD recovery limits specified in Table 10-2 are not met, the
failure to meet the recovery limits will not be attributed to the initial, inappropriate spiking levels. In such cases,
target spiking levels for MS samples will be targeted to be between 50 and 150 percent of the unspiked sample
concentration. The reference laboratory will use historical information to adjust the spike amounts or will adjust
sample amounts to a preset spike amount. The spiked and unspiked samples will be prepared such that the sample
mass and extract volume used for analysis will be the same. The MS/MSD acceptance criteria presented in
Table 10-2 are based on STL Tampa East historical data and STL Tampa East's experience in analyzing the
predemonstration investigation samples.
MS/MSDs for liquid PE samples for GRO analysis will also be prepared. STL Tampa East will spike 5 (iL of
40-(ig/mL GRO spike solution and surrogate into 5 mL of deionized water and an appropriate volume of diluted
sample.
10.2.1.4 Extract Duplicates
For GRO and EDRO analyses, extract duplicates will be evaluated to determine the precision associated with
laboratory analytical procedures following soil sample extraction. STL Tampa East will sample duplicate aliquots
of the GRO and EDRO extracts for analysis. Comparison of MS/MSD RPD results with extract duplicate RPD
results should indicate whether any out-of-control situation associated with MS/MSD precision occurred during the
extraction or analytical procedures.
10.2.1.5 LCS/LCSDs
For GRO and EDRO analyses, LCS/LCSD results will be evaluated to determine whether observed deviations for
MS/MSD samples and extract duplicates were caused by a matrix effect. Ottawa sand will be spiked with matrix
spiking compounds to generate soil LCS/LCSDs. The spiking compounds will be the same as those for MS/MSDs.
The spiking levels for GRO and EDRO soil LCS/LCSDs will be 20 and 50 mg/kg, respectively. Five mL of deionized
water and 100 (iL of methanol will be spiked with 5 (iL of 40-(ig/mL GRO spike solution to generate liquid PE
sample LCS/LCSDs for GRO analysis. The LCS/LCSD acceptance criteria presented in Table 10-2 are based on STL
Tampa East historical data.
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10.2.1.6 Laboratory Duplicate
For percent moisture analysis, laboratory duplicates will be evaluated to determine the precision associated with
laboratory analytical procedures for the entire method. STL Tampa East will sample duplicate aliquots of soil
samples for GRO and EDRO analyses.
10.2.2 Field Measurement Device QC Checks
QC checks for field measurement devices will be used to evaluate the quality of field TPH measurements. The
frequencies, acceptance criteria, and corrective actions for QC checks proposed by the developers for the
demonstration are presented in Table 10-2. In many cases, the devices do not have established QC checks. Tetra
Tech discussed such situations with the developers, explained the significance of QC checks, and gave the developers
an opportunity to propose QC checks and associated frequencies, acceptance criteria, and corrective actions. As
shown in Table 10-2, QC check information for the devices is incomplete or unavailable in a few cases. During the
demonstration, if the technology developers choose to modify the proposed QC checks listed in Table 10-2, Tetra
Tech will record the modifications in field logbooks.
10.2.3 Sample Collection QC Checks
QC checks for sample collection will be used to evaluate the quality of sample collection activities. In general, the
QC checks will be used to (1) assess the representativeness of the samples and (2) ensure that the degree to which
the analytical data are representative of actual demonstration area conditions is known and documented. QC checks
for sample collection will consist of field triplicates, the time required for sample homogenization, and temperature
blanks. Acceptance criteria and associated corrective actions for sample collection QC checks are presented in
Table 10-2. No internal QC checks are recommended for the PID. According to the PID manufacturer, the quality
of sample measurements is controlled by performing a daily calibration check using a disposable cylinder containing
isobutylene. The PID is readjusted if its reading deviates from the known concentration.
Field triplicate samples for GRO, EDRO, and TPH analyses will be collected to evaluate whether a sample is
adequately homogenized in the field prior to filling of sample containers. Such an evaluation can be made by taking
into account the analytical precision results achieved for MS/MSDs, LCS/LCSDs, and extract duplicates. Field
triplicate samples will be submitted to the developers and STL Tampa East as blind samples (that is, the developers
and STL Tampa East will not know which samples are replicates). The developers and STL Tampa East will not be
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responsible for comparing sample analytical results to the acceptance criteria. Tetra Tech will conduct this
comparison after data verification and validation are complete.
Other sample collection parameters identified in Table 10-1 (for example, sampling location and groundwater level)
do not require QC checks because (1) measurement precision cannot be verified with repeated measurements and
(2) measurement accuracy cannot be assessed using another procedure that is considered to be more reliable or
accurate.
10.3 Calculation of Data Quality Indicators
This section presents the procedures that will be used to calculate the following data quality indicators: precision,
accuracy, completeness, and representativeness. Data analysis procedures that will be used to determine the MDLs
of each fie Id measurement device and the reference method are presented under primary objective PI in Section 4.3.
10.3.1 Precision
Precision will be evaluated using the RPD when two measurements are made and using the RSD when more than two
measurements are made. The RPD for GRO, EDRO, and TPH analyses will be estimated for MS/MSD samples,
extract duplicates, LCS/LCSD, and laboratory duplicates, as applicable. The RPD between the analyte concentrations
measured in the MS and MSD samples will be calculated using Equation 10-1.
iMS-MSDl
RPD = —!- !— x100 (10-1)
0.5(MS + MSD)
where
RPD = Relative percent difference
MS = Analyte concentration in MS sample
MSD = Analyte concentration in MSD sample
In Equation 10-1, MS and MSD will be replaced by LCS and LCSD for LCS/LCSD analyte concentrations and by
E and ED for extract and extract duplicate analyte concentrations, respectively. The RPD between percent moisture
measurements will also be calculated using Equation 10-1, where MS and MSD will be replaced by S and D for the
sample and duplicate sample percent moisture measurements, respectively. In addition, the RPD will be estimated
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for sample homogenization time and sample analysis time in the field. For these parameters, two simultaneous
stopwatch readings (Tj and T2) will replace the MS/MSD analyte concentrations (MS and MSB) in Equation 10-1.
The QC check procedure for time measurement will end when either Tj or T2 equals 5 minutes.
The RSD will be used to estimate precision for soil field triplicate analyses. The RSD among field triplicate
analytical results will be calculated using Equation 4-7.
10.3.2 Accuracy
Accuracy will be estimated for sample analyses for GRO and EDRO by calculating %R for MS and LCS samples
using Equation 10-2. The developers will use the same equation to calculate accuracy for spiked samples, as
applicable.
(c.-c)
%R = J x 100 (10-2)
^t
where
%R = Percent recovery
Cj = Measured concentration in spiked sample aliquot
C0 = Measured concentration in unspiked sample aliquot
Ct = Actual concentration of spike added
Equation 10-2 will also be used to calculate %R for surrogates, where
Cj = Measured surrogate concentration in spiked sample aliquot
C0 = Zero assumed because surrogate will not be present in sample
Ct = Actual concentration of surrogate added
Estimation of accuracy for percent moisture analyses and sample collection measurements is not applicable to the
demonstration. The accuracy of field measurement devices will be addressed under primary objective P2, which is
discussed in Chapter 4.
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10.3.3 Completeness
Completeness will be reported as the percentage of measurements judged to be valid. Equation 10-3 will be used to
calculate %C.
%C = —x100 (10-3)
where
%C = Percent completeness
V = Number of measurements judged to be valid
T = Total number of measurements planned
10.3.4 Representativeness
Representativeness will be evaluated in relation to the demonstration design. Field triplicate samples will be
collected in each demonstration area, and their analytical results will be compared to determine representativeness.
In addition, the results of the MS/MSD and extract duplicate sample analyses (see Section 10.3.1) may also be helpful
in evaluating the representativeness of the demonstration data.
10.4 QA Reports
Effective management of demonstration data collection efforts will require timely assessment and review of these
efforts. Effective interaction and feedback among project team members will therefore be essential. When
appropriate, the Tetra Tech project manager will discuss QA issues with the EPA project manager as they arise. The
Tetra Tech project manager will also summarize QA issues and their resolutions in monthly status reports to the EPA
project manager. QA issues may pertain to the following matters:
Deviations from the demonstration plan
• Corrective action activities
• Outstanding issues and proposed resolutions
Audit results
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10.5 Special QC Requirements
For the demonstration, Tetra Tech has identified special QC requirements. First, STL Tampa East will analyze soil
samples for GRO and EDRO using a modified version of SW-846 Method 8015B that requires special QC
procedures. The proj ect-specific procedures for sample preparation and analysis for GRO and EDRO are summarized
in Tables 9-2 and 9-3, respectively. Second, field triplicates, MS/MSDs, and extract duplicates will be collected at
a frequency of one per depth interval in each sampling area for analysis by the developers and STL Tampa East,
which corresponds to a frequency of about one for every four environmental samples. Typically, field replicates are
collected at a frequency of 1 for every 10 environmental samples and MS/MSDs are collected at a frequency of 1 for
every 20 environmental samples. Extract duplicates are typically not collected for soil organic analyses.
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Chapter 11
Audits and Corrective Actions
Demonstration measurement systems and associated data will be assessed both on a day-to-day basis by Tetra Tech
proj ect personnel (routine assessments) and on a periodic basis by independent personnel (audits). Corrective actions
will be formulated and implemented in response to any data quality issues that arise during routine assessments or
audits. Routine assessments and corrective actions for field measurement device and laboratory calibrations are
presented in Chapters 8 and 9, respectively. Chapter 10 presents routine assessments and corrective actions
associated with field and laboratory QC procedures.
Although routine assessment is generally the most effective means to identify data quality issues, personnel directly
involved in a project may not always recognize a data quality issue. Therefore, audits will be conducted to provide
an independent view of demonstration measurement systems and data as well as additional assurance that data quality
issues are being identified and appropriate corrective actions are being taken.
QA audits are independent assessments of measurement systems and associated data and are more rigorous than
routine assessments. QA audits may be internal or external and most commonly incorporate technical system reviews
and analysis of blind or double-blind PE samples. For the demonstration, internal QA audits will be conducted by
Tetra Tech's proj ect technical consultant, Jerry Parr of Catalyst, at the direction of the Tetra Tech SITE QA manager.
The Tetra Tech project manager will be present during all audits conducted for the demonstration. External QA
audits will be conducted by an independent organization such as the EPA.
As part of the predemonstration investigation, Tetra Tech's field sampling activities, including sample collection,
homogenization, containerization, packaging, and shipment, were audited by Catalyst. STL Tampa East's sample
receipt and storage, chain-of-custody, preparation, analysis, and data reporting procedures for the predemonstration
investigation were also audited by Tetra Tech and Catalyst. The findings of these internal technical system audits
(TSA) were discussed with the EPA project manager and other demonstration participants.
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System audits, performance audits, and associated corrective action procedures are described below.
11.1
System Audits
System audits include thorough evaluations of field and laboratory sampling and measurement systems. For the
demonstration, such audits will be conducted at the direction of the EPA project manager, the EPA QA officer, or
the Tetra Tech SITE QA manager.
For the demonstration, Catalyst will conduct an internal TSA of field sampling and measurement systems during
Tetra Tech's sampling activities and the developers' TPH measurement activities, respectively. In addition, Tetra
Tech and Catalyst will conduct an in-process TSA of STL Tampa East's critical measurement activities. Specifically,
STL Tampa East will be audited to examine its measurement of GRO, EDRO, and percent moisture in soil samples
and of GRO and EDRO in liquid PE samples.
The activities that will be audited during field sampling, field measurement, and laboratory measurement TSAs are
summarized in Table 11-1.
Table 11-1. Activities to be Assessed During Field Sampling, Field Measurement, and Laboratory Measurement Technical System Audits
Field Sampling Activity
Field Measurement Activity
Laboratory Measurement Activity
Sample collection at Navy BVC site
Sample homogenization
Sample containerization
Field QA/QC
Field documentation
Decontamination
Sample labeling, packaging, and shipping
Project management and QA activities that
may impact data quality
Standards preparation (as applicable)
Calibration
Sample measurement
Data reporting
QA/QC procedures
Project management and QA activities that
may impact data quality
Sample receipt and storage
Internal chain-of-custody procedures
Sample preparation
Standards preparation and storage; use of
second-source standards
Calibration
QA/QC procedures
Data reduction, validation, and reporting
Project management and QA activities that
may impact data quality
Notes:
BVC = Base Ventura County
QA = Quality assurance
QC = Quality control
External TSAs of field sampling and field and laboratory measurement activities may also be conducted by the EPA
at the discretion of the EPA project manager and QA officer. If the EPA elects to perform a field TSA, Tetra Tech
will coordinate an internal TSA with the EPA's TSA and will schedule the audits to occur on consecutive days. The
internal TSA will then be identified as a pre-audit and will be used to identify issues for resolution during the EPA's
TSA. If the EPA elects not to perform an external field or laboratory TSA, Tetra Tech will include the EPA project
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manager and QA officer in the debriefing for each internal TSA and will submit all TSA documentation to the EPA
for review.
Internal TSAs will be conducted in accordance with (1) Tetra Tech's internal guidance for SITE projects and
(2) applicable EPA technical directives and guidance. Based on Tetra Tech's internal guidance, the audit process
to be implemented by the assigned auditor for a laboratory audit is summarized below.
A checklist is developed based on the EPA-approved demonstration plan and analytical methods identified
in the demonstration plan.
• Actual laboratory activities are observed and compared to the activities described in the EPA-approved
demonstration plan and in the analytical methods using the checklist.
Nonconformances and corrective actions are discussed on site; any immediate corrective action is observed
and documented, when possible.
• A draft TSA report is prepared to document any observed nonconformance as well as any immediate,
corrective action that was implemented.
• The draft TSA report is reviewed by Tetra Tech personnel for technical, editorial, and overall quality.
• The draft TSA report is distributed to the laboratory, the EPA project manager and QA officer, the Tetra
Tech project manager and SITE QA manager, and the Catalyst project technical consultant.
Any laboratory response to the draft TSA report is reviewed to assess its impact on the issue or proposed
corrective action.
• A final TSA report is prepared, subjected to Tetra Tech's internal review process, and distributed to the
laboratory, the EPA project manager and QA officer, the Tetra Tech project manager and SITE QA manager,
and the Catalyst project technical consultant.
11.2 Performance Audits
As part of the predemonstration investigation, double-blind PE samples were analyzed by the developers and STL
Tampa East. The findings and this performance audit were discussed with the EPA project manager and all other
demonstration participants.
As directed by the EPA project manager, a performance audit of field measurement device and STL Tampa East
measurement activities will be conducted for GRO and EDRO analyses of soil and liquid samples during the
demonstration. Tetra Tech will obtain PE samples for GRO and EDRO analyses from ERA and will have the
developers and STL Tampa East analyze them as blind samples. Chapter 4 discusses the PE samples that will be used
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for the demonstration. The results of the PE sample analyses will be reviewed by Tetra Tech and will be reported
to the EPA project manager, the developers, and the STL Tampa East project manager. Performance audit findings,
any nonconformances, and their resolutions will be documented in the DER for the demonstration.
11.3 Corrective Action Procedures
If a problem is detected during a system or performance audit, the following procedures will be followed:
• The Tetra Tech project manager will immediately discuss the problem and any corrective action to be taken
with the field or laboratory personnel responsible, the Catalyst project technical consultant, and all other
appropriate personnel.
• The Tetra Tech project manager, the Catalyst project technical consultant, the developer or the laboratory
project and QA managers (as appropriate), and the EPA project manager will develop a plausible course of
corrective action.
• The Tetra Tech project manager and the developer or the laboratory project manager (as appropriate) will
implement the corrective action and assess its effectiveness.
The audit report and associated response will serve as the documentation of the problem and corrective
action. The Tetra Tech project manager and the developer or laboratory project manager (as appropriate)
will be responsible for ensuring that corrective actions identified through the audit process are fully
implemented.
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Chapter 12
Data Management
To ensure that demonstration data are scientifically valid, defensible, and comparable, appropriate procedures will
be used to perform data management. This chapter describes (1) data reduction, (2) data review, (3) data reporting,
and (4) data storage procedures for the demonstration.
12.1 Data Reduction
Each analytical method selected for the demonstration and each innovative TPH field measurement device's
instruction manual contain detailed instructions and equations for calculating compound concentrations and other
parameters. Data will be reduced to the units presented in Table 10-1 using the procedures described in the analytical
methods. When appropriate, TPH results will be corrected for solvent dilution to account for moisture present in soil
samples. For example, if a soil sample contains 20 percent moisture, the GRO analytical result will be multiplied
by 1.2 to calculate the GRO concentration in mg/kg on a wet weight basis and adjusted for methanol dilution. For
liquid PE samples, concentrations will be reported in mg/L of diluted extract. These concentrations will be converted
to mg/L of sample by Tetra Tech using the appropriate dilution factor.
12.2 Data Review
A review of field and laboratory analytical data will be conducted by each developer and STL Tampa East,
respectively. Tetra Tech will also conduct a review of all field and laboratory data. The review processes that will
be used for field and laboratory analytical data are described below.
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12.2.1 Data Review by Developers
Each developer will review all results generated by its field measurement device. At a minimum, the developer will
report measurement results in mg/kg TPH on a wet weight basis. The developer's GRO and EDRO measurements
may also be reported, if applicable. The developer's assessment of the investigative sample data and QC results will
be summarized for discussion with the Tetra Tech and EPA project managers.
12.2.2 Data Review by STL Tampa East
STL Tampa East will report measurement results for GRO, DRO, oil range organics (greater than C28 through C40),
and percent moisture. All soil sample GRO, DRO, and oil range organic results will be reported in mg/kg on a wet
weight basis. Review of 100 percent of the data will be conducted by STL Tampa East in accordance with a three-
level review process. Level 1 and 2 reviews will be conducted by a laboratory analyst and supervisor, respectively,
and will serve as a validation of the analytical data by those involved in analyzing the samples. The Level 3 review
will be performed by the laboratory project manager and will serve as a final check of the completeness of each data
package. Specific actions that will be performed during the three-level review process are presented below.
During the Level 1 review, a laboratory analyst will verify the following:
Sample preparation information is correct and complete and includes documentation of standards and sample
amounts.
• Analysis information is correct and complete and includes proper identification of analysis outputs (charts,
chromatograms, and others).
Analytical results are correct and complete, and include calculations or verifications of instrument
calibrations, QC results, and quantitative sample results with appropriate qualifiers.
• The appropriate analytical methods have been followed and are identified in the project records.
• Proper documentation procedures have been followed.
• All nonconformances have been documented.
• Project-specific sample preparation and analytical requirements have been met.
• The data generated have been reported with the number of significant figures specified by the analytical
methods or as appropriate.
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Following the Level 1 review, the Level 2 review will be performed by the laboratory analyst's supervisor or a
designee to ensure that the Level 1 review has been completed correctly. The Level 2 review will include an
evaluation of all items required for each raw data package. Also included in this review will be an assessment of data
acceptability based on the following elements:
• Adherence of the procedures used to the required analytical methods
• Correct interpretation of chromatograms
• Correctness of numerical input when computer programs are used (checked randomly)
• Correct identification and quantitation of constituents with appropriate qualifiers
• Acceptability of QC results
• Documentation that instruments were operating in accordance with method specifications (including those
for calibrations and performance checks)
• Documentation of dilution factors and standard concentrations
• Adherence to sample holding times
The Level 2 review will also serve as a verification that the process followed by the laboratory analyst is correct with
regard to the following:
The analytical procedures follow the methods and specific instructions in the project QA summary
memorandum issued by the laboratory project manager.
• Any nonconformances have been addressed through corrective actions that are defined in a laboratory
nonconformance memorandum.
Valid interpretations have been made during examination of the data, and the review comments of the
laboratory analyst are correct.
• Each raw data package contains all the necessary documentation for data review and report production, and
results are reported in a manner consistent with the method used for preparation of data reports.
Following the Level 2 review, the Level 3 review will be performed by the laboratory project manager. This review
will serve to verify the completeness of each data package and to ensure that demonstration requirements have been
met for the analyses performed. The laboratory project manager will verify the following:
• Analytical results are presented for every sample in the analytical batch, reporting group, or sample lot.
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• Every demonstration parameter or target compound is reported with either a value or reporting limit.
• The correct units and correct numbers of significant figures are used.
• All identifications of nonconformances, including holding time violations, and data evaluation statements
that involve data quality are accompanied by clearly expressed comments from the laboratory.
Each final data report is completely legible, contains all the supporting documentation required for the
demonstration, and is in the format required by Tetra Tech.
In addition to the three-level review described above, the STL Tampa East QA manager will perform a full review
of the first data package for each analysis to ensure that appropriate data generation procedures are followed. This
level of review is not routinely performed by STL Tampa East and has been specifically required by Tetra Tech.
During laboratory reviews of data, problems associated with analytical nonconformances will be identified, and the
problems and proposed resolutions will be discussed with the Tetra Tech project manager. Analytical
nonconformances are defined as QC data lying outside a specific QA objective range (control limits) for precision
or accuracy for a given analytical method. If QC data are outside control limits, the laboratory will determine the
probable causes of the problems. If necessary, the samples involved will be re-prepared or reanalyzed, and typically
only the reanalysis results will be reported. However, if a problem involves the sample matrix, both initial and
reanalysis results will be reported and identified in the data package. If sample reanalysis is not feasible, the initial
analysis results will be reported, and these results will be flagged and identified in the data package.
12.2.3 Data Review by Tetra Tech
In addition to the three-level review process that will be used by STL Tampa East, the Tetra Tech project manager
or his designee (for example, Mr. Parr of Catalyst) will review all laboratory and field measurement device results,
including case or sample lot narratives and QC sample results, based on demonstration objectives. The Tetra Tech
project manager or his designee will also conduct a complete data validation for 10 percent of the data as an
independent check on reference method or device performance. If this validation reveals no oversights or problems,
Tetra Tech will consider all data to be acceptable. If oversights or problems are identified, however, a complete data
validation for 100 percent of the data will be conducted by the Tetra Tech proj ect manager or his designee. This data
validation will be conducted using EPA CLP "National Functional Guidelines for Organic Data Review" (EPA
1994a), as applicable. Tetra Tech's assessment of the data and QC results will be summarized for discussion with
the EPA project manager and incorporation into the DER.
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During its data review, Tetra Tech will identify project outlier data and will report these data to the EPA project
manager. Project outlier data are defined as sample data outside specified acceptance limits established about the
central tendency estimator (the arithmetic mean) of the data set for a given area or for all areas taken together. For
data known or assumed to be normally distributed, the specified acceptance limits will be the 95 percent confidence
limits defined by the Student's two-tailed t-distribution. Consistent procedures will be used to identify outliers for
both laboratory and field data. No data will be rejected simply because they are statistical outliers. However, Tetra
Tech will conduct a thorough check to identify the reasons for the outliers and will provide the EPA proj ect manager
with an explanation of why some data appear to be outliers.
12.3 Data Reporting
Each developer and STL Tampa East will prepare and submit data packages reporting the results of field and
laboratory measurements, respectively. STL Tampa East will also prepare and submit electronic data deliverables
(EDD). Tetra Tech will use the data submittals to prepare the ITVR for each field measurement device and the DER
for the entire demonstration. Described below are the data reporting requirements for (1) developer data packages,
(2) STL Tampa East data packages, (3) STL Tampa East EDDs, (4) ITVRs, and (5) the DER.
12.3.1 Developer Data Packages
The developers will compile field measurement device results on standard forms provided by Tetra Tech. The forms
will contain sample identification numbers and spaces for a developer to enter GRO, EDRO, and TPH results, as
appropriate.
12.3.2 STL Tampa East Data Packages
STL Tampa East will prepare full EPA CLP-style data packages in accordance with instructions provided in
Exhibit B of the most recent EPA CLP statement of work for organic analysis. Each full data package will contain
all the information in the summary data package and all associated raw data for the samples in one sample lot. A
sample lot is a group of 20 or fewer samples for a given work order that are received over a period of 14 days or less.
The summary data package will consist of a case narrative, copies of all associated chain-of-custody forms and
sample receipt notices, sample results, and QA/QC summaries. The case narrative will include the following items:
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• The laboratory name, project name, project number, sample lot number, and work order number as well as
a table that cross-references field and laboratory sample identification numbers
A general description of the work performed, including sample preparation and analysis procedures and
methods used
• A discussion of any deviations from the guidelines and procedures specified in the analytical method, work
order, or demonstration plan
A detailed discussion of all sample shipping, receipt, preparation, analysis, and QC deficiencies
Copies of all nonconformance and corrective action forms describing the nature of each nonconformance and
the reanalysis or other corrective action taken
• A thorough explanation of all cases of manual integration unless each manual integration and its rationale
are clearly indicated in the raw data sheets
A statement identifying samples whose results may have been impacted by baseline rise
The following statement, signed and dated by the laboratory project manager or a duly authorized designee,
with the signer's name and title clearly printed below:
"I certify that these data are technically accurate, complete, and in compliance with the terms and
conditions of the contract other than the conditions detailed above. Release of the data contained
in this hard copy data package and its electronic data deliverable submitted on diskette has been
authorized by the laboratory project manager or a designee as verified by the following signature."
All documentation in each full data package, including chromatograms, instrument printouts, calibration records, and
QC results, will be clearly labeled with the laboratory standard number or laboratory QC sample number, as
applicable. All raw data deliverables will be complete enough and presented in such a way that requantification of
the final results using the raw data would be possible and straightforward. Table 12-1 outlines the required full data
package format; this format reflects the ordering of a full data package for organic analysis in accordance with EPA
CLP statement of work OLM04.1 (EPA 1999).
When required by an analytical method, EPA CLP-style forms will be modified or supplemented with additional
information, forms, or documentation. STL Tampa East will provide Tetra Tech with two bound copies of each full
data package by July 31, 2000.
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Table 12-1. Full Data Package Format for Gasoline Range Organic and Extended Diesel Range Organic Analyses
Section I Case Narrative
1. Case narrative
2. Copies of nonconformance and corrective action forms
3. Chain-of-custody forms
4. Copies of condition upon sample receipt forms
Section II Sample Results for the following:
1. Environmental samples, including sample surrogate recoveries, dilutions, and reanalyses.
All results will include concentration units, reporting limits, and method detection limits.
Section III Quality Assurance and Quality Control Summary Results for the following:
1. Method and instrument blanks
2. Surrogate recoveries
3. Matrix spike and matrix spike duplicate recoveries and relative percent differences
4. Laboratory control sample and laboratory control sample duplicate recoveries and relative percent differences
5. Extract duplicate relative percent differences
6. Other quality control results, as applicable.
All results will include concentration units and reporting limits.
Section IV Sample Raw Data and all associated raw data for the following:
1. Environmental samples, including sample screenings, dilutions, and reanalyses.
All chromatograms will identify start and stop retention times used for integration.
Section V Quality Assurance and Quality Control Raw Data and all associated raw data for the following:
1. Method and instrument blanks
2. Matrix spike and matrix spike duplicate samples
3. Laboratory control samples and laboratory control sample duplicates
4. Extract duplicates
5. Other quality control results, as applicable.
All chromatograms will identify start and stop retention times used for integration.
Section VI Standard Raw Data and all associated raw data for the following:
1. Initial calibrations and retention time information
2. Continuing calibration verifications and retention time information
Section VII Other Raw Data
1. Percent moisture for soil samples for extended diesel range organic analysis
2. Sample extraction and cleanup logs
3. Instrument analysis log for each instrument used
4. Standard preparation logs specifying initial and final concentrations for each standard used
5. The formula and an example calculation for the initial calibration and continuing calibration
6. The formula and an example calculation for sample results
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The completed data packages will be approved by the STL Tampa East and Tetra Tech project managers before they
are used to prepare the ITVRs and DER.
12.3.3 STL Tampa East Electronic Data Deliverable^
For each sample lot, STL Tampa East will provide Tetra Tech with an EDD. All results for an sample lot will be
complied in one electronic file on a 3.5-inch computer diskette. The diskette will be clearly labeled with the
following information:
Laboratory name
Project name and number
• Sample lot number
• Work order number
EDD file name and date prepared
Creation of associated extract files will be an automated process. STL Tampa East will use an automated laboratory
information management system to produce the EDD in accordance with project requirements. Manual creation of
the deliverable (that is, data entry by hand) is unacceptable, and manual editing will be avoided or kept to a minimum.
STL Tampa East will verify all EDDs internally before submitting them to Tetra Tech. Each EDD will exactly
correspond to the hard copy data, and no duplicated data will be submitted. STL Tampa East will provide Tetra Tech
with one copy of each EDD by July 31, 2000.
12.3.4 Innovative Technology Verification Reports
In accordance with the demonstration plan, Tetra Tech will evaluate the performance and cost data collected for each
field measurement device demonstrated and will prepare an ITVR for the device. Each ITVR will be a focused report
of about 100 pages and will primarily include the following:
• An introduction
• A description of the field measurement device
• Site descriptions and the demonstration design
A description of the reference method and its performance
A description of the device's performance
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• An economic analysis
• A summary of demonstration results
Tetra Tech will prepare individual ITVRs in accordance with the format specified in the "Handbook for Preparing
Office of Research and Development Reports" (EPA 1995); its March 16,1998, update; and project-specific guidance
from the EPA project manager. The reports will be written in such a way that a reader with a basic science
background can understand their contents and make an informed decision regarding the performance of the devices.
The ITVRs will undergo a rigorous review process that will include reviews by the EPA project manager, the
developers, and external peer reviewers.
12.3.5 Data Evaluation Report
Tetra Tech will prepare a DER containing tabular summaries of investigative and QA/QC data from the
demonstration as well as results of technical system and performance audits. The DER will primarily discuss the
following:
Predemonstration investigation activities
Demonstration activities
• Postdemonstration activities
• Deviations from the demonstration plan
Investigative sample data
QA/QC data
• Audit results
12.4 Data Storage
The STL Tampa East analysts responsible for performing measurements will enter raw data into logbooks or on data
sheets. In accordance with standard document control procedures, the laboratory will maintain on file the original
logbooks or data sheets, which will be signed and dated by the laboratory analysts responsible for them. Similar
procedures will be used for all data entered directly into the laboratory information management system. Separate
instrument logs will also be maintained by the laboratory to allow reconstruction of the run sequences for individual
instruments. STL Tampa East will maintain all raw data, including raw instrument output on tape or diskette, on file
for 5 years after the submittal of the data packages to Tetra Tech. Data documents will be kept in secure archive file
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cabinets accessible only to designated laboratory personnel. The data will be disposed of upon receipt of EPA
instructions to do so or after 5 years, whichever is sooner.
A central project file for the demonstration will be established in the document control room of Tetra Tech's Chicago,
Illinois, office. This file will be a repository for all relevant field and laboratory project documentation. All project
documentation will be placed in the central file within 1 week of its receipt or generation by Tetra Tech. The
document control room will be accessible only to authorized personnel and will be secure. Tetra Tech will offer the
central file to the EPA at the end of the demonstration project but will maintain the central file until the end of the
SITE contract if requested to do so.
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Chapter 13
Health and Safety Procedures
This chapter defines health and safety requirements and designates protocols to be followed during demonstration
activities at the Navy BVC, Kelly AFB, and PC sites. These activities will include oversight of Geoprobe® operation,
soil sampling and sample management, and oversight of innovative TPH field measurement devices operation. This
chapter addresses items specified under Occupational Safety and Health Administration (OSHA) Title 29 of the CFR,
Section 1910.120 (b), "Final Rule," and will be available to all personnel who may be exposed to hazardous
conditions on site, including Tetra Tech, subcontractor, and developer personnel participating in the demonstration
and all site visitors, such as regulatory agency representatives. All personnel on site, including Tetra Tech and
subcontractor employees and site visitors, must be informed of site emergency response procedures and any potential
fire, explosion, health, or safety hazards associated with on-site activities. This chapter summarizes potential hazards
and defines protective measures planned for the demonstration activities. Developers, EPA personnel,
subcontractors, and site visitors may choose to follow the Tetra Tech health and safety procedures described in this
chapter. However, each employer is directly and fully responsible for the health and safety of its own employee;
Tetra Tech assumes no responsibility for non-Tetra Tech personnel.
The health and safety procedures described in this chapter have been reviewed and approved by the Tetra Tech HSR
or a designee and the Tetra Tech project manager (see the Reviews and Approvals form at the end of this chapter).
Protocols established in this chapter are based on site conditions, health and safety hazards known or anticipated to
be present on site, and available site data. The health and safety procedures described in this chapter are intended
solely for use during the proposed activities described in this demonstration plan. Specifications herein are subject
to review and revision based on actual conditions encountered in the field during demonstration activities. Significant
revisions to the health and safety procedures must be approved by the Tetra Tech project manager and the Tetra Tech
HSR. Tetra Tech employees must also follow safety requirements taught during safety training and described in the
Tetra Tech, Inc., "Health and Safety Manual."
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This chapter is organized in the following 10 sections:
Health and Safety Personnel and Procedure Enforcement (Section 13.1)
Site Background (Section 13.2)
• Site-Specific Hazard Evaluation (Section 13.3)
• Training Requirements (Section 13.4)
Personal Protection Requirements (Section 13.5)
Medical Surveillance (Section 13.6)
• Environmental Monitoring and Sampling (Section 13.7)
• Site Control (Section 13.8)
• Decontamination (Section 13.9)
• Emergency Response Planning (Section 13.10)
13.1 Health and Safety Personnel and Procedure Enforcement
This section describes responsibilities of project personnel; summarizes requirements for subcontractors, developers,
and visitors who wish to enter the Navy BVC, Kelly AFB, and PC sites; and discusses enforcement of health and
safety procedures.
13.1.1 Project Personnel
The following personnel and organizations are associated with planned activities at the demonstration sites. The
organizational structure will be reviewed and updated as necessary during the course of the project.
Name Responsibility Telephone No.
Client Representative:
Stephen Billets EPA project manager (702)798-2232
Site Representatives:
Navy BVC site: Ernest Lory Site contact (805)982-1299
Kelly AFB site: AmyWhitley Site contact (210)925-3100
PC site: Jay Simonds Site contact (317)228-6240
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Name
Tetra Tech Personnel:
Kirankumar Topudurti
Eric Monschein
Jill Ciraulo
Judith Wagner
Subcontractors:
Navy BVC site: Vironex
Environmental Field
Services
Kelly AFB site: Venture II
Environmental Drilling,
Inc.
Responsibility
Project manager
Field manager
Site safety coordinator (SSC)
HSR
Geoprobe® operator
Geoprobe® operator
PC site: Handex of Indiana Geoprobe® operator
Telephone No.
(312)856-8742
(312)856-8753
(312)946-6479
(847)818-7192
(800) 847-6639
(800) 662-5412
(317)228-6240
The Tetra Tech project manager, field manager, SSC, and HSR will be responsible for implementation and
enforcement of the health and safety procedures. Their duties and the expectations for Tetra Tech employees are
described in the following sections.
13.1.1.1
Project Manager and Field Manager
The Tetra Tech proj ect manager has ultimate responsibility for ensuring implementation of the requirements set forth
in this chapter. Some of this responsibility may be fulfilled through delegation of duties to site-dedicated personnel
that report directly to the project manager. The project manager will regularly confer with site personnel regarding
health and safety compliance.
The Tetra Tech field manager will oversee and direct demonstration activities and will have day-to-day responsibility
for ensuring implementation of the health and safety procedures. Subcontractor compliance with the health and
safety procedures will be monitored by the field manager. The field manager will report any health and safety-related
issues directly to the project manager.
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13.1.1.2 Site Safety Coordinator
The Tetra Tech SSC will be appointed by the Tetra Tech project manager and will be responsible for field
implementation of tasks and procedures discussed in this chapter, including air monitoring, establishing a
decontamination protocol, and ensuring the signing of the Daily Tailgate Safety Meeting form (Form HST-2 in
Appendix C) by all personnel working on site. The SSC will have advanced field work experience and will be
familiar with health and safety requirements specific to the project. The SSC will also maintain the Daily Site Log
(Form SSC-1 in Appendix C).
13.1.1.3 Health and Safety Representative
The Tetra Tech HSR is responsible for administration of the company health and safety program. The HSR will act
in an advisory capacity to the Tetra Tech project manager and personnel regarding project-specific health and safety
issues. The project manager will establish a liaison between representatives of the EPA; representatives of the Navy
BVC, Kelly AFB, and PC sites; and the HSR for matters relating to health and safety.
13.1.1.4 Tetra Tech Employees
Tetra Tech employees are expected to fully participate in implementing the site-specific health and safety procedures
by obtaining necessary training, attending site safety meetings, always wearing designated PPE, complying with site
safety and health rules, and advising the Tetra Tech SSC of health and safety concerns at the sites.
13.1.2 Subcontractors and Developers
Subcontractor personnel and the developers will be provided with a copy of this chapter. Subcontractor personnel
and the developers must comply with all applicable 29 CFR 1910.120 training, fit testing, and medical surveillance
requirements, as applicable. Subcontractors and the developers are responsible for providing PPE required for their
personnel (see Section 13.5.1, Protective Equipment and Clothing) and are directly responsible for the health and
safety of their employees. The developers will have access only to the PRA at the Navy BVC site.
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13.1.3 Visitors
All site visitors will be briefed on the site-specific health and safety procedures. Site visitors will be escorted by
Tetra Tech personnel during the visitors' day activities.
13.1.4 Health and Safety Procedure Enforcement
The health and safety procedures described in this chapter apply to all demonstration activities and all Tetra Tech
personnel working on the Navy BVC, Kelly AFB, and PC sites. Violators of the procedures will be verbally notified
upon the first violation, and the violation will be noted by the Tetra Tech SSC in a field logbook. Upon a second
violation, the violator will be notified in writing, and the Tetra Tech project manager and the violator's supervisor
will be notified. A third violation will result in a written notification and the violator's eviction from the site. The
written notification will be sent to Tetra Tech human resources development and the Tetra Tech HSR.
Personnel will be encouraged to report to the Tetra Tech SSC any conditions or practices that they consider to be
detrimental to their health or safety or that they believe are in violation of applicable health and safety standards.
Such reports may be made orally or in writing. Personnel who believe that an imminent danger threatens human
health or the environment will be encouraged to bring the matter to the immediate attention of the SSC for resolution.
At least one copy of this chapter will be available on site for all site personnel. Minor changes to the health and
safety procedures discussed in this chapter will be discussed at the beginning of each work day by the SSC at the
daily tailgate safety meeting and will be noted in the field logbook. Significant procedure revisions must be discussed
with the Tetra Tech HSR and project manager.
13.2 Site Background
The following sections describe the demonstration sites and the activities planned for the demonstration.
13.2.1 Demonstration Site Descriptions
Chapter 3 describes the Navy BVC, Kelly AFB, and PC sites. Figures showing the site locations and layouts are also
included in Chapter 3.
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13.2.2 Planned Demonstration Activities
Sample collection and handling procedures to be followed at each of the three sites are fully described in Chapter 7.
The planned demonstration activities include the following tasks:
Oversight of soil sample collection using a subcontractor-operated Geoprobe® at the Kelly AFB and PC sites
and in two areas of the Navy BVC site (the FFA and NEX Service Station Area)
• Collection of soil samples by Tetra Tech in the PRA of the Navy BVC site using a Split Core Sampler
• Management of all soil samples collected at the Navy BVC, Kelly AFB, and PC sites including sectioning
core tube liners, characterizing soil samples, homogenizing soil samples, preparing samples for shipment to
STL Tampa East, and transferring samples to the developers at the Navy BVC site
• Oversight of TPH field measurement activities at the Navy BVC site
13.3 Site-Specific Hazard Evaluation
Demonstration activities and physical features of the demonstration sites may expose field personnel to a variety of
hazards. This section provides information on potential hazards related to demonstration activities and the nature
of hazardous material impacts. Potential chemical and physical hazards related to demonstration activities are
discussed below.
13.3.1 Chemical Hazards
Chemical hazards that may be encountered at the sites involve volatile organic compounds (VOC), inorganic
compounds, and petroleum hydrocarbons. The results of previous site investigations indicate that VOCs and
inorganic compounds are present in the three sites. A summary of site characteristics, including TPH concentrations,
based on data collected during the predemonstration investigation is presented in Table 3-1 of Chapter 3. General
information on VOCs and inorganic compounds at the sites is provided in Sections 13.3.1.1 and 13.3.1.2,
respectively. A hazard evaluation of petroleum distillate fuel products is provided in Tetra Tech Safe Work Practice
(SWP) 6-25, which will be available on site. These chemicals pose various physical, chemical, and toxicological
hazards. Potential routes of exposure to these chemicals include dermal (skin) contact, inhalation, and ingestion.
The chemicals may also contaminate equipment, vehicles, instruments, and personnel. The overall health threat
associated with exposure to these chemicals is uncertain because (1) actual concentrations that personnel could be
exposed to cannot be predicted, (2) the actual duration of exposure is unknown, and (3) the effects of low-level
exposure to a mixture of chemicals cannot be predicted. However, Tetra Tech believes that the potential for high-
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level exposure is limited. Table 13-1 provides a task hazard analysis of the planned demonstration activities listed
in Section 13.2.2.
Table 13-2 lists the materials, which may be brought to the sites by Tetra Tech or the developers. Material Safety
Data Sheets (MSDS) summarize health and safety information for hazardous materials that will be brought to the
Navy BVC site, such as laboratory reagents, decontamination solutions, and sample preservatives. Tetra Tech and
the developers are responsible for making the MSDSs available on site as specified in Table 13-2.
13.3.1.1 Volatile Organic Compounds
Generally, VOCs are central nervous system depressants. Exposure to some VOCs may occur through skin
absorption. General symptoms of VOC exposure, both acute and chronic, may include euphoria, headache, weakness,
dizziness, nausea, narcosis, and possibly coma. Certain VOCs are also skin and eye irritants.
13.3.1.2 Inorganic Compounds
Inorganic compounds do not have carbon in their molecular structure. Heavy metals such as lead are inorganic
compounds. The symptoms of acute exposure to inorganic compounds include but are not restricted to abdominal
pain, hypertension, anemia, insomnia, and restrictive pulmonary function. Chronic exposure to some metals may lead
to development of cancer.
13.3.2 Physical Hazards
Physical hazards associated with demonstration activities present a potential threat to on-site personnel. Dangers are
posed by heavy equipment, utility and power lines, slippery surfaces, unseen obstacles, noise, heat, cold, and poor
illumination.
Injuries may result, for example, from the following:
Accidents caused by slipping, tripping, or falling
Use of improper lifting techniques
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Table 13-2. Demonstration Participant Responsibilities for Providing Material Safety Data Sheets
Participant Responsible for Providing Material Safety Data Sheet
CHEMetrics
Wilks
Horiba
Dexsil®
ESC
site LAB®
SDI
Tetra Tech EM Inc.
Chemical
Aluminum chloride, anhydrous
Dichloromethane
Sodium sulfate, anhydrous, crystalline
Freon 113
Sodium sulfate, anhydrous, crystalline
Vertrel® MCA, a hydrochlorofluorocarbon extraction solvent
Chlorobenzene
Diesel calibration standard
Hexadecane
Isooctane
S-316 extraction solvent
Sodium sulfate, anhydrous, crystalline
Spiking material
Developer solution
Methanol-based extraction solvent
Mineral oil
Anthracene
Methanol
Naphthalene
Calibration standards
Methanol
Detergent solution
Hydrogen peroxide
m-Xylene
Methanol
Phosphate buffer solution
Sulfuric acid, 0.5 percent
Tetramethylbenzidine
Alconox®
• Use of moving or rotating equipment
• Equipment mobilization and operation (such as electrocution from contact with overhead or underground
power lines)
Use of improperly maintained equipment
Injuries resulting from physical hazards can be avoided by using SWPs and employing caution when working with
machinery. Specific SWPs applicable to the demonstration are listed in Section 13.8.5 and will be available on site
during the demonstration. To ensure safe working conditions, the Tetra Tech SSC will conduct and document regular
safety inspections and will make sure that all workers and visitors are informed of any potential physical hazards
related to the sites. Additional physical hazards that have been identified at the sites include the following:
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• Use of instruments powered by DC
• Use of instruments with ultraviolet or infrared light sources
13.4 Training Requirements
All Tetra Tech personnel who may be exposed to hazardous conditions on site will be required to meet training
requirements outlined in 29 CFR 1910.120, "Hazardous Waste Operations and Emergency Response." All personnel
and visitors entering the sites will be required to sign the Daily Tailgate Safety Meeting form (Form HST-2 in
Appendix C).
Before activities begin at the Navy BVC site, the Tetra Tech SSC will present a briefing for all personnel who will
participate in on-site activities. The following topics will be addressed during the prework briefing:
• Names of the SSC and a designated alternate
• Site history
• Work tasks
• Hazardous chemicals that may be encountered on site
• Physical hazards that may be encountered on site
• PPE, including type or types of respiratory protection to be used for work tasks
• Training requirements
• Environmental surveillance (air monitoring) equipment use and maintenance
• Action levels and situations requiring upgrade or downgrade of level of protection
• Site control measures, including site communications, control zones, and SWPs
• Decontamination procedures
• Emergency communication signals and codes
• Environmental accident emergency procedures (in case contamination spreads outside the exclusion zone)
• Personnel exposure and accident emergency procedures (in case of falls, exposure to hazardous substances,
and other hazardous situations)
• Fire and explosion emergency procedures
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• Emergency telephone numbers
• Emergency routes
Any other health and safety-related issues that may arise before on-site activities begin will also be discussed during
the prework briefing.
Issues that arise during implementation of on-site activities will be addressed during tailgate safety meetings to be
held daily before the workday or shift begins. Such issues will be documented in the Daily Tailgate Safety Meeting
form (Form HST-2 in Appendix C). Any changes in procedures or site-specific health and safety-related matters will
be addressed during these meetings.
13.5 Personal Protection Requirements
The levels of personal protection to be used for work tasks at the Navy BVC, Kelly AFB, and PC sites have been
selected based on known or anticipated physical hazards; types and concentrations of contaminants that may be
encountered on site; and contaminant properties, toxicity, exposure routes, and matrixes. The following sections
describe protective equipment and clothing; reassessment of protection levels; limitations of protective clothing; and
respirator selection, use, and maintenance.
13.5.1 Protective Equipment and Clothing
Personnel will wear protective equipment when (1) demonstration activities involve known or suspected atmospheric
contamination; (2) demonstration activities may generate vapors, gases, or particulates; or (3) direct contact with
hazardous materials may occur. The anticipated levels of protection selected for use by field personnel during
demonstration activities are listed in Table 13-1, Task Hazard Analysis. Based on the anticipated hazard level,
personnel will initially perform field tasks in Level D or Modified Level D protection. If site conditions or the results
of air monitoring performed during on-site activities warrant a higher level of protection, all field personnel will
withdraw from the site, immediately notify the Tetra Tech SSC, and wait for further instructions. Descriptions of
equipment and clothing required for Level D, Modified Level D, Level C, and Level B protection are provided below.
• Level D
Coveralls or work clothes, if applicable
Boots with steel-toe protection and steel shanks
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A hard hat (face shield optional), if applicable
Disposable gloves (latex or nitrile), if applicable
Safety glasses or goggles
Hearing protection (for areas with a noise level exceeding 85 decibels on the A-weighted scale)
Modified Level D
Coveralls or work clothes, if applicable
Chemical-resistant clothing (such as Tyvek® or Saranex® coveralls)
Outer gloves (neoprene, nitrile, or other), if applicable
Disposable inner gloves (latex or vinyl)
Boots with steel-toe protection and steel shanks
Disposable boot covers or chemical-resistant outer boots
Safety glasses or goggles
A hard hat (face shield optional)
Hearing protection (for areas with a noise level exceeding 85 decibels on the A-weighted scale)
Level C
Coveralls or work clothes, if applicable
Chemical-resistant clothing (such as Tyvek® or Saranex® coveralls)
Outer gloves (neoprene, nitrile, or other), if applicable
Disposable inner gloves (latex or vinyl)
Boots with steel-toe protection and steel shanks
Disposable boot covers or chemical-resistant outer boots
A full- or half-face, air-purifying respirator with National Institute for Occupational Safety and
Health (NIOSH)-approved cartridges to protect against organic vapors, dust, fumes, and mists
(cartridges used for gas and vapors must be replaced in accordance with the change-out schedule
described in the Respiratory Hazard Assessment form [Form RP-2 in Appendix C])
Safety glasses or goggles (with half-face respirator only)
A hard hat (face shield optional)
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Hearing protection (for areas with a noise level exceeding 85 decibels on the A-weighted scale)
Level B
Chemical-resistant clothing (such as Tyvek® or Saranex® coveralls)
Outer gloves (neoprene, nitrile, or other)
Disposable inner gloves (latex or vinyl)
Boots with steel-toe protection and steel shanks
Disposable boot covers or chemical-resistant outer boots
A NIOSH-approved, pressure-demand airline respirator with a 5-minute escape cylinder or self-
contained breathing apparatus (SCBA)
A hard hat (face shield optional)
Hearing protection (for areas with a noise level exceeding 85 decibels on the A-weighted scale)
13.5.2 Reassessment of Protection Levels
PPE levels will be upgraded or downgraded based on a change in site conditions or investigation findings. When
a significant change in site conditions occurs, hazards will be reassessed. Some indicators of the need for
reassessment are as follows:
• Commencement of a new work phase, such as the start of a significantly different sampling activity or work
that begins on a different portion of a site
A change in job tasks during a work phase
A change of season or weather
• Temperature extremes or individual medical considerations limiting the effectiveness of PPE
Discovery of contaminants other than those previously identified
A change in ambient levels of airborne contaminants (see the action levels listed in Table 13-3)
A change in work scope that affects the degree of contact with contaminated media
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13.5.3 Limitations of Protective Clothing
PPE clothing ensembles designated for use during demonstration activities have been selected to provide protection
against contaminants at known or anticipated on-site concentrations and physical states. However, no protective
garment, glove, or boot is entirely chemical-resistant, and no protective clothing provides protection against all types
of chemicals. Permeation of a given chemical through PPE depends on the contaminant concentration, environmental
conditions, physical condition of the protective garment, and resistance of the garment to the specific contaminant.
Chemical permeation may continue even after the source of contamination has been removed from the garment.
All on-site personnel will use the procedures presented below to obtain optimum performance from PPE.
• When chemical-protective coveralls become contaminated, don a new, clean garment after each rest break
or at the beginning of each shift.
Inspect all clothing, gloves, and boots both before and during use for the following:
Imperfect seams
Nonuniform coatings
Tears
Poorly functioning closures
Inspect reusable garments, boots, and gloves both before and during use for visible signs of chemical
permeation, such as the following:
Swelling
Discoloration
Stiffness
Brittleness
Cracks
Any sign of puncture
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Any sign of abrasion
Reusable gloves, boots, or coveralls exhibiting any of the characteristics listed above must be discarded. Reusable
PPE will be decontaminated in accordance with procedures described in Section 13.9 and will be neatly stored in the
support zone away from work zones.
13.5.4 Respirator Selection, Use, and Maintenance
Tetra Tech personnel will be informed of the proper use, maintenance, and limitations of respirators during annual
health and safety refresher training and the prework briefing. Any on-site personnel who will use a tight-fitting
respirator must pass a qualitative fit test for the respirator that follows the fit testing protocol provided in Appendix A
of the OSHA respirator standard (29 CFR 1910.134). Fit testing must be repeated annually or when a new type of
respirator is used.
Respirator selection is based on assessment of the nature and extent of hazardous atmospheres anticipated during
demonstration activities. This assessment will include a reasonable estimate of employee exposure to respiratory
hazards and identification of each contaminant's anticipated chemical form and physical state.
For each work task requiring respirator use at the Navy BVC, Kelly AFB, and PC sites, a respiratory hazard
assessment will be conducted. A blank Respiratory Hazard Assessment form (Form RP-2) is included in Appendix C.
Amendments to the health and safety procedures described in this chapter and to Form RP-2 will be discussed during
daily tailgate safety meetings and will be documented in the field logbook.
When an atmospheric contaminant is an identified gas or vapor and its concentration is known or can be reasonably
estimated, respiratory protection options include the following:
• An atmosphere-supplying respirator (air-line or SCBA)
• An air-purifying respirator equipped with a NIOSH-certified, end-of-service-life indicator (ESLI) for the
identified contaminant. If no ESLI is available, a change-out schedule for cartridges must be developed
based on objective data or information. Respirator cartridge selection and change-out schedules will be
evaluated by the HSR at the time of the respiratory hazard assessment. The Respiratory Hazard Assessment
form (Form RP-2) will describe the data used as the basis for the cartridge change-out schedule and the
proposed change schedule.
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For protection against participate contaminants, approved respirators can include the following:
An atmosphere-supplying respirator
A respirator equipped with a filter certified by NIOSH under 32 CFR Part 11 or 42 CFR Part 84 as a PI00
filter (formerly known as a high-efficiency particulate [HEPA] air filter)
For any tasks performed in Level C PPE, a full- or half-face, air-purifying respirator equipped with NIOSH-approved
cartridges or filters will be selected to protect against vapors, gases, and aerosols.
Air-purifying respirators will be used only in conjunction with breathing-space air monitoring, which must be
conducted in adherence to the action levels outlined in Table 13-3. Air-purifying respirators will be used only when
they can provide protection against the substances encountered on site.
Factors precluding use of Level C and air-purifying respirators are as follows:
• Oxygen-deficient atmosphere (less than 19.5 percent oxygen)
• Concentrations of substances that may be immediately dangerous to life and health
• Confined or unventilated areas that may contain airborne contaminants not yet characterized
• Unknown contaminant concentrations or concentrations that may exceed the maximum use levels for
designated cartridges documented in the selected cartridge manufacturer's instructions
Unidentified contaminants
High relative humidity (more than 85 percent, which reduces the sorbent life of the cartridges)
Respirator cartridges with an undetermined service life
Use, cleaning, and maintenance of respirators are described in Tetra Tech SWP 6-27, Respirator Cleaning Procedures,
and SWP 6-28, Safe Work Practices for Use of Respirators.
13.6 Medical Surveillance
The following sections describe Tetra Tech's medical surveillance program, including health monitoring
requirements, site-specific medical monitoring, and medical support and follow-up requirements. Procedures
documented in these sections will be followed for all activities at the Navy BVC, Kelly AFB, and PC sites.
Additional requirements are defined in the Tetra Tech, Inc., "Health and Safety Manual."
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13.6.1 Health Monitoring Requirements
All Tetra Tech personnel involved in on-site activities at the Navy BVC, Kelly AFB, and PC sites must participate
in a health monitoring program as required by 29 CFR 1910.120(f). Tetra Tech has established a health monitoring
program with WorkCare, Inc., of Orange, California. Under this program, Tetra Tech personnel receive baseline and
annual or biennial physical examinations consisting of the following:
• Complete medical and work history
• Physical examination
• Vision screening
• Audiometric screening
• Pulmonary function test
• Resting electrocardiogram
Chest x-ray (required once every 3 years)
Blood chemistry, including hematology and serum
• Urinalysis
For each employee, Tetra Tech receives a copy of the examining physician's written opinion after postexamination
laboratory tests have been completed; the Tetra Tech employee also receives a copy of the written opinion. This
opinion includes the following information (in accordance with 29 CFR 1910.120[f][7]):
The results of the medical examination and tests
The physician's opinion as to whether the employee has any medical conditions that would place the
employee at an increased risk of health impairment from work involving hazardous waste operations or
during an emergency response
The physician's recommended limitations, if any, on the employee's assigned work; special emphasis is
placed on fitness for duty, including the ability to wear any required PPE under conditions expected on site
(for example, temperature extremes)
A statement that the employee has been informed by the physician of the medical examination results and
of any medical conditions that require further examination or treatment
All subcontractors must have health monitoring programs conducted by their own clinics in compliance with 29 CFR
1910.120(f). Any visitor or observer at the site will be required to provide records in compliance with 29 CFR
1910.120(f) before entering the site.
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13.6.2 Site-Specific Medical Monitoring
For activities at the Navy BVC, Kelly AFB, and PC sites, no specific medical tests will be required before individuals
enter the exclusion zone or decontamination zone (see Section 13.8.2, Site Control Zones).
13.6.3 Medical Support and Follow- Up Requirements
As a follow-up to an injury requiring care beyond basic first aid or to possible exposure above established exposure
limits, all Tetra Tech employees are entitled to and encouraged to seek medical attention and physical testing. Such
injuries and exposures must be reported to the Tetra Tech HSR. Depending on the type of injury or exposure, follow-
up testing, if required, must be performed within 24 to 48 hours of the incident. It will be the responsibility of Tetra
Tech's medical consultant to advise the type of test required to accurately monitor for exposure effects. The Accident
and Illness Investigation Report (Form AR-1 in Appendix C) must be completed by the Tetra Tech SSC in the event
of an accident, illness, or injury. A copy of this form must be forwarded to the HSR for use in determining the
recordability of the incident and for inclusion in Tetra Tech's medical surveillance records.
13.7 Environmental Monitoring and Sampling
Environmental monitoring or sampling will be conducted to assess personnel exposure levels as well as site or
ambient conditions and to determine appropriate levels of PPE for work tasks. The following sections discuss initial
and background air monitoring, personal monitoring, ambient air monitoring, monitoring parameters and devices,
use and maintenance of survey equipment, thermal stress monitoring, and noise monitoring. Site-specific air
monitoring requirements and action levels are provided in Table 13-3.
13.7.1 Initial and Background Air Monitoring
Initial air monitoring of the work area will be performed before a work task begins. This monitoring will be
performed using real-time field survey instrumentation. Air will also be monitored at the beginning of each workday
to identify any potentially hazardous situation that might have developed during off-shift periods.
Operations at the sites may result in variable background levels of airborne compounds. Airborne compounds may
be released from vehicles, blowing dust, material transfers, and so on. These sources can complicate evaluation of
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contaminant emissions during project tasks. Therefore, several upwind and prework measurements will be taken to
assess contributions to airborne contamination by other potential sources.
13.7.2 Personal Monitoring
The employees working closest to a source of contamination have the highest likelihood of exposure to airborne
contaminant concentrations that may exceed established exposure limits. Therefore, selective monitoring of the
workers who are closest to a source of contaminant generation will be conducted during demonstration activities.
Personal monitoring will be conducted in the breathing zone and, if a worker is wearing respiratory protective
equipment, outside the face piece.
13.7.3 Ambient Air Monitoring
Most tasks will require monitoring of the general work area or ambient site conditions. Ambient monitoring will
generally be conducted using direct-reading survey instrumentation or compound-specific instruments or detector
tubes.
Initial ambient air monitoring will be performed as a minimum requirement when any of the situations listed below
arise.
Work begins on a different portion of a site.
Contaminants other than those previously identified are encountered.
A different type of operation is initiated
Workers handle leaking containers or work in areas with obvious liquid contamination (for example, spill
or lagoon areas).
• Obvious lithologic changes are noticed during drilling activities.
• Workers experience physical difficulties.
Periodic ambient air monitoring will be performed at the frequency listed in Table 13-3.
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13.7.4 Monitoring Parameters and Devices
The following sections briefly describe the use and limitations of instruments used to monitor for organic vapors,
known compounds, combustible atmospheres, percent oxygen, external exposure to radiation, and particulates. Site-
specific air monitoring requirements and action levels are listed in Table 13-3.
All monitors will be calibrated in accordance with manufacturer recommendations at the beginning of every workday,
if possible. Calibration results along with air monitoring data will be recorded in the field logbook.
13.7.4.1 Organic Vapors
A direct-reading organic vapor monitor, such as an FID or a PID, will be used to determine the presence of VOCs.
Table 13-3 specifies the instrument that will be used for the demonstration. The concentrations of individual VOCs
of concern cannot usually be determined using this instrument because the detector responds to the total VOC
mixture.
13.7.4.2 Known Compounds
Compound-specific monitoring will not be conducted during the demonstration. However, if individual compounds
must be identified, compound-specific instrumentation or colorimetric detector tubes may be required. Generally,
action levels for known compounds are set at one-half the permissible exposure limit (PEL) or threshold limit value
(TLV) of the compound with the lowest PEL or TLV.
13.7.4.3 Combustible Atmospheres
When a flammable compound reaches a certain concentration in air, it can become explosive when exposed to an
ignition source. The lowest concentration able to support combustion is known as the lower explosive limit (LEL).
Each flammable compound has its own LEL. Monitoring indicates how close to this limit the airborne concentration
of a flammable compound is. Demonstration activities will cease when the airborne concentration of any flammable
vapor or gas reaches 25 percent of its LEL (10 percent in a confined space). The monitoring device, monitoring
frequency, and general action levels for combustible atmospheres to be used during demonstration activities are
outlined in Table 13-3.
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13.7.4.4 Percent Oxygen
Hazardous conditions exist whenever the oxygen level is too high or too low. Monitoring for percent oxygen is
conducted to verify that a safe oxygen level is present for work activities. Workers must never enter or remain in
low-oxygen atmospheres unless they are wearing supplied air respirators (air-line or SCBA). An oxygen-enriched
atmosphere is hazardous because it causes an increased risk of fire. Based on the expected work conditions at the
sites, percent oxygen monitoring is not required for the demonstration.
13.7.4.5 External Exposure to Radiation
Based on site conditions, no radiation hazard is expected to be encountered at any of the sites. Therefore, radiation
monitoring will not be conducted during the demonstration. However, if the potential for external exposure to
radiation exists, all personnel will be required to wear radiation exposure monitoring devices while working on site.
Personal exposure monitoring devices may include a thermoluminescence detector (TLD), a standard film badge, or
a pocket dosimeter. Monitoring devices are to be left on site at the end of each working day in a location removed
from any source material. An outside vendor will supply TLDs, film badges, or dosimeters and will perform
laboratory analyses on TLDs and film badges. The external radiation exposure limit for on-site personnel will be
1.25 Roentgen-equivalent man units (Rem) per 3 months with a 5-Rem maximum per year.
If necessary, radiation detectors will be used to determine the types and levels of radiation present on site.
Appropriate instrumentation, such as alpha or gamma meters and Geiger counters, will be used.
13.7.4.6 Particulates
Based on site conditions, no particulate hazard is expected to be encountered at any of the sites. Therefore,
particulate monitoring will not be conducted during the demonstration. Aerosols are a group of airborne materials
that include particulates, fumes, mists, and smoke. Particulates are the primary aerosol of concern at hazardous waste
sites. If climatic conditions, surface soil conditions, or site operations (such as excavation activities) adversely impact
ambient air quality by increasing particulate matter for extended periods of time, air monitoring using a direct-reading
instrument for particulates may become necessary. If elevated (visible) particulate matter conditions persist for
5 minutes or longer, the Tetra Tech SSC is responsible for sampling the breathing zone with a particulate monitor.
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Generally, particulate monitors are capable of measuring both solid and liquid particulates within the size range of
0.1 to 10 (im (the respirable range). A monitor indicates the concentration of these particulates in units of mg per
cubic meter of air.
Action levels for particulates will be based on the type of dust and hazardous materials that may contribute to the
composition of the particulates and will be determined with the assistance of the Tetra Tech HSR or a designee.
13.7.5 Use and Maintenance of Survey Equipment
All personnel using field survey equipment must have training in its operation, limitations, and maintenance.
Maintenance and internal or electronic calibration will be performed in accordance with manufacturer
recommendations by individuals familiar with the equipment before its use on site. Repairs, maintenance, and
internal or electronic calibration of the equipment will be recorded in equipment maintenance logbooks. The
equipment maintenance logbook for each instrument will be kept in that instrument's case. For rented monitoring
equipment, repairs and maintenance will be conducted by the rental company. Results of routine calibration will be
recorded in the field logbook.
Air monitoring equipment (such as combustible gas indicators, oxygen meters, and PIDs) will be calibrated before
work begins. Only basic maintenance (such as changing batteries) will be performed by on-site personnel. Any
additional maintenance or repairs will be performed by a trained service technician.
13.7.6 Thermal Stress Monitoring
Heat stress and cold stress are common and serious threats at hazardous waste sites. SWPs 6-15 and 6-16 discuss
heat and cold stress, respectively, and include monitoring methods appropriate for the season and location of work.
Based on anticipated site conditions during the demonstration, SWP 6-15 will be available on site.
13.7.7 Noise Monitoring
In most cases, high noise levels at a work site are caused by heavy equipment, such as drill rigs and backhoes, or
sources associated with the work site, such as factory equipment and vehicles. When noise levels at the Navy BVC,
Kelly AFB, or PC site are suspected to equal or exceed an 8-hour time-weighted average (TWA) of 85 decibels on
an A-weighted scale in slow response mode (dBA), the Tetra Tech SSC will evaluate the work area to characterize
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the noise source and exposure levels. The SSC will use a simple rule-of-thumb test to determine whether noise levels
exceed 85 dBA. The test requires the SSC to determine how loudly he must speak to be heard at an arm's length from
another person. If the SSC must raise his voice to be heard, the average noise level likely exceeds 85 dBA.
If employees are exposed to noise levels that exceed the action level of 85 dBA, hearing protection must be worn.
The protectors will be ear plugs or muffs that provide sufficient attenuation to limit noise exposure to less than
85 dBA. The SSC will supervise use of hearing protectors on site, as necessary. Table 13-3 lists the monitoring
method and action level to be used.
13.8 Site Control
Site control is an essential component of implementing health and safety procedures. The following sections discuss
measures and procedures for site control, including on-site communications, site control zones, site access control,
site safety inspections, and SWPs.
13.8.1 On-Site Communications
Successful communication between field teams and personnel in the support zone is essential. The following
communication systems will be available during demonstration activities:
• Cellular telephones
• Hard-wired telephones in the sample management trailer in the PRA at the Navy BVC site
The hand signals listed below will be used by on-site personnel in emergency situations or when verbal
communication is difficult.
Signal Definition
Hands clutching throat Out of air or cannot breathe
Hands on top of head Need assistance
Thumbs up Okay, I am all right, or I understand
Thumbs down No or negative
Arms waving upright Send backup support
Gripping partner's wrist Exit area immediately
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13.8.2 Site Control Zones
To control the spread of contamination and employee exposures to chemical and physical hazards, on-site work areas
may be divided into an exclusion zone, a decontamination zone, and a support zone. Access to the exclusion and
decontamination zones will be restricted to authorized personnel. Any visitors to these areas must present proper
identification and be authorized to be on site. The Tetra Tech SSC will identify work areas that visitors or personnel
are authorized to enter and will enforce site control measures.
The following sections describe the exclusion zone, the decontamination zone, and the support zone as well as
procedures to be followed in each.
13.8.2.1 Zone 1: Exclusion Zone
An exclusion zone includes areas where contamination is either known or likely to be present or, because of work
activity, has the potential to cause harm to personnel. The perimeter of the exclusion zone and an appropriate radius
around work task areas will be demarcated by a physical barrier, such as barricade tape or traffic cones, to restrict
access. A daily roster with the date of each person's entrance into the exclusion zone; the person's name, signature,
and organization; and the time of entry and exit will be kept for all personnel working in the zone. Visitors will not
be permitted to enter the exclusion zone without proper qualifications, equipment, and Tetra Tech SSC authorization.
Work tasks that may require establishment of an exclusion zone include the following:
Collection of soil samples using a Geoprobe® or Split Core Sampler
Sample management activities in the PRA
13.8.2.2 Zone 2: Decontamination Zone
A decontamination zone will be required at the Navy BVC, Kelly AFB, and PC sites. The decontamination zone will
contain facilities to decontaminate personnel and portable equipment. The equipment decontamination procedures
that Tetra Tech will follow are described in Section 7.3. Decontamination of Geoprobe® components will be
performed by the Geoprobe® operators. Visitors will not be permitted to enter the decontamination zone without
proper qualifications and Tetra Tech SSC authorization.
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13.8.2.3 Zone 3: Support Zone
A support zone may consist of any uncontaminated and nonhazardous part of a site. The support zone should be
situated in an area generally upwind of any exclusion zone and in a location where the chance of encountering
hazardous materials or conditions is minimal. Site visitors not meeting the training, medical surveillance, and PPE
requirements defined in this chapter must stay in the support zone.
13.8.3 Site Access Control
The PRA and FFA at the Navy BVC site are fully fenced, and access to this site is controlled by a security system
that requires visitor passes to be issued before access is allowed. The NEX Service Station Area, however, is not
fenced; site representatives will be present during sampling in this area to control visitor access.
The sampling area at the Kelly AFB site is bounded by a locked, chain-link fence. Tetra Tech and subcontractor
personnel will be escorted by the demonstration representative while on site.
The sampling area at the PC site is generally bounded by fencing. Tetra Tech and subcontractor personnel will be
escorted by the PC site environmental contractor at all times.
13.8.4 Site Safety Inspections
Periodic site safety inspections will be conducted by the Tetra Tech SSC to ensure safe work areas and compliance
with the health and safety procedures described in this chapter. Results of the site safety inspections will be recorded
in the field logbook or on a Field Audit Checklist (Form AF-1 in Appendix C).
13.8.5 Safe Work Practices
The following SWPs apply to the demonstration activities. These SWPs will be available on site.
SWP 6-1, General Safe Work Practices
• SWP 6-14, Spill and Discharge Control Practices
SWP 6-15, Heat Stress
SWP 6-25, Oil and Petroleum Distillate Fuel Product Hazards
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• SWP 6-27, Respirator Cleaning Procedures
• SWP 6-28, Safe Work Practices for Use of Respirators
13.9 Decontamination
Decontamination is the process of removing or neutralizing contaminants on personnel or equipment. When properly
conducted, decontamination procedures protect workers from contaminants that may have accumulated on PPE, tools,
and other equipment. Proper decontamination also prevents transport of potentially harmful materials to
uncontaminated areas. Personnel and equipment decontamination procedures are described in the following sections.
13.9.1 Personnel Decontamination
Personnel decontamination at the demonstration sites will be limited by using disposable PPE whenever possible.
Any personnel decontamination procedures will follow guidance in the Occupational Safety and Health Guidance
Manual for Hazardous Waste Site Activities (NIOSH and others 1985). Personnel and PPE will be decontaminated
with potable water or a mixture of detergent and water. Liquid and solid wastes generated during decontamination
will be collected and drummed.
The decontamination procedures listed below will be conducted if personnel decontamination is required.
• Wash neoprene boots or disposable booties with a Liquinox® or Alconox® solution, and rinse them with
water. Remove and retain neoprene boots for reuse, if possible. Place disposable booties in plastic bags for
disposal.
• Wash outer gloves in a Liquinox® or Alconox® solution, and rinse them in water. Remove outer gloves, and
place them in a plastic bag for disposal.
Remove chemical-resistant clothing, and place it in a plastic bag for disposal.
Remove the air-purifying respirator, if used, and place the spent filter in a plastic bag for disposal. Change
the filter in accordance with the Respiratory Hazard Assessment form (Form RP-2 in Appendix C). Clean
and disinfect the respirator in accordance with SWP 6-27, and place it in a plastic bag for storage.
Remove inner gloves, and place them in a plastic bag for disposal.
Thoroughly wash the hands and face with water and soap.
Used, disposable PPE will be collected in scalable containers and will be disposed of in accordance with procedures
described in Section 7.3. Personnel decontamination procedures may be modified on site, if necessary.
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13.9.2 Equipment Decontamination
Decontamination of all sampling and field monitoring equipment used during demonstration activities will be
required. Decontamination of Geoprobe® components will be performed by the Geoprobe® operators.
Sampling equipment such as the Split Core Sampler will be decontaminated before and after each use as described
below.
• Scrub the equipment with a brush in a bucket containing Liquinox® or Alconox® solution and distilled water.
• Triple-rinse the equipment with distilled water, and allow it to air-dry.
• Reassemble the equipment, and place it on plastic or aluminum foil in a clean area. If aluminum foil is used,
wrap the equipment with the dull side of the aluminum foil toward the equipment.
13.10 Emergency Response Planning
This section describes emergency response planning procedures to be implemented for the demonstration. This
section is consistent with local, state, and federal disaster and emergency management plans. The following sections
discuss pre-emergency planning, personnel roles and lines of authority, emergency recognition and prevention,
evacuation routes and procedures, emergency contacts and notifications, hospital route directions, emergency medical
treatment procedures, protective equipment failure, fire or explosion, weather-related emergencies, spills or leaks,
emergency equipment and facilities, and reporting.
13.10.1 Pre-Emergency Planning
During the prework briefing and daily tailgate safety meetings, all on-site employees will be trained in and reminded
of the provisions of Section 13.10, site communication systems, and site evacuation routes. The emergency response
provisions will be reviewed on a regular basis by the Tetra Tech SSC and will be revised, if necessary, to ensure that
they are adequate and consistent with prevailing site conditions.
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13.10.2 Personnel Roles and Lines of Authority
The Tetra Tech SSC has primary responsibility for responding to and correcting emergency situations and for taking
appropriate measures to ensure the safety of on-site personnel and the public. Possible actions may include
evacuation of personnel from site areas. The SSC is also responsible for ensuring that corrective measures have been
implemented, appropriate authorities have been notified, and follow-up reports have been completed.
Individual subcontractors are required to cooperate with the SSC within the parameters of their scopes of work.
Personnel are required to report all injuries, illnesses, spills, fires, and property damage to the SSC. The SSC must
be notified of any on-site emergencies and is responsible for ensuring that the appropriate emergency procedures
described in this section are followed.
13.10.3 Emergency Recognition and Prevention
Table 13-1 provides information on the hazards associated with the different tasks planned for the demonstration
sites. On-site personnel will be made familiar with this information and with techniques of hazard recognition
through prework training and site-specific briefings.
13.10.4 Evacuation Routes and Procedures
In the event of an emergency that necessitates evacuation of a work task area or a site, the Tetra Tech SSC will
contact all nearby personnel using the on-site communications discussed in Section 13.8.1 to advise the personnel
of the emergency. The personnel will proceed along site roads to a safe area upwind from the hazard source. The
personnel will remain in that area until the SSC or an authorized individual provides further instructions.
13.10.5 Emergency Contacts and Notifications
Appendixes B-l, B-2, and B-3 provide the names and telephone numbers of emergency contact personnel for the
Navy BVC, Kelly AFB, and PC sites, respectively. The information in these appendixes must be posted on site or
must be readily available at all times. In the event of a medical emergency, personnel will notify the appropriate
emergency organization and will take direction from the Tetra Tech SSC. In the event of a fire, explosion, or spill
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at a site, the SSC will notify the appropriate local, state, and federal agencies and will follow procedures discussed
in Section 13.10.9 or 13.10.11.
13.10.6 Hospital Route Directions
Before performing any demonstration activities at a site, Tetra Tech personnel will conduct a pre-emergency hospital
run to familiarize themselves with the route to the local hospital. Maps showing the appropriate hospital routes are
provided in Appendixes B-l (Navy BVC site), B-2 (Kelly AFB site), and B-3 (PC site). These maps must be posted
on site.
13.10.7 Emergency Medical Treatment Procedures
A person who becomes ill or injured during work tasks may require decontamination. If the illness or injury is minor,
any decontamination necessary will be completed and first aid will be administered prior to patient transport. If the
patient's condition is serious, partial decontamination will be completed at a minimum (such as complete disrobing
of the person and redressing the person in clean coveralls or wrapping the person in a blanket). First aid will be
administered until an ambulance or paramedics arrive. All injuries and illnesses must be immediately reported to
the Tetra Tech project manager and HSR.
Any person transported to a clinic or hospital for chemical exposure treatment will be accompanied by information
on the chemical that he or she has been exposed to at the site, if possible.
13.10.8 Protective Equipment Failure
If any worker in the exclusion zone experiences a failure of protective equipment (either engineering controls or PPE)
that affects his or her personal protection, the worker and all coworkers will immediately leave the exclusion zone.
Re-entry to the exclusion zone will not be permitted until (1) the protective equipment has been repaired or replaced,
(2) the cause of the equipment failure has been determined, and (3) equipment failure is no longer considered to be
a threat.
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13.10.9 Fire or Explosion
In the event of a fire or explosion on site, the local fire department will be immediately summoned. The Tetra Tech
SSC or a site representative will advise the fire department of the location and nature of any hazardous materials
involved. Appropriate provisions of Section 13.10 will be implemented by on-site personnel.
13.10.10 Weather-Related Emergencies
Site work will not be conducted during severe weather conditions, including high-speed winds or lightning. In the
event of severe weather, field personnel will stop work, secure and lower all equipment (for example, drilling masts),
and leave the site.
Thermal stress caused by excessive heat may occur as a result of extreme temperatures, workload, or the PPE used.
Heat stress treatment will be administered as described in SWP 6-15, which will be available on site. Cold stress is
not anticipated during the demonstration.
13.10.11 Spills or Leaks
In the event of a severe spill or a leak, site personnel will follow the procedures listed below.
• Evacuate the affected area, and relocate personnel to an upwind location.
• Inform the Tetra Tech SSC, a Tetra Tech office, and a site representative immediately.
• Locate the source of the spill or leak, and stop the flow if it is safe to do so.
• Begin containment and recovery of spilled or leaked materials.
• Notify appropriate local, state, and federal agencies.
Additional information on spill and leak control is presented in SWP 6-14, which will be available on site.
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13.10.12 Emergency Equipment and Facilities
The following emergency equipment and facilities will be available on site:
• First aid kit
Eye wash (portable)
• Fire extinguisher (only in sample management trailer in PRA)
• Site telephone (only in sample management trailer in PRA)
• Cellular telephone
• Drums
13.10.13 Reporting
All emergency situations require follow-up and reporting. Appendix C contains the Tetra Tech Accident and Illness
Investigation Report (Form AR-1). This report must be completed and submitted to the Tetra Tech project manager
within 24 hours of an emergency situation. The project manager will review the report and then forward it to the
Tetra Tech HSR for review. The report must include proposed actions to prevent similar incidents from occurring.
The HSR must be fully informed of the corrective action process so that she may implement applicable elements of
the process at other sites.
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REVIEWS AND APPROVALS
CLIENT NAME: EPA
CONTRACT NO.: 68-C5-0037 WORK ASSIGNMENT NO.: 47
NAVY BVC SITE
PORT HUENEME, CALIFORNIA
KELLY AFB SITE
SAN ANTONIO, TEXAS
PC SITE
NORTH-CENTRAL INDIANA
We the undersigned have read and approve of the health and safety procedures presented in this chapter for
on-site work activities at the Navy BVC, Kelly AFB, and PC sites.
Name
Signature
Date
Judith Wagner
Tetra Tech HSR
Kirankumar Topudurti
Tetra Tech Project Manager
2.000
This certifies that Tetra Tech has assessed the type, risk level, and severity of hazards for the project and has
selected appropriate personal protective equipment for on-site personnel in accordance with OSHA Title 29 of
the CFR, Section 1910.132.
Certified by
Judith Wagner
Tetra Tech
Technical Reviewer
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Chapter 14
References
AEHS. 1999. "State Soil Standards Survey." Soil & Groundwater. December 1999/January 2000.
ACGIH. 1999. "Threshold Limit Values and Biological Exposure Indices."
California Environmental Protection Agency. 1999. Memorandum Regarding Guidance for Petroleum Hydrocarbon
Analysis. From Bart Simmons, Chief, Hazardous Materials Laboratory. To Interested Parties. October 21.
Dean, John A. 1995. Analytical Chemistry Handbook. McGraw-Hill, Inc. New York, New York.
Dryoff, George V. Editor. 1993. "Manual of Significance of Tests for Petroleum Products." ASTM Manual Series:
MNL 1. 6th Edition.
EPA. 1983. "Methods for Chemical Analysis of Water and Waste." Revision. Environmental Monitoring and
Support Laboratory. Cincinnati, OH. EPA 600-4-79-020. March.
EPA. 1994. "U.S. EPA Contract Laboratory Program National Functional Guidelines for Organic Data Review."
OSWER Washington, DC. Publication 9240.1-05. February.
EPA. 1995. "Handbook for Preparing Office of Research and Development Reports." ORD. Washington, DC.
EPA/600/K-95-002. August.
EPA. 1996a. "A Guidance Manual for the Preparation of Site Characterization and Monitoring Technology
Demonstration Plans." NERL. October.
EPA. 1996b. "Test Methods for Evaluating Solid Waste." Volumes 1A through 1C. SW-846. Third Edition.
Update III. OSWER. Washington, DC. December.
EPA. 1998. "Quality Assurance Project Plan Requirements for Applied Research Projects." Unpublished.
NRMRL.
EPA. 1999. "Contract Laboratory Program Statement of Work for Organics Analysis, Multi-Media, Multi-
Concentration." Revision OLM04.1. February.
Florida Department of Environmental Protection. 1996. "FL-PRO Laboratory Memorandum." Bureau of Waste
Cleanup. Accessed on April 21. On-Line Address: www.dep.state.fl.us/labs/docs/flpro.htm
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Fox, Marye Anne, and James K. Whitesell. 1994. Organic Chemistry. Jones and Bartlett Publishers, Inc. Boston,
Massachusetts.
Fritz, James S., and George H. Schenk. 1987. Quantitative Analytical Chemistry. Allyn and Bacon, Inc. Boston,
Massachusetts. Fifth Edition.
Gary, J.H., and G.E. Handwerk. 1993. Petroleum Refining: Technology and Economics. Marcel Dekker, Inc. New
York, New York.
HNU Systems, Inc. 1985. "Instruction Manual - Trace Gas Analyzer, HNU Model PI 101." December.
MapQuest.com, Inc. (MapQuest). 1999. Driving Directions. Accessed on December 30. On-Line Address:
http://mapquest.com/
Massachusetts Department of Environmental Protection. 2000. "VPH/EPH Documents." Bureau of Waste Site
Cleanup. Accessed on April 13. On-Line Address: www.state.ma.us/dep/bwsc/vp_eph.htm
NIOSH. 1997. "Pocket Guide to Chemical Hazards." U.S. Department of Health and Human Services. U.S.
Government Printing Office. Washington, DC. June.
NIOSH, OSHA, U.S. Coast Guard, and EPA. 1985. Occupational Safety and Health Guidance Manual for
Hazardous Waste Site Activities. October.
Parker, Sybil. 1984. Dictionary of Scientific and Technical Terms. McGraw-Hill, Inc. New York, New York.
Third Edition.
Rittenburg, James H. 1990. Development and Application of Immunoassay for Food Analysis. Elsevier Applied
Science. London, England, and New York, New York.
SDL 1999. "PETRO Soil Test Technical Guide."
SDL 2000. "Harnessing the Antibody—The Fundamentals of Enzyme Immunoassay."
Simard, R.G., Ichiro Hasegawa, William Bandaruk, and C. E. Headington. 1951. "Infrared Spectrophotometric
Determination of Oil and Phenols in Water." Analytical Chemistry. Volume 23, No. 10. October. Pages
1384 to 1387.
Speight, J.G. 1991. The Chemistry and Technology of Petroleum. Marcel Dekker, Inc. New York, New York.
Tetra Tech, Inc. 1999. "Health and Safety Manual."
Texas Natural Resource Conservation Commission. 2000. "Waste Updates." Accessed on April 13. On-Line
Address: www.tnrcc.state.tx.us/permitting/wastenews.htm#additional
Willard, Hobart H., Lynne L. Merrit, Jr., John A. Dean, and Frank A. Settle, Jr. 1988. Instrumental Methods of
Analysis. Wadsworth Publishing Company. Belmont, California. Seventh Edition.
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Appendix A
Review of Predemonstration Investigation Procedures and Results
Several findings of the predemonstration sampling and analysis investigation and the developers' review comments
on the predemonstration investigation results were instrumental in developing the sampling and analysis procedures
for the demonstration. This section discusses those findings and presents Tetra Tech's responses to developer
comments on predemonstration investigation results.
A.I Selected Predemonstration Investigation Findings
This section summarizes the findings of the predemonstration investigation that impacted the demonstration
approach. Based on these findings, improvements were made to predemonstration investigation sampling and
analysis procedures before the procedures were adapted for the demonstration.
A. 1.1 Use ofNitrile Gloves During Sample Preparation
During the predemonstration investigation, nitrile gloves were used by the field sampling team for most sample
preparation; however, when the supply of nitrile gloves was depleted, locally available plastic gloves were used. Use
of plastic gloves resulted in phthalate contamination of predemonstration investigation samples. Therefore, as
described in Section 7.1.3.1, only nitrile gloves will be used by the field sampling team during the demonstration.
A. 1.2 Selection of Sampling Depth Intervals at Kelly AFB Site
During the demonstration, soil samples will be collected in the B-38 Area of the Kelly AFB Site at the four locations
sampled during the predemonstration investigation. However, the depth intervals that will be sampled during the
demonstration will differ from those sampled during the predemonstration investigation because the predemonstration
investigation samples contained only trace concentrations of TPH. Based on discussions with the demonstration site
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representative after the predemonstration investigation, it was determined that most of the contamination in the B-3 8
Area can be found at or near the water table. Therefore, the depth intervals to be sampled during the demonstration
will be 2 feet above and 2 feet below the water table. For the purposes of this demonstration plan, Tetra Tech
assumes that the surface of the water table will be about 20 feet bgs during the demonstration. This assumption is
based on previous groundwater-level data provided by the site representative. Using a water-level indicator, Tetra
Tech will measure the exact depth to groundwater in four monitoring wells near the B-3 8 Area at the time of the
demonstration. Tetra Tech will then calculate an average depth to groundwater and will collect soil samples 2 feet
above and 2 feet below the average water table depth. Therefore, as described in Section 7.1.1.2, soil samples will
likely be collected from two depth intervals—18 to 20 and 20 to 22 feet bgs—at the four sampling locations.
A. 1.3 Spiking of Low- and Medium-Level PE Samples
During the predemonstration investigation, methanol and Freon 113 were used as carriers for low-level soil PE
samples. After reviewing STL Tampa East results for these samples, Tetra Tech determined that the samples
prepared using methanol as a carrier contained up to 40 percent lower levels of TPH than those prepared using
Freon 113 as a carrier. According to the manufacturer of EnCores, using methanol as the carrier in an EnCore may
have caused the sampler's viton ring to swell, opening the pores on the viton ring; as a result, some of the volatiles
in the sample may have escaped. As described in Section 7.1.3.2, to address this potential loss of volatiles, ERA will
spike the low- and medium-level PE samples prepared using methanol with 40 percent higher TPH levels than those
actually requested by Tetra Tech.
A.2 Tetra Tech Responses to Developer Comments on Predemonstration Investigation
Results
This section summarizes technical issues raised by developers based on their review of the predemonstration
investigation results and presents Tetra Tech's responses to the developers' comments. In Sections A.2.1 through
A.2.11, each developer comment is presented in italics and is followed by Tetra Tech's response. Improvements were
made to predemonstration investigation sampling and analysis procedures based on developer comments before the
procedures were adapted for the demonstration.
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A. 2.1 Field Sample Homogenization Procedure
Developer Comment. When a given sample was divided into two aliquots, each aliquot extracted and analyzed
separately, the analysis results for the two aliquots did not always match.
Tetra Tech Response. STL Tampa East's blind field triplicate analytical results showed that (1) when samples did
not contain clay, the RSD was only 5 percent (a high level of precision for soil samples), and (2) when samples
contained a significant amount of clay, the RSD was about 25 percent (a typical level of precision for soil samples).
Therefore, the field sample homogenization procedure produced acceptable results.
A. 2.2 Interference of Complex Matrixes in Analysis
Developer Comment. The nature of soil samples resulted in bubbling on acidification (perhaps because of high
carbonate in soil), thick, gelatinous emulsion (perhaps because of high clay in soil), or precipitation of elemental
sulfur (perhaps because ofsulfide in soil). These complex matrixes might have caused some analytical problems.
Tetra Tech Response. Tetra Tech acknowledges the validity of the comment. However, the environmental samples
were collected in five different areas; depending on the analytical method used, such problems may not be uncommon
in environmental sample analysis. The developers can make method modifications to address problems observed
during the predemonstration investigation, if necessary.
A.2.3 Choosing Not to Analyze Samples from a Given Sampling Area
Developer Comment. Would it be possible to exclude samples from the phytoremediation area because our kit is
not designed [to] measure compounds that are heavier than diesel?
Tetra Tech Response. A developer may choose not to analyze samples collected in a given area provided that the
developer informs Tetra Tech of this choice in advance. To be fair to all the developers and to potential users of the
field measurement devices, each ITVR will identify all the scenarios that are part of the demonstration approach
(samples collected in five areas and PE samples) and will state that the developer chose not to analyze samples
collected in a given area because its field measurement device is not designed to analyze such samples (for example,
samples containing compounds heavier than diesel).
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A. 2.4 Low, Medium, and High Classification of Environmental Samples
Developer Comment. For the actual demonstration, we would propose running samples greater than 200 ppm
[mg/kg] because it appears that many samples will be above this level.
Tetra Tech Response. The predemonstration investigation results show that no area's samples will all have TPH
concentrations less than 200 mg/kg. To establish a reasonable starting point, samples will be identified as low-level
(<100 mg/kg), medium-level (100 to 1,000 mg/kg) and high-level (>1,000 mg/kg). PE samples will be identified
as such in their sample identification numbers, and their concentration levels will be identified as low, medium, or
high. No backup environmental or PE samples will be provided.
A.2.5 STL Tampa East's Analytical Results for Blank and PE Samples
Developer Comment 1. We noticed that STL Tampa East actually reported a higher value in the blank sample than
for the triplicate series of reporting limits and wondered if their reporting limits needed adjusting and if this might
have implications for their environmental sample results. In addition, we noted the apparent reporting discrepancy
with the stated certified values for those samples. The blank sample has a certified value of<45 while an actual
number, (26 mg/kg), is reported for the triplicate series.
Developer Comment 2. The fact that STL Tampa East failed in the PE blank analysis (reporting 52 ppm [mg/kg]
for a certified value of < 45 ppm [mg/kg]) is very disturbing. However, as a result, it could be reasoned that since
the laboratory could not reasonably demonstrate accuracy at low concentrations, everything below 50ppm [mg/kg]
is void.
Tetra Tech Response. STL Tampa East reported a higher value for the blank sample than for the triplicate series
of reporting limit samples because STL Tampa East analyzed the blank sample for both GRO and EDRO but the
triplicate reporting limit samples for GRO only. The triplicate reporting limit samples were analyzed for GRO only
because it was not clear that they were spiked with weathered gasoline instead of fresh gasoline. Recent information
provided by ERA indicates that the blank soil (processed garden soil) has low levels of EDRO. During the
demonstration, these issues will be addressed as follows: (1) all PE samples containing GRO will be analyzed for
both GRO and EDRO because weathered gasoline contains a significant quantity of TPH in the EDRO range and
(2) low-level PE samples (<100 mg/kg) will be prepared using Ottawa sand, not processed garden soil.
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ERA's certified values for the blank soil were <15 mg/kg gasoline and <45 mg/kg TPH. ERA has informed Tetra
Tech that the certified TPH value was based on infrared analysis, not GC/FID analysis. According to ERA, should
the blank soil be subjected to GC/FID analysis, the certified value will be greater, particularly in the EDRO range.
Because a GC/FID method is the reference method for the project, ERA will attempt to provide the certified value
based on the GC/FID method.
The reasons for the apparent reporting discrepancy associated with the stated certified value are as follows: (1) the
blank soil result was based on infrared analysis, and (2) like STL Tampa East, ERA analyzed the reporting limit
samples only for GRO. Tetra Tech will try to obtain an appropriate certified value for the blank soil and will have
all GRO PE samples analyzed for both GRO and EDRO.
A. 2.6 Comparing Field Measurement Device Results with Acceptance Limits
Developer Comment. We understand that vendor results will be compared with the stated acceptance limits. We
wanted to make a comment that if these limits were derived from the inter-laboratory results in which laboratories
used Soxhlet/GC methods of analysis, it may not be appropriate to hold [compare] the field test results that rely on
much less rigorous extraction methods [to the acceptance limits].
Tetra Tech Response. The basis of the evaluation will be a comparison of the performance of a field measurement
device with that of the reference method selected for the project. PE samples will be used primarily to verify that
the laboratory's performance is acceptable. However, as stated in Section 4.2, for comparisons with field
measurement device results, the laboratory results will not be adjusted based on the recoveries observed during PE
sample analysis. Any consistent data trends will be discussed in each ITVR to explain the differences between the
laboratory and field measurement device results. In practice, the recoveries observed for LCS/LCSD, MS/MSD, and
PE samples are not used to correct investigative sample results. In addition, the soil characteristics of the PE samples
will not be the same as those of all the investigative samples.
According to ERA, not all laboratories that contributed to the development of the acceptance limits used the same
extraction method, but they did use a GC/FID for analysis. The reference method selected for the proj ect is a method
used for TPH measurement by about 75 percent of the states in the United States.
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A. 2.7 Acceptance Limits for PE Samples
Developer Comment. How were the acceptance limits for PE samples determined? Why do you favor lower
recovery concentrations to higher?
Tetra Tech Response. The acceptance limits were derived by ERA based on historical mean recovery values for
similar types of samples. The acceptance limits were evenly distributed about the historical mean recovery values.
However, these acceptance limits were not evenly distributed about the certified values because the certified values
were not corrected for the historical mean recovery values. Therefore, the acceptance limits may seem to have been
biased low or high, depending on whether the certified values were higher or lower than the historical mean recovery
values.
A. 2.8 Quantification of TPH by STL Tampa East
Developer Comment. There are some subtle details about the laboratory analysis that I think need to be considered.
This consideration goes to the heart of the difficulty of this project and that is the fact that TPH is a method defined
parameter. If the laboratory is measuring one thing and the field methods are measuring another they will never
agree. The most obvious manifestation of this is the performance of the laboratory on the PE samples. As you can
see the reference laboratory was at the low end in reporting the EDRO results. Does this mean that all of the
laboratory results are low on all of the field samples as well?
Tetra Tech Response. The laboratory procedure for TPH measurement is described in Section 9.1 so that it is clear
what the laboratory will measure. Tetra Tech performed a detailed review of calibration data and observed that the
average response factor for hydrocarbons in the C10 to C28 range was less than the average response factor for
hydrocarbons in the C10 to C40 range. The reason for this decrease could not be defined with the limited data
available. However, Tetra Tech believes that the decrease may have been due to a reduced area in the chromatogram
for the early-eluting compounds in the DRO standard (C10 to C14), possibly because of the use of the split/splitless
injection system. This belief is based on Section 4.1.3 of SW-846 Method 8000, which indicates that the response
for labile compounds may decrease in split/splitless injection systems.
To address the problem of low recoveries, the demonstration samples for EDRO analysis will be quantified over two
ranges: (1) C10 (greater than n-decane) through C28 (including n-octacosane), which is the typical DRO range, and
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(2) C28 (greater than n-octacosane) through C40 (n-tetracontane), which extends the DRO range. The sum of these
two values will be reported as EDRO.
A. 2.9 Solubility of C10 to C40 Standard in Methylene Chloride
Developer Comment. Our laboratory people observed that C10 to C40 standard will not completely dissolve in
methylene chloride. I think that this information on the methylene chloride and the low recoveries on the PE samples
indicate that we should consider an alternative to the current method.
Tetra Tech Response. Solubility constraints were not observed by STL Tampa East during initial calibration or
sample analysis—that is, no precipitation was observed. The reason for the low recoveries and the proposed
approach to address the issue are discussed in Section A.2.8. As stated in Section A.2.6, more than 75 percent of the
states in the United States use a method based on SW-846 Method 8015B for GC/FID analysis.
A. 2.10 Presentation of Demonstration Results on Wet Weight Basis
Developer Comment. Regarding the certified values for PE samples, the wet weight and dry weight results have
to be different from each other.
Tetra Tech Response. ERA provided certified values on a dry weight basis. The PE sample certified values in the
predemonstration investigation data summary tables provided to the developers are presented on a dry weight basis.
For the demonstration, all analytical results will be presented on a wet weight basis.
A.2.11 Use of TPH Results for Field Measurement Devices
Developer Comment. For the B38 PE series, shouldn 't the field device GRO results (instead of TPH) be compared
with STL Tampa East's GRO results? What are the GRO and EDRO concentrations for all confirmatory results?
Tetra Tech Response. The TPH results were used because not all the field measurement devices can measure GRO
and EDRO separately. During the demonstration, STL Tampa East will analyze all GRO-containing samples for both
GRO and EDRO because weathered gasoline will have a significant portion of TPH that eludes in the early EDRO
range. The GRO and EDRO results for all confirmatory samples were provided.
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Appendix B
Emergency Information
Appendix B-l, Navy Base Ventura County Site
Appendix B-2, Kelly Air Force Base Site
Appendix B-3, Petroleum Company Site
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Appendix B-l
Emergency Information
Navy Base Ventura County Site
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EMERGENCY INFORMATION
(POST ON SITE)
EMERGENCY CONTACTS AND ROUTE TO HOSPITAL
NAVY BASE VENTURA COUNTY SITE
Emergency Contact
Telephone No.
U.S. Coast Guard National Response Center
InfoTrac
Fire Department
Police Department
Tetra Tech EM Inc. Personnel:
Human Resources Representative: Norman Endlich
Health and Safety Representative: Judith Wagner
Office Health and Safety Coordinator: Carrie Haag
Project Manager: Kirankumar Topudurti
Site Safety Coordinator: Jill Ciraulo
Client Contact:
U.S. Environmental Protection Agency Project Manager: Stephen Billets
(800)424-8801
(800)535-5053
911
911
(703) 390-0626
(847)818-7192
(312)856-8748
(312)856-8742
(312)946-6479
(702) 798-2232
Medical Emergency
Hospital Name: St. John's Regional Medical Center
Hospital Address: 1500 N. Rose Avenue
Oxnard, CA 93030
Hospital Telephone No.:
Ambulance Telephone No.:
Emergency - 911
General - (805) 988-2500
911
Route to Hospital: (see Page 238 for hospital route map)
From the site, drive north on Ventura Road to Gonzales Road. Turn east (right) on Gonzales Road, and
proceed to Rose Avenue. Turn south (right) onto Rose Avenue. St. John's Regional Medical Center, will
be on the left near the intersection of Gonzales Road and Rose Avenue.
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EMERGENCY INFORMATION
(POST ON SITE)
HOSPITAL ROUTE MAP
NAVY BASE VENTURA COUNTY SITE
Gonzales Rd.
Doris Ave.
Oxnard Airport Urgent Care Center
1555 West 5th St., Oxnard CA.
985-5599 -~^^
W. 5th, St.
Wooley Road
Channel Island Blvd.
Navy Base Ventura County
St. John's Regional Medical
Center, 1500 N. Rose Ave
Oxnard, CA. 988-2500
Pleasant Valley Rd.
OXNARD
238
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Appendix B-2
Emergency Information
Kelly Air Force Base Site
239
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EMERGENCY INFORMATION
(POST ON SITE)
EMERGENCY CONTACTS AND ROUTE TO HOSPITAL
KELLY AIR FORCE BASE SITE
Emergency Contact
Telephone No.
U.S. Coast Guard National Response Center
InfoTrac
Fire Department
Police Department
Tetra Tech EM Inc. Personnel:
Human Resources Representative: Norman Endlich
Health and Safety Representative: Judith Wagner
Office Health and Safety Coordinator: Carrie Haag
Project Manager: Kirankumar Topudurti
Site Safety Coordinator: Jill Ciraulo
Client Contact:
U.S. Environmental Protection Agency Project Manager: Stephen Billets
(800)424-8801
(800)535-5053
911
911
(703) 390-0626
(847)818-7192
(312)856-8748
(312)856-8742
(312)946-6479
(702) 798-2232
Medical Emergency
Hospital Name: Wilford Hall Medical Center
Hospital Address: 2200 Bergquist Drive
San Antonio, TX 78236
Hospital Telephone No.:
Ambulance Telephone No.:
Emergency - 911
General-(210) 292-73 31
911
Route to Hospital: (see Page 241 for hospital route map)
From the site, proceed to General McMullen Road, and head north to Highway 90. Turn left onto
Highway 90, and head west to S.W. Military Drive. Turn left onto S.W. Military Drive, and head south to
Wilford Hall Medical Center, which is on the left.
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Appendix B-3
Emergency Information
Petroleum Company Site
242
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EMERGENCY INFORMATION
(POST ON SITE)
EMERGENCY CONTACTS AND ROUTE TO HOSPITAL
PETROLEUM COMPANY SITE
Emergency Contact
Telephone No.
U.S. Coast Guard National Response Center
InfoTrac
Fire Department
Police Department
Tetra Tech EM Inc. Personnel:
Human Resources Representative: Norman Endlich
Health and Safety Representative: Judith Wagner
Office Health and Safety Coordinator: Carrie Haag
Project Manager: Kirankumar Topudurti
Site Safety Coordinator: Jill Ciraulo
Client Contact:
U.S. Environmental Protection Agency Project Manager: Stephen Billets
(800)424-8801
(800)535-5053
911
911
(703) 390-0626
(847)818-7192
(312)856-8748
(312)856-8742
(312)946-6479
(702) 798-2232
Medical Emergency
Hospital Name: Home Hospital
Hospital Address: 2400 South Street
Lafayette, IN 47904
Hospital Telephone No.:
Ambulance Telephone No.
Emergency - 911
General-(317) 477-6811
911
Route to Hospital: (see Page 244 for hospital route map)
From the site take State Route (SR) 43 south to Interstate 65. Take Interstate 65 South to SR 26 (South
Street). Go west on SR 26. Home Hospital is on the north (right) side of SR 26.
243
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Appendix C
Tetra Tech, Inc., Forms
Daily Tailgate Safety Meeting Form (Form HST-2)
Daily Site Log (Form SSC-1)
Accident and Illness Investigation Report (Form AR-1)
Field Audit Checklist (Form AF-1)
Respiratory Hazard Assessment (Form RP-2)
245
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TETRA TECH, INC.
DAILY TAILGATE SAFETY MEETING FORM
Date: Time: Project No.
Client: Site Location:
Site Activities Planned for Today:
Safety Topics Discussed
Protective clothing and equipment:
Chemical hazards:
Physical hazards:
Environmental and biohazards:
Equipment hazards:
Decontamination procedures:
Other:
Review of emergency procedures:
Employee Questions or Comments:
FormHST-2 Page 1 of 2
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TETRA TECH, INC.
DAILY TAILGATE SAFETY MEETING FORM (Continued)
Attendees
Printed Name
Signature
Meeting Conducted by:
Name
Title
Signature
Form HST-2
Page 2 of 2
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"1
TETRA TECH, INC.
DAILY SITE LOG
Site Name:
Date:
Name (print)
Time
Company
In
Out
Comments:
FormSSC-l
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TETRA TECH, INC.
ACCIDENT AND ILLNESS INVESTIGATION REPORT
To:
Regional or Subsidiary Health and Safety Representative
Cc:
Workers Compensation Administrator
Project Name:
Prepared by:
Position:
Office:
Project No.
Telephone:
Fax:
Information Regarding Injured or 111 Employee
Name:
Home address:
Home telephone:
Office:
Gender: Ml I F
Marital status:
Date of birth:
No. of dependents:
Occupation (regular job title):
Department:
Social Security Number:
Date of Accident:
Time of Accident:
Location of Accident
Street address:
City, state, and zip code:
County:
Was place of accident or exposure on employer's premises Yes
No
Narrative Description of How Accident Occurred: (Explain what the employee was doing and how the accident
occurred.)
Did the employee die? Yes CD No I I
Was employee performing regular job duties? Yes O No O
Was safety equipment provided? Yes Q No Q
Was safety equipment used? Yes Q No I I
Note: Attach any police reports or related diagrams to this accident report.
FormAR-l
Page 1 of 3
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TETRA TECH, INC.
ACCIDENT AND ILLNESS INVESTIGATION REPORT (Continued)
Witness(es):
Name:
Address:
Telephone:
Nature of Illness or Injury and Part of Body Affected:
Describe the Object or Substance which Directly Injured the Employee:
Medical Treatment Required:
O No O Yes O First Aid Only
Physician's Name:
Hospital or Office Name:
Address:
Telephone No.:
Lost Work Days:
O No. of Lost Work Days
Last Date Worked
Time Employee Left Work
Date Employee Returned to Work
O No. of Restricted Work Days
I I None
Corrective Action(s) Taken by Unit Reporting the Accident:
Corrective Action Still to be Taken (by whom and when):
Name of Tetra Tech employee the injury or illness was first reported to:
Date of Report:
Time of Report:
FormAR-l
Page 2 of 3
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TETRA TECH, INC.
ACCIDENT AND ILLNESS INVESTIGATION REPORT (Continued)
Printed Name
Signature
Telephone No.
Date
Project or Office Manager
Site Safety Coordinator
Injured Employee
To be completed by Human Resources:
SSN:
Date of hire:
Wage information: $
Position at time of hire
Current position:
per
Hire date in current job:
(hour, day, week, or month)
Shift hours:
State in which employee was hired:
Status: O Full-time Q Part-time Hours per week:
Temporary job end date:
Days per week:
To be completed during report to workers' compensation insurance carrier:
Date reported: Reported by:
Confirmation number:
Name of contact:
Field office of claims adjuster:
FormAR-l
Page 3 of 3
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TETRA TECH, INC.
FIELD AUDIT CHECKLIST
Project Name: _
Field Location:
Project Manager:
Project No.:
Completed by:
Site Safety Coordinator:
General Items
Health and Safety Plan Requirements
1
2
3
4
5
6
7
8
9
10
11
12
Approved health and safety plan (HASP) on site or available
Names of on-site personnel recorded in field logbook or daily log
HASP compliance agreement form signed by all on-site personnel
Material Safety Data Sheets on site or available
Designated site safety coordinator present
Daily tailgate safety meetings conducted and documented
On-site personnel meet HASP requirements for medical examinations, fit
testing, and training (including subcontractors)
Compliance with specified safe work practices
Documentation of training, medical examinations, and fit tests available
from employer
Exclusion, decontamination, and support zones delineated and enforced
Windsock or ribbons in place to indicate wind direction
Illness and injury prevention program reports completed (California only)
Emergency Planning
13
14
15
16
17
18
Emergency telephone numbers posted
Emergency route to hospital posted
Local emergency providers notified of site activities
Adequate safety equipment inventory available
First aid provider and supplies available
Eyewash stations in place
Air Monitoring
19
20
21
23
Monitoring equipment specified in HASP available and in working order
Monitoring equipment calibrated and calibration records available
Personnel know how to operate monitoring equipment and equipment
manuals available on site
Environmental and personnel monitoring performed as specified in HASP
In Compliance?
Yes
No
NA
Form AF-1
Page 1 of2
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TETRA TECH, INC.
FIELD AUDIT CHECKLIST (Continued)
Safety Items
Personal Protection
1
2
3
4
5
6
7
8
9
Splash suit
Chemical protective clothing
Safety glasses or goggles
Gloves
Overboots
Hard hat
Dust mask
Hearing protection
Respirator
Instrumentation
10
11
12
Combustible gas meter
Oxygen meter
Organic vapor analyzer
Supplies
13
14
15
Decontamination equipment and supplies
Fire extinguishers
Spill cleanup supplies
In Compliance?
Yes
No
NA
Corrective Action Taken During Audit:
Corrective Action Still Needed:
Note: NA = Not applicable
Auditor's Signature
Site Safety Coordinator's Signature
Date
Form AF-1
Page 2 of 2
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TETRA TECH, INC.
RESPIRATORY HAZARD ASSESSMENT
Project Name: Project No.:
Location: Project Manager:
Type: Q Baseline Q Reassessment Date:
Valid for days
Job/Task Description: E] Routine
H] Escape
Hazard Identification and Source: Workplace Factors:
Temperature:
Humidity:
Other:
Chemical:
PEL:
ACGIH TLV:
Form (part/gas/vapor):
IDLH:
Eye Irritant (Y/N):
Skin Absorption(Y/N):
Monitoring (Y/N) :*
Frequency:
Maximum Concentration
Estimated:**
* Monitoring Method:
D PID D NIOSH method:
DFID D Vapor badge:
D Detector tube: D Other:
* * If concentrations exceed the immediately dangerous to life and health
(IDLH) value, use air-supplied systems.
Cartridge/Filter Selection
DNIOO DRIOO DPIOO
D N99 D R99 D P99
D N95 D R95 D P95
H] Organic vapor E] Acid gas
H] Ammonia E] Mercury E] Formaldehyde
D Combo:
D Other:
Completed by Date
User Factors:
Work rate:
Protective clothing:
Other:
Respirator Type:
1 1 Half-face disposable Brand:
1 1 Half-face reusable Brand:
D Full-face
Brand:
| | Air-supplied airline Brand:
D Air-supplied SCBA Brand:
DPAPR
D ESCBA
Brand:
Brand:
Vapor and Gas Cartridge Exchange:
ESLI: D Yes Q No
Exchange frequency:
Basis for Exchange Frequency
Q Manufacturer's data Q Workplace simulations
H] Experimental methods E] AIHA "Rules of Thumb"
H] Predictive modeling E] Analogous chemical structure
D OSHA Regulation:
D Other:
Reviewed by Date
Form RP-2
Page 1 of2
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RESPIRATORY HAZARD ASSESSMENT (Continued)
DEFINITIONS AND ACRONYMS
ACGIH American Conference of Governmental Industrial Hygienists
AIHA American Industrial Hygiene Association
ESLI End of service life indicator
FID Flame ionization detector
IDLH Immediately dangerous to life and health
NIOSH National Institute for Occupational Safety and Health
N100/99/95 Non-oil-proof particulate filter
OSHA Occupational Safety and Health Administration
P100/99/95 Oil-proof particulate filter
PEL Permissible exposure limit
PID Photoionization detector
PPE Personal protective equipment
Rl00/99/95 Oil-resistant particulate filter
SCBA Self-contained breathing apparatus
TLV Threshold limit value
Note: This form must be reviewed by a regional health and safety representative or subsidiary health
and safety representative (or designee) only and must be attached to the site-specific health and
safety plan once completed. A copy must also be placed in the project files.
Form RP-2
Page 2 of 2
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