Field-Based Site Characterization
Technologies Course
Participant Manual
fcEPA
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•nter
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&EPA
£0460
Field-Based Site Characterization Technologies Course
Course Evaluation
Please take a few moments to answer the following questions about the design and content of
the course. Please use the comments sections to note changes you recommend making to the
modules.
Please check the appropriate box.
I represent: Q EPA Q State Q DOE Q DoD Q Other
lam: Q RPM Q OSC Q SAM Q Other
Number of years experience with site characterization
Please give the course a grade {A, B, C, D, F)
When applicable, please use the following key in responding to the statements.
SA- Strongly Agree A- Agree U-Undecided D- Disagree SD- Strongly Disagree
Module 1: Introduction
1. The module adequately explained current
trends for innovative site characterization
technologies.
SA A U D SD
Q a a a a
2. The module provided a good overview of
important initiatives related to site
characterization technologies.
a a a a a
Comments:
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Module 2: Overview of Field-Based Site
Characterization
1. The amount of information provided to
participants was adequate.
SA A U D SD
a a a a a
2. The module effectively explained the
philosophy of site characterization.
a a a a a
3. The module effectively explains the relationship
between site characterization technologies and
QAPPs (DQO process).
a a a a a
Comments:
Module 3: Sampling Platforms and Direct-Push
Technologies
1. The module provided an adequate amount of
information for:
Platforms for in-situ technologies
• Direct-push technologies
a a a a a
a a a a a
2. The graphics and pictures were helpful in
understanding the differences between the
technologies.
a a a a a
Comments:
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Module 4: Geophysical Characterization
Techniques
SA
U
SD
The module provided an adequate review of the
scientific principles behind the following
technology categories:
• In-situ geophysics
• Borehole geophysics
Surface geophysics
a a a a a
a a a a a
a a a a a
2. The discussion of the issues common to all
technologies was adequate.
a a a a a
Please respond to the following statements
about instrument integration/data interpretation:
A good balance of technical and practical
information was presented in the discussions of
the following technologies:
• Surface instruments
• In-situ instruments
• Borehole instruments
Time allocated for the hands-on activity was
adequate.
a a
a a
a a
a a
a a
a a
a a
a a
a
a
a
a
Comments:
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Modules 5 & 6:
Organic and Inorganic
Chemical Characterization
SA A U 0 SD
1. The modules present well balanced course
material for organic and inorganic analytical
technologies and hands-on experience for site
characterization.
• Organics
• Inorganics
a a a a a
a a a a a
The modules present information on data
interpretation that will be useful to me in my job.
• Organics
• Inorganics
a a a a a
a a a a a
The modules provide a useful foundation to
select the most efficient and cost effective
technology to characterize a given site.
• Organics
• Inorganics
Q a a a a
a a a a a
4. The structure of each hands-on activity was
adequate to demonstrate applications for real
life situations.
• Organics
• Inorganics
a a a a a
a a a a a
Comments:
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Module 8: Site Characterization Exercise
1. The exercise helped me to synthesize I~~l PI l~~l
information presented during the course and I-J U *-J
apply my knowledge.
2. The instructions for completing the exercise
were clearly presented.
3. Time allotted for the exercise was adequate.
Comments:
Module 7: Sources for Site Characterization SA A U D SD
Technology Information
1. Adequate information on available resources is i—| i—| i—i i—i
presented in this module. U I^J (.J U
2. The handouts, references, and information on i—| i—| i—| i—| i—|
resources on the Internet will be useful to me <-J ^ "—• I-J >—*
when I return to my job.
Comments:
i — | i — | i — | i — | i — |
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Workshop Wrap-up
SA
U
SD
1. Overall, the level of participant interaction
during the course was appropriate.
2. Overall, I was pleased with the following
aspects of the course.
• Delivery approach
• Pertinent examples
• Hands-on exercises
• Participant examples
a a a a a
a
a
Q
a
a
a
a
a
a
a
a
a
a a
a a
a a
a a
3. The participant materials were easy to follow
and easy to use.
Q a a a a
4. The following specific topics on technologies should be:
Omitted:
Emphasized less:
Added:
Emphasized more:
5. The following topics were:
Most informative:
Least informative:
6. The following topics were:
Most relevant to my job:
Least relevant to my job:
-------
7. Are there technologies that you would like to see?
Added to this course:
Omitted from this course:
Use the space below to note additional suggestions you have for improving the course.
Thank you!
Please return this form to a course facilitator.
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Regional Representatives to the
Consortium for Site Characterization Technology
Region 1
Scott Clifford
U.S. EPA Region 1
60 Westview St.
Lexington, MA 02173
Phone:(781)860-4631
Fax: (781) 860-4397
John Smaldone
U.S. EPA Region 1
Office Of Site Remediation and Restoration
Immediate Office (Mail Code - HIO)
John F. Kennedy Federal Building
90 Canal Street
Boston, MA 02203
Phone: (617)223-5519
Fax: (617)573-9662
Nora J. Conlon, Ph.D.
U.S. EPA Region 1
EQA
60 Westview St.
Lexington, MA 01810-3185
Phone:781-860-4335
Fax: 781-860-4397
Jim Cabot (alternate)
U.S. EPA Region 1
John F. Kennedy Federal Building (SPI)
90 Canal Street
Boston, MA 02203
Phone: (617)565-4899
Fax:(617)565-3415
Region 2
Peter Savoia
U.S. EPA Region 2
2890 Woodbridge Avenue
Edison, NJ 08837-3679
Phone: (908)906-6171
Fax: (908)321-6622
Region 2 (cont.)
Dennis Munhall
U.S. EPA Region 2
290 Broadway
18th Floor-PRS
New York, NY 10007
Phone:(212)637-4343
Fax: (212) 637-3256
Region 3
James M. McCreary (3HW30)
Senior Site Assessment Program Manager
U.S. EPA Region 3
841 Chestnut Building
Philadelphia, PA 19107
Phone: (215)566-3030
Fax:(215)566-3254
Mindi Snoparsky (3HW41)
U.S. EPA Region 3
HWMD
841 Chestnut Building
Philadelphia, PA 19107
Phone:(215)566-3316
Fax: (215) 566-3001
Jim Barron
U.S. EPA, Region 3
Quality Assessment Branch
ESD Central Regional Lab
201 Defense Highway
Annapolis, MD
Phone:(410)573-2600
Fax: (410) 573-2702
Regional Representatives
-------
Region 4
Doug McCurry
U.S. EPA Region 4
Waste Division
100 Alabama Street, S.W.
Atlanta, GA 30303
Phone: (404) 562-8649
Fax :
Mike Birch
U.S. EPA Region 4/ESD
960 College Station Road
Athens, GA 30605
Phone: (706)355-8552
Fax:
Al Hanke
U.S. EPA Region 4
Waste Division
100 Alabama Street, S.W.
Atlanta, GA 30303
Phone: (404)562-8633
Fax:
Region 5
Ida Levin
U.S. EPA Region 5
Superfund Division
Technical Support Section, SRT-4J
77 West Jackson Boulevard
Chicago, II. 60604
Phone: (312)886-6254
Fax: (312)353-9281
Region 6
Scott Ellinger
U.S. EPA Region 6
Fountain Place
1445 Ross Ave.
Dallas, TX 75200-2733
Phone:(214)665-8408
Fax:(214)665-6762
Region 6 (cont.)
Don Williams
U.S. EPA Region 6
Fountain Place
1445 Ross Ave.
Dallas, TX 75200-2733
Phone: (214) 665-2197
Fax: (214) 665-6660
Michael Daggett
U.S. EPA/Region 6
10625 Fallstone Road
Houston, Texas 77099
Phone: (713)983-2109
Fax: (713)983-2124
Doug Lipka (alternate)
U.S. EPA/Region 6
10625 Fallstone Road
Houston, Texas 77099
Phone: (713)983-2200
Fax:(713)983-2124
Region7
Paul Doherty
U.S. EPA Region 7 (SUPR)
726 Minnesota Ave.
Kansas City, KS 66101
Phone:(913)551-7924
Fax:(913)551-7063
Diane Easley
U.S. EPA Region 7
726 Minnesota Avenue
Kansas City, KS 66101
Phone:(913)551-7797
FAX: (913) 551-7063
Robert Greenall
U.S. EPA Region 7
25 Funston Rd.
Kansas City, KS 66115
Phone:(913)551-5097
Fax:(913)551-5218
Regional Representatives
-------
Region 8
Russell LeClerc
U.S. EPA Region 8
999 18th St. Suite 500
Denver, CO 80202-2405
Phone:(303)312-6693
Fax: (303)312-6067
Luke D. Chavez
U.S. EPA Region 8 (8EPR-ER)
999 18th St. Suite 500
Denver, CO 80202-2405
Phone: (303)312-6512
Fax: (303)312-6071
Region 9
Vance Fong
U.S. EPA Region 9 (P-3-2)
75 Hawthorne Street
San Francisco, CA 94105
Phone: (415)744-1492
Fax:(415)744-1476
Matt Mitguard
U.S. EPA Region 9 (H-8-2)
75 Hawthorne Street
San Francisco, CA 94105
Phone: (415) 744-2329
Region 10
Gerald Dodo
USEPA Region 10 Laboratory
7411 Beach Dr. East
Port Orchard, WA 98366
Phone: (360)871-8728
Fax: (360)871-8747
Bruce Woods
EPA Region 10
1200 6th Ave. M/S OEA-095
Seattle, WA 98101
Phone: (206)553-1193
Fax: (206) 553-8210
ORD/NERL-LV
Eric Koglin
U.S. EPA NERL
P.O. Box 93478
Las Vegas, NV 89193-3478
Phone: (702) 798-2432
Fax: (702)798-2261
Steve Billets
U.S. EPA NERL
P.O. Box 93478
Las Vegas, NV 89193-3478
Phone: (702) 798-2232
FAX (702) 798-2261
Headquarters
Bonnie Robinson
U.S. EPA/OSWER/OSW
401 M St., SW (5303W)
Washington, DC 20460
Phone: (703) 308-8622
Fax: (703) 308-8638
Robert Hitzig
U.S. EPA/OSWER/OUST
401 M St., SW (5403G)
Washington, DC 20460
Phone:(703)603-7158
Fax:(703)603-9163
Howard Fribush
U.S. EPA/OSWER/OERR
401 M St., SW (5204G)
Washington, DC 20460
Phone:(703)603-8831
Fax:(703)603-9112
Scott Fredericks
U.S. EPA/OSWER/OERR
401 M St., SW (5204G)
Washington, DC 20460
Phone: (703) 603-8833
Fax:(703)603-9103
Regional Representatives
-------
Headquarters (cont.)
Joe LaFornara
U.S. EPA/ERT
Raritan Depot (MS-101)
2890 Woodbridge Ave.
Edison, NJ 08837-3679
Phone: (908)321-6740
Fax: (908)321-6724
Dan Powell
U.S. EPA/OSWER/TIO
401MSt.,SW(5102G)
Washington, DC 20460
Phone:(703)603-7196
Fax:(703)603-9135
Ann Eleanor
U.S. EPA/OSWER/TIO
401MSt.,SW(5102G)
Washington, DC 20460
Phone:(703)603-7199
Fax:(703)603-9135
Regional Representatives
4
-------
List of Acronyms
M9/L
2,4-D
ASE
ASTM
ASV
BNA
BTEX
CEPPO
CERCLA
CERI
CFR
CLP
CLU-IN
CMECC
CPT
CRM
CSCT
CVAA
CWA
DC
DCE
DDT
DNT
DoD
DOE
ORE
DSO
ECD
EDXRF
EIA
ELCD
Micrograms per Liter
2,4-Dichlorophenoxyacetic Acid
Accelerated Solvent Extraction
American Society for Testing and Materials
Anode Stripping Voltammetry
Base Neutral Acids
Benzene, Toluene, Ethylbenzene, and Xylene
Chemical Emergency Preparedness and Prevention Office
Comprehensive Environmental Response, Compensation and Liability Act
Center for Environmental Research Information
Code of Federal Regulations
Contract Laboratory Procedure
Hazardous Waste Clean-Up Information World Wide Web Site
California Military Environmental Coordination Committee
Cone Penetrometer
Certified Reference Materials
Consortium for Site Characterization Technology
Cold Vapor Atomic Absorption
Clean Water Act
Direct Current
1,2-Dichloroethene
Dichlorodiphenyl Trichloroethane
Dinitrotoluene
Department of Defense
Department of Energy
Destruction and Removal Efficiency
Digital Storage Oscilloscope
Electron Capture Detector
Energy Dispersive X-Ray Fluorescence
Enzyme Immunoassay
Electron Conductivity Detector
I
-------
List of Acronyms
ELISA
EPA
EPC
ESA
ESC
ETG
ETV
eV
FIA
FID
FOCS
FP
FPXRF
FRN
FT-IR
FVD
GC/MS
GFAA
GHz
GPO
GPR
GWRTAC
HMX
HPLC
HUD
ICP
ISE
ITER
ITRC
LBS
LCD
Enzyme-Linked Immunosorbent Assays
U.S. Environmental Protection Agency
Electronic Pressure Control
Electrostatic Analyzer
Expedited Site Characterization
Environmental Technologies Group
Environmental Technology Verification
Electron Volt
Fluorescent Immunoassay
Flame lonization Detector
Fiber Optic Chemical Sensors
Fundamental Parameters
Field-Portable X-Ray Fluorescence
Federal Register Notice
Fourier Transform Infrared [spectroscopy]
Fluorescence Versus Depth
Gas Chromatography/Mass Spectrometry
Graphite Furnace Atomic Absorption
Gigahertz
Government Printing Office
Ground Penetrating Radar
Ground Water Remediation Technologies Analysis Center
Cyclotetramethylene Tetranitramine
High Performance Liquid Chromatography
U.S. Department of Housing and Urban Development
Inductively Coupled Plasma
Ion-Specific Electrode
Innovative Technology Evaluation Reports
Interstate Technology Regulatory Cooperation
Laser-Induced Breakdown Spectroscopy
Liquid Crystal Display
-------
List of Acronyms
LCS
LIF
MCA
MCL
MDL
MEK
MHz
MIBK
MS
MSA
MSD
MW
NCEPI
NERL
NETAC
NIST
nm
NMR
NPD
NTIS
OECA
OERR
OMA
ORD
OSW
OSWER
OUST
PAH
PAWS
PCB
PCE
Laboratory Control Spikes
Laser Induced Fluorescence
Multichannel Analyzers
Maximum Contaminant Levels
Minimum Detection Limit
Methyl Ethyl Ketone
Megahertz
Methyl Iso-Butyl Ketone
Matrix Spikes
Mine Safety Appliances
Matrix Spike Duplicates
Molecular Weight
National Center for Environmental Publications and Information
National Exposure Research Laboratory
National Environmental Technologies Analysis Center
National Institute of Standards and Technology
Nanometers
Nuclear Magnetic Resource
Nitrogen-Phosphorous Detector
National Technical Information Service
Office of Enforcement and Compliance Assurance
Office of Emergency Remedial Response
Optical Multichannel Analyzer
Office of Research and Development
Office of Solid Waste
Office of Solid Waste and Emergency Response
Office of Underground Storage Tanks
Polynuclear Aromatic Hydrocarbons
Portable Acoustic Wave Sensor
Polychlorinated Btphenyls
Tetrachloroethene
-------
List of Acronyms
PDA
PE
PFK
PID
PMT
ppb
PPE
ppm
ppt
PRC
PVC
QA/QC
QAPP
RCRA
RDX
RFI
RI/FS
RIA
ROST™
RPD
RPD
RSD
RT
SAWS
SCAPS
SDI
SDWA
SITE
SPE
SRM
SSCS
Photodiode Array
Performance Evaluation
Pertluorokerosene
Photoionization Detector
Photomultiplier Tube
Parts per Billion
Personal Protective Equipment
Parts Per Million
Parts per Trillion
PRC Environmental Management, Inc.
Polyvinylchloride
Quality Assurance/Quality Control
Quality Assurance Process Plan
Resource Conservation and Recovery Act
Trimethylenetrinitramine
RCRA Facility Investigation
Remedial Investigation/Feasibility Study
Radioimmunoassay
Rapid Optical Screening Tool
Relative Percent Difference
Relative Percent Differences
Relative Standard Deviation
Retention Time
Surface Acoustic Wave Sensor
Site Characterization and Analysis Penetrometer System
Strategic Diagnostics, Inc.
Safe Drinking Water Act
Superfund Innovative Technology Evaluation
Solid Phase Extraction
Standard Reference Materials
Site-Specific Calibration Sample
-------
List of Acronyms
STEL Short-Term Exposure Limits
SVOC Semi-Volatile Organic Compounds
TCA Trichloroethane
TCD Thermal Conductivity Detector
TCE Trichloroethene
TDS Tota! Dissolved Solids
THM Trihalomethanes
TIC Total Ion Chromatorgram
TIO Technology Innovation Office
TNT Trinitrotoluene
TTHM Total Trihalomethanes
TWA Time Weighted Averages
UV Ultraviolet
VIS Visible
VOA Volatile Organic Analysis
VOC Volatile Organic Compounds
WTM Wavelength-Time-Matrices
XRF X-Ray Fluorescence
-------
-------
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-------
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Field-Based Site
Characterization
Technologies Course
Presented by the U.S.
Environmental Protection
Agency's Technology
Innovation Office
EPA IN-I
This material has been funded wholly by EPA under Contract Number 68-W-99-003. Mention
of trade names or commercial products does not constitute endorsement or recommendation for
use.
IN-1
Module: Introduction
-------
Module Overview
4 Objective: To provide a general workshop overview
+ Key Points
»Instructor introductions
» Course goals and objectives
» EPA policy regarding innovative technologies
» Course organization
» Group assignments
EPA
IN-2
Notes:
The introduction to the course will cover the following topics: (1) instructor introductions, (2)
course goals and objectives, (3) EPA policy regarding innovative technologies, (4) course
organization, and (5) group assignments.
Module: Introduction
-------
Introduction Topics
c^ 4 Instructor introductions
+Course goals and objectives
4 EPA policy regarding innovative technologies
* Course organization
4 Group assignments
IN-3
IN-3
Module: Introduction
-------
Introduction Topics
* Instructor introductions
*=> •Course goals and objectives
• EPA policy regarding innovative technologies
• Course organization
• Group assignments
EPA
IN-4
Notes:
The following slides will examine the course goals and objectives.
IN-4
Module: introduction
-------
Course Goals
4- Introduce field-based site characterization
technologies
*The technologies course complements the Strategies
for Field-Based Analysis and Sampling Techniques
course
• Match field-based site characterization technologies to
project-specific objectives
4 Describe the practical considerations for applying the
various field-based site characterization technologies
4- Give participants hands-on experience in the use of
common field-based site characterization technologies
IN-5
Notes:
This course will give participants a detailed introduction to a wide array of field-based
technologies that can be used on site to analyze chemical contaminants and the physical
nature of environmental media. The general principles of operation for each class of
field-based site characterization technologies will be discussed. Participants will be given
enough information to understand the operational procedures well enough to evaluate
whether a given technology application is viable. However, the course is not intended to
teach participants how to operate the instruments.
The information about field-based technologies presented in this course, including
information about principles to enhance the effectiveness of QA/QC techniques,
complements the Strategies for Field-Based Analysis and Sampling Techniques course.
Participants will be able to match applicable field-based site characterization technologies
to objectives specific to a given project.
Participants will become aware of the advantages and limitations of each technology, the
logistics necessary to use each field-based site characterization technology, and the
sampling design and implementation considerations necessary to improve data quality.
Finally, participants will be given hands-on experience in using the most common field-
based site characterization technologies and the interpretation of the data they produce.
IN-5
Module: Introduction
-------
General Course Objectives
4- Identify levels of data quality achievable
• List possible interferences to be expected
4 List the logistical requirements
» portable
»transportable
• List factors that affect the quality of data
produced
4* Describe the characteristics of the measurement
IN-6
Notes:
For each technology, the following general course objectives apply:
- Identify levels of data quality based on performance data. EPA's Superfund
guidance has two levels of data quality: screening and definitive. California
Military Environmental Coordination Committee (CMECC) guidance has three
levels of data quality: good, fair, and poor.
— List natural and manmade interferences for each technology. This information is
essential in determining the applicability of a technology at a given site.
- List the logistical requirements for each technology. This information will allow
potential users to plan more reliably for the use of field technologies.
- Portable—self-contained units that require only a battery or common
electrical supply and that can operate without stable environmental
conditions
- Transportable—multicomponent systems that may require high voltage
power (220 volts), climate control, stable electrical current, and physical
stability (for example, a mobile laboratory setting)
IN-6
Module: Introduction
-------
List factors that affect the quality of data produced by the chemical and physical
analytical technologies. This information will be essential for the development of
a Quality Assurance Project Plan (QAPP) and it will dictate how a given
technology will be applied.
Describe what is being measured, if the measurement is quantitative or
qualitative, and the units of the measurement being generated.
IN-7
Module: Introduction
-------
Notes:
Introduction Topics
4- Instructor introductions
4 Course goals and objectives
•EPA policy regarding innovative technologies
4 Course organization
• Group assignments
EPA
IN-7
As an introduction to this course, it is important to have a basic understanding of EPA's
policy on innovative technologies. The following slides address this important point
through examination of EPA policy directions.
IN-X
Module: Introduction
-------
Field Measurement and Monitoring
encourages
+ OSWER Policy Directive 9380.0-25
use and evaluation
+ OSWER and ORD outreach programs support use
+ States encourage use at LIST sites
*• EPA has emphasized inclusion in SW-846
IN-8
Notes:
EPA's Policy Directive 9380.0-25 was released April 29, 1996. The directive was issued
by Elliott Laws, former Assistant Administrator of EPA. The directive openly
encourages the evaluation and use of new field measurement and monitoring methods.
Specific branches of EPA addressed in the policy directive include: the Office of Solid
Waste and Emergency Response's (OSWER) Office of Emergency and Remedial
Response (OERR), Office of Underground Storage Tanks (OUST), and Office of
Chemical Emergency Preparedness and Prevention (CEPPO); the Office of Enforcement
and Compliance Assurance (OECA); the Federal Facility Leadership Council, and EPA's
Brownfields coordinators.
Innovative cleanup and field measurement technologies are targeted in the policy
directive.
The OSWER directive places the use of innovative technologies as one of the
Administration's highest priorities. This initiative is intended to improve environmental
actions while reducing the cost and time needed to remediate a site. This course is an
extension of the policy and is designed to increase awareness of innovative technologies,
as well as provide guidance on how to use these technologies in the most effective
manner.
IN-9
Module: Introduction
-------
Quotes from Directive 9380.0-25 (printed in its entirety at the end of this module):
- "I would like to recognize and accelerate the trend toward greater use of
appropriate field methods."
— "EPA should support the use of new site assessment methods where they are
appropriate as either a complement or alternative to conventional sampling and
off-site analysis techniques in Superfund, RCRA, and UST actions."
- "....in specific cases, re-examination of DQOs may be appropriate so that we do
not unnecessarily exclude cost-effective methods because of overly stringent
requirements."
OSWER and the Office of Research and Development (ORD) have begun many outreach
and support programs to support and encourage the use of new and innovative field
measurement and monitoring technologies. These outreach and support actions include:
the Superfund Innovative Technology Evaluation (SITE) Program and the Environmental
Technology Verification (ETV) Site Characterization and Monitoring Technology Pilot.
OERR, ORD, and TIO have prepared a report on successful uses of field screening
technologies by EPA and other federal agencies.
A number of states have actively encouraged the use of field sampling and analysis at
underground storage tank (UST) sites and, in at least one case, have required the use of
field analysis in order for sites to qualify for reimbursement from the state fund.
EPA has shortened the time frame (from 30 months, to less than 18) for updates of SW-
846 and has emphasized the inclusion of field analytical techniques. The Office of Solid
Waste (OSW), who promulgates SW-846 methods, also is focusing on performance-
based measurements instead of "prescriptive" testing procedures.
m
For additional information on this topic, refer to page A-l at the end of this module.
IN-10
Module: Introduction
-------
Supporting Field-Based Site
Characterization Technologies
+ Site Characterization and Monitoring
Technologies Pilot
» Purpose
» Evaluation reports and verification statements
» Upcoming verification projects
» Promoting acceptance
4- Brownf ields
4- RCRA Corrective Action
IN-9
Notes:
The Site Characterization and Monitoring Technology Pilot is one of the 12 pilots
established under EPA's ETV program.
The pilot is a partnership program involving DOE's Sandia National Laboratories
(New Mexico) and Oak Ridge National Laboratory (Tennessee) to verify
commercially available site characterization and environmental monitoring
technologies.
The pilot began in the sring of 1995. To date, 29 innovative technologies have
been verified including: two cone pentrometer-deployed sensers, two field-
portable gas chromatograph/mass spectrometers (GC/MS), seven field-portable x-
ray fluorescence (FPXRF) analyzers, seven PCB field analytical technologies, six
soil/soil gas sampling technologies, and five well-head monitoring technologies
for measuring VOCs in water. Verification statements and reports are available
for each of these technologies.
EPA is actively promoting the use of field-based site characterization techniques at
Brownfields sites. For example, field-based site characterization techniques were
successfully used at sites in New Orleans and Arkansas under the Response Action
Contract (RAC) in EPA Region 6.
1N-U
Module: Introduction
-------
RCRA Corrective Action: The following excerpt was taken from the May 1, 1996,
Federal Register: Innovative Site Characterization Technologies. In the 1990 proposal,
EPA recommended a focused approach to site characterization activities. EPA continues
to support data collection approaches that focus on information needed to support
decisions. The Agency has seen tremendous improvements in site characterization
efficiency when innovative approaches are used, especially those that rely on rapid
sample collection (e.g., direct-push technologies) and on-site analytical techniques
(e.g., sensor technologies, assay kits, field gas chromatography/mass spectrometry
(GC/MS), X-ray fluorescence. Depending on the data quality objectives for a particular
site, confirmatory laboratory analyses may also be necessary.
The benefits of using innovative site characterization technologies are magnified when a
work plan is used only to convey strategies, methods, DQOs, and general areas subject to
investigation, and exact sample locations are left to be determined based on iterative on-
site data collection and analysis. Some of the benefits of using innovative
characterization techniques, along with iterative decision-making include: rapid sample
collection and analysis allowing for on-site decision making and optimization of the
investigation effort; enhanced three-dimensional understanding of the site because of the
greater number of data points available for a known commitment of resources; better
identification of actual or potential risks to human health and environmental receptors;
and, more rapid assessment of the need for interim actions.
Program implementors and facility owners/operators should take advantage of
innovative characterization technologies. Likewise, EPA encourages officials to be
receptive to innovative approaches which can significantly improve the quality, as well as
the cost- and time-effectiveness, of site characterization.
IN-12
Module: Introduction
-------
Supporting Field-Based Site
Characterization Technologies
(continued)
4 Innovative site characterization technology status
report
+ EPA REACH IT Web site
4 Navy/EPA field analytical technology screening
matrix
+ Expedited site characterization
guidance/presumptive characterization
IN-10
Notes:
TIO has compiled data collected from the EPA regions on past applications of innovative
field technologies to develop a report on their status. The report provides information on
over 200 applications of technologies such as field GC/MS, XRF, cone penetrometer
deployed LIF, and immunoassay techniques. For each application, the report includes
information on media and pollutants for which the technology was used; on reported
advantages and limitations; and costs when available. The report helps project managers
determine where the technologies have been used before and provides a point of contact
for each application who may be able to answer questions and concerns about the
technologies.
Questions about the status report should be referred to John Kingscott of TIO at
(703)603-7189.
The EPA REmediation And CHaracterization Innovative Technologies (EPA REACH IT)
web site is an electronic "yellow-pages" for field analytical technologies. This on-line
searchable database contains information about vendors, their field analytical
technologies, as well as specific technology application and performance information.
The information is provided by the vendors and can be searched by media, contaminants,
site type, technologies, and vendors to determine appropriate technologies and their
applicability for a specific site need. The system contains information on over 150
analytical, sampling, geophysical, and extraction technologies. The EPA REACH IT web
site homepage is at ()
IN-13
Module: Introduction
-------
Questions about EPA REACH IT Web site should be referred to the help line at
(800) 245-4505.
The Navy/EPA screening matrix is modeled after the Air Force/EPA treatment
technologies matrix developed in 1993. The matrix is intended to provide, in a poster
format, comparative screening information on analytical and sampling technologies. The
goal of the matrix is to ensure that project managers are aware of the full-range of
technology options available to them to assess and characterize contamination at their
sites. The matrix identifies as many as 75 sampling and analytical technologies and
provides comparative information along parameters such as media, contaminant,
applicability to various characterization phases (for example, screening, characterization,
and monitoring), cost, time requirements, detection limits, and quantitative data
capabilities.
Questions about this project should be directed to Dan Powell of TIO at (703) 603-7196.
TIO is working with representatives of the Superfund and RCRA Corrective Action
programs to provide guidance to EPA staff on the use of expedited processes and the
applicability of expedited site characterization and field technologies to both waste
programs. This effort will include a compilation and analysis of the various processes
currently in use by other organizations (Department of Energy's [DOE] SAFER,
Argonne's "Quicksite," American Society for Testing and Materials' (ASTM) standards
on expedited site characterization).
In addition, EPA is developing "presumptive" site characterizations for four common site
types. By developing templates for characterizing sites common to the Superfund, RCRA
Corrective Action, and Brown fields programs, the EPA seeks to increase understanding
and acceptance of field technologies by showing where reliable field methods can best be
used.
Questions about this project should be directed to Dan Powell of EPA's Superfund
program at (703) 603-8836.
IN-14
Module: Introduction
-------
Notes:
Introduction Topics
• Instructor introductions
• Course goals and objectives
• EPA policy regarding innovative technologies
• Course organization
• Group assignments
&EPA
IN-11
The following slides present the organization of this course. The course is designed as a
series of modules, each targeting specific areas of field-based site characterization. The
primary focus of the course is on technical issues; however, non-technical issues, such as
policy and resources, also are covered.
IN-15
Module: Introduction
-------
Workshop Organization
• Module 2: Overview of Field-Based Site Characterization
Technologies
* Module 3: Sampling Platforms and Direct Push
Technologies
• Module 4: Geophysical Characterization Techniques and
Data Interpretation
• Module 5: Organic Chemical Characterization
Techniques and Data Interpretation
• Module 6: Inorganic Chemical Characterization
Techniques and Data Interpretation
* Module 7: Sources for Field-Based Site Characterization
Technology Information
EPA IN-12
Notes:
Module 2: Overview of Field-Based Site Characterization. This module will address
implementation of site characterization techniques through discussion and presentation of
case studies which reflect the value of on-site analyses, real-time data production, and
detailed examinations of how site characterization technology selection affects QAPPs.
In addition, this module will briefly address the impact of sampling design on site
characterization. For deliveries of the three-day course, the major methods (total
platforms) for introducing sensors into subsurface soil or groundwater will be discussed
briefly.
Module 3: Sampling Platforms and Direct-Push Technologies. This module will
present factors to be considered in the use of two distinct approaches to sampling of
subsurface soils; drilling platforms and direct-push technologies. The basic components,
applications, and advantages and limitations of each will be discussed. Instructors will
use real-life examples to illustrate how the technologies are used to collect samples.
Instructors will discuss technologies that can be integrated with chemical and physical
sensors for performing in situ analyses. The chemical and physical sensors will be
discussed in detail during the geophysical, organic, and inorganic modules.
Module 4: Geophysical Characterization Techniques and Data Interpretation. This
module will present factors to consider when applying geophysical tools. The basic
components of each technology, principals of operation, common applications,
interferences, data interpretation, factors to consider in a QAPP, and advantages and
limitations will be discussed. Instructors will use real-life examples to illustrate how
IN-16
Module: Introduction
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these technologies can be integrated and how the combined data are interpreted. A brief
review of emerging technologies and methods will be given. For deliveries of the three-
day course, hands-on activities will be conducted.
Module 5: Organic Chemical Characterization Techniques and Data
Interpretation. This module will present factors to consider when applying organic
chemical characterization techniques. The basic components of each technology,
principals of operation, common applications, interferences, data interpretation, factors to
consider in a QAPP, and advantages and limitations will be discussed. Instructors will
use real-life examples to illustrate how these technologies can be integrated and how the
combined data are interpreted. A brief review of emerging technologies and methods will
be given. For deliveries of the three-day course, hands-on activities will be conducted.
Module 6: Inorganic Chemical Characterization Techniques and Data
Interpretation. This module will present factors to consider when applying inorganic
chemical characterization techniques. The basic components of each technology,
principals of operation, common applications, interferences, data interpretation, factors to
consider in a QAPP, and advantages and limitations will be discussed. Instructors will
use real-life examples to illustrate how these technologies can be integrated and how the
combined data are interpreted. A brief review of emerging technologies and methods will
be given. For deliveries of the three-day course, hands-on activities will be conducted.
Module 7: Sources for Site Characterization Technology Information. This module
will introduce participants to major publications and electronic sources of information
regarding site characterization technologies.
For deliveries of the three-day version of the course, participants will be given site
characterization problems to solve. This activity will be conducted in groups and it will
involve class presentations and group critiques of each presentation. The instructors will
assess the effectiveness of the course based on the results of the group exercises.
IN-17
Module: Introduction
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Introduction Topics
4 Instructor introductions
• Course goals and objectives
• EPA policy regarding innovative technologies
• Course organization
•Group assignments
&EPA
IN-13
IN-18
Module: Introduction
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UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
WASHINGTON. D.C- 20460
APR 29 1906
CX FCC C-
SOlO WASTE 4-.I ?•.'
MEMORANDUM OSWER DIRECTIVE
9380.0-25
SUBJECT: Initiatives to Promote^ Innovative Technology in Waste
Management Prog]
FROM: Elliott P. Law
Assistant Admini
TO: Superfund, RCRA, UST and-'CEPF National Policy Managers
Federal Facilities Leadership Council
Brownfields Coordinators
Environmental technology development and commercialization
are a top national priority for this Administration. I want to
add my personal commitment to this goal, and stress its
importance for the long-term hazardous waste remediation
challenge that lies ahead. This directive describes several
initiatives to facilitate the testing, demonstration, and use of
innovative cleanup and field measurement technologies.
s-
While we are in a time of uncertainty regarding ultimate
changes to the Superfund law, all parties share an urgent need to
improve the performance as well as lower the cost of site
cleanup. In addition, cleanups continue (and are increasing in
pace) in our other programs as well as the many emerging
voluntary state and local programs.
We have made considerable progress using new technologies in
the Superfund, RCRA, and Underground Storage Tank programs. In
the Superfund program better than half of the recent remedial
cleanup decisions for source control call for technologies which
were not available when the law was reauthorized in 1986. The
UST program has seen tremendous growth in the application of
alternatives to pump and treat or landfilling of petroleum
contaminated, media. Tens of thousands of UST sites are employing
approaches such as bioremediation, soil vapor extraction, air
sparging and natural attenuation either in combination with
traditional technologies or as the sole method of cleanup. The
large remaining cleanup needs in EPA programs, as veil as the
formidable future requirements for state and other federal
agencies, provide a continuing impetus to find less expensive and
more effective solutions.
Atcycfed/ftocyciabl*
AMM ««h SofCaneu Ink «n p*p* rat
•Mrin* «Ira* SOX ntcy*** tt«r
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These initiatives recognize that the state of remediation
science today requires us to take experimental approaches. They
are based on cooperation with other government and private
entities that share our interest in developing the next
generation of remediation technologies. They envision
partnerships with agencies, states, and the private sector to
jointly develop and apply solutions which will allow us to
protect public health and the environment more efficiently. While
these initiatives are directed primarily to programs we
implement, many states are actively pursuing innovative
approaches and may find these initiatives to be of value.
I look forward to your proposals and efforts to promote the
development and implementation of these potentially high payoff
solutions.
The following initiatives apply, as appropriate, to UST
cleanups, RCRA Corrective Action, Superfund Fund lead,
Responsible Party Lead, and Federal Facility Lead removal and
remedial sites.
ATTACHMENT
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Promotion of Innovative Technologies in
Waste Management Programs
Place a Higher Priority on Innovative Treatment and Characterization
Technologies
1. Routinely Consider Innovative Treatment Technologies ffbere
Treatment Is Appropriate
OSWER encourages reasonable risk-taking in selecting
innovative technologies for treating contaminated soils, sludges,
and groundwater. EPA regional and headquarters managers should
support Remedial Project Managers, On-Scene Coordinators, and
other remedial action decision-makers in using new technologies.
A recent analysis of Superfund Feasibility Studies found
cases where innovative technologies were eliminated from
consideration because they required testing to determine their
applicability at a particular site. Promising new technologies
should not be eliminated from consideration solely because of
uncertainties in their performance and cost, particularly when a
timely treatability study could resolve those uncertainties.
There is potential tension between our conr.itment to site
cleanup targets and advancing innovative technology. When an
innovative technology has potential site-specific and/or program-
wide benefits, do not be risk averse toward adopting it despite
possible impacts on the schedule for project completion. TIO is
prepared to assist Regions in evaluation of the potential
programmatic benefits of innovative approaches and adjustment, as
appropriate, of regional commitments. Regions may wish to
consider using performance management and award systems to foster
risk taking by project managers. ' ""'._-
Headquarters will ensure that Presumptive Remedy revisions
incorporate new technologies in a timely fashion. Furthermore,
we will expand interagency efforts to gather cost and performance
information for completed full-scale innovative cleanups.
In the RCRA context, EPA has.revised its Treatability study
Sample Exclusion regulations (40 CFR 261.4(e)-(f))to allow
treatability studies on up to 10,000 kg. of media (soil, debris,
sediment and ground water) contaminated with non-acute hazardous
waste without the requirement for permitting and manifesting.
This revision should help make treatability studies easier to
implement.
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For actions under RCRA, regulatory staff will be in a
position of reviewing proposals from owner/operators, and
possibly discussing options with their state counterparts.
Program managers should encourage owner/operators to consider
innovative approaches and, where appropriate, direct parties to
sources of assistance and information.
2. Encourage Evaluation and Use of New Field Measurement/
Monitoring Methods
Traditional approaches to on-site sampling and reliance on
off-site analysis have been time consuming and expensive. This
has had an adverse effect on site characterization and remedy
implementation efforts. New field sampling and analytical
approaches offer the potential for considerable time and cost
savings compared to conventional monitoring and measurement '
procedures.
I would like to recognize and accelerate the trend toward
greater use of appropriate field methods. EPA's Brownfields
Initiative - with the objective of encouraging productive reuse
of the land - provides a new and unique opportunity to try
approaches that make sense from a practical engineering
perspective. EPA technical assistance resources can be made
available to assist Brownfield site managers who wish to consider
innovative approaches to site characterization and monitoring.
EPA should support the use of new site assessment methods
where they are appropriate as either a complement or alternative
to conventional sampling and off-site analysis techniques in
Superfund, RCRA and UST actions. The ultimate objective is to
provide a flexible investigative posture involving a mix of field
screening and analytical approaches combined with traditional
sampling and off-site laboratory analysis, where appropriate and
necessary. -.-..•-.
A number of these new approaches appear able "to consistently
provide data of known quality and thus nay be able to meet
established Data Quality Objectives (DQOs).! Nevertheless, in
specific cases, re-examination of DQOs nay be appropriate so that
we do not unnecessarily exclude cost-effective methods because of
overly stringent requirements.
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OSWER headquarters and the Office of Research and
Development (ORD) have begun several supporting efforts:
A new data base of on-site methods - Vendor FACTS - is
nov available.
The Consortium for Site Characterization Technology, a
cooperative public-private venture, is conducting
consensus performance evaluations of field screening
technologies. Region III and X managers represent EPA
users1 interests on the Board of Advisors of this
venture.
in cooperation with OERR and ORD, TIO is preparing a
status report on successful field screening usage by
EPA and other federal agencies to serve as a reference
and referral guide.
A number of State UST programs are actively promoting
field sampling and analysis to characterize leaking UST
sites, in at least one case requiring that field
analytical methods be used if the responsible parties
expect reimbursement from the state Fund. OUST is
developing a new manual to help regulators oversee
expedited site characterization.
We have significantly shortened the time frame for
including new methods in SW-846. Furthermore, a nunber
of new inuTiUno-assay and other cost saving techniques
for qualitative site characterization will be included
in the forthcoming update of SW-846.
3. support the Use of Innovative Approaches for Groundwater
Remediation
We have made substantial progress in implementing innovative
technologies for source control-. However, we" are not'making the
sane progress with groundwater remediation technologies. Most
existing groundwater remedies involve pumping water to the
surface, where it is treated by conventional methods ("pump and
treat"). In the Superfund program, fewer than six percent of
selected groundwater remedies involve in situ methods. The longer
lead-tine for results from groundwater projects causes additional
delays in bringing new approaches into widespread use.
Regions should be mindful of the potential of new in-situ
processes such as permeable barrier treatment walls and dual-
phase extraction wells to speed cleanups and provide cost
savings. The nunber of opportunities provided for responsible
evaluation of new approaches is an appropriate neasure of progran
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success. Sites which are currently stabilized - i.e., by
providing plume control through pump and treat - are excellent
candidate "test beds' for promising alternatives. Cooperation
with other federal agencies, states, and private interests to
jointly demonstrate and evaluate promising in-situ groundwater
technologies is encouraged.
Some states may have restrictions on the re-injection of
treated ground water as veil as the injection of amendments to
enhance degradation or flushing. Regions should look for
opportunities to work with states for at least limited variances
to allow the demonstration and use of promising new technologies.
"Pump and Treat1 is no longer the dominant remediation
method for leaking UST sites with contaminated groundwater(It is
now used at 29% of UST groundwater sites.). Natural Attenuation
has been deemed acceptable at 47% of the groundwater sites,
followed by air sparging, bioremediation, and dual phase
extraction.
To help coordinate work in this area, we have established a
Ground Water Remediation Technologies Analysis Center (GWRTAC)at
the National Environmental Technologies Applications Center
(NETAC)in association with the University of Pittsburgh. The
Center will collect and distribute information on trends in
research, development and application activities; perform
technology transfer; and conduct meetings with stakeholders to
foster technology inproversnt. The Center will serve as a
technical resource complementary to the ORD laboratories.
GWRTAC's toll free number is 800-373-1973, and the World-Wide
Web home page is http://vw.chmr.gwrtac.
Reduce Impediments to Innovative Technology Development ami Use
Regulatory Impediments
4. streamline RCR* permits and Orders for Innovative Treatment
Technology Development and Use
Regions are encouraged to use the flexibility already
provided by existing statutes and regulations to bring promising
new technologies into the field. We need to work more as team
members, rather than traditional regulators, to coordinate with
EPA laboratories, other federal agencies, states and the private
sector in pursuit of our common interest of furthering new
processes. He need to identify opportunities for streamlining
our requirements while still fulfilling our responsibility to
protect public health and the environment. Additionally, ve need
to set our technical priorities so limited resources can be
directed to projects with the greatest potential benefits.
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a. consider Alternatives to Conventional Permits
While issues related to RCRA permitting nay be addressed in
the future (through the Hazardous Waste Identification
Rule(HWlR), the Permit Improvements Team, and RCRA
reauthorization), Regions should consider the application of
existing alternatives to conventional RCRA Corrective Action,
Research, Development and Demonstration (RD&D), and Subpart X
permits for pilot and full-scale applications of new technology.
As you know, RCRA permits are not required at petroleum UST
and Superfund sites. At CERCLA sites and RCRA interim status
facilities, enforcement orders nay be used to enable testing and
use of new technologies. At permitted facilities, Regions should
encourage authorized states to consider using the flexibility
provided in temporary authorizations of the permit modifications
rule and the flexible standards for temporary units. For non-
Super fund, non-RCRA, and non-UST sites, it is possible that state
orders may be used in lieu of permit requirements.
b. Avoid Unnecessary Regulatory Control
When considering new technology applications, we need to ask
ourselves whether prior assurance that cleanup standards will be
met is necessary. For treatability studies and demonstration
projects, seeking assurance of success as a precondition to
testing makes little sense since this is the purpose of the
investigation itself.
For full-scale remediation, ex-situ processes are often
required to dem'onstrate compliance as part of start-up
activities. Furthermore, responsible parties and owners/
operators remain ultimately responsible for site cleanup and
adherence to standards.
. For RCRA corrective action, the ability to attain media
dleanup standards is one of four General Standards for Remedies.
Since owner/operators continue to be responsible for meeting
cleanup standards, it is appropriate that proposed remedies be
evaluated on the basis of reasonable likelihood, subject as
appropriate to verification testing and performance monitoring.
To the extent possible, we should avoid being overly prescriptive
regarding technical design and operation when we consider new
technology applications.
Risks of cross-media transfer and worker exposure depend on
site specific conditions in addition to the technology under
consideration. For some contaminants, technologies such as
bioremediation and .soil washing present particularly Minor risk,
and an appropriate level of regulatory control should be applied.
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c. Recognize the special Needs of in-situ Processes
Although the recently-revised treatability study rule will
help to ease many of the testing restrictions currently
inhibiting nev technology development, there vill still be
situations where testing on larger quantities of waste may be
needed, particularly for in-situ approaches. While there nay be
specific exceptions, in-situ testing generally poses minimal
exposure risk. Concerns about spreading contamination should be
viewed in light of the scale of the project and weighed against
the benefits which will accrue from the field experience and
associated lessons learned. Sites with existing containment
systems, such as slurry walls, may provide locations which are
particularly well-suited for testing new processes.
As previously mentioned, the development of new in-situ
groundwater technologies is a particular OSWER priority. Due to
the lead times required to get results, we should work to get
these projects into the field as soon as possible.
5. Encourage State Adoption of aad streamline EPA Authorization
to Administer the Treatability Study Sample Exclusion Rule
As mentioned earlier, we recently amended regulations that
facilitate the development and evaluation of hazardous waste
remediation technologies by increasing the quantity of
contaminated material that may undergo treatability testing while
remaining conditionally exempt from regulation under RCRA (e.g.,
manifesting and permitting) . The regulation allows treatability
studies on up to 10,000 kg of media (soil, debris, sediment and
groundwater) contaminated with non-acute hazardous waste and
allows up to two years studies involving bioremediation.
While lessening regulatory impediments, the rule retains
notification,.-record-keeping, and reporting requirements. Since
the rule is an optional provision, full .effectiveness depends on
adoption by states with delegated RCRA programs.
EPA is 'currently evaluating changes to its regulations that
will expedite the revision of authorized state programs. During
the time this regulatory effort is moving forward, EPA strongly
encourages Regions to act promptly on requests for authorization
for the revised Treatability Study Sample Exclusion Rule. 40 CFR
270.21 provides considerable flexibility in the amount of
information EPA requires for state program revision.
Because this rule is not complex and is less stringent than
the current provisions, a minimum amount of information can be
required. States should apply for authorization for this rule by
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simply sending a letter to the appropriate Regional office,
certifying that equivalent provisions have been adopted. The
state should also submit a copy of its final regulations or other
authorities.
6. Utilize Federal Facilities as Sites for Conducting
Technology Development and Demonstrations
An EPA Policy for Innovative Environmental Technologies at
Federal Facilities, signed by Administrator Browner in August
1994, documents EPA's commitment to promote the use of Federal
facilities as demonstration and testing centers for innovative
environmental technologies. Federal facilities offer unique
opportunities for the development and application of both field
site characterization and cleanup technologies. Regions are
encouraged to work with states, as co-regulators to ensure
acceptance, and with other federal agencies to promote testing
and use of new approaches. Cooperative efforts are needed to
develop permit conditions which do not unreasonably restrict
technology demonstrations at Federal facilities.
The policy "encourages the incorporation of inm ative
technology conditions in appropriate EPA/Federal agency cleanup
and compliance agreements..." As appropriate. Regions should be
flexible in setting cleanup milestones and make adjustments where
appropriate.
OECA's Federal Facilities Enforcement Office will implement
a pilot program through the Environmental Technology Initiative.
The pilot will seek opportunities to utilize the flexibility that
enforcement mechanisms may offer.
Informational Impediments
7. Build aa: Institutional Knowledge Base of Remediation
Technology Experience • • •- ~
We are.finally reaching the point where a meaningful number
of cleanups involving innovative technologies are being
completed. It is important that the often hard-won experience
from these early applications be readily available to assist
other remedial action decision makers. In cooperation vita other
federal agencies through the Federal Remediation Technologies
Roundtable, OSWER has developed a Guide to Documenting Cost and
Performance tor Remediation Projects (EPA-542-B-95-002/Mar 95).
TIO has taken the lead in working with Regions and the
Departments of Defense and Energy to prepare an initial set of
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project reports and is working on a second round. Thirty-seven
reports are currently available in three volumes and will be
available on the World Hide Web in 1996. This work is an
important follow-on to technology demonstration reports prepared
by the Superfund Innovative Technology Evaluation (SITE)program.
It is time to transition to a posture of preparing completed
project reports as a normal part of the site remediation effort.
OERR recently issued guidance regarding tasking our contractors
to prepare reports in a specified format. TIO will continue to
provide assistance in completing these reports and will develop
additional means of ensuring widest possible dissemination of
this valuable information.
Since approximately 70% of Superfund sites are Responsible
Party lead, cooperation with the private sector is an important
component of obtaining remedy implementation information. We
will work with OECA and Regions to develop mechanisms to elicit
remedy cost and performance information from RPs at selected RP
lead cleanups.
Region 1 has volunteered to work with headquarters staff and
states in Region 1 on a short pilot effort to refine the
mechanics of implementing this initiative.
Share Risk of Using Innovative Treatment Technologies
8. EPA Will Share the Risk of Implementing Innovative
Technology With Responsible Parties at Superfund Sites
The prospect of paying twice if a remedy fails discourages
innovation. As a Superfund reform initiative, EPA has agreed to
share the risk for a limited number of approved projects by
"underwriting" the use of certain promising innovative
approaches. If the innovative remedy fails to perform as
: required, EPA will contribute up to 50% of the cost of the 'faile
remedy if additional remedial action is required, up to a -
specified maximum amount.
This initiative will encourage PRPs to assume a more active
role in technology development. Projects will include leading-
edge environmental technologies and early application of units
with significant potential for lowering costs or improving
performance.
Guidelines to implement this program, announced in concept
as a Superfund Reform, are being revised based on regional
comments. To date, one project has been approved. He plan to
approve a limited number of pilot projects this fiscal year.
8
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9. Indemnify Innovative Technology Response Action Contractor*
The Superfund Response Action Contractor Indemnification
Final Guidelines, published on January 25, 1993, provide that EPA
may offer indemnification to Innovative Technology (IT)
subcontractors. Prime contractors have informed EPA that the
prospect of being responsible and accountable for the actions of
the IT subcontractor and not being indemnified has inhibited
prime contractors from fully utilizing innovative technologies.
To encourage prime contractors to use innovative
technologies, EPA will provide indemnification to both the prime
contractor and to its IT subcontractor. The indemnification
agreements with the prime contractor and the IT subcontractor
will have identical deductibles, limits and terms.
I would also like to clarify that prime contractors are not
required to solicit IT subcontracts using the competition factor
outlined in the Final Guidelines for new response action contract
solicitations. Prime contractors should request pe nission to
include indemnification provisions from the EPA Administrative
Contracting Officer prior to releasing the solicitation.
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Field-Based Site Characterization Philosophy
Overview of Field-Based
Characterization
OV-1
OV-I
Module: Overview of Field-Based Site Characterization
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Field-Based Site Characterization Philosophy
Module Overview
+Objective: To present approaches and tools for
field-based site characterization
OV-2
Notes:
The objective of this module is to present the reasons why field-based site
characterization is used, how it can be applied, and what can affect the quality of data
generated. The module also will present an overview of some types of technologies used
to facilitate field-based site characterization.
OV-2
Module: Overview of Field-Based Site Characterization
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Field-Based Site Characterization Philosophy
Overview of Field-Based Site
Characterization
• Field-based site characterization philosophy
4 Components of field-based site characterization
OV-3
OV-3
Module: Overview of Field-Based Site Characterization
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Field-Based Site Characterization Philosophy
Field-Based Site Characterization
Philosophy
• Streamline the site characterization and remedial
processes
• Minimize mobilizations to a site
• Produce more data on a site at lower costs
relative to conventional approaches
• Produce data in near real time
• Produce measurable data quality
OV-4
Notes:
On-site qualitative or quantitative characterization of a site's physical or chemical
features is determined by near real-time data acquisition. This approach to site
characterization often is referred to as "field screening."
Overall, field analysis can streamline field activities because it allows for contingency-
based characterization or remediation. Field analysis provides flexibility to the project
manager that traditional off-site analysis does not.
Field analysis allows real-time decision-making that will minimize the number of
mobilizations necessary to characterize a site. This will reduce costs. The cost savings
also can be applied to remediation monitoring. For example, data from a cone
penetrometer-laser induced fluorescence (LIF) system can be used to determine locations
for monitoring wells. Many site characterizations and removal actions can be completed
in a single mobilization. This is due to the flexibility of a sampling plan driven by results
of field analysis.
OV-4
Module: Overview of Field-Based Site Characterization
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Field-Based Site Characterization Philosophy
Field analysis is almost always faster than conventional analysis using an off-site
laboratory, for example: EM-31 or ground penetrating radar (GPR) versus trenching; or
on-site gas chromatography (GC) analysis versus off-site GC analysis. Because of the
speed of data production and relative lower cost, more characterization data generally is
produced. For example, for $3,000 you could analyze approximately 20 samples at an
off-site laboratory for volatile organic compounds (VOC). For the same cost, including
approximately $1,500 for a chemist, you could analyze 30 to 50 samples per day for 5
days (150 to 250 total samples) with on-site analysis.
The turnaround time involved with sending data to an off-site laboratory can vary from
several weeks to several months. Faster analysis is possible with off-site laboratories,
but, it has an associated higher cost. Generally, cutting the normal turnaround time in
half doubles the cost of the analysis at an off-site laboratory. Field analysis produces data
for individual samples, often within 1 hour, and for batches of 30 to 50 samples, within
24 hours. This "real-time" data is important because it allows for contingency-based
decisions to be made by the project manager which cannot be made using traditional off-
site analysis.
Field analysis should incorporate sufficient quality assurance/quality control (QA/QC)
procedures to allow evaluation of data quality. Sufficient QA/QC procedures often are
assured through the collection of confirmatory samples.
OV-5
Module: Overview of Field-Based Site Characterization
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Field-Based Site Characterization Philosophy
Common Applications of Field
Analysis
Real-time identification and characterization of
contaminant sources (Brownfields and
accelerated site characterization)
Real-time definition of magnitude and extent of
contamination during remedial investigations
Real-time monitoring of removal actions
Monitoring of remedial actions
Nonintrusive characterization of the subsurface
Nonintrusive identification of buried materials
EPA
Notes:
Real-time identification and characterization of contaminant sources often is used to aid
in removal of a source. With field analysis, the identification and characterization
activities can occur simultaneously or in rapid succession.
Real-time identification of the extent and magnitude of contamination often is used to
fully characterize a site in a single mobilization of equipment, and to identify "essential"
sampling locations.
Real-time monitoring allows removal actions to continue without delay for confirmation
analysis, and it restricts removal to only materials identified as hazardous.
Monitoring of remedial actions, either during implementation or long term, allows for an
assessment of the effectiveness of remedial actions.
Nonintrusive characterization of the subsurface allows for locating soils, trenches,
groundwater, and bedrock without drilling. This aspect can be important in landfills or
other hazardous environments.
Nonintrusive identification allows for locating buried materials while eliminating the
potential for damaging the material.
OV-6
Module: Overview of Field-Based Site Characterization
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Field-Based Site Characterization Philosophy
Advantages of Field Analysis
+ Detection limits generally below risk-based or
removal action levels
4- Fast data turnaround allows contingency-based
site characterization or remediation
4 Greatly reduces the need for repeated site visits
+ Reduces the number of samples sent off-site for
analysis
* Helps monitor data quality objectives
^On-site removal action monitoring
OV-6
Notes:
Risk-based or removal action levels are the target of field analysis, not necessarily SW-
846 method detection levels. Risk-based action levels can be based on various exposure
scenarios, such as potential impact to groundwater.
The concept of a contingency-based approach to site characterization or remediation
provides flexibility to projects. This approach allows real-time data to guide a project,
providing a better chance for meeting project objectives. A contingency-based approach
only is viable if a sampling plan is written with specific objectives and methods for
reaching those objectives. This type of approach to site characterization allows dynamic
sampling that targets only areas of concern.
Reducing the need for repeated site visits and reducing analytical and consultant costs
both contribute to cost savings associated with faster site characterization and
remediation.
Only confirmation samples or compliance samples are required to be sent to off-site
laboratories for a higher level of data quality analysis. Using field analysis reduces the
analytical (off-site) resources required for analyzing samples that do not directly address
project objectives.
OV-7
Module: Overview of Field-Based Site Characterization
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Field-Based Site Characterization Philosophy
Using on-site analysis will help to identify strategic samples to be sent for off-site
analysis which, in turn, helps to monitor the data quality objectives of the project such as
monitoring for proper decontamination of equipment or homogeneity of field duplicates.
On-site removal action monitoring saves costs by reducing the need for down time of the
removal contractor or remobilization due to delays in obtaining analytical results.
OV-8
Module: Overview of Field-Based Site Characterization
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Field-Based Site Characterization Philosophy
Limitations of Field Analysis
^Often difficult to obtain regulatory approval
4 Requires a higher level of training for field personnel
* Data acceptability generally dependent on
comparability with off-site analysis
4 Can cost more in the short term
+ Requires some knowledge of the site contaminants
(potential)
4 Requires some knowledge of the site and its
stratigraphy
&EPA
OV-7
Notes:
m
The notion that it is difficult to obtain regulatory approval of analytical results obtained in
the field often is tied to the misconception that only SW-846 methods are acceptable.
Using a performance-based assessment of field analysis data quality should minimize
these concerns. EPA is beginning to stress performance-based evaluations of data quality
as opposed to a blanket acceptance of data produced by SW-846 methods. Some state
regulations may require that SW-846 methods be used.
For additional information on this topic, refer to page A~l at the end of this module.
Generally, trained geophysicists or chemists are needed to lead field analysis teams. In
addition, the effective use of field analysis in a contingency-based approach requires
personnel experienced in site characterization and remediation.
Performance often is judged by comparing the results of confirmatory analysis to field-
based results. This approach can delay evaluation of the field analysis data until the
project is complete. The risk can be minimized by strong analytical QA/QC and the
running of performance evaluation (PE) samples. Geophysical data can be checked in the
field through limited intrusive sampling in select areas.
OV-9
Module: Overview of Field-Based Site Characterization
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Field-Based Site Characterization Philosophy
Completing a site characterization in a single year or less requires more up-front capital
than stretching the process out over several years. For example, assume there is a facility
with an annual environmental budget of $50,000. A Resource Conservation and
Recovery Act (RCRA) Facility Investigation (RFI) could be done in a single year for
$250,000 using a field-based approach; however, this amount is much more than the
approved annual budget. In many cases, facility managers would be compelled to select a
conventional approach taking many years and generally costing more in the long run.
Potential or actual contaminants present must be known so that specific analytical
approaches can be used. If field analysis is applied only where potential contaminants
have been identified, dual column or mass spectrometer confirmation of constituents for
early samples is required to allow for more reliable compound identification. This also
can be a problem using a traditional methodology if the wrong analytical methods are
selected.
An understanding of potential interferences and the subsurface is needed to evaluate the
potential usefulness of geophysical tools.
•OV-10
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Components of Field-Based Site Characterization
Overview of Field-Based Site
Characterization
*• Field-based site characterization philosophy
=>• Components of field-based site characterization
OV-8
OV-ll
Module: Overview of Field-Based Site Characterization
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Components of Field-Based Site Characterization
Notes:
Components of Field-Based
Characterization
^Quality assurance project plans
4 Project scoping (choosing technologies)
* Sample measurements ex situ versus in situ
+ Data quality levels
* Data comparison
OV-9
The following slides will discuss the various components of a routine site
characterization. Detailed discussion of such issues as data quality objectives is provided
in a complementary course entitled Strategies for Field-Based Analytical and Sampling
Technologies Course, also offered by EPA's Technology Innovation Office (TIO).
OV-12
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Components of Field-Based Site Characterization
Quality Assurance Project Plans
4- Objectives for site characterization
4 Means of assessing whether objectives have
been met
+ Specific field activity plans match site
characterization tools and sampling to objectives
+QA/QC measures to assure the data is useable
OV-10
Notes:
The objective must be measurable.
Specific measurements must be made to assess whether objectives have been met.
OV-13
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Components of Field-Based Site Characterization
Specific field activity plans should be written to describe site characterization tools and
sampling methods required to meet project objectives. These plans for data collection
will include sampling, geophysical, and analytical methods
QA/QC measures will be of two types: (1) those implemented in the field to monitor the
relative quality of the data being produced (for example, split samples to assess sample
homogenization and PE samples for analytical systems) and (2) those involving off-site
confirmation of on-site data, most often, analysis as confirmatory samples of 10 to 20
percent of the total number of samples collected.
OV-14 •
Module: Overview of Field-Based Site Characterization
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Components of Field-Based Site Characterization
Effective Project Scoping
Know what the field analysis technology
measures
the factors controlling the performance of a
field analysis technology
Match sampling tools to site characterization
technologies
Have specific objectives for use of field analysis
data
EPA
OV-11
OV-15 •
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Components of Field-Based Site Characterization
Ex Situ versus In Situ Technologies
^^^^| Ex s/fulechnoloqiGb In situ technologies ^^^
€
Physical collection of sample
Containerization, preservation, and holding time
of sample
Loss of volatiles during sampling prior to
analysis
Archival of sample for Further analysis
Can analyze both discrete and composite
sample
Can be analyzed from numerous sampling
platforms
r EPA
Sample analyzed in place (no physical evidence
of sample)
No containerization, preservation, or holding time
requirements apply
Minimal loss of volatiles
No archival of sample for further analysis
Can only analyze discrete sample
Must have device to advance the sensor into the
medium
OV-12
Notes:
Ex situ analytical technologies require some type of physical collection of samples;
therefore, such technologies have both advantages and limitations. That is, the sample
must be taken to the instrument for analysis. One example of ex situ analytical
technology is immunoassay analysis of polychlorinated biphenyls (PCS).
In situ analytical technologies do not require collection of samples. Simply stated, the
instrument is brought into contact with the sample in place; without removal of the
medium and placement in containers. One example of in situ analytical technology is the
laser-induced fluorescence analysis of fuels by the Geoprobe or Site Characterization and
Analysis Penetrometer System (SCAPS).
Note that some instruments can be used in either type of application; some models of gas
chromatographs can be taken directly to the medium for analysis (gaseous media only),
while, for other models, the sample (or solvent extract of the sample) is injected in a fixed
instrument.
Data quality may be jeopardized when incorrect containers or preservatives are used
during sample collection. In situ analytical technologies do not require that samples be
placed in containers and preserved.
When volatile organic compounds are the constituents of concern, placing samples in
containers may result in the loss of analytes. When in situ analytical technologies are
OV-I6'
Module: Overview of Field-Based Site Characterization
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Components of Field-Based Site Characterization
used, loss of analytes is minimized because the medium is not exposed directly to surface
conditions.
When ex situ analytical technologies are used, both discrete and composite samples may
be collected. When in situ analytical technologies are used, only discrete samples of the
medium are analyzed. The use of a field-based in situ analytical technology may reduce
expenses enough to analyze a larger number of discrete samples, giving the data user
better spatial distribution of contaminants.
Ex situ analyses can be performed on samples collected by all sampling devices currently
in use, while, for in situ analyses, the sensing device of the instrument must be placed
directly into the sample medium. The placement of sensing devices into subsurface soil
or groundwater, for example, requires the use of specially designed advancement systems.
Those systems will be discussed in detail in the next module.
OV-17-
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Components of Field-Based Site Characterization
Levels of Data Quality and Usability
+Superfund data categories
» Screening (qualitative and quantitative)
» Definitive
+ Removal site assessment and removal action
4- RCRA corrective action DQOs
4 Risk assessment (qualitative and quantitative)
OV-13
Notes:
In EPA's Data Quality Objectives Process for Superfund, September 1993, only two
levels of data quality, are defined, screening and definitive.
- Screening data are generated by rapid, less precise methods of analysis, with less
rigorous sample preparation. The steps in sample preparation may be restricted to
simple procedures, such as dilution with a solvent, instead of elaborate extraction
and digestion and cleanup. Screening data allow identification and quantification
of analytes, although the quantification may be relatively imprecise. At least 10
percent of screening data are confirmed through analytical methods and QA/QC
procedures and criteria associated with definitive data. Screening data without
associated confirmation data are not considered to be data of known quality.
Screening data may be further divided into two categories that are not specified in
the Superfund guidance: qualitative (presence or absence) or quantitative.
- Definitive data are generated through application of rigorous analytical methods,
such as approved EPA reference methods. Data are analyte-specific, with
OV-I8-
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confirmation of the identity and concentration of the analyte. Methods produce
tangible raw data (for example, chromatograms, spectra, digital values) in the
form of paper printouts or computer-generated electronic files. Data may be
generated at the site or at an off-site location, as long as the QA/QC requirements
are satisfied. Either analytical or total measurement error must be determined if
the data are to be considered definitive.
According to OSWER Directive 9360.4-01, QA/QC Guidance for Removal Activities,
on-scene coordinators (OSC) use three types of quality assurance objectives (QAO) and
DQOs. The levels are similar to the levels in the Superfund guidance, with screening data
categorized as qualitative or quantitative data.
In an excerpt from the May 1, 1996, Federal Register concerning RCRA corrective
actions, EPA encouraged program implementors and facility owners or operators to use
the DQO approach to define the extent of data collection that is sufficient to support
decisions about corrective action. EPA concluded that site investigations can be
expedited considerably when DQOs are established carefully. For additional information
about incorporating DQOs in the decision-making process at RCRA facilities, see:
Chapter One of SW-846, Test Methods for Evaluating Solid Waste,
Physical/Chemical Methods, Third Edition, as amended by Update I, July 1992;
- Final Guidance for the Data Quality Objective Process, EPA QA/G-4, September
1994
- Quality Assurance Project Plans for RCRA Ground-Water Monitoring and
Corrective Action Activities, EPA, Sylvia Lowrance and H. Matthew Bills, July
1993.
Under a qualitative risk assessment, the analysis is general in nature and usually consists
of a determination of the presence or absence of a potentially toxic constituent. For those
reasons, field analytical techniques that can supply such data would be sufficient. For a
quantitative risk assessment, data must be of much higher quality. The usability criteria
for a quantitative risk assessment are:
- Data sources
- Documentation
- Analytical methods and quantitative limits
- Data quality indicators
- Data review
m
For additional information about this topic, refer to page A-1 at the end of this module.
OV-19'
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Additional Information
Table of Contents
Field-Based Site Characterization Philosophy A-2
Quality Assurance Project Plans A-21
Data Quality and Usability A-22
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Field-Based Site Characterization Philosophy
DISCLAIMER IN SW-846 MANUAL
Mention of trade names or commercial products does not constitute endorsement or
recommendation for use by the EPA.
SW-846 methods are designed to be used with equipment from any manufacturer that results in
suitable method performance (as assessed by accuracy, precision, detection limits and matrix
compatibility). In several SW-846 methods, equipment specifications and settings are given for
the specific instrument used during method development, or subsequently approved for use in the
method. These references are made to provide the best possible guidance to laboratories using
this manual. Equipment not specified in the method may be used as long as the laboratory
achieves equivalent or superior method performance. If alternate equipment is used, the
laboratory must follow the manufacturer's instructions for their particular instrument.
Since many types and sizes of glassware and supplies are commercially available, and since it is
possible to prepare reagents and standards in many different ways, those specified in these
methods may be replaced by any similar type as long as this substitution does not affect the
overall quality of the analyses.
A-2
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Field-Based Site Characterization Philosophy
Selected Slides From:
ANALYTICAL STRATEGY
FOR THE
RCRA PROGRAM:
A PERFORMANCE-BASED APPROACH
By Barry Lesnik, Office of Solid Waste
1997
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Field-Based Site Characterization Philosophy
WHAT IS SW-846?
Test Methods for Evaluating Solid Waste, or SW-
846, is the compendium of analytical and test
methods approved by EPA's Office of Solid Waste
(OSW) for use in determining regulatory
compliance under the Resource Conservation and
Recovery Act (RCRA).
SW-846 functions primarily as a guidance
document setting forth acceptable, although not
required, methods to be implemented by the user,
as appropriate, in responding to RCRA-related
sampling and analysis requirements.
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Field-Based Site Characterization Philosophy
MANDATORY APPLICATIONS OF SW-846
METHODS
• These applications where the use of SW-846
methods is mandatory can be grouped into the
following five categories:
4 Determination of a hazardous waste
characteristic
4 Determination of free liquid (Method
9095)
4 Analyses associated with submission of
delisting petition
4 Analyses associated with a hazardous
waste incinerator trial burn
4 Determination of air emissions from
process equipment
• Specific regulatory citations are listed on the
following slides
A-5
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Field-Based Site Characterization Philosophy
MANDATORY APPLICATIONS OF SW-846
METHODS (CONTD.)
• The RCRA applications listed in 40 CFR Parts
260 through 270 where the use of SW-846
methods is mandatory are the following:
(1) § 260.22(d)(1)(i) - Submission of data in
support of petitions to exclude a waste
produced at a particular facility (i.e.,
delisting petitions);
(2) § 261.22(a)(1) and (2) - Evaluation of
waste against the corrosivity
characteristic;
(3) § 261.24(a) - Leaching procedure for
evaluation of waste against the toxicity
characteristic;
A-6
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Field-Based Site Characterization Philosophy
MANDATORY APPLICATIONS OF SW-846
METHODS (CONTD.)
(4) § 261.35(b)(2)(iii)(A) - Testing rinsates
from wood preserving cleaning processes;
(5) §§ 264.190(3), 264.314(c), 265.190(a),
and 265.314(d) - Evaluation of waste to
determine if free liquid is a component of
the waste;
(6) §§ 264.1034(d)(1)(iii) and
265.1034(d)(1)(iii) - Testing total organic
concentration of air emission standards for
process vents;
(7) §§ 264.1063{d)(2) and 265.1063{d)(2) -
Testing total organic concentration of air
emission standards for equipment leaks;
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Field-Based Site Characterization Philosophy
MANDATORY APPLICATIONS OF SW-846
METHODS (CONTD.)
(8) § 266.106(a) - Analysis In support of
compliance with standards to control
metals emissions from burning hazardous
waste in boilers and industrial furnaces;
(9) § 266.112(b)(1) and (2)(i) - Certain
analyses in support of exclusion from the
definition of a hazardous waste of a
residue which was derived from burning
hazardous waste in boilers and industrial
furnaces;
(10) § 268.32(i) - Evaluation of a waste to
determine if it is a liquid for purposes of
certain land disposal prohibitions;
(11) §§ 268.40(a), (b) and (f), 268.41 (a), and
268.43(a) - Leaching procedure for
evaluation of waste to determine
compliance with land disposal treatment
standards;
A-8
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Field-Based Site Characterization Philosophy
MANDATORY APPLICATIONS OF SW-846
METHODS (CONTD.)
(12) § 268.7(a) - Leaching procedure for
evaluation of a waste to determine if the
waste is restricted from land disposal;
(13) §§ 270.19(c)(1)(iii) and (iv), and
270.62(b)(2)(i)(C) and (D) - Analysis and
approximate quantification of the
hazardous constituents identified in the
waste prior to conducting a trial burn in
support of an application for a hazardous
waste incineration permit; and
(14) §§ 270.22(a)(2)(ii)(B) and 270.66(c)(2)(i)
and (ii) - Analysis conducted in support of
a destruction and removal efficiency (DRE)
trial burn waiver for boilers and industrial
furnaces burning low risk wastes, and
analysis and approximate quantisation
conducted for a trial burn in support of an
application for a permit to burn hazardous
waste in a boiler and industrial furnace.
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Field-Based Site Characterization Philosophy
MANDATORY APPLICATIONS OF SW-846
METHODS (CONTD.)
• Authorized States can also require use of SW-
846 methods for any or all applications in their
RCRA Programs.
• EPA Regions do not have the statutory
authority to require the use of SW-846
methods for non-mandatory applications.
• Third Edition (September, 1986) as amended
by Updates I (July, 1992), II (September,
1994), MA (August, 1993), and MB (February,
1995) methods are required to be used for
mandatory applications.
.A-IO.
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Field-Based Site Characterization Philosophy
USE OF DRAFT SW-846 METHODS
Draft methods are methods that have passed
Technical Workgroup review, but have not yet
been promulgated by FRN.
Since draft SW-846 methods fall into the "Any
reliable method" category, they can be used in
all applications for which the use of SW-846
methods is not mandatory and for which they
are effective.
Proposed Third Update methods were
distributed to SW-846 subscribers by GPO in
August, 1995.
Fourth Update methods will be available from
OSW Methods Section Office as they are
completed.
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Field-Based Site Characterization Philosophy
FLEXIBILITY OF RCRA METHODS
RCRA specifies "what" needs to be
determined, and leaves the "how" up to the
analyst.
Monitoring requirements under RCRA Subtitle
C specify only that the analyst must
demonstrate that he can determine the
analytes of concern in the matrix of concern at
the regulatory level of concern.
SW-846 methods may be modified to meet
the requirements of specific applications
whether their use is mandatory or not:
4 Preface and Overview
* Disclaimer
4 Sees. 2.1.1. and 2.1.2 of Chapter Two
-A-I2.
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ORGANIZATION OF SW-846 (CONTD.)
CHAPTER TOPIC
One
Two
Three
Four
Five
Six
Quality Control
Choosing the Correct
Procedure
Metallic Analytes
Organic Analytes
Miscellaneous Test Methods
Properties
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Field-Based Site Characterization Philosophy
ORGANIZATION OF SW-846 (CONTD.)
CHAPTER TOPIC
Seven
Eight
Nine
Ten
Eleven
Twelve
Thirteen
Characteristics-Introduction and
Regulatory Definitions
Methods for Determining
Characteristics
Sampling Plan
Sampling Methods
Ground Water Monitoring
Land Treatment Monitoring
Incineration
.A-14.
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Additional Information
Oxxx
001 x
002x
003x
004x
005x
006x
01 xx
1xxx
10xx
11 xx
13xx
3xxx
30xx
35xx
36xx
38xx
4xxx
40xx
45xx
46xx
5xxx
50xx
505x
6xxx
60xx
62xx
65xx
7xxx
8xxx
80xx
81 xx
82xx
83xx
832x
84xx
85xx
9xxx
901x
902x
903x
904x
905x
Field-Based Site Characterization Philosophy
SW 846 (3RD ED.) METHODS NUMBERING SYSTEM
Method No. Method Type
Sampling
Air Sampling - Stack - Volatile Organics
Air Sampling - Stack - Semivolatile Organics
Air Sampling - Stack - Volatile Organics
Air Sampling - Stack - Volatile Organics
Air Sampling - Stack - Acid Gases
Air Sampling - Stack - Metals
Air Sampling - Ambient
Characteristics
Ignitability
Corrosivity
Extraction/Leaching Procedures
Sample Preparation
Metals/Inorganics
Organic Extraction or Dilution
Extract Cleanup
Organic Screening
Immunoassay
Organic Analytes (Screening)
Metals (Screening)
Organic Analytes (Assay)
Volatile Organics/Combustion Preparative Methods
Volatile Organic Preparation/Sample Introduction
Combustion Preparative Methods
Metals/Inorganic Determinative
ICP Determinative
X-ray Determinative
Electrochemical Determinative
Individual Metals/Inorganic Determinative (Primarily AA with Some Other
Techniques)
Organic Determinative
GC Determinative/Various Detectors
GC Determinative/Various Detectors
GC Determinative/Mass Spec Detectors
HPLC Determinative/Various Detectors
HPLC Determinative/Mass Spec Detectors
IR Determinative
UV/Vis Determinative
Miscellaneous Analytes and Test
Cyanide
Organic Halogen
Sulfur Containing Anions
PH
Specific Conductance/ton Chromatography (Anions) Determinative
•A-I5-
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SW-846 (3RD ED.) METHODS NUMBERING SYSTEM (CONTD.)
906x Nonspecific Organics (TOC, Phenolics)
907x Oil and Grease/Chlorine in Used Oil
908x Cation Exchange Capacity
909x Land Disposal Restrictions Test
9xxx Miscellaneous Analytes and Test (Contd.)
91 Ox Saturated Hydraulic Conductivity, Saturated
Leachate Conductivity and Intrinsic Permeability
913x Microbiological
92xx Anions - Nitrate/Chloride
921x Anions Determinative - Ion-Selective Electrode
93xx Radionuctides
931x Radioactivity
•A-I6.
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COMPARISON OF SW-846 METHODS WITH
OFFICE OF WATER METHODS
SW-846 METHODS
WATER METHODS
Regulations specify "what"
but not "how"
Normally not required for use
for most RCRA applications
Demonstration that a new
method works for its
intended application
Modular Methods
Regulations specify "what"
and "how"
Required to be used for all CWA
and SDWA applications
Formal Alternative Test Procedure
through EMSL-Ci to demonstrate
equivalency to existing method
All-Inclusive Methods
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COMPARISON OF SW-846 METHODS WITH
OFFICE OF WATER METHODS (CONTD.)
SW-846 METHODS
Built-in Flexibility per
Disclaimer and Chapter Two
Multiple Media and Matrices
Incorporated by Reference
in 40 CFR
Performance-based
WATER METHODS
Very little allowable flexibility
(Methods to be performed as
written)
One type of Medium (Water)
Published in 40 CFR.
Prescriptive
.A-I8.
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Field-Based Site Characterization Philosophy
COMPARISON OF SW-846 METHODS WITH
CLP METHODS
SW-846 METHODS
CLP METHODS
Analytical methods
Regulations specify "what"
but not "how"
Contracts, usually adapted from SW-846 or
OW methods (Any method can be used)
Contracts specify "what"
and "how"
Normally not required for use Required to be used for all CLP
for most RCRA applications contracts
Modular Methods
Performance-based
All-Inclusive Methods for Soil or
Water Media
Prescriptive
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Field-Based Site Characterization Philosophy
COMPARISON OF SW-846 METHODS WITH
CLP METHODS (CONTD.)
SW-846 METHODS
Built-in Flexibility per
Disclaimer and Chapter Two
Multiple Media and Matrices
Incorporated by Reference
in 40 CFR
CLP METHODS
Very little allowable flexibility
(Methods to be performed as written)
Allowable flexibility is in choice of
methods to be included in a contract.
Multiple media and matrices (Usually
water and soil)
Not regulatory in nature. Any
appropriate method can be used in a CLP
contract.
.A-20.
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Additional Information
Quality Assurance Project Plans
Example Screening Data Correction
* Regress the screening data as the independent variable [x] against the confirmatory data
as the dependent variable [y]. Generally, this will be done on log transformed data. The
transformation is necessary to assure that variance between the field analysis data and the
confirmatory laboratory data does not vary with concentration. This approach is not
appropriate if information regarding a single action level concentration is required. This
approach is generally applicable when data span one or more orders of magnitude.
The 8 step process of correcting data to more closely match the reference data follows:
1.
2.
7.
8.
Conduct sampling and analysis.
Select 10 to 20 percent of the sampling locations for resampling. These resampling
locations can be evenly distributed over the range of concentrations measured or they can
focus on an action level concentration range.
Resample the selected locations. Thoroughly homogenize (if appropriate) the samples
and have each sample analyzed by the field-based analysis method and the confirmation
method.
Tabulate the resulting data with reference data in the y-axis column (dependent variable)
and the field-based analytical data in the x-axis column (independent variable).
Transform this data to the equivalent Iog10 value for each concentration (if the data spans
at least one order of magnitude or a concentration dependant on performance is
observed.)
Conduct a linear regression analysis and determine the r, y-intercept and slope of the
relationship. The r should be greater than 0.70 to proceed (this r2 level will depend on a
project's data quality objectives).
Place the regression parameters into Equation 1:
Y (log,0 corrected field analysis data)
(log!() raw field analysis data) +Y-intercept
slope"
(Equation 1)
Use the above equation with the log,() transformed field analysis results from Step 1
above and calculate the equivalent log,0 corrected field analysis data.
Take the anti-log 10 (10 '%>'nnrfo™d ">"e«ed field-hascd da';'i) of the equivalent log,,, corrected
field-based analytical data calculated in Step 7, These resulting values represent the
corrected field-based analytical data.
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Additional Information
Data Quality and Usability
Superfund Data Categories
• QA/QC elements of screening data include sample documentation; chain of custody;
sampling design approach; initial and continuing calibration; determination and
documentation of detection limits; analyte identification and quantitation; analytical
method precision determination; and definitive confirmation.
• Definitive data QA/QC elements include all of the above screening QA/QC elements plus
QC blanks, matrix spike recoveries, PE samples {where specified), and total measurement
error determination.
RCRA Corrective Action
• Tailored Data Quality Objectives. Program implementors and facility owner/operators
should tailor data gathering strategies to the purpose for which the data will be used. The
overall degree of data quality or uncertainty that a decision maker is willing to accept is
referred to as the Data Quality Objective (DQO) for a decision. The DQO is used to
specify the quality of the data, usually in terms of precision, bias, representativeness,
comparability and completeness. The DQO approach applies to the entire measurement
system (e.g., sampling locations, methods of collection and handling, field analysis, etc.),
not just to laboratory analytical operations. In general, EPA has found that DQOs can and
should be used to ensure that environmental data are scientifically valid, defensible, and
of an appropriate level of quality given the intended use for the data.
• Program implementors and facility owners/operators using innovative site
characterization and assessment approaches should pay particular attention to DQOs. For
example, an objective of the early stages of an investigation could be to identify the
presence of gross contamination. In this context, a DQO could include a higher method
detection limit (e.g., parts per million) that could be obtained with cost-effective field
screening technologies. In contrast, a very low method detection limit (parts per billion
or parts per trillion) could be an appropriate DQO to determine if groundwater is fit for
human consumption.
.A-22.
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Additional Information
Data Quality and Usability
Removal Site Assessments and Removal Actions
• Integration of DQOs and Quality Assurance Objectives (QAO) are possible depending
upon the specific QA requirements of the OSC. Tentative DQOs and QAOs have been
assigned for each analytical parameter. These DQOs and QAOs are subject to
modification and clarification by the respective data users. Three types of QAOs and
DQOs are briefly described below:
— QAO 1: QAO 1 is appropriate when the situation requires rapid turnaround, non-
rigorous methods of analysis and quality assurance. The resultant data are non-
definitive for analyte quantitation. Methods will be applied per standard operating
procedures and equipment manufacturers specification. The activities appropriate
to QAO 1 include, but are not limited to:
Hazard categorization;
Preliminary or continuing evaluation of:
— pollutant identification;
— chemical properties of samples;
— extent and degree of contamination;
— waste compatibility;
- pollutant plume definition: and,
— health and safety
— QAQ 2: This is the QAO level most frequently used by EPA's removal program.
QAO 2 is appropriate when sampling objectives require qualitative and
quantitative verification of a proportion of the findings (10 percent or more of the
samples). The results of the substantiated data give an associated level of
confidence to the remaining 90 percent of the data set. The analytical methods for
verification must be either a published EPA method, a regionally accepted standard
operating procedure (SOP), or be accepted by the on-scene coordinator (OSC) and
reviewed for adequacy and completeness by the EPA regional Data Quality
Control Officer. The activities appropriate for QAO 2 include, but are not limited
to:
Hazard categorization;
- Verification of:
— chemical properties of samples;
— extent and degree of contamination;
— pollutant plume definition;
— pollutant identification; and,
— the need to continue removal activities.
- Treatment, disposal, and removal selection method;
Definitive health risk or environmental impact assessment;
A-23-
Module: Overview of Field-Based Site Characterization
-------
Additional Information
Data Quality and Usability
Responsible party identification;
- Enforcement action; and,
Definitive removal verification
QAO3: This QAO level requires both qualitative and quantitative verification of
results and the use of PE samples is mandatory. This quality objective is intended
to give the OSC the highest level of confidence for a select group of "critical
samples" so he can make a decision based on an action level with regard to, but not
limited to:
- Treatment, disposal, and removal action method selection;
Definitive health risk or environmental impact assessment;
Responsible party identification;
- Enforcement action; and,
Definitive cleanup verification
DQO Level 1 (field screening): This DQO level is defined as field screening, or
analysis using field portable instruments. Results often are not compound specific
and not quantitative, but results are available real time. This DQO level is the least
costly of the analytical options. This DQO is roughly equivalent to QAO 1.
DQOJLevel 2 (field analysis): This DQO applies to field analysis using more
sophisticated portable analytical instruments; the instruments may be set up in a
mobile laboratory on site. There is a wide range in the quality of data that can be
generated. The quality of the data depends on the use of suitable calibration
standards, reference material, and sample preparation equipment; and the training
of the operator. Results are available real time or within several hours. This DQO
is equivalent to either QAO 1 or QAO 2, depending on whether or not 10 percent
or more verification samples are sent for off-site analysis using EPA-approved
methods.
POO Level 3 (laboratory analysis): For this DQO, all analyses are performed in an
off-site analytical laboratory. Level 3 may or may not use contract laboratory
program (CLP) procedures and may or may not use the validation or
documentation procedures required of the CLP Level 4 analysis. The laboratory
may or may not be a CLP laboratory. Generally, this DQO would correspond to
QAO 2. However, verification of at least 10 percent of the data still would be
required (for example, the GC method of analyzing a second sample a second time
using a dissimilar column or different oven conditions).
-A-24.
Module: Overview of Field-Based Site Characterization
\
-------
Additional Information
Data Quality and Usability
Six Usability Criteria for Risk Assessment Data
• It is recognized that there are a variety of potential sources of data (field screening, field
analytical, and fixed analytical). If data from multiple sources are going to be used, care
must be taken to only combine data of comparable sources for the quantitative
assessment.
• Sample collection and analysis procedures must be fully and accurately documented to
substantiate the reliability of the data derived from its analysis. The major types of
documents are QAPPs, SOPs, field and analytical records, and chain-of-custody records.
• Analytical methods selected should have detection limits that are at or below facility-
specific screening or clean up levels. There are several general human health based-
clean-up or remediation goals that have been published by EPA Regions 3 and 9, and
EPA also has proposed soil screening levels. For protection of ecological health, EPA
Region 5 developed ecological data quality levels (EDQL) to determine adequate
detection and quantitation limits.
• Data Quality Indicators (DQI) need to be identified early on with the risk assessor during
the DQO development process. The five DQIs are completeness, comparability,
representativeness, precision, and accuracy.
» The required level of review should be established as part of the DQO development
process. When data are going to be used in a quantitative risk assessment, there needs to
be a high level of confidence in the data. This would include review of surrogate spikes,
recovery spikes, general criteria (holding times), calculations, and transcriptions. The
level of review is dependent on each project and its objectives and budget, and should be
outlined in the QAPP.
• These reports should clearly specify what problems have been identified with the data and
document any corrective action that has taken place.
Source: EPA. 1992. Guidance for Data Usability in Risk Assessment (Part B). Publication
number 9285.7-09B. Office of Emergency and Remedial Response. Washington, DC. May.
A-25-
Module: Overview of Field-Based Site Characterization
-------
-------
Platforms for In Situ Technologies
Sampling Platforms and
Direct-Push Technologies
EPA
SP-1
SP-1
Module: Sampling Platforms and Direct Push Technologies
-------
Platforms for In Situ Technologies
Platforms for In Situ Technologies
+Conventional Drilling
» Cable tool
» Auger
» Rotary
» Resonant sonic
4 Direct-push (hydraulic) techniques
»Cone penetrometer
» Hammer
&EPA
SP-2
Notes:
There are four common classes of conventional drilling. Each has the potential to be used
as an advancement platform and will be discussed in subsequent slides.
There are two common classes of direct push techniques. Each type will be discussed in
subsequent slides.
SP-2
Module: Sampling Platforms and Direct Push Technologies
-------
Platforms for In Situ Technologies
Cable Tool Drilling
•^Oldest method of drilling
4 Drills a borehole by pulverizing the matrix
* Advances casing by driving it into the ground
+ Removes pulverized matrix with a bailer
*• Provides either a cased hole (unstable formation)
or an open hole (stable formation) for sensor
application
&EPA
(continued)
SP-3
Notes:
Cable tool drilling, or percussion drilling, involves the raising and lowering of cutting
tools in the borehole.
The process is slower than other, more advanced drilling methods.
A large bailer is used to empty formation debris from the casing. No drilling fluids are
used; however, it sometimes is necessary to add water to aid in removing drill cuttings.
SP-3
Module: Sampling Platforms and Direct Push Technologies
-------
Platforms for In Situ Technologies
Cable Tool Drilling (continued)
l&EPA
Bailer
Stationary Sheave
SP-4
Notes:
The diagram shows a typical cable tool drill rig of the type commonly used for
environmental applications.
SP-4
Module: Sampling Platforms and Direct Push Technologies
-------
Platforms for In Situ Technologies
Notes:
Auger Drilling
+Advances a hollow stem or solid stem auger with
rotation
+ Used on unconsolidated formations
establish contact with the undisturbed soil, a
sensor must be pushed beyond the terminal
point for the drilling
Sensors or samples are advanced ahead of the
cutting bit
(continued)
SP-5
This drilling method (whether by solid or hollow stem) is one of the most commonly used
conventional methods for unconsolidated and semiconsolidated formations. It can be
employed without introducing foreign material into the borehole.
Continuous flight (solid-stem) augers must be withdrawn before sampling. Sampling and
sensor application can be conducted through a hollow-stem auger. Hollow-stem augers
serve as temporary casing. The steel of a hollow stem auger can interfere with some
types of borehole geophysical instruments.
This type of drilling generally is applied only to soils and weathered bedrock. Other
means of drilling are more effective on more lithified materials.
SP-5
Module: Sampling Platforms and Direct Push Technologies
-------
Platforms for In Situ Technologies
Auger Drilling (continued)
+ Saturated sands may intrude into the hollow-
stem auger
4 Dry sand will not maintain an open hole without
casing
(continued)
SP-6
Notes:
When samples are withdrawn from a hollow-stem auger, or if they are collected below
the water table, sands can heave into the augers, preventing further sampling or borehole
advancement.
Continuous-flight augers cannot be used in dry sands or other noncohesive soils, since the
borehole would collapse upon withdrawal of the auger.
SP-6
Module: Sampling Platforms and Direct Push Technologies
-------
Platforms for In Situ Technologies
Auger Drilling (continued)
EPA
rod inside hollow
stem for removing
plug
flight
removable plug
(continued)
SP-7
Notes:
This diagram shows a typical hollow-stem auger of the type used in environmental
applications.
SP-7
Module: Sampling Platforms and Direct Push Technologies
-------
Platforms for In Situ Technologies
Auger Drilling (continued)
EPA
SP-8
Notes:
This diagram shows a typical continuous-flight auger of the type used in environmental
applications.
SP-8
Module: Sampling Platforms and Direct Push Technologies
-------
Platforms for In Situ Technologies
Rotary Drilling
• Advances an open borehole, using drilling fluid
(air, water, or drilling mud) and a rotary drill bit
Can operate in unconsolidated or consolidated
matrices
Provides an open hole for a sensor
Drilling fluids mix with cuttings and contact the
formation, thereby potentially increasing the
amount of investigation-derived waste generated
Cannot record sensor data continuously during
advancement of the borehole
(continued)
SP-9
Notes:
This type of drilling method involves the advancement of a rotating drill, using
circulating drilling fluids to keep the borehole from collapsing and to carry drill cuttings
out of the borehole. Circulating fluids can cross-contaminate a borehole.
This type of drilling method can be applied to both unconsolidated and consolidated
formations. Generally, this type of drilling method is applied to soils that contain
boulders or bedrock.
Sensors can be advanced through the open borehole through the drilling fluids, or a
casing can be introduced into the borehole and the drilling fluids removed.
The presence of potentially contaminated drilling fluid increases the amount of
investigation-derived wastes generated.
Current technology does not allow the use of sensors during advancement of the borehole.
SP-9
Module: Sampling Platforms and Direct Push Techno/ogles
-------
Platforms for In Situ Technologies
Rotary Drilling (continued)
EPA
Casing Hammar
(in up [non-
driving] position)
Return Flow
(air and formation
cutlings)
Power Swivel
(top-head drive)
Drill Pipe
SP-10
Notes:
This diagram shows a typical rotary drill rig of the type commonly used in environmental
applications.
SP-10
Module: Sampling Platforms and Direct Push Technologies
-------
Platforms for In Situ Technologies
Resonant Sonic Drilling (Rotasonic)
4 Advances single- or double-walled casing, using
vibration
4 Vibrations could change the distribution of
contaminants in the formation
4 Provides a cased hole
4 Generally 2 to 5 times more expensive than
auger drilling
4 Relative to other drilling methods, produces the
least amount of investigation-derived waste
(continued) SFM1
Notes:
Advancing the casing and sampling with vibrations can change the physical
characteristics of a formation and, in some cases, heat the soil. This drilling method is
most effective in unconsolidated matrices. Boulders can stop advancement of the casing.
The high-frequency vibrations could alter the natural distribution of contamination in a
formation. Such occurrence may be most likely at the capillary fringe or in the presence
of soil that is nearly saturated with contaminants.
This drilling technique provides either a cased borehole or an open borehole (if the
formation permits). Any sensors used with this technology must be advanced through the
casing or open borehole and into the formation. Current technology does not allow
concurrent use of in situ sensor equipment.
The limited number of these drill rigs available and the relatively high-cost for their
construction and maintenance increases the relative cost of using this type of drilling
method, compared with the cost of more common methods.
No soil cuttings are produced during advancement of the borehole. The only soil waste
produced by this drilling method is associated with the samples it produces.
SP-11
Module: Sampling Platforms and Direct Push Technologies
-------
Platforms for In Situ Technologies
I
lesonant Sonic Drilling (continued)
High-frequency -*^^jj|
sinusoidal along i~
axis of drill pipe \—
tf B
Drill pipe >>
Rotating and
vibrating drill bit ^__^ L.
^*C
Counter rotating rol ers
^S
^^~^jl4 H"?h power
jS oscillator
=f
rifd harmonic standing
ive, set up in drill pipe
Note:
Horizontal arrows
represent vertical motion
of the particles of material
of the drill pipe
4^ EPA (continued) sp-i2
Notes:
This diagram shows the basic principles of rotasonic drilling.
SP-I2
Module: Sampling Platforms and Direct Push Technologies
-------
Platforms for In Situ Technologies
Resonant Sonic Drilling (continued)
Sonic Vibratory
Mead
Drill Pipe and
Core Barrel
Hydraulic Drill Center Drilling Platform
&EPA
(continued)
SP-13
Notes:
This diagram shows a typical rotasonic drill rig of the type commonly used in
environmental applications.
SP-13
Module: Sampling Platforms and Direct Push Techno/ogles
-------
Platforms for In Situ Technologies
Re
sonant Sonic Drilling (continued)
Grade Level
Step-1
Inner drill pipe and corn bM are
advanced by vibration lOleetinto
the sediments lo obtain a continuous t
core sample Depending on job
requirements, runs of 1 loot to 20
feet can be made
4-1/2 inc
••**>
Qrade Level
Step-3
Outer drill pipe and bit are left in
place while the inner drill p$e is
sample. I
•
h<
in
••a
Kits*
vde
IIIIUIIIH
Gwl, Level
Step-2
Outer drill pipe and core Bit ere
advanced by vibration down over the
inner dnH pipe to hold the borehole 1
open while the core sample is
removed.
e diameter, « 1/4
diameter
Grade Level
I 1
Outer dril ptie remains al 1 0 leet.
20'
Inner dntl ppe and core bit are
advanced an additional 1 o leet.
Steps 2 through 4 are repeated until 1
target depth is reached.
•_L
o-
1_
inch outside diameter
)'
)'
*.& EPA SP-u
Notes:
This diagram shows the four steps of the rotasonic drilling method.
SP-14
Module: Sampling Platforms and Direct Push Technologies
-------
Direct Push Technologies
Direct-Push Technologies
4 Technology capable of providing geotechnical
data and subsurface samples
*• Uses hydraulic pressure to advance geotechnical
tools and sampling devices
+ Examples
»Cone penetrometers (SCAPS, ROST)
» Hydraulic hammer method (Geoprobe®)
EPA
SP-15
Notes:
Direct-push technologies are capable of collecting geotechnical data by advancing
analytical devices like: piezocones; resistivity probes; laser-induced fluorometer (LIF)
probes; sleeve-friction, tip-resistance, and pore-pressure probes, as well as soil, water,
and soil gas samplers. Those techniques are described in detail in other modules of this
manual.
As opposed to auger techniques in which soil is removed and a borehole is produced,
direct-push technologies advance geotechnical tools or subsurface sampling devices by
using the weight of the truck or a hydraulic hammer to "push" the rod into the formation
to be investigated.
Cone penetrometer systems, such as the Site Characterization and Analysis Penetrometer
System (SCAPS), usually are mounted on 20-ton trucks as illustrated in Slide SP-17. The
weight of the truck is used to advance the cone with an analytical or sampling device.
Hydraulic hammer systems (Geoprobe®) are mounted on a variety of vehicles, including
vans, pickup trucks, trailers, and all-terrain vehicles (ATV). Doing so is possible because
hydraulic pressure, rather than the weight of the vehicle, is used to advance the smaller-
diameter probe.
SP-J5
Module: Sampling Platforms and Direct Push Technologies
-------
Direct Push Technologies
Cone Penetrometer Method
4 Uses a static reaction force to advance the
sensor
• Currently has sensors for physical and chemical
site characterization
• Structure of the formation can limit penetration
depth greatly
• Can provide continuous sensor data during a
push
(continued)
SP-16
Notes:
The static reaction force generally is equal to the weight of the truck. That weight is
supplemented with steel weights. Cone penetrometer trucks that weigh more than 15 tons
are common.
Physical sensors include sleeve-friction and tip-resistance sensors that map soil texture.
Chemical sensors, as well as downhole desorption or sampling techniques, have been
developed to detect, delineate, and monitor sites contaminated with petroleum, volatile
organic compounds (VOC), metals, and explosives.
This technology can be used only in unconsolidated material. Soft layers overlying hard
layers, as well as rocks, sometimes can limit penetration.
Sensors generally are deployed and used during the advancement of the borehole.
SP-16
Module: Sampling Platforms and Direct Push Technologies
-------
Direct Push Technologies
Cone Penetrometer Method
(continued)
Vehicle
» Push probe
» Configurations
— Sensoring
— Sampling
» Ground capability
» Equipment
decontamination
» Hazardous environment
protection
Data Acquisition and Analysis
» Acquisition - sensors
» Analysis
» Visualization
Data
Processing
Space
20-Ton Push Truck
A EPA
SP-17
Notes:
This diagram shows a common cone penetrometer system.
SP-17
Module: Sampling Platforms and Direct Push Technologies
-------
Direct Push Technologies
Hydraulic Hammer Method
*• Uses a combination of static reaction force and
dynamic loading (hammering) to drive probes
into the subsurface
*• Drives smaller-diameter rods or sensors into the
subsurface (relative to a cone penetrometer rig)
record sensor data continuously during a
push
EPA
(continued)
SP-18
Notes:
These rigs generally weigh less than four tons. To compensate for the reduced reaction
force, many of the rigs also employ hydraulic hammers to help advance sensors or
samplers. The technology can be used only in unconsolidated formations. Currently, the
sensor technology is limited to conductivity sensors.
The sample size generally is smaller than the sampler used with a cone penetrometer. A
number of samples may be required to provide a volume sufficient to allow analysis.
The sensors are advanced as the borehole is advanced.
SP-18
Module: Sampling Platforms and Direct Push Technologies
-------
Direct Push Technologies
Hydraulic Hammer Method
(continued)
SP-19
Notes:
This is a photograph of a common hydraulic push unit that also uses a hydraulic hammer
to advance sensors or samplers.
SP-19
Module: Sampling Platforms and Direct Push Technologies
-------
Direct Push Technologies
Notes:
Advantages - Direct-Push
Technologies
Reduction in the amount of investigation-derived
waste generated
No foreign substances permanently introduced
into the formation
Reduction in time necessary for investigation,
with increased areal coverage
EPA
SP-20
Direct-push technologies do not generate "cuttings" like traditional borings. Therefore,
there is no potentially contaminated soil to eliminate. Costs of investigation therefore are
reduced, and the process is expedited and simplified.
Unlike conventional drilling techniques, direct-push technologies do not introduce items
like well casings into the sampling zone. Therefore, the potential for contamination is
reduced.
Direct-push techniques are quicker and more mobile than traditional methods. Therefore,
sampling and data collection are faster, reducing the time necessary to complete the
investigation and increasing the number of sample points.
SP-20
Module: Sampling Platforms and Direct Push Technologies
-------
Direct Push Technologies
Limitations - Direct-Push
Technologies
* Limited to unconsolidated materials
4 Geological stratification can limit use
EPA
SP-21
Notes:
Direct-push technologies generally are limited to unconsolidated materials. They cannot
be used to penetrate rock layers, concrete footings or foundations, or other high-density
barriers.
Changes in geological density can be a limitation. The presence of soft layers overlying
hard layers can cause alteration in the alignment of the probe and, ultimately bending or
breaking of the rod.
SP-21
Module: Sampling Platforms and Direct Push Technologies
-------
-------
Geophysical Characterization
Techniques and Data Uses
EPA
GT-1
GT-1
Module: Geophysical Characterization Techniques and Data Interpretation
-------
Introduction
Module Overview
+Objective: Identify and understand factors to be
considered in scoping, executing, or reviewing
projects that involve geophysical instruments and
techniques
GT-2
Notes:
This module is intended to provide a foundation for making better decisions about the use
of geophysical techniques in support of environmental projects.
The key points described in this module cover fundamental principles of operation of
various instruments, common applications, interferences and limitations, data uses, and
data quality.
GT-2
Module: Geophysical Characterization Techniques and Data Interpretation
-------
Introduction
Notes:
Introduction
+ Geophysics is the study of fundamental principles
and laws of physics to investigate the earth and
its environment
4 Geophysical methods include:
»//? situ: Involves contact with media; minimal
physical disturbances
» Borehole: Involves contact with media; creates
a boring in media
» Surface: Involves little or no contact with
subsurface media; minimai physical disturbance
EPA
GT-3
This module addresses both the theory and the practical aspects of geophysical
techniques. As such, a basic, conceptual understanding of gravitational and
electromagnetic fields is helpful in understanding the material that follows.
In situ geophysical measurements typically are made by placing a probe or sensor into the
media of interest in such a way that causes minimal disturbance of the media.
Borehole geophysical measurements are made only after a boring has been made into the
media of interest. The sensor itself may not actually contact the walls of the borehole.
Surface geophysical techniques usually result in no significant disturbance of the
subsurface media. Surface sensors may be in contact with the ground surface or held
above the ground surface.
GT-3
Module: Geophysical Characterization Techniques and Data Interpretation
-------
-------
In Situ
Geophysical Characterization
Techniques and Data Interpretation
+ Borehole
4 Surf ace
4 Emerging and Innovative Approaches and
Instruments
+ Hands-on Activity for Geophysical Analysis
,8, EPA
IG-1
IG-1
Module: Geophysical Characterization Techniques and Data Interpretation
-------
In Situ
In Situ Geophysical Methods
Resistivity
Sleeve-friction, tip-resistance, and pore-pressure
IG-2
Notes:
Resistivity is defined as the resistance to electrical current of a three-dimensional
medium.
- Measurements of resistivity commonly are used for preliminary evaluation of the
variation in subsurface resistivity related to lateral or vertical changes in geologic
materials or contaminants. The technique often is referred to as direct current
(DC) resistivity.
- Measurements of resistivity often are used to determine the depth to bedrock,
identify clay zones, and determine the depth of refuse in a landfill.
Sleeve-friction, tip-resistance, and pore-pressure measurements commonly are used for
stratigraphic logging in relatively soft soils (low resistance to an advancing probe), as
well as for identifying certain hydrogeologic parameters.
IG-2
Module: Geophysical Characterization Techniques and Data Interpretation
-------
In Situ
Resistivity: Physical Basis
+Ohm's Law
V = IR
Voltage = current x resistance
* Electrical resistivities of common materials
4 Contact resistances
+Apparent resistivity
EPA
IG-3
Notes:
Resistance (R) is measured in ohms when current (I) is in amps and potential (V) is in
volts. The resistance of a unit cube to current flowing between opposite faces is termed
resistivity. Resistivity is measured in units of ohm-rneters (fl-m). The reciprocal quantity
is conductivity, measured in units of milliSiemans per meter (mS/m).
The resistivity of a rock is roughly equal to the resistivity of the pore fluid divided by the
fractional porosity. In general, soils have lower resistivity than rock, and clay soils have
lower resistivity than coarse-textured soils.
Measurement of resistivity in the earth is defined as apparent resistivity because it is
unlikely that the material into which electrodes are inserted, and of which measurements
are taken, is homogenous.
IG-3
Module: Geophysical Characterization Techniques and Data Interpretation
-------
In Situ
Typical Values of Electrical Resistivity of Earth Materials
Earth Material
Saline groundwater
Clay soil
Fresh groundwater
Calcareous shale (or Chalk)
Sand (SP1, moderately to highly saturated)
Shale (mudstone/claystone)
Shale (siltstone)
Limestone (low-density)
Volcanic flow rock (scoriaceous basalt)
Lodgement (dense, clayey, basal) till
Sandstone, uncemented
Ablation (dry, loose, cohesionless) till
Fluvial sands and gravels (GW1, unsaturated)
Loose, poorly sorted sand (SP, unsaturated)
Metamorphic rock
Crystalline igneous rock
Limestone (high-density)
Resistivity Range (Q-m)
0.01 -
1 -
2 -
10 -
20 -
1 -
50 -
100 -
300 -
50 -
30 -
1,000 -
1,000 -
1,000 -
50 -
100 -
1,000 -
1
30
50
100
200
500
1,000
1,000
1,000
5,000
10,000
10,000
10,000
100,000
1,000,000
1,000,000
1,000,000
1 GW and SP above are Unified Soil Classification terms for well-graded gravel and poorly-
graded sand, respectively
JG-4
Module: Geophysical Characterization Techniques and Data Interpretation
-------
In Situ
Resistivity: Instruments
4 Generators and transmitters
*• Receivers and detectors
* Microprocessor control
4> Costs
IG-4
Notes:
The device that applies a measured current in a resistivity survey is known as the
transmitter. Transmitters usually are designed to reverse the direction of the current, with
a cycle time from 0.5 to 2 seconds. The reversal of the current helps minimize electrode
polarization effects. Power is provided by a battery or a generator.
Voltage measuring devices often are referred to as receivers.
In newer instruments, the transmitter and receiver equipment generally are housed in a
single unit, with microprocessor control and internal data storage.
Earth resistivity meters can be rented for approximately $300 per month or $10 per day,
with a mobilization fee of about $65.
IG-5
Module: Geophysical Characterization Techniques and Data Interpretation
-------
In Situ
Resistivity: Survey Practice
Electrodes and arrays
Resistivity profiling
• Resistivity depth-sounding
Limitations and interferences
&EPA
IG-5
Notes:
Current electrodes typically are metal stakes. Voltage electrodes can be metal, but more
often consist of a "pot" of nonpolarizing material, such as porcelain or unglazed ceramic.
Inside the pot is a copper rod surrounded by copper sulfate solution. Contact with the
ground is made through the solution, which leaks into the base of the pot. Electrodes are
placed in well-defined geometric patterns known as arrays. Commonly used arrays
include the Wenner, Schlumberger, dipole-dipole, and gradient arrays.
Resistivity profiling is a technique in which transects are used to detect lateral changes in
subsurface resistivity. The geometric perimeters of the array are kept constant, and the
depth of penetration therefore varies only with changes in sub urface materials and
variations in layering of geologic materials.
The resistivity depth-sounding technique uses arrays in which the distances between some
or all of the electrodes are increased systematically. Apparent resistivities are plotted
against changes in the geometry of the array. With this technique, information about the
change in resistivity as a function of depth is inferred.
Some limitations and interferences include: (1) contact resistance effects; (2) effects of
cultural features, such as buried utilities; and (3) noise levels at the site. Data
interpretation is another potential limitation because it is fairly subjective and requires an
expert. Resistivity surveys also are relatively slow because of the need to move
electrodes and cables between each measurement.
IG-6
Module: Geophysical Characterization Techniques and Data Interpretation
-------
In Situ
Field Arra
• . «»
| WENNER ARRAY ^^^H
surface
• SCHLUMBERGER ARRAY 1
surface CE
A
• DIPOLE-DIPOLE ARRAY •
surface
PE - Poter
4? EPA CE-Curre
ys for the Resistivity Method
CE [pi pil CE
I a , a i a
IP! pil
M N
1 i Q£>
CE CE PE F
a a to 5a a
EXPLANATION
tial electrode © - Voltmeter a - Electrode "a" sp
nt electrode © - Current source A.M.N.B - Electrod
CE
A
5E
i
acing
a locations IG"6
Notes:
Shown are three of the commonly used DC resistivity arrays.
IG-7
Module: Geophysical Characterization Techniques and Data Interpretation
-------
In Situ
Vertical Electrical Sounding
Examples
ScMimb*rgtr
Apparent
Rwisttvity, P,
In Ohm-M«t«r*
Eloctrod* Seeing, AB/2. in tot (ft[
ID 20 50 100
SOO 1000 KCO BOO 10.000
. i ,,,,! . . , i ,.,,!
trrtr
DNHMfimliii
» 100 2« 500 1000 2000 MOO 10.000
EPA
Eltctrode Spicing, Afl/2, In mttm
IQ-7
1G-8
Module: Geophysical Characterization Techniques and Data Interpretation
-------
I
Example of Electrical Profiling
EPA
100
£ I M
8; 10."
* 50
0 10 20 M Meiers
0 100 Feel
Honzonial Scale
VES4
Notes:
In Situ
iG-e
The data shown at the top of the figure are taken at two electrode spacings. Wider
spacing usually provides information about deeper subsurface materials.
The information at the bottom of the figure is an interpretation of the data. "VES 4" is a
vertical electric sounding. Likely, the data from VES 4 indicate the presence of three
geologic layers within the depth of investigation of the sounding.
IG-9
Module: Geophysical Characterization Techniques and Data Interpretation
-------
In Situ
Sleeve-Friction, Tip-Resistance, and
Pore-Pressure: Physical Basis
4- Sleeve-friction
*• Tip-resistance
*• Measured pore-pressure
* Excess pore-pressure
• Inclination
1 Conical point (10 cm2)
2 Load cell
3 Strain gage
4 Friction sleeve (1,50 cmz)
5 Adjustment ring
6 Waterproof bushing
7 Cable
8 Connection with rods
&EPA
IG-9
Notes:
Sleeve-friction, tip-resistance, and pore-pressure measurements commonly are used for
stratigraphic logging in soft soils, as well as for identifying specific hydrogeologic
properties.
The friction ratio is the ratio of sleeve-friction to tip-resistance, expressed as a percent.
Sleeve-friction is the resistance to penetration developed on the side walls of a tool being
pushed through the subsurface, which is equal to the sum of friction and adhesion. The
resistance to penetration developed at the tip of a tool being pushed through the
subsurface is the tip-resistance, which is equal to the vertical force applied to the tool
divided by its horizontally projected area.
If a pressure transducer is added to the tool being pushed through the subsurface, the
response of soil pore water pressure to the penetration can be measured. The technique is
similar to that used for monitoring in situ pore water pressures with push-in piezometers,
except for the added factor of dynamic pressures related to penetration. If advancement
of the tool ceases, the pressures related to penetration will dissipate and the in situ pore
water pressure can be measured. The total measured pressure is equal to the in situ
pressure, plus the excess pressure developed by penetration.
Inclination is a measure of the plumbness of the tool as it advances into the subsurface.
IG-10
Module: Geophysical Characterization Techniques and Data Interpretation
-------
In Situ
Notes:
Sleeve-Friction, Tip-Resistance, and
Pore-Pressure: Instruments
Penetrometer tip
» Sensors
» Sensor cables
Sounding or push rods
Truck-mounted
hydraulic ram
Data acquisition system
• Porous probe
groundwater sampler
Costs
Penetrometer tips typically house tip-resistance, sleeve-friction, and piezometer sensors in
a conical tip and cylindrical friction sleeve. Tips typically are about 5 inches long with a
cross-sectional area from 1.5 to 2.5 square inches. The sensors are connected to the
surface by electronic cables.
Push rods typically are 1 meter in length. Sensor cables are inserted through the push
rods and connected to a data acquisition system at the surface.
A hydraulic ram is used to push the penetrometer tip and push rods into the subsurface.
A multichannel data acquisition system is used at the surface to record and provide
preliminary analysis of the sensor data.
Recently, a conventional cone penetrometer system has been coupled with a porous probe
groundwater sampler for use in environmental applications.
Typical costs for a cone penetrometer truck with lithologic and sampling tools can vary
from approximately $1,000 to $2,000 per day, with mobilization costs additional.
IG-II
Module: Geophysical Characterization Techniques and Data Interpretation
-------
In Situ
Water tank and
steam cleaner
Computer
data acquisition
system
Hydraulic
ram
Rod wash chamber
Friction
I resistance
I !
Electrical
conductivity
;V^ Piezometer
Cone end beari
resistan
100+ ft depth
capability
7G-/2
Module: Geophysical Characterization Techniques and Data Interpretation
-------
In Situ
Notes:
Sleeve-Friction, Tip-Resistance, and
Pore-Pressure: Survey Practice
*• Penetrometer calibration
4 Constant rate advancement of penetrometer
+ Pore-pressure dissipation tests
4- Generation of logs
EPA
IG-11
The penetrometer tool is calibrated at a zero-load reading in air and water before and after
advancement into the subsurface.
The penetrometer tool is advanced into the subsurface at a controlled rate of 1 to 2
centimeters per second.
Penetration may be halted at any time to allow measurement of pore-pressure dissipation.
The excess pore-pressure decay over time may be used to calculate a coefficient of
consolidation that subsequently can be used to estimate the hydraulic conductivity.
Field plots or logs of tip-resistance, sleeve-friction, friction ratio, pore-pressure, and
differential pore-pressure are generated in real time.
1C-13
Module: Geophysical Characterization Techniques and Data Interpretation
-------
In Situ
Schematic of a Radiation Detection
Probe
Grew'tube
Blow-out plug
Santilla&on gamrra sensor
Mudwek
Water seal
Two-axis tilt sensor
Sleeve load cell
Tip load call
Pom-pressure gage
Fluid-til «J portal
Water seal
&EPA
Integral signal cat*
tedpormnfWw
68" email tip
16-12
Notes:
This figure illustrates the various components of a radiation detection probe. Active and
passive systems have been developed or are under development. The sensitivity of the
probes varies, and they can be used to detect radionuclides or soil density. The
Waterways Experiment Station (U.S. Army Corps of Engineers) is developing a system
that has a sodium iodide detector that measures gross gamma radiation and spectral data
at selected depths.
IG-14
Module: Geophysical Characterization Techniques and Data Interpretation
-------
In Situ
Sleeve-Friction, Tip-Resistance, and
Pore-Pressure: Interpretation
• Stratigraphy
from tip-
resistance and
friction ratio
EPA
5
2 4 6.8
FRICTION RATIO (%)
" Heavily overconsoltdatodor csmented
IG-13
Notes:
The graphic depicts a correlation chart used to determine soil type on the basis of data on
friction ratio and tip-resistance.
The friction ratio and tip-resistance data are collected continuously as the penetrometer is
advanced into the subsurface. Site stratigraphy is inferred by comparing the relationship
observed between friction ratio and tip-resistance as a function of depth. The scale for
tip-resistance is logarithmic.
In general, sandy soils have high tip-resistence and low friction ratios, while soils that
have high clay content have lower tip-resistence and higher friction ratios.
1C-15
Module: Geophysical Characterization Techniques and Data Interpretation
-------
In Situ
Sleeve-Friction, Tip-Resistance, and
Pore-Pressure: Case Studies
CONE BEARING SUM-FRICTION FRICTION RATIO PORE-PRESSURE RESISTIVITY STATIGRAPHY
Fs(Bf) «(\) U(Bsi) (ohnHn) COMMENTS
js a T. ---'--
o
IG-14
Notes:
The graphic illustrates common ways of presenting sleeve-friction, tip-resistance, and
pore-pressure data. The figure has a geologic cross-section format that shows the relative
locations of penetrometer measurements. Friction ratio and tip-resistance data are
displayed on the cross-section for direct comparison with the implied stratigraphy. The
figure also provides more detailed penetrometer data (including pore-pressure and friction
resistance logs) for a single measurement location.
1C-16
Module: Geophysical Characterization Techniques and Data Interpretation
-------
In Situ
Sleeve-Friction, Tip-Resistance, and
Pore-Pressure: Interpretation
* Stratigraphy
from tip-
resistance and
friction ratio
4 6
FRICTION RATIO {%)
' Over-consolidated
" Heavily overcon sol dated or cemented
IG-13
Notes:
The graphic depicts a correlation chart used to determine soil type on the basis of data on
friction ratio and tip-resistance.
The friction ratio and tip-resistance data are collected continuously as the penetrometer is
advanced into the subsurface. Site stratigraphy is inferred by comparing the relationship
observed between friction ratio and tip-resistance as a function of depth. The scale for
tip-resistance is logarithmic.
In general, sandy soils have high tip-resistence and low friction ratios, while soils that
have high clay content have lower tip-resistence and higher friction ratios.
1C-15
Module: Geophysical Characterization Techniques and Data Interpretation
-------
In Situ
Sleeve-Friction, Tip-Resistance, and
Pore-Pressure: Case Studies
•,x,w < .^i^Q^g^gggggiliimiHH^MMMgHi
CONE SEARING SLEEVE-FRICTION FRICTION RATIO PORE-PRESSURE RES|STIV|TY 5TATIGRAPHY
200 0 2.5 0
(odriMllj COMMENTS
rs .10 o w o «
IG-14
Notes:
The graphic illustrates common ways of presenting sleeve-friction, tip-resistance, and
pore-pressure data. The figure has a geologic cross-section format that shows the relative
locations of penetrometer measurements. Friction ratio and tip-resistance data are
displayed on the cross-section for direct comparison with the implied stratigraphy. The
figure also provides more detailed penetrometer data (including pore-pressure and friction
resistance logs) for a single measurement location.
IG-16
Module: Geophysical Characterization Techniques and Data Interpretation
-------
Borehole
Geophysical Characterization
Techniques and Data Interpretation
4 In situ
+ Borehole
4 Surface
4-Emerging and Innovative Approaches and
Instruments
4 Hands-on Activity for Geophysical Analysis
&EPA
BQ-1
BG-I
Module: Geophysical Characterization Techniques and Data Interpretation
-------
Borehole
Borehole Geophysical Methods
• Evaluation of heterogeneous
conditions
+ Information about geologic
control and rapid interpretation
of data
4> In situ analysis of physical
parameters
• Site-specific application
BG-2
Notes:
Environmental investigations typically are conducted in areas in which heterogeneous
conditions predominate.
Borehole geophysics can be used to obtain valuable data, including information about
geologic control and in situ analysis of physical parameters, especially in the vertical
dimension.
With borehole geophysical data, rapid and objective interpretation is possible. When
combined with surface geophysics, application of borehole geophysical methods offers a
three-dimensional understanding of conditions.
Selection of a logging program should be considered carefully. Factors such as project
goals, geophysical information desired, instrumentation, and surface and subsurface
conditions will affect the logging program. No logging program exists that is perfect for
every project, and there is no unique response for every log.
BG-2
Module: Geophysical Characterization Techniques and Data Interpretation
-------
Borehole
Borehole Geophysical Methods
4 Electrical and
magnetic
+ Nuclear (gamma
and neutron)
* Caliper
+ Sonic
4- Video
4- Nuclear magnetic
resonance
&EPA
tXMJIl. Cfl
W-
»"
<
«
C'
• ; ; .
5:
./'
«>
CM** „
WA
o
1^4
f.*AMPf >' GAMWA
KIUCIIOH LOC » pvf CASFO Mar
KJtcrr*
•"^
I . -J*4j
; ^k~~-<
r-a
'
•
'^,v- ffa^.
-' '• f~
-.
— ~-~r.
t
<^
J^3^-
>
!
:.:i M
*>
/—
^
, jra'Sl u"
MXJCTION LOC « PV': •~.»t»n Mnl^
BG-3
Notes:
Electrical and magnetic borehole logging techniques generally are used for (1) identifying
general lithology, (2) performing stratigraphic correlation studies, and (3) performing
water quality studies.
Nuclear borehole logging techniques generally are used for (1) identifying clay and shale
layers, (2) performing stratigraphic correlation studies, and (3) measuring bulk density,
porosity, and moisture content.
Caliper borehole logging techniques generally are used in conjunction with other
borehole methods. The caliper log identifies changes in the diameter of the borehole as a
function of depth.
Sonic borehole logging techniques generally are used for (1) performing lithologic
characterization, (2) measuring porosity, and (3) identifying fractures and solution
openings.
Video borehole logging techniques generally are used for (1) inspecting the integrity of
monitoring well casings, (2) identifying fractures and solution openings, and
(3) performing lithologic characterization.
Nuclear magnetic resonance techniques generally are used for evaluating porosity,
permeability, moisture content, and water content.
BG-3
Module: Geophysical Characterization Techniques and Data Interpretation
-------
Borehole
Other borehole logging techniques include (1) dipmeter surveying that identifies the
correlation of sedimentary structures and fractures and (2) directional surveying that
identifies the position of the borehole.
It is important to realize that application of such methods as neutron and gamma-gamma
(nuclear techniques) requires a radioactive source. Use of such sources requires a special
license and may not be allowed in some states.
For additional information about this topic, refer to page A-l at the end of this module.
BG-4
Module: Geophysical Characterization Techniques and Data Interpretation
-------
Borehole
Stratigraphic Correlation Based On
Gamma and Resistivity Logs
EPA
BG-4
Notes:
This illustration shows three boreholes spaced approximately 100 feet apart. The vertical
differences are related to changes in surface elevation. Notice the similarities in the
measured gamma and resistivity from borehole to borehole in this excellent example of
Stratigraphic correlation of geologic units. The gamma data are shown on the left, while
the apparent resistivity is shown on the right of each borehole. Low resistivity and high
gamma count are likely related to clay zones or fine-grained geologic materials.
BG-5
Module: Geophysical Characterization Techniques and Data Interpretation
-------
Borehole
Overview
Instrument
packages and
coincident grid
surveys
EPA
QE-5
Notes:
It is common practice to combine several instruments (for example, caliper, gamma ray,
and neutron) in one "package" and obtain measurements simultaneously in a single
downhole logging run. Similar approaches are used for surface geophysics when two or
more sensors can be mounted to a survey vehicle in a package format. Both downhole
and surface geophysics approaches use multiple sensors or instruments to obtain
measurements during a single run or transect. As an alternative, two or more sensors can
be used in the same borehole or along the same transect, but not simultaneously. That
approach often is referred to as coincident surveying or the multisensor approach.
BG-6
Module: Geophysical Characterization Techniques and Data Interpretation
-------
Borehole
Gamma Neutron Acoustic Velocity Caliper
Spontaneous Long-Normal
Lithology Potential Resistivity
Limestone"
Gypsum v
Freshwater
Salinewater
Anhydrite
Single-Point Temperature
Resistance
BG-7
Module: Geophysical Characterization Techniques and Data Interpretation
-------
-------
Surface
Geophysical Characterization
Techniques and Data Interpretation
*• In situ
+ Borehole
• Surface
4 Emerging and Innovative Approaches and
Instruments
* Hands-on Activity for Geophysical Analysis
se-i
SG-I
Module: Geophysical Characterization Techniques and Data Interpretation
-------
Surface
Surface Geophysical Methods
*• Magnetic surveys
^Conductivity surveys
•*Ground-penetrating radar (GPR) surveys
+ Seismic surveys
&EPA
SG-2
Notes:
Magnetic surveys rely on measurements of the earth's magnetic field or on how that field
changes spatially. Anomalous measurements may indicate the presence of buried ferrous
materials.
Conductivity surveys use measurements of the electrical conductivity of the subsurface to
identify changes in geologic material at shallow depths, conductive contaminant plumes,
or areas in which waste has been disposed of.
Ground-penetrating radar (GPR) surveys rely on transmitting pulses of radio waves into
the subsurface and measuring waves that are scattered back to the surface. GPR survey
techniques typically are used for identifying the locations of buried objects, mapping
shallow groundwater surfaces, or mapping various geologic formations.
Seismic survey techniques are used primarily for mapping geologic contacts and
structural features in the subsurface. Both refraction and reflection methodologies
commonly are used in environmental investigations.
SG-2
Module: Geophysical Characterization Techniques and Data Interpretation
-------
Surface
Notes:
Magnetic Field
Found in the vicinity
of a magnetic body
or electrical medium
that is carrying
current
EPA
SG-3
The earth's magnetic field induces a magnetic moment per unit volume in buried
ferromagnetic debris (bottom), causing a local perturbation (anomaly) in total magnetic
field (top).
The total magnetic field measured is a vector sum of the ambient earth's magnetic field,
plus local perturbations caused by buried objects.
SG-3
Module: Geophysical Characterization Techniques and Data Interpretation
-------
Surface
Notes:
Magnetic Surveys: Physical Basis
Magnetic susceptibility
• Remanent magnetism
and susceptibilities of
earth materials
Magnetic field of the
earth
"ro
D
b
00 06
12
18
24
Time (hrs)
&EPA
SG-4
A body placed in a magnetic field acquires a magnetization that typically is proportional
to the field. The constant of proportionality is known as the magnetic susceptibility. For
most natural materials, susceptibility is very low. However, ferromagnetic and
ferrimagnetic materials have relatively high magnetic susceptibilities. The susceptibility
of a rock typically depends only on its magnetite content. Sediments and acid igneous
rocks have relatively low susceptibilities, while basalts, gabbros, and serpentinites usually
have relatively high susceptibilities.
Ferromagnetic and ferrimagnetic materials have permanent magnetic moments in the
absence of external magnetic fields. An object that exhibits a magnetic moment is
characterized by a tendency to rotate into alignment when exposed to a magnetic field.
The magnetic field of the earth originates from electric currents in the liquid outer core.
Earth's magnetic field strengths typically are expressed in units of nanoTesla (nT). The
field varies during the day because of changes in the strength and direction of currents
circulating in the ionosphere; those changes are referred to as diurnal variation. Sunspot
and solar flare activity can create irregular disturbances in the magnetic field. Such
changes are referred to as magnetic storms.
SG-4
Module: Geophysical Characterization Techniques and Data Interpretation
-------
Surface
Magnetic Surveys: Instruments
Proton magnetometer
reads total magnetic
field
Fluxgate and cesium
magnetometers are
often used for gradient
readings
&EPA
SG-5
Notes:
Proton precession, fluxgate, and cesium vapor magnetometers used for surface
geophysical surveys are portable, self-contained units that require a single operator. Most
modern proton precession, fluxgate, and cesium vapor magnetometers support recording
and retrieval of data.
Proton precession magnetometers can be rented for approximately $300 per month or $10
per day, with a mobilization fee of about $95. The cesium vapor magnetometer can be
rented for approximately $1,770 per month or $59 per day, with a mobilization fee of
about $95. A fluxgate magnetic locator can be rented for approximately $180 per month
or $6 per day, with a mobilization fee of about $55.
SG-5
Module: Geophysical Characterization Techniques and Data Interpretation
-------
Surface
Magnetic Surveys: Survey Practice
Survey grids
Monitoring of diurnal variation
40-
30-
20-
10-
0,0
_
1
0 2
^5>
Dfum
0 3
0 4
0 5
0
j,
N
EPA
SG-6
Notes:
Proton precession instruments usually are used to obtain measurements along regularly
spaced grid points. Fluxgate magnetometers are used in serpentine search or clearance
patterns, in addition to the grid-based data acquisition approach. Cesium vapor
magnetometers are used extensively today because they support rapid acquisition and
storage of data.
When total field measurements are being obtained, as is the case with long baseline
instruments, a separate stationary magnetometer should be used to measure diurnal
changes in the ambient magnetic field, as well as possible effects of magnetic storms.
Magnetic measurements are susceptible to noise related to ferrous content of buildings,
fences, vehicles, and utility fixtures.
SG-6
Module: Geophysical Characterization Techniques and Data Interpretation
-------
Surface
Total Intensity of the Earth s
Magnetic Field
Notes:
W H5" I8(l~ US"
:XPRF.SSED1N K1UKJAMMAS
SOURCE; US S H «
SG-7
This figure shows that the intensity of earth's magnetic field varies throughout the world.
SG-7
Module: Geophysical Characterization Techniques and Data Interpretation
-------
Surface
Magnetic Surveys: Interpretation
^Contouring-based interpretation
Sample Total Field Anomalies
Axes (ft)
X: 0-100
Y: 23-89
Anomaly X
1
2
3
28.19
35.88
58.50
Y
61.97
46.93
72.70
Depth
1.87
3.16
2.91
Size
88
186
165
Test Dipoles: 175 millimeter (mm) § 3 ft (2). 90 mm @ 2 ft
SG-8
Notes:
Various means of spatial predication can be used to prepare contour maps that illustrate
variation in magnetic properties across an area of interest. Contours of total field or
gradient commonly are used as interpretation tools.
This figure shows three magnetic anomalies buried at three depths.
Notice that the direction and intensity of the anomaly vary, likely according to the
remanent magnetization, orientation, size, and depth of the object.
SG-8
Module: Geophysical Characterization Techniques and Data Interpretation
-------
Surface
Notes:
Electromagnetic Wave
* Disturbance that propagates outward from any
electrical charge that oscillates or is accelerated
* Consists of vibrating electric and magnetic
fields that move at the speed of light and are at
right angles to each other and the direction of
motion.
EPA
SG-9
An electromagnetic wave exhibits both electrical and magnetic properties. Because of the
dual characteristics, it is affected by any electrical or magnetic fields that it encounters as
it propagates from its source.
Electromagnetic waves move at the speed of light in the absence of matter, but exhibit
different propagation speeds when in different media. Electromagnetic waves may be
scattered (including reflection and refraction behaviors) by changes in propagation media,
electrical fields, or magnetic fields.
SG-9
Module: Geophysical Characterization Techniques and Data Interpretation
-------
Surface
Electro
Chemical «emeit»
Oil polluton
Shape, size, position,
luminescence gas - absorbance
Shorelines ^^"^
Water bodies
Relief-tectonics ;
mag
Wivelenglh
Angstrom
: 0.03 -
3-
30-
300-
-^:
330-
0.3 Centimeter-
[ '-
30-
30-
300-
3003-
netic Spectrum
Gamma ray
X Ray (soft)
Ultra violet
Visible light
Infrared
Radar
Ultra short
Shortwave
Middle and
K>ng wave
Frequency
Hertz (Hi) /
-IP- /
MO" /
-vfy
- 10" ^^
Ultra violet
Vioiet
Blue
Grew
Yellow
Orange
Red
Infrared
Water penetfatcn, visibte sinoended
pericte. mtar decolonzatnn
Vegetation, damage to vegetation.
identification, recognition
HO"-~_
Wavelength In Micnm
"\ r
-IflS »-
Con
onm
Nwr
Middle
Far
Temperature of the surface
grouping of mete
- 1649-C
-538-C
-MO'C
-100'C
-78'C
1
tin ontnw] noBBon
Notes:
The electromagnetic spectrum is a continuous range of radiation extending from radio
waves to gamma rays. All waves are the same in nature, differing only in frequency and
wavelength.
SG-IO
Module: Geophysical Characterization Techniques and Data Interpretation
-------
Surface
Electromagnetic Conductivity Surveys
* Active
electromagnetic
induction
techniques
+ Applications
» Profiling
» Sounding
SECONDARY FIELDS FROM
CURRENT LOOP SENSED BY
RECEIVER COL
&EPA
SQ-11
Notes:
Conductivity methods also are known as active electromagnetic induction techniques.
Conductivity methods can be used to detect both ferrous and nonferrous metallic objects
or materials.
Conductivity methods use a transmitter coil to establish an alternating magnetic field that
induces electrical current flows in the earth. The induced currents generate a secondary
magnetic field that is sensed by a receiver coil. The character and magnitude of the
secondary field are governed by the frequency of the transmitted current and the
distribution and magnitude of the electrical properties in the nearby subsurface.
Profiling is accomplished by making fixed-depth measurements along a traverse line.
Sounding is accomplished by making measurements at various depths at a fixed location.
SG-IJ
Module: Geophysical Characterization Techniques and Data Interpretation
-------
Surface
Notes:
Conductivity Surveys: Instruments
4- Fixed geometry
instruments
4 Variable
geometry
instruments
4 Costs
Fixed geometry (that is, the coil spacing is fixed) instruments designed for use by a single
operator may be used for continuous or station-based recording of measurements.
Variable geometry instruments consist of two flexible connected coils. The instruments
typically require two operators.
A fixed-geometry instrument (for example, an EM-31) can be rented for approximately
$1,370 per month or $44 per day, with a mobilization fee of about $150. A variable
geometry instrument (for example, an EM-34) can be rented for approximately $ 1,770 per
month or $59 per day, with a mobilization fee of about $195.
SG-12
Module: Geophysical Characterization Techniques and Data Interpretation
-------
Surface
Notes:
Conductivity Surveys: Survey
Practice
• Data acquisition
+Conductivity is influenced by soil and rock
properties
*• Effects of cultural features
SG-13
Approaches to conductivity surveys are very similar to resistivity approaches. Profiles
involve continuous or station-based conductivity measurements obtained along a transect.
Measurements can be obtained along a grid of transects to support contouring of the data.
Data usually are recorded digitally for rapid transfer to a computer for processing.
Most soil and rock minerals have low conductivities when dry. A unique conductivity
value cannot be assigned to a particular material because of variations in composition and
structure of soils and in pore fluids.
The presence of surface conductors (for example, railroad tracks) must be noted carefully
in the survey log.
SG-13
Module: Geophysical Characterization Techniques and Data Interpretation
-------
Surface
Range of Electrical Conductivities
in Natural Soil and Rock
Conductivity (milllS/m)
10' 10' 1 Id'1
Clay and Marl
Loam
Top Soil
Clayey Soils
Sandy Soils
Loose Soils
River Sand and Gravel
Glacial Till
Chalk
Limestones
Sandstones
Basalt
Crystalline Rocks
SG-14
Notes:
This illustration shows the range of conductivity that can be encountered in various
terrain materials from a variety of climatic zones. The ranges have been compiled for
different terrain materials from a variety of survey and laboratory measurements.
SG-14
Module: Geophysical Characterization Techniques and Data Interpretation
-------
Surface
Conductivity Surveys: Interpretation
• Data
contouring
ms..nll 80-15
Notes:
Various means of spatial prediction similar to the surface magnetics method can be used
to prepare contour maps that illustrate variation of subsurface conductivity across an area *
of interest.
SG-15
Module: Geophysical Characterization Techniques and Data Interpretation
-------
Surface
LEGEND:
» MONITORING
• PIEZOMETER
• UTILITY POLE
o" MANHOLE
a'C»TCllB*>7TM
- RAILROAD TRACKS
SG-16
Module: Geophysical Characterization Techniques and Data Interpretation
-------
Surface
GPR Surveys: Physical Basis
4- Principles of GPR
4 Generation of the electromagnetic wave
4 Propagation and scattering of the
electromagnetic wave
4 Applications
+• Limitations
SG-16
Notes:
GPR technologies use the transmission of pulses of electromagnetic energy (radar waves)
into the ground. The signals transmitted travel into the ground and are reflected by buried
objects. Reflected signals travel back to the receiving unit, are recorded, and are
processed into an image.
GPR transmitter antennas are designed to radiate a broadband pulse of only a few
nanoseconds' duration when excited. For optimal performance, the GPR antenna should
be positioned perpendicular to the ground surface.
The propagation of electromagnetic waves in the subsurface is primarily dependent on the
frequency of the wave, conductivity of the ground, soil moisture content, and relative
permittivity of the subsurface. Abrupt changes in conductivity or relative permittivity
create interfaces in the subsurface where reflection or refraction can occur.
Under optimal conditions, GPR technologies are capable of detecting both metallic and
nonmetallic objects.
The main limitation of GPR is its reduced effectiveness in highly conductive soils (such
as wet clay soils).
SG-I7'
Module: Geophysical Characterization Techniques and Data Interpretation
-------
Surface
GPR Surveys: Instruments
4 Instrumentation
of GPR systems
* Costs
LAYERED
MATERIAL
SG-17
Notes:
GPR instruments consist of a control unit, antennas and cables, a printer or digital data
recorder, and a power supply. The control unit generates timing signals to key the
transmitter on and off and synchronize the keying with the receiver. The unit controls the
scan rate, the time range over which echoes are compiled, and the gain applied to the
echoes. The transmitting antenna is excited by a semiconductor device (therefore, it is a
transducer). A separate, but identical, receiver is used because echoes can return from
near-surface targets before the transmitting antenna has stopped radiating. Transmitting
antenna frequency ranges of 80 megahertz (MHz) to 500 MHz are used most often in
environmental applications.
GPR equipment can be rented for approximately $3,000 to $7,000 per month or $150 to
$350 per day, depending on accessories. Typical mobilization fees are approximately
$300.
SG-I8
Module: Geophysical Characterization Techniques and Data Interpretation
-------
Surface
Complete GPR System
SG-18
Notes:
This is a photograph of a complete, portable GPR system, the Subsurface Interface Radar
(SIR) 2 system developed by Geophysical Survey Systems Inc. (GSSI). The system
consists of a real-time color display and controller that is carried by the operator, a battery
pack, a thermal printer (for hard copies of data), and a GPR antenna. In this case, a high-
frequency antenna is used to detect shallow targets — for example, to determine the
thickness of reinforced concrete pavement.
SG-19
Module: Geophysical Characterization Techniques and Data Interpretation
-------
Surface
Multiple-Channel GPR System
J&EPA
SG-19
Notes:
The system shown in this illustration is a GSSI SIR-10 GPR system. The instrument is an
earlier version of the SIR-2 of the real-time color display of GPR data. The system is
plugged into an AC-DC converter that is connected to a vehicle battery. The bottom unit
contains a computer and tape recorder. The upper unit is a controller and color monitor.
A medium-frequency GPR antenna (likely 300 MHz) is shown in the background of the
illustration. The system is still used extensively.
SG-20 •
Module: Geophysical Characterization Techniques and Data Interpretation
-------
Surface
Low-Frequency Bistatic GPR
Antenna
EPA
SG-20
Notes:
This illustration shows a pair of 100 MHz GPR antennae. The antennae are designed for.
deeper exploration. An operator is shown pulling the antennae across the ground surface.
Also shown in the foreground is the cable that supplies power to the antennae and
transmits signals back to the controller-receiver.
SG-21
Module: Geophysical Characterization Techniques and Data Interpretation
-------
Surface
GPR Surveys: Survey Practice
4- Selection of
frequency °
4 Transect profiles = 10
DISTANCE
(0
o
§
ut
50
- <
<>
EPA
SG-21
Notes:
GPR frequencies are selected on the basis of resolution requirements and target depths.
In general, lower-frequency transducers provide a greater depth of penetration, but also
lower resolution compared with higher-frequency transducers. Surveys can be performed
with more than one transducer if no single frequency is adequate.
Profiles generally are obtained as the transducer is moved along transects. The
profile—either printed on a strip chart or recorded and viewed on a video screen—usually
is interpreted in the field. Digitally recorded data also can be subjected to filtering and
enhancement to support additional interpretation. The transducer can be moved along the
transect manually or by a vehicle. In either case, the operator should strive to move the
transducer at a constant speed.
SG-22
Module: Geophysical Characterization Techniques and Data Interpretation
-------
Surface
GPR Surveys: Interpretation
• Profiles and qualitative signal for pattern recognition
&EPA
N;
> r^ Diffraction Patterns
Radar Pro* 500 mH2 antenna
SQ-22
Notes:
The interpretation of unprocessed GPR data is relatively subjective and yields only
approximate information about the shape and location of buried objects. The depth of
investigation typically is no greater than 10 to 15 meters and may be considerably less in
soils that exhibit relatively high electrical conductivity. For example, a near-surface steel
underground storage tank (UST) buried in sand could be completely invisible to GPR if it
were covered by a 6-inch layer of highly conductive, clay-rich soil. Further, the
equipment is relatively bulky, and its operation requires a power source (such as a car
battery).
SG-23
Module: Geophysical Characterization Techniques and Data Interpretation
-------
Surface
GPR Surveys: Interpretation
10-
EPA
SG-23
Notes:
This slide shows the interpretation of the data presented in Slide SG-22.
SG-24
Module: Geophysical Characterization Techniques and Data Interpretation
-------
Surface
GPR Surveys: Interpretation
' -SSgf^g^"*~5^? " •":: '
;..«.i,«^. *"'sp»* 'p*^%^jijjpif^^7'"<*^'''<*NFj;- '•' ; J'**^"
-•••-»*—^-*»ft*'.•****» *«)|r.» „ ^^WW**^- ^*--lJ.^-IUl.,*'^ - ^ •' <4* I*..
<^t,t-K.>tH- 1^-M^***-^., l^-rf^m.
EPA Profle 500 mHz antenna
SQ-24
Notes:
The GPR survey data shown on the slide were obtained from the area above a suspected
tank. Note how these data differ from those shown in Slide SG-22.
No depth scale is present. Generally, the data show distance on the horizontal axis and
time in nanoseconds on the vertical scale.
Calibration of the velocity of wave propagation is necessary to determine the depth of an
object.
5C-25
Module: Geophysical Characterization Techniques and Data Interpretation
-------
Surface
GPR Surveys: Interpretation
- pavement
10
Distance (ft)
20 30
,— reinforced concrete slab
/ 40 45 50 55
SQ-25
Notes:
This illustration shows an interpreted rectangular tank and fill under pavement and a
reinforced concrete slab. It often is difficult to see beneath reinforced concrete. The
reinforcing rods must be far enough apart for the signal to pass by them, and the soils
must be of low conductivity.
SG-26
Module: Geophysical Characterization Techniques and Data Interpretation
-------
Surface
GPR Surveys: Interpretation
Horizontal Distance in Meters
0*20
0-.50
0*60
Notes:
This GPR record shows a variety of subsurface interpreted features. For an untrained .
observer, it is difficult to identify the subsurface features. Notice that the interpreter has
labeled several items as possible and probable. It is difficult to determine what
subsurface features are present without prior knowledge of a site.
SG-27 •
Module: Geophysical Characterization Techniques and Data Interpretation
-------
Surface
GPR Surveys: Interpretation
500m Hz Distatic profile
Hydrogeologic Investigation
Well soled faro-grained sand
EPA
Notes:
Wilier lab*
Topofdntt
SG-27
This illustration shows favorable results that identify the water table and the top of glacial
drift material over bedrock. In this case, the glacial drift material must be low in
conductivity, or the survey would not be successful in mapping the interpreted
information. GPR surveys work well in clean sand, a low conductivity material.
Module: Geophysical Characterization Techniques and Data Interpretation
-------
Surface
Seismic Surveys: Physical Basis
^ Types of elastic waves
* Seismic velocities
+ Interface effects
Shot Point
Recording Geophonn
I Overburden
I Bedrock
Whw»wtocity,V,»V,
SG-28
Notes:
When a sound wave travels in air, the molecules oscillate backward and forward in the
direction of energy transport. This type of wave propagates as a series of compressions
and expansions. It is referred to as a P-wave.
P-waves propagate in a solid matrix as do S-waves, which are oscillations at right angles
to the direction of energy transport. P and S wavefronts expand throughout the matrix
and are termed body waves.
In both refraction and reflection surveys, information about subsurface conditions is
derived by evaluating the travel times of various wavepaths between sources and
receivers.
As is the case with EM and sonic waves, scattering phenomena (including refraction and
reflection) and energy partitioning occur when a seismic wave encounters an interface
between two different types of rock.
SG-29
Module: Geophysical Characterization Techniques and Data Interpretation
-------
Surface
Seismic Refraction
Seismograph>—-a
Geophone
V,
EPA
SG-29
Notes:
Refracted waves travel down through the overburden, are critically refracted below the
interface of the overburden and the bedrock, and then travel upward through the
overburden to the geophone. Along those paths, refracted waves travel at bedrock
velocities below the interface of the overburden and the bedrock and at overburden
velocities along the upward and downward paths.
SG-30 •
Module: Geophysical Characterization Techniques and Data interpretation
-------
Surface
Seismic Reflection
V,
&EPA
Seismograph
-
,«-*" shot point *~-^
tl
'* A-
Geophone
SG-30
Notes:
• Reflected waves travel down to the interfaces of the overburden and the bedrock and are
reflected back up at the same angle to the geophone. Reflected waves travel at
overburden velocities along their entire paths.
SG-3I
Module: Geophysical Characterization Techniques and Data Interpretation
-------
Surface
Seismic Surveys: Instruments
+ Seismic sources
* Geophones
* Seismographs
4- Costs
SG-31
Notes:
Traditional seismic sources are explosive charges, such as dynamite; however, impact and
vibratory sources are coming into use more widely.
A geophone generally consists of a wire coil wound on a high-permeability magnetic core
suspended by a spring in the field of a permanent magnet. If the coil moves relative to
the magnet, voltages are induced and current flows to an external circuit. The current is
proportional to the velocity of the coil through the magnetic field.
Seismic signals travel from geophones to recorders through cables as varying electric
currents. Seismographs are devices that record, filter or enhance, and display or print the
signals returning from the geophones.
Seismic instruments can be rented for approximately $1,000 to $3,000 per month or $75
to $150 per day, with a mobilization fee of approximately $150 to $300, depending on the
configuration desired.
• SG-32
Module: Geophysical Characterization Techniques and Data Interpretation
-------
Surface
Seismic Surveys: Interpretation
&EPA
Wr*V* -~ ,*»'3j£i^«3fe--£ty!£
••?•*•'.«•-'::'; -:' V. -r^StJaagfcK-'';:
SG-32
SG-33
Module: Geophysical Characterization Techniques and Data Interpretation
-------
Surface
Processed Reflection Record
EPA
SG-33
Notes:
The final product of a seismic reflection survey is obtained after significant processing of
data. Distance versus time plots are converted into distance versus depth plots. Often,
layers or structure is plotted on the interpretation map.
SG-34
Module: Geophysical Characterization Techniques and Data Interpretation
-------
Surface
Refraction Analysis
H50
HI
Q
100
1000
500 DISTANCE (ft)
-500
12SO ft/see
SG-34
Notes:
Seismic refraction data usually are processed by software that follows the general
reciprocal method. Multiple shot points are used on the ends and at the center of the
spread.
The profile shows variations in velocity among three layers. Low velocity likely
represents unconsolidated sediments, while the high velocity represents bedrock.
SC-35
Module: Geophysical Characterization Techniques and Data Interpretation
-------
-------
Emerging and Innovative Approaches and Instruments
Geophysical Characterization
Techniques and Data Interpretation
• In situ
+ Borehole
• Surface
<=> •Emerging and Innovative Approaches and
Instruments
• Hands-on Activity for Geophysical Analysis
QE-1
GE-1
Module: Geophysical Characterization Techniques and Data Interpretation
-------
Emerging and Innovative Approaches and Instruments
Emerging and Innovative Methods
and Instruments
4 Ordnance detection with instrument packages
4- Mapping of hydrocarbon plumes
4 Multiple-frequency electromagnetic profiler
4 Transient electromagnetics
GE-2
Notes:
Significant resources are being focused on developing surface package approaches to
locate subsurface ordnance characterized by little or no ferromagnetic content. Typically,
the sensor package is mounted on a vehicle that is equipped with software-based analysis
and global positioning system equipment to support real-time mapping of results.
Combination GPR and magnetic packages are common.
A combined surface to borehole geophysical survey technology has been developed to
identify subsurface contamination with hydrocarbons. The technology uses induction
electrical resistivity survey techniques and can identify hydrocarbon contamination
because petroleum products are highly resistive to electrical currents. Data are processed
to create a three-dimensional representation of the subsurface contamination.
Using a fixed coil separation, the frequency domain, EM profiling system simultaneously
measures frequencies between 330 Hertz (Hz) and 20,000 Hz. The variable frequency
capability allows frequency sounding, rather than geometric sounding.
High-resolution transient electromagnetics (TEM) has been used most commonly in
mineral exploration but is well suited to environmental applications. The flexibility of
loop sizes and geometries and faster transmitter turnoff times yield shallower soundings.
GE-2
Module: Geophysical Characterization Techniques and Data Interpretation
-------
Emerging and Innovative Approaches and Instruments
Model GEM-300 Variable Frequency
Electromagnetic Profiler
EPA
GE-3
Notes:
The GEM-300, introduced in the spring of 1998 for commercial use, is a frequency
domain, electromagnetic system. It can he configured to simultaneously measure as many
as 16 frequencies between 330 Hz and 20.000 H/.. The user can select frequencies that
provide the best results for a specific application.
GE-3
Module: Geophysical Characterization Techniques and Data Interpretation
-------
Emerging and Innovative Approaches and Instruments
Electromagnetic Profiling
Metal Plate
1 ft Deep
Vertical Drum
6 It Deep
EPA
1350 Hz In-Phase Horizontal Dipole Measurement
(scale in meters)
GE-4
Notes:
The slide shows an example of data collected with a new multifrequency GEM 300
system.
These data were taken over a known geophysical test site. The detail of the three objects
detected is obvious. A frequency of 1,350 Hz was used in taking the data.
The system is similar to the Geonics EM-31, the industry standard terrain conductivity
meter. The primary difference between the two systems is that GEM-300 is lightweight
(18 pounds) and provides multifrequency measurements. Output is apparent conductivity
measured in milliSiemans per meter and in-phase measured in parts per million, an
indication of metal in the subsurface.
GE-4
Module: Geophysical Characterization Techniques and Data Interpretation
-------
Emerging and Innovative Approaches and Instruments
Setup of the NanoTEM System
EPA
GE-5
Notes:
This diagram shows the basic setup of the NanoTEM system developed by Zonge
Engineering. The system is a time-domain, electromagnetic method that consists of an
electromagnetic transmitter (NT-20), a multifunction receiver (GDP-32), and a battery
power source. The transmitter energizes a transmitter loop, creating EM fields in the
subsurface. The EM fields in turn create secondary fields in the ground that are sensed by
a three-axis receiver loop and recorded as voltages in the receiver.
The system is useful in metal detection, mapping of lateral and vertical changes in ground
conductivity, location of underground storage tanks, and mapping of landfill boundaries.
This system is similar to the Geonics Protem system, developed in the 1970s. The
primary difference between the two systems is that the NanoTEM is a multifunction
system used for both time-domain EM surveys and DC resistivity-induced polarization
surveys. Additional components may be necessary to perform additional surveys. The
NanoTEM also records data at earlier time.
GE-5
Module: Geophysical Characterization Techniques and Data Interpretation
-------
-------
Hands-on Activity for Geophysical Analysis
Geophysical Characterization
Techniques and Data Interpretation
• In situ
+ Borehole
* Surface
* Emerging and Innovative Approaches and
Instruments
• Hands-on Activity for Geophysical Analysis
EPA
GH-1
GH-1
Module: Geophysical Characterization Techniques and Data Interpretation
-------
Hands-on Activity for Geophysical Analysis
Hands-on Instrument Exercise
* Cesium vapor magnetics
+ GPR
4- Noncontacting terrain conductivity
&EPA
GH-2
Notes:
The hands-on exercise will include the use of a GeoMetrics G858 cesium vapor
magnetometer, Geophysical Survey Systems SIR-3 with 500 MHZ transducer GPR
System, and Geonics EM-31DC noncontacting terrain conductivity instrument.
GH-2
Module: Geophysical Characterization Techniques and Data Interpretation
-------
Additional Information
Table of Contents
Borehole Geophysical Methods A-2
Surface Geophysical Methods A-14
A-l
Module: Geophysical Characterization Techniques and Data Interpretation
-------
Additional Information
Borehole Geophysical Methods
Electrical and Magnetic - Physical Basis
X
\
Electric current in aqueous solutions is carried by the ions of dissolved salts migrating
through the fluid in response to an applied electric field. In contrast to ionic conduction,
electric current in a mineral or rock matrix is carried by electrons. In most minerals,
especially silicates and carbonates, conduction in the matrix is negligible (the resistivities
are typically greater than 107 ohm-meters). The electrical resistivity of most rocks is
controlled by the pore fluids because the resistivity of the solid matrix is extremely high
compared to that of the fluids.
Archie's equation states that resistivity is proportional to the fractional porosity raised to
a power of between about 1.2 and 1.8, depending on the shape of the matrix grains. This
value (fractional porosity raised to the power) is sometimes referred to as the formation
factor.
The magnetic field observed in an uncased borehole consists of the sum of the normal
ambient field of the earth and a superimposed field caused by induced and remanant
magnetism. Induced magnetism occurs when a material with magnetic susceptibility is
placed in a magnetic field. The induced field has a strength proportional to the
susceptibility and the strength of the applied field. The induced field is of the same sign
as the applied field, so the total field is increased. Remanant magnetism is that observed
in the absence of an applied field.
A-2
Module: Geophysical Characterization Techniques and Data Interpretation
-------
Additional Information
Borehole Geophysical Methods
Electrical and Magnetic - Survey Practice
* The survey is typically supported by a single truck that carries both the winch and
cable—the drawworks—and data recording equipment. Video display or strip chart
recorders are generally used during the survey to support field interpretation of the log. A
measure wheel is used as a primary means of measuring depth. Tools are generally
lowered rapidly and measurements are recorded during the return to the surface. Uniform
tool speed and accurate depth measurement are important factors.
• Galvanic resistivity logging requires an uncased boring and the presence of fluid. Older
galvanic resistivity tools measure the voltage at one or two points in response to a
constant current input. More recent designs are adaptive so that current is varied to
maintain a zero voltage gradient at specific locations on the tool. Since galvanic contact
is required, the tool may be designed to press against the borehole wall by using one or
more hydraulic decentralizing arms.
• Inductive tools do not require contact and may, therefore, be used in dry boreholes
without the use of decentralizing arms. Some older design inductive tools require the
presence of nonconductive drilling fluids.
• Spontaneous potential tools must be operated in uncased borings that are filled with water
or drilling fluid. This process generally requires a fluid with a total dissolved solids
(TDS) greater than 10,000 milligrams per liter (mg/L) to obtain reliable measurements.
• Dielectric tools commonly operate at a frequency of about 1 gigahertz (GHz) (note this
for later comparison to ground penetrating radar [GPR] frequencies in the range of 500
megahertz [MHZj) and consist of a transmitter and receivers mounted on the side of the
tool. The tool is held against the borehole wall by means of a decentralizing arm.
Dielectric tools can be operated in uncased borings or non-metallically cased borings
under wet or dry conditions.
• Susceptibility, fluxgate, and proton precession tools do not rely on contact with the
borehole wall and can be operated in wet or dry conditions.
A-3
Module: Geophysical Characterization Techniques and Data Interpretation
-------
Additional Information
Borehole Geophysical Methods
Electrical and Magnetic - Interpretation
B
Saturation logging
Lithology logging
— magnetic
[Ill
z
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/
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Lithology logging
— galvanic
resistivity
Tto hmW T«
«M girt. MM
M MM W
Sq»
KM '
Water saturation can be estimated based on galvanic resistivity data through the use of a
resistivity-porosity cross-plot. The plot shown on Figure A illustrates lines of constant
saturation. Porosity data is obtained through the use of a separate borehole method.
Lithology studies are sometimes supported by magnetic total intensity data (Figure B). In
most cases, total intensity data is supplemented by additional logging techniques. Note
that the first stratigraphic interface identified in the graphic is based on neutron log data.
The use of resistivity data to identify bedding planes is illustrated in Figure C. The
dashed lines represent actual resistivity of the structure, while the solid lines represent
measured resistivity.
A-4
Module: Geophysical Characterization Techniques and Data Interpretation
-------
Additional Information
Borehole Geophysical Methods
Nuclear (Gamma and Neutron) - Physical Basis
nMC-Wvt *
___^ ^ *^^f *~^+-^~'.'~ PavlFD- - m*t
Nuclides and energy states. A nuclide is a specific nuclear species with a given number
of protons and a given number of neutrons. Each nuclide has its own set of energy levels
with energies characteristic of that nuclide. When a nuclide changes from one state to
another with lower energy, it often emits a particle or gamma ray.
Gamma radiation interactions with matter. The interactions of radiation can be used
to infer properties of interest in downhole geophysics. Some minerals contain elements
(potassium, thorium, uranium) that are natural sources of gamma radiation. The number
of gamma photons transmitted through a given thickness of a matrix is a function of the
density, gamma energy, and atomic number of the matrix. Consequently, the number of
gamma photons detected at some distance from an artificial source can be used to infer
quantities of interest.
Neutron interactions with matter. The number of neutrons passing through a given
thickness of a matrix depends primarily on the hydrogen content of the medium, so the
number of neutrons detected at some distance from a source can be used to infer the
hydrogen content, water content, or porosity.
Neutron-induced gamma rays. When neutrons interact with matter, gamma rays are
often emitted. The number and energy of the gamma photons are characteristic of the
elements from which they are emitted, so they can be used to infer the presence of certain
elements.
A-5
Module: Geophysical Characterization Techniques and Data Interpretation
-------
Additional Information
Borehole Geophysical Methods
Nuciear (Gamma and Neutron) - Survey Practice
• Basic logging procedure. Except in the case of neutron-induced gamma logs that
generally require a separate computer van, the survey is typically supported by a single
truck that carries both the winch and cable—the drawworks—and data recording
equipment. Video display or strip chart recorders are generally used during the survey to
support field interpretation of the log. A measure wheel is used as a primary means of
measuring depth. Tools are generally lowered rapidly and measurements are recorded
during the return to the surface. Nuclear surveys require slow logging speeds (compared
to the relatively fast speed that is acceptable for resistivity logging) and some approaches
require the tool to be stationary at each interval of interest. Because nuclear methods are
highly sensitive to attenuation of gamma radiation or neutrons, the tools are often
decentralized in the borehole. Variations in borehole shape and the presence or absence
of borehole fluids are additional factors to consider.
• Gamma tools. Gamma tools are relatively inexpensive and do not require the use of
radioactive sources. In general only qualitative analysis is performed using gamma
logging data. Smaller diameter tools have inherently larger signal-to-noise ratios and
sensitivity of all gamma tools is typically reduced by the presence of drilling fluids,
casings, and irregularly shaped boreholes.
* Gamma backscattering tools. Gamma backscattering tools typically provide a primary
source of data that can be used to determine bulk density, porosity, and moisture content.
The tools require additional care and expense in handling because of the presence of a
radioactive source. The instruments are susceptible to considerable electronic drift and
require frequent calibration. More accurate estimates of formation parameters are
obtained when core samples are obtained for laboratory determination of dry bulk density.
• Neutron tools. Neutron tools also require radioactive sources and thus require special
handling, however, they provide a good means of measuring moisture content. Boron,
cadmium, chloride, and hydrocarbons are sources of interference. Resolution is
decreased with increasing depth of measurement.
A-6
Module: Geophysical Characterization Techniques and Data Interpretation
-------
Additional Information
Borehole Geophysical Methods
Nuclear (Gamma and Neutron) - Interpretation
& QUARTZ SAND
—» DOLOMITE
GAS - FILLED
"• ^ HOLE
10 20
POROSITY (%)
The graphic illustrates the use of empirically derived calibration curves to relate porosity
to neutron count rates. If the formation being measured does not correspond to one of the
calibration curves, corrections are required.
A-7
Module: Geophysical Characterization Techniques and Data Interpretation
-------
Additional Information
Borehole Geophysical Methods
Caliper
(fitting arm
ceil ipring aid threaded red with bait-bearing nut
DC • motor electronic section
After a borehole has been drilled, it is often useful to determine its true size and shape. A
caliper instrument can be used to generate a caliper log for this purpose.
Most caliper tools are mechanical and consist of several arms which are pushed out
against the wall of the borehole using springs driven by hydraulic pressure. A transducer
is used to measure the angle of the arm. This measurement can be converted to the
distance from the center of the tool to the wall. Although, most caliper tools are
mechanical, acoustic caliper tools have also been developed.
Data from many types of downhole geophysical methods, especially nuclear and acoustic,
are affected by changes in the distance from the tool to the wall of the hole. When caliper
logs indicate a rough hole, these effects must be considered in interpreting data.
A-8
Module: Geophysical Characterization Techniques and Data Interpretation
-------
Additional Information
Borehole Geophysical Methods
Sonic-Physical Basis
The propagation velocity and attenuation of sound waves in rock depends on many
properties of the rock, especially density, porosity, saturation, and the amount of
fracturing. When a wave encounters a significant (that is, large in relation to the wave
length) interface or boundary in a rock, it may be transmitted across the boundary,
completely reflected by the boundary, or experience a combination of transmission and
reflection. In such cases where partial transmission and partial reflection occurs, the
energy of the incident wave is partitioned at the boundary. When the wave velocities of
the matrices on either side of the boundary differ, the direction and speed of a transmitted
wave may change. This effect is known as refraction.
Attenuation of waves and wave energy is dependent on the same factors as velocity.
Consecutive partitioning of wave energies can be a significant cause of attenuation.
Friction effects in homogeneous, solid media (that is, no boundaries or interfaces) also
contributes to attenuation.
The figure shows the relationship between velocity and porosity for a water saturated
sandstone. The relationship is determined empirically in a laboratory and then used to
calibrate logging equipment.
A-9
Module: Geophysical Characterization Techniques and Data Interpretation
-------
Additional Information
Borehole Geophysical Methods
Sonic-Interpretation
A computer van is generally used in conjunction with the logging truck to support field
interpretation of sonic logs. The graphic illustrates signals caused by reflections of waves
from a fracture. When the sonic tool straddles the fracture, a characteristic "X-shaped"
pattern is observed. When the tool is on either side of the interface, a "V-shaped" pattern
is observed. Super positioning of the two characteristic signals often results in a
"W-shaped" pattern, some of these patterns are present in the graphic.
.A-IO.
Module: Geophysical Characterization Techniques and Data Interpretation
-------
Additional Information
Borehole Geophysical Methods
Video
Downhole video or television cameras provide real-time, color video images as the
camera is lowered through a borehole. The cameras are typically attached to viewing
equipment at the surface using a waterproof video cable.
Note that acoustic/sonic televiewers provide graphical output of returning
wavefronts—although this is not a true video image, the concept is similar.
In uncased boreholes, lithology and some structural features may be evident from the
video feed. Contamination, such as fuel oil in a light colored sand matrix, also is
sometimes evident. The device also can be used to inspect the structural integrity of
monitoring wells. Video logs may be generated in cased or uncased borings regardless of
the presence or absence of fluids.
A-1I-
Module: Geophysical Characterization Techniques and Data Interpretation
-------
Additional Information
Borehole Geophysical Methods
Nuclear Magnetic Resonance
200
When a strong magnetic field is applied to atomic nuclei, the nuclei tend to align in the
direction of the field. This effect is most pronounced with nuclei having a relatively large
magnetic moment that are exposed to a strong, uniform magnetic field. The hydrogen
nucleus (effectively a proton) has a significant magnetic moment, so the presence of
proton-rich fluids (such as water) can be inferred by measuring the characteristics of the
alignment.
The time required for alignment to occur after the field is applied, and the amount of time
required for the alignment to degrade after the field is removed, are measurable and are
known as alignment and relaxation times, respectively. The relaxing nuclei cause
changes in magnetic flux in the nuclei's vicinity. These changes in flux can be correlated
to the relative abundance of protons in the vicinity of the tool. A quantity known as the
free fluid index (which is correlated to the pore space containing an unbound fluid, such
as water) can be derived by measuring flux changes during the nuclei relaxation process.
Through the use of the Kozeny equation, the free fluid index and relaxation times can be
correlated to the permeability of a saturated formation. Tools designed for this purpose
are used to generate permeability logs. Although nuclear magnetic resonance tools
generally provide more precise characterization of free fluids than other methods, their
use is limited to relatively large uncased boreholes (diameter greater than 6 inches) which
contain fluids.
The graphic illustrates the magnetic thermal relaxation measurements for protons
contained in the pore space of a consolidated sandstone.
.A-12.
Module: Geophysical Characterization Techniques and Data Interpretation
-------
Additional Information
Borehole Geophysical Methods
Other
if. CURVE
f
\
CROSS SEHION
TRUE DIP ANGLE
*' t? tf !•'
>,
N
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*
When boreholes deviate significantly from vertical (due to geologic and drilling
conditions) or in cases where horizontal drilling techniques are used, it is often necessary
to determine the exact orientation of the borehole. Directional survey tools that
incorporate gyroscopic or magnetic determination of position have been developed for
this purpose. These tools typically provide position information in cylindrical coordinates
(depth, inclination, and azimuth).
Dipmeters are designed to measure the strike and dip of planar features which are
intercepted by the borehole. The tools usually incorporate several electrical resistivity
sensors as well as a directional survey tool. The logs are particularly useful for
identifying geologic unconformities in the subsurface.
A-13-
Module: Geophysical Characterization Techniques and Data Interpretation
-------
Additional Information
Surface Geophysical Methods
Seismic Surveys—Survey Practice
ShotD
ShotC
ShotB
Shot A
o o o o o o Depth points. Shot A
o o o o o o Depth points, Shot 8
o o o o o o Depth points. Shot C
o o o o o o Depih points. Shot D
i i
Spread length is the distance between the source and the nearest geophone. For shallow
reflection work, it may be as little as 2 meters (for low intensity sources) or around 10
meters (for high intensity sources). For very shallow seismic reflection work, several
geophones, but typically less than 5, may be connected to a single seismograph channel.
This arrangement is known as a geophone array. Likewise, several impacts or explosions
at different locations may be used as a source. Reflection events are not recorded in
depth, but in two-way travel time. Seismic velocity data are needed to convert time data
into depth estimates.
A line of geophones laid out for a refraction survey is commonly referred to as a spread.
In general, the deeper the target, the longer the spread should be. Some field crews use a
rule-of-thumb that the spread length should be eight times the expected depth. Arrays
(multiple geophones connected to a single channel) are not commonly used for refraction
work. To obtain sufficient information about both direct and refracted waves, a series of
four or more shots (in different locations relative to the spread) is used. In most
refraction surveys, some of the shots are fired very close to the end of the spreads to
provide information about direct wave velocity. Remote or "long" shots are sometimes
used so that the arrival times of the direct and refracted waves are separated.
.A-14.
Module: Geophysical Characterization Techniques and Data Interpretation
-------
Additional Information
Surface Geophysical Methods
Field interpretation of seismic data is very important because the success of the survey
depends on factors (shot positions, geophone layouts, and so forth) that can be varied in
many combinations to obtain sufficient data to meet the survey objectives. Survey work
is relatively time and labor intensive.
A-I5*
Module: Geophysical Characterization Techniques and Data Interpretation
-------
-------
Organic Chemical
Characterization
Techniques and Data
Interpretation
OT-1
OT-I
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Module Overview
Objective: Introduce participants to different
field-based technologies that can be used to
characterize organic contamination at a site and
for specified applications beyond
characterization.
OT-2
Notes:
This module will present information regarding factors to consider when using various
analytical tools to characterize contaminants from organic compounds at a site. The basic
components of each technology, principles of operation, common applications (matrix
and analytes), logistical requirements, interferences, performance factors, data
interpretation, data quality, factors affecting data quality, and advantages and limitations
will be discussed.
In addition, specific applications of each technology beyond characterization will be
discussed.
OT-2
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Hand-Held Survey Instruments
Organic Chemical Characterization
Techniques and Data Interpretation
[=>*• Hand-Held Survey Instruments
^Colorimetric Indicators
4 Fluorescence Analyzers
^Immunoassay
4-Gas Chromatography
4 Infrared Spectroscopy
4 Chemical Sensors
4 Emerging and Innovative Approaches and
Instruments
+• Hands-on Activity for Organic Analysis
HH-1
HH-l
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Hand-Held Survey Instruments
Topic Overview
+Objective: Obtain a theoretical and practical
understanding of:
»How instruments are used to assess organic
constituents in environmental media
»The quality of data produced by the instrument
» The intended use of data (data usability)
* Topics
» Photoionization detectors (PID)
» Flame ionization detectors (FID)
+Applications other than characterization
HH-2
Notes:
This section will include a discussion of photoionization detectors (PID) and flame
ionization detectors (FID), their operational characteristics, the quality of the data they
produce, and the usability of those data.
PID: A hand-held PID is commonly used to detect volatile organic compounds
(VOC) in air or emanating from water and soil. Examples of VOCs that the PID
will detect include: benzene, toluene, ethylbenzene, and xylenes (BTEX),
chlorinated VOCs (trichloroethene [TCE], tetrachloroethene [PCE], vinyl
chloride, 1,2-dichloroethene [DCE], and petroleum hydrocarbons [gasoline, diesel
fuel, and jet fuel ]).
- FID: A hand-held FID is commonly used to detect VOCs in air or emanating
from water and soil. Examples of VOCs that the FID will detect include: methyl
iso-butyl ketone (MIBK), methyl ethyl ketone (MEK), BTEX, and petroleum
hydrocarbons (gasoline, diesel fuel, and jet fuel).
For additional information on this topic, refer to page A-l at the end of this module.
HH-2
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Hand-Held Survey Instruments
Comparison of Measurements
4 PID: Measures change of signal as compounds
are ionized by an ultraviolet lamp
^ FID: Measures change of signal as compounds
burn in a flame
4 Classes of compounds detected
»PID: VOCs, solvents, explosives/propeliants
»FID: Petroleum hydrocarbons, solvents
HH-3
Notes:
A PID consists of a special ultraviolet lamp (10.2 electron volt [eV], 10.6 eV, or 11.7 eV)
that emits energy that is sufficient to ionize BTEX compounds and some chlorinated
VOCs. For a VOC to be detected, its ionization potential (IP) has to be below the
ionization energy of the lamp. The closer the IP is to the energy of the lamp (as long as it
is below the ionization energy of the lamp), the more sensitive the PID is to that
compound.
A FID detects compounds by burning the VOC in a hydrogen flame. The VOCs are
delivered to the flame by an internal pump.
HH-3
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Hand-Held Survey Instruments
Sample Preparation
• Samples can be collected in glass jars, plastic
bags, or vials for headspace measurements
4 Matrix can be measured in situ
4 Samples may require heating if ambient
temperature is below room temperature
HH-4
Notes:
PID and ionization potential can be used to detect the following VOCs:
- Vinyl chloride (potential carcinogen), 9.99 eV
- TCE (potential carcinogen), 9.45 eV
PCE (potential carcinogen), 9.32 eV
- Chloroform (potential carcinogen), 11.42 eV
- Carbon tetrachloride (potential carcinogen), 11.47 eV
Naphthalene, 8.12 eV
- Benzene (potential carcinogen), 9.24 eV
Toluene, 8.82 eV
1,1,1 -trichloroethane (TCA), 11.0 eV
Xyienes, 8.5 eV
A FID is used primarily to identify nonhalogenated aromatic and straight-chained
petroleum hydrocarbons (BTEX, gasoline, diesel) and some solvents such as MEK and
MIBK. A FID will not detect halogenated VOCs unless they are present at levels of at
least 0.5 parts per million (ppm).
Minimal sample preparation is required to use a hand-held PID or FID. If ambient
temperatures are low (below freezing), the samples may need to be heated to volatilize
the VOCs.
HH-4
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Hand-Held Survey Instruments
Why would a PID lamp energy of 10.6 eV be selected for analysis of VOCs rather than a
higher lamp energy, for example 11.0 eV?
HH-5
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Hand-Held Survey Instruments
Notes:
Main Uses
* Helps determine proper personal protective
equipment (PPE)
* Screens soil, water, or air samples
+Assesses peak short-term exposure limits (STEL)
and time-weighted averages (TWA) in real time
EPA
HH-5
Hand-held PIDs or FIDs are very efficient for providing a quick assessment of the total
concentrations of VOCs regardless of the matrix being analyzed. The instruments can
provide a valuable assessment of the level of personal protective equipment (PPE)
necessary to enter and work in the site environment by providing an assessment of short-
term exposure limits (STEL) or time-weighted averages (TWA).
HH-6
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Hand-Held Survey Instruments
Quality Control (QC) Measures
+ Calibrate instrument with standard gases
* Accuracy - verify calibration with standard gas
* Precision - perform replicate measurements
* Sensitivity - low ppm range
&EPA
HH-6
Notes:
Quality control (QC) is limited with these instruments.
• Standard gases are used to calibrate these instruments. For example, isobutylene gas
usually is used in calibrating FIDs. Single-point calibration is standard.
• Standard gases may be used to verify calibration and provide measurements of accuracy.
• Precision can be calculated by analyzing samples in duplicate or taking replicate
measurements; however, gaseous conditions are often difficult to replicate.
• PIDs and FIDs can detect analytes in the low ppm range (about 0.5 ppm).
HH-7
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Hand-Held Survey Instruments
Dynamic Range
PID: Approximately 0.5 to 2,000 ppm (varies
among manufacturers)
FID: Approximately 0.5 to 50,000 ppm (varies
among manufacturers)
HH-7
Notes:
Ranges of 0.5 to 2,000 ppm for the PID and 0.5 to 50,000 ppm for the FID are
approximate averages as listed by numerous manufacturers. The dynamic range will vary
from manufacturer to manufacturer.
HH-8
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Hand-Held Survey Instruments
Type of Data Produced
Screening Level
» Semiqualitative - noncompound-specific
» Semiquantitative - total detectable
concentration
» Results reported in ppm or percent
»LimitedQC
» Direct reading instrument
Some instruments have chromatographic
capabilities for limited compound separation
HH-8
Notes:
Data quality for PIDs and FIDs is considered screening level for several reasons:
• The instruments cannot differentiate among individual constituents in a mixture,
therefore, results are considered to be semiqualitative.
• The instruments are not compound-specific. Therefore, individual compounds cannot be
quantified and results are considered to be semiqualitative. In addition, the calibration is
based on the response of one compound (isobutylene). Data indicate the total
concentration of detectable organic compounds.
• Air measurements, such as head space concentrations, may be difficult to correlate with
the soil or water sample concentrations in soil or water samples.
• Traditional QC measures are not readily applicable to the instruments. Instruments are
calibrated with a single analyte, while they respond to the total concentration of a mixture
of analytes.
• Results are displayed through direct readouts in near real time. Most instruments do not
generate hard copies of data, but data can be downloaded to a computer.
HH-9
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Hand-Held Survey Instruments
Photoionization Detector
Advantages
» Compact and field portable
» Real-time data processing (instantaneous readout)
» No flame or carrier gases needed
"Intrinsically safe
Limitations
» Sample port can become clogged
» Sensitive to moisture
» Noncompound-specific
» Temperature sensitive
» Battery and bulb life
EPA
HH-9
Notes:
Many of the instruments are compact and can to be held in one hand. This is an
advantage for assessing VOC concentrations when Level A or B PPE is required and
when a large site is involved. Once the pump is turned on and the instrument is
calibrated, ppm or percent levels are continually displayed on the lithium crystal display
(LCD). In addition, there are no carrier gases or flame gases necessary to operate the
PID, making the instrument safe to use. The PID instrument is a non-destructive
technique.
The sample port can become clogged if it is accidentally jammed into the soil. Unless
GC capabilities are used, the PID only gives "total" detectable VOC results. It cannot
distinguish between different VOCs. The PID is extremely sensitive to moisture. When
moisture collects on the lamp, the PID does not function. The lamp must be removed and
dried before the PID can function. This limitation could shut down the investigation for a
short or long period of time. The operating temperature range of the PID is
approximately 20°F to 110°F. Problems have been encountered when temperatures are
at or below freezing (32 °F). Batteries last approximately eight hours before needing to
be recharged. The PID lamp must be changed periodically.
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Hand-Held Survey Instruments
Notes:
Flame lonization Detector
• Advantages
» Compact and field portable
» Real-time data processing (instantaneous readout)
Limitations
» Noncompound-specific (unless equipped with a
gas chromatograph)
» Less sensitive to chlorinated compounds
» Requires hydrogen for a flame gas
» Sample port can become clogged
» Battery life
EPA
HH-10
Like the PID, many of the FID instruments are small enough to be held in one hand.
Once the pump is turned on and the instrument is calibrated, ppm or percent levels are
continually displayed on the LCD. The FID is not very sensitive to halogenated VOCs;
therefore, if only aromatic or straight-chained petroleum hydrocarbon contamination is of
concern, any halogenated VOCs present will not interfere. Also, the FID is not as
sensitive to moisture as the PID.
Unless GC capabilities are used, the FID provides "total" detectable VOC results, not
individual compound results. The FID is not sensitive to halogenated VOCs. The
instrument is a destructive technique. Hydrogen gas is required, which is FLAMMABLE
and provides an open ignition source that may result in explosion in an explosive
environment. Like the PID, the sample port may become clogged. Batteries must be
recharged or changed frequently (approximately every eight hours of operation).
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Hand-Held Survey Instruments
HH-11
•HH-12-
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Hand-Held Survey Instruments
EPA
HH-12
Notes:
Typical rental costs for hand-held PID instruments range from $150 to $300 per week or
$500 to $1,000 per month. Typical purchase prices for these types of instruments range
from $4,000 to $6,000.
Typical rental costs for hand-held FID instruments range from $200 to $300 per week or
$800 to $1,000 per month. Typical purchase prices for these types of instruments range
from $7,000 to $10,000.
•HH-13
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Hand-Held Survey Instruments
Notes:
Applications Other Than
Characterization
+Well-head screening for VOCs
* Head-space sample screening for VOCs
+ Fence-line monitoring
HH-13
In addition to characterization, hand-held survey instruments can be used for the
following types of applications:
- In soil vapor extraction systems, well heads can be monitored for VOCs with
hand-held survey instruments to optimize the vacuum system.
- Head spaces of drums or samples can be "sniffed" to screen for VOCs.
- Some instruments have data loggers (and alarms) that allow storage of data in
memory; such instruments can be placed at a fence line to detect fugitive
emissions.
•HH-I4-
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Colorimetric Indicators
Organic Chemical Characterization
Techniques and Data Interpretation
+ Hand-Held Survey Instruments
c=» Colorimetric Indicators
+ Fluorescence Analyzers
^Immunoassay
4 Gas Chromatography
* Infrared Spectroscopy
* Chemical Sensors
^Emerging and Innovative Approaches and
Instruments
*• Hands-on Activity for Organic Analysis
EPA
CI-1
CI-1
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
r
Colorimetric Indicators
Topic Overview
4Topic Description: Explains the operation and
use of several colorimetric indicators
^Technologies
»Indicator tubes for air and soil gas
» Reagent kits for water and solid matrices
* Applications other than characterization
CI-2
Notes:
This topic explains the operation and application of multiple colorimetric indicators to
determine various organic compounds in air, soil gas, soil, and water.
The following technologies will be discussed: (1) indicator tubes for air and soil gas and
(2) reagent kits for water and solids. This section wiJl discuss several types of
colorimetric test kits.
CI-2
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Colorimetric Indicators
Indicator Tubes
•Application
• Media monitored
• Detectable analytes
• Detection limits
• Equipment
• Compound identification and determination of
semiquantitative concentrations
• Operator experience level
CI-3
Notes:
Indicator tubes are used to characterize ambient air on a hazardous waste site. They are
most often used for health and safety monitoring, either indoors or outdoors. They can be
placed in a tank, down a sewer, at the top of a monitoring well, or in many other
locations. They are very small and portable. The data from these indicator tubes is
qualitative screening at best.
Air and soil gas are the primary media monitored with this technology.
Colorimetric indicator tubes are commercially available for nearly 300 gases and vapors
(both organic and inorganic), including common industrial gases and solvents.
Most indicator tubes have detection limits in the ppm range. A few can detect
compounds down to the mid-parts per billion (ppb) range.
The only equipment necessary in addition to the indicator tubes as a hand pump. The
pumps can be rented or purchased; purchase price is approximately $300 to $400. The
indicator tubes normally are sold in quantities of 10 per box. Each tube costs from
approximately $3 to $10.
The indicator tubes are sealed glass detector tubes filled with a reagent specifically
sensitive to a target gas. The tube tips are broken, the tube is inserted into the pump with
the arrow pointing down, and a precise volume of air is drawn through the tube as
specified in the manufacturer's instructions. If the target gas is present, a color change
Cl-3
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Cotorimetric Indicators
will occur in the tube's reagent layer. The length of the color stain is proportional to the
gas concentration and can be read by means of a printed scale on the tube.
Use of indicator tubes generally provides semiquantitative results because of the
subjectivity of visually measuring the length of the color stain. However, Draeger
recently introduced a portable chip measurement system (CMS) that should provide more
accurate results. The chips, which are calibrated by the manufacturer, contain 10
capillaries that are filled with a special reagent material that reacts in a similar way as an
indicator tube would. When the chip is inserted into an analyzer, it informs the analyzer
of the name of the analyte, measuring range, maximum measuring time, calibration data,
algorithm data, and required flow. The result is displayed in ppm on the analyzer.
Because of the relatively basic nature of this technique and the ease of operation, the test
can be performed by nontechnical personnel who have minimal training in the operation
of the instrument.
CI-4
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Colorimetric Indicators
EPA
CI-4
C7-5
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Colorimetric Indicators
Reagent Kits
* Application
* Media monitored
*• Detectable analytes
* Equipment
+Compound identification
* Compound quantitation
+Operator experience level
CI-5
Notes:
The primary use of reagent kits is for screening media for specific analytes by measuring
the color that the reaction produces. The intensity of color is proportional to the
concentration of the analyte.
Reagent kits may be designed for analysis of water; however, many kits provide solvents
to be used in extracting analytes from solids into a liquid medium for measurement.
Typical organic analytes detectable by reagent kits include petroleum hydrocarbons,
benzene, toluene, ethylbenzene, and xylenes (BTEX), polychlorinated biphenyls (PCB),
polynuclear aromatic hydrocarbons (PAH), trihalomethanes, and nitroaromatics
(explosives such as trinitrolotoluene [TNT]).
Basic equipment includes sample containers, reagents, standards, and a
spectrophotometer. Accessories may include graduated cylinders, pipets, balances,
extraction apparatus, and timers.
Compounds are identified when reagents that are specific to target analytes or groups of
compounds are used to develop color. Different reagent kits use compound-specific
chemical reactions that produce color in the visible spectrum.
Compounds are quantified when the intensity of the color produced can be compared with
the color of known standard concentrations. The level of certainty will vary greatly
according to whether the intensity of the color is compared visually with a color wheel or
Cf-6
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Colorimetric Indicators
calibrated spectrometers are used to measure the intensity of the color against calibration
standards.
Reagent kits are easy to use, but basic instruction and experience in their operation may
be necessary. Nontechnical personnel who have some training can use the reagent kits.
Because of the potential for interferences, interpretation of the data may require a basic
understanding of chemistry.
CI-7
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Colorimetric Indicators
Notes:
Examples of Reagent Kits
+ Hanby Field Test Kits
+ Dexsil® Clor-N-Oil and Clor-N-Soil Test Kits
+ Dexsil®PetroFLAG
^AccuSensor®
*• Envirol Quick Test™
EPA
CI-6
This list of reagent kits, though not comprehensive, represents the diverse group of
products that are available commercially and widely used.
A brief discussion of each reagent kit follows.
CI-8
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Colorimetric Indicators
Hanby Test Kits
*• Detect aromatic hydrocarbons in soil and water
* Friedel-Crafts reaction
* Measurement device
* Limitations
+ Data quality level
* Additional information
&EPA
CI-7
Notes:
The Hanby test kits are capable of providing analytical results for petroleum fuels and
constituents such as gasoline, diesel fuel, jet fuel, crude oil, motor oil, BTEX, PAHs, as
well as PCBs in soil and water samples. Typical detection limits are 1.0 milligram per
kilogram (mg/kg) for soil and 0.10 milligram per liter (mg/L) for water. The typical
range of the test is 1.0 to 1,000 mg/kg for soil and 0.10 to 20 mg/L for water.
In 1990, EPA published the Hanby Method in EPA/530/UST-90-003, "Field
Measurements: Dependable Data When You Need It." In August 1995, the Hanby
Method was documented in another publication, EPA/540/R-95/515, describing its use in
the analysis of soils contaminated with pentachlorophenol (PCP)-containing oils and
solvents in the Superfund Innovative Technology Evaluation (SITE) program.
Comparisons of the intensity of color produced can be made either (1) visually with a
color chart or (2) photometrically with a reflective photometer.
Limitations include:
- Inaccurate color comparison because of limited visual acuity or dark-colored
extract.
If petroleum fuel contains highly refined alkanes (hence, absent aromatic
compounds), concentrations can be underestimated.
Cl-9
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Colorimetric Indicators
- If more than one type of aromatic compound is present, interpretation of results
may be inaccurate.
In general, this reagent kit provides qualitative to quantitative screening-level data with
appropriate definitive confirmation. The type of color comparison made will determine
the level of quantitation.
C1-IO
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Colorimetric Indicators
CI-8
CI-11
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Colorimetric Indicators
Dexsil® Clor-N-Oil and Clor-N-Soil
Test Kits
4- Detect PCBs in oil, soil, or wipes
4> Chloride stripping reaction
4- Measurement device
» Colorimetrically
» Chloride-specific electrode
4 Limitations
• Data quality level
4- EPA SW-846 Methods
4 Additional information
CI-9
Notes:
These reagent kits are capable of detecting PCBs in oil, soil, or wipe samples.
Colorimetric kits are available at the following reference concentrations:
Clor-N-Oil kits: 20, 50, 100, or 500 ppm Aroclor 1242.
CIor-N-Soil kits: 50 ppm Aroclor 1242.
PCBs are extracted from the sample medium with an organic solvent. The organic
extract is treated with metallic sodium to strip chlorine from the biphenyl compound as
chloride ions. An acidic buffer is added to the extract to quench any unreacted sodium
and to transfer the chloride into the aqueous phase. Chloride ions in the aqueous phase
are measured Colorimetrically by using an indicator solution of mercuric nitrate and
diphenyl carbazone. The diphenyl carbazone and mercury complex creates a vivid purple
color. The development of the purple color is inversely proportional to the chloride
content in the aqueous phase. The purple color indicates the absence of chloride, and
therefore the absence of PCBs in the sample. A yellow or clear color indicates the
presence of chloride, and therefore the presence of PCBs in the sample.
Chloride can be measured Colorimetrically or through the use of a chloride-specific
electrode.
- In the Colorimetric determination, the color is compared visually with a color
chart. Because kits are prepared at specific concentrations, the color change will
Cl-12
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Colorimetric Indicators
determine only whether the concentration of PCBs is greater than or less than the
target concentration.
- Using the chloride-specific electrode, quantitative measurements of chloride can
be obtained.
- Dexsil currently markets an instrument called the L2000 chloride analyzer that is a
chloride-specific electrode. The chemical process used by the L2000 is similar to
that used in the colorimetric reaction, except that the L2000 uses an ion-specific
electrode to quantify the contamination in the sample. The instrument takes a
reading from the electrode and converts the reading into ppm of PCB. The
reading is a quantitative measurement, with a detection limit of 5 ppm. The
instrument is capable of measuring chloride as Aroclor 1242, Aroclor 1260,
Askarel A, or total chlorine.
Limitations include:
- Inaccurate color comparison because of limited visual acuity or dark-colored
extract.
Interferences (false positives or biased high results) may arise from the presence
of other chlorinated organics, such as pesticides or chlorinated solvents.
- Test kits and the L2000 are designed to determine concentrations of chloride with
regard to Aroclor 1242 or Aroclor 1260. If other Aroclors are present, the results
may be biased high or low, depending upon the degree of chlorination of the
known, compared with that of the standard Aroclor.
- Inorganic chloride salts present in road salt or seawater may produce false
positives or biased high results.
In general, the colorimetric reagent kit provides qualitative to semiquantitative screening-
level data. The L2000 kit produces qualitative to quantitative screening-level data.
To date, three methods have been promulgated in EPA SW-846 Methods:
Method 9077: Test Methods for Total Chlorine in New and Used Petroleum
Products (Field Test Kit Methods)
Method 9078: Screening Test Method for PCBs in Soil
Method 9079: Screening Test Method for PCBs in Oil
In a demonstration conducted under EPA's SITE program, the Dexsil Clor-N-Soil pit and
the L2000 were evaluated for accuracy in detection of PCBs in soil samples.
CI-I3
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Colorimetric Indicators
EPA
CI-10
CI-14
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Colorimetric Indicators
Dexsil® PetroFLAG™
+ Detects petroleum hydrocarbons in soil
+Turbidity development
+ Measurement device
^Potential limitations
4 Provides quantitative results
+ EPA SW-846 Method
EPA
CI-11
Notes:
PetroFLAG™ detects and provides quantitative results for gasoline, diesel fuel, jet fuel,
fuel oil, motor oil, transformer oil, hydraulic fluid, greases, and many other types of
hydrocarbons in soil. The dynamic range of the test kit is 20 to 2000 ppm.
After the analyzer is calibrated, the following steps are conducted: ten grams of soil is
weighed into a labeled tube using the electronic balance. The extraction solvent is added
to the tube and it is shaken intermittently for 4 minutes and allowed to settle for 5
minutes. The resultant extract is filtered into a via] containing development solution and
allowed to react for 10 minutes. The filtration step is important because the analyzer
essentially measures the "turbidity" or "optical density" of the final solution, so soil
particles would interfere with the test. Approximately 25 samples can be analyzed per
hour.
The vial containing the developed color solution is placed in the colorimeter and a
quantitative reading is taken, revealing the concentration of hydrocarbons contained in the
soil sample. PetroFLAG™ will detect hydrocarbons over the range of 20 to 2,000 ppm.
Higher concentrations can be measured by diluting the sample or using a smaller sample
size. The PetroFLAG™ system exhibits a lower detection limit of about 20 ppm for
heavier hydrocarbons such as oil and grease. The detection limit for light fuels is higher,
for example, 200 ppm for jet fuel, and 400 ppm for weathered gasoline. The heavier
hydrocarbons are larger molecules which provide for a more "turbid" final solution,
therefore, increasing the sensitivity of the analyzer.
CI-I5
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Colorimetric Indicators
False positives may occur if naturally occurring waxes and oils, such as vegetable oils,
are present in the sample. For accurate quantitation with PetroFLAG™, the analyte being
tested must be known so that the user can choose the correct calibration. If the type of
hydrocarbon being analyzed is unknown, a conservative calibration can be used to
provide an approximate concentration of the total hydrocarbons present. The
manufacturer claims that the analyzer should be recalibrated if the ambient temperature
varies by ±10 C from the time of original calibration.
Because turbidity is measured quantitatively, the resultant data on petroleum
hydrocarbons are considered quantitative.
There is a draft SW-846 Method 9074 proposed for Update 4A for this test. It is entitled
"Turbidimetric Screening Method for Total Recoverable Hydrocarbons in Soil."
Cl-16
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Colorimetric Indicators
EPA
CI-12
C/-/7
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Colorimetric Indicators
AccuSensor®
• Measures TCE and trihalomethanes (THM) in water
4- Based on Fuj'iwara reaction
4 Analysis in four steps
4 Potential interferences
• Qualitative to quantitative screening level data
CM 3
Notes:
The AccuSensor® can determine the presence of TCE in water samples with a minimum
detection level of 5 ppb. It measures total trihalomethanes (THM) (chloroform,
bromodichloromethane, chlorodibromomethane, and bromoform) in equivalent
chloroform in water with a minimum detection level of 10 parts per billion (ppb). Tests
for detecting BTEX and PCE also exist.
The principal of operation of the AccuSensor® is based on the Fujiwara reaction. The
Fujiwara reaction was first reported in 1916 and is the reaction of geminal species with
pyridine in the presence of water and hydroxide ions to form a visible light absorbing
product.
The AccuSensor® operates using the following steps. First, a water sample is poured into
a standard 40-mL volatile organic analysis (VGA) vial to the bottom of the threads and an
AccuSensor® cap is screwed on and shaken for 30 seconds to establish the headspace
concentration of the volatile species. Second, the cap is inserted into the back of the
meter, and the lever on the side of the cap is turned to expose a porous Teflon membrane.
Next, the volatile analytes in the headspace will permeate through the membrane where it
encounters the Fujiwara reagent. The degree of absorbance is measured by the sensing
unit over a 5-minute period, after which the concentration in ppb is displayed by the
meter.
The headspace concentration, analyte diffusion rate, and reaction kinetics are all
dependent on temperature. The AccuSensor® meter, therefore, incorporates a thermistor
a-18
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Colorimetric Indicators
and software which provide automatic temperature compensation across an operating
range of 0 to 50 C. The major interferant for TCE measurements is chloroform, which
can cause an error of 40 percent when present at a concentration equal to that of TCE.
There also is a potential for cross interference between readings of TCE and THMs.
These compounds may react with each other if they are present at high enough
concentrations.
Cl-19
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Colorimetric Indicators
Envirol Quick Test
* Measures PCP, TNT, and carcinogenic PAHs
4 Two process method
» Envirometer instrument standardization and
calibration
» Sample extraction and analysis
• Potential interferences
• Qualitative to quantitative screening level data
EPA
CI-14
Notes:
The Envirol Quick Test'M provides quantitative results for identifying PCP in soil and
water, trinitrotoluene (TNT) in soil, and carcinogenic PAHs in soil. The Envirol Quick
Test™ uses a photochemical reaction which produces a color proportional to the
concentration of the analyte of interest. The dynamic range of the test is 1.5 to 90 ppm
for PCP in soil; 1.5 to 90 ppm for PCP in water; 3 to 100 ppm for TNT in soil; and 1 to
3,000 ppm for carcinogenic PAHs in soil.
The Envirometer, a small portable photometer, is standardized daily or as needed using
three standards provided with each test kit. The standard curve for the photochemical
reaction is stored electronically in the Envirometer. The Envirometer standardization is
verified using a continuing calibration verification solution also provided with each test
kit. A soil sample is weighed, extracted with a solvent, and then filtered. The soil extract
is mixed with acidic water (for PCP only) and passed through a solid phase extraction
(SPE) cartridge. This step helps to reduce interference. The analyte of interest is eluted
from the SPE cartridge using another solvent. The eluent solution is mixed with the
Envirol Quick Test™ reagent and transferred to a cuvette. The cuvette is placed in the
Envirometer and the degree of absorbance of the sample is measured and converted into
concentration of PCP, TNT, or carcinogenic PAHs. The entire extraction and analysis
steps require about 20 to 30 minutes.
The Envirol Quick Test1" has shown no interferences from creosote, fuel oil, or PCBs for
the PCP test. The presence of tri- and tetrachlorophenols can result in positive
interference for PCP. Mono- and dichlorophenols must be present at relatively high
CI-20
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Colorimetric Indicators
concentrations to be detected by the PCP test. Creosote has been shown to interfere with
the carcinogenic PAH test at a concentration of 5 ppm. Most explosives showed no
interference at levels of 500 ppm with the TNT test. At a concentration of 50 ppm, tetryl
will interfere with the TNT test.
Cl-21
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Colorimetric Indicators
Applications Other Than
Characterization
+ Monitoring operating conditions of a remediation
system
* Wastewater treatment
4 Health and safety monitoring
CI-15
Notes:
Colorimetric test kits can be used to:
- Monitor the operating conditions of a remediation system. For example, it may be
necessary to monitor hydrogen peroxide in remedial systems that use oxidation to
decompose organics.
- Monitor hardness (by measuring cations) and other conditions of influent and
effluent water.
- Measure ambient air in the breathing zone of field personnel.
CI-22
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Fluorescence Analyzers
Organic Chemical Characterization
Techniques and Data Interpretation
* Hand-Held Survey Instruments
^Colorimetric Indicators
c=>+ Fluorescence Analyzers
^Immunoassay
*Gas Chromatography
+ Infrared Spectroscopy
* Chemical Sensors
+ Emerging and Innovative Approaches and
Instruments
+ Hands-on Activity for Organic Analysis
EPA
FA-1
FA-J
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Fluorescence Analyzers
Notes:
Topic Overview
4Topic description: Explains the operation and
application of laser-induced fluorescence (LIF)
systems
+ Key points
»Scope and application
» Method description and system components
» Two major systems
» System comparisons
» Fluorescence plots
» Advantages/limitations
» Data quality
» Comparison studies
FA-2
This topic explains the operation, application of and the data produced by two commonly
used cone-penetrometer-deployed laser-induced fluorescence (LIF) systems that are used
to characterize petroleum contamination in the subsurface.
The following key points are discussed: (1) scope and application, (2) a description of
the method and system components, (3) differences between the two major systems,
(4) comparison of systems, (5) examples of fluorescence plots, (6) advantages and
limitations, (7) data quality, and (8) comparison studies.
FA-2
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Fluorescence Analyzers
Laser-Induced Fluorescence
* Scope and application
» Petroleum products
» Screening data (relative magnitude of
contamination)
4- Method description and system components
»Cone penetrometer
» Laser
» Fiber optics
» Sapphire window
» Detection system
FA-3
Notes:
LIF is used for real-time, in-situ, field screening of petroleum hydrocarbons in subsurface
soil and groundwater. The technology is intended to provide qualitative to
semiquantitative information about the distribution of subsurface petroleum
contamination. It can detect gasoline, diesel fuel, jet fuels, fuel oil, motor oil, grease, and
coal tar in the subsurface. This screening data can be used to guide an investigation or
removal action or to delineate the boundaries of a subsurface contamination plume prior
to installing monitoring wells or taking soil samples.
Exact detection limits are difficult to determine and will vary between sites and
petroleum products. Site-specific detection limits vary from levels of 50 to 1,000 mg/kg.
The method uses a fiber optic-based LIF sensor system deployed with a standard 20 ton
cone penetrometer (CPT). Light at a specific wavelength generated from a laser is passed
down a fiber optic cable to a sapphire window in the tip of the CPT rod string. The light
causes aromatic components in the petroleum such as PAHs to fluoresce. The induced
fluorescence from the PAHs in the soil adjacent to the sapphire window is returned over a
second fiber to the surface where it is quantified using a detector system. The intensity of
the fluorescence is used as an indicator of the relative contaminant concentration. The
peak wavelength and intensity provide information about petroleum product type or
potential interferences.
FA-3
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Fluorescence Analyzers
FA-4
FA -4
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Fluorescence Analyzers
FA-5
FA-5
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Fluorescence Analyzers
FA-ti
FA -6
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Fluorescence Analyzers
LIF - Two Major Systems
* Site Characterization and Analysis Penetrometer
System (SCAPS) LIF
4 Rapid Optical Screening Tool (ROST™)
+ System comparisons
» Development
» Availability
» Deployment
» Components
» Calibration
FA-7
Notes:
The Site Characterization and Analysis Penetrometer System (SCAPS) LIF system was
developed through a collaborative effort of the Army, Navy, and Air Force under the Tri-
Services Program. The Rapid Optical Screening Tool (ROST™) system was developed by
Loral Corporation and Dakota Technologies, Inc.
SCAPS is available only through the U.S. Army Corps of Engineers (USAGE) and the
U.S. Navy. ROST™ is available commercially through Fugro, Inc.
Both sensing devices can be used with CPT rigs designed for direct push technology.
They also can be used in conjunction with stratigraphic sensing devices.
The primary differences between the two systems are the laser and the detector systems.
- Laser systems — The SCAPS LIF system uses a pulsed nitrogen laser that
produces light at a wavelength of 337 nanometers (nm). The ROST'" system uses
a tunable dye laser that can produce light at variable wavelengths chosen by the
operator. The preferred mode of operation is to lock the excitation wavelength at
290 nm.
Detector systems — The SCAPS LIF system uses a photodiode array (PDA) and
optical multichannel analyzer (OMA) as the fluorescence detector. The PDA and
OMA quantify the fluorescence emissions spectrum from 350 to 720 nm. As the
SCAPS LIF sensor is pushed into the soil, real-time plots are generated of depth
FA-7
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Fluorescence Analyzers
versus maximum fluorescence intensity and the wavelength at which the
maximum intensity occurs. The detection system for the ROST™ consists of a
monochromator, a photomultiplier tube (PMT), and digital storage oscilloscope
(DSO). The monochromator acts as a variable wavelength narrow bandpass filter.
By acquiring fluorescence data at a series of wavelengths, the fluorescence
technician can determine the wavelength of maximum intensity in the
fluorescence spectrum. The light passing through the monochromator at this
wavelength is converted to an electrical signal by the PMT. The signal from the
PMT is fed to the DSO, which displays the waveform (fluorescence intensity as a
function of time following the excitation laser pulse).
The CPT rig is set up over the designated location for a push. The SCAPS LIF sensor's
response is checked using a standard rhodamine solution held against the sapphire
window before and after each push. The SCAPS LIF sensor is calibrated using spiked
soil samples representative of the site. Diesel fuel marine standard or other petroleum
hydrocarbons with a fluorescence response appropriate for the site are used to spike the
soil samples. The ROST™ system is calibrated with a proprietary blend of synthetic
motor oil and other substances. Fluorescence emissions are measured at four
wavelengths (340, 390, 440, and 490 nm). The data system is calibrated to read 100
percent fluorescence based on the fluorescence standard at the predetermined emission
monitoring wavelength. All subsequent data is reported as a percent fluorescence relative
to the standard.
FA-8
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Fluorescence Analyzers
LASER-INDUCED FLUORESCENCE SYSTEMS COMPARISON
Property
Development
Availability
Deployment
Components (laser and detection
system)
Calibration
Results and fluorescence plots
(dynamic and static plots)
SCAPS
Collaborative effort between U.S.
Army, Navy, and Air Force under
the Tri-Services Program
U.S. Army Corps of Engineers,
U.S. Navy
Optional sensing tool on a CPT rig
Pulsed nitrogen laser that produces
light at a wavelength of 337 nm
with a photodiode array and optical
multichannel analyzer detecting
between 350 and 720 nm
Uses soil samples that are
representative of site spiked with
diesel fuel or other appropriate fuel
standard
As a percent fluorescence of
calibration standard
- Fluorescence intensity at
maximum wavelength versus
depth
- Fluorescence intensity versus
wavelength
ROST
Loral Corporation and Dakota
Technologies, Inc.
Fugro, Inc.
Optional sensing tool on a CPT rig
Tuneable dye laser that produces
light at variable wavelengths
(preferred wavelength 290 nm)
with a monochrometer,
photomultiplier tube, and digital
storage oscilloscope detecting
between 300 to 500 nm
Uses a proprietary blend of
synthetic motor oil or other
appropriate fuel standard
As a percent fluorescence of
calibration standard
- Fluorescence intensity at
maximum wavelength versus
depth
Fluorescence intensity versus
time versus wavelength (3-D
plot)
Notes:
nm = Nanometers
ROST = Rapid optical screening tool
SCAPS = Site characterization and analysis penetrometer system
3-D = Three-dimensional
FA-9
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
FluorescenceAnalyzers
LIF - Fluorescence Plots
+ SCAPS LIF
» Fluorescence intensity at maximum wavelength
versus depth
» Fluorescence intensity versus wavelength
+ ROST™
» Dynamic mode: fluorescence versus depth
(FVD)
» Static mode: wavelength-time-matrices (WTM)
FA-8
Notes:
For the SCAPS LIF system, a semiquantitative representation of the subsurface
contamination is gathered from the plots of real-time fluorescence intensity versus depth.
A qualitative measure of different types of petroleum products can be gathered from plots
of fluorescence intensity versus wavelength.
In the dynamic mode, the ROST™ system operator chooses the excitation laser
wavelength and fluorescence emission monitoring wavelength and they are held constant.
The fluorescence intensity is plotted as a function of depth below ground surface. Once
areas of significant contamination have been identified in the dynamic mode, the CPT is
held at a fixed depth and the ROST™ can be operated in the static mode to identify the
general class of contamination present. During the static mode, ROST™ can obtain
wavelength-time-matrices (WTM) which represent a 3-dimensional plot of relative
fluorescence intensity versus fluorescence lifetime versus wavelength. WTMs produce
contaminant class specific three-dimensional figures. This data can be used to identify
the type of fuel that is present. Normally, in the static mode, the excitation wavelength is
held constant and the emission monitoring wavelength is varied.
FA-IO
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Fluorescence Analyzers
SCAPS LIF Fluorescence Intensity
Versus Depth
-------
Fluorescence Analyzers
10-
20-
30-
40 J
CPT based SOIL
CLASSIFICATION
1 3 & a J ,8
012345
Fluorescence
Intensity
Norn Count. Smftt BKGND
0 20000 40000
10000 30000
Fluorescence
Intensity
Norm Court* Sam pit BKGNO
too 10000
10 1000 100000
Wavelength
at Peak (nm)
350 400 450 500 550
-10
-30
.40
Project: Atlantic
FA-12
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Fluorescence Analyzers
SCAPS LIF Fluorescence Intensity
Versus Wavelength
4.000
3,000
i 2,000
1,000
300 350 400 450 500 550 600 650 700
Wavelength (nm)
EPA
FA-10
Notes:
This figure shows the maximum fluorescence intensity versus wavelength for the SCAPS
LIF at a site which had both coal tar and gasoline contamination. The "lighter"
components from the gasoline fluoresce at the shorter wavelengths, whereas the "heavier"
components from the coal tar fluoresce at the longer wavelengths. The gasoline was
encountered at a shallower depth, and the coal tar at a deeper depth.
FA-13
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Fluorescence Analyzers
ROST™ FVD Plot
&EPA
800
aoo
Atlantic, Iowa - Node 4 - FVP A 148,01
4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40
Atlantic. Iowa • Node 4- FVD A14B 02
16 18 20 22 24 26 28 30 32 34 36 38 40
Depth (ft)
FA-11
Notes:
This FVD plot was generated with the ROST™ operated in the dynamic mode. This FVD
plot also was generated at a site with gasoline and coal tar contamination. The gasoline
contamination is indicated by the increased fluorescence intensity between 8 and 20 feet
bgs. The coal tar contamination is indicated by the increased fluorescence intensity
between 22 and 32 feet.
FA -14
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Fluorescence Analyzers
ROST " WTM Plot
ROST TYPICAL WTM - ATLANTIC SITE
100-
300 3iO 460 4$0 500
Wavelength (nm)
100-
300 3^0 400 430 500
Wavelength (nm)
300 ado 460 4 So 500
Wavelength (nm)
Notes: A. Node 2,21'(approx.), Identified as Coal Tar
B. Node 4,17.19', Identified as Coal Tar and Gasoline
C. Recovered Product (Gasoline)
FA-12
Notes:
This ROST™ WTM plot shows a "fingerprint" of the different types of contamination
found at the Atlantic site. The ROST™ was operated in the static mode to generate these
plots. The "heavier" contamination produced longer maximum fluorescence
wavelengths.
FA -15
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Fluorescence Analyzers
LIF - Advantages and Limitations
Advantages
» Real-time data
» Production rate
» Spatial resolution
» No drill cuttings/reduced decontamination
» Cost on large projects
Limitations
» Technical expertise required
» Poor quantitative correlation
» Cost on small projects
» Maintenance
» Stratigraphy and depth constraints
» Potential interferences
EPA
FA-13
Notes:
The primary advantage of using these systems is their ability to provide real-time
chemical, as well as geological, information while in the field. This data can reduce and
focus the amount of physical sampling and laboratory analysis, as well as optimize
monitoring well placement. Both systems are capable of achieving 300 feet of pushes in
a 10-hour work day. The vertical spatial resolution is near 2.0 cm, which allows small
zones of contamination to be delineated that might be missed by conventional sampling
protocols. The holes can be grouted as the push rod is pulled from the hole. Also, the
push rod can be decontaminated remotely as it is retracted from the hole. All the
decontamination fluids are containerized in the process. During a SITE demonstration,
three sites were characterized using the SCAPS LIF system and the ROST™ system at a
cost of $20,000 and $41,200, respectively. These costs can be compared to the
approximate $43,000 using conventional drilling methods and on-site analytical
capabilities. Both systems cost less than the reference methods and produced almost
1,200 more data points in a real-time fashion, as opposed to waiting hours or days for the
data.
The operation of the SCAPS LIF system or the ROST™ system takes considerable
experience. It takes many days and numerous projects to become familiar with the
operation of the technology.
Although these sensors provide a relative degree of contamination that closely matches
reference method data, little direct, quantitative correlation has been found to individual
or classes of petroleum compounds. The cost of one of these systems may be prohibitive
FA-16
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Fluorescence Analyzers
on small-scale projects. They have primarily been used at large sites such as Department
of Defense (DoD) and Department of Energy (DOE) facilities. Some maintenance of the
CPT tools and the LIF sensors is required and breakdowns can be expected on long-term
projects. Downtime due to breakage of fiber optic cables and push rods, fogging of the
sapphire window, and problems with the grout pump or decontamination unit may occur.
These systems can only be used where direct push is feasible, such as in unconsolidated
sediments. The sensors are limited to a depth of 50 meters because of attenuation in the
optical fiber umbilical cord. Minerals such as calcite and naturally occurring organic
matter also can fluoresce, which may cause interference problems.
FA-17'
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Fluorescence Analyzers
LIF - Data Quality and Comparison
Studies
• Data quality is sufficient for qualitative screening
» Relative intensities may be considered
quantitative screening level data
+ Comparison studies
»SITE demonstration
» State of California certification
» ETV validation
EPA
FA-14
Notes:
The SCAPS LIF and ROST™ systems were evaluated in 1994 during a demonstration
conducted under EPA's SITE program. The two systems were demonstrated at three sites
in the Midwest that had varying concentrations of coal tar waste and petroleum fuels, and
a range of soil textures. A qualitative assessment was made by comparing subsurface
contaminant cross sections generated from either SCAPS LIF or ROST™ data to cross
sections prepared using conventional methods (hollow stem auger rig and EPA-approved
analytical methods) for the three sites. For both systems, the chemical cross sections
were comparable to the conventional methods. The chemical cross sections for both
systems showed close agreement to the conventional method cross sections in identifying
low, medium, and high zones of contamination. Generally, the relative fluorescence
intensity was positively related to the TPH and total PAH concentrations. However, a
good, quantitative correlation between the fluorescence intensity and individual or classes
of petroleum compounds could not be found for either system. In only one case during
the demonstration did either system not identify fluorescence above background for zones
sampled that indicated contamination in the hundreds of ppm range by the conventional
methods. The results of the SITE demonstration for both systems can be found in
individual Innovative Technology Evaluation Reports (ITER).
Technology field validation studies at nine sites were conducted for the state of California
for the SCAPS LIF system. Between 16 and 45 CPT pushes, along with 3 to 8
confirmation soil sample borings, were completed at each site. For the 164 TPH analyses
completed, there were 9, or 5.5 percent, false positives and 12, or 7.3 percent, false
FA-I8
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Fluorescence Analyzers
negatives. For the 164 total recoverable petroleum hydrocarbon analyses, there were 6, or
3.7 percent, false positives and 16, or 9.8 percent, false negatives.
LJF data should be used as screening level data and has been demonstrated through
comparison studies. The California Military Environmental Coordination Committee
(CMECC) guidance lists LEF as a screening tool and indicates that it should not be used
to generate definitive data.
Would this be an appropriate technology to identify individual BTEX or PAH
concentrations at a site for risk assessment purposes?
FA-I9
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
-------
Immunoassay
Organic Chemical Characterization
Techniques and Data Interpretation
* Hand-Held Survey Instruments
^Colorimetric Indicators
4 Fluorescence Analyzers
c^^ Immunoassay
+ Gas Chromatography
> Infrared Spectroscopy
* Chemical Sensors
4-Emerging and Innovative Approaches and
Instruments
4- Hands-on Activity for Organic Analysis
EPA
01-1
OI-I
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Immunoassay
Topic Overview
Topic Description: Explains the operation and
application of immunoassay techniques
Key Points
» Theory of operation
» Method description
» Analytes and detection limits
» Sample preparation
» Performance factors
» Quality control
» Advantages and limitations
» Methods (SW-846)
» Applications other than characterization
EPA
OI-2
Notes:
This section discusses the principle of operation and application of and the data produced
by immunoassay techniques used to characterize a wide array of organic constituents in
soil and water.
The following key points are discussed: (1) theory of operation, (2) method description,
(3) application (analytes and media), (4) sample preparation and procedural notes,
(5) performance factors, (6) quality control, (7) advantages and limitations, (8) methods
(SW-846), and (9) applications other than characterization.
OI-2
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Immunoassay
Immunoassay
Theory of operation
» Antibody/target analyte interaction
»Fits "lock and key" model
» Quantitation performed by monitoring color
change
EPA
OI-3
Notes:
Immunoassay is an analytical technique that takes advantage of the ability of antibodies to
selectively bind to the target analytes in a sample matrix, such as soil or water.
The binding sites on an antibody attach precisely and noncovalently to the antigen (the
target analyte). The antibody will not respond to dissimilar substances. The strength of
the antibody-antigen bond is known as the affinity constant.
Quantitation is performed by monitoring either visually or with a spectrophotometer for a
change in the color of the reaction.
01-3
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Immunoassay
Schematic of Antibody-Antigen
Interaction
Binding Site
Anatomy of an Antibody
Much like a lock and key, the
binding sites on an antibody
attach precisely to the
antigenic determinants ot
corresponding antigens.
EPA
Antlgenic Determinant
Light Polypeptide Chains -
Antigen
— Binding Site
Disulfide Bond
Heavy Polypeptld* Chains
Antigens with
Inappropriate Determinant*
Notes:
This figure shows the interaction between an antibody and antigen. Much like a lock and
key, the binding sites on an antibody attach precisely and noncovalently to the antigenic
determinants of corresponding antigens. This molecule has two binding sites at the top of
its "Y" shape.
m
For additional information on this topic, refer to page A-l at the end of this module.
OI-4
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Immunoassay
Types of Immunoassay
* Enzyme immunoassay (EIA)
^Radioimmunoassay (RIA)
^Fluorescent immunoassay (FIA)
,8, EPA
OI-5
Notes:
Environmental field analysis primarily uses enzyme-linked immunosorbent assays
(ELISA). In an ELISA, the enzyme is coupled to the target analyte to form an enzyme
conjugate, which serves as the tracer. The enzyme is the label, or tag, which later can be
detected when it causes a color change. The enzyme does not interfere with the analyte's
binding to the antibody, nor does the analyte affect the enzyme's activity. ELISA is
preferred over other methods because it can be optimized for speed, sensitivity, and
selectivity, and it is safer because it contains no radioactive materials. ELISA has a
longer shelf life and simpler procedures than other immunoassay methods.
Radioimmunoassay (RIA) is less desirable for environmental analysis for several reasons.
First, it is not as field portable as other immunoassay methods, (2) the half-life of the
commonly used 125I is short, and (3) there are hazards associated with handling
radioactive materials.
Two different types of fluorescent immunoassay (FIA) have been used. An automated
flow injection immunoanalysis has been developed to detect pesticides in water samples.
This format consists of specific antibodies immobilized onto a membrane. Reagents are
pumped in a time-controlled manner through the sensitized membrane. The enzyme
product of a fluorogenic substrate is measured downstream by a fluorescence detector.
This technique can be used to monitor water supplies, pesticide runoff, and industrial
effluents for pollution control. A second type of FIA uses a fluorescent probe with an
antibody-coated fiber to measure PCB concentrations and can distinguish between the
different Aroclors (congeners).
01-5
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Immunoassay
Method Description
+ Antibody-coating
+ Sample and enzyme conjugate addition
+ Competitive binding reaction
* Color formation
*• Measurement of color
OI-6
Notes:
In order for the immunoassay technique to work, the antibodies must be coated onto a
small test tube, microwell, magnetic particles, or latex particles. The antibodies are
coated on the inside surface of the test tube or microwell. If they are coated onto
magnetic particles or latex particles, they are added in solution with the sample and
enzyme conjugate. There are only a limited number of antibody binding sites.
The sample containing the target analyte and the enzyme conjugate (the enzyme
commonly is horseradish peroxidase or alkaline phosphatase) are added together in a test
tube, microwell, or other device to competitively bind to the antibodies.
The analyte in the sample competes with a known amount of enzyme conjugate for a
limited number of antibody binding sites. According to the law of mass action, the more
analyte there is in the sample, the more enzyme conjugate it will displace from the
binding sites. By measuring the amount of enzyme conjugate bound to the antibody, the
original analyte concentration can be determined. The amount of bound conjugate is
inversely proportional to the amount of analyte contained in the sample. This action is a
timed incubation step. After the incubation step is over, the excess unbound enzyme
conjugate is washed (removed) from the test tube.
Next, an enzyme substrate (hydrogen peroxide) and a chromogen (tetramethylbenzidene)
are added to the test tube to cause the formation of the color (often blue). This action also
is a timed step. At the end of a specified time period, a stop solution (sulfuric acid
solution) is added to stop the formation of color. Because the amount of bound enzyme
OI-6
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Immunoassay
conjugate determines the amount of color, the amount of color is inversely proportional to
the amount of analyte present in the sample.
The color of the sample can be compared visually with a negative control for a "yes/no"
or qualitative result. A semiquantitative result can be obtained by using a differential
photometer to compare the degree of absorbance of a sample to that of a standard or
standards. Lastly, a quantitative result can be obtained by generating a calibration curve
of absorbance versus concentration using a spectrophotometer, standards, and a zero
solution. The absorbance of the sample can be read from the spectrophotometer and
converted into concentration.
OI-7
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Immunoassay
Competitive Binding Reaction
Start with an antibody-coaled tube
or well.
Add sample and labeled antigen.
Labeled and unlafceled antigens
compete for a limited number of
binding sites.
Remove unbound antigen.
Add substrate and chromogen
Enzyme-substrate reaction
causes chromogen to turn color.
Less color means more analyle.
Y
KEY TO ILLUSTRATION
Antibody
^ Antig«n in sample (analyle)
O Labeled antigen
/f Substrate
• * Cfiromogen
OI-7
Notes:
This schematic shows the principal components of the competitive binding reaction,
which is fundamental to ELISA techniques.
O1-8
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Immunoassay
EPA
OI-8
OI-9
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Immunoassay
Analytes and Detection Limits
Compounds
Soil
Water
TPH
BTEX
PAHs
Pesticides
PCBs
POP
Explosives
2 to 150 ppm
1 to 5 ppm
0.2 to 25 ppm
1 to 100 ppb
0.1 to 1.0 ppm
0.1 to 0.5 ppm
0.2 to 1.0 ppm
0.1 to 0.5 ppm
10 to 500 ppb
1 to 500 ppb
50pptto 10 ppb
Less than 1.0 ppb
0.1 to 5 ppb
0.5 to 5 ppb
OI-9
Notes:
This group includes gasoline, diesel fuel, jet fuels, BTEX, and PAHs in soil and water.
For the BTEX and PAHs, the immunoassay test kits will provide a total BTEX or PAH
concentration, but will not give concentrations for individual compounds. There also is a
carcinogenic PAH test kit on the market. The test kits do not perform well for heavy-
petroleum products such as motor oil or grease or highly degraded petroleum fuels
because the immunoassay test kits primarily key off of the lighter aromatic constituents.
There is the potential for false negatives in this case.
There are immunoassay test kits for numerous pesticides and herbicides such as: triazine
herbicides, 2,4-dichlorophenoxyacetic acid (2,4-D), organophosphates, cyclodienes,
carbamates, dichlorodiphenyl trichloroethane (DDT), and many others that can be done in
soil and water. Some immunoassay test kits only respond to one compound, while others
will respond to an entire class of similar compounds.
Immunoassay test kits can detect PCBs in soil, water, and wipe samples. These kits
cannot distinguish between the different PCB congeners (Aroclors).
Pentachlorophenol (PCP) is a common chlorophenol contaminant of soil and water found
at wood treating sites. Immunoassay test kits also will respond with differing degrees to
other chlorophenols.
Ol-JO
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Immunoassay
Immunoassay test kits can detect the nitroaromatics such as TNT and dinitrotoluene
(DNT), as well as cyclotetramethylene tetranitramine (HMX) and
trimethylenetrinitramine (RDX) in soil and water.
The detection limits for the target analytes (ppm, ppb, and parts per trillion [ppt]) will
vary depending on the complexity of the matrix, interferences, and the manufacturer of
the test kit.
OI-ll
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Immunoassay
Sample Preparation
+Water: Little or none
collection and extraction kit
extraction process
» Weigh out sample
» Add extraction solvent
» Shake and wait for solution to settle
» Filter extract
» Dilute extract with buffer solution
01-10
Notes:
Water samples require no sample preparation unless they are turbid. If they contain
sediment, they have to be filtered through a 0.45-micrometer filter prior to analysis. The
requirement for little or no sample preparation for water samples is one of the advantages
of an immunoassay technique over other conventional analytical methods.
The soil collection and extraction kit only is needed if soil samples are analyzed. The kit
includes: 1) soil collection devices, 2) filters, 3) extract solution (often methanol), 4)
extract collection vials, and 5) diluent (buffer) solution. It is sold separately from the
immunoassay test kit. This kit will vary slightly from one manufacturer to another, but
will contain all the materials listed on the slide. The kit will come in one or two small,
easily portable cardboard boxes. A typical soil collection and extraction kit will contain
enough materials to collect and extract from 4 to 20 soil samples.
Five to 10 grams of a soil sample is weighed into a plastic soil collection device. Ten to
20 mL of solvent is added to extract the target analytes. Methanol or a methanol/water
mixture usually is used as an extraction solvent. The mixture then is shaken (put on a
vortex mixer) for 1 to 2 minutes and then the mixture is allowed to settle for a few
minutes. Some manufacturers add steel balls to the collection devices to help break up
the soil particles. After the mixture settles, a filter cap is placed on the plastic collection
device and the extract is filtered into a vial. Lastly, the extract is diluted with a buffer
solution so that the matrix of the solution is similar to the standards used for calibration.
The diluted extract then is ready for analysis. Manufacturers provide step-by-step
instructions with the kits to guide the user through the extraction steps.
OI-12
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Immunoassay
Would a TPH immunoassay test kit be expected to perform well to characterize a heavy
petroleum fuel in a clay soil?
OI-I3
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Immunoassay
Cross Reactivity
Definition
Examples; PCBs, PCP, BTEX, PAHs,
explosives, pesticides
Considerations for use
&EPA
Notes:
Cross reactivity is the degree to which an antibody will bind to a substance other than its
target. This usually occurs with compounds of similar structure. The manufacturer will
provide the user with information on cross reactivity for similar compounds to that of the
target analyte. This information is presented in terms of the concentration of another
compound that produces a detectable response (or interference) for the immunoassay test
kit. Sometimes it can take 100 to 1,000 times the concentration of another compound to
cause an interference.
In the case of PCBs, an immunoassay test kit is designed and calibrated for a specific
Aroclor such as 1242, 1248, or 1254. The PCB test kit will respond slightly differently
to the different Aroclors because of the varying degree of chlorination; therefore, a test kit
might underestimate or overestimate results depending on the Aroclor that is present at a
site. Besides PCP, a PCP test kit may respond to the tetra-, tri-, and di-chlorophenols.
The tetrachlorophenols are most likely to cause a response, but this usually is not a
problem because tetrachlorophenols often are not found at wood-treating sites. The PAH
test kits give a "total" PAH concentration and cannot provide the user with individual
PAH concentrations. The PAH test kits often are most sensitive to four or five specific
PAHs. As with the PAHs, a BTEX test kit will respond to all six BTEX components
with differing degrees, but will not provide the user with individual compound
concentration. A test kit designed to analyze for TNT may also respond to 1,3,5-
trinitrobenzene, DNT, tetryl, and others. A test kit designed for a specific pesticide or
herbicide may also respond to compounds in the same family such as triazines,
cyclodienes, carbamates, organophosphates, chloroacetanilides, and chlorophenoxy
O1-14
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Immunoassay
herbicides. A pesticide test kit also may respond to metabolites of the parent pesticide
with similar sensitivity.
Cross reactivity or response to similar compounds, such as in the case of petroleum
constituents or pesticides, can be desirable if the user is looking for a number of
constituents and is not particularly concerned with individual compound identification but
whether or not contamination is present at a site. Cross reactivity is undesirable if the
user is particularly interested in the concentration of a specific compound and does not
want interferences from other similar compounds. This situation can cause false positives
to occur. For example, if a user is primarily interested in the benzene concentration in
soil or groundwater at a gasoline-contaminated site, the use of immunoassay will
probably not be the best choice for on-site analysis. This knowledge can be particularly
important for defining the extent of contamination or when performing a risk assessment.
It is imperative to have some knowledge of the contaminants of concern at a site prior to
the selection of an immunoassay test kit.
01-15
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Immunoassay
Quality Control
+Calibration standards
+ Method blanks
+ Laboratory duplicates
• Matrix spikes (MS) and matrix spike duplicates
(MSD)
+Control samples
*• Performance evaluation (PE) samples
01-12
Notes:
Whether using a quantitative or semiquantitative test kit, calibration standards are
analyzed with each batch of samples. This analysis helps to ensure that the standards
were analyzed under the same conditions as the samples that are being checked against
the standards. For quantitative test kits, it is typical to generate a calibration curve using
three standards and a zero standard. The manufacturer will specify that the calibration
curve have a minimum correlation coefficient (for example, 0.99) to be acceptable. In the
case of a semiquantitative test kit, the standards usually are run in duplicate and the
manufacturer will specify that the variation in absorbency or optical density be within a
certain range to be acceptable.
Method blanks are samples that are taken throughout all the sample preparation and
analysis steps to monitor for contaminants inherent in any of the disposable supplies or
reagents; for cross contamination due to poor pipetting; or for contamination due to any
other sources such as poor decontamination procedures on any reusable items. One
method blank should be analyzed per every 20 real samples. The sample should not
contain any target analytes above the method detection limit (MDL).
Duplicate analyses are two analyses performed on the same sample. Laboratory
duplicates are used to monitor the precision or reproducibility of the analytical technique.
OI-16
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Immunoassay
Laboratory duplicates should be analyzed at a frequency of 1 per every 20 real samples.
The variation between the results should be consistent with results published in literature
provided by the manufacturer.
Matrix spikes (MS) and matrix spike duplicates (MSD) are used to evaluate the extraction
efficiency of the method and are another check of precision. The samples are prepared by
spiking a known concentration of a target analyte into a sample representative of the
matrix being analyzed. The spiking solution can be purchased from the manufacturer or
another reputable vendor. MSs and MSDs are more crucial for soil samples because of
the complexity of the soil matrix. MSs and MSDs should be analyzed at a frequency of
1 per every 20 real samples.
Control samples are used to assess the accuracy of the method. These samples are
solutions of known concentrations often supplied by the manufacturer. They are to be
analyzed with each set of calibration standards prior to the analysis of the samples. The
control sample will have an acceptance range around the known concentration. The
concentration obtained by the user for the control sample must fall in this range for the
method to be considered accurate.
Performance evaluation (PE) samples may be used as another check of accuracy of the
method. These samples are solutions with known concentrations of target analytes. The
user usually will know they are PE samples, but should not know the concentration of the
PE samples nor the acceptance range around the true concentration. The PE samples
must be purchased from a different vendor than the control sample.
OI-17
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Immunoassay
OI-13
Of-18
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Immunoassay
Analysis Procedural Notes
4 Step-by-step instructions provided by
manufacturer
4- Batch samples
4 Consistent technique is key
*• Avoid cross contamination
OI-14
Notes:
The manufacturer will provide a one-page summary of the step-by-step instructions.
Most immunoassay test kits follow a "cook book" type of procedure. They are developed
so that a novice can use them proficiently. The analysis steps follow the basic procedure
as described earlier under "Method Description."
The test kits are designed to analyze batches of 10 to 20 samples at a time. It is not
efficient to analyze two or three samples simultaneously because there are several timed
steps and standards involved and sometimes control samples have to be analyzed with
each batch. Once the analysis process is started, all samples have to be carried through
the timed steps in equal fashion. This requirement also is the reason why too many
(greater than 30) samples can not be analyzed simultaneously. It is difficult to maintain
the time schedule with too many samples.
Consistency is especially crucial for all the timed steps and with the user's pipetting
technique. To obtain the greatest precision, the pipetting of reagents must be consistent
for each sample. It is important to add reagents to the bottom of the test tubes to help
assure consistent quantities of reagents are added to the test mixture. This step can be
monitored by duplicating standards and analyzing control samples. The pipetting
technique for novices may provide the greatest learning curve.
Cross contamination can be avoided by using clean pipet tips for each sample addition
and by avoiding contact between reagent droplets on the tubes and pipet tips. The
reagents should be added without splashing. A method blank should be analyzed to
monitor for cross contamination.
OI-19
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Immunoassay
Analysis Times
* Extraction time: About 5 minutes per soil sample
4 About 30 minutes to 1 hour for analysis
^Throughput
» Water: 50 to 60 samples per day
»Soil: 30 to 50 samples per day
EPA
OI-15
Notes:
This includes the time to weigh the sample, add the extraction solvent, shake the sample,
let it settle, filter the extract, and dilute the extract. Time also is needed to label the vials
that contain the sample extract. The extraction time may be slightly longer if the soil
matrix is a clay that requires additional shaking.
Often, a batch of 20 to 25 samples can be analyzed together in the analysis time of 30
minutes to 1 hour.
Throughput is less for soil samples than for water samples because no extraction is
needed for the water samples. The actual throughput depends on several factors: (1) the
experience of the operator; (2) the size of the batches of samples analyzed together; (3)
the exact brand of immunoassay test kit; (4) the number of dilutions required if using a
quantitative test kit; and (5) the number of quality control samples analyzed with the
investigative samples. Sometimes it is not possible to achieve the throughput listed
above if samples only are being delivered to the analyst a few at a time. The analyst may
have to wait until a complete batch of samples is received prior to analysis.
OI-20
Module: Organic Chemical Characterization Techniques and Data Interpretation
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fmmunoassay
Advantages
Field portable
Little training time
Rapid
Inexpensive
Wide range of analytes
Low detection limits
EPA
OI-16
Notes:
All necessary supplies and reagents come in two to three small boxes that easily can be
transported to a site in the trunk of a car or van. Tests can be run on a small table, a
counter, or the tailgate of a truck. No electricity is required for operation.
A beginner can learn how to use an immunoassay test kit in a day or less. Most people
often become proficient at using a test kit after analyzing just two or three batches of
samples. The test kits are specifically designed so that anyone can operate them; although
it does help to have some environmental and chemistry background.
A throughput of 30 to 50 samples a day is achievable. No sample preparation is required
for water samples.
The cost of analysis usually will range from $10 to $30 per sample for water and $20 to
$40 per sample for soil, not including labor. The cost per sample will decrease with
larger numbers of samples.
Immunoassay test kits, by nature, are not limited to a specific class of compounds such as
VOCs or semi-volatile organic compounds (SVOC), like some other analytical methods.
For water samples, the detection limits for virtually all analytes are less than applicable
maximum contaminant levels (MCL). In many cases, for analytes such as pesticides, the
detection limits in water are an order of magnitude below MCLs. In soil, the detection
limits are comparable to, or below, conventional analytical techniques, and below most
action levels or remediation goals.
07-27
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Immunoassay
Limitations
4 Prior knowledge of analytes present at site
4- Reagents may need to be refrigerated
^Cross reactivity to similar compounds (false
positives)
^Semiquantitative analysis in some cases
>Long development time for new antibodies and
methods
EPA
01-17
Notes:
If immunoassay test kits are to be used efficiently and effectively, prior knowledge of
analytes and potential interferences is necessary. This also may require more than one
trip to a site.
The requirement to refrigerate reagents will add to logistical needs because a cooler or
refrigerator will be required on site.
If multiple similar compounds are found at a site, it may be difficult to accurately
quantify the individual compounds because of interferences between them causing false
positives.
If data quality objectives for a project require quantitative data, then semiquantitative test
kits will not be appropriate.
These tests can take a long time to run. It can be expensive to develop new antibodies
and immunoassay test kits for new analytes.
OI-22
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Immunoassay
SW-846 Methods
*4000-series methods
+ Update III to the third edition of EPA's SW-846
methods
^Analytes: PCP, 2,4-D, PCBs, TPH, PAHs,
toxaphene, chlordane, DDT, TNT, and RDX
OI-18
Notes:
Immunoassay is now a widely accepted field analytic technology as demonstrated by the
number of methods published in SW-846.
Method Number
Method Name
4010
4015
4020
4030
4035
4040
4041
4042
4050
4051
Screening for PCP by Immunoassay
2,4-D in Water and Soil by Immunoassay
PCBs in Soil by Immunoassay
TPH in Soil by Immunoassay
Soil Screening for PAHs by Immunoassay
Toxaphene in Soil by Immunoassay
Chlordane in Soil by Immunoassay
DDT in Soil by Immunoassay
TNT Explosives in Water and Soil by Immunoassay
RDX Explosives in Water and Soil by Immunoassay
OI-23
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Immunoassay
Applications Other Than
Characterization
+ Monitor progress of removal action
+ Monitor treatment during remediation
+Waste characterization
OI-19
Notes:
Immunoassay analysis can be used to monitor removal actions.
The use of immunoassay with daily confirmation samples sent to an off-site laboratory,
allows more frequent monitoring of treated samples than other approaches can.
Immunoassay analysis can be used to characterize investigation-derived waste (IDW) to
determine how many waste samples should be sent off site for analysis.
07-24
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Gas Chromatography
Organic Chemical Characterization
Techniques and Data Interpretation
+ Hand-Held Survey Instruments
^Colorimetric Indicators
+ Fluorescence Analyzers
^Immunoassay
^4^ Gas Chromatography
* Infrared Spectroscopy
* Chemical Sensors
^Emerging and Innovative Approaches and
Instruments
*• Hands-on Activity for Organic Analysis
GC-1
GC-1
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Gas Chromatography
Notes:
Topic Overview
+Topic Description: Explains the operation and
application of gas Chromatography (GC)
* Key Points
» GC components
» Columns and compound separation
» Detectors
"Applications of GC, including VOC, SVOC, and
fast analysis
» Quality control
»Innovations in GC
» Applications other than characterization
This topic discusses the principle of operation and application of and the data produced
by gas Chromatography (GC) to characterize a wide array of organic constituents in soil
and water.
The key points discussed in this section include: (1) components of GC; (2) columns and
compound separation; (3) detectors; (4) applications of GC, which include VOCs,
SVOCs, and fast analysis; (5) quality control; (6) innovations in GC; and (7) applications
other than site characterization. The two primary components to be discussed are
columns and detectors. Discussion of analysis for VOCs will include information on
direct injection (soil gas and air); static headspace extraction; and purge-and-trap
methods.
GC-2
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Gas Chromatography
Notes:
Applications
Analysis of organic compounds in water, soil, soil gas,
and ambient air in the following settings:
» Site characterization
» Stationary source testing or monitoring
» Hazardous waste site for determining personal
protective equipment (PPE) level
» Fenceline monitoring during removal or remediation
activities
» Emergency response testing
Field portable versus transportable (mobile laboratory)
EPA
GC-3
GC is a widely used technique for field-based analysis. The technique can be used to
generate data of known quality in the settings listed on the slide above.
The following slides depict the use of GCs in several settings. Note that the degree of
portability of GCs varies by manufacturer and intended use.
GC-3
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Gas Chromatography
GC-4
GC-4
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Gas Chromatography
HAPSITE by INFICON
HAPSITE Field-Portable GC/MS
EPA
GC-S
CC-5
Module: Organic Chemical Characterization Techniques and Data Interpretation
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GasChromatography
6C-6
GC-6
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Gas Chromatography
GC-7
GC-7
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Gas Chromatoqraphy
Components of a Gas
Chromatographic System
Gas
Controls
Injector
MB
Column Oven
Gas Chromatograph
Data
System
- Integator
-PC
-Data Acquisition Software
EPA
GC-8
Notes:
The primary components of a GC include:
(1) injection port
(2) column
(3) integrator or data acquisition system
(4) detectors
Other parts include:
(1) autosampler(s)
(2) control panel, electronic pressure control (EPC)
(3) injection port liners
(4) septa
(5) ferrules
(6) flow controllers
The carrier gas is introduced in the injection port where the sample is volatilized and
swept through the column, and where the compounds are separated. The carrier
gas/sample mixture then enters the detector where the compounds are identified. The
signal from the detector then is amplified and displayed by the data system.
GC-8
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Gas Chromatography
GC Column
+ Capillary columns used for environmental
analysis
* Column variables:
» Stationary phase
» Carrier gas and flow rate
» Length
» Diameter
GC-9
Notes:
A capillary column is an open tube made of fused silica with an outer coating of durable
plastic and an inner coating of stationary-phase material. Some capillary columns have a
second outer covering of stainless steel to withstand the higher pressure required to
analyze alcohols, ketone, and VOCs by the purge-and-trap method.
Application of the GC can be optimized by adjusting the following variables:
- Stationary phase - A solid or liquid compound that is covalently bonded to the
silica surface of the column. The polarities of the compounds of interest dictate
the choice of stationary phase, under the rule "like dissolves like." Commonly
used stationary phases include polysiloxane, carbowax, and alumina.
- Carrier gas - The mobile phase is composed of an inert carrier gas, usually
nitrogen, helium, or hydrogen. The sample constituents are transformed into the
gaseous phase and are carried along the column during separation. By increasing
the speed (flow rate) of the carrier gas, the analysis time can be reduced; however,
optimal resolution may be compromised, especially when nitrogen is used. For
hydrogen and helium, high flow rates can be used successfully to reduce the
analysis time without compromising resolution; a faster flow rate also sweeps the
injector more efficiently, improving introduction of the sample into the column.
GC-9
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Gas Chromatography
Length - Capillary columns vary in length from 15 to 100 meters. For
environmental analysis, 30- to 60-meter columns typically are used. Shortening
the length of the column can shorten the analysis time; however, optimal
resolution may be compromised under such circumstances.
Diameter - Diameters of capillary columns are less than 1 millimeter, while those
of packed columns may be as large as 2 millimeters. The smaller diameter
produces finer resolution and greater sensitivity, but can handle only a small
volume of sample (1 to 2 microliters).
•GC-10-
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Gas Chromatography
1
<
'rinciples of Compound Separation
>Gas chromatographic interactions
» Resolving target analyte(s) on the column
^- — Heat ^
Gas *" l^V"" ^T^X^^^ Stationary
\K\\\\\\\\\\ "DILULII
| A rhase
Target Analyte ^- Column
^L EPA GC-10
Notes:
The graphic depicts target analytes on the column.
The first step in the separation process is that the molecules evaporate from the column
wall into the gas phase. The molecule then hits a particle of the carrier gas and either
loses or gains energy. Molecules then hit sites in the stationary phase and remain until
overcoming the intermolecular forces. The interaction between gaseous molecules and
the stationary phase produces separation of compounds.
The mobile phase is comprised of the carrier gas, which usually is nitrogen, helium, or
hydrogen. The compounds are transformed into the gaseous phase either by headspace or
purge and trap (for VOCs) or during injection by heat transformation through the
injection port liner and heat through the column (for SVOCs). The compounds are
carried through the column using the carrier gas (nitrogen, helium, or hydrogen).
What modification would you make to a capillary column to decrease analysis time?
•GC-1I
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Gas Chromatography
Principles of Compound Separation
(continued)
. .
GC-11
Notes:
In figure (a), the compounds are introduced to the column.
In figure (b), the triangular-shaped compound resides on the stationary phase (column
coating) and the circular compound resides in the mobile phase (carrier gas).
In figure (c), compound separation continues with time.
In figure (d), the compounds finally are separated.
•GC-12-
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Gas Chromatography
Chromatograms
DB-5
2
DB-1701
It 1 I W II I .
EPA
GC-12
Notes:
This slide depicts the differences in compound separation with the use of two columns.
Dual column analysis is a valuable QC tool for confirming the identification of a
compound.
GC-I3-
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Gas Chromatography
Gas Chromatography Detectors
Applications
Dvtodof
PK>
no
ECO
ELCD
TCD
NPD
MS
Aromatic
VOC*
X
X
X
CntonralKl
VOC*
X
X
X
X
X
SSST
X
X
X
or
PMrtldd**
CwStart*
X
X
X
X [ X
svoc*
and
PCS*
X
X
X
X
Dtoxkw
X
X
X
LanctfW
X
X
SL EPA GC-13
Notes:
This table identifies the detectors most suitable for the classes of compounds typically of
concern in environmental investigations.
Note that the MS detector is the most versatile. The MS is used widely in place of
conventional GC detectors; however, its versatility comes at a sacrifice. The following
slides will discuss the basic operation of the MS, spectral interpretation, and limitations
of the detector.
Would methylene chloride be a good solvent for samples analyzed using an ECD? Why
or why not?
If an ECD and FID were both required to be plumbed in series, which detector would be
plumbed first? Why?
• GC-/4
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Gas Chromatography
Would an ECD identify BTEX components? Why or why not?
Which of the detectors listed in the table is the most appropriate for the analysis of
mevinphos? Why?
GC-/5'
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Gas Chromatography
Photoionization Detector (PID)
lonization mechanism - Ultraviolet lamp of known
energy
• Measurement - Change in current as ions are
collected on electrode
Compounds detected - benzene, toluene,
ethylbenzene, and xylene (BTEX), VOCs (aromatic
and chlorinated), and petroleum constituents
Qualities - Non-destructive, sensitive to water,
needs recalibration often
Sensitivity - High (part per billion to part per trillion)
EPA
GC-14
Notes:
A photoionization detector (PID) consists of a special ultraviolet lamp, ranging in energy
from 9.5 to 11.7 eV, mounted on a low-volume flow-through cell. As constituents of the
sample pass through the cell, they are energized and ionized. The ions are collected at
positively charged electrodes, where the change in current is measured.
The 10.2 eV lamp emits ultraviolet light at 121 nanometers (nm), which is sufficient to
ionize BTEX compounds and hexane. A few halogenated compounds that have
ionization potentials of less than 11.7 eV can be detected by the higher-energy PID. The
PID is more selective than the FID.
The PID can detect VOCs (aromatic and chlorinated) and petroleum constituents
including BTEX. The PID can detect BTEX in the low ppb to high part per trillion (ppt)
range.
The PID is a nondestructive detector that can be used in series before other detectors.
Using multiple detectors extends the range of compounds that can be detected in one
analysis. PID is sensitive to water and must be recalibrated more often than the FID.
•GC-16-
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Gas Chromatography
Flame lonization Detector (FID)
4- lonization mechanism - Hydrogen-fueled flame
4 Measurement - Change in current as ions are
collected on electrode
+ Compounds detected - BTEX, VOCs (aromatic
and chlorinated), petroleum constituents,
SVOCs, and PCBs
* Qualities - Destructive, sensitive to water, wide
linear range, longer analyte list
4 Sensitivity - High (part per billion to part per
trillion)
EPA
GC-15
Notes:
A flame ionization detector (FID) consists of a stainless steel jet constructed so that
carrier gas exiting the column flows through the jet, mixes with hydrogen, and bums at
the tip of the jet. Hydrocarbons and other molecules which ionize in the flame are
attracted to a metal collector electrode located just to the side of the flame. The resulting
electron current is amplified by a special electrometer amplifier which converts very
small currents to millivolts.
The FID is sensitive to almost all molecules that contain hydrocarbons. Examples
include aromatic and chlorinated VOCs, petroleum constituents, SVOCs, and PCBs.
The FID is a destructive detector that can be used in series only after nondestructive
detectors. The FID is sensitive to water, but has a wider linear range of detection than the
PID. The FID also can detect more compounds than the PID.
The FID can detect compounds that contain the low ppb to high ppt range.
GC-77-
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Gas Chromatography
Electron Capture Detector (ECD)
*• lonization mechanism - Beta particles (electrons)
emitted from Ni-63 source
*• Measurement - Change in electron current as
ions disrupt the stable electron cloud
* Compounds detected - Electronegative
molecules (halogenated)
+ Qualities - Non-destructive, sensitive to water,
radioactive source, requires reconditioning
* Sensitivity - High (part per billion to part per
trillion)
&EPA
GC-16
Notes:
An electron capture detector (ECD) consists of a sealed stainless steel cylinder that
contains radioactive nickel-63. The nickel-63 emits beta particles (electrons) which
collide with the carrier gas molecules ionizing them in the process. A stable cloud of free
electrons thus forms in the ECD cell. When an electronegative molecule such as a
halogenated molecule enters the cell, it immediately combines with one of the free
electrons which temporarily reduces the number of free electrons. The detector
electronics pulse at a variable rate to measure the electrons remaining in the cell.
The ECD is highly sensitive to electronegative molecules (those capable of producing
negatively charged ions) such as halogenated compounds or those that contain nitrogen.
The ECD readily detects chlorinated pesticides, halogenated solvents, PCBs, and dioxins.
The ECD is a nondestructive detector that can be used in series before other detectors.
The ECD is sensitive to water that affects the condition of the Ni-63 foil that covers the
detector. The foil must be reconditioned when its sensitivity diminishes. Because the
ECD contains a radioactive source, some states require that users be licensed to receive
and handle the detector.
The ECD can detect halogenated compounds in the low ppb to ppt range. The more
halogenated the molecule, the more sensitive the detector is to that compound. For
example, the ECD is orders of magnitude more sensitive to carbon tetrachloride than to
vinyl chloride.
•GC-J8'
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Gas Chromatography
Electrolytic Conductivity Detector
(ELCD)
*• lonization mechanism - Hydrogen-fueled flame
+ Measurement - Change in electrolytic
conductivity of cell from combustion products
* Compounds detected - Halogenated compounds
* Qualities - Destructive, high degree of
maintenance, wide linear range
* Sensitivity - High (parts per billion to parts per
trillion
GC-17
Notes:
An electrolytic conductivity detector (ELCD) is a halogen-specific detector that operates
on electrolytical conductivity principles. Organic compounds eluding from a GC column
form combustion products as they are mixed with hydrogen gas over a nickel catalyst at
1,000°C in a quartz tube furnace. For example, organic chlorides form hydrochloric acid
(HC1). The HC1 readily ionizes and changes the electrolytic conductivity which is
monitored by the ELCD.
The ELCD is a halogen-specific detector. The ELCD readily detects chlorinated
pesticides, halogenated solvents, PCBs, and dioxins.
The ELCD is a destructive detector that can be used in series only after nondestructive
detectors. The ELCD requires a higher degree of maintenance than other detectors. It
also has a wider linear range than the ECD.
The ELCD can detect halogenated compounds in the low ppb to ppt range. The degree of
halogenation has less effect on sensitivity than is the case with the ECD. Detection limits
for compounds are similar, even though the degree of halogenation may vary.
GC-19'
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Gas Chromatography
Thermal Conductivity Detector (TCD)
-.-*- •$*,&• • ••w
-------
Gas Chromatography
Nitrogen-Phosphorus Detector (NPD)
4> lonization mechanism - Hydrogen-fueled flame
with heated thermoionic bead
+ Measurement - Change in current as nitrogen or
phosphorus ions collect on electrode
+Compounds detected - Nitrogen and
phosphorus-containing compounds
+ Qualities - Destructive, sensitive to water,
thermoionic bead must be replaced
+ Sensitivity - High (part per billion)
EPA
GC-19
Notes:
The nitrogen-phosphorus detector (NPD) is similar to the FID, except that the hydrogen
gas flow rate is reduced to 1 to 3 milliliters per minute (mL/min), and an electrically
heated thermionic bead is positioned just above the jet orifice. Analyte molecules exiting
the column collide with the hot bead, and the nitrogen or phosphorus react and liberate an
electron. The electron is attracted to the same collector electrode and electrometer
amplifier used in the FID.
The NPD is sensitive to nitrogen and compounds that contain phosphorus. The NPD
typically is used in analysis for organophosphorus pesticides. In addition, it is used in
analysis of nitroamomatics (explosives).
The NPD is a destructive detector that can be used in series only after nondestructive
detectors. The NPD is sensitive to water that affects the condition of the thermoionic
bead. The active element on the bead eventually will become depleted and require
replacement.
The NPD can detect nitrogen and compounds that contain phosphorus in the ppb range.
Reduced sensitivity often indicates the depletion of the active element on the thermoionic
bead.
• GC-21
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Gas Chromatography
Mass Spectrometer
• Used extensively as detector for GC
- SW-846 method 8260B (volatiles)
SW-846 method 8270C (semivolatiles)
Most commonly used mass spectrometer is quadrupole
mass filter
» Quadrupole for low resolution analysis
» Magnetic sector for high resolution
• Definitive identification of a wide range of organic
compounds, very sensitive, quantitative analysis
GC-20
Notes:
Two types of MS are used for GC-MS analysis: (1) the quadrupole MS and (2) magnetic
sector MS. The quadrupole MS, interfaced with capillary-column GC, is the MS most
commonly used in an environmental laboratory. The sample extract is injected onto the
capillary column of the GC, where the individual compounds in the complex mixture are
separated. The individual compounds elute through the column at different rates into the
MS for detection.
The most significant information derived from the mass spectrometric analysis of a
compound is the molecular weight (MW), followed by the profile of the mass spectrum.
Each organic compound has a unique MW and mass spectrum. Based on this uniqueness,
an unknown compound can be identified through library search software. A
computerized search of an unknown analyte against this library will generate the
unknown's identification with a high confidence level.
The compromise associated with the use of MS rather than conventional detectors is
reduced sensitivity to many compounds, especially the chlorinated pesticides and
aromatic phenols. One way to counter that effect is to use magnetic sector MS (high
resolution).
Magnetic sector MS is also known as high resolution MS and has a high level of
sensitivity. For example, the MS is capable of analyzing for dioxins at levels of ppt in
soils and parts per quadrillion (ppq) in waters. Quantitative analysis is also possible
because of the direct relationship between concentration and peak intensity of the
analytes. Typically, high resolution MS is not used for field-based analysis because of the
size and stability requirements of the instrument.
GC-22 •
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Gas Chromatography
aptctnim
r«cord*r
EPA
GC-21
Notes:
The individual eluted compound is directed into the ion source of the MS through a
heated interface where the molecules are fragmented into ions. These ions are passed
through the mass analyzer, for differentiation into individual ions. These ions then are
detected by an electron multiplier, and the resulting signal is sent to a data system for
further processing. The results of the data analysis are used to generate graphical
representations showing a total ion chromatogram (TIC), spectrum of each peak
generated in the TIC and the result of the library search for the identification of the
compound. The individual TIC and ion peak intensities are directly related to the
concentration of the analyte in the sample extract which makes the GC-MS an extremely
powerful analytical tool for positive identification and quantitation of organic
compounds.
• GC-2 3 •
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Gas Chromatography
Total Ion Chromatogram and Mass Spectrums
High probs
compound
«*
1^07.
_ .
Mdinon. 1
1 2fWiaVM
1
Ac^K^bufeilMftw
fcjHcJ*
TI».>* sto idoo is!oo
Figure I. Total ion cbromalogram of VQC's analysis
bility spectral matching agreement was noted in the identification of volatile organic
s On-board mass spectral libraries allowed immediate identification of compounds on-site.
f .1 .... ..
Figure 2. 2-Bulanone at retention lime 8.03 min.
h^^^MWWUU
Figure 3. 2 Pentanone at retention time 10.16 min.
GC-22
Notes:
The slide depicts the mass spectrometric data from VOC analysis. Figure 1 shows the
total ion chromatogram of a mixture of analytes detected in the sample. Figure 2 shows
the mass spectrum at a retention time (RT) of 8.03 minutes (top) and mass spectral library
searched reference (bottom). The peak at 8.03 minutes is confirmed as 2-butanone by the
library search. Figure 3 shows the mass spectrum of TIC peak at RT 10.17 minutes (top),
and library search result (bottom) identified this peak as 2-pentanone.
GC-24 •
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Gas Chromatography
Total Ion Chromatogram and Mass Spectrums
1e*07-
MIK
2-Butonone
TIM->
Acetic add. butyl ester
Prapanoic
t
1500
Figure 1. Total ion chromatogram of VOC's analysis.
High probability spectral matching agreement was noted in the identification of volatile
organic compounds. On-board mass spectral libraries allowed immediate identification
of compounds on-site.
Uxnteva
SJOO-
Uiwdvc*
5000-
t
• 1. 3
j
a
t
to
Jl .
J.imc
E-ButaPMi
1
7
i ' '
1
7
( f
A '
»e
'""•a*""*
2
97 It1 IS
" ' ido ' ' ' '
2
ido
I10Z54.0I-.1
1(S MO 207 229 242
150 260
««C1
ISO 200
(IrtNn. WW Goal
MM 72 91 •
Figure 2. 2-Butanone at retention time 8.03 min.
U»d«
sooo.
ttv^fwi
SQQO -
JJ7 »%
r
• t. i
^
27
-V ^
* 4
4
I t
jj) 4)
jdint
(-Pent»non
i
, * ?( 1 111
d» ab 160
«»352-pB*
1
58 71 «
' "*' 'V "ib" " "100
e
137 158 179 133
io ' ' "iJo ' ' "ite" ito
~«n
io ' iJo iii lio
Re! No. MW Qual
•6283S IE 17 •
Figure 3. 2-Pentanone at retention time 10.16 min.
• GC-25 •
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Gas Chromatography
VOCs: Chlorinated and Aromatic
+Three methods of analysis
» Direct injection—ambient air and soil gas
» Static headspace extraction—soil and water
» Purge and trap extraction—soil and water
EPA
GC-23
Notes:
Methods of analysis for VOCs include direct injection for ambient air and soil gas, and
static headspace extraction or purge and trap extraction for soil and water. These
techniques will be discussed in the following slides.
Analytes of interest include: (1) halogenated VOCs, including vinyl chloride, methylene
chloride, trichloroethene (TCE), tetrachloroethene (PCE), trichloroethane (TCA),
chloroform, carbon tetrachloride, and ethylene dibromide; (2) nonhalogenated VOCs
(solvents), including methyl iso-butyl ketone (MIBK), methyl ethyl ketone (MEK), and
acetone; (3) aromatic compounds, including BTEX and chlorobenzenes; and (4) fuels,
including gasoline, diesel fuel, jet fuel, and kerosene.
• GC-26 •
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Gas Chromatography
Ambient Air Gas
+ Applications
* Sample collection
* Analysis
» Instrumentation
» Detection limits
» Run times
4 Advantages
4- Limitations
EPA
GC-24
Notes:
On site air analysis can be used to test for VOCs in stationary source testing (emission
inventory), hazardous waste site testing to determine appropriate levels of PPE, fenceline
monitoring during remediation activities, and emergency response testing.
The preferred mode of sample collection for quick analysis is to directly draw a sample of
ambient air into the on site GC or GC/MS using an internal pump in the analytical
instrumentation. Air samples also may be collected in Tedlar bags, Summa® canisters, or
Tenax tubes, or using solid phase microextraction (SPME) devices. The use of these
other sampling containers will require that an air sample (1 to 5 mL) be withdrawn from
the sample container or desorbed from the sorbent and injected into the GC system.
(Only applies to Tedlar bags and Summa® canisters. Tenax and SPME will need some
desorption technique.)
On site analysis of air generally is conducted using a portable GC system or GC/MS
configuration. Transportable GCs (larger, laboratory-grade instruments) can also be used
but provide far more logistical problems. The detection limits for air analysis will range
considerably depending on the method of sample collection and GC system. Typical
detection limits will range from 5 to 200 parts per billion by volume (ppbv). Detection
limits will be considerably lower if the analytes are concentrated on some type of
absorbant material and desorbed versus directly drawn into the analytical system via a
sampling pump. Analytical times for VOCs should be less than 10 minutes per sample.
A GC/MS system can either be used to provide qualitative to semiquantitative data in a
survey mode or quantitative data in an analytical or selective ion monitoring (SIM) mode.
•GC-27-
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Gas Chromatography
The advantages of on-site air monitoring is the quick data which allows flexibility for on-
site personnel and the project manager.
If conducting emissions testing, samples high in moisture content or acid content will
have to be pretreated prior to analysis. If a MS is not used, exact analyte identification
(coelution problems) may not be possible in complex mixtures.
GC-28 •
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Gas Chromatography
Soil Gas Analysis
• Applications
• Direct injection/detection limits
• Sample containers
• Injection volume
• Holding time
•Advantages
• Limitations
EPA
GC-25
Notes:
Soil gas analysis commonly is used to identify "hot spots" or source areas of VOCs in the
subsurface. It also can be used to approximate the extent of a subsurface plume.
The detection limit for most VOCs is 10 nanograms per liter (r|g/L). Calibrations consist
of direct injection using an air standard mix or methanol-based standards. The
concentration is reported in T|g/L. One liter of air weighs approximately 1 gram.
Therefore on a weight basis, r|g/L is approximately equivalent to ppb.
Typical sample containers include glass bulbs, Tedlar bags, Summa® canisters, syringes
or 22 or 40-mL vials. Teflon®-coated syringes, plungers, or stop-cocks should be
avoided, because some VOCs (for example, 1,1,1-TCA) are strongly sorbed to Teflon®
surfaces.
Usually inject approximately 1 to 5 mL of the sample into the GC column. However, this
action may result in more rapid deterioration of the column stationary phase and
oxidation of the ECD foil.
Holding time is 12 hours.
The advantages of soil gas analysis are that it is rapid, inexpensive, provides real-time
results, and causes minimal disturbance to the site.
. GC-29'
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Gas Chromatography
One limitation of soil gas analysis is that it does not always reflect a true soil
concentration. The technique is limited to high volatility and low solubility compounds.
Coelution problems can occur in complex mixtures if a MS is not used. Sample
carryover or cross contamination may be a problem in highly concentrated samples.
Decontamination of syringes is crucial, especially for chlorinated VOCs.
GC-30-
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Gas Chromatography
Static Headspace Extraction
and water analysis
+Theory of operation
+Analysis times
+ Detection limits
+ Sample collection and preparation
+ SW-846 Method 5021 "Volatile Organic
Compounds in Soils and Other Solid Matrices
Using Equilibrium Headspace Analysis"
GC-26
Notes:
Static headspace extraction is widely used in determining VOCs in waste water, soil, and
drinking water. This extraction method is highly productive and cost effective, requiring
minimal sample preparation.
Efficiency of headspace extraction is based on soil and water partition coefficients of the
analytes.
Based on Henry's Law.
H = P/X
where
H = Henry's Law constant (atm-mVmole-K)
P = pressure of gas above liquid (atm)
X = equilibrium mole fraction of dissolved gas at 1 atm (mole/m3)
Two stages: (1) Diffusion of analyte into the headspace
(2) Diffusion of analyte back into the matrix
A steady state equilibrium is reached when the concentration in the headspace is equal to
the concentration in the matrix.
Low viscosity liquids reach equilibrium faster. Solids take longer.
GC-31
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Gas Chromatography
A constant heat time is recommended for samples that do not reach equilibrium within a
reasonable time.
Analysis time ranges from 10 to 30 minutes depending on number and boiling point of
analytes of interest.
Detection limits for BTEX compounds and most chlorinated VOCs are in the range of 1
to 10 ppb; detection limits for TPH-purgeable compounds are 1 to 10 ppm in water and
10 to 50 ppm in soil.
Water samples can be collected in 40 mL volatile organic analysis (VOA) vials or directly
in a 22-mL headspace vial. Soil samples can be collected in a 4-ounce glass jar or
directly into a 22-mL headspace vial. Mass or volume is measured into a headspace vial
(generally 5 mL or 5 grams). No sample preparation is required for water samples.
Sample preparation for soil samples may vary depending on the initial analyte
concentration and soil type. For high concentration soil samples (ppm levels), studies
have shown that methanol-flood achieves the greatest extraction efficiency. An aliquot of
the methanol can then be analyzed using the static headspace technique. Methanol-flood
techniques, however, are not appropriate for soil samples that contain less than 200
mg/kg of an analyte due to the dilution effect. For these low concentration soil samples,
Method 5021 recommends the addition of an aqueous matrix modifying solution. For
field analysis, the addition of a matrix modifier may not be necessary due to the quick
analysis times.
How can detection limits be lowered for headspace extraction?
• GC-32 •
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Gas Chromatography
Principles of Operation Sequence:
Headspace Sampling
Heating and mixing
Pressurize mode
Pressure equilibration
Loop fill time
Loop equilibration
Injection time
GC-27
Notes:
Listed below are the steps in the operational sequence of an automated headspace sampler.
• The sample is introduced to the platen heated zone and allowed to equilibrate at a fixed
temperature for a fixed time period. Typical heating temperatures range from 40 to 80°C.
Heating times vary from 10 to 30 minutes. After the sample is heated, it is then mixed to
help volatilization into the headspace.
• Next, the vial is raised onto a needle and pressurization gas (nitrogen) fills the vial to a
pressure of 3 to 27 pounds per square inch (psi).
• The pressure in the vial is then allowed to equilibrate for 0.5 to 2.5 minutes.
• The vent valve is then opened and the pressure in the vial displaces the headspace through
the sample loop, filling the loop at the proper loop fill time. Pressure in the vial will
equal atmospheric pressure. Loop volumes can range from 0.1 to 5 mL. Typical loop
volumes used are 1 or 2 mL.
• After the loop fill, the vent valve and pressure valve are closed, allowing the sample
vapor to equilibrate and pressure and flows to stabilize.
• When the GC-ready signal is received by the headspace unit, the 6-port valve rotates and
the sample loop contents are transferred to a heated line with column carrier gas. Carrier
gas then back flushes the loop, sweeping through the heated transfer line into the GC
injection port (0.3 to 6 minutes).
GC-33 •
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Gas Chromatography
&EPA
GC-28
Notes:
This figure shows the Tekmar™ 7000 headspace unit with the 7050 sample carousel.
Other manufacturers of headspace autosamplers include Hewlett-Packard and Perkin
Elmer.
. GC-34 •
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Gas Chromatography
Purge-and-Trap: Theory of
Operation and Advantages
4 Theory of operation
4 Dynamic process
4SW-846 methods 5030A and 5035
EPA
GC-29
Notes:
Helium is bubbled through the solution at ambient temperature and the volatiles are
transferred from the matrix to the vapor phase. The volatiles are then swept through the
sorbent column where they are trapped. Then, the sorbent column is heated and
backflushed with helium gas to desorb the components. The components are then
transferred to a GC via a heated line, where they are separated using the appropriate
column and detected using a MS or other detector. Typically, a 5 mL sample is used for
water analysis and a 5 gram sample is used for soil and sediment analysis.
The primary advantage of purge and trap over static headspace is that it is a dynamic
process. It is a more efficient extraction technique for those VOCs which have a higher
octanol/water partition coefficient, especially in soils with high organic matter content.
Purge and trap is the recommended VOC extraction technique used for GC analysis. The
recommended extraction methods are 5030A and 5035.
GC-35
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Gas Chromatography
GC-30
GC-36 •
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Gas Chromatography
c
\
Comparison of Attributes of Headspace
fersus Purge-and-Trap Analysis
V*1«l*» ,
System process
Solvent use
Sample
preparation
Sample
decontamination
Upper dynamic
range
Detection limit
Loss of
contaminants
Cost
Space
requirements
Throughput
:'':•:;•'. IlliltlpttH '. .:-::
Static
Minimal solvent use
Weigh sample in headspace vial
No transferring vessels to
decontaminate
Limited due to saturation of headspace
before equilibrium reached
No mechanism for concentration of
compounds
If headspace vial is nol properly
crimped, compounds may be lost
during pressurization
Less than purge and trap system
Less space than purge and trap
system
50 samples per day
.•"." ••, , .• ^MipttiatMp . •:•:•::=:
Dynamic
Minimal solvent use
Weigh sample: transfer to separata purge vessel
Reusable purge vessels must be decontaminated
Not limited by headspace saturation because the
compounds are purged in a dynamic system
Ability to purge for long periods of time and
concentrate compounds onto trap before analysis
Less loss of compounds because purge vial is not
pressurized: outlet goes directly to trap: however, loss
of compounds during sample transfer may occur
More than headspace system
More spaca than headspace system and requires more
plumbing
20 samples per day
•j^ EPA GC-31
Notes:
The headspace technique is a static process, while purge-and-trap is a dynamic process.
Some of the differences between the two processes are listed in the table above.
Use of organic solvents is comparable for the two techniques; however, for purge-and-
trap analysis, water is used as a solvent for soil purging, increasing the amount of liquid
waste produced in the field laboratory.
For headspace analysis, samples can be collected directly into preweighed headspace
vials; no transferring of sample is required. For purge-and-trap analysis, a measured
amount of sample must be weighed and then transferred into a specially designed purge
vessel. The purge vessels are reusable glassware and must be decontaminated. Use of
such vessels increases the potential for carryover contamination.
Because the headspace process is static, the headspace can become saturated before
equilibrium is reached between the medium (soil or water) and the headspace
concentration. Therefore, high concentrations of compounds may not be transferred
efficiently to the headspace and subsequently detected. Results for high-concentration
samples may be biased low. In purge-and-trap analysis, compounds can be purged
continuously from the medium and collected onto the trap, allowing higher
concentrations to be transferred and detected effectively.
•GC-37-
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Gas Chromatography
Because the headspace system does not allow for concentration of compounds onto a trap
over a period of time (like the purge-and-trap system), trace amounts of compounds that
are not mobilized effectively at equilibrium may not be detected.
Both systems have the potential for loss of compounds. During pressurization of the
headspace vial, compounds can be lost if the cap is not properly sealed. In the purge-and-
trap system, loss of compounds will occur as a result of volatilization during the weighing
of the sample and its transfer to the purge vessel.
The cost of the purge-and-trap system is typically more than that of a comparable
headspace system.
The headspace system is an attachment to the GC that requires little additional bench
space; however, the purge-and-trap system is a separate stand-alone system that may
require twice as much bench space as the GC alone.
The throughput of the headspace system is significantly larger than that of the purge-and-
trap system, primarily because the purge-and-trap system requires more handling,
transfer, purging, and decontamination of samples than the headspace system.
Comparative studies have been performed and are presented in the additional information
section of this module.
Variable
System process
Solvent use
Sample
preparation
Sample
decontamination
Upper dynamic
range
Detection limit
Loss of
contaminants
Cost
Space
requirements
Throughput
Headspace
Static
Minimal use of solvent
Weigh sample in headspace
vial
No transfer vessels to
decontaminate
Limited because of saturation
of headspace before
equilibrium is reached
No mechanism for
concentration of compounds
If headspace vial is not
properly crimped, compounds
may be lost during
pressurization
Less than that of purge-and-
trap system
Less space than purge-and-
trap system
50 samples per day
Purge and Trap
Dynamic
Minimal use of solvent
Weigh sample; transfer to separate purge
vessel
Reusable purge vessels must be
decontaminated
Not limited by headspace saturation
because the compounds are purged in a
dynamic system
Ability to purge for long periods of time
and concentrate compounds onto trap
before analysis
Less loss of compounds because purge
vial is not pressurized; outlet goes directly
to trap; however, foss of compounds may
occur during transfer of a sample
More than headspace system
More space than headspace system and
requires more plumbing
20 samples per day
- GC-38 •
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Gas Chromatography
Plot of Headspace Versus Purge-
and-Trap Data for Soil Analysis
&EPA
10,000
1,000
w
I
100
10
• TDCE
• Ben.
. TC6
a Toi
10
100 1.000
PT/GC/MS(M9/g)
10.000
Figure 3. log-log plot of mean concentrations (pg/g) of all high-
level VOC determinations in the fortified Point Barrow soil.
GC-32
Notes:
This slide depicts a log-log plot of mean concentrations (yug/g) of high-level VOCs in a
spiked sample of soil, analyzed by headspace analysis and purge-and-trap analysis.
Note how the concentrations identified by headspace are significantly lower than the
concentrations identified by the purge-and-trap method.
GC-39'
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Gas Chromatograph y
Plots of Headspace Versus Purge-and-Trap Data for Soil Analysis
1000
log-tog pM of mMn eonewmfl
VOC d«MnM«flon* In ft* torMwl USATHAMA Ml. Stop* «nd eor-
raMton o»«lctoK tar •* port*. OJM l»ni*»Uuii« m fm terOTM PoM BMTUW t
10MO
100 ZOO 300
PT/GOMS (M9*fll
ngw*4. Umvpttof mMn(M)/a)Mm-U-*NeraMhy«*Mind Figures, tog-tog pkM of mwn (M/g) MeHoraMhyMiw OCE) «nd
- - - - - - Stop* end vai«t«
-------
Gas Chromatography
SVOC Compounds
+ Classes of compounds
» PAHs, PCBs, pesticides, herbicides, dioxin,
phenols, phthalates, amines, and amides
*• Types of extraction
» Solvent extraction
-Traditional soxhlet, liquid-liquid, or
sonication
—Abbreviated field methods
—Accelerated solvent extraction (ASE)
—Microwave-assisted extraction (MAE)
QC-33
Notes:
Semivolatile compounds that are analyzed in soil and water and corresponding methods
are listed below.
Compound Class
Phenols
Phthalates
Amines
Chlorinated pesticides
PCBs
PAHs
Chlorinated hydrocarbons
Organophosphorus compounds
Chlorinated herbicides
SVOCs/base neutral acids (BNA)
Dioxin
SW-846 Method
8041(GC-FIDorECD)
8061A (GC-ECD)
8070A (GC-NPD)
8081A (GC-ECD)
8082 (GC-ECD)
8100 (GC-FID)
8121 (GC-ECD)
8141A (GC-NPD or FPD)
8151A (GC-ECD)
8270C (GC/MS)
8280 (GC/MS)
8290 (GC/High-Res MS)
In the past, typical "formal lab" extraction methods included soxhlet, liquid-liquid, and
sonication. More recently, accelerated solvent extraction (ASE) has become the
extraction method of choice because it is more rapid and uses less solvent. Microwave-
assisted extraction (MAE) is another extraction method that is promising for fixed
laboratory analysis because it too is more rapid and uses less solvent compared to the
"older" solvent extraction methods.
• GC-41
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Gas Chromatography
The key in the field is to simplify the solvent extraction methods to minimize solvent
waste, save time, and reduce cost. Typical solvents used in the field include hexane,
methanol, methylene chloride, and methyl tert-butyl ether (MTBE). Simplified field,
solvent extraction methods normally do not include a cleanup step. A concentration step
may also be eliminated if elevated detection limits are acceptable. ASE and MSB are not
as commonly used in the field (especially on small projects) because of the initial expense
of the equipment and other logistical constraints such as power and space requirements.
• GC-42 •
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Gas Chromatography
SVOC Compounds (continued)
4Types of extraction (continued)
» Minimal solvent or solvent-free
-Supercritical fluid extraction (SFE)
-Solid phase extraction (SPE)
—Solid phase microextraction (SPME)
-Thermal desorption
&EPA
GC-34
Notes:
Extraction techniques that use a minimal amount of solvent are preferred for field
applications. The techniques listed above fit into this category. Although supercritical
fluid extraction (SFE) is an EPA-approved technique for fixed-laboratory applications, it
has not gained wide use in the field because of the expense of the apparatus and limited
portability. Solid-phase extraction (SPE) and solid-phase microextraction (SPME) are
ideal techniques for field use because they are rapid, use little or no solvent, simple, and
inexpensive. SPE is primarily limited to water samples, although it can be used as a
cleanup technique for liquid extracts of solid samples. SPME has gained much more
popularity in the last 2 to 3 years. Its advantage over SPE is that it can be used for both
VOCs and SVOCs and no solvent is required. Thermal desorption for SVOCs is
analogous to a more rigorous static headspace extraction for VOCs. It also is convenient
for field use because it is simple, rapid, and requires no solvent.
GC-43 •
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Gas Chromatography
Summary of Extraction Techniques
GC-35
• GC-44 •
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
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Gas Chromatography
Notes:
Interferences
* Coelution of analytes
+ Sample carryover and equipment contamination
4-Multicomponent compound interferences with
individual analytes
» Petroleum with BTEX and PAHs
» PCBs with chlorinated pesticides
GC-36
Coelution of analytes is where two compounds elute at the same relative retention time.
Peaks 11 (cis-1, 2-dichIoroethene) and 12 (2,2-dichloropropane) coelute on the ELCD.
What GC parameter or column characteristic can be changed to reduce the coelution?
Sample carryover and equipment contamination occurs when highly concentrated samples
are analyzed and residue of that sample is not purged before the analysis of the next
sample. Therefore, peaks will be present in the next sample that are not representative of
that sample. An instrument blank should be analyzed, and no peaks should be present
before sample analysis continues.
GC-46 •
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Gas Chromatography
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The graphic above illustrates the petroleum interference with BTEX components.
GC-47-
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Gas Chromatography
Fast GC
• Very small GCs
• Shortened columns
4 VOCs in less than two minutes
• SVOCs in less than five minutes
• Applications: sensitivity and resolution
GC-37
Notes:
Fast GC units are small (about the size of a briefcase), lightweight (less than 15 pounds),
and modular (meaning components such as injectors, columns, and detectors can easily
be changed out for different analyses). These GCs are battery powered and have internal
gas supplies. The ovens in these GCs are usually isothermal.
One of the critical components of fast GCs is the small column which is usually 0.10
millimeter (mm) in diameter and less than three meters long. These small columns allow
for the rapid analysis of VOCs and SVOCs and high sample throughput. These GCs are
used mostly for analyzing for VOCs.
Most VOCs, such as chlorinated VOCs and aromatics, can be analyzed in less than two
minutes. This turn around time is in comparison to 15 to 20 minutes required for a
typical GC analysis.
SVOCs can be analyzed in less than five minutes. This is in comparison to 20 to 30
minutes required for a typical GC analysis.
The primary drawback of these fast GCs is resolution and sensitivity. Because of the
quick analysis times, many VOCs or SVOCs will coelute on a column. These GCs will
perform adequately if there are only a few target VOCs or SVOCs at a site, but will not
work if many VOCs or SVOCs exist. Detection limits may be in the ppm range instead
of ppb range, which is still acceptable for identifying "hot spots.'"
GC-48 •
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Gas Chromatography
Quality Control
+ External standard calibration
^Continuing calibration
* Method and instrument blanks
4PE samples
* MS/MSD samples
* Laboratory duplicates
* Surrogate spikes
* Laboratory control samples (LCS)
column confirmation
EPA
GC-38
Notes:
External standard calibration generally consists of a three-point or five-point calibration.
A medium level standard (continuing calibration) is analyzed once a day to check the
response of the instrument compared to the average response of the initial calibration.
Method blanks are analyzed to check for laboratory-induced contamination and
instrument blanks are analyzed to check for contamination induced by the instrument
(usually by sample carryover). Method blanks are especially critical in soil gas analysis
when chlorinated VOCs are target analytes.
Performance evaluation (PE) samples are spiked matrix samples that have certified
concentrations of analytes and that can be purchased from reputable vendors (for
example, Environmental Resource Associates or Absolute Standards). They are usually
analyzed "blind" by the analyst (meaning the analyst does not know what analytes are
present or their concentrations). The analyst must report the proper analytes and
concentrations within the certified concentration ranges for the laboratory's accuracy to
be acceptable. PE samples are normally not analyzed for soil gas or ambient air analysis.
Matrix spike/matrix spike duplicate (MS/MSD) samples are analyzed to check for
extraction efficiency of the analytical system. Percent recoveries are calculated and must
fall within an acceptable range for the extraction efficiency to be acceptable. Percent
recoveries are also compared to each other by calculating relative percent differences
• GC-49 •
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Gas Chromatography
(RPD) to assess the precision of a method. MS/MSDs are not typically run for soil gas or
ambient air analysis.
Laboratory duplicates are analyzed to assess the precision of the method and homogeneity
of the sample. The laboratory duplicates consist of the analysis of two aliquots of the
same sample. The results from the laboratory duplicates are compared to each other
through RPD calculations.
Surrogate spikes are necessary to evaluate the extraction efficiency on a per sample basis.
A surrogate compound is one that is chemically similar to the target compounds but does
not coelute with any of them. A percent recovery of the known spiked concentration is
calculated for each sample and compared to site specific control limits. (Not typically
analyzed in soil gas or ambient air samples.)
Laboratory control samples (LCS) consist of a sample matrix spiked with a known
concentration of standard purchased from a separate vendor other than the one from
which the calibration standards were purchased. The percent recovery for all analytes
must be within an acceptable range for the accuracy of the calibration to be acceptable.
Dual column analysis allows confirmation of the compound identity and concentration of
a compound. This is especially important when MS is not used for confirmation.
. GC-50 •
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Gas Chromatography
Notes:
Level of Data Quality
* Screening or definitive
4- Depends on DQOs and end use of data
*• Depends on level of quality needed, QC can be
added or deleted
&EPA
GC-39
Data quality levels have now been replaced with two categories - screening or definitive.
DQOs are needed before deciding on what QC procedures and data acceptance levels to
use at a particular site.
For additional information on this topic, refer to page A-l at the end of this module.
• GC-51
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Gas Chromatography
Innovations in GC
Pulsed flame-photometric detector
» Similar to conventional flame-photometric
detector
» Uses time gates to select N and S
» Used for chemical agents that contain nitrogen
or sulfur
» Commercially available
EPA
GC-40
Notes:
Like the conventional flame photometric detector (FPD) used for GC analysis, the pulsed-
flame photometric detector (PFPD) uses a continuous hydrogen-air flame for ionization
of species. The ionization generates excited chemiluminescent species that can be
measured photometrically. With the FPD, the sulfur species emission (536 nm) or the
phosphorus species emission (394 nm) can be measured selectively with a narrow-band
interference filter. The newer PFPD can measure the sulfur and phosphorus species
simultaneously with a wide-band optical filter and the addition of the domain of time to
the analysis.
In the PFPD, the pulsed flame produces the individual chemiluminescent species in a
time-dependent manner. Therefore, one or more time gates can be set up in the detector,
signaling the processor to focus on the sulfur and phosphorus emissions, while rejecting
the hydrocarbon interferences.
Methods currently are being developed for detecting chemical agents that contain sulfur
and phosphorus (such as mustard gas, Sarin, and VX). GC/PFPD can be used in
characterizing facilities at which chemical agents were made or in performing emergency
response when the presence of chemical agents is suspected.
The small portable GC is available commercially through the CMS Field Products Group
of OI Analytical.
• GC-52 •
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Gas Chromatography
FM-2000 Field GC with PFPD
The photograph is an example of a portable GC, the FM-2000 Field GC with PFPD.
GC-53 •
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Gas Chromatography
Applications Other Than
Characterization
Monitor stack emissions
Monitor removal action
Monitor remediation treatment
Perform waste characterization
Monitor water treatment
Monitor for health and safety considerations
GC-41
Notes:
In addition to characterization, GC can be used for the following applications:
- Monitor emissions from thermal oxidizers used during on-site remedial actions
using GC and the appropriate detector.
- Rapidly analyze samples generated during remedial or removal actions to help
evaluate the effectiveness of the cleanup.
- Screen samples to characterize a waste. This information can be used to
consolidate a waste stream before profiling.
- Analyze water samples to evaluate the effectiveness of water treatment systems.
- Monitor atmospheres to ensure that environments are safe for workers. For
example, GCs can be used to help establish PPE levels.
GC-54
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
0
I
c
(1
-------
-------
Infrared Spectroscopy
Organic Chemical Characterization
Techniques and Data Interpretation
+ Hand-Held Survey Instruments
^Colorimetric Indicators
* Fluorescence Analyzers
^Immunoassay
4 Gas Chromatography
c=>+ Infrared Spectroscopy
+ Chemical Sensors
* Emerging and Innovative Approaches and
Instruments
+ Hands-on Activity for Organic Analysis
IS-1
IS-1
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Infrared Spectroscopy
Infrared Spectroscopy
*• Established analytical technique
+ Portable instrumentation
+Air monitoring technique
4- Preferred technique
IS-2
Notes:
Infrared Spectroscopy is an established analytical technique that identifies compounds by
fingerprint spectra. A sample's molecular constituents are revealed through their
characteristic frequency-dependent absorption bands. Laboratory infrared (IR)
instruments have been around for many years in fixed laboratory settings.
Recently, manufacturers of the instruments have significantly reduced their overall size
and power requirements to perform field analysis, while increasing their durability.
Types of portable instrumentation include Long Range Gas Monitors, Open Path Infrared
Flammable Gas Detectors and Infrared Ambient Air Monitors, and Long Path Open Path
Fourier Transform Infrared (FTIR) systems.
IR's primary use in the environmental field is for air monitoring for VOCs. Applications
for which IR is suitable include fence-line or site perimeter monitoring, worker exposure
monitoring, emission rate assessment, air impact measurement during emergency
removals, air impact evaluation during remedial actions, vapor suppression technique
evaluation, accidental release early warning systems, and industrial facility monitoring.
In infrared detection, FTIR Spectroscopy is the preferred method. This fact is due to the
multiple, rapid scanning attributes of interferometry.
fS-2
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Infrared Spectroscopy
Fourier Transform Infrared
Spectroscopy
+ History of open-path FTIR
+Theory of open-path FTIR
+ Reported concentrations
IS-3
Notes:
Open-path FTIR was first employed at waste sites in 1990. Its use has grown as the
technology has improved and matured. It has been employed at numerous sites over the
last few years for applications in fugitive industrial emissions, industrial health and safety
monitoring, and indoor air assessments. Recently, manufacturers of FTIR have
reconfigured the systems into high-powered, durable projectors and mirrors for use in
field applications. In October 1996, EPA issued Toxic Compendium Method TO-16
recognizing open-path FTIR as an ambient air monitoring method.
The open-path FTIR system can be likened to a "particle counter" which sums up the
total amount of energy that a target chemical absorbs between the FTIR and the
retroreflector. The FTIR itself cannot distinguish where along the beampath the burden
of the concentration lies, nor can it distinguish between a narrow concentrated plume or a
broad diluted plume that is contained within its beampath. This can be resolved by
combining meteorological data with the FTIR data.
Concentrations reported by these portable IR systems may be reported as either "path
averaged" or "path-integrated." A path-averaged concentration is computed by dividing
the measured amount of the chemical by the path distance. Typically, path-averaged
concentrations are reported in units of ppm or ppb. A path-integrated concentration does
not average the measured chemical over the pathlength and is typically reported as ppm-
meters or ppb-meters. FTIR can provide detection limits in the low ppb range for many
compounds.
IS-3
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Infrared Spectroscopy
Fourier Transform Infrared
Spectroscopy (continued)
+Concept of spectral dispersion
* Components
+ Detectors
» Thermal
» Photon
IS-4
Notes:
Conventional spectrophotometers use a diffraction grating to achieve the spectral
dispersion. Fourier transform optics use the source radiation that passes into a
Michaelson interferometer (which consists of a beam splitter and moving mirror) to
achieve the spectral dispersion. The beam splitter transmits half of the incident radiation
from the source to a moving mirror, the other half is reflected to a stationary mirror. Each
component reflected by the two mirrors returns to the beam splitter. The moving mirror
affects the relative path length of the two beams, thus introducing a phase difference. The
amplitudes of the waves are combined to form an interferogram, and the resulting
encoded beam passes on to the sample compartment and is seen by the detector. By
translating the moving mirror, the spectral range is covered by the range of path
difference reached. The detector signal results in an interferogram consisting of the
complex Fourier transform of the spectrum. A specially written computer program is
used to obtain the spectrum by carrying out an inverse Fourier transformation.
A typical FTIR system consists of an IR source, a Michelson interferometer, a
beamsplitter, a helium-neon laser for beam alignment, a collimating telescope, and a
detector. The pathlength for most systems is about 500 meters. This provides long path
coverage.
There are two classes of detectors used when longer than 1.2 micrometer Cum)
wavelengths are being considered. Otherwise, the same detection methods for ultraviolet
and visible radiation are used.
IS-4
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Infrared Spectroscopy
Thermal Detectors: A physical property of the detector is altered when the infrared
radiation produces heat. The active element is blackened and thermally insulated from its
substrate. These detectors perform at room temperature. Usually within milliseconds
after the radiation ceases, the element returns to the substrate temperature. The triglyceryl
sulphate detector is a common type of pyroelectric detector.
Photon Detectors: With a photon detector, the incident photons interact with a
semiconductor. This interaction results in electrons and holes; the internal photoelectric
effect. Less than 1 microsecond is the usual response time. Cryogenic cooling is
required. Mercuric cadmium telluride detectors are a common detector in this class and
are much more sensitive than pyroelectric detectors.
1S-5
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Infrared Spectroscopy
Fourier Transform Infrared
Spectroscopy (continued)
EPA
IS-5
IS-6
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Infrared Spectroscopy
Typical Daily Routine Activities
4- Premonitoring site assessment
+ Premonitoring equipment setup
4 Premonitoring QA/QC
4 Data collection and reporting
4 Post-monitoring QA/QC
+ Post-monitoring site closure
EPA
IS-6
Notes:
Determine the location(s) of anticipated emission sources. Review weather forecast
information to determine potential for precipitation. If precipitation is unlikely,
determine pollutant transport conditions (wind speed and direction). Determine the
configuration of the source projector and retroreflector
Set up and warm up the FTIR. Document locations of the unit and retroreflecter. Set up
portable computers and set up and check functionality of the meteorological monitoring
system.
Conduct background measurements. Conduct instrument performance checks, using a
target compound to assess accuracy. Prepare cells with a surrogate compound for
demonstration of instrument functionality and precision.
Collect open-path data (usually a 5- or 10-minute data run); run analysis routine and
report target compound concentrations in near-real-time. Emission rates and predicted
receptor or fenceline concentrations may also be reported.
Conduct instrument performance checks using a target compound as a standard.
Download data and analysis results to diskettes.
Secure all equipment on location or move to a secure location.
75-7
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Infrared Spectroscopy
Advantages
+ Over conventional dispersive techniques
» Continuous scans
» High signal to noise ratio
» No slits or gratings
• Over traditional air sampling techniques
» Real time data
» Archived data
» Path-integrated samples
» Compound speciation
» Remote sensing
» Cost effectiveness
&EPA
IS-7
Notes:
Advantages over conventional dispersive techniques
- Consistently scans the infrared spectrum in fractions of a second at moderate
resolution throughout its optical range. Very useful where fast, repetitive
scanning is needed.
Simultaneously measures all wavelengths. Scans are added. The signal is N times
stronger, noise is N112 as great, therefore the signal-to-noise advantage is Nm.
- There are no slits or gratings, thus energy throughput is high and more energy is at
the detector where it is needed most.
Advantages of open path FTIR over traditional air sampling techniques include: (1) real
time data collection and reporting, (2) archived data can be re-analyzed for new
compounds, (3) generation of a path-integrated concentration yields contaminant
information along the entire pathlengths and not just at a single point, (4) compound
speciation of any compound with an IR absorbance, (5) no sample collection, handling, or
preparation is necessary, and (6) cost effectiveness versus multiple discrete sampling
points.
IS-8
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Infrared Spectroscopy
Notes:
Limitations
*• Beam divergence (over 500 meters)
* Atmospheric constituents
4 Misalignments
4 Beam blocks
4 Equipment size
4 Equipment complexity
EPA
IS-8
The minimum detection limits are influenced by factors such as water vapor, pathlength,
and chemical interferences. The signal can be reduced in several ways: due to beam
divergence; through atmospheric absorption due to water and scattering of the IR source
from particulates; misalignment due to operator error, wind, or temperature; and beam
blocks such as pedestrian vehicles and buildings. Because some systems have a
retroreflector composed of beveled gold-plated mirrors, alignment is not as critical as
using flat mirrors. Minor fluctuations in alignment do not affect the instrument
performance.
Another disadvantage of FTIR versus some of the air field screening methods is the
relatively large size of the equipment and in certain applications the need to have an
experienced operator.
fS-9
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
-------
Chemical Sensors
Organic Chemical Characterization
Techniques and Data Interpretation
* Hand-Held Survey Instruments
^Colorimetric Indicators
+ Fluorescence Analyzers
^Immunoassay
+ Gas Chromatography
4 Infrared Spectroscopy
^>* Chemical Sensors
+ Emerging and Innovative Approaches and
Instruments
4- Hands-on Activity for Organic Analysis
EPA
cs-i
CS"-/
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Chemical Sensors
Notes:
Topic Overview
^ Topic Description: Explains the operation and
use of a few types of chemical sensors for field
analysis of organic compounds
4 Technologies
» Surface acoustic wave sensors (SAWS)
» Fiber optic chemical sensors
» Biosensors
4 Applications other than characterization
EPA
CS-2
This section highlights the operational principles of three types of chemical sensors for
field analysis of organic compounds.
The following technologies will be discussed: (1) surface acoustic wave sensors
(SAWS), (2) fiber optic chemical sensors, and (3) biosensors.
This section also discusses applications of chemical sensors other than site
characterization.
CS-2
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Chemical Sensors
Chemical Sensors
Chemical sensor configuration for
Transducers
* Electrodes
* Transistors
* Optical fibers
* Photodiodes
* Thermistors
* Semiconductors
* Piezo devices
* Surface acoustic
wave devices
^ EPA
Electrical Output Signal
t
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t
Physiochemical change
••••^•••^•B
t ^^
c )
t
Molecular or ion recognition
t
Analyte in complex sample matrix
portable monitors
Detection Methods
* Electrochemical
* Optical
* Thermal
• Mass variation
"** Interface
*"* Sensing layer
CS-3
Notes:
There are a variety of chemical sensors. A chemical sensor has been defined as a
transducer which provides direct information about the chemical composition of its
environment. A sensor consists of a physical layer and a chemically selective layer.
Chemical sensors are designed for mass, electrochemical, optical, or thermal sensing.
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Chemical Sensors
SAWS
+ Principle of operation
»Chemical coating
» Change in mass
^Analytes of interest
* Selectivity and sensitivity
EPA
CS-4
Notes:
Individual SAWS respond based on the selectivity of the coating. An individual SAWS
will respond to only one compound if the coating provides selective adsorption of only
one compound.
SAWS have primarily been used to detect gases and VOCs, both halogenated and
nonhalogenated, in the vapor phase. SAWS are small devices that have been used as
detectors on GCs.
Individual SAWS often will respond only to one compound, depending on the coating.
The use of a sensor array provides greatly increased selectivity and reliability over a
single sensor. Single sensors cannot determine if an interfering species is present that
might invalidate the measurement. Sensor arrays offer the possibility of detecting and
quantifying multiple analytes in the same system. Minimum detection limits are about 1
to 10 ppm for typical VOCs and can be reduced to 10 to 100 ppb using a preconcentrator.
These detection limits are high compared to conventional analytical techniques.
CS-4
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Chemical Sensors
SAWS
* Temperature and humidity effects
*• Portable acoustic wave sensor (PAWS) systems
» On-line monitoring of off-gas streams
» Real-time analysis of gas samples
»In situ monitoring
*• Evaluation studies
,8, EPA
CS-5
Notes:
Temperature can have a direct affect on the frequency of oscillation through the
coefficient of thermal expansion of the substrate and it can also affect the acoustic
properties of the chemically sorbent coating. A technique that is often used for
temperature compensation is to use a second sensor, nearly identical to the first, that is
maintained at the same temperature, but not exposed to the target chemical. No coating is
perfectly hydrophobia, therefore, water uptake will always occur. However, this water
uptake results in a sensor response. Even though the device is much less sensitive to
humidity than to VOCs, some response to changes in humidity is observed. The use of
adsorbents can reduce the effects of humidity.
A benchtop portable acoustic wave sensor (PAWS) system is about the size of a shoe box
and has been developed for real-time monitoring of isolated VOCs. Using a notebook
computer, with an easy-to-operate routine, real-time presentation of VOC concentration is
possible. The bench-top PAWS system has been used at the Hanford, Washington site
and the Savannah River, Georgia site in two modes: (1) for detecting residual VOCs
(TCE and carbon tetrachloride) in treated off-gas streams containing high acid
concentrations; and (2) for rapid, real-time monitoring of samples pulled to the surface
from a cone penetrometer probe. Last, a downhole PAWS system with associated
packers has been developed for in situ monitoring of VOCs in vadose zone boreholes
with diameters over 4 inches. The downhole system provided continuous in situ
monitoring of carbon tetrachloride concentrations from 10 to 20,000 ppm.
CS-5
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Chemical Sensors
Results from the PCB in soil demonstration are available on the Clu-in.org site (http//clu-
in.org/publ.htm). At the clu-in.org site, click on Publications & Software and then go to
ETV Site Characterization and Monitoring Technology Pilot: Technology Verification
Statements. Then click on Index of Verification Statements, then PCB Analysis
Technologies, and finally Electronic Sensor Technology 4100 Vapor Detector.
CS-6
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Chemical Sensors
Fiber Optic Chemical Sensors
* Intrinsic FOGS
+ Coating-based sensors
» Core
» Coating
"Refractive index
4 VOCs in water and soil gas
»In situ measurements
» Detection limits
EPA
CS-6
Notes:
Intrinsic fiber optic chemical sensors (FOCS) use the fiber directly as the detector. These
sensors are the types of FOCS discussed in this section. Extrinsic FOCS, which are used
in the environmental field, simply use the fiber as a means to transport light.
Measurement techniques are selected from absorption, refractive index, fluorescence, or
polarization. Many of the FOCS that have been commercially developed and used are
coating-based sensors. An optical fiber is usually made up of two basic parts, the core
with a refractive index, and the cladding with a different refractive index. In a FOCS, a
portion of the cladding is replaced by a proprietary coating, which selectively and
reversibly adsorbs the organic target analytes. The coating adsorbs organics while
repelling water. The interaction between the organic target analytes and the coating
changes the refractive index of the coating. This change in the index alters the amount of
light transmitted to the detector. The resultant loss of light reaching the detector
correlates to the concentration of organics present in the sample.
The FOCS have primarily been developed to measure volatile petroleum constituents
such as BTEX and chlorinated VOCs such as TCE, PCE, and carbon tetrachloride in
water and air or soil gas. The probes have been developed to be placed down monitoring
wells to provide in situ measurements of VOC concentrations in groundwater. The
probes also can detect light or dense nonaqueous phase liquids. In addition, the probes
are being designed to be more durable to allow for advancement down hole, such as with
a cone penetrometer rig, to provide real time VOC measurements in soil gas, soil, and
groundwater. Typical detection limits are around 1 ppm for water. Lower detection
limits are achievable with some modifications.
CS-7
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Chemical Sensors
FOCS - Principle of
Operation
I
&EPA
CS-7
Notes:
This is a representative example of how an intrinsic FOCS operates. The sensing element
in FOCS incorporates a short optical fiber core with a hydrophobic/organophilic chemical
coating. Light is launched into the fiber from a light emitting diode (LED) and detected
at the opposite end by a photodiode. A reference detector monitors the LED output and
compensates for light source fluctuations.
The amount of light transmitted to the detector is dependent upon the difference in the
refractive index of the optical fiber core and the chemical coating.
When the probe is immersed into the water containing VOCs, the VOCs partition into the
organophilic coating and change the effective refractive index of the coating allowing
light to escape. The resultant loss of light reaching the detector correlates to the
concentration of VOCs present.
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Chemical Sensors
FOCS - Advantages and Limitations
Advantages over other kinds of sensors
»In situ determination
» Easy to miniaturize
» Fairly flexible
» Accessibility to difficult locations
» Multielement and nondestructive analysis
Limitations
» Not specific
» Temperature and time dependence
» Number of reversible reactions is limited
» Lower dynamic ranges than electrodes
» Sensor lifetime is limited
EPA
CS-8
Notes:
The way these sensors are designed, they are capable of providing in situ determination
and real-time analyte monitoring. They are easy to miniaturize because optical fibers
have very small diameters. Optical fibers can be bent within certain limits without
damage. They can be used in hazardous places and locations in which access is difficult
because of the ability of optical fibers to transmit optical signals over long distances.
Multielement analysis is possible using various fibers and a single central unit. Optical
fibers can carry more information than electrical cables.
Many FOCS are not compound specific, therefore, they will react to many VOCs and will
give only a concentration for total VOCs. The detection limits are high compared with
conventional analytical methods. These sensors are mainly used to detect gross
contamination. Some of the sensors are temperature and time dependent. A temperature
sensor can be put in the probe containing the FOCS to compensate for temperature
effects. Because the sensor is based on diffusion, the measured concentration may vary
with time that the FOCS is in contact with the target analyte. Therefore, it is critical that
an equilibrium be reached before a measurement is taken. Most readings will stabilize in
5 to 10 minutes. The number of reversible reactions is limited, so in many cases probes
have to be regenerated. They usually have lower dynamic ranges than electrodes. The
sensor lifetime is limited.
CS-9
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Chemical Sensors
FOCS - Example Technologies
4> PetroSense®
^ChemSensor®
+ SMART CABLE
*• Prototypes
&EPA
CS-9
Notes:
The PetroSense® PHA-100 portable hydrocarbon analyzer can provide quantitative data
for petroleum hydrocarbons in water and soil gas. The PHA-100 consists of a portable
instrument with a probe containing the sensor on a 100 foot cable. The PetroSense®
CMS-5000 continuous monitoring system consists of a data acquisition system and 1 to
16 digital hydrocarbon probes. The CMS-5000 can be used for leak detection around
aboveground and underground storage tanks. The cost of the PHA-100 is between $7,000
and $10,000. It can be rented for $100 per day, S300 per week, or $1,000 per month.
The ChemSensor® provides total VOC concentrations in water and soil gas. It consists of
the sensor mounted in a one-inch probe attached to a 100-foot tape. It can be purchased
for $5,000 or rented for $200 per day or $300 per week.
The SMART CABLE contains two different sensors: Type I sensors provide a
recognition signal by irreversibly cutting the fiber; Type II sensors divert the light in a
reversible manner. Type I sensors rely on the swelling and dissolution of polymers to
selectively generate a cutting force. Type II sensors cost $200 per probe.
Prototype (benchtop models) FOCS are currently being developed and experimented with
at such places as Tufts University and many of the national laboratories. A prototype
pocket-sized solid-state optical waveguide chemical sensor (using similar FOCS
technology) to be used as a personal dosimeter to monitor for toxic species has been
developed by FiberChem, Inc. (FCI) and personnel from Bechtel Nevada with funding
from DOE.
CS-10
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Chemical Sensors
Biosensors
4 Components
» Sensing element
» Transducer
+ Detectable analytes
» Organics
»Inorganics
+ Prototype instrumentation
EPA
CS-10
Notes:
Biosensors have been defined as a subgroup of chemical sensors in which a biologically
based mechanism is used for analyte detection. The sensing element is an enzyme,
antibody, deoxyribonucleic acid (DNA), or microorganism. The transducer is an
electrochemical device (measures change in voltage or current), acoustic device
(measures change in frequency as a result of a change in mass bound to the surface of the
device), or optical device (measures change in fluorescence, absorbance, or reflectance).
Examples of detectable organic analytes using biosensors include PCBs, chlorinated
pesticides, organophosphorus pesticides, triazine herbicides, PAHs, phenols, TNT, and
benzene. Examples of detectable inorganic analytes include nitrite, nitrate, and heavy
metals. Biosensors are primarily used to monitor aqueous solutions or air. The
biosensors can serve to monitor for toxicity of compounds in air.
Most of the biosensors have been developed by academic institutions, EPA, DOE, and
DoD entities and are only in a prototype model. Little commercialization has been done
to date.
For additional information on this topic, refer to page A-J at the end of this module.
CS-/J
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Chemical Sensors
Notes:
Applications Other Than
Characterization
* Health and safety monitoring
* Ambient air monitoring around a treatment or
industrial process
+ Monitor removal actions
* Monitor remedial actions
CS-11
Chemical sensors can be used for the following applications other than site
characterization:
- Chemical sensors can be used to monitor atmospheres to ensure safe work
environments.
- Chemical sensors are used in industrial environments as a continuous monitor for
fugitive emissions or to evaluate the effectiveness of treatment.
- Sensors can be used to monitor hazardous material removal actions to evaluate the
effectiveness of the removal process.
- Likewise, sensors can be used to monitor the effectiveness of remediation actions.
CS-I2
Module; Organic Chemical Characterization Techniques and Data Interpretation
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Emerging and Innovative Approaches and Instruments
Organic Chemical Characterization
Techniques and Data Interpretation
• Hand-Held Survey Instruments
• Colorimetric Indicators
• Fluorescence Analyzers
• Immunoassay
• Gas Chromatography
• Infrared Spectroscopy
• Chemical Sensors
• Emerging and Innovative Approaches and
Instruments
• Hands-on Activity for Organic Analysis
OE-1
OE-l
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Emerging and Innovative Approaches and Instruments
Notes:
Topic Overview
+Topic Description: Highlights a few of the more
innovative approaches for field analysis of
organic compounds
* Technologies
» Direct push downhole sensing techniques
» Field portable scanning spectrofluorometer
» Sub-critical water extraction
OE-2
This section highlights some new innovations on existing technologies or innovative
approaches to field analysis of organic compounds.
The following technologies will be discussed: (1) direct push downhole techniques, (2)
field portable scanning spectrofluorometer, and (3) sub-critical water extraction. In many
cases, commercially-available equipment currently cannot be found for these
technologies.
OE-2
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Emerging and Innovative Approaches and Instruments
Direct Push Downhole Sensing
Techniques—Cone Penetrometer Rig
Sensors
* Membrane Organics Monitor (PDPMOM)
+Thermal Desorption for VOCs
»SCAPS Thermal Desorption Sampler Probe
»SCAPS Hydrosparge Sensor Probe
»CPT Dynamic Thermal Desorption (DTD) Probe
»CPTCone Sipper
»Tufts Thermal Extractor-Cone Penetrometer
TECP)
+ Spectral Gamma Probe for gamma radiation
+X-ray Fluorescence (XRF) Probe for metals
EPA
OE-3
Notes:
The Tri-Services SCAPS program is designed to provide DoD with a rapid and cost-
effective means of characterizing subsurface conditions at DoD sites undergoing
installation restoration. DoD has identified four areas of contamination concern:
petroleum, oil, and lubricants (POL); VOCs; heavy metals; and explosives contamination.
The LIF technology for POL detection has already been discussed. This section will
focus on the downhole VOC, explosives, radionuclide, and metal sensor systems.
This SCAPS system consists of the sampling module, or the passive dual planar
membrane organics monitor (PDPMOM), and the analyzer, or the direct sampling ion
trap mass spectrometer (DSITMS). This system was designed primarily to test for VOCs
in the vadose zone. Field tests of this system have been conducted at Dover Air Force
Base. The sampling module can be retrieved or remain as an implant. Subsurface VOC
vapors diffuse through the sampler membrane wall and are transported to the surface for
analysis by direct sampling ion trap or other analytical devices. The PDPMOM may be
operated in a dynamic mode or a static mode.
Several different versions of downhole thermal desorption or sparging devices have been
developed for the determination of VOCs or "lighter" SVOCs in the subsurface (soil and
water). The thermal desorption soil devices use a heated sleeve on the sampling probe to
desorb the VOCs or SVOCs. The analytes are then transferred to the surface for analysis
by ion trap mass spectrometry or high speed gas chromatography (HSGC). Some of these
devices have to stop to collect a sample while others can continuously collect and analyze
while being pushed. The groundwater sparging devices take a few minutes to come to
OE-3
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Emerging and Innovative Approaches and Instruments
equilibrium. The water sample is often sparged with helium gas and the analytes are
transferred to the surface and analyzed as previously described.
* The U.S. Army Corps of Engineers (USAGE) has reengineered a spectral gamma probe
for the detection of gamma emissions in the subsurface while reducing the exposure of
workers. The probe is designed for used with the SCAPS system.
• The USAGE has also reengineered an XRF probe for the detection of metals in the
subsurface. The probe is also designed for use with the SCAPS system.
OE-4
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Emerging and Innovative Approaches and Instruments
Direct Push Downhole Techniques
(continued)
^ Electrochemical Sensors
» Explosives sensor
» Chlorinated volatile organics sensor (RCI sensor)
4 Solvent sensor
» Fiber optic Raman spectroscopy (FORS)
» Surface enhanced Raman spectroscopy (SERS)
^Geoprobe® membrane interface probe (MIP)
OE-4
Notes:
Under the SCAPS program, DoD has experimented with two other downhole sensors.
The first is an explosives sensor. The SCAPS design for the explosives sensor uses a
probe with a heating element that is isolated from direct contact with the soil to vaporize
and decompose explosive compounds into nitrogen-containing gaseous products. The
evolved gases are drawn into the probe through an internal vapor sweep gas stream and
detected using a NO sensor in the probe in concert with a CO sensor. This duo permits
discrimination of organic nitrogen compounds from inorganic compounds such as
fertilizers. The RCI sensor responds to chlorinated organic vapors. A pneumatic system
transports soil vapors through open ports to the RCI sensor in the probe. The RCI sensor
responds to chlorinated vapors at concentrations as low as 1 ppm and has a virtually
unlimited upper range.
A fiber optic cone penetrometer was built to detect subsurface chlorinated solvent
contamination using conventional Raman spectroscopy. It was found that detection of
solvent contamination was difficult due to background fluorescence, soil matrix effects,
and the inherent insensitivity of the Raman technique. Significant enhancements of the
Raman signal were observed with SERS. The SERS active substrate needs to be in direct
contact with the sample. This requires that the sample be brought inside the probe for
analysis, which overcomes matrix effects due to soil type. The SERS substrates can be
modified with coatings to make the surface more selective.
OE-5
Module; Organic Chemical Characterization Techniques and Data Interpretation
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Emerging and Innovative Approaches and Instruments
• Geoprobe® Systems has developed a commercially-available MIP. As the MIP is pushed
into the subsurface, VOCs come into contact with the heated surface of the MIP polymer
membrane. Once the VOCs are sorbed into the membrane, VOC molecules will rapidly
diffuse across the membrane. Nitrogen, helium, or clean air may be used to transport the
VOCs to the surface for analysis by some type of GC detector. The MIP is considered to
be a semiquantitative tool. The MIP can be used in both saturated and unsaturated soils.
Detection limits of approximately 1 mg/L for benzene or 5 mg/L for dissolved phase
chlorinated VOCs can be expected. The MIP has been used extensively at many fuel-
contaminated or UST sites in Kansas.
OE-6
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Emerging and Innovative Approaches and Instruments
Field Portable Scanning
Spectrofluorometer
+ Development - EPA ORD
* Application - petroleum hydrocarbons
* Sample preparation
4-Analysis parameters
4 Screening technique
&EPA
OE-5
Notes:
EPA's Office of Research and Development (ORD), National Exposure Research
Laboratory (NERL), Characterization Research Division in Las Vegas, Nevada (CRD-
LV), has evaluated the performance of a prototype portable scanning ultraviolet-visible
fluorescence instrument as a screening tool.
The field portable scanning Spectrofluorometer (FPSS) can rapidly detect the type and
relative amount of hydrocarbon contamination in soil and water samples.
During the evaluation, soil (2 grams) and water samples were extracted with iso-octane
prior to analysis. About 3.0 mL of extract were transferred into a quart cuvette for
analysis by FPSS.
The extracts were rapidly scanned from 210 to 480 nm in the synchronous fluorescence
mode. Spectra from environmental samples were compared to site-specific standards.
Data on both the type and relative concentration of hydrocarbon contamination were
generated. Synchronous fluorescence spectrometry may offer a fast, cost-effective,
comprehensive alternative to chromatographic methods of analysis.
OE-7
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Emerging and Innovative Approaches and Instruments
Sub-Critical Water Extraction
* Aspects of sub-critical water
* Applications
» Extraction of SVOCs from solids
»Coupled with SPE or SPME
* Advantages
4- Limitations
OE-6
Notes:
Sub-critical water is hot water (50 to 300°C) maintained as a liquid under pressure (5-100
atmospheres).
Depending on the temperature and pressure, sub-critical water has the capacity to extract
polar and nonpolar SVOCs from solid samples. Polar organics such as phenols and
amines extract at 50 to 100°C. More nonpolar organics such as PAHs are difficult to
extract and require temperatures of 200 to 300 °C. Another extension of this extraction is
to use it in conjunction with solid phase extraction (SPE) or solid phase microextraction
(SPME) to adsorb the analytes from the aqueous extract. The SPE or SPME devices may
then be analyzed in the field or sent to a fixed laboratory.
The primary advantage of this method is that it does not use any traditional solvents. It
also has the potential to be a rapid and inexpensive field method.
Limitations of sub-critical water extraction include:
- Requires optimization for the groups of analyte extracted (for example, plenols,
PCBs, PAHs, etc.)
- Not currently field-portable
- Requires experience in setup and extraction
OE-8
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Hands-on Activity
Organic Chemical Characterization
Techniques and Data Interpretation
+ Hand-Held Survey Instruments
^Colorimetric Indicators
* Fluorescence Analyzers
+ Immunoassay
*Gas Chromatography
+ Infrared Spectroscopy
* Chemical Sensors
+ Emerging and Innovative Approaches and
Instruments
£=>• Hands-on Activity for Organic Analysis
EPA
OH-1
OH-I
Module: Organic Chemical Characterization Techniques and Data Interpretation
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-------
Additional Information
Table of Contents
Hand-Held Survey Instruments A-2
Immunoassay A-8
Gas Chromatography A-13
Chemical Sensors A-40
A-I
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Additional Information
Hand-Held Survey Instruments
PID Manufacturers Reference Sheets
These instruments vary in size and capabilities. The following is a general description of each
manufacturer's PID:
Foxboro: TVA 1000 Vapor Analyzer (PID/FID)
Dynamic range PID: 0 to 2,000 ppm
FID: 0 to 50,000 ppm
- Minimum detectable level:
PID: 100 parts per billion (ppb) benzene
FID: 300 ppb hexane
Readout: Bar graph and 4-digit LCD
- Response time: 2 seconds
- Two rechargeable batteries with an operating time of 8 hours
Dimensions: 13.5 x 10.3 x 3.2 inches
- Unit weight: 12 pounds
Rae Systems: MicroRAE®, MiniRAE®, ToxiRAE®
- Dynamic range: 0 to 999.99 ppm with 0.1 ppm resolution
1,000 to 1,999 ppm with 1 ppm resolution
- Response time: less than 3 seconds
- Humidity range: 0 to 100 percent relative humidity (noncondensing)
- Rechargeable lead-acid battery with an operating time of 8 hours (MicroRAE®)
and 10 hours (MiniRAE®). ToxiRAE® has a nickel-cadmium battery or alkaline
battery and operating time is 12 hours
Operating temperature of the ToxiRAE® is 14 ° F to 104 ° F
- Dimensions of the ToxiRAE® are: 6 x 1.75 x 1 inches
- Weight of the ToxiRAE® is 6.4 ounces
- Shipping weight of the MicroRAE® is approximately 12 pounds
HnU: Model 101 PID/Model DL-101-2 with data logger
Model 101 PID
Dynamic range: 0.1 to 2,000 ppm
Linear range: 0.1 to 400 ppm
- Detection limit: 0.1 ppm
Ambient humidity: 0 to 90 percent relative humidity
(noncondensing)
A-2
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Additional Information
Hand-Held Survey Instruments
PID Manufacturers Reference Sheets (continued)
Dimensions:
probe
monitor
Weight:
probe
monitor
2.5 x 11.24 inches
8.25 x 5.25 x 6.5 inches
20 ounces
7 pounds
Model DL-101-2 with data logger
Dynamic range:
Response time:
Ambient humidity:
Power source:
Dimensions:
Unit weight:
Read-out:
0.1 to 2,000 ppm
less than 3 seconds
0 to 95 percent relative humidity (noncondensing)
Rechargeable nickel-cadmium battery with 8-hour
life at 23 °C
8x3x6 inches
7 pounds
LCD display
MSA: Gas Corder PID, Passport PID
Gas Corder PID
Dynamic range: 0.1 to 2,000 ppm
Datalogging memory: 25 kilobytes
Disk drive: 3.5-inch, 1.4 megabyte; RS-232C
Power source: Rechargeable lead-acid (gell-cell) battery with
8-hour life
Dimensions: 17 x 8 x 8 inches
Unit weight: 10 pounds
Passport PID
- Dynamic range:
Response time:
- Humidity range:
- Power source:
0.1 to 500 ppm Isobutylene (minimum detectable
quantity: 0.1 ppm Isobutylene)
less than 3 seconds
0 to 95 percent relative humidity (noncondensing)
Rechargeable nickel-cadmium battery pack with
8-hour life
A-3
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Additional Information
Hand-Held Survey Instruments
PID Manufacturers Reference Sheets (continued)
- Dimensions:
- Unit weight:
Photovac: MicroTip™, Snapshot™
- MicroTip™
- Dynamic range:
- Keyboard:
8x4x4 inches
3 pounds
0.1 to 2,000 ppm Isobutylene equivalent
LCD display; 16-key silicone with tactile feedback
Power source: Sealed lead-acid, field-replaceable pack with 4-hour
life
Datalogging memory: 25 kilobytes
Serial output: RS232 (300 to 19,200 baud)
Audio output: Continuous concentration-modulated tone or tone
on alarm only
Temperature range:
Humidity range:
Dimensions:
Unit weight:
MicroTip
32°Ftol05°F
0 to 100 percent relative humidity (noncondensing)
16.8 x 3.75 x 5.75 inches
6 pounds
Snapshot™
MicroTip HL 5.5 pounds
Dynamic range:
Keyboard:
Power source:
Temperature range:
Humidity range:
Dimensions:
Unit weight:
0.1 to 2,000 ppm Isobutylene equivalent
LCD display; 19-key silicone with tactile feedback
Automatically charges and maintains full charge in
battery pack with operating time of 4 to 6 hours
50°Fto 105°F
0 to 100 percent relative humidity (noncondensing)
14 x 5 x 9 inches
8.3 pounds
Thermo Environmental Instruments, Inc.: OVM 580 PID
Dynamic range:
Minimum detection:
Response time:
0 to 2,000 ppm, resolution to 0.1 ppm; 200 to
2,000 ppm, resolution to I ppm
0.1 ppm benzene in air matrix
2 seconds at 400 milliliters per minute sample flow
A-4
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Additional Information
Hand-Held Survey Instruments
PID Manufacturers Reference Sheets (continued)
Power source:
Dimensions:
Unit weight:
Rechargeable 1.2-volt, lead-acid (gel cell) battery
with operating time of 8 to 10 hours
6.75 x 5.75 x 10 inches
6 pounds
A-5
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Additional Information
Hand-Held Survey Instruments
FID Manufacturers Reference Sheets
These instruments vary in size and capabilities. The following is a general description of each
manufacturer's FID:
Foxboro: TVA 1000 Vapor Analyzer (PID/FID), OVA 128 and OVA 108
TVA 1000 Vapor Analyzer
Dynamic range
PID:
FID:
Minimum detectable level
PID:
FID:
Readout:
Response time:
0 to 2,000 ppm
0 to 50,000 ppm
100 ppb Benzene
300 ppb Hexane
Bar graph and 4-digit LCD
2 seconds
Two rechargeable batteries with an operating time of 8 hours
Dimensions: 13.5 x 10.3 x 3.2 inches
Unit weight: 12 pounds
OVA 128 and OVA 108
- Dynamic range:
OVA 108:
OVA 128:
- Readout:
- Response time:
- Power source:
- Dimensions:
- Unit weight:
Photovac: MiroFID
Dynamic range:
Minimum detectable level:
Readout:
Response time:
Power source:
Dimensions:
Unit weight:
Oto 10,000 ppm
Oto 1,000 ppm
Directly on hand-held probe
2 seconds, 90 percent scale response
Rechargeable lead-acid batteries with an
operating time of 8 hours
12 x 9.3 x 5 inches
12 pounds
0.1 to 50,000 ppm
0.5 ppm Methane
Directly on hand-held probe, LCD
Less than 3 seconds to 90 percent of full
scale
Rechargeable lead-acid batteries with an
operating time of 15 hours
17.1 x 3.85 x 7.4 inches
8.1 pounds
A-6
Module; Organic Chemical Characterization Techniques and Data Interpretation
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Additional information
Hand-Held Survey Instruments
FID Manufacturers Reference Sheets (continued)
• Thermo Environmental Instruments, Inc.: 680 Portable Hydrocarbon Meter
Dynamic range:
Readout:
Power source:
Dimensions:
Unit weight:
Oto 100 ppm
0 to 20,000 ppm
Directly on hand-held probe, LCD
Rechargeable lead-acid batteries with an
operating time of 8 to 10 hours
12.5 x 11.5 x 2.6 inches
11 pounds
Heath Green Machine: DETECTO-PAK® OVD
Dynamic range:
Readout:
Power source:
Dimensions:
Unit weight:
0 to 10,000 ppm
Directly on hand-held probe, meter
Rechargeable nickel-cadmium batteries with
an operating time of 8 to 10 hours
10.5 x 3.75 x 5.75 inches
7 pounds
A-7
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Additional Information
Immunoassay
Antibody Production
• A small mammal (rabbit, guinea pig, mouse) is immunized with the antigen and produces
antibodies of the desired characteristics. The antigen is the target substance that triggers
the response from the mammal in the form of antibodies. One animal can yield enough
antibody-rich serum (antiserum) for hundreds of thousands or millions of tests.
• Some molecules are too small to induce the immune response or be immunogenic. In this
case, the small molecule can be turned into an immunogen by covalently attaching it to a
large carrier macromolecule, such as bovine serum albumin. The small molecule will
now stimulate antibody production when it is injected into the animal. This small
molecule made immunogenic is called a hapten.
• The antibody's affinity for the antigen determines its sensitivity. A specific antibody will
bind primarily to the target and ignore similar compounds. Antibody specificity is
measured in terms of cross reactivity or to what degree the antibody will bind to a
substance other than its target. Specificity is commonly measured by determining how
much of another substance is necessary to create a 50 percent reduction in the assay
response.
• Polyclonal antibodies come directly from animal antisera which contains a mixture of
antibodies with varied specificities and affinities. Polyclonal antibodies recognize several
of a molecule's determinants which tends to make them more sensitive and less specific
than monoclonal antibodies. Monoclonal antibodies are the product of one cell line,
assuring an indefinite supply of uniform reagent and consistency from test to test.
Monoclonal antibodies are more specific than polyclonal antibodies because they usually
bind to just one determinant. However, using a monoclonal antibody can result in cross
reactivity if that determinant is common to other substances.
A-8
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Additional Information
Immunoassay
Comparison Studies
The results of an immunoassay test kit for PCBs in soil were compared to confirmatory
laboratory results using the Contract Laboratory Program (CLP) method for PCBs. The
results of this demonstration have been published by EPA in an ITER, document number
EPA/540/R-95/517.
The immunoassay test kit was calibrated in the semiquantitative mode in two ways:
using three Aroclor 1242 standards (5, 10, and 50 mg/kg) and using one Aroclor 1248
standard (10 mg/kg). When using the Aroclor 1242 calibration, the immunoassay test kit
analyzed 52 samples. When compared to the confirmatory laboratory results, the test kit
produced 28 correct results, 24 false positives, and no false negatives. When using the
Aroclor 1248 calibration, the immunoassay test kit analyzed 94 samples. When
compared to the confirmatory laboratory results, the test kit produced 75 correct results,
19 false positives, and no false negatives. Most semiquantitative test kits are designed to
be conservative, and the results of this demonstration confirmed that fact.
The immunoassay test kit was calibrated with three Aroclor 1242 standards (5, 10, and 50
mg/kg) in the quantitative mode. The immunoassay test kit and confirmatory laboratory
produced detectable PCB results for 89 soil samples. A linear regression analysis was
used to compare the two data sets. The regression line that was calculated had a r of
0.87, a y-intercept of 17.8 mg/kg, and a slope of 0.76. The regression analysis indicated
that there was a good correlation between the two data sets, but that 10 to 20 percent of
soil samples from an investigation would have to be sent off site to correct the results for
a better match to the confirmatory laboratory results. Also, when the quantitative
immunoassay data was plotted against the confirmatory laboratory results using 10 mg/kg
as a critical action level, no false negatives occurred.
The results of three immunoassay test kits for PCP in soil and water were compared to
confirmatory laboratory results using EPA SW-846 methods for PCP. Samples were
collected from two sites to evaluate the effect of two different carrier solvents for PCP:
diesel fuel and a butane-isopropyl ether mixture. The results of this demonstration have
been published by EPA in an ITER, document number EPA/540/R-95/514.
Penta RISc® Test System-This was a semiquantitative test kit that produced results in the
following concentration ranges: (1) below 0.5 mg/kg, (2) between 0.5 and 5 mg/kg,
(3) between 5 and 50 mg/kg, and (4) greater than 50 mg/kg. The comparability study
with the confirmatory laboratory consisted of 114 pairs of data for the soil samples.
Overall, 83 of 114 times, or 73 percent of the time, the immunoassay test kit was correct.
Of the other 31 times, the technology gave 21 false positive results (18 percent) and 10
false negative results (9 percent). All of the false negatives were produced from samples
containing less than 10 mg/kg of PCP. The immunoassay test kit had a higher percentage
A-9
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Additional Information
Immunoassay
Comparison Studies (continued)
of correct results from the soil samples that had diesel fuel as a carrier. In a comparison
of 19 water sample results, the immunoassay test kit produced nine correct results, eight
false positive results, and two false negative results.
• Penta RaPID Assay®-This was a quantitative test kit that used a calibration curve
generated using three standards for soil and water. The linear range for the water samples
is 0.10 to 10.0 micrograms per liter (jUg/L) and 0.10 to 10.0 mg/kg for soil samples. A
regression analysis was conducted on the immunoassay versus confirmatory laboratory
data sets on 90 soil samples collected from the two sites. The regression of the entire data
set produced a r2 of 0.81, a y-intercept of 28 mg/kg and a slope of 0.43. This regression
analysis indicated a good correlation between the two data sets, but the slope indicates
that the immunoassay test kit was underestimating PCP concentrations, especially for
samples that had PCP concentrations greater than 100 mg/kg. This immunoassay test kit
had a higher r2 (0.90) for soil samples with diesel fuel as the PCP carrier than for soil
samples with the butane-isopropyl ether mixture as a carrier, which had a r2 of 0.65. A
regression analysis on 19 water samples produced a r2 of 0.75 between the immunoassay
test kit and the confirmatory laboratory results.
• EnviroGard™ Test Kit-During the demonstration, this test kit was found to produce a
large number of false negative results and poor precision when high concentrations of
PCP were found in a sample. As a result, the manufacturer changed part of the analytical
protocol for the test kit. The revised test kit was never evaluated. This test kit is no
longer commercially-available.
• A quantitative PAH test kit was used to analyze 35 soil samples and 10 water samples. It
was speculated during the use of the immunoassay test kit that the high concentrations of
the straight chain hydrocarbons were causing interferences for the samples. When the
analytical results were received from the confirmatory laboratory, it was discovered that
most of the immunoassay test results were an order of magnitude higher or more than the
immunoassay results producing a high degree of false positives. This occurrence was
most likely due to the interference from the other petroleum constituents.
• A semiquantitative TPH test kit was used to analyze groundwater samples suspected of
containing petroleum contamination. Nearly all the immunoassay results showed no
detectable petroleum contamination in the water samples. However, the confirmatory
laboratory found detectable levels of heavier petroleum products (for example, motor oil)
in most of the water samples. This occurrence produced a high false negative rate for the
immunoassay test kit. The problem was that the TPH immunoassay test kit primarily
responds to the lighter aromatic constituents in the petroleum products which were not
•A-10.
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Additional Information
Immunoassay
Comparison Studies (continued)
present in the heavy petroleum products at this site. This was a good example of the
importance of knowing the contamination prior to the use of an immunoassay test kit.
At the end of fiscal year 1998, EPA anticipates having available for distribution the final
report summarizing the results of a demonstration of Strategic Diagnostics, Inc.'s (SDI)
Ohmicron RaPID assay system for PCB analysis. The demonstration, conducted under
EPA's ETV Program, was designed to detect and measure PCBs in soil and solvent
extracts. The results of the demonstration showed that the system for PCB analysis can
provide useful, cost-effective data for environmental problem-solving and decision-
making. As with any technology solution, the user ultimately must determine whether it
is appropriate for the application and the project DQOs.
A-1I-
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Additional Information
Immunoassay
Inlet/Injection Techniques
• The capillary inlet system is designed for capillary columns. The volume that can be
injected into the column is limited to approximately 2 microliters (/^L) and typically is
used for pesticide and PCB analysis. The system has less column bleed and retention
time shift.
• The packed inlet system is designed mainly for packed, wide-bore columns. However, an
adapter can be used to enable capillary columns to be used. The system is used mainly
for volatile analysis using a headspace extraction technique and allows a larger volume of
gas to be loaded onto the GC for analysis.
• The split technique is the most common. The column flow is split at the injector. The
technique is used for high concentration samples.
• The splitless technique is used for trace level analysis.
• The on-column technique does not involve vaporization, but instead the sample is
deposited directly into the column with a syringe. This technique provides the optimum
in capillary column performance by eliminating discrimination and degradation effects
that can result from using a vaporization technique. The technique is well suited for high
boiling point compounds.
• Packed column injectors that have been converted to accept megabore capillary columns
(0.45 and 0.53 millimeter inner diameter) are very simple and relatively trouble free.
Larger volume injections of up to 6 ,uL can be tolerated.
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Additional Information
Gas Chromatography
History of Chromatography
• The history of Chromatography spans nearly a century. Not only is Chromatography used
in the environmental field, but it is used extensively in the forensic and pharmaceutical
fields. Environmental uses include the analysis of: (1) phenols, (2) phthalates,
(3) petroleum hydrocarbons, (4) BTEX, (5) halogenated VOCs, (6) PAHs, (7) explosives,
(8) dioxins, (9) organochlorine and organophosphorous pesticides, (10) PCBs, and
(11) herbicides.
A-I3-
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Additional Information
Gas Chromatography
GC Interactions — Stationary Phase
\xx\\\x\\\\\
Carrier Gas-
Stationary
Phase
Target Analyte
The stationary phase is a polymer that is coated onto the inner wall of the fused silica
tubing. The thickness, uniformity, and chemical nature of the stationary phase are
extremely important. It is the stationary phase that has the greatest influence on the
separations obtained. The most common capillary stationary phases are silicone
polymers:
R
I
-t-0-Si-]n-
I
R
where
R = CH3 (methyl), or
CH2CH2CH2CN (cyanopropyl), or
CH2CH2C¥j (trifluoropropyl), or
C6H5 (phenyl [benzene ring])
O = oxygen
Si = silica
n = number of silicone groups
The amount of substitution on the polysiloxane backbone distinguishes each phase and its
properties. The phase description refers to the amount and type of substitution on the
polysiloxane backbone. For example, a (5 percent-phenyl)-methyl phase has two phenyl
groups bonded to 2.5 percent, by number, of the silicon atoms: the remaining 97.5
percent of the silicon atoms have methyl groups bonded to them
•A-14.
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Additional Information
Gas Chromatography
GC Interactions — Stationary Phase (continued)
Another widely used stationary phase is polyethylene glycol:
where
HO-[CH2-CH2-O-]nH
H = hydrogen
O = oxygen
C = carbon
n = number of ethylene oxide groups
The major disadvantage to polyethylene glycol phases is their high susceptibility to
structural damage by oxygen at elevated temperatures.
The molecule is held in the stationary phase. It makes numerous trips to the surface
and/or down into the stationary phase. The higher the temperature, the higher the kinetic
energy, and therefore the faster the GC process.
It is the stationary phase that determines the relative retention (elution order) of the
compounds. Focusing only on the column, the stationary phase determines the relative
amount of time required for two compounds to travel through the column. Selectivity can
be thought of as the ability of the stationary phase to differentiate between two
compounds by virtue of a difference in their chemical or physical properties. If there are
no discernible differences between two compounds, then coelution occurs. Stationary
phases and solute factors, such as polarizability, solubility, magnitude of dipoles, and
hydrogen bonding, will influence selectivity. Because of the inexactness of these
characteristics, predictions and precise explanations of solute separations are very
difficult.
Selectively of the column's stationary phase is based on its affinity for compounds with
similar molecular characteristics. For example, a polar stationary film will attack more
polar compounds.
Why does increasing film thickness increase retention time?
A greater film thickness increases the time the molecule travels from the surface to
column wall and back.
A-I5-
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Additional Information
Gas Chromatography
Inlet/Injection Techniques
• The capillary inlet system is designed for capillary columns. The volume that can be
injected into the column is limited to approximately 2 microliters (uL) and typically is
used for pesticide and PCB analysis. The system has less column bleed and retention
time shift.
• The packed inlet system is designed mainly for packed, wide-bore columns. However, an
adapter can be used to enable capillary columns to be used. The system is used mainly
for volatile analysis using a headspace extraction technique and allows a larger volume of
gas to be loaded onto the GC for analysis.
• The split technique is the most common. The column flow is split at the injector. The
technique is used for high concentration samples.
• The splitless technique is used for trace level analysis.
• The on-column technique does not involve vaporization, but instead the sample is
deposited directly into the column with a syringe. This technique provides the optimum
in capillary column performance by eliminating discrimination and degradation effects
that can result from using a vaporization technique. The technique is well suited for high
boiling point compounds.
• Packed column injectors that have been converted to accept megabore capillary columns
(0.45 and 0.53 millimeter inner diameter) are very simple and relatively trouble free.
Larger volume injections of up to 6 //L can be tolerated.
•A-16.
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Additional information
Gas Chromatography
Column Types
Megabore capillary columns are the most common columns used in environmental
analysis. Some of the common capillary columns used for SVOC analysis include:
From J&W Scientific: DB-608, DB-1701, DB-5,DB-1, DB-Dioxin, DB-
TPH, and dual column DB-17/1701P
From Hewlett Packard: HP-5, HP-1, HP-35, HP-1701, HP-608, and HP-
1301
FromRestek: RtX®-50, RtX®-35, dual column RtX®-1701 /MXT®-1701,
and RtX®-2330 (for dioxin), RtX*-5/MXT*-5 dual column
Some of the common capillary columns used for VOC analysis include:
From J&W Scientific: DB-624, DB-VRX, DB-5022, and dual column
DB-624/VRX
From Hewlett Packard: HP-VOC and HP-624
From Restek: RtX-502.2, RtX®-624, and dual column RtX®-624/
MXT®-624
An example of a stainless steel column is RtX®-5, which is an unbreakable fused silica-
lined stainless steel column. The column withstands higher temperatures and is used for
analyzing for alcohols, ketones, and VOCs by purge-and-trap.
A-17-
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Additional Information
Gas Chromatography
Photoionization Detector (PID)
• This figure shows a typical PID housing and associated column connections found in
GCs. A PID uses ultraviolet radiation from lamps with energies ranging from 9.5 to
11.7eV to produce ionization of solute molecules. The ions are collected at a positively
charged electrode and the current is measured. Compounds such as aromatic VOCs and
some chlorinated VOCs whose ionization potentials are lower than the lamp ionizing
energy give a response.
PHOTOIONIZATION DETECTOR
Column
DctKtorEidt
Ion ChamtMr
LampSouro
• A-18.
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Additional Information
Gas Chromatography
Flame lonization Detector (FID)
• Hydrogen is introduced in the tip of the jet, which serves as the flame gas. Typical
hydrogen flow rates associated with FID analysis are approximately 30 milliliters per
minute (mL/min). Zero grade air flow rates are approximately 300-350 rnL/min. A good
balance is needed between the air, hydrogen, and carrier gas to provide a good flame for
ionization.
Inlet
Hj
Inlet
FID Collector
Assembly
Flame lonization Detector (FID)
A-19-
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Additional Information
Gas Chromatography
Electron Capture Detector (ECD)
• An ECD is a very common detector for pesticides, PCBs, and chlorinated volatile
analysis. ECDs have an interior chamber that is plated with 63Ni. For shipment, users are
required to have a license for handling radioactive substances.
• The linearity is < 104
Detector Systems
Electron capture detector (ECD)
Column
Electron Capture Detector (ECD)
•A-20.
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Additional Information
Gas Chromatography
Electrolytic Conductivity Detector (ELCD)
• An electrolytic conductivity detector (ELCD) is a halogen-specific detector that operates
on electrolytical conductivity principles. Organic compounds eluting from GC column
form combustion products as they are mixed with hydrogen gas over a nickel catalyst at
1,000°C in a quartz tube furnace. For example, organic chlorides form hydrochloric acid
(HC1). The HC1 readily ionizes and changes the electrolytic conductivity which is
monitored by the ELCD. The ELCD requires a high degree of maintenance and is a
destructive detector.
HALL DETECTOR
Modified
Union
Teflon TUbe
Column Seal Ring
Connection Retainer
Solvent
Return
Gas Chromatography
A-21'
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Additional Information
Thermal Conductivity Detector (TCD)
• The response of the TCD is dependent upon molecular geometry. The heat transfer from
the hot wire to the walls of the measuring and reference cells of the TCD is affected in the
mobile phase by the molecules of the solute and the carrier gas. A low TCD response is
found when comparing:
- Branched with unbranched aliphatic hydrocarbons
- Cyclic hydrocarbons with open-chain species
- Molecules containing heavy atoms such as mercury, iodine, or bromine
• Either hydrogen or helium is needed as carrier gas. A TCD typically is not used for trace
analysis. Packed columns are used with TCD to increase sample volume, which will
increase sensitivity.
HP 5890 SERIES II TCD Cell
VENT (60 mVmn) VENT (60 mfmm)
Switching Column Switching
Flow 1 (off) Row Row 2 (on)
nwmwl ConductMty Mwtor (TOO)
30 mVirin 30 n*mii 0 ntfirot
Switching Column Switching
flow 1 (on) Row Row 2 (Off)
•A-22.
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Additional Information
Gas Chromatography
Nitrogen - Phosphorus Detector (NPD)
• This figure depicts an NPD. An NPD is suitable for capillary GC and trace analysis. It is
highly specific for nitrogen and phosphorus and its linearity is similar to the FID.
NPD Collector
Assembly
Air Inlet
H 2 Inlet
Nitrogen-Phosphorus Detector (NPD)
A-23-
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Additional Information
Gas Chromatography
Theory of Operation: Headspace Analysis
• The concentration of the analytes in the vial's headspace increases with time until it
reaches a steady state condition known as equilibrium. This phenomenon is known as the
optimum condition.
Equilibrium Curve
A [X]G=0 Equilibrium
Condition
Degradation
AT
Heating Time
[ X ]= Concentration of analyte in gas phase of headspace
AT = Change in heating time
A [ X] Q= Change in concentration of [ X ] G
This is an example of a sample that exhibits increasing concentrations of an analyte over
time, without reaching equilibrium.
Non-Equilibrating Sample
[X]G
Heating Time
[ X ]= Concentration of analyte in gas phase of headspace
AT = Change in heating time
A [ X] = Change in concentration of [ X ]
•A-24.
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Additional Information
Gas Chromatography
Headspace Analysis: Other Equipment
• Analytical instrumentation
• Laboratory equipment
Solvents for standard preparation (pesticide-grade hexane and/or purge and trap-
grade methanol)
Certified standards
Weight balance (accurate to 0.01 g) for weighing soil samples
Disposal pipettes (1, 10, and/or 25 mL)
Drummond micropippetes (10, 50, and 100 ^L)
- Hamilton syringe 10 ^L
- Headspace sample vials, caps, and septa
- Clean matrix for standard analysis
A-25-
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Additional Information
Gas Chromatography
Theory of Operation: Purge and Trap
Notes:
• Helium is bubbled through the solution at ambient temperature and the volatiles are
transferred from the matrix to the vapor phase. The volatiles are then swept through the
sorbent column where they are trapped. Then, the sorbent column is heated and
backflushed with helium gas to desorb the components. The components are then
transferred to a GC via a heated line, where they are separated using the appropriate
column and detected using a mass spectrometer. Typically 5 mL are used for water
analysis and 5 grams are used for soil and sediment analysis.
• Packing materials include: (1) 2,6-diphenylene oxide polymer, (2) methyl silicone
packing, (3) silica gel, or (4) coconut charcoal.
• The following graphic is the Tekmar purge and trap, a type of purge vessel.
Trailer Line To GC.
H«at«IVjUeQw»
.A-26.
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Additional Information
Gas Chromatography
Theory of Operation: Purge and Trap (continued)
• The following graphic is a purge vessel
optional Focm Trap
lnt*l t /4 in O, D
wtwi 11* MI O O
ntol V* in O D
10 on H i 4 ""f O
The following graphic depicts trap schematics.
Racking Detail
Construction Detail
1 S ctn Tomax OC
' 1 ern 33t OV-1
— Trap Into*
4-27-
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Additional Information
Gas Chromatography
Headspace Analysis: Advantages
• If low VOC concentrations (ppb levels) are encountered, the only solvent use is for
preparation of standards and QC solutions. If high VOC concentrations (ppm levels) are
encountered in soil, methanol is needed for the methanol-flood sample preparation.
Minimal solvent use is critical in the field because of the difficulty of disposing of the
used solvent.
• Sample preparation often times merely consists of weighing the headspace vial with the
sample and adding surrogate solution to the sample. This requires less than 5 minutes per
sample.
• Automated headspace samplers are less expensive to purchase or rent than purge-and-trap
systems.
• Static headspace results have been shown to be comparable to purge-and-trap results for
most VOCs as demonstrated in the Hewitt et al. (1992), paper at the back of this module.
• Automated headspace samplers require little counter space and require little maintenance.
There is also no glassware cleaning or decontamination associated with these systems.
• Fifty samples can easily be analyzed in one day using static headspace extraction. The
low cost, rapid turnaround times, and simple sample preparation make headspace analysis
an attractive method for field analysis.
-A-28.
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Additional Information
Gas Chromatography
Headspace Analysis: Limitations
• Positive analyte identification is not possible unless a dual column or mass spectrometer
is used.
• A steady state equilibrium is reached where the concentration in the headspace is equal to
the concentration in the matrix. However, with a saturated sample, the equilibrium is not
reached.
• Extraction efficiency may be poor from soil samples that contain a high amount of clay or
organic matter.
• Samples with high concentrations of chlorinated VOCs can lead to contamination of the
internal valving system of the headspace autosampler. This can cause carry-over
problems between samples.
• If the crimp-top cap of the headspace vial is not properly crimped on, VOC loss can occur
from around the cap, especially during heating of the vial.
,4-29-
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Additional Information
Gas Chromatography
Purge and Trap: Limitations
The main limitations are the sample preparation, cost, and high maintenance
requirements.
Because samples must be weighed (or measured) into a separate purge vessel, it is more
time-costly than head-space.
Cleaning of glassware often is required with purge and trap while not required for
headspace apparatus.
Purchase costs for an automated purge and trap apparatus may be up to $5,000 greater
than an automated headspace system. There is additional labor cost associated with
operation and maintenance of a purge and trap apparatus.
Purge and trap systems require more plumbing, gases, and more space than headspace
units.
•A-30.
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Additional Information
Gas Chromatography
Comparison of Headspace and Purge and Trap Technologies
• The data for the water comparison is shown in the table on page GC-38. The RPD values
range from 0 to 46 percent. No false negatives were reported by the on-site laboratory.
RPD is calculated by dividing the difference in the results by their average. It is reported
as an absolute value.
• The figure on page GC-39 shows the affect of Henry's Law when high concentration
samples are analyzed by headspace. The headspace/GC values are lower than those from
purge and trap/GC/mass spectrometry. All other figures show good correlation between
the two methods.
A-3I-
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Additional Information
Gas Chromatography
VOC RPD COMPARISON FOR WATER ANALYSIS
Compound
Chloroform
Chloroform
Chloroform
Chloroform
Chloroform
Chloroform
Chloroform
Dibromochloromethane
Dibromochloromethane
Bromoform
Bromoform
Bromodichloromethane
On-site Results
fetfL)
1.3
1.2
ND
1.9
125.0
8.8
7.0
2.6
2.3
23
27.4
20.9
Confirmatory
Laboratory Result
(Mg/L)
1.2
1.5
ND
1.9
200
8.8
ND
1.9
1.8
21
20
27
RPD (%)
8
22
Not calculated
0
46
0
False positive
31
24
9
31
25.5
• A-32.
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Additional Information
Gas Chromatography
Solvent Extraction
• Separatory funnel liquid-liquid extraction (SW-846 method 35 IOC)
— Water matrix only
- Extraction time is approximately two to three hours
• Typically one liter of a water sample at a specific pH is serially extracted with methylene
chloride using a separately funnel. The extract is then dried, concentrated using nitrogen
blowdown, and exchanged into an appropriate solvent.
Continuous liquid-liquid extraction (SW-846 method 3520C)
- Water matrix
- Extraction time is approximately 18 to 24 hours
• Continuous liquid-liquid extraction is a more intense extraction technique but the time
required is considerably longer.
Soxhlet extraction (SW-846 method 3540C)
- Soil and sediment or waste
- Extraction time is approximately 16 to 24 hours
• Typically, 10 grams of solid sample is mixed with anhydrous sodium sulfate and
extracted using a soxhlet extractor. The extract is then dried, concentrated, and
transferred into an appropriate solvent for analysis.
* Automated soxhlet extraction (SW-846 method 3541)
- Soil and sediment or waste
• An automated soxhlet typically reduces extraction time by a factor of 4 to 10 and
decreases the amount of solvent.
O.I. Analytic (Soxtheim®)
- Tecator, Perstorp Analytical Inc. (Soxtec®)
• The automated soxhlet is used for pesticides, PCBs, and PAHs.
A-33-
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Additional Information
Gas Chromatography
Accelerated Solvent Extractor f ASE) Device
The graphic depicts Dionex's ASE™ 200.
ASE ' 200
ACCELERATED
SOLVHN'l EXIKACTOK
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Additional Information
Gas Chromatography
Solid Phase Extraction (SPE)
SPE Process
- Select packing which will absorb compounds of interest
- Select solvent which will elute compounds of interest, but not contaminants
- Sample may require pH adjustment
- Retain compounds of interest on the packing
- Elute the contaminants
- Elute the compounds of" interest
• Typically, 15 mL of a water sample are extracted using a specific SPE cartridge for the
analytes of interest. The cartridges contain silica gel-based, bonded phase packings.
Solutions are passed through these tubes by using either vacuum or positive pressure.
Samples can be prepared cither for HPLC or GC.
• For a solid phase extractor, first, condition the tube to activate the tubing. Condition
solvents depend on the tube packing. Next, add aliquot of sample and wash. Rinse the
packing with a small volume (usually 2(X) /uL to 2 mL) of a solution that removes the
compounds of interest.
• Column types and suppliers
Extract-Clean™ by Alltech Associates, Inc.
- B&J Solid Phase System by Burdick & Jackson, Division of Baxter
Accuband® by J & W Scientific
BAKERBOND SPE by J.T. Baker, Inc.
- Supelclean by Supclco, Inc.
- Bond-Elut® by Varian Sample Preparation Products
- Clean Screen'* by Worldwide Monitoring
• There are numerous manufacturers of SPE cartridges and supplies. The target compound
must be known to select the appropriate cartridge.
• Extraction time equals approximately 1 to 2 minutes per step
• Used for extraction of pesticides, PCBs, explosives, triazine herbicides, hydrocarbons,
phthalate esters, and phenols
A-35-
Module: Organic Chemical Characterization Techniques and Data Interpretation
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Additional Information
Gas Chromatography
Solid Phase Extraction Principles
Solid phase extraction utilizes the same analyte/sorbent interactions that are exploited in ihe powerful separation technique of high
performance liquid Chromatography (HPLC). Bond Elut extraction cartridges are packed with a variety of surface-modified
bonded silica sorbents which selectively retain specific classes of chemical compounds from a given matrix. As an example, the
Bond Elut strong cation exchanger (SCX) can be used to retain the cationic drug, amphetamine, from urine. The more specific the
interaction between the sorbent and analyte, the cleaner the Final extract.
Bonded silica sorbents are in many ways the ideal materials for chromatographic isolation, primarily due to the number of
different functional groups that can be readily bonded lo the silica surface. In addition, bonded silicas are rigid supports that do
not shrink or swell; possess very large surface areas due to porosity; are stable under a wide range of aqueous and organic solvent
conditions; and form a clean, non-leachable substrate upon which the bonded functional groups arc attached.
Solid phase extraction consists of four basic steps
The most common goals of an extraction protocol are clean-up, concentrate, and solvent exchange (e.g., aqueous to organic) prior
to analysis. Solid phase extraction achieves these goals in four simple steps. They are:
Conditioning: Preparing the cartridge for
reproducible interaction with the sample
matrix by solvating the sorbent bed. This is
done by passing a volume of an appropriate
solvent through the cartridge, followed by a
volume of a liquid similar in nature to the
sample matrix. A common example of
cartridge conditioning would be to pass
methanol. followed by water, through a Cl 8
cartridge prior to extraction of an aqueous
sample matrix,
Retention: Applying the sample to the
conditioned cartridge results in the analyle.
and perhaps other matrix components, being
retained on the sorbent surface due to one or
more specific chemical interactions (e.g.
Van der Waals or "non-polar" interactions
between the hydrocarbon chain of a C18
bonded phase). It should be pointed out that
the matrix contaminants may pass through
the cartridge unretained, hence cleaning up
the sample even at the retention or loading
step.
Rinsing: Passing solvents through the
cartridge rinses away additional interfering
compounds while leaving the analyte
undisturbed within the sorbent bed. A
common rinse solvent for a non-polar
extraction on a C18 sorbent would be water.
Elution: Passing an appropriate solvent
through the cartridge which is specifically
chosen to disrupt the analyte-sorbent
interaction, resulting in selective elution of
the analyte. To use a non-polar extraction
example again, an organic solvent such as
methanol would be a sufficiently strong
solvent to disrupt the interaction between
most non-polar analytes and a Cl 8 bonded
phase.
Jl
V
V
CONDITIONING
Conditioning the sorbent prior to sample
application ensures reproducible retention
at the compound d interest (the isolate).
^
components
J
V
V
I
V
V
V
RINSE
A Rinse the columns to remove undesired
matrix components
ELtmON
•Undesired components remain
•Purified and concentrated isolate read)
lor analysis
Principles of solid phase extraction
Source: Varian Sample Preparation Catalog, 1996
• A-36.
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Additional Information
Thermal Desorption
Gas Chromatography
Desorption can be achieved using solvents such as hexane, trichlorethylene, carbon
disulphide, and chloroform. The resulting aliquot is analyzed by GC. For example,
Perkin-Elmer has an automatic thermal desorption instrument, the ATD50, which can
analyze up to 50 sample tubes in a run. Sampling may be done by pumped or diffusive
sampling of volatiles from gas, liquid, or solid samples; direct analysis of solid samples;
or direct adsorption of liquid samples placed in a sample tube. These tubes are then
placed in a desorption oven where thermal desorption is carried out either by a single or
two-stage process. The vapors are passed directly onto the column in the single stage
method, whereas in the latter process, the desorbed vapors are collected in an electrically
cooled trap and concentrated.
A-37-
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Additional Information
Gas Chromatography
Supercritical Fluid Theory
100
80
.Q
"o.
60
40
20
*!
t40°LC Fluid extr
l7kbar SFC
CP
?
Liquid
Extr.
,'£ High ^
Pressure
GC
Tr
\
GC
-50
0
+50
Carbon dioxide is the most frequently used supercritical solvent. The critical point of
carbon dioxide is (304.21 Kevin, 73.825 bar, 0.466 grams per centimeter cubed) the point
at which the vapor pressure and temperature are such that the solvent is in both the liquid
and gas phase. At this point, the vapor density and the liquid density are equal. At any
temperature above the critical point only one phase exists, the supercritical phase.
Supercritical fluid extraction (SFE) process
- Process by which a fluid phase having intermediate properties between a gas and a
liquid affects the solubilities of solutes
- Supercritical fluid solvents have lower viscosities and higher diffusivities, which
allows a more efficient transfer of solutes from sample matrices
-A-38.
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Additional Information
Gas Chromatography
Supercritical Fluid Theory (continued)
- The solubility of fluids can be adjusted by mechanical compression of the
extraction fluid
- Allows extraction at lower temperatures, which could be advantageous for
temperature sensitive compounds that break down
Solubility of fluids can be adjusted. Lower extraction temperatures could lead to less
breakdown of temperature sensitive compounds.
Possible supercritical solvents
- Ethylene, carbon dioxide, nitrous oxide, propane, methanol, water, ammonia,
n-pentane
A disadvantage of this method is that it is specific to each group of analytes and it
requires tremendous method development.
The reference, "Changing Role of Extraction in Preparation of Solid Samples" is included
in your manual at the end of this module.
A-39-
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Additional Information
Chemical Sensors
Bioluminescence
Used as a rapid bioassay that determines toxicity to a specific strain of microorganism.
Specific luminescent microorganisms emit light as a normal consequence of respiration.
Chemicals which are toxic to the bacteria cause a reduction in light output proportional to
the strength of the toxin.
There are three products marketed by Azur Environmental called Microtox Acute
Toxicity Test, Microtox Chronic Toxicity Test, and Mutatox. Mutatox tests for detection
of mutagenicity and genotoxicity. The Mutatox test is based on chemicals which cause
genetic damage that, in turn, cause the induction of light output in an otherwise dark
strain of bacteria. The Microtox tests have the same limitation which afflicts all bioassay
techniques — the toxicity, mutagenicity, or genotoxicity can be measured, but the nature
of the contaminant must still be determined by chemical analysis.
The system consists of two parts: the microorganism reagent and a luminometer. The
reagent is lyophilized microorganisms. The reagent is consistent in its response to toxic
materials and can be stored up to 18 months in a freezer before use. The luminometer is
rugged and weighs under 30 pounds. A computer is often linked to the luminometer to
provide processing and storage capabilities.
The reagent is activated with reconstitution solution. The reagent is then added to a
serially diluted sample and growth media series. In the acute toxicity test, light is
measured after 5 and 15 minutes. For the chronic test, the growth media is incubated for
24 hours at 27 °C and the light levels are measured. The chronic test is 100 times more
sensitive than the acute test. The acute test can easily screen thirty samples per hour and
develop full dose-response data on three samples per hour. The American Society for
Testing and Materials (ASTM) uses Microtox in standard D5660-95 for water and soil.
The Water Environment Federation has included Microtox as a method in "Standard
Methods for the Examination of Water and Wastewater," 19th Edition, under section
8550.
•A-40.
Module: Organic Chemical Characterization Techniques and Data Interpretation
-------
Analysis of Volatile Organic
Compounds in
Soil Using Static Headspace
Extraction
Greg O'Neil, TVoomy Cappel
Paul Kester & Denise Sherman
Tekmar
P.O. Box 459576
Cincinnati, OH 45242-9576
-------
-------
ABSTRACT
Soil analysis poses unique analytical challenges due to the wide
variability of the matrix. Use of static headspace analysis allows the
analyst to control sample to sample matrix variations. This paper
describes analytical considerations for successful quantitative
analysis of volatile organic compounds in soil.
-------
-------
Thae is a need to develop a better analytical mttbod to d» analysis o^
study isolates Ac problems associated with soils analysis. Tliese difficulties can be overc^^
italic headspace techniques.
Currently. soils analysis it performed with purge and trap/gat cbromatogntphy. There are fundamental
differences between purge and trap and stalk headspace. Purge and trap is a continuous gas extraction
where an exhaustive purge of the sample transfers me analyst lh>m*e»anjple»flietr;ap,wlrichisthen
desorbed to the OC column. Quaniitatioa is based on recovery of internal standards, as is typical within
EPA methods as shown in equation 1:
tfwp vnhm^ of |hp nmffix pf»»*e *n the viaL When 1C ia very small die phase ratio
becomes extremely important When K is large the phase ratio is relatively unimportant
In static headspacc, die sample Is placed in a vial and sealed with a teflon-faced septum, and a crimp
cap. The vial is placed in the heated zone of me 7000 and alkwed » equilibiate over tirne. The vial is
slightly ovoprcsaurizEd with pressurizatioa gas, typically heQnrn, to the vUL The sample loop is then
-------
fiBed by opening a vent valve ^w
controll
sample through, die loop, filing At loop. Sample loop
Pressure Regulator (VIPR), set to t value appmarimatdy than the vial pr
This increase in pressure
exerts backpressure in the loop, compressing toe sample during loop fill. The contents of the loop are
then swept into the GC injection port
Rguiel shows the pnx*sscfequiHbrating a two-phase ia^
concentration in the gas phase (CJ increases over time untfl equilibrium i* readied, n^resented by the
flat portion of the curve. This is where the rate of the analytes leaving the sample equals the cate of die
analytes reentering ihe sample, giving maximnxn sensitivity and precisioaAder some point la dine a
toss of response through degradation wiU occur. This degradation is a result of a combination of factors:
thermal degradation, leaks fiom the septum, and ad$orptk» of analyst »rfwseptnm and watt* of the
vial
FTgurel
icl
.f
HEATING TIME
iawc i snows a senes CT pi
vei> low partition coeffitia
imaoncoeniaenaior various anaiytes. inese are literature vaioes snowing
Ms for aDtanes, okfins, and aromatics, and much higher partition coefficieiAB
Tahiti
PARTTION COEFFICIENTS FOR CLASSES OF
ORGANICS IN WATER AT 50°C
PARAFFINS: K ALCOHOLS: K
HcnM XJ15 RtlmnMl 1150
ffcf<6 <011 a~ftopsflol 770
OLEFIN5: ALDEHYDES;
Btneae-l J093 AccoMohyi* 99
JnBDIBQDH& JUHp AQFODBIDOsUQBDyiilC O9
tiepaut-l J090 a-B^jnldeftytte 44
AROMAT1CS: KSTONB5:
.ftiiiiiffj i5 Aoccouc 190
«•»_•_ A 4 mgf-iitl-A-l7l-, , jf^ ^ , ,„ _ * sg A
EuKDEDO jff-1 1 JDO^DTZWiyaABBDQD iJ^
_ ^^ * - - « a ^j>— .^ — i_-.v ji _. -^. — * •
(rxywEQK 1^9 jpcoiyjeiiiyiuKioB 11
-------
for polar compounds, such as ketooes, aldeiryties, and a!cofao&
it:
Eq.3
Where
cbe partition coefficient
Ac concentration of the sample matriy
the concentration of the gas phase
For sensitivity reasons, a large anatyte concentration in the gas phase is desired. As that concentration
increases, the partition coefficient becomes very small TOcrefore, the tower the paitbkxi coefficient the
easier it U to get toe analyte into the gas phase and analyze by static headspace.
For polar compounds, such u alcohols, it is a typical anatytiad procedure to add salt to change the
partition coefficient to a small value* driving the anarytc into the hcadspace- This technique is called
"salting out". In the homologous series of the alcohols, as the aliphatic character of the alcohol
the partition coefficient decreases.
EXPERIMENTAL
This work was performed with a Tekmar 7000/7O50Headsp«ce Autosamplcr equipped with a CC/FID.
Experimental parameters appear u Tables 2 and 3.
The soil samples were weighed into a 22tnl vial to which a matrix modifying solution and internal
Table 2
7000/7058 SOILS PARAMETERS
Static Equffibraifan Study
VJJML:
Loop Six:
Sample Size
PMICD Ttjnpctuuit!
PfateiBquflttocjoo:
2ml
YaflSoo:
Mix:
MbcFbwo:
S b^tttv:
PtUKxizc Time:
lYeauri Bqofl;
Loop Fin:
[jMpKfl*°**
Omb.
10 mm.-160 mia. in 10 mia.
73. Suit
OFF
OFF
OFF
OFF
OflSrato.
0.10 mia.
OOS
VaN* TbmporatBn
Line Tempottore:
L^ectknpervaL
«S"C
Tabte3
GC CONDITIONS
SoHs VQC Analjsb liy Headspace Extraction
Carrier Gas:
GC
CobaM:
Ftaae iuatatioo Detectoi
IBID 0>x 3.0 odf
nmi Tfctnporatw
u^BCtnyi TcoytntnK;
Detector Tempatatare
-------
The «lt dwscffl «l»aM not be » ctki^
can
relume
TIM
Figure 2B.
EquiKbratfon Times in Water
withMbdng
• l. c. 4-lricJilir«Mnz«n«
i • *
f^ « *
-------
QPTOMDC involves muting the sample by tapping the vial with t auxin f tod from the outside. The
sample tombktm the vM so analyteiinofe
extraction to occur.
Table 4 shows that area counts are increased and USD values are improved with mixing. These
improved raniltc occur doa in minim^r^ Thermal ficpPSWE time.
T«We4
REPfwucraiLrrY OF AROMATXCS IN WATER
Totocae
B*r
O-Xyfeue
326
336
353
32*
213
225
Tffl
SB
18
20
18
13
11
13
9
RSD
52
44
52
5.6
372
411
472
400
220
255
225
52
5
4
8
7
5
5
6
RSD
U
IJ)
1.7
U
11
Zl
Standardization of the instrument was performed using the fpffl evaporation technique (EET) to produce
a gas phase standard for which response factors are generated. This wax created by injecting 1-20
ffiicrolitcn of a liquid phase nxthanolic standard into a neadspace vial, followed by hcttiflg the vial ID
85°C. On a daily basis a tail evaporation check standard was ran to ensure that the instrument was not
drifting, and results had to be within 20% of initial values from the beginning of the study in order to
continue operation. The standard used was an Accu Standard 302.2A standard. The internal standards/
surrogates used for quantitation were dibroroofloaromethane, tohiene-dS, and bromofluorobenzene.
A soil sample was placed in a vial, along with a matrix modifying solution that is equilibcated over time
(Fig. 3A). This curve was completely unlike that observed for an aqueous sample in Figure 1. Upon
initial heating there was a rapid rise in the concentration of the hgadspaCTS followed by a rapid loss, and
Figure 3 A
Total C^vs Equilibration Tfane •
No Mix thne/VariabJe equffibratioii times
-------
tbea « voy unstable hnuontal path along the plot, not really approaching equilibrium. The total $a
eqoiHbnttkio tin* wwU hours. Miring the sample
hour tf evidenced by * marc horizontal path ak^ tbe plot (R^ 3BX However, there was still a
ngstficam difference in the appearance of tbt«qoitbr«lk»curv«ob8avediiifigw«l.TT» rapid ilae
followed by the rapid fall was attributed to die tfaree-phaaesyttcmooncaioodiiitheviat
Figure 3B
Target Compounds 1-3 v* Mixing Time
19 U It If JO jl
Time
Ibmp.
Mixing
Time
lenip.
Mixing
Spike
Diffusion
Spike
Adsorption
Spike at
Equilibrium
Initially the analytes qpiked into dte soil pgztitiooed into the liquid phase of the matrix modifying
solution, cabficqacady analytes paithioaed also into ^head^ac^ There was a T»pid low of tbeaoalyte
fiom the spiko on the ncftce of tbe soil nmpto. The mil w«i tvoken op wWnntbdBf.inc«eaainf I»
fafl evipantioa technique. Use of internal standards in tMf fastoOT proA»«d reliable, qoafldtativc,
reproducible resuhs across the entire range of USEPA Mcth^M^lftnalytc^Furiticr^ these ictemal
standard* wwe added prior to headspaee cxtractk
SOIL MATRIX VARIATIONS
The mote yjg
fp with analyzing sofl aampld i»thc large number of variable* involved.
Seven have been identified. Bach soil sample em ht»e t wide nngc of conditions widun each of
the variable*. Therefore soils can have a large number of pomutationia^ combinations of
The first condition is ionic strength. Salt content of a sofl changes the partition coefficient, primarily of
polar compounds. Theirforewthu partition cocfbVaeirtdu^
headfp*« changes. Inocdatocontiolthisatr^ctcf theanalysii,atttuiatedsa^
-------
the sample to control its ionic xtrentgth, mating it ccflstantfivead) of the sample to be analyzed.
The accood variable is Ac pR the pH is adjusted low to prevent dc&y^^
spontaneously at 85^ within a sampte Tnc inatrix notifying solution
forces the pH to remain at 2 to prevail defaydiohalogenatkro reactions. These reactions are the loss of
nydiochloric acid across a chkviiuucdalkWtofonnahalogeitatedalkene.
The thixdavriagbfe is biotogical activity. Biological activity within the sample can cause degradation of
anaiyies during the storage time. Sanmk«arcreqnired»beirjaintainedataieinperatBirof4^ the
icwaingofthepHtoZactsasapmemnve. Sah content of the nMirknx)difying solution also acts »
inhibU biologic*! activity by kffling bacteria.
The foonh variable fc moisture. Samples vtiy in moisture content as they come in from the field. The
way to compensate far this 1» so drive die cancentratkm of water m the sanmle to remain constant by
The sample and headspace go to a consistent
coocemratioQ of water due 10 maintaining a constant irapcnitoiv within the san^de and
The fifth variable » sample lurfacc area. Satcjrfcs have a variety of smface areas, depending on their
composition. Some may be citmaped^whifcciAeninay be very fine paniculate. By mixing, the sample
is brotan apart, iocreasing the surface area. TMi can be achieved by mixing within the instrument and/
or pro-sonicating the sample. Dnving the samples toward constant surf ace area reduces the avenge
distance an analyte traveU to be extracted from die sample. Thii nnprova extraction efficiency and
reproducibdlity.
The sixth vaiiabk panuoeter i«
phase ratio. A highly dense
leaving an exttonely large hi*n
fuch as a sandy toil, occupies a very small votome within the vial,
An equal maw of a low density soil, such at top aoti, occupies a
large volume widuo die vial, with a comparatively small volume of headrace. If an atudyte has a very
low partition coefficient, this variation in phase ratio between soil densities becomes extremely
important Therefore, different result* for noa-pol8jc«gamc» in soU samples can be obUined if phase
ratios are not controlled. The addition of the matrix modifying solution brings the samples to a more
constant phase ratio. The effect of density types of soils wiA and withmn a matrix inodifvug solution is
shown as Table 5. Without a matrix modifying solution there is an 8-foU difference in the phase ratia
Table 5
EFFECTS OF MATRIX MODIFICATION/PRESERVATIVE
SOLUTION VOLUME ON PHASE RATIO
2g evil in
Soflonty
Soil* Solution
TopBoU(0.4SglAal)
446
19.20
33.00
•Changes 8x
056
1J03
1.11
-------
By adding «n equal volume of the nuttrix
to each cample, in this (aue 10ml, only a 2-
foW change in fee phase xitio occon between high. tod few density soil sunptei.
The last variable which affects soil sample* rcwlttiidwoc^nfcaxucniof thcsan^.Humic
materials, sogh as top ^te«l to be vwyadsorpttete
whkhireiiioiganfcaadl&fidntt
roneeaintk»sctfaaaly«eswDaU(to
login** the extnxrioa ability of tte
its sotvating strength, removing die volatile o^ttkafmn the soil ittelf. Once the analytesvc in ifae
liquid phase fcey tee easfly partitioned into the gas phase.
Figure 4 shows the effects of ibe soil manic typt on pattitk>iing.Tb* sandy seal sboro at the boom of
the figure shows the best response far all analyses. The middfectaon*aogrm is the clay soft, which
sJxrwa somewhat cimflar recoveries ahhooglt not qoitt as food at the higher inoJenilarii^bt>,sodi as
oaphthaleoe and hexachlocobotadicne. 11»e top aoQ Aon&tttm^towretavatoBXwtetaafa
of •MlytM dna m it* aAtorpnm natntu TVt nwdrftrftiy ftffpf fff ^^ ffftlKff Ifhfd Wit1"** tV *TMft»*
modiiying solution is 10 select tbe appropriate organic inxfilier. Once selected, the oooditions for an
sample matrices wiH be driven to equivalency ppqriTiflz in reliable datff from any sample type.
Effect of Soil Matrix Type Upon Partitioning
-------
There arc »evea verifies wtoft have been idrati^
of ioflsaot?lei.Tbe»e variables OCOT io
for soQ samples. Uaeof s matrix modifying »lutk» combined with hottodniijdBg/ic^
thecoodilkiiisofiliesanipfeiDbecoiB^
This allows analysis of the anslytes within die samples 10 be «oooavM^sucoe«afuUy.iciiably, and
with good precision and accuracy. Tne me of n»lt^in«iutf sttndanbwWch art « true field
surrogrtcswanbined with the matra
step in tins nKan± projea is to finafia»
soiuiioii. develop a diffosed sta^daid for analytes ao^
fer its use. GC/MS BPB tmnng wifl be totomated wing the fiiH evaporation tecteilqiic.'nie end lesult
will be « rctiabk method ftir collecting and analyzing soil SMapki,whtte4esainpleishandksdoooein
die field and the vial is never opened again. THswrnprevrmtosjofanaiyiKthiwigh voljttili
addition of uEpuritic* from the lab air.
MikeMaikolov.BPRwcarc^CScvclan^OH
Tom Herman, Northern Lake Services Labonttoty, Qamden, WI
Tom BelUr, USEPA EMSL, Cincinnati, OH
Pedro Flores, TM Oncinnati. OH
TOTflL P. 12
-------
-------
Environ. SO. Tfchnot 18*2. 29, 1932-1938
Comparison of Analytical Methods for Determination of Volatile Organic
Compounds In Soils
Aton 0. Hewitt,* Paul H. Mfyaraa. DanM C. Laggatt, and ThomM P. J*r*kw
U.S. Army Cold Regions Research and Eng(n«*ring Laboratory, 72 Lyrrw Road, Hanover. New Hampshire 03755-1290
• This study compares aqueous extraction headspace/gas
chromatography and purge-and-trap gas chromatogra-
phy/maaa spectrometry (EPA SW-846, method 8240) for
the determination of four volatile organic compound*
(VOCs) in soil Comparisons were performed on two
fortified soils and two soils obtained from sites where
hazardous waste had been spilled or disposed. In only two
of the cases studied were significant differences consist-
ently found; for the two most hydropbobic compounds in
a high organic carbon soil and for TCE in a field-contam-
inated soil that had previously shown slow aqueous VOC
desorption. Our findings strongly suggest that aqueous
extraction/headspace GC using a portable instrument can
be used to screen soils on site for VOCs, providing rapid
same-day results, that will consistently identify the pres-
ence of these analytea and provide quantitative results
which are generally not significantly different from slower
more expensive, laboratory-based purge-and-trap analysis.
Introduction
Volatile organic compounds (VOCs) are the most fre-
quently encountered contaminants at hazardous waste sites
(1, 2). Because of their pervasiveness and transience in
soils, VOCs have drawn considerable attention. Sorption
of nonpolar VOC vapors in the subsoil zone has been
shown to depend on the availability of water, since these
two constituents often compete'for the same sites (3,4).
In the absence of moisture, mineral surfaces (clays) and
organic matter provide sites for VOC sorption; as moisture
increases less sites are available, and VOCs partition with
the water phase. Vadose zone soils typically have little
organic matter (<3%); thus, a sample preparation method
that uses water as an extractant and/or dispersion medium
could potentially displace the majority of VOCs, which
exist weakly sorbed to clays, as components of soil solution
or as transient vapors in unoccupied pore spaces.
Currently, protocols specify the collection of bulk soil
samples from which subsamples are removed in the labo-
ratory for VOC analysis (5). Many samples result in "bekw
detection* or background concentrations. Screening co-
located soils on site or upon receipt by the contracted
laboratory would permit more efficient selection of samples
for expensive purge-and-trap gas chromatograph mass
spectrometer (PT/GC/MS) analysis. Also, the capability
of preforming on-site analysis would allow for timeiy de-
cisions to be made during site characterization or cleanup
(6).
A headspace/gas chromatographic (HS/GC) method,
well-suited for on-site screening of VOCs, has been the
subject of several recent papers (7-10). Results comparable
to purge-and-trap gas chromatographic (PT/GC) analysis
for VOCs in aqueous samples have been reported (10,11).
Method comparisons for soil samples, however, have suf-
fered from heterogeneity of field samples or have been
limited to soils treated directly with MeOH-"doped* spikes
(12). Additionally, both methods of comparison often
failed to maintain critical variables such as holding time
and extent of sample disturbance constant, thus further
T*bU I. Physical Ptopertto* of th» Compounds of Interett*
character-
istic
compound
TDCE
TCE
86.7«
IBS (20)'
Ben
80.lt
135 (20)'
Tol
boiling point 48*
CC)
K,,, 86* IBS (20)' 135(20)' 490(20)'
(mL/mL)
water tolub 6000(20)' 1100(25)* 1780(20)* 515(20)*
(mf/L)
Henry'ikw 0.0055(25)' 0.0067(25)' 0.0099 (20X 0.0067 (25/
200(14)* 60(20)* 76(20)' 22(20*
moj)
vapor
prewure
(mm)
•TDCE. tran*-l,2-diehloroethylene; TCE, trichloroethylrae;
Ben, berutene; Tol, toluene. Kt/w, octenol/mter partition coeffi-
cient. Value* in pannthMM an the cormpondinf temperature*
(•C). 'Reference 15. 'Reference 16. 'Reference 17. 'Reference
18. 'Reference 19. 'Reference 20.
confounding intennethod comparisons (12).
This study, performed at the Cold Regions Research and
Engineering Laboratory (CRUEL) during the past year,
compares measured concentrations of four VOCs in two
laboratory-fortified soils and TCE in two field soils.
Procedures used in the preparation and handling of both
laboratory-fortified and field samples were identical prior
to extraction and analysis. Spiking was accomplished by
a vapor fortification procedure that is analogous to the
exposure of unsaturated soils to vapors originating from
a separate contaminant phase. tnin«-l,2-DichloroethyIene
(TDCE), trichioroethylene (TCE), benzene (Ben), and
toluene (Tol) were selected because they represent con-
tamination with industrial solvents and petroleum prod-
ucts an! they are freqiiently found at hazardous waste sites
(13). Some relevant physical properties are given in Table
I. Preparing VOC-contaminated soil samples by vapor
fortification allows for a more rigorous method evaluation
than is possible using solvent-spiking techniques currently
practiced in many QA/QC programs. Since no VOC
performance evaluation samples are available at present
for soils, the assessment of sample determination accuracy
relies on solution spike and recovery tests. The volatility
of VOCs has made matrix spiking a difficult task. Gen-
erally, VOC spiking is performed by introducing doped
MeOH aliquots directly to the purge chamber of a
purge-and-trap system that contains the matrix sample of
concern. This method is of limited value for it only
evaluates the determinative step, providing no information
on the efficiency of soil extraction. Soils fortified by vapor
treatment require both an extraction and a determinative
step, thus providing a more comprehensive evaluation of
a method's performance.
The objective of this study was to evaluate a on-site
sample preparation and analysis method for VOCs in soils
in relation to an accepted laboratory procedure. The
sample preparation and analysis methods compared were
1932 Environ. Scl. Tachnol.. Vol. 26. No. 10. 1992
0013-936X/92/0926-1932S03.00/0 © 1992 American Ctwmical Society
-------
Table II. Characteristics of Soili
soils
Point
USATHAMA Barrow,
»td AK CRREL CUrkwn
6.69 0.08 0.13
20.1 <5 12
iOO 17 22
<0.1 <0.1 10
characteristic
organic carbon (%) 1.45
cl«y(%) 53.6
% moisture* (%) 1.43
dipenion rate* <0.1
(DUB)
•ASTM D2216-66 (i.e., weight percent relative to dried soil).
'Time required to disperse 2 g of soil in 30 mL of water by hand
shaking.
water extraction HS/GC/pnotoionization detection (PID)
and PT/GC/MS (5). Aqueous-HS/GC sample prepara-
tion and analysis were streamlined for field screening ap-
plications. Water was used aa the extracting agent, hand
shaking/agitation to partition the VOCs into the aqueous
phase, and a portable GC for determination. Sample
preparation for PT/GC/MS analysis depended on the
anticipated soil VOC concentration. For anticipated
concentrations of greater than 1 pg/g> soil samples are
extracted with methanol and an aliquot of the extract is
analyzed by PT/GC/MS. For samples expected to contain
less than 1 pg/g, the sample is added directly to a special
vessel from which VOCs are purged directly after adding
water and heating the slurry to 40 °C.
Materials and Methods
Regardless of sample history, all subsamples were han-
dled with identical procedures prior to extraction and
analyzed within 8 h of collection, with the exception of the
second set of PT/GC/MS analyses of subsamples taken
from the Clarkson TCE-contaminated soiL
Vapor Fortification Treatment. Two soils (the U.S.
Army Toxic and Hazardous Materials Agency (USA-
THAMA) standard soil no. AO46 and a soil obtained from
Point Barrow, AK) were fortified using a vapor treatment
method (12.14). Characteristics of these soils are listed
in Table H. No VOCs were detectable in either toil prior
to fortification. For subsample treatment, soils were
weighed into 40-mL volatile organic analysis (VOA) vials
and positioned uncapped on a perforated aluminum plate
inside a large desiccator. These VOA vials served as the
subsample vessel during fortification treatment and ex-
traction and often for analysis (MeOH aliquot! were re-
moved for the high-level PT/GC/MS analysis). An open
Petri dish containing the fortification solution was placed
under the samples (Figure 1). To attain the appropriate
concentrations, high-level samples used 2.00 g of soil and
1.00 g was used for the low-level samples. Empty viak were
included to check for sorption onto vial walls.
The fortification solution was prepared by combining
reagent-grade Tol (1.21 g), TDCE (0.603 g), TCE (0.586
g), and Ben (0.3S1 g) in MeOH and diluting to 100 mL in
a volumetric flask. Concentrations of VOCs in the soils
ranging from 100 to 1000 jjg/g wen obtained after expo-
sure to the equilibrium vapor above a 50-mL aliquot of this
solution in the fortification chamber. A second high-level
fortified soil in the 1-100 pg/g concentration range was
obtained by exposing the soils to the vaporfrom a 50-mL
aliquot of a 1:1 dilution of this solution with tetraethyiene
glycol dimethyl ether (tetraglyme). Low-level concentra-
tions (0.1-10 0g/g) were achieved by exposing the soils to
vapors from 10-mL aliquots of 1:10 and 1:20 dilutions of
this solution with tetraglyme. Vapor fortification treat-
ment periods were 4 days and between 39 and 46 days.
VOA Viols
with and without Sail
vapor
V N
IT**
«.
IV.
m,,,,cL,
Desiccator
t
Perforated
Plate
Peln Dish with Exposure Solution
Of VOC»
1. Vapor fortfflcatto
Each fortification treatment started with 12 laboratory
air-dried subsamples of each soil and four empty vials so
that two complete method comparisons could be per-
formed. The comparison set comprised six subsamples of
each soil and two empty vials; thus, triplicate soil sub-
samples and a single empty vial (control) were analyzed
by each method of analysis. After removal from the de-
siccator, the vials were aspirated for 10 min by placing
them along the front edge of an exhaust hood. This step
was necessary because the amount of VOC vapor remain-
ing in the headspace of each vial was significant. Aspi-
ration for 10 min lowered the VOCs in empty vials below
detection. After aspiration, prealiquoted volumes of the
appropriate solvents were rapidly added if necessary, and
the vials were capped.
Field Sample*. Several soil subsamples were collected
either 3 ft below the surface with a Veihmeyer tube or from
the surface with a shovel at the Cold Regions Research and
Engineering Laboratory (CRREL). Samples were taken
from several locations near known sources of contamina-
tion. A second field soil was obtained as a bulk sample
(~40 g) from Dr. S. G. Pavtostathis of Clarkson University.
This soil was selected because it is so poorly dispersed by
water (Table II), and in a previous study it had demon-
strated slow aqueous desorption of TCE (21). The
Clarkson soil was refrigerated after receipt and subsampled
after 2,11, and 162 days of storage.
Field soils were rapidly subsampled once brought into
contact with the atmosphere by taking 1.5-mL soil plugs
with a tipless 10-mL plastic syringe (22). Depending on
the method, the soil plugs were placed randomly into
preweighed VOA vials that were empty or that contained
either water or MeOH. Six sets of quintuplicate subsam-
ples were collected from the CRREL site, and three sets
of triplicate subsamples were removed from the bulk
Clarkson soil
Standards. The combined analyte solution prepared
as the fortification solution also served as the analytical
stock standard. Without further dilution, this stock
standard was used for the analyses in the 100-1000 jig/g
concentration range. Table ffl lists the dilutions necessary
for the other concentration ranges. The stock solution was
refrigerated at 4 °C, and dilutions were prepared daily as
needed. A new stock was prepared monthly. Both in-
strumental methods used the same analytical standards
for calibration.
Extraction and Analysis of VOCs Present in Soils.
a. Aqueous Extraction HS/GC Analysis. Consistent
with previous studies (11, 22), samples and blanks were
extracted with 30 mL of deionized water (Type 1, Millipore
Environ. Scl. Techno!., Vol. 26, No. 10, 1992 1033
-------
T.bJe III. Volume, of Stock Standard U«ed for til*
Different BufM of Expected VOC Concentrations in the
Soil
1000 p
working
ltd*
voL working
•tdfor
etlibntion OtL)
voLMeOH
extract at h*a
-------
Table IV. Intanwtbod CoatneiiioB of traa*-U DicMoiwthylM* (TDCB). TyioUoreetBylrae (TCK), Ben
Tolorae (Tol) for BUca-Leiei Fortified Sells
Mean Concn* * SD Oif/f) for Vapor Treatment Undiluted MeOH Stock
39-day Mptum*
(Ben), and
TDCE
Ban
TCE
Tol
TDCB
B«n
TCE
Tol
4-day expomin
HS/GC
72 J * 5.9*
117 * 6.6
214 * 9.8
492* 21
148*4.0
198*10
319*27
689*76
PT/GC/MS
USATHAMA Standard SoU
66.0 * 2.6*
94.3 * 2.2
202*16*
629*66'
Point Banow. AK, SoU
170 * 9.1
204*5.0*
444*12
1120 * 5.8
HS/GC
136*11
184 * 4.0
372 * 9.6
885*90
226*10
266*14
416*24
927*63
PT/GC/MS
122*19*
177*34*
380*105*
1660*427
230* 12*
281*32*
613 * 57
2740*61
Mean Coneiu * SD (*c/i) for Vapor Treatment: 50:60 Mixture of MeOH Stock and TetragiynM
4-day npoMiM
39-day exposure
TDCE
Beo
TCE
Tol
TDCE
Ben
TCE
Tol
HS/GC
1.63 * 0.11*
8.76 * 0.19
11.7*0.40
42.9 * 1.50
12.3 * 0.40
29.1 * 2.9
34.1*2.9
87.8 * 9.6
PT/GC/MS
USATHAMA Standard Soil
1.84 * 0.68*
6.67 * 1.30
9.22 * 1.68*
33.3*34
Point Barrow, AK. Soil
22.0*3.0
39.0 * 1.8
117 * 8.3
HS/GC
1.71 * 0.15
8.76 * 0.09
11.6 * 0.29
43.4 * 2.2
11.7 * 0.70
26.7 * 0.29
34.2 * 0.35
96.2 * 1.2
PT/GC/MS
4.93 * 1.34
7.33 * 1.42*
15.1 * 2.4*
41.4 * 4.9*
19.1 * 0.70
26.9 * 1.9*
53.0 * 2.3
134 * 8.1
* HS/GC and PT/GC/MS analyiet w*n not itatbticaJly diffmnt at tlw 96% confidence level 'Mean and itandard deviation (tali) for
triplicate MmplM.
10.000 r-
300
200 —
100 I—
VOC det*iT*iattona to ttw
3. Hera th« plot shows that the majority of point*, fall
below the unity axes, another means of demonstrating that
the MeOH-PT/GC/MS analyiu fc^neraJly quantified
greater soil VOC concentrationt. For this toil the overall
average VOC concentration differences between these two
methods (19%) increased with time, from 11 to 28%.
When we group Ben and TDCE, and TCE and Tot, sep-
arating the compounds with the two lowest and two highest
K0/m (Table I), plots of the mean concentrations deter-
mined by the two methods show very different behavior
(Figures 4 and 5). The linear regression of the mean
TDCE and Ben concentrations had a correlation coefficient
100 200
PT/GC/MS (MO/g)
300
Mhyla
Ltoaer ptot of mean (MO/8) rtw-l^-oTc
ben»ne<8w) concentrators In fortMM to**. Stops and oorrekrOon
coefficient. 0.944 end 0.993.
,
and Tol concentrations again shows the majority of points
below the unity axes. The fact that water was less able
to extract these hydrophobic VOCs is not surprising and
agrees with previous works (7, 24-261 which have addreend
the influence of soil organic matter on partition coeffi-
cients. Thus the difference in method performance with
the two soils is probably due to the high (6.69%) organic
carbon in Point Barrow soil compared to 1.45% for the
USATHAMA soil
Environ. SO. Techno!.. Vol. 26. No. 10. 1992 1838
-------
Table V. UtWraethod ConparieoB
(Tol) for Low LOT) Fortified Soil.
i (TDCB), TrieUoroetayton* (ICE), Brazen* (B»n>. Tolnene
Mean Concni ± SD Tt* difference was found for
all analytes in the USATHAMA aofl or for Ben and TDCE
in the Point Barrow soil, but difference*, ware observed for
TCE and Tol in that soil. Hera the difference can be
attributed to the physical process of extracting the VOC«,
showing that a dynamic proceoa ia more efficient than a
static one for nuns transfer, since both methods uae water.
This effect can be observed by spiking an organic matter
rich sofl water shiny. VOCs, particularly those with higher
KO/V will be sorbed to a greater extent by the organic
matter, showing reduced static vapor-phase concentrations
when compared to an aqueous solution or to an aqueous
low organic matter soil slurry (27).
Field Sample*. Method comparison using the two
field-contaminated soils was performed for TCE on nine
subeample sets (Table VI). Both methods of analysis
showed no false negatives; however, different analyte
variances for the sous wen apparent. The large variations
for the CRUEL soil demonstrates the problem of inter-
method comparisons using field soils which are heteroge-
neous. No significant differences were found between the
two methods for CRREL soil because of the very poor
precision for both methods (Table VI). For the Clarkson
soil, however, good sample precision produced statistically
different means in every case with the mean concentrations
obtained by aqueous-HS/GC always less than the
MeOH-PT/GC/MS values. Here the difference is not as
likely due to the organic matter present in the Clarkson
soil (Table II) as to slow desorption kinetics (21,28,29).
To teat this hypothesis, a simple experiment was per-
formed on the third Clarkson soO subset After the initial
headspace analysis, two of the soil subaamples were reex-
tracted twice with water. The soil and water phases were
separated by centrifuging the suspension at 2300 rpm for
lOmin. Only 28 of the 30 mL of water was recovered and
replaced. Results were corrected for this small carryover.
As previously, analyses for this soil were performed after
10 m'n of sample agitation (immediate, •«^«i«*««»Mi agitation
showed no discemable increase in the headspace concen-
tration). The third replicate never had the partition so-
lution changed, but experienced all of the physical agita-
tion received by the other two subsamples. A 6-h time
period lapsed between the initial and final analysis for all
of these subsamples. The results of this test are presented
in Table VH. Clearly, equilibrium had not been achieved
after 10 min of agitation and the low result* are due to slow
1936 Envtroo. Scl. Techno).. Vol. 26. No. 10. 1992
-------
T«bU VI. iBtarmethod Comparison for Trichloroethyleiw
(TCE) IB Field-Contaminated SoU
TCE conoai Qig/g)
HS/GC PT/GC/MS
Mich-Level Comparison: CRREL Soil
Subtample Set 1
18.3.11.4. 6.47, 3.60,10.7 83.6* 3.31, 28.7, 4.33,151
10.1 * 5.68» 9.71 * 12.7*
Subsampie Set 2
14.3, 9.00, 4.86.12.3,16.8 4.40,11.7. 36.0, 46.5, 36.9
11.4 * 4.66 26.9 ± 17.8*
Subsampie S«t 3
4.42, 3.36, 2.87. 4.07, 1.60 2J60, 1.23, 3.66, 80.7 * 3.69
3.26 ± 1.11 2.74 * 1.14*
Subsaznple Set 4
0.68, 1.14, 1.42. 1.57, 0.72 0.66,0.70, 3.46* 0.70,0.36
0.976 ± 0.609 0.60 ± 0.16*
Subtample Set 5
1.42, 0.89, 13.8, 10.2. 4.39 0.44, 1.18, 2.07, 1.71, 7.83*
6.14 ± 5.66 1.35 ± 0.71'
High-Level Comparison: ClarksonSoil
3.83, 3.44. 4.17
3.81 ± 0.37
3.45. 3.54. 3.81
3.60 ± 0.19
2.38, 3.16. 2.66
2.73 ± 0.40
Subsampie Set 1 (2 Days)
8.77,9.89,11.5
10.0 * 1.37
SubMmple Set 2 (11 Days)
7.87. 7.71. 8.07
7.88 ± 0.18
SubMmple Set 3 (165 Days)
3.54, 4.36. 4.16
4.02 ± 0.43
Low-Level Comparison: CRREL SoU
Subeamplee
0.172.0.171. 0.132, 0.288, 0.133 0.188, 0.066, 0.261,0.289,0.274
0.179 ±0.064 0.216*0.092*
•Outlier u determined by Dixon's teet (19) at the 96% confi-
dent* level. * Average end standard deviation (j*/f). 'HS/GC
and PT/GC/MS analyses were not statistically different at the
95% confidence level.
Table VII. CoBcentratloas («/«) of TCB IB HS Samples
after CiuBalatiTe Acitatioa anoVer Bepemted Aqoeeus
Extraction of the CUrksoa Soil
extraction
subaample
Wl'
W2»
W3-
Ut
4.14
2.66
2nd
1.24
L53
3rd
0.62
0.69
npleagiti
total
4.24
4.14
4M
4.42 * 0.40
after each sequential
•Analyzed after 10 min of
extraction. 'Analyzed after 30 min of cumulative sample agit
performed in 10-min intervals over the couree of 6 h.
desorption kinetics. Inadditic
nparison of the mean
of these three determination* (4.42 ± 0.40) with the mean
of the MeOH-PT/GC/MS (4.02 ± 0.43) shows no statis-
tical difference. This finding agrees with these earlier
studies (21,27,28) and emphasizes that the extraction of
soil VOCs in some cases is sensitive to the degree of agi-
tation and length of equilibration.
Screening for VOCs in Soils. This evaluation of
VOCs in fortified and field soils probes beyond the ob-
jective of sample screening and reveals some of the limi-
tation* and strengths of the aqueous-HS sample prepa-
ration and portable GC analysis when compared to a
.> method. With regard to
screening, the water extraction MS sample preparation and
portable GC analysis technique always produced results
comparable to PT/GC/MS. The largest discrepancies in
concentrations for this intermethod comparison occurred
for a soil with unusually high organic carbon content and
for a soil that previously had demonstrated stow aqueous
desotption of VOCs (21). Even in these two cases water
extraction HS/GC analysis provided concentration esti-
mates that were greater than 30% of those determined by
PT/GC/MS analysis following MeOH extraction.
Nonhomogeneity of VOCs in soils, as demonstrated by
the TCE levels in the CRREL soil, dictates that several
subsamples or composite samples be taken for proper site
assessment Costs of performing PT/GC/MS analyses
may limit the number of samples collected for laboratory
analysis, thereby reducing the ability to assess analyte
variability at discrete locations. A simple procedure that
can be used on site, although providing somewhat less
accurate VOC concentrations, allows for more intensive
sampling, i.e., more representative evaluation of contam-
inant distribution. Analysis by either aqueous-HS/GC or
PT/GC/MS may be of equal merit if individual subsam-
pies are taken for VOC concentrations in soils where spatial
variability exists (22).
Summary and Conclusions. Headspace sample
preparation and analysis with a portable gas chromato-
graph does not use hazardous chemicals and is ideally
suited for on-site screening. From its inception, this
procedure minimized sample
thereby reducing the possibility of false negatives. In the
work reported here, no false negatives were obtained and
quantitative results comparable to laboratory PT/GC/MS
were obtained in all cases tested. Thus, once the VOCs
of concern have been identified, aqueous-HS/GC analysis
can fill a void between the quality of analysis necessary
for litigation purposes and preliminary soQ gas monitoring.
Universal recognition of simple transportable site assess-
ment methods can expedite investigations and lower the
coats of §oQ VOC analysis.
Acknowledgment!
We thank Dr. T. M. Spittler for providing the infor-
mation concerning headspace gas chromatography and
nondistruptive sample collection techniques, Dr. S. G.
Pavlostathis for providing a contaminated soil and in-
sightful comments, and Dr. C. L. Grant for critical review
of the text
BegJstry Ne. TDCE. 156-60-5; TCE, 79-01-6; Ben, 71-43-2;
To), 108-88-3,
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Chemicala in Ground Water, Houston, TX. Nov 1986; pp
13-16.
(2) Zarrahi, K.; Cross-Smiecinaki. A. J.; Starks, T. Second
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Feb 1991; pp 236-262.
(3) Chiou, C T.; Shoup, T. D. Environ. Set. TtehnoL IMS, 19,
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(4) Chiou, C. T. Theoretical considerations of the partition
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in Soilr, Sawhney, B. L, Brawn, K., Eds. SSSA Spec. Publ.
198», No. 22. 1.
(5) Teit Method* for Evaluating Solid Watte: 1986; U.S.
Environmental Protection Agency, U.S. Department of
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£nv*nn. Set TechnoL 199t, 30, 1938-1943
Commerce, National Technical Infonnation Service:
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(6) Spinier. T. M.; Clifford, W. S.; Fitch, I* G. National Water
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236-246.
(7) Kianf, P. H.; Grob, R.L.J. Environ. Sei. Health IMC. 21,
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(B) Griffith, T. J.; Robbins, G. A.; Spittler T. M. Proceeding*,
FOCUS Conference on Eastern Regional Water Issues,
National Water Well Association, Sept, Stanford, CT, 1988;
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(9) Robbins. G. A.; Roe, V. D.; Stuart. J. D.; Griffith, T. J.
Proceeding*, NWWA/API Conference on Petroleum Hy-
drocarbona and Organic Chemical* in Ground Water-Pre-
vention Detection and Restoration, Nov, Houston, TX,
1987; pp 307-315.
(10) Stuart, J. D.; Wang. 84 Robbins, G. A. Second International
Symposium, Field Screening Methods for Hazardous Waste
and Toxic Chemicals, Feb, Las Vegas, NV, 1991; pp
407-414.
(11) Dirti, E. A., Jr.; Singley K. F. Anal. Chem. 1979,51.1809.
(12) Hewitt, A. D.; Miyares, P. H.; Leggett, D. C-; Jenkins, T.
F. SR91-4; USA Cold Regions Research and Engineering
Laboratory, Hanover, NH, 1991.
(13) Lewis, T. E.; Crockett, A. B.; Siegrist, R. L.; Zarrabi, K.
EPA/590/4-91/001; Technology Innovation Office, Office
of Solid Waste and Emergency Response, U.S. EPA.
Washington, DC, 1991.
(14) Jenkins, T. F.; Schumacher, P. W. SR87-22; USA Cold
Regions Research and Engineering Laboratory, Hanover.
NH, 1987.
(IS) Verschueren, K. Handbook of Environmental Data on
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(16) McGovern, E. W. Ind. Eng. Chem. IMS, 35, 1230.
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25.274.
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(23) Dixon. W. J. Biometnc* 1953, March, 74.
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(26) Boyd, S. A.; Sun. S. Environ. Sei. Teehnol. 1990,24,142.
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F. CR92-6; U.S. Cold Regions Research and Engineering
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(28) Smith, J. A.; Chiou, C. T.; Hammer, J. A.; Kile, D. E,
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Received for review January 27, 1992. Revued manuscript re-
ceived May 13,1992. Accepted June 16,1992. Funding for thi*
work wot provided by the U.S. Army Toxic and Hatardou*
Material* Agency. Durant Grave*, Project Monitor. Thi* pub-
lication reflect* the personal view* of the author* and doe* not
*ugge*t or reflect policy, practice*, program*, or doctrine of the
(7.5. Army or Government of the United State*.
Effect of Sulfur Dioxide on the Formation Mechanism of Polychlorlnated
Dibenzodloxln and Dlbenzofuran in Municipal Waste Combustors
Brian K. Guiwtt*
Air and Energy Engineering Research Laboratory, U.S. Environmental Protection Agency,
Research Triangle Park, North Caroena 27711
Kevin R. Bruce and Law* O. Beach
Acurex Corporation, P.O. Box 13109. Research Triangle Park. North Caroena 27709
• The effect of sulfur dioxide on the formation media
of polychlorinated dibenzodioxin (PCDD) and poly-
chlorinated dibenzofuran (PCDF) in the postcombustion,
downstream region (500-300 °C) of a municipal waste
eombuator (MWC) was investigated. Laboratory experi-
ments ainmlating the flue gaaee and particle environment
of an MWC examined PCDD production under varying
conditions. Effects on the concentration of an organic-
chlorinating constituent, Clj, through both homogeneous
reaction with SO, and deactivation of a C Vforming cat-
alyst [Cu(II)] were **»m'm»A Experimental results suggest
that the reaction of Cu(ID with SOj to form CuSO4 renders
the catalyst less active, decreasing PCDD formation.
However, this inactivity is not a result of decreased Clj
formation, but rather of reduced ability of Cu(£D to pro-
mote a second catalytic step of biaryi synthesis. These
findings suggest that the apparent lack of PCDD and
PCDF in the emissions from coal-fired combustors may
be due to the relatively high concentrations of S02.
1. Introduction
While significant amounts of polychlorinated dibenzo-
dioxin (PCDD) and polychlorinated dibenzofuran (PCDF)
have been detected in the emissions of municipal waste
combustors (MWCs), the same cannot be unequivocally
sakl of emissioni from coal-fired combustors. Despite the
presence of chlorine and organic ring structures in both
systems and the ability of coal fly ash to aid chlorination
of organics (1), tetrschlorinatad dibenzodioxin (TCDD) was
not detected in effluent sampling from a combined
coal/municipal waste plant (2), nor were noteworthy
amounts found on coal fly ash (3). These results, however,
are inconsistent with laboratory studies (4) producing
chlorodioxina from experiments with bituminous coal It
is possible that conditions within MWCs are sufficient to
promote the in situ formation of PCDD and PCDF, while
this is not true of coal-fired combustors. Examination of
the similarities and differences between conditions in
MWCs and coal-fired combustors will thus not only en-
lighten the mechanism of PCDD and PCDF formation but
also may suggest potential methods for preventing the
formation of PCDD and PCDF.
Laboratory research has successfully produced PCDD
and PCDF through simulating postfurnace conditions of
MWCs. Experiments with MWC fly ash have shown
substantial PCDD and PCDF formation when treated
183S Environ. Sei. Techno).. Vol. 26. No. 10. 1992
0013-936X/92/0926-1938S03.00/0
-------
-------
VOLATILE
METHOD 5021
S_
USING EQUIP
OTHER SOLID MATRICES
1.0 SCOPE AND APPLICATION v
1.1 Method 5021 is a general purpos« method for the preparation of
volatile organic compounds (VOCs) in soils/sediments and solid wastes for
determination by ,gas chromatography <6C) .or gas
-------
CoraDQund
CAS No.'
Tetrachloroethene
Toluene
1,2,4-Tri chlorobenzene
1,1\ i-Trichloroethane
1,1,2-Tr1chl oroethane
Trichloroethene
Tri chl orofluoronethane
1 r 2,3-Trtchloropropane
Vinyl chloride
o-Xylene
a-Xylene
p-Xylene
127-18-4
108-88-3
120-82-1
7,1-55*6
79-00-5
79-01-6
75-69-4
96-18-4
75-01-4
95-47-6
108-38-3
106-42-3
Gasoline Rang* Petro1eum Hydrocarbons
* Chemical Abstract Services Registry Number.
1.2 Method detection Units (MOL), using Method 8260, are coopound,
matrix, and instrunent dependent and vary from approximately 0.1 to 3.4 ^g/kg.
The applicable concentration range of this method is approximately 10 or 20
Mg/kg to*200 M9/kg. Analytes that are inefficiently extracted fro* the soil
will not be detected when present at low concehtratlons, but they can be Measured
with acceptable accuracy and precision when present in sufficient concentrations.
1.3 The following coapounds may also be analyzed by this procedure or may
be used as surrogates: .- _
CoBMund Na»e
CAS No.'
Broenbenzene .
n -Butyl Benzene
sec-Butyl benzene
tert - Butyl benzene
2-Chlorotoluene
4-Chlorotoluene
ci s - 1 , 2 -Dichloroethene
1 , 3 -01 chl oropropane
2 , 2-01 chl oropropane
1,1-Dichloropropene
I sopropyl benzene
4-Isopropyltolaene
n-Propyl benzene
1 , 2 » 3-Tri chl orobenzene
1 ,2,4-TrlMthylbenzene
' 1, 3, 5-Tri«ethyl benzene
108-86-1
104-51-8
135-98-8
98-06-6
95-49-8
106-43-4
156-59-4
142-28-9
590-20-7
563-58-6
98-82-8
99-87-6
103-65-1
87-61-6
95-63-6
108-67-8
* Chemical Abstract Services Registry Number.
5021 - 2
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1.4 Alternatively, th« method may be utilized as an automated sample
Introduction device as a neans for screening samples for volatile organics. A
suggested configuration is to interface it to Method 8021 bat use very minimal
calibration and quality control, .i.e., "a reagent blank *nd a single calibration
standard, to obtain semiquantitative data.
,. 1.5 Method 5021, nay be appl icabl e together compounds that have sufficient
volatility to be removed from the soil matrix using the conditions described In
this method. It may also be applicable to both listed, and n on-Us ted target
analytes^ in other matrices. .
1.6 This method is restricted to use by, or under the supervision of,
analysts experienced in volatile organic analysis in general and specifically the
use of equilibrium headspace devices interfaced to the determinative method
selected by the analyst. '
2.0 SUMMARY OF METHOD
2.1 Volatile organic compounds (VOCs) are determined .from at least a 2 g
soil sample by placing the sample into a crimp-seal or screw top glass headspace
vial at time of sampling. Each soil sample is fortified with a matrix modifying
solution and Internal standards and surrogate compounds. This-may be done either
in the field or in the laboratory Upon receipt of samples'. Additional sample is
collected in a VOA vial for dry weight determination and for high concentration
determination if the sample concentration requires it. In the laboratory, the
ytals are rotated to allow for diffusion of the internal standards and surrogates.
throughout the matrix. The vials art~plact4 In:the autosampler carousel and
maintained at room temperature. Approximately 1 hour prior to analysis, the
Individual vials are moved .to a heated zone and allowed to equilibrate. The
sample is then-mixed by mechanical vibration while the elevated temperature is
maintained. Tint autosampler then pressurizes tne vial with helium, .allows a
portion to enter a sample loop which 1s then swept through a heated transfer line
onto the GC column. Determinative analysis is performed-using the appropriate
GC or GC/MS method.
3.0 INTERFERENCES
3.1 Volatile organic analyses art subject to major interference problems
because of the prevalence of volatile organics 1n a laboratory. See Method 5000,
Sec.. 3.0 for common problems and precautions to be followed.
3.2 The sample matrix Itself can cause severe interferences by one of
several processes or a combination of these processes; These include, but are
not necessarily limited to, the absorption potential of the soil, the biological
activity of the soil, and the actual composition of the soil. Soils high in oily
material and- organic sludge wastes inhibit the partitioning of the volatile
target analytes into the headspace, therefore, recoveries will be low. This so-
called "matrix effect" can'be difficult, if not Impossible, to overcome. It Is
recommended that surrogates or additional deuterated compounds (for GC/MS
methods) be added to a matrix and analyzed to determine the percent recovery of
these compounds. The calculated percent recovery can give some indication of the
degree of the matrix effect, but not necessarily correct for it. Alternatively,
5021 - 3
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the use of the high concentration procedure In.thl^inethqd'^h'ould nrifrimize the
problem with oily waste and. other organic sludge wastes.
4.0 EQUIPMENT ANO SUPPLIES
4.1 Sample Containers - Clear glass, 22 mL soil vials, compatible with the
analytical system. The vial must be capable of being hermetically sealed in the
field (either crimp cap or screw cap) and be equipped with a Teflon*-lined septum
which demonstrates minimum bleed at elevated temperatures while maintaining the
seal. Ideally, the vials and septa should have a uniform tare weight. Prior to
use, wash the vials and septa with detergent solution, then rinse with tap
followed by distilled water. Place vials and septa in an oven at 105'C for 1
hour, then remove and allow to cool. Store in an area free of organic solvents.
\
4.2 Headspace System - The system described 1n this method utilizes a
totally automated equilibrium headspace analyzer. Such systems are available
from several commercial sources. The system used must meet the following
specifications. - . .
i
4.2.1 It must be capable of establishing a reproducible equilibrium
at elevated temperatures between a wide variety of sample types and the
headspace. Once this is done, the system must be capable of accurately
injecting a representative portion of the headspace Into a gas
chromatograph fitted with a capillary column. Tills must be accomplished
without adversely affecting the chromatography or the detector. The
conditions selected for the equipment used in developing this method are
listed in Sec. 7.0. Other equipment and conditions may be used if the
analyst generates and records accuracy, precision, and MOL data that are
comparable to the data in Sec. 9.0 of Method 8260; The equipment used to
develop this method and generate the accuracy and precision data listed in
Method 8260 was a Tekmar Model 7000 Equilibrium Heidspace Autosampter and
a Tekmar 7050 Carousel (Tekmar Co., 7143 East Kemper Road, Cincinnati, OH
45249).
4.3 Field Sampling Equipment
4.3.1 A soil sampler which delivers at least 2 g of soil is
necessary, e.g., Purge-and-Trap Soil Sampler Model 3780PT (Associated
Design and Manufacturing Company, 814 North Henry Street, Alexandria, VA
22314), or equivalent.
4.3.2 An automatic syringe or bottle-top dispenser calibrated to
deliver 10.0 ml of matrix modifier solution, e.g., Automatic Vaccinator
Model C1377SN (MASCO, 901 Jamesvllle Ave., P.O. Box 901, Fort Atkinson, WI
53538), or equivalent.
4-.3.S An automatic syringe calibrated to deliver internal standards
and surrogate analytes.
4.3.4 Crimping tool for sample vials. If using screw top vials,
this is not needed.
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4.4 Miscellaneous Equipment
4v4.1 VOA vials - 40 o,r 60 ml VGA vials with Teflon*-faced septa
and crimp seal caps or screw'top caps. . These vials will be used for
sainple, screening, high concentration "analysis (if needed) and dry weight
determination. -. s ,
5.0 REAGENTS ; , . :
5.1 Organic-Free Reagent Water. All references to water in this method
refer to organic-free reagent water, as defined in Chapter One.
5.2 Methanol, CHjOH - Pesticide quality or equivalent. Store away from
other solvents. Purchase in small quantities (i Liter or 1 Liter size) to
minimize contamination*
5.3 See the determinative method and Method 5000 for guidance on the
preparation of stock standards and a secondary standard for internal standards,
calibration'standards, and surrogates. :
5.3.1 Calibration spiking solutions -Prepare ftve- spiking
solutions in methariol that centaln all the target analytes and the
surrogate standards. The concentrations of the calibration solutions
should be such that the addition of 1.0 jiL of each -.to- the22 ml vials will
bracket the analytical range of the detector, e.g:, for Method 8260 the
suggested concentration range for target anal ytes and surrogates is 5, 10,
20, 40 and 50 mg/L. The suggested concentration of-Internal standards is
20 ng/L (Internal standards may be onrltted for the GC methods if desired).
The internal' standard may be added separately using 1.0 pi or .premixed
with.the calibration standards, maintaining a 20 ng/L concentration in each
calibration standard. These concentrations may vary depending on the
. relative sensitivity of the GC/KS system or any other determinative method
that is utilized.
5.3.2 Internal and surrogate standards - Follow'the recommendations
of the deternrinative methods for the selection of Internal and surrogate
standards. A concentration of 20 mg/L in methanoT for both internal and
surrogate standards will be needed for spiking each sample. If
determination is by GC, external standard calibration may be preferred and
the Internal standard 1s omitted. The concentration may vary depending on
the relative sensitivity of the GC/MS system or any other determinative
method that 1s utilized. \
5.4 Blank Preparation - Transfer 10.0 mL (Sec. 5.6) of matrix modifying
solution to a sample vial. Add the prescribed amounts of the internal standards
and surrogate compounds, and seal the vial. Place it 1n the autosanpler and
analyze in the sane manner as an unknown sample. Analyzing the blank in this way
will indicate possible problems with the autosaapler as well as the headspace
device. . ' •
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5.5 Preparation of Calibration Standards - Prepare canoration stana«ras
in Che same manner as the blanks (Sec. 5.4) using the standards prepared in Sec.
5.3.1. ' -.-.<• '•• •-•• -v^; .*.. y „«;•.-• -,._ ;. .. .- -
5.6 Matrix Modifying Solution - Using a. pH meter, add concentrated
phosphoric tctd-(H,M«) dropwise to 500 mL of organic-free reagent water until
the pH is 2. Add 180 g of NaCl. Mix well until all components are dissolved.
Analyze a 10.0 mL portion fro* each batch per Sec. 5.4 to verify that the
solution is free of contaminants. Store in a sealea bottle in an area free of
organic chemicals at 4*C.
WARNING: The .matrix modifying solution may not be appropriate for soil
samples having organic carbon content. See Sec. 6,1.2.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING .
6.1 Two alternative procedures are presented for >ow concentration sample
collection in special headspace sample Vials. In either case, collect 3 or 4
vials of sample from each sampling point to allow sample remnalysis If necessary.
In addition, a separate portion of sample 1s taken for dry weight determination
and high concentration analysis (if necessary). Prepare, a trip blank in the
laboratory prior to shipping the sample vials to the field. Add 10.0 mi. of
matrix modifying solution to a clean 2Z mL sample vial (Sec. 4.1}. The Internal
and surrogate standards are added Just prior to analysis.
6.1.1 Without matrix modifying solution and standards - Standard 22
mL crimp cap or screw top glass headspace vials (Sec. 4.1) with
Teflon*-faced septa are used. Add 2-3 m (approximately 2 g) of the soil
sample (using the purge-and-trap sail sampler. Sec. 4.3.1) to a tared 22
mL headspace vial and seal immediately with the Teflon9 side of the septum
facing toward the sample. The samples should be Introduced into the vials
gently to reduce agitation which might drive off volatile compounds.
NOTE: If High concentrations of volatile organic* are expected (greater than 200
M9A9>» collection of the sample in the 22 mL vial without the addition
of matrix modifying solution allows direct addition of methanol as per the
high concentration method in Sec. 7.5.
6.1.2 tilth matrix modifying solution .and standards - Add 2-3 cm
(approximately 2 g) of soil sample to a tared 22 mL soil vial using a
purge-and~trap soil sampler (Sec. 4.3.1). Add 10.0 mL of matrix modifying
solution and the appropriate amount of internal and surrogate standards
called for In the determinative method. Seal the vial Immediately with
the Teflon* side of the septum facing toward the sample. The sample must
remain hermetically sealed until the septum is punctured by the headspace
analyzer.
WARNING: Preliminary Indications are that soil samples having organic carbon
content may yield low recoveries when the matrix modifying solution
(Sec: 5.6) is used. The matrix modifying solution may not be
appropriate for these samples.
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6.1.3 Prepare a field blank by adding 10.0 ml of matrix modifying
solution plus internal and surrogate standards to a clean 22 ml vial.
NOTE: The addition of^ the matrix modifying solution and the. internal and
surrogate standards at the time of sampling (Sec. 6.1^2) is the preferred
option! unless high concentrations of vol atile organic* are expected. The
matrix modifying solution minimizes dehydrohal ogenat i on reactions through
pH adjustaent., eVtmlnates b1odegradat1on of the analytes and minimizes
losses of analytes by volatility since the vfal is not opened in the
laboratory. The; downside is increased opportunity for contamination of
the matrix modifier and standards fn a field sampling situation. Also,
skilled personnel are required to precisely and accurately add- the matrix
modifying sol at ion, and especially the internal and surrogate standards.
These problems are minimized when added In the laboratory (Sec. 6.1.1) ,
however, there is the likelihood of significant losses of volatile
analytes when the vial is reopened in -the laboratory.
6.1.4 Fill a 40 or 66 ml VOA vial from each sampling point to use
for dry weight determination* sample screening and for high concentration
anal ysis-(1f. necessary). Sample screening is optional since there is no
danger of contaminating the headspace device because of carryover from a
high concentration sample.
6.2 Sample Storage
.1 Store samples at 4*C until analysis. The sample storage area
must be free of organic solvent vapors. ^
6.2.2 All samples should be analyzed .within 14 days of collection.
Samples not analyzed within this period oust be noted and data are
. considered minimum values.
7.0 PROCEDURE
7.1 Sample screening - This method (using the low concentration approach),
used in conjunction with either Methods 8015 (GC/FID) or 8021 (GC/PID/ELCD), may
be used as a sample screening 'method prior to any of the sample introduction -
GC/MS configurations to assist the analyst in determining the approximate
concentration of volat 11 eVrganjcs present 1n a sample. This is especially
critical prior to the use of volatile organic analysis by purge -and -trap to
prevent the contamination of the system by high concentration samples. It can
also be helpful prior to the use of this headspace method, to determine whether
to proceed with the low concentration method or the high concentration method.
High concentrations of volatile* will not contaminate the headspace device.
However, it may create contamination problems in the GC or GC/MS system.
Whenever this method is utilized for sample screening, very minimal calibration
and QC are suggested. In most cases, a reagent blank and a single point
calibration are sufficient.
7.2 Determination of sample % dry weight - In certain cases, sample
results are desired based on dry-weight basis. When such data are desired, a
portion of sample for this determination should be weighed out from the 40 or 60
ml VOA vial (Sec. 6.1.3).
5021 - 7 Revision 0
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WARNING: The drying oven should be contained in a hood or vented.
Significant laboratory contamination «ay.•.• result from ;a heavily
contaminated hazardous waste sample.
7.2.1 Immediately after neighing the sample for extraction, weigh
5-10 g of the sample into a tared crucible. Determine the % dry weight of
the sample by drying overnight at 105*C. Allow to cool in a desiccator
before weighing. Calculate the % dry weight as follows:
X dry weight - o of drv sample x 100
.g-of sample
7.3 The low Concentration Method utilizing an equilibrium headspace
technique is found in Sec. 7.4 and sample preparation for the High Concentration
Method Is found in Sec. 7.5. The high concentration method is recommended for
samples that obviously contain oily material or organic sludge waste (see Sec.
3.3). See Method 5000, Sec. 7.0 for guidance on the selection of a GC or GC/MS
determinative method, for the analysis of gasoline, use Method 8021 with GC/PID
for BTEX 1n series with Method 8015 with the GC/FIO detector for hydrocarbons.
If GC/MS analysis is preferred for BTEX in gasoline, follow Method 8260.
7.4 low concentration method for soil/sediment and solid waste amenable
to the equilibrium htadspace method. (Approximate concentration range of 0.5 to
200 jig/kg -the concentration range is dependent upon the'determinative method
and the sensitivity of each analyte.)
7.4.1 Calibration: Prior to using this introduction technique for
any GC or GC/MS method, the system oust be calibrated. General
calibration procedures are discussed in Method 8000, while the
determinative methods and Method 5000 provide specific information on
calibration and preparation of standards. Normally, external standard
calibration is preferred for the GC methods because of possible
interference problems with" internal standards. If Interferences are not
a problem, based on historical data, internal standard calibration is
acceptable. The GC/MS methods normally utilize internal standard
calibration. The GC/MS methods require Instrument tuning prior to
proceeding with calibration.
7.4.1.1 Initial calibration: Prepare five 22 ml vials, as
described, in Sec. 5.5, and a reagent blank (Sec. 5.4), and proceed
according to Sec. 7.4.2 and the determinative method selected. The
nixing step 1s eliminated since no soil is present in the vial.
7.4.1.2 Calibration verification: Prepare a single 22 ml
vial as described In Sec. 5.S by spiking with the midconcentration
calibration standard. Proceed according to Sec. 7.4.2.4 (beginning
by placing the vial Into the autbsampler) and the determinative
method.
7.4.2 Headspace operating conditions - The conditions described
throughout Sec. 7.4 were experimentally optimized using the equipment
described in Sec. 4.2.1. If other systems are utilized, it is recommended
that the manufacturer's conditions be followed. However, the criteria for
this configuration in Method 8260 must be met or exceeded.
5021 - 8
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7.4.2.1 This method is designed for a 2 g sample size. The
sample is prepared in the field by adding 2 g of the soil sample to
the 22 ml crimp-seal or screw top glass heads-pace vial as described
In Sec. 6.1. ,
7.4.2.2 Prior to analysis, weigh the sealed vial and its
contents to 0,01 g- If the matrix modifying solution was added at
the time of sampling (Sec. 6.1.2), the tare weight includes the 10
raL of matrix modifying solution.
7.4.2.3 If the matrix modifying solution was not added at the
time of sampling (Sec. 6.1.1), unseal the vial, rapidly add 10.0 art.
of matrix modifying solution and J ML of the 20 mg/L internal (If
necessary) and surrogate standards (individually or.as a mixture).
Immediately reseal the vial."
NOTE: Only open and prepare one vial at a time to minimize loss of volatile
organics.
7.4.2.4 Mix the samples (on a rotator or shaker) for at least
2 nin. Place the vials in the autosampler carrousel at room
temperature. The individual vials- are moved to a heating zone, and
allowed to equilibrate for 50 m1n at 85'C. Each sample is then
mixed by mechanical vibration for 10 .win at a mix power of 7.67
Watts while maintaining the temperature at 85*C. The, vial is
allowed to pressure equilibrate for 5 sec.. The autosampler then
raises the vial causing a stationary needle to puncture the septum,
and pressurize the vial with helium at 10 psi.
7.4.2.5 The pressurized headspace is then vented through a 1
mL sample loop to the atmosphere for 15 .sec. The sample is
equilibrated within the loop for 5 sec. Finally the carrier gas, at
a flow rate of 1.0 ml/mln, backflushes the sample loop sweeping the
sample through the heated transfer line onto the GC column.
7.4.2.6 Proceed with the analysis as per the determinative
method of choice.
7.5 High concentration method .
7.5.1 If the sample was collected by Sec. 6.1.1 with no matrix
modifying solution added at time of sampling, add 10.0 mL of methanol to
the .high level soil sample within the tared 22 mL vial. (Weigh the sample
to the nearest 0.01 g prior to the addition of methanol.)
7.5.2 Otherwise, transfer approximately 2 g of sample from the 40
or 60 mL VOA vial Into a tared 22 mL sample vial (Sec. 5.1). Add 10.0 mL
of methanol.
7.5.3 Mix by shaking for 10 min at room temperature. Decant 2 aiL
of the methanol to a screw top vial with Teflon* faced septa and seal.
Withdraw 10 j*L, or appropriate volume of extract from Table 2, and inject
into a 22 mL vial containing 10.0 mL of matrix modifying solution and
internal standards (if required) and surrogates. Analyze by the headspace
5021 - 9 Revision 0
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procedure Oy placing me Vial into LUC auvu&ier auu HI uv.eevjmy mtu
Sec. 7.4.2.4.
8.0 QUALITY CONTROL
'8.1 Refer to Chapter One for specific quality control procedures and
Method 5000 for sample preparation QC procedures.
8.2 Before processing any samples, the analyst should demonstrate through
the analysis of an organic-free reagent water method blank that all glassware and,
reagents are interference free. Each tine a set of samples is extracted, or
there is a change in reagents, a method blank should be processed as a. safeguard
against chronic laboratory contamination. The blank samples should be carried
through all stages of the sample preparation and measurement.
8.3 Initial Demonstration of Proficiency - Each laboratory must
demonstrate initial proficiency with each sample preparation and determinative
method combination it utilizes, by generating data of acceptable accuracy and
precision for target analytes In a clean matrix. The laboratory must also repeat
the following operations whenever new staff are trained or significant changes
In instrumentation are made. See Sec. 8.0 of Methods 5000 and 8000 for
information on how to accomplish this demonstration.
8.4 Sample Quality Control for Preparation and Analysis - See Sec. 8.0 in
Method 5000 and Method 8000 for procedures to follow to demonstrate acceptable
continuing performance on each set of samples to be analyzed. This includes the
method blank, either a matrix spike/matrix spike duplicate or a matrix spike and
duplicate sample analysis, a laboratory control sample (LCS) and the addition of
surrogates to each sample and QC sample.
8.5 It is recommended that the laboratory adopt additional quality
assurance practices' for use with this method. The specific practices that are
most productive depend upon the needs of the laboratory and the nature of the
samples. Whenever possible, the laboratory should analyze standard reference
materials and participate in relevant performance evaluation studies.
9.0 METHOD PERFORMANCE
9.1 Single laboratory accuracy and precision data were obtained for the
method analytes in two soil matrices: sand and a surface garden soil. These data
are found in tables in Method 8260.
10.0 REFERENCES
1. Flores, P., Bellar, T., 'Determination of Volatile Organic Compounds in
Soils using Equilibrium Heidspace Analysis and Capillary Column Gas
Chromatography/Mass Spectrometry", U.S. Environmental Protection, Agency,
Office of Research and Development, Environmental Monitoring Systems
Laboratory, Cincinnati, OH, December, 1992.
5021 - 10
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2. Code of Federal Regulations. 40, Ch. 1, Part 136,,Appendix B.
3. loffe, B.Y., Vitenberg, A.S., "Headspace Analysis and Related Methods in
Gas Chromatography", John Wiley and Sons, 1984.
5021 - 11 Revision 0
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Method
Number
8015
8021
8260
TABLE 1
DETERMINATIVE METHODS INTERFACED TO METHOD -5021
Method Name
Nonhalogenated Volatile Organic* Using GC/FID
Halogenated and Aromatic Volatile* by GC with Detectors in
Series: Capillary Column
Volatile Organic* by GC/MS: Capillary Column
TABLE 2
QUANTITY OF METHANOL EXTRACT REQUIRED FOR ANALYSIS OF
HIGH-CONCENTRATION SOILS/SEDIMENTS
Approximate
Concentration Range
Volume of
Methanol Extract*
500-10,000
1,000-20,000 jig/kg
5,000-100,000 M5/kg
25,000-500,000 pg/kg
100
100 ML
SO M!
10 ML
of 1/50 dilution "
Calculate appropriate dilution factor for concentrations exceeding this
table.
* The volume of methanol added to 5 mL of water being purged should be
kept constant. Therefore, add to the 5 mL syringe whatever volume
of methanol is necessary to maintain a volume of 100 uL added to the
syringe.
b Dilute an aliquot of the nethanol extract and then -take 100
analysis.
for
5021 - 12
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METHOD 5021 ;
VLOLATILE ORGANIC COHPOUNOS IN SOILS AND OTHER SOLID MATRICES
USING EQUILIBRIUM HEADSPACE ANALYSIS
1
r
7.2 0*t*n««M MMM
dry «»«•«««.
7.4.2 K«Mlr«M 1O.O n*.
7.S.J Ms »v
far 1O mM». of
intMt iftM.13 mi vi«)
ettiniMM IO.O mC •(
5021 - 13
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Inorganic Chemical
Characterization
Techniques and Data
Interpretation
IT-1
IT-J
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
Module Overview
Objective: Introduce participants to different
field-based technologies that can be used to
characterize inorganic contamination at a site
and for specified applications beyond
characterization.
EPA
IT-2
Notes:
This module will present information regarding factors to consider when using various
analytical tools to characterize inorganic contamination at a site. The basic components
of each technology, principles of operation, common applications (matrix and analytes),
logistical requirements, interferences, performance factors, data interpretation, data
quality, factors affecting data quality, and advantages and limitations will be discussed.
In addition, specific applications of each technology beyond characterization will be
discussed.
IT-2
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
X-Ray Fluorescence
Inorganic Chemical Characterization
Techniques and Data Interpretation
• X-Ray Fluorescence
* Mercury Vapor Analyzers
^Immunoassay
*• Anode Stripping Voltammetry
+ Graphite Furnace Atomic Absorption Spectroscopy
^Cyanide Measurement Techniques
* Water Quality Measurement Techniques
+ Emerging and Innovative Approaches and
Instruments
+ Hands-on Activity for Inorganic Analysis
EPA
XR -
XR-1
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
X-Ray Fluorescence
Topic Overview
• Topic Description: Explains the operation and use of field
portable x-ray fluorescence analyzers for detecting metals
in various media
+ Key Points
» Scope and application
» Theory of operation
» System components
» Interferences
» Calibration
» Sample preparation
» Quality control
» Data comparability
» Advantages and limitations
» Applications other than characterization
Notes:
This section explains the operation and application of using field portable x-ray
fluorescence (XRF) analyzers to detect metals in various media, especially soil.
The following key points are discussed: (1) scope and application, (2) theory of
operation, (3) system components. (4) interferences, (5) calibration, (6) sample
preparation, (7) quality control, (8) data comparability, (9) advantages and limitations,
and (10) applications other than characterization.
XR-2
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
X-Ray Fluorescence
Energy Dispersive XRF
4 Scope and application
» Metals in soil and sediment
» Lead in paint and house dust
» Metals in air filters
» Metals in water
XR-3
Notes:
One of the primary uses of energy dispersive X-ray fluorescence (EDXRF) is to detect
metals (and other elements such as arsenic and selenium) in soil and sediment. EDXRF
analyzers have been used to characterize metals in soils for more than 20 years.
Generally, elements of atomic number 16 (sulfur) through 92 (uranium) can be detected
and quantitated with a field portable X-ray fluorescence (FPXRF) analyzer. Some of the
primary elements of environmental concern that can be identified by EDXRF include
arsenic, barium, cadmium, chromium, copper, lead, mercury, selenium, silver, and zinc.
FPXRF instruments are also used as an effective and nondestructive tool for measuring
lead in paint and in house dust. The presence of lead in paint and house dust is one of the
most common sources of lead ingested by children. Most homes constructed or painted
prior to 1976 contain lead-based paint. The U.S. Department of Housing and Urban
Development (HUD) has guidelines on the inspection and abatement of public housing
developments in which lead paint was used. HUD considers any paint surface with a lead
content greater than 1 milligram per square centimeter (mg/cm:) to be a lead-based paint
surface.
Another common use of FPXRF analyzers is to measure metals concentrations on air
filters. If the volume of air that has passed through the air filter is known, metals
concentrations suspended on particulates in the air can be calculated. FPXRF analyzers
can also be used to monitor air emissions from industrial processes or from remediation
processes at a hazardous waste site.
XR-3
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
X-Ray Fluorescence
A more recent use of FPXRF analyzers is to detect metals in water. The water samples
have to be filtered and pre-concentrated using an ion exchange membrane to achieve
detection limits in the low parts per billion (ppb) range below applicable maximum
contaminant levels (MCL). Many FPXRF manufacturers are currently conducting
research to refine the water sample preparation procedures to make FPXRF analysis a
viable field analytical technique for metals in water.
Can XRF analysis identify individual species of chromium III and chromium VI?
XR-4
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
X-Ray Fluorescence
EDXRF - Theory of Operation
+ Irradiate samples with X-rays
* Incident X-rays cause inner shell electrons to be
ejected from atom
* Vacancies in inner shell are filled by outer
electrons cascading down
^Cascading electrons produce characteristic
X-rays
XR-4
Notes:
Samples are bombarded with X-ruys (photons of energy) produced by radioisotopes such
as iron-55 (Fe-55), cobalt-57 (Co-57), cadmium-109 (Cd-109), or americium-241 (Am-
241). When a sample is irradiated with X-rays, the source X-rays may undergo scattering
or absorption by sample atoms.
If the X-ray source energy is greater than the absorption edge energy of the inner shell
electron, inner shell electrons are ejected from the atom, creating vacancies.
The electron vacancies are filled by electrons cascading in from outer shell electrons.
Electrons in outer shells have higher energy states than inner shell electrons, and the outer
shell electrons give off energy as they cascade down.
The rearrangement of electrons results in emission of X-rays characteristic of the given
atom. The emission of X-rays, in this manner, is termed X-ray fluorescence. A
qualitative analysis is made by observing the energy of the characteristic X-rays. A
quantitative analysis is made by measuring the X-ray intensity.
XR-5
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
X-Ray Fluorescence
Schematic Diagram of XRF Process
X-ray adsorption and
photoelectron ejection.
X-ray fluorescence transitions.
&EPA
XR-5
Notes:
The K, L, and M shells are the three electron shells generally involved in emission of
X-rays during FPXRF analysis. The most commonly measured X-ray emissions are from
the K and L shells. For "light" atoms like chromium, arsenic, and cadmium, a K-shell
electron is ejected. For "heavy" atoms like lead, mercury, and uranium, an L-shell
electron is ejected.
Each characteristic X-ray line is defined with the letter K, L, or M, which signifies which
shell had the original vacancy and by a subscript alpha (a) or beta (0), which indicates the
higher shell from which electrons fell to fill the vacancy and produce the X-ray. The K0
transition is on average 6 to 7 times more probable than the Kp transition; therefore, the
K,, line is approximately 7 times more intense than the K^ line for a given element,
making the Kn line the choice for quantitation purposes.
The K lines for a given element are the most energetic lines and are the preferred lines for
analysis. For a given atom, the X-rays emitted from L transitions are always less
energetic than those emitted from K transitions. Unlike the K lines, the main L lines (La
and Lp) for an element are of nearly equal intensity. The choice of one or the other
depends on what interfering elements might be present. The L emission lines are useful
for analyses involving elements of atomic number 58 (cerium) through 92 (uranium).
XR-6
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
X-Ray Fluorescence
Radioisotope Sources
+ Source energy greater than the energy of the
target analyte
+ Multiple elements can be determined
* Multiple sources per analyzer
+ X-ray tubes not common
,@rEPA
XR-6
Notes:
An X-ray source can excite characteristic X-rays from an element only if the source
energy is greater than the absorption edge energy for the particular line of the element.
FPXRF is more sensitive to an element with an absorption edge energy close to, but less
than, the excitation energy of the source. For example, with the use of a cadmium-109
source that produces a source of photons at 22.1 kiloelectron volts (keV), FPXRF would
exhibit better sensitivity for zirconium, which has a K line energy of 15.7 keV than for
chromium, which has a K line energy of 5.41 keV.
Elements that are typically analyzed by the individual sources include:
Co-57: Lead (Pb) in paint
Fe-55: Sulfur (S), potassium (K), calcium (Ca), titanium (Ti), and chromium (Cr)
Cd-109: Vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel
(Ni), copper (Cu), zinc (Zn), arsenic (As), selenium (Se), strontium (Sr), zirconium (Zr).
molybdenum (Mo), mercury (Hg), lead (Pb), rubidium (Rb), and uranium (U)
Am-241: Cadmium (Cd), tin (Sn), antimony (Sb), barium (Ba), and silver (Ag)
FPXRF instruments can have more than one source. Typical arrangements include Cd-
109 and Am-241 or Fe-55, Cd-109, and Am-241.
XR-7
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
X-Ray Fluorescence
Instraments with X-ray tubes as sources are not commonly used in the field because of
the larger power requirements for the X-ray tube and the added weight of the instrument.
Can an FPXRF instrument analyze for cadmium using the Cd-109 source?
Radioisotope Sources
Source
Co-57
Fe-55
Cd-109
Am-241
Cm-244
Activity
millicuries
(mCi)
40
20-50
5-30
5-30
60- 100
Half-
Life
(Year)
0.75
2.7
1.3
458
17.8
Excitation Energy
121.9
5.9
22.1,25.0, and 88.03
26.4 and 59.6
14.2
Elemental Analysis Range
Cobalt to cerium
Barium to lead
Sulfur to chromium
Molybdenum to
barium
Calcium to rhodium
Tantalum to lead
Barium to uranium
Copper to thulium
Tungsten to uranium
Titanium to selenium
Lanthanum to lead
K Lines
L Lines
K Lines
L Lines
K Lines
K Lines
L Lines
K Lines
L Lines
K Lines
L Lines
XR-8
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
X-Ray Fluorescence
Modes of Operation
In situ: Point-and-shoot mode
Intrusive: Requires collection of sample
EPA
XR-7
Notes:
For in situ operation, the window of the probe is placed in direct contact with the surface
to be analyzed. The probe of the instrument is operated much like a gun. Because
analyses in this mode are very quick (less than one minute) and heterogeneity can be a
concern, it is typical to take three to four measurements in a small area and average the
values to determine the concentrations of metals.
For intrusive operation, a sample is collected, prepared, and placed in a 31 - or 40-
millimeter (mm) polyethylene sample cup. The sample cup is placed in a covered sample
chamber for analysis.
FPXRF instruments are available that can analyze samples in either mode; others have
only one mode of operation.
XR-9
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
X-Ray Fluorescence
&EPA
XR-B
Notes:
This slide depicts an FPXRF instrument used in the "point-und-shoof mode.
•XR-IO-
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
X-Ray Fluorescence
XR-9
Notes:
This slide depicts another FPXRF instrument used in the point-and-shoot mode.
•XR-11
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
X-Ray Fluorescence
Detectors
+ Gas-filled proportional counters
» Durable, lightweight, efficient
» Poorer resolution
^Solid-state detectors
» Lithium drifted silicon (Si[Li]), mercuric iodide
(Hgl2), and silicon pin diode
» Better resolution
&EPA
XR-10
Notes:
A gas-filled, proportional counter detector is an ionization chamber filled with a mixture
of noble and other gases. An X-ray photon entering the chamber ionizes the gas atoms.
The electric charge produced is collected and provides an electric signal that is directly
proportional to the energy of the X-ray photon absorbed by the gas in the detector. These
are efficient detectors but have only a resolution of 250 electron volts (eV).
During the operation of a solid-state detector, an X-ray photon strikes a biased, solid-state
crystal and loses energy in the crystal by producing electron-hole pairs. The electric
charge produced is collected and provides a current pulse that is directly proportional to
the energy of the X-ray photon absorbed by the crystal of the detector.
Common solid-state detectors include Si(Li), HgI2, and silicon pin diode. The Si(Li)
detector must be cooled to at least -90 °C either with liquid nitrogen or by thermoelectric
cooling using the Peltier effect. It has a resolution of 170 eV. The HgI2 detector operates
at a moderately subambient temperature cooled using the Peltier effect. It has a
resolution of 270 to 300 eV. The silicon pin diode detector operates near ambient
temperatures and is only slightly cooled using the Peltier effect. It has a resolution of 250
eV.
•XR-12-
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
X-Ray Fluorescence
What would be a logistical advantage of using an FPXRF instrument with a HgI2 detector
versus one with a Si(Li) detector?
•XR-J3-
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
X-Ray Fluorescence
Detector Resolution
Resolution Comparison
Sampling containing
CuandZn(1:1)
Hgl2 Detector:
5% (300eV)
Resolution
B.OD TOO 4.00 900
Energy KeV
Proportional
Counter
13% Resolution
EPA
Si (Li) Detector „
2.5%(170eV) 0.1
Resolution o
Cu Ka4 »Zn Ka
ZnKp
e.oo 900
Energy KeV
Cu Ka 1 '
\r
».OO 400
Energy KeV
XR-11
Notes:
This figure shows the resolution differences of some of the common FPXRF detectors
and the effect of quantitation of metals with x-ray lines of similar energy values.
•XR-14-
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
X-Ray Fluorescence
Interferences
Physical matrix effects
High moisture content
Inconsistent positioning of samples
Chemical matrix effects (absorption and
enhancement phenomena)
Spectral interferences (peak overlaps)
&EPA
XR-12
Notes:
Physical matrix effects result from variations in the physical character of the sample, such
as particle size, uniformity, homogeneity, and surface condition. Field studies have
shown heterogeneity of the sample generally has the largest impact on comparability with
confirmatory samples. Every effort should be made to thoroughly homogenize soil
samples before analysis. One way to reduce particle size effects is to grind and sieve all
soil samples to a uniform particle size.
Moisture contents above 20 percent may cause problems. This error can be minimized by
drying, preferably by using a convection or toaster oven. Microwave drying can increase
variability between FPXRF data and confirmatory data and can cause arcing when metal
fragments are present in the sample.
Inconsistent positioning of samples in front of the probe window is a potential source of
error because the X-ray signal decreases as the distance from the radioactive source
increases. This error is minimized by maintaining the same distance between the window
and the sample. For best results, the window of the probe should be in direct contact with
the sample.
Chemical matrix effects can occur as X-ray absorption and enhancement phenomena.
Examples include: iron tends to absorb copper X-rays, while chromium will be enhanced
in the presence of iron. The effects can be corrected mathematically through the software
of the FPXRF instrument.
•XR-15-
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
X-Ray Fluorescence
If the energy difference between two peaks in eVs is less than the resolution of the
detector in eVs, then the detector will not be able to fully resolve the peaks. Examples
include the overlap of the iron K^ peak with the cobalt Ka peak or the arsenic Ka peak
with the lead La peak. In the arsenic and lead case, lead can be measured from the lead Lp
peak. Arsenic can still be measured from the arsenic Ka peak with the use of
mathematical corrections that subtract out the lead interference. Arsenic concentrations
cannot be efficiently calculated for samples with lead to arsenic ratios of 10 to 1 or more.
Would it be prudent to dry soil samples if mercury was the target analyte?
•XR-16-
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
X-Ray Fluorescence
Calibration of FPXRF Instruments
+ Fundamental parameters
*• Empirical
+Compton normalization
XR-13
Notes:
The fundamental parameters (FP) calibration is a "standardless" calibration that relies on
the spectrometer's response to pure elements and uses built-in mathematical algorithms to
compensate for matrix effects. FPXRF instruments that employ fundamental parameters
or similar mathematical models in minimizing matrix effects typically do not require site-
specific calibration standards (SSCS). The FP calibration is performed by the
manufacturer. If the FP calibration model is to be optimized, the analyst can adjust the
calibration curves (slope and y-intercept) on the basis of results from check samples.
An empirical calibration can be performed using SSCSs, site-typical standards, or other
standards prepared from concentrated metals solutions. The use of SSCSs are preferable
because they closely match the sample matrix. SSCSs are well prepared samples collected
from the site of interest that have analyte concentrations determined by inductively
coupled plasma (ICP), atomic absorption (AA), or other EPA-approved methods. The
standards should contain all the analytes of interest and interfering analytes.
The Compton normalization method is based on analysis of a single, certified standard,
such as an SRM or SSCS, and normalization for the Compton peak. The Compton peak is
produced from incoherent backscattering of X-ray radiation from the excitation source and
is present in the spectrum of every sample. The Compton peak intensity changes with
differing matrices. Normalizing to the Compton peak can reduce problems with varying
matrix effects among samples.
•XR-17-
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
X-Ray Fluorescence
Sample Preparation
In situ
» Remove nonrepresentative debris
» Smooth, flat surface
» Not saturated
Intrusive
» Homogenize
» Remove nonrepresentative debris
»Dry
» Sieve
EPA
XR-14
Notes:
In situ or "point and shoot" analysis requires little sample preparation. First, any
nonrepresentative debris, such as rocks, pebbles, leaves, vegetation, roots, and so forth,
should be removed from the soil surface. Second, the surface must be smooth so that the
probe window makes good contact with the soil surface. Last, the soil surface should not
be saturated such that ponded water exists.
For intrusive analysis, the sample must first be collected. After the sample is collected, the
most critical sample preparation step is thorough homogenization. Mixing the sample in a
plastic bag works well. Any large nonrepresentative debris should be removed from the
sample. If the sample is not wet (less than 20 percent moisture) and is not high in clay
content, it can be sieved in the field prior to placing it in a container. If the sample has
greater than 20 percent moisture, the sample should be dried, preferably in a convection or
toaster oven. Microwave drying is discouraged because it can increase variability of
results and arcing can occur when metal fragments are present in the sample. After the
sample is dried, it should be ground with a mortar and pestle and passed through a 40- or
60-mesh sieve. The sample is placed in a 31- or 40-mm polyethylene cup and covered
with Mylar film.
•XR-J8-
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
X-Ray Fluorescence
Quality Control
4 Energy calibration checks
* Blanks
» Instrument
» Method
+ Calibration verification checks
+ Precision
* Detection limits
*• Reporting results
EPA
XR-15
Notes:
Energy calibration check samples consist of a pure element, such as iron, lead, or copper,
that are analyzed to determine whether the characteristic X-ray lines are shifting, which
would indicate drift within the instrument. This check also serves as a gain check in the
event that ambient temperatures are fluctuating greatly (greater than 10 to 20 °F). The
energy calibration check should be run at a frequency consistent with the manufacturer's
recommendations. Generally, this would be at the beginning of each working day, after
the batteries are changed or the instrument is shut off, at the end of each working day, and
at any other time when the instrument operator believes that drift is occurring during
analysis.
Two types of blanks may be used during FPXRF analysis. The first is an instrument
blank. An instrument blank is used to verify that no contamination exists in the
spectrometer or on the probe window. The instrument blank can be silicon dioxide, a
Teflon block, a quartz block, "clean sand," or lithium carbonate. The instrument blank
should be analyzed at a minimum of once per day and preferably once every 20 samples.
The instrument blank should not contain any target analytes above the method detection
limit (MDL). The second type of blank is a method blank. The method blank is used to
monitor for laboratory-induced contaminants or interferences. The method blank can be
"clean" silica sand or lithium carbonate that undergoes the same sample preparation
procedures as the samples. The method blank should be analyzed at the same frequency as
the instrument blank and should not contain any target analytes above the MDL.
•XR-19-
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
X-Ray Fluorescence
Calibration verification check samples are used to check the accuracy of the instrument
and assess the stability and consistency of the analysis of the target analytes. The check
sample can be an SSCS or an SRM such as the National Institute of Standards and
Technology (NIST) SRMs, which contain the target analytes, preferably at concentrations
near any action levels for the site. Examples of NIST SRMs that can be used include
SRMs 2709, 2710, and 2711. The check sample should be run at the beginning and end of
each day. The percent difference (%D) between the true value and measured value should
be less than 20 percent. Commercial performance evaluation (PE) samples that are
prepared for ICP or AA methods are not recommended for an accuracy check because they
often contain analytes at low concentrations and are certified using ICP or AA methods,
not XRF or other "total metals" methods.
Precision or reproducibility of FPXRF measurements is monitored by analyzing a sample
with low, medium, and high concentrations of target analytes. A minimum of one
precision sample should be run per day by conducting 7 to 10 replicate measurements on a
sample. The precision is assessed by calculating a relative standard deviation (RSD) for
the replicate measurements. The RSD values should be less than 20 percent for most
analytes except chromium, which should be less than 30 percent. It is especially important
to know the precision of the instrument near action levels. The precision is dependent on
analyte concentrations; as the concentration increases, the precision increases. The
measurement time for each source also will affect precision. Shorter source measurement
times (30 seconds) have less precision, and generally are used for initial screening or
delineation of hot-spots. Longer measurement times (300-600 seconds) have greater
precision and typically are used to meet stringent requirements for precision and accuracy.
The results for replicate measurements of a low-concentration sample can be used to
generate an average site-specific MDL. The MDL is defined as three times the standard
deviation (SD) of the results for a low concentration sample. With the exception of
chromium, the MDLs for most analytes are in the range of 40 to 200 mg/kg.
In FPXRF analysis, the SD from counting statistics is defined as the square root of the
gross counts for the target analyte peak. On the data print out from most FPXRF
instruments, the SD of the measurement will be given. Most manufacturers state that if
the measured value is less than three times its counting statistics SD, the value should not
be reported. It is possible for an analyte measurement to be above three times its SD, but
below the MDL, calculated from the replicate measurements. In this case, it is advisable
to qualify the data as estimated with a "J."
•XR-20-
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
X-Ray Fluorescence
Instrument Precision
Analyte
Antimony
Arsenic
Barium
Chromium
Copper
Iron
Lead
Zinc
Average RSD at 5 to 10 Times the Method Detection Limit
TN
9000
6.54
5.33
4.02
22.25
7.03
1.78
6.45
7.27
TNLead
Analyzer
NR
4.11
NR
25.78
9.11
1.67
5.93
7.48
X-MET
920-P
NR
3.23
3.31
22.72
8.49
1.55
5.05
4.26
X-MET
920-MP
NR
1.91
5.91
3.91
9.12
NR
7.56
2.28
XL
Spectrum
Analyzer
NR
9,20
NR
No Data
13.20
3.30
6,50
11,20
MAP
Spectrum
Analyzer
NR
6.68
NR
NR
14.86
NR
12.16
0.83
SEFA-P
Analyzer
7.20
No Data
6.99
No Data
2.54
2.44
4.86
No Data
Notes:
mg/kg Milligrams per kilogram
NR Not reported
NA Not applicable; analyte was reported by the FPXRF instrument, but was not al high enough
concentrations lor MDL to be determined
& EPA XR'18
Notes:
This table shows precision data represented as RSD values for seven common FPXRF
instruments. Notice that precision is good for most metals, except chromium, with RSD
values less than 10 percent. The XL spectrum analyzer and MAP spectrum analyzer have
detectors with poorer resolution, which causes slightly poorer precision for some metals.
This table shows the performance of a FPXRF instrument during the analysis of
commercial PE samples.
•XR-21
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
X-Ray Fluorescence
Precisioi
»
-------
X-Ray Fluorescence
Precision Versus Concentration
50
40
Q 30
CO
DC
I 20
8
1 0
•N-
4 6
Thousands
Copper Concentration (mg/kg)
10
40
30
g
Q
W in
CC 20
s
1 0
t-
t
Z 4
Thousands
Lead Concentration (mg/kg)
•A7J-23-
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
X-Ray Fluorescence
Precision-based MDLs (mg/kg)
4
Analyte
Antimony
Arsenic
Barium
Chromium
Copper
Lead
Nickel
Zinc
Precision-based MDLs (mg/kg
TN9000
55
60
60
200
85
45
100
80
TNLead
Analyzer
NR
50
NR
460
115
40
NR
95
X-MET
920-P
NR
55
30
210
75
45
NA
70
X-MET
920-MP
NR
50
400
110
100
100
NA
NA
) by Instrument
XL
Spectrum
Analyzer
NR
110
NR
900
125
75
NA
110
MAP
Spectrum
Analyzer
NR
225
NR
NR
525
165
NR
NA
Motes:
ng/kg Milligrams per k logram
MR Not reported
>JA Not applicable; analyte was reported by the FPXRF instrument, but was not at high
enough concentrations for MDL to be determined
* EPA XR'18
Notes:
This table shows the calculated precision-based MDLs for six FPXRF instruments using
data from an EPA SITE demonstration. The MDLs were three times the SD of replicate
measurements. Note the high MDL for chromium, which is a difficult analyte for FPXRF
analysis. Again, the FPXRF instruments on the right side of the table had detectors with
poorer resolution; therefore, their MDLs were higher.
>XR-24-
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
X-Ray Fluorescence
Comparability to Confirmatory
Analysis
+ SITE demonstration
+Creation of EPA SW-846 draft method 6200
+ Regression analysis
EPA
XR-19
Notes:
During an EPA SITE demonstration in 1995, seven FPXRF instruments were evaluated at
two sites. The FPXRF instruments analyzed over 300 soil samples from three different
soil textures that underwent four different preparation methods. The soil samples
contained several metals ranging in concentration from nondetect to tens of thousands of
mg/kg. The primary target metals were arsenic, barium, chromium, copper, lead, and zinc.
The results of the demonstration were published in six innovative technical evaluation
reports (ITER).
The results of the SITE demonstration also were used to create EPA SW-846 method 6200
for FPXRF analysis of soils and sediments for metals. This method has been published in
the Proposed Update 4 to the EPA SW-846 Methods.
The FPXRF data was compared to data generated by EPA Methods 3050 and 6010
through regression analysis. Homogeneity of the soil sample was found to be the most
critical factor when comparing the FPXRF data to the confirmatory data. In general, the
correlation coefficients from the regression analysis were 0.90 or greater for arsenic,
copper, lead, and zinc, and 0.70 or greater for barium and chromium. In general, the
FPXRF instruments tended to overestimate barium and chromium concentrations.
•XR-25-
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
X-Ray Fluorescence
Effect of Preparation on Data Comparability
EPA
XR-20
Notes:
This figure shows the effect of sample preparation on data comparability. Note that the
scatter of the data was significantly reduced between the in situ unprepared and the in situ
prepared steps. Homogenization of the sample took place between these two sample
preparation steps.
•XR-26-
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
Q>
u
I
I
a
s
t
•5
a
I
I
.§
u
i
*3
S
i
-------
X-Ray Fluorescence
R
C
&
egressi
ompara
All Data
Sand
-oam
Clav
Pr?p1
Preo2
Pret>3
Preo4
All Data
Sand
Loam
Clay
Prepl
Prep 2
Preo3
Preo4
on Parameters3 for
ibility Study
Am
n
.sj.6_
359
.445
3
204
2Q5_
202
201
r»
0.95
0.97
J3,96_
0.91
O.98
0.98
0.96
MltB
Int.
1.62
1.41
1.51
2.69
1.38
1.20
1.45
0.96
0.98
0.96
0.85
0.95
0.99
0.98
Lm
n
1205
357
451
397
30 5_
298
302
300
r»
0.92
0.94
0.93
0.90
0.80
0.97
0.98
0.96
•d
hit.
1.66
1.41
1.62
2.40
1.88
1.41
1.26
138
Stan*
0.95
0.96
0.97
0.90
0.86
0.96
0.99
1.00
Cor
n
984
385
465
136
256
246
236
246
..I*
_QJ3 ....
0.94
.__Q,92
0.46
0.87
0.96
0.97
0.96
Z
ft
1103
329
423
351
— 28fi_
272
274
271
f
0.89
0.93
0.85
0.90
. 0,7.9..
0.95
0.93
0.94
itwr
Int.
...zia
1.26
-zoa_.
16.60
3,89
2.04
1.45
1.99
Slop*
. ...0,33
JiSSL_
0.95
0.57
0.87
0.93
0.99
0.96
nc :'
biL
1.86
1.78
2.57
1.70
1.8S
1.32
1.41
Stoo*
Q.95
0.93
0.90
JJ.9B
0.87
0.93
1.00
1.01
Notts:
a These regression parameters are based on r2 Coefficient ol determination
__- logto transformed data Int. Y-intereept.
EPA n Number of data points. — No applicable data.
XR-21
Notes:
This table shows the regression parameters for four metals based on the comparability
study between a FPXRF instrument and EPA methods 3050 and 6010. The correlation
coefficients r2 generally were higher than 0.9 and slopes close to 1.0 for arsenic, copper,
lead, and zinc. Note the most dramatic improvement in r values between preparation 1
and 2 for all metals; this was due to homogenization.
•XR-28'
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
X-Ray Fluorescence
Regression Parameters for Comparability Study"
AH Data
Sand
Loam
Clay
Prep 1
Prep 2
Prep 3
Prep 4
Arsenic
n
816
359
445
3
204
205
202
201
r2
0.95
0.97
0.96
—
0.91
0.98
0.98
0.96
Int.
1.62
1.41
1.51
—
2.69
1.38
1.20
1.45
Slope
0.96
0.98
0.96
—
0.85
0.95
0.99
0.98
Copper
n
984
385
463
136
256
246
236
246
r2
0.93
0.94
0.92
0.46
0.87
0.96
0.97
0.96
Int.
2.19
1.26
2.09
16.60
3.89
2.04
1.45
1.99
Slope
0.93
0.99
0.95
0.57
0.87
0.93
0.99
0.96
All Data
Sand
Loam
Clay
Prep 1
Prep 2
Prep 3
Prep 4
Lead
n
1205
357
451
397
305
298
302
300
r2
0.92
0.94
0.93
0.90
0.80
0.97
0.98
0.96
Int.
1.66
1.41
1.62
2.40
2.88
1.41
1.26
1.38
Slope
0.95
0.96
0.97
0.90
0.86
0.96
0.99
1.00
Zinc
n
1103
329
423
351
286
272
274
271
r2
0.89
0.93
0.85
0.90
0.79
0.95
0.93
0.94
Int.
1.86
1.78
2.57
1.70
3.16
1.86
1.32
1.41
Slope
0.95
0.93
0.90
0.98
0.87
0.93
1.00
1.01
Notes:
a
n
r2
Int.
These regression parameters are based on logic transformed data
Number of data points.
Coefficient of determination.
Y-intercept.
No applicable data.
•XR-29-
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
X-Ray Fluorescence
Advantages of XRF
+ Portable
4- Fast analysis
4 Multi-element analysis technique
*• No waste generated
*• Easy to operate
* Little sample preparation
4 Nondestructive technique
EPA
XR-22
Notes:
Most instruments weigh less than 30 pounds and can be operated without battery power
for eight to ten hours.
A sample can be analyzed in less than five minutes. A throughput of 50 to 100 samples in
a day can be achieved.
As many as 35 elements can be analyzed in a single analysis with multiple sources.
Because no solvents or acids are used for sample extraction, there is no waste generated,
which eliminates disposal costs.
Most operators can be trained in one to two days. The software is menu-driven. No data
manipulation is required. Instruments are marketed for use by general scientists.
Little or no sample preparation is required which enhances sample throughput and saves
time and money.
The sample is not destroyed during preparation or analysis; therefore, it is possible to
perform replicate analyses on the same sample and send the same sample for confirmatory
analysis to perform comparability studies. The sample also may be archived for later use
as a soil standard.
•XR-30-
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
X-Ray Fluorescence
Limitations of XRF
*• Relatively high detection limits
* Matrix-variable results (interferences)
+Acquisition of soil standards
* Radioactive sources
+ Dewar and liquid nitrogen needed
XR-23
Notes:
Detection limits for chromium are 200 mg/kg or greater. Action levels for some elements,
such as arsenic or cadmium, may be below the detection limits of XRF.
Elemental concentrations between different soil types or matrices may change which can
cause interferences such as between arsenic and lead. Site-specific calibration standards
can compensate for some of these effects.
Soil standards are difficult to obtain. One of the best sources is SRMs from NIST. The
standards are expensive, and may cost from $200 to $500 each.
In some states, a specific license is required to operate some of the FPXRF instruments.
The total cost to attend a radiation safety course, obtain the necessary paperwork, and pay
the fee for the license can range from $500 to $1,000. The Cd-109 source should be
replaced or reshimmed every two to four years. The cost of replacement is approximately
$2,000 to $5,000.
The instruments that have a Si(Li) detector will require liquid nitrogen and a dewar to hold
the liquid nitrogen. This requirement adds time and cost to a project in order to:
(1) find a source of liquid nitrogen near the site, (2) purchase the liquid nitrogen, and
(3) spend the time each day filling the internal dewar of the instrument and allowing the
Si(Li) detector to cool down prior to analysis.
For additional information on this topic, refer to page A-l at the end of this module.
•XR-3J'
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
X-Ray Fluorescence
Applications Other Than
Characterization
*• Metal plating facilities
*• Scrap yards and recycling facilities
*• Foundries
* Mitigation and monitoring
XR-24
Notes:
XRF analyzers have a number of applications other than for characterization. Examples of
these applications include:
- In metal plating operations, used to identify impurities in metal solutions and
coatings on surfaces as well as determine when it is necessary to renew dip-tank
solutions.
- In scrap and recycling operations, used to separate various metals for recycling,
resmelting, or reuse.
- At foundries, used to determine concentrations of metals in sand.
Use in mitigation and monitoring applications. Primary uses include determination
of concentrations of metals in water treatment plant sludge; determination of
airborne lead exposure levels in on-site filter media; and performance of dust wipe
sample analysis for lead and other metals.
-XR-32-
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
X-Ray Fluorescence
EPA
XR-25
•XR-33-
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
X-Ray Fluorescence
-iva^.-'*
. •- -•*>*. j**"*1-'* '*•
± .* »•-
fe^^
XR-26
•XR-34-
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
X-Ray Fluorescence
FPXRF Used for In Situ Testing Mode
XR-27
•XR-35'
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
X-Ray Fluorescence
FPXRF Set Up for On-Site
Laboratory Analysis
EPA
XR-28
•XR-36-
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
Mercury Vapor Analyzers
Inorganic Chemical Characterization
Techniques and Data Interpretation
+X-Ray Fluorescence
c=> + Mercury Vapor Analyzers
+ Immune-assay
*•Anode Stripping Voltammetry
4 Graphite Furnace Atomic Absorption Spectroscopy
4-Cyanide Measurement Techniques
4 Water Quality Measurement Techniques
4 Emerging and Innovative Approaches and
Instruments
4 Hands-on Activity for Inorganic Analysis
MV-l
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
Mercury Vapor Analyzers
Notes:
Topic Overview
4 Topic Description: Explains the application of
mercury vapor analyzers to various matrices
^ Key Points
» Applications
» Major sources of mercury
» Portability
» Operation
» Potential interferences
&EPA
MV-2
This section explains the operation and application of using mercury vapor analyzers to
detect mercury vapors in various sample types including air, water, soil, biological (for
example, fish and vegetation), and geological samples.
The following key points are discussed: (1) application, (2) major sources of mercury,
(3) portability, (4) operation, and (5) potential interferences.
MV-2
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
Mercury Vapor Analyzers
Application of Mercury Vapor
Detectors
+ Low-level atmospheric measurements
4-Toxic-level measurements
MV-3
Notes:
Low-level ambient air analyzers provide continuous monitoring of total gaseous mercury,
with a detection limit of <0. 1 ,ug/m3 and an update rate of 2.5 minutes.
Applications include providing background measurements, plume profiling, landfill
monitoring, power plant monitoring, and seismic prediction.
Toxic-level measurements typically require more portable, hand-held units for
applications such as mercury surveys, spill response, hazardous waste site monitoring,
and mercury exclusion tests.
The detection levels of hand-held units (down to 3 ^g/m3) may not be sensitive enough to
determine whether EPA's risk-based ambient air levels are met.
MV-3
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
Mercury Vapor Analyzers
Major Sources of Mercury
Coal-fired power plants (largest)
Gold refining (Amazon River basin)
Pulp and paper mills (Chlor-Alkali plants)
• Battery manufacturers
Fluorescent lamps
Electrical industry
Metals smelting
Mercury mining
Petroleum refining
EPA
MV-4
Notes:
Despite the relative natural abundance of mercury, most of the mercury in the biosphere is
anthropogenic (believed to have originated from human activity).
Anthropogenic mercury may be dispersed through the atmosphere. As a result,
background levels of mercury throughout the Northern Hemisphere are in the range of 1
to 2
Atmospheric wet and dry deposition is believed to be the main pathway for entry of
mercury into the ecosystem.
MV-4
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
Mercury Vapor Analyzers
Portable and Operations
+ Portable instruments
» Hand-held
» Table-top
+ Operation of analyzers
EPA
MV-5
Notes:
Some instrument models (true field-portable) are light-weight, weighing less than 10
pounds, and are battery-powered with an operating time as many as six hours.
Other models (self-contained ambient air analyzers) are table-top size, weigh 50 to 100
pounds, and require 110 volt power supply. They can operate continuously at remote
locations for as long as three months.
The analyzers are easy to use and contain menu-driven software. They often contain a
funnel-shaped device that draws vapors from the soil surface or ambient air into the
analysis chamber. Most analyzers use a gold film technology on a wheatstone bridge as a
sensor. When mercury is present, it will adsorb to the thin gold film sensor, which
undergoes a change in electrical resistence proportional to the mass of mercury adsorbed
onto its surface. For continuous operations, the analyzer is configured with two identical
cartridges, alternately sampling and analyzing.
The hand-held analyzers provide a response within 4 to 30 seconds. The table-top
analyzers have a programable update rate with standard reading every 2.5 minutes.
MV-5
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
Mercury Vapor Analyzers
Data Quality
+Accuracy
+ Sensitivity
4 Range
4 Potential Interferences
MV-6
Notes:
Hand-held detectors generally have an accuracy of ±1% to 5% with a sensitivity down to
about 3 (Ug/m3 (micrograms per cubic meter). Table-top analyzers can have accuracy of
1% and a sensitivity of 0.0001 yug/m3 (a sensitivity that is four orders of magnitude
lower).
The specific type of mercury detector to be used is determined by the purpose of analysis
and quality of data required.
The typical range of concentrations for hand-held instruments is from 3 /ug/m3 to
1,000 ,ug/m3. The typical range of concentrations for table-top analyzers is from
0.0001 ^g/m3 to approximately 5
Mercury vapor analyzers are cross sensitive to carbon monoxide and sulfur compounds.
These compounds will pass directly through the unit's internal filters and go directly to
the detector. This effect will result in erratic detections which will be indicated on the
display. This can occur in both the survey and sample modes. Generally, during the
cleanup of mercury and its vapor, a sulfur-based compound is used to convert elemental
mercury into a mercuric salt. Care must be taken to pay attention to the instrument to
determine if it is detecting mercury or the sulfur compound. Avoid surveying areas where
there may be combustible sources present because of the generation of carbon monoxide.
Along the same lines, smoking in the vicinity of the instrument should be avoided.
MV-6
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
r
Mercury Vapor Analyzers
Applications Other Than
Characterization
* Ambient air monitoring
* Exhaust air monitoring
*• Process monitoring
* Monitoring of mercury in chlorine plants
MV-7
Notes:
Examples of applications of mercury vapor analyzers for uses other than for
characterization include:
- Can obtain continuous or discrete measurements in gases (air, nitrogen, hydrogen,
or natural gas) or liquid samples (process water).
- Interface with printers, PCs, dataloggers, recorders, and modems.
Most capable of site-specific settings for status and alarm outputs.
- Monitoring concentrations of mercury in cell rooms of chlorine plants is
important in the protection of people who work in those plants and may be
required in some countries.
Name two types of sites that are likely to have mercury waste.
MV-7
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
-------
Immunoassay
Inorganic Chemical Characterization
Techniques and Data Interpretation
..; ,,,.€, ,.<^^^j4f%i?ai!4WitMi!)(ia(KMMttMH^HHMIII^^
^X-Ray Fluorescence
*• Mercury Vapor Analyzers
c=c> 4- Immunoassay
4 Anode Stripping Voltammetry
4 Graphite Furnace Atomic Absorption Spectroscopy
4 Cyanide Measurement Techniques
4 Water Quality Measurement Techniques
4 Emerging and Innovative Approaches and
Instruments
4 Hands-on Activity for Inorganic Analysis
EPA "-1
fl-1
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
fmmunoassay
Notes:
Topic Overview
* Topic Description: Explains the use of
immunoassay test kits to detect mercury in soil and
water
+ Key Points
» Summary of method
» Apparatus and materials
» Analysis procedures
»interferences
» Quality control
» Method performance
11-2
This section explains the operation and application of using immunoassay test kits to
detect mercury in soil and water.
The following key points are discussed: (1) summary of method, (2) apparatus and
materials, (3) analysis procedures, (4) interferences, (5) quality control, and (6) method
performance.
11-2
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
Immunoassay
Immunoassay
+ BiMelyze field screening test
>> Mercury in soil and water
» Detection limits
+ Intended use
+ Summary of method
* Apparatus and materials
>> Extraction kit
» Assay kit
» Other supplies
EPA
11-3
Notes:
The only commercially available inorganics immunoassay test kit is the BiMelyze
immunoassay for mercury in soil and water. The kit is manufactured by BioNebraska. It
determines inorganic mercuric (+2) ions in soil and water. In the quantitative mode, it
has a detection limit of 0.5 parts per million {ppm) for soil and 0.25 parts per bilion (ppb)
for water. The overall dynamic test range for the immunoassay is 0.5 ppm to 40 ppm for
soil. In general, it is difficult to develop antibodies for metals because they are so small.
Therefore, very few immunoassay test kits are available for metals.
BiMelyze test kits are intended for site-specific field sampling activities. The results of
the immunoassay generally qualify as screening-level data, subject to confirmation by a
definitive analysis (identification and quantification, that is, EPA method 7470 or 7471),
applied for the most part to positive results.
For water samples, no sample preparation is required. For soil samples, the mercury is
extracted with a mixture of hydrochloric and nitric acids, buffered, and then added to the
mercury assay tubes or wells. After the addition of antibody, conjugate, and substrate, the
presence or absence of mercury is determined colorimetrically. The color of the sample is
compared to standards, either visually or with a photometer for semiquantitative or
quantitative results.
A soil extraction kit is needed for soil analysis. All the reagents and supplies necessary to
extract 16 soil samples come in a small cardboard box. This kit also contains a negative
control standard and two positive control standards at 5 and 15 ppm. The cost of this kit
11-3
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
Immunoassay
is approximately $95. The user must supply the acids, balance, timer, laboratory tissues,
and disposable gloves. BiMelyze offers a 96-microwell plate assay kit for quantitative
laboratory analysis at a price of approximately $450. BiMelyze also offers a 16-tube field
screening, semiquantitative kit. The tube kit contains all the reagents and supplies
necessary to perform 16 analyses. The cost of the tube kit plus the soil extraction kit is
approximately $335. The immunoassay kit is stable for 6 months when stored at 4 °C. A
500-milliliter (mL) squirt bottle and graduated cylinder must be purchased separately.
BiMelyze offers a differential photometer for approximately $935. The differential
photometer is small and can be operated without battery power.
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
Immunoassay
Analysis Procedures
sample
4 Add antibody
4-Add conjugate
4- Add substrate
4 Add stop solution
4 Read absorbance
EPA
lt-4
Notes:
The BiMelyze immunoassay requires the sequential addition of four reagents, with a five-
minute incubation period for each. The sample is added to a tube that contains a protein
bound to a solid support. Any mercuric ion in the sample wili bind to the protein. The
sample is incubated for five minutes and then the tube is rinsed twice with distilled water.
Next, an anti-mercury antibody is added to the sample tube, which binds to the mercury.
The sample tubes are incubated for five minutes and then rinsed twice with a buffered
rinse. This rinse removes unbound antibody. A conjugate is then added and incubated
for five minutes. Next, a substrate (hydrogen peroxide and a chromophore) is added to
each tube and the peroxidase reaction is allowed to proceed for 15 minutes. The amount
of anti-mercury antibody bound is detected by binding the horseradish peroxide-labeled
secondary antibodies to the primary anti-mercury antibodies. The amount of bluish-green
color in the tube is a function of the amount of mercury in the sample. The intensity of
the color is proportional to the log of the mercury concentration. Color development is
terminated by addition of a stop solution. The absorbance is measured at 405 nanometers
(nm) and compared to the appropriate control. For the semiquantitative tube assay,
results will be reported as less than 5 ppm, between 5 and 15 ppm, and greater than 15
11-5
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
Immunoassay
Interferences, Quality Control, Method
Performance, and Confirmation
+ Interferences
» Other metals
» Radioactivity
4 Quality control
4 Method performance
» Analysis time
» Analysis of certified reference materials
» Comparison to other analytical methods
» Draft EPA SW-846 Method 4500
* Confirmation
EPA
11-5
Notes:
Numerous metals such as barium, cadmium, lead, silver, chromium, arsenic, copper, iron,
nickel, strontium, zinc, and thallium have not caused interference at concentrations up to
100 milligrams per liter (mg/L) in solution. Radiation may be a concern when using these
kits at mixed waste sites. Several factors influence the effect of radiation on
biomolecules such as enzymes. The most important factor is radiation dose. It is known
that thousands of rads are required to significantly reduce the catalytic activity of
enzymes. Therefore, considering the large sample dilution, small volumes assayed, and
short incubation times involved, bioassays are an effective method even with highly
radioactive samples.
Because reactions in immunoassays depend strongly on temperature and the integrity of
the reagents, absolute absorbance values for control samples may not be reproduced.
Therefore, negative and positive mercury controls must be included with each assay. The
manufacturer has established acceptable absorbance values for the control standards. It
also is imperative not to use test kits after their expiration date and to use the test kits
within their specified storage and operating temperatures limits.
A trained user should be able to analyze 20 to 40 soil samples in a day. Semiquantitative
results are found to be accurate in all cases for certified reference soils with
concentrations ranging from 1 to 122 ppm. In a study of 69 soil samples collected from a
Superfund site, the mercury immunoassay semiquantitative results were compared to
mercury results from cold vapor atomic absorption (CVAA). Nine of the 69 results (13
percent) were found to be false positives and two were found to be false negatives (2.9
II-6
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
Immunoassay
percent). Three of the false positive results occurred in samples quantitated using the
CVAA method at 4.1 to 4.7 ppm, where the immunoassay method gave results of 5 to 15
ppm. All the method performance data can be found in Draft EPA SW-846 Method
4500, to be included in Update 4.
In the absence of other regulations and guidelines, and in the case of samples of largely
unknown composition, confirmatory analysis is needed for every positive immunoassay
result. Users should note the requirement for extended digestion to convert methyl
mercury into a chemical form detected by the assay. No negative determinations can be
made without taking into account the specificity of the assay and its possible
susceptibility to interferences and matrix effects.
In the absence of other regulations and guidelines, the California Environmental
Protection Agency recommends that assay results be confirmed in the following manner:
(a) For the delineation of mercury contamination in a coherent mass of soil, the required
frequency of confirmation by an approved method resulting in identification and
quantification is at least 10 percent of the samples that test positive (above the
detection limit).
(b) Ten to twenty percent of samples with results above the detection level but below the
target or action level should be confirmed by an approved, fully quantitative method.
(c) Five to ten percent of all samples with negative (below detection limit) results should
be confirmed by an approved method.
For additional information about this topic, refer to page A-l at the end of this module.
II-7
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
Immunoassay
Applications Other Than
Characterization
Monitor progress of removal action/remediation
Measure mercury in animal tissue
Measure mercury on building and equipment
surfaces
11-6
Notes:
Immunoassay analysis can be used to monitor removal actions and with adequate
confirmation sampling, allows more frequent testing of samples than other approaches.
Immunoassay analysis can be used to determine the levels of mercury in animal tissues,
principally seafood.
Immunoassay can be used to measure mercury on wipe test samples on building and
equipment surfaces.
11-8
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
Anode Stripping Voltammetry
Inorganic Chemical Characterization
Techniques and Data Interpretation
+ X-Ray Fluorescence
4 Mercury Vapor Analyzers
4 Immunoassay
^ Anode Stripping Voltammetry
+ Graphite Furnace Atomic Absorption Spectroscopy
+ Cyanide Measurement Techniques
4 Water Quality Measurement Techniques
4 Emerging and Innovative Approaches and
Instruments
4 Hands-on Activity for Inorganic Analysis
EPA AS'1
AS-1
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
Anode Stripping Voltammetry
Topic Overview
Topic Description: Explains the operation and use of
anode stripping voltammetry for detecting metals in
various matrices
Key Points
» Principles of operation
» Application
»Instrumentation
» Analysis procedures
» Method performance
»Interferences
» Advantages and limitations
» Applications other than characterization
EPA AS'2
Notes:
This section explains the operation and application of anode stripping voltammetry
(ASV) in detecting metals in waters, soil solutions, soil extracts, and plant nutrient
solutions.
ASV is just one specific analytical technique (but probably the most widely used) under
the general electroanalytical term of voltammetry. Voltammetry encompasses all current-
voltage techniques that involve application of various potentials to the indicator electrode
in relation to the reference electrode, with the resulting current measured at the potential
for oxidation or reduction of the analyte.
The following key points are discussed: (1) principles of operation, (2) application,
(3) instrumentation, (4) analysis procedures, (5) method performance, (6) inteferences,
(7) advantages and limitations, and (8) applications other than characterization.
AS-2
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
Anode Stripping Voltammetry
Anode Stripping Voltammetry (ASV)
*• Principles of operation
» Electrolysis step
» Stripping step
» Metal determination
» Quantitation
4 Application
» Metals in water
» EPA SW-846 methods
AS-3
Notes:
ASV analysis involves a two-step process consisting; of 1) an electrolysis step; and 2) a
stripping step.
1. The first step involves applying a negative potential to the working electrode
which (1) reduces the metal ions, (2) preconcentrates the metal ions, and
(3) deposits them on a working electrode. The electrolysis step usually is
performed using a hanging mercury drop electrode, mercury thin film electrode, or
glassy carbon electrode. This step usually takes between 30 seconds and 2
minutes.
2. During the second, or stripping, step, a constant oxidizing current is applied to the
working electrode and the metals are stripped back into solution. The potential of
the working electrode is measured during stripping, resulting in a plot of potential
over time. Metals present in a sample are identified by their characteristic
potential. As long as a metal is being stripped off, the potential remains stable.
The stripping time for a metal is proportional to its amount in solution and serves
as the basis for making a quantitative determination. The concentration of several
metals can be determined during a single measurement, since each metal is
oxidized at a different potential.
ASV can detect virtually all metals of interest in water and soil solutions, including
antimony, arsenic, copper, chromium, cadmium, cobalt, lead, mercury, nickel, selenium,
silver, and zinc. Mercury, antimony, and arsenic are typically analyzed using the gold
AS-3
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
Anode Stripping Voltamtnetry
film-plated, glassy carbon electrode. Two ASV methods are currently in the EPA SW-
846 methods, one for arsenic and one for mercury.
ft
Can ASV techniques distinguish between different species {oxidation states) of the same
metal?
AS-4
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
Anode Stripping Voltammetry
ASV Principles of Operation
Step 1: Plat out metals on
electrode surface by applying
negative potential
Pb
r
Pb2+
Electrolysis Step
Step 2: Measure time as
metal film is redissolved by
applying constant current
Pb
i
Pb:
,2+
Anodic Stripping Step
AS-4
Notes:
This figure shows the principles of operation of ASV.
Different anodic stripping scans, including linear sweep, differential pulse, and
alternating current, have been used successfully. Differential pulse is the most commonly
used scan because it provides the greatest sensitivity.
AS-5
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
Anode Stripping Voltammetry
Stripping Curves
POTENTIAL-TIME
CURVE
1200
1000
I-
1 600
f *00
^ 200
0
50
100 150 200 250 300
Time (ms)
DERIVATIVE-POTENTIAL
CURVE
1200
I00°
E 800
I
400
200
0
'cadmiuni
lead
0.5
1 1.5 2
dVdE (mS/mV)
2.5
AS-5
Notes:
The figure on the left is used for making a qualitative identification of the individual
metals. The figure on the right is used for quantitation of the metals.
AS-6
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
Anode Stripping Voftammetry
Portable Instruments
Metalyzer™ 3000
» Meter
» Disposable sensors
> PaceScan™ 2000
EPA
AS-6
Notes:
Two different portable instruments currently are available. The Metalyzer™ 3000 is
manufactured by Environmental Technologies Group, Inc. (ETC). The Metalyzer™ 3000
system consists of a meter and disposable sensors. The meter contains an interface for
the disposable sensor, a membrane keypad, a liquid crystal display (LCD), the electronics
necessary to perform the analyses, a battery pack, and a microprocessor capable of
calculating the metal concentration. The meter weighs about 3 pounds and is powered by
rechargeable batteries. These batteries are able to run about 50 tests between recharging.
The meter also may be powered through an external power adaptor or from a 12-volt
automobile cigarette lighter. The meter can store data for up to 300 tests and can be
purchased for approximately $4,200.
The disposable sensors consist of a polypropylene housing containing a screen-printed
electrode and a reagent sealed in a glass ampule. Each lot of sensors is precalibrated at
the factory. The meter is calibrated by inserting a calibration chip into the meter. The
calibration chip is packed in each box of disposable sensors and contains the calibration
factors for a given lot of sensors. Each sensor is capable of analyzing for a specific
individual or group of metals. Each box of 20 sensors costs approximately $300 per box.
The PaceScan™ 2000 instrument is manufactured by Pace Environs, Inc. The instrument
kit includes the ASV instrument, instruction manual, electrode holder, sample holder, and
a precision pipettor. The ASV instrument weighs less than 1 pound. The testing kit for
the PaceScan™ 2000 includes 25 single-use disposable electrodes (mercury-impregnated
AS-7
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
Anode Stripping Vottammetry
carbon printed onto cut-to-size-and-shape plastic), 25 electrolyte tablets, a pack of plastic
stirring rods, 25 plastic 5-m.L test vials, and 25 plastic 50-mL sample tubes with screw
caps.
AS-8
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
Anode Stripping Voltammetry
Analysis Procedures
Metalyzer™3000
»The use of disposable sensors makes
analyses simple
PaceScan™ 2000
»Analyses involves use of acid solutions
EPA
AS-7
Notes:
The simple design of the sensor for the Metalyzer™ 3000 allows for measurements to be
performed by nontechnical personnel. The analysis involves the use of disposable
sensors and a few simple steps. After filling, the disposable sensors are inserted into the
meter which automatically reads the sensor and begins analysis. The concentration of one
or more metals will be displayed on the LCD in 1 to 5 minutes.
When using the PaceScan™ 2000, the sample first is acidified with nitric acid to achieve
a 4 percent nitric acid solution. Next, approximately 5 mL of the acidified solution is
poured into the 5-mL test vial. Then, an electrolyte tablet is added to the test vial. The
ASV instrument is then started according to the instruction manual. An unused electrode
is inserted into the electrode holder. When prompted by the instrument's controls, the
electrode is plunged into the test solution and the metal concentration in the solution is
measured. After about 45 seconds, the instrument display shows the analytical results.
AS-9
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
Anode Stripping Voltammetry
Method Performance
+ Detection limits
* Analysis time
* Coefficient of variation
+ Spike recoveries
* Comparison to other methods
&EPA
AS-8
Notes:
Detection limits for metals in water range from 1 to 100 ppb. Most of the detection limits
are below applicable MCLs. The linear range of the instruments spans nearly two orders
of magnitude for most metals. Laboratory-grade instrumentation can achieve detection
limits less than 1 ppb.
Analyses can be completed in less than 5 minutes per sample.
The coefficient of variation (CV) is 10 percent or less on replicate analyses.
Several solutions analyzed by the PaceScan™ 2000 were spiked with lead at four
different concentrations ranging from 116 to 898 micrograms per liter (yug/L). Multiple
analyses were conducted on these solutions. The average percent recovery was 99.9
percent with a standard deviation of 2.1 percent.
Lead data (nine data points) produced from the PaceScan™ 2000 were regressed against
ICP data. The regression analysis produced a line with a slope equal to 0.97, a y-intercept
of 0.07, and a correlation coefficient of 0.9885. Metalyzer™ 3000 data for lead and
copper also has shown good correlation to atomic absorption data.
AS-IO
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
Anode Stripping Voltammetry
Linear Range
ASV PEAK AREA
(0
1
JC
ffl
o
a.
$
Q,
100
80
SO
40
20
0
C
• • M . • _X^
! ; i M ix^ i
: : : ^^x^1 : ; !
; !^: i ; i ; !
^ . : i ' : : :
20 40 60 80 100
Cadmium Cone (ppb)
3500
3000
2500
2000
1500
tooo
500
500 1000 1500
Copper Cone (ppb)
zooo
AS-9
Notes:
These figures show the ASV linear range for cadmium and copper.
AS-II
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
Anode Stripping Vo/tammetry
ASV Comparison to AA Methods
CORRELATION BETWEEN ASV AND AA
3"
a
^
01
Q>
QC
S5
0.
100
80
60
40
20
0
c
Lead
! : ; . i ; . /.'"
: : : : : S"
; : : .^-' : :
'. : : ,"' • : :
! I Ur"" l • .
i ^\ \ ; • i
x-K; M : : : : i
20 40 60 80 100
AA Results (ppb)
Copper
2500
Q.ZOOO
&.
"^1500
22
giooo
cc
< 500
CO
Q- o
600 1000 1500 2000
AA Results (ppb)
2500
&EPA
AS-10
Notes:
These figures show the correlation between ASV data {generated by the Metalyzer™
3000) and atomic absorption (AA) data for lead and copper.
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
Anode Stripping Voltammetry
Interferences
* Complexing agents
* Surfactants
* Overlapping metals
4 Intermetallic effect
AS-11
Notes:
Complexing agents can interfere with stripping measurements by forming a complex with
the analyte such that the potential of the complex does not lie in the potential window of
the analyte. This effect is minimized by including a strong acid in the reagent which
prevents complex formation when the complexing agents are present up to 50 ppm.
Surfactants can cause major errors in electroanalytical measurements since they adsorb on
the electrode surface. This problem can be minimized for the Metalyzer™ 3000 by
coating the working electrode surface with a proprietary coating which is permeable to
the analytes of interest, but not the surfactants. Even with the coating, studies have
shown, for the Metalyzer™ 3000, that when the surfactants are present at concentrations
of 50 ppm, cadmium, copper and lead concentrations can be reduced by as much as 87
percent. However, this method is an improvement over conventional uncoated electrode
systems, which exhibit errors at surfactant concentrations as low as 1 ppm.
Metals with oxidation potentials close to that of the analytes may interfere if the
instrument does not have sufficient resolution to resolve the overlapping peaks. Studies
with bismuth, iron, nickel, and zinc at concentrations of 10 ppm did not cause
interferences for cadmium, copper, or lead using the Metalyzer™ 3000.
Metals which form intermetallic compounds with the analytes may result in erroneously
low analyte concentration readings, since the oxidation potential of the intermetallic
compound is rarely near that of the original analyte. The intermetallic effect can cause
significant changes in the peak areas of copper and cadmium, especially in the presence
of zinc. The Metalyzer™ 3000 compensates for this effect by adjusting the peak areas for
known intermetallic effects.
AS-J3
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
Anode Stripping Voltammetry
Advantages
4- Easy to operate
*• Little sample preparation
4 Fast analysis time
4 Portable instrumentation
* Inexpensive
AS-12
Notes:
The instruments that are currently available are made for nontechnical users. The
software in the instruments is menu driven and easy to learn.
There is no involved sample digestion or extraction required prior to analysis. The
samples simply have to be acidified, which is normally done in the field. The
manufacturers provide all the necessary reagents to perform the analysis.
With analysis times of less than 5 minutes, it is possible to analyze 50 samples in a day.
The ASV instruments are light-weight (one to three pounds) and so small they can nearly
fit in a person's hand. They can operate on battery power for eight hours, on automobile
power supply, or on regular 110 volt power supply. There are few logistical constraints
on these instruments.
Once the portable instrument has been purchased, the cost of analyzing a sample (not
including labor) is $15 to $20 per sample, which is much less than using conventional
ICP or AA analysis for multiple analytes.
AS-14
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
Anode Stripping Voltammetry
Limitations
detects free metals in solution
4 Interferences from surfactants and other metals
^ Mercury waste
4- Batch to batch variation in disposable sensors
EPA
AS-13
Notes:
The ASV method cannot detect metals that are complexed or are not in solution.
The presence of surfactants or other metals can cause underestimation of target analyte
concentrations if they are present at high enough concentrations.
EPA's Office of Solid Waste (OSW) has taken the position that it will not promote a
method that generates even a small amount of hazardous waste. In this case, a small
amount of mercury waste is generated from the mercury drop. The current ASV methods
in SW-846 use a gold thin-film coated electrode.
The ASV technique for commercially-available instruments that use disposable sensors
has suffered from inconsistencies in the production of the disposable sensors.
AS-15
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
Anode Stripping Voltammetry
Applications Other Than
Characterization
* Prospecting for mines
+Acid mine drainage studies
* Laboratory research
EPA
AS-14
Notes:
Examples of applications of voltammetric techniques other than for characterization
include:
- ASV instrumentation and techniques have been used to identify metals in surface
waters, thereby locating potential metal mining sites.
- In addition, ASV has been used in acid mine drainage studies to identify potential
sulfidic materials associated with mineable bodies of ore.
- Because ASV and other voltammetric techniques can detect low-level
concentrations of metals and identify species of analytes, they are useful for
laboratory research.
AS-16
Module: Inorganic Chemical Characterization Techniques and Data interpretation
-------
Graphite Furnace Atomic Absorption Spectroscopy
Inorganic Chemical Characterization
Techniques and Data Interpretation
+X-Ray Fluorescence
+ Mercury Vapor Analyzers
^Immunoassay
*Anode Stripping Voltammetry
^> + Graphite Furnace Atomic Absorption
Spectroscopy
^Cyanide Measurement Techniques
^ Water Quality Measurement Techniques
+ Emerging and Innovative Approaches and
Instruments
*• Hands-on Activity for Inorganic Analysis
GF-1
GF-J
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
Graphite Furnace Atomic Absorption Spectroscopy
Notes:
Topic Overview
+Topic Description: Explains the use of graphite
furnace atomic absorption (GFAA) for detecting
metals in water
^ Key Points
» Application
» Logistical requirements
»Interferences
» Sample analysis
» Quality control
» Advantages and limitations
» Applications other than characterization
EPA
QF-2
This topic explains the operation and application of graphite furnace atomic absorption
(GFAA) in the detection of metals in water.
The graphite furnace is an electrothermal atomizer system that is used along with atomic
absorption spectroscopy.
This technology has been available for some 30 years. The technique is based on the fact
that free atoms will absorb light at frequencies, or wavelengths, characteristic of the
element of interest.
The following key points are discussed: (1) application, (2) logistical requirements,
(3) interferences, (4) sample analysis, (5) quality control, (6) advantages and limitations,
and (7) applications other than characterization.
GF-2
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
Graphite Furnace Atomic Absorption Spectroscopy
Applications and Logistical
Requirements
* Theory of operation
+Application: Metals in water
+Analysis time of 1 to 5 minutes
+ Logistical needs
GF-3
Notes:
The graphite furnace is used to provide thermal energy to break chemical bonds and form
free ground-state atoms necessary for atomic absorption. Ground-state atoms absorb
energy in the form of light and are elevated to an excited state. The amount of light
energy absorbed increases as the concentration of the selected element increases.
The graphite furnace can produce temperatures as high as 3,000°C, compared with
2,300°C to 2,900°C produced by flame. The atomizer assembly consists of a graphite
tube placed horizontally in the light path of the spectrometer. The assembly is housed in
a water-cooled jacket with inert gas (usually argon) flow internal and external to the
graphite tube.
GFAA has been used primarily in the field for the analysis of some metals in water.
GFAA could be used to determine metals in soil, but the sample preparation for metals in
soil is extensive and is not practical for field applications.
Samples are analyzed in triplicate; it takes between 1 to 5 minutes for sample analysis.
Most recently, GFAAs have fast-furnace designs that feature constant temperature zones,
end-heated graphite tubes, and automatic samplers.
Logistical needs include: reagents for sample preparation and analysis, matrix modifiers,
and 220-volt electricity source. In addition, there are many analytical components to the
GFAA system that require significant space and climate stability in a mobile laboratory.
GF-3
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
Graphite Furnace Atomic Absorption Spectroscopy
GFAA
*Very good detection limits
» Generally 10 to 100 times more sensitive than
flame AA or ICP for most elements
typically used for Group I and II elements
GF-4
Notes:
Typical metals analyzed by GFAA and their detection limits are shown in the table below.
Element
A1
AS
Cd
Cr
Ni
Pb
Se
Tl
Ti
V
Detection Limit
-------
Graphite Furnace Atomic Absorption Spectroscopy
Interferences
* Chemical (matrix)
4 Spectral
^ lonization
EPA
GF-5
Notes:
The GFAA technique is subject to chemical, spectral, and ionization interferences. The
composition of the sample matrix can have a major effect on analysis.
- Chemical interferences occur when the atoms are not completely free or in their
ground-state.
- Spectral interferences occur when atomic or molecular species other than the
element being analyzed absorb energy at the wavelength of interest.
- lonization interferences occur when the furnace causes complete removal of
electrons from an atom, thereby lowering the concentration of ground-state atoms
available for light absorption.
GF-5
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
Graphite Furnace Atomic Absorption Spectroscopy
Sources of Sample Contamination
4 Glassware, polypropylene, or Teflon containers
* Pi pet tips
*• Reagents
^Autosampler cups
4 Graphite tubes
GF-6
Notes:
Contamination of the sample can be a major source of error because of the extreme
sensitivities achieved with the furnace. The sample preparation work area should be kept
clean. This requirement is especially important in a field laboratory. It is easy for dust to
blow into a trailer and contaminate the analytical equipment and glassware.
Use precleaned glassware or acid-wash the glassware.
Use trace-metal-grade pipet tips.
Use trace-metal-grade distilled, deionized water and nitric acid.
Make sure no dust accumulates in the autosampler cups.
Use pyrolytically-coated and high quality graphite tubes.
GF-6
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
Graphite Furnace Atomic Absorption Spectroscopy
Notes:
Preparing Samples
+ Acidification
*• Filtration (dissolved metals analysis)
^Centrifugation (turbid samples)
+Addition of matrix modifiers
* Holding time of 6 months
GF-7
Water samples should be acidified with nitric acid to a pH of less than 2.
If dissolved metals analysis is required, the water samples should be filtered through a
0.45 micrometer (urn) filter.
If the water samples are very turbid, they should be centrifuged prior to analysis or
allowed to settle.
To alleviate interferences, matrix modifiers should be added.
The water samples have a holding time of 6 months after they are preserved. In the field,
most water samples are analyzed within a few hours after collection.
GF-7
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
Graphite Furnace Atomic Absorption Spectroscopy
Sample Analysis
^ Check for contamination (for example, highly
colored samples)
+Analyze samples in triplicate
* Dilute sample if absorbance is out of range
* Periodically change graphite tube
» Poor reproducibility
» Pitting of tube
GF-8
Notes:
The color of the water samples can give some indication of contamination. As an
example, if the water samples are a greenish color, they may have a high nickel content,
or if they are a bluish color, they may have a high copper content. A good rule to follow
is to analyze clear samples followed by highly colored samples. The highly colored
samples may need to be diluted prior to analysis.
The result for the sample is the average for the triplicate analyses.
The sample must be diluted if the absorbance is outside of the calibration range.
The latest generation of graphite tubes can perform more than 1,000 firings with loss of
sensitivity of less than 10 percent. Typically, GFAA has a smaller linear concentration
range, compared with flame AA or ICP. The graphite tube should be changed after every
200-800 burns because it becomes pitted and can result in poor reproducibility.
GF-8
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
Graphite Furnace Atomic Absorption Spectroscopy
Quality Control
+ Continuing calibration
*• Method blanks
^ Matrix spikes
+ Laboratory control samples
GF-9
Notes:
A continuing calibration should be performed after every 10 samples and consists of
analyzing one of the midlevel standards. The percent recovery of the continuing
calibration should be 90 to 110 percent.
Method blanks are analyzed with each batch of 20 samples analyzed. Method blanks
monitor laboratory-induced contaminants or interferences. A method blank must not
contain any analyte above the practical quantitation limit.
Matrix spike (MS) and matrix spike duplicates (MSD) are analyzed to evaluate the
efficiency of the sample preparation and precision of the analysis. MS-MSDs are
prepared with each batch of 20 samples. The advisory control limits for spike recovery
are 50 to 150 percent. The advisory control limit for RPD in water samples is 25 percent.
Laboratory control samples (LCS) are used to evaluate the accuracy of the analysis. The
LCSs are obtained from outside sources and contain known amounts of metals. The
results of the analysis of the LCSs are compared to the known true values. Control limits
are usually provided by the supplier of the LCS. The results obtained should fall within
the published range of acceptance values. When no control limits are provided, the range
of 50 to 150 percent should be used.
GF-9
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
Graphite Furnace Atomic Absorption Spectroscopy
Advantages Over Other Trace-Metal
Analysis Techniques
+ Increased sensitivity and detection limits
4 Multiple-element analysis
Slower spectral interferences than ICP
+ Smaller sample size
,g, EPA
GF-10
Notes:
GFAA generally can be 10 to 100 times more sensitive than flame AA or ICP for the
elements that can be detected (elements in Group I on the Periodic Table).
Newer GFAA have multilamp capabilities that allow analysis for eight elements in a
sample automatically.
Sample volumes for GFAA usually are less than 100 uL (0.1 ml), with 20 uL a typical
sample volume.
GF-10'
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
Graphite Furnace Atomic Absorption Spectroscopy
Notes:
Limitations Over Other Trace-Metal
Analysis Techniques
Longer analysis time than flame analysis
Limited dynamic range
Higher chemical (matrix) interferences
truly field portable; must be set up in a
mobile lab
• Power and space requirements (220-volt power
source)
EPA
GF-11
Even with faster furnace analysis and autosamplers, the speed of analysis is slower than
flame AA and ICP.
The linear concentration range for GFAA has been estimated at 102 units, compared with
10' for flame AA and 105 for ICP.
Even though GFAAs may require a mobile laboratory and 220-volt power, state-of-the-art
GFAAs are much more compact. The latest models are controlled by a PC with
instrument-specific software.
GF-11
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
Graphite Furnace Atomic Absorption Spectroscopy
Applications Other Than
Characterization
Metal plating facilities
Mitigation and monitoring
GF-12
Notes:
Metal concentrations in treatment plant sludge and water samples can be used to monitor
treatment efficiency, discharge limitations, and disposal requirements.
GF-12 •
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
Cyanide Measurement Techniques
Inorganic Chemical Characterization
Techniques and Data Interpretation
Fluorescence
4 Mercury Vapor Analyzers
+ Immunoassay
+ Anode Stripping Voltammetry
+ Graphite Furnace Atomic Absorption Spectroscopy
+ Cyanide Measurement Techniques
4 Water Quality Measurement Techniques
+ Emerging and Innovative Approaches and
Instruments
+ Hands-on Activity for Inorganic Analysis
EPA
CM-1
CM-I
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
Cyanide Measurement Techniques
Notes:
Topic Overview
+Topic Description: Explains the operation and
application of cyanide measuring and monitoring
techniques in various matrices
+ Key Points
» Scope and application
» Matrices
» Types of sensors
» Applications other than characterization
CM-2
This topic explains the operation and application of, and data produced by, various types
of techniques for measuring cyanide in air, water, soils, and wastestock.
The following key points are discussed: (!) scope and application, (2) matrices for use,
and (3) types of commercially available sensors and instruments; and (4) applications
other than characterization.
CM-2
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
Cyanide Measurement Techniques
Cyanide Measurement Matrices
» Single gas and multiple gas monitors
» Health and safety monitoring
CM-3
Notes:
Several companies manufacture portable air monitors for measuring hydrogen cyanide.
These instruments are used primarily for health and safety monitoring. The monitors are
equipped with audio and visual alarms to alert the user when hydrogen cyanide has been
detected at a concentration threatening to health. The monitors can detect hydrogen
cyanide concentrations from I to 100 ppm.
CM-3
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
Cyanide Measurement Techniques
Cyanide Measurement Matrices
(continued)
+Aqueous (water, wastewater, seawater)
» Transportable Monitors
» Cyanide ion-specific electrodes
» CNField analyzer
» Colorimetric test kits
+ Non-aqueous (soils, wasterock)
EPA
CM-4
Notes:
Sophisticated mobile laboratory monitors are available for monitoring water and
wastewater streams. Units consist of a computer, a sample pump, filters, and a
potentiometric detector. (Essentially, such units duplicate a manual titration with known
endpoint, except the units are more accurate because volumes are measured with great
accuracy and repeatability).
These mobile laboratory monitors use a potentiometric titration using silver nitrate and
have an effective range from 200 ppb to > 2,000 ppm. Analysis can be completed in 10
minutes, with 1 percent variation in repeatability. The whole monitor unit can be
configured, optimized, and operating within some 90 minutes.
Cyanide also can be detected in aqueous solutions through the use of a cyanide ion-
specific electrode (ISE) or an amperometric technique. Cyanide ISEs are usually a solid-
state combination or solid-state half-cell that can be purchased from such manufacturers
as Orion and pHoenix Electrode Company. The electrodes can measure cyanide
concentrations from 0.2 to 260 ppm.
The cyanide electrodes can be used with any ISE/pH meter to display cyanide
concentrations directly in ppm.
Perstorp Analytical Environmental manufactures the CNField cyanide testing system.
This field analyzer measures total and weak acid-dissociable cyanide in water. The field
unit features rapid and safe amperometric detection and one-button operation.
CM-4
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
Cyanide Measurement Techniques
Cyanide can be identified in aqueous solutions with portable colorimeters and with basic
color-disc field-test kits. Detection limits for both portable colorimeters and the color
disc are approximately 0.2 ppm. The Hach Company sells both varieties.
For samples of a nonaqueous matrix, digestion and extraction procedures must be
conducted, typically using strong (nitric) to weak (acetic) acids, diethylenetriaminepenta-
acetic acid (DTPA), or water.
CM-5
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
Cyanide Measurement Techniques
Portable Colorimeters
Hach Company DR/700 Colorimeter
CM-5
Notes:
The portable colorimeter has interchangeable filter modules that contain stored
calibrations for 75 chemical analysis tests. It is not necessary to generate calibration
curves, thereby saving time.
With 10 modules, wavelengths ranging from 420 to 810 nanameters (nn) can be covered.
Results can be read in three modes: (1) concentration; (2) absorbance; (3) percent
transmittance.
The colorimeter with one filter module costs about $600 and additional modules cost $40
to $60 each.
CM-6
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
Cyanide Measurement Techniques
Notes:
Applications Other Than
Characterization
Metal plating facilities
Mining and milling operations
Mitigation and monitoring
EPA
CM-6
Examples of applications of cyanide sensors for other than characterization include:
Determine cyanide concentrations in wastewater streams to monitor treatment
efficiencies and discharge requirements.
- Determine cyanide and metal-cyanide species concentrations to select activated
carbon for removing cyanide and metals at mines.
CM-7
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
-------
Water Quality Measurement Techniques
Inorganic Chemical Characterization
Techniques and Data Interpretation
• X-Ray Fluorescence
• Mercury Vapor Analyzers
• Immunoassay
• Anode Stripping Voltammetry
• Graphite Furnace Atomic Absorption Spectroscopy
4 Cyanide Measurement Techniques
• Water Quality Measurement Techniques
• Emerging and Innovative Approaches and
Instruments
• Hands-on Activity for Inorganic Analysis
EPA
WQ-1
WQ-1
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
Water Quality Measurement Techniques
Notes:
Topic Overview
«• Topic Description: Highlights the primary water
quality parameters measured in the field and
techniques for measuring inorganics in water.
4 Key Points
» Reasons for measurement
»Instrumentation
» Types of data
» Advantages and limitations
» Applications other than characterization
WQ-2
This topic describes the primary water quality parameters measured in the field and
explains the principle of operation, application, and data produced for various types of
instruments and field test kits used for detecting inorganic constituents in water.
The following key points are discussed: (1) reasons for collecting each water quality
parameter; (2) types of instruments and field-test kits used for analysis of water quality;
(3) types of data collected, including detailed information about low-flow (micropurge)
groundwater sampling; (4) advantages and limitations of different technologies; and (5)
applications other than characterization.
WQ-2
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
Water Quality Measurement Techniques
Water Quality Parameters
+ Temperature
* Specific conductivity
* Turbidity
+ Oxidation-reduction potential (ORP, Redox, eH)
^ Dissolved oxygen (biochemical oxygen demand)
EPA
WQ-3
Notes:
The typical water quality parameters that are measured on site include temperature, pH,
specific conductivity (salinity and total dissolved solids), turbidity, redox potential,
dissolved oxygen, and sometimes biochemical oxygen demand (BOD). Other parameters
that may be of interest but are not usually measured on site or are measured using
colorimetric methods discussed later in this section include hardness, chemical oxygen
demand, carbon dioxide, total organic carbon, alkalinity, acidity, and individual cations
and anions.
Temperature is the measure of heat present in water.
pH is the measure of hydrogen ion activity is a solution; below 7 is acidic, pH 7 is
neutral, above 7 is alkaline or basic.
Conductivity is a measure of the ability of water to pass electrical current and is inversely
related to the resistence of a solution. Specific conductivity is where the conductivity
reading has been corrected to 25°C.
Turbidity is the measure of clarity of a solution.
Oxidation-reduction potential (ORP) reflects the extent of oxidation of the solution.
Dissolved oxygen is the measure of the amount of oxygen present in water and available
for respiration.
WQ-3
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
Water Quality Measurement Techniques
Notes:
Reasons for Measurement
4 General water quality
^Groundwater monitoring well development
4Groundwater monitoring well purging and
sampling
• Groundwater remedial decisions
* Surface water quality
*• Point-source and non-point source decisions
WQ-4
When developing or purging groundwater monitoring wells prior to sampling, it is
necessary to ensure, at a minimum, that temperature, pH, and specific conductivity have
stabilized to within ±10 percent for consecutive measurements. When developing a
monitoring well, turbidity measurements must be below a certain value to ensure that all
sediments (fines) have been removed from the well screen. Some state agencies or other
regulatory agencies also require that redox potential and dissolved oxygen be monitored
during well development and purging.
Determinations of long-term surface water quality are necessary for establishing baseline
data and identifying sources of potential contaminants. With multiparameter probes and
data recorders, surface water sampling programs can collect continuous data (from
5- minutes to multiple-hour intervals).
WQ-4
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
Water Quality Measurement Techniques
Types of Instrumentation
+ Downhole sensors or probes
+ Uphole sensors or probes
*• Flow-through cells
EPA
WQ-5
Notes:
These water quality parameters can be measured downhole or at the well head. The
preferred technique is to measure the parameters downhole to obtain more representative
measurements as most parameters will change when the water sample is brought to the
surface. Companies have developed probes that can be lowered down 2-inch or 4-inch
wells to measure one or multiple parameters. These probes are attached to an electronics
unit by a cable. Many of the downhole probes also come with a depth gauge. Most field-
portable instruments are small, lightweight, and battery operated. The instruments
generally come in plastic carrying cases and can be purchased or rented from various
companies.
WQ-5'
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
Water Quality Measurement Techniques
Current Trends in Groundwater
Sampling
Flow (Micropurge) Sampling
WQ-6
Notes:
In the past, groundwater in the well casing was not believed to be representative of the
aquifer, and therefore purging of the well casing was required. While field studies have
indicated that, generally, this is not the case, monitoring wells are purged to eliminate the
effects of atmospheric oxygen and possible sorption of contaminants to casing and filter-
pack materials.
The low-flow purging technique pumps water at a reduced velocity, resulting in minimal
drawdown of the water level (less than 0.3 foot).
A submersible pump with adjustable discharge valve, peristaltic pump, or bladder pump
is installed in the well. The pump intake is set at mid-screen (screen length 10 feet or
less), unless discrete vertical interval sampling is desired. The pump should have
discharge adjustable to 0.1 to 0.5 liter/minute.
The well is purged, while minimizing drawdown to less than 0.3 foot. Water quality
parameters (pH, specific conductance, turbidity, temperature, and dissolved oxygen) are
monitored during the pumping with a flow-through cell.
WQ-6
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
Water Quality Measurement Techniques
Key Aspects of Low-Flow Sampling
+• Identify aquifer heterogeneity
4 Evaluate colloidal transport
be used with hydraulic push technologies
&EPA
WQ-7
Notes:
Low-flow sampling can be used to target discrete screen intervals or sample zones of
higher permeability or can identify plume thickness or preferential flow zones that may be
less than screen length.
Low-flow sampling can assist in the evaluation of transport of a mobile reactive solid
phase. Examples include secondary clay minerals, organic materials, hydrous Fe, Al or
Mn oxides viruses of bacteria. Low-flow sampling can eliminate the need for filtration,
which can result in underestimation of the contaminant load.
Low-flow sampling can be used with hydraulic-push samplers for groundwater samples at
discrete intervals.
WQ-7-
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
Water Quality Measurement Techniques
Low-Flow (Micropurge) Sampling -
Advantages
+ Reduced purge volume
+ Reduced need to filter
^Improved sample representiveness because less
entrainment of particulate
+Able to collect discrete samples
&EPA
WQ-8
Notes:
Reduced purge water quantities and need to filtrate will reduce investigative derived
waste and associated costs.
Sample contaminants may be more representative (especially for organic contaminants).
Discrete samples can be collected from vertical strata with high potential for
contamination.
WQ-8
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
Water Quality Measurement Techniques
Notes:
Low-Flow (Micropurge) Sampling
Disadvantages
4- Higher equipment and capital costs
+ Longer field set up time
+ Somewhat increased training
* Comparison to older data sets may not be
possible
WQ-9
The pump, tubing, flow-through cells, and measurement probes are more expensive than
traditional bailers and require more time and training.
Low-flow sampling may be more appropriate for new site characterizations to avoid
problems with data comparability from traditional sampling results.
WQ-9
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
Water Quality Measurement Techniques
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species and transition metals species. Very low
redox values can indicate highly contaminated
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Can impact remedial decisions.
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Water Quality Measurement Techniques
Water Quality Test Kits
+ Single Parameter Kits
4 Multiple-Parameter Kits
* Application-Design Kits
4 Pocket Colorimeter
WQ-11
Notes:
Single-parameter test kits include the reagents, instructions, and a colorimetric
measurement indicator. Depending on the accuracy required and budget considerations,
the color intensity (which depends on the concentration of the analyte) can be measured
by color charts or wheels, or a portable colorimeter (photometer). The photometer
provides greater accuracy but is more expensive than color charts or wheels.
Multiple-parameter field test kits typically cover from 10 to 25 common water quality
parameters. Some typical parameters and their measurement concentration ranges (in
mg/L) are listed in the table below.
Test
Acidity
Alkalinity
Chloride
Chromium
Copper
Hardness
Iron - Total
Nitrogen - Nitrate
Phosphorus - Total
Sulfide
Range (mg/L)
10-4,000
10-4,000
0-20
0- 1
0-5
10-4,000
0-5
0-30
0-2.5
0-0.6
Source: Hach Company, 1999
WQ-12-
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
Water Quality Measurement Techniques
Application-design kits are intended for specific industries and field applications. Such
kits are combinations of single parameter tests. Some typical application designs are:
acid mine drainage, aquaculture, surface finishing, wastewater, water ecology, and
limnology.
Small, portable colorimeters (hand-held filter photometer) have been developed to
improve the accuracy of results. Each colorimeter is preprogrammed for a single
parameter and provides direct readouts in concentration units. Such small photometers
usually cost from $300 to $500, depending on the analyte.
•WQ-13-
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
Water Quality Measurement Techniques
Color Indicator Test Strips
+Water quality parameters
» Nitrates
» Hardness
»pH
+Qualitative results
+Advantages and limitations
EPA
WQ-12
Notes:
Test strips are rigid plastic or polyvinylchloride strips with a carrier attached at one end.
The carrier is previously impregnated with a suitable colorimetric reagent that develops a
particular color when it contacts the analyte of interest. The intensity of the color is
proportionate to the concentration of the analyte. and results are considered to be
qualitative. Measurement is made by comparing the color intensity with a color chart
provided or with some type of photometer.
Test strips are used for water quality analysis, but their use is declining. Some of the
parameters measured include: cations (for example, ammonium, iron, potassium,
sodium, and others), anions (for example, chloride, nitrate, nitrite, and others), hardness
(such as calcium carbonate), and pH.
The advantages of the test strips are that they are inexpensive, easy to use, and provide
quick results. Each test strip often costs less than $1.00. Measurements can be obtained
in a few seconds.
One limitation of colorimetric kits is that only qualitative to semiqualitative results can be
obtained. The reduced data quality is the result of the subjectivity involved in
determining intensity of the color by consulting color charts and wheels.
WQ-14-
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
Water Quality Measurement Techniques
One of the limitations of the colorimetric test kits is that when used with the color charts
and color wheels, the color intensity results are only qualitative (or possibly
semiquantitative) and the visual readings can be subjective. Some test kits have been
shown to overestimate results.
For additional information on this topic, refer to page A-l at the end of this module.
•WQ-15-
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
Water Quality Measurement Techniques
Pocket Colorimeter
EPA
WQ-13
WQ-/6-
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
Water Quality Measurement Techniques
Quality Assurance for Water Quality
Measurement Techniques
4 Verify the setup and operation of the instrument
» Mode of operation (in situ or ex situ)
» Operator experience
+ Determine data quality requirements
» Screening (qualitative, semiquantitative, and
quantitative)
+ Compare screening data to reference laboratory
analysis
EPA
WQ-14
Notes:
Proper setup and operation of the instrument is ensured by:
- Calibrating the instrument with buffer or standard solutions
- Verifying calibration against certified standards
In addition, it is important to identify the mode of operation. Specifically, in situ
operation means that measurements are taken directly from the medium in place; no
collection of discrete samples is necessary. Ex situ operation requires the collection of
discrete samples that may require specific preservatives. To ensure that measurements
are taken reliably, the operator must have appropriate and adequate experience with the
specific measurement technique.
Qualitative and semiquantitative results can be obtained by using commercially available
field test kits that contain reagents and produce colorimetric responses that can be
measured with limited accuracy. Semiquantitative and quantitative results can be
obtained from field-portable meters equipped with specific probes specific to the analytes
of interest.
For screening-level data, confirmatory samples should be collected and analyzed by a
reliable off-site analytical laboratory. Comparisons of the results of the confirmation
analysis with the screening results should be made by a least squares linear regression
analysis. The correlation coefficient (r) for the results should be equal to or greater than
0.7, if the screening data are to be considered acceptable.
•WQ-17-
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
Water Quality Measurement Techniques
Notes:
Applications Other Than
Characterization
Monitoring lakes and streams
Monitoring oceans
WO-15
Examples of applications of water quality measurement techniques other than site
characterization include:
- Determine baseline resource numbers for environmental impact analyses.
- Measuring water quality for non-point pollution.
- Long-term monitoring of fisheries and climate change.
WQ-18-
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
Emerging and Innovative Approaches
Inorganic Chemical Characterization
Techniques and Data Interpretation
Fluorescence
*• Mercury Vapor Analyzers
^Immunoassay
*• Anode Stripping Voltammetry
^Graphite Furnace Atomic Absorption Spectroscopy
* Cyanide Measurement Techniques
4- Water Quality Measurement Techniques
• Emerging and Innovative Approaches and
Instruments
4 Hands-on Activity for Inorganic Analysis
EPA
IE'<
IE-1
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
Emerging and Innovative Approaches
Notes:
Emerging and Innovative
Approaches for Inorganics Analysis
*•Topic Description: Highlights three of the more
innovative approaches for field analysis of
inorganics and new tests and procedures
4 Technologies
» Portable datalogging spectrophotometer
» Laser-induced breakdown spectroscopy
» Field portable ion chromatography
4 New and emerging tests and procedures
&EPA
IE-2
This topic highlights some new innovations on existing technologies or innovative
approaches to field analysis of inorganics.
The following technologies will be discussed: (1) portable datalogging
spectrophotometer, (2) laser-induced breakdown spectroscopy, and (3) field portable ion
chromatography, (4) new and emerging tests and procedures.
IE-2
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
Emerging and Innovative Approaches
Portable Datalogging
Spectrophotometer
* Scope and application
»Colorimetric testing
^Instrumentation (accessories)
EPA
IE-3
Notes:
Many analyses for inorganic compounds rely on colorimetric testing provided by
spectrophotometers. Hach has developed a truly field-portable, microprocessor-
controlled, single-beam datalogging Spectrophotometer for analyzing water samples.
The Spectrophotometer weighs 4.4 pounds and is powered by a rechargeable battery
(good for approximately 1,000 measurements) or by connection to a standard outlet.
The Hach DR/2010 has a wavelength range of 400 to 900 nm, with wavelength accuracy
of 2 nm.
The datalogger can store as many as 1,000 readings. Data can be recalled and
downloaded to a serial printer or a PC for processing and review.
The basic Spectrophotometer can be equipped with flow-through cells, an immunoassay
tube adapter, and outdoor light and dust covers.
IE-3
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
Emerging and Innovative Approaches
Laser-Induced Breakdown
Spectroscopy
4 Scope and application
» Metals in soil
»ln situ or downhole technique
+ Method description and instrumentation
» Laser light
» Plasma formation
» Light emission
» Fiber optics
» Detection system
EPA
IE-4
Notes:
A portable laser-induced breakdown spectroscopy (LIBS) has been developed for
detection of metal contaminants on surfaces.
LIBS has been adapted for the in situ detection of metals or other elemental
concentrations in soil and in aerosols. The LIBS technique also has been used
experimentally with a downhole cone penetrometer for detection of metals in subsurface
soil. The detection limits for portable LIBS systems are somewhat variable, but the
literature suggests a detection limit for lead of 50 to 300 milligrams per kilogram.
In LIBS, laser light is focused on a small spot on a sample. The vaporized material forms
a short-lived plasma, which emits light that is collected and carried by a fiber optics cable
to a spectrograph and detector for quantitation. LIBS instrumentation is compact and
requires only line-of-sight access to the soil material. LIBS instrumentation has been
developed by Los Alamos National Laboratory. Personnel at the U.S. Army Engineer
Waterways Experiment Station and Naval Command, Control, and Ocean Surveillance
Center have experimented with downhole LIBS systems associated with the SCAPS
program.
IE-4
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
Emerging and Innovative Approaches
Field Portable Ion Chromatography
Scope and application
» Cations and anions in water
Instrumentation
» Eppendorf-Biotronik 1C 2001-2
»Lazarlab Model ICM-180
&EPA
IE-5
Notes:
Field portable ion chromatography (1C) is a form of liquid chromatography that can be
used to determine cations such as metals and anions (nitrate, chloride, sulfate, etc.) in
water samples. 1C uses ion-exchange resins to separate atomic and molecular ions based
on their interaction with the resin.
Field-portable ICs are commercially available (for example, Eppendorf-Biotronik 1C
2001-2 and Lazarlab Model ICM-180). The instrument weighs approximately 30 pounds
and can be powered by either a rechargeable battery pack or a 110-volt AC. The software
to run the instrument runs easily from a notebook computer.
ICs can be used in conjunction with liquid chromatography (LC) and high-pressure liquid
chromatography (HPLC) systems.
DOE tested the use of the Eppendorf-Biotronik 1C for analysis for uranium in water
samples from the Femald, Ohio site. This study found that the instrument provided
detection limits of less than 10 ppb in less than five minutes, while producing accurate,
reproducible results in the concentration range of 10 to 40 ppb.
IE-5
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
Emerging and Innovative Approaches
New and Emerging Tests and
Procedures
> Micro pH and Ion Electrodes
Rapid Silver Test Kit
High-range total Nitrogen Procedure
EPA
tE-6
Notes:
Microelectrodes can measure pH and common ions in less than one drop of liquid.
Typical ions include bromide, calcium, chloride, copper, cyanide, iodide, potassium,
silver, sodium, and sulfide. Microion electrodes can measure a concentration as low as
1 ppm.
Hach developed the Rapid Silver Test Kit as a simple test for silver in the range of 0 to
50 ppb. This visual analysis is designed for testing for silver in natural waters, drinking
water, wastewater, landfill leachates, and other applications in which trace amounts of
silver must be detected.
The high-range total nitrogen procedure was developed recently to measure nitrogen
loads on influent and effluent streams (near 0 to 150 mg/L as N). The procedure,
developed by Hach. uses a test "N" tube methodology with self-contained reagents to
minimize concerns about disposal.
IE-6
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
Hands-on Activity
Inorganic Chemical Characterization
Techniques and Data Interpretation
Fluorescence
4 Mercury Vapor Analyzers
4 Immunoassay
4 Anode Stripping Voltammetry
4 Graphite Furnace Atomic Absorption Spectroscopy
4 Cyanide Measurement Techniques
4 Water Quality Measurement Techniques
4 Emerging and Innovative Approaches and
Instruments
• Hands-on Activity for Inorganic Analysis
EPA
IH-1
IH-J
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
-------
Additional Information
Table of Contents
X-Ray Fluorescence A-2
Immunoassay A-5
Water Quality Measurement Techniques A-7
A-l
Module: Inorganic Chemical Compounds Techniques and Data Interpretation
-------
Additional Information
X-Ray Fluorescence
Operating Conditions
The selection of the radioisotope sources for analysis depends on the analytes of interest.
The analyst should choose a source that provides excitation energy that is greater than,
but close to, the absorption edge of the analytes of interest. Sometimes it is necessary to
analyze samples with more than one source if many analytes are desired.
The source count times will depend on the age of the sources, strength of sources,
analytes of interest, and action levels or detection limits that need to be achieved. Typical
count times range from 30 to 300 seconds per source. Shorter count times are often used
for the point-and shoot mode. Longer count times will result in lower detection limits
and better precision and accuracy, but will slow throughput. The general rule of thumb
for XRF analysis is that it requires a four-fold increase in count time to cut the detection
limit in half. The analyst must balance the increased sensitivity with the reduced
throughput. A throughput of 50 to 100 samples is achievable if someone is available to
help prepare samples.
A-2
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
Additional Information
Notes:
n
mg/kg
MDL
X-Ray Fluorescence
Performance on Commercial PE Samples
Analyte
n
Percent
Within
Acceptance
Range
Mean
Percent
Recovery
Range of
Percent
Recovery
Concentration
Range (mg/kg)
ERA PE Samples
Antimony
Arsenic
Barium
Cadmium
Copper
Iron
Lead
Nickel
Zinc
3
4
4
2
4
4
4
1
3
100
100
0
0
75
0
75
0
67
311
101
762
172
131
195
112
169
114
270 - 344
72 - 120
446- 1,064
156- 188
113- 174
168-240
72 - 146
169
107- 121
56-99
65 - 349
111 -319
90-131
88- 196
7,130- 10,400
52 - 208
135
101 -259
Certified Reference Materials
Antimony
Arsenic
Barium
Cadmium
Chromium
Copper
Iron
Lead
Nickel
Zinc
1
1
2
2
1
4
3
4
1
4
100
100
0
100
100
100
67
75
100
50
149
108
270
115
99
92
110
103
108
92
149
108
193 - 347
101 - 129
99
61 - 142
78 - 154
66 - 139
108
41 - 130
4,955
397
342 - 586
362 - 432
161,500
279 - 4,792
6,481 - 191,650
120 - 144,740
13,279
546-22,217
Number of samples with detectable analyte concentrations.
Milligrams per kilogram.
Method detection limit.
A-3
Module: Inorganic Chemical Compounds Techniques and Data Interpretation
-------
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Additional Information
Immunoassay
Principle of the Mercury Immunoassay
• The schematic diagram shows the principle of the mercury immunoassay method. The
schematic shows the major steps and the reagents used to perform the assay.
• Schematic definitions:
(1) GSH = mercury antibody.
(2) Hg = mercury in the sample.
(3) HRP = horseradish peroxidase.
Principle of the Mercury Immunoassay
w « w w
9999
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-5
Module: Inorganic Chemical Compounds Techniques and Data Interpretation
-------
Additional Information
Immunoassay
Mercury SPOT Kit
• Developed by Mercury Science, Inc.
• Based on a mercury-selective enzyme
• Semiquantitative test: Presence or absence of blue spot
• Detection limit of 1 mg/kg
• Analysis in less than 10 minutes
* Cost is $ 14 per sample
A-6
Module: Inorganic Chemical Characterization Techniques and Data Interpretation
-------
Additional Information
Water Quality Measurement
NITRATE IN GROUNDWATER ON- AND OFF-SITE ANALYTICAL RESULTS
Sample I.D. No.
GP10I-W1
GP102-W1
GP103-W1
GP104-W1
GP105-W1
GP106-W1
GPI06-W1D
GP107-WI
GP107-W1D
GP108-WI
GP109-W1
GP110-W1
GP1I1-W1
GP1I9-W1
GP120-WI
GPI23-WI
GP124-WI
GP129-W1
GP13I-W1
PWOOI
PW002
PW002D
PW003
PW004
PW005
PW006
Sample Date
10/15/97
10/14/97
10/14/97
10/14/97
10/15/97
10/15/97
10/15/97
10/15/97
10/15/97
10/15/97
10/15/97
10/15/97
10/15/97
10/16/97
10/16/97
10/16/97
10/16/97
10/17/97
10/17/97
10/15/97
10/16/97
10/16/97
10/16/97
10/16/97
10/16/97
10/17/97
On-Site Nitrate Result
(mg/L)
34
23
23
17
23
23
23
17
17
57
23
17
11
Not Detected
Not Detected
Not Detected
Not Detected
11
11
57
5.7
5.7
Not Detected
57
23
Not Detected
Off-Site Nitrate
Result
(mg/L)
15.8
13.8
13.8
7.89
7.75
14.6
13.9
10.2
10.6
31.4
12.3
8.96
8.01
0.106
Not Detected
0.307
Not Detected
8.24
7.1
28.6
2.71
2.76
0.176
26
15
Not Detected
Factor
2.15
1.67
1.67
2.15
2.97
1.58
1.65
1.67
1.60
1.82
1.87
1.90
1.37
Not Applicable
Not Applicable
Not Applicable
Not Applicable
1 .33
1.55
1.99
2.10
2.07
Not Applicable
2.19
1.53
Not Applicable
Note: This table demonstrates comparability between semiquantitative nitrate test strip results
and EPA Method 353.2 results for water samples. The factor is the nitrate test strip result
divided by the confirmatory (EPA Method 353.2) result.
A-7
Module: Inorganic Chemical Compounds Techniques and Data Interpretation
-------
-------
Sources
Sources of Site Characterization
Technology Information
EPA
S-1
Notes:
This module presents a number of sources of information about site characterization
technologies. The module summarizes each resource and describes how to obtain the
resource. In many cases, resources are available on the Internet.
S-1
Module: Sources of Site Characterization Technology Information
-------
Sources
Notes:
Sources of Site Characterization
Technology Information
+• Federal agencies, organizations, programs, and
partnerships
*• Laboratories
+Technical staff
+ Internet information
^ Software
* Publication clearinghouses
4 Publications
S-2
Government institutions and private organizations continually develop resources related
to innovative technologies for site characterization. Access to information about such
new technologies can be an invaluable asset to those responsible for site characterization.
In addition to various organizations, programs, and partnerships, there are both electronic
and print (paper) sources of information about site characterization technologies. This
module includes a description of many relevant resources. The instructors have made a
number of resources available for participants to browse through during breaks in the
course.
S-2
Module: Sources of Site Characterization Technology Information
-------
Sources
Sources of Site Characterization
Technology Information
• Federal agencies, organizations, programs,
and partnerships
• Laboratories
•Technical staff
• Internet information
• Software
• Publication clearinghouses
• Publications
&EPA
S-3
S-3
Module: Sources of Site Characterization Technology Information
-------
Sources
Federal Agencies, Organizations,
Programs, and Partnerships
«vr
S-4
Notes:
Technology Innovation Office (TIO). The U.S. Environmental Protection Agency's
(EPA) TIO was created in 1990 to act as an advocate for new technologies. TIO's
mission is to increase the application of innovative treatment technologies to
contaminated waste sites, soils, and ground water. To meet that mission, and in order to
improve the remediation process, TIO has expanded its focus to include site
characterization technologies. TIO has encouraged and relied upon cooperative ventures
with other partners to accomplish many of its goals. This effort to effectively use
resources has led to numerous joint efforts that have enhanced both remediation and site
characterization. For more information about TIO, contact Jeff Heimerman of EPA's
TIO at (703) 603-7191 or by e-mail at heimennan.jeff@epa.gov.
Information about this resource is available on the Internet at:
www.epa,gov/swertiol
Office of Research and Development (ORD). ORD is the scientific and technological
arm of EPA. Comprising of three headquarters offices, three national research
laboratories, and two national centers, ORD promotes a basic strategy of risk assessment
and risk management to remediate environmental and human health problems. ORD
focuses on the advancement of basic, peer-reviewed scientific research and the
implementation of cost-effective, common-sense technology. Fundamental to ORD's
mission is a partnership with the academic scientific community. ORD provides research
S-4
Module: Sources of Site Characterization Technology Information
-------
Sources
grants and fellowships to help develop the sound environmental research necessary to
ensure that policy and regulatory decisions are effective. ORD also implements such
programs as the Superfund Innovative Technology Evaluation (SITE) program and EPA's
Environmental Technology Verification (ETV) program. For more information about
ORD, contact Norine Noonan of EPA's ORD at (202) 564-6620 or by e-mail at
noonan.norine @ epa.gov.
Information about this resource is available on the Internet at:
www.epa.gov/ORD/
SITE Program. EPA's Office of Solid Waste and Emergency Response (OSWER) and
ORD established the SITE program in response to the 1986 Superfund Amendments and
Reauthorization Act (SARA), which recognized the need for an "alternative or innovative
treatment technology research and demonstration program." The SITE program is
administered by ORD's National Risk Management Research Laboratory (NRMRL),
formerly the Risk Reduction Engineering Laboratory (RREL), headquartered in
Cincinnati, Ohio. For more information about the SITE program, contact William
Frietsch at (919) 541-5451 or by e-mail at frietsch.bill@epa.gov.
Information about this resource is available on the Internet at:
www.epa.gov/ORD/SITE/
Technology Support Center for Monitoring and Site Characterization. The
Technology Support Center (TSC) for Monitoring and Site Characterization is one of the
many component programs administered by the SITE program through ORD's National
Exposure Research Laboratory (NERL), Environmental Sciences Division - Las Vegas
(ESD-LV). The goal of the center is to assess and verify the performance of innovative
and alternative monitoring, measurement, and site characterization technologies for
better, faster, and more cost-effective production of real-time data during site
characterization and remediation.
Information about this resource is available on the Internet at:
www.epa.gov/crdlvweb/tsc/tsc.htm
ETV Program. The ETV program seeks to provide credible performance data on
environmental technologies from independent third parties under the auspices of EPA.
The program verifies the performance of innovative technical solutions to problems that
threaten human health or the environment. Managed by EPA's ORD under the
President's Environmental Technology Initiative (ETI), ETV was created to substantially
accelerate the entrance of new environmental technologies into the domestic and
international marketplaces. It provides buyers of technologies, developers of those
technologies, consulting engineers, states, and EPA regions with high-quality data on the
S-5
Module: Sources of Site Characterization Technology Information
-------
Sources
performance of new technologies. ETV expands on past verification efforts, such as
those conducted under the SITE program for remediation technologies. ETV currently
implements 12 pilot projects, including the ETV Site Characterization and Monitoring
Technology Pilot, discussed below. For more information about the ETV program,
contact Sarah Bauer by e-mail at bauer.sarah@epa.gov.
Information about this resource is available on the Internet at:
www. epa.gov/etv/index.htm
ETV Site Characterization and Monitoring Technologies Pilot. The Site
Characterization and Monitoring Technology pilot was established as one of 12 pilot
projects currently implemented by EPA's ETV program to increase the acceptance and
use of innovative site characterization and monitoring technologies by establishing a
process for independent third-party verification of the performance of the technologies.
The Site Characterization and Monitoring Technology pilot is a partnership program of
EPA, the U.S. Department of Defense (DoD), and the U.S. Department of Energy (DOE)
that is responsible for evaluating and verifying the performance of innovative and
alternative monitoring, measurement, and site characterization technologies. The Site
Characterization and Monitoring Technologies pilot provides support for technology
developers, evaluates and verifies data generated during technology demonstrations, and
develops and disseminates information about the performance of site characterization
technologies. Under the pilot, a third-party verification organization (DOE's Oak Ridge
and Sandia national laboratories) develops demonstration plans, conducts evaluations,
and writes environmental technology verification reports. According to the needs of
users, the pilot annually solicits vendors, selects appropriate technologies, and conducts
performance evaluations. Technologies are selected on the basis of their applicability to
the identified need, their maturity (commercially ready, full-scale units), and the
willingness of the vendors to participate. After the field evaluation, the pilot produces a
detailed technical report on each technology, accompanied by a verification statement
signed by a representative of EPA that summarizes key findings. Since 1995, ETV's Site
Characterization and Monitoring Technology Pilot has verified 29 innovative
technologies that include two cone penetrometer-deployed sensors, two field portable gas
chromatograph/mass spectrometers (GC/MS), seven field portable X-ray fluorescence
(FPXRF) analyzers, seven PCB field analytical technologies, six soil/soil gas sampling
technologies, and five well-head monitoring volatile organic compounds (VOC).
Verification statements and reports have been issued for all of these technologies. For
more information about ETV's Site Characterization and Monitoring Technology Pilot,
contact Eric Koglm of EPA NERL at (702) 798-2432 or by e-mail at
koglin.eric@epa.gov.
Information about this resource is available on the Internet at:
www. epa.gov/etv/02/02_main.htm
S-6
Module: Sources of Site Characterization Technology Information
-------
Sources
Rapid Commercialization Initiative (RCI) Program. RCI is a cooperative effort
among federal, state, and private organizations to expedite the application of new
environmental technologies. The participating federal agencies include the Department
of Commerce (Commerce), DoD, DOE, and EPA. State-level organizations involved
include the California Environmental Protection Agency (CalEPA), the Southern States
Energy Board, and the Western Governors' Association. The program uses cooperative
demonstration projects to identify barriers to the acceptance and use of new technologies
and attempts to remove those barriers, when possible. Each of the program's 10
individual projects demonstrates a specific environmental technology.
Information about this resource is available on the Internet at:
rci.gnet.org
Federal Remediation Technologies Roundtable (FRTR). The FRTR was created to
establish exchange among federal agencies of information about remediation and site
characterization technologies that have been applied at hazardous waste sites. The
consortium of federal agencies analyzes specific problems related to wastes and site
remediation and develops strategies to benefit all interested parties. Member agencies
include: EPA, DoD, the U.S. Army Corps of Engineers (USAGE), DOE, and the U.S.
Department of Interior (DOI).
Information about this resource i.s available on (he Internet at:
www.frtr.gov
5-7
Module: Sources of Site Characterization Technology Information
-------
Sources
Federal Agencies, Organizations,
Programs, and Partnerships
Crosscutting
News &
Events
Reports &
Publications
Mission /Vision Program Contacts
Site Map Fo«dbacK
CMST
Technologies
Related Links
Site Archive
S-5
Notes:
Characterization, Monitoring, and Sensor Technology Crosscutting Program
(CMST-CP). The purpose of the CMST-CP is to make appropriate characterization,
monitoring, and sensor technologies available to DOE's Office of Waste Management
(EM-30), Office of Environmental Restoration (EM-40), and the Office of Facility
Transition and Management (EM-60). CMST-CP identifies technology gaps, coordinates
technology development initiatives, and manages resources to bring about effective
development of technologies and to provide cost-effective solutions to cleanup problems,
Information about this resource is available on the Internet at:
www.cmst.org
Module: Sources of Site Characterization Technology Information
-------
Sources
Federal Agencies, Organizations,
Programs, and Partnerships
SERDP
Strategic Environmental Research
and Development Program
Improving Mission Readiness Through
Environmental Research
Environmental Security
Technology Certification
Program
EPA
S-6
Notes:
SCAPS Research, Development, and Technology Demonstration Program. Under
the sponsorship of the U.S. Army Environmental Center (AEC), the U.S. Army Engineer
Waterways Experiment Station (WES), undertook the SCAPS Research, Development,
and Technology Demonstration program to provide DoD with a rapid and cost-effective
means of characterizing soil conditions at DoD sites undergoing restoration. WES works
in partnership with the U.S. Naval Command, Control, and Ocean Surveillance Center
and the U.S. Air Force Armstrong Laboratory to accelerate and coordinate the tri-service
SCAPS technology development, demonstration, and technology transfer effort under the
sponsorship of the Strategic Environmental Research and Development Program
(SERDP), discussed below. EPA has joined with the tri-service SCAPS developers to
conduct validation studies that will lead to regulatory acceptance of SCAPS contaminant-
sensing and sampling technologies. For more information about SCAPS, contact
Mr. John Ballard of WES at (601) 634-2446 or by e-mail at ballarjl@exl.wes.army.mil.
Information about this resource ix available on the Internet at:
www. wes.army.mil/eVscaps.html
S-9
Module: Sources of Site Characterization Technology Information
-------
Sources
I
SERDP. SERDP is DoD's premier mechanism for the development and transfer of
technologies for use in environmental restoration. It was established by Congress in 1990
as an initiative led by DoD, in partnership with DOE and EPA. SERDP's goals are to
promote the maximum exchange of information; to minimize duplication in
environmental research, development, and demonstration activities; and to provide for the
identification and support of programs of basic and applied research, development, and
demonstration of technologies useful in: (1) facilitating environmental compliance,
remediation, and restoration activities; (2) minimizing generation of waste, including
reduction at the source; and (3) substitute nonhazardous, nontoxic, nonpolluting, and
other environmentally sound materials and substances for more harmful materials.
Information about this resource is available on the Internet at:
www.serdp.gov
Environmental Security Technology Certification Program (ESTCP). The goal of
ESTCP is to demonstrate and validate promising, innovative technologies that target
DoD's most urgent environmental needs. The technologies provide a return on
investment through cost savings and improved efficiency. ESTCP's strategy is to select
laboratory-proven technologies that have broad application in DoD and in the
marketplace. The projects are moved aggressively to the field for rigorous trials that
document their cost, performance, and market potential.
Information about this resource is available on the Internet at:
www.estcp.org
S-IO
Module: Sources of Site Characterization Technology Information
-------
Sources
Federal Agencies, Organizations,
Programs, and Partnerships
AIR & WASTE MANAGEMENT ASSOCIATION
A WMA
,8, EPA
S-7
Notes:
Air & Waste Management Association (A&WMA). A&WMA is a nonprofit
technical, scientific, and educational organization that has more than 16,000 members in
65 countries. Founded in 1907, the association provides a forum through which all
viewpoints on environmental issues (technical, scientific, economic, social, political, and
risk assessment) are considered. Members of the association plan, develop, and present
programs that are designed to encourage the exchange of information, enhance skills and
knowledge, and increase the efficiency and effectiveness of environmental professionals.
The diversity of the association's membership ensures that the programs are
multidisciplinary and multimedia in nature. A&WMA also sponsors various specialty
conferences, including the conference Field Screening Methods for Hazardous Wastes
and Toxic Chemicals.
Information about this resource is available on the Internet at:
www.awma.org
Module: Sources of Site Characterization Technology Information
-------
Sources
Sources of Site Characterization
Technology Information
+ Federal agencies, organizations, programs,
and partnerships
4- Laboratories
4Technical staff
+ Internet information
4 Software
4-Publication clearinghouses
4 Publications
S-8
5-72
Module: Sources of Site Characterization Technology Information
-------
Sources
Laboratories
,8, EPA
NATIONAL EXPOSURE RESEARCH LABORATORY
IKHA Horns 1JQKD Home] INER1. Hntiu-1
Notes:
EPA ORD National Exposure Research Laboratory (NERL), ESD. BSD conducts
research, development, and technology transfer programs related to environmental
exposures to ecological and human receptors. ESD develops methods for characterizing
chemical and physical stressors, with special emphasis on ecological exposure. ESD
develops landscape and regional assessment capabilities through the use of remote
sensing and advanced spatial analysis techniques. ESD conducts analytical chemistry
research and applies advanced monitoring technology to issues related to surface and
subsurface contamination. To carry out its functions, ESD applies a multidisciplinary,
multimedia approach in both laboratory and field settings.
ESD also provides the TSC for Monitoring and Site Characterization. The TSC was
established in 1987 and initially specialized in supporting remedial project managers
(RPMs) and on-scene coordinators (OSCs) in EPA's Superfund program. In 1991, ESD
began providing technical support. When work at a site is required, the TSC mobilizes to
aid the regions in screening and site characterization. The diversity of expertise available
through the TSC allows ESD to work with RPMs and OSCs throughout the site
characterization process (for example, from planning and design to analysis and data
interpretation). Often, additional research needs are identified or protocols for
experimental sampling design are developed. The technical focus of the TSC includes
the following: site characterization technologies, such as field-portable x-ray
fluorescence, soil gas measurement, special analytical services, geographical information
systems (CIS) and data interpretation, chemical analysis, radiochemical analysis.
S-13
Module: Sources of Site Characterization Technology Information
-------
Sources
geophysics, quality assurance, geostatistics, statistical design, and publications. In
addition to providing direct technical support, TSC facilitates technical communication to
the EPA regions through the Technology Transfer Project. Fact sheets and issue papers
help keep EPA staff up-to-date on the services available through the TSC and the
scientific community informed about innovations in technology.
_ Information about this resource is available on the Internet at:
www.epa.gov/crdlvweb
S-J4
Module: Sources of Site Characterization Technology Information
-------
Sources
Laboratories
Anres-t'flborator
Environmental Technology
Development Program
solution??.
o!imcM(«{ />
S-10
Notes:
The Ames Laboratory Environmental Technology Development Program. DOE
established the Ames Laboratory Environmental Technology Development Program,
located in Ames, Iowa on the campus of Iowa State University, through its Environmental
Management Division. Although initially intended to meet the cleanup challenges posed
by DOE's own sites, Ames Laboratory currently seeks to develop better, faster, and
cheaper approaches to cleanup problems faced by both public- and private-sector
organizations. One such approach is expedited site characterization (ESC). ESC is a
team effort among DOE's environmental restoration program, EPA, state regulators, and
Westinghouse Savannah River Corporation. The approach has brought together
geophysical, geotechnical, hydrologic, analytical, and computer software technologies to
expedite site characterization at DOE's Savannah River site in Georgia.
Information about this resource can he accessed on the Internet at:
www.etd.atneslab.gov
S-15
Module: Sources of Site Characterization Technology Information
-------
Sources
Laboratories
Ridge National Laboratory (ORNL)
Chemical and Analytical Sciences Division
,8, EPA
S-11
Notes:
Oak Ridge National Laboratory (ORNL) Chemical and Analytical Sciences
Division. ORNL is an integral part of the Site Characterization and Monitoring
Technology Pilot Program conducted under EPA's ETV program. The Sampling and
Analysis Group of ORNL's Chemical and Analytical Sciences Division, in partnership
with the EPA's NERL and DOE, is conducting performance verification demonstrations
of innovative, commercially available and near-commercially available for field
characterization and monitoring. For more information about ORNL, contact Roger A.
Jenkins at (423) 576-8594 or by e-mail atjenkinsra@ornl.gov.
Information about this resource Is available on the Internet at:
www.ornl.gov/divisions/casd
S-16
Module: Sources of Site Characterization Technology Information
-------
Sources
Laboratories
Welcome to
... exceptional service In the national Interest.
EPA
S-12
Notes:
Sandia National Laboratories, Environmental Restoration Technologies (ERT)
Department. The ERT department at Sandia National Laboratories is developing
environmental restoration technologies through funding from DOE's Office of Science
and Technology (OST). Key goals of the ERT are to develop and demonstrate innovative
environmental technologies, to transfer those technologies to the environmental
restoration community throughout the DOE complex for routine use, and to
commercialize those technologies. To hasten the adoption of successfully demonstrated
technologies by the DOE complex and other federal agencies, and to expedite the transfer
of technologies to the private sector for commercialization, the ERT department involves
outside participants in its activities. The department's relationship with industry allows
exchange of information, ideas, resources, and experience. The ERT department also
fosters the involvement of stakeholders and regulatory authorities in the effort to build
support for innovative technologies. Key concerns include reducing the amount of time
necessary to meet permitting requirements, reducing the costs of meeting those
requirements, minimizing duplicative and unnecessarily sequential requirements,
increasing deployment, obtaining interstate cooperation, increasing the number of
technologies permitted, and achieving faster commercialization. For more information
about characterization technologies, contact Thomas Burford at (505) 844-9893 or by e-
mail at tdburfo@sandia.gov. For more information about monitoring technologies,
contact George Allen at (505) 844-9769 or by e-mail at gcallen@xandia.gov.
Information about this resource is available on the Internet at:
www.sandia.gov/eesector/em/emrt.html
S-17
Module: Sources of Site Characterization Technology Information
-------
Sources
Sources of Site Characterization
Technology Information
• Federal agencies, organizations, programs,
and partnerships
4- Laboratories
• Technical staff
• Internet information
4-Software
• Publication clearinghouses
• Publications
,8, EPA
S-13
S-J8
Module: Sources of Site Characterization Technology Information
-------
Sources
Technical Staff
*• General information
+ Specific technical support
S-14
Notes:
For general information about site characterization and monitoring technologies, contact:
Daniel Powell
U.S. Environmental Protection Agency
Technology Innovation Office
401 M Street, SW (MC 5102G)
Washington, DC 20460
Phone: (703)603-7196
Fax: (703)603-9135
E-mail: powett.dan@epa.gov
For general information about electronic sources of information about site
characterization and monitoring technologies contact:
Gary Turner
U.S. Environmental Protection Agency
Technology Innovation Office
401 M Street, SW (MC 5102G)
Washington, DC 20460
Phone: (703)603-9902
Fax: (703)603-9135
E-mail: turner.gary@epa.gov
S-19
Module: Sources of Site Characterization Technology Information
-------
Sources
For specific technical support for site characterization and monitoring technologies,
contact:
Eric Koglin
U.S. Environmental Protection Agency
National Exposure Research Laboratory (NERL)
Office of Research and Development
P.O. Box 93478
Las Vegas, NV 89193-3478
Phone: (702)798-2432
Fax: (702)798-2261
E-mail: koglin.eric@epa.gov
S-20
Module: Sources of Site Characterization Technology Information
-------
Sources
Sources of Site Characterization
Technology Information
• Federal agencies, organizations, programs,
and partnerships
• Laboratories
•Technical staff
• Internet information
• Software
• Publication clearinghouses
• Publications
EPA
S-15
S-21
Module: Sources of Site Characterization Technology Information
-------
Sources
Internet Information
he Haartou* Wafie Clean-up InfcnwJioa Web S« promdef
I / nfonnatum about onontive treatment technologies to the hazardous
JL wwte rtxnetfcation comnumity. It dfi»cnb« progranu, organtsliatis.
pubbcaboni and oihir tools for fedtfal and state pertoimd, conmlutg
en^ooss, lechnology devdopers and vendors, rernedaftion conlracurs, rwoarchrrs,
:ommun«y group*, aod in4m4ual ctstos Th« me «u developed by tfceIT S
Enwrotmunta] Protection Agency bul ji miotded 41 a forum for ad waste remedHtion
EPA
infornvitHHi xi tlw n (.t I
-NewPuDiications
Boning Courv, ana conference*
conurwnty nterestcdxi technology
devaopmem
S-16
Notes:
The Hazardous Waste Clean-Up Information (CLU-IN) Web Site. The CLU-IN Web
site provides information about innovative treatment and site characterization
technologies to the hazardous waste remediation community. It describes programs,
organizations, publications, and other tools for federal and state personnel, consulting
engineers, technology developers and vendors, remediation contractors, researchers,
community groups, and individual citizens. Note that a wealth of information is available
on this Internet site and through the links to other Internet sites it provides.
Links on CLU-IN that are of particular interest to those seeking additional information
include:
What's hot? What's new?
Publications and Software
Site Remediation Technologies
Site Characterization
Partnerships, Consortia, and Roundtables
This resource is available on the Internet at:
Regulatory Information
Vendor Support
Internet and Online Resources
International Updates
Tech Direct (see page S-25 for more
information about this resource)
www.clu-in.org
S-22
Module: Sources of Site Characterization Technology Information
-------
Sources
Internet Information
&EPA
III!*
WMconw to EPA REACH IT
AC»wri«i*ifwi A™* CHsr^tff^Miter In™*;***. TW*™»*V«-«
flffcCH !T14 a n«* Astern denied ID search, visw, download. *n«j [>nm infomwtan
bout innovative rffmotjiation and eb*'»«*^zafec'1 technologies.
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Satact Guided Svareb (bulletl) Of Advanced Soared below
Find tecnnclQaies for treatment of a particular contaminated medium.
• Flnct tfrcnnoioQi»5 for c
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-------
Sources
Internet Information
45, EPA
iteo Stales
Agoncy
JEPA Releases Guidance an High Production Cheiflicdls
IP A Htm
Ogr Mission:
"...to protect
human health and to
safeguard the natural
environment..'
I prowse | What's New | Comments | Text Version!
http:/Anw«f epa.gov/
This page last upaatec on February 22.1999
Ncbce of Use
EPA Server information
S-18
Notes:
EPA Home Page. The EPA home page provides a search engine for identifying
resources available from EPA and obtaining those resources. Links include:
About EPA
News and Events
Laws and Regulations
Contracts, Grants, and Environmental Financing
- Projects & Programs
- Publications
- Databases and Software
- Other resources
To extract or and all resources about site characterization methods or techniques, click on
the search link located at the bottom of the screen, then simply type in key words relevant
to the types of resources you are looking for. Key words or phrases should be typed in
quotes — for example, "field portable immunoassay" or simply "immunoassay." All
resources found with the key words you enter will be extracted from the server. In many
cases, documents and software can be downloaded or printed immediately. Other
resources can be ordered through the on-line service provided.
This resource is available on the Internet at:
www.epa.gov
S-24
Module: Sources of Site Characterization Technology Information
-------
Sources
Internet Information
?. Membership Information
MvmrtoiDl Upturn
vndo> Support
Tech Direct, hosted by the U.S. EPA's Technology Innovation Office, is an
information service that highlights new publications and events of interest to
._ site remediation and site assessment professionals. At the beginning of every
month, the service, via e-mail, will distribute a message describing the
availability of publications and events. For publications, the message will
explain how to obtain a hard copy or how to download an electronic version.
S-19
Notes:
TechDirect. TechDirect, hosted by EPA's TIO, is an information service that highlights
new publications and events of interest to environmental professionals. Information
about site characterization and remediation are available free of charge through this
Internet subscription service. Approximately once a month, the service distributes by
electronic mail a message that describes publications available and events scheduled. For
publications, the message explains how to obtain a hard copy or how to download an
electronic version from the Internet. For more information about TechDirect, contact Jeff
Heimerman at (703) 603-7191 or by e-mail at heimerman.jeff@epa.gov.
This resource is available on the Internet at:
www.clu-in.org/techdrct
5-25
Module: Sources of Site Characterization Technology Information
-------
Sources
Inte
&EPA
met Information
day.net*
Environmental Professional's Homepage
&WB*nrf krOZA OcoErviromncntiJ Technologies. Inc.
onfomnoitil nnndtnti *md mutilation profedonils.
IGovammait Aetndes, F«4tnl| | [Covmunait Aunria. Stattl IKMUIadam KtfiraieM. Ftdtrall |
ITh. EP Virtual DefktoDt | ILoiiladon. F«knH | ISnrch Endnnl | [WI.FKTP T«h.i.( cooneri
crwhlo. If thb b yout Oru v«c plttit ufct • nbutfr to Ibd en whj w«W Ken. If TOO havt b«o h«n
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futiuujtl 1^&gifi\ BB
H£Q3g| jg^gTTIJ gj,|Bn»l.»T»OII
S-20
Notes
clay.net® Environmental Professional's Homepage, clay.net® is a "one stop shop," a
quickly loaded work platform for rapid retrieval of information, designed specifically for
environmental professionals. It is sponsored by GZA GeoEnvironmental Technologies,
Inc. Resources from numerous sources can be obtained through this Internet site by links
and search engines, clay.net® provides the following links:
- Government agencies, federal
- Government agencies, state
- Regulations references, federal
- Health and safety issues
- Professional associations
This resource is available on the Internet at:
Conferences, bulletins, announcements
The EP virtual desktop
Legislation, federal
Search engines
EPA-ERTP training courses
www.clay.net
5-26
Module: Sources of Site Characterization Technology Information
-------
Sources
Internet Information
Environmental
links
ENVIRONMENTAL
C-K
ASSOCIATES • INC
CONSONANTS
EPA
S-21
Notes:
Environmental Links. C-K Associates, Inc. offers an Internet site called Environmental
Links. The consolidated platform provides access to resources related to various
environmental topics. Environmental Links includes the following links:
- Federal environmental sites
- Industry and environmental associations
- Health and safety
- State environmental agencies
This resource is available on the Internet at:
- Search engine websites
- Support sites
- Miscellaneous sites
www.c-ka.com/c-k/pages/linkpage.htm
5-27
Module: Sources of S/te Characterization Technology Information
-------
Sources
Internet Information
envtEonnient&techidpgy
Tech Know20
ycET w
R?59BSil^^^^^^^^5^t^^?55"-!'!-,
^EPA
sfe A R T H V I S I O N
^,V<
S-22
Notes:
The Global Network of Environment & Technology (GNET). GNET is an on-line
environmental technology and business center developed by the Global Environment and
Technology Foundation (GETF), in cooperation with DOE. GNET was designed to bring
together representatives of government, industry, states, academia, and the public to
identify and use the best, most cost-effective methods to remediate contaminated sites.
Other affiliates of GNET linked to this Internet site are described below.
Information about this resource is available on the Internet at:
www.gnet.org
TechKnow2 °. TechKnow is an on-line database built into GNET, which allows Internet
users to share and receive technical solutions to environmental problems immediately.
Technologies are categorized by contaminant, medium and name. Profiles of
technologies include summaries and information about stage of development, status as
intellectual property, and cost. Information about availability of licensing and contact
information also are included. Users may access the TechKnow database by visiting the
GNET home page and clicking on the TechKnow database button or by visiting the Web
site directly from the address indicated below.
This resource is available on the Internet at:
www.techknow.org
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Sources
GETF. GETF is a not-for-profit corporation that promotes the development and use of
innovative technology to achieve sustainable development. GETF has brought industry,
government, and communities together to address environmental challenges and
innovative solutions. GETF's mission is to help institutions (1) build interconnected
information and educational networks to facilitate the dissemination of best practices and
best ideas, (2) promote new technologies and practices that enable individuals and
institutions to make breakthrough improvements in both the quality and environmental
effects of what we produce and consume, and (3) establish lasting communities of interest
among key institutions and people that historically have not worked together. For more
information about GETF, contact Stuart Claggett at (703) 750-6401.
This resource is available on the Internet at:
www.getf.org
Verification/Certification of Environmental Technology (VCET). VCET is an on-
line repository of information about verification and certification of environmental
technologies for all stakeholders, including technology developers, vendors, state
permitting officials, regulators, end users, environmental engineering consulting firms,
and financial groups. The Web site provides stakeholders information to help make
decisions about the use and transfer of technologies.
This resource is available on the Internet at:
www.getf.org/vcet
Earthvision. Earthvision provides up-to-date environmental news and information about
various topics related to business and technology, sustainability, education, policy and
advocacy, and recreation.
This resource is available on the Internet at:
www.earthvision.net
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Module: Sources of Site Characterization Technology Information
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Sources
Sources of Site Characterization
Technology Information
• Federal agencies, organizations, programs,
and partnerships
• Laboratories
•Technical staff
• Internet information
>• Software
• Publication clearinghouses
• Publications
EPA
S-23
S-30
Module: Sources of Site Characterization Technology Information
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1
Sources
Software
ite Characterization CD-ROM
S-24
Notes:
Site Characterization CD-ROM (EPA 600-C-96-001). The Site Characterization
CD-ROM, developed by NERL's ESD-LV, compiles guidance documents and related
software to aid environmental professionals in the complex, multidisciplinary process of
characterizing hazardous waste sites. The CD-ROM is a compilation of computer
programs related to EPA's RCRA and Superfund programs that can be printed, as well as
searched by key words. Using the CD-ROM requires a personal computer with DOS
Version 3.0 or higher, 640K of RAM, and 3 MB of hard disk space. A math co-processor
is recommended but not required. The CD-ROM can be purchased on-line through the
National Technical Information Service (NTIS) Internet site.
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Module: Sources of Site Characterization Technology Information
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Sources
Software
* Business Gold
EPA
S-25
Notes:
Business Gold. Business Gold is an electronic bulletin board system (BBS) operated by
the National Technology Transfer Center (NTTC) that provides access to the latest
information about the newest technologies available through the research and
development programs of federal government agencies. All information on the system
can be downloaded free of charge. The system provides information about a directory of
federal laboratory resources; information about current assistance program solicitations,
state and regional technology and assistance programs; current news and announcements;
a technology transfer conference calendar; and information about government software
information centers, databases, and user guides. For information about the BBS, call
(800) 678-6882.
This resource is available on the Internet at:
www.frtr.gov/matrix2/appd_c/appdjc03.html
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Module: Sources of Site Characterization Technology Information
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Sources
Software
4 Site Characterization Technology Web Site
3-26
Notes:
EPA's Technology Innovative Office along with the U.S. Army Corps of Engineers is
developing a web site containing detailed information about a variety of site
characterization and monitoring technologies. Information provided on each technology
will include:
Description -
- Typical Uses -
Theory of Operation
- System Components -
Mode of Operation -
- Performance Specs -
- Target Analytes
Example technologies listed in the web site include:
X-Ray Fluorescence
Infrared Spectroscopy
Immunoassay
Graphite Furnace Atomic Absorption Spectroscopy
Mass Spectroscopy
Laser Induced Fluorescence
Advantages
Limitations
Cost Data
Documented Past Use
Vendors/Instruments
Verification/Evaluation Reports
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Sources
The web site will be online by late Fall of 1999 and will be available through the CLU-IN
web site . Look for an announcement in TechDirect regarding specific
details about its availability.
The Site Characterization Technology Encyclopedia web site contains information on
field-portable site characterization technologies for hazardous waste. The web site is
offered by the Office of Solid Waste and Emergency Response Technology Innovation
Office (TIO) of the United States Environmental Protection Agency (EPA).
This resource is available on the Internet at:
clu-in.org
S-34
Module: Sources of Site Characterization Technology Information
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Sources
Sources of Site Characterization
Technology Information
^ Federal agencies, organizations, programs,
and partnerships
4 Laboratories
+Technical staff
* Internet information
* Software
• Publication clearinghouses
*• Publications
S-27
S-35
Module: Sources of Site Characterization Technology Information
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Sources
Publication Clearinghouses
+Government Printing Office (GPO)
+ National Service Center for Environmental
Publications (NSCEP), formerly the National Center
for Environmental Publications and Information
(NCEPI)
* National Technical Information Service (NTIS)
4Technology Transfer and Support Division (TTSD),
formerly the Center for Environmental Research
Information (CERI)
+ EPA Document Numbering System
S-28
Notes:
Publication Clearinghouses. EPA has four publication clearinghouses, from which EPA
personnel and the public can obtain information about innovative technologies. Printed
publications from these clearinghouses can be obtained directly from the publication
clearinghouse or through the Internet. Many documents mentioned and distributed during this
course are available from one of the four major clearinghouses free of charge:
Government Printing Office (GPO)
- National Service Center for Environmental Publications (NSCEP), formerly the
National Center for Environmental Publications and Information (NCEPI)
- National Technical Information Service (NTIS)
- Technology Transfer and Support Division (TTSD), formerly the Center for
Environmental Research Information (CERI)
• GPO. GPO prints, binds, and distributes the publications of Congress, as well as other
federal agencies. GPO sells through mail orders and federal bookstores approximately
12,000 printed and electronic publications that originate from various federal agencies.
GPO also administers the depository library program through which selected federal
publications are made available to libraries throughout the country. GPO also provides
on-line access to more than 70 databases of federal government publications. Searchable
databases on Wide Area Information Server (WAIS) also are available free of charge to
the public through participation in federal depository libraries or directly through the
Internet site identified below. Environmentally publications are accessible through the
S-36
Module: Sources of Site Characterization Technology Information
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Sources
GPO WAIS. GPO operates daily, Monday through Friday, 7:30 a.m. to 4:00 p.m. eastern
time.
Government Printing Office
Superintendent of Documents
PO Box 371954
Pittsburgh, PA 15250-7954
Telephone: (202) 512 1800 Fax: (202) 512-2250
Information about this resource is available on the Internet at:
www.access.gpo.gov/getdocs.html
NSCEP. NSCEP, formerly NCEPI, is a central repository and distribution center for all
EPA documents. NSCEP maintains an in-house inventory of 5,000 current EPA
publications available to the public free of charge. Each month, NSCEP distributes more
than 420,000 documents to an international audience. NSCEP offers an online EPA
Publications Catalog to facilitate ordering of publications. Orders must be limited to five
titles per two-week period. As supplies are depleted, the solicitor is referred to NTIS,
GPO, or the Educational Resource Information Center (ERIC) to obtain copies of
documents at cost. NSCEP operates daily, Monday through Friday, 7:00 a.m. to 5:30
p.m. central time.
National Service Center for Environmental Publications
PO Box 42419
Cincinnati, OH 45242
Telephone: (513) 489-8190 Fax: (513) 489-8695
This resource is available on the Internet at:
www.epa.gov/ncepihom
NTIS. NTIS is the central source for government-sponsored U.S. and worldwide
scientific, technical, engineering, and business-related information. As a self-supporting
agency of Commerce Department's Technology Administration, NTIS covers its business
and operating expenses with the sale of its products and services. Its collection of almost
three million publications includes business and management studies, international
marketing reports, materials and chemical science data, information about technology
innovations, and training tools. Information is available in the following formats:
audiovisual, CD-ROM, diskette, microfiche, print and on line. NTIS acquires
information from more than 200 U.S. federal agencies, government agencies, and
international organizations. NTIS operates daily, Monday through Friday, 8:30 a.m. to
5:00 p.m., eastern time.
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Module: Sources of Site Characterization Technology Information
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Sources
National Technical Information Service
Technology Administration
U.S. Department of Commerce
Springfield, VA 22161
Order Desk: (703)605-6000
Fax: (703)605-0900
This resource is available on the Internet at:
www.ntis.gov
TTSD, formerly CERI. TTSD is the focal point for the exchange of scientific and
technical environmental information produced by EPA. Technology Transfer and
Support Division publishes brochures, capsule and summary reports, handbooks,
newsletters, project reports, and manuals. The office operates daily, Monday through
Friday, 8:00 a.m. to 4:30 p.m., eastern time.
- Technology Transfer and Support Division
26 West Martin Luther King Drive
Cincinnati, OH 45268
Telephone: (513) 569-7562
Fax:(513)569-7566
This resource is available on the Internet at:
www.epa.gov/ttbnrmrl/ceri.htm
EPA Document Numbering System. The following paragraphs briefly explain the
significance of prefixes used in EPA document numbers to help determine the appropriate
resource from which to order a particular document.
- Publications beginning with EPA number 540, 542, 600, 625, or 630 may be
available through the TTSD. The documents are available free of charge, but
supplies may be limited. Documents that are not in stock at TTSD may be
available through NSCEP or may be purchased from NTIS. Before you purchase
documents, you may wish to contact a technical librarian to determine whether the
document you need is available free of charge. Always include the EPA
document number in all orders.
- Publications beginning with EPA number 510, 542, 600, or 630 may be available
through NSCEP. Single copies are available free of charge while supplies last.
Documents that are out of stock must be ordered from NTIS. Always include the
EPA document number in all orders.
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Module: Sources of Site Characterization Technology Information
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Sources
Publications beginning with PB numbers or directives issued by EPA's OSWER
can be purchased from NTIS. Always include the EPA document number in all
orders.
EPA staff or members of the public who have difficulty finding a document can
call the RCRA, Underground Storage Tank (UST), Superfund, and Emergency
Planning and Community Right-to-Know Act (EPCRA) Hotline at 1-800-424-
9346, or at (703) 412-9810 for all locations in the Washington, D.C. local calling
area. The hotline operates daily Monday through Friday, 9:00 a.m. through 6:00
p.m., eastern time. Hotline staff can help callers locate documents and assist them
in placing orders. Government employees may order many documents that have
EPA publication numbers free of charge from NSCEP.
S-39
Module: Sources of Site Characterization Technology Information
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Sources
Sources of Site Characterization
Technology Information
• Federal agencies, organizations, programs,
and partnerships
• Laboratories
•Technical staff
• Internet information
• Software
• Publication clearinghouses
• Publications
&EPA
S-29
S-40
Module: Sources of Site Characterization Technology Information
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Sources
Publications
* EPA publications
» Brochures, bulletins, and fact sheets
» Guidance documents
» Newsletters
» Technical reports
4Non-EPA publications
» Guidance documents
"Journals
» Magazines and tabloids
» Newsletters
S-30
S-41
Module: Sources of Site Characterization Technology Information
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Sources
Publications
EPA publications
» Brochures, bulletins, and fact sheets
» Guidance documents
» Newsletters
» Technical reports
Notes:
EPA publishes a number of brochures, bulletins, and fact sheets that summarize information
about specific organizations, programs, partnerships, and technologies related to site
characterization. Many of the publications are accessible on the Internet or through a publication
clearinghouse. A detailed list of those documents is provided at the end of this module.
EPA publishes various guidance documents on site characterization technologies. The guidance
documents are:
• Field Sampling and Analysis Technologies Matrix. The Field Sampling and Analysis
Technologies Matrix, developed by member agencies of FRTR, is a matrix and reference
guide that makes users aware of the site characterization technologies available to them
and provides them with an understanding of the applicability of various technologies to
their particular problems. The matrix provides a general understanding of state-of-the-art
technologies for site characterization to enhance transfer of technology information and
allow comparison of competing technologies.
Information about this resource is available on the Internet at:
www.frtr.gov
S-42
Module: Sources of Site Characterization Technology Information
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Sources
• TIO is working with the Superfund and RCRA corrective action programs to provide
guidance to EPA staff on the use of expedited processes and the applicability of expedited
site characterization and field technologies to the waste programs. EPA also is beginning
to develop "presumptive" site characterization methods for four common site types to
increase the understanding and acceptance of field technologies among EPA staff.
Questions about the project should be directed to Michael Kurd of the Superfund program
at (703) 603-8836.
Two newsletters published by EPA provide information about site characterization technologies.
The newsletters are:
- Ground Water Currents (542-N-98-008). The newsletter provides information
about innovative treatment technologies for characterization and remediation of
groundwater contamination. It also provides information about development and
demonstrations, new regulations, and conferences and publications.
This resource is available on the Internet at:
clu-in.org/publ.htm
Tech Trends (EPA 542-N-99-001). The newsletter focuses on applied
technologies for site characterization and remediation. The newsletter can be
downloaded free of charge from the Internet site identified below.
This resource is available on the Internet at:
clu-in.org/publ.htm
Other publications, such as technical reports, also provide valuable information about site
characterization technologies. Many of the publications are accessible on the Internet or can be
obtained from a publications clearinghouse. A few particularly useful examples of such reports
are described below.
• Innovative Technology Evaluation Reports (ITER) and Innovative Technology
Verification Reports (ITVR). Innovative technology demonstrations or verification
projects are performed under the CSCT or SITE programs. At the conclusion of
demonstrations or verifications, ITERs or ITVRs are prepared to document the
performance of the technology demonstrated. Fact sheets or technology briefs (one- or
two-page documents) also are prepared for each technology. Some examples of these
documents are provided as handouts during this workshop.
• Status Report on Field Analytical and Characterization Technologies. EPA's TIO is
compiling data collected from the EPA regions on past applications of innovative field-
based technologies. The report establishes baseline information about more than 100
sites at which field-based technologies have been used to date. Questions about the status
report should be referred to John Kingscott of TIO at (703) 603-7189.
S-43
Module: Sources of Site Characterization Technology Information
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Sources
Publications
^Non-EPA publications
>> Guidance documents
» Journals
» Magazines and tabloids
» Newsletters
EPA
S-32
Notes:
Several guidance documents on site characterization or on related topics are available from two
sources outside EPA: the California Military Environmental Coordination Committee (CMECC)
and the American Society for Testing and Materials (ASTM). The majority of private-sector
guidance documents related to field-based site characterization or expedited site characterization
are available from ASTM. The guidance documents include:
• CMECC Guidance. The CMECC guidance discusses the application field
analytical technologies. It also provides a matrix of performance characteristics
for several immunoassay, CPT, LIE, and FPXRF technologies. Copies of this
document can be obtained by calling (916) 227-4368.
• Standard Guide for Site Characteristics for Environmental Purposes, With
Emphasis on Soil, Rock, the Vadose Zone, and Groundwater. This ASTM
guidance covers the selection of the various ASTM standards that are applicable
in the investigation of soil, rock, the vadose zone, groundwater, and other media,
when the investigations have an environmental purpose. This document can be
obtained from Power Engineering Books, Ltd. at (800) 667-3155.
• Standard Provisional Guide for Expedited Site Characterization of
Hazardous Waste Contaminated Sites. This ASTM provisional guide describes
a method of ESC. This document can be obtained through Power Engineering
Books, Ltd. at (800) 667-3155.
S-44
Module: Sources of Site Characterization Technology Information
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Sources
Information about this resource is available on the Internet at:
^^^* powerengbooks.com/booklsts/astm.html
Journals on site characterization technologies or related topics are available from several sources.
The sources are included in the additional information provided at the end of this module.
One magazine and two tabloids provide information about site characterization technologies.
Those publications are:
- American Environmental Laboratory
Publication Type: Tabloid
Target Audience: Associations and Businesses
Publisher: International Scientific Communications Inc.
Telephone: (203)926-9300 Fax: (203)926-9310
- Environmental Testing & Analysis
Publication Type: Magazine
Target Audience: Businesses
Publisher: Target Group, Inc.
Telephone: (818)842-4777
- Environmental Testing & Analysis News
Publication Type: Tabloid
Target Audience: Businesses
Publisher: Target Group, Inc. (Don Meeker)
Telephone: (818)842-4777
Two newsletters provide information about site characterization technologies. Those newsletters
are:
- Environmental Technologies
Publication Type: Newsletter
Target Audience: Businesses and Consumers
Publisher: Environmental Management
Telephone: (505)667-2211
- The Bio-Cleanup Report
Publication Type: Newsletter
Target Audience: Businesses and Consumers
Publisher: King Communications Group
Telephone: (202)638-4260 Fax: (202)662-9719
S-45
Module: Sources of Site Characterization Technology Information
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Additional Information
Table of Contents
EPA Brochures, Bulletins, and Fact Sheets A-2
EPA Guidance Documents A-6
EPA Software A-8
EPA Technical Reports A-10
Non-EPA Guidance Documents A-14
Non-EPA Internet Information A-15
Non-EPA Journals A-16
Non-EPA Technical Reports A-17
A-l
Module: Sources of Site Characterization Technology Information
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Additional Information
EPA Brochures, Bulletins, and Fact Sheets
GENERAL
Bibliography for Innovative Site Clean-Up Technologies (EPA 542-B-98-001). The
brochure is a comprehensive guide to information resources available on innovative site
cleanup technologies. The bibliography lists resources for technology survey reports;
EPA program information; groundwater (in situ) treatment; thermal treatment;
bioremediation; soil vapor extraction and enhancements; physical and chemical
treatment; site characterization; other conferences and international surveys; technical
support; community relations; bulletin board systems, databases, software, and the
Internet; technology newsletters; and innovative site remediation engineering technology
monographs. The document also provides titles, document numbers, and ordering
information. The document can be downloaded free of charge from the CLU-IN Internet
site at .
• Characterization Protocol for Radioactive Contaminated Soils (PB92-963354). The
fact sheet describes physical separation technologies that may be useful in characterizing
sites at which soils are contaminated with radioactive wastes. It provides information
about the use of physical separation technologies to reduce the volume of radioactive soil
on site.
Clean-Up Information (CLU-IN) Home Page on the World Wide Web
(EPA 542-F-97-002). The fact sheet describes TIO's CLU-IN Internet site. The Internet
site provides information about innovative site characterization and remediation
technologies. It describes programs, organizations, publications, and other tools for EPA
and other federal and state personnel, consulting engineers, technology developers and
vendors, remediation contractors, researchers, community groups, and individual citizens.
The home page can be accessed through the Internet at .
• Promoting Innovative Technologies at Brownfields Sites (EPA 542-F-96-032).
The fact sheet summarizes EPA's efforts to promote innovative technologies at
Brownfields sites. EPA's TIO offers assistance to Brownfields stakeholders in meeting
the challenges of site cleanup and redevelopment. TIO is developing two guides which
provide Brownfields stakeholders with a better understanding of technology options as
they proceed through the basic steps involved in cleaning up Brownfields sites. The
"Road Map to Understanding Innovative Technology Options for Brownfields
Investigation and Cleanup" provides a general description of the steps involved in the
cleanup and redevelopment of Brownfields sites to connect these steps and phases with
technology options." "A Tool Kit of Information Resources for Brownfields
Investigation and Cleanup" describes the resources identified in the Road Map, explains
how to obtain the publications, and provides a "starter kit" of important information
resources to help Brownfields stakeholders gain an understanding of technologies for site
characterization and cleanup.
A-2
Module: Sources of Site Characterization Technology Information
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Additional Information
* Site Characterization and Monitoring: Bibliography of EPA Information Resources
(EPA-542-B-98-003). The bulletin provides a bibliography that lists information
resources, both publications and electronic databases, that focus on evaluation and use of
innovative site characterization and monitoring technologies. The bulletin also provides
information on obtaining copies of the documents, and can be downloaded free of charge
from the CLU-IN internet site at .
ORGANIZATIONS, PROGRAMS, AND PARTNERSHIPS
• Consortium for Site Characterization Technology—Innovative Technology
Verification Reports Fact Sheet ( EPA-542-F-97-020). The CSCT is a partnership
program involving EPA, DoD, and DOE that is responsible for evaluating and verifying
the performance of innovative site characterization technologies. The fact sheet describes
the mission of the CSCT and its activities and identifies points of contacts. The
document can be downloaded free of charge from the CLU-IN Internet site at
.
• Environmental Technology Verification Program (EPA 600-F-97-005). The brochure
highlights the Environmental Technology Pilot Partnerships that are currently underway
throughout the U.S. Information targeting the pilot managers is available for the various
technologies referenced in this publication. The brochure can be downloaded free of
charge from the ETV Internet site at .
• Superfund Innovative Technology Evaluation Program: Emerging Technology
Program (EPA 540-F-95-502). The SITE program encourages the development of
innovative technologies for faster, more effective, and less costly treatment of hazardous
waste. The brochure provides information about the Emerging Technology Program of
SITE, including its purpose, background, and components, as well as the results of the
program. The brochure also provides contact information.
• Superfund Innovative Technology Evaluation Program: Fact Sheet (EPA 542-F-95-
009). The fact sheet provides information about the SITE program and describes efforts
to advance the development, evaluation, and commercialization of innovative
technologies used to assess and clean up hazardous waste sites, includes a description of
the components of the program, as well as a summary of the benefits and stages of
technology development. A list of documents available from EPA's NRMRL also is
included. The fact sheet also provides information on obtaining copies of the documents
and videotapes.
A-3
Module: Sources of Site Characterization Technology Information
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Additional Information
SOFTWARE
Vendor Field Analytical Characterization Technology System (Vendor FACTS) 3.0
Bulletin (EPA 542-N-98-002). The bulletin informs technology users of the composition
of Vendor FACTS and technology vendors of the opportunities Vendor FACTS can offer
them. The bulletin also provides information on obtaining copies of the software and
user manual, and system requirements, as well as a registration and order forms. A list of
the names of vendors, the types of technology used, and the contaminants monitored also
is provided. The document can be downloaded free of charge from the CLU-IN Internet
site at .
TECHNOLOGIES
Cone Penetrometer/Laser Induced Fluorescence (LIF) (EPA 542-F-96-009b).
The brochure highlights Cone Penetrometer LIF, a field screening method that couples a
fiber optic-based chemical sensor system to a truck-mounted cone penetrometer. The
time and place for demonstration of this technology are presented as well as who
participated.
Consortium for Site Characterization (CSCT): Technology Verification Area Fact
Sheets. The CSCT has developed three verification area fact sheets for PCB analysis
technologies, soil/soil gas technologies, and wellhead monitoring for volatile organic
compounds. The fact sheets can be downloaded free of charge from the CLU-IN Internet
site at .
PCB Analysis Technologies Fact Sheet (EPA 542-F-97-021). The
technologies featured within this category are all field-deployable and
provide for screening, measurement, and characterization of
polychlorinated biphenyl (PCB) contamination. The techniques include:
quantification of PCB concentrations in soil, dielectric fluid, and surface
wipe samples; immunoassay (colorimetric analysis); and on-site gas
chromatograph analysis.
Soil/Soil Gas Sampling Technologies Fact Sheet (EPA 542-F-97-022).
The technologies featured within this category are all field deployable and
provide for sampling of soil and soil gas for screening, measurement, and
characterization of volatile and semi-volatile contaminants. Some
technologies also cover metals. The techniques include: two samplers
advanced by direct push techniques; a hand-operated percussive soil
sampler; and two soil gas absorbers.
A -4
Module: Sources of Site Characterization Technology Information
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Additional Information
Wellhead Monitoring for Volatile Organic Compounds Fact Sheet
(EPA 542-F-97-023). The technologies featured within this category
include a sensor providing real-time detection of TCE and other
trihalomethanes, field portable gas chromatograph/mass spectrometers,
and a multi-gas photoacoustic spectroscopy unit.
Field Portable X-Ray Fluorescence (FPXRF) (EPA 542-F-96-009a).
The brochure highlights FPXRF, a site-screening procedure using a small portable
instrument that addresses the need for a rapid turnaround, low-cost method for on-site
analysis of inorganic contaminants. The time and place of the demonstration of this
technology are presented a well as who participated.
Portable Gas Chromatograph/Mass Spectrometer (EPA 542-F-96-009c).
The brochure highlights GC/MS, a method recommended by EPA for the analysis of
semivolatile organic compounds. The time and place for demonstration of this
technology are presented as well as who participated.
A-5
Module: Sources of Site Characterization Technology Information
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Additional Information
EPA Guidance Documents
A Guidance Manual for the Preparation of Site Characterization and Monitoring
Technology Demonstration Plans. Interim Final, October 1996. The guidance
document can be downloaded free of charge from the Internet at
.
Air/Superfund National Technical Guidance Study Series. Volume 5. Procedures for
Air Dispersion Modeling at Superfund Sites (PB95-193124). The document can be
obtained from NTIS for $27.00.
DNAPL Site Evaluation (PB93-150217). The manual provides information about the
treatment of sites contaminated with dense nonaqueous phase liquids (DNAPL),
particularly chlorinated solvents. It discusses several issues related to the characterization
of such sites, including the risk of inducing migration of DNAPLs by drilling, pumping,
or conducting other field activities; the use of special sampling and measurement to
assess the presence and migration potential of DNAPLs; the development of cost-
effective characterization strategies that account for chemical transport processes of
DNAPLs; and the collection of data required to select and implement a remedy. The
manual also describes and evaluates activities that can be used to determine the presence
and fate and transport of subsurface DNAPL contamination.
Expedited Site Assessment Tools for Underground Storage Tank Sites: A Guide for
Regulators (EPA 510-B-97-001). Produced by EPA's Office of Underground Storage
Tanks (OUST), the manual is designed to help state and federal regulators with
responsibility for USTs to evaluate conventional and new site assessment technologies
and promote the use of expedited site assessments. The manual covers five major issues
related to UST site assessments: the expedited site assessment process; surface
geophysical methods for UST site investigations; soil-gas surveys; direct push
technologies; and field analytical methods for the analysis of petroleum hydrocarbons.
The equipment and methods presented in this manual are evaluated in terms of
applicability, advantages, and limitations for use at petroleum UST sites.
Promotion of Innovative Technologies in Waste Management Programs: OSWER
Policy Directive 9380.0-25. The guidance document can be downloaded free of charge
from the CLU-IN Internet site at .
Tool Kit of Information Resources for Brownfields Investigation and Cleanup
(EPA 542-B-97-001). The publication is a companion to the Brownfields Road Map.
The tool kit provides abstracts and access information about a variety of resources
including electronic databases, newsletters, regulatory and policy guidance, and technical
reports. The document can be downloaded free of charge from the CLU-IN Internet site
at .
A-6
Module: Sources of Site Characterization Technology Information
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Additional Information
Rood Map to Understanding Innovative Technology Options for Brownfields
Investigation and Cleanup (EPA 542-B-97-002). The document focuses on the site
characterization and cleanup phase of Brownfields redevelopment. It provides a
framework of logical steps involved in the characterization and cleanup of a Brownfields
site in order to link technology options and resources to each of these steps. The
document can be downloaded free of charge from the CLU-IN Internet site at
< http://clu~in.com/pubindex.htm>, or can be ordered from NCEPI. In addition, the
Road Map is linked to an accompanying Tool Kit of Information Resources for
Brownfields Investigation and Cleanup, with describes the information resources
developed by EPA to support innovative characterization and clean-up technologies.
Access to EPA's Brownfields Home Page is available via link at
.
A-7
Module: Sources of Site Characterization Technology Information
-------
Additional Information
EPA Software
Site Characterization CD-ROM. The Site Characterization CD-ROM developed by
NERL contains the following documents and software:
- Bibliography of Ground Water Sampling Methods
Compendium of Superfund Program Publications (EPA 540-8-91-014).
Data Quality Objectives for Superfund (EPA 540-R-93-071).
- Description and Sampling of Contaminated Soils: A Field Pocket Guide
(EPA 625-12-91-002).
Field Screening Methods Catalog (EPA 540-2-8-005).
- Guidance for Conducting Remedial Investigations and Feasibility Studies
Under CERCLA (EPA 540-G-89-004).
- Guidance for Performing Preliminary Assessments Under CERCLA
(EPA540-G-91-013).
- Handbook of Suggested Practices for the Design and Installation of Ground
Water Monitoring Wells (EPA 600-4-89-034).
Preliminary Assessment Guidance for FY88 (OSWER 9345.0-01).
- Preparation Aids for the Development of Category I Quality Assurance Project
Plans (EPA 600-8-91-003).
- Preparation of Soil Sampling Protocols: Sampling Techniques and Strategies
(EPA600-R-92-129).
- RCRA Ground Water Monitoring Technical Enforcement Guidance Document
(OSWER 9950.01).
Soil Sampling Quality Assurance User's Guide (EPA 600-8-89-046).
Superfund Exposure Assessment Manual (EPA 540-1-88-001).
Vadose Zone Monitoring for Hazardous Waste Sties (EPA 600-X-83-064).
A-8
Module: Sources of Site Characterization Technology Information
-------
Additional Information
ASSESS Version LI A (PB93-505154). ASSESS is an interactive QA/QC
program designed to assist the user in statistically determining the quality of data
from soil samples.
Decision Error Feasibility Trials (DEFT) Version 4.0. The DEFT software
allows a decision maker or member of a planning team to quickly generate cost
information about several sampling designs based on data quality objectives
(DQO). A user's guide is available on the CD-ROM.
Geostatistical Environmental Assessment Software (Geo-EAS) Version 1.2.1
(PB93-504967). Geo-EAS offers environmental scientists an interactive tool for
performing two-dimensional geostatistical analyses of spatially distributed data.
Extensive use of screen graphics such as maps, histograms, scatter plots, and
variograms helps the user search for patterns, correlations, and problems in a data
set. A user's guide also is available on the CD-ROM.
Geophysics Advisor Expert System Version 2.0 (PB93-505162). The program
considers several geophysical methods of determining the location of
contamination and providing site characterization to make recommendations on
the best methods to use at a specific site. Version 2.0 also includes a database of
the physical and chemical properties of 94 substances selected from EPA's
National Priorities List (NPL).
Scout Version 2.0. Scout is a user-friendly and menu-driven program that
provides a graphical display of data in a multidimensional format that allows
visual inspection of data, accentuates obvious outliers, and provides an easy
means of comparing one data set with another. A user's guide also is available on
the CD-ROM.
A-9
Module: Sources of Site Characterization Technology Information
-------
Additional Information
EPA Technical Reports
GENERAL
• Abstract Proceedings: Superfund Technical Support Project General Meeting, Athens,
Georgia 12/3/90 -12/6/90 (PB93-205862). The document is a collection of abstracts
from a workshop on the Superfund Technical Support Project held in Athens, Georgia in
December 1990. Several papers include discussions of technical issues, such as causes
and effects of well turbidity; characterization of heterogeneous hazardous wastes;
computer-aided assessment of contaminated sites; metal partitioning from incineration of
soils and debris; and RCRA groundwater monitoring regulations. Other abstracts
describe various programs, including the Superfund Technical Liaison Program, the SITE
program, and the U.S. Army Corps of Engineers laboratory support program for EPA
regions. In addition, other summaries provide information about the Remedial Response
Construction Cost Estimating System (RACES) and other databases. Fourier Transform
Infrared Spectroscopy (FT-IR) and the MINTEQA2 Geochemical Equilibrium Model are
described in other abstracts, along with a range of issues related to technical support for
Superfund.
• Completed North American Innovative Technology Demonstration Project
(EPA 542-B-96-002, PB96-153127). The report summarizes more than 300 innovative
technology field demonstration projects that have been completed in North America. The
demonstration projects listed include those performed, co-sponsored, or funded through
programs developed by EPA, the military services, DOE, the U.S. Department of Interior
(DOI), the government of Canada, and the State of California. The report summarizes
key information from available demonstration projects in a single document and presents
that information in a manner that enables project managers and other interested persons to
easily identify innovative technologies that may be appropriate to their particular site
remediation needs. The report highlights key features of the demonstrations, including
contaminants treated, site types, technology types, technology vendors, project sponsors,
and technical reports available. The report can be downloaded free of charge from the
CLU-IN Internet site at .
• Sampling of Contaminated Sites (PB92-110436). The paper discusses the development
of sampling plans to identify and characterize contaminants that may exist at a site. It
also describes the components of a sampling plan and identifies issues that should not be
overlooked during the sampling of contaminants.
Technology Transfer Highlights (EPA 625-N-96-001). The document identifies and
describes information resources developed by EPA's CERI. The document lists resources
for manuals; technical capsule reports; seminar publications; brochures; handbooks;
guides to pollution prevention; summary reports; environmental regulations and technical
publications; and software. It also provides titles, document numbers, and ordering
information.
.A-10.
Module: Sources of Site Characterization Technology Information
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Additional Information
TECHNOLOGIES
Field Analytical and Site Characterization Technologies - Summary of Applications
(EPA-542-R-97-011). The report provides information about experiences in the use of
field analytical and site characterization technologies at contaminated sites drawn from
204 applications of the technologies. For each technology, information is presented on
the types of pollutants and media for which the technology was used; reported advantages
and limitations of the technology; and cost data for the technology, when available.
Information was obtained from federal and state site managers and from the Vendor Field
Analytical and Characterization Technologies System (Vendor FACTS) database. The
document can be downloaded free of charge from the CLU-IN Internet site at
.
Innovative Technology Evaluation Reports (ITER). Some of the following reports are
available on the Internet and can be downloaded free of charge from the CLU-IN Internet
site at or can be ordered through NCEPI.
Characterization of Chromium-Contaminated Soils Using Field-Portable X-
Ray Fluorescence (PB94-210457). In 1990, EPA, the U.S. Coast Guard, and the
Robert S. Kerr Environmental Research Laboratory initiated a cooperative effort
to evaluate various methods of site characterization at sites contaminated with
metals, particularly chromium. This document provides technical information
about the evaluation that used FPXRF technologies to assess and characterize
such soils.
Clor-N-Soil PCS Test Kit L2000 PCB/CMoride Analyzer (EPA-540-R-95-518).
The report summarizes the evaluation of two field screening technologies, the
Clor-N-Soil Test Kit and the L2000 PCB/Chloride Analyzer, which were
demonstrated in Kansas City, Missouri in August 1992. The technologies are
used to detect PCBs in soil.
Development of a Battery-Operated Portable Synchronous Luminescence
Spectrofluorometer (PB94-170032). The document describes a field screening
method that may be useful in characterizing sites at which contaminated
groundwater or hazardous waste is present. Battery-operated portable
synchronous luminescence spectrofluorometers are used to conduct trace analyses
of such contaminants as polynuclear aromatic hydrocarbons (PAH), creosote, and
polychlorinated biphenyls (PCB) in complex mixtures. The report also describes
the components of the instrument and provides an evaluation of its effectiveness
when used to analyze soil samples.
A-1I-
Module: Sources of Site Characterization Technology Information
-------
Additional Information
EnviroGard PCS Test Kit (EPA 540-R-95 -517). The report describes the
demonstration and evaluation of the EnviroGard PCB Test developed by
Millipore, Inc. The technology was demonstrated in Kansas City, Missouri in
August 1992.
Field Analytical Screening Program: PCB Method (EPA-540-R-95-528). The
report presents information on the demonstration of the EPA Region 7 Superfund
Field Analytical Screening Program (FASP) methods for determining PCP
contamination in soil and water. The FASP PCP Method was developed by the
EPA Superfund Branch for use at Superfund sites. This method was
demonstrated in Morrisville, North Carolina in August 1993.
HNU - Hanby PCP Immunoassay Test Kit (EPA-540-R-95-515). The report
describes the demonstration of the HNU-Hanby Environmental Test Kit. The kit
was demonstrated in Morrisville, North Carolina in August 1993.
PCP Immunoassay Technologies (EPA-540-R-95-514). The report describes the
demonstration and evaluation of three immunoassay field screening technologies
designed to determine PCP contamination in soil and water. The three
technologies were the Penta RISc Test System, the Penta PaPID Assay, and the
Enviro Gard PCP Test Kit. The technologies were demonstrated in Morrisville,
North Carolina in August 1993. The objectives of the demonstration were to
evaluate the accuracy and precision of each technology in detecting high and low
levels of PCP as well as the specificity of each technology.
Rapid Optical Screen Tool (ROST™) (EPA 540-R-95-519). In August 1994, the
ROST™ was evaluated. The report chronicles the development of ROST™, its
capabilities, associated equipment, and accessories. Further, the report evaluates
how closely the results obtained using the technology compare to the results
obtained using the referenced methods.
Site Characterization Analysis Penetrometer System (SCAPS) LIF Sensor
(EPA-540-R-95-520). In August 1994, the SCAPS was evaluated. The report
chronicles the development of the SCAPS technology, its capabilities, associated
equipment, and accessories. Further, the report evaluates how closely the results
obtained using the technology compare to the results obtained using conventional
reference methods.
Superfund Innovative Technology Evaluation (SITE) Technology Profiles - Ninth
Edition (EPA 540-R-97-502). The document, prepared between August 1996 and
December 1996, is intended as a reference guide for those interested in technologies
demonstrated in the SITE Demonstration, Emerging Technology, and Characterization
and Monitoring programs. The two-page profiles are organized into two sections for each
program, completed and ongoing projects, and are presented in alphabetical order by
•A-/2.
Module: Sources of Site Characterization Technology Information
-------
Additional Information
developer name. The document can be downloaded free of charge from the CLU-IN
Internet site at .
Technology Verification Statement and Reports from the Consortium for Site
Characterization and Technology (CSCT). The following CSCT verification
statements and reports can be downloaded free of charge from the CLU-IN Internet site at
.
Bruker-Franzen Analytical Systems, Inc. EM 640. The technology
described is a field portable gas chromatograph/mass spectrometer.
Rapid Optional Screening Tool (ROST™). The technology described is
a cone-penetrometer-deployed sensor which detects petroleum
hydrocarbons in-situ.
Site Characterization and Analysis Penetrometer System (SCAPS).
The technology described is a cone-penetrometer-deployed sensor which is
used for the detection of petroleum hydrocarbons in-situ.
Viking Instruments Corporation Spectratrak 672. The technology
described is a field portable gas chromatograph/mass spectrometer.
A-I3-
Module: Sources of Site Characterization Technology Information
-------
Additional Information
Non-EPA Guidance Documents
Environmental Guide to the Internet, 3rd Edition
Publication Type: Book
Authors: Carol Briggs-Erickson and Toni Murphy
Tel: (301)921-2345
Field Analytical Measurement Technologies, Applications, and Selection.
April 1996. California Environmental Coordination Committee (CMECC).
.A-14.
Module: Sources of Site Characterization Technology Information
-------
Additional Information
Non-EPA Internet Information
A list of non-EPA Internet sources of information is provided at the end of this module, after the
list of additional information.
A-J5-
Module: Sources of Site Characterization Technology Information
-------
Additional Information
Non-EPA Journals
CRC Critical Reviews in Science and Technology
Publication Type: Journal
Publisher: CRC Press, Inc.
Tel: (800) 272-7737 Fax: (800) 374-3401
Environmental Science and Technology
Publication Type: Journal
Target Audience: Businesses, Associations
Publisher: American Chemical Society (Robert Bovenschulte)
Tel: (800)333-9511 Fax: (614)447-3671
Environmental Technology: Journal of Advanced Science & Engineering
Publication Type: Journal
Target Audience: Businesses
Publisher: Campbell Publishing
Tel: (404)324-6746 Fax: (770)324-1177
Field Analytical Chemistry and Technology
Publication Type: Journal
Target Audience: Consumers, Associations
Publisher: John Wiley & Sons, Inc.
Tel: (212)850-6000 Fax: (212)850-6088
.A-16.
Module: Sources of Site Characterization Technology Information
-------
Additional Information
Non-EPA Technical Reports
The following are two additional books which provide a comprehensive compilation of reports
on various site characterization field screening methods published by A&WMA.
• Field Screening Methods for Hazardous Wastes and Toxic Chemicals, VIP-47,
Volume 1. Proceedings of and International Specialty Conference, Las Vegas, Nevada,
February 22-24, 1995. Sponsored by the Air & Waste Management Association.
• Field Screening Methods for Hazardous Wastes and Toxic Chemicals, VIP-47,
Volume 2. Proceedings of and International Specialty Conference, Las Vegas, Nevada,
February 22-24, 1995. Sponsored by the Air & Waste Management Association.
A-I7-
Module: Sources of Site Characterization Technology Information
-------
-------
TOOLKIT OF ADDITIONAL NON-EPA
INTERNET SOURCES OF INFORMATION ON INNOVATIVE TECHNOLOGIES
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also examine the oversight and management of the Environmental Technology Development Process (ETDP) and the r
Director of Defense Research and Engineering (DDR&E) and Deputy Under Secretary of Defense for Environmental Se
(DUSD(ES)). The respective roles of the Strategic Environmental Research and Development Program (SERDP), Envi
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are a number of promising environmental technology initiatives and their potential benefits to DOD. The article includes
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ailable resources and tools:
the Phvtoremediation link to access various sources of information on this technoloay.
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engineering, design, construction, consultation, test and evaluation, technology implementation, and ma
technology to enhance the effectiveness and efficiency of our customers; uses existing technology wher
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export their successes throughout the Navy. Two shore installations w
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Samples of available resources and tools:
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appropriate characterization, monitoring, and sensor technology to DOE's Office of Waste Management (EM-30),
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SITE CHARACTERIZATION
EXERCISES
Site Characterization Exercises
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SCENARIO #1
The following is a scenario in which you are tasked to perform a preliminary assessment (PA) to
determine whether the site has contaminated soil or groundwater. You will need to design the
geophysical and analytical approach for this PA. Many factors have been left out of the scenario,
requiring that you make some assumptions based on your own experience and knowledge. You
will identify and explain your assumptions and provide a detailed explanation for all actions
taken or not taken.
You and another member of your company arrive at an abandoned chemical storage facility to
conduct a PA for the U.S. Environmental Protection Agency (EPA). EPA already has conducted
a removal action and all free product and contaminated waste have been removed. Information
provided by the removal team indicates that the facility contains an office building and a main
storage building. Approximately 2,500 drums and other containers of various materials,
including chlorinated and aromatic solvents, polychlorinated biphenyl (PCB) transformer oils,
and chlorinated pesticides were removed from the site. Many of the drums were rusted or
leaking. The removal team located a third small building just inside the fence at the rear of the
property and within 25 yards of a river, which flows into the drinking water supply for the town.
The removal team found several additional drums and containers, many in a deteriorated state —
these drums and containers had been removed. There are liquid stains on the wooden floor and a
strong chemical odor can be detected from the doorway. The removal team did not conduct any
evacuation activities.
Staining is visible on the concrete floor in the warehouse. The back yard of the plant has areas of
soil with no vegetation. Signs of recent earth excavation are present in the back yard, with new
gravel spread over portions of the yard.
Your review of the scene finds the fence surrounding the property has been knocked down at
several locations and several doors to the main building and office building, including one of
eight overhead loading bay doors, have been forced open. The facility is situated in a mixed
residential and commercial neighborhood and there is evidence of trespassing on the property.
Site Characterization Exercises
-------
25 YD. FENCE LINE
c
Scenario 1
J
Site Characterization Exercises
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SCENARIO #2
The following is a scenario in which you are tasked to perform a site inspection (SI) to determine
the extent of contamination. Many factors have been left out of the scenario, requiring that you
make some assumptions based on your own experience and knowledge. You will identify and
explain your assumptions and provide a detailed explanation for all actions taken or not taken.
You and a team of employees from your company have been tasked to complete an SI at a plating
company. The following information was obtained from the preliminary assessment (PA) report,
which was conducted by the state.
The company operated as a metal plating shop on a 1.5-acre lot. Residential areas are located
nearby and site access is unrestricted. The company operated from 1975 to 1988 when the
operator filed for bankruptcy under chapter 11 of the U.S. bankruptcy codes.
In addition to a vacant concrete building, a trailer is located at the site. Miscellaneous solid
waste, consisting of debris, several hundred tires, and household waste is scattered on the surface
at the site. Five known sources of contamination have been identified:
1. An 80 gallon chlorinated solvent spill, which occurred in 1979, in the southeast corner of
the property. Four monitoring wells were installed in 1980.
2. Materials formerly located in tanks and other containers at the site, which have spilled
onto the floor and into the floor drains (which are now sealed). The floor drains are
connected to a dry well and leach field.
3. Cyanide, volatile organic compounds, and evaluated concentrations of metals have been
found in soils on site.
4. Other plating wastes disposed of on the property, the exact nature and amount of which
are unknown.
5. A 1,000-gallon underground heating oil tank used to supply auxiliary heat.
In 1980, groundwater in the four on-site monitoring wells was found to be contaminated with
trichloroethylene; tetrachloroethylene; 1,1,1-trichloroethane, 1,2-dichloroethylene, chromium and
cadmium at levels above the Federal Drinking Water Levels. No municipal supply wells are
located within four miles of the site. The nearest residence and private well is located 250 feet
south.
The site is underlain by at least 30 feet of poorly sorted coarse to fine sands with varying
amounts of gravel and silt. Soils in the area have been extensively disturbed by urbanization.
The bedrock in the area is composed of Precambrian quartzite. The water table was encountered
at a depth of 10 feet. The groundwater Hows in a southwest direction and may discharge to the
Khol River.
Site Characterization Exercises
-------
Topography at the site is relatively flat. The potential surface water runoff pathway is from an
on-site storm drain that discharges into a 10-acre wetland 900 feet northwest of the site. The
wetland is adjacent to the river which flows in a southerly direction to the west of the site. Ten
miles downstream of the site is the Khol River, which is designated as a State Scenic Waterway.
The river is classified as a Class C water body (suitable for fish and wildlife habitat, recreational
boating, and industrial processes and cooling). There are no drinking water intakes located
downstream of the site.
Site Characterization Exercises
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Residence
Underground
Oil Tank
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( 1979 \
V_Spill )
Tires
#2
Monitoring We Us
( Scenano 2
Wetlands
Site Characterization Exercises
-------
SCENARIO #3
The following is a scenario in which you are tasked to perform a preliminary assessment (PA) to
determine whether the site is contaminated and to identify any contaminants of concern. You
need to design the geophysical and analytical approach for this PA. Many factors have been left
out of the scenario, requiring that you make some assumptions based on your own experience
and knowledge. You will identify and explain your assumptions and provide a detailed
explanation for all actions taken or not taken.
A saddle tannery operated at the site from 1891 to 1973 on a 16-acre tract of land along the banks
of a river. It currently is used for an industrial salvage operation. The site is divided
approximately in half by railroad tracks. North of the tracks, there is a building, several piles of
split batteries, and a number of concrete and wood vats, some empty, others containing liquids.
South of the tracks is the former lagoon area. The site is easily accessible to the public. There
are no fences or other barriers around its perimeter. Five workers are employed on the site in the
industrial salvage operation.
The industrial salvage operation may have caused soil contamination on the north side of the
property in limited areas. Battery splitting for lead reclamation is restricted to several areas
throughout the facility. The second potential contamination source is the large pieces of
salvaging equipment which arc leaking petroleum-based products.
A large concrete vat. filled with a liquid of unknown origin, was found in one corner of the
facility. The liquid is thought to be a naphtha-based tannin that contains naphthalene, xylene,
anthracene, and toluene The vat is hooked to the underground piping system and the
connections are showing signs of aging. The structural integrity of the vat is questionable. The
liquid has been removed and is being stored on-site in a double walled, stainless steel tank.
During the tannery's operation, all manufacturing and processing operations occurred on the
north side of the property, and the lagooning operations occurred to the south. Common
compounds used in the tanning process arc naphthalene, phenol, xylenes.
The surface water runoff from the site flows directly into a drainage ditch, which flows
approximately 330 yards before it empties into the river. The lagoon area runoff flows directly
into the river. These runoff pathways arc well defined and show signs of stressed vegetation.
In 1990, the State Water Control Board (SWCB) sampled the discharge from the lagoon area
after a complaint was received reporting that the leachate was entering the river. While at the
site, SWCB also sampled standing water on the lagoons. Results showed elevated levels of
arsenic and chromium.
Site Characterization Exercises
-------
WOODEN VATS
ACCESS ROAD
RECLAMATION
CENTER
FORMER
TANNERY
BATTERIES
,/
CONCRETE
VATS
niniiiii irmnrnr
FORMER LAGOONS
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X
RIVER
Scenario 3 J
Site Characterization Exercises
-------
SCENARIO # 4
The following is a scenario in which you are tasked to perform a preliminary assessment (PA) to
determine whether the site is contaminated and to identify any contaminants of concern. You
need to design the geophysical and analytical approach for this PA. Many factors have been left
out of the scenario, requiring that you make some assumptions based on your experience and
knowledge. You will identify and explain your assumptions and provide a detailed explanation
for all your actions.
A 25-acre site encompasses the location of a former chemical repackaging plant and associated
warehouses. The surrounding land use is primarily industrial and the closest residences are
located one mile from the site. From 1945 to 1980, the site was the location of a lead and copper
smelter. From 1974 to 1988, the facility primarily repackaged TCE and 1,1,1-TCA for
distribution. During a seven year period, the plant discharged liquids into an adjacent marsh
which drains into a nearby creek. The creek, located north of the site, is a potential wetland and
is home to the nearly extinct Striped Hooting Frog. Rail cars of TCE and 1,1,1 -TCA would be
off-loaded from the rail spur. The TCE and 1,1,1-TCA would then be packaged into one and
three gallon cans for wholesale distribution. Chemicals such as benzene, xylene, and toluene
also are stored at the site. Past reports indicate that pails, cans, and drums may have been buried
between the rail spur and creek.
Storm water runoff from the site generally flows toward a drainage ditch which discharges into
the creek. Groundwater is anticipated to be 10 feet below ground surface. The alluvial aquifer in
the area is used by residences located one to two miles away.
Site Characterization Exercises
-------
RIVER
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