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: 	

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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

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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

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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

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                                                                     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

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                                                                     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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                                                                                         i

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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

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       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

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            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

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       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

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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

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            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
Module:  Overview of Field-Based Site Characterization

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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
Module: Overview of Field-Based Site Characterization

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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
                       Module: Overview of Field-Based Site Characterization

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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 •
                       Module: Overview of Field-Based Site Characterization

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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-
                             Module: Overview of Field-Based Site Characterization

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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-
Module: Overview of Field-Based Site Characterization

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Components of Field-Based Site Characterization
              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'
                             Module:  Overview of Field-Based Site Characterization

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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
                                      A-I
                          Module: Overview of Field-Based Site Characterization

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Additional Information
               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
Module:  Overview of Field-Based Site Characterization

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                             Additional Information
     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
                  A-3
            Module: Overview of Field-Based Site Characterization

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Additional Information
         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.
                         A-4
Module: Overview of Field-Based Site Characterization

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                                   Additional Information
      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
              Module: Overview of Field-Based Site Characterization

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Additional Information
         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
Module: Overview of Field-Based Site Characterization

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                                  Additional Information
      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;
                      A-7
              Module: Overview of Field-Based Site Characterization

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Additional Information
         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
Module: Overview of Field-Based Site Characterization

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                                   Additional Information
      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.
                      A-9
               Module: Overview of Field-Based Site Characterization

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Additional Information
        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.
Module: Overview of Field-Based Site Characterization

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                               Additional Information
  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.
                  A-ll-
           Module: Overview of Field-Based Site Characterization

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Additional Information
         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.
Module: Overview of Field-Based Site Characterization

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                                 Additional Information
    Field-Based Site Characterization Philosophy
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
                    A-13-
             Module: Overview of Field-Based Site Characterization

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Additional Information
         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.
Module: Overview of Field-Based Site Characterization

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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-
                             Module:  Overview of Field-Based Site Characterization

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Additional Information
               Field-Based Site Characterization Philosophy
                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.
Module:  Overview of Field-Based Site Characterization

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                                           Additional Information
        Field-Based Site Characterization Philosophy
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
                           A-I7-
                   Module: Overview of Field-Based S/te Characterization

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Additional Information
          Field-Based Site Characterization Philosophy
  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.
Module: Overview of field-Based Site Characterization

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                                             Additional Information
         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
                            A-I9-
                   Module:  Overview of Field-Based Site Characterization

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Additional Information
           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.
Module:  Overview of Field-Based Site Characterization

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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.
                                          A-2I-
                              Module:  Overview of Field-Based Site Characterization

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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.
Module:  Overview of Field-Based Site Characterization

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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

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             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
\

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                                                                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

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                        Platforms for In Situ Technologies
Sampling Platforms and
Direct-Push Technologies
EPA
                                     SP-1
                 SP-1
      Module: Sampling Platforms and Direct Push Technologies

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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

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                                             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

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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

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                                              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

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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

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                                             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

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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

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                                               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

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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

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                                               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

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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

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                                             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

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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

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                                                       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

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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

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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

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-------
               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

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                          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

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                             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

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                                                        Additional Information
                            Table of Contents





Borehole Geophysical Methods	A-2



Surface Geophysical Methods	A-14
                                     A-l
        Module: Geophysical Characterization Techniques and Data Interpretation

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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

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                                                                 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

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Additional Information
                       Borehole Geophysical Methods
Electrical and Magnetic - Interpretation
                                          B
Saturation logging
Lithology logging
 — magnetic
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          Pofowiy *
                                                             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

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                                                              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
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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

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                                                      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

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                                     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

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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

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                                                  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

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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

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                                                 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

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Hand-Held Survey Instruments
                                                             HH-11
                                  •HH-12-
Module: Organic Chemical Characterization Techniques and Data Interpretation

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                                                   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

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                                           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

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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

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                                                           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

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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

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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

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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

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                                                             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

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                                                          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

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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

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                                                           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

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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

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                                          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

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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

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Fluorescence Analyzers
                                                               FA-4
                                   FA -4
Module: Organic Chemical Characterization Techniques and Data Interpretation

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                                                   Fluorescence Analyzers
                                                             FA-5
                                  FA-5
Module: Organic Chemical Characterization Techniques and Data Interpretation

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Fluorescence Analyzers
                                                               FA-ti
                                   FA -6
Module: Organic Chemical Characterization Techniques and Data Interpretation

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                                                        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

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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

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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

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                                                        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

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                                                      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

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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

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                                                               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

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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

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                                                           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

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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

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                                                           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

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                                                  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

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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

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                                                                      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

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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

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                                                            Immunoassay
            EPA
                                                             OI-8
                                  OI-9
Module: Organic Chemical Characterization Techniques and Data Interpretation

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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
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                -  -  -  - -  -  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
                             OOOOOWOJ
                             IftflftftflftA
                         CJi-
                                            5536
                                                       €A5-I 11.169
                                                    —  GAS 2 13.860
  Data File Name   t
  Operator         :
  Instrument       :
  Sample Name      t
  Run Time Bar Code:
  Acquired on      :
  Report created ont
  last Recallb on  :
  Multiplier       :
Cs\HPCHEM\1\DATA\008R0701.O
Bryce Smith
5890 GC
UnleadCae H20 L3
18 OCt 95
21 OCt 95
21 OCt 95
1
03:38 AM
10107 AM
10:03 AM
Page Number
Vial Number
Injection Number
Sequence Line
Instrument Method
Analysis Method
Sample Amount
TSTD Amount
1
8
1
7
VOC1.MTH
GAS.NTH
0
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

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                                                           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

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-------
                                               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

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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

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                                                                  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
Transducer
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

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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

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                                                                 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

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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
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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
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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
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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
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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
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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
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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
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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
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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.
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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-
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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-
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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.
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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-
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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.
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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-
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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.
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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-
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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.
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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'
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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.
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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-
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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.
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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

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                                                             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

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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

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                                                             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

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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

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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

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                         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

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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

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                                     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

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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

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 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,

Literature Cited
  (1) Plumb, R H.. Jr.; Pitchford, A. M. Presented at the Na-
     tional Water Well Association/American Petroleum In-
     stituts Conference on Petroleum Hydrocarbons sad Organic
     Chemicala in Ground Water, Houston, TX. Nov 1986; pp
     13-16.
  (2) Zarrahi, K.; Cross-Smiecinaki. A.  J.; Starks, T. Second
     International Symposium, Field Screening Methods for
     Hazardous Waste and Toxic Chemicals, 14, Las Vegas. NV,
     Feb 1991; pp 236-262.
  (3) Chiou, C T.; Shoup, T. D. Environ. Set. TtehnoL IMS, 19,
     1196.
  (4) Chiou, C. T. Theoretical considerations of the partition
     uptake  of nonionk organic compounds by soil organic
     matter.  In Rtactioniand Movement of Organic Chemical*
     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

           Environ. Sd. Techno*..  Vol. 29. No. 10, 1992  1*17

-------
                                      £nv*nn. Set TechnoL 199t, 30, 1938-1943
      Commerce,  National  Technical Infonnation Service:
      Washington. DC, 1986; VoL IB.
   (6) Spinier. T. M.; Clifford, W. S.; Fitch, I* G. National Water
      Well Association Meeting, Nov. Denver, CO, 1985; pp
      236-246.
   (7) Kianf, P. H.; Grob, R.L.J. Environ. Sei. Health IMC. 21,
      71.
   (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;
      pp 223-248.
   (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
      Organic Chemical*; Van Nostrand Roinhnld-  New York.
      1983.
        (16) McGovern, E. W. Ind. Eng. Chem. IMS, 35, 1230.
        (17) Haneefa, L.; Leo, A. Subttituent Constant* far Correlation
            Analyiit in Chemistry and Biology. Elsevier Amsterdam,
            1979.
        (18) McDuffie, B. Chemotphere 1981,10, 73.
        (19) Mine. J.; Mookerjee, P. K. J. Org. Chem. 1975, 40, 292.
        (20) Rabtrt»,P.V^Dund^u,P.G.Environ.Sei.TeehnoLl96A,
            17,484.
        (21) Pavlostathis. S. G.; Jagkl. K. Environ. Set. Teehnol. 1991,
            25.274.
        (22) Spittler, T. M., personal communication, U.S. Environ-
            mental Protection Agency, Environmental Services Divi-
            sion-Region 1, Lexington, MA, 1989.
        (23) Dixon. W. J. Biometnc* 1953, March, 74.
        (24) Karickhoff, S. W.; Brown, D. S.; Scott, T. A. Water Re*.
            1979, 73, 241.
        (25) Chiou, C. T.; Porter, P. E.;  Schmeddtng, D. W. Environ.
            Sei. Teehnol. 1983,17. 227.
        (26) Boyd, S. A.; Sun. S. Environ. Sei. Teehnol. 1990,24,142.
        (27) Hewitt. A. D.; Miyares. P. H.; Leggett. D. C.; Jenkins, T.
            F. CR92-6; U.S. Cold Regions Research and Engineering
            Laboratory. Hanover, NH.  1992.
        (28) Smith, J. A.; Chiou, C. T.; Hammer,  J. A.; Kile, D. E,
            Environ. Sei. Teehnol. 1990,24, 676.
        (29) Sewhney, B. L.; Gent, M. P. N. Clay* Clay Miner. 1990,
            38.14.

      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  
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         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
              Revision 0
            January 1995

-------
       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
  Revision 0
January 1995

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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.
                                   5021 - 4
  Revision 0
January 1995

-------
       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.                              .   '     •
                                   5021 -5                         Revision 0
                                                                  January  1995

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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.
                                   5021 - 6
  Revision 0
January 1995

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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
                                                                   January 1995

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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
                                                                  January 1995

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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
  Revision 0
January 1995

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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
                                                                 January 1995

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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
                                                          Revision 0
                                                        January 1995

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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
  Revision  0
January 1995

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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

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                                              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

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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

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                                                               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

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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

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                                                             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

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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

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                                                             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

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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

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                                                              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

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                                                                       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

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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

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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

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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

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                                      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

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                                                      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

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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

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                                                       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

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                       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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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
O O O O
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          o o n n
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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

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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

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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-3
                      S-3
    Module: Sources of Site Characterization Technology Information

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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

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                                                                       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

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                                                                        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

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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

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                                                                        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

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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

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                                                                         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

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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

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                                                                               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

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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

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                                                                              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

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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.
                               Fcchnoloyy Usco
                               DISCLAIMER
                               Satact Guided Svareb (bulletl) Of Advanced Soared  below
                                Find tecnnclQaies for treatment of a particular contaminated medium.
                               • Flnct tfrcnnoioQi»5 for c
                                                    or rn3n
-------
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

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                                                                                     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 |

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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

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                                                                         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
                                       S-28
Module: Sources of Site Characterization Technology Information

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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
                                   5-29
            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-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.
                                      S-31
                 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
                                        S-32
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
                                       S-33
                 Module: Sources of Site Characterization Technology Information

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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.
                                  S-37
           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.
                                        S-38
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

-------
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

-------
                                                  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

-------
                                                                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

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                                                           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

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                                                   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

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                                                               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

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                                                              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

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                                                       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

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                                                          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

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                                                          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

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                                                             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

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                                                             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

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TOOLKIT OF ADDITIONAL NON-EPA
INTERNET SOURCES OF INFORMATION ON INNOVATIVE TECHNOLOGIES
AS OF APRIL 1998

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environmental solutions through the development of technologies and their subsequent transfer to the user community).
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
Security Technology Certification Program (ESTCP), and supporting efforts by the military components are reviewed. Al
are a number of promising environmental technology initiatives and their potential benefits to DOD. The article includes
Wide Web site and Internet addresses.

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he U.S. Army Corps of Engineers Innovative Technology Program was created to inform, encourag
ipment of effectively demonstrated innovative technology for environmental investigation and reme
ailable resources and tools:
the Phvtoremediation link to access various sources of information on this technoloay.
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Description: NFESC is the Navy's center for specialized facilities engineering and technology. NFESC
engineering, design, construction, consultation, test and evaluation, technology implementation, and ma
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Characterization, Monitoring, and Sensor Technology Crosscutting Program (CMST-CP)
http://cmst.ameslab.gov/cmst/
Description: The purpose of the Characterization, Monitoring, and Sensor Technology Crosscutting Program (Ch
appropriate characterization, monitoring, and sensor technology to DOE's Office of Waste Management (EM-30),
Restoration (EM-40), and Office of Facility Transition and Management (EM-60). The technology development m
appropriate to EM-30/40/60 needs. Furthermore, the required technologies must be delivered and implemented wl
to ensure that available DOE and other national resources are focused on the most pressing needs, management
development is concentrated on the following focus areas : subsurface contaminants; high-level waste tank remec
characterization, treatment, and disposal; and facility transitioning, decommissioning, and final disposition. All the
characterization and monitoring development needs; technology that is developed for one focus area can often be
another. The CMST-CP identifies technology gaps, integrates technology development, and leverages resources 1
development and to provide cost-effective solutions.
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•• Click on the CMST Crosscuttinq loao to find links to the four focus areas. Link to any of those areas to c
and resources about those areas.
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problems at DOE facilities. These innovative technologies are funded through DOE's Office of Technology Deveic
Online contains site maps, technology profiles, and technology diagrams. The technology profile was completed b
each technology. The name of the principal investigator is included in each technology profile to facilitate easy tra
detailed descriptions of the technologies have been peer reviewed by scientists and engineers from a variety of or
in the system is of high quality. ProTech Online is designed for the citizen, regulator, technology user, and researc
about environmental cleanup activities at DOE sites. ProTech Online enhances DOE's technology development a
activities, facilitates public and business comment on the innovative technologies, increases national exposure for
technology transfer activities. DOE is integrating the technologies from Integrated Demonstrations (contained in P
Information on these technologies will be distributed by DOE-OTD in the future.
Samples of available resources and tools:
• Click on the ProTech 3.1 link to download the original Macintosh version of ProTech 3.1 .
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SITE CHARACTERIZATION
       EXERCISES
                     Site Characterization Exercises

-------
                                     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

-------
                                     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

-------
 Residence
                                    Underground

                                     Oil Tank
        r\
        (   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

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                               WOODEN VATS
    ACCESS ROAD
                  RECLAMATION
                    CENTER
                          FORMER
                          TANNERY
             BATTERIES
               ,/
                                            CONCRETE
                                              VATS
    niniiiii	irmnrnr	
                        FORMER LAGOONS
                      "/
                                 i i
                                . J L.
X
                     RIVER
                        Scenario 3 J
Site Characterization Exercises

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                                     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

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                                   RIVER
                       
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