OCR error (C:\Conversion\JobRoot\00000CDK\tiff\20013JO9.tif): Unspecified error
-------
SYMPOSIUM COMMITTEE
Eric N. Koglin
Edward J. Poziomek
Ishwar Aggarwal
Roger Jenkins
Stephen Billets
Environmental Monitoring Systems Laboratory
U.S. Environmental Protection Agency
Las Vegas, Nevada
Old Dominion University
Department of Chemistry and Biochemistry
Norfolk, Virginia
Naval Research Laboratory
Washington, D.C.
Oak Ridge National Laboratory
Analytical Chemistry Division
Oak Ridge, Tennessee
Environmental Monitoring Systems Laboratory
U.S. Environmental Protection Agency
Las Vegas, Nevada
I
-------
Contents PART ONE - PLATFORMS
Wednesday, February 22,1995
Page
1 Immunochemical-Based Methods
3 Cone Penetrometer Deployed Sensors
5 Chemical Sensors
7 Portable Gas Chromatography
Thursday, February 23,1995
Page
10 Air Monitoring Technologies
12 Sampling and Sample Handling
14 Recent Technology Advances
16 Case Studies in Field Screening
18 New Developments in Monitoring and Measurement Methods
20 Expedited Site Investigations and Rapid Turnaround Methods
22 Field Screening Issues
24 Use of Laser-Based Technologies
26 Laboratory Platforms and Vehicles
Friday, February 24,1995
Page
28 Information Processing
30 Radionuclides
32 Methods Comparison
34 Data Management and Visualization
36 X-ray Fluorescence Spectrometry
-------
PART TWO - POSTERS Contents
Wednesday, February 22,1995
Page
40 Air Monitoring Technologies
43 Case Studies and Practical Applications
49 Chemical Sensors
55 Cone Penetrometer Deployed Sensors
59 Data Handling and Systems Integration
60 Emerging Technologies and New Developments
Thursday, February 23,1995
Page
67 Field Mobile GC/MS
69 Field Test Kits
72 Gas Chromatography
74 Immunochemical-Based Methods
81 Ion Mobility Spectrometry
84 Non-Invasive Technologies
85 Quality Assurance
87 Radionuclides
88 Sampling and Sample Handling
90 X-ray Fluorescence Spectrometry
Numbers listed in the Author Index refer to page numbers. Numbers printed above each abstract can be
used to locate the poster in the exhibit hall.
-------
Inununochemical-Based Methods
VALIDATION OF AN IMMUNOASSAY FIELD SCREEN FOR
TRICHLOROETHYLENE (TCE)
Robert T. Hudak, James M. Melby, Dale V. Onisk, James W. Stave, Strategic Diagnostics
Incorporated, 128 Sandy Drive, Newark, Delaware 19713
Trichloroethylene (TCE) is a volatile organic compound that was routinely used as a common solvent
in various industrial applications throughout the world. Because of its prevalent use, frequent releases
of this compound from accidental spills, leaking above or below ground storage tanks and improper
disposal practices have lead to environmental contamination. Due to its potential teratogenic, muta-
genic and carcinogenic properties coupled with a partition coefficient that suggests that it can migrate
quickly through soil, federal regulations have been enacted to limit TCE levels in the environment.
An immunoassay that specifically detects TCE has been developed for use as a cost effective field
screening method to assess the levels of environmental TCE contamination in soil and water.
A major contribution from the costs associated with a hazardous site characterization and clean-up
can be attributed to analytical testing. Gas Chromatography (GC) and Gas Chromatography-Mass
Spectroscopy (GCMS) are costly and time-consuming analytical methods typically used to analyze
environmental pollutants. The emergence of immunoassay to environmental testing offers an accu-
rate and low cost alternative. The.portable TCE enzyme immunoassay is quick, highly specific and
user friendly. The components of this kit include TCE specific antibodies covalently linked to small
latex particles and TCE derivative linked to alkaline phosphatase. To use this product, soil is extract-
ed in solvent, diluted with the supplied buffer, then processed in the kit. Alternately, a water sample
can be analyzed by diluting it in the supplied buffer. Either the diluted water or the diluted soil
extract is added to a reaction vial containing the TCE antibody latex particles and TCE derivative
alkaline phosphatase. The TCE in the sample competes with the TCE derivative alkaline phosphatase
for binding sites on the antibody. The mixture is poured into a filtering device, washed and a color-
less enzyme substrate is added. The presence of the alkaline phosphatase catalyzes the formation of
colored product that is inversely proportional to the concentration of TCE in the sample. To deter-
mine the TCE concentration, the color produced by the sample can be read with a hand held reflec-
tometer or the color can be matched to a color concentration card.
To assess the performance of this method, several field study comparisons of the immunoassay versus
GC were performed. In the field, samples were split into two (2) aliquots: one (1) aliquot was ana-
lyzed on site using the D TECH™ TCE test while the remaining aliquot was sent to a certified lab for
SW-846 method 601/602(m) analysis. The results, turn-around time and costs of each analysis tech-
nique show the immunoassay method correlates with method 601/602(m), produces results within
twenty (20) minutes and yields average analytical cost savings between 30 and 50%.
AN IMMUNOSENSOR SYSTEM FOR ON-SITE FIELD-SCREENING OF ENVI-
RONMENTAL SAMPLES
TL. Fare, M.D. Cabelli, CD.T. Dahlin, SM. Dallas, PH. Thompson, JL. Schwartz, J.C. Silvia, SS.
Wiedman, Ohmicron Corporation, Newtown, PA 18940
Immunoassay technology designed for environmental and toxic organic analytes produces tests that
are rapid, reliable, and portable. Building on Ohmicron's commercial pesticide and toxic organic
immunoassays, the SmartSense™ system, a portable, electrode-based immunoassay, has been devel-
oped for on-site screening. The objective of this paper is to document the system sensitivity and
robustness for field use. The system has been validated in-house and its performance confirmed in
field trials. Results from the validation procedures and field trials for atrazdne, a model analyte for
the system, will be presented.
Taking advantage of the electrode-based measurement, the immunoassay protocol has been designed
to require as few reagents as possible and minimal user interaction. The operator is guided through
the protocol by a portable instrument with an on-screen menu and keypad. Results are reported as
positive (negative) if the sample is greater (less) than a user-defined action level. Robustness is inte-
grated into the immunoassay system by the appropriate choice of pipettes, reagent volumes, protocol,
and instrument design. Total assay time for on-site testing has been kept to less than 15 minutes for
four test results.
Polymer-coated platinum electrodes are used to monitor the signal from the immunochemistry. A
high-precision gravure coating process has been used to achieve uniform characteristics over an elec-
trode lot Control of the polymer coating enables the reproducibility necessary for precise results.
Results are presented for an action level of 3 ppb atrazine. A plot of percent positives vs. concentra-
tion for spiked high-purity water samples shows a transition from less than 10% (false) positive to
90% positive occurs over the range from 1.5 ppb to 3.0 ppb; there is high confidence in 0% positives
lower than 1.0 ppb and 100% positives above 3.5 ppb. On-site field data confirm the laboratory
results and comparison to traditional analytical methods or alternatives will be made, as appropriate.
Results from samples extracted from a variety of environmental matrices and the effects of interfer-
ences and cross reactivities will be discussed in light of validation findings.
1 Wednesday, February 22, 1995
-------
Immunochemical-Based Methods
A FIBER OPTIC FLUOROIMMUNOSENSOR FOR THE DETECTION OF
POLYCHLORINATED BIPHENYLS
'Kim R. Rogers, 'jeanette M. Van Emon, 2Rick Kline,2Jeremy Wright, 3Qinchun Zhao, and 3Mohyee
E. Eldefrawi, 'U.S. EPA, EMSL-LV, P.O. Box 93478, Las Vegas, NV 89193, Department of
Pharmaceutic Sciences, School of Pharmacy, UMAB, Baltimore, MD 21201, Department of
Pharmacology and Experimental Therapeutics, School of Medicine, UMAB, Baltimore, MD 21201
There currently exists a critical and growing need for real-time and in situ methods for detection of
environmental pollutants such as polychlorinated biphenyls (PCBs). Herein reported is a evanescent
wave fluoroimmunosensor for measurement of PCBs. 2,4,5-trichlorophenoxy butyric acid was cross-
linked to fluorescein ethyleneamine (FL-2,4,S-TB) and used as an optical signal generator. Protein A
purified IgG obtained from anti-PCB serum, was immobilized on quartz fibers and used as the biolog-
ical sensing element in a wave guide fluorometer manufactured by ORD Inc. The optical signal was
generated by the binding of the fluorescent probes FL-2.4.5-TB to the antibody (Ab)-coated fiber.
Fluorescent probe concentrations in the nM range resulted in reversible binding. Several Aroclors
inhibited binding of the fluorescent probe (FL-2,4,5-TB) in a concentration-dependent manner.
Aroclor 1248 was detected from the ppb to ppm range with a detection limit of 1 ppb. Detection of
PCBs in ground water and soil extracts will also be discussed.
NOTICE: The information in this abstract was funded, in part, by the U.S. EPA under Cooperative
Agreement CR-820460-02-0 with UMAB. The U.S. EPA, through its Office of Research and
Development (ORD), has prepared this abstract for a proposed presentation. It does not necessarily
reflect the views of the EPA or ORD.
ENVIRONMENTAL MERCURY MEASUREMENT BY IMMUNOASSAY
Craig Schweitzer, Product Development Manager, L. Carlson, Scientist, B. Holmquist, Vice President
of Research and Development, M. Riddell, Managing Director, D. Wylie, Consultant, BioNebraska,
Inc., Lincoln, Nebraska, 68524
Immunochemical-based analytical methods are commonly used in the medical diagnostic field, but
only recently have they been adapted for field-portable environmental applications. BioNebraska has
developed an immunoassay, based upon a novel monoclonal antibody to mercuric ions, for the detec-
tion of mercury in environmental samples. The user-friendly BiMelyze* Mercury Tube Immuno-
assay generates semi-quantitative results rapidly and economically relative to traditional analytical
methods. In this presentation we will demonstrate the use of this method with environmental matri-
ces and discuss ongoing in-house and independent field results.
Sample preparation and analysis can be completed in the field for numerous samples in less than 40
minutes. Mercury is first extracted from the sample by digestion using a separate kit available from
BioNebraska. Typically 5 grams of soil or sediment representative of the area being tested is treated
with a mixture of hydrochloric acid, nitric acid and water (2:1:1) for ten minutes with shaking. The
sample is then buffered, filtered and diluted by means of filter-tipped dropper bottles provided in the
soil extraction kit, and analyzed by the immunoassay. National Institute of Standards and
Technology (NIST)-traceable standards, included in the kit, are extracted at the same time as the
unknown samples. The immunochemical analysis consists of four simple steps using four supplied
reagents. The unknown or standard is first added to a test tube coated with a metal binding protein
that serves to capture the mercuric ions. After a water rinse, mouse anti-mercury antibody is added
that specifically binds to the immobilized mercury. The tubes are then washed with a detergent and
water to remove unbound antibody. The amount of anti-mercury antibody bound is detected by
adding a second antibody, horseradish peroxidase-labeled rabbit antibody, that binds specifically to
the mercury antibody. The tubes are washed as above and substrate added. The oxidation of the sub-
strate, catalyzed by the horseradish peroxidase, produces a green chromophore with an absorbance
proportional to the mercury concentration. Color development is terminated by addition of stop solu-
tion. The absorbance is read at 405 nm using a field-portable differential photometer available from
BioNebraska. A separate assay format using a 96-well-plate provides quantitative analyses of large
numbers of samples in a laboratory setting.
The inherent limit of detection for mercuric ions in aqueous samples is 0.25 ppb and 0.5 ppm for
soils. The method is highly selective for mercury with essentially no interference by other metals or
matrices. Thus, the assay is well-suited for low-cost, real-time, user friendly field screening of mer-
cury in soils, sediment and water producing results that correlate well with traditional analytical
methods.
Wednesday, February 22,1995
-------
Cone Penetrometer Deployed Sensors
FIBER OPTIC INFRARED REFLECTANCE PROBE FOR DETECTION OF
AROMATIC CONSTITUENTS OF FUEL IN SOIL
KJ. Swing, T. Bilodeau, G. Nau, and ID. Agganval, Naval Research Laboratory, Code 56032,
Washington, D C. 20375, T. King, R. Clark, USGS, Branch of Geophysics, P.O. Box 25046 MS 964,
Denver, CO 80225, G. Robitaille, USAEC, Aberdeen Proving Ground, MD 21010
Contamination of soil with petroleum fuels is a significant environmental problem in both the public
and private sector. Over the course of many years, fuel spillage during everyday refueling operations
have caused significant contamination of the subsurface soils with aliphatic and aromatic hydrocar-
bons. Additionally, fire spills due to leaks in storage tanks or transfer Lines have also contributed sig-
nificantly to soil contamination. Fuels such as JP-5 are mixtures of alkanes, saturated ring com-
pounds, oleftns, and aromatic compounds (single and polyaromalic). Of particular interest are the
aromatic constituents of the fuel such as benzenes, naphthalenes, tetralins, etc. Some fuels, such as
JP-S, can be composed of as much as 25 wt% of these aromatic additives. In order to remediate sites
contaminated with fuels cost effectively, monitoring techniques which can identify and quantify the
amount of contaminant in the soil are needed. The goal of the current work is to develop a fiber optic
IR reflectance sensor for use in the cone penctrometer to detect both the hydrocarbon fuel and the
aromatic additives in the soil. By using chalcogimde or fluoride optical fibers, the spectral window
from 3 urn to 6 urn (the sapphire window cutoff) is available for detection and quantilation of fuel
contamination in the soil. Results for aromatics and hydrocarbon fuels in various soil matrices will
be discussed with respect to detection limit, sample preparation, and best spectral range to use for
achieving the lowest detection limit.
Acknowledgment: The authors wish to thank the United States Army Environmental Center for sup-
porting this program.
IN SITU MEASUREMENT OF VOLATILE ORGANIC COMPOUNDS IN
GROUNDWATER BY METHODS COUPLED TO THE CONE PENETROMETER
Paul V. Doskey, Joseph H. Aldstadt, Jacqueline M. Kuo, Molly S. Coslanza, and Mitchell D.
Erickson, Environmental Research Division, Argonne National Laboratory, 9700 S. Cass Avenue,
Argonne, IL 60439
The sampling of subsurface materials via cone penetrometry provides a minimally intrusive, efficient,
and cost-effective method for obtaining samples for the analysis of contaminants in groundwater, soil,
and soil gas. On-site analysis of samples collected by this methodology has been demonstrated to
facilitate the characterization of sites by making real-time, interactive sampling decisions possible.
Devices that isolate the contaminants from groundwater and soil within the cone penetrometer (CPT)
and are directly Linked to analytical instrumentation at the surface would further increase the speed
and accuracy of on-site analysis. The overall goal of our investigation is to develop methods and
technology that will couple a CPT with field-deployable instrumentation, including gas chromatogra-
phy/mass spectrometry, to directly transfer volatile organic compounds (VOCs) and semi-volatile
organic compounds from subsurface material at depth to the analytical instrument in the field to pro-
vide near-real time analysis. Our presentation will focus on methods and technology to isolate VOCs
from groundwater with analysis by multidetector gas chromatography (GC).
The approach involves the development of a methodology that incorporates a sparging vessel to purge
VOCs from a confined volume of groundwater in the CPT, transports the analytes to a preconcentra-
tion device at the surface through a heated transfer line, and provides quantitative analysis by multi-
detector GC. The critical aspect of this approach is the quantitative transfer of VOCs from the
groundwater to the preconcentration device at the surface. Tubings composed of stainless steel, nick-
el, and two types of Teflon* were evaluated as transfer line materials. The materials were tested by
using a dynamic dilution apparatus in which a certified gas standard containing chloroform,
methylchloroform, carbon tetrachloride, tetrachloroethylene, benzene, and toluene is mixed with air
containing various concentrations of water. The concentration of the target analytes generated by the
apparatus is determined via the analysis of samples collected on graphitized carbon black directly
from the dilution manifold. The transfer line is then attached to the manifold, and several discrete
volumes of gas are drawn through the tubing and collected on graphitized carbon black. Clean air is
then drawn through the tubing to determine the extent of sorption. The sensitivity of the transfer of
VOCs through the tubing to (1) the water content of the gas stream and (2) the temperature of the
transfer Line was determined. Sparging vessels of Teflon* and stainless steel were fabricated to fit
within a standard purge-and-trap concentrator. Recoveries of analytes from spiked water samples
were determined and compared to those obtained with a standard glass sparging vessel. Results from
laboratory tests of a prototype of the ground water sampler that fits within a CPT will also be present-
ed. This work was supported by the U.S. Department of Energy under Contract No. W-31-109-Eng-
38 as part of the Characterization, Monitoring, and Sensor Technology Integrated Program of the
Office of Technology Development.
The submitted manuscript has been authored by a contractor of the U.S. Government under contract
No. W-31-109-ENG-38. Accordingly, the U.S. Government retains a nonexclusive, royalty-free
license to publish or reproduce the published form of this contribution, or allow others to do so, for
U.S. Government purposes.
3 Wednesday, February 22, 1995
-------
Cone Penetrometer Deployed Sensors
A CASE STUDY COMPARING THE USE OF LASER INDUCED FLUORES-
CENCE WITH CONE PENETROMETER TESTING TO MORE CONVENTION-
AL SCREENING METHODS
K. Barley, Unisys Corporation, Corporate Environmental Affairs, P.O. Box 203, Paoli, PA 19301,
and Keith Rapp, Unisys Corporation, Corporate Environmental Affairs, 3199 Pilot Knob Road,
Eagan, MN 55121
Site assessments utilizing in-situ techniques to characterize subsurface stratigraphy and contaminant
distribution are becoming more accepted and commonly used. Laser Induced Fluorescence (LIF)
spectroscopy with Cone Penetrometer Testing (CPT) is a new technology that provides data on
stratigraphy and petroleum hydrocarbons (PHCs) in the subsurface environment. This paper presents
a comparison of LIF combined with CPT to more conventional characterization methods at a manu-
facturing site in Nebraska.
Over the last two years, LIF technological advances have lead to LIF equipment with improved dura-
bility, reduced bulk and weight, and integrated systems with CPT equipment. The technology has
recently been piloted in a variety of field and soil conditions. These advances, along with the need
for rapid in-situ information on the horizontal and vertical distribution of PHCs, have resulted in
equipment that is now available for commercial applications.
The LIF equipment consists of a tunable laser located in a CPT truck which is connected by a fiber
optic cable to a small sapphire window located on the cone penetromeler probe. Light generated
from the laser is directed into the side of the borehole and onto the soil and groundwater. The light
produced by the laser is at a wavelength which allows the PHC molecules to absorb photons, causing
PHC materials to fluoresce. The fluorescence is returned through the sapphire window and conveyed
by fiber optic cable to a detection system within the truck. The incoming data is processed and
data depicting fluorescence versus depth is continuously measured and recorded as the CPT push
proceeds.
The Nebraska technology demonstration site was formerly used to manufacture farm equipment.
Various PHCs were stored in underground storage tanks across the site. Two PHC spill areas have
been identified; one primarily consisting of xylenes, and the other a mixture of diesel fuel oil and
kerosene. Free phase and dissolved product exist at both locations. The near surface geology con-
sists of up to 35 feet of unconsolidated silly sand and gravel overlying sandstone. The water table is
found between 5 and 10 feet below the ground surface.
In each spill area, a grid area with about 20 equally spaced probe locations 50 feet apart was estab-
lished. Within a 3-foot radius of each grid point, the following test program was designed: soil gas
samples for on-site PHC analyses; LJF/CPT data to 20 feet; and hollow stem auger drilling with con-
tinuous split spoon sampling, organic vapor screening, and soil sample collection for off-site PHC
analyses every 5 feet to a completion depth of 20 feet.
These data are qualitatively and quantitatively compared. Data collected suggest that each method
provides qualitatively useful site screening information. However, significant variations in time, data
interpretation, and methodology are of interest. This paper presents these findings, and also compares
test lime and cost, along with the advantages and disadvantages of each method. *"
DEVELOPMENT OF AN IN SITU VOLATILE ORGANIC CHEMICAL ANALY-
SIS SYSTEM
Karen F. Myers, James M. Brannon, Ann B. Strong, Stafford S. Cooper, Richard A. Karn, Cynthia B.
Price, Dan Y. Eng, US Army Corps of Engineers Waterways Experiment Station, Vicksburg,
Mississippi 39180-6199 U.S.A.
Conventional subsurface contaminant mapping technology involving borings and laboratory analysis
of soil samples is time consuming and expensive and often results in inadequate descriptions of conta-
minant plumes. Application of advanced chemical techniques to cone penetromeler technology pro-
vides a means for real time detection and mapping of contamination in the subsurface. Development
of an in-situ volatile organic sampler for the cone penetromeler and an analytical system 10 detect ppb
levels of BTEX compounds and TCE has been developed al the USAGE Waterways Expenmem
Station. The sampler is pushed to a desired depth in the subsurface, an interior rod is retracted, and a
measured volume of soil is sampled and purged in place. Volatilized compounds are transferred to
the surface where they are trapped on lenax and desorbed on a field portable gas chromaiograph. The
soil sample is then expelled, and the cone penelromeler pushed to a new depth where the process is
repeated. Experimental results for different soils and contaminants are discussed.
Wednesday, February 22, 1995 4
-------
Chemical Sensors
DEVELOPMENT OF MULTIANALYTE SENSOR ARRAYS FOR CONTINUOUS
MONITORING OF POLLUTANTS
Brian G. Healey, Siaieel Chadha, and David R. Walt, Max Tiskler Laboratory for Organic Chemistry,
Tufts University, Medford, MA 02155, Fred P. Milanovich, James Richards and Steve Brown,
Measurement Sciences Group, Physics Department, Lawrence Livermore National Lab, Livermore,
CA 94550
Industrial development has led to the release of numerous hazardous materials into the environment,
posing a potential threat to surrounding waters. Environmental analysis of sites contaminated by sev-
eral chemicals calls for continuous monitoring of multiple analytes. Monitoring can be achieved by
using imaging bundles (300-400um in diameter), containing several thousand individual optical fibers
for the fabrication of sensors. Multiple sensor sites are created at the distal end of the fiber by immo-
bilizing different analyte specific fluorescent dyes. By coupling these imaging fibers to a charge cou-
pled device (CCD), one has the ability to spatially and spectrally discriminate the multiple sensing
sites simultaneously and hence monitor analyte concentrations.
Prior to immobilization of the dye the distal end of the fiber is functionalized to permit covalenl
attachment of the polymer matrix. Discrete regions of the Tiber bundle are successively illuminated
through the proximal end so as to photo-polymerize the polymer matrix containing the fluorescent
dyes.
Current studies focus on the development of a multi-analyte sensor for monitoring Al+3, pH, hydro-
carbons and uranyl ion. For the monitoring of Al , a variety of indicators are being evaluated for
their applicability to sensor design. Lumogallion immobilized in poly HEMA shows considerable
sensitivity and dynamic range. The fluorescent indicator eosin has been identified as the indicator for
monitoring pH in the range 2.0 - 4.5. The indicator can be immobilized in an analogous fashion to
fluorescein3 (pH 4.5 - 8.0). Hydrocarbon sensors have been fabricated from different photo-polymers
that show response to several hydrocarbons using Nile Red as the indicator.
The current instrumentation used for the measurement of fluorescence intensities is built around an
Olympus microscope, using a Hg-Xe arc lamp for excitation and a CCD camera for spatial detection
of the fluorescent intensities. Computer controlled filter wheels provide the necessary wavelength
selection. However, a field portable instrument capable of radiomelric measurements is being devel-
oped. The development of the multianalyte sensors and Held trials will be presented.
The concept of multianalyte sensors is certainly not limited to the analytes mentioned above. As addi-
tional analyte specific reagents and other tramduction mechanisms are identified, these sensors will
find greater scope of applicability. Due to its miniature design and ease of fabrication such sensors
should be particularly valuable for continuous in-situ monitoring of pollutants.
References
1 . Hydes, D. J., Liss, P. S. Analyst 1976, 101, 922.
2. Saari, L. A., Seitz, W. R. Anal. Chem. 1983, 55, 667.
3. Barnard, S. M., Walt, D. R. Science 1993, 251, 927.
DETERMINATION OF SOLID/VAPOR PHASE INTERACTIONS ON
QUARTZ CRYSTAL MICROBALANCES USING MOLECULAR MODELING
Robert L. Curiale, Harry Reid Center for Environmental Studies - University of Nevada-Las Vegas,
Las Vegas, Nevada 89154-4009, Martha E. Dominguez. Harry Reid Center for Environmental Studies
- University of Nevada-Las Vegas, Nevada 89154-4009, Kathleen A. Robins, Department of
Chemistry, University of Nevada-Las Vegas, Las Vegas, Nevada 89154-4003, Edward J. Poziomek*.
Harry Reid Center for Environmental Studies - University of Nevada-Las Vegas, Las Vegas, Nevada
89154-4009
A major technology barrier in the development of many chemical sensors is the lack of recognition
coatings to achieve selectivity and sensitivity. The major objective of the present work is to investi-
gate the utility of molecular modeling in predicting and interpreting recognition coating/analyte inter-
actions. Quartz Crystal Microbalances (QCMs) coaled with polyethylenimine (PEI) were studied
with carboxylic acid vapors. Linear Solvation Energy Relationships {LSER) derived from gas/liquid
chromatography (GLC) bonded-phase solute-solvent interactions have proven useful in studying the
effects of coating/analyte interactions on QCM devices. These relationships incorporate dispersion,
polarity-polarizabilily, and hydrogen bonding forces to model the interactions: they have been used
successfully to predict coating/analyte binding affinities. In this study a homologous series of four
carboxylic acids vapors (acetic, propanoic, butanoic, pentanoic) were selected to interact with PEI
coatings. LSER values for each acid indicate that each additional methylene constituent increases the
dispersion force interactions between the coating and analyte with a resultant increase in binding
affinity. QCM devices (10 MHz) were dip-coated in a solutions of PEI and methanol and allowed to
dry at room temperature to provide five thin film coatings measuring 0.69 kHz, 0.72 kHz, 1.7 kHz,
4.1 kHz, and 4.4 kHz. The acid vapors were introduced separately over the QCM devices, and the
piezoelectric wave frequency changes due to absorption of the acid analytes on the PEI coating were
recorded. After correcting for vapor pressure and molecular weight, the acids were ranked according
to their interaction (corrected frequency change) with the coating. Linear relationships between coat-
ing thickness and acid interaction were observed for each acid (^=0.990-0.996). Since the LSER val-
ues of polarity, polarizability, and hydrogen bonding are essentially the same for each acid, it is
believed that the slope of each line is related to the amount of dispersion interaction occurring which,
as mentioned above, relates directly to binding affinity.
Comparison of experimental results with LSER values show similar agreement with regard to ana-
lyte/coating binding affinities. Semi-empirical (AMI) calculated dipole moments coincide trendwise
with LSER values for polarity. Slopes of the plots relating frequency change versus coating thick-
ness, indicative of dispersive interactions, coincide trendwise with semi-empirically calculated Van
der Waal force values. Data analysis suggests for dispersive interactions, that a linear relationship
(^=.960) exists between experimental slope values and calculated molecular modeling values. These
results are promising and suggest that computer modeling may prove useful in predicting and inter-
preting sensor coating/analyte interactions.
Notice: The authors acknowledge support from the Advanced Research Projects Agency
(Contract-DAAD05-92-C-0286)
* Present address: Department of Chemistry and Biochemistry, Old Dominion University, Norfolk,
VA 23529-0216
5 Wednesday, February 22, 1995
-------
Chemical Sensors
CHEMILUMINESCENT CHEMICAL SENSORS FOR INORGANIC AND
ORGANIC VAPORS
G.E. Collins and SL. Rose-Pehrsson, Naval Research Laboratory, Chemistry Division, Code 6113,
Washington DC. 20375-5342
Chemilummescence techniques have been successfully applied to the detection of numerous chemical
analytes, including metals, polycyclic aromatic hydrocarbons, and various oxidizing and reducing
agents. The fundamental attractions of chemiluminescence are its high sensitivity, wide dynamic
range, and simplicity of instrumentation. Typically, chemiluminescenl reagents are incorporated into
flow injection analysis schemes which enable the detection of photons arising from chemical reac-
tions with oxidants or feductants. Because of the continuous generation of waste that arises from
these systems, and because of the increasing demand for simple, remote chemical sensors, we have
begun investigating the possibilities inherent with incorporating chemiluminescent reagents within
hydrogels and polymeric thin films for the detection of inorganic and organic toxic chemicals. By
careful consideration of the chemiluminescence reagent, metal catalyst, polymeric support film and
pH of these thin films, some selectivity can be tailored into the chemical sensors. Inslrumentally, the
detection cell consists simply of a small cavity supporting the polymeric thin film behind a glass win-
dow. A photomultiplier tube is positioned directly in front of the window, while a small, hand-held
vacuum pump is used to sample the air directly across the surface of the film. Current efforts are
being made to extend this technology to fiber optics for remote sensing.
2,4,6-Trichlorophenyloxalate (TCPO), in the presence of a strong fluorescer such as perylene, is a
highly sensitive and selective chemiluminescenl monitor for H2O2 levels in solution. Unlike other
chemiluminescenl reagent schemes, the nature of the mechanism lends itself to this high degree of
selectivity. We have found that the incorporation of TCPO and perylene within a polymeric thin film,
such as poly(ethylcneirnine), also permits the detection of low ppm levels of N(X in air. The use of
3-aminophlhalhydrazide (luminol), while being much less selective, is significantly more sensitive to
certain toxic chemicals. The incorporation of luminol and Fe(IQ) within a polyvinylalcohol hydrogel
gives a film with superior sensitivity toward NO2 (detection limit of 0.46 ppb and a response time on
the order of seconds). The hydrogel serves as an effective means for eliminating humidity problems
associated with other polymeric films. By substantially increasing the concentration of KOH con-
tained within the film, the sensor becomes responsive to trace levels of Or A detection limit of < 2
ppm oxygen in nitrogen (signal/noise = 3:1) was obtained with response tunes of less than a second.
Other toxic gases which we have formulated chemiluminescent thin films for include SO2 and
hydrazine, NjH4. Recently, we have investigated the use of a heated Pi filament as a pre-oxidative
step prior to passage of the gas stream across the film surface. This has permitted the sensitive detec-
tion of CC14, CHC^ and Cttfl^ in the low ppm regime. The advantage is that the filament can be
easily turned on or off, depending upon the sensing needs of the user. Discussions will center about a
complete analytical characterization of the capabilities and shortfalls of these chemiluminescent
chemical sensors.
FIBER OPTIC SPECTROELECTROCHEMICAL SENSING OF
TRICHLOROETHYLENE
J. Bella, M. Carrabba, K. Forney, and J. Haas, EIC Laboratories Inc., Ill Downey St. Norwood,
MA 02062
The necessity of techniques for in situ/real-time sensing and monitoring of chlorinated hydrocarbon
solvents is becoming increasingly apparent because of the ubiquitous presence of these contaminants
in groundwater. Traditional laboratory sampling methods have several disadvantages such as long
turnaround time, expense, manpower, and doubts about sample integrity, particularly for volatile
compounds. In addition, traditional techniques are also not capable of providing early warning of the
presence of these contaminants. The combination of optical fiber technology, originally developed in
the telecommunication industry, with spectroscopy, however, has led to the continuing development
of new sensing techniques which address the drawbacks of traditional methods.
Our approach to monitoring and sensing of chlorinated hydrocarbon contaminants, particularly
trichloroethylene (TCH), incorporates spectroscopy and electrochemistry with fiber-optic sensing
techniques. Spectroelectrochemical fiber optic sensing or SEFOS is, in principle, a controllable
chemical sensing technique which can be adapted to fiber-optic sampling applications such as
groundwater monitoring in wells or site analysis/assessment via cone penetrometers. With SEFOS,
an electrochemical method is used to reduce TCE into a reactive intermediate. The TCE reactive
intermediate then reacts with the relevant functional groups of a "trapping" reagent resulting in
changes in the spectroscopic behavior of the reagent. The spectral changes can be used to sense TCE
at levels approaching regulatory limits.
This paper will describe recent developments of the SEFOS technique for the detection of TCE and
will discuss the advantages of SEFOS over present methods of monitoring chlorinated hydrocarbons.
The optimum conditions needed for SEFOS as well as relevant analytical data will be presented.
•*(*«
Wednesday, February 22, 1995
-------
Portable Gas Chromatography
UNATTENDED SCREENING FOR VINYL CHLORIDE AND CARBON TETRA-
CHLORIDE IN AIR FROM PART PER TRILLION TO UPPER PART PER MIL-
LION LEVEL USING A COMBINATION OF ARGON IONIZATION AND ELEC-
TRON CAPTURE DETECTORS
Dr. A. Luunberg, President, Neil J. Lander, Product Specialist, Sentex Systems Inc., 553 Broad
Avenue, Ridgefield, NJ 07657
The need to screen the atmosphere for background levels of Vinyl Chloride and Carbon Tetrachloride
led to the development of a self-contained portable gas chromatograph for just such a purpose.
Furthermore, the instrument was designed to operate in an automated, unattended fashion for a con-
siderable duration.
The Argon lonization Detector (AID) will detect compounds whose ionization potential is 11.7 eV or
less. The Electron Capture Detector (ECD) is primarily used to detect extremely low levels of com-
pounds which have a high affinity for electrons, such as halogenated compounds. Thus Vinyl
Chloride (lonization Potential = 10.00 eV) and Carbon Tetrachloride (lonization Potential = 11.28
eV) can be detected with the AID. The combination of these detectors provides for a full range of
detection from the sub pan per trillion level to the high part per million level. Sub PPB to low PPB
levels of Vinyl Chloride (0.1 to 1.0 PPB, for example) were detected using the AID in combination
with a trap built specifically for this purpose. Sub PPT to low PPT levels of Carbon Tetrachloride
were detected using the ECD in combination with the trap. Low PPT to high PPT levels were detect-
ed using the ECD in combination with an automated sampling loop PPB levels and up were detected
using the AID in combination with the trap. Finally, PPM levels and up were detected using the AID
in combination with a sampling loop.
The gas chromatograph was periodically recalibrated with certified standards of Vinyl Chloride and
Carbon Telrachlonde. The entire operation of the gas chromatograph could be monitored via modem.
The portability and flexibility of such a system promises extremely low level detectabtlity of such
compounds on site and on an unattended, automated basis.
A NEW PORTABLE MICRO GAS CHROMATOGRAPH FOR ENVIRONMEN-
TAL ANALYSIS
E.B. Overton, K.R. Carney, H.P. Dharmasena, A.M. Mainga, U. Ehrmann, Institute for
Environmental Studies, 42 Atkinson Hall, Louisiana State University, Baton Rouge, Louisiana
A truly portable gas chromatograph for field-screening of both volatile and semivolatile organic envi-
ronmental compounds has been developed and tested at LSU - Institute for Environmental Studies.
Based on a novel capillary column heating technique and a heated injection port, the new Micro-GC
is capable of analyzing samples with retention indices of up to at least 2000 in a period of about three
minutes. In addition to achieving isothermal capillary column temperature control, the new Micro-
GC is also capable of performing ultra fast temperature-programming rates (up to 10° C/s) using less
than 50 watts of maximum electrical power. Thus, it is possible to operate this instrument in the field
using portable battery power. Its use of narrow bore capillary columns (100 urn i.d.) implies that it
uses minimum amounts of carrier gas. Thus, the combination of isothermal and temperature-pro-
gramming control in our portable Micro-GC at less than SO watts maximum power implies the ability
to perform field separations of organic compounds with widely varying boiling temperatures.
7 Wednesday, February 22,1995
-------
Portable Gas Chromaiography
DESIGN CONSIDERATIONS FOR A NOVEL MINIATURIZED TANDEM GC
METHOD FOR FIELD SCREENING APPLICATIONS
Sue Anne Sheya, William H. McClennen, Henk L.C. Meiuelaar and Neil S. Arnold*. Center for Micro
Analysis and Reaction Chemistry, University of Utah. Salt Lake City, UT84112, *FemloScan
Corporation, Sail Lake City, UT 84105
A rapid, automated gas and vapor sample injection technique for capillary columns reported by
Arnold el al. [1] enables operation of two GC columns in tandem (GC/GC) in such a way that a two-
dimensional gas chromatogram can be obtained. This requires rapid repetitive injections of the eluent
from the first column onto the second column. Typically the first column is operating in an isother-
mal or temperature programmed mode with a total run time of 100-1000 seconds and average peak
widths in the 10-25 second range whereas the second column operates at the same temperature as the
first but with repetitive injections at 2-5 second intervals and average peak widths in the 50-250 mil-
lisecond range (also depending on the type of detector used).
The power of this type of two-dimensional GC analysis has been convincingly demonstrated by Liu
and Phillips [2] using a rapid thermal desorplion device in combination with cryotrapping of eluenl
from the first column. A disadvantage of their method, however, is the high power usage level asso-
ciated with the cooling and desorption cycles. Also, the associated contraction and expansion of the
carrier gas flow may complicate the chromatographic conditions. Finally, only a limited range of
compounds can be analyzed due to the specific vapor pressure requirements for successful operation
of trap-and-desorb schemes. Highly volatile species run the risk of being incompletely trapped
whereas low volatile, and particularly polar, species may become irreversibly adsorbed.
None of these problems is inherent in the approach chosen by us. However, compared to the Phillips
method, our technique is potentially less sensitive due to the lack of a "cryocentration" step. Between
the sampling intervals of the second column the effluent of the first column is vented. On the other
hand, proper design of the GC separation conditions, permits the analyte concentrations within the
column effluent to remain relatively close to those in the original sample. As long as a concentration
sensitive detector is used with sufficiently low dead volume and signal response time to match the
operating requirements of the second column, the loss of effluent due to the low duty cycle of the lat-
ter does not have a major effect on overall sensitivity. Design considerations as well as preliminary
performance data will be presented. The choice of the detector, a particularly critical area in ultrahigh
speed GC, will be discussed in detail.
1. Arnold, N.S., McClennen, W.H., Meuzelaar. H.L.C., Anal. Chem., 63 (1991), 299.
2. Liu. Z., Phillips, J.B., J. Chromatogr. Sci.. 29 (1991) 227.
DETERMINATION OF BTX AND BUTADIENE IN AIR BY HAND-HELD GAS
CHROMATOGRAPHY
P. A. David andR. E. Pauls, Amoco Corporation, P O. Box 3011, MS F-5, NapervUle, 1L 60566
The need for rapid, cost-effective and actionable field analytical data has fueled the development of
portable instrumentation. In the lasl few years, we have successfully utilized "transportable or lug-
gable" field gas chromatographs for remediation and worker health and safety applications. Recently,
a hand-held portable gas chromatograph has become commercially-available. Our general approach
for new field analytical technology is to validate instrument performance under laboratory conditions
using simulated field samples prior to field testing the instrument under "real-world" conditions.
This presentation will discuss laboratory validation and field implementation of the Pholovac
Snapshot hand-held gas chromatograph for determination of benzene, toluene and xylenes (BTX) and
butadiene in air. Interaction between the vendor, research and development and field operators was
essential in successful implementation of this technology. Reliable portable GC data has been
obtained from field applications such as soil vapor, fugative emissions and general area monitoring.
In the initial field tests, laboratory GC analyses were utilized to validate field GC results.
The quality of the field data is highly dependent on proper training of field operators. The knowledge
of instrument operation is important but generation of reliable field data requires the implementation
of field QC protocols. Minimum field QC protocol consists of calibration with a certified gas blend,
calibration checks and blank analyses. This strategy has been used by instrument operators with a
variety of skill levels to obtain reliable field GC data.
Wednesday, February 22, 1995 8
-------
Portable Gas Chromatography
HANDHELD GC INSTRUMENTATION FOR CHEMICAL WEAPONS CONVEN-
TION TREATY VERIFICATION INSPECTIONS
PM. Holland. R.V. Miatacich, JF. Everson. W. Foreman. M. Leone, and WJ. Naumann.
Detection Technologies Group, SWL, Inc., P.O. Bon 6770, Santa Barbara, CA 93160
Advanced field screening technology for toxic chemicals will play a crucial role in treaty verification
inspections for the new Chemical Weapons Convention (CWC). Because CWC treaty inspections are
projected to take place on short notice and in many different locales worldwide, highly portable and
self-contained chemical instrumentation packages can be especially valuable. Furthermore, the
schedule of chemicals covered by the CWC encompasses a wide range of volatilities and chemical
properties making the requirements for chemical instrumentation especially challenging. In response
to these needs, we have developed an advanced handheld instrument based on an innovative, ultra-
low thermal mass miniaturized gas chromatograph (GC) for rapid detection of treaty prohibited chem-
ical weapons materials and precursor chemicals. This GC consists of an integrated capillary column,
heater and temperature sensor which allows computer controlled temperature ramp rates as high as
10 °C/sec. Besides the GC, the instrument incorporates a miniature trap preconcentrator, miniature
dual flame photometric detectors (FPD) for phosphorus and sulfur compounds, and advanced signal
processing. The instrument is self contained, can detect a wide range of both volatile and semi-
volatile compounds, and is designed for handheld operation during treaty inspections.
9 Wednesday, February 22, 1995
-------
Air Monitoring Technologies
OPEN-PATH ATMOSPHERIC MONITORING WITH A LOW-RESOLUTION FT-
IR SPECTROMETER
Peter K. Griffiths, Robert L. Richardson and Changjiang Zhu, Department of Chemistry, University of
Idaho, Moscow, ID 83844-2343
Contemporary approaches to open-path atmospheric monitoring by Fourier transform infrared (FT-
[R) spectrometry involve measurements that are usually made at relatively high resolution with
expensive instrumentation. These instruments can be heavy and difficult to move. Their performance
is also limited by excessive absorption of water vapor across much of the mid-infrared spectrum. In
this paper, we will demonstrate the feasibility of constructing a less expensive system that is designed
to operate at significantly lower resolution than contemporary instrumentation, thereby reducing the
cost and weight. Measurement at low resolution also enables measurements of some components
absorbing at wavelengths that are usually masked by absorption due to water vapor to be observed at
short palhlengths.
In the system to be described, radiation from a conventional infrared source is passed through a small
cube-comer interferometer to a nonstandard retrorefleclor. The return beam is collected at unusually
high efficiency and focused onto the detector for measurement of the imcrferogram. The efficiency
of this optical arrangement is sufficiently high that liquid nitrogen cooled mercury cadmium telluride
(MCT) detectors are no longer needed and either an ambient temperature deuterated tnglycine sulfale
(DTGS) pyroelectric bolometer or a Peltier-cooled Zn-doped MCT detector can be used.
The data processing requirements for interferograms measured using this system include the use of
optimized apodizalion functions to maintain Beer's law linearity for major atmospheric components
(especially water vapor). Multivariate algorithms for multicomponent quantitative analysis have been
compared, with partial least squares regression proving to have the best performance for vapor-phase
species.
After a description of the instrument that has been constructed in our laboratory, the relative perfor-
mances of the DTGS and Zn-doped MCT detectors will be compared. In addition, the performance
of the prototype version of this instrument and a conventional open-path FI'-IR spectrometer will be
described.
FTIR OPEN-PATH ABSORPTION MEASUREMENTS OF HAZARDOUS COM-
POUNDS ON AN INDUSTRIAL SITE AND A WASTE SITE IN GERMANY
K. Weber, T, Lamp, J. Weidemann, G. van Haren, Fachhochschule Diisseldorf, FB04, Labor fur
Umwettmeptechnik. Josef-Gockeln-Slr. 9, 40474 Diisseldorf, Germany
Kl'IR open-path absorption measurements found different applications as a screening method for haz-
ardous compounds. Important advantages are:
• Several compounds can be measured.
• On-line measurements are possible in principle.
• Remote measurements can often be made where the access is otherwise not possible.
• No poisoning of the sensor occurs.
This method has been applied by our laboratory to measurements at an industrial sue and a waste site.
Recent results will be presented. Some quality assurance issues will be addressed.
10 Thursday. February 23, 1995
-------
Air Monitoring Technologies
AIR MONITORING WITH A COHERENT INFRARED DIFFERENTIAL
ABSORPTION LIDAR
PJ. Richter, I. Piczeli, SzJidrdcz, Technical University of Budapest, Department of Atomic Physics,
Hungary and K.C. Herndon, Florida Slate University, CBTR, USA
A coherent infrared differential absorption lidar was developed thai is capable of remote detection of
several atmospheric molecular pollutants. Typical detectable components are ammonia, phosgene
acetone, toluene, hydrogen cyanide, benzene etc.
Enhanced operation of the lidar system was demonstrated by using an "autodyne" detection scheme
with appropriate selection of the laser sources. This allowed keeping mass (250 kg) and power con-
sumption (1,5 kW) of the system low while sensitivities in the column content range of 10"'-10"3
(mg/m3)km for ranges up to 3 km could be achieved. Results of field tests and system performance
will be given.
DETECTION OF EMISSION SOURCES USING PASSIVE-REMOTE FOURIER
TRANSFORM INFRARED SPECTROSCOPY
Jack C. Demirgian, Susan M. Mocha, and Shauna M. Darby, Argonne National Laboratory, Argonne,
IL 60439, and John Ditillo, Edgewood Research and Development Center, Aberdeen Proving
Ground, MD
The detection of environmentally hazardous chemicals is possible with open-path and fixed-point
methods, such as open-path Fourier transform infrared (FITR) spectroscopy and canister collection
followed by gas chromatography/mass spectroscopy (GC/MS). While these methods detect chemical
plumes, they cannot trace the plumes to their source. Tracing a plume to its source is important to
determine responsibility for the release of fugitive emissions and to repair leaks. Source detection is
also important for determining environmental compliance. Light, mobile instrumentation with real-
time data analysis is essential for tracking a plume to its source.
Passive-remote FITR systems are light and transportable. Data analysis can be performed in near real
time. The basic system consists of an interferometer, focusing optics, and a detector. Data are trans-
mitted directly to a laptop computer. All the systems discussed can be hand carried to facilitate
detection of the plume source. The instrumentation uses ambient energy as its infrared source.
This instrumentation was used to detect a low pathlenglh release of parts per million-meter (ppm-m)
concentration. A 1 ppm-m release corresponds to a 1 ppm chemical release that has a width of one
meter. This release would be identical to a 10 ppm release with a width of 0.1 m. These releases
were performed using a specially designed vaporizer with an orifice of 10 cm on a side. The FTTR
spectrometers detected plumes of this size from distances of roughly 50 m. After a plume was delect-
ed, hand-held Fl'lK spectrometers were used to track the plume to its source. Plumes can be delected
from open windows and other low leak-rate sources. Larger passive-remote units mounted on a tri-
pod or a moving vehicle can also be used to initially detect a plume originating from a far-away
source. Then, smaller units can be employed to deteci ihe actual source.
Thursday, February 23, 1995 11
-------
Sampling and Sample Handling
TECHNIQUES FOR PREPARATION OF FIELD STANDARDS FOR VGA
ANALYSIS OF WATER, SOILS AND AIR
TM. Spinier, USEPA Regional Lab, 60 Weslview St., Lexington, MA 02173 and S. Stepenuch, Keene
Slate College, 229 Main St.. Keene. NH 03431
With the widespread use of field methods to assess contamination of the environment arises a need to
prepare accurate standards for field analysis that are suited to the study at hand. The use of typical
laboratory standards (lOOOug/cc MeOH solutions) is very unsatisfactory because of the complex mix-
tures typically used in these standards. Where a site investigation has shown the need to measure
accurately one or two chlorinated solvents or a few aromatic solvents (e.g. BTHX) it is counterpro-
ductive to send into the field a complex mixture containing ten to thirty solvents. This paper will dis-
cuss three methods for preparing standards for VOA analysis of water, soil and air samples in the
field.
The first method is simply to prepare methanol concentrates from neat standards using a very simple
technique that requires no analytical balance or other complicated laboratory equipment. Accurate
standards can be prepared in minutes using a graduated cylinder or pipe! and a ten-microliter syringe.
Standards can be prepared singly for later mixing or as simple mixtures in methanol which match the
expected complexity of the field contamination.
The second method is to prepare liquid-liquid equilibrium solutions of individual solvents of interest
which are then held for future use. These standards are constantly at solubility equilibrium and it is
only necessary to know the solubility of each solvent at room temperature. Dilutions can be made
rapidly from the saturated aqueous phase of these solutions for subsequent headspace analysis of
water or soil-water mixtures. It is also possible to prepare volatile-in-air standards from these saturat-
ed aqueous solutions with a high degree of accuracy in just minutes in the field.
A third procedure is to simply make up a dilute solution of any solvent in water, taking care to keep
the mixture under the solubility limit. While these standards require special care in preparation, and
have a much shorter useful life than the first two methods, they are readily prepared and can often
serve a special need (e.g. an unusual solvent not often encountered in the field, and for which no
readily available standards exist).
Preparation techniques will be discussed and some of the pitfalls which could prevent accurate results
will be examined.
SOIL MOISTURE VARIABILITY AS AN INDICATOR OF SOIL VOC VARI-
ABILITY
MM. Minntch andJ.H. Zimmerman, Lockheed Environmental Systems and Technologies Co., Las
Vegas, NV 89119, BA. Schumacher, USEPA Environmental Monitoring Systems Laboratory, Las
Vegas, NV 89193-3478
The main objective of this study was to determine the effect of the soil sample size on the precision
of volatile organic compound (VOC) measurements. EPA's high-level screening procedure (included
in SW-846 Method 5030/5035) was used to measure VOCs in 2, 20, and 100-g soil samples. The
high-level procedure extracts soil VOCs into methanol and analyzes an aliquot of methanol by purge
and-lrap/gas chromatography. To increase the sensitivity of the procedure, the soil:methanol ratio
was modified from 1:10 to 1:1 (g:mL) and the extraction time was lengthened from 2 min to several
days. Extraction into a liquid permits subsampling variable amounts from a more homogeneous
media. Use of an optimum/larger sample size to minimize short-range variability, can limit the num-
ber of samples needed to characterize a site and provide better, more representative data.
Short-range variability in soil VOC concentrations are effected by (but not limited to) soil texture and
organic carbon content. Likewise, short-range variability in the soil moisture content is effected by
soil texture and organic carbon content. Replicates of soil VOC concentrations and soil moisture con-
tents were measured as functions of sample size. The study was performed at VOC-contaminated
field sites in New York and Nevada to provide data in widely varying soils and climates. Correl-
ations of the variability in VOC concentrations and soil moisture with sample size were generated.
Variability in soil moisture content with sample size can be used to estimate an appropriate sample
size for measuring soil VOCs.
The U.S. Environmental Protection Agency (EPA), through its Office of Research and Development
(ORD), prepared this abstract for an oral presentation. It does not necessarily reflect the views of the
EPA or ORD.
1? Tmrrsdav February 71 1995
-------
Sampling and Sample Handling
NEW MODULAR TWO STAGE PRECONCENTRATOR FOR VOCs IN AIR
AM. Mainga, E£. Overton, ATJf. Carney, M.T. Stewart, Hf. Dharmasena, Institute for
Environmental Studies, 42 Atkinson Hall, Louisiana Stale University, Baton Rouge, Louisiana
Attempts to lower detection limits of VOCs for field deployable instruments has led to the construc-
tion of a new two stage solid sorbent concentrator. Previous success of sample preconcentration with
an enhanced version of a microchip gas chromalograph has been built upon by the incorporation of a
concentrating and focusing trap. With the use of computer actuated valves, heaters, and flow con-
trollers this modular device is capable of interfacing with several presently available microchip GCs
as well as benchtop GCs. The combination of specific adsorbents allow a large volume of ambient
air to be concentrated on a large sorbent trap and subsequently focused into a narrow desorption band
from a micro trap. This process enables present micro gas chromalographs to analyze a wide range of
VOCs at sub ppb levels using less than 50 watts (peak) of electrical power. The presentation will
evaluate desorption curves as well as concentration factors for a variety of compounds under varying
sorption conditions and demonstrate the applicability of this concentrating device for both field and
laboratory analysis.
DIRECT TRACE ANALYSIS OF VOLATILE ORGANIC COMPOUNDS IN AIR
USING A FIELD-DEPLOYABLE ION TRAP MASS SPECTROMETER WITH
FILTERED NOISE FIELDS
Sydney M. Gordon, Patrick J. Callahan, and Donald V. Kenny, Atmospheric Science and Applied
Technology, Battelle Memorial Institute, Columbus, OH 43201,andJD. Pleil and WA. McClenny,
U.S. Environmental Protection Agency, AREAL, Research Triangle Park, NC 27711
There is increasing interest in the development of field portable mass spectrometers to monitor toxic
air pollutants in real-time. A direct air sampling ion trap mass spectrometer has been evaluated in the
laboratory under controlled conditions. An environmental test chamber was used as the source of the
target compound mixtures at known concentrations. Measurements were made of nonpolar and polar
volatile organic compounds (VOCs) at trace levels, using the ion trap technology with two direct air
sampling interfaces (semipermeable membrane; glow discharge ionization source).
The system is based on Teledyne's research-grade 3DQ Discovery™ three-dimensional quadrupole
ion trap. Application of filtered noise field (FNF) technology minimizes the effects due to space
charging normally associated with ion traps. It also provides a unique means of simultaneously iso-
lating individual target compounds in complex mixtures. It is, therefore, capable of true selective ion
monitoring and, when operated in the MS/MS mode, permits unambiguous characterization of indi-
vidual compounds with high sensitivity and specificity. The instrument is small and lightweight, and
can be easily deployed in the field. We have evaluated the operation of the combination system with
a semipermeable tubular membrane and an atmospheric sampling glow discharge ionization source
for the measurement of selected VOCs in air.
Preliminary results obtained with the combination direct air sampling/FNF/ion trap system have
helped to delineate the advantages and disadvantages of the two direct air sampling interfaces.
Experiments were performed to evaluate the specificity, sensitivity, response time, and effects of rela-
uve humidity on the real-time detection of nonpolar and polar VOCs. This presentation will describe
measures that are being investigated to improve the specificity and sensitivity of the devices.
The information in this document has been funded wholly or in part by the U.S. Environmental
Protection Agency under Cooperative Agreement CR 822062-01-0 to Battelle Memorial Institute. It
has been subjected to Agency review and approved for publication. Mention of trade names or com-
mercial products does not constitute endorsement or recommendation for use.
Thursday, February 23, 1995 13
-------
Recent Technology Advances
MINIATURE ION MOBILITY SPECTROMETER DETECTOR
A. Peter Snyder, Charles S. Harden, US. Army Edgewood Research, Development and Engineering
Center, Aberdeen Proving Ground, MD 21010-0068, Robert B. Turner, John H. Adams, Sieve J
Taylor and John Fitzgerald, Graseby Dynamics, Watford, Herts, UJf., Robert Bradshaw, Bulstrode
Technology, Hemel Hempslead, Herts, U.K.
Ion mobility spectrometry (IMS) has been a laboratory phenomenon for the last 25 years, while a
hand portable unit with proven field capabilities, the Chemical Agent Monitor (CAM), has been in the
military inventory for approximately a decade. The inherent simplicity of IMS and its operation at
atmospheric pressure and ambient temperature conditions made it an attractive technology to transi-
tion from the laboratory to the field. Analyte ionization requires no power since this is effected by a
mckel-63 source. In NATO venues, the units are used for real-time (seconds) detection of very small
amounts of nerve and blister agents. Nerve agents are phosphoryl-containing compounds, and a per-
fect marriage was formed between that class of analytes and IMS. This is because IMS is extremely
sensitive and relatively specific to phosphoryl functional groups.
Recently, IMS technology has been reduced in size to that approximating a small VCR-sized remote
control hand unit A number of revolutionary changes have occurred with respect to conventional
IMS resulting in significantly lower power usage. The unit operates on demand and automatically
powers down after a sample interrogation. The system has the capability of taking a background IMS
scan of itself prior to sample introduction in both polarity modes, and then a scan of a sample in both
polarity modes. Positive and negative ion difference spectra are the resultant information, and this
entire sequence occurs in 2-3 seconds. The unit automatically turns off or can be programmed for
repetitive sampling at defined intervals. The conventional pump motors which introduce, circulate
and remove the sample airstream have been replaced with a molecular sieve passive system that uses
no power and ensures a dry IMS system. The sample introduction system motors have been replaced
with a small audio speaker that is usually found in commercial wire-rimmed radio headsets. The dis-
placement of the speaker cone, typically a few 100 microlilers, dictates the volume of sample ingest-
ed. The ionization source operates on either a nickel-63 radiation ring or a nonradioactive carbon
fiber corona discharge source. With respect to the highly regulated issue of radiation, the nonradioac-
tive ion source is the more attractive version.
Single and mixtures of illicit drug synthesis and purification solvents and drug precursor molecules
were tested with the device for detection and characterization purposes and which comprise a test set
of compounds that are of interest to drug and law enforcement agencies. Compounds include
methanol, cyclohexanone, diethylether, phenyl-2-propanone, acetic acid, acetone, isopropanol and
methylethylkelone. Mixtures containing equal and different concentrations of the drug solvent and
precursor compounds were tested for their detection of presence by headspace vapor analysis with
respect to single compound ion mobility spectra.
It appears that the palm-size IMS unit has the potential of being a practical analytical tool for indoor
use and it is projected to have the potential for outdoor use.
REMOTE ELECTRODE FOR MONITORING METAL CONTAMINANTS
J Wang, New Mexico Slate, Las Cruces, NM 88003 and K. Olsen. Ballelle PNL, Richland, WA 99352
The development, characterization and testing of a remote electrode, for downhole monitoring of
trace metals will be described. Based on the highly sensitive electrochemical stripping analysis, the
novel sensor (connected to a long communication cable) addresses various challenges of remote mon-
itoring. Convenient quantitation of ppb concentrations of copper, mercury or lead, will be reported.
The new indwelling probe should be very attractive for the immediate detection of sudden metal cont-
aminations or for providing feedback during cleanup activities, and may thus revolutionize the way
by which heavy meals are monitored.
Financial support from the WERC program and Bauelle PNL is acknowledged.
14 Thursday, February 23,1995
-------
Recent Technology Advances
DEVELOPMENT AND EVALUATION OF AN OPTIMIZED MULTIPLEX
ARRAY DETECTOR RAMAN SYSTEM FOR FIELD ENVIRONMENTAL
ANALYSIS
M. Banner Denton and Dan A. Gilmore, Department of Chemistry, The University of Arizona,
Tucson, AZ 85721
An optimized, compact Raman system for field environmental analysis is being developed. This sys-
tem is based on diode laser excitation fiber optic probe technology, a triple grating imaging spectrom-
eter, and a start-of-the-art scientific CCD camera and software. Emphasis has centered on optimizing
the Raman apparatus, determining the best fiber optic probe technology that will allow remote sens-
ing (i.e. down a well or simultaneous multipoint monitoring), establishing quality control procedures,
and developing camera control and data analysis software. Sensitivity for a variety of compounds
will be presented demonstrating major reductions in detection limits. New technologies which may
improve detection limit considerably farther will be discussed. Problems associated with fiber optic
probe technology including the need to eliminate the Raman signal from the silica probe fibers, which
can become an interference when the fiber length is more than a few meters, will be considered.
Software for camera control and data analysis using LabVIEW for Windows (National Instruments), a
graphical Windows-based programming language, will be presented which demonstrates the flexibili-
ty and ease of use needed for a field instrument that would be difficult to achieve with current com-
mercial camera controller software in a single program.
A HAND-PORTABLE INSTRUMENT SYSTEM FOR THE REAL-TIME ANALY-
SIS OF CHLORINATED ORGANIC COMPOUND CONTAMINATION
W J. Buttner and J.R. Sutler, Transducer Research, Inc., 999 Chicago Avenue, Naperville. 1L 60565,
and C. Nakaishi, Morgantown Energy Technology Center, 3610 Collins Ferry Road, Morganlown,
WV26507
Chlorinated solvents (e.g., carbon tetrachloride, trichloroethylene) were used extensively as degreas-
ing agents at government and industrial facilities and represent a major environmental contamination
at many of these sites. Because of the toxicity of chlorinated organic compounds, reliable methods
for the rapid and sensitive detection are necessary. In 1991, Transducer Research, Inc. (TRI) devel-
oped a new chemical sensor which responds selectively to vapors of chlorinated solvents. No sensor
response is observed with common hydrocarbon organic compounds such as BTXs (benzene, toluene,
xylcne) or POLs (petroleum, oil, lubricants), and in fact, no non-halogen containing chemical has
been identified which induces a measurable response. While the sensor does exhibit a small response
to brominated compounds, and an even smaller response to iodine and fluorine compounds, it
responds quickly, reversibly, and with a high sensitivity to vapors of chlorine compounds. Using the
organic chemist's shorthand notation "R-Q" for a chlorine-containing organic molecule, the sensor
has been called it the "RCL sensor".
To exploit the analytical capabilities of the RCL sensor, an advanced chlorinated organic vapor moni-
tor was designed and built. The RCL MONITOR was designed to analyze individual samples or
monitor an area with automated repetitive analyses. Samples between 0 and 500 ppm can be deter-
mined in 90 s with a lower detection limit of 0.2 ppm using the hand-portable instrument. In addition
to the development of the RCL MONITOR, advanced sampler systems have been developed to: (1)
extend the dynamic range of the instrument through autodilution of the vapor and (2) allow chemical
analyses to be performed for condensed phase contamination with a unique closed-loop recirculation
sampler. When interfaced to these specialized samplers, the RCL analyzer is capable of measuring
chlorinated solvent contamination in the vapor phase up to 5000 ppm and in water and other con-
densed media from 10 to over 10,000 ppb^.
The performance of RCL MONITOR was demonstrated in field tests at several DOE facilities.
Several important applications have been identified in which measurement and monitoring of chlori-
nated hydrocarbons is essential. These include:
• Environmental Compliance
Health and Safety
• Clean-up Process Monitor
• Environmental Modeling
• Site Characterization
Case studies for each identified application are currently underway. Initial results have demonstrated
that the performance of the RCL MONITOR compares favorably to CLP methods now in use.
Work performed under DOE Contract: DE-AC21-92MC29118
Thursday, February 23, 1995 15
-------
Case Studies in Field Screening
"FIELD SCREENING" SAMPLING METHODS USED IN PLACE OF "STAN-
DARD" SAMPLING METHODS TO PROVIDE DEFINITIVE DATA FOR THE
INVESTIGATION OF A NATIONAL PRIORITY LIST SITE
Jtffery R. Carter, Hazardous Waste Remedial Actions Program, Martin Marietta Energy Systems,
Inc , Oak Ridge, Tennessee, Dr. Milton Beck, Dover Air Force Base, Dover, Delaware, Robert Lyon.
Dames & Moore, Inc., Belhesda, Maryland
The objective of this presentation is to report the effective use of "field screening" sample collection
methods in place of "standard" sample collection methods to provide definitive data at a National
Priority List (NPL) Site.
The "standard" method of collecting samples in unconsolidated material uses an auger drilling rig;
soil samples are collected using split-spoon samplers; and groundwaier samples are collected from
monitoring wells. This methodology is time consuming, costly, and creates added wastes (e.g., drill
cuttings and large volumes of purge waters). Geoprobe™ sampling devices can be used to collect
soil and groundwaier samples significantly faster, and with a minimum of generated wastes.
Although considered a "field screening" sample collection method, the Geoprobe™ sampling system
can be used to collect samples with comparable quality to "standard" sampling methods and can pro-
vide defensible data to support site status decisions.
The U.S. Environmental Protection Agency (EPA) placed Dover Air Force Base (AFB), Dover,
Delaware, on the NPL because of the presence of contaminated soil and groundwaier. Nine major
areas of associated constituents and 59 individual sites were identified. A basewide Remedial
Investigation (RI) is under way to define the extent of contamination. To accelerate the investigation,
a field screening program was initiated before the RI. This program utilized soil gas and geophysical
surveys, Geoprobe™ sampling, *nd oil-site and fixed-base laboratory sample analyses. The program
provided a clearer picture of conditions at the Base and allowed a more efficient use of resources dur-
ing the RI.
Normally "screening" samples are submitted to a field laboratory, which provides analytical results at
EPA Level Q data quality. Level II data are, by EPA definition, not acceptable for use in Risk
Assessments and, therefore, are not acceptable in supporting final decisions on sites. However, dur-
ing the field screening program at Dover AFB, an innovation on the normal procedure was imple-
mented. Fifty-nine of the 203 groundwater samples and all 16 soil samples collected were submitted
to an EPA Contract Laboratory Program (CLP) facility for analyses. The CLP laboratory provided
analytical results at EPA Level IV data quality. Level IV data are usable for Human Health Risk
Assessments and can support final decisions on sites (e.g., no further action). The decision to use this
approach was reached by the Dover project team, which included staff from EPA Region ID, to expe-
dite the decision-making process and move forward on addressing the environmental challenges at the
Base.
Using "screening" sampling methods instead of "standard" methods provided other benefits to the
project, including:
• saving more than $200,000 in sample collection alone,
• eliminating drilling waste,
• saving a minimum of 2SO project/work-hours, and
• reducing the duration of field activities by approximately 20 days.
In summary, "screening" sampling methods are acceptable for collecting samples that can be used to
support final decisions on the status of sites and also provide cost and time savings over "standard"
sampling methods.
A COMBINED TECHNOLOGY APPROACH TO MULTILEVEL GROUND-
WATER SCREENING
A. Tingle, Analysas Inc.*, Oak Ridge, Tennessee, L. Baker, Automated Sciences Group**, Oak Ridge,
Tennessee, D. Long, Hazardous Waste Remedial Action Program, Martin Marietta Energy Systems,
Inc., Oak Ridge, Tennessee, and M. Miracle, Advanced Sciences Inc.***, Oak Ridge, Tennessee
Several commercially available technologies were combined to rapidly characterize a historical fuel
spill in a sand and gravel outwash aquifer. Historical data indicate that possibly 1 to 6 million gallons
of aviation gasoline had been discharged at the source area from 1955 to 1970. The Remedial
Investigation (RI) at this site indicates fuel-related contamination in the capillary fringe beneath the
source area. Rapid horizontal groundwater velocities (-1.7 ft/day) and the 39-year time span between
the first discharge and the present could possibly place any resulting groundwater contamination far
from the source. Downgradienl groundwater wells installed during the RI show no significant conta-
mination, which suggests that the groundwater wells installed during the RI were not screened in the
plume, the quantities of fuel released at the site were much lower than estimated, or degradation of
the fuels is taking place.
To determine the presence and extent or absence of fuel-related contamination and the possibility of
past or ongoing biodegradation associated with this site, several technologies were integrated into the
field program. Drive point technology (i.e., Geoprobe) was selected as the intrusive sampling method
because it (1) provides rapid sampling rates, (2) reduces investigation-derived waste (it minimizes
purge volumes because it uses l-in.-diam casings and generates no drill cuttings), and (3) minimizes
formation disturbance because it uses small-diameter drive rods and rotary motion is lacking. This
technology advanced a 1 -in.-OD steel drive rod into the aquifer to depths ranging from 72 to 120 ft
below ground surface. After advancement to the desired depth, a screen was extended from the I-in.
rods, and an inertia! pump was used to sample groundwaier. Groundwaier sampling began al the bot-
tom of the boring and continued al discrete 10-ft intervals to the water table. Eh, pH, specific con-
ductivity, turbidity, temperature, and dissolved oxygen were measured in a closed cell apparatus and
recorded at each interval A mobile on-site field laboratory analyzed samples from each interval for
fuel-related compounds, total petroleum hydrocarbons, and dissolved carbon dioxide and bicarbonate.
Accurate locations for each sample point were determined using global positioning system technolo-
gy. Although existing groundwaier maps were used in the initial placement of the Geoprobe borings,
locations were adjusted in the field based on the data generated in the field laboratory. After the
screening phase, permanent 1-in. stainless steel monitoring wells with prepacked stainless steel
screens were installed using drive point technology.
Advantages of combining drive point technology, a mobile laboratory, a global positioning system,
and other technologies include (1) minimization of investigation-derived waste, (2) minimization of
formation disturbance, (3) rapid generation of multilevel groundwaier screening data to facilitate deci-
sion making while in the field (27 days in the field at 30 sampling locations analyzing 190 samples
plus quality control samples and installing iwo permanent monitoring wells), and (4) generation of a
complete data set by one field team in one mobilization effort. This combined approach to site inves-
tigations resulted in a significant savings of lime and money for the client
The submitted manuscript has been authorized by a contractor of the U.S. Government under contract
DE-AC05-84OR21400 with the U.S. Department of Energy. Accordingly, the U.S. Government
retains a paid-up, nonexclusive, irrevocable, worldwide license to publish or reproduce the published
form of this contribution, prepare derivative works, distribute copies to the public, and perform pub-
licly and display publicly, or allow others to do so, for U.S. Government purposes.
16 Thursday, February 23,1995
*Work performed by Analysas Corp. under general order contract 30B-9778C with Martin Marietta
Energy Systems, Inc.
"Work performed by Automated Sciences Group, Inc., under general order contract 30B-9778C with
Martin Marietta Energy Systems, Inc.
***Work performed under general order contract 77B-99I67C with Advanced Sciences, Inc. with
Martin Marietta Energy Systems, Inc.
The submitted manuscript has been authored by a contractor of the U.S. Government under contract
DE-AC05-84OR21400 with the U.S. Department of Energy. Accordingly, the U.S. Govemmenl
retains a paid-up, nonexclusive, irrevocable, worldwide license to publish or reproduce the published
form of this contribution, prepare derivative works, distribute copies to the public and perform pub-
licly and display publicly, or allow others to do so, for the U.S. Government.
-------
Case Studies in Field Screening
FIELD ANALYTICAL SUPPORT DURING SUPERFUND SITE REMEDIATION
William L. Goldschmidt, David R. Catherman, and David E. Gallis, Ph.D., ERM, Inc.
The ERM-FAST* service provided field analytical support for two projects involving soils remedia-
tion at superfund sites in northeastern Pennsylvania and southern New Jersey. These case studies
offer illustrations of the effectiveness of field analysis for vastly differing site contaminants and
exemplify the power of "real time" field analytical support in reducing time and expense during a
project's remedial phase.
The first CERCLA site involved an active manufacturing facility in northeastern Pennsylvania where
remediation of the site soils centered around 12 volatile organic compounds (VOCs) which included
aromatic and chlorinated alkene hydrocarbons. The EPA required "clean soil" levels to be less than
100 parts per billion (ppb) of "total teachable" volatiles. It was determined that the entire list of com-
pounds could be resolved and detected using a portable Photo vac® 10S70 gas chromatograph/pho-
toionization detector TT/PID). QA/QC protocols and SOPs were developed at an analytical data
quality level consi - "ji CLP protocols. Customized data processing software was developed to
meet the field data ocliverables requirements and to facilitate the validation process. The on-site
facility results verses CLP laboratory results for TCE and PCE in 100 split sample analyses were con-
sistent with respect to "clean" soils and "dirty" soils.
The second CERCLA remediation site was a former lagoon area in the southern New Jersey contain-
ing sludge bands and sods with elevated levels of chromium, copper, and nickel. The selected
remedy utilized "Soil Washing" which required quick analytical feedback to determine optimal plant
operating efficiency and to determine the extent of excavation required in each area. The real-time
analytical results required by the plant had to be representative of CLP results in order to ensure com-
parability with EPA required analyses. X-Ray Fluorescence (XRF) Spectroscopy was selected as the
appropriate analytical instrumentation and methodology. A data comparability study was performed
to ascertain the dynamic accuracy range of the instrument compared to CLP laboratory results. A
correlation between the field XRF and CLP laboratory results for 20 authentic split samples was sta-
tistically very good for all three analytes even though the samples contained contamination well
below the action levels.
As illustrated by these case studies, field analytical data has proven to be a powerful tool toward
proper, complete, and cost-effective execution of remedial efforts. When "real-time" data is available
for many interrelated aspects of a project, otherwise tedious remedial efforts can become relatively
inexpensive and quickly paced. Both of the cases presented resulted in substantial savings on analyti-
cal cost as well as the savings realized through efficient and effective process and schedule manage-
ment. However, these benefits can only be realized through proper analytical strategies developed
around well-defined project and data quality objectives.
INTEGRATED TECHNOLOGIES TO EVALUATE THE IMPACT OF EMIS-
SIONS AT A PETROLEUM RECOVERY SUPERFUND SITE
Gregory M. Zarus, Scott A. Wagaman, MiguelJ. Trespalacious, Roy F. Weston, IncJREAC,
2890 Woodbridge Ave. Edison. NJ 08837-3679. Rodney D. Turpin, U.S. EPAJERT, Tina Forester,
ATSDR. John Meyer. U.S. EPAISES Region VI, Mark Hanson. US. EPA/AEB, Region VI
The integration of several technologies proved successful in assessing the air pathway impact of site
emissions on a neighboring community. This presentation will illustrate the results of integrating sev-
eral technologies to assess the impact of volatile organic compounds (VOCs) from a petroleum recov-
ery superfund site on the ambient air quality of an adjacent neighborhood. The technologies integrat-
ed include:
• TAGA analysis
• GC FID analysis
microchip GC analysis
• GC AID analysis
GC/MS analysis
• Flux chamber sampling
• Summa canister sampling
air dispersion modeling
The Trace Atmospheric Gas Analyzer (TAGA) mobile mass spectrometer/mass spectrometer
(MS/MS) was used to monitor the air concentrations while traveling the roads of the neighboring
community and to analyze samples collected by other methods (i.e.. tedlar bag grab samples). Seven
flame ionization detector (FID) gas chromalographs (GCs) were placed on site and transmitted read-
ings to the command post where they were logged at 15-minute intervals. A field portable capillary
column microchip GC was used for detecting and quantifying compounds in soil gas samples. A
GC/MS analyzer and a lap-top PC-controlled field portable GC argon ionization detector (AID) were
used to confirm the TAGA results conducted on grab samples. Flux chambers were used to collect
air samples on top of buried lagoons in order to determine the emission rate of each lagoon indepen-
dently. Summa canisters were used to collect ambient air, flux, and soil gas samples. These samples
were sent to labs for analysis to confirm all analyses. Air dispersion modeling allowed for the back-
calculation of emission rates from the site operations and the determination of short- and long-term
impacts from the site's air emissions.
The integration of these technologies facilitated:
• the estimation of emissions from buried waste lagoons
• the estimation of emissions from site operations
• the identification of additional or incidental sources
• the confirmation of modeling procedures
• the estimation of background concentrations
the estimation of impact from sue emissions
Thursday, February 23, 1995 17
-------
New Developments in Monitoring and Measurement Methods
ENVIRONMENTAL AND ATMOSPHERIC MEASUREMENTS AND DATA COL-
LECTION FROM A HOT AIR BALLOON
Steven M. Watson, 545TGITF. 5948 Southgate Ave, Hill AFB. UT 84056, Robert T. Kroutil, US Army,
ERDEC, APG, MD 21010, Trevor Spencer, Colin Flynn, Robert Eason*. Timothy Holloway, Defence
Research Agency, St Andrews Road. Malvern. Wares WR8 3PS, UK 44-684-895644, 'Now with
Procurement Executive, Ministry of Defence, London, UK, Gary Lumsdon, Institute of Aviation
Medicine (Royal Air Force), Farnborough, Hants, UK, Pierre Sokolski, Stan Thomas, High Energy
Astrophysics Institute, Department of Physics, University of Utah, Salt Lake City, UT, Ken C. llerr,
JeffL. Hall, GJ. Schere, and ML. Polak, Environmental Monitoring and Technology Dept., Space
and Environment Technology Center, The Aerospace Corporation, Los Angeles, CA
Tethered and free-flying manned hot air balloons have been demonstrated as platforms for various
atmospheric measurements and remote sensing tasks. We have been successfully accomplishing
these tasks since the winter of 1993. These platforms are inexpensive to operate, do not cause atmos-
pheric disturbances due to high speed flight, are extremely stable and free of vibrations inherent in
aircraft structures. The equipment operated and tested on the balloons includes, but not limited to,
various spectrometers, high resolution CCD cameras, mid- and far-infrared cameras, a radiometer, a
FLJR system, video recording equipment, ozone and nitrogen oxide analyzers, collection canisters,
aerodynamic particle sizer with associated computer equipment, lethersonde, and a 2.9kW portable
generator carried beneath the balloon providing power to the equipment Vertical profiling of pollu-
tants have been accomplished in wintertime inversions and summertime conditions in urban areas of
Utah. At the Dugway Proving Grounds, we have flown the balloon into diesel and fog oil smokes
generated by turbine generators to obtain particle size distributions. The Defence Research Agency,
pan of the United Kingdom's Ministry of Defence, teamed with the 545 Test Group, Utah Test and
Training Range, Hill AFB, Utah, to acquire data on atmospheric transmission through slant paths
from 0 to 30 degrees, with the horizontal, at various ranges. Measurements of the image profile of a
focussed argon ion User beam were made with « high resolution CCD camera in the balloon. Fast
radiometric scans of the balloon were attempted from a radiometer located on the ground. Fourier
transform infrared (FTTR) spectrometers operating in the 8 to 12 micron region were used in conjunc-
tion with a coaligned Inframetrics infrared camera, with various narrowband filters, to characterize
chemical plumes being emitted from a simulated industrial suck. The instruments were mounted in
the hot air balloon operated at several different altitudes in order to measure the near field (0-800
meter) plume characteristics at different effective horizontal resolutions and to assess the sensitivity
of these instruments for measurements in the far field regime. We will be performing an experiment
where there will be controlled releases and collections of gases in order to provide truth data for mea-
surements that will be taken by a CO2 lidar system. Ultraviolet scattering and absorption experiments
have been carried out at the Dugway Proving Grounds, UT with the Cosmic Ray Research Team of
the University of Utah using their High Resolution ultraviolet sensor arrays. This paper will present
and discuss the results of these tests. In addition, results from other tests performed with the balloon,
to include remote sensing through various obscurants and a lest of a low cost optical tracking system,
will be presented.
NEW ADVANCES IN SOIL GAS SURVEYS: CONTINUOUS MONITORING
USING A MASS SPECTROMETER (SVS-MS)
Emma P. Popek, Laboratory Director, Peter C. Balas, President, Onsile Environmental Laboratories,
Inc., 5500 Boscell Common, Fremont, CA 94538
Onsite Environmental Laboratories, Inc. (ONSITE) of Fremont, Ca. has integrated a Viking
SpectraTrak 620 GC/MS system with conventional direct push soil gas survey hardware to produce
an innovative approach to soil vapor surveys. Hundreds of data points may be obtained each day
with a complete Mass Spectrometer (MS) scan of each soil gas sample at an analysis cost of $7 to
$20 per point.
SVS-MS significantly improves the quality and increases the quantity of analytical data available
through soil vapor surveys. Current methodologies limit the number of samples per day by the run
time of the GC and the required detectors for the specific analytes. ONSlTE's new methodology
enables clients to receive their data in 3D at the end of the day so that they may evaluate activities
and make decisions in real time.
Using argon as an internal standard, ONSITE is able to quantilale contaminants more accurately, by
eliminating the inherent error in determining sample volume using conventional methods.
Utilizing the MS scan, ONSITE is able to measure not only the target compounds but also such trac-
ers of aerobic and anaerobic bacterial activity in soil as CX>2, CH4 and H^S. These key indicators
may provide critical information to the geoscientist evaluating the subsurface conditions.
Data acquisition, or "analysis lime" as is referred to in conventional soil gas surveys, is no longer an
issue with ONSlTE's new process. The soil gas is introduced directly lo the MS via a silicon rubber
membrane resulting in real time, instantaneous results. Project managers in the field are now able to
evaluate the subsurface conditions in real time as the probe is being advanced.
18 Thursday, February 23, 1995
-------
New Developments in Monitoring and Measurement Methods
MICELLAR ELECTROKINETIC CHROMATOGRAPHY: A NEW TOOL FOR
FIELD-SCREENING OF SEMIVOLATILES
William C. Brumley, U.S. EPA. EMSL-LV, P.O. Box 93478, Las Vegas. NV 89193-3478
Micellar electrokinetic chromatography (MEKC), one of many operational modes of capillary elec-
trophoresis (CE), is a new technology with great potential for field screening. MEKC is a powerful
and simple separation/determinative technique when coupled with ultraviolet/visible or laser-induced
fluorescence detection. MEKC can be combined with recent developments in supercritical fluid
extraction (SFE) and solid phase extraction (SPE) to achieve very rapid sample analysis. The U.S.
EPA Environmental Monitoring Systems Laboratory, Las Vegas, has an active interest in extraction
technology as well as separation/determinative techniques. One of the goals of our research using
MEKC has been to reduce the time of SFE/SPE/MEKC to an average of about 6 to 9 mm. per sam-
ple. The power of MEKC will be shown for typical semivolatile analytes, such as phenols, anilines,
and polynuclear aromatic hydrocarbons. Advantages of MEKC over other techniques (e.g., gas chro-
matography and liquid chromatography) include complete regeneration of buffer/micellar agent and
complete capillary rinsing between samples; use of inexpensive fused silica columns; rapid separa-
tions of analytes on short capillaries; inherently high on-column sensitivity; high theoretical plate
numbers; and ruggedness. Ultraminiaturization of the CE technique and sub-second separation times
have also been demonstrated by other researchers.
Notice: The U.S. Environmental Protection Agency (EPA), through its Office of Research and
Development (ORD), prepared this abstract for a proposed oral presentation. It does not necessarily
reflect the views of the EPA or ORD.
ENVIRONMENTAL APPLICATIONS OF A SIMPLE BIOLUMINESCENCE
DEVICE
Peter J. Stopa, Gary J. Herman, Jennifer Petering, and Lawn Harbor, U.S. Army Edgewood
Research Development, and Engineering Center, Research and Technology Directorate, Aberdeen
Proving Ground, MD, 21010-5423, and Lawrence Loomis, David Miller, Maryann Childs, and David
Bernstein, New Horizons Diagnostics, Inc., 9110 Red Branch Road, Columbia, MD, 21045-2014
The measurement of Adenosine Tri-Phosphate (ATP) has classically been used as a means to monitor
the presence of bacteria in clinical materials, particularly urine; however, the instrumentation,
reagents, and variability of the technique have excluded its use in environmental applications. A sys-
tem is described here which has simplified the performance of this measurement and may result in the
use of bioluminescence as a means to monitor fluxes in the biomass of the environment.
The classical system utilized liquid reagents with a rather large, cumbersome detector system.
Advances in drying techniques and miniaturized electronics have resulted in the development of a
potentially field-deployable system. The reagents are stabilized by spray-drying them on to a ticket
and the electronics Tit into a device about the size of a large calculator. The sample is introduced into
a tube and filtered to remove imerferents. Other pretreatment steps may include lysis of somatic
cells. A bacteria/pollen specific lytic agent is then added, and the sample is then transferred to the
test ticket. It is then placed into the instrument and read.
Results in both the laboratory and the field show that the system has a sensitivity of about \Qr organ-
isms/ml for both sporulated and vegetative bacteria. Several pollens have also been evaluated and
shown to be reactive. Work is continuing in the evaluation of other biological materials, such as
mold spores.
The data suggests that this device can be interfaced with simple sampler devices and used as means to
monitor the biomass content of air and water. Environmental applications could include such areas as
sludge analysis and indoor-air quality. Several examples of the applications of this technology to
these areas will be discussed.
Thursday, February 23, 1995 19
-------
Expedited Site Investigations and Rapid Turnaround Methods
EXPEDITED SITE CHARACTERIZATION (ESC) USING THE M3 APPROACH
M3 = MASSIVE, MODERATE, MINIMUM
5. Tindall, Bechlel Environmental Inc., San Francisco, CA
The main objective of this approach is to quickly and cost effectively identify and classify potential
Areas of Concern (AOCs) as "clean" or contaminated, thus allowing potentially responsible parties
(PRPs) to save limited resources by ceasing costly investigations and undertaking removal type
actions expeditiously. The ESC M* approach also overcomes the high degree of uncertainty typically
associated with traditional site investigations resulting from a lack of comprehensive scoping. Thus,
EPA Region DC has agreed to accept and use, for risk assessment purposes, the data generated from
the ESC M3 approach, providing the data quality is known and confirmation analyses are performed.
The extraordinary benefit will be to eliminate any further action on those AOCs found to be clean
using this approach. Finally this approach reduces the large number of non-delect samples that are
customarily submitted for CLP-type (i.e.. Contract Laboratory Program) analyses.
The ESC M3 approach consists of the following three steps: Step 1) a "massive" sampling effort is
first conducted at an AOC (e.g., 200 samples are collected using a grid approach); the samples are
analyzed on a daily basis using real time onsite methods and field screening (FS)-type data are gener-
ated; Step 2) a "moderate" sampling effort is then conducted (e.g., 20 splits of the Step 1 samples
from "clean" locations in a clean AOC or a lesser amount of splits from "hot" locations in a contami-
nated AOC, along with boundary location [extent] samples) to provide onsite verification of the FS-
type data; the samples are analyzed using onsite CLP-type methods and field quanulation (FQ)-type
data are generated with an agreed upon level of QC; and finally. Step 3) a "minimum" sampling
effort is conducted (e.g., 4 splits of the Step 2 samples from "clean" locations for a clean AOC and
from "hot" and boundary locations for a contaminated AOC) to provide verification of the FQ-type
data; these confirmation samples are sent to an offsilc laboratory for analysis, and CLP-type data are
generated.
Note that both the FS and FQ steps will generate quantitative results (i.e., concentration values for
every analyte). The main difference is in the level of precision. Studies have shown the FS data pre-
cision to be comparable to CLP-type precision. While the level of QC for the CLP-type data is
known, the appropriate levels and amounts of QC for the FS-type and FQ-type data still need to be
defined.
All FS-type and FQ-type data will be loaded into an onsite data management system with three-
dimensional (3-D) visualization capabilities. These data will be viewed by site managers onsile and
by Remedial Project Managers (including regulatory agencies) via modem transmissions at the end of
each day. Thus, remedial decisions will be made on * daily basis, rather than, as is typical of current
practices, months or years after each phase of the site characterization field work has been completed.
It is possible that only one field investigative effon will be required using this approach since data
gaps can be seen on a daily basis and then accounted for on succeeding days while the investigation is
ongoing. Remobilization time and costs can be eliminated greatly accelerating the remedial process
while drastically reducing the costs.
Recent cost estimates at a Federal Facility in California have shown this approach can realize a sub-
stantial cost savings when compared to the traditional RI/FS site characterization approach. This
approach is being planned for implementation at two Federal Facilities during the summer/fall of
1994. Case studies will be presented at the February 22-24,1994 FS Symposium in Las Vegas, NV.
20 Thursday, February 23, 1995
ACCELERATED SITE INVESTIGATION USING FIELD SCREENING METH-
ODS: A CASE STUDY OF A TEAM APPROACH
Michael E. Barber, Analytical Technologies, Inc.-FAS and Dr. Brian Abraham, Site Works, Inc.
Field screening data is becoming a necessary tool for environmental site investigations. The use of
mobile and close-support laboratories has allowed for rapid, informed decision-making and is evolv-
ing a new approach to site investigations. Analytical Technologies, Inc. and Site Works, Inc. have
teamed to provide quick turnaround data to support a large scale site investigation under the Navy
Clean program during the summer of 1994. The teaming arrangement on this project has combined
each company's expertise into an integrated analytical laboratory providing high volume, quick turn-
around methods for TRPH, PCB's, PNA's, and metals. The methods used include fast GC/MS (SIM)
for volatile and semivolalile organics, field transportable ICAP for metals, and portable IR for TRPH.
This paper will discuss the use of field screening data and a team approach to providing on sue ana-
lytical services. Issues such as mobilization, quality assurance, data quality objectives, operating con-
siderations, and field support of a long-term, remote project will be discussed.
-------
Expedited Site Investigations and Rapid Turnaround Methods
THE USE OF RAPID TURN-AROUND HEATED HEADSPACE/GAS CHRO-
MATOGRAPHY TO SUPPORT REGULATORY SOIL CLEAN-UP STANDARDS
James S. Alwell & Chris G. Evans, Sevee and Maker Engineers, Inc.. Cumberland, ME 04002,
Richard Guerra, Lockheed Sanders, Inc., Nashua, NH 03061, Thomas L. Francoeur, TerraChem
Consultants, Inc., Yarmouth, ME 04096
Previous studies have indicated that gas chromalography can be effective as a screening tool to delin-
eate areas of contamination on-site; however, there are few data supporting the use of a field laborato-
ry to fully support a large scale site rernediations. In recent years analytical instrumentation has
evolved to withstand the rigors of field work, and field analysis has coincidentally evolved from a
"screening" tool to a true support tool able to provide useable data in defense of state soil clean-up
criteria. A water extraction/heated headspace method was selected for this project because of its pre-
cision, accuracy and ability to turnaround as many as 30 environmental samples per day per instru-
ment. In addition to evaluating soil clean-up criteria analytical data enabled the remediation contrac-
tor to optimize the treatment systems and focus their effort.
During this project approximately 2500 samples were analyzed in the field laboratory over a period of
seven months using the heated headspace method. The state and project requirements, in addition to
the duration and volume of samples involved, required that a well denned QA/QC program be imple-
mented and enforced. Quality control criteria were established to emulate standard USEPA GC pro-
tocols (Methods 8000/8010/8020) for calibrations, blanks, surrogate spikes, laboratory control sam-
ples, field duplicates, matrix spikes, and independent check standards. Site specific control limits for
these measures were often more restrictive than the recommendations of the standard method. In
addition to these internal QA/QC measures, approximately 10% of the samples were split with a certi-
fied laboratory for USEPA method 8010/8020 analysis. Using these data an extensive database was
established quantitatively evaluating the precision, accuracy, representativeness, comparability and
completeness of the field heated headspace method.
This paper discusses the heated headspace method, sample handling and analytical protocols as well
as the project and Data Quality Objectives. Extensive statistical analysis of both the internal laborato-
ry QC data and the independent spb't data validate the heated headspace method as a viable "stand-
alone" alternative to off-site analysis. The paper discusses the strengths and limitations of the on-site
method, and how it can best be incorporated into today's budget and time sensitive remediation
projects.
TANDEM LEVEL II AND LEVEL HI FIELD ANALYSES FOR IN-FIELD DECI-
SION MAKING
David E. Gallis, Environmental Resources Management, Inc., 855 Springdale Drive, Elton, PA
19341, JeffChrislenson, Viking Instruments Corp., 12007 Sunrise Valley Drive, Reston, VA 22091-
3406
In order to provide cost effective and timely analytical support for a site investigation in central
Pennsylvania, Environmental Resources Management-Field Analytical Services Technologies (ERM-
FAST*) performed field soil analyses targeting both Level D and Level HI data quality objectives.
Of specific concern were 17 volatile organic compound, including the less volatile dichlorobenzenes.
The soil levels of these contaminants of interest were required on a rapid turnaround basis in order to
make decisions regarding subsequent boring locations and other analytical logistics.
For 50 anticipated boring locations, rapid turnaround Level II analyses were needed for each of 5
intervals per boring. Rapid turnaround head space analyses (ca. two hours) were performed on-site
using a Perkin-Elmer Autosystem GC with a PID and an ELCD in series. These Level n GC results
were used to determine the best locations for subsequent borings, the most illustrative three of five
intervals to be analyzed by on-site GC/MS for Level in data quality, and to infer the proper dilution
factor for each sample analyzed by on-site GC/MS. On-site GC/MS was performed using a Viking
640 GC/MS system with cryo focussing, and in accordance with SW-846 Method 8260.
Presented is a statistical comparison of on-site GC/MS, GC, and commercial laboratory confirmation
analyses. Project cost, time and strategic benefits are also discussed, as well as instrument perfor-
mance and instrument selection strategy.
Thursday, February 23. 1995 21
-------
Field Screening Issues
THE DIFFUSION OF INNOVATIONS IN THE ENVIRONMENTAL MARKET-
PLACE
John Moore Jr., HNU Systems, Inc., 160 Charlemont Street, Newton, MA 02161
Recently, there has been much talk by public officials, industry and others about the need to facilitate
the adoption of new technologies within the environmental marketplace. Currently there are a num-
ber of barriers that exist which hinder the adoption process. These barriers include: permit and com-
pliance programs and requirements, the trend to legislate technological solutions, balkamzed regulato-
ry programs, a dearth of education and training programs in the use of new technologies, and the lack
of neutral third party evaluation and validation of new technologies.
While all these barriers play some role in the adoption process, often the degree to which a specific
barner hinders the use of an innovative technology is not well understood. Therefore, individuals
both in the public and private sector, may develop solutions to perceived barriers that ultimately may
have very little impact in increasing the rate of adoption for a new technology.
To address the issue of barriers to technology adoption, one must first obtain a fundamental under-
standing of how a new technology is diffused within a given sector of the environmental marketplace.
Without this understanding, the barriers that one may try to alleviate may not be the critical barriers
that are hindering the use of a new technology.
This presentation will identify some of the most critical barriers that currently hinder technology
adoption. Secondly, the various methods by which technologies are diffused into the environmental
marketplace will be described. Examples will be given where changes in policy to encourage tech-
nology adoption have not had the intended impact due to the lack of consideration for the diffusion
process. The presentation will conclude with recommendations of how to incorporate the knowledge
of diffusion processes into technology adoption policies, leading to greater success for new technolo-
gy developers in the environmental marketplace.
IMPEDIMENTS TO NEW TECHNOLOGIES FOR HAZARDOUS AIR POLLU-
TANT MONITORING
Elizabeth McGralh, Center for Process Analytical Chemistry, University of Washington, Seattle, WA
and Michael Dellarco, Office of Research and Development, US Environmental Protection Agency,
Washington, DC
'Ihis presentation describes policy and legulatory impediments encountered in efforts to foster and
adopt new measurement technologies for hazardous air pollutant monitoring required by the Clean
Air Act of 1990. Through the Center for Process Analytical Chemistry, a National Science
Foundation public-private research partnership program, our work has revealed that introduction of
new monitoring methods is not limited by technology nor market considerations but by regulatory
impediments. Cooperation between petroleum industry members of CPAC and the EPA to identify
and introduce new technologies indicates that a variety of instrumentation could be applied to haz-
ardous air pollutant monitoring required by these new regulations. Yet, Agency programs are ill
equipped to enlist them. We have found that formal rule making procedures do not always reach
interested scientists and lack flexibility to incorporate new technologies. Communication of Agency
research interests and programs with the private sector could be improved; participation in scientific
meetings and workshops apparently is not enough to stimulate collaboration. Agency surveys of new
technologies are incomplete. Surveys do not sample the technical community adequately.
Frequently, industry responses lack detail. Technical support, essential to define performance accep-
tance criteria, protocol review, and quality assurance guidance is not widely available. Yet these
ingredients are essential for industry to invest in research of promising technologies. We have taken
steps to improve opportunities. Through formation of a workgroup, efforts are underway to produce a
directory of organizations and individuals to improve the coverage of Agency technology surveys and
to improve industry participation in these surveys. Through collaborative field studies, efforts are
underway to identify regulatory barriers, enlist the support of Agency officials to reduce or eliminate
them, and to develop performance criteria, protocol reviews, and data evaluations that will foster
investment by industry in new monitoring technology research. From this experience, performance
criteria, quality assurance requirements, and comparability demonstrations will be defined in more
detail for subsequent studies. The take home message from our work indicates that greater effort to
identify and reduce regulatory barriers is warranted to foster the introduction and application of new
technologies for environmental monitoring.
22 Thursday, February 23.1995
-------
Field Screening Issues
A SUMMARY OF METHODS FOR FIELD ANALYSIS OF HYDROCARBON
CONTAMINATED SOIL AND GROUNDWATER
Nathan Thompson, Land Tech Remedial, Inc., Ealontown, NJ 07724, Roy Chaudel, IT Corporation,
Washington, DC 20036-3390, Dominick DeAngelis, Mobil Oil Corporation, Princeton, NJ 08543-
1039, and Roger Claff, American Petroleum Institute, Washington, DC 20005
A variety of improved field-based technologies, methods, and procedures are being used to perform
rapid and cost-effective analysis of organic compounds in a more streamlined process than is possible
with conventional assessments. In many of these investigations, the appropriate use of these methods
can result in an effective characterization with increased spatial and temporal information in less time
and with fewer phases of assessment than is typically done using conventional sampling technologies
and off-site or fixed-base laboratories. Although the use of field analytical methods for conducting
on-site analysis of hydrocarbon-contaminated soil and groundwater is increasing, such methods are
not currently in wide use primarily for the following reasons: (1) the lack of regulatory acceptance,
(2) the perception that field analytical methods do not provide data of adequate quality for making
decisions, and (3) the perception that field analytical methods do not necessarily result in cost sav-
ings.
The American Petroleum Institute (API) is currently developing a series of technical documents to
address key issues that technical, project management, and regulatory personnel may need to know in
order to select and use these field analytical methods to their full potential. The overall objective of
this project is to develop technical guidance in a series of documents to be used in establishing an
independent set of field analytical methods that do not require constant validation by comparison lab-
oratories and can be used in on-site decision making.
This paper will discuss these documents being developed by presenting an overview of the following:
(1) a compendium of recognized and emerging Field analytical methods, (2) a framework for the
appropriate selection and use of recognized field analytical methods in the site characterization/cor-
rective action process, and (3) a protocol for producing and evaluating field performance data. The
compendium focuses on the most widely used field analytical technologies including total organic
vapor analyzers, portable gas chromatographs, immunoassay and colormetric kits, infrared detectors,
and dissolved oxygen/reduction-oxidation potential electrodes. The compendium also lists other field
analytical techniques that are not as widely used but show promise for future application. The frame-
work provides a characterization process based on site-specific considerations and goals and identifies
the advantages and limitations of different field analytical methods in achieving site-specific goals.
lhc Held performance protocol provides a means to establish method performance and to meet data
quality objectives using field-generated analytical data. These documents can assist in generating
higher quality, reproducible, and standardized field analytical data in order to minimize the use of
costly and time consuming off-site sample analysis, and increase the credibility and use of field data
for risk evaluation and remedial decision making.
FIELD IMPLEMENTATION COMPLEXITIES OF EPA DEVELOPMENTAL
AND REAL-TIME METHODS DURING REMEDIATION AT REMOTE HAZ-
ARDOUS WASTE SITES: CASE STUDY
Elizabeth L. Green, Eagle Environmental Health, Inc., Elizabeth A. Cunningham, Tenneco, Inc., Carl
Grabinski, Joslyn Corporation
The objective of this presentation is to provide insight into the complexities of field implementation
of EPA developmental methods and real-time monitoring methods for polynuclear aromatic hydrocar-
bons, penlachlorophenol, particulates and metals at remote hazardous waste site remediations.
Ambient air monitoring was conducted at an abandoned creosoting plant in Louisiana in order to
characterize the potential off-site migration of selected constituents through the air pathway during
remediation of the site. Off-site migration of constituents was a concern due to the close proximity of
commercial and residential areas to the site. In addition, real-time monitoring was conducted so that
site activities could be adjusted based on action levels in a timely fashion in order to reduce any unac-
ceptable levels of constituents identified by the real-time monitoring.
Ambient air monitoring was conducted for polynuclear aromatic hydrocarbons and pentachlorophenol
using EPA TO-13 method; and for total suspended particulates and metals using the method from 40
CFR, part 50, Appendix B. Real-time monitoring was conducted for particulates using a Mini-Ram
and for organics using a MSA Gascorder photo-ionization detector. Monitoring was conducted over
the course of a year (1992) in three phases. Approximately 8,000 data points were generated during
the course of this project.
Field implementation of multiple developmental and real-time methods presents many challenges. In
particular, relative to developmental methods, laboratories are generally unfamiliar with the develop-
mental and analytical methods and often do not maintain the required media and equipment because
of the limited demand for the method. Additionally, because the method is not routinely performed
by many laboratories, the potential idiosyncracies of the method may not be well understood and
therefore quality control procedures may not be well established. Poor turnaround times due to unan-
ticipated analytical complications can also have a significant impact on the usefulness of the data on
an ongoing basis.
From a logistic standpoint, many factors must be considered in order to implement a successful air
monitoring program which will provide defensible data. Seemingly minor factors such as the source
of effective power at remote locations (because generators can produce contaminants which could
bias organic results) can have a significant negative impact if not appropriately considered in the ini-
tial planning of the project. In addition, daily start-up and shut down procedures of multiple pieces
of equipment involving many different methods can put strains on manpower and quality control
procedures.
Finally, a management system for large amounts of data must be prc-designed with the end points in
mind in order to place the data in a usable format that facilitates statistical analysis and reporting at
the completion of the project.
Thursday, February 23, 1995 23
-------
Use of Laser-Based Technologies
LASER-INDUCED FLUORESCENCE (LIF) SPECTROSCOPY OF POLYNU-
CLEAR AROMATIC COMPOUNDS (PAC) AND MINERAL OILS IN HUMIC
ACID- AND SOIL-CONTAINING COMPARTMENTS
II.-G. Lohmannsroben, M. U. Kumkt and Th. Rock, Institulfur Physikalische und Theorelische
Chemie, TU Braunschweig, Hans-Sommer-Slr. 10. D-38106 Braunschweig
Laser spectroscopy has been established as an imponant tool in environmental research. Among the
various spectroscopic techniques employed, laser-induced fluorescence (LIF) is distinguished by out-
standing sensitivity and high selectivity, and has therefore found considerable fundamental and practi-
cal interest However, due to the heterogeneity and opacity of soil matrices, the qualitative and quan-
titative investigation of fluorescence signals obtained from soil-containing environmental compart-
ments imposes usually considerable experimental difficulties.
In order to investigate the benefits and limitations of luminescence analysis in humic acid- and soil-
containing samples we use selected PAC as model fluorophores and mineral oils as realistic contami-
nants. Single- and multi-channel stationary and lime-resolved fluorescence measurements were per-
formed to obtain basic photophysical information and experimental data relevant for the ui-situ and
on-line analysis of soil-containing samples. Results of the following investigations will be presented:
• Investigation of the quenching of PAC fluorescence by humic acids. The combination of
stationary and time-resolved measurements provides insight in the mechanisms of fluorescence
quenching and in fluorphore/humic acid-interactions.
• LIF-measurements directly from the surface of soils doped with model and mineral oils.
Quantitative relationships between fluorescence intensities and concentrations were obtained in
ranges relevant for realistic PAC and mineral oil contamination of soils.
• In-situ and on-line LIF-measurements on soil columns and in bioreactors. The determina-
tion of probability distributions of fluorescence signal intensities yield information about the distribu-
tion of the contaminants on the soil surface and the degree of heterogeneity in these systems.
The results obtained in these studies will be evaluated with regard to the development and application
of in-situ and on-line luminescence analytical methods under conditions realistic e.g. for soil deconta-
mination processing.
THE INFLUENCE OF PAH CONCENTRATION AND DISTRIBUTION ON
REAL-TIME IN SITU MEASUREMENTS OF PETROLEUM PRODUCTS IN
SOILS USING LASER INDUCED FLUORESCENCE
G.5. Douglas, Battelle Environmental Systems <& Technology Division, Diabury, Massachusetts, S.H.
Lieberman, Naval Command, Control and Ocean Surveillance Center, RDT&E Division, San Diego,
California, W.C. McGinnis, Naval Command, Control and Ocean Surveillance Center, RDTAE
Division, San Diego, California, C. Peven, Ballelle Environmental Systems & Technology Division,
Duxbury, Massachusetts
This paper describes the results of a real-time, in situ survey using laser induced fluorescence tech-
niques to evaluate the extent and type of hydrocarbon product contamination in soil. Real-time soil
petroleum product measurements were made through the sapphire window of a probe that was pushed
into the soil from a truck-mounted cone penetrometer lest (CPT) system. A 337-nm excitation source
induced fluorescence in polynuclear aromatic hydrocarbons (PAH) present in petroleum products, and
the signal measured with a fluoromeler. After removal of the soil probe, a split spoon coring system
was used to collect discrete soil samples down the push hole. Additional discrete laser induced fluo-
rescence measurements were made using soil removed from composites of six inch split spoon cores.
Discrete soil samples were also collected from the homogenized six inch split spoon core, extracted
and analyzed for over forty parent and alkyl substituted PAH compounds by gas chromatography/
mass spectrometry using a modified EPA Method 8270. The modifications were: 1) redefinition of
the surrogate and internal standard, and target analyte list to include primarily diagnostic hydrocarbon
compounds, 2) the use of selected ion monitoring to increase analytical sensitivity, and 3) the quan-
tification of alkylaled PAH homologues (e.g., C, to C4-phenanthrenes, etc.). This method produced
data that was used to identify product types present in the soil, determine linkages between samples
and source products, and provided a basis for evaluating the relationship between PAH concentrations
and laser induced fluorescence measurements made in the soil borings. Total PAH and individual
PAH concentrations in the soil were evaluated relative to product type and laser induced fluorescence
response using principal component analysis.
The laser induced fluorescence system used in this study was found to provide continuous and reli-
able real-lime hydrocarbon profiles - a dramatic advantage over time consuming and costly discrete
sampling/analysis methods traditionally used for site monitoring well placement, monitoring of reme-
diation countermeasures, or tracking hydrocarbon contamination to sources.
24 Thursday, February 23,1995
-------
Use of Laser-Based Technologies
A FIELD SCREENING METHOD FOR TRACE ELEMENTS IN SOIL
Israel Schechter, Dept. of Chemistry, Technion - Israel Institute of Technology, Haifa 32 000, Israel,
Reinnard Niessner, Institute for Hydrochemislry, Technical University of Munich, Marchioninistr. 17,
D-81377 Munich, Germany
A field screening method for heavy metals in soils, sand and sewage sludge samples has been studied
by means of time resolved optical emission specuometiy from laser induced plasma. The instrumen-
tal setup has been developed as a fast screening detector for a future application as an on-line and in-
situ method. A solid state laser pulse is focused onto the sample to produce plasma. An optical fiber
system is used to collect the light emitted from the plasma. Spectral and temporal resolutions are
obtained by means of a small spectrograph and an intensified photodiode array. Several experimental
parameters have been optimized. This method enables fast analysis, without any chemical prepara-
tion of the samples. Various factors affecting the detection limits and the quality of the analysis have
been investigated. These include aerosol production, crater formation, size effects, timing effects,
laser intensities and humidity. In order to improve reproducibility of elemental analysis, a special
data analysis program has been developed. It consists of a data analysis program and of the Principal
Component Regression (PCR) calibration technique, which utilizes many spectral lines for each ele-
ment. A special renormalization algorithm has been tested for internal calibration. The computer
program provides good calibration plots and detection limits in the 10 ug g ' range, which are usually
below the ecological requirements.
LASER INDUCED BREAKDOWN SPECTROSCOPY FOR RAPID DELIN-
EATION OF METALS IN SOILS
Greg Theriault, Computer Sciences Corporation, 4045 Hancock Street, San Diego CA 92110,
Stephen H. Lieberman, Naval Command, Control and Ocean Surveillance Center, RDTA.E Division
521,53475 Strothe Road, San Diego, CA 92152-6325
Laser Induced Breakdown Spectroscopy (LIBS) has been used effectively in recent years as a rapid
method for classification of metal surfaces. The established technique involves a laser beam which is
tightly focused onto a metal surface to initiate the formation of a plasma. The time resolved emission
of the plasma is collected and analyzed to reveal the characteristic spectral signature of the metal.
The present work addresses the potential application of LIBS over fiber optic cables as a real time in-
situ metal contamination field screening tool for use in soils in conjunction with a cone penetrometer.
In this application the intense beam of a Nd:YAG laser is launched into a fiber optic cable and subse-
quently focused onto a soil sample spiked with a metal contaminant. The system limiting factors of
required surface power density, fiber optic damage threshold, and signal collection efficiency will be
addressed.
Thursday, February 23, 1995 25
-------
Laboratory Platforms and Vehicles
PORTABLE AIR MONITORING LABORATORIES
D. Ehntholt, K. Beltis, J. McCullough, and J. Valentine, Arthur D. Ullie, Inc.. 15 Acorn Park,
Cambridge, MA 02140
The U.S. Army contracted with Arthur D. Little, Inc. to design, fabricate, test and deliver a suite of
specialized testing laboratory facilities for manned and unmanned use to support Project Retrograde,
the removal of chemical munitions from West Germany. This project, which was earned out for the
Chemical Research, Development and Engineering Center (CRDEC) of the U.S. Armament,
Munitions, and Chemical Command (AMCCOM), was specifically focussed on designing and build-
ing facilities which would be used to perform the vital functions of monitoring the air at many points
on the transport vessels for any traces of the chemical agents which might inadvertently escape from
the munitions cargo.
The design and fabrication planning had to incorporate the following key needs, among others:
• The nature of the mission was such that all apparatus, materials, spare pans for both appa-
ratus and equipment, and utility needs had to be carried with the suite of labs. There would be no
supply depot or repair/spares accessible during the mission;
• The facilities had to be fully self-contained within standard International Shipping
Organization (ISO) van/containers, and mounted/supported to withstand stresses of shipping and
intended use; all spare parts were to be carried in the ISO containers;
• The facilities and utilities had to accommodate and support the intended chemical measure-
ment techniques, principally specialized sample collection/transfer operations and gas chromalogra-
phy, including the handling of small amounts of toxic chemical agent materials to prepare instrument
calibration standards over the enure mission duration;
• The portable air monitoring laboratories were to be manned full-time by three persons
while the lest shelters would have automated test equipment and be manned only on a part-time basis;
There was a requirement for equipment redundancy to ensure no interruption in laboratory
function, and the equipment mounting/location and spare part storage had to be appropriate;
• The laboratory function could not be interrupted by loss of external electrical power or by
extremes in vessel motion, including + or - 30° roll;
HVAC and special air filtration would be required to provide a comfortable work environ-
ment and an over-pressure of "clean" air to prevent incursion of agent-contaminated air in the event
of any cargo leakage.
Lessons learned during the successful design and operation will be discussed.
FIELD SCREENING FOR MILITARY UNIQUE COMPOUNDS UTILIZING THE
REAL TIME ANALYTICAL PLATFORM (RTAP)
Uday J. Mehla, U.S. Army, ERDEC, Monitoring Branch, Bldg E3330, APG, MD 21010 and Donald
G. Paul, Dynalherm Analytical Instruments inc., P.O. Box 159, Kellon, PA 19346
The U.S. Army Operations Directorate, Chemical Support Division, Monitoring Branch monitors air-
borne levels of a variety of military compounds to ensure worker safety and the protection of the
environment at sites where chemical agents are used or stored and during disposal operations. Ilie
monitoring system fielded in the Real Time Analytical Platform is based on an air sampling technique
using solid sorbent collection and thermal desorption technology combined with capillary gas chro-
malography with multiple gas chromatography detectors. The mobile unit is equipped to analyze a
vanety of surely compounds, delivering documentation to meet regulatory requirements with a high
level of sensitivity, selectivity, extensive dynamic range with excellent linearity, in real time or near-
real time. The system can sample continuously through a healed transfer hose for direct, on-line
requirements such as site monitoring projects, or easily switch to off-site sampling capability using
solid sorbent cartridges for sample collection that are relumed to the mobile unit or laboratory for
analysis.
The RTAP analytical system replaces multiple methods using diverse instrumentation with a single
instrument configuration. Training time is reduced, since technicians are able to analyze a wide vari-
ety of compounds with the same instruments using very similar methods. Wet chemistry procedures
that generated hazardous wasle have been eliminated, resulting in savings on decontamination and
disposal expenses.
This paper will describe the instrumentation, its use for both screening and confirmation of various
chemical surely maienals, and describe how the units have been fielded as part of emergency
response efforts at several sites.
26 Thursday, February 23, 1995
-------
Laboratory Platforms and Vehicles
GEOPHYSICAL SURVEYING USING A REMOTELY CONTROLLED VEHICLE
A J. Harlick, Automated Sciences Group, Inc.*, Oliver Springs, Tennessee, DJ. Green, Directorate of
Safety, Health, and Environment, Aberdeen Proving Ground, Edgewood, Maryland, P.A. Franzen,
Hazardous Waste Remedial Action Program, Martin Marietta Energy Systems, Inc., Oak Ridge,
Tennessee 37831
A remote characterization system (RCS) will be used at the Aberdeen Proving Grounds (APG),
Edgewood Area in August 1994 to execute geophysical surveys of -300 acres at Carroll Island and
20 acres at Graces Quarters. The intent of the program is to verify the boundaries of potential burial
or disposal sites identified during previous investigations demarcated by pits, mounds, or depressions
and to check for new areas identified during site walkovers.
The RCS development was a coordinated effort between Pacific Northwest Laboratories, Oak Ridge
National Laboratory. Idaho National Engineering Laboratory, and Sandia National Laboratories. The
remotely piloted vehicle can be equipped with various types of equipment including magnetometers,
electromagnetic induction sensors, ground-penetrating radar (GPR), gamma radiation detectors, and
photoionization detectors. The vehicle is designed with a minimum of metal to present a low electro-
magnetic signature to each of the sensors, thereby limiting interference with sensor operation. A base
station houses the controls and monitors. Control commands sent from the base station and data from
two video cameras mounted on the front and back of the RCS are used to "drive" the vehicle. The
commands are transmitted via an ethemet link on a microwave frequency. Sensor readings flow con-
tinuously from the RCS to the base station. A differential global positioning system (GPS) is used to
track the position of the vehicle in real time to submeter accuracy. The GPS data can be processed to
achieve an accuracy to within 15 cm.
Some of the intended APG Edgewood Area sites have had previous geophysical surveys performed,
including an EM-31 electromagnetic survey. The proposed RCS program— consisting of GPR, mag-
netometer, and EM-61 electromagnetic surveys—has been designed (1) to confirm previous geophysi-
cal surveys; (2) to supplement previous geophysical survey results, specifically through the use of the
more-sensitive EM-61; and (3) to collect data in site areas previously inaccessible to traditional geo-
physical methods. A benefit of using the RCS is that it can access marshy areas and areas with
uneven terrain that were difficult to get to during previous surveys. Also, because the three tools
(GPR, magnetometer, and EM-61) will be on the RCS simultaneously, the survey will be more time
effective than if traditional survey methods are used.
The intent of this study is to demonstrate the versatility of the RCS and the application to sites with
access problems such as unsuitable terrain and to areas in which contamination levels are dangerous
to humans. Additionally, the ability of the RCS to carry more than one sensor tool during operation
will eliminate the need for multiple traverses (per geophysical tool) over difficult terrain.
A VEHICLE MOUNTED MULTISENSOR ARRAY FOR WASTE SITE CHARAC-
TERIZATION
Chris W. Baumgart. Christopher A. Ciarcia, and Tom W. Tunnell, EGAG Energy Measurements,
Inc., Los Alamos Operations, Los Alamos, New Mexico, 87544, Steven Cave and Jim Creager, EGAG
Energy Measurements, Kirtland Operations, Albuquerque, New Mexico, 87196.
OBJECTIVE
This presentation will provide a brief overview of the IGMMDT sensors and of the IGMMDT inte-
grated system design. Preliminary results of field tests of the IGMMDT array will be presented. The
potential applicability of the IGMMDT platform, its sensors, and its data analysis algorithms to field
screening and site characterization for hazardous wastes and toxic chemicals will also be discussed.
TYPE OF TESTING AND EVALUATION TO BE CONDUCTED
The Improved Ground Mobile Mine Detection Testbed (IGMMDT) is a vehicle mounted, multi-sen-
sor array designed and fielded for the U.S. Army's Ft. Belvoir Countermine technology group. The
purpose of IGMMDT is to locate, identify, and mark anti-tank and anti-personnel land mines making
use of multiple sensor technology and data fusion to correlate sensory inputs. The sensor array con-
sists of ground penetrating radar, metal detectors, dual-band infrared, and optical cameras. Data col-
lected by these sensors are processed in real-time (100's of milliseconds) using high speed signal and
image processing hardware. The data from each sensory channel is processed at two levels. The first
level of processing (low level inference) uses advanced signal and image processing techniques to
analyze the data acquired by the sensor to locate and identify threats (mines) in the sensor's field-of-
view. The second level of processing (high level inference) then forms a consensus of the outputs
from the low level inference processes of all the sensors to make a final threal/non-lhreal decision. A
neural network is used to perform the high level inferencing and is trained to correlate the outputs
from the different sensors over a range of environmental conditions and identify threats. IGMMDT is
designed to be a modular sensor testbed which provides rapid site survey capability and in-situ data
analysis for site characterization. As such, different and newly emerging sensor technologies may be
easily integrated onto the array, including those that are used for the mapping and characterization of
hazardous waste sites or for the detection and characterization of unexploded ordnance (UXO).
*Work performed by Automated Sciences Group, Inc., under general order contract number 30B-
9778C with Martin Marietta Energy Systems, Inc.
The submitted manuscript has been authored by a contractor of the U.S. Government under contract
DE-AC05-84OR21400 with the U.S. Department of Energy. Accordingly, the U.S. Government
retains a paid-up, nonexclusive, irrevocable, worldwide license to publish or reproduce the published
form of this contribution, prepare derivative works, distribute copies to the public, and perform pub-
licly and display publicly, or allow others to do so, for U.S. Government purposes.
Thursday, February 23, 1995 27
-------
Information Processing
E-SMART: A STANDARD APPROACH TO REAL-TIME, IN SITU ENVIRON-
MENTAL MONITORING AND PROCESS CONTROL NETWORKS
J.S. Leffler, K. Boline, W. Wier, General Atomics, NRT Division, FOB 85608, San Diego, California
92186, and BJ. Nielsen, Armstrong Laboratory AL/EQ, Site Remediation R&D Division, Tyndall
AFB, FL 32403
To meet growing environmental needs, both the government and the private sector are developing
better sensors for a wide range of chemical and radiological contaminants for use in real-time, in situ
environmental monitoring applications such as in situ bioremediation or post closure monitoring.
However, it is desirable to ensure that the resulting sensors utilize a standard approach to network
communications so that data or operating commands can be exchanged between any smart sensor,
actuator, or control computer system on the network. This goal will allow sensors or other remedia-
tion process control devices such as valves or pumps to be easily installed, configured, and operated
within large, heterogeneous environmental monitoring networks including sensors and actuators of
different types from different manufacturers. It will also ensure that the data generated by diverse
environmental sensors can be combined and analyzed in useful ways. Furthermore, this goal pro-
moles the use of modular hardware and software components allowing for greater flexibility and
lower cost in designing and implementing a monitoring network.
The Environmental Systems Management, Analysis and Reporting Network (E-SMART) was devel-
oped by General Atomics for the US Air Force Armstrong Laboratory in response to these needs.
E-SMART is a fully integrated environmental monitoring system with expert system capabilities. It
should significantly reduce the costs for environmental monitoring network installation, configuration
and operation, help ensure environmental compliance at monitoring sites, and reduce health and
safety risks.
The two key goals of E-SMART are: (1) to create an openly available standard for interconnecting
environmental monitoring sensors into sensor and remediation process control networks, and (2) to
develop an intelligent information processing system to collect, manage, and analyze the resulting
sensor data and to provide process control capabilities. E-SMART achieves the first goal through the
use of microcontroller technology to standardize environmental sensor data and command protocols
over a digital communications network. Any sensor or environmental monitoring equipment manu-
facturer will be able to implement the E-SMART environmental network standard using commercial-
ly available and cost-effective electronic components. The second goal of providing intelligent infor-
mation processing power is achieved through the use of Microsoft Windows™-based network man-
agement, data management, expert system and user-friendly graphical interfaces. E-SMART inte-
grates these technologies into a cost-effective, user-friendly system that gives the system operator
complete, real time environmental monitoring and control capabilities.
A number of E-SMART-compatible sensors are now being developed. These sensors are designed to
measure hydrological parameters, nonspecific hydrocarbon vapor concentrations, and specific chemi-
cal analyte concentrations in gas and liquid phase. E-SMART compatible radiation sensors have also
been proposed. The development status of these sensors, preliminary at field test results, and the per-
formance of the E-SMART system will be discussed.
ENHANCING THE SAMPLING PROCEDURE THROUGH A GEOSTATISTICAL
ANALYSIS
Karen Boomer, Environmental Mathematician, Zenilech Corporation, 1931 West Grant Road,
Tucson, Arizona 85745, Richard Brazier, MSc, Graduate Student, Applied Mathematics Department,
University of Arizona, Tucson, Arizona
Field screening technologies are increasingly integrated into environmental investigative and remedia-
tion activities. Obvious advantages include rapid, cost-effective results. However, with discrete sam-
pling points, there remains uncertainty in the estimation from field screening data to application of
further on-site activities. Geostatistics is a branch of applied statistics which is particularly suited to
environmental interpolation questions because of its dependence on the spatial correlation. Thus, dis-
crete field screening sample information is transformed into a contour plot, with associated confi-
dence intervals, used to plan future sampling activities or remediation options.
Geostalislics as a tool in the development of the sampling and analysis plan has not yet been fully
explored. Clearly, the frequency and spacing of the field screening locations will affect the overall
precision of the geostatistical analysis. Using a combination of synthetic and hard data, the relation-
ship between the sample locations and the precision of the kriging estimates has been explored. This
research indicates that there are some minimum spatial requirements which must be imposed upon the
field screening data in order to ensure that precision criteria are met.
The geostatistical analysis enhances the information provided by the raw data alone. It provides
insight into the spatial disposition of the contaminant as well as the possible intervariable relation-
ships. This approach has been used with raw data generated from x-ray fluorescence spectrometers,
Hydropunch groundwaler investigations, immunoassay technology, and seismic field screening tech-
nologies.
Friday, February 24, 1995 28
-------
Information Processing
USE OF EDGE DETECTION AND FFT FILTERING TECHNIQUES TO REJECT
FLUORESCENCE IN RAMAN SPECTRA
PA. Mosier-Boss, S.H. Lieberman, and K. Newbery, Naval Command, Control and Octan
Surveillance Center, RDT A E Division, San Diego, CA 92123-5000
Although Raman spectroscopy is a useful technique to identify and quantitate species in a given
matrix, it has been limited in its applicability by fluorescence. Often the lasers used in Raman studies
are at wavelengths that stimulate fluorescence. As a phenomenon, fluorescence is approximately 106-
10* times stronger than Raman scattering. There are two approaches to overcoming this problem.
One is to adjust the experimental technique such that fluorescence does not occur, or is much
reduced; i.e., use an excitation wavelength which does not stimulate fluorescence. The other
approach is to extract the Raman signal contained within the fluorescence signal. This approach
includes such techniques as shifted Raman difference spectroscopy (SERDS)', polarization modula-
tion , and picosecond pulsing and gating3 which takes advantage of the disparity between vibrational
and fluorescence lifetimes. However, these approaches require instrumental modifications which can
be costly and complex.
Since Raman signals are very narrow and fluorescence appears as a very broad band, we began to
investigate the possibility of using first derivative spectroscopy, also referred to as edge detection, and
fast Fourier transform (FFT) filtering techniques to discriminate between the two. It was found that
both edge detection and FFT filtering were effective in rejecting fluorescence in spectra exhibiting
reduced noise levels as a result of signal averaging. With regard to edge detection, smoothing the
data prior to taking the derivative greatly improves the final results. The greatest disadvantage of
edge detection is that we are not accustomed to looking at Raman spectra in a derivative representa-
tion. However, with curve-fining, the derivative curves can be converted into conventional Raman
spectra. In FFT filtering, the fluorescence and Raman signals are separated in the Fourier domain,
with the fluorescence occurring at low frequencies. Multiplying the Fourier domain spectrum by a
high pass filter eliminates the low frequency spectral features while allowing the high frequency fea-
tures through thereby rejecting fluorescence. The main advantage of edge detection and FFT filtering
is that they require no modifications of the existing instrumentation. Furthermore, there are commer-
cially available software packages which will lake first derivatives of spectra and perform FFTs on a
real-time basis making it possible to manipulate the spectral data as it is received.
REFERENCES
1. A.P. Shreve, NJ. Cherepy, and R.A. Mamies, Appl. Spectrosc., 46, 708 (1992).
2. S.M. Angel, M.K. DeArmond, K.W. Hanck, and D.W. Wertz, Anal. Chem., 56, 3000
(1984).
3. R.P. van Duyne, D.L. Jeanmaire, and D.F. Shriver, Anal. Chem., 46,213 (1974).
EXPERT AIR MONITORING SYSTEM (EXAMS): AN EXPERT SYSTEM TO
USE FTIR FOR AIR MONITORING
J£. D'Arcy (Afl) and S.P. Levine (A), (A) University of Michigan, School of Public Health, Ann
Arbor, Ml 48109-2029, (B) General Motors Co. Biomedical Research, 30500 Mound Road, Warren,
Ml 48090-9055
The goal of this research was to investigate the feasibility of developing an MS-Windows-based
expert system for monitoring workplace air by FTTR spectrometry. The expert system includes both
expert, algorithmic and blackboard components, as well as a well-developed user interface. The
expert system enables the non-spectroscopist to correctly utilize this powerful analytical technique.
In a complementary fashion, the expert system also allows the non-environmental specialist who has
skills in spectroscopy to correctly interpret the environmental significance of results obtained using
FTTR.
This expert system currently operates in occupational environments with known atmospheric contam-
inants, but with the ability to flag the presence of unanticipated compounds. Decision tracing allows
the experienced user to evaluate the expert system's decisions. Quality assurance methods address
the quality of the reported data.
The expert system was evaluated against previously published results and found to perform as well or
better than the expert spectroscopists. Evaluation of the system using five gas mixtures of varied
complexity against eight expert spectroscopists gave results equal to or better than the experts.
29 Friday, February 24, 1995
-------
Radionuclides
ASSESSMENT OF RADIATION CONTAMINATION AT AN ABANDONED TIN
SMELTER FACILITY IN GALVESTON COUNTY, TEXAS
Joe M. Cornelius, PhD., Ecology and Environment, Inc., Houston, Texas, Thomas P. Laiche,
Ecology and Environment, Inc., Albuquerque, New Mexico, Warren B. Zehner, OSC U.S.
Environmental Protection Agency, Region 6, Houston, Texas
Since 1992 Ecology and Environment, Inc. (E & E) has been conducting a site assessment under the
direction of the Region 6 United Slates Environmental Protection Agency (US EPA) to determine the
nature and extent of radiation contamination at the Tex Tin Corporation Site located in Texas City,
Galveston County, Texas. The site comprises approximately 170 acres and was originally construct-
ed by the US government as a World War D emergency tin supply plant. The facility processed tin
ore from 1941 until 1989, producing Grade A tin ingots and waste products; primarily an iron-rich
acidic liquid and a solid slag. The facility smelted secondary copper from 1989-91. Several haz-
ardous waste units occur on-site, including wastewaler treatment ponds, gypsum slurry ponds, a pond
of acidic liquid waste, several closed acid ponds, drums of spent catalyst material, a licensed radioac-
tive landfill containing depleted uranium, several slag piles with elevated levels of naturally occurring
radioactive materials (NORM), and other slag piles of various sizes.
Elevated gamma radiation levels were identified using rapid field screening surveys with a micro-
Roentgen (uR) meter. Detailed surveys were conducted at locations with radiation levels elevated
above background by recording gamma radiation levels at approximately 15 foot grid intervals using
a uR meter at a height of one meter above the soil surface, and a 1x1 inch sodium iodide (Nal) detec-
tor at the soil surface. Positional coordinates of each survey point were determined using a Global
Positioning System (GPS). All data were recorded on the GPS data logger. Approximately 1500 data
points were collected over 10 acres. Data were analyzed using geostatisucal modeling and kriging to
develop highly accurate contour maps of gamma radiation levels. Radiation levels recorded during
the survey ranged from less than 10 uR/hour (background) to more than 500 uR/hour.
Gamma spectroscopic analysis was performed using a field-portable multichannel analyzer (MAC)
system connected to a 3x3 inch Nal detector. This system was used to determine gamma-emitting
radionuclide composition and activity from samples collected on site. Results from the gamma sur-
vey were used to establish 30 sample locations from which 4-ounce composite samples were collect-
ed. Slag and soil material from an additional 15 sample locations were collected, dried and graded.
The 4-ounce containers were filled with material from eight different particle size fractions from each
location, for a total of 120 samples. MCA spectra were obtained from each sample. Radium-226
activity levels ranged from below detection limits to more than 200 picocuries per gram. Ten percent
of the samples were sent to an outside radiochemistry lab for confirmation analysis. The field screen-
ing results and the laboratory results showed a close correspondence.
Radon flux rates were also measured from slag piles on the site using large area charcoal collectors
(LACCs). For each of three sample dales, forty samples were collected for 24 hours from five loca-
tions. Positional coordinates of sample locations were determined using GPS. Estimated radon flux
rates were less than one picocurie per square meter per second.
FIELD TESTS OF PASSIVE ALPHA DETECTORS AT THE NEVADA TEST
SITE AND THE ROCKY FLATS PLANT FOR SCREENING OF RADIOLOGI-
CALLY CONTAMINATED SOILS
K£. Meyer, R.B. Gammage, and C.S. Dudney, Health Sciences Research Division, Oak Ridge
National Laboratory, Oak Ridge, TN, 3783 J-6379
Two types of passive alpha detectors, developed for indoor radon measurements, have been field test-
ed for applications to screening of alpha-emitting contaminants (e.g. Pu, Am, U, Th) in soils. Electrct
loruzation chambers (EIC's) measure air ionization due to alpha emission from the soil surface, while
Alpha Track Detectors (ATD's) register alpha panicles as microscopic damage pits. The detectors
are inexpensive, rugged, simple to use, and respond reproducibly and linearly over two orders of
magnitude of contamination levels. It was found that alpha emission rates varied widely with soil
composition, so procedures were developed for establishing site-specific detector calibrations. Both
types of detectors were deployed directly on the surface of soils contaminated with Pu-239/240 and
Am 241 at the Nevada Test Site and the Rocky Flats Plant. Deployment times of 5 mms to 72 hours
were necessary in order to reliably detect contamination levels of 200nCi/g down to lOOpCi/g. The
advantages of the EIC detectors were found to be their immediate on-sile readout capability, while the
primary advantages of the ATD detectors were their insensitivity to beta/gamma radiations and ability
to indicate the presence of hot particles. Techniques were developed to discriminate against environ-
mental radon and background o/pVT radiations. ATD's in the form of long narrow strips, deployed in
stake-driven holes, were used to obtain contamination depth profiles quickly and reproducibly.
Progress on the development of a field-deployable ATD etching and analysis system will be reported.
Friday, February 24, 1995 30
-------
Radionuclides
USE OF PASSIVE ALPHA DETECTORS TO SCREEN FOR URANIUM CONTA-
MINATION IN A FIELD AT FERNALD, OHIO
Charles 5. Dudney, K.E. Meyer, KJ). Gammage, and Health Sciences Research Division, Oak Ridge
National Laboratory. Oak Ridge, TN 37831-6379, R.V. Wheeler andM. Salaskey, Landauer, Inc., 2
Science Drive, Glenwood, IL 60425-1586, P. Kotrappa, Rod Elec, Inc., 57I4C, Industry Lane,
Frederick, MD 21701
Among techniques that ire well established for making passive, time-integrated measurements of air-
borne alpha activity in indoor environments, two are readily adaptable to the task of measuring alpha
activity in situ for cases where soil has become contaminated. One technique (Alter and Fleischer,
Health Physics 40:693-702, 1981) involves exposure of small (1cm x 2cm) plastic slabs (called alpha
track detectors or ATDs) to air or soil containing alpha radioactivity which induces radiation damage
sites. Following exposure, chemical etching enlarges the damaged sites. Optical scanning of the etch
pits allows estimation of alpha activity concentration. The other technique (Kotrappa et al.. Health
Physics 41:35-46,1981) involves exposure of small chambers, called electret iomzation chambers
(EICs), holding electrostatically polarized Teflon* discs. Alpha particles entering the air space within
the chamber induce a cloud of secondary electrons that neutralize the charge on the disc. The rale of
discharge is proportional to alpha activity concentration in air or on soil surfaces. Because several
isotopes of uranium give off high energy (4-5 MeV) alpha panicles when the atoms undergo
radioactive decay, it is possible to use either ATDs or EICs to measure uranium contamination in soil.
An integrated demonstration program, hosted by the Fernald Environmental Restoration Management
Company, has been established for investigating technologies applicable to the characterization and
remediation of soils contaminated with uranium. During the summer of 1994, the staff of the inte-
grated demonstration program conducted an intercomparison of several characterization technologies
well-suited to the task of mapping the location and amount of uranium contamination in soil. A site
was selected and prepared. Over a two-month period several technologies were demonstrated. The
hosts prepared a set of homogenized soil samples for calibration purposes to be used by all technolo-
gies. A set of measurement sites were laid out and all technologies were applied to the marked sites.
This paper will present the preliminary results from a field test at Femald in 1993 as well as results
obtained al the intercomparison. Results have shown:
(1) measurement costs are low, around S10 per measurement plus site labor for placement and
retrieval of devices,
(2) calibration coefficients are consistent among soil samples from a particular DOE site but vary
among sites,
(3) moisture condensation occurs on detectors left overnight and this interferes with the measure-
ment process, and
(4) there is very good agreement between the two techniques (r~>0.85).
In addition, measurement accuracies and uncertainties will be discussed.
NON-CONVENTIONAL PASSIVE SENSORS FOR MONITORING TRITIUM ON
SURFACES*
R.B. Gammage, KE. Meyer, and C.S. Dudney, Health Sciences Research Division, Oak Ridge
National Laboratory, P.O. Box 2008, Oak Ridge, Tennessee 37831-6379
This work targets development of two types of small passive, solid-state detectors for in-situ measure-
ment of tritium, or other weak beta-emitting radionuclides, on surfaces. One type of detector, the
exoelectron dosimeter, is "aspirin-tablet" in size and shape; the other type is an electret ionization
chamber (EIC) whose dimensions resemble a "sand dollar." Preliminary testing shows that quantita-
tive measurements are realized with exposure times of only a few tens of minutes and about one hour
with the exoelectron dosimeters and EIC, respectively, (at the DOE release guideline of 5000
dpm/lOOcm2 of fixed beta contamination). Hence it is possible to make quick screening measure-
ments for characterizing the extent and concentration of surface tritium problems or verifying that
post cleanup is satisfactory. Further development is desirable to produce a secure source of thin-layer
exoelectron dosimeter that have improved physical strength. The small size of the detectors allows
deployment in locations difficult to access with gas-flow proportional counters. Both types of inte-
grating device cost only a few dollars and are reusable. Measurements can, therefore, be made in the
field that are faster, cheaper, safer and in several respects, better than those possible with the baseline
monitoring technology.
•Research sponsored by U.S. Department of Energy under contract DE-AC05-84OR21400 with
Martin Marietta Energy Systems, Inc.
31 Friday, February 24, 1995
-------
Methods Comparison
FIELD SCREENING ANALYSIS VS LABORATORY ANALYSIS FOR SOIL AND
GROUNDWATER, A COMPARISON
C. W. Stanley, Hazardous Waste Remedial Action Program, Martin Marietta Energy Systems, Inc ,
Oak Ridge, Tennessee 37831, WL. Wilder, Martin Marietta Energy Systems, Inc, Oak Ridge,
Tennessee 37831, D.B. Bonn, Advanced Sciences, Inc., Oliver Springs, Tennessee
The Hazardous Waste Remedial Actions Program is a federal facilities environmental services center
operated by Martin Marietta Energy Systems, Inc., for the Department of Energy. Since its inception
in 1985, HAZWRAP has conducted Remedial Investigations and environmental studies at more than
500 federal facilities, encompassing thousands of individual sites. As pan of its mission, HAZWRAP
also identifies, evaluates, and demonstrates new and innovative technologies and technical approaches
to address environmental problems.
The goal of optimizing laboratory analysis with field screening of soil and groundwater to delineate
the extent of contamination has been a standard approach of HAZWRAP led investigations for the
past six years. Field screening with analysis has provided a more thorough characterization of conta-
mination, reduced the number of laboratory samples, reduced field iterations, and allowed for more
accurate assessments of site conditions. During that time, differing sampling and analytical tech-
niques have been used to perform field screening on projects throughout the United Stales.
A comprehensive comparison of field screening vs laboratory data for soil and groundwater from
many of these projects is presented to determine the effectiveness of field screening. Factors such as
sample handling, analytical method, soil type, geographic region, and sampling approach will be pre-
sented to identify trends and lessons learned to help verify the utility of field screening and hopefully
to guide future efforts.
The submitted manuscript has been authored by a contractor of the U.S. Government under contract
DE-AC05-84OR21400 with the U.S. Department of Energy. Accordingly, the U.S. Government
retains a paid-up, nonexclusive, irrevocable, worldwide license to publish or reproduce the published
form of this contribution, prepare derivative works, distribute copies to the public, and perform pub-
licly and display publicly, or allow others to do so, for U.S. Government purposes.
COMPARISON OF FIELD SCREENING TECHNIQUES WITH FUEL-CONTAM-
INATED SOILS
Chris Klopp, Wisconsin DNR. and David Turriff, EN CHEM Inc.
Field Screening is an important part of conducting cost effective and comprehensive site investiga-
tions. The use of field screening has been limited compared with its potential role at contaminated
sites. Regulators limit the use of field screening (in lieu of laboratory analyses), in part, because there
is little information on the accuracy and precision of field screening techniques. In addition, soil col-
lection techniques, which are thought to have a significant effect on results, have received little atten-
tion by regulators.
The heterogeneity of the soil matrix makes it difficult to study field screening and soil collection tech-
niques by comparing field and lab analysis of collocated samples taken in the field. Our study used a
technique to homogenize soil samples developed by Paul King of P&D Environmental. This tech-
nique consists of using a mixing barrel that is rotated to equilibrate the soil. To simulate "real" soil
samples, we used soils taken from actual leaking underground storage tank (LUST) sites. After the
soils were equilibrated with respect to concentration, samples were taken for several field screening
techniques, and for laboratory analysis. Separate studies used the same equilibration system to pre-
pare soils for comparison of soil collection techniques.
The field screening techniques compared were:
Field GC
Jar Headspace
Lab in a Bag (1JAB)
Immunoassay
The soil collection methods compared were:
EN CORE sampler
Brass Tube
Graef Anholt Schoelmer (GAS) sampler
Soil Syringe
Spatula
All field screening analyses were performed in triplicate Gasoline contaminated soils were laborato-
ry analyzed using the Wisconsin Modified Gasoline Range Organics (GRO) method in series with
EPA method 8020. Diesel contaminated soils were laboratory analyzed using the Wisconsin
Modified Diesel Range Organics (DRO) method.
Results that will be discussed include:
1. Accuracy and precision of the field screening techniques.
2. Strengths, weaknesses and special considerations of each screening method.
3. Recommendations for appropriate use of each field screening techniques.
4. What methods of sample collection and storage are appropriate when samples won't be analyzed
immediately.
Friday, February 24.1995 32
-------
Methods Comparison
INTERCOMPARISON OF IN SITU MEASUREMENTS OF PETROLEUM
HYDROCARBONS USING A CONE PENETROMETER DEPLOYED LASER-
INDUCED FLUORESCENCE (LIF) SENSOR WITH CONVENTIONAL LABORA-
TORY-BASED MEASUREMENTS
SH. Lieberman, Naval Command Control and Ocean Surveillance Center, RDTAE Division, San
Diego, CA 92152, W.C. McGinnis, Computer Sciences Corporation, San Diego, CA 92110, PM.
Slang and D. McHugh, PRC Environmental Management, Inc., San Diego, CA 92110
The Tri-Service (Army, Navy, Air Force) Site Characterization and Analysis Penetrometer System
(SCAPS) program conducted the first demonstration of the use of real-time chemical sensors
deployed with a cone penetrometer for delineation of subsurface contaminant plumes. The spectro-
scopic based sensor uses an optical Tiber (up to 100 meters long) to transmit 337 nanometer excitation
energy from a pulsed nitrogen laser located at the surface through a sapphire window in the pen-
etrometer probe. Fluorescence induced in aromatic hydrocarbons in the soil that contacts the window
is returned to the surface over a second optical fiber where it is spectrally quantified using a photodi-
ode array detector. Over the last several years this first generation nitrogen laser-based LIF sensor
and more recently the "tunable" wavelength based LIF system have been demonstrated at many dif-
ferent sites. However, until recently, there has not been a well orchestrated effort to compare sensor
results with conventional laboratory-based chemical measurements.
In this paper we report the results of a comprehensive field validation effort in which measurements
from the cone penetrometer deployed LIF sensor are compared directly with results from convention-
al laboratory-based chemical analyses of samples collected using traditional methods. To minimize
spatial and temporal variability associated with sampling, discrete samples were collected immediate-
ly after push measurements by overdrilling the push hole with an auger and collecting soil samples
with a split spoon sampler. Secondary fluorescence measurements were made on splits of the labora-
tory samples to provide direct comparison with laboratory results. All discrete samples were ana
lyzed by EPA methods 418.1. Total Recoverable Petroleum Hydrocarbons (TRPH) and EPA method
8015, Total Petroleum Hydrocarbons (TPH). At some sites samples were also analyzed for Semi-
Volatile Organic Compounds (SVOC), EPA Method 8270, and/or an enhanced 8270 that quantifies
40 individual polynuclear aromatic hydrocarbons (PAHs).
Results from three sites investigated to date (an active fuel tank farm, an abandoned fuel farm and a
fire fighting training facility) indicate that the in situ sensor data agrees with TPH measurements on a
detect/non-detect basis 91% of the time. Fluorescence data agrees with TRPH results 78% of the
time which compares favorably with the agreement (83%) between the two lab methods (TRPH and
TPH). Correlation of quantitative data will also be discussed.
COMPARISON OF SOIL PRESERVATION AND ANALYSIS METHODS FOR
VOC ANALYTES
David Turriff, EN CHEM Inc., and Chris Klopp, Wisconsin DNK
A number of studies have identified a problem with loss of volatiles using traditional VOC methods.
Many of these studies have compared traditional techniques with methods using methanol to preserve
soil samples. A question still to be answered is "How long can VOC samples be held using tradition-
al techniques as compared with methanol preservation methods?" Decisions are made everyday based
on VOC data of questionable validity. It is important that the methods and holding times for volatiles
be founded on scientific data that ensures quality and representative data.
The heterogeneity of the soil matrix makes it difficult to study holding times and compare analytical
techniques using analysis of collocated samples taken in the field. Our study used a technique to
homogenize soil samples developed by Paul King of P&D Environmental. This technique consists of
using a mixing barrel that is rotated to equilibrate the soil. To simulate "real" soil samples, we used
soils taken from actual leaking underground storage tank (LUST) sites. After the soils were equili-
brated with respect to concentration, samples were taken for 3 analytical techniques and several hold-
ing times.
The holding times and analytical techniques used were:
EN CORE Method
Store in EN CORE sampler, methanol preserve, store at 4 C, analyze using Wisconsin Modified
Gasoline Range Organics (GRO) method in series with EPA method 8020 or Wisconsin Modified
Diesel Range Organics (DRO) method. Holding times investigated were immediate preservation, 2
hours, 6 hours, 12 hours, 24 hours, 48 hours, 6 days, 10 days, and 14 days.
WDNR Method
Sample using EN CORE sampler and store in 60 ml VOC vial with headspace in the vial, methanol
preserve, store at 4 C, analyze using Wisconsin Modified GRO method in series with EPA method
8020 or Wisconsin Modified DRO method. Holding times investigated were immediate preservation,
2 hours, 6 hours, 12 hours, 24 hours, 48 hours, 6 days, 10 days, and 14 days.
Traditional "EPA" Method
Sample using a spatula and store in 2 oz jar with no headspace, store at 4 C, subsample and analyze
using Wisconsin Modified GRO method in series with EPA method 8020 or Wisconsin Modified
DRO method. Holding times investigated were 48 hours, 6 days, 14 days.
Results that will be discussed include:
1. Performance of each analytical method.
2. Reasonable holding times for the techniques.
3. The relationship of holding time and sample storage.
33 Friday, February 24, 1995
-------
Data Management and Visualization
PROPER USE OF STATISTICAL ANALYSIS FOR EVALUATING AND MAXI-
MIZING THE UTILITY OF FIELD ANALYTICAL DATA
Thomas L. Francoeur. TerraCHem Consultants. Inc.. P.O. Box 850, Yarmouth, ME 04096, Stephen A
Turner, ABB Environmental Services. Inc., 110 Free Street, Portland, ME 04101, Matthew Hnalov,
Jacobs Engineering Group, Inc., ISO Way cross Road, Cincinnati, OH45240
In the past several years field chemistry has been recognized as an integral component of sue and
remedial investigations. The appeal of these methods has been low cost, rapid turnaround and the
ability to generate many data points. It is common for an investigation using field chemistry to pro-
duce two or three orders of magnitude more data than the traditional off-site laboratory approach for
the same cost This latter point has created an unforeseen and often unaddressed problem of examin-
ing, interpreting and manipulating a large volume of data. Statistical analysis is well-equipped to
address these issues, but only if properly applied. The availability of powerful microcomputers and
software packages offering statistical tools has also increased dramatically over the past few years,
but unfortunately these tools do not address statistical theory concerning when or how to apply the
various tests. Consequently, if statistical theory is applied at all, conclusions are often drawn based
on improperly applied statistical analysis.
This paper focuses on the basic statistical tools available to investigators, as well as when and how
these tools should be applied. Few sets of environmental data are normally distributed (i.e. follow a
Gaussian distribution), yet statistical procedures which assume normally distributed data are arbitrari-
ly and most often applied. This paper examines how to determine whether or not a set of data is nor-
mally distributed, if and how the data can be transformed to meet the assumptions of normality, and
the consequences of using Gaussian-based statistical techniques on non-Gaussian data sets. USEPA
often requires that field analytical results and be compared to off-site results. Based on the observed
distribution, the appropriate statistical technique (analysis of variance [ANOVAJ, non-parametric sta-
tistics, etc.) can be selected. Interpretation of the various statistical tests is also discussed.
Statistical analysis should be applied during the planning stage to ensure sufficient samples will be
collected to achieve a desired level of confidence, during the field work to optimize sampling loca-
tions, and after the field work to determine the reliability and comparability of the data, trends within
the data, or predictive model relationships. This paper discusses several case studies of both correctly
and incorrectly applied statistical analysis, and it will demonstrate how, if correctly applied, statistics
can generate a tremendous cost savings to a project. For example, using statistical analysis, an empiri-
cal, site-specific model was generated illustrating the relationship between total elemental analysis in
the field and TCLP laboratory analysis, thereby reducing laboratory costs by 60%.
Statistical analysis is the "missing link" to an integrated approach to site/remedial investigations using
field analytical data. It is imperative that quantitative statistical methods are used to draw conclusions
from field chemical data that has been generated with extensive QA/QC protocols to be as quantita-
tive as possible. Statistical analysis can be used to extract more information from a given data set
than is readily apparent. This type of analysis and interpretation can also reduce costs and inaccurate
data interpretation by not having to repeat work as a result of lack, or inappropriate application of,
statistical analysis.
ASSESSING THE USABILITY OF X-RAY FLUORESCENCE DATA
Richard W. Chappell, Ph D.. Camp Dresser & McKee Inc., 1331 17lh Street, Suite 1200, Denver,
Colorado 80202.
Energy dispersive X-ray fluorescence (EDXKF) is an important and open essential analytical method
for characterizing inorganic contaminants in soils at hazardous waste sites. Its ability to generate
real-time results at low cost has made EDXRF the typical choice for obtaining field screening data.
These same attributes, along with the availability of more sophisticated instrumentation, have lead to
an increased interest in using EDXRF to obtain high quality data for remedial investigation, remedial
design and remedial action. Often, however, the evaluation of EDXRF data usability compares it
with wet chemical methods and neglects critical data quality issues in risk assessment. Since EDXRF
is a non-contract laboratory program (CLP) method, specific guidance for evaluating data usability is
lacking. This paper examines statistical methods for evaluating EDXRF data usability based on
uncertainty requirements of the baseline risk assessment and remediation process, using data from
several recent soils investigations. Results indicate that evaluation of EDXRF data should emphasize
detection limits, false-positives and false-negatives, along with application of the common CLP data
quality criteria, and that strict reliance on the correlation between EDXRF and CLP (confirmation)
data is often inappropriate. In addition, matrix effects, which are often of concern but seldom proper-
ly addressed, should be evaluated with regard to data quality objectives and inherent spatial variabili-
ty of contaminants. Consideration of these and other issues is important in assessing EDXRF data
quality and establishing a consistent approach for assessing data usability.
Friday, February 24, 1995 34
-------
Data Management and Visualization
THREE-DIMENSIONAL COMPUTER VISUALIZATION OF FIELD SCREEN-
ING INFORMATION: EXAMPLES AND APPLICATIONS
Lorie A. Baiter, P.O., Automated Sciences Group*, Oak Ridge, Tennessee 37831, and Wayne
HammoHS, Analysas Corporation**, Oak Ridge, Tennessee 37830
The first step in conducting environmental investigations is the development of a conceptual model of
the area to be investigated, including the probable distribution of contaminants. Sampling locations
are based on this conceptual model. Field screening techniques allow the investigator to confirm or
revise the conceptual model as the investigation is being conducted and provide the investigator with
real-time information about groundwater contamination at discrete depth intervals. This information
enhances accurate well screen placement and optimization of subsequent well locations. The obvious
benefits of field screening are reducing the time and cost associated with field investigations and
defining the nature and extent of contamination in one field effort.
Groundwater field screening techniques also provide a profusion of information that is essential in
interpreting contaminant fate and transport, selecting remedial alternatives, and designing remediation
systems. 1 •>
-------
X-ray Fluorescence Spectrometry
ASSESSMENT OF LEAD IN SOIL, DUST AND PAINT USING A PORTABLE
HIGH RESOLUTION XRF ANALYSER
Tom Spilller, U.S. EPA Region 1. John Moore Jr., HNU Systems. Inc.
One of ihe most significant changes in the field of Lead Poisoning Prevention is a growing realization
that testing young children for blood lead levels does not prevent children from being exposed but
only hopes to minimize further damage. With nearly 300,000 young children at risk of lead poison-
ing, it is imperative that a new approach be taken. Pretesting of the child's environment prior to it's
6th through 36th months of life, (this is the most critical time because of the characteristic hand-to-
mouth activity such children exhibit) allows the opportunity for appropriate steps to be taken to pre-
vent poisoning. Studies increasingly show that one of the most significant lead exposure pathways is
via soil ingestion. Therefore, testing for lead should encompass the total home environment, includ-
ing both inside and outside testing for lead in paint, housedust, and soil.
The only viable instrument for monitoring lead in paint, soil, and housedust is the portable XRF
analyser. We have tested a new XRF instrument, manufactured by HNU Systems, that has the advan-
tages of easy portability, simple operation, complete data storage, no substrate interferences and good
response to moderate levels of lead in paint, soil and housedust (300-500 ppm range).
With easy to follow procedures for calibration, sample collection and sample analysis, this instrument
allows any user, with proper training, to rapidly perform an assessment of lead in a home environ-
ment. This assessment would be performed both prior to and after any remediation. Post-remediation
assessment is critical since many children are inadvertently poisoned each year by well-meaning
efforts to remove lead paint.
While this study focuses on lead contamination and the role of portable XRF in monitoring and pro-
tection of children, this instrument also has the capability to rapidly assess other heavy metals in envi-
ronmental samples because of the high-resolution capabilities of the detector.
MULTIPHASIC USE OF AN X-MET 880 XRF TO DETECT LEAD IN SOIL AT
THE IDAHO NATIONAL ENGINEERING LABORATORY
Isabel K. Anderson, David F. Gianotto, EG&G Idaho, Inc.. Idaho Falls, Idaho
An X-MET 880 energy dispersive x-ray fluorescence spectrometer (XRF) with dual-source probe was
successfully utilized to characterize two sites of lead contaminated soil at the Idaho National
Engineering Laboratory (1NEL). Tasks in the sampling and analysis plan accomplished using the
XRF included:
• Semi-quantitative screening to determine a) samples sent for SW-846 analysis and
b) locating hot-spots for vertical coring. Semi-quantitative analysis of selected samples
using SW-846 results to develop calibration curve
Quantitative analysis of samples for risk assessment and characterization
• In-situ measurement of asphalt and cement fissures
• Analysis of metal debns removed from the sites for recycling or disposal
A 15-foot systematic grid layout was used to assess the spatial distribution of contamination.
Transects laid along prominent wind directions were used to evaluate the airborne transport of conta-
minants. Subplots were used to estimate the variation in contaminant concentrations between sample
points.
Semi-quantitative soil analyses were performed by calibrating the XRF with similar soil standards,
collecting, sieving, and drying samples, and performing a direct measurement "in the bag". Semi-
quantitative results were used to select samples for SW-846 analysis, which would provide the com-
parative data for site-specific calibration standards (SSCS). The SSCS were used to re-calibrate the
XRF and provide quantitative data for use in nsk assessment and characterization.
The locations of asphalt and concrete fissures were documented to characterize the distribution of
contamination in hard to sample areas. Analyzing scrap metal collected from the sites allowed a
determination to be made if the scrap was lead, and, if so, the purity of the lead.
The X-MET 880 was used for a wide spectrum of needs, providing data in a timely and cost effective
manner. The alternative would have been to collect fewer samples and send the samples for more
costly CLP analysis. Limiting the sample locations may have missed significant hot-spots due to the
heterogeneous nature of each site.
Friday, February 24, 1995 36
-------
X-ray Fluorescence Spectrometry
PORTABLE X-RAY FLUORESCENCE SPECTROMETRY IN SUPPORT OF A
SUPERFUND ACCELERATED CLEAN-UP MODEL (SACM) PROJECT - A
CASE STUDY
L.P. Kaelin, Roy F. Weslon. Inc., Edison, NJ 08S37, G. Powell and G. Prince, U.S. Environmental
Protection Agency Environmental Response Team, Edison, NJ 08837, S. Hawthorn, U.S.
Environmental Protection Agency Region VIII, Denver, CO 80202, and D. Taylor, Utah Department
of Environmental Quality, Salt Lake City, UT84114
The U.S. Environmental Protection Agency (U.S. EPA), in an effort to accelerate the assessment and
remediation of Superfund sites, has developed a fast track program called the Superfund Accelerated
Clean-Up Model (SACM). The purpose of SACM is to pull together various existing programs
under a single umbrella to streamline the administrative and discuss making process, thereby reduc-
ing site clean-up time and costs.
Innovative screening methods, such as field portable x-ray fluorescence spectrometry (FPXRF), were
used at a SACM site called Salt Lake Valley Smelters (SLVS) to delineate the extent of lead contam-
ination in surface soils. Over 1700 surface soil samples were collected, analyzed and depicted, using
geo-statistical modelling software, during a two week period in July 1992, at the SLVS site. Salt
Lake County, Utah.
An inter-agency SACM task force was assembled to assess the extent of lead contamination due to
historic lead smelting activities. The SLVS SACM task force was spearheaded by Region VHI of the
U.S. Environmental Protection Agency (U.S. EPA) and the Utah Department of Environmental
Quality (UDEQ). Technical support was provided by the U.S. EPA Environmental Response Team
(U.S. EPA/ERT). This support included sample preparation and the use of four FPXRF by field
chemists and technicians from WESTON's Response Engineering and Analytical Contract (REAC)
and Technical Assistance Team (TAT) projects. In addition, the U.S. EPA/ERT and REAC provided
daily on-site posting and modelling of FPXRF data, which aided in directing sampling efforts for the
following day.
Sampling of surface soils from 15 separate abandoned or inactive smelter sites, grouped into 8 differ-
ent area, over an area of several square miles, was performed by the U.S. EPA Region VHI TATs,
the UDEQ, the U.S. EPA/ERT, and the U.S. Coast Guard Pacific Coast Strike Team.
Sample management, tracking and quality assurance and control (QA/QC) were of paramount con-
cern. Numerous agencies were collecting and submitting samples from difference areas, at the same
time. In addition, the progress of the sampling efforts, and the distribution of lead contamination
needed to be assessed daily in order to properly schedule man-power and materials, as well as
address public right-to-know concerns.
A unique sample code was developed which would identify a specific area location and its northing
(y) and easting (x) coordinates on a systematic grid which was laid out over each of the 8 areas.
Once collected and labelled, the sample could be tracked during the preparation, FPXRF analysis,
data reduction, posting and modelling phases, on a daily basis. A software program was written to
download the data from the FPXRFs to directly generate files that could be print FPXRF results for
immediate use, and files that could be imported into the geo-statistical modeling programs. The pro-
gram not only eliminated transcription errors, but also reduced the time necessary for the daily post-
ing and modelling of FPXRF data.
FPXRFs lend themselves to the rapid generation of on-site data. This data can be used to determine
spacial distribution of metals, and to direct future site activities on a daily basis. QA/QC protocols
were developed in continually ensure data integrity, and the proper use of the FPXRFs
instrumc"! , : .
SCREENING FOR METALS IN VARIOUS MATRICES BY PORTABLE X-RAY
FLUORESCENCE SPECTROMETRY/SINGLE REFERENCE STANDARD CALI-
BRATION
Alan D. Hewitt, U.S. Army Cold Regions Research and Engineering Laboratory, 72 Lyme Road,
Hanover, NH. 03755-1290
X-ray fluorescence (XRF) spectrometry is a nondestructive method of total metal analysis that may
require very little sample preparation. For this reason, XRF has been used to identify and quantify
metals in solid matrices during remedial investigations and feasibility studies (RI/FS) of suspected
hazardous waste sites. Most past studies with field-portable XRF analysis have relied on matrix
matched standards for either the fundamental parameter or empirical coefficients methods of instru-
mental calibration. The paucity of certified reference materials currently available for fundamental
parameter applications and the need to prepare multiple sets of standards for empirical coefficient
analyses can delay the initiation of a site investigation by several weeks when several sample matri-
ces are encountered.
To avoid delays at the start of a site investigation, an alternative instrumental calibration method has
been proposed that requires only a single reference material of with a particle size (5600 mm) and
moisture content similar to those of the samples to be analyzed. This reference material is used to
establish element-specific response factors and the corresponding Compton Ka peak intensity. The
latter parameter is used for correcting matrix differences between the reference standard and the sam-
ples.
This study was conducted to evaluate the single standard/incoherent (Compton KO) backscattering
normalization approach for quantifying metals in certified, field- and laboratory-prepared environ-
mental samples. The results obtained using this method of calibration satisfied the data quality objec-
tives for field screening of soils, dust, paint chips, and incinerated sludge sample matrices. These
findings, along with a description of this alternative XRF calibration method, will be presented.
37 Friday, February 24, 1995
-------
Air Monitoring Technologies
HIGH-SPEED GAS CHROMATOGRAPHY AIR MONITORING INSTRUMENT
FOR SITE REMEDIATION AND HAZARDOUS WASTE DISPOSAL APPLICA-
TIONS
Richard D. Sacks, Department of Chemistry, University of Michigan, Ann Arbor, Michigan,
48109-1055, Mark A. Klemp, Chromalofasl. Inc., 912 N. Mam Street, Suite 14, Ann Arbor,
Michigan, 48104
Contaminated site remediation and hazardous waste disposal activities pose considerable health risks
to workers as well as to communities down wind from these activities. Special clothing and other
safety precautions often are required to minimize potential worker exposure. Often these safety pre-
cautions reduce the efficiency of the remediation and cleanup activities. Improved, real-time monitor-
ing of ambient air is necessary in order to reduce these health risks and improve the efficiency of
these activities. Since many of the volatile organic compounds (VOCs) pose significant risks at even
very low concentrations, high sensitivity monitoring techniques are required. In addition, because of
the wide range of possible contaminants, high specificity is important for the reliable assessment of
potential worker and adjacent community exposure.
Gas chromatography (GC) is used frequently for the analysis of VOCs. GC is characterized by high
sensitivity, excellent selectivity, good accuracy and precision and excessively long analysis times.
Recently, high-speed GC instruments have been developed which use a gas cooled and electrically
heated cryotrapping device for sample gas collection and introduction. The metal cold trap tube is
cooled by a continuous flow of cold gas. A vacuum pump is used to pull ambient air into the trap
tube. Following sample collection, the flow direction through the trap tube is reversed, and the tube
is rapidly heated using a capacitive discharge power supply. This results in the generation of a very
narrow sample vapor plug which is introduced into the separation column.
Design features and preliminary results will be presented for a high-speed GC instrument for ambient
air monitoring. The instrument is designed for high-speed analysis with a cycle time of about ten sec-
onds. A relatively short capillary separation column is used with unusually high earner gas flow
rates. While complete separation of all components may not be obtained on this timeframe, decision
quality data is generated regarding contamination levels. Since sample vapor is cryointegrated (pre-
concentrated) in the cold trap tube, detection limits (volume/volume basis) in the low ppb range are
obtained for most VOCs. Lower detection limits with enhanced selectivity for aromatic compounds
and for chlorinated hydrocarbon compounds can be achieved with high-speed GC by the use of pho-
toionization detectors and electron capture detectors, respectively. However, because of the very
short timeframe of these measurements, chromatographic performance may be sacrificed. These
trade-offs will be discussed. The cryofocusing sample collection and inlet system descried here has
good tolerance for water vapor, and water saturated samples up to about 1.0 mL can be collected and
introduced into the high-speed GC instrument with minimal loss in sample collection and chromato-
graphic performance. Data comparing dry and water saturated samples will be presented.
An important advantage of the high-speed GC air monitoring instrument is higher sensitivity than can
be achieved with either User based spectroscopes or solid slate sensors. By the use of selective
detectors, greater specificity also can be achieved than with these other methods. These features
should significantly reduce the risk of worker and adjacent community exposure to VOCs during site
remediation and hazardous waste cleanup activities.
A MOBILE C02-LIDAR-SYSTEM FOR THE MONITORING OF HAZARDOUS
TRACE GASES IN INDUSTRIAL AREAS
T. Stuffier, V. Klein, M. Kesch, Kayser-Threde GmbH, Wolfratshauserstr. 44, 81379 Munchen
A compact, tunable CO2 lidar system for field use has been developed. This instrument will be used
to monitor e.g. halogenated ethane, halogenated methane, ammonia and ozone in the vicinity of
industrial areas. The measurement principle is based on the DAS-technique (Differential Absorption
Spectroscopy) in the spectral range from 9-11 urn for a maximum distance of 5 km.
In a first step topographic targets are used as diffuse reflectors, that means the results of the measure-
ments are path integrated concentrations of the detected gas. The topographic targets deliver high,
reliable and stable signals which leads to a high SNR and therefore to low detection limits for the
trace gases. In a next step a range resolved system is planned, which should be combined with a
FTIR-interferometer as a powerful station for environmental monitoring.
The heart of the lidar is a compact dual chamber CO2 laser, delivering two parallel laser beams. Both
lasers share a common gas volume and can be triggered independently with a pulse repetition rale for
each laser of up to 30 Hz (burst mode for 10 seconds: 100 Hz). Since the laser is air cooled, auxiliary
devices such as circulator pumps, cooling hoses elc. are not needed. The resonator consists of the
discharge gaps, two reflective gratings (135 grooves/mm) for the spectral tuning and two highly
reflecuve oulpul couplers (R=80%, f=10m). The length of the resonator is 0.7 m. The iwo laser
beams are s-polarized and are combined by a special beam combining optics.
This syslem can be operated with a LCD-touchscreen (64 sensible fields), which is integrated in an
industrial PC (VME bus). Therefore it is not necessary to use an external keyboard or a monitor to
run the lidar. The results of the measurements can also be shown on the LCD-screen.
In comparison to other lidar systems this device is remarkably smaller and lighter thus resulting in
significant flexibility. The compact size of the syslem makes the use and handling easier, h increas-
es the mobility and leads to a shorter lime of access 10 measurement results.
The concept of combining the CO2 lidar system and a FTIR interferometer would unit in a useful way
the analytical capability of a FTIR (complete spectral coverage from 2 um up to about 15 um) and the
possibilities of operating a range resolving CO2 lidar system (active sounding).
41 Wednesday, February 22, 1995
-------
Air Monitoring Technologies
PASSIVE FT-IR FOR ATMOSPHERIC ASSESSMENT OF VOLATILE ORGANIC
COMPOUNDS (VOCs)
C.T. Chaffin, TL. Marshall, AeroSurvey, Inc.. P.O. Box 1163, Manhattan, KS 66502, W.G. Fateley,
KM. Hammaker, Department of Chemistry, WillardHall, Kansas Stale University, Manhattan, KS
66506
With the success and acceptance of active open-path FT-IR atmospheric monitoring techniques in
recent years, interest has been building in the potential of passive FT-IR techniques for site character-
ization and regulatory applications. Although much of the instrumentation and theory involved in
active and passive FT-IR atmospheric monitoring are similar, passive FT-IR analyses offer additional
challenges which must be addressed if passive techniques are to be developed for routine use.
In this talk, the similarities and differences between active and passive FT-IR atmospheric monitoring
will be discussed. The results of recent field investigations will be used to illustrate the additional
problems associated with passive analysis as well as to provide a realistic estimate of the potential
performance of passive FT-IR techniques in many applications with current instrumentation.
MOBILE MONITORING TO IDENTIFY SOURCES AND EVALUATE IMPACT:
A RECEPTOR MODELING STUDY USING THE TAGA 6000E
Gregory M. Zarus, Scott A Wagaman, David B. Mickunas, Mark Bernick, Roy F. Weslon, IncJREAC.
and Rodney Turpin, U.S. EPAlERT, 2890 Woodbridge Ave.. Edison, NJ 08837-3679
A receptor modeling procedure has been developed in conjunction with mobile monitoring to identify
and quantify emissions from sites with several potential sources. The characterization of these
sources allows for the evaluation of the impact of their emissions. The combination of mobile moni-
toring and modeling provides an accurate account of each source's contribution to the ambient air
quality using data received during initial monitoring runs and confirms the results provided by subse-
quent monitoring runs.
The modeling employs the Fugitive Dust Model (FDM) because of its iterative area source algorithm
and its versatility to evaluate impacts of paniculate or vaporous emissions. Emissions from the poten-
tial sources were umlized in order to estimate their relative impact on the downwind receptors.
Mobile monitoring was conducted using the Sciex™ Trace Atmospheric Gas Analyzer (TAGA)
6000E, a mass spectrometer/mass spectrometer (MS/MS). The TAGA collected and determined the
concentrations of selected VOCs at 2.25 second intervals during mobile monitoring at the receptors of
interest. This report will focus on the detection and dispersion of vinyl chloride/1,2-dichloroethane.
The TAGA data revealed concentration distributions skewed in manners which implied that the cross
sections of the plumes were taken from several angles. Each plume's cross section was then separat-
ed and compared against concentrations calculated by the model. The potential sources whose pre-
dicted concentrations did not correlate to the observed concentrations were disregarded. The emis-
sion rales of those that showed good correlation were scaled to produce receptor concentrations simi-
lar to those observed by the TAGA.
After all of the sources were identified and their emissions quantified, the impact on receptors within
the neighborhood were estimated. The concentrations estimated by this procedure were then com-
pared to those collected by the TAGA during later sampling runs. The predicted average concentra-
tion across the plume was within ±5 percent of the plume-averaged TAGA values and the predicted
peak concentrations were underestimated by 25 percent. These values fall well within acceptable val-
ues for modeling.
TAGA mobile monitoring provides an exceptional database for locating and evaluating sources
because each datum is supported by an adjacent datum (2.25 seconds apart); this not only provides a
quantity at a specific geographic location but allows for the determination, in a Lagrangian sense, of
where that geographic position is located within the plume. The tandem use of modeling and TAGA
mobile monitoring provides an excellent method for evaluating impacts from sites with numerous
potential sources because it:
removes the need for sampling at each source individually,
• provides a method for self verification, and
• does not produce unrealizable extrapolation of results beyond the fenceline.
Wednesday, February 22, 1995 42
-------
Case Studies and Practical Applications
FIELD VALIDATION OF GORE-SORBERSM SCREENING SURVEYS AT SITES
CONTAINING HIGH MOLECULAR WEIGHT PETROLEUM PRODUCTS
Mark B. Stutman, Mark J. Wrigley, P.G., Environmental Products Group, W.L Gore
-------
Case Studies and Practical Applications
10
COMPARISON OF MEASUREMENTS WITH PETROSENSE* PORTABLE
HYDROCARBON ANALYZER (PHA-100) AND LABORATORY ANALYSIS OF
BAILED SAMPLES (EPA METHOD 8015M) WHEN USED IN MONITORING
SPARGING PROCESS
Thomas Wing, FCI Environmental, Inc., 1181 Crier Drive, Building B, Las Vegas, Nevada 89119,
and Michael A. Sword, EJ.T., Converse Environmental Consultants Southwest, 4670 South Polaris
Avenue, Las Vegas, Nevada 89103-5615
The PetroSense* PHA-100 portable hydrocaibon analyzer has been used in a project lo measure the
concentration of hydrocarbons at an inactive UST site, and in another project to give real time infor-
mation regarding sparging. The measurements made by the PHA-100 were compared to a gas chro-
malographic (GC) analysis performed by an independent commercial laboratory using EPA Method
8015M and EPA Method 624.
There are two popular methods for removing hydrocarbons and other contaminants from water being
evaluated. One is use of pump and treatment with carbon or air stripping, and the other is use of a
sparging process consisting of injecting air through the water to strip them. The sparging process
consists of drilling wells into the contaminated water, injecting air into one well, and monitoring the
other wells placed around the injection well for both the amounts of air flow, and measuring the cont-
amination levels. The current process to determine the contaminant level is taking samples according
to EPA Method 8015M and EPA Method 624 to obtain concentration levels, which can take from one
to ten days.
The use of the analyzer in a sparging application was to provide a relative reading of the concentra-
tion levels in real time to assist in process evaluation. Measurements with the PHA-100 analyzer can
be either absolute or relative. Analytical operation will give (based on a p-xylene equivalent) read-
ings within a ± 3ppm accuracy in water and ±100ppm in vapor. The typical relaUve screening read-
ings are for determining if hydrocarbons are present, and whether the concentration is increasing or
decreasing.
The readings confirmed that the sparging process was working. The levels of hydrocarbons measured
15ppm and were decreasing, indicating that the hydrocarbon envelop was moving. Using the real time
information, the technician was able to quickly confirm process operation.
**
The ability to obtain quick relative reading in direct PPM readings is extremely useful in the field.
The analyzer readings were able to provide immediate values to help determine if the process was
working, and help trouble shoot problems with the installation. The analyzer values will not provide
the absolute values required for determining if a site has been cleaned, but by correlation with the lab-
oratory results, will provide indications of progress. The final determination will still have to be
accomplished through normal laboratory controlled analyses, but the value of being able to determine
if the process is working quickly without waiting for lab analysis definitely provides real value in
having such an analyzer as a standard field tool.
Based on the study of the two projects, the real time measurements should reduce the costs of labora-
tory analysis on larger projects. ,
FIBER OPTIC CHEMICAL SENSOR (FOCS™) TECHNOLOGY FOR THE
DETECTION OF HYDROCARBONS IN AIR AND DISSOLVED IN WATER:
PETROSENSE* PORTABLE HYDROCARBON ANALYZER (PHA 100) AND
THE PETROSENSE* CMS 5000
Devinder P. Saini, Roger Himka, and Stan Klainer, FCI Environmental, 1181 Grier Drive, Building
B, Las Vegas, Nevada 89119
Due to the ever increasing pollution created by hydrocarbon storage and transport, there is a need for
rapid sensing results, and low cost field instrumentation. The information acquired by the instrumen-
tation needs to be real time, accurate and reliable. This information should be obtained in-situ for the
best possible results.
The PetroSense* Portable Hydrocarbon Analyzer (PHA 100) and the PetroSense* CMS 5000 for
continuous monitoring, are instruments which can detect the presence of hydrocarbons dissolved in
water as well as detect hydrocarbons in the air. They allow the user to obtain real time in situ data on
hydrocarbon levels present. They can also measure the progress of any remediation that is occurring.
Both the PetroSense* PHA 100 and the PetroSense* CMS 5000 use fiber optic chemical sensor
(FOCS ) technology. The refractive index of a proprietary coating on the side of an optical fiber is
modified by the presence of hydrocarbons. This modification results in a change of light received by
a photo detector. The change in the light signal is proportional lo the concentration of hydrocarbons
present in water or air. The fiber is housed in a probe which also contains the electronics. The probe
is rugged and water proof.
In this paper we will discuss in detail the fiber optic chemical sensor (FOCS ) technology used, its
advantages and disadvantages over the existing technology, and the performance of the probes and
instruments in the laboratory and the field will also be discussed.
Wednesday, February 22, 1995 44
-------
Case Studies and Practical Applications
11
12
THE ROLE OF OPTICAL CHEMICAL SENSORS IN ENVIRONMENTAL
APPLICATIONS
Stanley M. Klainer and Devinder Saini, FCI Environmental, Inc.. 1181 Crier Drive. Building B, Las
Vegas. Nevada 89 J19
With the ever increasing regulations on pollution control there now exists an increasing demand for
sensors to detect pollution in the environment. Manufacturers are required by the EPA to quantify
their emissions of over 300 toxic chemicals that arc discharged, recycled or disposed of. For the
emissions to be properly quantified there is a need for instrumentation that can be used in-situ in the
field to provide real time information.
Most analytical methods used today are not suitable for the field. They were primarily designed for
the laboratory, and are not easily transferable to the field. There is clearly a need for new technolo-
gies to step in and fill the gap that now exists between what is required and what is achievable.
Optical sensor technology is something that could fill the gap. Some of the most sensitive analytical
techniques, such as Fluorescence, Absorption and Refractive index, are based on optics. FCI
Environmental has recently introduced two instruments that can measure dissolved hydrocarbons in
water as well as in the air. These instruments are the PetroSense Portable Hydrocarbon Analyzer
(PHA 100) and the PetroSense* CMS 5000 for continuous monitoring of hydrocarbons. They pro-
vide real time in-situ data on the hydrocarbon levels present in water and air.
In this paper we will be discussing new sensors that will meet the needs of the industry. These will
include multi parameter probes with optical sensors that can sense more than one pollutant. Sensors
for heavy metals, oxygen. Carbon dioxide etc. The requirements for a good field sensor and Us appli-
cation in the real environment will also be discussed.
USE OF FIELD SCREENING TO DELINEATE A LOW-LEVEL GROUND-
WATER PLUME OF ETHYLENE DIBROMIDE
Michael J. Gunderson, Hazardous Waste Remedial Actions Program, Martin Marietta Energy
Systems, Inc., Oak Ridge, Tennessee, Nelson M. Breton, ABB Environmental Services, Inc., Portland,
Maine, Edward L. Pesce, National Guard Bureau, Olis Air National Guard Base, Massachusetts
During routine groundwaler sampling of monitoring wells downgradient of a groundwaler extraction
system under construction at the Massachusetts Military Reservation, trace levels of ethylene dibro-
mide (EDB) were discovered in one monitoring well. The groundwaler extraction system was
designed to contain a chlorinated solvent (predominantly dichloroethylene, trichloroethylene, and
tetrachloroethylene) plume. The occurrence of EDB was not anticipated and had only recently been
added as a contaminant of concern for ongoing Base investigations. Because of its low state regulato-
ry limit in groundwaler (0.02 ug/L) and potential impact on the location of the extraction system, a
two-phased field screening approach was undertaken to confirm the presence/absence and extent of
BOB. The initial field effort consisted of sampling and analysis of existing wells to confirm the
detection and determine if an upgradiem source could be identified.
Approximately 30 samples were sent to a local laboratory for analysis of EDB and volatile organic
compounds (VOCs). The sampling confirmed the EDB previously detected; however, other EDB
analytical results were negative at a detection limit of 0.01 pg/L. With regulatory concurrence, an
investigation to determine the extent of the EDB contamination in the vicinity of the extraction sys-
tem and potential impact on design was undertaken. The investigation relied on screened hollow-
stem auger sampling of groundwaler at discrete intervals with on-site analysis of EDB and VOCs
(modified EPA Methods 504 and 8010/8020). The detection limit for EDB was 0.005 ug/L.
Confirmation samples (10% of total screening samples) were collected and submitted to a fixed-base
laboratory (EPA Methods 504 and 8010/8020) to support the field screening data. Construction of
the extraction system was delayed during the investigation. Eight deep (i.e., approximately 200 ft)
screened auger borings were sampled at ten ft intervals to delineate the extent of the EDB and VOC
contamination and to determine its relationship to the chlorinated solvent plume targeted for
extraction.
Field screening results confirmed that EDB and VOCs were downgradient of the extraction system.
Based on the screening data of compounds detected, the relative concentrations of the VOCs, and the
intervals of detection, it was concluded that the EDB and VOCs represented a separate contaminant
plume deeper in the aquifer than the solvent plume. These conclusions were later confirmed with
Contract Laboratory Program (CLP) samples collected from new and existing wells. Based on field
screening data and with regulatory concurrence, it was determined that the extraction system design
would not require modification. The delay in the extraction system construction totalled 66 days with
an additional cost of $10,800. However, the use of screening data versus CLP data saved approxi-
mately 60 days. This would have severely impacted the construction schedule and resulted in signifi-
cant additional costs.
45 Wednesday, February 22, 1995
-------
Case Studies and Practical Applications
13
14
CASE STUDIES ON SCREENING SOIL SAMPLES FOR TNT AND CHLOR-
DANE AND PRACTICAL ASPECTS FOR BRINGING THESE FIELD SCREEN-
ING METHODS INTO THE LABORATORY
Dennis Hooton, Midwest Research Institute, Kansas City, Missouri, 64110
The objective of this paper is to sh»re specific experiences with screening analyses for explosives
(TNT) and pesticide (chlordane) residues in soil matrices. In addition, the paper will include a dis-
cussion of the practical aspects of adapting these analytical methods for screening purposes and the
QA/QC aspects of performing this work under restrictive time and cost limitations.
Over the last several years. Midwest Research Institute (MRI) has analyzed hundreds of soil samples
for various regulatory-based programs. Quality control data will be presented to show method preci-
sion, matrix effects, and spiked chemical recovery that have been achieved for this work. In addition.
data will also be presented for representative samples which have been reanalyzed using EPA
methodologies to confirm the absence or concentration of the screened analytes.
MRI has been successful in effectively controlling operational factors which impact cost and tune of
analyses. In the absence of a fully functional on-site laboratory, alternatives are suggested which
make it possible to provide valid analysis results within 24 hours of sample collection, including
transport to the laboratory. Options and alternatives will be discussed for data validation and commu-
nication of results to help stream-line the reporting process without sacrificing data quality and docu-
mentary evidence.
This paper provides further support for the use of screening methods as a tool in environmental inves-
tigations, improving a program's effectiveness through a broader-base of sample results and more
selective use of expensive EPA methods for confirmations! analyses.
AIR MONITORING AND SAMPLING TECHNIQUES USED IN SUPPORT OF A
CLEANUP ACTION AT AN INACTIVE DRUM RECYCLING FACILITY
Alan Humphrey, U.S. EPA/Environmental Response Team, 2890 Woodbridge Ave., Edison, NJ 08837,
Steven P. Schuetz, Philip Solinski, David Mickunas, Roy F. Westoni'Response, Engineering, and
Analytical Contract, 2890 Woodbridge Ave., Edison, NJ 08837
The U.S. Environmental Protection Agency Environmental Response Team (ERT) is a national and
international response team utilized by the U.S. EPA, as well, as other federal, state and local agen-
cies, whenever they encounter particularly dangerous or technically complex situations. The U.S.
EPA Region VIII On-Scene Coordinator (OSC) requested the assistance of the U.S. EPA/ERT and its
Response, Engineering and Analytical Contract (REAC) to perform air sampling/monitoring for
volatile organic compounds (VOCs) and sulfur containing compounds during soil removal and solidi-
fication activities at an abandoned drum recycling site.
The main objective of the air monitoring and sampling during three phases of work was to provide
quality data immediately or within hours to effectively direct cleanup activities and ensure the safety
of the nearby workers and citizens. As the work proceeded, problem compounds with low odor
thresholds were discovered, slowing the cleanup and creating more demand for field analytical tech-
niques with sensitivity and selectivity for the target compounds of concern. An overview of each
phase of site cleanup and associated air monitoring/sampling is presented. Selected equipment and
techniques which provided rapid data on-site will be highlighted and the results briefly discussed.
Wednesday, February 22, 1995 46
-------
Case Studies and Practical Applications
15
16
FIELD GAS CHROMATOGRAPHY ANALYSIS AS INPUT FOR VADOSE ZONE
MODELING: A CASE STUDY
Daniel B. Oakley, Hazardous Waste Remedial Action Program, Martin Marietta Energy Systems,
Inc., Oak Ridge, Tennessee, and Mark Gardiner, IT Corporation, Knoxville, Tennessee
Many field programs use relatively inexpensive field screening techniques to gather a large data base.
Typically, confirmation samples are selected for laboratory analysis based on these screening data,
and this practice significantly increases project costs. At Williams Air Force Base (AFB) in Mesa,
Arizona, jet fuel contamination in the vadose zone was characterized using field gas chromatograph
(GC) analysis only. Because of the thick vadose zone at Williams AFB (210 ft), it was desirable to
develop a field program that gathered enough data to adequately characterize the site for multiphase
flow and transport modeling in a cost-effective manner.
Because the data would be used only as input into the modeling effort, the project team decided to
maximize the amount of field screening data while eliminating the fixed-base laboratory data. The
field program included drilling 15 borings to the groundwater table (210 ft), collecting split-spoon
soil samples at 10-ft intervals, and analyzing all samples for total petroleum hydrocarbons (Modified
8015 JP-4 standard) and benzene, toluene, ethylbenzene, and xylenes (Method 8020) using an on-sue
field GC. Because of the large quantity of samples, field GC costs were approximately one-half of
fixed-base laboratory costs. Additional soil samples were collected for geotechnical analyses, thus
providing additional model input parameters including vertical hydraulic conductivity, grain-size
analysis, porosity, and bulk density. The data were input into the two-dimensional Multiphase Flow
and Transport Computer Model (MOTRANS). The model was calibrated to existing site conditions
by simulating a jet fuel spill near ground surface and projecting migration for 20 years. This corre-
sponds to the estimated amount of time since the first fuel spill. The modeled jet fuel distribution in
the vadose zone closely resembles the existing distribution as determined by field GC analysis.
Because the model can reproduce current conditions by simulating a historical spill, there is increased
confidence in model predictions of future fuel migration. MOTRANS does predict that the fuel will
continue to migrate through the vadose zone and impact groundwater for the next 25 years.
This project demonstrates the successful delineation of a thick vadose zone using cost-efficient field
GC methods only for chemical analysis. By reproducing a historical spill at the site, modeling accu-
rately simulated the subsurface distribution of fuel contamination as determined by field GC analysis
of subsurface soil samples. This accurate simulation of known conditions provides confidence in the
model predictions of fuel migration in the vadose zone for the next 25 years.
The submitted manuscript has been authored by a contractor of the U.S. Government under contract
DE-AC05-84OR21400 with the U.S. Department of Energy. Accordingly, the U.S. Government
retains a paid-up, nonexclusive, irrevocable, worldwide license to publish or reproduce the published
form of this contribution, prepare derivative works, distribute copies to the public, and perform pub-
licly and display publicly, or allow others to do so, for U.S. Government purposes.
A PRACTICAL APPLICATION OF HEWITT'S AQUEOUS EXTRACTION
AND HEADSPACE FIELD GC SCREENING TECHNIQUE FOR VOCs IN SOIL
SAMPLES
Laurie H. Ekes, Seth Frisbie, PhD, and Craig MacPhee. ENSR Consulting and Engineering, 35
Nagog Park, Acton, MA 01720
A site for a confidential client consists of approximately nine (9) acres in the Upper Peninsula of
Michigan. Since the 1930's, the site was used for the disposal of wood tar wastes from the produc-
tion of charcoal briquettes and chemicals derived from wood. Following evaluation of several reme-
dial alternatives; excavation, removal, shipment by rail and landfdling of the wood tar materials was
selected as the most viable solution. The recommended approach was reviewed by Michigan
Department of Natural Resources (MDNR) and ENSR was the designated engineer and construction
manager for this project.
The major task of the interim response required removal of all visibly contaminated material (over
70,000 tons) while minimizing potential community impacts. Toxic Characteristic Leaching
Procedure (TCLP) regulatory levels for volatile organic compounds were used as guidelines for load-
ing the tar waste.
In order to assure that material being loaded into railroad cars met the waste characteristic require-
ments of the landfill to which it was being sent and to assure that it was properly manifested as non-
hazardous; ENSR successfully employed a Photovac Model lOSPlus field GC with a Photoionizalion
detector (PID) to screen large quantities of soil samples. The screening method is a modification of
the EPA medium level VOC soil analysis and includes soil sample preservation and extraction into
methanol with subsequent analysis of an aliquot of the extract headspace equilibrium over 30 ml of
water in a 40 ml VGA vial. Total analysis time per sample was under 20 minutes. Analytical proto-
col will be presented with associated quality assurance/quality control data for samples from this site.
Ten percent of the samples were sent for laboratory confirmation by EPA method SW846/8240. This
comparison data will also be presented.
Use of this field screening during one of the most severe winters in the Upper Peninsula saved the
client over $200,000 in laboratory costs and enabled work to progress in a timely fashion with mini-
mal impacts on the surrounding community.
47 Wednesday, February 22, 1995
-------
Case Studies and Practical Applications
17
GAS CHROMATOGRAPHIC MONITORING OF TANK HEADSPACE VAPOR
SAMPLE QUALITY
Rampur S. Viswanalh*. Richard A. Westberg, Weslinghouse Hanford Company, Special Analytical
Studies. P.O. Box 1970. MISN: S3-90, Richland. Washington. 99352.
Hanford site situated in the south central part of Washington State was used for nuclear material pro-
cessing beginning in the early forties. The chemicals and solvents used in the nuclear material pro-
cessing generated large amount of waste. The chemical waste has been stored in large tanks (0.5 to
1.0 million gallon capacity) since then. Many of these tanks are about SO years old. The determina-
tion of tank headspace vapor composition is extremely complex and important since this information
has a potential to help resolve critical safety issues such as: hydrogen generation, flammable gases,
and noxious vapors. This information on vapor phase composition of inorganic and organic com-
pounds is essential to help develop a strategy for safe storage of waste in the tanks, for long periods
of time. In view of the nature of the problems, complexity, and sensitivity associated with such tanks,
characterization of the tank headspace vapors pose several challenges. Such as, little information is
known about the nature of the tank waste and chemical pathways which generate noxious vapors, the
potential for explosion or flammability, and employee exposure to toxic vapors and radiation. This
paper presents the data on the use of a heated probe to draw tank headspace vapor sample; a heated
manifold mounted on a field sampling truck for automated sample collection using a series of valves,
flow controllers, pressure transducers, and thermocouples; SUMMA canisters and sorbant tubes as
media for sample collection; and a gas chromatograph for checking the vapor sample integrity/unifor-
mity. This presentation focusses on the gas chromatographic data in particular, and attempts to
describe a mechanism to monitor the vapor sample quality, by determining the total non-methane
organic compounds in the sample stream.
* Principal Author
Wednesday, February 22, 1995 48
-------
Chemical Sensors
18
19
ADAPTING THE BRUEL & KJAER MULTI-GAS MONITOR-TYPE 1302 TO
MEASURE SELECTED VOLATILE ORGANIC CHEMICALS (VOCs) IN SOIL
MA. Palauskyf, L.C. Waters', K.W. Counts2 and KA. Jenkins1, Chemical and Analytical Sciences
Division , and Computing and Telecommunications Division , Oak Ridge National Laboratory, Oak
Ridge, TN 37831-6120
The Bruel i Kjaer Multi-gas Monitor-Type 1302 can simultaneously measure up to 5 different
gases/vapors in a single air sample by using up to 5 different optical filters combined with a photoa-
coustic detection method. The analytical method has previously been validated for the measurement
of VOCs in water and submitted to the DOE Methods Compendium (Method OS030). In that
method, VOCs are purged with air from water samples into a Tedlar bag, and the bag's contents are
sampled and measured using the Multi-gas Monitor. Currently, the analytical method is being modi-
fied for use to measure VOCs in soil. The approach being taken is to dilute the test soil samples with
water and to purge the VOCs from the resulting slurry, with a flow of air, into a Tedlar bag.
Subsequent analysis of the bag's contents is the same as was described for VOCs in water. Effective
purging of the sample is the key to this method. For example, it is essential that the sample be con-
stantly mixed to prevent the soil from settling which dramatically decreases the effectiveness of the
purge. Various purge parameters, such as the most effective method of mixing the slurry, rate of air
flow, size and shape of the purge vessel, sample size and water to soil ratio, are being investigated.
Results describing the effectiveness of the method for measuring chloroform, carbon tetrachlonde,
trichloroethylene, tetrachloroethylene and acetone in soil will be presented.
Research sponsored by the Office of Technology Development, U.S. Department of Energy, under
contract DE-AC05-84OR21400 with Martin Marietta Energy Systems, Inc.
"The submitted manuscript has been authored by a contractor of the U.S. Government under contract
No. DE-AC05-84OR21400. Accordingly, the U.S. Government retains a nonexclusive, royalty-free
license to publish or reproduce the published form of this contribution, or allow others to do so, for
U.S. Government purposes."
FIBER OPTIC RAMAN VOC VAPOR SENSOR
KJ. Ewing, T. Bilodeau, G. Nau, ID. Aggarwal, Naval Research Laboratory, Code 56032,
Washington, DC. 20375
Contamination of the environment by volatile organic compounds such as aromatics and chlorinated
hydrocarbons is a significant problem in both surface waters, ground waters, and soils. The objective
of the current work at NRL is the development of a sensitive, highly selective fiber optic Raman
spectrometnc sensor capable of detecting ppm levels of VOC's in both the air and water. The NRL
Raman probe utilizes a polymenc adsorbent to concentrate the VOC vapor in the optical path of the
Raman probe; the Raman spectrum of the VOC adsorbed into the polymer is then acquired. The
probe response is fully reversible for a number of different VOC's such as benzene, toluene, TCE,
and carbon tetrachlonde. At high levels of vapor (mg/L) the probe can be internally referenced using
either polymer or silica Raman lines as a reference. Low levels of VOC's (ppm(v)) can be detected
via spectral subtraction of a reference spectrum from the VOC containing spectrum.
Acknowledgments: The authors would like to thank the Office of Naval Research for support of this
project. We would also like to thank Angela Ervin and Dr. Dave Venezky of the Chemistry Division
at NRL for their help.
49 Wednesday, February 22, 1995
-------
Chemical Sensors
20
21
DEVELOPMENT OF SELECTIVE MASS SENSORS FOR FIELD MONITORING
OF ORGANIC VAPORS
Martha E. Doming uez, Robert L. Curiale, and Edward J. Poiiomelf, Harry Reid Center for
Environmental Studies, University of Nevada-Las Vegas, Las Vegas, Nevada 89154-4009,
Alain Quere, Departamenlo at Quimica Analltica, Facultad de Quimica, Universidad Nacional
Aul6noma de Mexico, Cd. Universitaria 04510, Mexico, D.F.
The detection of potentially harmful vapors at low concentrations is a current need in many environ-
mental monitoring applications. Chemical seniors have promising advantages for field measurement
of pollutants. These advantages include lower cost, smaller size of instrumentation, and simpler oper-
ation than traditional analytical techniques. Mass sensors have the additional advantage of high sensi-
tivity, but they lack specificity. This limitation can be overcome with the use of recognition coatings
that will selectively interact with the analytes of interest. The objective of this work is to develop
recognition coatings that provide both selective and sensitive interactions with vapors (e.g., acids,
amines, and hydrocarbons). These coatings can be used with quartz crystal microbalance (QCM) or
surface acoustic wave (SAW) mass sensors.
Various amine polymers have been examined as candidate coatings for interaction with the analytes.
Commonly, the coating process involves polymer materials dissolved in a suitable solvent and then
deposited on a sensor surface. In this study an emerging coaling technique was explored. Materials
were deposited onto the sensor surface from vapor streams of volatile substances activated through
plasma discharge. This process allows preparation and deposition of recognition coatings to be done
in one step. Coating materials were characterized by measuring their reactivity with different vapor
analytes using linear energy solvation relationships (LSER). These relationships were used in this
study to characterize commercially available and plasma deposited coatings. An LSER equation was
defined and used to predict the reactivity of the coating material toward specific vapors. The equa-
tions have predicted correctly the interaction strength for other vapors. This method allows
researchers to design coaling materials which selectively react with specific analytes of interest.
Notice: The authors acknowledge support from the Advanced Research Projects Agency (Contract-
DAAD05-92-C-0027).
'Present address: Department of Chemistry and Biochemistry, Old Dominion University, Norfolk,
VA 23529-0216
USE OF ULTRASOUND IN MONITORING CHEMICAL CONTAMINATION IN
WATER
Edward J. Poziomek and Grazyna E. Onechowska, Harry Reid Center for Environmental Studies,
University of Nevada-Las Vegas, Las Vegas NV 89154-4009, William H. Engelmann, US.
Environmental Protection Agency, Environmental Monitoring Systems Laboratory, Las Vegas, NV
89193-3478
The U.S. Environmental Protection Agency has been examining the potential of combining sonication
with other technologies for monitoring specific classes of organic pollutants in water. The present
research specifically addresses the use of ultrasonic processors to decompose contaminants such as
organochlorine compounds into products which can be detected using commercially available elec-
trodes as a field screening method. For example, changes in chloride, conductivity, and pH were
measured before and after sonication in order to detect the presence of organochlorine pollutants.
The results obtained are very promising. Chloride ion could be detected in aqueous solutions of low
ppm concentrations of carbon tetrachloride, chloroform, and trichloroethylene after one minute soni-
cation. The increases of chloride ion were accompanied by increases in conductivity and decreases of
pH. Ion chromatography of solutions before and after sonication showed that formate ion was also
formed. Aromatic and polyaromatic chloro compounds represented by chlorobenzene and poly-
chlorobiphenyls, respectively, did not form chloride ion as readily as did carbon tetrachloride, chloro-
form, and trichloroethylene. The potential of combining sonication with commercially available mea-
surement technologies for monitoring specific pollutants in water is judged to be high. The results
achieved with the organochlorine compounds tested served as proof-of-principle and formed a base of
information which can be used to develop field screening methods based on sonochemistry.
Notice: The U.S. Environmental Protection Agency (EPA), through its Office of Research and
Development (ORD), prepared this abstract for a proposed oral presentation. It does not necessarily
reflect the views of the EPA or ORD.
Wednesday, February 22, 1995 50
-------
Chemical Sensors
22
23
A FIBER OPTIC ABSORPTION SENSOR FOR THE DETECTION OF
VOLATILE ORGANIC COMPOUNDS IN AQUEOUS SOLUTIONS
Gregory L. Klunder, Lawrence Livermore National Laboratory, P.O. Box 808. L-371, Livermore, CA
94550, and Richard E. Russo, Lawrence Berkeley Laboratory. Berkeley, CA 94720
Extensive contamination of ground water from organic solvents has placed a large emphasis on the
development of instruments for remote in-situ sensing. Fiber optic chemical sensors (FOCSs) have
made a great deal of progress in this area. A core-based intrinsic fiber optic absorption sensor has
been developed in our laboratory for the detection of volatile organic compounds. The distal ends of
transmitting and receiving fibers are connected by a small cylindrical section of an optically clear sib-
cone rubber. The silicone rubber acts both as a light pipe and as a selective membrane into which the
analyte molecules can diffuse. The sensor has been used to detect volatile organics (trichloroethyl-
ene, 1,1-dichloroethylene, and benzene) in both aqueous solutions and in the vapor phase or head-
space. Absorption spectra obtained in the near-infrared (NIR) provide qualitative and quantitative
information about the analyte. Water, which has strong broad-band absorption in the NIR, is exclud-
ed from the spectra due to the hydrophobic properties of the silicone rubber. The rale limiting step is
shown to be the diffusion through the Nemstian boundary layer surrounding the sensor and not the
diffusion through the silicone polymer. The rate of analyte diffusion into the sensor, as measured by
the t^Q values (the time required for the sensor to reach 90% of the equilibrium value), is 5-10 min-
utes for measurements in aqueous solutions and on the order of 1 minute for measurements made in
the headspace. Results of the initial studies and current limits of detection will be presented.
OXYGEN AND CARBON DIOXIDE SOIL GAS SURVEY INSTRUMENT
Marc A. Portnoff, Jeffrey L. Hibner, Peter Prusko, Jim Rose, John Tabacchi, Carnegie Mellon
Research Institute, 4400 Fifth Avenue, Pittsburgh, PA 15213-2683
The work of Robbins el al.1 has demonstrated a correlation between the amount of soil contamination
at leaking underground storage tank sites, and the ratio of carbon dioxide to oxygen in the soil gas.
The focus of this project was to build a single site assessment instrument capable of accurately mea-
suring both carbon dioxide and oxygen over an extended concentration range of 0-21%. This instru-
ment offers the multiple benefits of simplified field measurements, reduced operator error, increased
precision, and lower sample costs.
Can recent advances in carbon dioxide and oxygen sensor technology be transferred for use in under-
ground storage tank site assessments? Historically, costly field tests would be performed to answer
this question. This project has evaluated sensor performance through laboratory testing designed to
parallel field conditions.
Sensor performance was measured with an automated system constructed to test the sensors as they
would be used in the field. Test conditions were carefully selected in order to obtain the most infor-
mation per data point. The oxygen and carbon dioxide levels were chosen to reflect gas compositions
of great interest for soil gas surveying. Methane, synthetic gasoline, water vapor, and hydrogen sul-
fide concentrations were chosen to reflect field conditions and to determine the effects of soil gas
vapors on oxygen and carbon dioxide sensor performance.
The test program characterized sensor response in terms of precision, accuracy (bias), response and
recovery, specificity, and stability. The sensors were also evaluated with respect to warm-up time,
power requirements, sample size, and costs. Oxygen and carbon dioxide vapor sensors used in the
following applications have been tested: health and safety monitoring, automobile emissions moni-
toring, building ventilation control and combustion control.
Electrochemical and paramagnetic oxygen sensors, and infrared carbon dioxide sensors show the
most promise for this application. They are relatively unaffected by soil gas vapors, respond in less
than one minute, and require gas samples of less than one liter. Sensor precision, accuracy and drift
values are belter than 3% of reading at high concentrations (20% oxygen or carbon dioxide). At
lower concentrations (1% oxygen or carbon dioxide) these values are sensor specific. The best sen-
sors having precision, accuracy and drift values that are better than 10% of reading.
Sensor performance versus cost will be reviewed. This will be followed by the presentation of the
performance specifications and measurements of a prototype soil gas survey instrument using a set of
the most appropriate oxygen and carbon dioxide sensors.
'Robbins, G. A., Brendan, Deyo, Binkhorst, G., "Use of Portable Oxygen and Carbon Dioxide
Detectors to Screen Soil Gas for Subsurface Gasoline Contamination", U.S. Environmental Protection
Agency, Environmental Monitoring Systems Laboratory, Office of Underground Storage Tanks, Las
Vegas, Nevada, CR-814542, and CR-817587, January 8, 1992.
51 Wednesday, February 22, 1995
-------
Chemical Sensors
24
25
FIBER OPTIC CHEMICAL/ENVIRONMENTAL SENSORS BASED ON ACTIVE
COATINGS
MJi. Shahriari, M. Krihak, J. HamUin ami S. Uhland, Rutgers University, Fiber Optic Materials
Research Program, P.O. Box 909, Piscalaway, NJ 08816
The use of optical waveguides for sensing physical and chemical parameters in chemical process
industries is a rapidly growing field. Simple amplitude or intensity modulated sensors are currently
used for chemical, biomedical and environmental monitoring and control.
The development of porous glass and plastic fiber optic technology, combined with pholochemicaUy
active coating techniques such as dye impregnated sol-gel coating as highly stable substrate have led
to a new class of high sensitivity, fiber optic chemical sensors exhibiting enhanced long term stability.
In these sensors, absorption or luminescence type indicators are encapsulated into highly durable
porous glass matrix which is coated on the surface of optical fibers. As a pioneer. Center for Fiber
Optic Research at Rutgers is currently developing sensors based on these new technologies ranging
from environmental industry to food process industry. Ground water monitoring and on-line monitor-
ing of food flavor are examples of these newly developed sensors.
A bncf review on fiber optic sensors and their applications in process control along with recent
progress in this area will be given. Also some of the recent progress on fiber optic sensors by
Rutgers' fiber optic sensor group including pH, ammonia gas, O2 and IX), H2S and other gas and liq-
uid systems will be presented.
DOWN HOLE ULTRAVIOLET FLUORESCENT DEVICE FOR MEASURING
IN SITU VOLATILE ORGANIC CONCENTRATIONS IN GROUND WATER
Clayton R. Morlock, Morlock Environmental, Inc., 23 Pine St., Lebanon, NH 03766
We have developed a miniature fluorescence device for measuring volatile organic compound con-
centrations in ground water in a well. The device consists a Hg vapor lamp, excitation filter, sample
chamber, emission filter and a miniature photomultiplier tube. Filters are chosen for optimal fluores-
cence signals from B'lT.X compounds. The current size of the instrument is approximately 4-inches
in diameter and 6 inches long. The instrument is lowered into a bore hole - tethered by a powerline
and data communication lines. It has instantaneous output. The current design has a flow through
cell which allows water to continuously pass through the cell while it is being lowered into the well.
We are in the process of bench and field testing, and refining the instrument. We believe that it will
be possible to build a device suitable for installation within a cone penetrometer. Our current detec-
tion limit for Benzene is about 10 ppmv. We anticipate that the lower detection limit can be substan-
tially reduced once further refinements are made. The intended use of the instrument is for rapid
assessment of VOCs in wells and for permanent installation in a well for long term monitoring.
Wednesday, February 22, 1995 52
-------
Chemical Sensors
26
27
ABOVE GROUND AND IN SITU FIELD SCREENING OF VOCs USING
PORTABLE ACOUSTIC WAVE SENSOR (PAWS) SYSTEMS
Gregory C. Frye, Don W. Gilbert", Richard W. Cernosek, Terry D. Steinfort, Sandia National
Laboratories, MS-0351, Albuquerque, New Mexico 87185, *Team Specialty Products, 11630 Cochili
SE, Albuquerque, New Mexico 87123
Surface acoustic wave (SAW) devices are extremely sensitive to changes in the mass or other physi-
cal properties of a thin film cast onto the device surface. For example, mass changes of tens of
picograms can be detected. Using thin films to absorb the chemical species of interest, this sensitivity
can be used to detect and monitor a wide range of volatile organic compounds (VOCs). Detection
levels with current systems range from 0.1 to 10 ppm for typical VOCs. Using elastomenc polymers
such as polyisobutylene, diffusional properties result in rapid (few seconds) and reversible responses
enabling real-time monitoring.
As with most sensors, some temperature and humidity sensitivity is inherent. Temperature sensitivity
is overcome by active temperature control, "on-chip" temperature measurement, and software com-
pensation. A new and effective system for the on-line determination of the sensor response when no
VOCs are present has been demonstrated. This system consists of a Nafion membrane for humidity
equilibration and a three-way valve to pass ambient air (scrubbed using an adsorbent if necessary) to
the sensor on demand. By incorporating this system for establishing sensor baseline, these systems
can be used on-line or in situ for long term monitoring.
Two basic portable acoustic wave sensor systems have been developed. Both contain two polymer-
coated SAW sensors, one acts as a reference and the other as the active sensor. Oscillator electronics
drive the sensors and provide two independent outputs, a mixed frequency that tracks changes in
wave velocity and a power detector voltage that tracks changes in wave attenuation. The ratio of
these two signals has been shown to provide limited discrimination of isolated chemical species while
the more sensitive frequency response can be used to quantify the isolated species. One system con-
sists of a shoe-box sized module interfaced to a notebook computer. This system has been demon-
strated for real-time, on-line monitoring of off-gas concentrations from soil vapor extractions. In
addition, monitoring of vapor samples drawn from vadose zone wells and from cone penetrometer
sampling probes has been demonstrated.
A second system consists of a down-hole probe with associated packers for isolating a selected sec-
tion of a well, a cable for power and data communication to a notebook computer at the surface, and a
stainless steel sampling line to compare the in situ measurements with surface analyses. Results from
both systems have demonstrated quantitative analysis of isolated species with simple and easy-to-use
hardware and software. Agreement with baseline instruments has been within 2% during some field
demonstrations. In addition, a wide dynamic range has been demonstrated: in one test, a 10 ppm
detection level was demonstrated with the same system that accurately measured 25,000 ppm from
another well. Current work is focused on extending the capabilities to mixture analysis using arrays of
SAW sensors and to water analysis using specially designed sampling modules.
HAND-HELD POTENTIOMETRIC STRIPPING ANALYZER FOR FIELD
SCREENING OF TOXIC METALS
J. Schmidt, C. DiBerardino, and H. Barrick, Environmental Technologies Group, Inc , 1400 Taylor
Avenue, P.O. Box 9840, Baltimore, MD 21284-9840
The combination of potentiometnc stripping analysis (PSA) and screen printed electrodes allows one
to perform groundwater heavy metal analysis in the field at low ppb levels. The instrumentation
required to perform multiple metal analyses with PSA is inexpensive and user-friendly. A typical
analysis can be completed in 2-3 minutes, and the selectivity and lack of oxygen interference of this
technique allows one to minimize sample preparation time.
Inexpensive disposable electrodes are now commercially available. When used with the proper
reagents, these electrodes are capable of delecting the following metals simultaneously: Pb, Cd, and
7n. During the next year, electrodes will be introduced which will delect all 14 EPA Priority
Pollutant Metals, many of them as multianalyte sets.
A typical analysis consists of adding sample, activating the reagents, placing several drops of the
solution on the disposable electrode, and pushing the "start" button on the electronics. The battery
operated hand-held electronics automatically analyzes the sample and reports the result. The LOD
and CV for most metals is 5 ppb and 5% respectively. No calibration in the field is necessary, since
the electronics automatically compensate the displayed result with an internal standard which is
included in the reagent. Preparing the instrument for the next sample involves removing the used
electrode and inserting a fresh electrode into the instrument.
The results of beta testing of the instrument with several types of aqueous samples in the field will be
summarized.
This work was performed at Sandia National Laboratories supported by the U.S. Department of
Energy under contract number DE-AC04-94AL8SOOO. This work was funded in pan by the DOE
Office of Technology Development
53 Wednesday. February 22, 1995
-------
Chemical Sensors
28
29
MULTIPLEXED FIBER-OPTIC FLUORESCENCE SENSORS FOR MEASURE-
MENT OF FUELS IN A MODEL AQUIFER
Terence L. Tipton, Tyndall AFB, FL, Brian S. Vogl, Bob Jones University, SC
A multiplexed Tiber-optic sensing system has been constructed for laboratory use in a model aquifer.
This system uses laser-induced fluorescence to measure fuel components in groundwater. Tunable
pulsed ultraviolet light is sent sequentially into an array of single-fiber optical sensors which are
inserted into wells. Preliminary results indicate that quantitative concentration measurements can be
made to approximately 1 ppb for strong fluorescers such as naphthalene, and that turbidity corrections
are feasible. The two objectives of this work are: 1) to examine fluorescence interferences (e.g. tur-
bidity, background humic fluorescence) under carefully controlled laboratory conditions to develop
methods for handling interferences encountered in field measurements; and 2) develop models for
pollutant transport in groundwater.
CHEMSENSOR®: RESPONSE TO GASOLINE AND DIESEL CONTAMINATED
GROUNDWATER
John M. Henshaw, PhD., ORS Environmental Systems, 7 Barnabas Road, Marion, MA 02738
ChemSensor is a rugged, field portable instrument capable of in-situ measurement of organic com-
pounds, especially volatile organic compounds (VOCs) in water and process streams. The response
to organic* is reversible, requiring only that the user clean and re-zero the probe between measure-
ments. ChemSensor gives field sampling personnel an indication of the concentration of organic con-
tamination at a site in real time. This helps in the assessment of leaking underground storage lank
(LIST) sites prior to receipt of analytical lab test results and also provides a tool for monitoring the
cleanup at a site over time. This paper discusses how to interpret the results obtained from
ChemSensor for site assessment at both gasoline and diesel contaminated UST sites.
ChemSensor consists of a probe connected to a meter via electrical cable that enables in-situ sampling
to standard depths up to 100 feet (custom lengths longer than 100 feet also available). The sensing
element of the probe is a quartz optical fiber coated with a hydrophobic and organophyllic chemical
coating sensitive to organic compounds. ChemSensor responds to virtually all organic species dis-
solved in water, dependent upon the aqueous solubility and refractive index of the compound.
Samples were obtained from both gasoline and diesel fuel contaminated sites and analyzed with
ChemSensor and in the laboratory using a gas chromatograph. A linear relationship between
ChemSensor and the gas chromatograph data was demonstrated for total BTEX (gasoline) and total
petroleum hydrocarbons (diesel fuel). A discussion of the interpretation of ChemSensor data for
monitoring contamination levels and remediation processes is presented.
The test results demonstrate that ChemSensor is a useful Held portable analytical tool for determining
concentrations of total organic compounds in water and a timely supplement to laboratory results.
Interpretation of the data from ChemSensor monitoring of a remediation site over time can give the
user an indication of the progress of the clean-up without requiring excessive characterization of the
response via confirmatory laboratory analysis. ChemSensor can also be used to optimize the collec-
tion of samples for laboratory analysis at a new site by indicating the level of contamination within
and among the wells in real time.
Wednesday, February 22, 1995 54
-------
Cone Penetrometer Deployed Sensors
30
31
NONAQUEOUS PHASE LIQUIDS: SEARCHING FOR THE NEEDLE IN THE
HAYSTACK
J Haas III, R. Forney, M. Carrabba, J. Bella, and K. Spencer, E1C Laboratories Inc., Ill
Downey St., Norwood, MA 02062, M. DiCollegaro andJ. Haas Jr., Department of Chemistry,
Gordon College, Wenham. MA 01984
Subsurface contamination by N on Aqueous Phase Liquids (NAPLs) is a major concern at many gov-
ernment and private sites because of the threat to drinking water supplies. The threat is a long-term
one, arising from the limited water solubility of NAPLs. In soil and below or on lop of a groundwa-
ter aquifer they can be present in small, undiluted "pools" that are depleted only very slowly by disso-
lution into large volumes of water. The result is widespread pollution that can continue for many
years if the NAPLs are not isolated and/or removed. However, NAPLs must first be located, a task
which is often difficult.
A promising approach to the problem of locating NAPLs is to utilize a cone penetromeler or other
minimally invasive device equipped with sensors that can locate contaminants in situ and in real time.
We have been developing and evaluating optical sensors based on Raman, fluorescence, and internal
reflection spectroscopies for locating common NAPL contaminants such as gasoline or jet fuel, and
chlorinated hydrocarbon solvents such as trichloroethylene, tetrachloroethylene, and carbon tetrachlo-
ride.
This paper will describe the development of the three, complementary approaches to NAPL
detection, discuss the merits and disadvantages of each, and present results obtained in the field at
U.S. Department of Energy sites using sensors integrated into a cone penetromeler.
THE ROLE OF CONE PENETRATION TESTING IN EXPEDITED SITE CHAR-
ACTERIZATION; A CASE HISTORY
GA Slenback, B H. Kjarlanson, Iowa State University, Civil and Construction Engineering, Ames,
Iowa 50011-3232, A. Bevolo, D. Wonder, Ames Laboratory, Technology Integration Program,
Sherman Place, 125 S. 3rd Si., Ames, Iowa 50010-6793 and K. Older, US Army Corps of Engineers,
Kansas City District, 601 East 12th Street, Kansas City, Missouri 64106-2896
Expedited site characterization (ESC) focuses on utilizing nonimrusive and minimally intrusive inves-
tigation techniques synergisucally to efficiently and effectively characterize hazardous waste sites. A
key aspect of the process is the use of rapid data collection, interpretation and visualization technolo-
gies to update the conceptual site model as the investigation proceeds. The USDOE's Ames
Laboratory has recently carried out a demonstration of the expedited site characterization process at a
former manufactured gas plant site. This paper focuses on the role of an innovative cone penetrome-
ler system. Site Characterization and Analysis Penetrometer System (SCAPS) in the ESC process.
The SCAPS unit utilizes tip and sleeve resistance measurements for continuous soil slratigraphic pro-
filing while simultaneously using either resistivity or laser induced fluorescence (LJF) to obtain fur-
ther subsurface information such as pore fluid characteristics and the presence of petroleum hydrocar-
bon products. Moreover, soil and groundwater samples may be obtained from selected depths while a
grouting plant is available to grout the penetromeler holes on completion of testing.
The geology of the site consists of surficial fill overlying clayey to sandy and gravelly alluvial and
glaciofluvial deposits overlying discontinuous clayey glacial tills in turn overlying limestone and
dolomite bedrock. In the light of the site geology and the fact that the main contaminant of interest is
a gas manufacturing residue DNAPL containing polycyclic aromatic hydrocarbons (PAH's), the main
objectives of the SCAPS program were to define the site stratigraphy, including the continuity of the
various units, define the surface topography of the lower clayey till unit to assist in tracking the trans-
port and fate of the DNAPL and to detect residual contamination in the subsurface. The SCAPS
results were integrated with the results of other non- or minimally intrusive techniques such as surface
geophysics and Geoprobe sampling and conductivity logging to develop the site model.
Data collected from the SCAPS investigation indicate that the three objectives defined above were
effectively met. SCAPS was able to clearly indicate the contacts between the various stratigraphic
units encountered over the site and in particular, provided useful information identifying the topogra-
phy of the lower clayey till unit overlying the bedrock. The agreement between the SCAPS strati-
graphic logs and logs from auger boreholes near some of the SCAPS locations was good. The LIF
probe was effective in detecting regions of contamination in the subsurface as PAH compounds tend
to have a relatively strong fluorescence response. Elevated LJF readings (above background) were
encountered at various levels in the stratigraphy indicating movement of the DNAPL down through
the stratigraphy. Elevated LJF readings were also recorded in the soil directly overlying the lower
clayey till indicating a tendency of the DNAPL to pool on this confining layer. These results com-
pare well with trends observed from the other investigation techniques. In summary, the SCAPS was
very effective in further defining the site geological model by providing continuous stratigraphic pro-
files at selected locations and in providing a good indication as to the fate and transport of the
DNAPL. Moreover, the availability of the data on a real time basis allowed for effective integration
of me SCAPS into the ESC process.
55 Wednesday, February 22, 1995
-------
Cone Penetrometer Deployed Sensors
32
33
REAL-TIME MONITORING OF VOLATILE CHLORINATED COMPOUNDS IN
THE SUBSURFACE ENVIRONMENT USING A HALOSNIF/CONE PENETROM-
ETER SYSTEM
KhrisB. Olsen, Norman C. Anheier, Jr., John C. Evans, Pacific Northwest Laboratory, P.O. Box 999,
Kichland, WA 99352, and Bruce R. Cassem, Westinghoiae Hanford Company, Kichland, WA 99352
The U.S. Environmental Protection Agency (EPA) has regulatory jurisdiction for the cleanup of haz-
ardous wastes sites designated by the Comprehensive Environmental Response, Compensation and
Liability Act (CERCLA), and Superfund Amendments and Reaulhorizauon Act (SARA). According
to EPA's guidance specific activities are required to characterize a site listed under CERCLA or
SARA. This activity includes a preliminary site investigation followed by a comprehensive remedial
site investigation. During remedial investigation site activities, various environmental samples are
collected including air, water, and soils and sediments. Because of the sheer volume of samples sent
to the laboratory for analysis and the high analytical cost associated to produce legally defensible ana-
lytical data, remedial investigations costs have skyrocketed. Clearly, alternative characterization tech-
nologies are needed. A new innovative technology being evaluated couples a cone penetromeler sys-
tem to a chlorinated compound specific detector system (HaloSnif). The cone penetrometer provides
access to the subsurface environment and the HaloSnif system measures the concentrations of volatile
chlorinated compounds in the gas phase (soil gas) in real-time.
Testing of the cone penelrometer/HaloSnif system was conducted at the U.S. Department of Energy's
Hanford Site located in southeastern Washington State. The lest location was adjacent to several
cribs that received from 500 to 1500 tons of CC14. The cone penetrometer system used consisted of a
30,900-kg vehicle pushing a 44.5 mm (OD) by 19 mm (ID) rod system equipped with a gas sampling
tip capable of sampling soil gas continuously. A 4.8-mm Teflon tube connected the gas sampling tip
to the gas sampling manifold of the HaloSnif System. Four pushes were conducted to a maximum
depth of 100 feet HaloSnif monitored the concentration of volatile chlorinated compounds, consist-
ing of greater than 95% carbon lelrachlonde and up to 5% chloroform, as a function of depth.
Maximum concentrations of volatile chlorinated compounds in soil gas exceed 20,000 ppm. During
overnight monitoring with HaloSnif, unexpected cyclic behavior in volatile chlorinated compounds
concentrations was observed. After several hours at 20,000 ppm the concentrations suddenly
decreased to 2000 ppm for several more hours, followed by an increase back to 20,000 ppm. This
behavior was observed by several other monitoring instruments. The following evening similar
behavior was also observed.
An in-depth description of the HaloSnif technology, concentration profiles of volatile chlorinated
compounds as a function of depth and time, and other relevant observations will be presented.
This project was funded by the U.S. Department of Energy (DOE), Office of Technology
Development under Contract DE-AC06-76RLO 1830. Pacific Northwest Laboratory is operated for
the DOE by Battelle Memorial Institute.
SITE CHARACTERIZATION USING THE CONE PENETROMETER
Alison 1. Harlick, Automated Sciences Group, Inc.", Oliver Springs, Tennessee, Frederick M.
Nelligan, Science Applications International Corporation, Bothell, Washington
An electric cone penetrometer testing (CPT) program and a groundwater CPT program were conduct-
ed at an active industrial waste treatment plant near San Diego, California, to characterize subsurface
stratigraphy and groundwater contamination to depths of 160 ft below ground surface (bgs). The
intent of the sampling program was (1) to characterize the subsurface geology and (2) to delineate
tnchloroethene and other solvent contamination within a specific site. The CPT was the preferred
testing method because of its ability to produce quantifiable slratigraphic data in log form. These
logs could be used to identify potential confining beds where dense nonaqueous phase liquid
(DNAPL) contamination (solvents) could pool. The stratigraphic information was used to determine
target depths for groundwater sampling.
Subsurface lithology was interpreted from electric CPT logs based on values for tip resistance, sleeve
friction, and pore pressure. Generally, clean, coarse-grained sands have higher tip strengths, lower
sleeve friction, and little excess pore pressure. Finer-grained silts and clays have lower tip strengths,
higher sleeve friction, and high excess pore pressure. To check the site's interpreted stratigraphy, a
CPT location was selected -10 ft from where a 270-ft continuously cored boring was completed.
Overall, the electric CPT log correlated well with the physical evidence from the boring. The ability
to quantify the electric CPT log by comparing it to the cores collected from the deep borehole was
important because the comparison provided defensible correlation between soil cores and the electric
CPT logs. The typical subsurface stratigraphy identified by the CPT log consisted of interbedded
sands and silts; significant horizons of silty clay (at 40 ft bgs) and clay (at 85 ft bgs) were identified
as confining intervals where DNAPLs pooled.
Twenty-two electric CPT holes were pushed to gather the data necessary to complete the subsurface
geologic interpretation and plan the groundwater sampling points. Ninety-four depth-discrete CPT
groundwater samples were collected from 23 locations. Samples were submitted to a fixed-base labo-
ratory for overnight turnaround and were analyzed for volatile organic compounds. EPA Level ID
data validation was performed on sample results so data could be used for a human health risk assess-
ment. Sufficient quality assurance/quality control samples were collected to accommodate this
requirement. Groundwater results demonstrated that the CPT accurately characterized the extent of
DNAPL contamination in the shallow groundwater above the first and second confining intervals.
The CPT samples consistently displayed highest concentrations immediately above confining layers,
with the zone above the 85-ft clay exhibiting the highest detects overall (i.e., 300,000 fig/L). Below
the 85-ft clay, contaminant concentrations dropped significantly to less than 1,000 Hg/L.
Using the CPT provided a cost-effective means to collect stratigraphic information lacking from pre-
vious investigations. Based on the CPT logs, depth-discrete samples were targeted for zones most
likely to accumulate DNAPLs. This methodology fully characterized the extent and magnitude of
contamination at the site. Local and state agencies overseeing this project were unanimous in sup-
porting the use of CPT technology and basing remedial action decisions on CPT data. Furthermore,
they believed the results to be more accurate than results from conventional monitoring wells.
•Work performed by Automated Sciences Group, Inc., under general order contract number 30B-
9778C with Martin Marietta Energy Systems, Inc.
The submitted manuscript has been authored by a contractor of the U.S. Government under contract
DE-AC05-84OR21400 wuh the U.S. Department of Energy. Accordingly, the U.S. Government
retains a paid-up, nonexclusive, irrevocable, worldwide license to publish or reproduce the published
form of this contribution, prepare derivative works, distribute copies to the public, and perform pub-
licly and display publicly, or allow others to do so, for U.S. Government purposes.
Wednesday, February 22, 1995 56
-------
Cone Penetrometer Deployed Sensors
34
35
REAL-TIME, CONTINUOUS MEASUREMENT OF SUBSURFACE PETROLEUM
CONTAMINATION WITH THE RAPID OPTICAL SCREENING TOOL (ROST)
Randy W. St. Germain and Gregory D. Gillispie, Dakota Technologies, Inc., 2301 12th Si. N.. Suite
E. Fargo. ND 58102
The development of a tunable laser system for in-situ chemical analysis via fiber optic spectroscopy
has been presented at the previous symposia in this series. At the last symposium (February 1993),
we reported initial results on subsurface detection of petroleum, oil, and lubricants by laser-induced
fluorescence cone penetrometer testing (LJF-CPT). Now the laser system has been commercialized
as the Rapid Optical Screening Tool (ROST). A consortium of Unisys Corporation; Dakota
Technologies, Inc.; North Dakota State University; and the United States Air Force, Armstrong
Laboratory has been awarded a Technology Reinvestment Project award from the Advanced Research
Projects Agency (ARPA) for productization of ROST.
ROST is an integrated package with many different possible applications beyond cone penetrometer
testing. The laser source, detector, and control analysis software are fully integrated. An important
design consideration has been making ROST compact and self-contained so that it can be convenient-
ly transported and deployed in a wide variety of environments. The repetition rate of the wavelength
tunable laser source has been upgraded to 50 pulses/second, compared to previous versions that oper-
ated at 10 pulses/second. With the higher pulse repetition rate, petroleum contamination can be con-
tinuously recorded at better than 1 cm spatial resolution while the cone penetrometer is advanced at
the standard rate (2 cm/second). The time response of the digital oscilloscope, which captures the
temporal profile of the pulsed fluorescence signal from the photomultiplier tube detector, has been
similarly upgraded. An optional array detector for simultaneous collection of the entire fluorescence
spectrum has been added.
The topics covered in this talk include: (1) a technical overview of the ROST hardware; (2) details of
its mobilization and installation for LJF-CPT work; (3) the data interface between ROST and the stan-
dard CPT geotechnical measurements; (4) lessons learned during day to day operation at many differ-
ent sites that pose a wide range of soil conditions and contaminant types.
PERFORMANCE CHARACTERIZATION OF THE RAPID OPTICAL SCREEN-
ING TOOL FOR LASER-INDUCED FLUORESCENCE CONE PENETROMETER
TESTING
Gregory D. Gillispie and Randy W. St. Germain, Dakota Technologies, Inc., 2301 12th St. N., Suite
E, Fargo. ND 58102
The Rapid Optical Screening Tool (ROST) is the commercial version of the tunable laser chemical
analysis system developed at North Dakota State University (NDSU) and reported at previous sym-
posia in this series. Dakota Technologies, Inc., Unisys Corporation, and NDSU are collaborating on
research and development to expand ROST's capabilities with support from a Technology
Reinvestment Project award.
The initial ROST application is detection of subsurface petroleum contamination by laser-induced flu-
orescence cone penetrometer testing (LJF-CPT). Research to answer questions about limits of detec-
tion, matrix effects, ability to distinguish different fuel contaminant types, reliability, etc. is in
progress. The actual field applications of ROST, which have already begun, will answer some of
these questions. The field program is backed by extensive laboratory studies, which are designed to
mimic as closely as possible the cone penetrometer environment. Limits of detection are being deter-
mined for many different soil and fuel type combinations under standardised conditions. The major
challenge in these studies is how to reliably spike samples, especially with volatile fuels such as gaso-
line and jet fuel. The same samples are used to test algorithms we have developed for classification
purposes. In one study, four different fuels (JP-4, diesel #2, unleaded gasoline, diesel fuel marine)
were spiked at three different concentrations (1000, 3000, and 10000 mg/kg) on three different soil
matnces. The 3000 ppm samples were used as a training set. Data then were acquired in random and
blind fashion for the 1000 and 10000 ppm samples. The classification accuracy with respect to fuel
type was 96%.
57 Wednesday, February 22, 1995
-------
Cone Penetrometer Deployed Sensors
36
37
FIELD PORTABLE PETROLEUM ANALYSIS FOR VALIDATION OF THE SITE
CHARACTERIZATION AND ANALYSIS PENETROMETER SYSTEM (SCAPS)
PETROLEUM, OIL AND LUBRICANT SENSOR
William M. Davis and Pauletle Jones, USAE Waterways Experiment Station, 3909 Halls Ferry Road,
Vicksburg, MS 39180, and Beth Porter, AScI Corporation, 1365 Beverly Road, McLean, VA 22101
A petroleum, oil and lubricant (POL) sensor for the Site Characterization and Analysis Penetrometer
System (SCAPS) system has been developed by the Tri-Services to characterize the distribution of
POL contamination on military sites. The sensor is based on the detection of POL contaminants
using a laser induced fluorescence (LIF) system. The SCAPS LIF sensor has been shown to be a
valuable tool for the rapid screening of POL contamination in the subsurface. However, many factors
can effect the LIF response of a particular fuel at a particular site. These include fuel type, age of
fuel spill (eg weathering), and soil type. The LIF sensor also delects fluorescence response from any
naturally occurring fluorophore, including humic substances and fluorescent minerals. These factors
lead to the development of an independent procedure for verification of the LJF sensor response.
This paper describes a field portable total recoverable petroleum hydrocarbon (TKPII) method based
on EPA Method 418.1 and its application to on site validation of the SCAPS POL sensor response at
a number of contaminated sites.
DEVELOPMENT AND TESTING OF CONE PENETROMETER SENSOR PROBE
FOR IN SITU DETECTION OF EXPLOSIVE CONTAMINANTS
Ernesto R. Cespedes, Stafford S. Cooper, and William M. Davis, USAE Waterways Experiment
Station, 3909 Halls Ferry Road, Vicksburg, Mississippi 39180, and William J. Bultner and William C.
Vickers, Transducer Research, Inc , 999 Chicago Avenue, Napervtlle, Illinois 60540
This paper describes the development and testing of a sensor probe for the Site Characterization and
Analysis Penetrometer System (SCAPS) for the in situ detection of TNT, RDX, HMX. and olher
nitrogen-containing soil contaminants. Initially, laboratory studies were conducted to determine the
feasibility of employing electrochemical sensors in combination with a pyrolyzer element for detect-
ing subsurface explosives contaminants. A method for the pyrolysis of explosives contaminants in
spiked soils was developed, and it was demonstrated that electrochemical sensing of the pyrolysis
products was sensitive, selective, reversible, and capable of broad dynamic range. A penetrometer
probe that accommodates the electrochemical sensors (including power supply and signal condition-
ing electronics), the pyrolyzer unit, the pneumatic components, and geophysical sensors (tip resis-
tance and sleeve friction sensors) for mapping soil stratigraphy was designed, fabricated and field
tested at contaminated sites. Laboratory data presented in this paper include system calibration
curves, lower detection limits, and estimates of the pyrolyzer's zone of influence in various soil matri-
ces. Results of recent field tests are presented, and include examples of sensor responses in contami-
nated and clean sites, together with corresponding laboratory analyses of field verification samples.
The prototype explosives sensor probe has demonstrated potential for SCAPS field screening and
monitoring applications. Continued development, testing, and validation efforts are planned for 1995.
Wednesday, February 22, 1995 58
-------
Data Handling and Systems Integration
38
39
QUANTITATIVE AND QUALITATIVE ANALYSIS OF SPECTRAL DATA
OBTAINED FROM AN INTEGRATED FIBER OPTIC FLUOROMETER AND
CONE PENETROMETER
John Andrews, Computer Sciences Corporation, 4045 Hancock Street, San Diego, CA 92 HO,
Stephen H. Lieberman, Naval Command, Control, Ocean Surveillance Center, Research,
Development. Test and Evaluation Division (NKaD), Code 521, San Diego, CA 92152-5000
The presentation describes the use of an artificial neural network based method for providing rapid
on-line analysis of fluorescence emission spectra. The method serves to generate a real time interpre-
tation of spectral data acquired in situ by the Navy's Site Characterization and Analysis Feneiromcter
System (SCAPS), an integrated optical fiber fluorometer / cone penetrometer site investigation tool
currently being used to delineate subsurface petroleum contamination.
Neural network pattern recognition allows for simultaneous qualitative and quantitative analysis of
raw spectral data. Quantitative estimation and speciation of different fresh and weathered petroleum
products is achieved even in the presence of strong spectral interferences, non-linear response curves,
and uncertain matrices. The method also provides for the rejection of spectral interferences arising
from natural fluorophores, thereby minimizing the possibility of reporting false positive results.
Spectral data collected both in the lab and in the field are used in the network development process to
train and test the algorithm. Performance of the neural algorithm is compared to that of muluvanate
statistical methods.
DATA MANAGEMENT IN SUPPORT OF A MULTI-MEDIA LEAD EXPOSURE
STUDY
L P. Kaelm and Frank McGuire', Roy F Weslon, Edison. NJ 08837. G Prince and R. Cibulskis, U S
Environmental Protection Agency Environmental Response Team, Edison, NJ 08837, S. Vance and S.
Hawthorn, US. Environmental Protection Agency Region VIII, Denver, CO 80202 and D. Taylor,
Utah Department of Environmental Quality, Salt Lake City, UT 84114
The possible exposure to lead contamination from various matrices was evaluated at a U.S.
Environmental Protection Agency (U.S. EPA) site under the Superfund Accelerated Clean-Up Model
(SACM) program. The SACM site was spearheaded by the U.S. EPA Region VOI and the Utah
Department of Environmental Quality (UDEQ). Technical support was provided by the U.S. EPA
Environmental Response Team (U.S EPA/ERT) and Roy F. Weston, under their Response
Engineering and Analytical Contract (REAC).
Fifteen abandoned or inactive smelter sites in Salt Lake County, Utah, were grouped into eight sepa-
rate areas. Over 1700 surface soil samples were analyzed for lead (Pb) by field portable x-ray fluo-
rescence spectrometer (FPXRF), revealing several areas of significant lead contamination. One of the
areas, to be called LEAD City from now on, was selected for an in-depth multi-media Pb exposure
assessment. LEAD City was selected not only for the presence of significant Pb levels, but also
because it is a residential area with many families having children six years old and younger.
Children under the age of six are highly suspectable to the adverse effects of Pb exposure, including
neurological and developmental disorders.
The realization that a vast amount of analytical data would be generated that would have to be linked
wilh demographics information such as: names, addresses, phone numbers, and number of children,
lead to the creation of a comprehensive database program. The database program must be able to
accept analytical data from numerous sources, link them wilh demographics information, and health-
nsk census, and be able to track the progress of the project. A program called LCITY_DB was creat-
ed by the U.S. EPA/ERT and REAC to address the above issues.
The LC1TY_DB program will generate unique sample identification codes, chain of custodies, import
data, (manually or electronically), schedule health-risk census appointments, and check for complete-
ness. A major function of the LCITY_DB program is the ability to sort and generate reports by
numerous indices, thereby allowing statistical and demographic evaluation of the LEAD City project.
One of the reports generated can be downloaded into the U.S. EPA's Integrated Uptake and Bio-
Kinetic model (IUBK), to predict blood Pb levels in children.
The LCITY_DB was used by the U.S. EPA Region VUl Technical Assistance Team (TAT), the Utah
Department of Environmental Quality (UDEQ), U.S. EPA Region Vffl lexicologists, the U.S.
EPA/ERT and REAC, from November 1992 to April 1993. The LCITY_DB program is easy to use,
wilh pull-down menus and programmed "hot keys". The LCTTY_DB program is a Microsoft DOS
executable program which can be ran on a standard XT type computer, with no special computer
training required.
Over 500 residences were investigated. At each residence, Pb in exterior soils and Pb-in-Paim (both
K and L lines) on interior and exterior surfaces were determined using two different FPXRFs. Pb in
tap waters and indoor dust, were determined via atomic absorption or inductively coupled plasma
emission spectroscopy, on only those residences with children six and under. For each of these resi-
dences, a comprehensive health-risk census was performed. Over 7000 Pb analysis were performed
on the various matrices at LEAD City. The LC1TY_DB program will be demonstrated with various
sorting routines and demographic reports showcased.
'Currently with R.O.W. Sciences
59 Wednesday, February 22, 1995
-------
Emerging Technologies and New Developments
40
41
NEW TECHNIQUES FOR SOIL VAPOR SAMPLING AND ANALYSIS
Byron D. Taylor, TVG Environmental, Inc.
The objective of the presentation is to discuss the research and development that has resulted in the
production of a new system for soil gas, extraction, sampling and analysis.
The technology is based on the in-situ increase of soil temperature and the reduction of atmospheric
pressure to facilitate the extraction and sampling of soil contaminants heretofore out of reach for
soil vapor analysis. Data from numerous field trials and applications will be included in the full
presentation.
The concept of inserting probes into the soil to extract and analyze evolved earth gases was reported
to have been first employed for analytical applications as early as 1853. It was not until 1975 that the
technique was first attempted as a means to detect and trace contaminants.
In order to expand the range of compounds suitable for soil vapor assessment, a new steam heated
vapor extraction well-point has been developed. The well-point allows for the introduction of high
pressure steam into a sintered, stainless steel diffusing material which provides a heat source within
the soil matrix. The introduction of steam in this manner not only adds heat to the subsurface soil
structure, but also ensures that drying of the soil does not occur during the vacuum extraction process.
In addition, the added moisture prevents the by-passing of atmospheric gasses at the surface from
infiltrating down to the vacuum extraction ports. Also, the former limitations of Henry's Law
Constant and vapor pressures are reduced by this sampling and extraction process.
In addition the heated sampling tip, the system employs an insertion process that minimizes distur-
bance and disruption of the sub-surface soil matrix and maximizes the seal around the probe rod.
These factors insure the maximum vacuum in the sampling zone and protect against the introduction
of diluting, surface air into the sample prior to analysis.
The newly developed steam-heated/vacuum extraction sampling point and Steam-Probe™ system
overcame many of the limitations of previous soil vapor assessment techniques. In addition to broad-
ening the range of compounds detectable by the process, it allows for the rapid assessment of a sue
and the horizontal and vertical plotting of a contaminant plume. Due to the reduced demand for bor-
ing equipment and laboratory services, results can be available instantaneously and at a significantly
reduced cost.
COMPARISON OF IR AND THERMAL EXTRACTION RESULTS FOR TOTAL
RECOVERABLE PETROLEUM HYDROCARBON ANALYSIS
Paulene Roberts, Charles Henry, Doug King* Ray Warden," and Edward Overlon, Institute for
Environmental Studies, 42 Atkinson Hall, Louisiana State University, Baton Rouge, LA 70803,
*Ruska Laboratories, Inc., 3601 Dunvale, Houston, TX 77063
New Total Petroleum Hydrocarbon (TPH) methodologies are evolving in response to restricted use
and possible elimination of chlorinated solvents. New techniques must meet or exceed the current
analytical standards for precision, accuracy, and extraction efficiency as defined by method 418.1.
This paper investigates the use of thermal extraction and flame iomzation detection as an alternative
method to the freon extraction followed by IR analysis for soils, (method 418.1, modified).
The noted advantages of thermal extraction are extraction without solvents, rapid extraction and
analysis time. With an flame ionization detector (FID) connected as a single unit to the thermal
extraction device, analysis and extraction are completed as a single operation with no loss of extract-
ed compounds due to transfer or solvent reduction. Through this form of TPH analysis a thermal
chromatogram, or thermogram, is created which provides qualitative as well as quantitative informa-
tion to potentially classify petroleum contaminated soils.
Both methods are compared using natural soils (sand, high organic, and silt/clay) spiked with various
oils at a range of concentrations. In addition, actual environmental samples were analyzed. All sam-
ples were analyzed by both techniques in replicate and results were statistically synthesized. Results
presented will include the range of compounds applicable for thermal extraction using the proposed
method. Matrix effects and interferences as well as extraction effectiveness relative to solvent extrac-
tion techniques will be discussed.
Wednesday, February 22, 1995 60
-------
Emerging Technologies and New Developments
42
43
FIELD APPLICATIONS OF FLOW CYTOMETRY
Peter J. Slopa, Lavon Harbor, and Gary J. Herman, Research and Technology Directorate, Advanced
Technology Department, US. Army Edgewood Research, Development, and Engineering Center,
APG. MD 21010-5423, and Stepahnie Ann Sincock, Science and Technology Corporation, 101
Research Drive, Hampton, VA, 23666-1340
Flow Cytometry (FC) is a spectroscope technique that allows one to interrogate the individual mem-
bers of a sample population for information on size, shape, and specific chemical properties. FC has
been the workhorse in the clinical hemstology laboratory for sortingAyping blood cell populations. It
has been proposed that the technique could serve as a possible platform for monitoring the environ-
ment for biological materials.
Preliminary results in the laboratory suggest that the technique can be very powerful. One may be
able to differentiate among naturally occurring aerosols, live and dead organisms, specific chemical
properties, and other properties. In addition, the instrument could serve as a possible biosensor plat-
form for immunological and DNA probe-based detection systems. Several authors have shown the
use of this technology as means to monitor water for the effectiveness of treatment for biological
materials.
This talk will focus on the applications of flow cytometry in the environmental area, propose some
strategies for implementation, and present some of the laboratory and field data to date.
POLYCYCLIC AROMATIC HYDROCARBONS FROM U.S. AND ANTARCTIC
SITES ANALYZED WITH SYNCHRONOUS FLUORESCENCE SPECTROME-
TRY
E Neat Arrack and James E. Pollard, Lockheed Environmental Systems and Technologies Company,
Las Vegas, NV 89119-3733, William H. Engelmann and Kenneth W. Brown, US. Environmental
Protection Agency, Environmental Monitoring Systems Laboratory, Las Vegas, NV 89193-3478, Juan
Vo-Dinh, Oak Ridge National Laboratory. Oak Ridge TN, 37831-6101, Femi M. Akindele, U.S.
Environmental Protection Agency, Region IV, Atlanta, GA 30365, Alan B. Crockett and Garold L.
Gresham, Idaho National Engineering Laboratory, Idaho Falls, ID 83415-2213
The U.S. Environmental Protection Agency (EPA) continues to search for innovative field methods
and instrumentation that are fast and inexpensive. EPA's Environmental Monitoring Systems
Laboratory in Las Vegas, Nevada (EMSL-LV) has sponsored the development of an advanced proto-
type portable scanning speclrofluorometer. This paper describes recent field performance at an EPA
Region IV site where it rapidly analyzed mixed poiycyclic aromatic hydrocarbons (PAHs). In each
case, soil samples from locations with suspected PAH contaminants were rapidly characterized in the
field using the UV- Vis synchronous fluorescence mode of operation. Synchronous scans of the
mixed PAHs provided excellent "spectral separation", showing the peaks of component PAHs in the
pollutant mixture.
In addition, sediment samples from Winter Quarter Bay, McMurdo Station in Antarctica were ana-
lyzed for PAHs. Levels of detection in the laboratory with synchronous mode was about 3 parts per
billion for anthracene, a typical PAH- The collaborating group at the Idaho National Engineering
Laboratory, whose Antarctic field work was supported by the National Science Foundation, used con-
ventional analytical procedures and these data were compared to the fluorescence data. Attempts
were also made to identify the sources of contamination which included diesel and jet fuels, bunker C
and lubricating oils.
Based on early field results, synchronous fluorescence shows great promise for use as a Held screen-
ing method for PAHs. While there are some limitations in utilizing this innovative and rapid field
screening technique, synchronous fluorescence offers several major advantages; these are discussed in
the paper.
Notice: The U.S. Environmental Protection Agency (EPA), through its Office of Research and
Development (ORD), prepared this abstract for a proposed oral presentation. It does not necessarily
reflect the views of the EPA or ORD.
61 Wednesday, February 22, 1995
-------
Emerging Technologies and New Developments
44
45
DEVELOPMENT AND TESTING OF A VOLATILE ORGANICS CONCENTRA-
TOR FOR USE IN WATER QUALITY ANALYSIS
D. Ehnlholl. I. Bodek and T. Slolki, Arthur D. Liltle, Inc., 15 Acorn Park, Cambridge, MA 02140
A new approach to the concentration and analysis of parts-per-billion levels of volatile organic com-
pounds in drinking water will be described. The technology requires only small (10 ml) samples of
water and no solvent use. It has been demonstrated using the compounds generally monitored by
EPA Method 524.2 using both GC/FID and GC/MS analytical finishes. Test results indicate that the
method has comparable detection limits for many compounds, but can analyze a wider range of com-
pounds and in some cases has detection limits which reach a factor of five lower. It is also expected
to facilitate field sampling of water sources and to be extendable to field sampling and analysis.
THE DEVELOPMENT OF A SOLVENT-FREE APPROACH FOR THE DETER-
MINATION OF PETROLEUM HYDROCARBON IN WATER PETROLEUM
HYDROCARBONS; WATER ANALYSIS
D. Ehntholt, I. Bodek and E. Miseo, Arthur D. Little, Inc., 15 Acorn Park, Cambridge, MA 02140
Efforts to develop methods for the determination of total petroleum hydrocarbon (TPH) content of
environmental samples which do not require the use of toxic or hazardous organic solvents are ongo-
ing. Alternate approaches include the use of supercritical fluid solvents such as carbon dioxide, and
organic solvents other than the freons.
We have developed a new technology which includes sample collection, concentration, separation (if
desired) and analysis steps necessary for the determination of petroleum hydrocarbon content of aque-
ous samples. No organic solvents are necessary to practice this technology, and sample handling can
be automated for use in the field or for laboratory analysis. Analyses have been performed on hydro-
carbon mixtures in water which contain carbon lengths up to tetradecane at individual compound con-
centrations in the low parts-per-million range.
The results of these analyses compare favorably with standard methods currently used for TPH analy-
ses of water samples.
Wednesday, February 22, 1995 62
-------
Emerging Technologies and New Developments
46
47
LABORATORY AND FIELD-SCALE TEST METHODOLOGY FOR RELIABLE
CHARACTERIZATION OF SOLIDIFIED/STABILIZED HAZARDOUS WASTES
K.E. Gray and Jon Holder, Center for Earth Sciences and Engineering, The University of Texas at
Austin. Texas, USA, M.YA. Mollah. TJt. Hess, KJC. Vempati and D.L. Cocke, Gill Chair of Analytical
Chemistry, Lamar University, Beaumont, Texas, USA
Laboratory test methodologies for field testing of solidification/stabilization (S/S) systems are
described. This research combines the expertise in soil/rock mechanical/flow-through testing capabil-
ities of the Center for Earth Sciences and Engineering (CESE) at the University of Texas and the S/S
chemistry capabilities of The Gill Chair of Analytical Chemistry at Lamar University to attack one of
the most important shortcomings of S/S remediation technology - the prediction of long-term stability
of selected S/S hazardous waste systems currently used or contemplated for use in remediation of
mixed wastes at DOE and DoO sites.
The TCLP leach test creates a worst-case environment for all attempts to correlate laboratory leaching
tests with field data have been unsuccessful. Leaching in S/S material is due to the movement of
water or other solvents through the pore structure, and leaching behavior can differ significantly from
that in the equilibrium configuration of a TCLP test. Two procedures have been used to more effec-
tively characterize real-world behavior 1) tests utilize flowing pore water to replicate field condi-
tions; and 2) reactions are accelerated by adjustments in flow rate, temperature, pressure, and/or sol-
vent chemistry. The laboratory testing systems at the CESE provide for simultaneous measurements
of chemical leaching behavior; bulk properties such as strength, mechanical deformation behavior,
porosity, and permeability; and physical properties such as wave velocities and electrical conductivi-
ty. Measurements of leaching behavior have been earned out for flow through 'intact' specimens and
for fracture flow through specimens subjected to failure stresses in the apparatus. These procedures
are used to establish: 1) procedures for accelerated testing of selected S/S systems; 2) appropriate
measured properties or indicators; 3) failure criteria in addition to acid leaching behavior, 4) a stan-
dard methodology for systematic data analysis and development of hypothesis, concepts, and models;
and 5) relationships between S/S formulations and durability and longevity.
Results are presented for measurements on test specimens of strontium in Portland cement, with and
without added fly ash, which have been subjected to sustained flow of low-pH fluid through laborato-
ry-scale specimens under modest pressure. The analysis of effluent pore fluid chemistry as a function
of time provides direct leaching behavior tinder simulated disposal conditions. Data from the test are
used with numerical simulations to provide an indication of correlation or a lack of correlation with
current certification standards and to extrapolate short-term laboratory performance to anticipated
repository time scales. In addition to the fluid chemistry analysis, analysis of physico-chemical prop-
erties on selected pre- and post-test specimens, using wet chemistry and bulk and surface characteri-
zation, are being done to determine mechanisms of binding and leaching.
INSTRUMENTATION FOR ON-SITE TRACE ORGANIC ANALYSIS OF SOIL,
WATER, AND AIR
S.A. Liebman (CECON Group, Inc.), T.P. Wampler, J.W. Washall, CDS Analytical, Inc., 7000
Limestone Rd., Oxford, PA 19363
Time-dependent information must be made available for site-assessment and remediation teams to
ensure effective decision-making regarding trace organics in soil, water, and air. Automated instru-
mentation and methods developed over the past decade are shown to provide qualitative and quantita-
tive data for a range of priority pollutants and toxic organics. Sample processing with thermal des-
orption and/or supercritical fluid extraction (SHE) are directed to target groups or chemical species for
rapid (5-30 min) screening or integrated on-line chromalographic and spectral analyses. Analytical
systems that focus on purge-and-lrap methods for water, thermal desorption for soils, or SFE of sor-
bent bed air cartridges are used with integral cryotrapping/detectors in automated method sequences.
Commercial instrumentation designed for integral sample processing (thermal and nonlhermal) with
enrichment/trapping is shown effectively interfaced with established chromatography (GC or SFC)
and versatile detectors, including flame ionization, photoionization, infrared, or mass spectral units.
Pre-programmed methods for selected organic targets permit in-field use with minimal operator train-
ing to detect and to identify species over wide concentration levels (percent to part-per trillion).
Interdisciplinary teams, such as demonstrated in DOE's Expedited Site Characterization program, are
thus provided with validated on-sile information for needed decision-making. Illustrations will be
given for data generation with compact, flexible organic analyzers that are combined with expert sys-
tem and neural network software packages to demonstrate the advantages of integrated intelligent
instrumentation for the environmental sciences.
63 Wednesday, February 22, 1995
-------
Emerging Technologies and New Developments
48
49
HELD TESTING OF A PORTABLE FIBER OPTIC CHEMICAL SENSOR FOR
CARBON TETRACHLORIDE, TRICHLOROETHYLENE AND CHLOROFORM
James C. Wells. David A. Gobeli, Harmesk Kumar, Puna, Inc., San Jose, California 95134- 2010,
and Roger Jenkins, Chemical and Analytical Sciences Division, Oak Ridge National Laboratory, Oak
Ridge, Tennessee 37831-6120
Purus, Inc. has developed and is testing a field transportable PurSense™ fiber optic chemical sensor.
Field evaluation of the PurSense™ unit will begin in July 1994, at Oak Ridge National Laboratory.
The configuration of the PurSense™ fiber optic chemical sensor is based upon a laboratory unit with
additional features to accommodate field analysis. The system may be battery operated and consists
of a flow optrode, integral VOA vial heater, reagent delivery and recovery system with removable
reagent pack, fiber optic transmitter-receiver, embedded micro controller, 2 line by 20 character LCD
and communication port. The sensor is contained in a carrying case measuring 46 x 30 x 20 cm. and
weighs less than 10 kg. The optrode is a miniature reaction chamber through which a chemical
reagent is pumped. The reagent reacts with gaseous halogenated compounds that diffuse in through a
gas permeable membrane to form a colored product. The concentration of the product is detected by
measuring the rate of change of the transmission of light from a 560 nm light emitting diode. The
analysis time is 2.5 minutes at the detection limit of 5 ug/L using a 20 ml aqueous sample.
Measurement methodology, sensor performance and reliability will be evaluated using reagents for
the semi-specific determination of ppb concentration levels of carbon letrachloride, tnchloroethylenc,
and chloroform in water, soil and gaseous samples. The results of this evaluation will be compared
with laboratory GC results to demonstrate the viability of using this sensor as a field screening and
monitoring tool.
THERMAL DESORPTION ANALYSES OF ENVIRONMENTAL SAMPLES
O J. Vetter and Y Ding (VETTER RESEARCH INC, COSTA MESA, CA)
Organic constituents at low concentrations in environmental samples are normally determined by
using either "purge &. trap" methods or various types of extraction methods followed by GC analysis.
Roth basic types of analysis method have numerous disadvantages. Many of these principal disad-
vantages are avoided by a third and novel type of "thermal desorption - trap" method.
The organic constituents of solid samples are thermally desorbed into a trap similar to that of the
"purge and trap" method. While this new method offers only marginal advantages over the conven-
tional "purge and trap" methods, this new method is far superior to any analysis method that relies on
sample extractions.
We developed the new "thermal desorption - trap" method as a replacement or alternative to US-EPA
methods 8020 ("purge & trap") as well as 8080 and 8100 (extraction methods). The new "thermal
desorption - trap) method allows us to determine PCBs (8080) and PNAs (8100) much more reliably
(better accuracy and precision) and at much lower Method Detection Limits (MDLs) than the more
conventional US-EPA methods 8080 and 8100. Combining this new thermal desorption methodology
with high resolution capillary gas chromatography, we can easily determine PNAs and PCBs down to
lower parts per trillion levels with high accuracy and precision.
We can also determine volatile aromatics (8020 replacement) with this new method. The new
method is far superior to US-EPA method 8020 if the solid sample is fairly dry. However, severe
technical problems caused by a high water content in the sample has not yet been resolved.
All of these "thermal desorplion - trap" methods can easily be performed either in the lab or the field.
Wednesday, February 22, 1995 64
-------
Emerging Technologies and New Developments
50
51
NON-PURGEABLE VOLATILE ORGANIC COMPOUNDS RAPIDLY DETER-
MINED BY GAS CHROMATOGRAPHY/MASS SPECTROMETRY USING
DIRECT AQUEOUS INJECTION
Steven M. Pyle and Alvin B. Marcus*. US. Environmental Protection Agency, EMSL-LV, Las Vegas,
NV 89193-3478, Linda S. Johnson. U.S. Environmental Protection Agency, NEIC, Denver, CO 80225
The ion Imp mass spectrometer, a recent commercial innovation, has made possible the detection of
organic compounds at the picogram level in the full-scan mode. Using uL sample injection volumes,
this translates into potential pans-per-billion sensitivity for the direct injection and analysis of aque-
ous environmental samples. Direct aqueous injection (DAI) is rapid, simple, and sensitive. It also
eliminates the need for waste-solvent disposal and is compatible with EPA pollution prevention poli-
cy. Compared with solvent extraction and purge and-trap preparatory methods, DAI is particularly
suited to analyzing aqueous samples for non-purgeable, poorly purgeable, or non-extractable, volatile
organic pollutants.
A DAI method was developed for the determination of 19 non-purgeable volatile organic compounds
for which no method currently exists. These polar liquids were spiked into distilled water at 1 - to
100-ppm levels and analyzed in triplicate using a fused-silica capillary column interfaced to an ion
trap mass spectrometer. Using internal standardization, the relative response factors and relative
retention times for the 19 compounds were determined. Duplicate data was collected using on-col-
umn and split injectors. Accuracy and method detection limits (MDLs) were calculated from 10
replicate injections of 2-ppm standards. For split injection, the average relative standard deviation
(%RSD) for the compounds was 19% and the average MDL was 800 ppb; for on-column injection,
the respective values were 13% and 800 ppb. Agreement with HP A-established criteria for 4-bromo-
fluorobenzene will also be shown.
Data from the EMSL-LV Analytical Sciences Division will be presented to show method limitations
involving injection volume and injector conditions (injection speed, insert type, temperature, etc).
Attempts to optimize method precision and peak shape will also be discussed.
•Senior Environmental Employee Program Enrolle hosted by the National Association for Hispanic
Elderly.
DESIGN CONCEPTS AND PERFORMANCE CRITERIA IN THE DEVELOP-
MENT OF A COMPACT, PERSON-PORTABLE GCYMS SYSTEM
B. Eckenrode, B. Starzynski, Viking Instruments Corporation, Reston, VA 22091, B. Andresen, G
Coults, Lawrence Livermore National Laboratory, Livermore, CA 94550
Lawrence Livermore National Laboratory and Viking Instruments Corporation have teamed together
to develop an advanced, very compact, person-portable GC/MS system for dual-use field analysis
applications, including rapid on-site screening for environmental contaminants. This research and
development project is sponsored by the U.S. Department of Energy, Program NN-20.
This compact GC/MS system incorporates a temperature-programmable, rapid-eluuon, low-thermal-
mass gas chromalograph with back-pressure regulation, split/sphtless capability, and sorbent cartridge
concentrator/thermal desorber, a hybrid ion/sorption vacuum pump developed by Lawrence
Livermore Laboratory; and the Hewlett-Packard model 5972 monolithic quadrupole mass analyzer.
The analyzer instrument weighs less than 44 pounds, and is packaged in a fabric carrying enclosure
the size of a brief case (19 x 8.5 x 15 inches). A compact external laptop computer provides all soft-
ware and signals for instrument control and data analysis.
This paper reviews the design concepts and performance criteria used in developing this new instru-
ment. Benchmark performance data and parameters are presented and discussed. Target environmen-
tal applications include emergency response analysis, soil gas screening, ambient air quality monitor-
ing, and hazardous waste site characterization.
65 Wednesday, February 22, 1995
-------
Emerging Technologies and New Developments
52
MODERN THIN-LAYER CHROMATOGRAPHY FOR FIELD-SCREENING:
DETERMINATION OF PHENOLS
William C. Brumley and Elizabeth M. Shafier, US. EPA, EMSL-LV, P.O. Box 93478, Las Vegas, NV
89193-3478
Thin-Layer chrornalography (TLC) has been relatively ignored in the U.S. for environmental analysis.
Most published work using TLC for environmental samples has involved pesticides. The U.S. EPA
Environmental Monitoring Systems Laboratory, Las Vegas, maintains a continuous interest in various
separation technologies as part of its methods research program. A number of intrinsic advantages
would be associated with field-screening methods based on TLC. Among these advantages is the liq-
uid chromatographic nature of the separation; gas chromatography, for example, depends on the
volatility of the analytes and coextractives. Other advantages of TLC include its low cost, simplicity
and capability of analyzing 20 to 40 sample extracts simultaneously. Examples are given of the sepa-
ration of selected phenols by TLC on silic gel plates and their determination using ultraviolet and flu-
orescence detection.
Notice: The U.S. Environmental Protection Agency (EPA), through its Office of Research and
Development (ORD), prepared this abstract for a proposed oral presentation. It does not necessarily
reflect the views of the EPA or ORD.
Wednesday, February 22, 1995 66
-------
Field Mobile GC/MS
53
54
ON-SITE ANALYSIS OF LANDFILL GAS AND LANDFILL GAS FIRED BOILER
EXHAUST
P. Williamson, South Coast Air Quality Management District, Diamond Bar, CA 91765-4182
Currently samples of landfill gas and landfill gas fired boiler exhaust are analyzed by a time-consum-
ing process of field sampling, sample transportation, and storage, followed by multiple analyses on
several different instruments; except for expedited samples this can take more than one day. Samples
of landfill gas are analyzed for BTX by GC/PID, chlorinated compounds by GC/ECD and sulfur
compounds by GC/SCD. Use of GC/MS allows simultaneous analysis of all three classes of com-
pounds with equivalent sensitivity. "On-Sile" analysis by GC/MS could potentially save many hours
of laboratory analysis time while providing additional spectral identity confirmation.
We used a Viking Spectra Trak 620 field-mobile GC/MS to analyze landfill gas and landfill gas fired
boiler exhaust on-site at Rio Hondo College with landfill gas from Puenle Hills Landfill. We also
took samples of the landfill-gas and boiler exhaust for later laboratory GC/PID and laboratory
GC/MS analysis at the SCAQMD lab. Comparing our laboratory analyses to on-site GC/MS analysis
shows that the field-mobile GC/MS is sufficiently sensitive for landfill gas and boiler exhaust sam-
ples.
Analysis of the landfill fuel gas and the boiler exhaust occurred simultaneously with sampling into
tedlar bags. On-site analysis took less lime than the taking of samples for later laboratory analysis.
The field-mobile GC/MS detected not only BTX, but chlorinated and sulfur containing compounds as
well. Several other compounds not routinely analyzed for (limonene, etc.,) were also detected by the
field-mobile GC/MS.
FIELD EVALUATION OF A PROTOTYPE MAN-PORTABLE GC/MS
Neil S. Arnold, Sue Anne Sheya*. Houssein Mihamou", Jacek Dworzanskt*, William H. McClennen*
and Henk L.C. Meuzelaar*, FemtoScan Corporation, 1549 South 1100 East, Salt Lake City, UT
84105, *University of Utah, Ctr. Micro Analysis A. Reaction Chemistry, 214 EMRL, Salt Lake City,
UT84I12
In recent years a man-portable gas chromatography/mass spectrometry (GC/MS) system has been
developed based on a Hewlett Packard 5971 MSD and a unique automated vapor sampling transfer
line GC system for direct sampling of ambient chemical vapors [1]. The vacuum system and power
supplies were replaced to facilitate operation on 24 vdc batteries for up to 4 hours after startup on a
transportable docking station. The gas chromatography was performed on a short capillary column
under isothermal conditions in a small oven to minimize power usage. Repetitive samples were taken
at -70 s intervals using an automated vapor sampling inlet [2].
In initial testing, the prototype system has been used for monitoring of gasoline vapors. Ambient lev-
els of 6.0 ppm benzene, 4.1 ppm toluene, 0.22 ppm ethylbenzene, 1,1 ppm m- and p-xylene and 0.25
ppm o-xylene were measured near a busy gas station [3]. The gradient mapping or source tracking
capabilities of the backpack mounted system have also been demonstrated in preliminary tests with a
simulated gasoline leak.
This paper will describe recent work to further evaluate the capabilities and limitations of the proto-
type system. In tests planned for summer 1994, the instrument will be used to monitor emissions
from one or more industrial sites. Results will be described in terms of the practical utility of
portable GC/MS for identification and quantitation of unknown vapors.
1. Arnold, N.S., Cole, P.A., Du, W.H., Watteyne, B., Urban, D.T., Meuzelaar, H.L.C., Proc. Intl.
Symp. on Field Screening Methods for Hazardous Wastes and Toxic Chemicals, Feb. 1993, Las
Vegas, 1993,2,915-931.
2. Arnold, N.S.. McClennen, Meuzelaar, H.L.C., Anal. Chem., 1991, 63. 299-304.
3. Du, W., Arnold, N.S., Cole, P.A., Watteyne, B., Urban, D.T., Meuzelaar, H.L.C., Proc. 41st
ASMS Conf. Mass Spectrom. All. Top., June 1993, San Francisco, 1993, 439.
Thursday, February 23, 1995 67
-------
Field Mobile GC/MS
55
56
VOLATILE ANALYSIS USING MOBILE GC/MS
G. Baykut, A Loudon, B. Nolke, Bruken-Franzen Analytik Gmbh, Bremen, Germany
Clearly the numerous advantages of field screening methods has increased the interest with those in
development of mobile technology and those in the field using these methods. In the past, the choice
was clear, if you needed GC/MS analyses, samples were sent to service laboratories. However,
advancements made in mobile quadrupole technology now offers those in the field an alternative -
realtime GC/MS results on site where the information is needed and can be used for immediate
response. The idea of this study is to show that GC/MS in the field can be used for full data analysis
and not limited to just field screening.
Analytical challenges in the "field" setting add to the already imposing difficulties in contamination
analysis. Using techniques and methods similar to those already developed for a laboratory setting, in
the past, seemed impossible. Due to these advances in mobile GC/MS technologies this is not only
possible but practical, cost effective, time efficient and easily implemented.
This study includes the analysis of volatile organic compounds using the mobile quadrupole GC/MS
Data illustrates a more complete analysis of volatile compounds rather than a screening of just BTBX
which, in the past, was all that was typically analyzed on site. The volatile analytes include com-
pounds ranging from chloromelhane to 1,1,2,2-tetrachloroethane. Analysis and data evaluation were
based on the volatile EPA methodologies, including tuning criteria, calibration and quantiution.
Samples were purged using a simplified purge and trap device and desorbed on to a DB624™ capil-
lary column. The mass spectrometer was tuned and evaluated according to EPA specifications using
Bromofluorobenzene. Full scan measurements were used for all analytical runs. Results from the
calibration curve and matrix samples will also be illustrated.
FIELD-PROVEN TRANSPORTABLE GC/MS: REAL-WORLD CASE STUDIES
AND SUCCESS STORIES
J. Christenson, B. Eckenrode, Viking Instruments Corporation, Reston, VA 22091, D. Gallis,
Environmental Resources Management Inc., Exton, PA 19341
Gas chromatography coupled with mass spectrometry (GC/MS) has evolved into being the preferred
technique for analyzing challenging environmental samples in complex matrices. In this paper we
present case studies and success stories in applying a field-proven, fully transportable GC/MS system
that is conveniently deployed to perform on-site GC/MS analysis, with results equivalent to benchtop
laboratory systems. This on site GC/MS analytical capability provides real-lime, decision-quality
data, while reducing sample handling delays, minimizing laboratory analysis costs, and eliminating
sample degradation, so analytical results accurately represent actual on-site conditions.
For environmental analysis, this on-site GC/MS capability performs detailed analyses of complex
sample matrices, with rigorous decision-quality QA/QC levels. This enables high-volume, accurate,
comprehensive analysis of soil, soil gas, air, stack emission, and water samples. Compared to the
customary practice of collecting samples and then sending these samples off-site to a laboratory, this
transportable on-site GC/MS capability saves time, improves accuracy, and eliminates costly labora-
tory analysis fees. Site characterization is accelerated, environmental remediation is streamlined,
costly delays and remobilizau'on are avoided.
Several real-world case studies are presented, including soil contamination characterization, ground
water analysis and plume delineation, emergency response environmental analysis, and air toxics
analysis.
68 Thursday, February 23, 1995
-------
Field Test Kits
57
58
A NEW FIELD TEST KIT FOR THE RAPID DETERMINATION OF DIESEL
FUEL IN SOIL
Jf. Schabron, N£>. Niss, BX. Han, andJK. Hart, Western Research Institute, 365 N. 9th Street,
Laramie, Wyoming 82071
A new test kit is available for evaluating diesel and other fuel contamination in soils. While the
Ficon extraction/infrared method estimates fuel concentration by measuring aliphatic C-H stretch,
approaches designed to replace this such as the immunoassay method and the method involving a
Fridel-Krafts alkylation reaction measure the aromatic component of fuel mixtures. Both of these
methods measure fuel aromatic content indirectly with visible color development. The new method
measures the aromatic components directly with a 254 run portable field photometer. The method
involves a 3-minule extraction of soil with a 10:1 ratio of isopropyl alcohol. Prior to extraction, (he
soil is treated with an agent to minimize the extraction of humic materials which can interfere. The
extract solution is passed through a syringe filler and the absorbance is read at 254 run The fuel con-
centration is calculated based on average relative response factors. Alternatively, the actual contami-
nant fuel can be used as a standard if it is known. The quantitation limit is about 75 mg/kg diesel in
soil. The method has been tested with a variety of soils and fuel types.
USE OF FIELD SCREENING TEST KITS TO DELINEATE HYDROCARBON
CONTAMINATION
Richard N. Molsbee*, Science and Technology, Inc., Oak Ridge, Tennessee 37831, and David W.
Bunri", Advanced Sciences, Inc., Oak Ridge, Tennessee 37831
Field screening test kits were recently used to delineate hydrocarbon contamination in sods along a
3000-ft long abandoned fuel line and distribution system. The purpose of using the kits was to mini-
mize characterization expenses while providing reliable and cost-effective information. More than
200 tests were run on soils at depths from surface to 12 ft below the land surface. The total petrole-
um hydrocarbon (TPH) test used immunoassay technology to detect TPH values below 10 ppm.
Fixed-base laboratory analyses were performed on 10% of the samples collected for field screening.
A review of the screening results and the fixed-based laboratory results show that the field tests were
comparable.
As a result of this screening effort, future site characterization efforts will be able to focus on specific
areas of soil contamination. The test kits selected and used were the Hach TPH in Soil Kits that use
the Environmental Product, Inc., PETRO RISc* Soil Test. The PETRO RISc* Soil Test has been
approved for inclusion in the third update of Test Methods for Solid Waste, SW-846, under EPA
Draft Method 4030. Using this technology eliminated the delay in waiting for laboratory results and
the higher costs associated with gas chromatography. Immunoassay kits are an important tool in field
screening efforts, and they save time and monies. By using a S150/sample for EPA Method 8020
(BTEX), a savings of more than $20,000 was realized. The time savings was realized by not having
any downtime while waiting for laboratory results.
*The authors are assigned to provide hydrogeological support to the Hazardous Waste Remedial
Actions Program, Martin Marietta Energy Systems, Inc.
The submitted manuscript has been authored by a contractor of the U.S. Government under contract
DE-AC05-84OR21400 with the U.S. Department of Energy. Accordingly, the U.S. Government
retains a paid-up, nonexclusive, irrevocable, worldwide license to publish or reproduce the published
form of this contribution, prepare derivative works, distribute copies to the public, and perform pub-
licly and display publicly, or allow others to do so, for U.S. Government purposes.
Thursday, February 23, 1995 69
-------
Field Test Kits
59
60
FIELD SCREENING METHOD FOR PICRIC ACID/AMMONIUM PICRATE IN
SOIL AND WATER
Philip G. Thorne and Thomas F Jenkins, US. Army Cold Regions Research and Engineering
Laboratory, Hanover. New Hampshire 03755-1290
Ammonium picrate (ammonium 2,4,6-trinitrophenoxide) was the principal explosive used in a num-
ber of armor-piercing shells, bombs and rocket warheads from the early 1900s until after World War
n. While it is no longer manufactured, wastes containing this component are still encountered at mil-
itary installations. In addition, approximately 8% of the demilitarization inventory contains ammoni-
um picrate. Picric acid (2,4,6-trinitrophenol) is a common industrial chemical with uses that include
dyeing fabric and leather, glass coloration and metal etching. Since the pKa of picric acid is 0.8, both
picric acid and ammonium picrate occur as the dissociated picrate ion in the environment. Because of
its high water solubility (about 10 g/L), picrate appears to be quite mobile in the soil profile. The
objective of the work described here was to develop simple field-screening methods for ammonium
picrale/picric acid in soil and water.
For soil a 20-g sample is extracted by manual shaking with 100 mL of acetone in a like manner to the
colorimetric screening methods for TNT and RDX. A 20-mL filtered aliquot is mixed with 20 ml. of
deionized water and passed through a 3-mL SPE-ALUMINA-A (Supelco) cartridge. Picrale is
retained on the alumina. Interferences are removed by passing through a 5-mL aliquot of melhanol
followed by a 2 to 3-mL aliquot of acetone. Picrate is eluted from the cartridge with 5 mL of acetone
which has been acidified with 2 drops of concentrated sulfuric acid. The elucnt is added to an addi-
tional 10 mL of unacidified acetone and the resulting solution should be colorless. The solution is
then diluted with 5 mL of deionized water and a change from colorless to yellow is indicative of the
presence of picrate at a concentration above 3 ug/g. The picrate concentration can be estimated from
the absorbance of the solution at 400 ran with a Method Detection Limit of 0.9 ug/g. The field
screening method was tested using several field-contaminated soils and the results compared favor-
ably to the laboratory HPLC method.
For water, a 2-L sample is passed through a 47-mm Empore Anion SPE Membrane (3M Corp.) which
retains picrate ion. A 10 mL rinse with methano] removes interferences. If the membrane remains
white, there is less than 2 ug/L of picrate. If the membrane turns yellow, it is rinsed with 10 mL of
acetone and one drop of a color-forming reagent (EnSys Inc. -TNT reagent) placed on the surface. A
pink Meisenheimer anion confirms the presence of picrate. If the membrane retains brown humic
materials, the color reagent produces a "rust" colored spot.
QUANTITATIVE FIELD MEASUREMENT OF TRINITROTOLUENE IN SOIL
Doug Peery, Daniel Brown, and Cora Huston, IT Corporation, Knoxville, Tennessee
The U.S. Army Corps of Engineers Cold Regions Research and Engineering Laboratory (CRREL),
under the direction of Dr. Thomas F. Jenkins, developed a colorimetric method for the rapid determi-
nation of 2,4,6-lrinitrotoluene (TNT) in soil. The test involves extracting soils with acetone and initi-
ating a reaction where nitroaromatic compounds in acetone form characteristically-colored solutions
in the presence of strong base. This lest was used in the field at two former TNT production facilities
that were undergoing remedial investigations. Much of the available information on the historical use
of this test indicates that it generally produces qualitative data. Matrix interference problems were
overcome on these projects to produce data that were quantitative and correlated well with data from
a commercial analytical laboratory. The test data were used to direct the efforts of the surface sam-
pling teams and drilling crews in selecting samples to define the levels and extent of TNT contamina-
tion at the sites. These data were also used to ensure personnel safety and compliance with
Department of Transportation (DOT) shipping regulations for selected samples containing TNT that
were sent off site for commercial laboratory analysis. The application of this test in the field to direct
project activities and to control project costs will be discussed in this paper. The comparability of the
field data with Level III analytical laboratory data will also be discussed.
70 Thursday. February 23, 1995
-------
Field Test Kits
61
62
THE COLORIMETRIC FIELD DETERMINATION OF 2,4-DINITROTOLUENE
IN SOIL
Doug Peery and Allen Bradley, IT Corporation, Knoxville, Tennessee
The U.S. Army Coips of Engineers Cold Regions Research and Engineering Laboratory (CRREL),
under the direction of Dr. Thomas F. Jenkins, has developed a colorimetric method for the rapid
determination of 2,4-dinitrotoluene (2,4-DNT) in soil. This analytical procedure is designed primarily
to yield qualitative data in soil matrices based on the intensity of the blue/violet color that develops
when indigenous 2,4-DNT chemically reacts with the test reagents. Results from this test method
were used to direct field sampling activities during a remedial investigation of an Army Ammunition
Plant in Tennessee. During the course of the project, problems were encountered with the method
that resulted in non-reproducible data. The test procedures were modified to improve performance of
the test on the soil matrices encountered at the site. The modified method produced semi-quantitative
test results that were used to select samples for mote extensive analytical characterization at a full ser-
vice off-site laboratory. Consequently, the ability to "screen" samples in the field resulted in reduced
off-site laboratory analytical costs. Further, the investigation team was able to gather the data needed
to support cleanup feasibility studies and risk assessments at the site using a single field mobilization.
This paper addresses the refinements made to the existing field lest method for 2,4-DNT and the
application of this method to aid in controlling project costs.
PHOTOACTIVATED LUMINESCENCE SPOT TEST FOR RAPID SCREENING
OF POLYCHLORINATED BIPHENYLS
T. Vo-Dinh, A. Pal, and T. Pal, Advanced Monitoring Development Group, Health Sciences Research
Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831-6101
The U.S. Department of Energy and the U.S. Environmental Protection Agency have a strong need
for screening capabilities for hazardous materials. Especially, there is a critical demand to have a
rapid and simple technique for screening polychlorinated biphenyls (PCBs) under field conditions.
The use of field screening analysis allows rapid decisions in a cleanup operation and reduces the need
for either return visits to a site by a cleanup crew or extensive and costly laboratory analyses of sam-
ples that contain no detectable levels of PCBs. Field screening techniques also reduce the cost of
remedial actions by preventing unnecessary excavation of uncontaminated soil.
This paper describes a new method based on enhanced phoioactivaied luminescence (EPL) for rapid
detection of polychlorinated biphenyls (PCBs). The EPL method described here is a unique proce-
dure combining several processes including (i) photoactivation by UV irradiation, (ii) excitation of
the pholoproduct complex, and (iii) fluorescence detection of the product. The EPL procedure is sim-
ple and rapid and can be performed as a spot test method under field conditions. The methodology
for determination of total chlorine content of complex PCB mixtures is described.
Thursday, February 23, 1995 71
-------
Gas Chromatography
63
64
FIELD DETERMINATION OF VOCs AT HAZARDOUS WASTE SITES
Daniel R. Coleman, Timothy M. Brice, Gary D. Sides, and Sandra T. Macon, CMS Research
Corporation, 200 Chase Park South, Suite 100, Birmingham, Alabama 35244
As the EPA increases its emphasis on actual remediation, there is a growing need for accurate and
reliable air-monitoring equipment that can perform on-site to provide air analyses for volatile organic
compounds (VOCs). Monitoring requirements are implemented through the Resource Conservation
and Recovery Act (RCRA) and the Superfund Amendments and Reauthorization Act (SARA). It is
often the case that the monitoring requirements are even more strict because of public pressure from
surrounding communities.
Automated gas chromatography provides a reliable means for on-site air monitoring for VOCs. With
careful selection of the GC column, column heating parameters, and the GC detector, an automatic
GC can be used to monitor for the presence of the target VOCs. This technology has been used at
two National Priority List (NPL) sites and in San Juan, Puerto Rico under the Superfund Innovative
Technology Evaluation (SITE) program. Details of the monitoring conditions, concentration data,
and monitoring system will be discussed.
FIELD SCREENING OF VOLATILE AND SEMI-VOLATILE ORGANIC POLLU-
TANTS USING A HEATED, PORTABLE MICRO GAS CHROMATOGRAPH
Mark W. Bruns, Ph.D., Debra L. Gonzalez, Microsensor Technology, Inc., MTI Analytical
Instruments, 41762 Christy Street, Fremont, California 94538
A heated, portable silicon micromachined gas chromalograph was designed, developed and recently
utilized in the characterization of volatile and some semi-volatile organic compound distribution in
soil at a site in the Midwest. The use of this system in the field allowed for the rapid, on-site charac-
terization and field screening of gasoline range VOCs and semi-volatiles (e.g., benzene, toluene, elh-
ylebenzene, and xylene; and naphthalene) and chlorinated hydrocarbon solvents in soil and assisted in
the geological mapping of environmental "hot spots." The sample inlet and introduction system of
the micro GC is heatable to 110°C to further extend the application range of the micro GC to samples
with high moisture content, high concentration of condensable vapors, and semi-volatile compounds.
Data will be presented on the use of the heated system in the characterization of the site with details
provided regarding the advantages of individual compound characterization, sampling for screening
purposes, and environmental screening in the field (to locate "hot spots") and in mobile laboratories
(to prevent overloading of GC/MS systems).
72 Thursday, February 23, 1995
-------
Gas Chromatography
65
66
FIELD VOC ANALYSIS FOR WATER AND SOIL, DEMONSTRATING LOW
PPB DETECTION LIMITS BY EMPIRICAL CALIBRATION
D B. Coiad, IT Corporation, San Bernardino, California, 92408
The use of a field gas chromatograph (GC) to determine the concentration of BTEX and halogenated
compounds in groundwater is demonstrated, and compared to laboratory analysis. Innovative empiri-
cal calibration, in the sample matrix increases the reliability and accuracy of the headspace analysis
with a field GC. Close correlation of results with fixed laboratory analysis demonstrate the accuracy
of this technique for field screening. Thermal augmentation of the sample is used to increase the
headspace concentration and reduce the detection limits to the 1-10 ppb range for water samples.
Methodology for the use of these methods for soil is presented, as will it be performed in cooperation
with the R. S. Kerr Environmental Research Laboratory, later this year. The use of sonication and
bag headspace extraction amend the accuracy of the method for soil analysis. In addition, the perfor-
mance of these analysis in a time critical, production oriented, site investigation with excellent results,
is well documented. The briefcase size, field GC and auxiliary equipment is capable of providing
accurate screening at EPA Quality Level tt+ in real time, at a very low cost. This method allows the
acceleration of site investigation and well/boring placement, with demonstrated quality.
VOLATILE ORGANIC HYDROCARBON ANALYSIS IN GROUND WATER
WITH AN IN SITU SPARGE SAMPLER AND FIELD GAS CHROMATOGRAPH
Clayton K. Morlock, Morlock Environmental, Inc., 23 Pine St., Lebanon, NH 03766
A device has been designed and tested which enables a ground water sample to be sparged within the
well and purged of volatile organic compounds (patent pending). The purge gas is subsequently col-
lected in an absorbent trap for conventional purge and trap gas chromatograph analysis. This method
is applicable as both a rapid screening technique when used in conjunction with an onsite gas chro-
matograph, as a sample collection procedure where an absorbent trap is transported to a lab rather
than a water sample and as part of a long term monitoring system for unattended ground water analy-
sis. This method was tested by comparing on-site gas chromatograph analysis of the sparge gas from
the in situ sparger to conventional purge and trap analysis of a ground water sample taken with a stan-
dard bailer. No water sample is required to be collected eliminating hazardous waste generation.
Analysis can be performed at discrete depths within the well. There is no sample storage or prepara-
tion involved, removing several sources of error. Since the objective of the procedure is to liberate
volatiles from the water sample, the problems with pumps and handling procedures that cause poor
volatile retention in water samples are eliminated. We are currently in the process of developing a
commercial product based on this concept.
Thursday, February 23, 1995 73
-------
Immunochemical-Based Methods
67
68
EVALUATION OF IMMUNOASSAY-BASED FIELD TEST KITS FOR THE
DETECTION OF PETROLEUM FUEL HYDROCARBONS IN SOIL
L.C. Waters'. MA. Palausky1, K.W. Counts2 and RA. Jenkins1. Chemical and Analytical Sciences
Division and Computing and Telecommunications Division , Oak Ridge National Laboratory, Oak
Ridge.TN 37831-6120
The objectives of this project are to identify, experimentally evaluate and implement the use of alter-
native field screening methods that are specific for environmental contaminants of interest and con-
cern to the Department of Energy. Immunochemical techniques are rapidly becoming a significant
component in the arsenal of field screening methods. Analytical results obtained by immunoassay
have been shown to correlate well with those obtained by traditional laboratory methods. Also, the
use of immunoassay-based field screening methods can significantly reduce the cost and time
required for environmental assessment For example, our previous experimental evaluations of
immunoassay-based tests for PCBs and mercury showed them to be effective, rapid and economical
field screening methods (Methods OS020 and MB 100, DOE Methods Compendium). We are cur-
rently evaluating the effectiveness of immunoassay-based test kits, from a number of sources, for
detecting fuel hydrocarbons (primarily BTEX) in soil. The formats of the kits being evaluated vary
significantly - from how the test sample is diluted for assay to how the test color reaction is devel-
oped and measured. Dilution schemes have been shown to be critical, due to the volatility of the ana-
lytes; and can result in false negative results. Kits, with which the color reaction development occurs
on a membranous filter, are subject to producing erroneous and erratic results if the test samples
and/or test reagents are compromised in such a way as to impede the normal flow rale through the fil-
ter. Results of these studies, with respect to the accuracy, reproducibility, sensitivity, working range,
cost and sample throughput, will be presented.
Research sponsored by the Office of Technology Development, U.S. Department of Energy, under
contract DE-AC05-84OR21400 with Martin Marietta Energy Systems, Inc.
"The submitted manuscript has been authored by a contractor of the U.S. Government under contract
No. DE-AC05-84OR21400. Accordingly, the U.S. Government retains a nonexclusive, royalty-free
license to publish or reproduce the published form of this contribution, or allow others to do so, for
U.S. Government purposes."
ON-SITE SOIL AND WATER ANALYSIS USING D TECH
FOR RDX AND TNT
IMMUNOASSAYS
George B. Teaney, Scientist, Robert T. Hudak, Sr. Scientist, James M. Melby, Group Leader,
Strategic Diagnostics Industries Incorporated, 128 Sandy Drive, Newark, DE19713
The secondary military explosives, trinitrotoluene (TNT) and hexahydro-l,3,5-trinitro-l,3,5-triazine
(RDX) are commonly found in soils and ground water at munition load and pack operations, and
demilitarization facilities. RDX is very mobile in soils, and is often used to indicate the leading edge
of an explosives plume, whereas the rate of migration of TNT in the soil is far less. The development
of the D TECH field screening methods for RDX and TNT in both soil and ground water have been
designed to greatly benefit the explosives remediation effort. The use of these inexpensive field
screening methods will reduce the total cost and improve the efficiency of site surveys and remedia-
tion projects. Field screening techniques can also circumvent the long turnaround time of laboratory
analysis by providing reliable on site results.
The portable RDX and TNT enzyme immunoassays (EIA) are quick, cost effective, highly specific,
and user friendly. The components of these EIAs include RDX or TNT specific antibodies (Ab)
covalently linked to small latex particles, an RDX or TNT analog which is covalently linked to alka-
line phosphause, and the free explosive in the water sample. The free explosive competes with the
enzyme linked analog for the Ab binding sites. The latex particles are then collected on a filter
device, washed, and an enzyme substrate is added. The amount of color produced is inversely pro-
portional to the concentration of free explosive in the water or soil sample, and can be determined
using a hand held reflectometer, or a color card. These assays have demonstrated 5 ppb sensitivity in
water samples and 0.5 ppm sensitivity in soils with minima] cross-reactivity and matrix effects.
The application of these tests in the field has been demonstrated at several sites across the United
Slates. Results from a 42 sample TNT field trial at Army Ammunition Plant reported 2% false posi-
tives and no false negative results. When confirmed by EPA SW-846 Method 8330, 74% of the sam-
ples were in direct agreement. During a series of RDX field trials, the RDX EIA reported 3% false
positives and no false negatives. In all field trials the EIA demonstrated a correlation coefficient of at
least 90% when compared with Method 8330. Results from larger field studies have shown these tests
to be cost and time effective as well as accurate.
74 Thursday, February 23, 1995
-------
Immunochemical-Based Methods
69
70
SIMPLIFYING SITE ASSESSMENT OF PAH USING IMMUNOASSAY DIRECT -
PCB FIELD SCREENING
Michael C. Mulienix, Robert T. Hudak, James M. Melby, and James W. Stave, Strategic Diagnostics
Incorporated, 128 Sandy Drive, Newark, DE 19713
Polycyclic aromatic hydrocarbons (PAH) are carcinogenic and mutagenic chemicals found in com-
bustion products and industrial waste materials. The carcinogenic nature of PAlls has led state and
federal agencies to control their levels in the environment. Until recently, site assessment of PAH
levels in soil was limited by the high cost and long turnaround time associated with analysis methods
used in commercial analytical laboratories. The recent development of PAH immunoassays provides
a rapid and cost effective alternative to the traditional analytical methods. One such immunoassay
was developed as a part of the D TECH™ line of environmental detection systems. This competitive
immunoassay uses anti-PAH antibodies immobilized on latex panicles. Antibody binding to an
enzyme labeled PAH analog is inhibited by free PAH extracted from soil samples or contained in
water samples. The immunoassay detects the majority of compounds on the EPA list of 16 PAH pri-
ority pollutants below the ppm level without cross reacting with BTEX, PCBs and other similar com-
pounds. Field samples of PAH were collected at both petrogenic and pyrolytic sites of contamination
and the PAH concentrations were determined by both the immunoassay and the EPA SW-846
GC/MS method 8270. Test results correlated between the two methods and the low number of false
negative and false positive results confirmed the assay's specificity for PAH. The immunoassay pro-
vides the advantages of rapid, on site analysis, and minimum sample preparation. Use of the
immunoassay results in a significant savings in the cost of analysis because the cost per assay is
lower than commercial analysis and only positive samples require additional confirmation by instru-
mental techniques. The simple format of the immunoassay allows personnel with minimal training to
reliably and accurately determine the PAH content of soils.
PCB DETECTION BY IMMUNOASSAY - A WIPE TEST FOR SURFACE CONT-
AMINATION
Joseph X. Dautlick, George B. Teaney, Robert T. Hudak, James M. Melby, Strategic Diagnostics
Industries Incorporated, 128 Sandy Drive, Newark. DE 19713
Immunoassay based field screening methods are gaining acceptance by the environmental diagnostics
industry for on-site characterization and remediation monitoring. Polychlorinated Biphenyl's (PCB),
a family of molecules classified as potential carcinogens, can be easily delected on-site by immunoas-
say screening methods. This results in reduced project cost and improved on-site efficiency, since
field screening immunoassays short cut the long turn around time of laboratory analysis while provid-
ing reliable results. On site wipe test technology for assessing PCB contamination on surfaces such
as walls and floors of PCB storage facilities has been developed to supplement the D TECH™ PCB
soil assay. This sampling technique can also be used to monitor for transformer leaks, spills and to
evaluate equipment decontamination processes. The D TECH PCB wipe test is quick, cost effective,
highly specific and user friendly. The surface is sampled by wiping a 100 cm2 area with a 1 cm2 pad
saturated with an exlractanl. The PCB is extracted from the sampling pad during a short extraction
step. The sample is filtered, diluted, and run in the D TECH PCB field screening system. The com-
ponents of the immunoassay include PCB specific antibodies (Ab) covalently linked to small latex
particles, a PCB analog which is covalently linked to alkaline phosphatase, and the free PCB from the
sample. The free PCB competes with the enzyme linked analog for the Ab binding sites. The latex
particles are then collected on a filter device, washed, and an enzyme substrate is added. The amount
of color produced is inversely proportional to the concentration of free PCB on the sample, and can
be determined using a hand held reflectomeler, or a color card. This assay has demonstrated 5 ug /
100 cm2 sensitivity to a broad spectrum of PCB Aroclors. Results from case studies will be dis-
cussed.
Thursday, February 23, 1995 75
-------
Inimunochemical-Based Methods
71
72
DETECTION OF PETROLEUM HYDROCARBONS IN SOIL AND WATER BY
IMMUNOASSAY
Michele Y. Selisker, C. McCaffrey, David P. Herzog and Jeanne A. llak, Ohmicron Corporation, 375
Pheasant Run, Newlown, PA 18940
Volatile aromatic hydrocarbons, which include BTEX (benzene, toluene, ethylbenzene and xylenes),
are prevalent contaminants at hazardous wastes sites across the United States as a result of spillage of
hydrocarbon fuels and leaking underground storage tanks. It has been estimated that 2 to 5 million
underground storage tanks containing petroleum hydrocarbons or chemicals are present in the United
States. Identifying the presence of hydrocarbon contamination is a high priority; suspected contami-
nated sites must be evaluated to map out a contamination plume, to determine if remediation is need-
ed or to determine the effectiveness of remediation.
Groundwater and soil sampling are widely used to assess contamination. Exposure via drinking
water, especially groundwaler, is of great concern and cause for much of the hydrocarbon and under-
ground storage tank regulations. The collection and analysis of soil and groundwater samples has
become a standard practice in site assessment and has gained wide acceptance of regulatory agencies.
However, accurate and precise characterization of a region is difficult due to inherent uncertainty in
measuring volatile organic compounds (VOCs). Sample collection, handling, storage and transport,
as well as large spatial and temporal variations can occur during sampling, which all contribute sub-
stantial error to accurate analysis.
A magnetic particle based enzyme immunoassay (El A) that detects small aromatic hydrocarbons was
developed. This assay offers several advantages over traditional testing methods (i.e. GC) including
speed, cost effectiveness and portability. The assay can be performed on site in less than one hour.
The assay can be coupled with simple extraction methods for analyzing petroleum hydrocarbons in
soil.
Several studies were conducted to evaluate the assay's performance in soil and water. In a study con-
ducted on water samples from locations across the U.S., recoveries of spiked Total BTEX averaged
greater than 99%, with results ranging from 87 to 119%; one false positive (1.8%) was observed.
Soils spiked with Total BTEX at concentrations ranging from 0.25 to 10 pom Total BTEX were
extracted, diluted and evaluated in the immunoassay. Recoveries averaged 113% with results ranging
from 104 to 120%. In another study with 30 soil samples spiked with gasolines, jet fuel, kerosene
and Total BTEX, the assay and recommended extraction procedure agreed well with results obtained
by EPA Method 8020 in determining the presence and degree of contamination. Additional study
results and data on the cross reactivity of the assay for various small aromatic hydrocarbons and
petroleum fuel mixtures (i.e. gasoline), will be presented.
DETERMINATION OF POLYNUCLEAR AROMATIC HYDROCARBONS
(PAHs) IN WATER AND SOIL BY A MAGNETIC PARTICLE-BASED ENZYME
IMMUNOASSAY
Fernando M. Rubio, Timothy S. Lawruk, Charles E. Lachman and David P. Herzog, Ohmicron
Environmental Diagnostics, 375 Pheasant Run, Newlown, Pennsylvania 18940, James R. Fleeker,
North Dakota State University, P.O. Box 5516, Fargo, North Dakota 58105
Use of immunoassays as field-screening methods to detect environmental contaminants has increased
dramatically over the past few years. Immunochemical assays are sensitive, rapid, reliable, cost-
effective and can be used for lab or field analysis. A magnetic particle-based immunoassay system
has been developed for the quantitation of Polynuclear Aromatic Hydrocarbons (PAHs) in water and
soil. Paramagnetic particles used as the solid-phase, allow for the precise addition of antibody and
rapid reaction kinetics. The magnetic particle-based immunoassay is ideally suited for on-siie investi-
gation and remediation processes to delineate PAHs contamination. This system includes easy-to-use
materials for collection, extraction, filtration and dilution of soil samples prior to analysis by
immunoassay. Water samples are analyzed directly without sample preparation. The method detects
PAHs, including anthracene, chrysene, fluoranlhene, phenanthrene, pyrene and benzo[a]pyrene, at
sub-parts per million levels in soil and at less than a part per billion in water. This PAHs ELJSA
compares favorably to HPLC determinations, and exhibits good precision and accuracy. The assay
procedure and detailed performance characteristics including precision, spike recovery and correlation
with U.S. EPA methods are discussed.
76 Thursday, February 23, 1995
-------
Immunochemical-Based Methods
73
74
A QUART/. CRYSTAL MICROBALANCE BIOSENSOR FOR MEASUREMENT
OF 2,4-D IN WATER
K R. Rogers, U.S. EPA, Environmental Monitoring Systems Laboratory, Las Vegas, NV 89193-3478,
and EJ. Paziomek and M. Yu, Harry Reid Center for Environmental Studies, University of Nevada-
Las Vegas, Las Vegas, NV 89154
Due to the proportional relationship between vibrational frequency and surface mass, the quartz crys-
tal microbalance (QCM) has been used to detect the accumulation of small quantities of chemical and
biological compounds on electrode covered quartz crystals. Classically, these devices have been used
to detect gasses and vapors which adhere to chemically selective coatings. Recently, however,
increasing attention has been focused on the use of QCMs in aqueous environments. Herein reported
is the development of an antibody-based QCM biosensor for measurement of (2,4-dichlorophenoxy)-
acetic acid (2,4-D) in aqueous systems. The dynamic range for the measurement of 2,4-D is 0.1 to 10
ppm.
A biotinylated-2,4-D coating antigen is immobilized on the gold electrode by means of a sponta-
neously formed streptavidin monolayer. 2,4-D (analyte) then competes with the surface-bound anti-
gen for binding to anti-2,4-D IgG labeled with alkaline phosphatase. The amount of labeled antibody
that binds to the crystal is inversely proportional to the analyte (2,4-D). The mass of the labeled anti-
body which binds to the crystal is then amplified by the enzyme catalyzed dimerizalion of 5-bromo-4-
chloroindolylphosphale (BC1P) which precipitates on the crystal surface. Consequently, the observed
rate of frequency change is inversely proportional to the concentration of 2,4-D to which the sensor
was exposed.
NOTICE: The U.S. Environmental Protection Agency (EPA), through its Office of Research and
Development (ORD), has prepared this abstract for a proposed presentation. It does not necessarily
reflect the views of the EPA or ORD.
DETECTION OF SMALL MOLECULES BY AN EVANESCENT WAVE FIBER
OPTIC BIOSENSOR
Lisa C. Shriver-Lake and Frances S Ligler, Center for Bio/Molecular Science and Engineering,
Naval Research Laboratory, Washington, DC 20375-5348
Detection of small molecules is important in environmental analyses as most pollutants are low mole-
cular weight compounds. Utilizing the specificity of antibodies, the rapid signal transduction of opti-
cal fibers and the signal -to-noise discrimination of fluorescence, an evanescent wave fiber optic-based
biosensor was modified for the detection of these molecules. To facilitate the isolation of personnel
and equipment from hazardous environments, long partially clad optical fibers are employed.
Antibodies were immobilized on the 10 cm sensing region at the distal portion of the optical fiber
probe. A 200 ul sample chamber was fabricated from a capillary tube. The core of the fiber in the
sensing region is tapered for maximum signal recovery. A competitive immunoassay was performed.
Basically, the small molecule competes with a fluorescently-labelled analog for the capture anubody
binding sites. As the level of analyte increases in the sample, the fluorescent signal decreases. Two
assays for the small molecules, trinitrotoluene (TNT) and polychlorinated biphenyl (PCB) will be
described. Detecuon levels of 10 ng/ml TNT (8 ppb) have been achieved with this sensor.
Thursday, February 23, 1995 77
-------
Immunochemical-Based Methods
75
76
IMMUNOASSAY PANEL PROFILE FOR DETECTING TOTAL PCB CONTENT
Stephen Friedman and Randy Allen, EnSys, Inc., Research Triangle Park, NC 27709, and John GUI,
Elizabeth Barren and Donald Berdahl, GE Corporate Research and Development, Schenectady, NY
12309
Immunoassay test kits are being widely used to provide rapid, inexpensive screening of soil samples
for the presence of PCBs at or above a given threshold value. Currently available immunoassay
methods are sensitive to aroclor preparations that contain the more highly chlorinated PCB congeners.
The interpretation of these tests is accomplished by comparison to an appropriate aroclor standard. If
PCB contamination at a site has undergone significant changes through weathering or biological
degradation, or if contamination has occurred from lower chlorinated species, the relative sensitivity
of available test methods is reduced. This paper describes the results of a program to develop and
demonstrate an Immunoassay Panel Method that normalizes the recovery of PCBs detected and there-
by provides an accurate representation of the total PCB content of a sample. The development and
validation of this method, and the associative correlation testing data using laboratory and environ-
mental samples, will be discussed.
PCB DETECTION BY THE CONTINUOUS FLOW IMMUNOSENSOR
'P. Charles, 2D. Conrad, 'A Kuslerbeck, and JF. Ligler, 'Center for Bio/Molecular Science and
Engineering, 2NRC Postdoctoral Fellow, Naval Research Laboratory, Washington DC 20375-5348
Increasingly, pollutants and hazardous waste materials have become a major problem within the envi-
ronmental community. The monitoring and detection of PCBs (polychlorinaled biphenyls) in soil,
waste water, and other remote sites have cost the government millions of dollars. This study demon-
strates a method of detecting and monitoring PCBs using a continuous flow immunosensor. Such an
assay involves the immobilization of antibodies raised against PCBs onto a solid support matrix. The
matrix is then saturated with the fluorescently labeled antigen. As the PCB is injected into the sys-
tem, this labeled antigen is displaced and its presence is monitored downstream. Preliminary results
have demonstrated detection sensitivities of less than 10 parts per million. This device and the effects
of such factors as antibody density, antibody orientation, and flow rate on its performance and detec-
tion capabilities will be presented.
78 Thursday, February 23, 1995
-------
Immunochemical-Based Methods
77
78
LIPOSOME-ENHANCED IMMUNOMIGRATION STRIPS FOR FIELD SCREEN-
ING OF TOXIC CHEMICALS
Stuart G. Reeves, Sui Ti A. Siebert, Mathew A. Roberts and Richard A. Durst, Analytical Chemistry
Laboratories, Cornell University, Geneva, NY 14456-0462
The use of liposomes containing encapsulated dye to provide instantaneous enhancement of signals
generated in competitive immunoassays is described. The application of this technology to
Immunomigration Strip field assays for environmental contaminants is demonstrated, using Alachlor
and PCBs as model analytes. The field assay as currently envisaged can be performed in two ways.
The first method involves immobilizing antibodies onto a nitrocellulose strip and allowing the sample
and analyte-tagged, dye-containing liposomes to migrate through this zone. Liposomes passing
through without binding, as a result of competition from the sample analyte, are totally bound in a
collection region, and the degree of color in this region is proportional to the analyte concentration.
The second design allows the antibody to react in a competitive manner with the analyte and the lipo-
somes in a homogeneous solution into which a test strip is subsequently placed. This test strip con-
tains a liposome capture zone but no antibody zone. The antibodies in solution are capable of causing
aggregation of the liposomes inversely proportional to the concentration of competing analyte, and
aggregated liposomes do not migrate up the strip. Thus the amount of liposome found in the capture
zone is again proportional to the amount of analyte present in the sample. The latter technique
appears to be more sensitive, and has the added advantage that the strip is generic rather than specific
for a particular analyte.
Using this technology, strip assays nave been developed that will measure either the herbicide
Alachlor or PCBs at the levels required by current regulations, as demonstrated by dose response data
for both analytes. Both of these assays are complete in less than 15 minutes, and multiple assays can
run at the same time. At present the quantitation of the colored zone is carried out by scanning the
strips with a computer scanner and measuring the greyscale density of the capture zone, but alterna-
tive methods of quantitation are actively being investigated.
A possible design for a convenient and user-friendly assay is presented, along with some options for
alternate strip designs and detection methodologies.
RAPID DIOXIN SCREENING BY ENZYME IMMUNOASSAY
Robert O. Harrison, Millipore Corp., ImmunoSystems, Inc., Scarborough ME 04074, Robert E
Carlson, Ecochem Research, Inc , Chaska, MN 55318, Hamid Shirkhan, Fluid Management Systems,
Inc , Watertown, MA 02172, Theresa Keimig, Midwest Research Institute, Kansas City, MO 64110
A system has been developed for rapid screening of 2,3,7,8-T.etraCJiloro]2ibenzo-p-Djoxin
(TCDD). The system uses a competitive inhibition Enzyme ImmunoAssay (EIA) based on a
mouse monoclonal antibody which is specific for TCOO and related congeners. Sample
preparation can be performed with a programmable automated extraction and cleanup system which
uses disposable Teflon clad columns. The extraction and cleanup system has been extensively vali-
dated by GC-MS for a variety of sample types. The sample preparation system allows immunoassay
analysis of soil, serum, water, and other matrices by taking each sample type to the same sample
preparation endpoint. Concentration factors and endpoint conditions are completely flexible and pro-
grammable. Immunoassay analysis is performed by the addition of a prepared sample extract in
organic solvent to an antibody coated microweU containing an aqueous sample diluent. This is mixed
and incubated for 30 minutes to allow the immobilized antibody to capture analyte from the sample.
The liquid is then removed and the well is washed to remove unbound materials. The well is then
incubated with a compelitor-HRP conjugate capable of binding specifically to the antibody sites not
occupied by TCDD. After 30 minutes, the unbound conjugate is washed away and enzyme substrate
is added for color development. The color generated is directly related to the amount of compeutor-
HRP bound in the second step, which is inversely related to the amount of analyte bound in the first
step. After 30 minutes, a slop solution is added and the developed color is read on a microplaic read-
er. The total time required for the EIA analysis of a prepared extract is less than 2 hours. Sensitivity
for TCDD is better than 0.1 ng/well, allowing sensitive analysis of a variety of environmental matri-
ces. Preliminary results indicate that it is possible to detect 10 ppb 2378-TCDD in soil by direct
analysis of crude soil extracts. Work is being directed toward simplification of the extraction proce-
dure and improvement of the interface with the automated sample cleanup system. The data present-
ed here demonstrate that this system should be useful for TCDD screening in many situations for a
variety of matrices. The system offers significant improvements in speed, sample throughput, and
cost compared to GC-MS.
Thursday, February 23, 1995 79
-------
Immunochemical-Based Methods
79
DEVELOPMENT OF AN ENZYME IMMUNOASSAY FOR THE DETECTION OF
TRINITROTOLUENE (TNT) IN SOIL AND WATER
Karen A. Larkin, Bruce S. Ferguson, Jonathan J. Mall, and Tilan S. Fan, ImmunoSyslems
Incorporated, Division o/Millipore Corporation, 4 Washington Avenue, Scarborough, ME 04074
2,4,6-Trinitrotoluene (TNT) is a toxic and persistent nilroatomatic compound currently found contam-
inating many government installations used for manufacture, storage or testing of explosives. The
estimated 1,100 contaminated sites in the U.S. are the center of a large remediation effort, which
could be streamlined by the use of a rapid, field-portable, inexpensive analytical method for TNT.
An enzyme immunoassay (EIA) has been developed which is capable of detecting as little as 0.5 ppb
TNT in water and 0.25 ppm TNT in soil. Rabbit polyclonal antibodies were raised against a TNT-
derivalive coupled to bovine serum albumin. These antibodies are coated on both polystyrene tubes
and 96-well microtiter plates. Water samples or soil extracts together with a TNT-horseradish peroxi-
dase conjugate are then added and compete for antibody binding sites. Excess conjugate is washed
away in a simple rinse step, and substrate (3,3't5,5'-tetramethylbenridine) is added; the amount of
color developed is inversely proportional to the concentration of TNT in the sample. This competi-
tive EIA is relatively specific: 4-amino-2,6-DNT and 2,6-DNT are only 20% as reactive as TNT, and
2,4-DNT shows approximately 1% cross-reactivity. Other common explosives and important
metabolites, such as RDX, HMX, nitroglycerin, and dichlorobenzcic acids, are essentially non-reac-
tive in this assay. The microtiter plate-based assay is complete in 90 minutes and is suitable for labo-
ratory use. The tube-based test is run in less than 30 minutes and is field-portable.
The soil extraction protocol employed for this assay utilizes methanol as the solvent and can be com-
pleted in 10 minutes. A simple dilution step is the only sample preparation that is required before
running soil extracts in the immunoassay. Water samples require no pre-ireatment, concentration or
extraction. Correlative data between this immunoassay and conventional analytical techniques will
show that the EIA has the potential to serve as a time and money-saving tool for soil and water sur-
vey and remediation.
80 Thursday, February 23. 1995
-------
Ion Mobility Spectrometry
80
81
DETERMINATION OF VINYL CHLORIDE IN SOIL-GAS SAMPLES BY GAS
CHROMATOGRAPHY COUPLED WITH ION MOBILITY SPECTROMETRY
TL. Jones, US. Environmental Protection Agency, Las Vegas. NV 89114, Herbert Hill, Greg
Simpson, and Maren Klasmeier, Washington Slate University, Pullman, WA 99164, Viorica Lopez-
Avila, Midwest Research Institute, Mountain View, CA 94043, and Gil Radolovich, Midwest Research
Institute, Kansas City, MO 64110
The advantages of ion mobility Spectrometry (IMS), such as ambient pressure operation, simplicity of
design, high sensitivity, speed of response, spectral output, and ability to respond to a large number of
compounds, make IMS technology attractive for a variety of field monitoring applications. A quanti-
tative, multicompound field detector based on IMS technology has not been successful, however,
because of technology limitations. For multicomponent samples, multiple ion-molecule reactions
result in confusing spectral information. Varying humidity can result in ion-water clusters that cause
errors in both the identification and quantification of the target analyte. These limitations could be
overcome through the addition of gas chromatography (GC) prior to high-temperature IMS. When
coupling GC to IMS, the following need to be considered: (a) Currently available IMS cells have a
relatively large internal volume (> 20 mL), reducing the chromatographic resolution; (h) smaller IMS
cells ate not capable of operating above 100°C; (c) the radioactive iomzalion cell limits the dynamic
range of the device to 2 to 3 orders of magnitude; and (d) most standard miniature cells have a mem-
brane inlet that does not allow direct interface with a GC column. We have overcome some of these
difficulties by interfacing GC with Fourier Transform IMS (FTIMS). We will present data on deter-
mining vinyl chloride in soil-gas samples by GC-FTIMS.
NOTICE: The U.S. Environmental Protection Agency (EPA), through its Office of Research and
Development (ORD), prepared this abstract for a proposed oral presentation. It does not necessarily
reflect the views of the EPA or ORD.
APPLICATION OF ION MOBILITY SPECTROMETRY TO DRUG DETECTION
IN MARINE ENVIRONMENTS
/ Richard Jadamec, Chih-Wu Su, Steve Rigdon, and LaVan Norwood, U.S. Coast Guard Research
and Development Center, 1082 Shennecossett Road, Groton. CT 06340-6096
One of the U.S. Coast Guard's missions is the search of maritime vessels for the presence of illicit
drugs. This mission requires that effective and efficient search and detection systems must have rapid
analysis processing capabilities and minimal sample preparation and concentration requirements.
The application of Ion Mobility Spectrometry (IMS) has been determined by previous investigators to
be effective in detecting trace quantities of illicit drugs. IMS is one of several technologies that the
U.S. Coast Guard R&D Center has been actively investigating since 1991 for use in the maritime
environment. The primary emphasis of these studies has been focused on the utility and performance
of this technology in realistic field environments and field situations. These research studies have
involved the use of IMS deployed in vans, mobile laboratories, and onboard U.S. Coast Guard
vessels.
Results of these field studies, in which greater than 7,000 samples from various types of vessels, con-
tainers, and cargo were collected and analyzed, will be presented.
Thursday, February 23, 1995 81
-------
Ion Mobility Spectrometry
82
83
ION MOBILITY SPECTROMETRY (IMS) FIELD SCREENING METHODS AND
ANALYSIS OF EXPLOSIVES IN CONTAMINATED SOILS
1. Avolio, R. DeBono, and P. Radwanski, Barringer Instrmtents Inc., New Providence, NJ 07974
The rapid on-dle «nd Ub analysis of §ofl samples oootammaled widi DNT. TOT, andRDXif
explored with IMS detection and variant sample preparation methods. Held screening for explosives
ii presently time consuming aid generate* considerable nnounu of additional chemical wastes. The
fieU nMdKx)iiiboUniited in the number of differemexpioaveidut can be analyzed.
The «te of • Barringer
tion sample i«sw*Ktii
ty
lONSCAN IMS system, which it comprised of a thermal desorp-
directly plumbed to die IMS reaction region and drift tube auembly
permits novel methods of sssiMfeoicp and sample inuodnction to be employed. Direct sampling,
sample torvation, and sample extraction ate all investigated and reported. Benefits of utilizing an
IONSCAN in tha analysis of foil tamples is the ability to simultaneously analyze up to 18 analyiei in
each sample in 4.8 tecondil Thotfoie it i* feanble to analyze for degradation producu ai well at the
target parent explore compounds.
1heK)NSCANt*atyte*wm typically {lerfomiednifagW
offeealncitdianiptotoltiicndmcllydeDMMosMt^ Additio-
nally 100 mg samples of soil were directly sohraled with assorted idventi on the sample filter with
varied success. Performing • 3 minute acetone extraction on the toil samples has yielded the best
overall results dint far with respect to limits of detection, and time required for sample preparation.
10 PPM or better limits of detection are achieved with this medwdology and an IONSCAN for DNT,
TNT, and RDX. Bated on these pieUminary results this work is being continued in both the lab and
co-site with tofl and water samples.
CHALLENGES OF DEVELOPING A GC/IMS BASED PERSONAL CHEMICAL
HAZARD DETECTOR
NtU S. Arnold, Jacek P. Dwonenold1. Hoik L.C. Mtuttlaar1 and William H. McCUnntnf,
FemtoScan Corporation, Salt Lake City, Utah and 'Ctnitrfor Micro Analysis and Reaction
Chemistry, University of Utah, Salt Lake City, Utah
Hand-portable gas chromaiography/ian mobility tpectromeuy (GC/IMS) techniques have been identi-
fied as a promising area of development for field and process related analytical problems. Recent
development of extremely small (15 in3) personal IMS detection devices offer new prospects for cre-
ating a miniaturized GC/IMS unit If a number of critical engineering obstacles can be overcome,
these units win find new applications for monitoring individual exposure to chemical hazards bated
on having considerable size and cost advantages over their predecessors. The successful development
of a combined GC/IMS personal detection system will require the combination of various innovative
solutions which have been suggested or applied to various chemical tensor, GC and IMS technolo-
gies.
This paper provides a feasibility examination of personal GC/IMS bated OB the automated vapor sam-
plmg-transfer line gas chromatognphy (AVS-TLGC) approach previously utilized in developing
hand-portable GC/IMS mstrumentation. Special focus is placed upon developing low power strate-
giet for implementing this approach. The means for achieving low power operation for extended per-
sonal use has focussed on pulsed, en-demand operation of die sampling systems, low (ambient) tem-
perature GC operation, reduced GC flow rates and pressure drops and modification of die internal
IMS system flows. Development efforts to date have utilized an existing prototype mun'atiire IMS
device, die GI-MINI from Graseby Ionics coupled with modified Enviroprobe AVS-TLGC equipment
developed by FemtoScan. Effect of parameters such asGCcohimn position, temperature and carrier
gas flow as well as IMS purge flows are examined for their effects upon sensitivity and resolution in
breadboard GC/IMS test instrument. An evaluation of die remaining engineering hurdles limiting die
development of personal GC/IMS are also presented.
Thnmd«v February 23. 1995
-------
Ion Mobility Spectrometry
84
85
FIELD SCREENING OF VOLATILE ORGANOCHLORINE COMPOUNDS
USING ION MOBILITY SPECTROMETRY
J. Stack", J. Flachowskf. M. Brodacki", and H.-K. Daring, "BRUKER-Saxonta Analytik GmbH,
Permoserstr. 15, 04318 Leipzig, FJt.G., bEnvironmental Research Centre Leipzig-Halle,
Permoserstr. IS, 04318 Leipzig. FAG.
The most common ion source used in ion mobility spectrometry (IMS) is still a Ni foil placed
inside the reaction region of the measuring cell. In atmospheric pressure ionizauon processes, water
clusters of the composition [rLO) H]+ or l(H-O) O.]~ are formed. These reactant ions undergo fur-
ther ion-molecule reactions with neutral gas-phase analytes to produce analyte "product ions". In
most cases, the positive or negative product ions formed are pseudo-molecular ions. In the negative
ion mode, especially halogenated compounds obey a typical dissociative electron capture reaction
(Equ. 1).
R-C1 +
CT + R
(1)
This reaction can be used to determine volatile organic compounds in different samples.
In this paper, we report applications of hand-held BRUKER RAID-1 ion mobility spectrometers for
the determination of the total amount of volatile organic halides in air samples, soil air, sludge, waste
water and on waste disposal sites. The measurements are compared with the results obtained by
mobile GC/MS - techniques and with the total amount of adsorbable or exlrac table organic halogens
(AOX/EOX) using the German standard method for the examination of water, waste water and sludge
(DIN 38 409, H 14). The results suggest that the obtained sum parameter correlates in most cases
with the well-known AOX/EOX value.
ON-SITE ANALYSIS OF OLD DEPOSITED CHEMICAL WARFARE AGENTS
BY COMBINED USE OF ION MOBILITY SPECTROMETRY AND MASS
SPECTROMETRY
/. Stack", J. Flachowskib, A. Adler", M. Brodackf, A. Loudonc and H.-R. Daring", "BRUKER-
Saxonia AnalyUk GmbH, Permoserslr. 15,04318 Leipzig, FR.G., ^Environmental Research Centre
Leipzig-Halle, Permoserslr. 15, 04318 Leipzig, F.R G., cBRUKER-Franzen Analytik GmbH,
Fahrenheitstr. 4, 28359 Bremen, FR G.
Over the last decade, Ion Mobility Spectrometry (IMS) has evolved into an inexpensive and powerful
technique for the detection of trace compounds. Most of the ion mobility spectrometers are rugged
and can be used as hand-held instruments in field analyses. If equipped with a 63Ni radioactive
source, especially compounds with a high proton or electron affinity can be detected at trace levels.
In general, a high proton or electron affinity is typical for toxic compounds. Therefore, on-site detec-
tion of hazardous substances is a typical application for IMS because
a) identification and quantification of hazardous compounds is possible within a few seconds,
which is essential for on-site personnel protection,
b) the method can be used for a very fast field screening as well as for measurements of indoor
contaminations or inspections of production sites
and
c) application of IMS reduces, as one result of the screening, the number of samples which have to
be investigated by standard laboratory methods, e.g., GC/MS.
The BRUKUR RAID 1 ion mobility spectrometer can either be used directly as an automatic warning
instrument programmable for up to ten compounds or with the aid of a data system if unknown com-
pounds have to be detected.
Examples given for the application of IMS instruments result from investigations of old production
sites of chemical warfare agents, ammunition plants or training areas. Chemical warfare agents and
their degradation products were analyzed in residues of the production processes, in the atmosphere
of bunkers used for storage, in soil air and in soil samples using a simple head space technique. In
most cases, IMS measurements were combined with GC/MS investigations. The results clearly indi-
cate, that GC/MS investigations confirm the findings of the IMS.
Thursday, February 23, 1995 83
-------
Non-Invasive Technologies
86
87
UXO DETECTION AT THE JEFFERSON PROVING GROUND, MADISON, IN
Michael Johnson, Steve Cave, Jim Creager and John Mathes, EGAG Energy Measurements, Kinland
Operations, Albuquerque, New Mexico, 87196
OBJECTIVE
The objective of thU project i* to quantitatively evaluate the effectiveness of high spatial frequency
sampling with the USRADS System and the Minefield Reconnaissance and Detector (MIRADOR)
System for locating, mapping and identifying subsurface unexploded ordnance (UXO), consisting of
bombs, missiles, mines, projectiles, submunitions and rockets.
TYPE OF TESTING AND EVALUATION TO BE CONDUCTED
A drive-over survey of the 40 acre Jefferson Proving Ground (JPG) test site will be conducted. The
USRADS System will record the NORADOR's location each second to an accuracy of +/- 6".
Markers will be placed in the MIRADOR's data files to correlate data with location.
MIRADOR beneficially combines the output* of multiple sensors, three Ground Penetrating Radars
(GPR's) and three Metal Detector* (MD't), to produce a composite result that is better than the result
from any single sensor. This data fusion process accommodates multiple sensor output data contain-
ing gaps, noise, dropouu, and other flaws, and still produces a good output result. Further, it
enhances detection and location of target objects.
Data from MIRADOR will be combined with results from other sensor technologies such as terrain
conductivity meters and various magnetometers (as selected by the Selection Committee from other
Chemrad technology demonstration proposals) to produce the best possible result.
These anomaly identifications will then be compared with the target information provided by the
Naval Explosive Ordnance Disposal Technology Division, Manager of JPG, to measure the effective-
ness of this approach for locating buried, unexploded ordnance.
PRELIMINARY RESULTS FROM A HELD SURVEY CONDUCTED WITH THE
AUTOMATED SUBSURFACE CHARACTERIZATION SYSTEM (ASCS)
Steven P. Cave, James D. Creager, EGAG Energy Measurements, Kirtland Operations, Albuquerque,
New Mexico, 87196, Chris W. Baumgarl, EGAG Energy Measurements, Los Alamos Operations, Los
Alamos, New Mexico, 87544
OBJECTIVE
The Automated Subsurface Characterization System (ASCS) is a portable system that uses a ground
conductivity sensor and a ground penetrating radar sensor to survey and characterize subsurface
objects, conditions, and geology. The objective is to demonstrate the system's capabilities by per-
forming an actual field survey and reducing and reporting the results. The concepts and technologies
employed are applicable to a wide range of hazardous waste, ordnance detection, and site survey and
monitoring tasks.
TYPE OF TESTING AND EVALUATION TO BE CONDUCTED
The specific application reported here is a survey of a chemical waste landfill site performed both
before and after injection of a subsurface grout barrier. The site, which has been used for various
chemical spill/burial applications, has been studied in detail and the gross physical and geological
properties are known. Scientists from Sandia National Laboratories Albuquerque will inject a combi-
nation of various grouts and waxes at selected locations and depths. The barriers will be injected
through boreholes for the purpose of minimizing the site subsurface permeability and the subsequent
migration of chemical waste material and groundwater. After injection and thorough curing of the
barriers, each injection location will be excavated to determine the integrity, continuity, uniformity,
and physical extent of the injected barriers.
A survey of the chemical waste site, performed both before and after the injection of the barrier, will
be performed with the ASCS. The results and findings (barrier characterization) from this survey will
be compared and contrasted with actual barrier conditions determined after excavation. In this way,
the suitability and applicability of an ASCS-like system that is portable, has hand-carried or man
pulled sensors, and which carries out data reduction essentially immediately will be demonstrated.
84 Thursday, February 23,1995
-------
Quality Assurance
88
89
1NTERLABORATORY EVALUATION OF VOLATILE ORGANIC COMPOUND
DETERMINATIONS IN SOILS PREPARED BY VAPOR FORTIFICATION
Alan D. Hewitt and Clarence L. Grant*, U.S. Army Cold Regions Research and Engineering
Laboratory. 72 Lyme Road, Hanover, NJI. 03755-1290, *Professor Emeritus, University of New
Hampshire
Despite the Urge number of vadose-zone soil samples routinely analyzed for volatile organic com-
pounds (VOCs), no secondary reference soils are available for procedures such as calibration evalua-
tion, quality assurance/quality control (QA/QC), and method comparisons. Currently the accuracy of
VOC determinations is usually estimated via solution spike and recovery tests. This approach fails to
mimic the extraction of real samples because of the large amount of carrier solvent and the insuffi-
cient contact time for natural sorption processes to occur.
Vapor equilibration for several days in a closed system was used to produce fortified sod samples
contained in 1.0-mL glass ampoules. This preparation method was soil specific, precise within and
between batches, and analyte concentration stability was demonstrated to exceed a 60-day holding
period. With such samples we were able for the first time, to our knowledge, to distribute samples
for inleriaboralory analysis where both extraction and determinative accuracy were evaluated togeth-
er. Each laboratory was sent duplicate sets of three different soil subsamples, each fortified with
trans-1,2-dichloroethylene (TDCE), trichloroethylene (TCE), benzene (Ben) and toluene (Tol). Each
soil set consisting of subsamples from two separate fortification batches. Twelve laboratories submit-
ted analyte concentration estimates for these soils using methanol extraction purge-and-trap gas chro
matography/mass spectromelry analysis (EPA, SW 846, Method 8240).
Statistical analysis resulted in the exclusion of all data from two of the laboratories due to substantial
systematic error. A improperly sealed ampoule necessitated exclusion of one data set for sod A, and
one set was excluded from soil B due to a very large (statistically significant) variance. Consequently
soils A and B were characterized using all the results from nine laboratories, while soil C data were
from ten laboratories. There were no significant differences (o=0.05) between batches for any ana-
lyte in any soil. The relative standard deviation, including random batch variation, ranged from 8.5%
to 28.2% for the 12 analyte/soil combinations. Half of the USDs were less than 10.0%, and the aver-
age was 12.6%. The best results were for Ben, while TDCE produced the largest uncertainties.
This round-robin study has confirmed that VOC vapor fortified sod subsamples can be reproducibly
prepared and, once sealed in glass ampoules, are stable during distribution so they can be used as sec-
ondary standards for various performance evaluation applications.
A DATABASE FOR EVALUATING FIELD-PORTABLE XRF PERFORMANCE
INFORMATION FROM HAZARDOUS WASTE SITES
Mark Bernick, Dennis J. Kalnicky, and Lawrence P. Kaelin, Roy F. Weston, Inc JREAC, Rajeshmal
Singhvi and George Prince, U.S Environmental Protection Agency, Office of Solid Waste and
Emergency Response, Office of Emergency and Remedial Response, Emergency Response Division,
Emergency Response Branch, 2890 Woodbridge Ave., Edison, NJ 08837-3679
The U.S. Environmental Protection Agency's (U.S. EPA)/Environmental Response Team (ERT) has
used field-portable X-ray fluorescence (FPXRF) instruments extensively to characterize metallic cont-
amination in soils and sediment. Rapid, on-site, multi-element analysis of large numbers of in-situ
and prepared samples provides near real-time data to guide cleanup/removal activities at hazardous
waste sites Currently, there is a high level of interest in FPXRF Quality Assurance/Quality Control
(QA/QC) results, since FPXRF is a relatively new environmental analytical technique.
Managing large amounts of FPXRF QA/QC data from many sites is difficult because it is typically
stored in separate project reports. Electronic management and evaluation of FPXRF performance is
desirable. A database, providing a means to store, summarize, compare, and manipulate FPXRF
QA/QC performance, is described. Data is entered from the keyboard, through picklists, or by import
of electronic files from other sources. Database functions provide easy access to, manipulation, and
sorting of, FPXRF QA/QC data. Additionally, an output menu provides a variety of pre-defined
report formats. This database quickly provides site-managers with realistic estimates of FPXRF
capabilities
Thursday, February 23, 1995 85
-------
Quality Assurance
90
FIELD SCREENING VS. FIELD ANALYSIS: DATA QUALITY OBJECTIVES IN
THE AGE OF ADVANCED ON-SITE INSTRUMENTATION
Eric D. Winegar, Marie J. Votes, David B. Curtis, Air Toxics Limited, 180 Blue Ravine Road, Suite B,
Folsom, CA 95630
Field analytical efforts nnge from true screening instruments such as hand-carried organic
vapor analyzers to full en-site laboratory-grade GC/MS instruments. Frequently, the end use of the
data is either unknown, or ill-defined, resulting in an inappropriate analytical technical approach.
Increasingly, data users are intending to use field data for all possible uses, from determining the
depth for bore-holes to modelling and risk assessment This broad mandate presents severe chal-
lenges to the field analysis effort.
One of these challenges is to educate data users who may not be accustomed to analytical methodolo-
gy and its terminology on the meaning of data quality. Often the term "screening" carries a negative
connotation for many users—implying much lower quality than laboratory analytical data. An under-
standing of the data quality that is attainable in the field from an EPA method context will counteract
that impression.
Another challenge lies in the need for sophisticated data reporting, often including input into databas-
es. Most field instruments are not amenable to more than simple reporting. This simple reporting
limitation can extend to the total data quality, since additional quality assurance data may not be easi-
ly incorporated into field reporting without significant additional effort.
The paper will review the EPA Data Quality Objective process vis-a-vis currently available field
instrumentation. Examples of the data quality obtainable from field instruments will be presented:
from routine field analysis to a one-analysis approach for all data uses. The data will show typical
limits to the quality of field generated data when the objective is to adhere to EPA method protocols.
86 Thursday, February 23,1995
-------
Radionuclides
91
92
SCREENING OF ALPHA CONTAMINATED SOILS USING LOW-RESOLUTION
ALPHA SPECTROSCOPY OF THICK SOIL SAMPLES
K.E. Meyer1, AC. Lucas*, CS. Dudney1, and J. Raj, 'Health Sciences Research Division, Oak
Ridge National Laboratory*, Oak Ridge, TN, 37831-6379. 28483 Trillium Drive, Chagrin Falls, OH
44023
High-resolution alpha spectroscopy has been used extensively as an analytical tool for identifying
unknown radiological contaminants in a variety of matrices. It has, however, been an expensive and
time-consuming procedure, primarily limited to the laboratory setting, due to the need to fabricate
very thin uniform "weightless" samples in order to preserve the high energy resolution of the system.
An alternative approach, using low-resolution alpha spectroscopy of thick samples, has been suggest-
ed by A. C. Lucas (Annual Meeting of the Health Physics Society, Atlanta, GA, June 1993). For the
case of thick samples, the energy spectrum of emitted particles is broad and rectangular in shape,
rather than being sharply peaked as in (he conventional case. The sharp high-energy edge of the ener-
gy spectrum corresponds to the discrete alpha energy usually associated with the radionuclide of con-
cern. Therefore, the spectrum analysis software may be configured to search for discrete edges in the
energy spectrum rather than sharp peaks. We have demonstrated that as many as eight different
radionuclides and progeny may be identified in a complicated spectrum. The advantages of this
approach over high-resolution spectroscopy include (1) low capital cost of equipment, (2) small foot-
print of equipment, allowing for deployment in a field laboratory, and (3) minimal sample prepara-
tion, leading to high throughputs. We have used this approach to analyze quantitatively National
Reference Material soils from Grand Junction and field samples from Femald, Ohio (for U and Th),
and contaminated soils from the Nevada Test Site and the Rocky Flats Plant (for Pu and Am).
'Research sponsored by the U.S. Department of Fjiergy, under contract No. DE-AC05-84OR21400
with Martin Marietta Energy Systems Inc.
NEW FIELD-DEPLOY ABLE IMAGE PROCESSING SYSTEM FOR SAME-DAY
ANALYSIS OF NUCLEAR TRACK DETECTORS
MA. Buckner1, K£. Meyer2, and CS. Dudney2, 'instruments and Controls Division, Oak Ridge
National Laboratory*, Oak Ridge, TN, 37831-6006. 2Health Sciences Research Division, Oak Ridge
National Laboratory, Oak Ridge, TN, 37831-6379.
Nuclear Track Detectors (NTD's) can be used for detecting alpha-emitting radiological contamination
(e.g. Pu, Am, U, Th) on surfaces and in soils. The primary disadvantage of this approach for field
screening applications is the time required for analysis of the detectors. At present it is necessary to
ship the detectors to a vendor, where they are etched and optically scanned, which incurs a tune delay
between retrieval and results of typically 2-7 days. A R&D team at ORNL has developed a prototype
analysis system which is sufficiently compact to be deployed in a van or on-site laboratory. The
complete system consists of etch/rinse tanks, optical microscope, stepping motors, CCD camera,
frame-grabber, and an image analysis software package. In addition to conventional gross counting
of etch pit densities, two new capabilities are under investigation. Hot particles are radioactive parti-
cles of high specific activity and small size. They pose a significant health hazard and are difficult to
detect. Alpha particles are emitted radially from hot particles, and therefore hot panicles generate
'starburst' clusters of tracks in a track detector with very characteristic patterns. The image analysis
system can be configured to search for and analyze these patterns, yielding quantitative size distribu-
tions of hot panicle contaminants. This information could be useful input lo the site remediation
plan. Using this approach, the presence of hot particles has been determined in soil samples from the
Nevada Test Site and Johnston Atoll. The second capability involves identification of radiological
contaminants. A group at the University of Bristol, UK, has demonstrated that detailed analysis of
the size and shape of individual alpha tracks can lead to a determination of the energy of the alpha
particle that generated the track. Alpha particles are emitted at discrete energies from different
radioisotopes, and therefore inexpensive and fast alpha spectroscopy can be carried out to identify
unknown alpha-emitting contaminants. Progress on optimizing the image analysis system for this
application will be reported.
•Research sponsored by the U.S. Department of Energy, under contract No. DE-AC05-84OR21400
with Martin Marietta Energy Systems Inc.
Thursday, February 23, 1995 87
-------
Sampling and Sample Handling
93
94
AN ANALYTICAL PROGRAM FOR DETERMINATION AND CONFIRMATION
OF AIRBORNE LEVELS OF CHEMICAL AGENT IN THE EVENT OF A SUS-
PECTED RELEASE
Donald G. Paul, Dynatherm Analytical Instruments, Inc., P.O. Box 159, Kelton, PA 19346 and
Edward M. Jakubowski. PhD., SciTcch Services, Inc., 1311 Continental Drive, Suite G, Abingdon,
MD 21009
The Monitoring Branch Laboratory of the U.S. Army Operations Directorate. Chemical Support
Division is uniquely outfitted to respond quickly when the need arises to identify and measure atmos-
pheric contamination levels of military unique compounds. Samples collected with a vacuum pump
on solid sorbent tubes are initially screened using gas chromalography (GC) and a sulfur/phosphorus
specific detector to determine and quantify the presence or absence of contaminants. Positive sam-
ples from the first stage of testing are subjected to subsequent analysis with different detectors to con-
firm genuine positives and eliminate false positives. Subsequent testing provides information during
follow-up and site remediation activities through screening of soil and other environmental samples.
Monitoring Branch uses Depot Area Air Monitoring Systems (DAAMS) technology in which a sam-
ple is collected onto a solid sorbent tube, and subsequently analyzed through thermal desorption of
the sample into a gas chromatograph equipped with a simultaneous dual Flame Photometric Detector
(FPD) for sulfur and phosphorus detection. Confirmation is accomplished using the same solid sor-
bent/thermal desorption/GC instrumentation with Atomic Emission Detection to confirm through ele-
mental analysis and Mass Spectrophotometric Detection for structural confirmation. Soil and other
environmental samples such as building debris are extracted manually using an organic solvent and
analyzed using DAAMS technology and the same variety of detectors.
Data generated during implementation of QA/QC programs for sample collection and analysis indi-
cates system responses are linear within a wide dynamic range. Results of precision and accuracy tri-
als as well as field tests during hazardous response activities are included in this presentation. A sin-
gle basic instrument system consisting of solid sorbent cartridges for sampling, concentration and
injection, with multiple GC detectors for screening and confirmation through elemental and structural
analysis, is able to carry out all monitoring activities, from initial confirmation of contamination
through characterization of the extent of the release and follow-up during remediation.
THERMAL SAMPLING HEAD AND SYSTEM FOR CONCRETE WALLS
CM. Penney, A.L. Ortiz, E. Barren, P. Slaver, RD. Lillquist, Sf. Feldman and DK. Berdahl, GE
Corporate Research and Development, Sckenectady, NY 12309
The objective of this work is to make available a means for rapid, non-destructive sampling of surface
and near surface semi-volatile contaminants on porous construction materials such as concrete. The
sampling head is designed to heat a 100 cm2 area of a typical surface to a temperature of 250 °C in
60-90 seconds. This head interfaces with a quick look detector (photoionization detector) and a mul-
lisample sorption tube collector to allow for sample recovery and laboratory analysis. First order
models of the thermal and diffusion properties of concrete suggest that the heated and sampled
regions extend several millimeters into the surface. The thermal performance of the sampling head
has been evaluated using buried thermocouples and an imaging pyrometer. The results of initial sam-
pling experiments on controlled laboratory samples and environmental surfaces will be discussed in
terms of sampling efficiency and model predictions.
88 Thursday, February 23,1995
-------
Sampling and Sample Handling
95
96
A MAN-PORTABLE SUPERCRITICAL FLUID EXTRACTION SYSTEM
B.W. Wright. WJI. Robins, and T.S. Zemanian, Chemical Sciences Department, Pacific Northwest
Laboratory*, Richland, WA 99352
Supercritical Fluid Extraction (SFE) is gaining acceptance as an alternative sample preparation
• method. Current extraction methods, which include Soxhlet and sonication methods, are time-con-
suming and require relatively large volumes of organic solvents which generate hazardous waste.
The liquid-like solvating power and rapid mass-transfer properties of supercritical fluids provide for
faster and more efficient extraction than is feasible with liquids. Because carbon dioxide or carbon
dioxide mixed with low percentages (e.g., <10%) of polar modifiers exhibit sufficient solvating power
to extract many analytes of interest, only small volumes of liquid solvent are required for SFE. In
addition, because SFE is amenable to automation, the technique is attractive for implementation in-
the-field.
A new prototype SFE instrument has been developed for the on-site preparation of solid samples for
subsequent analysis. The instrument is comprised of two pans, each of which satisfy weight and size
requirements for portability. They are, a generator module that supplies high pressure carbon dioxide
and an instrument briefcase containing extraction cells, flow restriction hardware, equipment for three
different methods of collection, control apparatus, and operating supplies. The generator module pro-
vides carbon dioxide at pressures to 2 kbar and incorporates no moving parts. The module allows
rapid loading without tools, due to novel finger-tight closures. Fluid from the generator is throttled to
extraction pressures not to exceed 700 bar, and is preheated for introduction to each of three extrac-
tion cells. Row may be switched between each of the three extraction cells, allowing operation of
one cell while depressurizing another and loading the third with sample. Extraction fluid modifiers
may be added to the extraction cells or introduced to the fluid flow from the generator. The heated
extraction cells feature rapid, finger-tight closures, which allow swift turnover in sample processing.
Extraction efficiency is enhanced by radial flow of the extraction medium through the sample, rather
than the typical axial flow. Samples are contained in sintered inserts that fit within the extraction
cells. Analyte collection may be accomplished using liquid solvent collection, adsorbent collection,
or restrictorless rapid depressurization collection. Robust control schemes allow operation at a wide
vanety of pressures and temperatures and the use of static, dynamic, or hybrid static dynamic extrac-
tion strategies.
The technical performance of the prototype instrument will be evaluated by comparison to Soxhlet
extraction using representative analytes and matrices. Operation aspects will be summarized based on
preliminary field demonstrations. Field ruggedness evaluations of the prototype instrument will also
be described.
This work was supported by the Office of Research and Development of the U.S. Department of
Energy and by the Defense Nuclear Agency through a Related Service Agreement with the U.S.
Department of Energy under Contract DE-AC06-76RLO 1830.
* Pacific Northwest Laboratory is operated by Battelle Memorial Institute.
PREPARATION OF TEDLAR® BAG WHOLE AIR STANDARD WITH A
SUMMA® CANISTER FOR FIELD VOC ANALYSIS
Elizabeth Denly, Hui Wang, ENSR Consulting and Engineering, 33 Industrial Way, Wilmington, MA
01887
As the application of field analyses of Tedlar* bag samples is growing, the standard preparation has
become more critical. Traditionally Tedlar bag standards were prepared by direct)y injecting a tar-
get compound mixture into a Tedlar bag pre-filled with zero air or nitrogen. It is very time consum-
ing because standards must be prepared daily due to Limned stabilities of volatile organic compounds
(VOCs) in a Tedlar bag. It also introduces several variables to the process of standard preparation,
such as the accuracy of the volume of zero air or nitrogen in the bag and the injection volume of stan-
dard mixture. A new application of Tedlar* bag standard preparation in the field will be introduced
in this paper. A pre-prepared SUMMA* canister standard with targeted VOCs is used to fill a
Tedlar* bag in the field each day. It takes advantage of long term stabilities of VOCs in a SUMMA*
canister, simplifies the process of Tedlar bag standard preparation in the field and limits the vari-
ables in the process to increase the reproduciblility. This paper describes the recent study of this
method. Its comparison with traditional method of Tedlar* bag preparation is discussed. The results
on reproduciblility, humidity effects, temperature dependency and time dependent stabilities will be
presented.
Thursday, February 23, 1995 89
-------
X-ray Fluorescence Spectrometry
97
98
OPTIMIZATION OF FUNDAMENTAL PARAMETER METHODS FOR
ANALYSIS OF HAZARDOUS MATERIALS WITH FIELD PORTABLE XRF
ANALYZERS
Dennis J. Kalnicky, Mark Btrnick, and Lawrence P. Katlin, Ray F. Weston, Inc.JREAC,
Rajeshmal Singhvi and George Prince, US. Environmental Protection Agency, Office of Solid Waste
and Emergency Response, Office of Emergency and Remedial Response, Emergency Response
Division, Emergency Response Branch. 2890 Woodbridge Ave.. Edison, NJ 08837-3679
Field portable X-ray Fluorescence (XRF) instalments hive been widely utilized by the U.S.
Environmental Protection Agency's (U.S. EPA) Environmental Response Team (ERT) to characterize
metallic waste contamination in soil and sediment. Rapid, on-site XRF analysis provides near real-
time data which may be used to guide cleanup/removal activities at hazardous waste sites.
Historically, XRF analyses based on site-specific calibration standards have not been useful for more
than one site and/or sample matrix. Fundamental Parameters (FP) techniques provide multi-site capa-
bilities by eliminating the requirement for site-specific standards. Inter-element matrix effects are
predicted theoretically and intensity response is normalized to a set of pure element standards. The
resultant application is, in principle, suitable for analysis of target elements for a given sample type
(soil, water, oil, thin films, etc.) at any site. However, uncertainties in the data used to generate theo-
retical coefficients may lead to errors and biases in FP analytical models based on them. Therefore,
adjustments based on assayed materials (such as MIST Standard Reference Materials, SRMs) may be
necessary to "fine-tune" results. This paper describes methods to "fine-tune" FP models for analysis
of hazardous materials in soil, sediment, and other matrices. The effectiveness of the approach will
be demonstrated utilizing a commercially available field portable XRF analyzer and associated PC
based software.
A NEW XRF METHOD FOR MEASURING THE CONCENTRATION OF
BURIED LEAD IN PAINT USING L X-RAYS
Charles Parsons and Lee Grodzins, Niton Corporation, Bedford, MA 01730
A new method has been developed that makes it possible to accurately and quickly determine the
absolute concentration of lead in lead paint (in mg/cm2) without knowledge of the composition or
thickness of the layers overlying the lead. The invention makes use of the fact that the ratio of the
mass attenuation coefficients for the LQ at 10.5 keV to the Ln at 12.6 keV is effectively independent
of the Z of paint layers. The theory and confirming experimental data will be presented for a lead
layer of 1 mg/cm2 buried by up to 200 mg/cm of non-lead paint (more than 1 mm thick). The new
method also gives a measure of the depth of the lead beneath the surface. We will describe the
NITON XL, which uses the invention to give the lead concentration and its depth index.
90 Thursday, February 23.1995
-------
X-ray Fluorescence Spectrometry
99
100
A NEW XRF INSTRUMENT FOR MEASURING THE CONCENTRATION OF
LEAD IN SOIL USING L X-RAYS
Lee Grodzins, Charles Parsons, Donald Sackett and Stephen Shefsky, NITON Corporation, Bedford,
MA 01730
We present a method for measuring lead in soil using L-shell x-ray fluorescence that is simpler than
fundamental parameters, yet reliable for large varieties of soil compositions. L-shell fluorescence x-
rays are an appealing alternative to K-shell x-rays for in-situ measurements of lead in soil because of
their superior sensitivity. One pitfall is that reliable measurements of lead levels at and below the
EPA and HUD action levels (500 and 1000 ppm respectively) require corrections for soil matrix
effects. One correction method, fundamental parameters, uses the entire measured energy spectrum
to estimate the soil composition and hence approximate the correction. This requires complex com-
puter algorithms and can be difficult to implement for a wide variety of soil types. We present results
for an alternative technique that is computationally much simpler yet capable of measuring lead levels
of at least 400-500 ppm in 10-20 seconds and perhaps as low as 100-200 ppm within 60 seconds or
less. Measurements of in-house soil matrices containing varying amounts of common soil con-
stituents such as FeO, SiO2, CaCOj, Zn, Sr, Ti and Al, as well as samples from field testing, will be
shown and compared to laboratory atomic absorption testing. Our technique combined with the
NITON XL lead paint detector yields a handheld field instrument that weighs less than 3 Ib, is capa-
ble of rapid measurements and costs far less than currently available XRF devices.
APPLICABILITY OF XRF AS AN IN-SITU ENVIRONMENTAL SENSOR
W.T. Elam and RJt. Whitlock, Naval Research Lab, Washington, DC 20375-5345 and J.V. Gilfrich,
SFA, Inc., Landover, MD
We have investigated the use of x-ray fluorescence as a sensor technology for in-situ, real-time envi-
ronmental applications such as the cone penetrometer and shipboard waste disposal. The applicability
of XRF to these situations depends on detection limits and matrix effects. To investigate these effects
for such a sensor, a laboratory mock-up was constructed using available components. The x-ray tube
was operated at very low power and an electrically cooled detector with a small active area was used.
The x-ray path lengths were kept short and an aperture and incident x-ray filter similar to those appro-
priate for the penetrometer sensor were used. Detection limits were determined for metals present in
soil samples and compared to solid waste regulatory limits. Quantitative measurements were made
both without matrix correction and using the fundamental parameters correction method. Results
were generally within 10% of the certified values. In addition, several novel ways of improving the
lower limits of detection to reach the drinking water regulatory limits have been explored. Issues
concerning the engineering involved with constructing a spectrometer within the physical constraint
of the penetrometer pipe were also investigated. Only small improvements over current state-of-the-
art would be required.
Thursday, February 23, 1995 91
-------
Author Index
Abraham, Brian, 20
Adams, John H., 14
Adler, A., 83
Aggarwal, I.D., 3,49
Akindele, Femi M., 61
Aldstadt, Joseph H., 3
Allen, Randy, 78
Amick, E. Neal, 61
Anderer, Brad, 43
Anderson, Isabel R., 36
Andresen, B., 65
Andrews, John, 59
Anheier, Jr., Norman C., 56
Arnold, Neil S., 8, 67, 82
Atwell, James S., 21
Avolio, J., 82
B
Baker, Lone A., 16, 35
Balas, Peter C., 18
Barber, Michael E., 20
Barren, Elizabeth, 78, 88
Barrick, H., 53
Baumgart, Chris W., 27, 84
Baykut, G., 68
Beck, Milton, 16
Bello, J., 6, 55
fields, K., 26
Berdahl, Donald, 78, 88
Bemick, Mark, 42, 85, 90
Bernstein, David, 19
Bevolo, A., 55
Bilodeau, T., 3,49
Bodek, I., 62
Boline, K., 28
Boomer, Karen, 28
BOrOcz, Sz., 11
Bradley, Allen, 71
Bradshaw, Robert, 14
Brannon, James M., 4
Brazier, Richard, 28
Breton, Nelson M., 45
Brice, Timothy M., 72
Brodacki, M., 83
Brown, Kenneth W., 61
Brown, Daniel, 70
Brown, Steve, 5
Brumley, William C., 19, 66
Bruns, Mark W., 72
Buckner, M.A., 87
Bunn, David W., 32, 69
Buttner, William J., 15,58
C
Cabelli, M.D., 1
Callahan, Patrick J., 13
Carlson, Robert E., 79
Carlson, L., 2
Carney, K.R., 7, 13
Carrabba, M., 6, 55
Carter, Jeffery R., 16
Cassem, Bruce R., 56
Catherman, David R., 17
Cave, Steven P., 27, 84
Cernosek, Richard W., 53
Cespedes, Ernesto R., 58
Chadha, Suneet, 5
Chaffin, C.T., 42
Chappell, Richard W., 34
Charles, P., 78
Chaudet, Roy, 23
Childs, Maryann, 19
Christenson, Jeff, 21, 68
Ciarcia, Christopher A., 27
Cibulskis, R., 59
Claff, Roger, 23
Clark, R., 3
Cocke, D.L., 63
Coleman, Daniel R., 72
Collins, G.E., 6
Conrad, D., 78
Costanza, Molly S., 3
Cooper, Stafford S., 4,58
Cornelius, Joe M., 30
Counts. R.W., 49, 74
Coutts, G., 65
Cozad, D.B., 73
Creager, James D., 27, 84
Crockett, Alan B., 61
Cunningham, Elizabeth A., 23
Curiale, Robert L., 5, 50
Curtis, David B., 86
D
D'Arcy, J.B., 29
Dahlin, C.D.T., 1
Dallas, S.M., 1
Darby, Shauna M., 11
Dautlick, Joseph X., 75
David, P.A., 8
Davis, William M., 58
DeAngelis, Dominick, 23
DeBono, R., 82
Dellarco, Michael, 22
Demirgian, Jack C., 11
Denly, Elizabeth, 89
Denton, M. Boimer, 15
Desai, Akhil, 43
Dharmasena, H.P., 7, 13
DiBerardino, C., 53
DiCollegaro, M., 55
Ding, Y., 64
Ditillo, John, 11
Dominguez, Martha E., 5, 50
DOring, H.-R., 83
Doskey, Paul V., 3
Douglas, G.S., 24
Dudney, Charles S., 30,31, 87
Durst, Richard A., 79
Dworzanski, Jacek P., 67, 82
E
Barley, K., 4
Eason, Robert, 18
Eckenrode, B., 65, 68
Ehntholt, D., 26, 62
Ehrmann, U., 7
Ekes, Laurie H., 47
Elam, W.T., 91
Eldefrawi, Mohyee E., 2
Eng, Dan Y., 4
Engelmann, William H., 50, 61
Erickson, Mitchell D., 3
Evans, John C., 56
Evans, Chris G., 21
Everson, J.F., 9
Ewing, K.J., 3,49
F
Fan, Titan S., 80
Fare, T.L., 1
Fateley, W.G., 42
Feldman, S.F., 88
Ferguson, Bruce S., 80
Fitzgerald, John, 14
Flachowski, J., 83
Flecker, James R., 76
Flynn, Colin, 18
Foreman, W., 9
Forester, Tina, 17
Forney, R., 6, 55
Francoeur, Thomas L., 21, 34
Franzen, P.A., 27
Friedman, Stephen, 78
Frisbie, Seth, 47
Frye, Gregory C., 53
G
Gallis, David E., 17, 21,68
Gammage, R.B., 30, 31
Gardiner, Mark, 47
Gianotto, David F., 36
Gilbert, Don W., 53
Gilfrich, J.V., 91
Gillispie, Gregory D., 57
Gilmore, Dan A., 15
Gobeli, David A., 64
Goldschmidt, William L., 17
Gonzalez, Debra L., 72
Gordon, Sydney M., 13
Grabinski, Carl, 23
Grant, Clarence L., 85
Gray, K.E., 63
Green, Elizabeth L., 23
Green, D.J., 27
92
-------
Author Index
Gresham, Garold L., 61
Griffiths, Peter R., 10
Grodzins, Lee, 90,91
Guerra, Richard, 21
Gui, John, 78
Gunderson, Michael J., 45
H
Haas. El John, 6, 55
Haas. Jr. Jon. 55
Hall, Jeff L.. 18
Hamblin, J., 52
Hammaker, R.M., 42
Mammons, Wayne, 35
Hanson, Mark, 17
Harbor, Lavon, 19. 61
Harden, Charles S., 14
Harlick, Alison J.. 27, 56
Harrison, Robert O., 79
Hart, B.K., 69
Hart, J.K.. 69
Hawthorn, S., 37, 59
Healey, Brian G.. 5
Henry, Charles, 60
Henshaw, John M., 54
Herman, Gary J., 19, 61
Hemdon, R.C., 11
Herr, Ken C., 18
Herzog, David P.. 76
Hess, T.R., 63
Hewitt, Alan D., 37, 85
Hibner, Jeffrey L., 51
Hill, Herbert, 81
Himka, Roger, 44
Hnatov, Matthew, 34
Holder, Jon, 63
Holland, P.M., 9
Holloway, Timothy, 18
Holmquist, B., 2
Hooton, Dennis, 46
Hudak, Robert T., 1.74,75
Humphrey, Alan, 46
Huston. Cora, 70
I
Itak, Jeanne A., 76
Jadamec, J. Richard, 81
Jakubowski, Edward M.. 88
Jenkins, Thomas F., 70
Jenkins, Roger A., 49, 64, 74
Johnson, Linda S., 65
Johnson, Michael, 84
Jones, Paulette, 58
Jones, T.L., 81
K
Kaelin, Lawrence P.. 37, 59, 85, 90
Kalnicky, Dennis J., 85, 90
Kam, Richard A., 4
Keimig, Theresa, 79
Kenny, Donald V., 13
King, Doug, 60
King, T., 3
Kjartanson, B.H., 55
Klainer, Stanley M., 44,45
Klasmeier, Maren, 81
Klein, V.. 41
Klemp, Mark A., 41
Kline, Rick, 2
Klopp, Chris, 32, 33
Klunder, Gregory L., 51
Kotrappa, P., 31
Krihak, M., 52
Kroutil, Robert T., 18
Kumar, Harmesh, 64
Kumke, M.U., 24
Kuo, Jacqueline M., 3
Kusterbeck, A., 78
L
Lachman, Charles E., 76
Laiche, Thomas P., 30
Lamp, T., 10
Lander, Neil J., 7
Larkin, Karen A., 80
Lawruk, Timothy S., 76
Leffler, J.S., 28
Leone, M., 9
Levine, S.P., 29
Lieberman, Stephen H., 24, 25, 29, 33, 59
Liebman, S.A., 63
Ligler, Frances S., 77,78
Lillquist, R.D., 88
Linenberg, A., 7
Lohmannsroben, H.-G., 24
Long, D., 16
Loomis, Lawrence, 19
Lopez-Avila, Viorica, 81
Loudon, A., 68, 83
Lucas, A.C., 87
Lumsdon, Gary, 18
Lyon, Robert, 16
M
Macha, Susan M., 11
Macon, Sandra T., 72
MacPhee, Craig, 47
Mainga, A.M., 7, 13
Marcus, Alvin B., 65
Marshall, T.L., 42
Mathes, John, 84
Matt, Jonathan J.. 80
McCaffrey, C.. 76
McClermen. William H.. 8. 67,82
McClenny, W.A., 13
McCullough, J., 26
McGinnis, W.C., 24, 33
McGrath, Elizabeth, 22
McGuire, Frank, 59
McHugh, D., 33
Mehta, Uday J., 26
Melby, James M., 1, 74, 75
Meuzelaar, Henk L.C., 8, 67, 82
Meyer, John, 17
Meyer, K.E., 30.31,87
Mickunas, David B., 42,46
Mihamou, Houssein, 67
Milanovich, Fred P., 5
Miller, David, 19
Minnich, M.M., 12
Miracle, M., 16
Miseo, E., 62
Mollah, M.Y.A., 63
Molsbee, Richard N., 69
Moore, John Jr., 22, 36
Morlock, Clayton R., 52, 73
Mosier-Boss, P.A., 29
Mullenix. Michael C.. 75
Mustacich, R.V., 9
Myers, Karen F.. 4
N
Nakaishi. C., 15
Nau,G.,3,49
Naumann, W.J., 9
Nelligan, Frederick M., 56
Newbery, R., 29
Nielsen, B.J., 28
Niessner, Reinhard, 25
Niss, N.D.. 69
Nolke, B., 68
Norwood, La Van, 81
O
Oakley. Daniel B.. 47
Older, K., 55
Olsen, Khris B., 14, 56
Onisk. Dale V.. 1
Ortiz. A.L., 88
Orzechowska, Grazyna E., 50
Overton, Edward, 7.13, 60
P
Pal, A., 71
Pal, T., 71
Palausky. M.A., 49. 74
Parsons. Charles, 90, 91
Paul, Donald G., 26, 88
Pauls, R.E., 8
Peczeli, I.. 11
Peery, Doug, 70, 71
Penney, CM., 88
Pesce, Edward L., 45
93
-------
Author Index
Petering, Jennifer, 19
Peven, C.. 24
Pletf, J.D., 13
Polak, M.L., 18
Pollard, James £., 61
Popek, Emma P., 18
Porter, Beth, 58
Portnoff, Marc A.. 51
Powell. G., 37
Poziomek, Edward J., 5, 50, 77
Price, Cynthia B., 4
Prince, George, 37, 59, 85, 90
Prusko, Peter, 51
Pyle, Steven M., 65
Q
Quere. Alain, 50
R
Radolovich, Gil, 81
Radwanski, P., 82
Rapp, Keith, 4
Rau, J., 87
Reeves, Stuart G., 79
Resch, M., 41
Richards, James, 5
Richardson, Robert L., 10
Richter. PJ.. 11
Riddell, M.. 2
Rigdon, Steve, 81
Roberts, Paulene, 60
Roberts, Mathew A., 79
Robins, W.H., 89
Robins, Kathleen A., 5
Robitaille, G., 3
Roch, Th., 24
Rogers, Kim R., 2, 77
Rose, Jim, 51
Rose-Pehrsson, S.L., 6
Rubio, Fernando, M., 76
Russo, Richard E., 51
Ryan, J., 40
94
Sackett, Donald, 91
Sacks, Richard D., 41
Saini, Devinder P., 44,45
Salaskey, M.. 31
Saraf, Sanjay, 43
Schabron, J.F., 69
Schechter, Israel, 25
Schere, G.J., 18
Schmidt, J., 53
Schuetz, Steven P., 46
Schumacher, B.A., 12
Schwartz, J.L., 1
Schweitzer, Craig, 2
Seeley, Ian, 40
Selisker, Michele Y.. 76
Shatter, Elizabeth M., 66
Shahriari, M.R., 52
Shefsky, Stephen, 91
Sheya, Sue Anne, 8, 67
Shirkhan, Hamid, 79
Shriver-Lake, Lisa C., 77
Sides, Gary D.. 72
Siebert, Sui Ti A., 79
Silvia, J.C., 1
Simpson, Greg, 81
Sincock, Stepahnie Arm, 61
Singhvi, Rajeshmal, 85, 90
Snyder, A. Peter, 14
Sokolski, Pierre, 18
Solinski, Philip, 46
Spencer, K., 55
Spencer, Trevor, 18
Spinier, Tom M., 12, 67
St. Germain, Randy W., 57
Stach, J., 83
Stang, PM., 33
Stanley. C.W.. 32
Starzynski, B., 65
Stave, James W.. 1, 75
Slaver, P., 88
Steinfort, Terry D., 53
Stenback, G.A.. 55
Stepenuch, S., 12
Stetter, J.R., 15
Stewart, M.T., 13
Stolki. T., 62
Stopa, Peter J., 19, 61
Strong, Ann B., 4
Stuffier, T.. 41
Stutman, Mark B., 43
Su, Chih-Wu, 81
Sword, Michael A., 44
T
Tabacchi, John, 51
Taylor, D., 37, 59
Taylor, Byron D., 60
Taylor, Steve J., 14
Teaney, George B., 74, 75
Theriault, Greg. 25
Thomas, Stan, 18
Thompson, P.M., 1
Thompson, Nathan, 23
Thorne, Philip G., 70
Tindall. S., 20
Tingle, A., 16
Tipler, A., 40
Tipton, Terence L., 54
Trespalacious, Miguel J., 17
Tunnell, Tom W., 27
Turner, Robert B., 14
Turner, Stephen A., 34
Turpin, Rodney D., 17,42
Turriff, David, 32, 33
u
Uhland, S., 52
V
Valentine, J., 26
Van Emon, Jeanetle M., 2
van Haren, G., 10
Vance, S., 59
Vempati, R.K., 63
Venkateswar, Raja, 43
Vetter, O.J., 64
Vickers, William C., 58
Viswanath, Rampur S., 48
Vo-Dinh, Tuan, 61, 71
Vogt, Brian S., 54
W
Wagaman, Scott A., 17, 42
Walt, David R., 5
Wampler,T.P.,63
Wang, Hui, 89
Wang. J.. 14
Washall, J.W.. 63
Waters, L.C., 49, 74
Watson, Steven M., 18
Weber, K., 10
Weidemann, J., 10
Wells, James C., 64
Westberg, Richard A., 48
Wheeler, R.V., 31
Whitlock, R.R., 91
Wiedman, S.S., 1
Wier, W., 28
Wilder, W.L., 32, 35
Williamson, P., 67
Winegar, Eric D., 86
Wing, Thomas, 44
Wonder, D., 55
Worden, Ray, 60
Wright, B.W., 89
Wright, Jeremy, 2
Wrigley, Mark J.. 43
Wylie, D., 2
Y
Yates, Marie J., 86
Yu. M., 77
Zarus, Gregory M., 17,42
Zehner, Warren B., 30
Zemanian, T.S., 89
Zhao, Qinchun, 2
Zhu, Changjiang, 10
Zimmerman, J.H., 12
------- |