FIELD TECHNOLOGIES FOR THE MEASUREMENT OF PCBst

Amy B. Dindal', Charles K. Bayne', Roger A. Jenkins', David M. Carden3, and Stephen Billets'

Lockheed Martin Energy Research Corporation Oak Ridge National Laboratory '

' Chemical and Analytical Sciences Division ZComputer Science and Mathematics Division

P.O. Box 2008 Oak Ridge, Tennessee 3783 1 -6 120

' L!. S. Department of Energy Oak Ridge Operations Office

Three Main Street Oak Ridge, Tennessee 37830

' U. S. Environmental Protection Agency National Exposure Research Laboratory

P.O. Box 93478 Las Vegas, Nevada 89 193-3478

t Research sponsored by the Environmental ProtecRon Agency, Nanonal Erposure Reseurch Laboratory, Las Vegas. Nevada. under tnteragency agreement 1824JO93-CI ond the Envtronmental Management Program. II. S. Depamnenr of Energy under contract DE-ACO5-96OR22464 wz rh Oak Rdge Nanonaf Laboratory, managed by LockheedMamn Energy Research Coporanon.

ABSTRACT The collaborative effort between the U. S. Environmental Protection Agency @PA), U. S. Department of Energy (DOE), and the Oak Ridge National Laboratory (ORNL) represents a viable team to administer, plan, execute, and report on demonstrations of commercially available field characterization and monitoring technologies. This effort is part of the EPA's Environmental TechnoIogy Verification 0 Program One of the overriding goals of this effort is to develop regulatory-accepted and cost effective alternatives to conventional fixed laboratory analyses through the identification 'and evaluation of innovative, field technologies.

A technology demonstration of polychlorinated biphenyl (PCB) field analytical techniques will occur during July 22 through 30, 1997. The demonstration will be conducted at a DOE site (ORNL) where there is a substantial repository of PCB-contaminated materials from multiple DOE sites. Technology developers with PCB' monitoring instrumentation will be evaluated. These imtnments will include field portable gas chromatographs with surface acoustic wave and electron capture detectors, and field analysis kits, such as immunoassay and ion specific electrode kits. These instruments are suitable for the quantification of PCBs in a variety of matrices. Soil and surface samples will be evaluated during the demonstration.

The demonstration will focus on the current DOE-Oak Ridge analytical needs to support Toxic Substance and .Control Act (TSCA) decisions, while allowing developers to showcase the features of their technologies.

INTRODUCTION The Consortium for Site Characterization Technology is a partnership between the Environmental Protection Agency (EPA), the Ikptmea of Energy (DOE) and Depament of Defense @OD). The Consortium is a part of the EPA's Environmental Technology Verification (ETV) program. DoD and DOE have established programs and facilities (testing venues) for testing, demonstrating, and evaluating the performance of monitoring, measurement and site characterization technologies. in addition to other technologies. As a partnership, the Consortium will offer valuable technical expertise to support the demonstration and verification of the performance of new and emerging technologies and will offer access to a wide array of testing venues.

A goal of the Consortium is to facilitate the acceptance and use of costeffective technologies applicable to a widc range of environmental problems. The Consortium will meet this goal by working with technology developers and other agencies in planning and conducting demonstrations,

DISCLAIMER

DISCLAIMER

This report was prepared as an account of work sponsored by a n agency of the United States Government. Neither the United States Government nor any agency thereof, nor any of their employees, make any warranty, express or implied, o r assumes any legal liabili- ty or responn'bility for the accuracy, completeness, or usefulness of any information, appa- ratus, product, o r process disdosed, or represents that its use would not infringe privately owned rights. Reference herein to any specific commercial product, process, or service by trade name, trademark, manufacturer, or otherwise does not necessarily constitute or imply its endorsement, recommendation, or favoring by the United States Government or any agency thereof. The views and opinions of authors expressed herein do not necessar- ily state or reflect those of the United States Government or any agency thereof.

evaluating data generated in demonstdons and managing and disseminating information. The Consortium is not intended to become another technology testing organization that must touch every technology, but rather it is designed to support existing demonstration efforts or developerdriven demonstrations.

A demonstration at the Oak Ridge National Laboratory ( O N ) will evaluate field analytical technologies which are capable of detecting and quantitating polychlorinated biphenyls (PCBs). A fundamental objective of this demonstration is to evaluate how well the technologies can assist in regulatory decision-making processes for PCB- contaminated waste. The EPA’s National E‘xposure Research Laboratory, Char,ct&~at io~ !?march Division-Las Vegas, Nevada and the DOE’S Environmental Management Program are sponsoring this project. ORNL will serve as the verification organization for the demonstration. ORNL’s role is to provide technical and administrative leadership and support in conducting the demonstration.

The purpose of this demonstration is to provide rigorous, statistidy defensible testing of field monitoring equipment for PCBs under actual field conditions. The intent is to accelerate the adoption of innovative technologies. Participation in the demonstration can provide a technology developer with EPA’s “blessing”, while potential users of the technology can be assured that their technology will perform properly under the conditions described.

The PCB technology demonstration will occur during July 92 through July 30, 1997. This manuscript will describe the goals of the demoristration, the experimental design, and which technologies are being evaluated. In the presentation of this manuscript, the results of the demonstration will be diSCUSSed.

PARTICIPANT SELECTION An initial list of 71 potential developers were idcntificd through searches of various information sources (journals. the Internet, and symposium proceedings). After each developer was contacted, a preliminary group of candidate technologies were selected, based on developer interest and relevance of the technology to the proposed demonstration. These developers were invited to attend a Developers Conference on F&ruary 19,1997, in Atlanta, GA (hosted by EPA Region 4). The purpose of this meeting was to bring together candidate participants and demonstration organizes for an exchange of information and to determine which technologies are suitable for participation in the demonstration. Representatives fmm the EPA. DOE. and ORNL attended the conference and provided technology developers with an overview of: (a) EPA’s technology

verification program, (b) the objectives for the demonstration, and (c) the benefits of participating in the program. Based on the detailed technoIogies descriptions that the developers presented at the conference, a group of developers were selected as the best candidatcs for participation in the demonstration. Final selection and qualification for the study was based on successful analyses of a series of predemonstration samples that were representative of the samples that would be analyzed in the actual demonstration. The final list of technology developers participating in the PCB demonstration are: Dexsil Corporation, Hach Corporalion, Sentex Systems. Inc.. Strategic Diagnostics, Inc., and Electronic Sensor Technology.

Dexsil Corporation The L2000 PCB analyzer is a field portable ion specific elecuodehstrurnent designed to quantify PCB conccntration in soil. dielectric fluids, and &ace wipes. PCB in soil can be quantified over a range of 3 ppm to 2000 ppm with the ability to extend the range over 2000 ppm by reducing the sample size. Total time for analysis of soil is 10 minutes. dielecuic fluid is 5 minutes and surface wipes is 12 minutes. Cost for Wsis of soil is $8.00 to $lO.OO/sample, dielectric fluid is $3.75 to $5.00/sample and $12.00 to $16.00/sample for surf= wipes. Sample preparation consists of extraction and dehalogenation of the PCB. The resulting chloride ions are then isolated in an aqueous buffered solution for analysis by the L2000 Analyzer.

Hach Corporation Hach will demonstrate an immunoassay test kit for PCBs. Samples. standards and reagents are added to test tubes coated with an antibody specific for PCBs. The concentration of PCBs in a sample is determined by comparing the developed color intensity to that of a PCB standard. The PCB concentration is inversely proportional to the color development; the lighter the color. thc higher the PCB concentration. This method is a semiquantitative screening method which indicates whcther the PCB concentration is above or below 1 pprn and/or 10 ppin threshold values.

Scntex Systems, Inc Sentcs will demonmte a field portable gas chromatograph with an electron capture detector. A procedure based on approved EPA methods will be performed to isothermally analyze Aroclor PCBs within fifteen minutes. utilizing a Sccntograph Plus II Portable GC with a short capillary column. The Scentograph Plus I1 is a complete anal!.tical system. The GC includes a sample injcction systcm. a precisely controlled column oven, detection system. gas flow regulation and electronics. The data management systcin is

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provided by a detachable laptop computer. The program that operates the GC collects, stores and processes data, which is saved to the hard disk drive. Data can be collected on the hard drive or on floppy disks. The Sentex operating program is user-friendly, and can be easily operated by a person with no previous computer experience. Prior to field analysis, the Scentograph Plus I1 can be calibrated with all the different Aroclor PCBs. The generated chromatograms of the standards are stored in memory. A special feature of the Sentex program allows the stored chromatograms to be grouped into sets. After each sample analysis, the set of calibration chromatograms can be recalled and the sample chromatogram will be superimposed against the chromatograms of the different standards in the set one at a time. This ficilitates fast pattern recognition and qualitative results. For increased accuracy, once an Aroclor PCB is identified in the sample, the corresponding standard of a chosen concentration is analyzed and the sample is quantified against this standard.

Strategic Diagnostics, I n c Formed by the 1996 mergers or Strategic Diagnostics, EnSys, and Ohmicron Environmental Diagnostics, SDI will demonstration three difference field testing formats of immunoassay test kits for PCBs. While the core technology for these products is the same, each utilizes a distinct format, provides differing result types, and is best suited to different field testing applications. The D TECH latex particle format provides very rapid (< 20 min) field testing capability with semiquantitative screening results. The D TECH test is ideal for rapid testing applications where a rough and fast yes/no answer is required, and where project resources do not permit training. The EnviroGard coated tube technology provides rapid semiquantitative field analysis with a higher level of analytical precision. The EnviroGard calibrators are set up represent common project action levels. The Ohmicron WID Assay magnetic particle format represents the highest level of analytical precision. The RaPID Assay format can be used to generate semiquantitative or quantitative results. It is ideal in high volume testing applications.

Electronic Sensor Technology Surface Acoustic WavdGas Chromatography (SAW/GC) pmvides a costeffective system for collecting real-time field screening data for characterization of vapor streams contaminated with organic compounds. The Model 4100 SAW/GC can be used in a field screening mode to produce chromatograms in 10 seconds. The 4100 consists of a portable gas chromatograph, a Surface Acoustic Wave Detector and a dynamic particlehapor sampling head. The components are shock mounted into a rugged field portable fiberglass shipping case. The solid state resonator has

excellent m e r y characteristics and provides sensitivity to picogram levels and spans a dynamic range of more than 8 orders of magnitude. .

Reference Laboratory The verification process is based on the presence of a statistidy validated data set against which the performance goals of the technology may be compared. The choice of an appropriate reference method and reference laboratory are critical to the success of the demonstration. The reference analytical method will be EPA SW-846 Method 8081. To assess the performance of the PCB field analytical technology, the data obtained using the technology will be compared to data obtained using conventional analytical methods. This decision is based on the experience of prospective 'laboratories with QA procedures, reporting requirements. and data quality parameters consistent with the goals of the Program. The laboratory must also demonstrate past proficiency with the method. Oak Ridge Sample Management office (SMO) has been tasked by DOE Oak Ridge Operations with maintaining a list of qualified laboratories to provide analytical services. These activities for the p m m e n t of commercial laboratory services are to support projects sponsored by the DOE Oak Ridge Operatioxis Ofiice The procedure serves to ensure that as an operation of a DOE contractor, LMES SMO maintains an optimum level of technical and administrative oversight on each project, and SMO commercial procurement activities comply with federai acquisition laws and LMES procurement policy. Using these procedures, ORNL selected LAS Laboratories. in Las Vegas. NV, as the reference laboratory.

EXPERIMENTAL DESIGN The fundamental areas of evaluation for the demonstration are: (a) assess performance relative to conventional analytical methods (b) examine the impact of sample matrix on performance, (c) determine the influence of environmental conditions on performance, and (d) observe the operational logistics of the technologies. A description of all demonstration elements are included in the technology demonstration plan, which is developed based on an EPA Guidance Manual [ 11.

Demonstration Site The demonstration ofpCB field analytical techniques will be conducted at the Oak Ridge National Laboratory (ORNL). which is managed by Lockheed Martin Energy Research Corporation, Oak Ridge. Tennessee. Field activities will occur at two sites at ORNL: the area west of Building 5507 (Site #1) and inside a controlled environmental atmosphere chamber (Site #2) which is located in Building 5507.

The controlled e.xperimenta1 atmosphere (CEA) facility

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consists of a room-size, walk-in chamber ten feet wide and twelve feet in length with air processing equipment for temperam, humidity, and slightly subambient pressure control at air circulation flow rates up to five hundred cubic feet per minute. The chamber is equipped with an environmental control system including reverse osmosis water purification supplying the chamber humidity control system. Highefficiency particulate air (HEPA) and activated charcoal filters are installed for recirculation and building exhaust filtration. Analytical instrument performance tests will take place entirely inside the CEA chamber to test performance in a climate which is different from the ambient outdoor conditions.

The developers Will analyze a similar set of samples outdoors and inside the chamber to assess the influence that difference environmental conditions (particularly temperature and relative humidity) have on the performance of the technology. Since the temperature and humidity will be relatively high (approximately 90°F and 90% RH) in Oak Ridge in late July, the chamber conditions will be set to cooler temperatures and lower relative humidity (approximately 65°F and 40% RH).

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Demonstration Samples The developers will analyze real environmental samples consisting of PCB-contaminated soils excavated at DOE facilities in Oak Ridge 0, Paducah (KY), and Portsmouth (OH). In Table 1 is presented a description of the environmental sail samples that will be evaluated. The

,sampies will be homogenized (dried, blended, sieved, and mixed) prior to distn’bution and analysis. Approximately six soils will also be spiked with PCB to increase the total concentration.

In addition to real environmental samples, performance evaluation (PE) soil samples will be analyzed. PE samples will be provided by Environmental Resource Associates (Arvada, Colorado) and EPA’s Office of Solid Waste and Emergency Response’s Analytical Operations Center.

There will also be an optional set of sample extracts for tlrc developers to evaluate. Since a PCB-contaminated surfacc cannot be homogenized and split like the soil samples such that comparable samples are distributed to all demonstration participants, a PCB-extract (in isooctane or methanol) will beaned. Demonstration Analyses A total of 104 soil anaJyw (68 environmental samples and 36 PE samples) will be performed at each site. All soils will be evaluated in quadruplicate. Concentrations of total PCB in the samples will range from 0.5 ppm to 700 ppm.

Approximately half of the developers will participate in the extract sample analyses. A total of 12 samples will be analyzed at each site. Two concentration levels (10 pg/100cm2 and 100 pg/100cm2) will be analyzed in quadruplicate.

AI1 of the sample identities will be unknown to the developers. The order of analyses will be randomized for each developer.

Summary of Design Features The study was designed to estimate both accuracy and the measurement precision of PCB field monitoring instruments. The design incorporates a total of 208 soil analyses of 25 unique environmental samples. Each sample will be analyzed in quadruplicate and paired with the reference laboratory’s results for all sample types and concentration levels.

RESULTS AND DISCUSSION The preparation of this manuscript was prior to the execution of the PCB demonmation. Developer results will be reported during the presentation of this manuscript.

Report Format Each developer will receive a technoiogy verification report describing their performance during the demonstration. Each report will contain a general demonstration description. The reports will be approved by EPA and will be externally peer-reviewed.

Characteristics to be Assessed Each technology’s performance will be assessed relative to tlic reference laboratory’s perforbance. The technologies will not be compared to each other, or be rated as thc ”best” or ”worst” technology.

The primary objectives of this demonstration are to evaluate the PCB field analytical technologies in the following areas: ( I ) how well each performs relative to conventional analytical methods, (2) the impacts of sample matrix variations on performance, (3) the sect that environmental conditions have on performance, (4) quality control results. and ( 5 ) the logistical and economic resources necessary to operate the technology. Secondary objectives for this demonstration are to evaluate each PCB field anal>.tical technique in terms of its reliability, ruggedness. cost. range of useMness, data quality, and ease of operation. Where possible, the performance will be compared to the performance of conventional analytical methods used in performing similar site characterization activities.

A verification statement will be issued by EPA for each technology as a brief summary of the findings of the

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demonstration. It will describe how well the technoIogy achieved the performance goals that the demonstration was designed to evaluate.

CONCLUSIONS This demonstration will provide technology developers with a rigorous, statistically defensible testing of their PCB field analytical technologies. Each technology will be assessed for its own merits, and not compared to the performance of the other demonstrating technologies. Those technology developers with acceptable performance during the demonstration will receive EPA's written acceptance of the technology, in the form of a verification statement.

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