A Pilot Study of Passive Diffusion Bag (PDB) Sampling in a Fractured Bedrock Environment

Thomas W. Biolsi, Steven G. Feldmann, and Barbara A. O’Grady, EA Engineering, Science, and Technology, Inc., 485 Route 1 South, Building C, Suite 260, Iselin, New Jersey 08830, Tel: 732-404-9370, Fax: 732-404-9382
Jeffery M. Dale, United States Navy, Engineering Field Activity Northeast, Naval Facilities Engineering Command, 10 Industrial Highway, Mail Stop No. 82, Lester, Pennsylvania 19113, Tel: 610-595-0567, Fax: 610-595-0555

In a joint effort between the Navy, United States Geological Survey, and EA Engineering, a pilot study of passive diffusion bag (PDB) sampling was conducted at the former Naval Air Warfare Center in Trenton, New Jersey.  The Navy currently operates and maintains a comprehensive ground-water extraction and treatment system for volatile organic compounds (VOCs) and ten metals at the site.  The Navy sought to evaluate a New Jersey Department of Environmental Protection (NJDEP)-acceptable ground-water sampling method that minimizes sampling costs and the treatment of purge water, without sacrificing data quality.  Research of sampling options led to the implementation of a pilot study on the use of PDB samplers.  The use of PDB samplers substantially reduces equipment and labor costs and produces virtually no investigation-derived waste, as compared to conventional purging and sampling techniques.  However, unlike typical PDB samplers that are usually constructed of polyethylene-based material and used to monitor for VOCs only, a regenerated cellulose-based material was used in this PDB pilot study in an attempt to also monitor inorganic parameters.  Samples from nine bedrock wells, representing a wide range of trichloroethene concentrations, were collected using PDB samplers, the Environmental Protection Agency’s low-flow method, and a modified version of the standard 3 to 5 well-volume purge method in March 2000 and March 2001.  The majority of the organic data indicate that the PDB samplers yielded similar results to conventional purging and sampling techniques.  Even though only minor sporadic concentrations of inorganic parameters were reported above the applicable reporting limits, similar results were observed for several metals including barium and manganese using the three sampling methods.  To gain regulatory acceptance by the NJDEP, additional data are being collected to further support the effectiveness of the PDB sampling technique for inorganic constituents.  The results of the assessments made to date will be presented for discussion.

 
Correlation of Field Analytical Detectors in the Analysis of Soil Contaminated with Diesel Fuel 

Clayton J. Clark II, Dept. of Civil & Coastal Engineering, University of Florida, P.O. Box 116580, Gainesville, FL 32611, Tel: 352-392-9537 ext.1440, Fax: 352-392-3394, Email: clark@ce.ufl.edu
Joseph J. Delfino, Dept. of Environmental Engineering Sciences, University of Florida, P.O. Box 116450, Gainesville, FL 32611, Tel: 352-392-9377, Fax: 352-392-3076, Email: jdelf@eng.ufl.edu

Analysis of soil by field instrumentation is widely used for preliminary soil contamination detection and site delineation.  Research was conducted to determine if there is a correlation between the data gathered by field analytical instruments in analyzing soil contaminated with diesel fuel.  One instrument was equipped with a flame ionization detector (FID) and the other a photoionization detector (PID).  The results showed that the concentration readings of the PID and FID displayed a linear relationship (R² = 0.94) for soil recently contaminated with diesel fuel.  However, for soil containing weathered diesel fuel in the field, a logarithmic relationship between the PID and FID readings was displayed.  It was also determined by laboratory experimentation that the PID and FID readings both exhibited log-linear decreases over time for uncovered diesel fuel contaminated soil. Analysis for the composition of diesel fuel, by volume, was also derived for the diesel fuel used in this research and it was found that the targeted volatile and semivolatile compared favorably with estimates found in the literature.  It was concluded that the PID and FID can both individually be used to evaluate soil contaminated by diesel fuel and might be interchangeable depending upon the need of the researcher.

EPA Performance Study for Field Measurement of Total Petroleum Hydrocarbons using Ultraviolet Fluorescence Technology

Steve Greason, Sitelab Corporation, 27 Greensboro Road, Hanover, NH  03755, Tel: 603-643-7800, Fax: 603-643-7900

The Sitelab UVF-3100 portable test kit was demonstrated under the U.S. Environmental Protection Agency Superfund Innovative Technology Program from 1999 to 2001.  The purpose of the demonstration was to collect reliable performance and cost data for the UVF-3100 and six other field measurement devices for total petroleum hydrocarbons (TPH) in soil.  In addition to assessing ease of device operation, the key objectives of the demonstration included determining the (1) method detection limit, (2) accuracy and precision, (3) effect of interferents and soil moisture content on TPH measurement, (4) sample throughput, and (5) TPH measurement costs for each device.  The demonstration involved analysis of both performance evaluation samples and environmental samples collected in five areas contaminated with gasoline, diesel, lubricating oil, or other petroleum products.   The performance and cost results for a given field measurement device were compared to those for an off-site laboratory reference method, “Test Methods for Evaluating Solid Waste” (SW-846) Method 8015B (modified). 

During the demonstration, siteLAB required less than 38 hours for TPH measurement of 212 samples.  The TPH measurement costs were as low as $7,090 for Sitelab’s UVF-3100 rental option compared to $42,500 for the reference method.  The method detection limits were determined to be 3.4 and 6.32 milligrams per kilogram for the UVF-3100 and reference method, respectively.  Sitelab was also the only developer who analyzed the samples for both GRO and DRO hydrocarbons separately (like the laboratory).  EPA reported the UVF-3100 exhibited good accuracy and precision, ease of use, and lack of sensitivity to interferents that are not petroleum hydrocarbons.  The demonstration findings collectively indicated that the UVF-3100 is a reliable field measurement device for TPH in soil.

A series of ten sub-posters illustrating Sitelab’s successful performance testing the SITE samples will be presented using data and references taken directly from the EPA’s Innovative Technology Verification Report (ITVR).    

Analysis of Volatile Organics in Produce Using Solid Phase Microextraction and GC/MS

C.K. Tan, Ph.D., Southwest Research Institute, 6220 Culebra Rd., San Antonio, Texas 78238, Tel: 210-522-2356
Kevin Shannon, Southwest Research Institute, 6220 Culebra Rd., San Antonio, Texas 78238, Tel: 210-522-3041
Robert Acosta, Southwest Research Institute, 6220 Culebra Rd., San Antonio, Texas 78238, Tel: 210-522-3840
Jesse Rodriguez, Southwest Research Institute, 6220 Culebra Rd., San Antonio, Texas 78238, Tel: 210-522-3840
Ron Porter, Ph.D., MitreTek, 13526 George Rd., San Antonio, Texas 78230, Tel: 210-479-0478

Public concern has recently focused on the potential impact of a contaminated shallow aquifer on fruit- and nut-bearing trees and plants drawing upon the contaminated aquifer as a source of hydration.  Residents who harvest and consumes these fruits and nuts from gardens and indigenous plant species may risk exposure to harmful chemicals.  An effort was undertaken by Southwest Research Institute (SwRI) to detect trace levels of volatile organic chemicals in fresh produce using solid phase microextraction (SPE) and gas chromatography and mass spectrometry (GC/MS).

Previous efforts to analyze produce and other foodstuffs for volatile organics have relied upon the use of cryogen to prevent target compound concentration losses during extraction and/or homogenization.  However, the effectiveness of the cryogen in retaining the volatile organic compounds, especially those having low molecular weights and low boiling points, was difficult to assess.  The challenge was to innovate a technique that overcomes the weaknesses of the cryogen approach.

Instead of submersion of the produce samples in liquid nitrogen then homogenizing in an industrial grinder or piercing the produce samples and submersion in salty water, the whole produce sample is weighed and transferred to a stainless steel bender fitted with an airtight sealed lid. Standards and heated water (to aid in volatilization) are spiked through a septum in the sampling port of the blender lid prior to high-speed homogenization, which drives target volatile organics into the contained headspace.  A needle-borne SPME fiber is introduced through the septum and exposed to the headspace, allowing for capture of volatile organics.  The needle/SPME fiber assembly is withdrawn from the blender and injected into the GC/MS.

The SPME approach has notable advantages over the other methods.  Since the entire produce sample is homogenized in a sealed container, compound concentration loss is minimized.  Extraction-to-analysis times are reduced considerably.  Detection limits are lower for a wide range of compounds and sample sizes.

Laboratory Determination of Diffusion Coefficient of Contaminant Ions using Clay Soil

Xi Yong-hui, Lecture, Master, School of Civil Engineering, Tongji University, 1239 Siping Road, Shanghai, 200092, China. Tel: 0086-021-65111745
Ren Jie , Master , Associate Professor, State Key-Laboratory of Concrete Research, School of Material Science and Engineering, Tongji University, 1239 Siping Road, Shanghai 200092, China, Tel: 0086-021-65989010
Hu Zhong-xiong, Professor, School of Civil Engineering, Tongji University, 1239 Siping Road, Shanghai, 200092, China, Tel: 0086-021-65635001

This paper describes a special laboratory device to determine diffusion coefficients of contaminant ions using clay soil .The technique is illustrated with a number of laboratory tests involving diffusion migration of contaminants through clay soil from Shanghai, China. The contaminants used in these tests are solutions of inorganic compounds (e.g., NaCl, CaCl₂,  KCl,ZnSO₄,CuSO₄ and so on). The device described in this paper is a rectangle box made up of polyethylene plastic plates of 0.3cm thickness, which have quality of good chemical stability. The device is divided into three parts by two polyethylene porous plates. The middle part contains the soil sample, and the other two parts contain source of contaminants and distilled water respectively. The water level of the two parts apart from the soil sample is equal. Contaminant ions migrate from the source solution to the distilled water through soil samples. The contaminant migration in these tests is controlled mainly by diffusion.  The results are consistent with the equation developed from the Fick’s second law, that is, the logarithm of concentration is linear with the square of diffusive distance. The concentration of contaminant ions at different specified distance of a soil sample is measured after a definite diffusion time .The data are arranged in a semi-logarithm co-ordinate system. The Diffusion coefficient can be calculated from the slope of a line. It is found from the experiment results that the diffusion coefficients of anions (e.g., Cl^-) through the clay are much larger than those of cations (e.g., Ca²⁺, Zn²⁺, Ni²⁺, Cd²⁺), and there are obvious relations between diameters and electric conductivities of divalent cations and diffusion coefficients. The results also show that adding of cement to soil reduces the diffusion velocity of contaminant ions greatly.

Large Volume Sample Stacking For Analysis Of EDTA By Capillary Electrophoresis

Lifeng Zhang, Centre for Advanced Water Technology, 18 Nanyang Drive, Singapore 637723 , Tel: 65-6794-3715, Fax: 65-6794-2791
Zhiwei Zhu, Centre for Advanced Water Technology, 18 Nanyang Drive, Singapore 637723, Tel: 65-6794-3865, Fax: 65-6794-2791
Arun Marimuthu, Centre for Advanced Water Technology, 18 Nanyang Drive, Singapore 637723, Tel: 65-6794-3718, Fax: 65-6794-2791
Zhaoguang Yang, Centre for Advanced Water Technology, 18 Nanyang Drive, Singapore 637723, Tel: 65-6794-1561, Fax: 65-6794-2791

 The widespread use of ethylenediaminetetraacetic acid (EDTA) has requested an urgent monitoring program regarding surface and drinking water. Analysing EDTA at low-level concentrations (such as mg/L in the environmental samples) is quite complex using the conventional GC/MS or HPLC methods. In this study, a simple, quick and sensitive capillary electrophoretic technique -large volume stacking using the EOF pump (LVSEP)- has been developed for determining EDTA in drinking water for the first time. It is based on a precapillary complexation of EDTA with Fe(III) ions, followed by large volume sample stacking and direct UV detection at 258 nm. The curve of peak response versus concentration was linear between 5.0 and 600.0 mg/L, as well as between 0.7 and 30.0 mg/L. The regression coefficients were 0.9988 and 0.9990, respectively. The detection limit of current technique for EDTA analysis was 0.2 mg/L with additional 10-fold preconcentration procedure, based on the signal-to-noise ratio of 3. As opposed to the classical CE method, a 1000-fold concentration factor could be smoothly achieved on this LVSEP method. To the best of our knowledge, it represents the highest sensitivity for EDTA analysis via CE. Several drinking water samples were tested by this novel method with satisfactory results.

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