RARE - Development of a Systematic Approach to Accurately Measure Trace Levels of VOCs in Soils

Abstract:

A majority of the contaminated sites within the United States contain volatile organic compounds (VOCs), either as industrial chlorinated solvents or petroleum products commonly referred to as BTEX (benzene, toluene, ethyl benzene, and xylene). The present EPA methods for low level VOC analyses (RCRA Methods 5035A and the CLP method), commonly referred to as volatile organic analyses (VOA), are very matrix dependent and therefore can be biased low. The VOCs diffuse into the micropores or are adsorbed onto the soil matrix. This negative method bias can result in false negative situations where significant contamination may go undetected. Also, water soluble compounds are a major problem with the present methods because their low purging efficiencies result in high detection levels.

Risk assessment is a crucial component of the site remediation decision-making process. The present EPA low level methods are not capable of measuring many VOCs at the required levels for risk assessment, EPA Region 3 Risk Based Concentration (RBC) levels, EPA Region 9 Preliminary Remediation Goals (PRG) levels, or the state cleanup levels. Recently at a University of Massachusetts Remediation Conference, a paper was presented on the magnitude of the problem and concluded that resolving this issue is critical for human health and ecological risk assessments. It is critical that EPA develops a method to accurately measure trace VOCs for the CLP Superfund program, RCRA and Brownfields site redevelopments, and the various state programs in Region 1. Some of the sites within New England where risk assessments are problematic include: Woburn, MA, Wells G & H, Otis Air Force Base, and Nyanza, MA. Below is a VOC target list for this project with the compounds identified that have low RBC and PRG quantitation levels.

Objective:

The objective of this project is to develop an analytical method which uses thermal desorption (200-300 degrees C) to extract and accurately measure VOCs in soil and sediment samples to satisfy the EPA and state regulatory program requirements. Thermal extraction will be examined because the technique is a simpler and more efficient extraction technique than the present EPA purge methods. VOCs shall be detected and quantified by a gas chromatograph/mass spectrometer (GC/MS).

Thermal extraction is also presently used for extracting semivolatile compounds in soil samples by RCRA Method 8275A. This fact encourages investigation of this technique for the quantification of both VOCs and semivolatile compounds. It is anticipated that the semivolatile compounds shall be analyzed by a second GC/MS. This will be the first ever dual GC/MS method.

Progress to Date:

Funding received for this RARE project on or about May 19, 2003.
RARE funding placed on GSA IAG on or about June 3, 2003 to support research. RARE funding removed from GSA due to GSA's internal review of all environmentally-based programs. New contract sought, via Contract Management Division (CMD) in RTP, using GSA Environmental Services Schedules. Package submitted to CMD in September 2003.
Conference calls between ORD and Region 1 to discuss progress and possible research directions are held on a monthly basis.
Initial purchases of the ice packs and freezer associated with this project were made on June 4 and June 20, 2003, respectively.
GSA Contract was awarded in December 2003.
A CRADA with the Archon Purge & Trap Instrumentation was initiated in February 2004.
A QAPP was completed in March 2004 and Phase 1 of the volatile organic compounds (VOCs) of interest was initiated. During the thermal optimization phase, several problems were encountered. The heating of the vial prior to extraction was eliminated because of loss of analyte probably due to pressurization of the vial during heating without purge gas flow and due to venting of contaminants around the purge needle that pierced the septa. Spiking of the vials was initially done through the septa but this also was eliminated because of loss of spiked contaminants with time while the vial waited in autosampler analysis. The thermal extraction evaluation has been done for the 40 to 120 degrees C temperatures and data are currently being evaluated. If higher temperatures are required, a higher temperature septa and top will be evaluated as the current septa and top have a maximum temperature of 130 degrees C.
The optimum temperature for the VOCs of interest was determined to be 60 degrees C.
GC/MS instrumentation for the analysis of semivolatile organic compounds (SVOCs) was procured in September 2004. Once the CRADA is in place, work will be initiated on modifications to an Archon autosampler for the evaluation of the semivolatile organic compounds of interest with the newly acquired instrumentation.
Phase 2 of the VOCs of interest was initiated. Three soils of varying organic carbon content were spiked and analyzed at varying moisture contents from dry to 50% moisture.
Contract change 10/1/2004.
The CRADA was finalized on October 21, 2004.
The modified Archon Purge & Trap Instrumentation was received on April 7, 2005 and installed on April 12, 2005.
Thermal extraction evaluation for the semivolatile organic compounds of interest has been done for the 150 to 200 degrees C temperatures and the data showed the best response and recoveries of the compounds of interest at 160 degrees C. To be able to achieve these higher temperatures, a metal cap was created to replace the plastic cap on the vials. Soils are being prepared for Phase 2 evaluation of the SVOCs.
Evaluation of VOCARB 3000 and 4000 purge traps was completed with the data showing the VOCARB 4000 trap the better trap for SVOCs.

Approach

This research project shall be conducted in several phases.

Phase 1. Method Development. The entire sample collection, preservation, and analysis process must be controlled to achieve accurate results. Initially, an appropriate sample collection vessel must be selected. The present VOA septa (Teflon-faced) and caps must be evaluated for their ability to withstand elevated temperatures (~150 degrees C) without degradation and/or artifact formation. Other chromatographic septa and cap materials may need to be tested should problems be encountered. This phase will be conducted by EPA and the results will be provided to the contractor for use in subsequent phases of the program.

Thermal Extraction: Thermal extraction is the principle for the proposed method. It must be optimized to exhaustively extract VOCs from samples with a wide range of moisture contents while minimizing any thermal degradation of the target compounds. Fortunately, most VOCs are thermally stable as demonstrated by a thermal desorption step at 250 degrees C from an absorbent in the present methods. The Archon autosampler will be initially used as the thermal extraction device.

A well-characterized soil starting material will be spiked to cover the complete boiling point range for VOCs and semivolatiles as identified in the attachment. Samples shall be prepared with minimal solvent (i.e., methanol) usage. If the minimal solvent usage results in too much GC/MS interference, a new set of spiked soil samples will be prepared following a different method. Samples will be stored at <7 degrees C prior to analysis.

Analyses will be performed following a modified SW-846 Method 5035A purge and trap without the addition of water. The method will be further modified to have purging temperatures tested at 40, 60, 80, 100, 120, and 140 degrees C.

Phase 2. Interference Checking. Both moisture and organic carbon can interfere with the extraction of VOCs. Three well-characterized soils with varying ranges of organic carbon contents will be spiked using the same VOC standard used in Phase 1. Six sets of spiked soils with the following moisture contents: dry, 10, 20, 30, 40, and 50% w:w will be prepared. Analyses of one set from each soil will be performed at 40, 60, 80, 100, 120, and 140 degrees C purging temperatures.

During the analysis, moisture interference will be removed using a combination of the VOCARB 3000 trap and the Tekmar Moisture Control Loop present in the Tekmar-Dohrmann 3100 Concentrator. If these techniques are insufficient to remove the moisture interference, other moisture removing techniques will be investigated.

Phase 3. Chromatographic Splitting. As discussed earlier, one of the objectives of this project is to extract VOCs and semivolatile compounds from the soil matrix. The semivolatile compounds must be separated and prevented from entering the GC/MS for VOC analysis. The split gas flow will be transferred to a second GC column that would enter another GC/MS to analyze the semivolatile fraction, creating the first ever dual GC/MS method.

Initially, once the two GC/MS systems are "connected," spiked soil samples shall be prepared in a similar manner as Phase 1. It should be noted that these samples will be analyzed using the optimized procedure defined in Phase 2; hence, the samples will be analyzed at 1 (and not 6) temperatures. If the splitting technique is successful, then a second full suite of spiked soils samples (for result verification) shall be prepared following the same requirement as in Phase 2.

Phase 4. Method Validation. An initial demonstration of capability (IDC) and method detection limit (MDL) study will be done. Internal quality control limits will be developed by running 25 internal quality control (QC) samples (IS area counts, surrogate recoveries, laboratory and field blanks, LFB, MS, MSD) on various matrices, some having high moisture (>70%) content. Various external QC samples from CLP, NIST, and ERT will be analyzed. A study will be conducted using performance evaluation materials (PEMs) and the results compared to the proposed (i.e., newly developed) method and the EPA low level method (SW-846 Methods 5035A and 8260) for the determination of VOCs in soils. All samples will be prepared in the same VOA vials, caps, and septa as used during Phases 1 and 2.

Phase 5. Sample Preservation. Using the method developed and validated in the earlier phases of this study, sample preservation techniques will be evaluated. Spiked soil samples will be prepared using the same VOC standard used in Phase 2. Sufficient samples shall be prepared to test the sample preservation techniques of storage at <7 degrees C, with the addition of 0.7 g of tribasic sodium phosphate dodecahydrate (Na₃PO₄·12H₂0) to each 5 g sample.

Staffing

Principal Investigators:

Brian Schumacher, Supervisory Physical Scientist
John Zimmerman, Resident Physical Scientist
Mike Hiatt, Chemist

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Send questions or comments to Steve Gardner
Email: gardner.steve@epa.gov