Bioavailability of PCBs from field-collected sediments: application of Tenax extraction and matrix-SPME techniques

Two chemical approaches, Tenax extraction and matrix solid phase microextraction (matrix-SPME), were evaluated for their potential to improve the prediction of bioavailability by equilibrium partitioning theory (EPT) across sediments with various characteristics. Biota-sediment accumulation factors (BSAFs) and body residues were quantified by exposing Lumbriculus variegatus to three PCB-contaminated field sediments. The concentration of PCBs in biota was positively correlated to the total PCB sediment concentration, the PCB concentration in the rapidly desorbing fraction estimated using Tenax extraction, and the PCB concentration on the SPME fibers. Results showed EPT was acceptable for estimating bioavailability from the tested sediments with sum PCB BSAFs of 1.18-2.47; however, it overestimated PCB bioavailability from sandy sediment. Both Tenax extraction and matrix-SPME, which take sequestration into account, reduced variability in prediction of PCB bioavailability across sediments, including the sandy sediment, and could be used as cost- and time-efficient alternatives for bioassay. Matrix-SPME was considered the better technique due to its ability to directly predict PCB body residues in the exposed biota and its potential use with in situ applications in the field.     

Natural attenuation of chlorinated solvent plumes at Texas dry cleaners

Dry cleaners are the largest users of perchloroethene (PCE) solvents in the United States. Releases from dry cleaners to soil and groundwater, however, remain largely unstudied. This article presents a database of 137 chlorinated solvent plumes at dry cleaners in Texas. The data indicate that PCE plumes are generally shorter in extent than those from industrial sites. Degradation products were observed at more than 80 percent of the sites with groundwater contamination. Calculated attenuation rates are on the order of one‐to‐three‐year half‐lives for PCE and its degradation products. The estimated cleanup timeframe for calculated attenuation rates is < 50 years. More research is needed to understand the presence of organic carbon sources at dry cleaners and its implications for natural attenuation. © 2004 Wiley Periodicals, Inc.     

Diffusive uptake in passive and active adsorbent sampling using thermal desorption tubes

Low flow active sampling techniques collecting vapors and gases using thermally desorbable adsorbents are now feasible and desirable in many applications as they permit long integration times, the potential for miniaturized sampling configurations, and other advantages. At very low air flow rates (< 1 ml min(-1)), diffusive uptake on adsorbents in conventional sorbent tubes may equal or exceed the active (pumped) uptake rate, and even at low flow rates (1-4 ml min(-1)), diffusive uptake may significantly bias measurements. Thus, corrections to account for the diffusive flux or means to limit the diffusive uptake are needed in low flow applications. This paper presents (1) a theoretical analysis of the role of diffusive and advective uptake for several sampling geometries of tube-type samplers; (2) experimental confirmation using both laboratory and field studies; (3) estimates of the tortuosity and porosity of the glass wool packing used to retain the adsorbent, parameters needed to estimate diffusive fluxes in passive and active sampling; (4) a demonstration that orifice-equipped low flow active samplers can reduce diffusive uptake and improve precision, and (5) a model predicting the saturated adsorbent layer that helps to account for the gradual decline in uptake rates seen in passive sampling. Diffusive uptake will depend on the tube configuration and diffusion coefficient of the substance of interest, but for conventional sampling tubes (0.4-0.5 cm id, 1.5 cm air gap), sample flow rates should be maintained above 1 to 4 ml min(-1) to keep errors below 5%. Laboratory experiments showed close agreement with theoretical calculations, and the field study using 1 to 4 d sampling periods and 0.3 ml min(-1) flows demonstrated that the orifice-equipped samplers essentially eliminated diffusive uptake. No significant practical difficulties are encountered using orifices, e.g., pressure drop is minimal. Experimental estimates of tortuosity (0.79 +/- 0.02) and porosity (0.92 +/- 0.10) of the glass wool packing (0.3 cm length) represent relatively little resistance to diffusion; however, variation in the packing and adsorbent placement can degrade the precision achievable by passive samplers. Diffusion barriers, consisting most simply of an orifice, may be used to lower the diffusive uptake. A needle-type orifice permits flows below 0.1 ml min(-1) and is suitable for sampling periods as long as several weeks, and it provided greater precision than conventional open-ended sampling tubes (8% compared to 13%). Finally, the gradual decrease in diffusive fluxes often seen in passive sampling is attributed to additional resistance posed by a saturated adsorbent layer, in agreement with a simple model based on total VOCs and specific adsorptivity of the adsorbent.