In Situ Determination of the Rate of Unassisted Degradation of Saturated-Zone Hydrocarbon Contamination

Abstract

A method to measure the in situ degradation rate of dissolved hydrocarbon contamination has been developed and applied at two locations at a field site. The method uses the rates of downward diffusion of oxygen and upward diffusion of carbon dioxide through the unsaturated zone, as calculated from vertical soil-gas concentration gradients, combined with stoichiometry to obtain two degradation rates in hydrocarbon mass per water table surface area per time. Values of 0.385 gram per m² per day and 0.52 gram per m² per day (based upon oxygen data) and 0.056 gram per m² per day and 0.12 gram per m² per day (based upon carbon dioxide data) were calculated at a field site with dissolved fuel contamination. This result of lower values from ground-air carbon dioxide concentrations is consistent with a significant fraction of the carbon dioxide produced being lost to the aqueous phase. Based upon a single-stage equilibrium phase-transfer model, gas/water volume ratios of 0.02 and 0.2 for the capillary fringe were calculated. Groundwater carbon dioxide fugacities and soil-gas carbon dioxide concentrations were used at the two locations and a third to determine whether the source of elevated soil carbon dioxide concentrations were unsaturated-zone hydrocarbon degradation or a saturated-zone process. This technique has potential applicability in setting risk-based remedial criteria and in allowing inclusion of the contribution of in situ degradation in remedial design. This can result in major remedial cost savings.