Anaerobic biodegradation of dissolved ethanol in a pilot-scale sand aquifer: Gas phase dynamics.

Groundwater contamination from ethanol (e.g., alternative fuels) can support vigorous biodegradation, with many possible reactions producing dissolved gases. The objective of this study was to improve the understanding of the development and evolution of trapped gas phase changes occurring within an ethanol plume undergoing biodegradation. The experiment performed involved highly detailed spatial and temporal monitoring of gas phase saturations using Time Domain Reflectometry probes embedded in a 2-dimensional (175 cm high × 525 cm long) synthetic aquifer (homogeneous sand tank with horizontal groundwater flow). Ethanol injection immediately promoted gas-producing reactions, including: fermentation, denitrification, sulphate-reduction and iron(III)-reduction, with methanogenesis developing between 69 and 109 days. Substantial in situ increases in trapped gas were observed over ~330 days, with maximum gas saturations reaching 27% of the pore volume. Despite sustained gas production, this maximum was never exceeded, likely due to the onset of gas phase mobilization (i.e., ebullition) upon reaching a buoyancy-capillarity threshold. Reductions in the quasi-saturated hydraulic conductivity, resulting from the gas phase accumulation, were restricted by ebullition to a factor of ≤2; but still appeared to alter the groundwater flow field. Overall, trapped gas saturations exhibited high spatial and temporal variability, including declines within the plume and increases outside of the plume. Influential factors included vertically-shifting ethanol inputs and resultant secondary redox reactions, microbial controls on redox zonation, ebullition, and altered groundwater flows. These observations have implications for the transport of gases and volatile compounds within plumes and above the water table at sites with groundwater contamination from ethanol or other highly degradable organics.

Anaerobic biodegradation of dissolved ethanol in a pilot-scale sand aquifer: Variability in plume (redox) biogeochemistry.

The use of ethanol in alternative fuels has led to contamination of groundwater with high concentrations of this easily biodegradable organic compound. Previous laboratory and field studies have shown vigorous biodegradation of ethanol plumes, with prevalence of reducing conditions and methanogenesis. The objective of this study was to further our understanding of the dynamic biogeochemistry processes, especially dissolved gas production, that may occur in developing and aging plume cores at sites with ethanol or other organic contamination of groundwater. The experiment performed involved highly-detailed spatial and temporal monitoring of ethanol biodegradation in a 2-dimensional (175cm high×525cm long) sand aquifer tank for 330days, with a vertical shift in plume position and increased nutrient inputs occurring at ~Day 100. Rapid onset of fermentation, denitrification, sulphate-reduction and iron(III)-reduction occurred following dissolved ethanol addition, with the eventual widespread development of methanogenesis. The detailed observations also demonstrate a redox zonation that supports the plume fringe concept, secondary reactions resulting from a changing/moving plume, and time lags for the various biodegradation processes. Additional highlights include: i) the highest dissolved H2 concentrations yet reported for groundwater, possibly linked to vigorous fermentation in the absence of common terminal electron-acceptors (i.e., dissolved oxygen, nitrate, and sulphate, and iron(III)-minerals) and methanogenesis; ii) evidence of phosphorus nutrient limitation, which stalled ethanol biodegradation and perhaps delayed the onset of methanogenesis; and iii) the occurrence of dissimilatory nitrate reduction to ammonium, which has not been reported for ethanol biodegradation to date.

Patterns of entrapped air dissolution in a two-dimensional pilot-scale synthetic aquifer.

Past studies of entrapped air dissolution have focused on one-dimensional laboratory columns. Here the multidimensional nature of entrapped air dissolution was investigated using an indoor tank (180 × 240 × 600 cm(3) ) simulating an unconfined sand aquifer with horizontal flow. Time domain reflectometry (TDR) probes directly measured entrapped air contents, while dissolved gas conditions were monitored with total dissolved gas pressure (PTDG ) probes. Dissolution occurred as a diffuse wedge-shaped front from the inlet downgradient, with preferential dissolution at depth. This pattern was mainly attributed to increased gas solubility, as shown by PTDG measurements. However, compression of entrapped air at greater depths, captured by TDR and leading to lower quasi-saturated hydraulic conductivities and thus greater velocities, also played a small role. Linear propagation of the dissolution front downgradient was observed at each depth, with both TDR and PTDG , with increasing rates with depth (e.g, 4.1 to 5.7× slower at 15 cm vs. 165 cm depth). PTDG values revealed equilibrium with the entrapped gas initially, being higher at greater depth and fluctuating with the barometric pressure, before declining concurrently with entrapped air contents to the lower PTDG of the source water. The observed dissolution pattern has long-term implications for a wide variety of groundwater management issues, from recharge to contaminant transport and remediation strategies, due to the persistence of entrapped air near the water table (potential timescale of years). This study also demonstrated the utility of PTDG probes for simple in situ measurements to detect entrapped air and monitor its dissolution.