Assessing weathered Endicott oil biodegradation in brackish water.

We evaluated the biodegradability of physically (WAF) and chemically (CEWAF) dispersed oil in brackish water (salinity ∼6.5 g/L), and the influence of nutrient availability (low nutrient-LN: background water vs. high nutrient-HN: addition of 100 mg NO3-N/L and 10mg PO4-P/L to background water) on oil biodegradation rates at 15±0.5 °C for 42 days. No oil removal occurred in WAF compared with CEWAF: 24% in HN and 14% in LN within two weeks. The oil biodegradation concerned mainly alkanes as confirmed by GC/MS analyses. Higher O2 consumption (10.30 mg L(-1) day(-1)) and CO2 production (3.89 mg CL(-1) day(-1)) were measured in HN compared with LN (O2: 2.79 mg L(-1) day(-1), CO2:0.18 mg CL(-1) day(-1)). Estimated biomass of hydrocarbon degraders and heterotrophic bacteria was at least an order of magnitude larger in HN than in LN. Combining dispersants with nutrients could enhance oil biodegradation and help improve oil spill mitigation responses.

Complex resistivity signatures of ethanol biodegradation in porous media.

Numerous adverse effects are associated with the accidental release of ethanol (EtOH) and its persistence in the subsurface. Geophysical techniques may permit non-invasive, real time monitoring of microbial degradation of hydrocarbon. We performed complex resistivity (CR) measurements in conjunction with geochemical data analysis on three microbial-stimulated and two control columns to investigate changes in electrical properties during EtOH biodegradation processes in porous media. A Debye Decomposition approach was applied to determine the chargeability (m), normalized chargeability (m(n)) and time constant (τ) of the polarization magnitude and relaxation length scale as a function of time. The CR responses showed a clear distinction between the bioaugmented and control columns in terms of real (σ') and imaginary (σ″) conductivity, phase (ϕ) and apparent formation factor (F(app)). Unlike the control columns, a substantial decrease in σ' and increase in F(app) occurred at an early time (within 4 days) of the experiment for all three bioaugmented columns. The observed decrease in σ' is opposite to previous studies on hydrocarbon biodegradation. These columns also exhibited increases in ϕ (up to ~9 mrad) and σ″ (up to two order of magnitude higher) 5 weeks after microbial inoculation. Variations in m and m(n) were consistent with temporal changes in ϕ and σ″ responses, respectively. Temporal geochemical changes and high resolution scanning electron microscopy imaging corroborated the CR findings, thus indicating the sensitivity of CR measurements to EtOH biodegradation processes. Our results offer insight into the potential application of CR measurements for long-term monitoring of biogeochemical and mineralogical changes during intrinsic and induced EtOH biodegradation in the subsurface.

Complex resistivity signatures of ethanol in sand-clay mixtures.

We performed complex resistivity (CR) measurements on laboratory columns to investigate changes in electrical properties as a result of varying ethanol (EtOH) concentration (0% to 30% v/v) in a sand-clay (bentonite) matrix. We applied Debye decomposition, a phenomenological model commonly used to fit CR data, to determine model parameters (time constant: τ, chargeability: m, and normalized chargeability: mn). The CR data showed a significant (P≤0.001) time-dependent variation in the clay driven polarization response (~12 mrad) for 0% EtOH concentration. This temporal variation probably results from the clay-water reaction kinetics trending towards equilibrium in the sand-clay-water system. The clay polarization is significantly suppressed (P≤0.001) for both measured phase (ϕ) and imaginary conductivity (σ″) with increasing EtOH concentration. Normalized chargeability consistently decreases (by up to a factor of ~2) as EtOH concentration increases from 0% to 10% and 10 to 20%, respectively. We propose that such suppression effects are associated with alterations in the electrical double layer (EDL) at the clay-fluid interface due to (a) strong EtOH adsorption on clay, and (b) complex intermolecular EtOH-water interactions and subsequent changes in ionic mobility on the surface in the EDL. Changes in the CR data following a change of the saturating fluid from EtOH 20% to plain water indicate strong hysteresis effects in the electrical response, which we attribute to persistent EtOH adsorption on clay. Our results demonstrate high sensitivity of CR measurements to clay-EtOH interactions in porous media, indicating the potential application of this technique for characterization and monitoring of ethanol contamination in sediments containing clays.

Electrical signatures of ethanol-liquid mixtures: implications for monitoring biofuels migration in the subsurface.

Ethanol (EtOH), an emerging contaminant with potential direct and indirect environmental effects, poses threats to water supplies when spilled in large volumes. A series of experiments was directed at understanding the electrical geophysical signatures arising from groundwater contamination by ethanol. Conductivity measurements were performed at the laboratory scale on EtOH-water mixtures (0 to 0.97 v/v EtOH) and EtOH-salt solution mixtures (0 to 0.99 v/v EtOH) with and without a sand matrix using a conductivity probe and a four-electrode electrical measurement over the low frequency range (1-1000 Hz). A Lichtenecker-Rother (L-R) type mixing model was used to simulate electrical conductivity as a function of EtOH concentration in the mixture. For all three experimental treatments increasing EtOH concentration resulted in a decrease in measured conductivity magnitude (|σ|). The applied L-R model fitted the experimental data at concentration ≤0.4v/v EtOH, presumably due to predominant and symmetric intermolecular (EtOH-water) interaction in the mixture. The deviation of the experimental |σ| data from the model prediction at higher EtOH concentrations may be associated with hydrophobic effects of EtOH-EtOH interactions in the mixture. The |σ| data presumably reflected changes in relative strength of the three types of interactions (water-water, EtOH-water, and EtOH-EtOH) occurring simultaneously in EtOH-water mixtures as the ratio of EtOH to water changed. No evidence of measurable polarization effects at the EtOH-water and EtOH-water-mineral interfaces over the investigated frequency range was found. Our results indicate the potential for using electrical measurements to characterize and monitor EtOH spills in the subsurface.