Impacts of water table fluctuations on actual and perceived natural source zone depletion rates.

A viable means of quantifying the rate of natural source zone depletion (NSZD) at hydrocarbon contaminated sites is by the measurement of carbon dioxide (CO2) and methane (CH4) effluxes at the surface. This methodology assumes that gas effluxes are reflective of actual contaminant degradation rates in the subsurface, which is only accurate for quasi-steady state conditions. However, in reality, subsurface systems are highly dynamic, often resulting in fluctuations of the water table. To quantify the effects of water table fluctuations on NSZD rates, a simulated biodiesel spill in a 400 cm long, 100 cm wide and 150 cm tall sandtank was subjected to lowering and raising the water table, while soil-gas chemistry and surface CO2 and CH4 effluxes were measured. Results show that water table fluctuations have both short-term (perceived) and long-term (actual) effects on NSZD rates, interpreted using surface efflux measurements. When the water table was lowered, surface effluxes immediately increased up to 3 and 344 times higher than baseline for CO2 and CH4 effluxes, respectively, due to the liberation of anaerobically produced gas accumulated below the water table. After this immediate release, the system then reached quasi-steady state conditions 1.4 to 1.6 times higher for CO2 than baseline conditions, attributed to increased aerobic degradation in the broadened and exposed smear zone. When the water table was raised, quasi-steady state CO2 and CH4 effluxes declined to values of 0.9 and 0.4 times baseline effluxes, respectively, implying that contaminant degradation rates were reduced due to submergence of the smear zone. The findings of this study show that the dynamic effects of water table fluctuations and redistribution of the contaminants affect surface effluxes as well as short-term (perceived) and long-term (actual) contaminant degradation rates. Therefore, water table fluctuations need to be considered when quantifying NSZD at contaminated sites using sparse temporal rate measurements to estimate NSZD rates for extended periods of time (e.g., annual rates).

Comparison of surficial CO2 efflux to other measures of subsurface crude oil degradation.

At a spill site near Bemidji, Minnesota, crude oil at the water table has been undergoing anaerobic biodegradation for over 30years. Previous work at this site has shown that methane produced from biodegradation of the oil migrates upward and is oxidized in a methanotrophic zone midway between the water table and the surface. To compare microbial activity measurement methods from multiple locations in the oil body, surficial carbon dioxide efflux, methanogen and methanotroph concentrations, and oil degradation state were collected. Carbon dioxide effluxes over the oil body averaged more than four times those at the background site. Methanotrophic bacteria concentrations measured using pmoA were over 10(5) times higher above the oil-contaminated sediments compared with the background site. Methanogenic archaea measured using mcrA ranged from 10(5) to over 10(7) in the oil and were below detection in the background. Methanogens correlated very well with methanotroph concentrations (r=0.99), n-alkylcyclohexane losses as a proxy for degradation state (r=-0.96), and somewhat less well with carbon dioxide efflux (r=0.92). Carbon dioxide efflux similarly correlated to methanotroph concentrations (r=0.90) and n-alkylcyclohexane losses (r=-0.91).

Methane emissions and contaminant degradation rates at sites affected by accidental releases of denatured fuel-grade ethanol.

The recent increase in the use of denatured fuel-grade ethanol (DFE) has enhanced the probability of its environmental release. Due to the highly labile nature of ethanol (EtOH), it is expected to rapidly biodegrade, increasing the potential for inducing methanogenic conditions in the subsurface. As environmental releases of DFE can be expected to occur at the ground surface or in the vadose zone (e.g., due to surficial spills from rail lines or tanker trucks and leaking underground storage tanks), the potential for methane (CH4) generation at DFE spill sites requires evaluation. An assessment is needed because high CH4 generation rates may lead to CH4 fluxes towards the ground surface, which is of particular concern if spills are located close to human habitation-related to concerns of soil vapor intrusion (SVI). This work demonstrates, for the first time, the measurement of surficial gas release rates at large volume DFE spill sites. Two study sites, near Cambria and Balaton, in MN are investigated. Total carbon emissions at the ground surface (summing carbon dioxide (CO2) and CH4 emissions) are used to quantify depth-integrated DFE degradation rates. Results from both sites demonstrate that substantial CO2 and CH4 emissions do occur-even years after a spill. However, large total carbon fluxes, and CH4 emissions in particular, were restricted to a localized area within the DFE source zone. At the Balaton site, estimates of total DFE carbon losses in the source zone ranged between 5 and 174 µmol m(-2) s(-1), and CH4 effluxes ranged between non-detect and 9 µmol m(-2) s(-1). At the Cambria site estimates of total DFE carbon losses in the source zone ranged between 8 and 500 µmol m(-2) s(-1), and CH4 effluxes ranged between non-detect and 393 µmol m(-2) s(-1). Substantial CH4 accumulation, coupled with oxygen (O2) depletion, measured in samples collected from custom-designed gas collection chambers at the Cambria site suggests that the development of explosion or asphyxiation hazards is possible in confined spaces above a rapidly degrading DFE release. However, the results also indicate that the development of such hazards is locally constrained, will require a high degree of soil moisture, close proximity to the source zone, a good connection between the soil and the confined space, and poorly aerated conditions.

CO2-efflux measurements for evaluating source zone natural attenuation rates in a petroleum hydrocarbon contaminated aquifer.

In order to gain regulatory approval for source zone natural attenuation (SZNA) at hydrocarbon-contaminated sites, knowledge regarding the extent of the contamination, its tendency to spread, and its longevity is required. However, reliable quantification of biodegradation rates, an important component of SZNA, remains a challenge. If the rate of CO(2) gas generation associated with contaminant degradation can be determined, it may be used as a proxy for the overall rate of subsurface biodegradation. Here, the CO(2)-efflux at the ground surface is measured using a dynamic closed chamber (DCC) method to evaluate whether this technique can be used to assess the areal extent of the contaminant source zone and the depth-integrated rate of contaminant mineralization. To this end, a field test was conducted at the Bemidji, MN, crude oil spill site. Results indicate that at the Bemidji site the CO(2)-efflux method is able to both delineate the source zone and distinguish between the rates of natural soil respiration and contaminant mineralization. The average CO(2)-efflux associated with contaminant degradation in the source zone is estimated at 2.6 µmol m(-2) s(-1), corresponding to a total petroleum hydrocarbon mineralization rate (expressed as C(10)H(22)) of 3.3 g m(-2) day(-1).