An experimental and computational study was performed to investigate the role of multi-component intra-NAPL diffusion on NAPL-water mass transfer. Molecular weight and the NAPL component concentrations were determined to be the most important parameters affecting intra-NAPL diffusion coefficients. Four NAPLs with different viscosities but the same quantified mass were simulated. For a spherical NAPL body, a combination of NAPL properties and interphase mass transfer rate can result in internal diffusion limitations. When the main intra-NAPL diffusion coefficients are in the range of self-diffusion coefficients (10 to 10 cm/s), dissolution is not limited by internal diffusion except for high mass transfer rate coefficients (>180 cm/day). For a complex and relatively high viscous NAPL (>50 g/(cm s)), smaller intra-NAPL diffusion coefficients (<10) are expected and even low mass transfer rate coefficients (~6 cm/day) can result in diffusion-limited dissolution.
Most of the prediction theories regarding dissolution of organic contaminants in the subsurface systems have been proposed based on the static water conditions; and the influence of water fluctuations on mass removal requires further investigations. In this study, it was intended to investigate the effects of water table fluctuations on biogeochemical properties of the contaminated soil at the smear zone between the vadose zone and the groundwater table. An automated 60 cm soil column system was developed and connected to a hydrostatic equilibrium reservoir to impose the water regime by using a multi-channel pump. Four homogenized hydrocarbon contaminated soil columns were constructed and two of them were fully saturated and remained under static water conditions while another two columns were operated under water table fluctuations between the soil surface and 40 cm below it. The experiments were run for 150 days and relevant geochemical indicators as well as dissolved phase concentrations were analyzed at 30 and 50 cm below the soil surface in all columns. The results indicated significant difference in terms of biodegradation effectiveness between the smear zones exposed to static and water table fluctuation conditions. This presentation will provide an overview of the experimental approach, mass removal efficiency, and key findings.
Biodegradation is a key process for the remediation of sites contaminated by petroleum hydrocarbons (PHCs), but this process is not well known for the (semi)-arid coastal environments where saline conditions and continuous water level fluctuations are common. This study differs from the limited previous studies on the biodegradation of PHCs in Qatari coastal soils mainly by its findings on the biodegradation kinetics of the selected PHCs of benzene and naphthalene by indigenous bacteria. Soil samples were collected above, across, and below the groundwater table at the eastern coast of Qatar within a depth of 0 to -40 cm. Environmental conditions combining low oxygen and high sulfate concentrations were considered in this study which could favor either or both aerobic and anaerobic bacteria including sulfate-reducing bacteria (SRB). The consideration of SRB was motivated by previously reported high sulfate concentrations in Qatari soil and groundwater. Low- and high-salinity conditions were applied in the experiments, and the results showed the sorption of the two PHCs on the soil samples. Sorption was dominant for naphthalene whereas the biodegradation process contributed the most for the removal of benzene from water. Losses of nitrate observed in the biodegradation experiments were attributed to the activity of nitrate-reducing bacteria (NRB). The results suggested that aerobic, NRB, and most likely SRB biodegraded the two PHCs, where the combined contribution of sorption and biodegradation in biotic microcosms led to considerable concentration losses of the two PHCs in the aqueous phase (31 to 58% after 21 to 35 days). Although benzene was degraded faster than naphthalene, the biodegradation of these two PHCs was in general very slow with rate coefficients in the order of 10-3 to 10-2 day-1 and the applied kinetic models fitted the experimental results very well. It is relevant to mention that these rate coefficients are the contribution from all the microbial groups in the soil and not from just one.
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