Reactive transport simulation of volatile organic compound removal in vertical flow soil filters

  • Federal Institute for Geosciences and Natural Resources (BGR)
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Vertical flow soil filters are an emerging technology for the treatment of groundwater contaminated with volatile organic carbon compounds. These filters are characterized by unsaturated flow conditions and high contaminant removal rates, but for the assessment of their remediation efficiency a sound distinction between biodegradation and volatilization is crucial. In this study, a vertical flow soil filter system exposed to intermittent feeding of contaminated groundwater leading to a highly transient flow pattern was simulated using the numerical model MIN3P. Simulated processes include (besides other reactions) the microbial degradation of aqueous species as well as their volatilization and advective-diffusive transport in the water phase and the soil air phase. Flow and transport processes were calibrated using measured field data and the model subsequently used to describe the removal of ammonium and two volatile organic contaminants - benzene and MTBE. Model results confirm experimentally observed high removal rates and show that both removal processes - biodegradation and volatilization - have the potential to significantly contribute to such removal. The contribution of each process depends on the design and operation of the filter system, the hydraulic properties of the filter material, and the degradation capacity of the microbial population. If these factors are sufficiently well combined volatile emissions can be avoided and observed contaminant removal can be nearly all attributed to biodegradation.

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BACKGROUND: Twelve vertical-flow experimental wetlands have been constructed using different compositions, and were operated in batch-flow mode to reduce pumping costs. Six wetlands were located indoors and six outdoors. Benzene was used as a representative example substance to assess the removal of low molecular weight petroleum compounds. RESULTS: Findings indicate that the constructed wetlands remove benzene (inflow of approximately 1.3 g L−1) from hydrocarbon-contaminated wastewater streams with better indoor (controlled environment) than outdoor treatment performances. Overall mean removal efficiencies for the experimental rig placed outside were as follows: benzene 85%, chemical oxygen demand (COD), 70%; ammonia-nitrogen, 83%; nitrate-nitrogen, 88%; ortho-phosphate-phosphorus, 58%. In comparison, removal efficiencies for the experimental rig placed indoors were higher: benzene 95%, COD, 80%; ammonia-nitrogen, 90%; nitrate-nitrogen, 94%; ortho-phosphate-phosphorus, 66%. Benzene removal was predominantly due to volatilization after 1 day of retention time. CONCLUSION: The use of aggregates (sand and gravel) and the presence of Phragmites australis (Cav.) Trin. ex Steud. resulted in no significant difference in terms of benzene, redox potential, dissolved oxygen, 5-day at 20 °C N-allylthiourea biochemical oxygen demand, COD and nutrients removal. Statistical differences were assessed by analysis of variance and Tukey HSD tests (P < 0.05). Copyright © 2007 Society of Chemical Industry
The two-way coupling that exists between biogeochemical reactions and vadose zone transport processes, in particular gas phase transport, determines the composition of soil gas. To explore these feedback processes quantitatively, multicomponent gas diffusion and advection are implemented into an existing reactive transport model that includes a full suite of geochemical reactions. Multicomponent gas diffusion is described on the basis of the dusty gas model, which accounts for all relevant gas diffusion mechanisms. The simulation of gas attenuation in partially saturated landfill soil covers, methane production, and oxidation in aquifers contaminated by organic compounds (e.g., an oil spill site) and pyrite oxidation in mine tailings demonstrate that both diffusive and advective gas transport can be affected by geochemical reactions. Methane oxidation in landfill covers reduces the existing upward pressure gradient, thereby decreasing the contribution of advective methane emissions to the atmosphere and enhancing the net flux of atmospheric oxygen into the soil column. At an oil spill site, methane oxidation causes a reversal in the direction of gas advection, which results in advective transport toward the zone of oxidation both from the ground surface and the deeper zone of methane production. Both diffusion and advection contribute to supply atmospheric oxygen into the subsurface, and methane emissions to the atmosphere are averted. During pyrite oxidation in mine tailings, pressure reduction in the reaction zone drives advective gas flow into the sediment column, enhancing the oxidation process. In carbonate-rich mine tailings, calcite dissolution releases carbon dioxide, which partly offsets the pressure reduction caused by O2 consumption.
Constructed wetlands (CWs) provide a natural way for simple, inexpensive, and robust wastewater treatment. Detailed understanding of CW functioning is difficult, because a large number of physical, chemical, and biological processes occur in parallel and influence each other. For this reason, CWs have long been seen as "black boxes" where wastewater enters and treated water leaves the system. Numerical models describing the biochemical transformation and degradation processes in CWs are promising tools to better understand CW functioning. The first part of this paper reviews published mechanistic models for CWs. Horizontal flow systems can be simulated when only water flow saturated conditions are considered; six models have been reviewed whereby a series or network of completely stirred tank reactors is most frequently used to describe the hydraulics. For modeling vertical flow CWs with intermittent loading, transient variably saturated flow models are required. Due to the intermittent loading, these systems are highly dynamic, adding to the complexity of the overall system. Five models of different complexity have been reviewed; three use the Richards equation to describe variably saturated flow, whereas the two others use simplified approaches. In the second part of the paper, the multicomponent reactive transport module CW2D is demonstrated. Simulation results for CWs treating domestic wastewater, combined sewer overflow, and surface water are presented. In general, a good match between simulation results and measured data could be achieved if the hydraulic behavior of the system could be described well. Based on the experience from these examples, the need for further model development is determined.
Vertical flow filters are containers filled with porous medium that are recharged from top and drained at the bottom, and are operated at partly saturated conditions. They have recently been suggested as treatment technology for groundwater containing volatile organic compounds (VOCs). Numerical reactive transport simulations were performed to investigate the relevance of different filter operation modes on biodegradation and/or volatilization of the contaminants and to evaluate the potential limitation of such remediation mean due to volatile emissions. On the basis of the data from a pilot-scale vertical flow filter intermittently fed with domestic waste water, model predictions on the system’s performance for the treatment of contaminated groundwater were derived. These simulations considered the transport and aerobic degradation of ammonium and two VOCs, benzene and methyl tertiary butyl ether (MTBE). In addition, the advective-diffusive gas-phase transport of volatile compounds as well as oxygen was simulated. Model predictions addressed the influence of depth and frequency of the intermittent groundwater injection, degradation rate kinetics, and the composition of the filter material. Simulation results show that for unfavorable operation conditions significant VOC emissions have to be considered and that operation modes limiting VOC emissions may limit aerobic biodegradation. However, a suitable combination of injection depth and composition of the filter material does facilitate high biodegradation rates while only little VOC emissions take place. Using such optimized operation modes would allow using vertical flow filter systems as remediation technology suitable for groundwater contaminated with volatile compounds.
Constructed wetlands for water cleanup have been in use for several years and are promising for cost-efficient remediation of large scale contamination. Within this study, flow conditions in layered vertical soil filters used for remediation of contaminated groundwater were investigated in detail by special discharge experiments and an attuned modeling study. Unsaturated water flow was measured in two vertical flow constructed wetlands for contaminated groundwater treatment at a site in eastern Germany. Numerical simulations were performed using the code MIN3P, in which variably saturated flow is based on the Richards equation. Soil hydraulic functions based on Van Genuchten coefficients and preferential flow characteristics were obtained by calibrating the model to measured data using self-adaptive evolution strategies with covariance matrix adaptation (CMA-ES). The presented inverse modeling procedure not only provides best fit parameterizations for separate and joint model objectives, but also utilizes the information from multiple restarts of the optimization algorithm to determine suitable parameter ranges and reveal potential correlations. The sequential automatic calibration is both straightforward and efficient even if different complex objective functions are considered.
Field investigations on the treatment of MTBE and benzene from contaminated groundwater in pilot or full-scale constructed wetlands are lacking hugely. The aim of this study was to develop a biological treatment technology that can be operated in an economic, reliable and robust mode over a long period of time. Two pilot-scale vertical-flow soil filter eco-technologies, a roughing filter (RF) and a polishing filter (PF) with plants (willows), were operated independently in a single-stage configuration and coupled together in a multi-stage (RF+PF) configuration to investigate the MTBE and benzene removal performances. Both filters were loaded with groundwater from a refinery site contaminated with MTBE and benzene as the main contaminants, with a mean concentration of 2970±816 and 13,966±1998 μg L(-1), respectively. Four different hydraulic loading rates (HLRs) with a stepwise increment of 60, 120, 240 and 480 L m(-2) d(-1) were applied over a period of 388 days in the single-stage operation. At the highest HLR of 480 L m(-2) d(-1), the mean concentrations of MTBE and benzene were found to be 550±133 and 65±123 μg L(-1) in the effluent of the RF. In the effluent of the PF system, respective mean MTBE and benzene concentrations of 49±77 and 0.5±0.2 μg L(-1) were obtained, which were well below the relevant MTBE and benzene limit values of 200 and 1 μg L(-1) for drinking water quality. But a dynamic fluctuation in the effluent MTBE concentration showed a lack of stability in regards to the increase in the measured values by nearly 10%, which were higher than the limit value. Therefore, both (RF+PF) filters were combined in a multi-stage configuration and the combined system proved to be more stable and effective with a highly efficient reduction of the MTBE and benzene concentrations in the effluent. Nearly 70% of MTBE and 98% of benzene were eliminated from the influent groundwater by the first vertical filter (RF) and the remaining amount was almost completely diminished (∼100% reduction) after passing through the second filter (PF), with a mean MTBE and benzene concentration of 5±10 and 0.6±0.2 μg L(-1) in the final effluent. The emission rate of volatile organic compounds mass into the air from the systems was less than 1% of the inflow mass loading rate. The results obtained in this study not only demonstrate the feasibility of vertical-flow soil filter systems for treating groundwater contaminated with MTBE and benzene, but can also be considered a major step forward towards their application under full-scale conditions for commercial purposes in the oil and gas industries.
Simulation of constructed wetlands has two main tasks: to obtain a better understanding of the processes in constructed wetlands, and to check and optimise existing design criteria. This paper shows simulation results for two indoor pilot-scale constructed wetlands for wastewater and surface water treatment respectively. The results presented and discussed are mainly focussed on the hydraulic behaviour of the constructed wetland systems. In addition results of reactive transport simulations with CW2D are shown. The multi-component reactive transport model CW2D (Constructed Wetlands 2 Dimensional) was developed to model transport and reactions of the main constituents of wastewater (organic matter, nitrogen, and phosphorus) in subsurface flow constructed wetlands. For the pilot-scale constructed wetlands a calibration of the flow model was possible and therefore the results of the reactive transport simulations with CW2D fit the measured data well. The further research needs regarding the simulation of subsurface flow constructed wetlands are discussed.
Constructed wetlands (CWs) use the same processes that occur in natural wetlands to improve water quality and are used worldwide to treat different qualities of water. This paper shows the results of an Austrian research project having the main goals to optimize vertical flow beds in terms of surface area requirement and nutrient removal, respectively. It could be shown that a subsurface vertical flow constructed wetland (SSVFCW) operated with an organic load of 20 g COD x m(-2) x d(-1) (corresponding to a specific surface area demand of 4 m2 per person) can fulfil the requirements of the Austrian standard regarding effluent concentrations and removal efficiencies. During the warmer months (May - October), when the temperature of the effluent is higher than 12 degrees C, the specific surface area might be further reduced. Even 2 m2 per person have been proven to be adequate. Enhanced nitrogen removal of 58% could be achieved with a two-stage system (first stage: grain size for main layer 1-4 mm, saturated drainage layer; and second stage: grain size for main layer 0.06-4 mm, free drainage) that was operated with an organic load of 80 g COD x m(-2) x d(-1) for the first stage (1 m2 per person), i.e. 40 g COD x m(-2) x d(-1) for the two-stage system (2 m2 per person). Although the two-stage system was operated with higher organic loads a higher effluent quality compared to a single-stage SSVFCW (grain size for main layer 0.06-4 mm, free drainage, organic load 20 g COD x m(-2) x d(-1)) could be reached.
Methane and trace organic gases produced in landfill waste are partly oxidized in the top 40 cm of landfill cover soils under aerobic conditions. The balance between the oxidation of landfill gases and the ingress of atmospheric oxygen into the soil cover determines the attenuation of emissions of methane, chlorofluorocarbons, and hydrochlorofluorocarbons to the atmosphere. This study was conducted to investigate the effect of oxidation reactions on the overall gas transport regime and to evaluate the contributions of various gas transport processes on methane attenuation in landfill cover soils. For this purpose, a reactive transport model that includes advection and the Dusty Gas Model for simulation of multicomponent gas diffusion was used. The simulations are constrained by data from a series of counter-gradient laboratory experiments. Diffusion typically accounts for over 99% of methane emission to the atmosphere. Oxygen supply into the soil column is driven exclusively by diffusion, whereas advection outward offsets part of the diffusive contribution. In the reaction zone, methane consumption reduces the pressure gradient, further decreasing the significance of advection near the top of the column. Simulations suggest that production of water or accumulation of exopolymeric substances due to microbially mediated methane oxidation can significantly reduce diffusive fluxes. Assuming a constant rate of methane production within a landfill, reduction of the diffusive transport properties, primarily due to exopolymeric substance production, may result in reduced methane attenuation due to limited O(2) -ingress.