Degradation of Six Selected Ultraviolet Filters in Aquifer Materials Under Various Redox Conditions

Laboratory biodegradation batch studies were performed to investigate the degradation behavior of six selected UV filters, namely benzophenone‐3 (BP‐3), 3‐(4‐methylbenzylidene) camphor (4‐MBC), Octyl 4‐methoxycinnamate (OMC), Octocrylene (OC), 2‐(3‐t‐butyl‐2‐hydroxy‐5‐methylphenyl)‐5‐chloro benzotriazole (UV‐326), and 2‐(2’‐hydroxy‐5’‐octylphenyl)‐benzotriazole (UV‐329) in an aquifer microcosm (groundwater and aquifer sediment mixture) under aerobic and anaerobic (nitrate, sulfate, and Fe(III) reducing) conditions within 77 d. The results from the biodegradation experiments showed that the six UV filters were degraded well in the aquifer materials under different redox conditions. Rapid biodegradation was observed for BP‐3 and OMC in the aquifer materials, with their half‐lives of 1.5‐8.8 d and 1.3‐5.2 d, respectively. In most cases, aerobic conditions were more favorable for the degradation of the UV filters in aquifer materials. Relatively slow degradation of 4‐MBC, UV‐326, and UV‐329 under anaerobic conditions was noted with their half‐lives ranging between 47 d and 126 d, indicating potential persistence in anaerobic aquifers. The results showed that redox conditions could have significant effects on biodegradation of the UV filters in aquifers.     

Fate of MTBE Relative to Benzene in a Gasoline-Contaminated Aquifer (1993–98)

Methyl tert -butyl ether (MTBE) and benzene have been measured since 1993 in a shallow, sandy aquifer contaminated by a mid-1980s release of gasoline containing fuel oxygenates. In wells downgradient of the release area, MTBK was detected before benzene, reflecting a chromatographic-like separation of these compounds in the direction of ground water flow. Higher concentrations of MTBE and benzene were measured in the deeper sampling ports of multilevel sampling wells located near the release area, and also up to 10 feet (3 m) below the water table surface in nested wells located farther from the release area. This distribution of higher concentrations at depth is caused by recharge events that deflect originally horizontal ground water flowlines. In the laboratory, microcosms containing aquifer material incubated with uniformly labeled ¹⁴C-MTBE under aerobic and anaerobic. Fe(III)-reducing conditions indicated a low but measurable biodegradation potential (<3%¹⁴C-MTBW as ¹⁴CO₂) after a seven-month incubation period, Tert -butyl alcohol (TBA), a proposed microbial-MTBE transformation intermediate, was detected in MTBE-contaminated wells, but TBA was also measured in unsaturated release area sediments. This suggests that TBA may have been present in the original fuel spilled and does not necessarily reflect microbial degradation of MTBE. Combined, these data suggest that milligram per liter to microgram per liter decreases in MTBE concentrations relative to benzene are caused by the natural attenuation processes of dilution and dispersion with less-contaminated ground water in the direction of flow rather than biodegradation at this point source gasoline release site.     

The Role of Bioattenuation in the Management of Aromatic Hydrocarbon Plumes in Aquifers

Ground water scientists have made significant advances in understanding the soil interactions, hydrogeology, fate and transport, and subsurface microbiology of aromatic hydrocarbons (BTEX) in aquifer systems. It is now generally recognized that a major factor responsible for the attenuation and mass reduction of BTEX in plumes is the widespread occurrence of hydrocarbon biodegradation by indigenous soil microorganisms in aquifer material. Most well-studied BTEX plumes that develop from the accidental release of gasoline fuels contain low levels of soluble hydrocarbons (< 1 to 5000 ppb) and have been shown to be spatially confined because of natural biotransformation mechanisms. These in situ processes are controlled by source and aquifer characteristics, permeability, sorption, and geochemical properties of the aquifer. Many laboratory subsoil-ground water microcosms and field studies (10 to 20 C) have demonstrated the rapid biodecay (1 to SO percent/day for microcosms and 0.5 to 1.5 percent/day for plumes) of these aromatic compounds under primarily aerobic conditions (i.e., those with sufficient dissolved oxygen). The ability to implement ground water bioremediation will depend upon our understanding of source control and aquifer recharge effects on the spatial distribution of plumes. In addition, estimating the biodegradation of sorbed BTEX, determining limits and potential for in situ biostimulation of soluble plumes, and establishing data requirements for predictive modeling of natural attenuation will be useful for this remediation technology. The use of these tools to manage ground water quality appears to represent the most practical alternative, particularly for low-risk ground water supplies.     

Analysis of recharge-induced geochemical change in a contaminated aquifer

Recharge events that deliver electron acceptors such as O2, NO3, SO4, and Fe3+ to anaerobic, contaminated aquifers are likely important for natural attenuation processes. However, the specific influence of recharge on (bio)geochemical processes in ground water systems is not well understood. The impact of a moderate-sized recharge event on ground water chemistry was evaluated at a shallow, sandy aquifer contaminated with waste fuels and chlorinated solvents. Multivariate statistical analyses coupled with three-dimensional visualization were used to analyze ground water chemistry data (including redox indicators, major ions, and physical parameters) to reveal associations between chemical parameters and to infer processes within the ground water plume. Factor analysis indicated that dominant chemical associations and their interpreted processes (anaerobic and aerobic microbial processes, mineral precipitation/dissolution, and temperature effects) did not change significantly after the spring recharge event of 2000. However, the relative importance of each of these processes within the plume changed. After the recharge event, the overall importance of aerobic processes increased from the fourth to the second most important factor, representing the variability within the data set. The anaerobic signatures became more complex, suggesting that zones with multiple terminal electron-accepting processes (TEAPs) likely occur in the same water mass. Three-dimensional visualization of well clusters showed that water samples with similar chemical associations occurred in distinct water masses within the aquifer. Water mass distinctions were not based on dominant TEAPs, suggesting that the recharge effects on TEAPs occurred primarily at the interface between infiltrating recharge water and the aquifer.     

A simple method for calculating growth rates of petroleum hydrocarbon plumes

Consumption of aquifer Fe(III) during biodegradation of ground water contaminants may result in expansion of a contaminant plume, changing the outlook for monitored natural attenuation. Data from two research sites contaminated with petroleum hydrocarbons show that toluene and xylenes degrade under methanogenic conditions, but the benzene and ethylbenzene plumes grow as aquifer Fe(III) supplies are depleted. By considering a one-dimensional reaction front in a constant unidirectional flow field, it is possible to derive a simple expression for the growth rate of a benzene plume. The method balances the mass flux of benzene with the Fe(III) content of the aquifer, assuming that the biodegradation reaction is instantaneous. The resulting expression shows that the benzene front migration is retarded relative to the ground water velocity by a factor that depends on the concentrations of hydrocarbon and bioavailable Fe(III). The method provides good agreement with benzene plumes at a crude oil study site in Minnesota and a gasoline site in South Carolina. Compared to the South Carolina site, the Minnesota site has 25% higher benzene flux but eight times the Fe(III), leading to about one-sixth the expansion rate. Although it was developed for benzene, toluene, ethylbenzene, and xylenes, the growth-rate estimation method may have applications to contaminant plumes from other persistent contaminant sources.     

Arsenic Cycling in Hydrocarbon Plumes: Secondary Effects of Natural Attenuation

Monitored natural attenuation is widely applied as a remediation strategy at hydrocarbon spill sites. Natural attenuation relies on biodegradation of hydrocarbons coupled with reduction of electron acceptors, including solid phase ferric iron (Fe(III)). Because arsenic (As) adsorbs to Fe‐hydroxides, a potential secondary effect of natural attenuation of hydrocarbons coupled with Fe(III) reduction is a release of naturally occurring As to groundwater. At a crude‐oil‐contaminated aquifer near Bemidji, Minnesota, anaerobic biodegradation of hydrocarbons coupled to Fe(III) reduction has been well documented. We collected groundwater samples at the site annually from 2009 to 2013 to examine if As is released to groundwater and, if so, to document relationships between As and Fe inside and outside of the dissolved hydrocarbon plume. Arsenic concentrations in groundwater in the plume reached 230 µg/L, whereas groundwater outside the plume contained less than 5 µg/L As. Combined with previous data from the Bemidji site, our results suggest that (1) naturally occurring As is associated with Fe‐hydroxides present in the glacially derived aquifer sediments; (2) introduction of hydrocarbons results in reduction of Fe‐hydroxides, releasing As and Fe to groundwater; (3) at the leading edge of the plume, As and Fe are removed from groundwater and retained on sediments; and (4) downgradient from the plume, patterns of As and Fe in groundwater are similar to background. We develop a conceptual model of secondary As release due to natural attenuation of hydrocarbons that can be applied to other sites where an influx of biodegradable organic carbon promotes Fe(III) reduction.     

Enhancement of In Situ Bioremediation of BTEX-Contaminated Ground Water by Oxygen Diffusion from Silicone Tubing

A field study of oxygen-enhanced biodegradation was carried out in a sandy iron-rich ground water system contaminated with gasoline hydrocarbons. Prior to the oxygen study, intrinsic microbial biodegradation in the contaminant plume had depleted dissolved oxygen and created anaerobic conditions. An oxygen diffusion system made of silicone polymer tubing was installed in an injection well within an oxygen delivery zone containing coarse highly permeable sand. During the study, this system delivered high dissolved oxygen (DO) levels (39 mg/L) to the ground water within a part of the plume. The ground water was sampled at a series of monitors in the test zone downgradient of the delivery well to determine the effect of oxygen on dissolved BTEX, ground water geochemistry, and microbially mediated biodegradation processes. The DO levels and Eh increased markedly at distances up to 2.3 m (7.5 feet) downgradient. Potential biofouling and iron precipitation effects did not clog the well screens or porous medium. The increased dissolved oxygen enhanced the population of aerobes while the activity of anaerobic sulfate-reducing bacteria and methanogens decreased. Based on concentration changes, the estimated total rate of BTEX biodegradation rose from 872 mg/day before enhancement to 2530 mg/day after 60 days of oxygen delivery. Increased oxygen flux to the test area could account for aerobic biodegradation of 1835 mg/day of the BTEX. The estimated rates of anaerobic biodegradation processes decreased based on the flux of sulfate, iron (II), and methane. Two contaminants in the plume, benzene and ethylbenzene, are not biodegraded as readily as toluene or xylenes under anaerobic conditions. Following oxygen enhancement, however, the benzene and ethylbenzene concentrations decreased about 98%, as did toluene and total xylenes.     

Oxygen-enhanced biodegradation of phenoxy acids in ground water at contaminated sites

The effects of adding oxygen to anaerobic aquifer materials on biodegradation of phenoxy acid herbicides were studied by laboratory experiments with aquifer material from two contaminated sites (a former agricultural machinery service and an old landfill). At both sites, the primary pollutants were phenoxy acids and related chlorophenols. It was found that addition of oxygen enhanced degradation of the six original phenoxy acids and six original chlorophenols. Inverse modeling on 14C 4-chloro-2-methylphenoxypropanoic acid (MCPP) degradation curves revealed that increasing the oxygen concentrations from <0.3 mg/L up to 7 to 8 mg/L shortened the lag phases (from approximately 150 d to 5 to 25 d) and increased first-order degradation rate constants by 1 order of magnitude (from approximately 5 x 10(-2) d(-1) to up to 30 x 10(-2) d(-1)). Additionally, the degree of MCPP mineralization was increased (30% to 50% mineralized at low oxygen concentrations and 50% to 70% mineralized at high oxygen concentrations, based on 14CO2 recovery). These positive effects on degradation were observed even at relatively low oxygen concentrations (2 mg/L). Furthermore, effects related to the addition of oxygen on the general geochemistry were studied. An oxygen consumption of 2.2 to 2.6 mg O2/g dw was observed due to oxidation of solid organic matter and, to some extent (0.5% to 11% of the total oxygen consumption), water-soluble compounds such as Fe2+, dissolved Mn, nonvolatile organic carbon, and NH4+. Overall, the results suggest that stimulated biodegradation by addition of oxygen might be a feasible remediation technology at herbicide-contaminated sites, although oxygen consumption by the sediment could limit the applicability.     

Reinterpreting the Importance of Oxygen‐Based Biodegradation in Chloroethene‐Contaminated Groundwater

Chlororespiration is common in shallow aquifer systems under conditions nominally identified as anoxic. Consequently, chlororespiration is a key component of remediation at many chloroethene‐contaminated sites. In some instances, limited accumulation of reductive dechlorination daughter products is interpreted as evidence that natural attenuation is not adequate for site remediation. This conclusion is justified when evidence for parent compound (tetrachloroethene, PCE, or trichloroethene, TCE) degradation is lacking. For many chloroethene‐contaminated shallow aquifer systems, however, nonconservative losses of the parent compounds are clear but the mass balance between parent compound attenuation and accumulation of reductive dechlorination daughter products is incomplete. Incomplete mass balance indicates a failure to account for important contaminant attenuation mechanisms and is consistent with contaminant degradation to nondiagnostic mineralization products like CO₂. While anoxic mineralization of chloroethene compounds has been proposed previously, recent results suggest that oxygen‐based mineralization of chloroethenes also can be significant at dissolved oxygen concentrations below the currently accepted field standard for nominally anoxic conditions. Thus, reassessment of the role and potential importance of low concentrations of oxygen in chloroethene biodegradation are needed, because mischaracterization of operant biodegradation processes can lead to expensive and ineffective remedial actions. A modified interpretive framework is provided for assessing the potential for chloroethene biodegradation under different redox conditions and the probable role of oxygen in chloroethene biodegradation.     

Estimating Aquifer Sensitivity to Nitrate Contamination Using Geochemical Information

Methods for predicting aquifer sensitivity to contamination typically ignore geochemical factors that affect the occurrence of contaminants such as nitrate. Use of geochemical information offers a simple and accurate method for estimating aquifer sensitivity to nitrate contamination. We developed a classification method in which nitrate-sensitive aquifers have dissolved oxygen concentrations > 1.0 mg/L, Eh values >250 mV, and either reduced iron concentrations < 0.1 mg/L or total iron concentrations < 0.7 mg/L. We tested the method in four Minnesota aquifer systems having different geochemical and hydrologic conditions. A surficial sand aquifer in central Minnesota exhibited geochemical zonation, with a rapid shift from aerobic to anaerobic conditions 5 m below the water table. A fractured bedrock aquifer in east-central Minnesota remained aerobic to depths of 50 m, except in areas where anaerobic ground water discharged upward from an underlying aquifer. A bedrock aquifer in southeast Minnesota exhibited aerobic conditions when overlain by surficial deposits lacking shale, whereas anaerobic conditions occurred under deposits that contained shale. Surficial sand aquifers in northwest Minnesota contained high concentrations of sulfate and were anaerobic throughout their extent. Nitrate-nitrogen was detected at concentrations exceeding 1 mg/L in 135 of 149 samples classified as sensitive. Nitrate was not detected in any of the 109 samples classified as not sensitive. We observed differences between our estimates of sensitivity and existing sensitivity maps, which are based on methods that do not consider aquifer geochemistry. Because dissolved oxygen, reduced iron, and Eh are readily measured in the field, use of geochemistry provides a quick and accurate way of assessing aquifer sensitivity to nitrate contamination.     

Spatial Variation in MTBE Biodegradation Activity of Aquifer Solids Samples Collected in the Vicinity of a Flow-Through Aerobic Biobarrier

The spatial variation in methyl tert-butyl ether (MTBE) biodegradation activity of aquifer solids samples collected in the vicinity of a flow-through aerobic biobarrier was assessed through use of standard laboratory microcosms. These were prepared by collecting soil cores at a range of locations and depths along different flow paths through the biobarrier. Sections of core samples were placed in sealed bottles with MTBE-free groundwater from the site. The groundwater was filtered to remove microbes, and sparged with O₂. The initial MTBE concentration in the microcosms was adjusted to about 1 mg/L. Biodegradation activity was characterized by the magnitude of MTBE concentration reductions occurred over 4 weeks relative to control microcosms. Sampling locations and depths were selected to allow investigation of relationships between MTBEdegrading activity and dissolved oxygen (DO) concentration, MTBE, soil type, and initial microbial conditions (biostimulated vs. bioaugmented). The results suggest a relatively wide-spread presence of MTBE-degrading microbial consortia, with varying levels of MTBE-degrading activity. Significant changes in activity were observed over 0.3-m vertical distances in the same location; for example, cores from the most upgradient sampling locations contained sections with no discernible MTBEbiodegradation over 4 weeks, as well as sections that achieved order-of-magnitude MTBE concentration reductions within 2 weeks. None of those cores, however, achieved MTBE biodegradation to nondetect levels (<0.005 mg/L), as was observed in some cores from downgradient locations. Cores from the bioaugmented regions had the highest frequency of MTBE biodegradation to nondetect levels among their sections suggesting a direct effect of the inoculum and its distribution when it was implanted. Most cores with no activity were associated with the upgradient, low-DO, and high-MTBE concentration field environments, but low-DO field environments also yielded MTBE-degrading samples. There were no other clear correlations between MTBE-degrading activity in the microcosms and the local field environment conditions at the time of sampling.     

Biodegradation and transport of benzene,toluene, and xylenes in a simulated aquifer: comparison of modelled and experimental results

Both laboratory experiments and numerical modelling were conducted to study the biodegradation and transport of benzene–toluene–xylenes (BTX) in a simulated semi‐confined aquifer. The factors incorporated into the numerical model include advection, hydrodynamic dispersion, adsorption, and biodegradation. The various physico‐chemical parameters required by the numerical model were measured experimentally. In the experimental portion of the study, BTX compounds were introduced into the aquifer sand. After the contaminants had been transported through the system, BTX concentrations were measured at 12 equally spaced wells. Subsequently, microorganisms obtained from the activated sludge of a sewage treatment plant and cultured in BTX mixtures were introduced into the aquifer through the 12 sampling wells. The distribution data for BTX adsorption by the aquifer sand form a nonlinear isotherm. The degree of adsorption by the sand varies, depending on the composition of the solute. The degradation time, measured from the time since the bacteria were added to the aquifer until a specific contaminant was no longer detectable, was 35–42 h for BTX. The dissolved oxygen, after degradation by BTX compounds and bacteria, was consumed by about 40–60% in the entire simulated aquifer; thus the aerobic conditions were maintained. This study provides insights for the biodegradation and transport of BTX in aquifers by numerical modelling and laboratory experiments. Experimental and numerical comparisons indicate that the results by Monod degradation kinetics are more accurate than those by the first‐order degradation kinetics. Copyright © 2002 John Wiley & Sons, Ltd.     

Benzene Dynamics and Biodegradation in Alluvial Aquifers Affected by River Fluctuations

The spatial distribution and temporal dynamics of a benzene plume in an alluvial aquifer strongly affected by river fluctuations was studied. Benzene concentrations, aquifer geochemistry datasets, past river morphology, and benzene degradation rates estimated in situ using stable carbon isotope enrichment were analyzed in concert with aquifer heterogeneity and river fluctuations. Geochemistry data demonstrated that benzene biodegradation was on‐going under sulfate reducing conditions. Long‐term monitoring of hydraulic heads and characterization of the alluvial aquifer formed the basis of a detailed modeled image of aquifer heterogeneity. Hydraulic conductivity was found to strongly correlate with benzene degradation, indicating that low hydraulic conductivity areas are capable of sustaining benzene anaerobic biodegradation provided the electron acceptor (SO₄^2–) does not become rate limiting. Modeling results demonstrated that the groundwater flux direction is reversed on annual basis when the river level rises up to 2 m, thereby forcing the infiltration of oxygenated surface water into the aquifer. The mobilization state of metal trace elements such as Zn, Cd, and As present in the aquifer predominantly depended on the strong potential gradient within the plume. However, infiltration of oxygenated water was found to trigger a change from strongly reducing to oxic conditions near the river, causing mobilization of previously immobile metal species and vice versa. MNA appears to be an appropriate remediation strategy in this type of dynamic environment provided that aquifer characterization and targeted monitoring of redox conditions are adequate and electron acceptors remain available until concentrations of toxic compounds reduce to acceptable levels.     

Removal of Volatile Organic Compounds in Vertical Flow Filters: Predictions from Reactive Transport Modeling

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.     

Effect of Biofuels on Biodegradation of Benzene and Toluene at Gasoline Spill Sites

The risk that benzene and toluene from spills of gasoline will impact drinking water wells is largely controlled by the natural anaerobic biodegradation of benzene and toluene. Benzene and toluene, as well as ethanol and other biofuels, are degraded under anaerobic conditions to the same pool of degradation products. Biodegradation of biofuels may produce concentrations of degradation products that make the thermodynamics for degradation of benzene and toluene infeasible under methanogenic conditions and produce larger plumes of benzene and toluene. This study evaluated the concentrations of fuel alcohols that are necessary to inhibit the anaerobic degradation of benzene and toluene under methanogenic conditions. At two ethanol spill sites, concentrations of ethanol greater ≥42 mg/L inhibited the anaerobic degradation of toluene. The pH and concentrations of acetate, dissolved inorganic carbon, and molecular hydrogen were used to calculate the Gibbs free energy for the biodegradation of toluene. In general, the anaerobic biodegradation of toluene was not thermodynamically feasible in water with ≥42 mg/L ethanol. In a microcosm study, when the concentrations of ethanol were ≥14 mg/L or the concentrations of n‐butanol were ≥16 mg/L, the biodegradation of the alcohols consistently produced concentrations of hydrogen, dissolved inorganic carbon, and acetate that would preclude natural anaerobic biodegradation of benzene and toluene by syntrophic organisms. In contrast, iso‐butanol and n‐propanol only occasionally produced conditions that would preclude the biodegradation of benzene and toluene.     

Depth-related influences on biodegradation rates of phenanthrene in polluted marine sediments of Puget Sound, WA

A whole-core injection method was used to determine depth-related rates of microbial mineralization of (14)C-phenanthrene added to both contaminated and clean marine sediments of Puget Sound, WA. For 26-day incubations under micro-aerobic conditions, conversions of (14)C-phenanthrene to (14)CO(2) in heavily PAH-contaminated sediments from two sites in Eagle Harbor were much higher (up to 30%) than those in clean sediments from nearby Blakely Harbor (<3%). The averaged (14)C-phenanthrene degradation rates in the surface sediment horizons (0-3 cm) were more rapid (2-3 times) than in the deeper sediment horizons examined (>6 cm), especially in the most PAH polluted EH9 site. Differences in mineralization were associated with properties of the sediments as a function of sediment depth, including grain-size distribution, PAH concentration, total organic matter and total bacterial abundance. When strictly anaerobic incubations (in N(2)/H(2)/CO(2) atmosphere) were used, the phenanthrene biodegradation rates at all sediment depths were two times slower than under micro-aerobic conditions, with methanogenesis observed after 24 days. The main rate-limiting factor for phenanthrene degradation under anaerobic conditions appeared to be the availability of suitable electron acceptors. Addition of calcium sulfate enhanced the first order rate coefficient (k(1) increased from 0.003 to 0.006 day(-1)), whereas addition of soluble nitrate, even at very low concentration (<0.5 mM), inhibited mineralization. Long-term storage of heavily polluted Eagle Harbor sediment as intact cores under micro-aerobic conditions also appeared to enhance anaerobic biodegradation rates (k(1) up to 0.11 day(-1)).     

The Effect of Oxygen on Anaerobic Color Removal of Azo Dye in a Sequencing Batch Reactor

In this study, various amounts of oxygen were added to the anaerobic phase of an anaerobic‐aerobic sequencing batch reactor (SBR) receiving azo dye remazol brilliant violet 5R to mimic the input of oxygen into the anaerobic zones of biological textile wastewater treatment plants. The effect of oxygen on the anaerobic biodegradative capability of the mixed microbial culture for remazol brilliant violet 5R was investigated. To investigate the effect of oxygen on anaerobic azo dye biodegradation, the anaerobic phase of the SBR cultures were exposed to a very low limited amount of oxygen for various air flow rates. Initially, an air flow rate of 20 mL/min was applied, further on the air flow rate in the anaerobic phase was increased up to 40 mL/min. System performance was determined by monitoring chemical oxygen demand, color removal rate, activities of anaerobic (azo reductase) and aerobic enzymes (catechol 2,3‐dioxygenase, catechol 1,2‐dioxygenase). The results of percentage COD reduction at each stage were similar for all runs, giving an overall reduction of 96%. Anaerobic color removal efficiency and azo reductase activity of anaerobic microorganisms were adversely affected by the addition of oxygen. Color removal efficiencies of the anaerobic phases decreased from 80% down to 42 and 38% for the limited oxygen conditions of 20 mL/min and 40 mL/min, respectively. It was observed that the activity of catechol 2,3‐dioxygenase and catechol 1,2‐dioxygenase, involved in breakage of aromatic rings, increased after they are exposed to oxygen limited conditions compared to fully anaerobic conditions. It was also observed that catechol 1,2‐dioxygenase enzyme activity increased by increasing the oxygen level on oxygen limited conditions in the anaerobic zone.     

Tidal influence on BTEX biodegradation in sandy coastal aquifers

A numerical study was conducted to investigate the influence of tides on the fate of terrestrially derived BTEX discharging through an unconfined aquifer to coastal waters. Previous studies have revealed that tide-induced seawater circulations create an active salt–freshwater mixing zone in the near-shore aquifer and alter the specific subsurface pathway for contaminants discharging to the coastal environment. Here the coupled density-dependent flow and multi-species reactive transport code PHWAT was used to examine the impact of these tidal effects on the aerobic biodegradation of BTEX released in a coastal aquifer and its subsequent loading to coastal waters. Simulations indicated that tides significantly enhance BTEX attenuation in the near-shore aquifer. They also reduce the rate of chemical transfer from the aquifer to the ocean and exit concentrations at the beach face. For the base case consisting of toluene transport and biodegradation, 79% of toluene initially released in the aquifer was attenuated prior to discharge with tides present, compared to only 1.8% for the non-tidal case. The magnitude of tidal forcing relative to the fresh groundwater flow rate was shown to influence significantly the extent of biodegradation as it controls the intensity of salt–freshwater mixing, period of exposure of the contaminant to the mixing zone and rate of oxygen delivery to the aquifer. The oxygen available for biodegradation also depends on the rate at which oxygen is consumed by natural processes such as organic matter decomposition. While simulations conducted with heterogeneous conductivity fields highlighted the uncertainties associated with predicting contaminant loadings, the study revealed overall that BTEX may undergo significant attenuation in tidally influenced aquifers prior to discharge.     

Ground Water Contamination from Creosote Sites

Field data from 44 waste sites contaminated with creosote have been compiled in a database. The data from each site included geological and hydrogeological parameters and the concentrations of creosote compounds in the ground water at various distances from the pollution sources. The creosote compounds that were measured included mononuclear aromatic hydrocarbons and polynuclear aromatic hydrocarbons (PAH) and phenols. Already 50 m down-gradient of the creosote waste sites, 90 percent of the concentrations were from three to 50 times lower than at the source, and most of the median concentrations were below detection limit (0.1 to 0.5 μg/L). The maximum concentrations of benzene, toluene, and xylenes (BTX) and phenols were much lower under aerobic than under anaerobic conditions. Among the phenols, the xylenols (dimethylphenols) appear in higher concentrations under aerobic conditions than phenol and the cresols do. The highest concentrations found were of the same order of magnitude as the calculated solubilities found in the literature, except the chrysene and benz(a)pyrene concentrations, which were one to two orders of magnitude higher than the solubilities.     

MNA as a Remedy for Arsenic Mobilized by Anthropogenic Inputs of Organic Carbon

The potential application of monitored natural attenuation (MNA) as a remedy for ground water contaminated with arsenic (As) is examined for a subset of contaminated sites, specifically those where naturally occurring As has been mobilized due to localized anthropogenic organic carbon (OC) releases. This includes sites subject to petroleum releases, exposure to landfill leachates, and OC additions for biostimulation of reductive dechlorination of chlorinated solvents. The key characteristic of these sites is that, under conditions prevailing before the anthropogenic OC introduction, the naturally occurring As in the subsurface was not mobile and did not adversely affect ground water quality. This suggests that, in the far-field (where background conditions are (re) established), As may be sequestered upon contact of the contaminated ground water with either or both the (uncontaminated) ambient ground water and the background aquifer minerals. The observed extents of elevated concentrations (or "footprints") of As and other chemical species, such as dissolved OC and iron (Fe), and related parameters, such as redox potential ( E _h) and dissolved oxygen, and their evolution over time can be used to assess the mobilization and sequestration of As and the potential feasibility of MNA as a remedial option. Ultimately, the capacity for As sequestration must be assessed in the context of the OC loading to the site, which may require "active" measures for source control. Monitoring is needed to confirm the continuing effectiveness of the MNA remedy or to indicate if contingency measures must be implemented.