Concentration effects on biotic and abiotic processes in the removal of 1,1,2-trichloroethane and vinyl chloride using carbon-amended ZVI.

A permeable reactive barrier, consisting of both zero valent iron (ZVI) and a biodegradable organic carbon, was evaluated for the remediation of 1,1,2-trichloroethane (1,1,2-TCA) contaminated groundwater. During an 888 day laboratory column study, degradation rates initially stabilized with a degradation half-life of 4.4±0.4 days. Based on the accumulation of vinyl chloride (VC) and limited production of 1,1-dichloroethene (1,1-DCE) and 1,2-dichloroethane (1,2-DCA), the dominant degradation pathway was likely abiotic dichloroelimination to form VC. Degradation of VC was not observed based on the accumulation of VC and limited ethene production. After a step reduction in the influent concentration of 1,1,2-TCA from 170±20 mg L(-1) to 39±11 mg L(-1), the degradation half-life decreased 5-fold to 0.83±0.17 days. The isotopic enrichment factor of 1,1,2-TCA also changed after the step reduction from -14.6±0.7‰ to -0.72±0.12‰, suggesting a possible change in the degradation mechanism from abiotic reductive degradation to biodegradation. Microbiological data suggested a co-culture of Desulfitobacterium and Dehalococcoides was responsible for the biodegradation of 1,1,2-TCA to ethene.

Colloid release and clogging in porous media: Effects of solution ionic strength and flow velocity.

The release and retention of in-situ colloids in aquifers play an important role in the sustainable operation of managed aquifer recharge (MAR) schemes. The processes of colloid release, retention, and associated permeability changes in consolidated aquifer sediments were studied by displacing native groundwater with reverse osmosis-treated (RO) water at various flow velocities. Significant amounts of colloid release occurred when: (i) the native groundwater was displaced by RO-water with a low ionic strength (IS), and (ii) the flow velocity was increased in a stepwise manner. The amount of colloid release and associated permeability reduction upon RO-water injection depended on the initial clay content of the core. The concentration of released colloids was relatively low and the permeability reduction was negligible for the core sample with a low clay content of about 1.3%. In contrast, core samples with about 6 and 7.5% clay content exhibited: (i) close to two orders of magnitude increase in effluent colloid concentration and (ii) more than 65% permeability reduction. Incremental improvement in the core permeability was achieved when the flow velocity increased, whereas a short flow interruption provided a considerable increase in the core permeability. This dependence of colloid release and permeability changes on flow velocity and colloid concentration was consistent with colloid retention and release at pore constrictions due to the mechanism of hydrodynamic bridging. A mathematical model was formulated to describe the processes of colloid release, transport, retention at pore constrictions, and subsequent permeability changes. Our experimental and modeling results indicated that only a small fraction of the in-situ colloids was released for any given change in the IS or flow velocity. Comparison of the fitted and experimentally measured effluent colloid concentrations and associated changes in the core permeability showed good agreement, indicating that the essential physics were accurately captured by the model.

Bacterial community and groundwater quality changes in an anaerobic aquifer during groundwater recharge with aerobic recycled water.

Managed aquifer recharge offers the opportunity to manage groundwater resources by storing water in aquifers when in surplus and thus increase the amount of groundwater available for abstraction during high demand. The Water Corporation of Western Australia (WA) is undertaking a Groundwater Replenishment Trial to evaluate the effects of recharging aerobic recycled water (secondary treated wastewater subjected to ultrafiltration, reverse osmosis, and ultraviolet disinfection) into the anaerobic Leederville aquifer in Perth, WA. Using culture-independent methods, this study showed the presence of Actinobacteria, Alphaproteobacteria, Bacilli, Betaproteobacteria, Cytophaga, Flavobacteria, Gammaproteobacteria, and Sphingobacteria, and a decrease in microbial diversity with an increase in depth of aquifer. Assessment of physico-chemical and microbiological properties of groundwater before and after recharge revealed that recharging the aquifer with aerobic recycled water resulted in elevated redox potentials in the aquifer and increased bacterial numbers, but reduced microbial diversity. The increase in bacterial numbers and reduced microbial diversity in groundwater could be a reflection of an increased denitrifier and sulfur-oxidizing populations in the aquifer, as a result of the increased availability of nitrate, oxygen, and residual organic matter. This is consistent with the geochemical data that showed pyrite oxidation and denitrification within the aquifer after recycled water recharge commenced.

Integrating spatial and temporal oxygen data to improve the quantification of in situ petroleum biodegradation rates.

Accurate estimation of biodegradation rates during remediation of petroleum impacted soil and groundwater is critical to avoid excessive costs and to ensure remedial effectiveness. Oxygen depth profiles or oxygen consumption over time are often used separately to estimate the magnitude and timeframe for biodegradation of petroleum hydrocarbons in soil and subsurface environments. Each method has limitations. Here we integrate spatial and temporal oxygen concentration data from a field experiment to develop better estimates and more reliably quantify biodegradation rates. During a nine-month bioremediation trial, 84 sets of respiration rate data (where aeration was halted and oxygen consumption was measured over time) were collected from in situ oxygen sensors at multiple locations and depths across a diesel non-aqueous phase liquid (NAPL) contaminated subsurface. Additionally, detailed vertical soil moisture (air-filled porosity) and NAPL content profiles were determined. The spatial and temporal oxygen concentration (respiration) data were modeled assuming one-dimensional diffusion of oxygen through the soil profile which was open to the atmosphere. Point and vertically averaged biodegradation rates were determined, and compared to modeled data from a previous field trial. Point estimates of biodegradation rates assuming no diffusion ranged up to 58 mg kg(-1) day(-1) while rates accounting for diffusion ranged up to 87 mg kg(-1) day(-1). Typically, accounting for diffusion increased point biodegradation rate estimates by 15-75% and vertically averaged rates by 60-80% depending on the averaging method adopted. Importantly, ignoring diffusion led to overestimation of biodegradation rates where the location of measurement was outside the zone of NAPL contamination. Over or underestimation of biodegradation rate estimates leads to cost implications for successful remediation of petroleum impacted sites.

On-line groundwater velocity probe: laboratory testing and field evaluation.

An automated on-line instrument has been developed to rapidly measure groundwater velocity within a screened well. The instrument consists of a carbon dioxide gas tracer that is periodically delivered to a permeable chamber located within a screened well. The rate of diffusion of the tracer through the wall of the permeable chamber was rapid and the effective diffusion into the groundwater was controlled by the mass transfer limitations at the groundwater/chamber interface with gas entrainment proportional to the groundwater velocity past the chamber. By periodically delivering the gas tracer and monitoring the reduction in concentration of the tracer from the permeable chamber, the groundwater velocity was determined multiple times daily. Laboratory experiments undertaken within a calibrated flow chamber have demonstrated that the instrument can be used to accurately and reliably determine groundwater flow velocities at 3h intervals for flow rates between 25 and 300 m y(-1). Field testing of the velocity probe at multiple well locations in a sandy aquifer gave velocities consistent with another monitoring technique (passive flux meter) and site modelling.

Aerobic bioremediation of 1,2 dichloroethane and vinyl chloride at field scale.

Aerobic bioremediation of 1,2 dichloroethane (1,2 DCA) and vinyl chloride (VC) was evaluated at field scale in a layered, silty and fine-sand anaerobic aquifer. Maximum concentrations of 1,2 DCA (2 g/L) and VC (0.75 g/L) in groundwater were within 25% and 70% of pure compound solubility, respectively. Aerobic conditions were induced by injecting air into sparging wells screened 20.5-21.5 m below ground (17-18 m below the water table). Using a cycle of 23 h of air injection followed by three days of no air injection, fifty days of air injection were accumulated over a 12 month period which included some longer periods of operational shutdown. Oxygen and volatile organic compound probes, and multilevel samplers were used to determine changes of the primary contaminants and the associated inorganic chemistry at multiple locations and depths. Air (oxygen) was distributed laterally up to 25 m from the sparge points, with oxygen partial pressures up to 0.7 atmospheres (28-35 mg/L in groundwater) near to the sparge points. The dissolved mass of 1,2 DCA and VC was reduced by greater than 99% over the 590 m(2) trial plot. Significantly, pH declined from nearly 11 to less than 9, and sulfate concentrations increased dramatically, suggesting the occurrence of mineral sulfide (e.g., pyrite) oxidation. Chloride and bicarbonate (aerobic biodegradation by-products) concentration increases were used to estimate that 300-1000 kg of chlorinated hydrocarbons were biodegraded, although the ratio of 1,2 DCA to VC that was biodegraded remained uncertain. The mass biodegraded was comparable but less than the 400-1400 kg of chlorinated compounds removed from the aqueous phase within a 10,000 m(3) volume of the aquifer. Due to the likely presence of non-aqueous phase liquid, the relative proportion of volatilisation compared to biodegradation could not be determined. The aerobic biodegradation rates were greater than those previously estimated from laboratory-based studies.

Integration of traditional and innovative characterization techniques for flux-based assessment of dense non-aqueous phase liquid (DNAPL) sites.

Key attributes of the source zone and the expanding dissolved plume at a trichloroethene (TCE) site in Australia were evaluated using trends in groundwater monitoring data along with data from on-line volatile organic compound (VOC) samplers and passive flux meters (PFMs) deployed in selected wells. These data indicate that: (1) residual TCE source mass in the saturated zone, estimated using two innovative techniques, is small ( approximately 10 kg), which is also reflected in small source mass discharge ( approximately 3 g/day); (2) the plume is disconnecting, based on TCE concentration contours and TCE fluxes in wells along a longitudinal transect; (3) there is minimal biodegradation, based on TCE mass discharge of approximately 6 g/day at a plume control plane approximately 175 m from source, which is also consistent with aerobic geochemical conditions observed in the plume; and (4) residual TCE in the vadose zone provides episodic inputs of TCE mass to the plume during infiltration/recharge events. TCE flux data also suggest that the small residual TCE source mass is present in the low-permeability zones, thus making source treatment difficult. Our analysis, based on a synthesis of the archived data and new data, suggests that source treatment is unwarranted, and that containment of the large TCE plume (approximately 1.2 km long, approximately 0.3 km wide; 17 m deep; approximately 2000-2500 kg TCE mass) or institutional controls, along with a long-term flux monitoring program, might be necessary. The flux-based site management approach outlined in this paper provides a novel way of looking beyond the complexities of groundwater contamination in heterogeneous domains, to make intelligent and informed site decisions based on strategic measurement of the appropriate metrics.

Quantification of vapor intrusion pathways into a slab-on-ground building under varying environmental conditions.

Potential hydrocarbon-vapor intrusion pathways into a building through a concrete slab-on-ground were investigated and quantified under a variety of environmental conditions to elucidate the potential mechanisms for indoor air contamination. Vapor discharge from the uncovered open ground soil adjacent to the building and subsequent advection into the building was unlikely due to the low soil-gas concentrations at the edge of the building as a result of aerobic biodegradation of hydrocarbon vapors. When the building's interior was under ambient pressure, a flux of vapors into the building due to molecular diffusion of vapors through the building's concrete slab (cyclohexane 11 and methylcyclohexane 31 mg m(-2) concrete slab day(-1)) and short-term (up to 8 h) cyclical pressure-driven advection of vapors through an artificial crack (cyclohexane 4.2 x 10(3) and methylcyclohexane 1.2 x 10(4) mg m(-2) cracks day(-1)) was observed. The average subslab vapor concentration under the center of the building was 25,000 microg L(-1). Based on the measured building's interiorvapor concentrations and the building's air exchange rate of 0.66 h(-1), diffusion of vapors through the concrete slab was the dominantvapor intrusion pathway and cyclical pressure exchanges resulted in a near zero advective flux. When the building's interior was under a reduced pressure (-12 Pa), advective transport through cracks or gaps in the concrete slab (cyclohexane 340 and methylcyclohexane 1100 mg m(-2) cracks day(-1)) was the dominant vapor intrusion pathway.

Zero valent iron remediation of a mixed brominated ethene contaminated groundwater.

The suitability of a granulated zero valent iron (ZVI) permeable reactive barrier (PRB) remediation strategy was investigated for tribromoethene (TriBE), cis-1,2-dibromoethene (c-DBE), trans-1,2-dibromoethene (t-DBE) and vinyl bromide (VB), via batch and large-scale column experiments that were subsequently analysed by reactive transport modelling. The brominated ethenes in both batch and large-scale column experiments showed rapid (compared to controls and natural attenuation) degradation in the presence of ZVI. In the large-scale column experiment, degradation half-lives were 0.35 days for TriBE, 0.50 days for c-DBE, 0.31 days for t-DBE and 0.40 days for VB, under site groundwater flow conditions, resulting in removal of brominated ethenes within the first 0.2 m of a 1.0 m thick ZVI layer, indicating that a PRB groundwater remediation strategy using ZVI could be used successfully. In the model simulations of the ZVI induced brominated ethene degradation, assuming a dominant reductive beta-elimination pathway via bromoacetylene and acetylene production, simulated organic compound concentrations corresponded well with both batch and large-scale column experimental data. Changes of inorganic reactants were also well captured by the simulations. The similar ZVI induced degradation pathway of TriBE and TCE suggests that outcomes from research on ZVI induced TCE remediation could also be applied to TriBE remediation.

Effects of increasing acidity on metal(loid) bioprecipitation in groundwater: column studies.

Large-scale column experiments were carried out over a period of 545 days to assess the effect of increasing acidity on bacterial denitrification, sulfate reduction, and metal(loid) bioprecipitation in groundwater affected by acid mine drainage. At a groundwater pH of 5.5, denitrification and Cu2+ removal, probably via malachite (Cu2(OH)2CO3) precipitation, were observed in the ethanol-amended column. Sulfate reduction, sulfide production, and Zn2+ removal were also observed, with Zn2+ removal observed in the zone of sulfate reduction, indicating likely precipitation as sphalerite (ZnS). Se6+ removal was also observed in the sulfate reducing zone, probably as direct bioreduction to elemental selenium via ethanol/acetate oxidation or sulfide oxidation precipitating elemental sulfur. A step decrease in groundwater pH from 5.5 to 4.25 resulted in increased denitrification and sulfate reduction half-lives, migration of both these redox zones along the ethanol-amended column, and the formation of an elevated Cu2+ plume. Additionally, an elevated Zn2+ plume formed in the previous sulfate reducing zone of the ethanol-amended column, suggesting dissolution of precipitated sphalerite as a result of the reduction in groundwater pH. As Cu2+ passed through the zone of sphalerite dissolution, SEM imaging and EDS detection suggested that Cu2+ removal had occurred via chalcocite (Cu2S) or covellite (CuS) precipitation.

Estimation of ethanol mass delivery to groundwater from silicone polymer mats.

Hollow-fiber silicone tubing, coiled and shaped as mats, has been evaluated for its potential to provide predictable delivery of ethanol to aquifers to promote reducing conditions for enhanced bioremediation of a range of contaminants in groundwater. A model was developed to predict the steady-state mass flux of diffusional ethanol delivery to an external aqueous phase from an aqueous ethanol solution present inside the polymer tubing mat, and an effective diffusion coefficient of ethanol through the silicone tubing of 1.22 x 10(-6) cm2 s(-1) was determined experimentally. The model was then validated in column-scale laboratory and field experiments where polymer mats configured as permeable reactive barriers maintained uniform diffusive delivery of ethanol. Steady-state mass flux delivery ratios of ethanol through the polymer tubing wall of 1.45 (+/-0.18) x 10(6) to 1.64 (+/-0.17) x 10(6) s cm(-1) were determined under laboratory conditions, and 2.43 (+/-1.47) x 10(6) s cm(-1) under field conditions, which were found to be statistically similar to model-predicted ethanol mass flux delivery ratios.

Origin of a mixed brominated ethene groundwater plume: contaminant degradation pathways and reactions.

On the basis of a combination of laboratory microcosm experiments, column sorption experiments, and the current spatial distribution of groundwater concentrations, the origin of a mixed brominated ethene groundwater plume and its degradation pathway were hypothesized. The contaminant groundwater plume was detected downgradient of a former mineral processing facility, and consisted of tribromoethene (TriBE), cis-1,2-dibromoethene (c-DBE), trans-1,2-dibromoethene (t-DBE), and vinyl bromide (VB). The combined laboratory and field data provided strong evidence that the origin of the mixed brominated ethene plume was a result of dissolution of the dense non-aqueous-phase liquid 1,1,2,2-tetrabromoethane (TBA) atthe presumed source zone, which degraded rapidly (half-life of 0.2 days) to form TriBE in near stoichiometric amounts. TriBE then degraded (half-life of 96 days) to form c-DBE, t-DBE, and VB via a reductive debromination degradation pathway. Slow degradation of c-DBE (half-life >220 days), t-DBE (half-life 220 days), and VB (half-life >220 days) coupled with their low retardation coefficients (1.2, 1.2, and 1.0 respectively) resulted in the formation of an extensive mixed brominated ethene contaminant plume. Without this clearer understanding of the mechanism for TBA degradation, the origin of the mixed brominated ethene groundwater contamination could have been misinterpreted, and inappropriate and ineffective source zone and groundwater remediation techniques could be applied.

Modeling of microbial dynamics and geochemical changes in a metal bioprecipitation experiment.

A biogeochemical transport modeling study was carried out to analyze large-scale laboratory column experiments in which ethanol was used as an electron donor to create favorable conditions for the immobilization of selected trace metals (Zn and Cu) in groundwater. Microbial activity was explicitly simulated to capture the dynamic changes of the redox zonation within the column (i) in the early phase of the experiment (microbial lag) and (ii) in response to a significant decrease in the pH of the feed solution introduced after 188 days. The simulated redox dynamics agreed well with the observations after the pH-dependency of microbial growth was incorporated into the microbial model. The study showed that residual minerals may have buffered the pH for a period after the pH of the feed solution was decreased. Where the buffering capacity was exhausted, the pH decreased, leading to a successive downstream movement of the redox boundaries. The simulations reproduced the Zn immobilization within the sulfate-reducing zone as well as its partial remobilization after this zone moved further downstream. The immobilization of Cu within the denitrifying zone could also be well explained by incorporating malachite (Cu2(OH)2CO3) precipitation in the simulations.