Bradley M. Patterson

The variability and intrinsic remediation of a BTEX plume in anaerobic sulphate-rich groundwater

Data from long-term groundwater sampling, limited coring, and associated studies are synthesised to assess the variability and intrinsic remediation/natural attenuation of a dissolved hydrocarbon plume in sulphate-rich anaerobic groundwater. Fine vertical scale (0.25- and 0.5-m depth intervals) and horizontal plume-scale (>400 m) characteristics of the plume were mapped over a 5-year period from 1991 to 1996. The plume of dissolved BTEX (benzene, toluene, ethylbenzene, xylene) and other organic compounds originated from leakage of gasoline from a subsurface fuel storage tank. The plume was up to 420 m long, less than 50 m wide and 3 m thick. In the first few years of monitoring, BTEX concentrations near the point of leakage were in approximate equilibrium with non-aqueous phase liquid (NAPL) gasoline. NAPL composition of core material and long-term trends in ratios of BTEX concentrations in groundwater indicated significant depletion (water washing, volatilisation and possibly biodegradation) of benzene from residual NAPL after 1992. Large fluctuations in BTEX concentrations in individual boreholes were shown to be largely attributable to seasonal groundwater flow variations. A combination of temporal and spatial groundwater quality data was required to adequately assess the stationarity of plumes, so as to allow inference of intrinsic remediation. Contoured concentration data for the period 1991 to 1996 indicated that plumes of toluene and o-xylene were, at best, only partially steady state (pseudo-steady state) due to seasonal groundwater flow changes. From this analysis, it was inferred that significant remediation by natural biodegradation was occurring for BTEX component plumes such as toluene and o-xylene, but provided no conclusive evidence of benzene biodegradation. Issues associated with field quantification of intrinsic remediation from groundwater sampling are highlighted. Preferential intrinsic biodegradation of selected organic compounds within the BTEX plume was shown to be occurring, in parallel with sulphate reduction and bicarbonate production. Ratios of average hydrocarbon concentrations to benzene for the period 1991 to 1992 were used to estimate degradation rates (half-lives) at various distances along the plume. The estimates varied with distance, the narrowest range being, for toluene, 110 to 260 days. These estimates were comparable to rates determined previously from an in situ tracer test and from plume-scale modelling.

Volatilisation and biodegradation during air sparging of dissolved BTEX-contaminated groundwater

Abstract The relative contributions of volatilisation and biodegradation are quantified for a field trial of air sparging for the remediation of groundwater contaminated with dissolved petroleum hydrocarbons. Groundwater in the unconfined sand aquifer at Kwinana in Western Australia was grossly contaminated by benzene, toluene, ethylbenzene, xylene (BTEX) and other dissolved organics from spills of gasoline. Multi-depth sampling bores, in situ oxygen sensors and neutron access tubes were used to determine changes in groundwater chemistry, oxygen utilisation and the fate of injected air in the aquifer. Oxygen utilisation was used to infer rates of biodegradation. A vadose zone soil vapour extraction system was used to quantify the volatile organic compounds (VOCs) that partitioned from the aqueous phase into the gas phase. Volatilisation was found to be the dominant mechanism for the removal of dissolved VOCs. This was indicated by the close correspondence between calculated masses and the timing of losses. The rate of removal was very rapid, with most organics removed within 3 days of the start of sparging. The rate of loss was also observed to follow the Henrys Law constant for the particular compounds. Estimating biodegradation of dissolved petroleum hydrocarbons was complicated by other sinks for dissolved O2, the presence of residual entrapped air in the aquifer and bulk movement of groundwater. However, biodegradation rates were at least an order of magnitude less than volatilisation rates over the period of greatest losses. It was also notable that dissolved VOCs were reduced over a larger volume of the aquifer than directly contacted by injected air. This may have been due to groundwater movement enhanced by stopping and starting sparging during the trial.

Fate of nine recycled water trace organic contaminants and metal(loid)s during managed aquifer recharge into a anaerobic aquifer: Column studies

Water quality changes associated with the passage of aerobic reverse osmosis (RO) treated recycled water through a deep anaerobic pyritic aquifer system was evaluated in sediment-filled laboratory columns as part of a managed aquifer recharge (MAR) strategy. The fate of nine recycled water trace organic compounds along with potential negative water quality changes such as the release of metal(loid)s were investigated in large-scale columns over a period of 12 months. The anaerobic geochemical conditions provided a suitable environment for denitrification, and rapid (half-life <1-25 days) degradation of the endocrine disrupting compounds (bisphenol A, 17beta-estradiol, 17alpha-ethynylestradiol), and iodipamide. However, pharmaceuticals (carbamazepine and oxazepam), disinfection by-products (N-nitrosodimethylamine, N-nitrosomorpholine) and iohexol did not degrade rapidly (half-life > 100 days). High retardation coefficients (R) determined for many of the trace organics (R 13 to 67) would increase aquifer residence time and be beneficial for many of the slow degrading compounds. However, for the trace organics with low R values (1.1-2.6) and slow degradation rates (half-life > 100 days), such as N-nitrosodimethylamine, N-nitrosomorpholine and iohexol, substantial biodegradation during aquifer passage may not occur and additional investigations are required. Only minor transient increases in some metal(loid) concentrations were observed, as a result of either pyrite oxidation, mineral dissolution or pH induced metal desorption, followed by metal re-sorption downgradient in the oxygen depleted zone.

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.

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.

Bioaugmentation of Atrazine and Fenamiphos Impacted Groundwater: Laboratory Evaluation

Abstract After the failure of a three-month pump-and-treat exercise to clean up an aquifer contaminated with the pesticides atrazine and fenamiphos, microcosm experiments using 14C-labeled compounds were undertaken to determine under what conditions bioremediation would be most effective, and to investigate the prospects for the use of bioaugmentation. The calculated half-lives for atrazine and fenamiphos mineralization to carbon dioxide in unamended, anaerobic aquifer material were 730 and 1,000 years, respectively. Oxygenation, coupled with bioaugmentation with enrichments of atrazine-mineralizing bacteria obtained from the contaminated site or an imported, atrazine-mineralizing pure strain, Pseudomonas sp. strain ADP, decreased the half-life of atrazine mineralization, to >20 days. Although strain ADP does not use atrazine as a source of carbon and energy, amendment of the aquifer material with citrate, which strain ADP uses as a source of carbon and energy, did not appreciably stimulate the mineralization rate of atrazine in the microcosms, suggesting that the aquifer contains enough natural organic carbon for atrazine mineralization. Aerobic enrichments of fenamiphos-degrading bacteria were prepared; however, oxygenation and bioaugmentation of aquifer material with these strains did not enhance mineralization of fenamiphos within the time constraints of the experiments. The shortest calculated half-life of fenamiphos mineralization in the microcosms was 6.8 years, which is exceedingly long compared with the half-life of fenamiphos in most surface soils.

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.

Combining coring and suction cup data to improve the monitoring of pesticides in sandy vadose zones: a field-release experiment

Soil coring and vertically and horizontally installed suction cup monitoring techniques were compared during a field release experiment conducted in an urban area of the Swan Coastal Plain of Western Australia. Sodium bromide and low concentrations of diazinon, chlorpyrifos, atrazine and fenamiphos were released into the vadose zone and rates of migration and mass loss with respect to a bromide tracer investigated. Only bromide and atrazine showed significant migration through the vadose zone. The relative half-life mass losses from the vadose zone of the pesticides ranged from 3 to >40 days. The use of soil coring complemented the use of vertically and horizontally installed suction cups for investigating relatively mobile non-volatile compounds, such as atrazine. Data from horizontally installed suction cups accounted for mass losses due to dilution and transport that could not be accounted for by coring, and enabled a better estimate of degradation and migration rates through the vadose zone. From core data alone, atrazine migration rates for the first 0.25 m were underestimated by more than 50% (0.0039 m day−1 compared to 0.013 m day−1), and removal rates (and inferred degradation rates) were overestimated by more than 100% (half-life of 14 days compared to a half-life of 40 days), compared with rates determined by using core data and horizontal suction cup data in combination. Migration rates may have been even further underestimated at greater depths.

Using polymer mats to biodegrade atrazine in groundwater: laboratory column experiments.

Large-scale column experiments were undertaken to evaluate the potential of in situ polymer mats to deliver oxygen into groundwater to induce biodegradation of the pesticides atrazine, terbutryn and fenamiphos contaminating groundwater in Perth, Western Australia. The polymer mats, composed of woven silicone (dimethylsiloxane) tubes and purged with air, were installed in 2-m-long flow-through soil columns. The polymer mats proved efficient in delivering dissolved oxygen to anaerobic groundwater. Dissolved oxygen concentrations increased from <0.2 mg l(-1) to approximately 4 mg l(-1). Degradation rates of atrazine in oxygenated groundwater were relatively high with a zero-order rate of 240-380 microg l(-1) or a first-order half-life of 0.35 days. Amendment with an additional carbon source showed no significant improvement in biodegradation rates, suggesting that organic carbon was not limiting biodegradation. Atrazine degradation rates estimated in the column experiments were similar to rates determined in laboratory culture experiments, using pure cultures of atrazine-mineralising bacteria. No significant degradation of terbutryn or fenamiphos was observed under the experimental conditions within the time frames of the study. Results from these experiments indicate that remediation of atrazine in a contaminated aquifer may be achievable by delivery of oxygen using an in situ polymer mat system.

Multiple lines of evidence to demonstrate vinyl chloride aerobic biodegradation in the vadose zone, and factors controlling rates

A field-based investigation was conducted at a contaminated site where the vadose zone was contaminated with a range of chlorinated hydrocarbons. The investigation consisted of groundwater and multilevel soil-gas monitoring of a range of contaminants and gases, along with isotope measurements and microbiology studies. The investigation provided multiple lines of evidence that demonstrated aerobic biodegradation of vinyl chloride (VC) was occurring in the vadose zone (i) above the on-site source zone, and (ii) above the downgradient off-site groundwater plume location. Data from both the on-site and off-site locations were consistent in showing substantially greater (an order of magnitude greater) rates of VC removal from the aerobic vadose zone compared to more recalcitrant contaminants trichloroethene (TCE) and tetrachloroethene (PCE). Soil gas VC isotope analysis showed substantial isotopic enrichment of VC (δ¹³C -5.2 to -10.9‰) compared to groundwater (δ¹³C -39.5‰) at the on-site location. Soil gas CO₂ isotope analysis at both locations showed that CO₂ was highly isotopically depleted (δ¹³C -28.8 to -33.3‰), compared to soil gas CO₂ data originating from natural sediment organic matter (δ¹³C= -14.7 to -21.3‰). The soil gas CO2 δ¹³C values were consistent with near-water table VC groundwater δ¹³C values (-36.8 to -39.5‰), suggesting CO₂ originating from aerobic biodegradation of VC. Bacteria that had functional genes (ethene monooxygenase (etnC) and epoxyalkane transferase (etnE)) involved in ethene metabolism and VC oxidation were more abundant at the source zone where oxygen co-existed with VC. The distribution of VC and oxygen vadose zone vapour plumes, together with long-term changes in soil gas CO₂ concentrations and temperature, provided information to elucidate the factors controlling aerobic biodegradation of VC in the vadose zone. Based on the overlapping VC and oxygen vadose zone vapour plumes, aerobic vapour biodegradation rates were independent of substrate (VC and/or oxygen) concentration. The high correlation (R=0.962 to 0.975) between CO₂ concentrations and temperature suggested that aerobic biodegradation of VC was controlled by bacterial activity that was regulated by the temperature within the vadose zone. When assessing a contaminated site for possible vapour intrusion into buildings, accounting for environmental conditions for aerobic biodegradation of VC in the vadose zone should improve the assessment of environmental risk of VC intrusion into buildings, enabling better identification and prioritisation of contaminated sites to be remediated.