Greg B. Davis

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.

The role of microbial populations in the containment of aromatic hydrocarbons in the subsurface.

A survey of soil gases associated with gasoline stations on theSwan Coastal Plain of Western Australia has shown that 20% leak detectable amountsof petroleum. The fates of volatile hydrocarbons in the vadose zone at one contaminatedsite, and dissolved hydrocarbons in groundwater at another site were followed in anumber of studies which are herein reviewed. Geochemical evidence from a plume ofhydrocarbon-contaminated groundwater has shown that sulfate reduction rapidly developedas the terminal electron accepting process. Toluene degradation but not benzene degradationwas linked to sulfate reduction. The sulfate-reducing bacteria isolated from the plumerepresented a new species, Desulfosporosinus meridiei. Strains of the speciesdo not mineralise 14C-toluene in pure culture. The addition of large numbersof cells and sulfate to microcosms did stimulate toluene mineralisation but not benzenemineralisation. Attempts to follow populations of sulfate-reducing bacteria byphospholipid signatures, or Desulfosporosinus meridiei by FISH in the plume were unsuccessful, but fluorescently-labeled polyclonal antibodies were successfully used.In the vadose zone at a different site, volatile hydrocarbons were consumed in thetop 0.5 m of the soil profile. The fastest measured rate of mineralisation of 14C-benzenein soils collected from the most active zone (6.5 mg kg-1 day-1) could accountfor the majority of the flux of hydrocarbon vapour towards the surface. The studiesconcluded that intrinsic remediation by subsurface microbial populations in groundwateron the Swan Coastal Plain can control transport of aromatic hydrocarbon contamination,except for the transport of benzene in groundwater. In the vadose zone, intrinsicremediation by the microbial populations in the soil profile can contain the transportof aromatic hydrocarbons, provided the physical transport of gases, inparticular oxygen from the atmosphere, is not impeded by structures.

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.

Modeling of DNAPL-Dissolution, rate-limited sorption and biodegradation reactions in groundwater systems

This article presents an approach for modeling the dissolution process of single component dense non-aqueous phase liquids (DNAPL), such as tetrachloroethene and trichloroethene, in a biologically reactive porous medium. In the proposed approach, the overall transport processes are conceptualized as three distinct reactions. Firstly, the dissolution (or dissolving) process of a residual DNAPL source zone is conceptualized as a mass-transfer limited reaction. Secondly, the contaminants dissolved from the DNAPL source are allowed to partition between sediment and water phases through a rate-limited sorption reaction. Finally, the contaminants in the solid and liquid phases are allowed to degrade by a set of kinetic-limited biological reactions. Although all of these three reaction processes have been researched in the past, little progress has been made towards understanding the combined effects of these processes. This work provides a rigorous mathematical model for describing the coupled effects of these three fundamental reactive transport mechanisms. The model equations are then solved using the general-purpose reactive transport code RT3D (Clement, 1997).

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.

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.

Dissolution of multi-component LNAPL gasolines: The effects of weathering and composition

The composition of light non-aqueous phase liquid (LNAPL) gasoline and other petroleum products changes profoundly over their life once released into aquifers. However limited attention has been given to how such changes affect key parameters such as the activity coefficients which control partitioning of components of petroleum fuel into groundwater and are used to predict long-term risk from fuel releases. Laboratory experiments were conducted on a range of fresh, weathered and synthetic gasoline mixtures designed to mimic the expected changes in composition in an aquifer. Weathered gasoline created under controlled evaporation and water washing, and naturally weathered gasoline, were investigated. Equilibrium concentrations in water and molar fractions in the gasoline mixtures were compared with equilibrium concentrations predicted by Raoults law assuming ideal behaviour of the solutions. The experiments carried out allowed the relative sensitivity of the activity coefficients of key risk drivers such as benzene, toluene, ethylbenzene and xylene (BTEX) compounds to be quantified with respect to the presence of other types of compounds and where the source LNAPL had undergone different types of weathering. Results differed for the mixtures examined but in some cases higher than predicted dissolved equilibrium concentrations showed non-ideal behaviour for toluene, benzene and xylenes. Comparison of the activity coefficients showed that the naturally weathered gasoline and a 50% evaporated unleaded gasoline present a similar range of values varying between 1.0 and 1.2, suggesting close to ideal partitioning between the LNAPL and water. The fresh and water-washed gasoline had higher values for the activity coefficient, from 1.2 to 1.4, indicating non-ideal partitioning. Results from synthetic mixtures demonstrated that these differences could be due to the different molar fractions of the nC5 and nC6 aliphatic hydrocarbons acting on the molecular interactions, while differences in molar volumes seemed to have less of an influence on ideality.

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.