Juliana Gardenalli de Freitas

Heterogeneous hyporheic zone dechlorination of a TCE groundwater plume discharging to an urban river reach

The typically elevated natural attenuation capacity of riverbed-hyporheic zones is expected to decrease chlorinated hydrocarbon (CHC) groundwater plume discharges to river receptors through dechlorination reactions. The aim of this study was to assess physico-chemical processes controlling field-scale variation in riverbed-hyporheic zone dechlorination of a TCE groundwater plume discharge to an urban river reach. The 50-m long pool-riffle-glide reach of the River Tame in Birmingham (UK) studied is a heterogeneous high energy river environment. The shallow riverbed was instrumented with a detailed network of multilevel samplers. Freeze coring revealed a geologically heterogeneous and poorly sorted riverbed. A chlorine number reduction approach provided a quantitative indicator of CHC dechlorination. Three sub-reaches of contrasting behaviour were identified. Greatest dechlorination occurred in the riffle sub-reach that was characterised by hyporheic zone flows, moderate sulphate concentrations and pH, anaerobic conditions, low iron, but elevated manganese concentrations with evidence of sulphate reduction. Transient hyporheic zone flows allowing input to varying riverbed depths of organic matter are anticipated to be a key control. The glide sub-reach displayed negligible dechlorination attributed to the predominant groundwater baseflow discharge condition, absence of hyporheic zone, transition to more oxic conditions and elevated sulphate concentrations expected to locally inhibit dechlorination. The tail-of-pool-riffle sub-reach exhibited patchy dechlorination that was attributed to sub-reach complexities including significant flow bypass of a low permeability, high organic matter, silty unit of high dechlorination potential. A process-based conceptual model of reach-scale dechlorination variability was developed. Key findings of practitioner relevance were: riverbed-hyporheic zone CHC dechlorination may provide only a partial, somewhat patchy barrier to CHC groundwater plume discharges to a surface water receptor; and, monitoring requirements to assess the variability in CHC attenuation within a reach are expected to be onerous. Further research on transient hyporheic zone dechlorination is recommended.

Denatured ethanol release into gasoline residuals, Part 1: source behaviour.

With the increasing use of ethanol in fuels, it is important to evaluate its fate when released into the environment. While ethanol is less toxic than other organic compounds present in fuels, one of the concerns is the impact ethanol might have on the fate of gasoline hydrocarbons in groundwater. One possible concern is the spill of denatured ethanol (E95: ethanol containing 5% denaturants, usually hydrocarbons) in sites with pre-existing gasoline contamination. In that scenario, ethanol is expected to increase the mobility of the NAPL phase by acting as a cosolvent and decreasing interfacial tension. To evaluate the E95 behaviour and its impacts on pre-existing gasoline, a field test was performed at the CFB-Borden aquifer. Initially gasoline contamination was created releasing 200 L of E10 (gasoline with 10% ethanol) into the unsaturated zone. One year later, 184 L of E95 was released on top of the gasoline contamination. The site was monitored using soil cores, multilevel wells and one glass access tube. At the end of the test, the source zone was excavated and the compounds remaining were quantified. E95 ethanol accumulated and remained within the capillary fringe and unsaturated zone for more than 200 days, despite ~1m oscillations in the water table. The gasoline mobility increased and it was redistributed in the source zone. Gasoline NAPL saturations in the soil increased two fold in the source zone. However, water table oscillations caused a separation between the NAPL and ethanol: NAPL was smeared and remained in deeper positions while ethanol moved upwards following the water table rise. Similarly, the E95 denaturants that initially were within the ethanol-rich phase became separated from ethanol after the water table oscillation, remaining below the ethanol rich zone. The separation between ethanol and hydrocarbons in the source after water table oscillation indicates that ethanols impact on hydrocarbon residuals is likely limited to early times.

Denatured ethanol release into gasoline residuals, Part 2: fate and transport.

When denatured ethanol (E95) is spilled in a site with previous gasoline contamination, it modifies the source distribution (Part 1). But it can also impact the transport and fate of hydrocarbons in the groundwater. Ethanol could cause an increase in dissolved concentrations and more persistent plumes due to cosolvency and decreased hydrocarbon biodegradation rates. To investigate these possibilities, two controlled releases were performed: first of E10 (gasoline with 10% ethanol) and one year later of E95 on top of the gasoline. Groundwater concentrations were monitored above and below the water table in multilevel wells. Soil cores and vapor samples were also collected over a period of approximately 400 days. Surprisingly, ethanol transport was very limited; at wells located 2.3m downgradient from the mid-point of the release trench, the maximum concentration measured was around 2400 mg/L. After 392 days, only 3% of the ethanol released migrated past 2.3 m, and no ethanol remained in the source. The processes that caused ethanol loss were likely volatilization, aerobic biodegradation in the unsaturated zone, and anaerobic biodegradation. Evidence that biodegradation was significant in the source zone includes increased CO2 concentrations in the vapor and the presence of biodegradation products (acetate concentrations up to 2300 mg/L). The position of the dissolved hydrocarbon plumes was slightly shifted, but the concentrations and mass flux remained within the same range as before the spill, indicating that cosolvency was not significant. Hydrocarbons in the groundwater were significantly biodegraded, with more than 63% of the mass being removed in 7.5m, even when ethanol was present in the groundwater. The impacts of ethanol on the hydrocarbon transport and fate were minimal, largely due to the separation of ethanol and hydrocarbons in the source (Part 1).