No abstract

The residual buildup and treatment of dissolved contaminants in low permeable zones (LPZs) is a particularly challenging issue for injection-based remedial treatments. Our objective was to improve the sweeping efficiency of permanganate into LPZs to treat dissolved-phase TCE. This was accomplished by conducting transport experiments that quantified the ability of xanthan-MnO4(-) solutions to penetrate and cover (i.e., sweep) an LPZ that was surrounded by transmissive sands. By incorporating the non-Newtonian fluid xanthan with MnO4(-), penetration of MnO4(-) into the LPZ improved dramatically and sweeping efficiency reached 100% in fewer pore volumes. To quantify how xanthan improved TCE removal, we spiked the LPZ and surrounding sands with (14)C-lableled TCE and used a multistep flooding procedure that quantified the mass of (14)C-TCE oxidized and bypassed during treatment. Results showed that TCE mass removal was 1.4 times greater in experiments where xanthan was employed. Combining xanthan with MnO4(-) also reduced the mass of TCE in the LPZ that was potentially available for rebound. By coupling a multiple species reactive transport model with the Brinkman equation for non-Newtonian flow, the simulated amount of (14)C-TCE oxidized during transport matched experimental results. These observations support the use of xanthan as a means of enhancing MnO4(-) delivery into LPZs for the treatment of dissolved-phase TCE.

The development of slow-release chemical oxidants for sub-surface remediation is a relatively new technology. Our objective was to develop slow-release persulfate-paraffin candles to treat BTEX-contaminated groundwater. Laboratory-scale candles were prepared by heating and mixing Na(2)S(2)O(8) with paraffin in a 2.25 to 1 ratio (w/w), and then pouring the heated mixture into circular molds that were 2.38 cm long and either 0.71 or 1.27 cm in diameter. Activator candles were prepared with FeSO(4) or zerovalent iron (ZVI) and wax. By treating benzoic acid and BTEX compounds with slow-release persulfate and ZVI candles, we observed rapid transformation of all contaminants. By using (14)C-labeled benzoic acid and benzene, we also confirmed mineralization (conversion to CO2) upon exposure to the candles. As the candles aged and were repeatedly exposed to fresh solutions, contaminant transformation rates slowed and removal rates became more linear (zero-order); this change in transformation kinetics mimicked the observed dissolution rates of the candles. By stacking persulfate and ZVI candles on top of each other in a saturated sand tank (14×14×2.5 cm) and spatially sampling around the candles with time, the dissolution patterns of the candles and zone of influence were determined. Results showed that as the candles dissolved and persulfate and iron diffused out into the sand matrix, benzoic acid or benzene concentrations (C(o)=1 mM) decreased by >90% within 7 d. These results support the use of slow-release persulfate and ZVI candles as a means of treating BTEX compounds in contaminated groundwater.

To evaluate the efficacy of permanganate to remove RDX under field conditions, a pilot-scale demonstration was performed in a 9 m by 15 m well field.Groundwater was extracted from a center extraction well, spiked with permanganate and bromide, and fed into two injection wells. Groundwater was then sampled biweekly for 8 weeks in monitoring wells down gradient of the injection zone. Results showed that RDX concentrations decreased 73 to 80% following injection. Despite problems encountered in getting the permanganate uniformly distributed across the injection zone, pilot-scale results provide proof-of-concept that permanganate can be used for in-situ chemical oxidation of RDX-contaminated groundwater.