Electrokinetic bioremediation of trichloroethylene and Cr/As co-contaminated soils with elevated sulfate.

Co-contaminants and complex subsurface conditions pose great challenges to site remediation. This study demonstrates the potential of electrokinetic bioremediation (EK-BIO) in treating co-contaminants of chlorinated solvents and heavy metals in low-permeability soils with elevated sulfate. EK-BIO columns were filled with field soils, and were fed by the electrolyte containing 20 mg/L trichloroethylene (TCE), 250 µM Cr(VI), 25 µM As(III), 10 mM lactate, and 10 mM sulfate. A dechlorinating consortium containing Dehalococcoides (Dhc) was injected several times during a 199-d treatment at ∼1 V/cm. Sulfate reduction, Cr/As immobilization, and complete TCE biodechlorination were observed sequentially. EK-BIO facilitated the delivery of lactate, Cr(VI)/As(III), and sulfate to the soils, creating favorable reductive conditions for contaminant removal. Supplementary batch experiments and metagenomic/transcriptomic analysis suggested that sulfate promoted the reductive immobilization of Cr(VI) by generating sulfide species, which subsequently enhanced TCE biodechlorination by alleviating Cr(VI) toxicity. The dechlorinating community displayed a high As(III) tolerance. Metagenomic binning analysis revealed the dechlorinating activity of Dhc and the potential synergistic effects from other bacteria in mitigating heavy metal toxicity. This study justified the feasibility of EK-BIO for co-contaminant treatment and provided mechanistic insights into EK-BIO treatment.

Real-time evaluation of natural organic matter deposition processes onto model environmental surfaces.

Natural organic matter (NOM) is ubiquitous in aqueous systems and dynamically partitions onto/from environmental surfaces. However, such interfacial processes have not been uniformly quantified in situ and in real time. In this work, adsorption and deposition processes of Suwannee River humic acid (SRHA) and Suwannee River fulvic acid (SRFA), as model NOM, were evaluated for a series of environmentally relevant interfaces. Real-time, interfacial phenomenon, including deposition, release, and adlayer viscoelastic properties, were quantified over a variety of water chemistries via quartz crystal microbalance with dissipation monitoring (QCM-D). Specifically, adlayer mass and deposition rates of SRHA and SRFA were evaluated as a function of NOM concentration/molecular weight (fraction), pH, electrolyte composition (type and concentration), and collector surface type. For these, the adsorption of SRHA onto aluminum oxide (Al2O3) and polystyrene (PS) surfaces follows the Langmuir isotherm model. Rapid, near-monolayer formation of SRHA/SRFA adlayers were observed on Al2O3, hydroxyapatite (HAP), and poly (l-lysine) (PLL) surfaces, but not on PS or iron oxide (Fe3O4) surfaces. The presence of divalent cations (Ca2+/Mg2+) at relatively low concentrations (0.5-5.0 mM) significantly enhances the mass of SRHA/SRFA deposited onto the surfaces of silica (SiO2), Al2O3, and PS. Viscoelastic properties of the adsorbed layer based on the ratio of dissipation to frequency revealed a relatively unique adlayer structure for SRHA in the presence of 5.0 mM Ca2+.

Hydrodechlorination of TCE in a circulated electrolytic column at high flow rate.

Palladium-catalytic hydrodechlorination of trichloroethylene (TCE) by cathodic H2 produced from water electrolysis has been tested. For a field in-well application, the flow rate is generally high. In this study, the performance of Pd-catalytic hydrodechlorination of TCE using cathodic H2 is evaluated under high flow rate (1 L min(-1)) in a circulated column system, as expected to occur in practice. An iron anode supports reduction conditions and it is used to enhance TCE hydrodechlorination. However, the precipitation occurs and high flow rate was evaluated to minimize its adverse effects on the process (electrode coverage, clogging, etc.). Under the conditions of 1 L min(-1) flow, 500 mA current, and 5 mg L(-1) initial TCE concentration, removal efficacy using iron anodes (96%) is significantly higher than by mixed metal oxide (MMO) anodes (66%). Two types of cathodes (MMO and copper foam) in the presence of Pd/Al2O3 catalyst under various currents (250, 125, and 62 mA) were used to evaluate the effect of cathode materials on TCE removal efficacy. The similar removal efficiencies were achieved for both cathodes, but more precipitation generated with copper foam cathode (based on the experiments done by authors). In addition to the well-known parameters such as current density, electrode materials, and initial TCE concentration, the high velocities of groundwater flow can have important implications, practically in relation to the flush out of precipitates. For potential field application, a cost-effective and sustainable in situ electrochemical process using a solar panel as power supply is being evaluated.

Efficient degradation of TCE in groundwater using Pd and electro-generated H2 and O2: a shift in pathway from hydrodechlorination to oxidation in the presence of ferrous ions.

Degradation of trichloroethylene (TCE) in simulated groundwater by Pd and electro-generated H(2) and O(2) is investigated in the absence and presence of Fe(II). In the absence of Fe(II), hydrodechlorination dominates TCE degradation, with accumulation of H(2)O(2) up to 17 mg/L. Under weak acidity, low concentrations of oxidizing •OH radicals are detected due to decomposition of H(2)O(2), slightly contributing to TCE degradation via oxidation. In the presence of Fe(II), the degradation efficiency of TCE at 396 µM improves to 94.9% within 80 min. The product distribution proves that the degradation pathway shifts from 79% hydrodechlorination in the absence of Fe(II) to 84% •OH oxidation in the presence of Fe(II). TCE degradation follows zeroth-order kinetics with rate constants increasing from 2.0 to 4.6 µM/min with increasing initial Fe(II) concentration from 0 to 27.3 mg/L at pH 4. A good correlation between TCE degradation rate constants and •OH generation rate constants confirms that •OH is the predominant reactive species for TCE oxidation. Presence of 10 mM Na(2)SO(4), NaCl, NaNO(3), NaHCO(3), K(2)SO(4), CaSO(4), and MgSO(4) does not significantly influence degradation, but sulfite and sulfide greatly enhance and slightly suppress degradation, respectively. A novel Pd-based electrochemical process is proposed for groundwater remediation.