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Electrokinetics is being applied in combination with common insituremediation technologies, e.g. permeable reactive barriers, bioremediation and in-situ chemical oxidation, to overcome experienced limitations in remediation of chlorinated ethenes in low-permeable subsurface soils. The purpose of this review is to evaluate state-of-theart for identification of major knowledge gaps to obtain robust and successful field-implementations. Some of the major knowledge gaps include the behavior and influence of induced transient changes in soil systems, transport velocities of chlorinated ethenes, and significance of site-specific parameters on transport velocities, e.g. heterogeneous soils and hydrogeochemistry. Furthermore, the various ways of reporting voltage distribution and transport rates complicate the comparison of transport velocities across studies. It was found, that for the combined EK-techniques, it is important to control the pH and redox changes caused by electrolysis for steady transport, uniform distribution of the electric field etc. Specifically for electrokinetically enhanced bioremediation, delivery of lactate and biodegrading bacteria is of the same order of magnitude. This review shows that enhancement of remediation technologies can be achieved by electrokinetics, but major knowledge gaps must be examined to mature EK as robust methods for successful remediation of chlorinated ethene contaminated sites. • EK-combined techniques overcome transport limitations experienced in low-permeable soils. • EK velocity of PCE and TCE is of comparable size to supplied reactants. • In EK-BIO, transport velocity of lactate and biodegrading bacteria are in the same order of magnitude. • General knowledge on the dependency of EK transport velocity on soil type is lacking. • Identified knowledge gaps must be filled in for robust and successful field-implementations. [ABSTRACT FROM AUTHOR]

There have been many studies on TCE degradation by synthesized nanoscale zero-valent iron (nZVIB) and commercial nanoscale zero-valent iron (nZVIH), but the effect of anaerobic corrosion on the dechlorination pathways and speciation distribution of chlorine is still unclear. Compared with nZVIH, nZVIB has a faster degradation rate of TCE and formation rate of Cl−(aq) (k SA, TCE = 3.67 ± 0.85 × 10−4 & 2.17 ± 0.13 × 10−4 L·h−1·m−2 and k obs, Cl − = 0.344 ± 0.027 & 0.166 ± 0.010 μM·h−1 for nZVIB & nZVIH, respectively). Based on the characterization of XRD, XPS and TEM during the anaerobic corrosion, the corrosion of nZVIB was dramatic under the dissolution-reprecipitation mechanism; but that of nZVIH was moderate and inward by maintaining the core-shell structure and shaping slightly rough and lumpy surface. Due to the different corrosion products (FeOOH for nZVIB and Fe 3 O 4 /γ-Fe 2 O 3 for nZVIH) and the catalysis of boron on the nZVIB surface, the preferential dechlorination pathway of TCE was not identical by hydrogenolysis (nZVIB) vs. reductive β-elimination (nZVIH). Meanwhile, the dechlorination pathway of nZVIH was similar to that of ZVI and the reductive pathway to acetylene bypassed the formation of more toxic VC. This study shows that the high reactivity of nZVIB results in rapid corrosion with the side effect of enhanced adsorption of VC while nZVIH has a stable core-shell structure and less sorbed chlorine, which provides a new sight to access the ecological risk of nZVI due to the overlooked effect of non-identical corrosion. Image 1 • Rapid corrosion of nZVIB with higher reactivity gains more adsorbed chlorine. • nZVIH with stable core-shell structure slowly corroded and sorbed less chlorine. • For nZVIB, TCE → cis -DCE → VC → ethylene via hydrogenolysis mainly. [ABSTRACT FROM AUTHOR]

S/mZVI is a promising material for groundwater remediation due to its excellent properties. However, the reactivity and electron selectivity toward target contaminant are critical. Thus, this study investigated the effect of complex groundwater chemistries (Milli-Q water, fresh groundwater and saline groundwater) on the reactivity of S/mZVI toward trichloroethylene (TCE), dechlorination pathway, hydrogen evolution kinetic, electron efficiency and aging behaviors. Results showed that sulfidation appreciably increased the reactivity and electron selectivity. The major degradation product of TCE dechlorination by S/mZVI was acetylene, which was consistent with TCE dechlorination by β-elimination. Moreover, reductive β-elimination was still the dominant dechlorination pathway for the application of S/mZVI in three groundwater conditions. However, the rates and the quantities of major products from TCE degradation varied significantly. S/mZVI in saline groundwater can maintain the reactivity towardTCE due to the protection of Fe0 by Fe 3 O 4 deposited on the surface. Thus, the higher TCE removal efficiency and less hydrogen accumulation resulted in the greatest electron efficiency (4.3–79.2%). Overall, S/mZVI was more effective for the application in saline groundwater. This study proved insight into the comprehensive evaluation and implications for the application of S/mZVI based technologies in saline contaminated groundwater. [Display omitted] • TCE dechlorination by S/mZVI and mZVI was investigated and compared in three media • TCE dechlorination by S/mZVI was mainly via β-elimination • Passive films with diverse structures and patterns were formed in three media • The highest electron efficiency (4.3–79.2%) was obtained in saline groundwater • S/mZVI-IRZ was more effective for the application in saline groundwater [ABSTRACT FROM AUTHOR]

1,4-dioxane is an emerging contaminant that was used as a corrosion inhibitor with chlorinated solvents. Metal-activated persulfate can degrade dioxane but reaction kinetics have typically been characterized by a rapid decrease during the first 30 min followed by either a slower decrease or no further change (i.e., plateau). Our objective was to identify the factors responsible for this plateau and then determine if slow-release formulations of sodium persulfate and Fe 0 could provide a more sustainable degradation treatment. We accomplished this by conducting batch experiments where Fe 0 -activated persulfate was used to treat dioxane. Treatment variables included the timing at which the dioxane was added to the Fe 0 -persulfate reaction (T = 0 and 30 min) and including various products of the Fe 0 -persulfate reaction at T = 0 min (Fe 2+ , Fe 3+ , and SO 4 2− ). Results showed that when dioxane was spiked into the reaction at 30 min, no degradation occurred; this is in stark contrast to the 60% decrease observed when added at T = 0 min. Adding Fe 2+ at the onset (T = 0 min) also severely halted the reaction and caused a plateau. This indicates that excess ferrous iron produced from the Fe 0 -persulfate reaction scavenges sulfate radicals and prevents further dioxane degradation. By limiting the release of Fe 0 in a slow-release wax formulation, degradation plateaus were avoided and 100% removal of dioxane observed. By using 14 C-labeled dioxane, we show that ∼40% of the dioxane carbon is mineralized within 6 d. These data support the use of slow-release persulfate and zerovalent iron to treat dioxane-contaminated water. [ABSTRACT FROM AUTHOR]

Many groundwater aquifers around the world are contaminated with trichloroethene (TCE), which can be harmful to human and ecosystem health. Permeable Reactive Barriers (PRB) are commonly used to remediate TCE-contaminated groundwaters especially when a point source is ill defined. Using biosolids from wastewater treatment plants as a PRB filling material can provide a source of carbon and nutrients for dechlorinating bacterial activity. However, under the anaerobic conditions of the PRB, methanogenesis can also occur which can adversely affect reductive dechlorination. We conducted bench scale experiments to evaluate the effect of biosolids on TCE reductive dechlorination and found that methanogenesis was significantly higher in the reactors amended with biosolids, but that reductive dechlorination did not decrease. Furthermore, the microbial communities in the biosolid-enhanced reactors were more abundant with obligate dechlorinators, such as Dehalobacter and Dehalogenimonas , than the reactors amended only with the dechlorinating culture. The biosolids enhanced the presence and abundance of methanogens and acetogens, which had a positive effect on maintaining an efficient dechlorinating microbial community and provided the necessary enzymes, cofactors, and electron donors. These results indicate that waste materials such as biosolids can be turned into a valuable resource for bioremediation of TCE and likely other contaminants. [Display omitted] • Application of alternative organic amendments for bioremediation of groundwater. • Sustainable and beneficial application of biosolids derived biomass. • Biologically active filling material for bioremediation of contaminated groundwater. • Biosolids derived amendment enhanced the presence and abundance of methanogens and acetogens. • Efficient maintenance of active dechlorinating microbial community with biosolids. [ABSTRACT FROM AUTHOR]

In this study, iron was deposited to titanium dioxide nanotube arrays (TNAs) by impregnation method to enhance its photocatalytic ability. The as-synthesized iron-modified TNAs (Fe-TNAs) was employed in a photoelectrochemical (PEC) system to degrade trichloroethylene (TCE). Results of AFE-SEM analysis showed that the iron nanoparticles (NPs) were successfully attached evenly to the nozzle of Fe-TNAs. Results of XRD analysis confirmed the findings of EDS and XPS, indicating the success of iron modification. The absorption wavelength of Fe-TNAs-27 mL red-shifts to 543 nm which corresponds to the band gap of 2.54 eV after iron modification. Mott–Schottky analysis yielded a donor density of 7.21 × 1020 and 2.30 × 1020/cm3 for TNAs and Fe-TNAs-27 mL, respectively. The photo-generated electrons had a lifetime (τ el) of 21.49 and 39.19 ms for TNAs and Fe-TNAs-27 mL, respectively, illustrating the reduce of recombination of photo-generated electron-hole pairs. process. PEC methods performed the most effective way to degrade TCE with a rate constant of 0.079 min−1 in Fe-TNAs PEC system. Mechanism of Fe-TNAs PEC system was proposed in detail. [Display omitted] • Fe-TNAs was synthesized successfully via impregnation deposition method. • Electron lifetime of TNAs was enhanced after iron modification. • TCE degradation was significantly enhanced by PEC system. • Mechanism of TCE degradation via Fe-TNAs in PEC system was investigated. [ABSTRACT FROM AUTHOR]

In 2009, we identified a TCE plume at an abandoned landfill that was located in a low permeable silty-clay aquifer. To treat the TCE, we manufactured slow-release potassium permanganate cylinders (oxidant candles) that had diameters of either 5.1 or 7.6 cm and were 91.4 cm long. In 2010, we compared two methods of candle installation by inserting equal masses of the oxidant candles (7.6-cm vs 5.1-cm dia). The 5.1-cm dia candles were inserted with direct-push rods while the 7.6-cm candles were housed in screens and lowered into 10 permanent wells. Since installation, the 7.6-cm oxidant candles have been refurbished approximately once per year by gently scraping off surface oxides. In 2012, we reported initial results; in this paper, we provide a 5-yr performance review since installation. Temporal sampling shows oxidant candles placed in wells have steadily reduced migrating TCE concentrations. Moreover, these candles still maintain an inner core of oxidant that has yet to contribute to the dissolution front and should provide several more years of service. Oxidant candles inserted by direct-push have stopped reducing TCE concentrations because a MnO 2 scale developed on the outside of the candles. To counteract oxide scaling, we fabricated a second generation of oxidant candles that contain sodium hexametaphosphate. Laboratory experiments (batch and flow-through) show that these second-generation permanganate candles have better release characteristics and are less prone to oxide scaling. This improvement should reduce the need to perform maintenance on candles placed in wells and provide greater longevity for candles inserted by direct-push. [ABSTRACT FROM AUTHOR]

Palladium-catalytic hydrodechlorination of trichloroethylene (TCE) by cathodic H 2 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 H 2 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/Al 2 O 3 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. [ABSTRACT FROM AUTHOR]

This work systematically compared the potential of a conventional fungal biofilter (BF) and a fungal biotrickling filter (BTF) for the abatement of a mixture of hydrophobic volatile organic compounds (VOCs). Candida subhashii was herein used for the first time, to the best of the author's knowledge, to remove n -hexane, trichloroethylene, toluene and α-pinene under aerobic conditions. C. subhashii immobilized on polyurethane foam supported steady state removal efficiencies of n -hexane, trichloroethylene, toluene and α-pinene of 25.4 ± 0.9%, 20.5 ± 1.0%, 19.6 ± 1.5% and 25.6 ± 2.8% in the BF, and 35.7 ± 0.9%, 24.0 ± 1.6%, 44.0 ± 1.7% and 26.2 ± 1.8% in the BTF, respectively, at relatively short gas residence times (30 s). The ability of C. subhashii to biodegrade n -hexane, TCE, toluene and α-pinene was confirmed in a batch test conducted in serum bottles, where a biodegradation pattern (toluene ≈ n -hexane > α-pinene > trichloroethylene) comparable to that recorded in the BF and BTF was recorded. [Display omitted] • A fungal BF and BTF treating hydrophobic VOCs were systematically compared. • subhashii supported an effective removal of VOCs at short EBRT of 30 s. • Fungal BTF supported a slightly higher VOC abatement performance than fungal BF. • The ability of C. subhashii to remove VOCs was also confirmed in batch assays. • A consistent biodegradation pattern was recorded: toluene ≈ n-hexane>α-pinene > TCE. [ABSTRACT FROM AUTHOR]

Field and laboratory tests were performed to evaluate the abiotic reaction of trichloroethene (TCE) in sedimentary rock matrices. Hydraulically conductive fractures, and the rock directly adjacent to the hydraulically conductive fractures, within a historically contaminated TCE bedrock aquifer were used as the basis for this study. These results were compared to previous work using rock that had not been exposed to TCE (Schaefer et al., 2013) to assess the impact of long-term TCE exposure on the abiotic dechlorination reaction, as the longevity of these reactions after long-term exposure to TCE was hitherto unknown. Results showed that potential abiotic TCE degradation products, including ethane, ethene, and acetylene, were present in the conductive fractures. Using minimally disturbed slices of rock core at and near the fracture faces, laboratory testing on the rocks confirmed that abiotic dechlorination reactions between the rock matrix and TCE were occurring. Abiotic daughter products measured in the laboratory under controlled conditions were consistent with those measured in the conductive fractures, except that propane also was observed as a daughter product. TCE degradation measured in the laboratory was well described by a first order rate constant through the 118-d study. Observed bulk first-order TCE degradation rate constants within the rock matrix were 1.3 × 10 −8 s −1 . These results clearly show that abiotic dechlorination of TCE is occurring within the rock matrix, despite decades of exposure to TCE. Furthermore, these observed rates of TCE dechlorination are expected to have a substantial impact on TCE migration and uptake/release from rock matrices. [ABSTRACT FROM AUTHOR]

Abstract: This study demonstrates differences in sorptive capacity of volatile organic compound (VOC) trichloroethylene (TCE) onto natural organic matter (NOM) coated and uncoated mineral surfaces above and below the NOM glass transition temperature. TCE sorption isotherms for dry NOM-mineral systems below the NOM glass transition temperature (Tg ) demonstrated sorption behavior characteristic of micropore filling, with sorption capacities reduced relative to uncoated mineral matrices. Such differences were not entirely associated with differences in surface areas of the coated and uncoated mineral matrices, but were likely associated with either a blockage of pore space available to the VOC or a kinetic limitation that does not allow the VOC access to the internal porosity of the model soil within the time periods of the experiment. TCE sorption in dry NOM-mineral matrices above the Tg , however, was described in terms of sorption within a more fluid, macromolecular dissolution medium that does not hinder access to mineral surfaces. Such observations have potential important implications for modeling the fate and transport of VOCs in soils and sediment systems. [Copyright &y& Elsevier]

Abstract: Biodegradation of trichloroethene (TCE) near a Dense Non Aqueous Phase Liquid (DNAPL) can enhance the dissolution rate of the DNAPL by increasing the concentration gradient at the DNAPL-water interface. Two-dimensional flow-through sand boxes containing a TCE DNAPL and inoculated with a TCE dechlorinating consortium were set up to measure this bio-enhanced dissolution under anaerobic conditions. The total mass of TCE and daughter products in the effluent of the biotic boxes was 3–6 fold larger than in the effluent of the abiotic box. However, the mass of daughter products only accounted for 19–55% of the total mass of chlorinated compounds in the effluent, suggesting that bio-enhanced dissolution factors were maximally 1.3–2.2. The enhanced dissolution most likely primarily resulted from variable DNAPL distribution rather than biodegradation. Specific dechlorination rates previously determined in a stirred liquid medium were used in a reactive transport model to identify the rate limiting factors. The model adequately simulated the overall TCE degradation when predicted resident microbial numbers approached observed values and indicated an enhancement factor for TCE dissolution of 1.01. The model shows that dechlorination of TCE in the 2D box was limited due to the short residence time and the self-inhibition of the TCE degradation. A parameter sensitivity analysis predicts that the bio-enhanced dissolution factor for this TCE source zone can only exceed a value of 2 if the TCE self-inhibition is drastically reduced (when a TCE tolerant dehalogenating community is present) or if the DNAPL is located in a low-permeable layer with a small Darcy velocity. [Copyright &y& Elsevier]

Abstract: Batch and column experiments were conducted with eucalyptus mulch and commercial compost to evaluate suitability of highly organic natural media to support anaerobic decomposition of trichloroethylene (TCE) in groundwater. Experimental data for TCE and its dechlorination byproducts were analyzed with Hydrus-1D model to estimate the partitioning and kinetic parameters for the sequential dechlorination reactions during TCE decomposition. The highly organic natural media allowed development of a bioactive zone capable of decomposing TCE under anaerobic conditions. The first order TCE biodecomposition reaction rates were 0.23 and 1.2d−1 in eucalyptus mulch and compost media, respectively. The retardation factors in the eucalyptus mulch and compost columns for TCE were 35 and 301, respectively. The results showed that natural organic soil amendments can effectively support the anaerobic bioactive zone for remediation of TCE contaminated groundwater. The natural organic media are effective environmentally sustainable materials for use in permeable reactive barriers. [Copyright &y& Elsevier]

Abstract: Past disposal of industrial solvents into unregulated landfills is a significant source of groundwater contamination. In 2009, we began investigating a former unregulated landfill with known trichloroethene (TCE) contamination. Our objective was to pinpoint the location of the plume and treat the TCE using in situ chemical oxidation (ISCO). We accomplished this by using electrical resistivity imaging (ERI) to survey the landfill and map the subsurface lithology. We then used the ERI survey maps to guide direct push groundwater sampling. A TCE plume (100–600μgL−1) was identified in a low permeable silty-clay aquifer (Kh =0.5md−1) that was within 6m of ground surface. To treat the TCE, we manufactured slow-release potassium permanganate candles (SRPCs) that were 91.4cm long and either 5.1cm or 7.6cm in dia. For comparison, we inserted equal masses of SRPCs (7.6-cm versus 5.1-cm dia) into the low permeable aquifer in staggered rows that intersected the TCE plume. The 5.1-cm dia candles were inserted using direct push rods while the 7.6-cm SRPCs were placed in 10 permanent wells. Pneumatic circulators that emitted small air bubbles were placed below the 7.6-cm SRPCs in the second year. Results 15months after installation showed significant TCE reductions in the 7.6-cm candle treatment zone (67–85%) and between 10% and 66% decrease in wells impacted by the direct push candles. These results support using slow-release permanganate candles as a means of treating chlorinated solvents in low permeable aquifers. [Copyright &y& Elsevier]

Abstract: Microbial reductive dechlorination of trichloroethene (TCE) and perchloroethene (PCE) in the vicinity of their dense non-aqueous phase liquid (DNAPL) has been shown to accelerate DNAPL dissolution. A three-layer diffusion-cell was developed to quantify this bio-enhanced dissolution and to measure the conditions near the DNAPL interface. The 12cm long diffusion-cell setup consists of a 5.5cm central porous layer (sand), a lower 3.5cm DNAPL layer and a top 3cm water layer. The water layer is frequently refreshed to remove chloroethenes at the upper boundary of the porous layer, while the DNAPL layer maintains the saturated chloroethene concentration at the lower boundary. Two abiotic and two biotic diffusion-cells with TCE DNAPL were tested. In the abiotic diffusion-cells, a linear steady state TCE concentration profile between the DNAPL and the water layer developed beyond 21d. In the biotic diffusion-cells, TCE was completely converted into cis-dichloroethene (cis-DCE) at 2.5cm distance of the DNAPL. Dechlorination was likely inhibited up to a distance of 1.5cm from the DNAPL, as in this part the TCE concentration exceeded the culture’s maximum tolerable concentration (2.5mM). The DNAPL dissolution fluxes were calculated from the TCE concentration gradient, measured at the interface of the DNAPL layer and the porous layer. Biotic fluxes were a factor 2.4 (standard deviation 0.2) larger than abiotic dissolution fluxes. This diffusion-cell setup can be used to study the factors affecting the bio-enhanced dissolution of DNAPL and to assess bioaugmentation, pH buffer addition and donor delivery strategies for source zones. [Copyright &y& Elsevier]

Batch and column experiments were performed to evaluate the transport, growth and dechlorination activity of Dehalococcoides sp. (DHC) during bioaugmentation for chlorinated ethenes. Batch experiments showed that the reductive dechlorination of trichloroethene (TCE), cis-1,2-dichloroethene (DCE), and vinyl chloride (VC), as well as growth of the DHC, were well described by the Monod kinetic model. The measured maximum utilization rate coefficients for TCE, DCE, and VC were 1.3×10−12, 5.2×10−13, and 1.4×10−12 mmol Cl− (cellh)−1, respectively. Results of the column experiments showed that dechlorination occurred throughout the length of the column, and that extractable DHC concentrations associated with the soil phase throughout the column were negligible relative to the aqueous phase concentrations. Dechlorination rates relative to aqueous DHC concentrations in the column were approximately 200-times greater than in the batch experiments. Additional batch experiments performed using column effluent water confirmed this result. Incorporation of these enhanced dechlorination kinetics in the transport model provided a reasonable prediction of the column data. Overall results of this study suggest that aqueous phase (as opposed to soil phase) DHC concentrations can be used to estimate dechlorination activity in saturated soils, and DHC dechlorination activity in porous media may be substantially greater than DHC dechlorination activity measured in batch experiments. [Copyright &y& Elsevier]

We report measurements of solubility limits for benzene, toluene, and TCE in systems that contain varying levels of biomass up to 0.13gmL−1 for TCE and 0.25gmL−1 for benzene and toluene. The solubility limit increased from 21 to 48mM when biomass (in the form of yeast) was added to aqueous batch systems containing benzene. The toluene solubility limit increased from 4.9 to greater than 20mM. For TCE, the solubility increased from 8mM to more than 1000mM. Solubility for TCE (trichloroethylene) was most heavily impacted by biomass levels, changing by two orders of magnitude as the microbial concentrations approach those in biofilms. [Copyright &y& Elsevier]

Reactive reductants of cement/Fe(II) systems in dechlorinating chlorinated hydrocarbons are unknown. This study initially evaluated reactivities of potential reactive agents of cement/Fe(II) systems such as hematite (α-Fe2O3), goethite (α-FeOOH), lepidocrocite (γ-FeOOH), akaganeite (β-FeOOH), ettringite (Ca6Al2(SO4)3(OH)12), Friedel’s salt (Ca4Al2Cl2(OH)12), and hydrocalumite (Ca2Al(OH)6(OH)·3H2O) in reductively dechlorinating trichloroethylene (TCE) in the presence of Fe(II). It was found that a hematite/Fe(II) system shows TCE degradation characteristics similar to those of cement/Fe(II) systems in terms of degradation kinetics, Fe(II) dose dependence, and final products distribution. It was therefore suspected that Fe(III)-containing phases of cement hydrates in cement/Fe(II) systems behaved similarly to the hematite. CaO, which was initially introduced as a pH buffer, was observed to participate in or catalyze the formation of reactive reductants in the hematite/Fe(II) system, because its addition enhanced the reactivities of hematite/Fe(II) systems. From the SEM (scanning electron microscope) and XRD (X-ray diffraction) analyses that were carried out on the solids from hematite/Fe(II) suspensions, it was discovered that a sulfate green rust with a hexagonal-plate structure was probably a reactive reductant for TCE. However, SEM analyses conducted on a cement/Fe(II) system showed that hexagonal-plate crystals, which were presumed to be sulfate green rusts, were much less abundant in the cement/Fe(II) than in the hematite/Fe(II) systems. It was not possible to identify any crystalline minerals in the cement/Fe(II) system by using XRD analysis, probably because of the complexity of the cement hydrates. These observations suggest that major reactive reductants of cement/Fe(II) systems may differ from those of hematite/Fe(II) systems. [Copyright &y& Elsevier]

Abstract: The variability of stable carbon isotope fractionation upon reductive dechlorination of tetra- and trichloroethene by several microbial strains was investigated to examine the uncertainties related to the in situ application of compound specific isotope analysis (CSIA) of chlorinated ethenes. Carbon isotope fractionation was investigated with a set of microorganisms representative for the currently known diversity of dehalorespirers: Dehalococcoides ethenogenes strain 195, Desulfitobacterium sp. strain Viet1, Desulfuromonas michiganensis and Geobacter lovleyi sp. strain SZ and compared to the previous reports using Sulfurospirillum spp. and Desulfitobacterium sp. strain PCE-S. Carbon isotope fractionation of tetrachloroethene (PCE) and trichlorethene (TCE) was highly variable ranging from the absence of significant fractionation to carbon isotope fractionation (εC) of 16.7 and 3.5–18.9 for PCE and TCE, respectively. Fractionation of both compounds by D. ethenogenes strain 195 (PCE: εC=6.0; TCE: εC=13.7) was similar to the literature data for mixed cultures containing Dehalococcoides spp. D. michiganensis (PCE: no significant fractionation; TCE: εC=3.5) and G. lovleyi sp. strain SZ (PCE no significant fractionation; TCE: εC=8.5) generated the lowest fractionation of all studied strains. Desulfitobacterium sp. strain Viet1 (PCE: εC=16.7) gave the highest enrichment factor for PCE. [Copyright &y& Elsevier]

In situ chemical oxidation (ISCO) using potassium permanganate (KMnO4) has been widely used as a practical approach for remediation of groundwater contaminated by chlorinated solvents like trichloroethylene. The most common applications are active flushing schemes, which target the destruction of some contaminant source by injecting concentrated permanganate ( solution into the subsurface over a short period of time. Despite many promising results, KMnO4 flushing is often frustrated by inefficiency associated with pore plugging by MnO2 and bypassing. Opportunities exist for the development of new ISCO systems based on KMnO4. The new scheme described in This paper uses controlled–release KMnO4 (CRP) as an active component in the well-based reactive barrier system. This scheme operates to control spreading of a dissolved contaminant plume. Prototype CRP was manufactured by dispersing fine KMnO4 granules in liquid crystal polymer resin matrix. Scanning electron microscope data verified the formation of micro-scale (ID=20–200μm) secondary capillary permeability through which is released by a reaction-diffusion process. Column and numerical simulation data indicated that the CRP could deliver in a controlled manner for several years without replenishment. A proof-of-concept flow-tank experiment and model simulations suggested that the CRP scheme could potentially be developed as a practical approach for in situ remediation of contaminated aquifers. This scheme may be suitable for remediation of sites where accessibility is limited or some low-concentration contaminant plume is extensive. Development of delivery systems that can facilitate lateral spreading and mixing of with the contaminant plume is warranted. [Copyright &y& Elsevier]

Abstract: Electrolytic dechlorination using a granular-graphite packed cathode is an alternative method for the remediation of chlorinated organic compounds. Its effectiveness under various conditions needs experimental investigation. Dechlorination of trichloroethylene (TCE) was conducted under various conditions in an electrolytic reactor with a platinum-gauze anode and a granular-graphite packed cathode. The higher the applied current, the more TCE was eliminated and more hydrogen and oxygen gasses were generated. Current efficiency decreased with a decrease in TCE concentration during each dechlorination experiment. But, the current efficiency concentration coefficient (CECC), which was defined as current efficiency divided by concentration, was a better indicator of current efficiency. The CECC was not significantly affected by current, but it varied with pH value. The pH effects were results of the involvement of electrolytes in the proton reduction and the electron transfer at the cathode. A lower pH value favored TCE dechlorination in potassium chloride, which is an electrolyte that was not involved in cathode reactions with protons and electrons. In ammonium acetate and potassium nitrate, which involve proton reduction and/or electron transfer, the pH value affected TCE dechlorination through proton limitation and electron competition. [Copyright &y& Elsevier]

Abstract: In this study, cellulose acetate (CA) supported Ni/Fe nanoparticles were prepared and the ability of these nanoparticles to remove trichloroethylene (TCE) from water was studied. The effects of TCE reduction by the nanoparticles and sorption by the CA support were accounted for separately in the model. CA supported post-coated Ni/Fe nanoparticles were used to investigate the effect of metal particle composition on the observed reduction rate constant. The results show that the metal mass normalized observed reduction rate constant was proportional to the Ni content in the post-coated Ni/Fe nanoparticles in the range of 0–14.3wt.%. This constant reached a maximum between 14.3 and 21.4wt.% and decreased with further increase in Ni content. CA supported co-reduced Ni/Fe bimetallic nanoparticles gave poorer performance compared to CA supported post-coated Ni/Fe bimetallic nanoparticles at the same Ni content in Ni/Fe nanoparticles. [Copyright &y& Elsevier]

The presence of organic immiscible liquids such as chlorinated solvents and fuels continues to be a primary source of risk for many hazardous waste sites. In this study, the standard miscible-displacement interfacial partitioning tracer test (IPTT) method was used for the first time to measure NAPL-water interfacial areas for a range of saturations. Multiple measurements were conducted for a natural quartz sand, with tetrachloroethene as the representative NAPL. The interfacial areas increased with decreasing water saturation. The measurements compared well to interfacial areas measured for the same sand with two alternative tracer methods, the mass-distribution batch method and the two-phase flow method. Measurements obtained with all three tracer-based methods exhibit a relatively large degree of variability. Thus, it is important to employ replication when using these methods. In contrast, interfacial areas measured with x-ray microtomography exhibit very small variability. However, the measured interfacial areas do not capture the contribution of surface-roughness to film-associated interfacial area. Each method has associated advantages and disadvantages, and it is important to be cognizant of them during their application. Image 1 • The IPTT method is used to measure NAPL-water interfacial area for different saturations. • The IPTT results are consistent with data obtained with other methods. • Variability of measured interfacial areas and potential sources are discussed. [ABSTRACT FROM AUTHOR]

Trichloroethylene (TCE), a widely used organic solvent, is a common environmental pollutant. Increasing evidence indicates that maternal TCE exposure is associated with congenital cardiac defects, but the underlining mechanisms remain largely unknown. In this study, we revealed that TCE exposure significantly induced heart defects and dysfunctions in zebrafish embryos. Heart tissues were dissected and subjected to high throughput sequencing and qPCR to identify differentially expressed miRNAs and mRNAs. The effects of miRNA were further verified by microinjection of antagomir or agomir. Reactive Oxygen Species (ROS) and cell proliferation were measured by using dichlorodihydrofluorescein diacetate (DCFH-DA) and EdU staining, respectively. Our results showed that 19 miRNAs were downregulated whereas 48 miRNAs were upregulated in the heart of zebrafish embryos. The downregulation of miR-133a and the upregulation of miR-182 were further validated. Moreover, we found that miR-133a agomir significantly alleviated the TCE-induced heart defects while miR-133a antagomir mimicked the toxic effect of TCE on heart development. Furthermore, miR-133a agomir significantly counteracted TCE-induced ROS production and excessive cell proliferation in the heart of zebrafish embryos. In conclusion, our results indicate that miR-133a mediates TCE-induced ROS generation, leading to excessive cell proliferation and heart defects. Image 1 • TCE induced extensive miRNA expression changes in the heart of zebrafish embryos. • miR-133a agomir counteracted TCE-induced heart defects. • TCE-induced oxidative stress enhanced cell proliferation. • miR-133a mediated TCE-induced oxidative stress and cell proliferation. [ABSTRACT FROM AUTHOR]