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Bioremediation through the injection of electron donors and bacterial cultures is effective at treating chlorinated solvent contamination. However, it has had limited application in low permeability zones where amendments cannot be delivered successfully. This field-scale study investigated the application of electrokinetics to enhance the delivery of lactate at a clay site contaminated with chlorinated solvents. Groundwater and soil samples were collected before, during and for 1 year after the 71-day field test and analyzed for a wide suite of chemical and biological parameters. Lactate was successfully delivered to all monitoring locations. Lactate emplacement resulted in the stimulation of bacterial populations, specifically within the phylum Firmicutes, which contains fermenters and strict anaerobes. This likely led to biodegradation, as the field trial resulted in significant decreases in both soil and aqueous phase chlorinated solvent concentrations. Contaminant decreases were also partially attributable to dilution, given evidence of some advective lactate flux. This research provides evidence that electrokinetically-enhanced bioremediation has potential as a treatment strategy for contaminated low permeability strata., (Copyright © 2021. Published by Elsevier Ltd.)

In situ chemical oxidation (ISCO) has demonstrated success in remediating soil and groundwater contaminated with chlorinated volatile organic compounds (CVOCs). However, its performance is often hindered in low-permeability or heterogeneous media due to an inability to effectively deliver the oxidants. This field-scale study investigated the novel approach of applying electrokinetics (EK) to enhance the delivery of persulfate in a low-permeability media and the ability of electrical resistance heating (ERH) to thermally activate the delivered persulfate. Results showed that 40% of the mass of total sulfur delivered was due to EK mechanisms, demonstrating that EK has the potential to enhance oxidant delivery. ERH may have activated some of the persulfate, but catalytic reactions with reduced forms of iron likely resulted in appreciable persulfate decomposition prior to ERH. Significant decreases (>80%) in the aqueous concentration of CVOCs was observed before and after ERH initiation, attributed to in situ transformation and physical processes (e.g., dilution). In situ transformation of CVOCs was assessed by compound-specific isotope analysis (CSIA) of 1,2-dichloroethane (1,2-DCA) samples collected after ERH application. Enrichment of 13 C was only measured in the well with appreciable persulfate breakthrough, confirming dechlorination of 1,2-DCA. Results from this field study demonstrate that EK and ERH can be used for persulfate delivery and activation for remediation of CVOCs in low-permeability media., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests:, (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Sulfidated nano zerovalent iron (S-nZVI), stabilized with carboxymethyl cellulose (CMC), was successfully synthesized on site and injected into the subsurface at a site contaminated with a broad range of chlorinated volatile organic compounds (cVOCs). Transport of CMC-S-nZVI to the monitoring wells, both downgradient and upgradient, resulted in a significant decrease in concentrations of aqueous-phase cVOCs. Short-term (0-17 days) total boron and chloride measurements indicated dilution and displacement in these wells. Importantly however, compound specific isotope analysis (CSIA), changes in concentrations of intermediates, and increase in ethene concentrations confirmed dechlorination of cVOCs. Dissolution from the DNAPL pool into the aqueous phase at the deepest levels (4.0-4.5 m bgs) was identifiable from the increased cVOCs concentrations during long-term monitoring. However, at the uppermost levels (∼1.5 m above the source zone) a contrasting trend was observed indicating successful dechlorination. Changes in cVOCs concentrations and CSIA data suggest both sequential hydrogenolysis as well as reductive β-elimination as the possible transformation mechanisms during the short-term abiotic and long-term biotic dechlorination. One of the most positive outcomes of this CMC-S-nZVI field treatment is the non-accumulation of lower chlorinated VOCs, particularly vinyl chloride. Post-treatment soil cores also revealed significant decreases in cVOCs concentrations throughout the targeted treatment zones. Results from this field study show that sulfidation is a suitable amendment for developing more efficient nZVI-based in situ remediation technologies., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Treatment of nano zerovalent iron (nZVI) with lower valent forms of sulfur compounds (sulfidation) has the potential to increase the selectivity and reactivity of nZVI with target contaminants and to decrease inter-particle aggregation for improving its mobility. These developments help in addressing some of the long-standing challenges associated with nZVI-based remediation treatments and are of great interest for in situ applications. Herein we report results from a field-scale project conducted at a contaminated site. Sulfidated nZVI (S-nZVI) was prepared on site by first synthesizing carboxymethyl cellulose (CMC) stabilized nZVI with sodium borohydride as a reductant and then sulfidating the nZVI suspension by adding sodium dithionite. Transmission electron microscopy (TEM) coupled with energy dispersive X-ray spectroscopy (EDS) of CMC-S-nZVI, from synthesis barrels, confirms the presence of both discrete spherical nZVI-like particles (∼90 nm) as well as larger irregular structures (∼500 nm) comprising of iron sulfides. This CMC-S-nZVI suspension was gravity fed into a sandy material and monitored through multiple multi-level monitoring wells. Samples collected from upstream and downstream wells suggest very good radial and vertical iron distribution. TEM-EDS analysis from the recovered well samples also indicates the presence of both nZVI-like particles as well as the larger flake-like structures, similar to those found in the injected CMC-S-nZVI suspension. This study shows that S-nZVI stabilized with CMC can be safely synthesized on site and is highly mobile and stable in the subsurface, demonstrating for the first time the field applicability of S-nZVI., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Back diffusion of contaminants from low permeability strata has inhibited site remediation and closure due to an inability to deliver remediants into these strata. This study demonstrates the potential of electrokinetics (EK) to significantly reduce back diffusion of chlorinated compounds from low permeability porous media. Experiments were conducted in a two-dimensional sandbox packed with vertical layers of coarse sand and silt contaminated with aqueous trichloroethene (TCE). Three experiments, each approximately 41 days in duration, compared EK-enhanced in situ chemical oxidation (EK-ISCO) to EK or ISCO alone. EK-ISCO successfully delivered the oxidant (permanganate, PM) throughout the silt cross-section while ISCO without EK resulted only in PM delivery to the edges of the silt layer fringes. EK-ISCO resulted in a 4.4-fold reduction in TCE concentrations in the coarse sand compared to a 3.5-fold reduction from ISCO alone. EK-ISCO with a 25 mA current was found to be more effective than with 300 mA current. Overall, this study suggests that electrokinetics coupled with an appropriate in situ remediation technique, such as ISCO, can enhance remediation of lower permeability strata and limit the extent of contaminant back diffusion., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Nano-scale zero valent iron (nZVI) has been used at a number of contaminated sites over the last decade. At most of these sites, significant decreases in contaminant concentrations have resulted from the application of nZVI. However, limited work has been completed investigating nZVI field-scale mobility. In this study, a field test was combined with numerical modeling to examine nZVI reactivity along with transport properties in variably saturated soils. The field test consisted of 142L of carboxymethyle cellulose (CMC) stabilized monometallic nZVI synthesized onsite and injected into a variably saturated zone. Periodic groundwater samples were collected from the injection well, as well as, from two monitoring wells to analyze for chlorinated solvents and other geochemistry indicators. This study showed that CMC stabilized monometallic nZVI was able to decrease tricholorethene (TCE) concentrations in groundwater by more than 99% from the historical TCE concentrations. A three dimensional, three phase, finite difference numerical simulator, (CompSim) was used to further investigate nZVI and polymer transport at the variably saturated site. The model was able to accurately predict the field observed head data without parameter fitting. In addition, the numerical simulator estimated the mass of nZVI delivered to the saturated and unsaturated zones and distinguished the nZVI phase (i.e. aqueous or attached). The simulation results showed that the injected slurry migrated radially outward from the injection well, and therefore nZVI transport was governed by injection velocity and viscosity of the injected solution. A suite of sensitivity analyses was performed to investigate the impact of different injection scenarios (e.g. different volume and injection rate) on nZVI migration. Simulation results showed that injection of a higher nZVI volume delivered more iron particles at a given distance; however, the travel distance was not proportional to the increase in volume. Moreover, simulation results showed that using a 1D transport equation to simulate nZVI migration in the subsurface may overestimate the travel distance. This is because the 1D transport equation assumes a constant velocity while pore water velocity radially decreases from the well during injection. This study suggests that on-site synthesized nZVI particles are mobile in the subsurface and that a numerical simulator can be a valuable tool for optimal design of nZVI field applications., (Copyright © 2015 Elsevier B.V. All rights reserved.)