Electrokinetically-enhanced emplacement of lactate in a chlorinated solvent contaminated clay site to promote bioremediation.

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.

Field test of electrokinetically-delivered thermally activated persulfate for remediation of chlorinated solvents in clay.

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 13C 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.

Sulfidated nano zerovalent iron (S-nZVI) for in situ treatment of chlorinated solvents: A field study.

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 ß-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.

Fate and transport of sulfidated nano zerovalent iron (S-nZVI): A field study.

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.

Low Permeability Zone Remediation via Oxidant Delivered by Electrokinetics and Activated by Electrical Resistance Heating: Proof of Concept.

This study proposes and proves (in concept) a novel approach of combining electrokinetic (EK)-assisted delivery of an oxidant, persulfate (PS), and low temperature electrical resistivity heating (ERH), to activate PS, to achieve remediation of contaminated, low permeability soil. This unique combination is able to overcome existing challenges in remediating low permeability materials, particularly associated with delivering remediants. A further benefit of the approach is the use of the same electrodes for both EK and ERH phases. Experiments were conducted in a laboratory-scale sand tank packed with silt and aqueous tetrachloroethene (PCE) and bracketed on each side by an electrode. EK first delivered unactivated PS throughout the silt. ERH then generated and sustained the target temperature to activate the PS. As a result, PCE concentrations decreased to below detection limit in the silt in a few weeks. Moreover, it was found that activating PS at ∼36 °C eliminated more PCE than activating it at >41 °C. It is expected this results from the reactive SO4•- radical being generated more slowly, which ensures more complete reaction with the contaminant. The novel application of EK-assisted PS delivery followed by low temperature ERH appears to be a viable strategy for low permeability contaminated soil remediation.

Electrokinetic-enhanced permanganate delivery and remediation of contaminated low permeability porous media.

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.

nZVI injection into variably saturated soils: Field and modeling study.

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.

Contributions of Abiotic and Biotic Dechlorination Following Carboxymethyl Cellulose Stabilized Nanoscale Zero Valent Iron Injection.

A pilot scale injection of nanoscale zerovalent iron (nZVI) stabilized with carboxymethyl cellulose (CMC) was performed at an active field site contaminated with a range of chlorinated volatile organic compounds (cVOC). The cVOC concentrations and microbial populations were monitored at the site before and after nZVI injection. The remedial injection successfully reduced parent compound concentrations on site. A period of abiotic degradation was followed by a period of enhanced biotic degradation. Results suggest that the nZVI/CMC injection created conditions that stimulated the native populations of organohalide-respiring microorganisms. The abundance of Dehalococcoides spp. immediately following the nZVI/CMC injection increased by 1 order of magnitude throughout the nZVI/CMC affected area relative to preinjection abundance. Distinctly higher cVOC degradation occurred as a result of the nZVI/CMC injection over a 3 week evaluation period when compared to control wells. This suggests that both abiotic and biotic degradation occurred following injection.