In-situ Chemical Reduction Research Articles

Microwave-enhanced thermal removal of organochlorine pesticide (chlordecone) from contaminated soils

Soil contamination with chlordecone, an organochlorine pesticide, is causing serious health problems, affecting crop production and local livestock valorization in the French West Indies. In-situ chemical reduction (ISCR) processes for soil remediation have shown promise but need improvement in terms of time, cost and effective treatment, particularly for andosol soil types. Our study shows that a 10-min microwave treatment significantly reduces chlordecone concentrations (50–90%) in contaminated andosol and nitisol soils. Dry andosol soils show the highest removal yields and reach a higher final temperature (350 °C). Microwave treatment is in all cases more effective or at least as effective as 60 min of conventional heating at a target temperature of 200 °C. The thermal response of andosol and nitisol to microwave exposure is different, as the former is likely to undergo thermal runaway, reaching high temperatures in a short time, resulting in highly efficient thermal removal of chlordecone. These results encourage further scale-up, particularly for the treatment of andosol soils due to their strong microwave response.

Vitamin C aqueous solution assisted in-situ reduction of graphene oxide in flexible thermoplastic polyurethane

Graphene oxide (GO) is usually used as a precursor of reduced GO (rGO) in polymer matrices for improving their properties. However, reduction degree of GO in conventional melt mixing is usually limited. In this work, thermoplastic polyurethane (TPU)/rGO nanocomposite is prepared via water-assisted mixing extrusion with vitamin C (VC) aqueous solution injection. In situ chemical reduction (ISCR) by the VC and in situ thermal reduction (ISTR) by the thermal energy from both extruder barrel heating and screw shear are simultaneously enhanced for the GO, which are indicated by disappearances of O–H peak at the FTIR spectrum and O–C=O peak at the XPS spectrum of the rGO powder extracted from the prepared nanocomposite. Thus high reduction degree of the GO is obtained (with C/O atom ratio of 9.83 for the extracted rGO powder). This is attributed to the following two aspects: (1) TPU chains plasticized by water can better intercalate into GO galleries, thus enhancing the stripping of oxygen-containing groups from GO surface and the ISTR of the GO; (2) the screw shear action helps to disperse the VC of the injected VC aqueous solution in the TPU melt and increase the contact between the VC and GO, therefore enhancing the ISCR of the GO. The prepared TPU/GO nanocomposite exhibits enhanced dielectric permittivity.

Microbial Transformation of Chlordecone and Two Transformation Products Formed During in situ Chemical Reduction.

Chlordecone (CLD) is a very persistent synthetic organochlorine pesticide found in the French West Indies. Recently published work has demonstrated the potential of zero-valent iron to dechlorinate CLD by in situ chemical reduction (ISCR) in soils under water-saturated conditions, forming mono- to penta-dechlorinated CLD transformation products. These transformation products are more mobile than CLD and less toxic; however, nothing is known about their further degradation, although increasing evidence of CLD biodegradation by bacteria is being found. The present study began with the enrichment from wastewater sludge of a CLD-transforming community which was then inoculated into fresh media in the presence of either CLD or two of the main ISCR transformation products, 10-monohydroCLD (-1Cl-CLD) and tri-hydroCLD (-3Cl-CLD). Carried out in triplicate batches and incubated at 38°C under anoxic conditions and in the dark, the cultures were sampled regularly during 3 months and analyzed for CLD, -1Cl-CLD, -3Cl-CLD, and possible transformation products by gas chromatography coupled to mass spectrometry. All batches showed a decrease in the amended substrates (CLD or hydroCLD). CLD degradation occurred with concomitant formation of a nine-carbon compound (pentachloroindene) and two sulfur-containing transformation products (chlordecthiol, CLD-SH; methyl chlordecsulfide, CLD-SCH3), demonstrating competing transformation pathways. In contrast, -1Cl-CLD and -3Cl-CLD only underwent a sequential reductive sulfidation/S-methylation process resulting in -1Cl-CLD-SH and -1Cl-CLD-SCH3 on the one hand, and -3Cl-CLD-SH, -3Cl-CLD-SCH3 on the other hand. Some sulfur-containing transformation products have been reported previously with single bacterial strains, but never in the presence of a complex microbial community. At the end of the experiment, bacterial and archaeal populations were investigated by 16S rRNA gene amplicon sequencing. The observed diversity was mostly similar in the CLD and -1Cl-CLD conditions to the inoculum with a dominant archaea genus, Methanobacterium, and four OTU affiliated to bacteria, identified at the family (Spirochaetaceae) or genus level (Desulfovibrio, Aminobacterium, and Soehngenia). On the other hand, in the -3Cl-CLD condition, although the same OTU were found, Clostridium sensu stricto 7, Candidatus Cloacimonas, and Proteiniphilum were also present at > 2% sequences. Presence of methanogens and sulfate-reducing bacteria could contribute to sulfidation and S-methylation biotransformations. Overall, these results contribute to increasing our knowledge on the biodegradability of CLD and its transformation products, helping to progress toward effective remediation solutions.

Laboratory study on the mobility of chlordecone and seven of its transformation products formed by chemical reduction in nitisol lysimeters of a banana plantation in Martinique (French Caribbean)

The contamination by chlordecone (CLD) of soils and water in the French Caribbean (FC) has major environmental and human health impacts. In Situ Chemical Reduction (ISCR) is a promising method to degrade CLD but it generates transformation products (TPs). Here, the fate and transport of CLD and its TPs have been studied using three lysimeters, 65–70 cm-long and 20 cm in diameter, collected from a CLD contaminated nitisol in the FC. A simulated ISCR remediation process (Sim-ISCR) was applied to the top 15 cm layer. An equivalent of 9.8 years of effective rainfall was simulated during the 451 days of the experiments. CLD and seven TPs were analyzed in soils, soil pore waters and outflow waters of the lysimeters before and after the Sim-ISCR. CLD concentration in the soil pore waters increases with depth. In the Sim-ISCR treated layer, the CLD contamination was lowered by 41 to 47% in the soil and by 48 to 73% in the soil pore water. In the lysimeters outflow, however, the CLD concentration was lowered by only 13 to 25%, the flux of CLD from the untreated 50–55 cm of the profile concealing much of the beneficial impact of treating the top 15 cm. Remediating by ISCR the topsoil only will therefore not be sufficient for preventing further CLD contamination of the underlying groundwater. Sim-ISCR generated 5-hydroCLD in soils and waters and, to a much lesser extent, a trihydroCLD, a tetrahydroCLD, a pentahydroCLD and a heptahydroCLD. 5-hydroCLD is more mobile than CLD, but it still interacts strongly with the soil. The 5-hydroCLD values measured in the outflow were up to a factor of 4.4 lower than in the treated soil pore waters, indicating some natural attenuation.

Assessment of 2,4-Dinitroanisole Transformation Using Compound-Specific Isotope Analysis after In Situ Chemical Reduction of Iron Oxides.

Ferrous iron-bearing minerals are important reductants in the contaminated subsurface, but their availability for the reduction of anthropogenic pollutants is often limited by competition with other electron acceptors including microorganisms and poor accessibility to Fe(II) in complex hydrogeologic settings. The supply of external electron donors through in situ chemical reduction (ISCR) has been proposed as one remediation approach, but the quantification of pollutant transformation is complicated by the perturbations introduced to the subsurface by ISCR. Here, we evaluate the application of compound specific isotope analysis (CSIA) for monitoring the reduction of 2,4-dinitroanisole (DNAN), a component of insensitive munitions formulations, by mineral-bound Fe(II) generated through ISCR of subsurface material from two field sites. Electron balances from laboratory experiments in batch and column reactors showed that 3.6% to 11% of the total Fe in the sediments was available for the reduction of DNAN and its partially reduced intermediates after dithionite treatment. The extent of DNAN reduction was successfully quantified from its N isotope fractionation measured in the column effluent based on the derivation of a N isotope enrichment factor, εN, derived from a comprehensive series of isotope fractionation experiments with numerous Fe(II)-bearing minerals as well as dithionite-reduced subsurface materials. Our observations illustrate the utility of CSIA as a robust approach to evaluate the success of in situ remediation through abiotic contaminant reduction.

Carbon isotope forensics for methane source identification

AbstractMethane (CH4) in ecosystems originates from ancient petroleum formed deep within the earth and/or via microbial fermentation of organic carbon and subsequent reduction of carbon dioxide (CO2). Given the complexity of different ecosystems, origins of CH4 present can be difficult to determine. This issue was realized in a situation where an antimethanogenic in situ chemical reduction (ISCR) remedial amendment containing organic carbon plus zero‐valent iron was applied to treat chlorinated solvents in groundwater at a former dry cleaner facility. The technology rapidly and effectively reduced the concentration of tetrachloroethene in groundwater thus meeting project goals without the stoichiometric accumulation of catabolites such as trichloroethene (TCE), cis‐1,2‐dichloroethene, or vinyl chloride and without excessive methanogenesis (e.g., <2 mg/L) in the treated area. However, approximately 9 months after treatment, increased levels of CH4 (from 5 to 10 mg/L) were observed downgradient from the treated area. The applied remedial amendment contained approximately 60% (weight basis) fermentation organic carbon and was therefore a potential source of this CH4. However, there was <500 mg/L total organic carbon in groundwater emanating from the upgradient treatment area which was unlikely sufficient to produce that much CH4. Moreover, the soil gas also contained benzene, toluene, ethylbenzene, and xylenes and other gasoline constituents. These data suggested that the presence of three gasoline/diesel underground storage tanks that were previously closed in place with no active remediation performed could be the source of elevated CH4. Thirdly, there were sewer lines, utilities, multiple gasoline stations, and industrial activities in the immediate area. With an initial assumption that CH4 source(s) could include the ISCR amendment over stimulation of production, gasoline sourced CH4 from nearby leaking lines, or sewage from local fractured pipes, carbon isotope analyses—radiocarbon (Δ14C) and stable carbon (δ13C)—were coupled with CH4 and CO2 concentration data from groundwater samples to determine the origin of respired carbon. The δ13C range for carbon sources respired in the process would be approximately −26.5‰ to −33.0‰ for the ISCR amendment and total petroleum hydrocarbons (TPH) residuals, respectively. Δ14C is approximately 0‰ and −999‰ for the ISCR amendment (young carbon) and TPH (old carbon), respectively. The isotopic signature of respired gasses confirmed that elevated CH4 downgradient of the treated area originated primarily from sewer gasses (or fermentation of liquids released from sewer lines). This study provides an overview of the capability to apply carbon isotope geochemistry to confirmation of remedial protocols and sources of anthropogenic carbon pools that conclusively identify the origin of CH4 in a complex ecosystem undergoing a remedial action.

Physico-chemical and agronomic results of soil remediation by In Situ Chemical Reduction applied to a chlordecone-contaminated nitisol at plot scale in a French Caribbean banana plantation.

The In Situ Chemical Reduction (ISCR) process was tested in a nitisol in a French Caribbean banana plantation using five different soil amendments. The addition of 2.8% or 4.0% of Zero Valent Iron (ZVI; dw/dw, 2 different trial plots) in the 0-40-cm soil layer lowered the initial chlordecone (CLD) concentration by up to 74% or 69% in 37days or 94days, with 75% of the decrease achieved after only 21 or 24days of treatment depending on the trial plot. The addition of commercially available Daramend® was also tested by applying the 6% dose (dw/dw) recommended by the manufacturer and using either the regular alfalfa-based product or a bagasse-based product specifically formulated for the study. Both significantly lowered CLD concentrations, but to a lesser extent than with the ZVI-only amendment. A bagasse-ZVI mixture prepared on site produced results slightly better than the two Daramend®. The percentage decreases in CLD concentrations were correlated with the negative redox potentials achieved. In all the trial plots, dechlorinated transformation products appeared in the soil and soil water as the CLD concentrations decreased, with H atoms replacing up to 4 and 7 of the 10 Cl atoms, respectively. None of these degradation products appeared to accumulate in the soil or soil water during the treatment. Instead, the reverse occurred, with an overall downward trend in their concentrations over time. The effects of ISCR treatment on agronomic and human health-related parameters were measured in three different crops. The radishes produced with some treatments were visually of lower quality or smaller in size than those grown in the control plots. Lower yields were observed for the cucumbers and sweet potatoes grown after applying the bagasse-based amendments. Mortality among cucumber seedlings was observed after treatment with ZVI only. Simple operational solutions should suffice to remedy these negative agronomic effects. As regards human health-related effects, the CLD concentrations in radishes grown with three of the amendments were significantly lower than in the two control plots and well below the maximum residue level (MRL), which was substantially exceeded in the radishes grown on untreated soil. For cucumbers, the treatments with regular Daramend® and with a local bagasse-ZVI mixture produced fruits with CLD below the MRL and also below the concentrations in one of the two control plots. As for the sweet potatoes, adding a bagasse-ZVI mixture had a significant positive effect by decreasing contamination below the levels in the two control plots and below the MRL.

FIELD APPLICATION OF A REAGENT FOR IN SITU CHEMICAL REDUCTION AND ENHANCED REDUCTIVE DICHLORINATION TREATMENT OF AN AQUIFER CONTAMINATED WITH TETRACHLOROETHYLENE (PCE), TRICHLOROETHYLENE, 1,1-DICHLOROETHYLENE, DICHLOROPROPANE AND 1,1,2,2-TETRACHLOROETHANE (R-130)

Groundwater at an abandoned industrial area near Bergamo, Italy, was historically contaminated by tetrachloroethylene (PCE) (>100 g/L) and, to a lesser extent, by trichlorethylene (TCE), dichloropropane (DP) and 1,1,2,2-tetrachloroethane (R-130). A liquid reagent (EHC Liquid) was selected for remediation of groundwater at the site. The reagent is provided in two parts: EHC Liquid Mix (a soluble organo-iron salt), and ELS Microemulsion (a lecithin-based carbon substrate), and is designed to promote both in situ chemical reduction (ISCR) and enhanced reductive dechlorination (ERD) to destroy chlorinated organic compounds. The two components are mixed with water and injected into the subsurface. Once in groundwater, EHC Liquid rapidly generates highly reduced conditions, favouring both biotic and abiotic dechlorination reactions. Less than 6 months after the injection of EHC Liquid in the main source area, concentrations of the target contaminants had reached the site-specific remediation target values (CSC Legislative Decree 152/06) in the main monitoring piezometers present in the area, thus demonstrating the effective establishment of enhanced biotic and abiotic reducing conditions and degradation of the target compounds.

Transport of chlordecone and two of its derivatives through a saturated nitisol column (Martinique, France)

Soils, surface and groundwater in Martinique (French West Indies) are contaminated by chlordecone (CLD), a highly persistent organochlorine pesticide. In Situ Chemical Reduction (ISCR) using zero valent iron has been tested as a remediation technique to lower CLD levels in soils but it produces derivatives whose fate in environment may differ from the parent molecule. Here, the transfer of CLD and two of its main derivatives resulting from ISCR, CLD5aH and a CLD-3Cl, have been investigated in untreated and treated nitisol from a banana plantation using column experiments (20 cm long and 2.5 cm in diameter) under saturated conditions. The circulation of CaCl2 10-2M solution, simulating the ionic strength of soil water, in untreated nitisol results in CLD concentrations in solutions that remain for decades above the threshold limit for drinking water. ISCR treatment lowers the CLD concentration by ~50% in soil and by a factor 3 in waters but they remain above the threshold values. CLD derivatives, CLD5aH and a CLD-3Cl and, to a lesser extent, a CLD-2Cl and a CLD-5Cl, are found in waters after treatment. Dechlorination increases the mobility of the derivatives with respect to the parent molecule, which is likely to induce their transfer to deeper soil layers than those treated by ISCR: CLD-3Cl is more mobile than CLD5aH which is more mobile than CLD. When the water is in contact with the contaminated soil, a period of fast desorption kinetic of CLD and its derivatives, followed by a period of slow kinetics are found. This attests the high risk for water contamination and the potential influence of rainfall events on the concentrations likely to be encountered in soil waters or in waters accumulated on the soil surface.

Development and Validation of Technologies for Remediation of 1,2,3-Trichloropropane in Groundwater

1,2,3-Trichloropropane (TCP) is a synthetic chemical with known and suspected human health effects associated with exposure. In response to the identification of TCP in environmental media, several states in the United States (US) have set maximum contaminant levels (MCLs) for TCP in drinking water and guidance values for TCP in groundwater. Current treatment methods for TCP in groundwater are limited and can be cost prohibitive. The purpose of this review is to summarize the state of knowledge on TCP remedial technologies and describe efforts to develop and validate promising treatment methods. In situ chemical reduction (ISCR) and in situ bioremediation (ISB) have shown the most potential for TCP remediation. ISCR of TCP by zero-valent zinc (ZVZ) has been evaluated for several years through bench-scale testing, field-scale column testing, and a pilot-scale ZVZ injection program. Additional injections are ongoing to assess the long-term efficacy of ISCR. ISB under anaerobic conditions has been evaluated in laboratory studies and at the field scale with bioaugmentation. Field-scale evaluation of ISB is also ongoing. This review provides an overview of TCP, including use, physicochemical properties, fate and transport, health effects, and current regulation. The states of treatment technologies for TCP are detailed, including granular activated carbon (GAC), ISCR, ISB, and chemical oxidation. Case studies and notable findings are described for ISCR and ISB. While knowledge gaps remain for ISCR and ISB, results to date for these technologies are encouraging.

In vivo comparison of the proangiogenic properties of chlordecone and three of its dechlorinated derivatives formed by in situ chemical reduction.

In situ chemical reduction (ISCR) has been identified as a possible way for the remediation of soils contaminated by chlordecone (CLD). Evidences provided by the literature indicate an association between the development of prostate cancer and CLD exposure (Multigner et al. 2010). In a previous in vitro study, we demonstrated that the two main dechlorinated CLD derivatives formed by ISCR, CLD-1Cl, and CLD-3Cl have lower cytotoxicity and proangiogenic properties than CLD itself (Legeay et al. 2017). By contrast, nothing is known on the in vivo proangiogenic effect of these dechlorinated derivatives. Based on in vitro data, the aims of this study were therefore to evaluate the in vivo influence of CLD and three of its dechlorinated metabolites in the control of neovascularization in a mice model of prostate cancer. The proangiogenic effect of CLD and three of its dechlorinated derivatives, CLD-1Cl, CLD-3Cl, and CLD-4Cl, was evaluated on a murine model of human prostate tumor (PC-3) treated, at two exposure levels: 33μg/kg and 1.7μg/kg respectively reflecting acute and chronic toxic exposure in human. The results of serum measurements show that, for the same ingested dose, the three metabolite concentrations were significantly lower than that of CLD. Dechlorination of CLD lead therefore to molecules that are biologically absorbed or metabolized, or both, faster than the parent molecule. Prostate tumor growth was lower in the groups treated by the three metabolites compared to the one treated by CLD. The vascularization measured on the tumor sections was inversely proportional to the rate of dechlorination, the treatment with CLD-4Cl showing no difference with control animals treated with only the vehicle oil used for all substances tested. We can therefore conclude that the proangiogenic effect of CLD is significantly decreased following the ISCR-resulting dechlorination. Further investigations are needed to elucidate the molecular mechanisms by which dechlorination of CLD reduces proangiogenic effects in prostate tumor.

Combined use of ISCR and biostimulation techniques in incomplete processes of reductive dehalogenation of chlorinated solvents

Pools of chloroethenes are more recalcitrant in the transition zone between aquifers and basal aquitards than those elsewhere in the aquifer. Although biodegradation of chloroethenes occur in this zone, it is a slow process and a remediation strategy is needed. The aim of this study was to demonstrate that combined strategy of biostimulation and in situ chemical reduction (ISCR) is more efficient than the two separated strategies. Four different microcosm experiments with sediment and groundwater of a selected field site where an aged perchloroethene (PCE)-pool exists at the bottom of a transition zone, were designed under i) natural conditions, ii) biostimulation with lactic acid, iii) in situ chemical reduction (ISCR) with zero valent iron (ZVI) and under iv) a combined strategy with lactic acid and ZVI. Biotic and abiotic dehalogenation, terminal electron acceptor processes and evolution of microbial communities were investigated for each experiment. The main results where: i) limited reductive dehalogenation of PCE occurs under sulfate-reducing conditions; ii) biostimulation with lactic acid promotes a more pronounced reductive dehalogenation of PCE in comparison under natural conditions, but resulted in an accumulation of cis-dichloroethene (cDCE); iii) ISCR with zero-valent iron (ZVI) facilitates a sustained dehalogenation of PCE and its metabolites to non-halogenated products, however, the iv) combined strategy results in the fastest and sustained dehalogenation of PCE to non-halogenated products in comparison of all four set-ups. These findings suggest that biostimulation and ISCR with ZVI are the most suitable strategy for a complete reductive dehalogenation of PCE-pools in the transition zone.

In-Situ Synthesis of Amorphous Co Nanoparticles Supported onto TiO₂ Nanofibers as a Catalyst for Hydrogen Generation from the Hydrolysis of Ammonia Borane.

Co0 nanoparticles supported on TiO2 nanofibers (nanocomposite) were prepared using a simple electrospinning technique and In-Situ chemical reduction. The synthesized nanocomposite was used to generate hydrogen from ammonia borane (AB). Standard characterization techniques revealed dense distribution of Co0 nanoparticles (Co NPs) onto the TiO2 nanofibers (TiO2 NFs) in the prepared nanocomposite. The introduced nanocomposite has been showed a good catalytic activity as compared to those unsupported Co NPs. As, the hydrogen evolutions for the nanocomposite and Co NPs were 3 mol in 23 min and 47 min, respectively. Furthermore, both the nanocomposite concentration and the temperature have a significant catalytic activity in the AB dehydrogenation. The nanocomposite also showed low effective activation energy of ~26.03 KJ · mol-1.

Two dechlorinated chlordecone derivatives formed by in situ chemical reduction are devoid of genotoxicity and mutagenicity and have lower proangiogenic properties compared to the parent compound.

Chlordecone (CLD) is a chlorinated hydrocarbon insecticide, now classified as a persistent organic pollutant. Several studies have previously reported that chronic exposure to CLD leads to hepatotoxicity, neurotoxicity, raises early child development and pregnancy complications, and increases the risk of liver and prostate cancer. In situ chemical reduction (ISCR) has been identified as a possible way for the remediation of soils contaminated by CLD. In the present study, the objectives were (i) to evaluate the genotoxicity and the mutagenicity of two CLD metabolites formed by ISCR, CLD-5a-hydro, or CLD-5-hydro (5a- or 5- according to CAS nomenclature; CLD-1Cl) and tri-hydroCLD (CLD-3Cl), and (ii) to explore the angiogenic properties of these molecules. Mutagenicity and genotoxicity were investigated using the Ames's technique on Salmonella typhimurium and the in vitro micronucleus micromethod with TK6 human lymphoblastoid cells. The proangiogenic properties were evaluated on the in vitro capillary network formation of human primary endothelial cells. Like CLD, the dechlorinated derivatives of CLD studied were devoid of genotoxic and mutagenic activity. In the assay targeting angiogenic properties, significantly lower microvessel lengths formed by endothelial cells were observed for the CLD-3Cl-treated cells compared to the CLD-treated cells for two of the three tested concentrations. These results suggest that dechlorinated CLD derivatives are devoid of mutagenicity and genotoxicity and have lower proangiogenic properties than CLD.

Selectivity of Nano Zerovalent Iron in In Situ Chemical Reduction: Challenges and Improvements

Nano zerovalent iron (nZVI) is a promising remediation technology utilizing in situ chemical reduction (ISCR) to clean up contaminated groundwater at hazardous waste sites. The small particle size and large surface area of nZVI result in high reactivity and rapid destruction of contaminants. Over the past 20 years, a great deal of research has advanced the nZVI technology from bench-scale tests to field-scale applications. However, to date, the overall number of well-characterized nZVI field deployments is still small compared to other alternative remedies that are more widely applied. Apart from the relatively high material cost of nZVI and questions regarding possible nanotoxicological side effects, one of the major obstacles to the widespread utilization of nZVI in the field is its short persistence in the environment due to natural reductant demand (NRD). The NRD for nZVI is predominantly due to reduction of water, but other reactions with naturally present oxidants (e.g., oxygen) occur, resulting in situ conditions that are reducing (high in ferrous iron phases and H2) but with little or no Fe(0). This article reviews the main biogeochemical processes that determine the selectivity and longevity of nZVI, summarizes data from prior (laboratory and field) studies on the longevity of various common types of nZVI, and describes modifications of nZVI that could improve its selectivity and longevity for full-scale applications of ISCR. © 2016 Wiley Periodicals, Inc.

Sulfidation of Nano Zerovalent Iron (nZVI) for Improved Selectivity During In-Situ Chemical Reduction (ISCR).

The high reactivity of nano zerovalent iron (nZVI) leads to inefficient treatment due to competition with various natural reductant demand (NRD) processes, especially the reduction of water to hydrogen. Here we show that this limitation can be alleviated by sulfidation (i.e., modification by reducing sulfur compounds). nZVI synthesized on carboxylmethylcelluose (CMC-nZVI) was sulfidated with either sulfide or dithionite. The reactivity of the resulting materials was examined with three complementary assays: (i) direct measurement of hydrogen production, (ii) reduction of a colorimetric redox probe (indigo disulfonate, I2S), and (iii) dechlorination of trichloroethylene (TCE). The results indicate that sulfidation at S/Fe molar ratios of ≥0.3, effectively eliminates reaction with water, but retains significant reactivity with TCE. However, sulfidation with sulfide leaves most of the nZVI as Fe(0), whereas dithionite converts a majority of the nZVI to FeS (thus consuming much of the reducing capacity originally provided by the Fe(0)). Simplified numerical models show that the reduction kinetics of I2S and TCE are mainly dependent on the initial reducing equivalents and that the TCE reduction rate is affected by the aging of FeS. Overall, the results suggest that pretreatment of nZVI with reducing sulfur compounds could result in substantial improvement in nZVI selectivity.

Reductive dechlorination of carbon tetrachloride using buffered alkaline ascorbic acid

Alkaline ascorbic acid (AA) was recently discovered as a novel in-situ chemical reduction (ISCR) reagent for remediating chlorinated solvents in the subsurface. For this ISCR process, the maintenance of an alkaline pH is essential. This study investigated the possibility of the reduction of carbon tetrachloride (CT) using alkaline AA solution buffered by phosphate and by NaOH. The results indicated that CT was reduced by AA, and chloroform (CF) was a major byproduct at a phosphate buffered pH of 12. However, CT was completely reduced by AA in 2M NaOH without CF formation. In the presence of iron/soil minerals, iron could be reduced by AA and Fe2+ tends to precipitate on the mineral surface to accelerate CT degradation. A simultaneous transfer of hydrogenolysis and dichloroelimination would occur under phosphate buffered pH 12. This implies that a high alkaline environment is a crucial factor for maintaining the dominant pathway of two electron transfer from dianionic AA to dehydroascorbic acid, and to undergo dichloroelimination of CT. Moreover, threonic acid and oxalic acid were identified to be the major AA decomposition products in alkaline solutions.

Assessing effects of site characteristics on remediation secondary life cycle impact with a generalised framework

The ‘sustainable remediation’ concept has been broadly embraced by industry and governments in recent years in both the US and Europe. However, there is a strong need for more research to enhance its ‘practicability’. In an attempt to fill this research gap, this study developed a generalised framework for selecting the most environmentally sustainable remedial technology under various site conditions. Four remediation technologies were evaluated: pump and treat (P&T), enhanced in situ bioremediation (EIB), permeable reactive barrier (PRB), and in situ chemical reduction (ISCR). Within the developed framework and examined site condition ranges, our results indicate that site characteristics have a profound effect on the life cycle impact of various remedial alternatives, thus providing insights and valuable information for determining what is considered the most desired remedy from an environmental sustainability perspective.

Field Evidence of Dissolution and Degradation Rates Enhancement During ISCR and ENA Treatments of Chlorinated Solvents

AbstractThis article presents field tests comparing two methods of treatment of chlorinated solvents undertaken at the same site. The site is an automobile factory where two chlorinated solvents (CS) plumes were identified. At the first source, in situ chemical reduction (ISCR) was applied, while at the second one, enhanced natural attenuation (ENA) was used. A set of specific multilevel sampling wells were installed approximately 20 m downgradient of the sources to estimate the efficiency of the treatments. The presence of a low‐permeability layer (source 1) or a thick oil lens (source 2) in the top part of the aquifer prevented the CS from reaching the bottom of the aquifer. These layers led to difficulties treating the contamination. At the ISCR and ENA treatment zones, the concentrations of tetrachloroethene (PCE) and trichloroethene (TCE) did not change significantly, while the concentration of metabolites (cis‐1,2‐DCE, vinyl chloride, and ethene) significantly increased 50 to 150 days after treatment. Due to high concentration of CS in the source zone, a mass balance calculation, including chlorine, was possible. It showed that around 1 to 2 percent of the injected products were used to reduce the CS. A detailed analysis and 1D analytical modeling of CS concentrations showed that the treatment led to a large (two to three times) increase in dissolution of the organic phase. This explains why, despite an efficient treatment, the PCE and TCE concentrations remained virtually unchanged. Degradation rates also increased due to the treatment. Due to some differences in the source‐zone chemistry, it was not possible to differentiate between the ISCR and ENA efficiencies. © 2013 Wiley Periodicals, Inc.

In situ remediation of PCE at a site with clayey lithology and a significant smear zone

AbstractGroundwater at the former Serry's Dry Cleaning site in Corvallis, Oregon, was impacted by chlorinated volatile organic compounds (CVOCs). The primary CVOCs impacting the site include tetrachloroethene, trichloroethene, dichloroethene, and vinyl chloride, which were detected at concentrations up to 22,000, 1,700, 3,100, and 7 μg/L, respectively, prior to treatment. Large seasonal fluctuations in groundwater CVOC concentrations indicated that a significant fraction of the CVOC mass was present in the smear zone. Field‐scale pilot tests were performed for the Oregon Department of Environmental Quality's Dry Cleaner Program to evaluate the performance of EHC® in situ chemical reduction (ISCR) technology. The pilot study involved evaluating field performance and physical distribution into low‐permeability soil using basic Geoprobe® injection tooling. The testing results confirmed that bioremediation enhanced by ISCR supported long‐term treatment at the site. This article describes the implementation and results of the tests. Performance data are available from a three‐year period following the injections, allowing for a discussion about sustained performance and reagent longevity. © 2010 Wiley Periodicals, Inc.