Dichloroethylene Research Articles

Aerobic biodegradation of chlorinated ethenes by Pseudonocardia sp. D17: Biodegradation ability without auxiliary substrates and concurrent biodegradation with 1,4-dioxane

Bioremediation is a promising approach for mitigating commingled contaminations of chlorinated ethenes (CEs) and 1,4-dioxane (DX). However, aerobic bioremediation to simultaneously remove CEs and DX remains challenging. This study aimed to explore the ability of Pseudonocardia sp. D17 (D17) to aerobically degrade CEs and its applicability for concurrent removal of CEs and DX. Aerobic degradation experiments of individual CEs revealed that D17 could degrade trichloroethene (TCE), three isomers of dichloroethene (DCE), and vinyl chloride (VC), and the trend of its degradation ability was cis-1,2-DCE (cDCE) > VC > TCE >trans-1,2-DCE > 1,1-DCE. Notably, the CE-degrading activity of D17 was expressed even without any auxiliary substrates. Further, when TCE, cDCE, or VC was co-present with DX (each at 1 mg/L), D17 could degrade both compounds without any significant inhibition (for TCE and cDCE) or with only a transient and reversible suspension of its DX degradation ability (for VC). These findings indicated that D17 is a promising agent for the aerobic bioremediation of CEs and DX co-contamination and provide novel insights into the future development of efficient aerobic bioremediation strategies.

Alleviating Chlorinated Alkane Inhibition on Dehalococcoides to Achieve Detoxification of Chlorinated Aliphatic Cocontaminants.

Cocontamination by multiple chlorinated solvents is a prevalent issue in groundwater, presenting a formidable challenge for effective remediation. Despite the recognition of this issue, a comprehensive assessment of microbial detoxification processes involving chloroethenes and associated cocontaminants, along with the underpinning microbiome, remains absent. Moreover, strategies to mitigate the inhibitory effects of cocontaminants have not been reported. Here, we revealed that chloroform exhibited the most potent inhibitory effects, followed by 1,1,1-trichloroethane and 1,1,2-trichloroethane, on dechlorination of dichloroethenes (DCEs) in Dehalococcoides-containing consortia. The observed inhibition could be attributed to suppression of biosynthesis and enzymatic activity of reductive dehalogenases and growth of Dehalococcoides. Notably, cocontaminants more profoundly inhibited Dehalococcoides populations harboring the vcrA gene than those possessing the tceA gene, thereby explaining the accumulation of vinyl chloride under cocontaminant stress. Nonetheless, we successfully ameliorated cocontaminant inhibition by augmentation with Desulfitobacterium sp. strain PR owing to its ability to attenuate cocontaminants, resulting in concurrent detoxification of DCEs, trichloroethanes, and chloroform. Microbial community analyses demonstrated obvious alterations in taxonomic composition, structure, and assembly of the dechlorinating microbiome in the presence of cocontaminants, and introduction of strain PR reshaped the dechlorinating microbiome to be similar to its original state in the absence of cocontaminants. Altogether, these findings contribute to developing bioremediation technologies to clean up challenging sites polluted with multiple chlorinated solvents.

Reciprocal Interactions of Abiotic and Biotic Dechlorination of Chloroethenes in Soil.

Chloroethenes (CEs) as common organic pollutants in soil could be attenuated via abiotic and biotic dechlorination. Nonetheless, information on the key catalyzing matter and their reciprocal interactions remains scarce. In this study, FeS was identified as a major catalyzing matter in soil for the abiotic dechlorination of CEs, and acetylene could be employed as an indicator of the FeS-mediated abiotic CE-dechlorination. Organohalide-respiring bacteria (OHRB)-mediated dechlorination enhanced abiotic CEs-to-acetylene potential by providing dichloroethenes (DCEs) and trichloroethene (TCE) since chlorination extent determined CEs-to-acetylene potential with an order of trans-DCE > cis-DCE > TCE > tetrachloroethene/PCE. In contrast, FeS was shown to inhibit OHRB-mediated dechlorination, inhibition of which could be alleviated by the addition of soil humic substances. Moreover, sulfate-reducing bacteria and fermenting microorganisms affected FeS-mediated abiotic dechlorination by re-generation of FeS and providing short chain fatty acids, respectively. A new scenario was proposed to elucidate major abiotic and biotic processes and their reciprocal interactions in determining the fate of CEs in soil. Our results may guide the sustainable management of CE-contaminated sites by providing insights into interactions of the abiotic and biotic dechlorination in soil.

Sequential Anaerobic/Aerobic Microbial Transformation of Chlorinated Ethenes: Use of Sustainable Approaches for Aquifer Decontamination

Chlorinated ethene contamination is a worldwide relevant health issue. In anaerobic aquifers, highly chlorinated ethenes are transformed by microbially-mediated organohalide respiration metabolism. For this reason, in the last few years, bioremediation interventions have been developed and employed in situ for aquifer decontamination. Biostimulation has been demonstrated to be efficient in enhancing organohalide respiration activity. The use of agrifood wastes that replace engineered substrates as biostimulants permits the low carbon impact of bioremediation treatment as part of a circular economy approach. The present work depicts the effects of available bio-based substrates and discusses their efficiency and impact on microbial communities when applied to contaminated aquifers. As a drawback of anaerobic organohalide respiration, there is the accumulation of more toxic lower-chlorinated ethenes. However, compounds such as dichloroethene (DCE) and vinyl chloride (VC) can be mineralized by metabolic and co-metabolic pathways in aerobic conditions. For this reason, sequential anaerobic/aerobic treatments proposed to stimulate the natural biotransformation activity can achieve complete degradation of chlorinated ethenes. The aim of this work is to provide an up-to-date revision of anaerobic/aerobic microbial transformation pathways towards chlorinated ethenes and to discuss their application in real scenarios and futurable microbial bioelectrochemical systems to remediate contaminated aquifers.

Electrochemical Dechlorination of Trichloroethylene by Manganese Phthalocyanine: Performance and Mechanisms

Trichloroethylene (TCE) is one of the most abundant persistent organic pollutant in subsurface environment. TCE can be reduced electrochemically, but the extremely negative applied potential limits the application of this technology. Manganese phthalocyanine (MnPc) catalyst was used for the electrochemical reductive dechlorination of TCE. The results show that MnPc can be reduced by electrons attachment at −-0.21 V, −-1.22 V and −-1.77 V, respectively. With the decrease of applied potential from −-0.3 V to −-1.8 V, the transformation from TCE to dichloroethylene (DCE) efficiency increased from 19.9% to 41.8% after 5 hours of reaction. Although the electron transfer ability was enhanced with applied potential decreasing, the intensive HER caused the electron selectivity decreased when MnPc attached more electrons. MnPc catalyze the electrochemical reduction of TCE, which has potential application on the remediation of TCE-contaminated groundwater.

Anti-passivation ability of sulfidated microscale zero valent iron and its application for 1,1,2,2-tetrachloroethane degradation.

The performance of sulfidated zero valent iron (ZVI) for the degradation of chlorinated hydrocarbons under aerobic conditions remains unclear. In this study, sulfidated microscale ZVI (S-mZVI) was prepared for 1,1,2,2-tetrachloroethane (TeCA) degradation under aerobic conditions. Compared with mZVI, S-mZVI showed excellent passivation resistance during the degradation of TeCA and its hydrolysis/reduction products. This was probably because the existence of FeSx shell (FeS/FeS2/FeSn) protected the internal ZVI core from passivation. Though the outer layer of FeSx shell could be oxidized to FeSn and Fe2(SO4)3 as the reaction proceeded, the inner layer remained stable, which maintained the fast electron transfer capability of S-mZVI. The high temperature could enhance the degradation of TeCA, without compromising the anti-passivation and reusability of S-mZVI. Even after the fifth cycle, S-mZVI could still efficiently degrade 90% of TeCA within 24h. Furthermore, it was found that the degradation of TeCA and its reduction products (e.g., dichloroethylene (DCE)) by S-mZVI relied on direct electron transfer and hydrogen radical (H•), respectively, which might explain the lower levels of toxic DCE in the S-mZVI system. This study provides valuable information for the practical application of S-mZVI in the treatment of wastewater containing halogenated hydrocarbons under ambient conditions.

Electrochemically Promoted Halogenation of Imidazoland-[1,2-a]pyridine with Dichloro(bromo)ethylene and Iodoform

Electrochemically Promoted Halogenation of Imidazoland-[1,2-a]pyridine with Dichloro(bromo)ethylene and Iodoform

General analytical solutions of multispecies advective-dispersive solute transport equations coupled with a complex reaction network

Stepwise reductive dechlorination of tetrachloroethene (PCE) to trichloroethene (TCE), three dichloroethylene (DCE) isomers (1,1-DCE, cis −1,2- DCE, and trans −1,2- DCE), vinyl chloride (VC), and ethane (ETH) may proceed under anaerobic conditions. However, most multispecies transport models for describing the plume migration of a chemical mixture comprising the original chlorinated solvent and its dechlorinated byproducts in the literature are often simplified to a sequential first-order reaction network which cannot account for the divergent reactions from TCE to the three DCE isomers and convergent reactions from the three DCE isomers to VC. In this study, general analytical solutions to multispecies transport equations with a complex reaction network were derived for a combination of semi-infinite and finite systems. The developed analytical solutions were robustly verified against a semi-analytical solution that can consider the same complex reaction network. The verification results indicated that the derived analytical solutions were accurate and robust. The general solutions derived in the present study were also used to investigate the effects of the outlet boundary conditions on solute transport involving a complex reaction network. The results showed that the analytical solution derived for infinite outlet BCs predicted lower concentrations of contaminants near the outlet boundary than those for finite outlet BCs. Moreover, a straight decay chain model may over- or under- estimate the DCE and VC concentrations compared to the multiple branching isomer reaction model. The developed analytical solutions with a complex reaction network provide more realistic and efficient tools for assessing the movement of chlorinated solvents and their degradation-related byproducts in soil–water systems.

Mass-Resolved Momentum Imaging of Three Dichloroethylene Isomers by Femtosecond Laser-Induced Coulomb Explosion

Coulomb explosion experiments using linearly polarized intense 60 fs laser pulses were conducted for structural characterization of three dichloroethylene (DCE) isomers, 1,1-DCE, cis-1,2-DCE, and trans-1,2-DCE. Under relatively low laser intensity at 1.8 × 1014 W/cm2, mass-resolved momentum imaging (MRMI) for selected fragment ions of 35Cl+ and C2+ revealed different patterns for the three isomers. The C2+ ion fragmented from multiply charged trans-1,2-DCE was forced to leave perpendicularly to the direction of the laser polarization, due to recoil forces from adjacent cations. In contrast, the fast ions of C2+ from cis-1,2-DCE exhibited an isotropic distribution, whereas the fast ions of C2+ from 1,1-DCE recoiled along the laser polarization together with the slow C2+ ions, and thereby distinction of the three isomers was demonstrated. Coulomb explosion occurs predominantly at specific orientation, which is useful for potential applications of MRMI analysis to molecular structure assays.

Identification of chlorohydrocarbon degradation pathways in aquitards using dual element compound-specific isotope measurements in aquifers

Compound-specific isotope analysis (CSIA) has been increasingly used to understand and quantify the (bio)degradation processes affecting chlorohydrocarbons in aquifer-aquitard systems. In this study, we aimed at investigating through reactive transport simulations if dual element (C, Cl) CSIA in aquifer samples can provide information about the occurring (bio)degradation pathways in the underlying aquitard. To that end, we modeled the continous dissolution of a 1,1,2,2-tetrachloroethane (TeCA) dense nonaqueous phase liquid (DNAPL) source in an aquifer as well as the resulting TeCA groundwater plume formation and diffusion into the underlying aquitard. The (bio)degradation of TeCA in the aquifer-aquitard system was simulated in four scenarios: TeCA biodegradation via dehydrohalogenation to trichloroethene (TCE) and TeCA dichloroelimination to dichloroethene (DCE) in the aquifer as well as in the aquitard. The simulations revealed that dual element (C, Cl) CSIA in the aquifer allows the disentanglement of whether TeCA degradation occurs in the aquifer or the aquitard and which (bio)degradation pathways occur in the aquitard. This demonstrates that chlorohydrocarbon (bio)degradation pathways in aquitards can be identified based on CSIA aquifer measurements only, which is an advantage as aquifers are easier to monitor than aquitards.

Efficacy of emerging technologies in addressing reductive dechlorination for environmental bioremediation: A review

Reductive dechlorination is a core pathway of chlorination in an anaerobic environment, which can be carried out by fermentative, methanogenic, iron and sulfate-reducing microorganisms. The present review showed the different metabolic ways of microbes with the emphasis on the anaerobic microbial dechlorination (including chemical, biological and nanotechnology-based strategies), that have been employed to mitigate the chlorinated pollutants. Chemical and nanomaterial science has made substantial advancement in several aspects of dechlorination over the past two decades, providing information about the process and the outcome of the reaction. However, these chemical processes are expensive to start with and pose ecological hazards. So, extensive research has been done to come up with eco-friendly biological alternatives). Under anaerobic conditions, dehalorespiring bacteria are capable of dechlorinating chloroethenes by mediating a stepwise replacement of chlorine with hydrogen resulting in the sequential conversion of perchloroethylene (PCE) to trichloroethylene (TCE), dichloroethylene (DCE) isomers, vinyl chloride (VC), and finally, ethane. Among many dehalorespiring bacterial isolates, only a few strains of the genus Dehalococcoides completely converted the chloroethenes to nontoxic ethane. In the paper we will, therefore, focus on this Dehalococcoides spp. Several factors influence the dechlorination activity between different dehalogenating bacteria. The vcrA and bvcA genes dechlorinate VC into ethene, which are essential for complete dechlorination. These pathways offer understanding of potential bioremediation of chlorinated aliphatic or aromatic compounds by Dehalococcoides with the likelihood of highly effective bioremediation.

Prediction of Dichloroethene Concentration in the Groundwater of a Contaminated Site Using XGBoost and LSTM.

Chlorinated aliphatic hydrocarbons (CAHs) are widely used in agriculture and industries and have become one of the most common groundwater contaminations. With the excellent performance of the deep learning method in predicting, LSTM and XGBoost were used to forecast dichloroethene (DCE) concentrations in a pesticide-contaminated site undergoing natural attenuation. The input variables included BTEX, vinyl chloride (VC), and five water quality indicators. In this study, the predictive performances of long short-term memory (LSTM) and extreme gradient boosting (XGBoost) were compared, and the influences of variables on models’ performances were evaluated. The results indicated XGBoost was more likely to capture DCE variation and was robust in high values, while the LSTM model presented better accuracy for all wells. The well with higher DCE concentrations would lower the model’s accuracy, and its influence was more evident in XGBoost than LSTM. The explanation of the SHapley Additive exPlanations (SHAP) value of each variable indicated high consistency with the rules of biodegradation in the real environment. LSTM and XGBoost could predict DCE concentrations through only using water quality variables, and LSTM performed better than XGBoost.

Isotope method to identify and quantify organic pollutant biodegradation during natural attenuation monitoring

AbstractBACKGROUNDOrganic pollution poses a huge threat to the environment and human health. It is necessary to evaluate the degree of the physical and chemical reactions of organic pollutants and to clarify the time and space laws of their degradation, so as to guide the pollution remediation work. This study aimed to evaluate the biodegradation process of typical pollutant components (benzene (BZ) and dichloroethylene (DCE)) in groundwater in a study area using the 13C compound specific isotope analysis, and to evaluate the differences in calculated degradation rates by using theoretical results.RESULTSThe field‐measured spatio‐temporal concentrations of BZ and DCE and the isotope data of 13C and 14C in groundwater proved the leading role of microorganisms in the degradation process. The BZ degradation extent (92.11%) was higher than that of DCE (83.67%) within 1 year, and indoor experiments verified this result. Microbial degradation extents calculated by 13C isotope were 85% and 79%, respectively. The first‐order degradation kinetic model verified the reasonability of the degradation results calculated by 13C isotope; the deviations of the degradation extents calculated by field‐measured data and 13C isotope are both <10%. In addition, BZ was more likely to degrade upstream of the groundwater flow path.CONCLUSIONBiodegradation was the most important attenuation method of BZ and DCE, but there were differences in the degradation abilities of BZ and DCE by biological action, and BZ was preferentially degraded over DCE in the groundwater flow path. © 2022 Society of Chemical Industry (SCI).

Dehalogenation of Chlorinated Ethenes to Ethene by a Novel Isolate, "Candidatus Dehalogenimonas etheniformans".

Dehalococcoides mccartyi strains harboring vinyl chloride (VC) reductive dehalogenase (RDase) genes are keystone bacteria for VC detoxification in groundwater aquifers, and bioremediation monitoring regimens focus on D. mccartyi biomarkers. We isolated a novel anaerobic bacterium, "Candidatus Dehalogenimonas etheniformans" strain GP, capable of respiratory dechlorination of VC to ethene. This bacterium couples formate and hydrogen (H2) oxidation to the reduction of trichloro-ethene (TCE), all dichloroethene (DCE) isomers, and VC with acetate as the carbon source. Cultures that received formate and H2 consumed the two electron donors concomitantly at similar rates. A 16S rRNA gene-targeted quantitative PCR (qPCR) assay measured growth yields of (1.2 ± 0.2) × 108 and (1.9 ± 0.2) × 108 cells per μmol of VC dechlorinated in cultures with H2 or formate as electron donor, respectively. About 1.5-fold higher cell numbers were measured with qPCR targeting cerA, a single-copy gene encoding a putative VC RDase. A VC dechlorination rate of 215 ± 40 μmol L-1 day-1 was measured at 30°C, with about 25% of this activity occurring at 15°C. Increasing NaCl concentrations progressively impacted VC dechlorination rates, and dechlorination ceased at 15 g NaCl L-1. During growth with TCE, all DCE isomers were intermediates. Tetrachloroethene was not dechlorinated and inhibited dechlorination of other chlorinated ethenes. Carbon monoxide formed and accumulated as a metabolic by-product in dechlorinating cultures and impacted reductive dechlorination activity. The isolation of a new Dehalogenimonas species able to effectively dechlorinate toxic chlorinated ethenes to benign ethene expands our understanding of the reductive dechlorination process, with implications for bioremediation and environmental monitoring. IMPORTANCE Chlorinated ethenes are risk drivers at many contaminated sites, and current bioremediation efforts focus on organohalide-respiring Dehalococcoides mccartyi strains to achieve detoxification. We isolated and characterized the first non-Dehalococcoides bacterium, "Candidatus Dehalogenimonas etheniformans" strain GP, capable of metabolic reductive dechlorination of TCE, all DCE isomers, and VC to environmentally benign ethene. In addition to hydrogen, the new isolate utilizes formate as electron donor for reductive dechlorination, providing opportunities for more effective electron donor delivery to the contaminated subsurface. The discovery that a broader microbial diversity can achieve detoxification of toxic chlorinated ethenes in anoxic aquifers illustrates the potential of naturally occurring microbes for biotechnological applications.

Performance and Mechanisms of Sulfidated Nanoscale Zero-Valent Iron Materials for Toxic TCE Removal from the Groundwater.

Trichloroethylene (TCE) is one of the most widely distributed pollutants in groundwater and poses serious risks to the environment and human health. In this study, sulfidated nanoscale zero-valent iron (S-nZVI) materials with different Fe/S molar ratios were synthesized by one-step methods. These materials degraded TCE in groundwater and followed a pathway that did not involve the production of toxic byproducts such as dichloroethenes (DCEs) and vinyl chloride (VC). The effects of sulfur content on TCE dechlorination by S-nZVI were thoroughly investigated in terms of TCE-removal efficiency, H2 evolution, and reaction rate. X-ray diffraction (XRD) and X-ray Photoelectron Spectroscopy (XPS) characterizations confirmed Fe(0) levels in S-nZVI were larger than for zero-valent iron (nZVI). An Fe/S molar ratio of 10 provided the highest TCE-removal efficiencies. Compared with nZVI, the 24-h TCE removal efficiencies of S-nZVI (Fe/S = 10) increased from 30.2% to 92.6%, and the Fe(0) consumed during a side-reaction of H2 evolution dropped from 77.0% to 12.8%. This indicated the incorporation of sulfur effectively inhibited H2 evolution and allowed more Fe(0) to react with TCE. Moreover, the pseudo-first-order kinetic rate constants of S-nZVI materials increased by up to 485% compared to nZVI. In addition, a TCE degradation was proposed based on the variation of detected degradation products. Noting that acetylene, ethylene, and ethane were detected rather than DCEs and VC confirmed that TCE degradation followed β-elimination with acetylene as the intermediate. These results demonstrated that sulfide modification significantly enhanced nZVI performance for TCE degradation, minimized toxic-byproduct formation, and mitigated health risks. This work provides some insight into the remediation of chlorinated-organic-compound-contaminated groundwater and protection from secondary pollution during remediation by adjusting the degradation pathway.

Removal of Trichloroethylene from Water by Bimetallic Ni/Fe Nanoparticles

Chlorinated organic solvents (COSs) are a significant threat to human beings. In this study, nanoscale bimetallic Ni/Fe particles were synthesized from the reaction of sodium borohydride (NaBH4) with the reduction of Ni2+ and Fe2+ in an aqueous solution. The synthesized nanoscale zero-valent iron (nZVI) and Ni-nZVI were characterized by SEM (scanning electron microscopy), XRD (X-ray diffractometer), Brunauer–Emmett–Teller (BET), and transmission electron microscopy (TEM). The removal performance of trichloroethylene (TCE) over the nZVI catalyst and Ni-nZVI was evaluated. Ni-nZVI with different Ni contents exhibited good reactivity towards the dechlorination of TCE over a 1h period, and the pseudo-first-order rate constant for TCE dechlorination by Ni-nZVI was 1.4–3.5 times higher than that of nZVI. Ni-nZVI with 5 wt% Ni contents exhibited the best dechlorination effect; the removal rates of TCE and its by-product dichloroethylene (DCE) were 100% and 63.69%, respectively. These results indicated that the Ni nanoparticles as the second dopant metal were better than nZVI for TCE degradation. This determination of the optimal Ni-NZVI load ratio provides a factual and theoretical basis for the subsequent application of nano-metal binding in the environment.

Degrading chlorinated aliphatics by reductive dechlorination of groundwater samples from the Santa Susana Field Laboratory

Microbial reductive dechlorination is one of the chosen methods for remediation of chlorinated compounds in anaerobic environments. In this study we examined the degradation of chlorinated aliphatics in groundwater samples from the Santa Susana Field Laboratory (SSFL) containing a concentration of 0.228 mM trichloroethylene (TCE) and 0.279 mM 1,2 dichloroethylene (DCE). We tested the influence of adding different carbon sources on the dechlorinating activity in batch cultures with and without dechlorinating bacteria. In-situ microcosms were established using SSFL groundwater supplemented with EVO (5%) (vol/vol) SRS emulsion and with or without species of Dehalocococcoides (DCB-1, DCB-2 or DCB-3). Emulsified vegetable oil (EVO) gave the highest dechlorinating activity with DCB-1 added compared to any other substrate addition tested. All three bacterial cultures tested had significant dechlorinating activities while the native populations in the SSFL groundwater samples only showed limited degradation of trichloroethylene into intermediates in the form of DCE, vinyl chloride and ethane. The conversion of chlorinated ethylenes (CEs) was optimal in the bioreactors amended with DCB-1 followed by DCB-2, and DCB-3 all supplemented with EVO. We further analyzed the TCE degradation first order kinetics in batch cultures and found that the culture with DCB-1 supplemented with EVO showed 43.59% and 51.38% increased degradation rate compared to the same condition with cultures of DCB-2 or DCB-3 added. The microcosm studies further showed that with DCB-1 and EVO, reductive dechlorination of TCE in the SSFL converted 90% of the input TCE to ethane with a degradation rate of 0.0039 mM/day.

In Situ Bioremediation of a Chlorinated Hydrocarbon Plume: A Superfund Site Field Pilot Test

The North Railroad Avenue Plume, discovered in 1989, contained chlorinated solvent groundwater plumes extending over 23.5 hectares (58 acres) and three hydrostratigraphic units. The source contaminant, tetrachloroethene, stemmed from release at a dry cleaner/laundromat business. The anaerobic biodegradation byproducts trichloroethene, isomers of dichloroethene (DCE), and vinyl chloride were detected in groundwater samples collected prior to remedial action. The impacted aquifers are the sole source drinking water aquifers for the communities near the site. Following the remedial investigation and feasibility study, the selected alternative for full-scale remedial action at the site was enhanced reductive dichlorination (ERD) focused on four treatment areas: the shallow source zone, the shallow hotspot area, the shallow downgradient area, and the deep zone. Pilot testing, which was conducted in the source zone and hotspot areas, is the subject of this paper. The primary objectives of the pilot test were to obtain the necessary information to select an ERD treatment formulation, dose, and frequency of dosing for use during full-scale remedial action, as well as to refine the site’s hydrogeologic conceptual site model and design parameters. Four (4) test cells, each of which contained well pairs of injection and downgradient extraction wells, were used to test ERD bio-amendment formulations: ethyl lactate, dairy whey, emulsified vegetable oil (EVO), and a combination of EVO and a hydrogen gas infusion. A conservative tracer, bromide, was added to the recirculation flow to record tracer breakthrough, peak, and dissipation at extraction wells. The results of these dipole tracer tests were used to reassess the hydraulic conductivity and hydrodynamic dispersity used in the remedial design. In addition to water quality analyses of contaminants and substrates, groundwater samples were also analyzed for biological analyses before, during, and after the addition of bioamendment. Analyses of phospholipid fatty acids and deoxyribonucleic acid (DNA) extracts from fresh groundwater samples informed decisions on the capacity for complete ERD without DCE stalling and tracked the shifts in the bacterial and archaeal taxonomy and phylogeny stemming from the addition of bioamendments. The pilot test concluded that EVO was the most suitable, considering (1) support of the native microbial consortia for ERD, (2) mechanics and hydraulics of the remediation system, and (3) sustainability/retention of the substrate in the subsurface. Along with EVO, the addition of a nutrient broth derived from brewery waste accelerated and sustained the desired conditions and microbial diversity and population levels. The pilot test results were also used to assess the utilization kinetics of the injected substrates based on total organic carbon (TOC) concentrations measured in the groundwater. After determining that substrate utilization followed Monod kinetics, a TOC threshold at 300 milligrams per liter, equivalent to approximately twice its half-saturation constant was established. Full scale treatment dosing and dose frequency were designed around this threshold, assuming the maximum substrate utilization would yield optimum ERD.

Synergy between ozonation and GAC filtration for chlorinated ethenes-contaminated groundwater treatment

Chlorinated ethenes are among the most frequently occurring groundwater contaminants. Pump and granular activated carbon (GAC) treatment is frequently applied to limit the spreading from point contaminations. Perchloroethene (PCE) and trichloroethene (TCE) sorb well to GAC, but dichloroethene (DCE) and vinyl chloride (VC) sorb poorly, thereby defining a low efficiency seen as amounts of GAC used. On the other hand, ozone reacts fast with VC and DCE, but slowly with PCE and TCE. We utilise for the first time the synergy between ozonation and GAC to treat chlorinated ethenes-contaminated groundwater as an upgrade to an existing GAC treatment installation. Laboratory experiments confirmed that VC and trans-DCE could be >90% removed with just 0.23 g O3/m3, corresponding to 0.18 mg O3/mg DOC. For cis-DCE, 1,1-DCE and TCE, ozone doses of 0.86, 0.87 and 2.8 mg O3/mg DOC, respectively, were required to remove 90%. In full-scale, trans-DCE and 1,1-DCE were completely removed with 1.6 g O3/m3, while only 90% of cis-DCE and 50% TCE were removed with this ozone dose. A relationship between extinction of fluorescence from naturally occurring organic matter with ozone, was used to gauge the ozone dose delivered in the full-scale system. This approach predicted precisely the removal of chlorinated ethenes. Finally, based on the obtained results, we estimated that an optimised ozone treatment would increase the lifetime of an activated carbon filters from 1.0 years to 7.2 years.

Application of Combined In Situ Chemical Reduction and Enhanced Bioremediation to Accelerate TCE Treatment in Groundwater

Groundwater at trichloroethylene (TCE)-contaminated sites lacks electron donors, which prolongs TCE’s natural attenuation process and delays treatment. Although adding electron donors, such as emulsified oil, accelerates TCE degradation, it also causes the accumulation of hazardous metabolites such as dichloroethylene (DCE) and vinyl chloride (VC). This study combined in situ chemical reduction using organo-iron compounds with enhanced in situ bioremediation using emulsified oil to accelerate TCE removal and minimize the accumulation of DCE and VC in groundwater. A self-made soybean oil emulsion (SOE) was used as the electron donor and was added to liquid ferrous lactate (FL), the chemical reductant. The combined in situ chemical reduction and enhanced in situ bioremediation achieved favorable results in a laboratory microcosm test and in an in situ biological field pilot test. Both tests revealed that SOE+FL accelerated TCE degradation and minimized the accumulation of DCE and VC to a greater extent than SOE alone after 160 days of observation. When FL was added in the microcosm test, the pH value decreased from 6.0 to 5.5; however, during the in situ biological pilot test, the on-site groundwater pH value did not exhibit obvious changes. Given the geology of the in situ pilot test site, the SOE+FL solution that was injected underground continued to be released for at least 90 days, suggesting that the solution’s radius of influence was at least 5 m.