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A multi-layered aquifer in an industrial area in the north of the Iberian Peninsula is severely contaminated with the chlorinated ethenes (CEs) tetrachloroethylene, trichloroethylene, cis-1,2-dichloroethylene, and vinyl chloride. Both shallow and deep aquifers are polluted, with two differentiated north and south CEs plumes. Hydrogeochemical and isotopic data (δ13C of CEs) evidenced natural attenuation of CEs. To select the optimal remediation strategy to clean-up the contamination plumes, laboratory treatability studies were performed, which confirmed the intrinsic biodegradation potential of the north and south shallow aquifers to fully dechlorinate CEs to ethene after injection of lactate, but also the combination of lactate and sulfidized mZVI as an alternative treatment for the north deep aquifer. In the lactate-amended microcosms, full dechlorination of CEs was accompanied by an increase in 16S rRNA gene copies of Dehalococcoides and Dehalogenimonas, and the tceA, vcrA and bvcA reductive dehalogenases. Three in situ pilot tests were implemented, which consisted in injections of lactate in the north and south shallow aquifers, and injections of lactate and sulfidized mZVI in the north deep aquifer. The hydrogeochemical, isotopic and molecular analyses used to monitor the pilot tests evidenced that results obtained mimicked the laboratory observations, albeit at different dechlorination rates. It is likely that the efficiency of the injections was affected by the amendment distribution. In addition, monitoring of the pilot tests in the shallow aquifers showed the release of CEs due to back diffusion from secondary sources, which limited the use of isotopic data for assessing treatment efficiency. In the pilot test that combined the injection of lactate and sulfidized mZVI, both biotic and abiotic pathways contributed to the production of ethene. This study demonstrates the usefulness of integrating different chemical, isotopic and biomolecular approaches for a more robust selection and implementation of optimal remediation strategies in CEs polluted sites.

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This study explored the potential reactivities of various reductants in inducing subsurface TCE degradation in natural soils. It was found that bisulfite (HSO3-) exhibited the ability to induce reduction in soil iron minerals, and increase the degradation of TCE in the soil slurry system; however, no TCE degradation occurred in the aqueous system. The role of TCE degradation by soil constituents, such as major soil mineral elements, Fe and humic acid (HA) on HSO3-, was examined in aqueous phase. It was seen that by themselves, the presence of Fe3+, HA, Fe2O3, FeOOH, and Fe3O4 did not result in substantial TCE removals. However, the presence of HSO3- can significantly induce iron reduction, producing a reducing condition that can result in complete TCE degradation. Furthermore, the reductive pathway was identified as the dominant degradation route via electron scavenging with periodate ion. To demonstrate the applicability of HSO3- reduction enhancement, a HSO3-/TCE mixed solution was flushed through a soil column, with gradually increased HSO3- concentrations, at a fixed flow rate, and also with varied flushing rates at a fixed HSO3- concentration. Based on our study, a 10 mM HSO3- solution may be effective for some environmental sites; however, each site requires specific evaluation based on contaminant concentrations and subsurface conditions.

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Application of in situ chemical oxidation or reduction (ISCO/ISCR) technologies for contaminated soil remediation and its subsequent impact on soil is gaining increased attention. Reductive reactivity, generated from green tea (GT) extract mixed with ferrous (Fe2+) ions under alkaline conditions (the alkaline GT/Fe2+ system), has been considered as a promising ISCR process; however, its impact on soil has never been studied. In this study, the impact of applying the alkaline GT/Fe2+ system on soil was evaluated by analyzing the variations of the soil microbial community, diversity, and richness using next-generation 16S rRNA amplicon sequencing while mimicking the lindane-contaminated soil remediation procedure. Lindane was reductively degraded by the alkaline GT/Fe2+ system with reaction rate constants of 0.014 to 0.057 µM/h depending on the lindane dosage. Environmental change to the alkaline condition significantly decreased the microbial diversity and richness, but the recovery of the influence was observed subsequently. Bacteria that mainly belong within the phylum Firmicutes, including Salipaludibacillus, Anaerobacillus, Bacillaceae, and Paenibacillaceae, were greatly enhanced due to the alkaline condition. Besides, the dominance of heterotrophic, iron-metabolic, lindane-catabolic, and facultative bacteria was observed in the other corresponding conditions. From the results of principal component analysis (PCA), although dominant microbes all shifted significantly at every lindane-existing condition, the set of optimal lindane treatment with the alkaline GT/Fe2+ system had a minimized effect on the plant growth-promoting bacteria (PGPB). Nitrogen-cycling-related PGPB is sensitive to all factors of the alkaline GT/Fe2+ system. However, the other types, including plant-growth-inducer producing, phosphate solubilizing, and siderophore producing PGPB, has less impact under the optimal treatment. Our results demonstrate that the alkaline GT/Fe2+ system is an effective and soil-ecosystem-friendly ISCR remediation technology for lindane contamination.

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Green tea (GT) leaves can be brewed into a solution rich in polyphenols that serve as effective reducing agents, and the complexes formed by combining green tea with ferrous ion (GT/Fe(II)) can provide an elevated reduction potential. The dissociated GT polyphenols at alkaline pH can dramatically increase the formation of GT/Fe(II) complexes. This experimental work evaluated the reductive reactivity of alkaline GT solution and GT/Fe(II) complexes (at pH 10) on 14 halogenated volatile organic compounds (VOCs). Carbon tetrachloride (CT), with a highest carbon oxidation state (COS) of IV, was observed to be degradable by the alkaline GT solution, while all others proved ineffective. The GT/Fe(II) complexes are very reactive and capable of degrading halogenated methanes, ethanes, and ethenes, in which chemical structures exhibit zero or positive COS values, and the chlorine or bromine atom is bonded at the saturated carbon atom, such as CT, chloroform, bromoform, dibromomethane, 1,1,1-trichloroethane, and 1,1,1,2-tetrachloroethane. The linear free energy relationship (LFER) approach was used to determine the overall reduction potentials (EH0) of the alkaline GT solution and GT/Fe(II) complexes, which were found to be -0.131 V and -0.368 V, respectively. These findings demonstrated that GT/Fe(II) complexes exhibit the potential to remediate halogenated contaminants and the EH0 information obtained in this study may serve as a reference in determining probable reactivity that contributes to degradation of environmental contaminants.

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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.

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Devising new versatile nano-adsorbents for efficient capturing of heavy metals in water represents one important direction for environmental remediation. Here, the application of a novel polyaniline@magnetic chitosan (PANI@MCTS) composite consisting of numerous nitrogen-containing functional groups and magnetic Fe3O4 nanoparticles was reported for the efficient treatment of chromium-containing wastewater. This material exhibited a fast adsorption kinetics (80% removal efficiency within 15 min) and strong adsorption capacity (186.6 mg(Cr(VI))•g-1(PANI@MCTS)) for removing Cr(VI) in water as well as an excellent magnetic separation ability. The adsorption of Cr(VI) was found to follow the Langmuir isotherm model and comply with the pseudo-second-order kinetics. More importantly, the PANI@MCTS could facilitate the in-situ chemical reduction of Cr(VI) to Cr(III) that enabled the detoxification treatment of Cr(VI) in water. XPS analysis revealed the simultaneous adsorption and in-situ chemical reduction of Cr(VI) on the PANI@MCTS, where the coordination and electrostatic interaction between Cr(VI) and the positively charged nitrogen containing functional groups contributed to the adsorption, and the = N-/-NH- groups served as active redox pair triggered the in-situ chemical reduction reaction. The recycle experiment showed an excellent stability of this material with >90% removal efficiency after five repeats of treatment. This work provides a promising alternative material for the effective treatment of chromium-containing wastewater.

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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: 33 µg/kg and 1.7 µg/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.

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The environmental persistence of hazardous organochlorine pesticides (OCPs) such as lindane has resulted in a need for the development of reliable remediation technology for the removal of OCPs. Green tea extract/Fe2+ under alkaline conditions is a potential green chemistry technology proven to be effective in reducing lindane. This study investigated the feasibility of directly using green tea leaves (GT-leaf) or cold-brew tea solution (GT-sol) with Fe2+ additives at (bi)carbonate buffered pH 10 to treat lindane in the aqueous phase. The polyphenol was gradually released in the GT-leaf system and reached a similar concentration as that in the GT-sol system (∼800 mg L-1 at pH 6.5). Based on the analytical results of lindane degradation byproducts, it was recognized that the reductive mechanism acts as a major pathway and alkaline hydrolysis is a minor pathway. However, physical adsorption rapidly removes lindane from the GT-leaf system. A comprehensive evaluation of lindane degradation, chlorobenzene formation, degradation kinetics, and chloride liberation were conducted for the alkaline GT-sol/Fe2+ system. The nonlinear simulations of the models developed showed good fits, with R2 > 0.96. This study highlights the potential for GT-sol/Fe2+ systems to remediate OCPs contamination.

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A seed-mediated electroless deposition (SMED) approach for fabrication of large-area and uniform gold nanoparticle films as efficient and reproducible as surface-enhanced Raman scattering (SERS) substrates was presented. This approach involved a seeding pretreatment procedure and a subsequent growth step. The former referred to activation of polylysine-coated glass slides in gold seed solution, and the latter required a careful control of the reactant concentration and reaction time. With the aid of gold seeds and appropriate reaction conditions, a large-area and uniform nanofilm with evenly distributed gold nanoparticles (Au NPs) was formed on the surface of the substrates after adding a mixed solution containing ascorbic acid and trisodium citrate. The morphology of the Au nanofilm was examined by scanning electron microscopy. The size evolution of Au NPs on the surface of the substrates was analyzed in detail. The nanofilm substrate was prepared by reaction conditions of the seeded activation process: 10 mL ascorbic acid and trisodium citrate mixture and 30 min of soaking time, which exhibited an excellent uniformity and reproducibility of SERS enhancement with relative standard deviation (RSD) values of less than 8% (particularly, a RSD value of 3% can be reached for the optimized measurement). Compared to the common electroless deposition, the seed-mediated electroless deposition possessed inherent advantages in controllability, reproducibility, and economic benefit.

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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.

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A novel surface coating with durable broad-spectrum antibacterial ability was prepared based on mussel-inspired dendritic polyglycerol (MI-dPG) embedded with copper nanoparticles (Cu NPs). The functional surface coating is fabricated via a facile dip-coating process followed by in situ reduction of copper ions with a MI-dPG coating to introduce Cu NPs into the coating matrix. This coating has been demonstrated to possess efficient long-term antibacterial properties against Escherichia coli (E. coli), Staphylococcus aureus (S. aureus), and kanamycin-resistant E. coli through an "attract-kill-release" strategy. The synergistic antibacterial activity of the coating was shown by the combination of two functions of the contact killing, reactive oxygen species production and Cu ions released from the coating. Furthermore, this coating inhibited biofilm formation and showed good compatibility to eukaryotic cells. Thus, this newly developed Cu NP-incorporated MI-dPG surface coating may find potential application in the design of antimicrobial coating, such as implantable devices.

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Nitro-aromatic compounds (NACs) such as 1,3-dinitrobenzene (1,3-DNB) contain the nitrogroup (-NO2), in which the N with a +III oxidation state accepts electrons. Water soluble ascorbic acid (AsA) at elevated pH produces electron transfer and governs the electron-donating pathway. The influence of the NaOH/AsA molar ratio on the degradation of 1,3-DNB was investigated. Using 0.21-2 M NaOH and 20-100 mM AsA, nearly complete 1,3-DNB removals (90-100%) were achieved within 0.5 h. On the basis of intermediates identified using GC/MS, the reduction pathways of 1,3-DNB can be categorized into step-by-step electron transfer, and condensation routes. A higher NaOH/AsA molar ratio would result in relatively higher AsA decomposition, promote the condensation route into the formation of azo- and azoxy-compounds, and ultimately reduce 1,3-DNB to 1,3-phenylenediamine. Contaminated soil flushing using 500 mM NaOH/100 mM AsA revealed that 1,3-DNB was completely degraded within 2 h. Based on these test results, the alkaline AsA treatment method is a potential remediation process for NACs contaminated soils.

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Alkaline ascorbic acid (AA) exhibits the potential to reductively degrade nitrobenzene (NB), which is the simplest of the nitroaromatic compounds. The nitro group (NO2(-)) of NB has a +III oxidation state of the N atom and tends to gain electrons. The effect of alkaline pH ranging from 9 to 13 was initially assessed and the results demonstrated that the solution pH, when approaching or above the pKa2 of AA (11.79), would increase reductive electron transfer to NB. The rate equation for the reactions between NB and AA at pH 12 can be described as r=((0.89±0.11)×10(-4) mM(1-(a+b))h(-1))×[NB](a=1.35±0.10)[AA](b=0.89±0.01). The GC/MS analytical method identified nitrosobenzene, azoxybenzene, and azobenzene as NB reduction intermediates, and aniline (AN) as a final product. These experimental results indicate that the alkaline AA reduction of NB to AN mainly proceeds via the direct route, consisting of a series of two-electron or four-electron transfers, and the condensation reaction plays a minor route. Preliminary evaluation of the remediation of spiked NB contaminated soils revealed that maintenance of alkaline pH and a higher water to soil ratio are essential for a successful alkaline AA application.

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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 Fe(2+) 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.

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Polychlorinated biphenyls (PCBs) are well-known for being hydrophobic and persistent in the environment. Although many treatment approaches have been demonstrated to result in degradation of PCBs in water or water/cosolvent systems, few examples exist where such approaches have been applied successfully for PCB degradation in soil-water systems. A possible explanation for the limited treatment of PCBs in soil-water systems is that reactants that are capable of degrading PCBs in the aqueous phase are unlikely to persist long enough to achieve meaningful treatment of slowly-desorbing PCBs associated with the soil phase. To investigate this explanation, laboratory studies were conducted to evaluate chemical reductants, including zero valent metals, palladium (Pd) catalyst, and emulsified zero valent iron (EZVI), for dechlorination of PCBs in the presence and absence of soil. In the absence of soil, Pd-catalyzed treatments (Pd with electrolytic ZVI or iron/aluminum alloy) achieved rapid destruction of a model PCB congener, 2-chlorobiphenyl, with half-lives ranging from 43 to 110 min. For treatment of soils containing Aroclor 1248 at an initial concentration of approximately 1,500 mg kg(-1), Pd-catalyzed treatments achieved no measurable enhancement over the background PCB depletion rate (i.e., that measured in the untreated control) of 5.3 mg kg(-1)week(-1). In the presence of soils, EZVI was the only approach evaluated that resulted in a clear enhancement in PCB dechlorination rates. EZVI achieved PCB concentration reductions of greater than 50% at an average rate of 19 mg kg(-1)week(-1). The results suggest that slow PCB desorption limits treatment effectiveness in soils.

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