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Nanoscale zero-valent iron (nZVI) is recognized as a powerful tool for the remediation of groundwater contaminated by chlorinated ethenes (CEs). This long-term field study explored nZVI-driven degradation of CEs supported by electrokinetic (EK) treatment, which positively affects nZVI longevity and migration, and its impact on indigenous bacteria. In particular, the impact of combined nZVI-EK treatment on organohalide-respiring bacteria, ethenotrophs and methanotrophs (all capable of CE degradation) was assessed using molecular genetic markers detecting Dehalococcoides spp., Desulfitobacterium spp., the reductive dehalogenase genes vcrA and bvcA and ethenotroph and methanotroph functional genes. The remediation treatment resulted in a rapid decrease of the major pollutant cis-1,2-dichloroethene (cDCE) by 75% in the affected area, followed by an increase in CE degradation products methane, ethane and ethene. The newly established geochemical conditions in the treated aquifer not only promoted growth of organohalide-respiring bacteria but also allowed for the concurrent presence of vinyl chloride- and cDCE-oxidizing methanotrophs and (especially) ethenotrophs, which proliferated preferentially in the vicinity of an anode where low levels of oxygen were produced. The nZVI treatment resulted in a temporary negative impact on indigenous bacteria in the application well close to the cathode; but even there, the microbiome was restored within 15 days. The nZVI-EK treatment proved highly effective in reducing CE contamination and creating a suitable environment for subsequent biodegradation by changing groundwater conditions, promoting transport of nutrients and improving CE availability to soil and groundwater bacteria., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

ISCO using activated sodium persulphate is a widely used technology for treating chlorinated solvent source zones. In sensitive areas, however, high groundwater sulphate concentrations following treatment may be a drawback. In situ biogeochemical transformation, a technology that degrades contaminants via reduced iron minerals formed by microbial activity, offers a potential solution for such sites, the bioreduction of sulphate and production of iron sulphides that abiotically degrade chlorinated ethenes acting as a secondary technology following ISCO. This study assesses this approach in the field using hydrochemical and molecular tools, solid phase analysis and geochemical modelling. Following a neutralisation and bioaugmentation, favourable conditions for iron- and sulphate-reducers were created, resulting in a remarkable increase in their relative abundance. The abundance of dechlorinating bacteria (Dehalococcoides mccartyi, Dehalobacter sp. and Desulfitobacterium spp.) remained low throughout this process. The activity of iron- and sulphate-reducers was further stimulated through application of magnetite plus starch and microiron plus starch, resulting in an increase in ferrous iron concentration (from

The extensive use of nanoscale zero-valent iron (nZVI) particles for groundwater treatment has been limited, in part, because of their non-selective reactivity and low mobility in aquatic environments. Herein, we describe and explore progressive changes in the reactivity and migration of aqueous dispersed nZVI particles under an applied DC electric field. Due to the applied electric field with an intensity of about 1 V cm -1 , the solution oxidation-reduction potential (ORP) remained as low as -200 mV for at least 32 days, which was in agreement with the persistence of the reduced iron species (mainly Fe(II)), and led to substantially prolonged reactivity of the original nZVI. The treatment of chlorinated ethenes (DCE > PCE > TCE) was markedly faster, individual CHC compounds were eliminated with the same kinetics and no lesser-chlorinated intermediates were accumulated, following thus the direct dechlorination scheme. When nZVI-dispersion flows towards the anode through vertical laboratory columns filled with quartz sand, significant enhancement of nZVI migration was recorded because of lower extent of nanoparticle aggregation and increased repulsion forces between the nanoparticles and the surface of silica dioxide. The results of this study have significant consequences for groundwater remediation, mainly for the treatment of slowly degradable DCE in real CHC contaminated groundwater, where it could improve the reactivity, the longevity and the migration of nZVI particles., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

In situ bioremediation (ISB) using reductive dechlorination is a widely accepted but relatively slow approach compared to other technologies for the treatment of groundwater contaminated by chlorinated ethenes (CVOCs). Due to the known positive kinetic effect on microbial metabolism, thermal enhancement may be a viable means of accelerating ISB. We tested thermally enhanced ISB in aquifers situated in sandy saprolite and underlying fractured granite. The system comprised pumping, heating and subsequent injection of contaminated groundwater aiming at an aquifer temperature of 20-30°C. A fermentable substrate (whey) was injected in separate batches. The test was monitored using hydrochemical and molecular tools (qPCR and NGS). The addition of the substrate and increase in temperature resulted in a rapid increase in the abundance of reductive dechlorinators (e.g., Dehalococcoides mccartyi, Dehalobacter sp. and functional genes vcrA and bvcA) and a strong increase in CVOC degradation. On day 34, the CVOC concentrations decreased by 87% to 96% in groundwater from the wells most affected by the heating and substrate. On day 103, the CVOC concentrations were below the LOQ resulting in degradation half-lives of 5 to 6days. Neither an increase in biomarkers nor a distinct decrease in the CVOC concentrations was observed in a deep well affected by the heating but not by the substrate. NGS analysis detected Chloroflexi dechlorinating genera (Dehalogenimonas and GIF9 and MSBL5 clades) and other genera capable of anaerobic metabolic degradation of CVOCs. Of these, bacteria of the genera Acetobacterium, Desulfomonile, Geobacter, Sulfurospirillum, Methanosarcina and Methanobacterium were stimulated by the substrate and heating. In contrast, groundwater from the deep well (affected by heating only) hosted representatives of aerobic metabolic and aerobic cometabolic CVOC degraders. The test results document that heating of the treated aquifer significantly accelerated the treatment process but only in the case of an abundant substrate., (Copyright © 2017. Published by Elsevier B.V.)

Biomolecular and hydrochemical tools were used to evaluate natural attenuation of chlorinated ethenes in a Quaternary alluvial aquifer located close to a historical source of large-scale tetrachloroethylene (PCE) contamination. Distinct stratification of redox zones was observed, despite the aquifer's small thickness (2.8 m). The uppermost zone of the target aquifer was characterised by oxygen- and nitrate-reducing conditions, with mixed iron- to sulphate-reducing conditions dominant in the lower zone, along with indications of methanogenesis. Natural attenuation of PCE was strongly influenced by redox heterogeneity, while higher levels of PCE degradation coincided with iron- to sulphate reducing conditions. Next generation sequencing of the middle and/or lower zones identified anaerobic bacteria (Firmicutes, Chloroflexi, Actinobacteria and Bacteroidetes) associated with reductive dechlorination. The relative abundance of dechlorinators (Dehalococcoides mccartyi, Dehalobacter sp.) identified by real-time PCR in soil from the lower levels supports the hypothesis that there is a significant potential for reductive dechlorination of PCE. Local conditions were insufficiently reducing for rapid complete dechlorination of PCE to harmless ethene. For reliable assessment of natural attenuation, or when designing monitoring or remedial systems, vertical stratification of key biological and hydrochemical markers should be analysed as standard, even in shallow aquifers., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

The production and use of chlorophenolic compounds in industry has led to the introduction of many xenobiotics, among them chlorophenols (CPs), into the environment. Five CPs are listed in the priority pollutant list of the U.S. EPA, with pentachlorophenol (PCP) even being proposed for listing under the Stockholm Convention as a persistent organic pollutant (POP). A green procedure for degrading such pollutants is greatly needed. The use of ferrate could be such a process. This paper studies the degradation of CPs (with an emphasis on PCP) in the presence of ferrate both in a spiked demineralized water system as well as in real contaminated groundwater. Results proved that ferrate was able to completely remove PCP from both water systems. Investigation of the effect of ferrate purity showed that even less pure and thus much cheaper ferrate was applicable. However, with decreasing ferrate purity, the degradability of CPs may be lower.

The paper describes a pilot remediation test combining two Cr(VI) geofixation methods - chemical reduction by nanoscale zero-valent iron (nZVI) and subsequent biotic reduction supported by whey. Combination of the methods exploited the advantages of both - a rapid decrease in Cr(VI) concentrations by nZVI, which prevented further spreading of the contamination and facilitated subsequent use of the cheaper biological method. Successive application of whey as an organic substrate to promote biotic reduction of Cr(VI) after application of nZVI resulted in a further and long-term decrease in the Cr(VI) contents in the groundwater. The effect of biotic reduction was observed even in a monitoring well located at a distance of 22 m from the substrate injection wells after 10 months. The results indicated a reciprocal effect of both the phases - nZVI oxidized to Fe(III) during the abiotic phase was microbially reduced back to Fe(II) and acted as a reducing agent for Cr(VI) even when the microbial density was already low due to the consumed substrate. Community analysis with pyrosequencing of the 16S rRNA genes further confirmed partial recycling of nZVI in the form of Fe(II), where the results showed that the Cr(VI) reducing process was mediated mainly by iron-reducing and sulfate-reducing bacteria., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Purpose: Nanoscale zero valent iron (NZVI) is emerging as a new option for the treatment of contaminated soil and groundwater targeting mainly chlorinated organic contaminants (e.g., solvents, pesticides) and inorganic anions or metals. The purpose of this article is to give a short overview of the practical experience with NZVI applications in Europe and to present a comparison to the situation in the USA. Furthermore, the reasons for the difference in technology use are discussed., Method: The results in this article are based on an extensive literature review and structured discussions in an expert workshop with experts from Europe and the USA. The evaluation of the experiences was based on a SWOT (strength, weakness, opportunity, threat) analysis., Result: There are significant differences in the extent and type of technology used between NZVI applications in Europe and the USA. In Europe, only three full-scale remediations with NZVI have been carried out so far, while NZVI is an established treatment method in the USA. Bimetallic particles and emulsified NZVI, which are extensively used in the USA, have not yet been applied in Europe. Economic constraints and the precautionary attitude in Europe raise questions regarding whether NZVI is a cost-effective method for aquifer remediation. Challenges to the commercialization of NZVI include mainly non-technical aspects such as the possibility of a public backlash, the fact that the technology is largely unknown to consultants, governments and site owners as well as the lack of long-term experiences., Conclusion: Despite these concerns, the results of the current field applications with respect to contaminant reduction are promising, and no major adverse impacts on the environment have been reported so far. It is thus expected that these trials will contribute to promoting the technology in Europe.