Dechlorination
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Two parallel pilot experiments were performed at Kurivody (Czech Republic) in order to compare two reductive remedial technologies for chlorinated ethenes - microbial dehalogenation assisted by lactate and chemical dehalogenation with zero-valent iron (nZVI) nanoparticles. The methods were applied at a site contaminated by tetrachlorethylene (PCE) and trichlorethylene (TCE), with total concentrations from 10 to 50 mg/l. Concentrations of chlorinated ethenes, inorganic components of interest, pH and oxidation reduction potential (ORP) were monitored at the site for a period up to 650 days. The method of biological reductive dechlorination supported by lactate showed a considerable removal of PCE and TCE, but temporary accumulation of transient reaction product 1,2-cis-dihloroethene. Reductive dechlorination with nZVI showed a significant reduction in the concentration of chlorinated ethenes without a formation of intermediate products. The development of pH showed only small changes due to the high buffering capacity of the aquifer. Both methods differ in the initial development of ORP, but over the long term showed similar values around 100 mV. Significant differences were observed for chemical oxygen demand, where groundwater after the application of nZVI showed no change in comparison to the application of lactate. The reductive effects of both agents were verified by changes in inorganic compound concentrations.
- MeSH
- chlor izolace a purifikace MeSH
- chlorované uhlovodíky chemie MeSH
- koncentrace vodíkových iontů MeSH
- kyselina mléčná chemie MeSH
- látky znečišťující životní prostředí chemie MeSH
- oxidace-redukce MeSH
- pilotní projekty MeSH
- regenerace a remediace životního prostředí metody MeSH
- železo chemie MeSH
- Publikační typ
- časopisecké články MeSH
- hodnotící studie MeSH
- práce podpořená grantem MeSH
- srovnávací studie MeSH
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.
- MeSH
- biodegradace MeSH
- chemické látky znečišťující vodu analýza MeSH
- Chloroflexi MeSH
- ethyleny analýza MeSH
- halogenace MeSH
- monitorování životního prostředí * MeSH
- podzemní voda chemie MeSH
- tetrachlorethylen chemie MeSH
- vysoce účinné nukleotidové sekvenování MeSH
- železo analýza MeSH
- Publikační typ
- časopisecké články MeSH
Photochemical degradation of atrazine under different conditions was studied and compared, namely degradation via photocatalysis on TiO2, UV C photolysis, and homogeneous photocatalysis in the presence of added ferric ions. The reaction rate constants in heterogeneous photocatalytic reactions on TiO2 and of photolytic degradation by means of UV C light are similar, 0.018 min(-1) and 0.020 min(-1), respectively. The reaction rate constants in homogeneous photocatalytic reactions with Fe(III) added depend strongly on the Fe(III) concentration, 0.0017 min(-1) for 1.6 × 10(-6) mol l(-1) Fe(III) to 0.105 min(-1) for 3.3 × 10(-4) mol l(-1) Fe(III). In all types of reactions, dechlorination was observed; in homogeneous photocatalytic reactions and in UV C (250-300 nm) photolysis, dechlorination proceeds with a 1 : 1 stoichiometry to atrazine degradation, in photocatalytic reactions on TiO2, dechlorination measured as chloride ion release reaches only 1/5 of the substrate degradation. In photocatalytic reactions on TiO2, mineralisation of 40% carbon was observed.
Iron-based materials used in water treatment and groundwater remediation-especially micro- and nanosized zerovalent iron (nZVI)-can be more effective when modified with lower-valent forms of sulfur (i.e., "sulfidated"). Controlled sulfidation for this purpose (using sulfide, dithionite, etc.) is the main topic of this review, but insights are derived by comparison with related and comparatively well-characterized processes such as corrosion of iron in sulfidic waters and abiotic natural attenuation by iron sulfide minerals. Material characterization shows that varying sulfidation protocols (e.g., concerted or sequential) and key operational variables (e.g., S/Fe ratio and sulfidation duration) result in materials with structures and morphologies ranging from core-shell to multiphase. A meta-analysis of available kinetic data for dechlorination under anoxic conditions, shows that sulfidation usually increases dechlorination rates, and simultaneously hydrogen production is suppressed. Therefore, sulfidation can greatly improve the efficiency of utilization of reducing equivalents for contaminant removal. This benefit is most likely due to inhibited corrosion as a result of sulfidation. Sulfidation may also favor desirable pathways of contaminant removal, such as (i) dechlorination by reductive elimination rather than hydrogenolysis and (ii) sequestration of metals as sulfides that could be resistant to reoxidation. Under oxic conditions, sulfidation is shown to enhance heterogeneous catalytic oxidation of contaminants. These net effects of sulfidation on contaminant removal by iron-based materials may substantially improve their practical utility for water treatment and remediation of contaminated groundwater.
Electric field assisted remediation using nano iron has shown outstanding results as well as economic benefits during pilot applications (Černíková et al., 2020). This method is based on donating electrons to the zero-valent iron that possess an inherently strong reductive capacity. The reduction of chlorinated hydrocarbons may be characterized by a decrease in contaminants or better still by the evolution of ethene and ethane originating from the reduction of chlorinated ethenes. The evolution of ethene and ethane was observed predominantly in the vicinity of the anode despite reduction processes being expected near the cathode - the electron donor. The reduction near the anode occurred due to dissolved Fe2+ ions, whose presence was suggested by a Pourbaix diagram that combines Eh/pH values to characterize electrochemical stabilities between different species. No products of dechlorination were observed in the area of the cathode due to presence of oxidized Fe in the form of Fe3+ or Fe(OH)4-. The experimental work described in this research provides a deeper view of the processes of electrochemical reductive dechlorination using zero-valent iron and DC. It also showed an increase in the efficiency compared to the method using zero-valent iron only.
A regiospecific and enantiospecific synthesis of tritium-labeled 28-homocastasterone is reported. Appropriate chlorocarbonate, efficiently synthesized from the starting 28-homocastasterone in an overall yield of 46%, undergoes catalytic tritium dechlorination by the T2 /Pd[0]/Et3 N system, providing 28-[3β-3 H]homocastasterone, in a good yield, radiochemical purity (>97%), and with a high specific activity (5.8 Ci/mmol).
- MeSH
- cholestanony chemie MeSH
- izotopové značení MeSH
- katalýza MeSH
- stereoizomerie MeSH
- tritium chemie MeSH
- Publikační typ
- časopisecké články MeSH
A low-permeability locality with heterogeneous geology contaminated primarily by tetrachloroethene (PCE) present partially in the free phase in the unsaturated zone was treated on a pilot scale via direct push pneumatic fracturing combined with the hydraulic delivery of a remediation suspension consisting of milled iron, sulphidated nanosized zerovalent iron and sand in guar gum solution. Afterwards, a whey solution was injected into the fractures as a carbon source for bacteria. The unsaturated and saturated zones were treated. Long-term monitoring of the groundwater revealed that the abiotic reduction of PCE and trichloroethene was the dominant remediation processes for several months after the injections. A complex microbial consortium was developed that was capable of effective, long-term chlorinated ethenes (ClE) dechlorination. The consortium consisted mainly of Dehalococcoides but also of other anaerobic bacterial strains capable of partial dechlorination of ClE, including the sulphate-reducing bacteria; Geobacter and Desulfitobacterium. The average chlorine number in the groundwater decreased from 3.65 to 1.38 within 2.5 years after the injections, while the average ClE concentration increased from 13.5 to 31.5 mgL-1 because of the substantial acceleration of the ClE mass-transfer to the groundwater caused by the treatment. The remediation processes remained fully active for 2.5 years.
Application of Fenton's reagent and enhanced reductive dechlorination are currently the most common remediation strategies resulting in removal of chlorinated ethenes. In this study, the influence of such techniques on organohalide-respiring bacteria was assessed at a site contaminated by chlorinated ethenes using a wide spectrum of molecular genetic markers, including 16S rRNA gene of the organohalide-respiring bacteria Dehaloccocoides spp., Desulfitobacterium and Dehalobacter; reductive dehalogenase genes (vcrA, bvcA) responsible for dechlorination of vinyl chloride and sulphate-reducing and denitrifying bacteria. In-situ application of hydrogen peroxide to induce a Fenton-like reaction caused an instantaneous decline in all markers below detection limit. Two weeks after application, the bvcA gene and Desulfitobacterium relative abundance increased to levels significantly higher than those prior to application. No significant decrease in the concentration of a range of chlorinated ethenes was observed due to the low hydrogen peroxide dose used. A clear increase in marker levels was also observed following in-situ application of sodium lactate, which resulted in a seven-fold increase in Desulfitobacterium and a three-fold increase in Dehaloccocoides spp. after 70 days. An increase in the vcrA gene corresponded with increase in Dehaloccocoides spp. Analysis of selected markers clearly revealed a positive response of organohalide-respiring bacteria to biostimulation and unexpectedly fast recovery after the Fenton-like reaction.
- MeSH
- Bacteria metabolismus MeSH
- bakteriální RNA genetika MeSH
- biodegradace MeSH
- chemické látky znečišťující vodu metabolismus MeSH
- chlor metabolismus MeSH
- chlorované uhlovodíky metabolismus MeSH
- genetické markery genetika MeSH
- katalýza * MeSH
- natriumlaktát aplikace a dávkování metabolismus MeSH
- oxidace-redukce MeSH
- RNA ribozomální 16S genetika MeSH
- Publikační typ
- časopisecké články MeSH
