Hexachlorocyclohexane (HCH) isomers represent a family of formerly widely utilized pesticides that are persistent, capable of undergoing long-range transport and tend to bioaccumulate in human and animal tissue. Their widespread global utilization coupled with a propensity to adversely impact human health and the environment translates into an urgent need to develop feasible methodologies by which to treat HCH-impacted groundwater and soil. The present study was conducted to evaluate the efficacy of two persulfate-based oxidants: peroxydisulfate (S2O8 (2-), PDS) and peroxymonosulfate (HSO5 (-), PMS) activated by electrochemical processes (EC) to treat HCH-impacted environmental media. This research demonstrated that the optimal experimental conditions (oxidant dose and electrical current) were 2 mM PDS and 20 mA for an aqueous solution of 4 μM of summed HCHs (ΣHCH). GC/MS full scan analysis revealed the presence of 2,4,6-trichlorophenol as the only detectable intermediate formed during electro-activated PDS treatment of ΣHCH. The investigated method was tested on leachate from a known HCHs-impacted site in Hajek, Czech Republic which contained 106 μg/l of ΣHCH and 129 μg/l of chlorobenzenes. Results from batch treatment showed positive results for electro-activated PDS but only negligible effectiveness for electro-activated PMS. In addition to explaining the efficacy of the electro-activated PDS, this research also explored the basis for the differing reactivities of these two persulfates.
Amongst all of the reducing agents that can be used in environmental remediation, zero valent iron (ZVI) is one of the most common due to its environmental acceptance, high reaction rate, good availability, and long-term stability. Moreover, ZVI mobility, stability and reactivity can be enhanced by the application of a DC electric current, ie electrokinetics (EK). In the study, six various slurries containing different ZVI were tested for their efficacy for chlorinated ethenes and ethanes degradation. Chlorinated compound concentrations, pH, oxidation-reduction potential (ORP) and conductivity were determined during the long-term kinetic test. Kinetic rate constants calculated for the degradation of three chlorinated ethenes (PCE, TCE and cis-DCE) concluded that EK brings substantial contribution to chlorinated compounds degradation. Nano-scale zero valent iron STAR had the highest reaction rates compare to the other ZVI tested. The performed study could serve as a preliminary assessment of various available ZVI before in-situ application.
A stall of cis-1,2-DCE and vinyl chloride (VC) is frequently observed during bioremediation of groundwater chloroethenes via reductive dechlorination. These chloroethenes may be oxidised by aerobic methanotrophs or ethenotrophs co-metabolically and/or metabolically. We assessed the potential for such oxidation at 12 sites (49 groundwater samples) using hydrochemical and molecular biological tools. Both ethenotroph (etnC and etnE) and methanotroph (mmoX and pmoA) functional genes were identified in 90% of samples, while reductive dehalogenase functional genes (vcrA and bvcA) were identified in 82%. All functional genes were simultaneously detected in 78% of samples, in actively biostimulated sites in 88% of samples. Correlation analysis revealed that cis-1,2-DCE concentration was positively correlated with vcrA, etnC and etnE, while VC concentration was correlated with etnC, etnE, vcrA and bvcA. However, feature selection based on random forest classification indicated a significant relationship for the vcrA in relation to cis-1,2-DCE, and vcrA, bvcA and etnE for VC and no prove of relationship between cis-1,2-DCE or VC and the methanotroph functional genes. Analysis of hydrochemical parameters indicated that aerobic oxidation of chloroethenes by ethenotrophs may take place under a range of redox conditions of aquifers and coincide with high ethene and VC concentrations.
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