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Oxidation-reduction reactions of copper-thiolate centres in Cu-thionein.

Cu-thionein from yeast was investigated by EPR spectroscopy to probe the oxidation state of copper, and the effects on it of oxidizing and reducing agents. At pH 0.2 the copper was released, but no EPR signal from Cu(II) was observed, unless air was present. Optical experiments did not detect any disulphide groups which might have been formed during anaerobic release of copper. The mercurial, p-hydroxymercuribenzoate caused the release of EPR-detectable copper only under aerobic conditions, and EDTA caused release of Cu(II) on heating. No reduction of the copper-thiolate units in Cu-thionein by ascorbate was detected. Potentiometric titrations with hexachloroiridate(IV) or hexacyanoferrate(III) produced several different Cu(II) EPR signals at various stages of oxidation. The former oxidizing agent required a lower oxidation-reduction potential (+350 mV) to oxidize the copper, than the latter (+410 mV) and neither titration was fully reversible. The EPR signal from Cu(II) oxidized by hexachloroiridate(IV) resembled that produced by p-hydroxy-mercuribenzoate in air, suggesting that the copper was released from its thiolate ligands. It is concluded that the EPR non-detectable copper in the native protein is Cu(I). Oxidation-reduction of the copper-thiolate clusters of Cu-thionein is proposed to be decisive for controlling storage and transport of cellular copper.

Biological Transport↗

Effectiveness of oxidation-reduction potential and pH as monitoring and control parameters for nitrogen removal in swine wastewater treatment by sequencing batch reactors.

Two bench-scale sequencing batch reactors (SBRs) were operated in a fixed hydraulic retention time study to investigate the effectiveness of oxidation-reduction potential (ORP), pH and dissolved oxygen as parameters for indicating denitrification followed by nitrification in SBRs for swine wastewater treatment. The ORP and pH profiles were monitored and evaluated under different denitrification and nitrification conditions with and without a supplemental carbon source. With a low C/N ratio, and using a suitable C/N ratio adjustment control, ORP and pH could be used as monitoring and control parameters in both the anoxic and oxic phases for practical swine wastewater treatment. High-level accumulation of nitrate was observed without any C/N ratio adjustment. In this case, ORP and pH were not useful for monitoring denitrification followed by nitrification in SBRs. According to our research, with regard to N removal, it would be better to use pH as a parameter during the oxic phase and ORP as a parameter during the anoxic phase. Using a suitable adjustment of a ON ratio in the influent by adding swine slurry, a high total nitrogen removal efficiency of up to 95.5% was reached. It was found that, in this case, the use of ORP and pH as parameters for real-time control processes was possible in swine wastewater treatment.

Journal Article↗