The transformation and toxicity of anthraquinone dyes during thermophilic (55 degrees C) and mesophilic (30 degrees C) anaerobic treatments.

We studied in batch assays the transformation and toxicity of anthraquinone dyes during incubations with anaerobic granular sludge under mesophilic (30 degrees C) and thermophilic (55 degrees C) conditions. Additionally, the electron shuttling capacity of the redox mediator anthraquinone-2-sulfonic acid (AQS) and subsequent increase on decolourisation rates was investigated on anthraquinone dyes. Compared with incubations at 30 degrees C, serum bottles at 55 degrees C presented distinctly higher decolourisation rates not only with an industrial wastewater containing anthraquinone dyes, but also with model compounds. Compared with batch assays at 30 degrees C, the first-order rate constant "k" of the Reactive Blue 5 (RB5) was enhanced 11-fold and 6-fold for bottles at 55 degrees C supplemented and free of AQS, respectively. However, the anthraquinone dye Reactive Blue 19 (RB19) demonstrated a very strong toxic effect on volatile fatty acids (VFA) degradation and methanogenesis at both 30 degrees C and 55 degrees C. The apparent inhibitory concentrations of RB19 exerting 50% reduction in methanogenic activity (IC50-value) were 55 mg l(-1) at 30 degrees C and 45 mg l(-1) at 55 degrees C. Further experiments at both temperatures revealed that RB19 was mainly toxic to methanogens, because the glucose oxidizers including acetogens, propionate-forming, butyrate-forming and ethanol-forming microorganisms were not affected by the dye toxicity.

Effect of different redox mediators during thermophilic azo dye reduction by anaerobic granular sludge and comparative study between mesophilic (30 degrees C) and thermophilic (55 degrees C) treatments for decolourisation of textile wastewaters.

The impact of different redox mediators on colour removal of azo dye model compounds and textile wastewater by thermophilic anaerobic granular sludge (55 degrees C) was investigated in batch assays. Additionally, a comparative study between mesophilic (30 degrees C) and thermophilic (55 degrees C) colour removal was performed with textile wastewater, either in the presence or absence of a redox mediator. The present work clearly evidences the advantage of colour removal at 55 degrees C compared with 30 degrees C when dealing with azo coloured wastewaters. The impact of the redox mediators anthraquinone-2,6-disulfonate (AQDS), anthraquinone-2-sulfonate (AQS) and riboflavin was evident with all dyes, increasing decolourisation rates up to 8-fold compared with the mediator-free incubations. The generation of the hydroquinone form AH2QDS, i.e. the reduced form of AQDS, was extremely accelerated at 55 degrees C compared with 30 degrees C. Furthermore, no lag-phase was observed at 55 degrees C. Based on the present results we postulate that the production/transfer of reducing equivalents was the process rate-limiting step, which was accelerated by the temperature increase. It is conclusively stated that 55 degrees C is a more effective temperature for azo dye reduction than 30 degrees C, which on the one hand can be attributed to the faster production/transfer of reducing equivalents, but also to the decrease in activation energy requirements.

Activated carbon as an electron acceptor and redox mediator during the anaerobic biotransformation of azo dyes.

Activated carbon (AC) has a long history of applications in environmental technology as an adsorbent of pollutants for the purification of drinking waters and wastewaters. Here we describe novel role of AC as redox mediator in accelerating the reductive transformation of pollutants as well as a terminal electron acceptor in the biological oxidation of an organic substrate. This study explores the use of AC as an immobilized redox mediator for the reduction of a recalcitrant azo dye (hydrolyzed Reactive Red 2) in laboratory-scale anaerobic bioreactors, using volatile fatty acids as electron donor. The incorporation of AC in the sludge bed greatly improved dye removal and formation of aniline, a dye reduction product. These results indicate that AC acts as a redox mediator. In supporting batch experiments, bacteria were shown to oxidize acetate at the expense of reducing AC. Furthermore, AC greatly accelerated the chemical reduction of an azo dye by sulfide. The results taken as a whole clearly suggest that AC accepts electrons from the microbial oxidation of organic acids and transfers the electrons to azo dyes, accelerating their reduction. A possible role of quinone surface groups in the catalysis is discussed.