Application of redox mediators to accelerate the transformation of reactive azo dyes in anaerobic bioreactors

Azo dyes are nonspecifically reduced under anaerobic conditions but the slo w rates at which reactive azo dyes are converted presents a serious problem for the application of anaerobic technology as a first stage in the comple te biodegradation of these compounds. As quinones have been found to cataly ze reductive transfers by acting as redox mediators, the application of ant hraquinone-2,6-disulfonic acid (AQDS) during continuous anaerobic treatment of the reactive azo dye, Reactive Red 2 (RR2), was evaluated. A mixture of volatile fatty acids was used as the electron-donating primary substrate. Batch experiments demonstrated that AQDS could increase the first-order rat e constant of RR2 reductive cleavage by one order of magnitude. In the cont inuous experiment, treatment of RR2 containing synthetic wastewater in a la b-scale upflow anaerobic sludge blanket (UASB) reactor yielded low dye remo val eciencies (< 30%). Consequently, severe toxicity problems occurred, eve ntually resulting in almost complete inhibition of the methanogenic activit y. Addition of catalytic concentrations of AQDS (19 muM) to the reactor inf luent caused an immediate increase in the dye removal efficiency and recove ry of biological activity. Ultimately, RR2 removal efficiency stabilized at 88%, and higher AQDS loads resulted in higher RR2 removal efficiencies (up to 98% at 155 muM AQDS). Examination of the RR2 decolorizing properties of dye-adapted reactor sludge and of nonadapted reactor seed sludge revealed that RR2 decolorization was principally a biologically driven transfer of r educing equivalents from endogenous and added substrates to the dye. Hydrog en, added in bulk, was clearly the preferred electron donor. Bacteria that couple dye decolorization to hydrogen oxidation were naturally present in s eed sludge. However, enrichment was required for the utilization of electro ns from volatile fatty acids for dye reduction. The stimulatory effect of A QDS on RR2 decolorization by AQDS-unadapted sludge was mainly due to assist ing the electron transfer from endogenous substrates in the sludge to the d ye. The stimulatory effect of AQDS on RR2 decolorization by sludge from the AQDS-exposed reactor was, in addition, strongly associated with the transf er of electrons from hydrogen and acetate to the dye, probably due to enric hment of specialized AQDS-reducing bacteria. (C) 2001 John Wiley & Sons, In c.