Evaluation of dissolved and immobilized redox mediators on dark fermentation: Driving to hydrogen or solventogenic pathway.

In this work, lawsone (LQ) and anthraquinone 2-sulphonate (AQS) (dissolved and covalently immobilized on activated carbon) were evaluated as redox mediators during the dark fermentation of glucose by a pretreated anaerobic sludge. Findings revealed that the use of dissolved LQ increased H2 production (10%), and dissolved AQS improved H2 production rate (11.4%). Furthermore, the total production of liquid byproducts (acetate, butyrate, ethanol, and butanol) was enhanced using dissolved (17%) and immobilized (36%) redox mediators. The established redox standard potentials of LQ and AQS suggested a possible interaction through electron transfer in cytochromes complexes for hydrogen production and the Bcd/EtfAB complex for volatile fatty acid formation.

Mechanism of anaerobic bio-reduction of azo dye assisted with lawsone-immobilized activated carbon.

Lawsone redox (LQ) mediator was covalently bound to granular activated carbon (GAC) by Fischer esterification. A high LQ adsorption capacity on GAC was achieved (∼230 mg/g), and desorption studies showed strong chemical stability. Furthermore, kinetic experiments with solid-phase redox mediator (RM) and their controls (soluble RM, GAC and anaerobic sludge) were tested for decolorization of congo red dye at initial concentration of 175 mg/L. Benzidine, a by-product of complete congo red reduction, was also measured by HPLC analysis along the kinetic experiments. The highest percentage of decolorization after 24 h of incubation was achieved in cultures with soluble (77%) and immobilized (70%) LQ. In contrast, low decolorization efficiency was reached in anaerobic bio-reduction assays with unmodified GAC (47%) and anaerobic sludge (28%) after 24 h. Removal of congo red by adsorption onto LQ-GAC was negligible. The rate of benzidine production was slower than decolorization rate, suggesting that one azo bond of congo red is selectively broke and followed by a slower breaking of the second azo bond, consequently, appearance of benzidine in solution. These issues could be attributed to the steric rearrangement and the inhibitory effects of the produced aromatic amines in the biotransformation process.

Quinone-functionalized activated carbon improves the reduction of congo red coupled to the removal of p-cresol in a UASB reactor.

In this research was immobilized anthraquinone-2-sulfonate (AQS) on granular activated carbon (GAC) to evaluate its capacity to reduce congo red (CR) in batch reactor and continuous UASB reactors. The removal of p-cresol coupled to the reduction of CR was also evaluated. Results show that the immobilization of AQS on GAC (GAC-AQS) achieved 0.469mmol/g, improving 2.85-times the electron-transferring capacity compared to unmodified GAC. In batch, incubations with GAC-AQS achieved a rate of decolorization of 2.64-fold higher than the observed with GAC. Decolorization efficiencies in UASB reactor with GAC-AQS were 83.9, 82, and 79.9% for periods I, II, and III; these values were 14.9-22.8% higher than the obtained by reactor with unmodified GAC using glucose as energy source. In the fourth period, glucose and p-cresol were simultaneously fed, increasing the decolorization efficiency to 87% for GAC-AQS and 72% for GAC. Finally, reactors efficiency decreased when p-cresol was the only energy source, but systems gradually recovered the decolorization efficiency up to 84% (GAC-AQS) and 71% (GAC) after 250 d. This study demonstrates the longest and efficient continuous UASB reactor operation for the reduction of electron-accepting contaminant in presence of quinone-functionalized GAC, but also using a recalcitrant pollutant as electron donor.