Anaerobic treatments have been described for the biodegradation of pollutants. However, the reactions proceed slowly due to the recalcitrant nature of these compounds. Carbon nanomaterials (CNM) intermediate in, and favor, the electron transfer, accelerating the anaerobic reduction of pollutants, which act as final electron acceptors. In the present work, different carbon nanotubes (CNT) with modified surface chemistry, namely CNT oxidized with HNO3 (CNT_HNO3) and CNT doped with nitrogen in a ball milling process (CNT_N_MB) were prepared using commercial CNT as a starting material. The new CNM were tested as redox mediators (RM), 0.1 g L-1, in the biological reduction of the azo dye, Acid Orange 10 (AO10), with an anaerobic granular sludge, over 48 h of reaction. Methane production was also assessed to verify the microorganism's activity and the CNM's effect on the methanogenic activity. An improvement in the biological removal of AO10 occurred with all CNM (above 90%), when compared with the control without CNM (only 32.4 ± 0.3%). The best results were obtained with CNT_N_MB, which achieved 98.2 ± 0.1% biological AO10 removal, and an 11-fold reduction rate increase. In order to confer magnetic properties to the CNM, tailored CNT were impregnated with 2% of iron-samples: CNT@2%Fe, CNT@2%Fe_N_MB, and CNT@2%Fe_HNO3. The better performance of the CNT doped with nitrogen was confirmed with CNT@2%Fe_N_MB, and the magnetic character facilitated its recovery after treatment, and did not affect its good catalytic properties. No dye removal was observed in the abiotic assays, so the removal was not due to adsorption on the CNM. Furthermore, the microorganism's viability was maintained during the assay and methane production was not affected by the presence of the CNM. Despite the toxic character of the aromatic amines formed, detoxification was observed after the biological process with thermally treated CNT.
Keywords: acid orange 10; biological reduction; by-products toxicity; tailored carbon nanotubes; toxicity.