Bonding form analysis of metals and sulfur fractionation in methanol-grown anaerobic granular sludge

This study investigates the metal and sulfur bonding form distribution in mesophilic (30 degrees C, pH 7) methanol-grown anaerobic granular sludge from upflow anaerobic sludge bed reactors operating at an organic loading rate of 3.8 g CH3OH-COD/L d. This was achieved by applying a modified Tessier sequential extraction scheme to investigate the metal bonding forms and a sequential extraction scheme for sulfur and simultaneously extracted metals to granular sludge samples of the reactors after 0, 22, 35 and 43 days of operation. Metals were also determined in the sulfur extracts. Co and Ni predominated in their oxidizable bonding forms, which increased together with the pseudo-total content during reactor operation. An omission of Co and Ni from the influent led to only a minor decline of the pseudo-total content in the sludge, mainly from the acid-soluble fraction. The ratio of simultaneously extracted metals (Co, Fe, Mn, Ni) to acid-volatile sulfides was lower than 1, indicating that the sludge contained sufficient sulfide to bind the metals as metal monosulfides. The bioavailability of metals in the methanol-grown anaerobic granular sludge investigated is therefore mainly controlled by sulfide formation/dissolution.