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The production of sludge (biosolids) during wastewater treatment is a major issue for water utilities. A main issue limiting its beneficial reuse on agricultural lands is the presence of toxic metals. The currently used metal reduction technologies achieve insufficient removal of metals that are bound to the organic fraction of the sludge. In this study, we propose and demonstrate a novel method that involves the addition of nitrite during sludge acidification to enhance metal removal. Using waste activated sludge collected from three full-scale wastewater treatment plants, we found that acidification to pH 2.0 achieved good Zn solubilization of around 70%, but only 3-7% of Cu was being dissolved. Nitrite addition to the acidified sludge at a concentration of 20 mg NO2(-)-N/L (equals to 19.2 mg HNO2-N/L), substantially enhanced Cu removal to 45-64%, while Zn removal was also increased to over 81%. Metal distribution analysis using sequential chemical extraction revealed that the improvement of Cu and Zn removal was mainly due to the release of the organically bound metal fraction. We hypothesize that free nitrous acid (HNO2, FNA) may assist in the (partial) disruption of extracellular polymeric substances (EPS) and the subsequent release and solubilization of fixed metals.

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