Nitration Processes of Acetaminophen in Nitrifying Activated Sludge

This work is an attempt to elucidate the quantitative significance of acetaminophen (APAP) nitration in nitrifying activated sludge and to propose a reaction mechanism for this process. The link between nitrification and nitration of APAP was investigated at different scales. Results from field studies showed the occurrence of 3-nitro-APAP and to a lesser extent 3-chloro-5-nitro-APAP at concentration levels in the 50−300 ng/L range in effluents of a full scale wastewater treatment plant (WWTP) operated with nitrogen removal, whereas 3-hydroxy-APAP was eliminated after the nitrification step. Batch experiments with nitrifying activated sludge confirmed APAP transformation by nitration and suggested that nitrifying bacteria may play a role in this transformation process through the release of reactive nitrogen species. In vitro assays provided evidence that nitration through the production of nitrous acid is a very unlikely pathway. In contrast, nitric oxide (•NO) produced by nitrifying bacteria is probably involved in APAP nitration through the formation of peroxynitrite in presence of superoxide anion. The production of 3-nitro-APAP would only account for a few percents of the total transformation rate of APAP in WWTPs. The production of nitrated derivatives is highly relevant because of the potential ecotoxicological risks of these compounds.