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This study presents a novel pre-treatment strategy using combined free nitrous acid (FNA i.e. HNO 2 ) and hydrogen peroxide (H 2 O 2 ) to enhance methane production from WAS, with the mechanisms investigated bio-molecularly. WAS from a full-scale plant was treated with FNA alone (1.54 mg N/L), H 2 O 2  alone (10–80 mg/g TS), and their combinations followed by biochemical methane potential tests. Combined FNA and H 2 O 2  pre-treatment substantially enhanced methane potential of WAS by 59–83%, compared to 13–23% and 56% with H 2 O 2  pre-treatment alone and FNA pre-treatment alone respectively. Model-based analysis indicated the increased methane potential was mainly associated with up to 163% increase in rapidly biodegradable fraction with combined pre-treatment. The molecular weight distribution and chemical structure analyses revealed the breakdown of soluble macromolecules with the combined pre-treatment caused by the deamination and oxidation of the typical functional groups in proteins, polysaccharides and phosphodiesters. These changes likely improved the biodegradability of WAS.

Combined free nitrous acid and hydrogen peroxide pre-treatment of waste activated sludge enhances methane production via organic molecule breakdown