Wastewater treatment plants (WWTP) are widely applied in practice to remove nutrients from wastewater and to minimize its impact when discharged to the environment. However, approximately 1/3 of the total organic carbon is converted into waste activated sludge (WAS), the treatment and disposal of which accounts for up to 20~60% of the overall costs of the wastewater treatment due to its poor biodegradability. In order to achieve sludge reduction and maximize the methane production from WAS, pre-treatment is often required. The overall objective of this thesis is to investigate the effects of free nitrous acid (FNA, i.e. HNO2) pre-treatment on the biodegradability of primary, secondary and digested sludges in WWTPs and also to reveal the mechanisms by which FNA works to improve the sludge degradability.The feasibility of a novel pre-treatment strategy using combined FNA and hydrogen peroxide (H2O2) to enhance methane production from WAS was investigated. WAS from a full-scale plant was treated with FNA alone (1.54 mg N/L), H2O2 alone (10~80 mg/g TS), and their combinations followed by biochemical methane potential (BMP) tests. Combined FNA and H2O2 pre-treatment substantially enhanced methane potential of WAS by 59~83%, compared to 13~23% and 56% with H2O2 pretreatment alone and FNA pre-treatment alone respectively. Model-based analysis indicated the increased methane potential was mainly associated with an increase of up to 163% in rapidly biodegradable fraction with combined pre-treatment. In some WWTPs, primary sludge (PS) and WAS are commonly mixed and digested simultaneously in the anaerobic digester. In order to reveal whether and how the PS and WAS should be jointly II treated by FNA in WWTPs, the effects and mechanisms of FNA pre-treatment on methane production from PS was studied. Full-scale derived PS was pre-treated with FNA at concentrations of 0~3.85 mg N/L followed by BMP tests. FNA treated PS was then centrifuged to separate the supernatant from the solid phase and BMP tests were performed on both fractions. The FNA pre-treatments resulted in methane potential reductions of 1~7%. The methane production from both supernatant and solid phases had also decreased. The molecular weight and chemical structure analysis of components of the soluble phase showed very limited release of readily biodegradable substances from PS with the FNA pre-treatment. As the FNA pre-treatment compromised the methane production from PS, this indicates that FNA-based sludge pre-treatment technology should be implemented solely on WAS to maximise the methane production from the two sludge streams.The ever increasing production of the two sludge streams occurring due to increased population will create challenges for handling, treatment and disposal of the sludge at current capacity, making it difficult to achieve the desirable sludge reduction efficiency in anaerobic digestion. Post anaerobic digestion of anaerobically digested sludge (ADS) has been applied to enhance sludge reduction, however, so far this has had on...