Underestimated humic acids release and influence on anaerobic digestion during sludge thermal hydrolysis

•Large amounts of HAs were released from sludge during THP.•Structural characteristics of HAs were altered during THP.•Influences of HAs on sludge digestion varied with the concentration and structure.•HAs inhibited sludge hydrolysis but improved methanogenesis at low concentration. Humic-like acids (HAs) are abundant in sewage sludge but mainly bonded with solids. Thus, their influences are often neglected in conventional digestion processes. Currently thermal hydrolysis pretreatment (THP) has been widely adopted in sludge anaerobic digestion (AD) to enhance hydrolysis of complex matters and further to improve methane production. However, the impacts of enhanced release of HAs and the mechanisms involved are not well understood and need to be further investigated because the substantial amounts of HAs present in AD could severely threaten the sludge AD processes. Results in the present study indicated that the concentration of soluble HAs in sludge was elevated by 90 times due to the THP, from 8 mg/L in raw sludge to 727 mg/L in the pretreated sludge hydrolyzed at 180 °C. Moreover, the structural characteristics of soluble HAs, including aromatic condensation degree, elemental composition and functional group, also showed substantial differences with the increased temperature of the THP. Furthermore, the release of HAs presented significant influences on sludge digestion. Acidification rate was inhibited by over 50% with 0.4 g/L of HAs, whereas methanogenesis was improved by nearly 200% with 0.8 g/L HAs and inhibited about 50% with 2.0 g/L. The activities of proteinase and co-enzyme F420 were decreased by 20% and increased by 19%, respectively, under HAs stress at 0.6 g/L for 5 days. Moreover, molecular structural changes of soluble HAs also contributed to the influences. Especially, the E4/E6 value representing the degree of HAs aromatic condensation and C/N ratio of soluble HAs were closely correlated with their inhibition degree to sludge hydrolysis. The findings of this study demonstrate that the influences of HAs are evident and also vary to the different steps of anaerobic digestion processes, which shall not be negligible during the sludge digestion that is with THP. Due to the rate-limiting step was methanogenesis in the AD process of pretreated sludge by thermal hydrolysis, HAs concentration was recommended at low level, for example around 1.0 g/L, to accelerate or not limit methanogenesis. [Display omitted]