Four identically configured anaerobic packed bed biofilm reactors were developed and employed in the continuous acidogenic digestion of olive mill wastewaters to produce volatile fatty acids (VFAs), which can be exploited in the biotechnological production of polyhydroxyalkanoates. Ceramic porous cubes or granular activated carbon were used as biofilm supports. Aside packing material, the role of temperature and organic loading rate (OLR) on VFA production yield and mixture composition were also studied. The process was monitored through a chemical, microbiological and molecular biology integrated procedure. The highest wastewater acidification yield was achieved with the ceramic-based technology at 25 °C, with an inlet COD and an OLR of about 17 g/L and 13 g/L/day, respectively. Under these conditions, about the 66% of the influent COD (not including its VFA content) was converted into VFAs, whose final amount represented more than 82% of the influent COD. In particular, acetic, propionic and butyric acids were the main VFAs by composing the 55.7, 21.5 and 14.4%, respectively, of the whole VFA mixture. Importantly, the relative concentrations of acetate and propionate were affected by the OLR parameter. The nature of the packing material remarkable influenced the process performances, by greatly affecting the biofilm bacterial community structure. In particular, ceramic cubes favoured the immobilization of Firmicutes of the genera Bacillus, Paenibacillus and Clostridium, which were probably involved in the VFA producing process.
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