Per- and polyfluoroalkyl substances (PFAS) are a group of fluorinated synthetic chemicals that are highly recalcitrant, toxic, and bio-accumulative and have been detected in biosolids worldwide, posing potential risks to humans and the environment. Recent studies suggest that the organic C-F bond in PFAS can be destructed and potentially mineralised into inorganic fluorides during thermal treatment. This study focuses on thermodynamic equilibrium investigations and the fate of fluorine compounds post-PFAS destruction during biosolid thermal treatment. The results indicate that gas-phase fluorine compounds are mainly hydrogen fluoride (HF) and alkali fluorides, whereas solid-phase fluorine compounds include alkaline earth fluorides and their spinels. High moisture and oxygen content in the volatiles increased the concentration of HF in the gas phase. However, adding minerals reduced the emission of HF in the gas phase significantly and enhanced the capture of fluorine as CaF₂ spinel in the solid phase. This study also investigates the effect of feedstock composition on the fate of fluorine. High ash content and low volatile matter in the feedstock reduced HF gas emissions and increased fluorine capture in the solid product. The findings of this work are useful in designing thermal systems with optimised operating conditions for minimising the release of fluorinated species during the thermal treatment of PFAS-containing biosolids.

Pyrolysis is gaining recognition as a sustainable solution for biosolid management, though scaling it commercially presents challenges. To address this, RMIT developed a novel integrated pyrolysis and gasification technology called PYROCO™, which was successfully tested in pilot-scale trials. This study introduces PYROCO™ and its application to produce biochar, highlighting the biochar properties of the results of the initial trials. In addition, an energy analysis using semi-empirical Aspen Plus modelling, paired with a preliminary techno-economic assessment, was carried out to evaluate the feasibility of this technology. The results show that the PYROCO™ pilot plant produced biochar with a ~30 wt% yield, featuring beneficial agronomic properties such as high organic carbon (210–220 g/kg) and nutrient contents (total P: 36–42 g/kg and total N: 16–18 g/kg). The system also effectively removed contaminants such as PFASs, PAHs, pharmaceuticals, and microplastics from the biochar and scrubber water and stack gas emissions. An energy analysis and Aspen Plus modelling showed that a commercial-scale PYROCO™ plant could operate energy self-sufficiently with biosolids containing >30% solids and with a minimum calorific value of 11 MJ/kg. The process generates excess energy for drying biosolids and for electricity generation. Profitability is sensitive to biochar price; prices rise from AUD 300 to AUD 1000 per tonne, the NPV improves from AUD 0.24 million to AUD 4.31 million, and the payback period shortens from 26 to 12 years. The low NPV and high payback period reflect the use of a relatively high discount rate of 8%, chosen to be on the conservative side given the novel nature of the technology.