A “cradle-to-grave” life cycle assessment is performed to identify the environmental issues of polyhydroxyalkanoates (PHAs) produced through a hybrid thermochemical-biological process using anaerobically digested sewage sludge (ADSS) as feedstock. The assessment includes a measure of the energy performance of the process. The system boundary includes: (i) Sludge pyrolysis followed by volatile fatty acids (VFAs) production; (ii) PHAs-enriched biomass production using a mixed microbial culture (MMC); (iii) PHAs extraction with dimethyl carbonate; and iv) PHAs end-of-life. Three scenarios differing in the use of the syngas produced by both pyrolysis and biochar gasification, and two more scenarios differing only in the external energy sources were evaluated. Results show a trade-off between environmental impacts at global scale, such as climate change and resources depletion, and those having an effect at the local/regional scale, such as acidification, eutrophication, and toxicity. Process configurations based only on the sludge-to-PHAs route require an external energy supply, which determines the highest impacts with respect to climate change, resources depletion, and water depletion. On the contrary, process configurations also integrating the sludge-to-energy route for self-sustainment imply more onsite sludge processing and combustion; this results in the highest values of eutrophication, ecotoxicity, and human toxicity. There is not a categorical winner among the investigated configurations; however, the use of a selected mix of external renewable sources while using sludge to produce PHAs only seems the best compromise. The results are comparable to those of both other PHAs production processes found in the literature and various fossil-based and bio-based polymers, in terms of both non-biogenic GHG emissions and energy demand. Further process advancements and technology improvement in high impact stages are required to make this PHAs production process a competitive candidate for the production of biopolymers on a wide scale.

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