Per-and polyfluoroalkyl substances (PFAS) are a large group of manmade chemicals that impose emerging environmental concerns. Among them, short-chain per-and polyfluorinated carboxylic acids represent an important subgroup used as building blocks of biologically active chemicals and functional materials. Some are also considered PFAS alternatives, and some could be byproducts of the physicochemical treatment of PFAS. However, little is known about the environmental fate of shortchain fluorinated carboxylic acids (FCAs) and their defluorination/ transformation by microorganisms. To fill the knowledge gap, we investigated the structure−reactivity relationships in the aerobic defluorination of C 3 −C 5 FCAs by activated sludge communities. Four structures exhibited greater than 20% defluorination, with 3,3,3-trifluoropropionic acid being almost completely defluorinated. We further analyzed the defluorination/transformation pathways and inferred the structures susceptible to aerobic microbial defluorination. We also demonstrated that the defluorination was via cometabolism. The findings advance the fundamental understanding of aerobic microbial defluorination and help assess the environmental fate of PFAS. Since some short-chain PFAS, such as 3,3,3-trifluoropropionic acid, are the incomplete defluorination byproducts of advanced reduction processes, their defluorination by activated sludge communities sheds light on the development of cost-effective chemical−biological PFAS treatment train systems.

Functional differentiation and metabolite exchange enable microbial consortia to perform complex metabolic tasks and efficiently cycle the nutrients. Inspired by the cooperative relationships in environmental microbial consortia, synthetic microbial consortia have great promise for studying the microbial interactions in nature and more importantly for various engineering applications. However, challenges coexist with promises, and the potential of consortium-based technologies is far from being fully harnessed. Thorough understanding of the underlying molecular mechanisms of microbial interactions is greatly needed for the rational design and optimization of defined consortia. These knowledge gaps could be potentially filled with the assistance of the ongoing revolution in systems biology and synthetic biology tools. As current fundamental and technical obstacles down the road being removed, we would expect new avenues with synthetic microbial consortia playing important roles in biological and environmental engineering processes such as bioproduction of desired chemicals and fuels, as well as biodegradation of persistent contaminants.

The recently discovered microbial reductive defluorination of two C 6 branched and unsaturated fluorinated carboxylic acids (FCAs) provided valuable insights into the environmental fate of per-and polyfluoroalkyl substances (PFASs) and potential bioremediation strategies. However, a systematic investigation is needed to further demonstrate the role of CC double bonds in the biodegradability of unsaturated PFASs. Here, we examined the structure-biodegradability relationships of 13 FCAs, including nine commercially available unsaturated FCAs and four structurally similar saturated ones, in an anaerobic defluorinating enrichment and an activated sludge community. The anaerobic and aerobic transformation/defluorination pathways were elucidated. The results showed that under anaerobic conditions, the α,β-unsaturation is crucial for FCA biotransformation via reductive defluorination and/or hydrogenation pathways. With sp 2 C−F bonds being substituted by C−H bonds, the reductive defluorination became less favorable than hydrogenation. Moreover, for the first time, we reported enhanced degradability and defluorination capability of specific unsaturated FCA structures with trifluoromethyl (−CF 3 ) branches at the α/β-carbon. Such FCA structures can undergo anaerobic abiotic defluorination in the presence of reducing agents and significant aerobic microbial defluorination. Given the diverse applications and emerging concerns of fluorochemicals, this work not only advances the fundamental understanding of the fate of unsaturated PFASs in natural and engineered environments but also may provide insights into the design of readily degradable fluorinated alternatives to existing PFAS compounds.