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Previous studies evaluating Vitamin B12 (VB12) with Ti(III)-citrate for potential use in in situ remediation of perfluorooctanesulfonate (PFOS) found that linear (L)-PFOS was unaltered. We explored if alternate reductants could overcome this limitation with a primary focus on nanoscale zerovalent zinc (nZn). Transformation over time with VB12-nZn was quantified at 22, 70, and 90 °C for PFOS, at 70 °C for perfluorohexanesulfonate (PFHxS), and VB12-nFe and VB12-Pd/nFe at 70 °C for PFOS. Only branched (br-) isomers were transformed generating F (no SO) and polyfluoroalkyl intermediates/products. The absence of L-PFOS transformation by VB12 appears to be due to the inability of L-perfluoroalkyl sulfonates to complex with VB12 and not an activation energy issue that can be overcome by stronger reductants/catalysts. At 90 °C, 95% of br-PFOS isomers were transformed within 5 days. Isomer-specific removal rates were positively correlated to the br-CF's proximity to the terminal CF. Br-PFHxS transformation was approximately two times slower with less defluorination than br-PFOS. C8/C7 and C6/C5 polyfluorinated sulfonates from br-PFOS and br-PFHxS, respectively, were identified as both intermediates and apparent dead-end products. Pathways included 4 F replaced by 2 H and a C═C bond, and serial F replacement by H with up to 12 F atoms removed from br-PFOS.

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