Fluorotelomer Alcohol BiodegradationDirect Evidence that Perfluorinated Carbon Chains Breakdown

There is increasing scientific interest to understand the environmental fate of fluorotelomer alcohols (FTOHs) and fluorotelomer-based products which may break down to FTOHs. Both are expected to enter aqueous waste streams, which would be processed in a wastewater treatment plant and therein subject to microbial biodegradation. We investigated the biodegradation of 3-14C, 1H,1H,2H,2H-perfluorodecanol [CF3(CF2)6(14)CF2CH2CH2OH, 14C-8-2 FTOH] in mixed bacterial culture and activated sludge. 14CO2 and 14C-organic volatiles in the headspace of the sealed bottles and bottles with continuous air flow were analyzed up to 4 months. After sample extraction with acetonitrile, 14C-labeled biotransformation products (metabolites) were quantified by LC/ARC (on-line liquid chromatography/ accurate radioisotope counting) and identified by quadrupole time-of-flight (Q-TOF) mass spectrometry and GC/MSD (mass selective detector). Three metabolites not yet reported in the literature have been identified as CF3(CF2)6(14)CHOHCH3 (7-2 sFTOH), CF3(CF2)6(14)CH=CHCOOH (7-3 unsaturated acid or 7-3 u acid), and CF3(CF2)6(14)CH=CHCONH2 (7-3 u amide) along with five previously reported metabolites [CF3(CF2)6(14)CF2CH2CHO (8-2 FTAL), CF3(CF2)6 (14)CF2CH2COOH (8-2 acid), CF3(CF2)6(14)CF=CHCOOH (8-2 u acid), CF3(CF2)6(14)CH2CH2COOH (7-3 acid), and CF3(CF2)6(14)COOH (PFOA)]. No CF3(CF2)6(14)CF2COOH (14C-PFNA) was observed, indicating that alpha-oxidation does not take place. It was found that strong adsorption to the activated sludge and subsequent transformation, even under continuous air flow, greatly reduced partitioning of 8-2 FTOH or any transformation products to air. CF3(CF2)4COOH (PFHA; perfluorohexanoic acid) was observed and increased in mixed bacterial culture over 28 days and accounted for about 1% of the initial 14C-8-2 FTOH concentration from day 28 to day 90. 14CO2 accounted for 1% of initial 14C in activated sludge with continuous air flow at day 1 and increased over time. In closed bottles, 14CO2 in the headspace of activated sludge medium increased to 12% of the available 14C over 135 days with periodic addition of ethanol, as compared to 3% when no additional ethanol was added. These results show that replenishment of organic carbon enhanced microbial mineralization of multiple--CF2--groups in the fluorocarbon chain of 14C-8-2 FTOH. At day 90 the net increase of fluoride ion in the mixed bacterial culture was 93 microg L(-1), equivalent to 12% of total mineralization (destruction) of the 14C-8-2 FTOH. These results demonstrate that perfluorinated carbon bonds of 14C-8-2 FTOH are defluorinated and mineralized by microorganisms under conditions which may occur in a wastewater treatment plant, forming shorter fluorinated carbon metabolites.