ABSTRACT
Biotransformation of fluorotelomer (FT) compounds, such as 8:2 FT alcohol (FTOH) is now recognized to be a source of perfluorooctanoic acid (PFOA) as well as other perfluoroalkyl acids. In this study, microbially mediated hydrolysis of FT industrial intermediates 8:2 FT acrylate (8:2 FTAC) and 8:2 FT methacrylate (8:2 FTMAC) was evaluated in aerobic soils for up to 105d. At designated times, triplicate microcosms were sacrificed by sampling the headspace for volatile FTOHs followed by sequential extraction of soil for the parent monomers as well as transient and terminal degradation products. Both FTAC and FTMAC were hydrolyzed at the ester linkage as evidenced by 8:2 FTOH production. 8:2 FTAC and FTMAC degraded rapidly with half-lives ⩽5d and 15d, respectively. Maximum 8:2 FTOH levels were 6-13mol% within 3-6d. Consistent with the known biotransformation pathway of 8:2 FTOH, FT carboxylic acids and perfluoroalkyl carboxylic acids were subsequently generated including up to 10.3mol% of PFOA (105d). A total mass balance (parent plus metabolites) of 50-75mol% was observed on the last sampling day. 7:2 sFTOH, a direct precursor to PFOA, unexpectedly increased throughout the incubation period. The likely, but unconfirmed, concomitant production of acrylic acids was proposed as altering expected degradation patterns. Biotransformation of 8:2 FTAC, 8:2 FTMAC, and previously reported 8:2 FT-stearate for the same soils revealed the effect of the non-fluorinated terminus group linked to the FT chain on the electronic differences that affect microbially-mediated ester cleavage rates.
Subject(s)
Acrylates/analysis , Environmental Monitoring/methods , Hydrocarbons, Fluorinated/analysis , Methacrylates/analysis , Soil Microbiology , Soil Pollutants/analysis , Acrylates/chemistry , Aerobiosis , Alcohols/chemistry , Biodegradation, Environmental , Biotransformation , Caprylates/analysis , Caprylates/chemistry , Carboxylic Acids/analysis , Carboxylic Acids/chemistry , Fluorocarbon Polymers , Fluorocarbons/analysis , Fluorocarbons/chemistry , Hydrocarbons, Fluorinated/chemistry , Methacrylates/chemistry , Models, Theoretical , Molecular Structure , Soil Pollutants/chemistryABSTRACT
The experimental approaches used in assessing the biodegradability of fluorotelomer-based surfactants and polymers have been under increasing scrutiny. These substances consist of an aliphatic or aromatic backbone linked to perfluoroethyl moieties by ester, ether or urethane linkages. These linkages when broken yield fluorotelomer alcohols (FTOHs), which are known to biotransform to a suite of polyfluorinated metabolites including perfluorinated carboxylic acids. Quantifying FTOH levels with minimal experimental artifacts is imperative in properly assessing the biotransformation potential and half-lives of fluorotelomer-based materials. We examined the potential for solvent-enhanced ester hydrolysis of fluorotelomer compounds with different hydrocarbon backbones including a monoester stearate (FTS), a citrate tri-ester (TBC), an acrylate (FTA), and a 2,4-toluenediamine urethane (FTU) in acetonitrile, methyl-t-butyl ether (MTBE), and ethyl acetate with live, autoclaved, 60Co-γ-irradiated, and heat-treated (400°C) soils. Substantial hydrolysis only occurred with FTS in live and γ-irradiated soils for which microbial enzymes are expected to be active, but not in autoclaved soils where enzymes are deactivated. Acetonitrile and methanol (solvents with higher dielectric constants) enhanced hydrolysis by an order of magnitude compared to less polar solvents such as MTBE and ethyl acetate. For example, in a 24-h extraction with acetonitrile of FTS-amended soil, >5wt.% FTOH was produced compared to <0.04wt.% in either ethyl acetate or MTBE. FTA hydrolysis was <0.7 wt.% after a 15-h extraction period and was not solvent dependent. No statistically significant solvent-enhanced hydrolysis was observed for TBC, FTA or FTU.
