Hydrolysis of fluorotelomer compounds leading to fluorotelomer alcohol production during solvent extractions of soils

Abstract

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, >5 wt.% FTOH was produced compared to <0.04 wt.% 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.