Fate of Polyfluoroalkyl Phosphate Diesters and Their Metabolites in Biosolids-Applied Soil: Biodegradation and Plant Uptake in Greenhouse and Field Experiments

Significant contamination of perfluoroalkyl acids (PFAAs) in wastewater treatment plant (WWTP) sludge implicates the practice of applying treated sludge or biosolids as a potential source of these chemicals onto agricultural farmlands. Recent efforts to characterize the sources of PFAAs in the environment have unveiled a number of fluorotelomer-based materials that are capable of degrading to the perfluoroalkyl carboxylates (PFCAs), such as the polyfluoroalkyl phosphate diesters (diPAPs), which have been detected in WWTP and paper fiber biosolids. Here, a greenhouse microcosm was used to investigate the fate of endogenous diPAPs and PFCAs present in WWTP and paper fiber biosolids upon amendment of these materials with soil that had been sown with Medicago truncatula plants. Biodegradation pathways and plant uptake were further elucidated in a separate greenhouse microcosm supplemented with high concentrations of 6:2 diPAP. Biosolid-amended soil exhibited increased concentrations of diPAPs (4-83 ng/g dry weight (dw)) and PFCAs (0.1-19 ng/g dw), as compared to control soils (nd-1.4 ng/g dw). Both plant uptake and biotransformation contributed to the observed decline in diPAP soil concentrations over time. Biotransformation was further evidenced by the degradation of 6:2 diPAP to its corresponding fluorotelomer intermediates and C4-C7 PFCAs. Substantial plant accumulation of endogenous PFCAs present in the biosolids (0.1-138 ng/g wet weight (ww)) and those produced from 6:2 diPAP degradation (100-58 000 ng/g ww) were observed within 1.5 months of application, with the congener profile dominated by the short-chain PFCAs (C4-C6). This pattern was corroborated by the inverse relationship observed between the plant soil accumulation factor (PSAF, C-plant/C-soil) and carbon chain length (p < 0.05, r = 0.90-0.97). These results were complemented by a field study in which the fate of diPAPs and PFCAs was investigated upon application of compost and paper fiber biosolids to two farm fields. Together, these studies provide the first evidence of soil biodegradation of diPAPs and the subsequent uptake of these chemicals and their metabolites into plants.