Non-extractable residues of perfluorooctanoic acid (PFOA) in soil

PER: and polyfluoroalkyl substances have gained increased attention due to their persistence, ubiquitous presence in the environment, and toxicity. We hypothesised that the formation of non-extractable residues [NER] occurs in soils and contributes to the overall persistence of these priority pollutants, and that NER formation is controlled by temperature. To test these hypotheses, we used ¹⁴C-labelled perfluorooctanoic acid [PFOA] as target compound, added it to two arable soils (Cambisol, Luvisol), and incubated them at 10 °C and 20 °C in the dark. To support potential co-metabolic decomposition, some samples were additionally fed with glucose to enhance microbial activity. The PFOA residues were then sequentially extracted using 0.01 M CaCl₂, followed by accelerated solvent extraction (ASE) with methanol or methanol/acetic acid after 0, 1, 3, 9, 30, 62, and 90 days of incubation. In addition, we monitored the release of ¹⁴C into the gas phase as well as [¹⁴C]-PFOA-NER after dry combustion and liquid scintillation counting. After 90 days, we found that the [¹⁴C]-PFOA content declined in the extraction order of CaCl₂ ((bio)available fraction) > ASE (residual fraction) > NER > gas fraction), with most rapid changes occurring in the first 9 days of incubation. NER formation was different in the two soils and reached 5-9% of the applied amount in the Cambisol and Luvisol, respectively. Noteworthy the proportion of ¹⁴C-PFOA in the (bio)available fraction remained relatively stable over time at 56-62% of the applied amount, indicating the reversible transfer into this fraction from a bi-exponentially declining residual (ASE) pool. These dissipation patterns were neither influenced by temperature nor by the addition of glucose. We conclude that NER exist for PFOA, but that the majority of PFOA remains in (bio)available form, thus maintaining toxicity and mobility in soil for prolonged periods of time.