The investigation of the enrichment behavior of identified PFAS and unknown PFAA-precursors in water and suspended particulate matter of the surface microlayer: A case study in Tianjin (China)

The surface microlayer (SML) is an important air water interface layer, known as the skin of the ocean, which has chemical enrichment properties. Chemical enrichment in the SML can affect the occurrence of pollutants in the underlying water and air samples. Although the enrichment of per- and polyfluorinated substances (PFAS), a class of persistent organic pollutants of high concern, has been reported in the SML, information on the behavior of unknown PFAA-precursors in SML is lacked, and it is not clear whether there is a similar PFAS enrichment in suspended particulate matter (SPM) in the SML. Therefore, to investigate these questions, we conducted a systematic survey of 24 PFAS in 11 paired water and SPM samples from the SML and underlying water (U50cm and U2m) from the Duliujian River, which flows to the Bohai sea in Tianjin, China. The ∑PFAS mean concentrations in the water and SPM samples were 38.2 ng/L and 64.6 ng/g dw, respectively. The PFAS concentrations of PFAS in the SML were higher than those in the underlying water, and the enrichment factors (EFs) were greater in the SPM than that in the water. The long-chain PFAS EFs were greater than those for short-chain PFAS, indicating that the EFs were positively correlated with the hydrophobicity. Moreover, by applying the total oxidizable precursor (TOP) assay, the unknown PFAA-precursors (C5-C12) in the water and SPM contributed 11.4∼86.4 mol% and 7.1∼88.0 mol% to total PFAS, respectively. The ecological risk of the targeted PFAS in the SML was relatively higher than that in the underlying water, indicating that PFAS in the SML require more attention. Preliminary estimates indicate that the PFAS-enriched SML is an important exposure route that poses a potential risk to wildlife in rivers and oceans.