Occurrence and Fate of Per- and Polyfluoroalkyl Substances (PFAS) in Atmosphere: Size-Dependent Gas-Particle Partitioning, Precipitation Scavenging, and Amplification.

The concerns about the fate of per- and polyfluoroalkyl substances (PFAS) in the atmosphere are continuously growing. In this study, size-fractionated particles, gas, and rainwater samples were simultaneously collected in Shijiazhuang, China, to investigate the multiphase distribution of PFAS in the atmosphere. Perfluoroalkyl carboxylic acids (PFCAs) dominated the total concentration of PFAS in atmospheric media. A strong positive relationship (0.79 < R2 < 0.99) was observed between the concentration of PFCAs and organic matter fraction (fOM) in different particle size fractions, while no such relationship for perfluoroalkyl sulfonic acids (PFSAs) and fOM, suggesting fOM may be an important factor influencing the size-dependent distribution of PFCAs. Temperature played a key role in the gas-particle partitioning of PFAS, while it did not significantly affect their particle-size-dependent distribution. The associative concentration fluctuation of particle and particle-bound PFAS during precipitation suggested that precipitation scavenging was an important mechanism for the removal of PFAS from the atmosphere. Furthermore, temporary increases in atmospheric PFAS concentrations were observed during the precipitation. Fugacity ratios of PFAS in rainwater and gas phase (log fR/fG ranged between 2.0 and 6.6) indicated a strong trend for PFAS to diffuse from the rainwater to the gas phase during the precipitation, which may explain that the concentration of PFAS in the gas phase continued to increase even at the end of the precipitation.

Mechanisms of propeller jet-induced migration, release, and distribution of perfluoroalkyl acids in sediment-water systems.

Perfluoroalkyl acids (PFAAs) are continuously accumulated in surface sediments due to extensive and long-term application. However, the mechanisms through which disturbances induced by ship propeller jets at the riverbed cause secondary release of PFAAs from sediments remain unclear. In this study, the effects of different propeller rotational speeds on PFAA migration, release, and distribution in multiphase media were investigated by performing indoor flume experiments combined with particle tracking velocimetry. Moreover, key factors influencing PFAA migration and distribution were identified, and partial least squares regression (PLS) method was applied to develop quantitative prediction models of relationships among hydrodynamics, physicochemical parameters, and PFAA distribution coefficients. The total PFAA concentrations (ΣPFAAs) in overlying water under propeller jet action exhibited transient characteristics and hysteresis with time after the disturbance. In contrast, the ΣPFAAs in suspended particulate matter (SPM) exhibited an upward trend throughout the process with consistent characteristics. The spatial distribution trends of PFAAs in overlying water and SPM at different propeller rotational speeds featured vertical variability and axial consistency. Furthermore, PFAA release from sediments was driven by axial flow velocity (Vx) and Reynolds normal stress Ryy, while PFAA release from porewater was inextricably linked to Reynolds stresses Rxx, Rxy, and Rzz (p < 0.05). PLS regression models showed that variations in Vorticity, dissolved organic carbon, and pH influenced the decreases in PFAA distribution coefficients between SPM and overlying water (KD-SW) as propeller rotational speed increased, except for very long-chain PFAAs (C > 10). The increases in PFAA distribution coefficients between sediment and porewater (KD-SP) were mainly determined by physicochemical parameters of sediments, and the direct effect of hydrodynamics was relatively weak. Our study provides valuable information regarding the migration and distribution of PFAAs in multiphase media under propeller jet disturbance (both during and after disturbance).