Particle size distribution and respiratory deposition estimates of airborne perfluoroalkyl acids during the haze period in the megacity of Shanghai

This study presents the particle size distribution and respiratory deposition estimates of airborne perfluoroalkyl acids (PFAAs) during the haze period. Size-segregated haze aerosols were collected from an urban location in Shanghai using an eight-stage air sampler. The samples were analyzed for eight PFAAs using ultra-high-performance liquid chromatography tandem triple quadrupole mass spectrometry. The quantification results showed that the concentrations of particle-bound Σ 8PFAAs ranged from 0.26 to 1.90 ng m⁻³ (mean: 1.44 ng m⁻³). All of the measured PFAAs particle size distributions had a bimodal mode that peaked respectively in accumulation size range (0.4 < Dp < 2.1 μm) and coarse size ranges (Dp > 2.1 μm), but the width of each distribution somewhat varied by compound. The emission source, molecular weight, and volatility of the PFAAs were important factors influencing the size distribution of particle-bound PFAAs. Of these compounds, PFUnDA presented a strong accumulation in the fine size range (average 75% associated with particles <2.1 μm), followed by PFOA (69%) and PFDA (64%). The human risk assessment of PFOS via inhalation was addressed and followed the same pattern as the size distribution, with a 2-fold higher risk for the fine particle fraction compared to the coarse particle fraction at urban sites. Approximately 30.3–82.0% of PFAA deposition (∑PFAA: 72.5%) in the alveolar region was associated with particles <2.1 μm, although the contribution of fine particles to the total PFAAs concentration in urban air was only 28–57% (∑8PFAAs: 48%). These results suggested that fine particles are significant contributors to the deposition of PFAAs in the alveolar region of the lung.