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The experimental results show that the PHS can provide valuable speciation information, sometimes different from that observed for HVS. For PM collected by PHS, we detected the larger contribution of oxygen-centered EPFRs, different decay behavior, and more consistent PAH distribution between different PM sizes compared to the PM from HVS. These results indicate that the isolation of samples from the ambient during HVS sampling and exposure to high-volume airflow may alter the chemical composition of the samples, while the PHS method cou