Optical properties, molecular characterizations, and oxidative potentials of different polarity levels of water-soluble organic matters in winter PM_2.5 in six China's megacities

Humic-like substances (HULIS) accounted for a great fraction of water-soluble organic matter (WSOM) in PM_2.5, which efficiently absorb ultraviolet (UV) radiation and pose climate and health impacts. In this study, the molecular structure, optical properties, and oxidative potential (OP) of acid- and neutral-HULIS (denoted as HULIS-a, and HULIS-n, respectively), and high-polarity WSOM (HP-WSOM) were investigated in winter PM_2.5 collected at six China's megacities. For both carbon levels and optical absorption coefficients (b_{abs_365}), HULIS-a/HULIS-n/HP-WSOM showed significant spatial differences. For each city, the carbon levels and b_{abs_365} follow a similar order of HULIS-n > HULIS-a > HP-WSOM. Besides, the b_{abs_365} of HULIS-n and HULIS-a showed the same order of Harbin > Beijing ≈ Wuhan > Xi'an > Guangzhou > Chengdu, while HP-WSOM exhibited an order of Wuhan > Chengdu > Xi'an > Harbin > Beijing > Guangzhou. Both HULIS-a and HULIS-n were abundant in aromatic and aliphatic compounds, whereas HP-WSOM was dominated by a carboxylic acid group. The OP (in unit of nmol H₂O₂ μg⁻¹C) followed the order of HP-WSOM > HULIS-a > HULIS-n in all the cities. The OPs of HULIS-a, HULIS-n, and HP-WSOM in Harbin and Beijing were much higher than those of other cities, attributing to the high contribution from biomass burning. Highly positive correlations between reactive oxygen species (ROS) of HULIS-a and MAE₃₆₅ were obtained in Chengdu, Wuhan, and Harbin, but ROS of HULIS-n had stronger correlation with MAE₃₆₅ in Harbin, Chengdu, and Xi'an.