Molecular Characterization of Cloud Water Samples Collected at the Puy de Dôme (France) by Fourier Transform Ion Cyclotron Resonance Mass Spectrometry.

Cloud droplets contain dynamic and complex pools of highly heterogeneous organic matter, resulting from the dissolution of both water-soluble organic carbon in atmospheric aerosol particles and gas-phase soluble species, and are constantly impacted by chemical, photochemical, and biological transformations. Cloud samples from two summer events, characterized by different air masses and physicochemical properties, were collected at the Puy de Dôme station in France, concentrated on a strata-X solid-phase extraction cartridge and directly infused using electrospray ionization in the negative mode coupled with ultrahigh-resolution mass spectrometry. A significantly higher number (n = 5258) of monoisotopic molecular formulas, assigned to CHO, CHNO, CHSO, and CHNSO, were identified in the cloud sample whose air mass had passed over the highly urbanized Paris region (J1) compared to the cloud sample whose air mass had passed over remote areas (n = 2896; J2). Van Krevelen diagrams revealed that lignins/CRAM-like, aliphatics/proteins-like, and lipids-like compounds were the most abundant classes in both samples. Comparison of our results with previously published data sets on atmospheric aqueous media indicated that the average O/C ratios reported in this work (0.37) are similar to those reported for fog water and for biogenic aerosols but are lower than the values measured for aerosols sampled in the atmosphere and for aerosols produced artificially in environmental chambers.