Classification of clouds sampled at the puy de Dôme (France) based on 10 yr of monitoring of their physicochemical properties

Abstract. Long-term monitoring of the chemical composition of clouds (73 cloud events representing 199 individual samples) sampled at the puy de Dôme (pdD) station (France) was performed between 2001 and 2011. Physicochemical parameters, as well as the concentrations of the major organic and inorganic constituents, were measured and analyzed by multicomponent statistical analysis. Along with the corresponding back-trajectory plots, this allowed for distinguishing four different categories of air masses reaching the summit of the pdD: polluted, continental, marine and highly marine. The statistical analysis led to the determination of criteria (concentrations of inorganic compounds, pH) that differentiate each category of air masses. Highly marine clouds exhibited high concentrations of Na⁺ and Cl⁻; the marine category presented lower concentration of ions but more elevated pH. Finally, the two remaining clusters were classified as "continental" and "polluted"; these clusters had the second-highest and highest levels of NH₄⁺, NO₃⁻, and SO₂⁴⁻, respectively. This unique data set of cloud chemical composition is then discussed as a function of this classification. Total organic carbon (TOC) is significantly higher in polluted air masses than in the other categories, which suggests additional anthropogenic sources. Concentrations of carboxylic acids and carbonyls represent around 10% of the organic matter in all categories of air masses and are studied for their relative importance. Iron concentrations are significantly higher for polluted air masses and iron is mainly present in its oxidation state (+II) in all categories of air masses. Finally, H₂O₂ concentrations are much more varied in marine and highly marine clouds than in polluted clouds, which are characterized by the lowest average concentration of H₂O₂. This data set provides concentration ranges of main inorganic and organic compounds for modeling purposes on multiphase cloud chemistry.