Origin of observed acidic–alkaline rains in a wet-only precipitation study in a Mediterranean coastal site, Patras, Greece

Major anions and cations were analyzed in a wet-only precipitation study for 16 months. The pH exhibited large variation, from 4.07 to 8.51 pH units. Twenty-eight percent of the observed rain volume had pH <5, whereas 42% of the rains had pH >6, as is usually observed in the Mediterranean. Comparison with our work of 15 years ago indicates a free acidity reduction by 18%, non-sea-salt sulfate ions reduction of 40% and nitrate ions reduction of 66%. Chloride and all cation concentrations were similar in the present work and that carried out in 1985–86 indicating similar sources, namely aerosol and crustal material as in MS. Calcium ions were the dominating neutralization ions. The annual wet-only deposition rates were calculated for the major species and were found to be comparable to those reported in past studies. Deposition of calcium ions dominates all deposited species, except sea salt, and indicates its significance in the neutralizing mechanisms of soils of the region, if neutralization is needed. Air mass back trajectories calculated for all analyzed samples, revealed four sectors of origin of air masses: NW to NE Europe, northern Africa, local and western Mediterranean, each with a specific chemistry. Cluster analysis and factor analysis also discriminated the samples by their sources. The main sources derived from the statistical analysis were: marine aerosols, alkalinity–acidity as inferred by the calcium ion concentrations from crustal sources and hydronium ions mainly from anthropogenic activities and ammonium salts of sulfate and nitrate also mainly from anthropogenic activities. These sources were closely correlated with the geographic sectors obtained from the air mass back trajectories.