17-Year study on the chemical composition of rain, snow and sleet in very dusty air (Krakow, Poland)

The paper presents the results of long-term (1996–2017) studies of the chemical composition of rain, snow and sleet in one of the cities with the highest concentrations of particulate matter in the air in Europe. The study included measurements of 45 chemical constituents of precipitation as well as its pH and EC. Concentrations of PM10, SO₂ and meteorological parameters were also analysed. Differences in Cl and Na concentrations were found depending on the type of precipitation (snow or rain). These differences are most probably caused by anthropogenic factors, however, to a small extent (~18–19%), they are associated with the total variability of the concentrations of these chemical constituents. The differences between the concentrations of the remaining constituents of precipitation analysed are of lesser or negligible importance. The main processes affecting the chemical composition of precipitation are the chemical weathering of suspended dust and the formation of mineral acid aerosols. These processes shape the chemical composition of both rain and snow in a similar manner. The differences between the chemical composition of rain and snow are the result of the concentrations of and mutual relations between selected chemical constituents and precipitation pH. An important factor affecting the pH of precipitation is the effectiveness of the chemical weathering of suspended dust, which may make the precipitation more alkaline. It is very likely that pH-buffering will occur, which can prevent the pH of precipitation from decreasing, especially in cold periods. Long-term observations of variability in the concentrations of the chemical constituents indicate a slight, but rather constant decrease in concentrations of most of the chemical constituents analysed, as well as in the concentrations of PM10 and SO₂ in the air in Krakow. The directions of these changes reflect, to a certain extent, the complex transformations of industrial, economic and social conditions in Krakow within that period. The typical ranges of variability of the recorded values of concentrations/measurement values of 22 chemical constituents and the physical characteristics of rain, sleet and snow presented in the paper can be used as reference ranges of these parameters, typical for an area with a significant degree of atmospheric dust pollution.