The chemical compositions (Na⁺, NH₄ ⁺, K⁺, Mg²⁺, Ca²⁺, Cl⁻, NO₂ ⁻, NO₃ ⁻, SO₄ ²⁻, HCO₃ ⁻) of wet precipitation and nitrogen isotope compositions δ¹⁵N(NH₄ ⁺) were studied from January to December 2010 in Wrocław (SW Poland). Results of a principle component analysis show that 82 % of the data variability can be explained by three main factors: 1) F1 (40 %) observed during vegetative season (electrical conductivity, HCO₃ ⁻, NO₃ ⁻, NO₂ ⁻, NH₄ ⁺ and SO₄ ²⁻), mainly controlling rainwater mineralization; 2) F2 (26 %) observed during vegetative and heating seasons (K⁺, Ca²⁺ and Mg²⁺), probably representing a combination of two processes: anthropogenic dusts and fertilizers application in agricultural fields, and 3) F3 (16 %) reported mainly during heating season (Na⁺ and Cl⁻) probably indicating the influence of marine aerosols. Variations of δ¹⁵N(NH₄ ⁺) from −11.5 to 18.5 ‰ identify three main pathways for the formation of NH₄ ⁺: 1) equilibrium fractionation between NH₃ and NH₄ ⁺; 2) kinetic exchange between NH₃ and NH₄ ⁺; 3) NH₄ ⁺ exchange between atmospheric salts particles and precipitation. The coupled chemical/statistical analysis and δ¹⁵N(NH₄ ⁺) approach shows that while fossil fuels burning is the main source of NH₄ ⁺ in precipitation during the heating season, during the vegetative season NH₄ ⁺ originates from local sewage irrigation fields in Osobowice or agricultural fertilizers.

We have applied both palynological and carbon and nitrogen isotopic analyses of PM10 (particulate matter with a diameter of 10 μm or less) to trace its origin and to assess the anthropogenic impact for the area under study. The PM10 samples were collected in Wrocław (SW Poland) by the Regional Inspectorate for Environment Protection during the year 2007. The usefulness of the palynological observations in the case of PM10 is much lower than that for total suspended particles due to the resolution of absorbed particles, but is still helpful for distinguishing C₃/C₄ plants that indicate long-distance transport of pollutants. The δ¹³C(PM10) values varied seasonally from−26.9 to−25.1‰. The δ¹⁵N(PM10) values showed chaotic fluctuations and varied from 5.0 to 13.7‰. Our results indicated that during the heating period, the PM10 particles in Wrocław are derived mainly from local home heaters, whereas in the growing period, PM10 particles are derived from local transport and are partially generated by the industrial application of coal combustion outside the city of Wrocław.