The size distribution and origin of elements bound to ambient particles: a case study of a Polish urban area

Ambient particulate matter (PM) was sampled in Zabrze (southern Poland) in the heating period of 2009. It was investigated for distribution of its mass and of the masses of its 18 component elements (S, Cl, K, Ca, Cr, Mn, Fe, Ni, Cu, Zn, Ge, As, Br, Sr, Cd, Sb, Ba, and Pb) among 13 PM size fractions. In the paper, the distribution modality of and the correlations between the ambient concentrations of these elements are discussed and interpreted in terms of the source apportionment of PM emissions. By weight, S, Cl, K, Ca, Cr, Mn, Fe, Ni, Cu, Zn, Ge, As, Br, Sr, Cd, Sb, Ba, and Pb were 10% of coarse and 9% of ultrafine particles. The collective mass of these elements was no more than 3.5 % of the mass of the particles with the aerodynamic diameter D p between 0.4 and 1.0 μm (PM₀.₄₋₁), whose ambient mass concentration was the highest. The PM mass size distribution for the sampling period is bimodal; it has the accumulation and coarse modes. The coarse particles were probably of the mineral/soil origin (characteristic elements: Ca, Fe, Sr, and Ba), being re-suspended polluted soil or road dust (characteristic elements: Ca, Fe, Sr, Ba, S, K, Cr, Cu, Zn, Br, Sb, Pb). The maxima of the density functions (modes) of the concentration distributions with respect to particle size of PM-bound S, Cl, K, Cu, Zn, Ge, Br, Cd, Sb, and Pb within the D p interval from 0.108 to 1.6 μm (accumulation PM particles) indicate the emissions from furnaces and road traffic. The distributions of PM-bound As, Mn, Ba, and Sr concentrations have their modes within D p ≤ 0.108 μm (nucleation PM particles), indicating the emissions from high-temperature processes (industrial sources or car engines). In this work, principal component analysis (PCA) is applied separately to each of the 13 fraction-related sets of the concentrations of the 18 PM-bound elements, and further, the fractions are grouped by their origin using cluster analysis (CA) applied to the 13 fraction-related first principal components (PC1). Four distinct groups of the PM fractions are identified: (PM₁.₆₋₂.₅, PM₂.₅₋₄.₄,), (PM₀.₀₃₋₀.₀₆, PM₀.₁₀₈₋₀.₁₇), (PM₀.₀₆₋₀.₁₀₈, PM₀.₁₇₋₀.₂₆, PM₀.₂₆₋₀.₄, PM₀.₄₋₀.₆₅, PM₀.₆₅₋₁, PM₁₋₁.₆), and (PM₄.₄₋₆.₈, PM₆.₈₋₁₀, PM>₁₀). The PM sources attributed to these groups by using PCA followed by CA are roughly the same as the sources from the apportionment done by analyzing the modality of the mass size distributions.