Abstract
The seasonal changes in ambient mass concentrations and chemical composition of fine particulate matter (PM(2.5)) were investigated in three locations in Poland. The analyses included PM(2.5)-bound hazardous benzo(a)pyrene (BaP), As, Ni, Cd, and Pb. The samples of PM(2.5) were collected daily in Katowice (southern Poland, urban background site), Gdańsk, and Diabla Góra (northern Poland, urban and regional background sites, respectively) during 1-year-long campaign in 2010. Based on monthly ambient concentrations of PM(2.5)-bound carbon (organic and elemental), water-soluble ions (Na(+), NH(4)(+), K(+), Mg(2+), Ca(2+), Cl(-), NO(3)(-), SO(4)(2-)), and elements As, Ni, Cd, Pb, Ti, Al, Fe, the chemical mass closure of PM(2.5) was checked for each of the four seasons of the year and for the heating and non-heating periods at each site. Also, the annual concentrations of PM(2.5) were determined and the annual PM(2.5) mass closure checked. At each measuring point, the PM(2.5) concentrations were high compared to its Polish yearly permissible value, 25 μg/m(3), and its concentrations elsewhere in Europe. The highest annual PM(2.5) concentration, 43 μg/m(3), occurred in Katowice; it was twice the annual PM(2.5) concentration in Gdańsk, and thrice the one in Diabla Góra. The high annual averages were due to very high monthly concentrations in the heating period, which were highest in the winter. PM(2.5) consisted mainly of carbonaceous matter (elemental carbon (EC) + organic matter (OM), the sum of elemental carbon, EC, and organic matter, OM; its annual mass contributions to PM(2.5) were 43, 31, and 33 % in Katowice, Gdansk, and Diabla Góra, respectively), secondary inorganic aerosol (SIA), the Na_Cl group, and crustal matter (CM)-in the decreasing order of their yearly mass contributions to PM(2.5). OM, EC, SIA, Na_Cl, and CM accounted for almost 81 % of the PM(2.5) mass in Katowice, 74 % in Gdańsk, and 90 % in Diabla Góra. The annual average toxic metal contribution to the PM(2.5) mass was not greater than 0.2 % at each site. In Katowice and Gdańsk, the yearly ambient BaP concentrations were high (15.4 and 3.2 ng/m(3), respectively); in rural Diabla Góra, the concentrations of BaP were almost equal to 1 ng/m(3), the Polish BaP annual limit. The great seasonal fluctuations of the shares of the component groups in PM(2.5) and of the concentrations of PM(2.5) and its components are due to the seasonal fluctuations of the emissions of PM and its precursors from hard and brown coal combustion for energy production, growing in a heating season, reaching maximum in winter, and decreasing in a non-heating period. In Gdańsk, northern Poland, especially in the spring and autumn, sea spray might have affected the chemical composition of PM(2.5). The greatest hazard from PM(2.5) occurs in Katowice, southern Poland, in winter, when very high concentrations of PM(2.5) and PM(2.5)-related carbonaceous matter, including BaP, are maintained by poor natural ventilation in cities, weather conditions, and the highest level of industrialization in Poland. In less industrialized northern Poland, where the aeration in cities is better and rather gaseous than solid fuels are used, the health hazard from ambient PM(2.5) is much lower.