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Organic matter sources in aerosol PM10 from Wrocław, Poland

Rybicki M., Górka M., Simoneit B.R.T., Marynowski L.

Geology, Geophysics and Environment

2014

Vol. 40, no. 1

122

The natural and anthropogenic contributions of hydrocarbon groups (aliphatic and aromatic), as well as total organic carbon, in atmospheric PM10 dust (particulate matter < 10 (µm) collected from Wrocław (SW Poland) were assessed using combined molecular (gas chromatography-mass spectrometry GC-MS) and stable carbon isotopic (isotope-ratio mass spectrometry IR-MS) analyses. The PM10 samples were taken using the hi-flow sampler Stamplex Air Division with Whatmann quartz filter (0.06237 m2), and a constant air flow of 1.13 m3/ min in the seasonal sampling program in 2007, and represent air pollution in all months of the year. The δ13C values of the total carbon varied seasonally from -27.6 to -25.3‰. The isotopic mass balance calculations showed greater coal burning input, reaching 70.5%, in the heating season and dominant transported sources 47.0% in the vegetative season. The δ13C values of the aliphatic fractions (from -36.6‰ to -29.4‰), indicated a dominant anthropogenic origin (gasoline/diesel/ coal combustion). The n-alkane distribution with relatively low CPI (carbon preference index) values confirmed that coal combustion and petroleum product use in vehicles were important sources of the PM10 in Wroclaw. On the other hand, high values of % WNA (wax n-alkane content), especially in vegetative season, and Cmax (carbon number maximum) ≥27 in 81% of the samples suggested that the influence of biogenic sources was also significant. Petroleum and coal combustion emissions were confirmed by the presence of hopanes and moretanes. The molecular analysis of the concentrations and diagnostic ratios of the polycyclic aromatic hydrocarbons (PAHs) and the δ13C values of the aromatic fractions (from -35.4‰ to -26.8‰) indicated that the main PAH sources were also represented collectively by combustion of liquid fuels and coal. Based on PAH discrimination diagrams it is also clear that the main organic carbon source is derived from coal, biomass and petroleum combustion in both seasons. However, taking into account the PAH concentrations during the vegetative and heating seasons, coal and biomass burning seem to be their major source. The high concentration of polar organic compounds such as levoglucosan, mannosan and galactosan confirmed a significant contribution of biomass burning to the total anthropogenic input, especially in the heating season. The general conclusions derived from coupling of organic tracer analysis and carbon isotopic data of PM10 was that the total carbon (including insoluble soot) is likely derived from fossil fuel combustion, while the extractable organic matter is a mixture from different sources with significant inputs of biomass burning. We have also shown that dominant organic tracers do not always represent the major input source in aerosol PM and the unresolved part of the organic matter (soot) is important in the carbon budget.