Abstract. Long-term monitoring of organic aerosol is important for epidemiological studies, validation of atmospheric models, and air quality management. In this study, we apply a recently developed filter-based offline methodology using an aerosol mass spectrometer (AMS) to investigate the regional and seasonal differences of contributing organic aerosol sources. We present offline AMS measurements for particulate matter smaller than 10 µm at nine stations in central Europe with different exposure characteristics for the entire year of 2013 (819 samples). The focus of this study is a detailed source apportionment analysis (using positive matrix factorization, PMF) including in-depth assessment of the related uncertainties. Primary organic aerosol (POA) is separated in three components: hydrocarbon-like OA related to traffic emissions (HOA), cooking OA (COA), and biomass burning OA (BBOA). We observe enhanced production of secondary organic aerosol (SOA) in summer, following the increase in biogenic emissions with temperature (summer oxygenated OA, SOOA). In addition, a SOA component was extracted that correlated with an anthropogenic secondary inorganic species that is dominant in winter (winter oxygenated OA, WOOA). A factor (sulfur-containing organic, SC-OA) explaining sulfur-containing fragments (CH 3 SO + 2 ), which has an event-driven temporal behaviour, was also identified. The relative yearly average factor contributions range from 4 to 14 % for HOA, from 3 to 11 % for COA, from 11 to 59 % for BBOA, from 5 to 23 % for SC-OA, from 14 to 27 % for WOOA, and from 15 to 38 % for SOOA. The uncertainty of the relative average factor contribution lies between 2 and 12 % of OA. At the sites north of the alpine crest, the sum of HOA, COA, and BBOA (POA) contributes less to OA (POA / OA = 0.3) than at the southern alpine valley sites (0.6). BBOA is the main contributor to POA with 87 % in alpine valleys and 42 % north of the alpine crest. Furthermore, the influence of primary biological particles (PBOAs), not resolved by PMF, is estimated and could contribute significantly to OA in PM 10 .

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Primary biological organic aerosols (PBOA) represent a major component of the coarse organic matter (OMCOARSE, aerodynamic diameter > 2.5 μm). Although this fraction affects human health and the climate, its quantification and chemical characterization currently remain elusive. We present the first quantification of the entire PBOACOARSE mass and its main sources by analyzing size-segregated filter samples collected during the summer and winter at the rural site of Payerne (Switzerland), representing a continental Europe background environment. The size-segregated water-soluble OM was analyzed by a newly developed offline aerosol mass spectrometric technique (AMS). Collected spectra were analyzed by three-dimensional positive matrix factorization (3D-PMF), showing that PBOA represented the main OMCOARSE source during summer and its contribution to PM10 was comparable to that of secondary organic aerosol. We found substantial cellulose contributions to OMCOARSE, which in combination with gas chromatography mass spectrometry molecular markers quantification, underlined the predominance of plant debris. Quantitative polymerase chain reaction (qPCR) analysis instead revealed that the sum of bacterial and fungal spores mass represented only a minor OMCOARSE fraction (<0.1%). X-ray photoelectron spectroscopic (XPS) analysis of C and N binding energies throughout the size fractions revealed an organic N increase in the PM10 compared to PM1 consistent with AMS observations.

This study reports spatial and temporal variability of Zn and Cu isotopes in atmospheric particulate matter (PM) collected in two major European cities with contrasting atmospheric pollution, Barcelona and London. We demonstrate that nontraditional stable isotopes identify source contributions of Zn and Cu and can play a major role in future air quality studies. In Barcelona, samples of fine PM were collected at street level at sites with variable traffic density. The isotopic signatures ranged between −0.13 ± 0.09 and −0.51 ± 0.05‰ for δ 66 Zn IRMM and between +0.04 ± 0.20 and +0.33 ± 0.15‰ for δ 65 Cu AE633 .Copper isotope signatures similar to those of Cu sulfides and Cu/ Sb ratios within the range typically found in brake wear suggest that nonexhaust emissions from vehicles are dominant. Negative Zn isotopic signatures characteristic for gaseous emissions from smelting and combustion and large enrichments of Zn and Cd suggest contribution from metallurgical industries. In London, samples of coarse PM collected on the top of a building over 18 months display isotope signatures ranging between +0.03 ± 0.04 and +0.49 ± 0.02‰ for δ 66 Zn IRMM and between +0.37 ± 0.17 and +0.97 ± 0.21‰ for δ 65 Cu AE633 . Heavy Cu isotope signatures (up to +0.97 ± 0.21‰) and higher enrichments and Cu/Sb ratios during winter time indicate important contribution from fossil fuel combustion. The positive δ 66 Zn IRMM signatures are in good agreement with signatures characteristic for ore concentrates used for the production of tires and galvanized materials, suggesting nonexhaust emissions from vehicles as the main source of Zn pollution.

International audienceWe investigated the seasonal trends of OA sources affecting the air quality of Marseille (France), which is the largest harbor of the Mediterranean Sea. This was achieved by measurements of nebulized filter extracts using an aerosol mass spectrometer (offline-AMS). In total 216 PM 2.5 (particulate matter with an aerodynamic diameter < 2.5 µm) filter samples were collected over 1 year from August 2011 to July 2012. These filters were used to create 54 composite samples which were analyzed by offline-AMS. The same samples were also analyzed for major water-soluble ions, metals, elemental and organic carbon (EC / OC), and organic markers, including n-alkanes, hopanes, polycyclic aromatic hydrocarbons (PAHs), lignin and cellulose pyrolysis products , and nitrocatechols. The application of positive matrix factorization (PMF) to the water-soluble AMS spectra enabled the extraction of five factors, related to hydrocarbon-like OA (HOA), cooking OA (COA), biomass burning OA (BBOA), oxygenated OA (OOA), and an industry-related OA (INDOA). Seasonal trends and relative contributions of OA sources were compared with the source apportionment of OA spectra collected from the AMS field deployment at the same station but in different years and for shorter monitoring periods (February 2011 and July 2008). Online-and offline-AMS source apportionment revealed comparable seasonal contribution of the different OA sources. Results revealed that BBOA was the dominant source during winter, representing on average 48 % of the OA, while during summer the main OA component was OOA (63 % of OA mass on average). HOA related to traffic emissions contributed on a yearly average 17 % to the OA mass, while COA was a minor source contributing 4 %. The contribution of INDOA was enhanced during winter (17 % during winter and 11 % during summer), consistent with an increased contribution from light alkanes, light PAHs (fluoranthene, pyrene, phenanthrene), and selenium, which is commonly considered as a unique coal combustion and coke production marker. Online-and offline-AMS source apportionments revealed evolving lev-oglucosan : BBOA ratios, which were higher during late autumn and March. A similar seasonality was observed in the ratios of cellulose combustion markers to lignin combustion markers, highlighting the contribution from cellulose-rich biomass combustion, possibly related to agricultural activities