22nd International Conference on Ion Beam Analysis, June 14 - 19, 2015- Opatija, Croatia Characterization and source apportionment of fine particulate sources at Rijeka, Croatia from 2013 to 2015 T. Ivošević1, E. Štelcer2, I. Bogdanović Radović3, D.D. Cohen2, I. Orlić4 1 Faculty of Engineering University of Rijeka, Vukovarska 58, HR-51000 Rijeka, Croatia (tatjana.ivosevic14@gmail.com) 2 Australian Nuclear Science and Technology Organisation, Locked Bag 2001, Kirrawee DC, NSW 2232, Australia 3 Laboratory for Ion Beam Interaction, Ruđer Bošković Institute, Bijenička 54, HR-10000 Zagreb, Croatia 4 Department of Physics University of Rijeka, Radmile Matejčić 2, HR-51000 Rijeka, Croatia ABSTRACT PM2.5 daily aerosol samples were collected in Rijeka, Croatia during period of 18 months (August 2013 to February 2015). In total, 259 samples were collected on Teflon filters and analyzed by Ion Beam Analysis (IBA) techniques PIXE and PIGE giving information for 21 elements from Na to Pb. Additionally, black carbon was determined with the Laser Integrated Plate Method. Results were statistically evaluated using Positive Matrix Factorization (PMF). Eight major pollution sources: auto, smoke, secondary sulfates, heavy oil combustion, sea spray, road dust, industry iron and soil dust were identified together with their relative contributions in total PM2.5 pollution. Figure 1 Sampling site of PM2.5 in Rijeka – yellow star; red star – TPP coal – coal powered thermal plant; violet star – TPP oil – oil powered thermal plant, blue triangle – Oil refinery; right – Port of Rijeka INTRODUCTION The City of Rijeka (lat. 45º21’N, long. 14º26’E) is the largest Croatian port, and the third city by size in the Republic of Croatia with approximately 130,000 inhabitants. The current cargo traffic in the port of Rijeka is of moderate intensity with approximately 10 Mt/year. At the same time, the harbor throughput is approximately 190,000 containers and 170,000 passengers per year. Industrial complex, oil powered thermal plant 320 MW (TPP) and oil refinery (OR), are located 9 km eastward from the city center. Other possible pollution sources in this region are coal powered thermal plant of 330 MW located at the Port Plomin (30 km southwest from Rijeka) and industrial complex located in Trieste (60 km northwest from Rijeka) with a very busy port, oil refinery and an 400 MW oil power plant (Fig 1). EXPERIMENTAL 1) Ruđer Bošković Institute (RBI), Zagreb, Croatia PIXE – 3 nA beam of 1.6 MeV proton beam, 5 mm diameter, collected charge 3 µC (detected Na to Pb) – two detectors; SDD VITUS H20 KETEK GmbH (30º rel. to the sample normal) for low energies and Si(Li) SSL80165 Canberra (45º) for high energies 2) Australian Nuclear Science and Technology Organisation (ANSTO), Kirrawee, Australia IBA – 12 nA beam of 2.6 MeV protons, 8 mm diameter, collection charge of 3 µC (detected Al to Pb) PIXE – SDD detector 165-VTX-EM Hitachi High-Technologies Science America, Inc (45º) PIGE – large volume Ge detector (5kV) Canberra GC3020 (detected Na) 3) Laboratory for elemental microanalysis (LEMA), Rijeka, Croatia LIPM – measured black carbon (BC) Table 1 Average source contributions to the total fine mass given in percentages. Additionally, shown are percentages of BC, K and S in each factor. RESULTS We applied Positive Matrix factorization (PMF) to identify sources of fine particulates. Eight source fingerprints are identified (Fig 2) from 259 samples and 22 elements (BC included). Obtained fingerprints are attributed to individual sources by taking into account knowledge of local conditions and experience related to the source composition. Factor % Mass % BC % K % S Auto 33.0 ± 3.5 46.9 1.4 3.9 Smoke 21.1 ± 2.1 27.9 65.6 2.4 Secondary sulfate 15.4 ± 2.5 0.5 5.1 80.9 Heavy Oil combustion 9.9 ± 2.7 11.7 3.3 8.2 Sea spray 9.1 ± 1.3 19.7 3.6 Road dust 6.0 ± 2.3 7.4 1.5 0.9 Industry iron 3.9 ± 2.1 5.6 0.8 Soil 1.4 ± 1.0 2.5 0.3 RESULTS Figure 5 Daily variations of PMF sources Figure 3 Correlation between V and Ni in „Heavy Oil combustion” Figure 4 Correlation between Al and Si in „Soil -event” Figure 2 Source apportionment of PM2.5 fraction in Rijeka for 2013-2015 CONCLUSION Positive matrix factorization technique was used to determine elemental source fingerprints and their relative contributions to the total mass of fine particles collected in Rijeka, Croatia. Our results are based on 259 aerosol samples collected in the period from August 2013 and February 2015. PIGE, PIXE and LIPM techniques were used to obtain concentrations, errors and MDLs for elements from Na to Pb, and anthropogenic component, BC. As expected, automobile, biomass burning (smoke) and industry were the dominant sources of air pollution in Rijeka. ACKNOWLEDGEMENT The authors are grateful to Mr. V. Mezak from the Port of Rijeka Authority, Mr. D. Kavre from the Oil powered thermal plant Rijeka, Ms. M. Mioč and Mr. Z. Ciganj from the Oil refinery Rijeka, Mr. D. Frka and Ms. A. Tomljanović from the Road Authority Rijeka, Mr. D. Mlinek from the National Meteorological and Hydrological Service for their contributions to this work.