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Within the project "Eco Map of Zagreb", 8 sensor sets (type AQMeshPod) were obtained for air quality measurement. Throughout 2018, a set of sensors was set up at an automatic measuring station at the Institute for Medical Research and Occupational Health (IMROH) for comparison with reference methods for air quality measurement. This automatic station is a city background station within the Zagreb network for air quality monitoring, where measurements of SO2, CO, NO2, O3, PM10 and PM2.5 are performed using standardized methods accredited to EN ISO / IEC 17025. The paper presents a comparison of mass concentrations of pollutants SO2, CO, NO2, O3, PM10 and PM2.5 determined by sensors and reference methods during 2018. For the gases, the hourly averages were compared and for the particle matter, 24- hour averages of concentrations. The raw data of the sensor and validated data of the reference devices were used. Negative data values from the sensor were replaced by the minimum detection limits of the reference methods. Data were compared using Student's t-test dependent samples and regression analysis. A Grubb test was performed to remove the outliers of data pairs from the database. The Grubb test is not applicable for gaseous pollutants due to high dispersion of results. For PM10 and PM2.5, the Grubb test is satisfactorily applied with a critical factor of 5% confidence level. In order to remove large deviations between the results obtained by sensors and by the reference methods for gaseous pollutants and in order to reduce the scattering of the results, data filtering was performed. The results where the deviation between sensors data and reference methods data over 90% were excluded in the filtering process. The Grubb test was performed over the new set of data. A comparison of sensor results with the results of reference methods showed a large scattering of all gaseous pollutants while the comparison for PM10 and PM2.5 indicated a satisfactory low dispersion. The results of regression analysis showed a significant seasonal dependence for all pollutants. There was a significant statistical difference between the reference method and sensors for the whole year and in all seasons for all gas pollutants as well as for PM10. For PM2.5 there was not a significant statistical difference for the whole year as well as in summer, while for other periods there was a statistically significant difference.

Particulate matter (PM) is a mixture of organic and inorganic substances that emerge from a wide range of natural and anthropogenic sources. Fine aerosol particles have been found to play a key role in global climate change, pollution problems and health hazards. PM1 particles (particulate matter with an aerodynamic diameter of less than 1 µm) are characterized by a high surface-area-to-volume ratio, having great potential risks for negative effects on human health. However, as air quality standards in most countries refer to PM10 (particulate matter with an aerodynamic diameter of less than 10 µm) and PM2.5 (particulate matter with an aerodynamic diameter of less than 2.5 µm) particle fractions, PM1 particle fraction measurements are not part of routine monitoring. The metals released by anthropogenic activities, bounded to fine particulate matter, are bioaccumulative and can cause severe disturbance of ecosystems because of their influence on biochemical mechanisms, not to mention the potential risks for different health outcomes. In this study, 24-hour samples of PM1 were collected at an urban background location in Zagreb, the capital of Croatia, during 2011 and 2016, using a low-volume reference sampler. The collected samples of particulate matter were prepared in nitric acid using a high pressure microwave digestion system. Nickel, arsenic, cadmium and lead were determined by inductively coupled plasma mass spectrometry (ICP MS). The objective of the study was to determine mass concentrations of nickel, arsenic, cadmium and lead in PM1 fraction in 2011 and 2016 and to compare the obtained data sets. The mean annual values in 2011 were 1.58 ng m-3, 0.45 ng m-3, 0.21 ng m-3 and 5.55 ng m-3 for Ni, As, Cd and Pb, respectively, and 0.14 ng m-3, 0.23 ng m-3, 0.13 ng m-3, and 4.33 ng m-3 in 2016 for Ni, As, Cd and Pb, respectively. Statistically significant differences between the years were found for all metals with higher concentrations determined in 2011 compared to 2016. A statistically significant difference was found between seasons as well, except in winter and autumn for As and Pb (in 2011) and As, Ni and Cd (in 2016), and in spring and summer for Ni (in 2011) and Ni, Cd and Pb (in 2016). The highest values during the colder part of the year were found for all of the determined metals which was expected because of the adverse weather conditions that make it difficult to circulate air.

Chemical composition of airborne particulate matter is of considerable importance regarding public health. Polycyclic aromatic hydrocarbons (PAH) are compounds known for their adverse effects on human health. Many of them are proven carcinogens, especially those with 5 and 6 aromatic rings which in ambient air are usually bounded to particulate matter. Benzo(a)pyrene (BaP) is often measured as their representative. Sarajevo (~450 000 inhabitants), the capital of Bosnia and Herzegovina, is one of the European cities with the poorest air quality. As a consequence of topography, meteorological conditions and extensive use of fossil fuels, daily PM10 mass concentrations during winter exceed 400 µg/m3. Measurements of PAH are not part of routine monitoring and only limited data are available from previous studies. The capital of Croatia, Zagreb (~800 000 inhabitants), is located approximately 300 km north-west from Sarajevo. PAH mass concentrations in Zagreb have been measured continuously since 1994 within local and national air quality monitoring networks. During winter 2017/2018, the SAFICA project (Sarajevo Canton Winter Field Campaign 2018) was carried out in order to characterise the organic and inorganic pollutants in the city of Sarajevo and its surroundings. This paper presents results of PAH measurements at one urban location in Sarajevo. 24-hour samples of PM10 particle fraction were collected during heating season, from 10 December 2017 to 26 February 2018. The analysis of PAH was performed using high performance liquid chromatography with a fluorescence detector. PAH mass concentrations in Sarajevo were compared with the results obtained in Zagreb during the same period. Average BaP concentrations in Sarajevo and Zagreb were 6.925 ng/m3 and 3.109 ng/m3, respectively. The contribution of BaP to the sum of PAH mass concentrations was similar at both locations (~ 11 %). However, much higher contributions of fluoranthene and pyrene were obtained in Sarajevo. Contributions of individual PAH and their diagnostic ratios indicated combustion of gasoline and diesel as a potential source of PAH (traffic) at both locations, as well as combustion of other liquid fossil fuels (petroleum, crude oil). Wood burning was occasionally indicated as a source in Zagreb, while in Sarajevo the contribution of coal combustion was evident. The total carcinogenic potency of PAH was estimated by calculating BaP equivalent concentrations using toxic equivalence factors from the literature and it was 10.052 ng/m3 and 4.506 ng/m3 in Sarajevo and Zagreb, respectively. BaP had the highest contribution to the total carcinogenic potency at both locations (69 and 67 %), followed by benzo(b)fluoranthene, dibenzo(a, h)anthracene and indeno(1, 2, 3-cd)pyrene.

The atmosphere is a carrier by which some natural and anthropogenic pollutants are transported. Deposition events are the most important mechanisms that remove organic compounds from the atmosphere to terrestrial and aquatic ecosystems. A method based on solid phase extraction (SPE), gas chromatography-mass spectrometry (GC-MS/MS) and gas chromatography with electron capture detector (GC- ECD) was developed for the determination of polycyclic aromatic compounds (PAHs) and polychlorinated biphenyls (PCBs) in atmospheric deposition samples. PAH compounds (fluoranthene (FLU), pyrene (PYR), benz(a)anthracene (BaA), chrysene (CHRY), benzo(b)fluoranthene (BbF), benzo(k)fluoranthene (BkF), benzo(j)fluoranthene (BjF), benzo(a)pyrene (BaP), benzo(e)pyrene (BeP), indeno(1, 2, 3- cd)pyrene (IP), dibenz(a, h)anthracene (DahA) and benzo(g, h, i)perylene (BghiP)) were analysed by GC-MS/MS and six indicator PCB congeners (PCB-28, PCB-52, PCB-101, PCB-138, PCB- 153 and PCB-180) were analysed by GC-ECD equipped with two micro electron-capture detectors and two gas chromatographic columns. Solid phase extraction on silica sorbent was suitable for accumulation of PAHs and PCBs from deposited matters. The extraction procedure was based by passing the whole sample volume through a silica cartridge with dichloromethane and n-hexane (1:1, v/v) as the eluting solvents. Prior to analysis, the eluate was dried with sodium anhydrous sulphate and evaporated under a stream of nitrogen to 2 mL. The method was applied for analysis of the 12 PAHs and six indicator PCBs in monthly total deposited matters samples collected by bulk method at an urban background station in Zagreb, Croatia during 2018. The levels and occurrence of PCBs corresponded to global environmental pollution with the highest PCB deposition rate determined in December. During the measurement period, the deposition rates of ∑12PAHs varied between 132.2 ng m-2 d-1 and 698.6 ng m-2 d- 1.

The aim of this study was to determine the mass concentration and the content of water-soluble anions (Cl-, NO3 -, SO4 2-) and cations (Na+, NH4 +, K+, Mg2 +, Ca2 +) in PM2.5 particle fraction, to investigate their relationship and there contribution to the total PM2.5 mass measured at site located in Rijeka, Croatia. Rijeka is the third-largest city in Croatia at Kvarner Bay on Adriatic Sea with developed petrochemical and metal industry, shipyards, oil refining and transportation especially maritime. Measuring site is a part of Croatian monitoring network for air quality classified as urban background site. Daily samples of PM2.5 particle fraction were collected over a year 2017 on PTFE filters using the low volume sampler Sven Leckel SEQ 47/50. Mass concentration of PM2.5 particle fraction was determined by gravimetric according to the standard HRN EN 12341:2014 (EN 12341:2014). The content of water-soluble inorganic anions and cations were determined using Thermo Scientific ICS-5000 capillary ion chromatograph. Results show that annual average PM2.5 mass concentration was 9.65 μg/m3 and didn't exceed limit value of 25 μg/m3 given by the Regulation on the level of pollutants in air (OG No. 117/12). The annual average mass concentrations of ions in PM2.5 particle fraction was in order SO4 2- > NH4 + > NO3 - > Ca2+ > K+ > Na+ > Cl- > Mg2+. Contribution of total anion mass and cation mass to the total PM2.5 mass were 25.4% and 12.8%, respectively. Contribution of each anion mass to the total anion mass were 84.8% , 14.2% and 0.9% for SO4 2-, NO3 - and Clrespectively, while contribution of each cation mass to the total cation mass were 6.6% , 72% , 6.2% , 1% and 13.3% for Na+, NH4 +, K+, Mg2+ and Ca2+, respectively. The prediction of the pollutant sources we ran the principal component analysis (PCA) which was performed using the statistical packages STATISTICA 13.0. After varimax rotation, the obtained four principal component factors were found to account for 86% of the variance. Factor loadings > 0.7 were considered significant.

Airborne particles are composed of inorganic species and organic compounds. Particle pollution includes “inhalable coarse particles” with diameters larger than 2.5 μm and smaller than 10 μm and “fine particles” with diameters of 2.5 μm or smaller. PM1 particles, with an aerodynamic diameter smaller than 1 μm, are considered to be of importance in the context of adverse health effects. The mass concentration of particulate matter (PM) is not the only important parameter for the assessment of health risks of atmospheric pollution. Many compounds bound to particulate matter, such as polycyclic aromatic hydrocarbons (PAH), are suspected to be genotoxic, mutagenic and carcinogenic. PAHs are organic compounds that consist of two or more aromatic rings. More than 500 PAHs have been identified in the air and they were among the first pollutants recognized as potential carcinogens. PAHs are products of the incomplete combustion of fossil fuels and other organic materials and originate from a variety of natural and industrial processes. In this study, PAHs in PM1 particle fraction were measured during one year (1/1/2018–31/12/2018). The measuring station was located in the northern residential part of Zagreb, the Croatian capital, close to a street with modest traffic. 24-hour samples of PM1 particle fraction were collected on quartz filters from about 50 m3 air using a low-volume sampler. The analysis was performed using a high performance liquid chromatograph (HPLC) with a fluorescence detector and time programmed changes in excitation and emission. Samples were analysed for the following PAHs: fluoranthene (Flu), pyrene (Pyr), benzo(a)anthracene (BaA), chrysene (Chry), benzo(j)fluoranthene (BjF), benzo(b)fluoranthene (BbF), benzo(k)fluoranthene (BkF), benzo(a)pyrene (BaP), dibenzo(ah)anthracene (DahA), benzo(ghi)perylene (BghiP), and indeno(1, 2, 3- cd)pyrene (IP). Significant differences were found between PAH concentrations during cold (January- March, October-December) and warm (April-September) periods of the year. During the cold period, BbF had the highest mass concentrations (0.215– 3.412 ngm-3), while during the warm period the highest mass concentrations was recorded for BghiP (0.067–0.277 ngm-3). During both periods, DahA had the lowest mass concentrations. The average monthly mass concentrations of BaP ranged from 0.038 ngm-3 in June to 2.826 ngm-3 in December (the annual average was 0.765 ngm- 3). In general, during the whole year mass concentrations of PAH characteristic for car exhaust (BghiP, IP, BbF) were higher than concentrations of Flu and Pyr, which originate mostly from domestic heating and biomass burning.

Rijeka is the principal seaport and third largest city in Croatia. The city's economy largely depends on shipbuilding and maritime transport. Rijeka has a humid subtropical climate with warm summers and relatively mild winters with frequent rainfall and cold (bura) winds. This study is the first on particulate matter with an equivalent aerodynamic diameter smaller than 2.5 μm (PM2.5) and the carbon content in it at a coastal urban background station. Mass concentrations of elemental (EC), organic (OC) and total carbon (TC) were investigated from January 1st 2017 to August 31st 2019. Sampling was conducted during 24- hour periods from approximately 55 m3 of ambient air on quartz fibre filters pre-fired at 850°C for 3 hours. Mass concentrations of 973 PM2.5 samples were determined gravimetrically according to the standard EN 12341:2014. Carbon content was measured by the thermal-optical transmittance method (TOT) using a carbon aerosol analyser with a flame ionization detector and EUSAAR_2 temperature program operating according to the standard EN 16909:2017. The average PM2.5 mass concentration (11.1 μg m-3) did not exceed the limit value of 25 μg m-3 and the maximum was observed in winter (51.3 μg m-3). Carbon mass concentrations revealed strong seasonality having its low in summer and high in winter. The average OC/EC mass ratio values of around 6.6 pointed to the influence of secondary organic aerosols. Average TC mass contribution to the total PM2.5 mass was 33 %, of which 20 % SOC (secondary OC), 7 % POC (primary OC) and 5 % EC. The high mass contribution of SOC to total OC mass (as much as 74 %) can be explained by the warm climate suitable for photochemical reactions and the formation of SOC from sea spray.