New Insight into the Measurements of Particle-Bound Metals in the Urban and Remote Atmospheres of the Sarajevo Canton and Modeled Impacts of Particulate Air Pollution in Bosnia and Herzegovina.

The Sarajevo Canton Winter Field Campaign 2018 (SAFICA) was a project that took place in winter 2017-2018 with an aim to characterize the chemical composition of aerosol in the Sarajevo Canton, Bosnia and Herzegovina (BiH), which has one of the worst air qualities in Europe. This paper presents the first characterization of the metals in PM10 (particulate matter aerodynamic diameters ≤10 µm) from continuous filter samples collected during an extended two-months winter period at the urban background Sarajevo and remote Ivan Sedlo sites. We report the results of 18 metals detected by inductively coupled plasma mass spectrometry (ICP-MS) and electrothermal atomic absorption spectrometry (ETAAS). The average mass concentrations of metals were higher at the Sarajevo site than at Ivan Sedlo and ranged from 0.050 ng/m3 (Co) to 188 ng/m3 (Fe) and from 0.021 ng/m3 (Co) to 61.8 ng/m3 (Fe), respectively. The BenMAP-CE model was used for estimating the annual BiH health (50% decrease in PM2.5 would save 4760+ lives) and economic benefits (costs of $2.29B) of improving the air quality. Additionally, the integrated energy and health assessment with the ExternE model provided an initial estimate of the additional health cost of BiH's energy system.

Associating Air Pollution with Cytokinesis-Block Micronucleus Assay Parameters in Lymphocytes of the General Population in Zagreb (Croatia).

Air pollution is recognized as one of the most serious public health issues worldwide and was declared to be a leading environmental cause of cancer deaths. At the same time, the cytokinesis-block micronucleus (CBMN) assay serves as a cancer predictive method that is extensively used in human biomonitoring for populations exposed to environmental contamination. The objective of this cross-sectional study is two-fold: to evaluate genomic instability in a sample (N = 130) of healthy, general population residents from Zagreb (Croatia), chronically exposed to different levels of air pollution, and to relate them to air pollution levels in the period from 2011 to 2015. Measured frequencies of CBMN assay parameters were in agreement with the baseline data for the general population of Croatia. Air pollution exposure was based on four factors obtained from a factor analysis of all exposure data obtained for the examined period. Based on the statistical results, we did not observe a significant positive association between any of the CBMN assay parameters tested and measured air pollution parameters for designated time windows, except for benzo(a)pyrene (B[a]P) that showed significant negative association. Our results show that measured air pollution parameters are largely below the regulatory limits, except for B[a]P, and as such, they do not affect CBMN assay parameters' frequency. Nevertheless, as air pollution is identified as a major health threat, it is necessary to conduct prospective studies investigating the effect of air pollution on genome integrity and human health.

Air pollution levels near crossroads with different traffic density and the estimation of health risk.

The aim of this study was to determine the influence of traffic density on air pollutant levels as well as to analyse the spatial and temporal distribution of particulate pollutants and their health risk. The following species related to traffic pollution were measured: PM10, elemental and organic carbon and polycyclic aromatic hydrocarbons (PAHs) in PM10 and gas pollutants (SO2, NO2 and CO). The measurements were carried out at four crossroad sites in the city. Samples of PM10 were collected over three periods (6 am to 2 pm, 2 pm to 10 pm and 10 pm to 6 am) on working days and weekends. Statistically significant differences were found between sampling sites for all pollutant concentrations, except for NO2. The highest mass concentrations of PM10, carbon and PAHs were observed in the south of the city with the highest traffic density. Concentrations of gasses (CO and NO2) showed high values in morning and in the late afternoon and evening (west and east). At all measuring sites, the highest concentration of particle-bound pollutants was mostly recorded during morning and afternoon, except at the south, where elevated PAHs concentrations were recorded during night period, which indicated that residential heating takes up a portion of pollution sources in this area. Although for most of the pollutants the concentrations varied during the day, statistically significant differences between sampling periods were not found. The highest health risk was obtained at the south, where it was scored as significant.

Air Pollution and Primary DNA Damage among Zagreb (Croatia) Residents: A Cross-Sectional Study.

More than eight million premature deaths annually can be attributed to air pollution, with 99% of the world's population residing in areas below recommended air quality standards. Hence, the present study aimed to examine the association between primary DNA damage and air pollution data among 123 participants enrolled between 2011 and 2015 in Zagreb, Croatia. While most measured air pollutants adhered to regulatory limits, benzo[a]pyrene concentrations bound to PM10 exceeded them. Factorial analysis narrowed down air pollution data to four exposure factors (particulate matter, two metal factors, and other pollutants). Despite the absence of significant positive associations between modeled air pollution exposure factors and comet assay descriptors (tail length, tail intensity, tail moment, and highly damaged nuclei), the critical health implications of air pollution warrant further investigations, particularly with biomarkers of exposure and different biomarkers of effect in populations facing air pollution exposure.

Sources, Ionic Composition and Acidic Properties of Bulk and Wet Atmospheric Deposition in the Eastern Middle Adriatic Region.

Atmospheric bulk and wet deposition samples were collected simultaneously at the background coastal site in the Eastern Middle Adriatic region in order to assess the impact of major ions (Cl-, NO3-, SO42-, Na+, K+, NH4+, Mg2+, Ca2+) on deposition acidity and distinguish the main sources. Higher ion levels were observed during the cold period, especially for Cl-, Na+, Mg2+ and K+. Dust intrusion caused significant increases in levels of Ca2+, Mg2+ and K+, while open-fire events increased the levels of K+. Deposition acidity showed seasonal differences as well as the influence of dust intrusion. Low ionic balance ratios indicated acidic deposition properties and the presence of organic anions. The highest neutralization ability was found for Ca2+, Na+ and NH4+. Several natural (marine, crustal) and anthropogenic sources were determined, as well as the formation of secondary aerosols. Wet deposition was characterized by higher contribution of sea salt fraction compared to bulk deposition and lower contribution of crustal fraction.

Winter mass concentrations of carbon species in PM10, PM 2.5 and PM1 in Zagreb air, Croatia.

The purpose of our investigation was to examine the mass concentrations of EC, OC and TC (EC + OC) in PM(10), PM(2.5) and PM(1) particle fractions. Daily PM(10), PM(2.5) and PM(1) samples were collected at an urban background monitoring site in Zagreb during winter 2009. Average OC and EC mass concentrations were 11.9 and 1.8 µg m(-3) in PM(10), 9.0 and 1.4 µg m(-3) in PM(2.5), and 5.5 and 1.1 µg m(-3) in PM(1). Average OC/EC ratios in PM(10), PM(2.5), and PM(1) were 7.4, 6.9 and 5.4, respectively.

Polycyclic aromatic hydrocarbons at different crossroads in Zagreb, Croatia.

Polycyclic aromatic hydrocarbons (PAHs) were measured in the PM(10) particle fraction collected at two different measuring sites in Zagreb, Croatia. In summer, concentrations of all PAHs at both sites were low. In winter, mass concentrations of all PAHs measured at southern site were much higher than those at north. Contents of all PAHs in the PM(10) particle fraction were much lower in summer than that in the winter period. For example, average content of BaP in PM(10) in summer was 2.26 ng/mg at site A and 4.17 ng/mg at site B, while in winter it was 34.72 and 46.69 ng/mg, respectively.

Machine Learning and Meteorological Normalization for Assessment of Particulate Matter Changes during the COVID-19 Lockdown in Zagreb, Croatia.

In this paper, the authors investigated changes in mass concentrations of particulate matter (PM) during the Coronavirus Disease of 2019 (COVID-19) lockdown. Daily samples of PM1, PM2.5 and PM10 fractions were measured at an urban background sampling site in Zagreb, Croatia from 2009 to late 2020. For the purpose of meteorological normalization, the mass concentrations were fed alongside meteorological and temporal data to Random Forest (RF) and LightGBM (LGB) models tuned by Bayesian optimization. The models' predictions were subsequently de-weathered by meteorological normalization using repeated random resampling of all predictive variables except the trend variable. Three pollution periods in 2020 were examined in detail: January and February, as pre-lockdown, the month of April as the lockdown period, as well as June and July as the "new normal". An evaluation using normalized mass concentrations of particulate matter and Analysis of variance (ANOVA) was conducted. The results showed that no significant differences were observed for PM1, PM2.5 and PM10 in April 2020-compared to the same period in 2018 and 2019. No significant changes were observed for the "new normal" as well. The results thus indicate that a reduction in mobility during COVID-19 lockdown in Zagreb, Croatia, did not significantly affect particulate matter concentration in the long-term..

Assessment of ozone concentration data from the northern Zagreb area, Croatia, for the period from 2003 to 2016.

A measurement station located in an urban area on the southern slope of the Medvednica Mountain (120 m a.s.l.), close to the Croatian capital Zagreb, provided data for an analysis of the photosmog in the city of Zagreb. Data for the period 2003-2016 obtained from this station and analysed in this work can also be compared with the nearby Puntijarka station (980 m a.s.l.) for which a similar analysis has already been carried out. In Puntijarka station analysis, it has been shown that there is most probably no significant change in ozone concentrations during the observed period. In this study the mean value of the annual ozone volume fractions showed a linear trend of 0.23 ppb yr-1, a growth that is in the worst case scenario among the lowest global prediction, while the seasonal (April-to-September) mean values had a trend of 0.32 ppb yr-1, which is a certain clearly observable growth. The 95-percentile values had trends of 0.009 ppb yr-1 (annual data) and -0.072 ppb yr-1 (seasonal data), respectively. Both of these values show very small changes if any at all. By using FT analysis, with the calculation of uncertainties, we have observed three prominent cycles of 169 ± 4 h (weekly cycle), 24 ± 1 h and 12 ± 1 h (diurnal cycles). Uncertainties were low which strongly indicate that the cycles are present. However, since high concentrations of ozone were observed only sporadically, ozone pollution in the northern part of Zagreb is at the present rather low. A Fourier transformation was used to analyse the data for periodic behaviour, which revealed the existence of diurnal and weekly modulations. Nevertheless, constant monitoring is important and will continue in the future as part of continuous monitoring of the ozone levels in the area.

Pollution levels and deposition processes of airborne organic pollutants over the central Adriatic area: Temporal variabilities and source identification.

First data on polycyclic aromatic hydrocarbons (PAHs) and nitro-aromatic compounds (NACs) in aerosols as well as of PAHs, polychlorinated biphenyls (PCBs) and NACs in bulk and wet atmospheric deposition samples were simultaneously obtained during 6-month-long field campaign at the costal central Adriatic area. Special attention was given to open-fire biomass burning episodes as extreme events common for the overall Mediterranean coastal area in order to gain a better understanding of the atmospheric variabilities and potential sources of trace organic pollutants in coastal environments. Diesel and gasoline combustion related to land and maritime traffic as well as occasional open-fire episodes (forest fires) were found to be the dominant pollution sources of PAHs in PM10 particles. NACs were determined almost exclusively in samples affected by biomass burning episodes. Open-fire episodes had a strong contribution to the overall NACs atmospheric deposition fluxes. Several chlorinated congeners of PCBs were predominantly contributed in deposition samples.

Radioactivity of soil in Croatia I: naturally occurring decay chains.

The assessment of environmental radioactivity much relies on radionuclide content in soil. This stems from the significant contribution of soil to both external and internal exposure to ionising radiation via direct emission of gamma radiation and soil-to-plant radionuclide transfer, respectively. This motivated us to carry out a systematic research on the radioactivity of soil in Croatia to obtain relevant data that can be used as a basis for understanding the related effects of geomorphological, biogeographical, and climatological properties of the environment. We collected samples of the surface layer of uncultivated soil (0-10 cm) at 138 sites from all over the country and measured them for radionuclide activity concentrations by means of high-resolution gamma-ray spectrometry. This resulted in radioactivity maps containing data on activity concentrations of representative radionuclides in the environment. In this paper, which is the first in our two-part presentation, we focus on the naturally occurring 232Th and 238U decay chains and their correlations with the diversity of Croatian regions. For both of the chains, activity concentrations were the highest in the Dinaric region, the lowest in the Pannonian region, and intermediate in the Adriatic region. Relatively high concentrations of 226Ra in the soil of the Dinaric region implied a possibility of an enhanced emanation of its progeny 222Rn into the air. Activity concentrations of 210Pb were additionally elevated in areas with dense vegetation, most probably due to an atmospheric deposition of airborne 210Pb onto the surface of plants and their eventual decomposition on the ground.

Radioactivity of soil in Croatia II: 137Cs, 40K, and absorbed dose rate.

We took samples of uncultivated soil from the surface layer (0-10 cm) at 138 sites from all over Croatia and measured their radionuclide activity concentrations with high-resolution gamma-ray spectrometry. This second part of our report brings the results on 40K and 137Cs to complement those on the 232Th and 238U decay chains addressed in the first part. Together they give the most complete picture of radioactivity of Croatian soil so far. Activity concentrations of 40K were the highest in the Pannonian region, and there was an opposite trend for 137Cs. We found that the concentrations of 137Cs tended to increase with altitude, annual precipitation, and vegetation density. The concentration ratio of 137Cs and K in soil, which indicates the potential for 137Cs entering food chains via uptake by plants, was the lowest in agriculturally important areas in the east of the Pannonian region. In addition, we used the obtained results on activity concentrations to calculate the related absorbed dose rate as a measure of external exposure to ionising radiation from soil. The sum of the absorbed dose rates for naturally occurring radionuclides and 137Cs showed that external exposure was generally the highest in the Dinaric region and Istrian Peninsula.

ESTIMATION OF AIRBORNE 106RU ACTIVITY CONCENTRATION FROM TOTAL BETA ACTIVITY OF PM10 PARTICLE FRACTIONS.

Airborne radioruthenium, as a result of an accidental release, presents a risk for occupational and public exposure. In fall 2017, a detection of 106Ru was reported by the European atmospheric radioactive contamination monitoring networks. We investigated the daily specific total beta activity of PM10 particle fractions samples. The presented method enables indirect determination of airborne 106Ru activity concentration from total beta activity, in case 106Ru was confirmed as single excess radiological pollutant. This allows for daily measurements and time-resolved 106Ru activity concentration data. We estimated the indicative committed effective dose due to 106Ru inhalation for the Croatian population during the exposure period. Although the estimated dose value of ~169.7 nSv, for ~6-d duration of ruthenium air pollution, was very low, it was ~40 times higher than the value for Hinh from inhalation of other radionuclides (90Sr + 137Cs + 40K + 7Be).

Pollution Sources and Carcinogenic Risk of PAHs in PM1 Particle Fraction in an Urban Area.

Airborne particles are composed of inorganic species and organic compounds. PM1 particles, with an aerodynamic diameter smaller than 1 µm, are considered to be important in the context of adverse health effects. Many compounds bound to particulate matter, such as polycyclic aromatic hydrocarbons (PAH), are suspected to be genotoxic, mutagenic, and carcinogenic. In this study, PAHs in the PM1 particle fraction were measured for 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. Significant differences were found between PAH concentrations during cold (January-March, October-December) and warm (April-September) periods of the year. In general, the mass concentrations of PAHs characteristic for car exhausts (benzo(ghi)perylene (BghiP), indeno(1,2,3-cd)pyrene (IP), and benzo(b)fluoranthene (BbF)) were higher during the whole year than concentrations of fluoranthene (Flu) and pyrene (Pyr), which originated mostly from domestic heating and biomass burning. Combustion of diesel and gasoline from vehicles was found to be one of the main PAH sources. The incremental lifetime cancer risk (ILCR) was estimated for three age groups of populations and the results were much lower than the acceptable risk level (1 × 10-6). However, more than ten times higher PAH concentrations in the cold part of the year, as well as associated health risk, emphasize the need for monitoring of PAHs in PM1. These data represent a valuable tool in future plans and actions to control PAH sources and to improve the quality of life of urban populations.

Acidic anions in PM10 particle fraction in Zagreb air, Croatia.

This paper presents the results of 7 years continuous measurement of acidic anions chlorides, nitrates, and sulphates in PM(10) particle fraction in the city of Zagreb, Croatia. The mean annual mass concentrations of the investigated anions in PM(10) particle fraction varied from 0.28 to 0.95 microg/m(3) for chlorides, from 3.21 to 7.87 microg/m(3) for nitrates and from 3.98 to 9.71 microg/m(3) for sulphates. The concentration levels of all measured anions showed significant seasonal differences. The most contributing to the PM(10) mass were sulphates, then nitrates, and then chlorides. The mobile source emission was an important contributor to particle mass.

PAH mass concentrations measured in PM10 particle fraction.

This paper presents daily, monthly and yearly variations of PAH mass concentrations measured in PM(10) particle fraction, collected at one measuring site in Zagreb air between 2001 and 2004, and seasonal differences in PAH mass concentrations in PM(10) samples collected from 21 March 2003 to 20 March 2004. Twenty-four hour samples were taken in the northern residential part of Zagreb using a low-volume (50 m(3)) sampler and glass or quartz filters. The analysis was performed using a high-performance liquid chromatograph (HPLC) and fluorescence detector with changeable excitation and emission wavelength. The annual average mass concentrations over the four-year measuring period for BaP ranged from 1.17 ng/m(3) in 2004 to 1.87 ng/m(3) in 2003 and were below the limit value (2 ng/m(3)) set by the Ordinance on Recommended and Limit Air Quality Values in Croatia. The highest concentrations of all PAHs measured in PM(10) samples collected from 21 March 2003 to 20 March 2004 were found in the winter and the lowest in the summer. Winter average of BaP was 2.94 ng/m(3) and summer average 0.12 ng/m(3). Autumn average was 2.76 ng/m(3) and was very similar to winter concentrations. Spring average of 0.58 ng/m(3) was higher than the summer average (0.12 ng/m(3)). Mass concentrations of all measured PAHs were much higher in the autumn than in the spring. Although annual averages for BaP did not exceed the limit value, autumn and winter BaP mass concentrations did, which calls for measures for reducing PAH emissions in the autumn and winter.

Polycyclic aromatic hydrocarbons in the air near gas field Molve.

Small-volume air samples (approximately 7 m3 per 24 h) of airborne PM10 particle fraction were collected on quartz fibre filters at two measuring sites in the vicinity of the gas field Molve in April and July 2006. It took five to seven days for each sample to collect and one month to collect five to seven samples. Mass concentrations of PM10 fractions were determined by gravimetry while PAHs were analysed using a HPLC with a fluorescent detector. The analysis included fluoranthene (Flu), pyrene (Pyr), benzo(a)anthracene (BaA), chrysene (Cry), benzo(b)fluoranthene (BbF), benzo(k)fluoranthene (BkF), benzo(a)pyrene (BaP), benzo(ghi)perylene (BghiP) and indene(1,2,3-cd)pyrene (Ind). Average concentrations of all PAHs in April at site A were slightly higher than at site B while in July they were lower and similar on both sites. Average BaP concentration measured at site A in April was 0.156 ng m(-3) and at site B 0.129 ng m(-3), while July BaP averages were 0.022 ng m(-3) at both sites. In both months, the mass concentration of BaP was lower than the limit value (1 ng m(-3)) and well below the tolerant value (2 ng m(-3)) set by a Croatian regulation of 2005. This suggests that the air near gas field Molve was of acceptable quality in respect to BaP at the time of the measurement.

Spatial and temporal distribution of platinum, palladium and rhodium in Zagreb air.

Platinum (Pt), palladium (Pd) and rhodium (Rh) are most widely used in the production of automotive catalytic converters that serve to reduce toxic emissions from motor vehicles. The aim of this study was to quantitatively determine the levels of platinum, palladium and rhodium in the PM10 and PM2.5 fraction of airborne particle matter and find their spatial and temporal distribution at different polluted areas of the city of Zagreb, Croatia. The method used in this paper included weekly sampling of airborne particle matter on quartz filters, microwave digestion in acid under high pressure and temperature, and analysis by inductively coupled plasma mass spectrometry (ICP MS). The results have shown that the highest mean values at all three sampling stations (North, Center, South) were obtained for palladium (3.856 pg m-3, 5.396 pg m-3, 5.600 pg m-3) and the lowest for rhodium (0.444 pg m-3, 0.643 pg m-3, 0.750 pg m-3). The average mass concentrations of platinum group elements (PGE) in PM10 increased for all three elements in the direction North < Center < South which had to do with the traffic load nearby the monitoring stations. The ratio of measured mass concentrations to all measuring stations was similar to platinum, palladium and rhodium content in automotive catalytic converters. Factor analysis grouped platinum, palladium and rhodium at all of the monitoring stations, and their relation to other metals together with the aforementioned results indicate that their main source of pollution is traffic or precisely automotive catalytic converters. At all three of the monitoring sites, higher values were measured during the colder part of the year. The results of measuring platinum, palladium and rhodium levels in the city of Zagreb are the first results of their kind for this area and will provide insights into the contribution of catalytic converters to the presence of these elements in the environment.

Analysis of Airborne Dust as a Result of Plaster Cast Sawing.

Plaster splints are used daily in surgical and orthopedic fields in order to immobilize injured children and adults. The aim of this study was to measure the aerodynamic diameter and concentration of dust particles in the air caused by sawing plaster splints (calcium sulfate dehy-drate). We performed fractional measurements of airborne dust particles. The measured particles, which can potentially be inhaled, may have a specific negative effect on human health. Measurements were conducted in laboratory research facilities that simulated hospital conditions within a casting room and the associated waiting room. Measurements within the casting room were made using two particle collector devices and one laser photometer. The measurement for the simulated waiting room was performed using the same principles and devices. The collected plaster dust particles differed in aerodynamic diameter and concentration according to the various locations observed. The highest concentration of particles of all sizes was recorded at the site of cast sawing. There was direct correlation between distance from the source and concentration of airborne particles; this concentration was lowest in the waiting room. The concentrations of plaster dust recorded were lower than the recommended minimal limit values for total and respiratory fractions in Croatia. Accordingly, it can be assumed that sawing of plaster splints has no harmful health effects on the exposed patients and health personnel.

Carbon species in PM10 particle fraction at different monitoring sites.

The aim of this study was to determine and compare the levels of elemental carbon (EC), organic carbon (OC) and polycyclic aromatic hydrocarbons (PAHs) mass concentrations in PM10 particles (particles with aerodynamic diameter less than 10 µm) between seasons (winter and summer) and at different monitoring sites (urban background and rural industrial). Daily samples of airborne particles were collected on pre-fired quartz fibre filters. PM10 mass concentrations were determined gravimetrically. Samples were analysed for OC and EC with the thermal/optical transmittance method (TOT) and for PAHs by high-performance liquid chromatography (HPLC) with a fluorescence detector. Measurements showed seasonal and spatial variations of mass concentrations for carbon species and for all of the measured PAHs (Flu, Pyr, Chry, BaA, BbF, BaP, BkF, BghiP and IP) in PM10 at the urban site and rural monitoring site described here. Diagnostic PAH ratios (Flu/(Flu + Pyr), BaA/(BaA + Cry), IP/(IP + BghiP), BaP/BghiP, IP/BghiP and BaP/(BaP + Chry)) make it possible to assess the sources of pollution, and these showed that diesel vehicles accounted for most pollution at the rural-industrial (RI) site in the summer, whereas coal and wood combustion were the causes of winter pollution. This difference between winter and summer PAH ratios were more expressed at the RI site than at the UB site because at the UB site the predominant heating fuel was gas. The OC/EC ratio yielded the same conclusion. Factor analysis showed that EC and OC originated from traffic at both sites, PAHs with 5 or more benzene rings originated from wood pellets industry or biomass burning, while Pyr and Flu originated from diesel combustion or as a consequence of different atmospheric behaviour - evaporation and participation in oxidation and photo oxidation processes.