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.

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.

Variabilities of biochemical properties of the sea surface microlayer: Insights to the atmospheric deposition impacts.

Atmospheric deposition (AD) of nutrients and its impact on the sea surface requires consideration of interfacial processes within the sea surface microlayer (SML), the ocean-atmosphere boundary layer of major importance for many global biogeochemical and climate-related processes. This study comprised a comprehensive dataset, including dissolved NO3-, NH4+ and PO43- in ambient aerosol particles, wet deposition and sea surface samples collected from February to July 2019 at a central Adriatic coastal site. The aerosol mean concentration of dissolved nitrogen (DIN = NO3- + NH4+) and PO43- were 48.8 ± 82.8 µmol m-3 and 0.8 ± 0.6 µmol m-3, respectively, while their total fluxes (dry + wet) ranged from 24.2 to 212.3 µmol m-2 d-1 (mean 123.2 ± 53.2 µmol m-2 d-1) and from 1.2 to 2.1 µmol m-2 d-1 (mean 1.5 ± 0.3 µmol m-2 d-1), respectively. Intensive local episodes of open biomass burning (BB) significantly increased aerosol DIN concentrations as well as DIN deposition fluxes, particularly altering the molar DIN/PO43- ratio of atmospheric samples. The DIN temporal patterns showed high variability in the SML (range 0.2-24.6 µmol L-1, mean 5.0 ± 7.1 µmol L-1) in contrast to the underlying water samples (range 0.5-4.2 µmol L-1, mean 1.9 ± 1.2 µmol L-1), with significant increases during BB periods. Variability in abundance of heterotrophic bacteria and autotrophs in the SML along with concentrations of bulk dissolved and particulate organic carbon as well as dissolved and particulate lipids and carbohydrates, gel particles and surfactants followed DIN enhancements with a two-week delay. This study showed that AD can affect the short-term scale enrichments of organic matter in the SML, especially when accompanied by BB emissions typical of the overall Mediterranean coastal environment. This could have strong implications for global air-sea exchange processes, including those of climate relevant gases, mediated by the SML.

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..

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.

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.

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.

Influence of lockdown caused by the COVID-19 pandemic on air pollution and carcinogenic content of particulate matter observed in Croatia.

Due to the pandemic of SARS-CoV-2 in Croatia, all unnecessary activities were prohibited during the designated lockdown period (March-May 2020). With reduced human activity, levels of some air pollutants decreased. In this study, mass concentrations of the PM1 particle fraction (particulate matter with an equivalent aerodynamic diameter < 1 µm) and polycyclic aromatic hydrocarbons (PAHs) in PM1 and NO2 were measured and compared with concentrations measured in the same period the year before. Air pollutant concentrations were measured at two measuring sites: urban residential and urban traffic. Our results show a concentration decrease by 35% for NO2 and PM1 particles and by 26% for total PAHs at the traffic measuring site. At the residential measuring site, only concentrations of NO2 decreased slightly, but PM1 particles and PAHs were similar to the year before.

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.

Carcinogenic organic content of particulate matter at urban locations with different pollution sources.

Polycyclic aromatic hydrocarbons (PAHs) 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 under normal tropospheric conditions are found in the particle-phase. Benzo(a)pyrene (BaP) is often measured as their general representative. Sarajevo, the capital of Bosnia and Herzegovina, is among the European cities with the poorest air quality. However, in Sarajevo PAHs are neither routinely measured within the air quality monitoring network nor have been a subject of extended, continuous field studies during the most polluted cold periods of the year. The capital of Croatia, Zagreb, is located approximately 300 km air distance north-west from Sarajevo. PAH mass concentrations in Zagreb have been measured continuously since 1994 within air quality monitoring networks. During winter 2017/2018, the SAFICA project (Sarajevo Canton Winter Field Campaign 2018) was carried out in order to characterize the chemical composition of organic and inorganic aerosol in the Sarajevo Canton. This paper presents the results of PAH measurements in the cities of Sarajevo and Zagreb at one urban location per city. Daily (24 h), continuous samples of PM10 (particulate matter with aerodynamic diameters ≤10 µm) were collected during heating season, from December 27, 2017 to February 27, 2018. Mass concentrations of eleven particle-phase PAHs in Sarajevo and Zagreb from filter samples collected during the same period were compared. The average BaP ambient mass concentrations in Sarajevo and Zagreb were 6.93 ng m-3 and 3.11 ng m-3, respectively. The contribution of BaP to the total PAH mass concentration was similar at both locations (11%). However, much higher contributions of particle-phase fluoranthene and pyrene were found in Sarajevo. Contributions of individual PAH, diagnostic ratios and factor analysis indicate that combustion of gasoline and diesel from vehicle traffic are a potential source of PAHs at both locations, as well as combustion of other liquid fossil fuels (petroleum and fuel oil). Wood burning was occasionally indicated as a PAH emission source in Zagreb, while in Sarajevo the contribution of PAHs from wood and coal combustion was more evident. Calculated value for total carcinogenic potency (TCP) of PAHs, which was estimated using toxic equivalence factors from the literature, in PM10 samples collected in Sarajevo was more than twice higher than in Zagreb (10.6 ng m-3 and 4.7 ng m-3, respectively). BaP had the highest contribution to the TCP at both locations (69 and 67%).

Experiences with the accreditation of the Institute for Medical Research and Occupational Health, Zagreb, Croatia.

Accreditation in accordance with the international General Requirements for the Competence of Testing and Calibration Laboratories (HRN EN ISO/IEC 17025 standard) has become a widely accepted method of quality management and objective evidence of technical competence, knowledge, and skills of testing and calibration laboratories. In 2010, the Institute for Medical Research and Occupational Health (IMROH) had its management system accredited against the HRN EN ISO/IEC 17025 standard for the following scopes: determination of radioactivity, testing of ambient air quality, and testing in the scope of ionising radiation protection. This accreditation encompassed three laboratories: Radiation Protection Unit, Environmental Hygiene Unit, and the Radiation Dosimetry and Radiobiology Unit. In accordance with the rules of the Croatian Accreditation Agency, the second re-accreditation is due in 2020. This paper describes and discusses the quality management system at IMROH over the ten years of its implementation. We share our experiences about non-conformities discovered during regular work, internal audits, and external audits performed by the Croatian Accreditation Agency. The accredited management system significantly improved the performance of the accredited units, and the Institute increased its visibility and marketing advantage, consequently improving its market position.

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.

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.

Concentrations of PAHs and other gaseous pollutants in the atmosphere of a rural area.

In this study, concentrations of polycyclic aromatic hydrocarbons (PAHs) bound to PM10 particles were measured in a Croatian rural area. Considering that by now only a limited number of studies have provided data on pollutant concentrations for rural areas, our aim was to do so by determining the PAH levels, their mutagenic effect and relationship with meteorological conditions and other gaseous pollutants (NO, NO2, NH3). In this investigation, samples of PM10 particles were collected on quartz filters for 1 month in the cold period and 1 month in the warm period of the year, 24 h a day. Diagnostic PAH concentration ratios and factor analysis were used as tools to identify and characterize the PAH sources. The PAHs found in the warm period of the year were characteristic for car exhaust emissions while the predominant source of these pollutants in the cold period was wood burning. The measurements showed much higher average concentrations of all PAHs in the cold period, most pronounced for fluoranthene 0.347 ng m(-3) and pyrene 0.223 ng m(-3). Mass concentrations of benzo(a)pyrene in the cold period ranged from 0.057 to 1.526 ng m(-3), while in the warm period they varied from 0.009 to 0.111 ng m(-3). Mutagenicity related to BaP (BaPMeq) was significantly higher during the cold period (1.095 ng m(-3)) than in the warm period (0.101 ng m(-3)).

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.

[Carbon in particulate matter in the air]. / Ugljik u lebdecim cesticama u zraku.

Carbon in Particulate Matter in the AirCarbon (Latin carbo) in elemental form appears as diamond, graphite, fullerene, and black amorphous carbon. Black amorphous carbon can be found in atmospheric aerosols and its main forms are elemental (EC), organic (OC), and carbonate (CC) carbon. Atmospheric carbon particles are transmitted through more than 70 sources of air pollutants. Elemental carbon is the primary pollutant, which results from incomplete combustion of fossil and biomass fuels. It also appears as soot, in sediment, soil, and ice core. Many quantitative determinations of elemental carbon are based on its chemical inertness, thermal stability, and visual features. Organic carbon includes organic compounds such as polycyclic aromatic hydrocarbons (PAH), polychlorinated biphenyls (PCB), polychlorinated dibenzo-p-dioxins and furans, polybrominated diphenylethers, and other organic pollutants are the products of combustion and formation of secondary organic aerosols.The aim of this paper was to describe different forms of carbon in the atmosphere, how they affect people, climate, and the atmosphere, and to give an overview of different methods for their determination.

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.