Search

Copyright of Kemija u Industriji is the property of Croatian Society of Chemical Engineers and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

Polycyclic aromatic hydrocarbons (PAHs) are one of the first atmospheric pollutants identified as suspected carcinogens. In ambient air, PAHs with higher molecular weights (more than 4 rings) are mostly bounded to particles. Particle size plays an important role in assessing health risks. The aim of this study was to compare concentrations of PAHs bound to particle fractions PM10, PM2.5 and PM1 (particles with a diameter smaller than 10 μm, 2.5 μm and 1 μm, respectively) as well as to estimate their carcinogenic potency. Measurements of ten PAHs were carried out in 2014 at urban location in the northern part of Zagreb, Croatia. 24-hour samples of PM10, PM2.5 and PM1 particle fraction were collected, forty per season. The PAH analysis was performed using high performance liquid chromatography with a fluorescence detector. The total carcinogenic potency (TCP) of PAHs was estimated by calculating benzo(a)pyrene equivalent concentrations using toxic equivalence factors from the literature. The average TCPs for the overall period were 4.287, 1.898 and 1.630 ng/m3 for PM10, PM2.5 and PM1, respectively. The lowest TCP was recorded in summer and the highest in winter. The highest contribution to the TCP were from benzo(a)pyrene, dibenzo(a,h)antrachene, indeno(1,2,3,cd)pyrene and benzo(b)fluoranthene and altogether they contributed between 91 and 94 % in all fractions and seasons. [ABSTRACT FROM AUTHOR]

Platinum group elements (PGE), in particular platinum (Pt), palladium (Pd) and rhodium (Rh) have a significant role in the operation of automotive catalytic converters whose purpose is to reduce emissions of gaseous pollutants into the air. Hot exhaust gases passing through catalytic converters cause damage to these systems leading to emissions of Pt, Pd and Rh in the environment and increase their levels in the air. Weekly PM10 samples were collected in 2017 at two monitoring stations (North - urban background and South - urban traffic) in Zagreb and mass concentrations of Pt, Pd and Rh were measured by inductively coupled plasma mass spectrometry (ICP-MS). The average annual mass concentrations for Pt, Pd and Rh were 0.373 pg m-3, 2.053 pg m-3 and 0.316 pg m-3 for monitoring station North and 0.681 pg m-3, 3.843 pg m-3 and 0.574 pg m-3 for monitoring station South, respectively. In this study, the relationship between Pt, Pd and Rh mass concentrations and meteorological parameters, including air temperature, relative humidity, precipitation, air pressure, wind direction and wind speed was analysed. The wind roses at both monitoring stations pointed to a common source for all three of the measured metals. At monitoring site North, the pollution was connected with winds from north and northeast, while at monitoring station South with winds from the southeast. [ABSTRACT FROM AUTHOR]

Monitoring of metals lead, cadmium and manganese in total suspended particulate matter started in 1971 in Zagreb and continued until 2005. Monitoring of lead in PM10 particles started in 1999 at one measuring site in the northern part of the city as an independent research project. In correspondence with the Croatian Air Protection Acts, monitoring of lead, cadmium and manganese in PM10 particles in Zagreb started at the beginning of 2006, while monitoring of nickel and arsenic started at the beginning of 2007, as a part of the official air quality monitoring network. Monitoring was carried out at five measuring sites located in the city centre and in the northern, southern, western and eastern parts of the city. Since 2011 monitoring of lead, cadmium, manganese, arsenic and nickel in PM10, PM2,5 and PM1 particles has been going on as an independent research project. Monitoring is conducted at one measuring site in the northern part of the city. The paper also presents the preliminary results of metal monitoring in PM10, PM2,5 and PM particles from January to February 2011. [ABSTRACT FROM AUTHOR]

Indoor air pollution is becoming a rising public health problem and is largely resulting from the burning of solid fuels and heating in households. Burning these fuels produces harmful compounds, such as particulate matter regarded as a major health risk, particularly affecting the onset and exacerbation of respiratory diseases. As exposure to polluted indoor air can cause DNA damage including DNA sd breaks as well as chromosomal damage, in this paper, we aim to provide an overview of the impact of indoor air pollution on DNA damage and genome stability by reviewing the scientific papers that have used the comet, micronucleus, and γ-H2AX assays. These methods are valuable tools in human biomonitoring and for studying the mechanisms of action of various pollutants, and are readily used for the assessment of primary DNA damage and genome instability induced by air pollutants by measuring different aspects of DNA and chromosomal damage. Based on our search, in selected studies (in vitro, animal models, and human biomonitoring), we found generally higher levels of DNA strand breaks and chromosomal damage due to indoor air pollutants compared to matched control or unexposed groups. In summary, our systematic review reveals the importance of the comet, micronucleus, and γ-H2AX assays as sensitive tools for the evaluation of DNA and genome damaging potential of different indoor air pollutants. Additionally, research in this particular direction is warranted since little is still known about the level of indoor air pollution in households or public buildings and its impact on genetic material. Future studies should focus on research investigating the possible impact of indoor air pollutants in complex mixtures on the genome and relate pollutants to possible health outcomes., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Breastfeeding provides numerous health benefits for both infants and mothers, promoting optimal growth and development while offering protection against various illnesses and diseases. This study investigated the levels of polychlorinated biphenyls (PCB), organochlorine pesticides (OCP) and polycyclic aromatic hydrocarbons (PAH) in human milk sampled in Zadar (Croatia). The primary objectives were twofold: firstly, to evaluate the individual impact of each compound on the total antioxidant capacity (TAC) value, and secondly, to assess associated health risks. Notably, this study presents pioneering and preliminary insights into PAH levels in Croatian human milk, contributing to the limited research on PAH in breast milk worldwide. PCB and OCP levels in Croatian human milk were found to be relatively lower compared to worldwide data. Conversely, PAH levels were comparatively higher, albeit with lower detection frequencies. A negative correlation was established between organic contaminant levels and antioxidative capacity, suggesting a potential link between higher antioxidative potential and lower organic contaminant levels. Diagnostic ratio pointed towards traffic emissions as the primary source of the detected PAH. The presence of PAH suggests potential health risk, underscoring the need for further in-depth investigation., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

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 PM 10 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.

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 - , NO 3 - , SO 4 2- , Na + , K + , NH 4 + , Mg 2+ , Ca 2+ ) on deposition acidity and distinguish the main sources. Higher ion levels were observed during the cold period, especially for Cl - , Na + , Mg 2+ and K + . Dust intrusion caused significant increases in levels of Ca 2+ , Mg 2+ 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 Ca 2+ , Na + and NH 4 + . 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.

This paper present seasonal variation in the equivalent concentration (BaP eq ) of PAHs in order to assess the potential cancer risk for two different groups of residents via ingestion, dermal contact and inhalation pathways. The possible ecological risk caused by PAH atmospheric deposition based on risk quotient was also estimated. A bulk (total, wet and dry) deposition and PM 10 particle fraction (particles with an equivalent aerodynamic diameter < 10 µm) were collected from June 2020 to May 2021 at an urban residential location in the northern part of Zagreb, Croatia. The monthly average of total equivalent BaP eq mass concentrations of PM 10 varied from 0.057 ng m -3 in July to 3.656 ng m -3 in December; the annul ∑BaP eq average was 1.348 ng m -3 . In bulk deposition, ∑BaP eq mass concentrations varied from 1.94 to 57.60 ng L -1 . In both investigated media, BaP had the highest contribution in carcinogenic activity. For PM 10 media, dermal absorption implied the greatest potential cancer risk, followed by ingestion and inhalation. For bulk media, a moderate ecological risk for BaA, BbF and BaP was observed according to the risk quotient approach.

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 NO 3 - , NH 4 + and PO 4 3- 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 = NO 3 - + NH 4 + ) and PO 4 3- 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/PO 4 3- 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., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

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.

The Sa rajevo Canton Winter Fi eld Ca mpaign 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 PM 10 (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/m 3 (Co) to 188 ng/m 3 (Fe) and from 0.021 ng/m 3 (Co) to 61.8 ng/m 3 (Fe), respectively. The BenMAP-CE model was used for estimating the annual BiH health (50% decrease in PM 2.5 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.

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 PM 1 , PM 2.5 and PM 10 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 PM 1 , PM 2.5 and PM 10 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..

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 PM 10 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., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

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: PM 10 , elemental and organic carbon and polycyclic aromatic hydrocarbons (PAHs) in PM 10 and gas pollutants (SO 2 , NO 2 and CO). The measurements were carried out at four crossroad sites in the city. Samples of PM 10 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 NO 2 . The highest mass concentrations of PM 10 , carbon and PAHs were observed in the south of the city with the highest traffic density. Concentrations of gasses (CO and NO 2 ) 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., (© 2021. The Author(s), under exclusive licence to Springer Nature B.V.)

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., (© 2021. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

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 PM 1 particle fraction (particulate matter with an equivalent aerodynamic diameter < 1 μm) and polycyclic aromatic hydrocarbons (PAHs) in PM 1 and NO 2 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 NO 2 and PM 1 particles and by 26% for total PAHs at the traffic measuring site. At the residential measuring site, only concentrations of NO 2 decreased slightly, but PM 1 particles and PAHs were similar to the year before., Competing Interests: Conflict of interestThe authors declare that they have no conflict of interest., (© Springer Nature B.V. 2020.)

Airborne particles are composed of inorganic species and organic compounds. PM 1 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 PM 1 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 PM 1 . 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., Competing Interests: The authors declare that they have no conflict of interest.

A method based on solid phase extraction (SPE), gas chromatography tandem mass spectrometry (GC-MS/MS) and gas chromatography with electron capture detector (GC-ECD) was developed for the determination of polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) in atmospheric deposition samples. Six indicator PCB congeners were analysed by GC-ECD equipped with two micro electron-capture detectors and two gas chromatographic columns, while 12 PAH compounds were analysed by GC-MS/MS. Solid phase extraction on silica sorbent proved 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 as the eluting solvents. Two different performances of a bulk collector were compared. The method was validated using field total deposited samples collected monthly over a year by bulk method at an urban background station in Zagreb, Croatia. The levels and occurrence of PCBs corresponded to global environmental pollution, with the deposition rates of ∑ 6 PCBs between 6 - 28 ng m -2 d -1 . The deposition rates of ∑ 12 PAHs varied between 132 and 714 ng m -2 d -1 during the warm period, whereas it achieved a significantly higher range of 171 to 1069 ng m -2 d -1 in the cold period., Competing Interests: Declaration of Competing Interest None, (Copyright © 2020 Elsevier B.V. All rights reserved.)

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 PM 10 (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 PM 10 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%)., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Polycyclic aromatic hydrocarbons (PAHs) that are bound to particulate matter can have adverse effects on human health. Particle size plays an important role in assessing health risks. The aim of this study was to compare concentrations of PAHs bound to particle fractions PM 10 , PM 2.5 , and PM₁, as well as to estimate their carcinogenic potency and relative contributions of the individual PAHs to the carcinogenic potency in relation to the size of the particle. Measurements of ten PAHs were carried out in 2014 at an urban location in the northern part of Zagreb, Croatia. 24-h samples of the PM 10 , PM 2.5 , and PM₁ particle fraction were collected over forty days per season. Carcinogenic potency of PAHs was estimated by calculating benzo(a)pyrene equivalent concentrations while using three different toxic equivalence factor (TEF) schemes. The total carcinogenic potency (TCP) and percentage contributions differed significantly depending on the TEF scheme used. The lowest PAH mass concentrations and TCPs were in summer and the highest in winter. The contributions of individual PAHs to the sum of PAH mass concentrations remained similar in all fractions and seasons, while in fractions PM 10⁻2.5 and PM 2.5⁻1 they varied significantly. Road traffic represented the important source of PAHs in all fractions and throughout all seasons. Other sources (wood and biomass burning, petroleum combustion) were also present, especially during winter as a consequence of household heating. The highest contribution to the TCP came from benzo(a)pyrene, dibenzo(ah)antrachene, indeno(1,2,3,cd)pyrene, and benzo(b)fluoranthene (together between 87% and 96%) in all fractions and seasons. In all cases, BaP showed the highest contribution to the TCP regardless relatively low contributions to the mass of total PAHs and it can be considered as a good representative for assessing the carcinogenicity of the PAH mixture. When comparing the TCP of PAHs in PM 10 and PM 2.5 fractions, it was found that about 21⁻26% of carcinogenic potency of the PAH mixture belonged to the PM 2.5 fraction. Comparison of TCP in PM 2.5 and PM₁ showed that about 86% of carcinogenic potency belonged to the PM₁ fraction, regardless of the TEF scheme used.

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 PM 10 and PM 2.5 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 PM 10 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., (Copyright © 2018 Elsevier B.V. All rights reserved.)

This study examined a method for determination of rhodium (Rh), palladium (Pd) and platinum (Pt) in particulate matter using standard solutions, model samples and certified reference materials (NIST 1648a and ERM CZ120). The method was based on microwave digestion followed by inductively coupled plasma mass spectrometry (ICP-MS). The results showed that the stability of the standard solution mixture of Rh, Pd and Pt was better when chlorides were present in the solution. A membrane filter and one type of quartz filter were the most adequate for analyzing platinum group elements (PGE). Respective limits of detection for Rh, Pd and Pt were 0.028, 0.503 and 0.0265 pg/m 3 with a membrane filter and 0.478, 4.530 and 0.070 pg/m 3 for one type of quartz filters. The sample matrix had no significant effects on the determination of three PGEs.

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., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

The aim of this study was to investigate whether nitrogen dioxide (NO2), ozone (O3), and certain meteorological conditions had an impact on cardiovascular disease (CVD)-related emergency department (ED) visits in the metropolitan area of Zagreb. This retrospective, ecological study included 20,228 patients with a cardiovascular disease as their primary diagnosis who were examined in the EDs of two Croatian University Hospitals, Sisters of Charity and Holy Spirit, in the study period July 2008-June 2010. The median of daily CVD-related ED visits during the study period was 28 and was the highest during winter. A significant negative correlation was found between CVD-related emergency visits and air temperature measured no more than three days prior to the visit, and the highest negative correlation coefficient was measured two days earlier (R=0.266, p≤0.001). The number of CVD-related emergency visits significantly correlated with the average NO2 concentration on the same day (R=0.191, p<0.001). The results of multiple stepwise regression analysis showed that the number of CVD-related emergency visits depended on air temperature, and NO2 and O3 concentrations. The higher the air temperatures, the lower the number of daily CVD-related emergency visits (p<0.001). An increase in NO2 concentrations (p=0.005) and a decrease in O3 concentrations of two days earlier (p=0.006) led to an increase in CVD-related ED visits. In conclusion, the decrease in O3 concentrations and the increase in NO2, even if below the legally binding thresholds, could be associated with an increase in CVD-related emergency visits and a similar effect was observed with lower temperature measured no more than three days prior to the visit.

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)).

Polycyclic aromatic hydrocarbons (PAHs) originate from a variety of natural and industrial processes. In this paper, concentrations of nine PAHs in PM10 particle fraction were measured concurrently at four different sites (rural, urban residential, urban traffic, and residential-industrial) in continental Croatia. Measurements at all of the four sites showed much higher average concentrations for all of the PAHs in the winter period. The highest winter average values were measured at the industrial site and the lowest at the rural and the urban residential site. In the summer, the highest average values were also measured in the industrial area, except for benzo(ghi)perylene and indeno(1,2,3-cd)pyrene, which showed the highest average values in the rural area. Factor analysis has been applied to PAH concentrations to identify their potential sources. Extracted factors have been interpreted on basis of previous studies and weather conditions. The diagnostic ratios calculated in this study indicated mixed sources at all of the sites. The contribution of gasoline and diesel from traffic was significant at all of the sites except for the urban industrial. In the winter, potential PAH sources also arose from wood combustion. The industrial site differed from the other sites with the highest influence of diesel sources and refinery during the summer months. The contribution of BaP in total carcinogenic activity exceeded 50 % in both seasons at all of the measured sites, which suggests that BaP could be suitable as a marker of the carcinogenic potential of a PAH mixture.

Central gas station of the natural gas borehole system Podravina is located near the village Molve. It delivers more than a quarter of total energy used in Croatia to its consumers. Over the years, adapting technology to increasingly demanding and rigorous standards in environmental protection has become paramount. Yet, despite all the industry has undertaken to address the risk of harmful substances entering the food chain, a multidisciplinary research team of independent scientists monitors the content of specific substances in all components of the ecosystem. This paper presents measurements of total sulphur contents in soil surface [(0 to 3) cm] and subsurface [(3 to 8) cm] layers (study period: autumn 2006 - spring 2010) and in plants (study period: spring 2000 - spring 2010), and the concentration of gaseous sulphur compounds in the air. Concentrations of hydrogen sulphide (H2S) and mercaptans (RSH) were measured from the summer of 2002 until the autumn of 2010, while concentrations of sulphur dioxide (SO2) were measured from the spring of 2008 until the autumn of 2010. The paper also shows total annual atmospheric sulphur (S-SO4) deposition at Bilogora measuring station (study period: 2001 - 2010). Average monthly concentrations of H2S in air varied between 0.2 μg m-3 and 2.0 μg m-3, RSH between 0.1 μg m-3 and 24.5 μg m-3, and SO2 between 0.4 μg m-3 and 2.8 μg m-3 depending on the location and the season of sampling. Mean values of total sulphur in soil and in Plantago lanceolata plant ranged between 610 mg kg-1 and 1,599 mg kg-1 and between 3,614 mg kg-1 and 4,342 mg kg-1, respectively, depending on the soil type, location, and sampling depth. Average values of total sulphur mass ratio for all examined single soil samples (n=80) were 1,080 mg kg-1 for both studied layers, and 4,108 mg kg-1 for all analysed plant samples (n=85). Average total annual atmospheric sulphur deposition at Bilogora measuring station was 6.3 kg of S-SO4 per hectare.

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.

The study examines the influence of naturally elevated ozone concentrations and some meteorological variables on the lung function of untrained volunteers walking in an unpolluted mountain area. Forty male participants between 18 and 70 years (smokers and nonsmokers) walked at the top of Medvednica Mountain near Zagreb, Croatia, at approximately 1000 m above sea level (a.s.l.) and engaged in other recreational activities for at least 1 hour. Forced vital capacity (FVC) and forced expiratory volume in 1 second (FEV(1)) of the participants were measured at arrival and before they left the mountain. Regression analysis showed a statistically significant influence of environmental variables on lung function tests. However, all variables together explained less than 35% variability of FVC and 41% variability of FEV(1). The results suggest that short-term exposure to ozone may affect lung function tests, but no more than temperature and humidity. FEV(1) was found to be more sensitive to ozone than FVC. Smoking habit also had an important role in subject's sensitivity to ozone.

Monitoring of zinc in total suspended particulate matter (TSPM) started in Zagreb, Croatia in 1972 at two measuring sites, located in the city centre and in the northern part of the city. Monitoring of zinc concentrations in PM₁₀ started in the northern part of the city in 2003. The obtained data show a decreasing trend of zinc in TSPM. Over the past 3 years, the measurement of zinc in PM₁₀ particles has been performed, and the obtained data, in comparison to zinc in TSPM, have shown that 82%-93% of zinc was in the small PM₁₀ particles.

Mercury concentrations in air were measured at three measuring sites in the vicinity of a waste dump Jakusevec in Zagreb, Croatia over a 4-year period, from the beginning to the end of remediation. Measurements at the beginning of the remediation show that the concentrations of mercury at all three measuring sites were relatively high. Annual mercury mass concentrations in 2001 were between 17 and 445 ng m(-3). Annual mercury averages in 2004 ranged from 8 to 10 ng m(-3). Mercury variations were analysed with regard to the meteorological conditions. The results of this investigation show that in regard to mercury, the remediation was successful.

Ozone concentrations were measured at three sites in Zagreb (Croatia) in the summer of 2005. Two measuring sites were in urban areas, while the third site was in a rural area about 30 km to the south from the centre of Zagreb. Hourly ozone averages varied between 1 microg m(-3) and 209 microg m(-3). Average concentrations were the lowest in the rural area, even though elevated concentrations were recorded occasionally. However, the weather conditions during measurements were untypical for that time of the year; over the summer of 2005 there were many rainy and cloudy days. Ozone concentrations at all three sites were the highest on Saturdays and Sundays, and the lowest on Thursdays. All the results were analysed with regard to the meteorological conditions (wind velocity and direction, temperature, relative humidity).

This article presents the results of 6 years (1999-2004) of monitoring acidic components (fluoride, chloride, nitrate, sulfate) and heavy metals (lead, cadmium, thallium) in total deposited matter (TDM) in the town of Sibenik and the National Park Kornati, Croatia, in order to determine their levels, spatial and temporal variations, and possible emission source. Bulk deposition samples were collected using the Bergerhoff samplers. TDM matter was determined gravimetrically. Acidic anions were analyzed using ion chromatography. Metallic components were determined by atomic absorption spectrometry. Results show that the levels of measured pollutants were relatively low compared to those reported in other investigations. Statistical analysis indicates that the measured pollutants originate from several sources such as resuspended soil, industry, road dust, traffic, and secondary aerosols as the most important. The levels of TDM show a slightly increasing trend at all sampling sites. A significant increasing trend in the levels of nitrate and sulfate in TDM could be the consequence of increasing traffic activity and urbanization. The significant increasing trend in the ratio between nitrate and sulfate in TDM indicates that the nitrate and sulfate relative contribution to acidification is increasing. The level of heavy metals in TDM was in order of lead > thallium > cadmium at all sampling sites with slightly decreasing trend.

The Tropospheric Ultraviolet-Visible (TUV) model, version 4.2 developed by Madronich (2003) was used to estimate the extent of ultraviolet (UV) exposure of general population in Croatia over the summer. Solar noon values (13 h local time, CEST) of the ultraviolet index (UVI) for the period April to October 2004 were calculated for 61 cities in Croatia. The results showed that the risk of sunburn at 13 h local time in clear weather was high between April and September (UVI > 7) and very high in July (UVI > 10). In July, the UVI exceeded 8 between 11 h and 15 h local time. In this study, we developed a simple approximate formula to estimate UVI. The formula includes data on the time, date, altitude and clouds. The difference between our estimate and the TUV model for the summer months of June, July and August at 10 h to 16 h local time was less than 10%.

In August 2003 Croatia experienced a heat-wave period during which elevated concentrations of particulate matter (PM10) and ozone in ambient air were measured. By applying the model of Stedman and Rooney et al., it was shown that a significant part of excess mortality during this period can be attributed to PM10 and ozone in ambient air.

The past few decades saw a rising interest in the role of hydrogen peroxide (H2O2) in atmospheric chemistry and its contribution to the formation of free radicals. Free radicals (oxidants) are formed by photochemical reactions between ozone and H2O2. Free radicals formed within cells can oxidise biomolecules, and this may lead to cell death and tissue injury. For this reason, free radicals are believed to cause more than 100 diseases. H2O2 has been suggested as a better indicator of atmospheric oxidation capacity than ozone. Atmospheric H2O2 can appear in the gas phase or in the aqueous phase. It shows typical diurnal and seasonal variations. However, measurements of H2O2 with expensive and sophisticated equipment are rare and limited to but a few sites in the world. Measurements in Greenland ice cores showed that H2O2 concentrations increased over the last 200 years and most of the increase has occurred over the last 20 years. Evaluations show that concentrations will still rise as a result of decreasing SO2 emission. H2O2 measurements have not been carried out in Croatia until now, and, accompanied by the existing longterm measurements of ozone and nitrogen oxides, they will provide an idea of the oxidative capacity of the atmosphere and its influence on oxidative stress.