Presence of polycyclic aromatic hydrocarbons and persistent organochlorine pollutants in human Milk: Evaluating their levels, association with Total antioxidant capacity, and risk assessment.

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.

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.

Polybrominated Diphenyl Ethers in Human Milk of Croatian First-Time Mothers: 2010 Versus 2020.

The presence of selected polybrominated diphenyl ethers (BDE-28, -47, -99, -100, -153, -154, and -183) was investigated in human milk samples collected from first-time mothers living in Zagreb, capital of Croatia. Samples from 2020 and 2010 were analyzed, and the first temporal comparison between the profiles and levels of these compounds in this area was obtained. A statistically significant difference between mass fractions depending on the sampling year was observed only for BDE-99, with values in 2020 higher than in 2010. BDE-153, whose median value (0.25 and 0.26 ng g-1 lipid weight (l.w.) in 2010 and 2020, respectively) did not decrease in the 10-year period, was the most frequently detected congener in samples from both years. ΣPBDEs ranged from < LOD to 3.53 ng g-1 l.w. (median 0.25 ng g-1 l.w.), and from 0.14 to 6.75 ng g-1 l.w. (median 0.55 ng g-1 l.w.) in 2010 and 2020, respectively. Maternal age and reported fish consumption had no effect on observed PBDE mass fractions, while for BDE-153, positive significant correlation (p > 0.05) was observed of its detected mass fraction with mother's body mass index (BMI) before pregnancy and after childbirth. Infants median estimated daily intake (EDI) via milk ingestion for ΣPBDE was higher in 2020 (3.221 ng kg-1 bw day-1) compared to 2010 (1.429 ng kg-1 bw day-1), but both values were well below threshold value, indicating that human milk consumption in this specific case is unlikely to raise health risks to infants.

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.

Carcinogenic Activity and Risk Assessment of PAHs in Ambient Air: PM10 Particle Fraction and Bulk Deposition.

This paper present seasonal variation in the equivalent concentration (BaPeq) 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 PM10 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 BaPeq mass concentrations of PM10 varied from 0.057 ng m-3 in July to 3.656 ng m-3 in December; the annul ∑BaPeq average was 1.348 ng m-3. In bulk deposition, ∑BaPeq 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 PM10 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.

Polybrominated diphenyl ethers and polycyclic aromatic hydrocarbons in dust from different indoor environments in Zagreb, Croatia: Levels and human exposure assessment.

The present study reports for the first time the levels of 7 polybrominated diphenyl ether (PBDE) congeners and 11 polycyclic aromatic hydrocarbons (PAH) measured in dust samples collected in 10 kindergartens, 11 workplaces, and 25 cars from Zagreb, Croatia. ΣPBDEs mass fractions were 3.11-14.42, 10-6 in the worst-case scenario indicated a potential risk, especially for professional drivers. Also, in the cases of elevated contaminant levels, toddlers are susceptible to a higher risk, despite the short time they spend in cars.

Polycyclic Aromatic Hydrocarbons in Indoor Dust in Croatia: Levels, Sources, and Human Health Risks.

Compounds that contribute to indoor pollution are regularly investigated due to the fact that people spend most of their time indoors. Worldwide investigations have shown that polycyclic aromatic hydrocarbons (PAHs) are present in indoor dust, but to the best of our knowledge, this paper reports for the first time the presence of PAHs in Croatian households. Eleven PAHs were analysed in house dust samples collected in the city of Zagreb and surroundings (N = 66). Their possible indoor sources and the associated health risks were assessed. Total mass fraction of detected PAHs ranged from 92.9 ng g-1 to 1504.1 ng g-1 (median 466.8 ng g-1), whereby four-ring compounds, Flu and Pyr, contributed the most. DahA was the only compound that did not show statistically significantly positive correlation with other analysed PAHs, indicating that it originated from different sources. Based on diagnostic ratios and principal component analysis (PCA), mixed sources contributed to PAHs levels present in Croatian households. Although our results indicate that Croatian house dusts are weakly polluted with PAHs, total ILCR values calculated for children and adults revealed that people exposed to the highest mass fractions of PAHs measured in this area are at elevated cancer risk.

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.

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%).

Measurement of dental crown wear -In vitro study.

The purpose of the study was to test new method for in vitro evaluation of dental material wear with 3D digitization procedure. Thirty dental crowns, made of polyetheretherketone and veneered with composite material, were subjected to wear test. The crown surface was digitized using coordinate measuring machine before and after the performed wear test. Mesh 3D models were reconstructed and average and maximum depth of lost material and volume loss was calculated (GOM Inspect 2016 software). Mean average depth value amounted 12±7 µm, maximum depth value was 42 µm, while mean volume loss was 0.0024 mm3. The smallest measured values were 4 µm for depth value and 0.0003 mm3 for volume loss. Coefficient of variation was very high for all tested parameters (>50%) as a result of data inconsistency. Within the limitations of applied methodology, the possibility of using coordinate measuring machine in measurement of dental material wear was confirmed.

Carcinogenic Potency of Airborne Polycyclic Aromatic Hydrocarbons in Relation to the Particle Fraction Size.

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 PM10, PM2.5, 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 PM10, PM2.5, 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 PM10⁻2.5 and PM2.5⁻1 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 PM10 and PM2.5 fractions, it was found that about 21⁻26% of carcinogenic potency of the PAH mixture belonged to the PM2.5 fraction. Comparison of TCP in PM2.5 and PM1 showed that about 86% of carcinogenic potency belonged to the PM1 fraction, regardless of the TEF scheme used.

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)).

Carcinogenic activity of polycyclic aromatic hydrocarbons bounded on particle fraction.

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.

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.

[Polycyclic aromatic hydrocarbons in air]. / Policiklicki aromatski ugljikovodici u zraku.

Polycyclic aromatic hydrocarbons (PAHs) are a large group of organic compounds consisting of two or more condense aromatic rings. They are products of incomplete combustion or pyrolysis of organic matter. Because some PAHs such as Benzo[a]pyrene (BaP) are proven carcinogens and mutagens, it is necessary to continuously monitor their concentrations in the air, water, and soil. PAHs with two or three aromatic rings are stable in the gas phase, while most PAHs with five or more aromatic rings bond to particles. Higher concentrations of PAHs are present in the atmosphere of urban areas, mostly in the winter, due to heating. In the summer, these concentrations drop because most PAHs are unstable at high temperatures and break down by oxidation and photooxidation. Measurements of PAHs in the air include sampling on the filter paper or solid adsorbent, extraction, and chromatographic analysis. This review presents the measurements of BaP in some locations in the world and compares them with the findings in Croatia.