Contamination levels, influencing factors, and risk assessment of polybrominated diphenyl ethers in house dust of northern Serbia.

Polybrominated diphenyl ethers (PBDEs) are a group of compounds that, due to their applications, are considered mainly indoor contaminants. To obtain the first information about the presence of PBDEs in Serbia, dust samples (n = 50) were collected in settlements in the northern Serbian province of Vojvodina. The selected/target congeners (BDE-28, 47, 99, 100, 153, 154, and 183) were extracted from house dust by microwave-assisted extraction technique, and purified extracts were analyzed on a dual-column gas chromatograph with micro-electron capture detectors. A wide range of ΣPBDEs was detected (0.295 to 394 ng g-1 dust), which reflects large differences in contamination among the examined homes. For the majority of samples (72%), ΣPBDEs were lower than 5 ng g-1 indicating that people living in Vojvodina province are exposed to low concentrations of PBDEs present in their households. Based on principal component analysis (PCA), balcony areas and age of the house positively correlate with the PBDE congeners with higher detection frequencies (≥ 50%), namely, with BDE-99, BDE-153, and BDE-183. Statistically significant positive correlation (p < 0.01) was obtained for BDE-99 and the number of household's members. Estimated daily intakes (EDItot) were calculated for ingestion and dermal absorption of dust for two age groups-adults and toddlers. These are the first data on PBDE status in the area of the Western Balkan, and the health risk assessment indicates that PBDE levels obtained in household dust do not pose a risk for human health.

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.

Metal(loid)s and persistent organic pollutants in yellow European eel from the Rasa River, Croatia.

The anthropogenic impact on the aquatic environment of the Rasa River (Croatia) was investigated through the analysis of seven polybrominated diphenyl ethers (PBDEs), seven polychlorinated biphenyls (PCBs), three DDT isomers, and 22 major and trace elements using yellow European eel (Anguilla anguilla L.) as a biological indicator of contamination. The obtained data indicated generally low contamination status in the surrounding area. Levels of all organic contaminants in muscle significantly increased with lipid content, length, weight and body condition. In both muscle and liver, most metal(loid)s decreased or remained unchanged with increasing size, while at downstream location only several elements (Cd, Cu, Fe, Na, Se, U, V, Zn) accumulated in the liver with fish growth. Spatial analysis revealed higher pressure of Ag, Cd, Cr, Mo, Tl, U, and V at the downstream location, revealing the potentially limited impact of historical coal mining industry on the lower reaches of the Rasa River.

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.

Trace elements in indoor dust-Children's health risk considering overall daily exposure.

Indoor dust presents an important source of daily exposure to toxic elements. The present study reports for the first time the levels of Al, As, Cd, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, Sb, Sn, Se, Sr, Tl, V, and Zn measured in dust samples collected from 10 kindergartens and 21 cars from Zagreb, Croatia. Based on the obtained data, we assessed the health risks from overall daily exposure to trace elements for children aged 2-6 years taking into account three pathways of dust intake-ingestion, dermal absorption, and inhalation. The median concentration of most elements was significantly higher in dust obtained from cars compared to kindergartens, especially in the cases of Co (11.62 vs. 3.60 mg kg-1 ), Cr (73.55 vs. 39.89 mg kg-1 ), Cu (186.33 vs. 26.01 mg kg-1 ), Mo (8.599 vs. 0.559 mg kg-1 ), Ni (37.05 vs. 17.38 mg kg-1 ), and Sn (9.238 vs. 1.159 mg kg-1 ). Oral intake was identified as the most important exposure pathway, except for Cr, Ni, and Sb where dermal contact was the main route of exposure. Health risk assessment indicated that no adverse effects are expected from overall exposure to trace elements. Although the cases of high exposure to toxic elements are not common in areas with no significant environmental pollutants, due to the health threat they may present even at low levels, their status should be carefully monitored.

PBDEs Found in House Dust Impact Human Lung Epithelial Cell Homeostasis.

The toxicity of eight polybrominated diphenyl ethers (PBDEs) congeners detected in environmental and biological samples (BDE-28, -47, -99, -100, -153, -154, -183, and -209) was evaluated on the epithelial lung cells. Exposure to these PBDEs increased membrane disruption and a release of lactate dehydrogenase, accompanied by oxidative stress in cells through the formation of reactive oxygen species (ROS) and a decrease in mitochondrial membrane potential. Interestingly, some of the tested PBDEs increased apoptotic markers as well. For several congeners, the observed toxicity was time dependent, meaning that even smaller concentrations of these compounds will have negative effects over time. Such time-dependent toxicity was also confirmed for cell treatment with a real house dust sample extract. This could be indicative with regard to the constant exposure to a mixture of PBDE congeners through different pathways in the organism and thereby presenting a risk for human health. As such, our findings point to the importance of further studies on the negative effects of PBDEs to understand their mechanism of action in detail.

Polybrominated diphenyl ethers and the multi-element profile of house dust in Croatia: Indoor sources, influencing factors of their accumulation and health risk assessment for humans.

Given the large amount of time people spend indoors today, human exposure to indoor contaminants causes increasing public health concerns. The present study reports for the first time the levels of 7 polybrominated diphenyl ether (PBDE) congeners, and 18 trace elements measured in dust samples collected in 68 households from Zagreb, Croatia. Based on the obtained data from dust analysis and the questionnaire on the house characteristics and habits of the residents, we aimed to assess the possible indoor sources of PBDEs/elements, and the associated health risks. Mass concentrations of ΣPBDE ranged from 0.16 and 200.09 ng g-1 dust (median 4.19 ng g-1 dust). The most frequently detected congeners were BDE-99 and BDE-183 found in >88% of samples, while for trace elements, Al, Fe, Zn, Mn and Cu were found at the highest concentrations (enumerated in the descending order). The regression analysis indicated that renovation, number of residents and hours spent using electronic devices are significant predictors for determining PBDE dust concentrations, while the house age, and the house area were identified as the most important contributors for most trace elements. Our health risk assessment considering dust ingestion and dermal absorption of analyzed dust indicated that no adverse health effects are expected in toddlers and adults from exposure to PBDEs or trace elements in house dust. However, calculating the worst case exposure scenario based on the maximum measured concentrations and high dust intake rates, it was estimated that there is a risk of potential adverse health effects for Co (HI > 1). Even though the cases of high exposure to toxic elements from dust are sporadic, and not common among the general population, this exposure scenario should be included whenever assessing the background exposure of children.

Optimization and validation of a two-step method for the determination of polybrominated diphenyl ethers in Croatian house dust samples.

Microwave-assisted extraction was applied as a method for extraction of seven polybrominated diphenyl ether (PBDE) congeners (28, 47, 99, 100, 153, 154, and 183) from house dust samples. Optimization of MAE experimental conditions was achieved using a multivariate design approach, and the results indicated that only the choice of extraction solvent had a statistically significant influence on extraction efficiency. The extract purification step was also investigated in detail with a goal to achieve effective cleaning, with minor solvent consumption. As the final operating conditions, 20 min MAE extraction from 1 g of dust with 20 mL of n-hexane : acetone (1 : 1, v/v) at 80 °C and extract purification on an in-lab prepared column containing 2 g of neutral silica and 4 g of acidified silica, whereby the PBDEs were eluted from the column with 15 mL of n-hexane : dichloromethane (4 : 1, v/v), were selected. The extracts were analyzed on a dual GC-µECD system, and GC-MS/MS was used as a confirmatory method. The performance of the optimized method was validated by analyzing spiked dust samples and a standard reference material (NIST 2585 "Organic Contaminants in House Dust"). Congener specific PBDE recovery ranged from 76% to 90% for the spiked samples (with very good repeatability; RSD < 7%) and the measured mass concentrations of selected PBDEs were in excellent agreement with certified values for a standard reference material. The proposed method was successfully applied to the analysis of targeted PBDEs in house dust samples.

Preliminary results on polybrominated diphenyl ether contamination status in Croatian households and insights into children's exposure.

Polybrominated diphenyl ether (PBDE) congeners were analyzed in house dust samples collected in Croatian households. ∑PBDEs ranged between 1.1 ng g-1 dust and 17662.4 ng g-1 dust with BDE-99 being the most dominant congener accounting for approximately 60 %. The estimated daily intake (EDI) for toddlers as the most vulnerable population group ranged from 0.003 to 55.04 and from 0.01 to 110.07 ng kg-1 bw day-1 in the central and worst case scenario, respectively. The EDI calculated for the dominant BDE-99 in the sample with the highest ∑PBDE was in the worst case scenario 68.99 ng kg-1 bw day-1, which was quite close to the reference dose of 100 ng kg-1 bw day-1.

Analysis of brominated flame retardants in the aquatic environment: a review.

The most common and consequently analysed brominated flame retardants (BFRs) are polybrominated biphenyls (PBBs), polybrominated diphenyl ethers (PBDEs), tetrabromobisphenol A (TBBPA), tetrabromobisphenol S (TBBPS), and hexabromocyclododecane (HBCD). As these persistent organic pollutants are widespread in the environment and have a number of harmful effects on human health, the production and use of most has been banned for several years. The aquatic environment is polluted by these compounds through their deposition from the atmosphere, sewage sludge, wastewater treatment plants, and landfills, and higher levels are found in areas with developed industry and agriculture and near landfills. Each compound also seems to show preference for specific compartments of the aquatic environment, i.e. water, sediment, or aquatic organisms, according to their physicochemical properties. The aim of this review was to take a closer look at the analysis of BFRs, as without reliable analysis we would not be able to determine their levels and distribution across the aquatic compartments and assess human exposure and health risks. Particularly worrying are the health risks associated with PBDEs in fish, whose levels generally exceed the permitted values.

Persistent organic pollutants in tissues of farmed tuna from the Adriatic Sea.

This study investigated the levels and distribution of polychlorinated biphenyls (PCBs) and organochlorine pesticides in three tissue types of farmed Bluefin tuna (Thunnus thynnus): muscle, liver and branchiae. Seven adult species were caught in 2015 at a tuna farm in the Croatian Adriatic. The organochlorine compound levels decreased in the following order: liver > muscle > branchiae while contaminant distribution in all three tissues followed the same order: ΣPCB ≫ ΣDDT > ΣHCH ~ HCB. The found POP levels indicated moderate pollution of farmed tuna and were below all limits set by current laws. Furthermore, no cytotoxic effect of the POP mixture extracted from tuna liver samples on human neuroblastoma cells was observed.

Legacy persistent organic pollutants (POPs) in archive samples of wild Bluefin tuna from the Mediterranean Sea.

Polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) were quantified in archive samples of dorsal white muscle of the wild Bluefin tuna (BFT) (n = 9) collected in the central Adriatic. PCBs were the predominant organochlorine (OC) compounds (60.8-69.4% of the total OC load) found. The contribution of HCB and ΣHCHs was significantly lower, ranging from

Levels and distribution of polybrominated diphenyl ethers in humans and environmental compartments: a comprehensive review of the last five years of research.

Polybrominated diphenyl ethers (PBDEs) are a class of brominated flame retardants (BFRs), present in the environment, animals, and humans. Their levels, distribution, and human exposure have been studied extensively, and over the last decade, various legal measures have been taken to prohibit or minimize their production and use due to the increasing amount of evidence of their harmful effects on human and animal health.Our aim here was to make a comprehensive and up-to-date review of the levels and distribution of PBDEs in the aquatic environment, air, and soil, in indoor dust, and in humans. To fulfill this, we searched through Web of Science for literature data reported in the last five years (2015-2019) on levels of at least six key PBDE congeners in abovementioned matrices. According to our summarized data, significant PBDE mass concentrations/fractions are still being detected in various sample types across the world, which implies that PBDE contamination is an ongoing problem. Secondary sources of PBDEs like contaminated soils and landfills, especially those with electronic and electrical waste (e-waste), represent a particular risk to the future and therefore require a special attention of scientists.

Introducing of modeling techniques in the research of POPs in breast milk - A pilot study.

This study used advanced statistical and machine learning methods to investigate organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) in breast milk, assuming that in a complex biological mixture, the pollutants emitted from the same source or with similar properties are statistically interrelated and possibly exhibit non-linear dynamics. The elaborated analyses such as Unmix source apportionment characterized individual source groups, while guided regularized random forest indicated the pollutant dependence on the ortho-chlorine atom attached to the congener's phenyl ring and mother's age. Mutual associations among PCBs were further discussed, but the results implied they were mostly not related to child delivery. PCB congeners -153, -180, -170, -118, -156, -105, and -138 appeared to be compounds of the outmost importance for mutual prediction with reference to their interrelations regarding chemical structure and metabolic processes in the mother's body. Finally, machine learning methods, which provided prediction relative errors lower than 30% and correlation coefficients higher than 0.90, suggested a possible strong non-linear relationship among the pollutants and consequently, the complexity of their pathways in the breast milk.

Assessment of multiple anthropogenic contaminants and their potential genotoxicity in the aquatic environment of Plitvice Lakes National Park, Croatia.

In this study, the influence of anthropogenic pollution on the aquatic environment of Plitvice Lakes National Park (PLNP) was investigated during 2011-2012 using a combination of chemical and cytogenetic analyses. Four groups of major contaminants [(volatile organic compounds: benzene, toluene, ethylbenzene, and xylenes (BTEX); persistent organochlorine pollutants: organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs); major and trace elements; anthropogenic radionuclides (90Sr, 134Cs, and 137Cs)] were determined in three aquatic compartments (water, sediment, fish). Mass fractions of inorganic constituents in different compartments reflected the geological background of the area, indicating their origin from predominantly natural sources. Levels of volatile and persistent organic compounds in water and fish, respectively, were very low, at levels typical for remote pristine areas. Analysis of anthropogenic radionuclides in water and sediment revealed elevated activity concentrations of 137Cs in water, and measurable 134Cs in the upper sediment layers from April 2011, possibly as a consequence of the Fukushima nuclear accident in March 2011. The potential genotoxicity of river and lake water and lake sediment was assessed under laboratory conditions using the alkaline comet assay on human peripheral blood lymphocytes, and measured levels of primary DNA damage were within acceptable boundaries. The results showed that despite the protected status of the park, anthropogenic impact exists in both its terrestrial and aquatic components. Although contaminant levels were low, further monitoring is recommended to make sure that they will not rise and cause potentially hazardous anthropogenic impacts.

Organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) in Cyprinidae fish: Towards hints of their arrangements using advanced classification methods.

To tackle the ever-present global concern regarding human exposure to persistent organic pollutants (POPs) via food products, this study strived to indicate associations between organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) in lake-fish tissue depending on the species and sampling season. Apart from the monitoring initiatives recommended in the Global Monitoring Plan for POPs, the study discussed 7 OCPs and 18 PCB congeners determined in three Cyprinidae species (rudd, carp, and Prussian carp) from Vransko Lake (Croatia), which are widely domesticated and reared as food fish across Europe and Asia. We exploit advanced classification algorithms, the Kohonen self-organizing maps (SOM) and Decision Trees (DT), to search for POP patterns typical for the investigated species. As indicated by SOM, some of the dioxin-like and non-dioxin-like PCBs (PCB-28, PCB-74, PCB-52, PCB-101, PCB-105, PCB-114, PCB-118, PCB-156 and PCB-157), α-HCH and ß-HCH caused dissimilarities among fish species, but regardless of their weight and length. To support these suggestions, DT analysis sequenced the fish species and seasons based on the concentration of heavier congeners. The presented assumptions indicated that the supplemental application of SOM and DT offers advantageous features over the usually rough interpretation of POPs pattern and over the single use of the methods.

Self-organizing maps for indications of airborne polychlorinated biphenyl (PCBs) and organochlorine pesticide (OCPs) dependence on spatial and meteorological parameters.

This paper investigates the relation of polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) in air samples with meteorological parameters (temperature, atmospheric pressure and relative humidity) using the Kohonen self-organizing map (SOM). Both gas- and particle-adsorbed phase of 20 PCB congeners and 7 OCPs including the three new ones (α-HCH, ß-HCH, and γ-HCH) listed in the Stockholm Convention were collected during a one-year period at urban locations in Zagreb (Croatia). Moving beyond existing studies, the SOM analysis showed that the meteorological characteristics of transient seasons such as spring had no influence on the dissimilarities in the behavior of PCBs and OCPs. Towards the identification of pollutant spatial patterns, the SOM did not isolate a clear phenomenon probably due to the absence of local pollution sources contributing to the elevated concentrations of these compounds. Overall, our results have shown that the SOM method, by recognizing significant differences among PCB and OCP seasonality, could be recommended in the analysis of pollutant distribution depending on temperature and atmospheric pressure.

Persistent Organochlorine Pollutants in Placentas Sampled from Women in Croatia and an Evaluation of Their DNA Damaging Potential In Vitro.

This study investigated the levels and distribution of 17 polychlorinated biphenyls (PCBs) and organochlorine pesticides (HCB, α-HCH, ß-HCH, γ-HCH, p,p'-DDE, p,p'-DDD, and p,p'-DDT) in placenta samples from women living in the coastal area of Croatia. During November 2012 to February 2013, 51 placenta samples were collected from healthy mothers. This study presents the first report about Croatian placenta samples. Each of the analysed compounds were found in all of the samples; all of the maximum values were < 1 ng g-1 w.w., and the highest median value found for PCB-28 was 11.2 pg g-1 w.w. PCBs and organochlorine pesticide (OCPs) present in placenta samples were tested for their genotoxic potential using the alkaline comet assay. The alkaline comet assay is one of the most reliable methods in assessing the DNA lesions that occurs in direct interaction of a chemical and the genome. The detected levels of PCBs and OCPs in the placenta did not pose a significant risk to the children's DNA during embryonic and foetal growth following short-term exposure. PCB and OCP concentrations in the placenta samples did not induce any significant primary damage to DNA in terms of DNA strand breaks and changes in the primary chemical structure, which could be detected by the alkaline comet assay.