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.

The impact of fullerenol nanoparticles on the growth of toxigenic Aspergillus flavus and aflatoxins production in vitro and in corn flour.

Antifungal and antimycotoxigenic activity of fullerenol nanoparticles (FNPs) were investigated on Aspergillus flavus growth isolated from a real food sample and aflatoxins (AFs) (AFB1 and AFB2 ) production. The final FNPs concentrations in in vitro and in commercial corn flour after the stationary incubation period of 7 and 14 days were in the range 0.16-80 µg/mL and 0.16-80 µg/g, respectively. Nanocharacterization of FNPs revealed an average size of 5-20 nm and a zeta potential of -35 mV. The highest degree of A. flavus mycelium growth inhibition (28%) after 7 days was observed for applied FNP concentration of 8.0 µg/mL, while after 14 days FNP concentration of 0.32 µg/mL led to the maximal inhibition of A. flavus mycelium growth (36%). Spearman's correlations analysis revealed a strong positive correlation between AFB1 and AFB2 concentrations in YES broth after 7 (R = 0.994, p < 0.05) and 14 days (R = 0.976), as well as between AFs concentrations and A. flavus mycelium mass after 7 (R = 0.786 for AFB1 and R = 0.766 for AFB2 ) and 14 days (R = 0.810 for AFB1 and R = 0.833 for AFB2 ). Paired samples t-test showed the existence of a statistically significant difference (p < 0.05) between the produced AFs concentrations after the incubation of 7 and 14 days. Regarding the artificially inoculated corn flour the lower applied FNP concentrations (0.16-0.8 µg/g) achieved a reduction of AFB1 up to 42% and 60% after 7 and 14 days, respectively.

Heavy elements in indoor dust from Serbian households: pollution status, sources, and potential health risks.

Occurrence of five heavy elements (HEs) was analyzed in indoor dust (n = 45) in households from four settlements in Vojvodina Province, Serbia. Overall medians (mg/kg) of Pb (5.6), Ni (5.2), Cu (27), and Cr (6.8) were below soil background values, while median for Cd (1.1) exceeded it. Pollution load index showed that the households' microenvironment in examined region might be regarded as unpolluted. Integrated pollution index revealed low contamination by Pb, Ni, and Cr, but high with Cu and Cd. Source apportionment by principal component analysis and positive matrix factorization suggested two possible sources: outdoor pollution and household materials. Hazard index was below safe limit (<1), indicating no adverse non-carcinogenic health effects. Estimated total carcinogenic risk for children and adult population was not negligible. Results indicated that attention should be paid to the presence of HE in indoors to conduct effective control measures and to ensure the health of the population.

A case study on the occurrence of polycyclic aromatic hydrocarbons in indoor dust of Serbian households: Distribution, source apportionment and health risk assessment.

This study was conducted in order to obtain the first insight into the occurrence, potential sources, and health risks of polycyclic aromatic hydrocarbons (PAHs) in indoor dust. Samples (n = 47) were collected from households in four settlements in the northern Serbian province of Vojvodina. Total concentrations of 16 EPA priority PAHs in the dust samples varied from 140 to 8265 µg kg-1. Mean and median values for all samples were 1825 and 1404 µg kg-1, respectively. According to the international guidelines for indoor environment, PAH content can be regarded as normal (<500 µg kg-1) for ∼6% of the samples, high (500-5000 µg kg-1) for ∼87% of the samples, and very high (5000-50000 µg kg1) for ∼6% of the samples. In all settlements, PAHs with 4 rings were the most prevalent (accounting for 40-53% of the total PAHs). They were followed by 3-ringed PAHs (29-40%), which indicates rather uniform PAH profiles in the analyzed dust. Based on diagnostic ratios, principal component analysis (PCA), and positive matrix factorization (PMF), pyrogenic sources, such as vehicle emissions and wood combustion were the dominant sources of PAHs in analyzed samples. Health risk assessment, which included incidental ingesting, inhaling and skin contact with PAHs in the analyzed dust, was evaluated by using the incremental lifetime cancer risk (ILCR) model. Median total ILCR was 3.88E-04 for children, and 3.73E-04 for adults. Results revealed that major contribution to quite high total ILCRs was brought by dermal contact and ingestion. Total cancer risk for indoor dust indicated that 85% of the studied locations exceeded 10-4. This implies risk of high concern, with potential adverse health effects. The results are valuable for future observation of PAHs in indoor environment. They are also useful for regional authorities who can use them to create policies which control sources of pollution.

Comprehensive assessment of heavy elements and evaluation of potential human health risk in the urban environment: a case study from Novi Sad, Serbia.

This study aimed to determine seasonal (summer vs. winter) and spatial distribution of the selected heavy elements (HEs) (As, Cd, Co, Cr, Cu, Ni, and Pb) in soil samples collected from a typical Central European town, Novi Sad, Serbia. The highest Pb concentrations were observed in summer because of intensive ground-flushing, whereas Cu had its highest concentration in winter, which may be attributed to traffic emissions. Source characterization and spatial distribution were carried out using cluster analysis (CA), principal component analysis (PCA), variogram calculation and theoretical model fitting, GIS-based geostatistical methods, and positive matrix factorization (PMF) data processing tools. Environmental impact of HEs found in different functional areas demonstrated that the quantified concentrations of Pb, As, Co, and Cu ranked soil as unpolluted to moderately polluted, while the presence of Co, Ni, and Cr classified urban soil as moderately polluted. Pollution load index (PLI) suggested a significant HEs enrichment while the new modified approach to Nemerow integrated risk index (NIRI) indicated high risk, being extreme for some selected locations. Machine learning classifiers were used for the first time to identify the differences between urban soil and dust samples in situations when simultaneous analysis of both matrices was carried out, as well as for temporal distribution (summer versus winter), based on the obtained concentration of HEs. Variogram calculation suggested that the pattern in spatial variability within the system emerged from the combined action of key structural factors (e.g., the parent soil material, landforms and topography, and climate) and random factors related to human activities. The estimated human health risk for two segments of the population revealed that ingestion is the primary route of exposure to HEs for children and adults.

Comprehensive characterization of PAHs profile in Serbian soils for conventional and organic production: potential sources and risk assessment.

This study presents a comprehensive characterization of occurrence and levels of 16 polycyclic aromatic hydrocarbons (PAHs) in arable soils used for conventional and organic production in northern and central part of Serbia as well as cross-border region with Hungary. Furthermore, this study includes a characterization of PAH sources and carcinogenic/non-carcinogenic human health risk for PAHs accumulated in analysed arable soils. The total concentration of 16 PAHs varied between 55 and 4584 µg kg-1 in agricultural soil used for conventional production and between 90 and 523 µg kg-1 in agricultural soil used for organic production. High molecular weight (HMW) PAHs were dominant compounds with similar contribution in both soil types (86% and 80% in conventional and in organic soil, respectively). Principal component analysis and diagnostic ratios of selected PAHs were used for identification of PAH sources in the analysed soils. Additionally, positive matrix factorization was applied for quantitative assessment. The results indicated that the major sources of PAHs were vehicle emissions, biomass and wood combustion, accounting for ~ 93% of PAHs. Exposure of farmers assessed through carcinogenic (TCR) and non-carcinogenic (THQ) risk did not exceed the acceptable threshold (TCR < 10-6 and THQ < 1). Oral ingestion was the main exposure route which accounted for 57% of TCR and 80% of THQ. It was followed by dermal contact. This investigation gives a valuable data insight into the PAHs presence in arable soils and reveals the absence of environmental and health risk. It also acknowledges the importance of comprehensive monitoring of these persistent pollutants.

Pollution status and health risk caused by heavy elements in the flooded soil and vegetables from typical agricultural region in Vojvodina Province, Serbia.

The investigation conducted in the Vojvodina Province, as a typical European and one of the biggest agricultural regions in the Balkans, offers the research methodology that could be used for any non/flooded agricultural region. The flood impact on heavy elements (HE) content in the flooded arable soil (n = 16) in relation to the control soil (n = 16) was examined, as well as their accumulation in the most often cultivated vegetables (n = 96) in the studied area. Results revealed that the flood did not significantly change the pseudo total HEs concentration in the soil as well as their amounts accumulated in different soil fractions. In both soils, only the average content of Ni exceeded the maximum permissible values set by Serbian soil quality standard which is in line with the Dutch standard. In comparison with the background values, notable enrichment is found for most of analyzed elements in both soils. Soil pollution status was assessed through several indices indicating that contamination range was in the domain from a moderate to a highly polluted. The principal component analysis demonstrated that soil contamination was probably originated from agricultural/anthropogenic activities (Cd, Cu, As, Pb), apart from Ni, Cr, and Co which came from natural weathering of the parent material. Carcinogenic and non-carcinogenic risks of selected HEs for Serbian population in the investigated region were below the threshold values. The average levels of Pb in investigated potato and carrot samples were higher than the maximum allowable concentrations established by EU/Serbian regulation. The total hazard quotients (THQ) of HEs through intake of analyzed vegetables were below the safe threshold (˂ 1), suggesting the absence of adverse health effects.

Does the application of human waste as a fertilization material in agricultural production pose adverse effects on human health attributable to contaminants of emerging concern?

The QuEChERS (quick, easy, cheap, effective, rugged, and safe) ultrasound-assisted method was successfully used to determine the presence of contaminants of emerging concern (CECs) in both the growing medium (i.e. soil) and vegetable samples (i.e. potato, onion, celery, parsnip and carrot) cultivated in household gardens under field conditions impacted by the application of livestock manure mixed with human waste. CECs with a broad range of physico-chemical properties including pharmaceuticals, plasticizers, herbicides, personal care products, and biocides were investigated. Among all studied CECs, diclofenac (DCL), carbamazepine, bisphenol A (BPA) and estrogenic hormones (estrone (E1), 17α-ethinyl estradiol (EE2)) were detected and quantified in vegetable samples with a concentration range from 0.114 to 13.3 ng/g fresh weight (f.w.), while BPA, E1, and EE2 were detected in soil samples with concentration ranges from 0.526 to 0.830 ng/g f.w., 0.121-0.199 ng/g f.w. and 0.118-0.333 ng/g f.w., respectively. DCL was only quantified above the limit of quantification in one soil sample (0.151 ng/g f.w.). The human health risk was estimated using the threshold of toxicological concern approach and a standard diet for two segments of the population (i.e. adult and child). The consumption of investigated vegetables contaminated with CECs poses no risk for the Serbian population.

Survey on the micro-pollutants presence in surface water system of northern Serbia and environmental and health risk assessment.

This study demonstrates the occurrence of 940 organic micro-pollutants in surface water of four rivers, one irrigation canal system, and two lakes in Vojvodina Province, the northern part of Serbia, summing in total eighteen samples. The number of detected chemicals ranged from 22 to 84, with 127 micro-pollutants detected at least once, representing 13% of the studied substances. The targeted compounds include n-alkanes, sterols, polycyclic aromatic hydrocarbons (PAHs), organochlorine pesticides polychlorinated biphenyls, pesticides, pharmaceutical active compounds, industrial chemicals, plasticizers, etc. Among the analysed compounds, sterols were the most dominant with maximum quantified concentrations. The substances which were quantified with frequency over 50% were two PAHs (2-methylnaphthalene, benzo(ghi)perylene), five sterols (cholesterol, cholestanol, stigmasterol, fucosterol, beta-sitosterol), three pharmaceuticals and personal care products (L-menthol, diethyltoluamide, caffeine), and ten household chemicals (4-tert-octylphenol, dimethyl phthalate, methyl palmitate, phenylethyl alcohol, 1-nonanol, alpha-terpineol, 2-phenoxy-ethanol, methyl myristate, acetophenone, and 2-ethyl-1-hexanol). The list of priority substances under the European Union Directive 2013/39/EU includes 49 priority substances (PSs) out of which 34 were analysed. Among these, eleven PSs were quantified, and only two compounds (fluoranthene and benzo (a) pyrene) exceeded EU Environmental Quality Standards targeted values. The obtained results were compared with the previously published data that dealt with the same targeted number of micro-pollutants in sediment samples. This revealed connections between the same sampling locations. Environmental risk assessment showed the existence of potential ecological risk as 72% of the obtained values for the ecological hazard index (HI) at investigated locations were higher that the targeted value (HI > 1). Estimated values for hazard quotient (HQ) and hazard index (HI) for non-carcinogenic risk were lower than the targeted value, indicating no non-carcinogenic risk through dermal contact and non-intentional ingestion of water. Estimated values for cancer risk were all below 1 × 10-6, which is not considered to pose significant human health risk.

Seasonal, spatial variations and risk assessment of heavy elements in street dust from Novi Sad, Serbia.

This is the first study carried out to determine the levels, spatial and temporal variations and risk indices of street dust in Serbia. Sixty street dust samples representing four functional areas: school, recreational, residential and industrial were collected from Novi Sad during summer and winter. The purpose was to obtain the concentration of seven heavy elements, evaluate the possible sources and degree of environmental pollution and human health risks. The average concentration of As, Cd, Co, Cr, Cu, Ni and Pb (mg/kg) during winter was: 7.96, 0.40, 7.73, 12.1, 57.6, 14.0 and 70.6, while in summer it was: 1.88, 0.54, 4.31, 60.1, 42.7, 28.1, and 62.5, respectively. Interpolation method together with the correlation matrix and the results of multivariate statistics supported anthropogenic origin of Pb, Cr and Cu, natural origin of Ni, Cd and As and mix origin of Co. Pollution indices such as geoaccumulation index (Igeo) indicated existence of unpolluted to extreme risk regarding to environmental pollution. Moreover, the potential pollution index (Er) showed low (Pb) to moderate (Ni) risk while potential risk index (RI) and modified potential risk index (mRI) indicated considerable and very high risks. Health risk assessment showed no non-carcinogenic risk of heavy elements for adults and children.

Micro-pollutants in sediment samples in the middle Danube region, Serbia: occurrence and risk assessment.

This is the first comprehensive study on the occurrence of 940 semi-volatile organic compounds including sterols, polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), pesticides, plasticizers, and other emerging compounds in 10 river and canal sediments collected in northern Serbia. For quantification of investigated compounds GC-MS-MS (selected reaction monitoring) and GC-MS (using both selected ion monitoring and total ion monitoring) methods were used. The number of detected compounds was in the range of 85-117, while the sum of the concentrations varied from 959 µg/kg dry-wt to 84,445 µg/kg dry-wt. Sterols were quantified with high frequency in nearly 100% of investigated samples suggesting that the studied rivers and canals have been contaminated by sewage. Regarding persistent organic compounds, p,p'-DDE, p,p'-DDD, and o,p'-DDT were the dominant members of organochlorine pesticides (OCPs). The concentration range of 11 quantified pesticides of 452 analyzed was from 0.564 to 61.6 µg/kg dry-wt, while the concentration range of 47 quantified PCBs of 90 analyzed was from 0.928 to 32.1 µg/kg dry-wt. OCPs (DDE, DDD, and γ-HCH) and several PAHs (fluoranthene, pyrene, phenanthrene, chrysene, benzo(a)anthracene, benzo(a)pyrene) exceeded the maximum values of the sediment quality guidelines. Contents of domestic compounds comprise a large proportion of the total contaminant concentration. Overall, the study reveals that river sediments in Vojvodina Province were moderately polluted mainly by domestic wastewater. The toxic equivalent quantity (TEQ) relative to benzo(a)pyrene and 2,3,7,8-tetrachlorodibenzodioxin for seven carcinogenic PAHs and six quantified dioxin-like PCBs ranged from 3.59 to 103 µg TEQ/kg and from 0.001 × 10-3 to 2.10 × 10-3 µg TEQ/kg, respectively, and were in the range or lower than the literature published data.

Seasonal variation and health risk assessment of organochlorine compounds in urban soils of Novi Sad, Serbia.

The aim of this paper was to determine spatial and seasonal variation of 6 indicator polychlorinated biphenyls (PCBs) and 18 organochlorine pesticides (OCPs) in urban soils of Novi Sad, Serbia. Sixty surface soil samples were collected during both winter and summer season, from different types of locations: schools, recreational areas, residential and industrial zones. Samples were treated using the method of accelerated solvent extraction, which allows simultaneous extraction and clean up of PCBs and OCPs. Targeted compounds were analyzed by GC-µECD and confirmed by GC-MS. The total concentrations of studied PCBs varied from

Determination of mycotoxins in biscuits, dried fruits and fruit jams: an assessment of human exposure.

A reliable, fast and simple method using UHPLC-MS/MS was developed for the determination of aflatoxins B1 (AFB1), G1 (AFG1), B2 (AFB2) and G2 (AFG2), ochratoxin A (OTA), deoxynivalenol (DON), zearalenone (ZEA), HT-2 toxin and T-2 toxin in crude extracts of biscuits with fruit filling, cookies, dried fruits and fruit jams. The method was successfully demonstrated on 39 samples of biscuits with fruit filling, 34 cookies, 14 dried fruits and 10 fruit jams. The mycotoxins detected in biscuits samples were ZEA, OTA, T-2 and AFB1 with an average concentrations of positive samples of 2.64, 4.10, 8.13 and 1.32 µg kg-1, respectively; while the mycotoxins detected in jam samples were AFB1, OTA, T-2 and AFB2 with an average concentrations of positive samples of 2.00, 17.7, 4.37 and 1.15 µg kg-1, respectively. The results showed that the majority of samples were in compliance with relevant regulations. However in eight samples of biscuits and three samples of fig jam the contents of OTA were higher than the existing OTA limits. The combined dietary exposure of selected mycotoxins was estimated for the first time for children, adolescents and adults. The estimated combined dietary exposures were all lower than the proposed value assumed to predict a possible risk scenario.

Assessment of perfluoroalkyl substances in food items at global scale.

This study assessed the levels of 21 perfluoroalkyl substances (PFASs) in 283 food items (38 from Brazil, 35 from Saudi Arabia, 174 from Spain and 36 from Serbia) among the most widely consumed foodstuffs in these geographical areas. These countries were chosen as representatives of the diet in South America, Western Asia, Mediterranean countries and South-Eastern Europe. The analysis of foodstuffs was carried out by turbulent flow chromatography (TFC) combined with liquid chromatography with triple quadrupole mass spectrometry (LC-QqQ-MS) using electrospray ionization (ESI) in negative mode. The analytical method was validated for the analysis of different foodstuff classes (cereals, fish, fruit, milk, ready-to-eat foods, oil and meat). The analytical parameters of the method fulfill the requirements specified in the Commission Recommendation 2010/161/EU. Recovery rates were in the range between 70% and 120%. For all the selected matrices, the method limits of detection (MLOD) and the method limits of quantification (MLOQ) were in the range of 5 to 650 pg/g and 17 to 2000 pg/g, respectively. In general trends, the concentrations of PFASs were in the pg/g or pg/mL levels. The more frequently detected compounds were perfluorooctane sulfonic acid (PFOS), perfluorooctanoic acid (PFOA) and perfluorobutanoic acid (PFBA). The prevalence of the eight-carbon chain compounds in biota indicates the high stability and bioaccumulation potential of these compounds. But, at the same time, the high frequency of the shorter chain compounds is also an indication of the use of replacement compounds in the new fluorinated materials. When comparing the compounds profile and their relative abundances in the samples from diverse origin, differences were identified. However, in absolute amounts of total PFASs no large differences were found between the studied countries. Fish and seafood were identified as the major PFASs contributors to the diet in all the countries. The total sum of PFASs in fresh fish and seafood was in the range from the MLOQ to 28ng/g ww. According to the FAO-WHO diets composition, the daily intake (DI) of PFASs was calculated for various age and gender groups in the different diets. The total PFASs food intake was estimated to be between 2300 and 3800 ng /person per day for the different diets. Finally, the risk intake (RI) was calculated for selected relevant compounds. The results have indicated that by far in no case the tolerable daily intake (TDI) (150, 1500, 50,000, 1,000,000, 150, 1500 ng/kg body weight, for perfluorohexanesulfonate (PFHxS), fluorotelomer alcohol (FTOH), perfluorobutanesulfonic acid (PFBS), perfluorobutanoic acid (PFBA), PFOS and PFOA, respectively) was exceeded.

Characterization of an extracellular laccase of Leptosphaerulina chartarum.

Laccase-producing fungi were isolated from air, using selective media with a chromogenic substrate to indicate enzyme activity. The best laccase producer strain proved to be a Leptosphaerulina chartarum isolate. Laccase production was investigated in the presence of various inducers in different cultivation conditions. The extracellular laccase was purified for further investigations. SDS-PAGE showed that this laccase is a monomeric protein of 38 kDa molecular weight. The enzyme is active in the pH-range of 3.5-6, with an optimum at pH 3.8. It is active in the 10-60 °C temperature range, with an optimum at 40 °C. After 20 min incubation at temperatures above 70 °C the enzyme lost its activity. Degradation of seven aniline and phenol compounds (2,4-dichlorophenol; 2-methyl-4-chlorophenol; 3-chloroaniline; 4-chloroaniline; 2,6-dimethylaniline; 3,4-dichloroaniline and 3-chloro-4-methylaniline) was investigated, with or without guaiacol (2-methoxyphenol) as mediator molecule. Addition of a mediator to the system significantly increased the degradation levels. These results confirmed that the isolated laccase is able to convert these harmful xenobiotics at in vitro conditions.