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.
•First survey on the occurrence of 940 substances in the middle part of the Danube Basin.•Micro-pollutants from canals water had higher abundance of contaminants that from river.•High level of sterols indicated dominant effect of untreated domestic wastewater.•Correlations among the groups of micro-pollutants indicated their common origin.•Ecological risk suggesting a potential for adverse effects on fish.
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.
•The first European data of seasonal variations on HEs presence in the street dust.•The street dust was sampled from different functional areas.•The first study on heavy elements risk assessment in street dust from Serbia.•Adjusted evaluation criteria for risk index and modified risk were applied.•Three source groups were identified based on multivariate statistical methods.
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.
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.
Display omitted
•Total PAHs in Serbian indoor environment varied in the range from 140 to 8265 μg kg−1.•87% of analyzed dust samples were high contaminated (500–5000 μg kg−1).•In all analyzed samples, PAHs with 4 rings were dominant, followed by 3-ringed PAHs.•Fuel and wood combustion were assigned to be the dominant PAH sources.•ILCR indicated that 85% of the studied locations were under the high risk.
The level of aflatoxin M1 (AFM1) in 50 milk samples collected from February to June 2013 from Serbian market or domestically produced was determined using simple non-specific sample preparation ...method based on solid phase extraction (Oasis HLB, Waters) and ultra-high performance liquid chromatography with heated electrospray ionization triple quadrupole mass spectrometry (UHPLC/HESI-MS/MS). The range of detection was between < LOD and 1.44 μg/kg with mean value of 0.30 μg/kg. Thirty-eight samples (76%) exceed the maximum level of 0.05 μg/kg sets by EU. The highest level of 1.44 μg/kg was found in raw sample of domestically produced milk while the lowest one in organic produced milk. The evaluation of the exposure degree of AFM1 through the milk consumption by the average Serbian citizen was estimated at levels of 1.420, 0.769 and 0.503 ng/kg bw/day during February, April and May, respectively. Estimation of the corresponding concentration of AFB1 in feedstuffs was evaluated as 18.75 μg/kg. The calculated hazard index of 7.1, 3.8 and 2.5 for February, April and May, respectively, was higher than 1 indicated serious risk of AFM1 to Serbian consumers. This work presents the first insight in the occurrence of AFM1 in milk collected in Serbia as well as mycotoxin intake through milk consumption by Serbian adult population.
•AFM1 was determined in 50 milk samples from the Serbian market.•Samples were prepared by SPE and the obtained extracts were analyzed with UHPLC–HESI-MS/MS.•Thirty-eight samples (76%) exceed the maximum level of 0.05 μg/kg sets by EU.•AFM1 daily intake and hazard index were estimated.•The corresponding concentration of AFB1 in feedstuffs was evaluated as 18.75 μg/kg.
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.
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.
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 650pg/g and 17 to 2000pg/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 3800ng /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, 1500ng/kg body weight, for perfluorohexanesulfonate (PFHxS), fluorotelomer alcohol (FTOH), perfluorobutanesulfonic acid (PFBS), perfluorobutanoic acid (PFBA), PFOS and PFOA, respectively) was exceeded.
•21 PFASs were assessed in 283 foods from Brazil, Saudi Arabia, Spain and Serbia.•Countries were selected as representatives of the diet of different world areas.•The most frequently detected compounds were PFOS, PFOA and PFBA.•PFASs food intake was estimated to be between 2300 and 3800 ng/person-day.•The results of RI have indicated that in no case TDI was exceeded.
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 <LOD to 18.9 ng g−1 (mean 2.84 ng g−1 and median value of 1.21 ng g−1) in winter and from <LOD to 24.6 ng g−1 (mean 3.27 ng g−1 and median value of 1.60 ng g−1) in summer. Regarding the OCPs analyzed, dichlorodiphenyltrichloroethanes (DDTs) were only detected in both seasons. The total concentration of DDTs ranging from <LOD to 86.3 ng g−1 (mean 7.57 ng g−1 and median value of 1.87 ng g−1) in summer and from <LOD to 182 ng g−1 (mean 15.6 ng g−1 and median value of 3.15 ng g−1) in winter. There were no significant difference between seasons for studied PCBs and DDTs. Spatial distribution of PCBs and DDTs were also evaluated using Arc GIS. Additional, principle component analysis was performed to evaluate relationships between PCBs, DDTs and soil characteristics. Positive correlation was observed among p,p′-DDE, p,p′-DDD and organic matter. The total lifetime carcinogenic risk indicated that the lifetime cancer risk was acceptable.
•Novel method of pressurized liquid extraction for PCBs and OCPs in soil was developed.•The results revealed that the seasonal variation of PCBs and DDTs was rather stable.•Health risk assessment suggested that Novi Sad is suitable as residential.•Profiles of DDTs indicated aged residues.•OCPs residues and PCBs in soil are not a serious public health threat in Novi Sad.
The occurrence and temporal variation of selected priority substances and contaminants of emerging concerns, i.e., eleven perfluorinated compounds (PFCs, belonging to perfluorosulphonates, ...perfluorocarboxylic acids, and perfluorinated sulphonamides) have been investigated in composite surface water samples of the Danube River at the upstream and downstream locations from the discharge point of wastewater. Among the analyzed compounds, six PFCs (PFOA, PFOS, PFHxA, PFNA, PFDA and PFUnA) were quantified. Overall, the detection frequency for most quantified compounds was very high (>90 %), only PFDA and PFUnA were quantified with less frequency, 33 and 67 %, respectively. The highest quantified concentrations of PFOA and PFOS were 14.9 ng/L (average 12.1 ng/L) and 14.2 ng/L (average 6.11 ng/L), respectively. These ones together with PFHxA (average 10.0 ng/L) were quantified at the highest concentrations in comparison to the other investigated compounds. However, the determined levels of PFOS during investigated sampling period, for all samples analyzed, were always lower than the maximum allowable concentration set for inland river waters but always higher than the environmental quality standard threshold value-AA-EQS of 0.65 ng/L sets by the Directive of European Parliament. Moreover, the levels of PFOA were always several times lower than the set AA-EQS value.
