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.

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.

Characterization and application of biochar-immobilized crude horseradish peroxidase for removal of phenol from water.

Biochar (BC) has attracted much attention as an environmentally friendly material for application in wastewater treatment. In this study, a suitability of wood-derived BC as a support for covalent immobilization of horseradish peroxidase (HRP) across glutaraldehide as crosslinker, known for the capability to remove phenol from water, was investigated. The efficiency of the immobilized HRP in removal of phenol (2 mM) from water at different reaction conditions (varying dosages of polyethylene glycol (PEG300) 0-750 mg/L; H2O2 1.5-3.5 mM, as well as reaction time 5-120 min) and the general toxicity of bio-treated water (Allium cepa test) were measured. All analyzes were performed for free enzyme as well. The immobilized enzyme showed the highest activity at temperature 30 °C and pH 7.0. The greatest efficiency of immobilized enzyme in phenol removing (90 %) was obtained by applying 2.5 mM H2O2 and 1.5 mg/L of PEG300 at pH 7.0 after 2 h of reaction period. After 4 washings, immobilized HRP retained more than 79 % activity with phenol removal of 64 %. Utilizing immobilized enzyme significantly reduces the toxicity of the tested water (80 %), which further suggested that it might be considered as an environmentally acceptable process for wastewater treatment. Possible degradation products remained in treated water were analyzed in water samples by liquid and gas chromatography with mass spectrometry, including also analysis of volatiles by solid phase microextraction technique; different phenol-base compounds were detected.

Seasonal occurrence and cancer risk assessment of polycyclic aromatic hydrocarbons in street dust from the Novi Sad city, Serbia.

This is the first investigation that identified seasonal occurrence, distribution and sources of 16 polycyclic aromatic hydrocarbons (PAHs) in 60 street dust samples collected within urban zone of Novi Sad, the second largest city in Serbia. The obtained results were further used for comprehensive assessment of carcinogenic risk of Serbian inhabitants exposed to PAHs present in street dust by the incremental lifetime cancer risk method. The total level of 16 PAHs ranged between 35 µg kg-1 and 2422 µg kg-1 in samples taken in summer and between 35 µg kg-1 and 587 µg kg-1 in samples taken in winter. In both seasons, 4-ring PAHs were the most dominant compounds and high molecular weight (HMW) PAHs had similar contribution (55% in summer and 65% in winter). The highest content was determined for fluoranthene (Fly) in both seasons (597 µg kg-1 in winter, 301 µg kg-1 in summer). The PAHs source apportionment was analyzed by principal component analysis (PCA) and diagnostic ratios, and combustion of petroleum seemed to be the main sources of the PAHs in street dust. The cancer risk level for children and adult were comparable for dermal contact and by ingestion, and ranged from 10-6 to 10-4 indicating a potential risk. Additionally, the total incremental life time cancer risk (ILCR) was assessed for children and adult population taking into account three possible exposure routs and the median total cancer risk was ˃10-5, with 7% of the samples having the risk ˃10-4 that should be considered of high concern with potential health problem. These results are the first of this kind for the whole Serbia and the Western Balkan region and can be considered as the base line for future research.

Polycyclic aromatic hydrocarbons in urban soil of Novi Sad, Serbia: occurrence and cancer risk assessment.

Contents of 16 polycyclic aromatic hydrocarbons were analyzed in 30 soil samples from 15 locations in Novi Sad, Serbia, assessing for the first time the corresponding health risks in the Serbian urban zone. Total concentrations were in the range of 22-2247 µg kg-1, with a mean and median value of 363 and 200 µg kg-1, respectively. Comparison with the relevant maximum allowed contents proposed by the Serbian government and with the Dutch target values implied that soils from the urban area of Novi Sad were "suitable as residential soils" and that no intervention would be needed if the current levels were retained. Seven diagnostic ratios were calculated, indicating the pyrogenic sources of PAHs as the dominant. Cancer risks in humans via accidental ingestion, inhalation of soil particles, and dermal contact with soil were estimated. Cancer risk for soil ingestion by children was the highest. The total lifetime carcinogenic risk as sum of individual cancer risks for seven carcinogenic polycyclic aromatic hydrocarbons was within the range 10-4 to 10-6, indicating acceptable risks at 30 and 47% of sites for children and adults, respectively. However, for the rest of the samples, total lifetime cancer risk was >10-4 indicating over the acceptable risk, even though the contents in soil were not of concern as the comparison with the environmental guidance previously showed. This could be explained by (a) the dominant concentrations of higher molecular weight compounds with 4 to 6 rings, among which there are compounds with higher toxicity equivalents, but also with (b) the extreme conditions used for the conservative risk assessment under maximal exposure frequency, exposure time, and ingestion rates.

Occurence of the phthalate esters in soil and street dust samples from the Novi Sad city area, Serbia, and the influence on the children's and adults' exposure.

This is the first study reporting the presence of 6 phthalic acid esters (PAEs) in 60 composite soil and street dust samples collected in the urban zone of Novi Sad, the second largest city in Serbia. The results were further used to assess children's and adults' PAEs nondietary daily intakes (DIs) through incidental soil and dust ingestion and/or dermal absorption. The study could be regarded as the important baseline for future monitoring of PAEs in the urban environments, particularly as it contributes to the rare data on PAEs occurence in the street dust. All 6 PAEs were detected in every analyzed soil and street dust samples from 0.0002mgkg(-1) to 4.82mgkg(-1), with the highest level obtained for di-(2-ethylhexyl) phthalate (DEHP), which was the most dominant PAE (70-96%). The highest total PAEs (Σ6PAEs) contents in soil (2.12mgkg(-1)) and street dust (5.45mgkg(-1)) samples were obtained for the samples from city parks. In all soil samples, Σ6PAEs exceeded the soil sustainable quality limit sets by the relevant Serbian Regulation, but were much lower than the limit requiring remediation measures. Concerning the estimated DIs, children were more susceptible to PAEs intake than adults regardless of the exposure routes. All the estimated DIs values were far below the known reference values.

Esterification of sludge palm oil as a pretreatment step for biodiesel production.

Acid esterification of sludge palm oil, having 50 mas.% free fatty acids, i.e., 50 g of dominant free fatty acid per 100 g of oil, was investigated with the objective of determining conditions for the efficient reduction of free fatty acids. The influences of sulphuric acid dosage and molar ratio of methanol to oil were studied, with the final intention to obtain feedstock with a free fatty acids content acceptable for biodiesel production by alkali-transesterification. Esterification was performed using different molar ratios of methanol to oil (3:1, 6:1 and 9:1) and varying the amount of H2SO4 catalyst (0.92 mas.%, 1.84 mas.% and 4.60 mas.%). Under the applied conditions, the sulphuric acid dosage of 4.60 mas.% resulted in the satisfactory decrease of the feedstock's free fatty acids for 6:1 and 9:1 molar ratios of methanol to oil. Thus, taking into account the economic reasoning, it can be concluded that approximately 5 mas.% of H2SO4 with 6:1 molar ratio of methanol to oily feedstock, might be regarded as the dosage necessary for satisfactory pretreatment of the feedstock to be further subjected to the alkaline transesterification. Finally, the effort to consolidate the information on acid esterification available in literature was made, contributing to knowledge on sustainable biodiesel production using the low-grade and low-cost sources.

Comparison of multianalyte proficiency test results by sum of ranking differences, principal component analysis, and hierarchical cluster analysis.

Sum of ranking differences (SRD) was applied for comparing multianalyte results obtained by several analytical methods used in one or in different laboratories, i.e., for ranking the overall performances of the methods (or laboratories) in simultaneous determination of the same set of analytes. The data sets for testing of the SRD applicability contained the results reported during one of the proficiency tests (PTs) organized by EU Reference Laboratory for Polycyclic Aromatic Hydrocarbons (EU-RL-PAH). In this way, the SRD was also tested as a discriminant method alternative to existing average performance scores used to compare mutlianalyte PT results. SRD should be used along with the z scores--the most commonly used PT performance statistics. SRD was further developed to handle the same rankings (ties) among laboratories. Two benchmark concentration series were selected as reference: (a) the assigned PAH concentrations (determined precisely beforehand by the EU-RL-PAH) and (b) the averages of all individual PAH concentrations determined by each laboratory. Ranking relative to the assigned values and also to the average (or median) values pointed to the laboratories with the most extreme results, as well as revealed groups of laboratories with similar overall performances. SRD reveals differences between methods or laboratories even if classical test(s) cannot. The ranking was validated using comparison of ranks by random numbers (a randomization test) and using seven folds cross-validation, which highlighted the similarities among the (methods used in) laboratories. Principal component analysis and hierarchical cluster analysis justified the findings based on SRD ranking/grouping. If the PAH-concentrations are row-scaled, (i.e., z scores are analyzed as input for ranking) SRD can still be used for checking the normality of errors. Moreover, cross-validation of SRD on z scores groups the laboratories similarly. The SRD technique is general in nature, i.e., it can be applied to any experimental problem in which multianalyte results obtained either by several analytical procedures, analysts, instruments, or laboratories need to be compared.

Distribution of heavy elements in urban and rural surface soils: the Novi Sad city and the surrounding settlements, Serbia.

Concentrations of ten heavy elements (Cd, Co, Cr, Cu, Fe, Hg, Mn, Ni, Pb, and Zn), as well as the pH values, organic matter contents, and electrical conductivities were measured in the surface soil samples collected from 21 sites of urban areas in the city of Novi Sad, the second largest city in Serbia, its suburban settlement and the nearby villages. Range of the heavy element concentrations was from 0.16 mg/kg (for Hg) to 18,994 mg/kg (for Fe). Significantly higher Hg and Mn concentrations were observed in subgroups with rural and market garden samples in comparison to the subgroups with urban and grassland samples, respectively, while the contents of Pb found in the grasslands subgroup were significantly higher than in the subgroup with market garden soils. Only one sample of urban soil exceeded the maximum permissible value for Zn set by the relevant Serbian legislation. According to the Dutch soil quality standard, the Cd and Co concentrations in majority of the examined soils were higher than the target values for unpolluted soil. The content of Hg was above the target value in 52% of the samples, most of them belonging to the subgroup of market garden soils. The results for the Novi Sad city area were compared to the relevant data available for other cities in the Western Balkan Countries. Principal component analysis of data revealed seven outlying samples, while the rest of the analyzed samples were grouped together indicating similar heavy element patterns most probably due to mixed emission sources.

Chemometric interpretation of heavy metal patterns in soils worldwide.

Principal component analysis (PCA) was applied on data sets containing levels of six heavy metals (Pb, Cu, Zn, Cd, Ni, Cr) in soils from different parts of the world in order to investigate the information captured in the global heavy metal patterns. Data used in this study consisted of the heavy metal contents determined in 23 soil samples from and around the Novi Sad city area in the Vojvodina Province, northern part of Serbia, together with those from the city of Banja Luka, the second largest city in Bosnia and Herzegovina, and the ones reported previously in the relevant literature in order to evaluate heavy metal distribution pattern in soils of different land-use types, as well as spatial and temporal differences in the patterns. The chemometric analysis was applied on the following input data sets: the overall set with all data gathered in this study containing 264 samples, and two sub sets obtained after dividing the overall set in accordance to the soil metal index, SMI, calculated here, i.e. the set of unpolluted soils having SMIs<100%, and the set of polluted soils with SMIs>100%. Additionally, univariate descriptive statistics and the Spearman's non-parametric rank correlation coefficients were calculated for these three sets. A Box-Cox transformation was used as a data pretreatment before the statistical methods applied. According to the results, it was seen that anthropogenic and background sources had different impact on the data variability in the case of polluted and unpolluted soils. The sample discrimination regarding the land-use types was more evident for the unpolluted soils than for the polluted ones. Using linear discriminant analysis, content of Cu was determined as a variable with a major discriminant capacity. The correct classification of 73.3% was achieved for predefined land-use types. Classification of the samples in accordance to the pollution level expressed as SMI was necessary in order to avoid the "masking" effect of the polluted soil patterns over the non-polluted ones.

Principal component analysis of indicator PCB profiles in breast milk from Poland.

Principal component analysis (PCA) was applied to a data set containing the levels of indicator polychlorinated biphenyls (PCBs) in human milk of mothers living in the Wielkopolska region, Poland, in order to investigate the information captured in the PCB patterns and to elucidate the relationship between PCB concentrations in milk and donor characteristics. According to the obtained PCA results milk fat content was the most influential factor affecting the PCB levels in milk of the Wielkopolska cohort. The lifestyle data collected from the questionnaire completed by the donors appeared to have no influence on PCB concentrations in breast milk. The score plots revealed the PCB contents of milk were quite low and uniform with a few outliers, without discrimination observed either between the primipareous and secundipareous females or between donors from the urban and rural areas. Comparison of the PCB levels and profiles of human milk from the Wielkopolska region and from various European and Asian locations made by PCA reflected a generally low background exposure and indicated the possible reasons for the outlying of some samples. In order to enhance the chances of observing the relationship between donor habits and PCB levels in breast milk it was suggested that the questionnaire be redesigned to gather information about vegetable product consumption and indoor air exposure.

Non-dioxin-like PCBs in crops and related products: Levels and intakes in Serbia.

Levels of six non-dioxin-like indicator PCBs in 36 composite samples of agricultural crops, related by-products and foodstuffs were pooled from a total of 938 individual samples collected in Serbia in 2002 and 2004. After extraction and cleanup, PCBs were determined by capillary GC using ECD. The highest total PCB levels were found in dried sugar beet pulp (2.89 ng g(-1) whole weight (ww)) and crude sunflower oil (1.83 ng g(-1) lipid), while the lowest levels were found in molasses (0.05 ng g(-1) ww). The calculated daily intake of PCBs for the crop products included in this study were compared with the maximum permissible risk (MPR) level established by the Dutch National Institute for Public Health and the Environment. Cereal products (flour, bread, pastry, pasta, cookies) were made a relatively large contribution (23% of MPR), while sugar (2% of MPR) and oil (4% of MPR) made a low and fairly uniform contribution to intake. The levels and intake of PCBs in Serbia were compared with data from other recent international surveys.

Organochlorine pesticides and polychlorinated biphenyls in surface soils of Novi Sad and bank sediment of the Danube River.

The contents of 16 organochlorine pesticides (OCPs) and six so-called indicator polychlorinated biphenyls (PCBs) were determined in the surface zone (0-5 cm) of soil and sediment samples, taken from different locations in the city of Novi Sad, capitol of Vojvodina Province (North of the Serbia) covering residential and commercial area, recreational and arable zone. The total organochlorine pesticides concentration in soil varied from 2.63 to 31.78 ng g(-1) dry weight, while the level in sediment was 10.35 ng g(-1) dry weight. Maximum content of identified individual organochlorine pesticide in soil samples was 10.40 ng g(-1) dry weight for p, p-DDE in the market garden and 6.31 ng g(-1) dry weight for p, p'-DDT in sediment of the Danube River, although their application is restricted in Serbia. Some of investigated PCBs were identified only in the soil samples from a park-school backyard in the city downtown (0.32 ng g(-1) dry weight) and market garden (0.22 ng g(-1) dry weight), and also in sediment sample from left bank of the Danube River (0.41 ng g(-1) dry weight). Data of the OCPs and PCBs present in this study were compared with the ones found for soils and river sediments throughout the world, and with limit values set by soil and sediment quality guidelines. Also, correlation between the levels of certain pesticides and soil characteristics (organic matter, pH and clay content) was investigated.

Principal component analysis for soil contamination with organochlorine compounds.

In order to investigate the distribution pattern of individual organochlorine compounds in soil samples collected from the sites (Canary Island - Spain, China, Germany, India, Romania, Russia, Serbia, Swiss, UK) affected by industrial activities to the more remote areas, principal component analysis was performed on the data taken from literature. Loading plots pointed out the strong correlation among the variables. Score plots revealed similar PCB- and OCP-soil patterns for majority of the investigated sites. Nevertheless, the temporal differences of PCB-soil loads have been identified: the late 1990s and early 2000s concentrations are similar to those of the early 1940s, and they are below the levels existed in 1980. The most pronounced PCB concentrations characterized the soil from 1966. For OCPs the influence of sites location on the detected concentration has been revealed: China and India were characterized by comparably higher loads of DDX (DDT and its metabolites) and of HCH-isomers, respectively.

Principal component analysis of trace elements in Serbian wheat.

Trace elements (Cu, Fe, Pb, Hg, Cd, As, Mn, Zn) were analyzed quantitatively in 14 wheat samples collected from fields in all Serbian growing regions, harvested in 2002. Microelements were determined according to an atomic absorption spectrophotometric method. Principal component analyses (PCA) were performed on data matrices consisting of contents of trace elements in wheats (columns) and all Serbian wheat-growing regions (rows). It was found that four principal components account for 87.2% of the total variance in the data. The plot of component loadings showed significant groupings for concentration of some microelements. The component scores indicated the similarities among the Serbian wheat-growing regions. The loading plot reveals that there is no need to measure all of the variables to achieve the same classification. It is enough to measure one variable per group. Naturally, this conclusion is valid only within the limits of the present study of wheat grain samples from different parts of Serbia.

Polycyclic aromatic hydrocarbons in surface soils of Novi Sad and bank sediment of the Danube River.

Concentrations of 16 EPA polycyclic aromatic hydrocarbons (PAHs) in the surface soil samples of Novi Sad city urban area and in the Danube bank sediment sample were measured in 2001. The sampling sites were chosen in order to cover the whole city area and the results correspond to a network of six representative sampling sites. The total content of PAHs ranged from 307 to 1452 microg/kg with arithmetic mean value of 667 microg/kg and median of 382 microg/kg that represented typical PAH level of soils throughout Novi Sad urban area. Value of total PAHs content obtained in bank sediment sample along the Danube River was 975 microg/kg. Benzo(a)pyrene known to be carcinogenic formed 6-14% of the sum concentration of the identified PAHs for all investigated samples. Data were compared with the ones found for soils and river sediments throughout the world, and with target values set by Dutch authorities for unpolluted soil. The total carcinogenic potency for each sampling site was calculated and compared with the ones obtained on the base of the target concentrations. It was revealed only one sampling site with carcinogenic potency below the value calculated for unpolluted soil.