Geochemical Fractionation and Assessment of Probabilistic Ecological Risk of Potential Toxic Elements in Sediments Using Monte Carlo Simulations.

The need for further research into potentially toxic elements in Serbian rivers led to an investigation of distributions, sources, and ecological risks in a sample base of sediments from 15 rivers. The analyses were carried out through both experimental and theoretical methods. Geochemical fractionation of Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, As, V, and Zn in sediments was studied using a sequential extraction procedure. Both a Håkanson risk index (RI) and a Monte Carlo simulation (MCS) were used in order to estimate ecological risk, applying the probability distribution of RI values instead of single-point calculations. In order to both further the development of the used method and include additional processes, software for the simulations was developed instead of using proprietary solutions. Metal fractionation showed high percentage recoveries of Cd, Cr, Co, Cu, Fe, Ni, and V in residual fractions. The high content of Pb, Mn, and Zn in mobile fractions might cause serious environmental concerns. In some localities, Cu and Cd could be problematic elements, since their mobility was high. An environmental assessment based on the described criteria provided risk levels varying from low to median (mainly contributed by Cd and Cu).

Natural and anthropogenic sources of chromium, nickel and cobalt in soils impacted by agricultural and industrial activity (Vojvodina, Serbia).

This study reports the contents and sources of chromium, nickel and cobalt, as well as Al, Ca, Mg, K, Fe and Mn in Vojvodina regions Srem and Central Banat area soil samples. Different methods were applied to identify the sources of the studied elements and to classify the latter as geogenic and/or anthropogenic: modified Tessier sequential extraction, calculation ratio of E/Al, XRPD, correlations and cluster analysis. The sampling methodology was according to the GEMAS project. The results show that increasing content of chromium, cobalt and nickel detected in studied soils can be explained by a distribution pattern and the presence of ultramafic and mafic parent rocks, as well as by significant anthropogenic pollution, mainly originating from the industry at some localities. The statistically significant difference between the content of Cr and Ni in soils of Srem and C. Banat is observed. The content of the studied elements is higher in soils of Srem. The normalization to Al indicating a presence of the anthropogenic sources which my significantly affect the content of Cr and Ni in the soils from Beocin, Ruma and Stara Pazova. There is no shown influence of eventual agrochemicals application on the Cr, Ni and Co content.

Integrated approach to environmental pollution investigation - Spatial and temporal patterns of potentially toxic elements and magnetic particles in vineyard through the entire grapevine season.

An integrated approach to the investigation of potentially toxic elements (PTEs) was applied to the soil and grapevine leaf samples collected from vineyard environment through the grapevine season. To investigate mobile and bioavailable concentrations of PTEs, six single extraction procedures and pseudo-total digestion were applied to the samples. The element concentrations in the samples were measured using inductively coupled plasma-optical emission spectrometry (ICP-OES) and inductively coupled plasma-mass spectrometry (ICP-MS). To assess atmospheric particle deposition, saturation isothermal remanent magnetisation (SIRM) was applied to the leaf samples. The obtained PTE concentrations in samples were used for calculating various ecological implications in the vineyard environment. The notable environmental pollution implications were estimated for As, B, Cd, Co, Cr, Cu, Mn, Ni and Sr. The environmental risk (RI) of the elements soluble under low-acid conditions influenced soil bioavailability risk. The most bioavailable elements from soil to leaves were Mn, Ni and Sr, followed by Cr and Cu. Cadmium and Co were strongly-bonded in the soil and were not bioavailable. The most suitable extractants for assessing bioavailability in the soil-leaf system were chelating agent Na2EDTA, and weak salt solutions CaCl2 and NH4NO3. The biological accumulation concentrations (BACs) of B, Ba, Cd, Co, Ni and Zn were decreasing in the leaves through the grapevine growing phases, that is contributed to the decreasing agrochemical application through the season. The BACs of Co, Cr, Sb and Pb, in July (veraison), were higher than in other phases, which indicate anthropogenic activities. According to correlations between biogeochemical index (BGI) and BAC, Cu and Na were mostly bioaccumulated from soil to leaves due to agrochemical applications, while bioaccumulation of B, Cd, Sb and Sr could be influenced by the other anthropogenic sources. Significant correlations between PTE concentrations and SIRM imply that leaves indicate Co, Cr and Ni air pollution in the vineyard environment.

Assessment of species-specific and temporal variations of major, trace and rare earth elements in vineyard ambient using moss bags.

Since the methodological parameters of moss bag biomonitoring have rarely been investigated for the application in agricultural areas, two mosses, Sphagnum girgensohnii (a species of the most recommended biomonitoring genus) and Hypnum cupressiforme (commonly available), were verified in a vineyard ambient. The moss bags were exposed along transects in six vineyard parcels during the grapevine season (March‒September 2015). To select an appropriate period for the reliable 'signal' of the element enrichment in the mosses, the bags were simultaneously exposed during five periods (3 × 2 months, 1 × 4 months, and 1 × 6 months). Assuming that vineyard is susceptible to contamination originated from different agricultural treatments, a wide range of elements (41) were determined in the moss and topsoil samples. The mosses were significantly enriched by the elements during the 2-month bag exposure which gradually increasing up to 6 months, but Cu and Ni exhibited the noticeable fluctuations during the grapevine season. However, the 6-month exposure of moss bags could be recommended for comparative studies among different vineyards because it reflects the ambient pollution comprising unpredictable treatments of grapevine applied during the whole season. Although higher element concentrations were determined in S. girgensohnii than H. cupressiforme, both species reflected the spatio-temporal changes in the ambient element content. Moreover, the significant correlation of the element (Cr, Cu, Sb, and Ti) concentrations between the mosses, and the same pairs of the elements correlated within the species, imply the comparable use of S. girgensohnii and H. cupressiforme in the vineyard (agricultural) ambient. Finally, both the moss bags and the soil analyses suggest that vineyard represents a dominant diffuse pollution source of As, Cr, Cu, Ni, Fe, and V.

The content of toxic and essential elements in trabecular and cortical femoral neck: a correlation with whole blood samples.

Pollution caused by heavy metals affects all forms of life. The aim of the study was to determine the content of toxic (Sr, Ni, Pb, V, Cd, U, Rb, As) and essential (Na, K, Ca, Mg, Zn, Cu, Se, Mn, Cr, Mo, Co) metals in the bone and whole blood samples, in regard to clinical means of long- and short-term exposure, respectively. For this purpose, the cortical and trabecular parts of femoral neck, as well as the blood samples, were collected to quantify bone-important metals by inductively coupled plasma (ICP)-based techniques. According to principal component analysis (PCA), the most influential metal discriminating blood samples was Cu, while all other quantified elements were present in higher amounts in the bones. Additionally, trabecular bones (TBs) could be characterized by higher content of Mo, Cr, V, Mn, Co, As, and Ni compared to cortical bones (CBs). Linear discrimination analysis (LDA) was successfully applied to distinguish trabecular bone from the cortical bone. Significant correlation between essential Ca and toxic Sr with other elements was found and discussed. This study provides novel data on the effects of metal pollutants on bone health hazards. The results obtained for investigating metals may serve as a baseline for further clinical investigations in the orthopedic fields.

Bioavailability of potentially toxic elements in soil-grapevine (leaf, skin, pulp and seed) system and environmental and health risk assessment.

Monitoring of potentially toxic elements in agricultural soil represents the first measure of caution regarding food safety, while research into element bioavailability should be a step forward in understanding the element transportation chain. This study was conducted in the grapevine growing area ("Oplenac Wine Route") for investigating element bioavailability in the soil-grapevine system accompanied by an assessment of the ecological implications and human health risk. Single extraction procedures (CH3COOH, Na2EDTA, CaCl2, NH4NO3 and deionised H2O) and digestion were performed to estimate the bioavailability of 22 elements (Al, As, B, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe, K, Li, Mg, Mn, Na, Ni, Pb, Sb, Sr, V and Zn) from the topsoil (0-30 cm) and subsoil (30-60 cm) to the grapevine parts (leaf, skin, pulp and seed) and wine. The extractants were effective comparing to the pseudo-total concentrations in following order Na2EDTA ˃ CH3COOH ˃ NH4NO3 ˃ CaCl2, H2O 2 h and 16 h. The most suitable extractants for assessing the bioavailability of the elements from the soil to the grapevine parts were CaCl2, NH4NO3 and Na2EDTA, but deionised H2O could be suitable, as well. The results showed that Ba was the most bioavailable element in the soil-grapevine system. Contamination factor implied a moderate contamination (1 < CF < 3) of the soil. The concentrations of Cr, Ni and Cd in the soil were above the maximum allowed concentrations. According to the biological accumulation coefficient (BAC), the grape seeds and grapevine leaves mostly accumulated Cu and Zn from the soil, respectively. Based on ratio factor (RF > 1), the influence of atmospheric deposition on the aerial grapevine parts (leaves and grape skin) was observed. Nevertheless, low adverse health risk effects (HI < 1 and R ≤ 1 × 10-6) were estimated for farmers and grape and wine consumers.

Synthesis, cytotoxic activity and DNA interaction studies of new dinuclear platinum(ii) complexes with an aromatic 1,5-naphthyridine bridging ligand: DNA binding mode of polynuclear platinum(ii) complexes in relation to the complex structure.

The synthesis, spectroscopic characterization, cytotoxic activity and DNA binding evaluation of seven new dinuclear platinum(ii) complexes Pt1-Pt7, with the general formula [{Pt(L)Cl}2(µ-1,5-nphe)](ClO4)2 (1,5-nphe is 1,5-naphthyridine; while L is two ammines (Pt1) or one bidentate coordinated diamine: ethylenediamine (Pt2), (±)-1,2-propylenediamine (Pt3), trans-(±)-1,2-diaminocyclohexane (Pt4), 1,3-propylenediamine (Pt5), 2,2-dimethyl-1,3-propylenediamine (Pt6), and 1,3-pentanediamine (Pt7)), were reported. In vitro cytotoxic activity of these complexes was evaluated against three tumor cell lines, murine colon carcinoma (CT26), murine mammary carcinoma (4T1) and murine lung cancer (LLC1) and two normal cell lines, murine mesenchymal stem cells (MSC) and human fibroblast (MRC-5) cells. The results of the MTT assay indicate that all investigated complexes have almost no cytotoxic effects on 4T1 and very low cytotoxicity toward LLC1 cell lines. In contrast to the effects on LLC1 and 4T1 cells, complexes Pt1 and Pt2 had significant cytotoxic activity toward CT26 cells. Complex Pt1 had a much lower IC50 value for activity on CT26 cells compared with cisplatin. In comparison with cisplatin, all dinuclear Pt1-Pt7 complexes showed lower cytotoxicity toward normal MSC and MRC-5 cells. In order to measure the amount of platinum(ii) complexes taken up by the cells, we quantified the cellular platinum content using inductively coupled plasma mass spectrometry (ICP-QMS). Molecular docking studies performed to evaluate the potential binding mode of dinuclear platinum(ii) complexes Pt1-Pt7 and their aqua derivatives W1-W7, respectively, at the double stranded DNA showed that groove spanning and backbone tracking are the most stable binding modes.

Assessment of major and trace element bioavailability in vineyard soil applying different single extraction procedures and pseudo-total digestion.

A different single extraction procedures (CH3COOH, Na2EDTA, CaCl2, NH4NO3, deionized water), and pseudo-total digestion (aqua regia) were applied to determine major (Al, Fe, K, Mn, Na, P, S, and Si) and trace (Cd, Co, Cr, Cu, Mo, Ni, Pb, V, and Zn) element bioavailability in a topsoil from the experimental vineyard ("Radmilovac", Belgrade, Serbia). For the first time, the extraction with deionized water during 16 h was tested as an alternative method for isolating bioavailable major and trace elements from the soil. Concentrations of the elements were determined by inductively coupled plasma - optical emission spectroscopy (ICP-OES). The extraction of Cu and S from the soil by deionized water during 16 h extracting, NH4NO3, and CaCl2 indicated that these elements could originate from the anthropogenic sources, such as fungicide. In addition according to the soil - plant experiment, performed as a preliminary experiment for future studies in vineyards, deionized water was recommended for isolation of bioavailable elements from grape seed and grape pulp; CH3COOH, Na2EDTA, CaCl2 and NH4NO3 for grape skin, while for assessment of leaf bioavailable elements from soil fraction, aqua regia was recommended. In addition, identification of similarities between the plant parts and the plant species were performed. Applying environmental risk assessment formulas, the most polluted vineyard parcel in the vineyard region "Radmilovac" was determined. The leaves of some grapevine species showed the high ability for accumulation some of the potentially toxic trace elements from the soil.

The first survey of airborne trace elements at airport using moss bag technique.

Air traffic represents an important way of social mobility in the world, and many ongoing discussions are related to the impacts that air transportation has on local air quality. In this study, moss Sphagnum girgensohnii was used for the first time in the assessment of trace element content at the international airport. The moss bags were exposed during the summer of 2013 at four sampling sites at the airport 'Nikola Tesla' (Belgrade, Serbia): runway (two), auxiliary runway and parking lot. According to the relative accumulation factor (RAF) and the limit of quantification of the moss bag technique (LOQT), the most abundant elements in the samples were Zn, Na, Cr, V, Cu and Fe. A comparison between the element concentrations at the airport and the corresponding values in different land use classes (urban central, suburban, industrial and green zones) across the city of Belgrade did not point out that the air traffic and associated activities significantly contribute to the trace element air pollution. This study emphasised an easy operational and robust (bio)monitoring, using moss bags as a suitable method for assessment of air quality within various microenvironments with restriction in positioning referent instrumental devices.

Comparison of single extraction procedures and the application of an index for the assessment of heavy metal bioavailability in river sediments.

Metals in sediments are present in different chemical forms which affect their ability to transfer. The objective of this body of work was to compare different extraction methods for the bioavailability evaluation of some elements, such as Ba, Cd, Co, Cr, Cu, Fe, K, Mg, Mn, Ni, Pb, V and Zn from Serbian river sediments. A bioavailability risk assessment index (BRAI) was used for the quantification of heavy metal bioavailability in the sediments. Actual and potential element availability was assessed by single extractions with mild (CaCl2 and CH3COONH4) and acidic (CH3COOH) extractants and complexing agents (EDTA). Aqua regia extraction was used for the determination of the pseudo-total element content in river sediments. In different single extraction tests, higher extraction of Cd, Cu, Zn and Pb was observed than for the other elements. The results of the single extraction tests revealed that there is a considerable chance of metal leaching from the sediments assessed in this study. When the BRAI was applied, the results showed a high risk of heavy metal bioavailability in Serbian river sediments.

Moss bag biomonitoring of airborne toxic element decrease on a small scale: A street study in Belgrade, Serbia.

A database of potentially hazardous substances, necessary for estimating the exposure of humans to air pollutants, may be deficient because of a limited number of regulatory monitoring stations. This study was inspired by undeniably harmful effects of human long-term exposure to intense traffic emissions in urban area. Moss bag biomonitors were used to characterize spatial variation of airborne toxic elements near crossroads and two- and one-lane streets. The Sphagnum girgensohnii and Hypnum cupressiforme moss bags were exposed for 10 weeks to 48 sampling sites across Belgrade (Serbia) during the summer of 2014. In addition, oven-drying pretreatment of the moss bags was tested. During the experimental period, traffic flows were estimated at each site by counting the number of vehicles during the rush hours. The concentrations of 39 elements were determined in the moss samples. There was no significant difference between the results obtained for nontreated and oven-dried moss bags. For the majority of elements, the moss bags identified a common pattern of decrease in the concentration from crossroads to two- and one-lane streets. The exposed moss bags were enriched with Sb, Cu and Cr. The correlation coefficients (r=0.65-0.70) between the moss concentrations of Cr, Cu, Fe and Sb and the site-counted traffic flows also confirmed a dependence of the airborne element content on traffic emissions. A strong correlation with traffic flows makes Sb, Cu and Cr reliable traffic tracers.

Distribution and mobility of heavy elements in floodplain agricultural soils along the Ibar River (Southern Serbia and Northern Kosovo). Chemometric investigation of pollutant sources and ecological risk assessment.

This work investigates the influence of a high-magnitude flood event on heavy elements (HEs) pollution and mobility in the agricultural soils along Ibar River in Southern Serbia and Northern Kosovo. The study area was one of the most important Pb/Zn industrial regions in Europe. Soil samples (n = 50) collected before and after the floods in May 2014 were subjected to the sequential extraction procedure proposed by the Community Bureau of Reference (BCR). The results indicated that the floods significantly increased not only the pseudo total concentrations of HEs in the soil but also their mobile and potentially bioavailable amounts. Moreover, higher concentrations (both pseudo total and potentially bioavailable) were found in the agricultural soils closer to the industrial hotspots. Principal component analysis and hierarchical cluster analysis successfully grouped the analyzed elements according to their anthropogenic or natural origin. The floods significantly increased the potential ecological risk of HEs associated with Pb/Zn industrial activities in the study area. The potential ecological risk of Cd after the floods was highest and should be of special concern.

Active moss biomonitoring for extensive screening of urban air pollution: Magnetic and chemical analyses.

In this study, active magnetic biomonitoring of moss for particulate air pollution and an assessment of heavy metals and polycyclic aromatic hydrocarbons (PAHs) were performed for the entire metropolitan area of Belgrade. Two mosses, Sphagnum girgensohnii (a species of the most recommended biomonitoring moss genus) and Hypnum cupressiforme (a common moss in the study area), were used. During the summer of 2013, moss bags were exposed at 153 sampling sites, forming a dense network of sites. A type II regression model was applied to test the interchangeable use of the two moss species. Significantly higher levels of all measured pollutants were recorded by S. girgensohnii in comparison with H. cupressiforme. Based on the results, the mosses could not be interchangeably used in urban areas, except for the biomonitoring of Cu. Nevertheless, according to the relative accumulation factors obtained for both moss species, similar city zones related to high, moderate and low levels of air pollution were distinguished. Moreover, new pollution hotspots, omitted by regulatory monitoring, were identified. The results demonstrate that moss magnetic analysis represents an effective first step for obtaining an overview of particulate air pollution before more expensive chemical analyses. Active moss biomonitoring could be applied as a pragmatic approach for optimizing the representativeness of regulatory monitoring networks.

Selenium, zinc, and copper plasma levels in patients with schizophrenia: relationship with metabolic risk factors.

The aim of this study was to determine the plasma selenium (Se), copper (Cu), and zinc (Zn) levels and to evaluate their possible association with metabolic syndrome (MetS) components in patients with schizophrenia. The study group consisted of 60 patients with schizophrenia and 60 sex- and age-matched healthy controls. Anthropometric measurements, blood pressure, and biochemical analysis of fasting blood were performed in all subjects. Patients with schizophrenia had significantly higher plasma Cu concentrations compared with controls (0.97 ± 0.31 vs. 0.77 ± 0.32 mg/L, p = 0.001). The plasma Cu concentration showed a positive correlation with plasma glucose and diastolic blood pressure in the patient groups (r s = 0.263, p < 0.05 and r s = 0.272, p < 0.05, respectively). The plasma Se level correlated positive with MetS score (r s = 0.385, p < 0.01), waist circumference (r s = 0.344, p < 0.05), plasma glucose (r s = 0.319, p < 0.05), and triglyceride concentrations (r s = 0.462, p < 0.001) in patients with schizophrenia. Plasma Zn did not correlate with any of the MetS components. These results suggest that alterations in plasma Cu and Se levels in medicated patients with schizophrenia could be associated with metabolic risk factors.