The pollution state and health risk assessment of potentially toxic elements (PTE) in soil and sediment samples of the petrochemical industry and its surrounding area are evaluated in this study. The ...pseudo-total contents of Ba, Cd, Co, Cu, Cr, Mn, Ni, Pb, V, Zn, As, Hg, and Se were measured by inductively coupled plasma-optical emission spectrometry (ICP/OES) in analyzed samples. Instead of determining total content, we performed aqua regia of the samples. The silicate matrix remained, and the quantities of elements that are within the silicate matrix do not represent an environmental danger. The soils from the chlor-alkali plant are highly polluted by Hg (the enrichment factor values were above 6000), and by Cu, Cd, Pb, and Zn, while the sediment samples from the wastewater channel are polluted with Cr, Cd, and Hg. The measured element contents are used for calculating health risk criteria for a composite worker (a worker who is exposed, long-term, during the work day) and for residential people. Hg is the element that mainly contributes to non-carcinogenic risks within the petrochemical area. The highest value of total carcinogenic risk obtained in the sediment sample from the wastewater channel, and the metal that mostly contributes is Cr. The areas closest to the petrochemical industry have higher values of health risk criteria parameters and pollution indices. The areas that are located further to the north and south from the petrochemical industry are less burdened with the analyzed elements, which is significant because the closest city and village are situated in those directions.
This study was performed in organic vineyard to assess integrated pollution in soil–plant–air system by potentially toxic elements (PTE). Concentrations of 26 PTE were determined in soil, grapevine, ...and air biomonitors (moss bags) using ICP-OES and ICP-MS. Environmental implication assessment of soil did not show pollution by PTE, except for B in samples collected in the middle of grapevine season (July). Despite low total Cd concentrations in soil, it has the highest influence on increase of environmental risk. Based on biological accumulation concentration (BAC), grapevine is not hyperaccumulator of PTE from soil. Advanced classification algorithm, Kohonen self-organizing map (SOM), was applied to compare environmental implications in organic with conventional vineyards. PTE concentrations were significantly lower in organic than conventional grapevine. PTE concentrations were higher in the outer (leaf and petiole) than in the inner grapevine parts (skin, pulp, and seed). Some airborne elements have an influence on outer grapevine parts, especially on leaves (ratio factor—RF > 1). Moss bag technique testified about lower enrichment of airborne elements compared with the conventional vineyard and urban microenvironments. Environmental and health risk assessments confirmed that organic production is harmless for field workers and grape consumers.
In the present work, we focused on two aspects of mercury (Hg) bioconcentration in the above-ground parts of Neoboletus luridiformis. In the first part, we monitored the bioconcentration potential of ...individual anatomical parts of a particular fruiting body and evaluated the obtained data by the spline interpolation method. In the second part, we focused on assessing the mercury content in 378 samples of N. luridiformis and associated samples of substrates from 38 localities with different levels of Hg content in Slovakia. From the obtained data of Hg content in samples of substrate and fungi, we evaluated ecological indicators (geoaccumulation index – Igeo, contamination factor – Cf a potential ecological risk – PER), bioconcentration indicators (bioconcentration factor – BCF; cap/stipe quotient – Qc/s) and health indicators (percentage of provisional tolerable weekly intake – %PTWI a target hazard quotient – THQ). Based on the Hg distribution results, the highest Hg content was found in the tubes & pores (3.86 mg/kg DW), followed by the flesh of cap (1.82 mg/kg DW). The lowest Hg content was in the stipe (1.23 mg/kg DW). The results of the BCF values indicate that the studied species can be included in the category of mercury accumulators. The results of the ecological indices representing the state of soil pollution pointed out that two localities (Malachov and Nižná Slaná) stood apart from all monitored localities and showed a state of an extremely disturbed environment. This fact was also reflected in the values of Hg content in the fruiting bodies of the studied mushroom species. In the case of the consumption of mushrooms from these localities, it can be stated that long-term and regular consumption could have a negative non-carcinogenic effect on the health of consumers. It was confirmed by the %PTWI (Malachov: 57.8%; Nižná Slaná: 53.2%) and THQ (Malachov: 1.11 Nižná Slaná: 1.02). The locality Čačín-Jelšovec is interesting from the bioconcentration characteristics point of view, where the level of environmental pollution was the lowest (Hg content in the soil was below the background value) compared to other localities, however, the THQ value was the highest (1.29).
•The interpolation method is an effective and low-cost alternative to the expensive visualization methods of element content in mushrooms.•The Hg content in the spore-forming part of the mushroom increased in a radial direction.•The spore-forming part of the mushroom contained more than 50% of the total Hg content in the whole fruiting body.•The first study aimed at the evaluation of Hg content in mushrooms on the national level.
(1) Background: An increasing use of pharmaceutics imposes a need for the permanent development of efficient strategies, including the tailoring of highly specific new materials for their removal ...from the environment. Photocatalytic degradation has been the subject of increasing interest of the researchers in the field. (2) Methods: This paper is focused on the investigation of the possibility to deposit a thin metal layer on a TiO2 surface and study its photocatalytic performance for the degradation of ciprofloxacin using a combination of theoretical and experimental methods. (3) Results: Based on the extensive DFT screening of 24 d-metals’ adhesion on TiO2, Cu was selected for further work, due to the satisfactory expected stability and good availability. The (Cu)TiO2 was successfully synthesized and characterized with XRD, SEM+EDS and UV-Vis spectrophotometry. The uniformly distributed copper on the TiO2 surface corresponds to the binding on high-affinity oxygen-rich sites, as proposed with DFT calculations. The photocatalytic degradation rate of ciprofloxacin was improved by about a factor of 1.5 compared to the bare non-modified TiO2. (4) Conclusions: The observed result was ascribed to the ability of adsorbed Cu to impede the agglomeration of TiO2 and increase the active catalytic area, and bandgap narrowing predicted with DFT calculations.
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.
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•The moss element concentrations increased during 2‒4‒6-month exposure in vineyard.•The concentrations of Cu and Ni markedly fluctuated during the grapevine season.•Six-month of the moss exposure is suggested for comparative studies among vineyards.•S. girgensohnii and H. cupressiforme are comparable for the biomonitoring in vineyards.
In order to further define the potential use of FTIR-ATR spectroscopy, as a non-destructive and reliable technique, for the analysis of the characteristics of post stamps, certified originals of the ...Principality of Serbia stamps (?Prince Michael issues?) issued in 1866 and 1868 as well as their forgeries were analyzed. Spectra enabling the comparison of the paper, dye and glue of stamps of so-called ?Vienna issues?, having denominations of 10 (orange-yellow), 20 (pink) and 40 para (blue) and ?Belgrade issues? (1 para-green and 2 para-reddish brown), as well as 24 expert-certified forgeries, were taken. It was shown that the applied technology was, in most of the cases, a fast and suitable technique for establishing clear differences between the spectral characteristics of the paper and dye used for the original stamps, and forgeries that were most probably made decades after the printing of the genuine stamps. The differences between printings of the same issues of the genuine stamps were also elaborated. It is proposed, for the first time in philatelic history, the possibility that ?Vienna issues? stamps may have been printed on two different papers, and, having in mind the technology of printing in the 19th century, potentially, not even at the same time or in the same printing house.
Presented research aimed to develop an alternative approach for the estimation of biosorption capability of sunflower husk. The acid-pretreated sunflower biomass was characterized by scanning ...electron microscopy combined with energy dispersive X-Ray spectroscopy (SEM-EDX) analysis and Fourier transform infrared (FTIR) spectroscopy. Biosorption efficiency has been evaluated using inductively coupled plasma optical emission spectroscopy (ICP-OES) and laser-induced breakdown spectroscopy (LIBS). The adsorption capacity of the adsorbent was determined as the function of the pH of the solution, the initial concentration of heavy metal solutions, and contact time. The optimal conditions were achieved after 15 min of contact at pH 6, while the percentage of the removal was from 80.0?98.7 %, depending on the element. The results obtained from the kinetic and isotherm studies show that maximum adsorption of ions was quickly reached and followed the pseudo-second-order kinetic model. Real samples were tested and obtained Ni values by LIBS method were 3100?200 and 1240?100 mg kg-1, while estimated values by the ICP-OES were 2995?20 and 1130?10 mg kg-1, respectively. The obtained results prove that LIBS method can be used as a ?green alternative? for the evaluation of biosorption efficiency.
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•Phenolic profile and mineral composition of 22 grapevine leaf samples was determined.•Leaf samples were collected in two different regions in Serbia.•International and Serbian ...autochthonous white and red varieties were studied.•Discrimination of leaves based on geographical origin was achieved.•An interspecies hybrid ‘Petra’ was shown to be atypical sample.
This research was designed to determine phenolics content, radical scavenging activity and mineral composition of 22 grapevine leaves of diverse varietal origin. Samples were collected from two vineyards located in Central Serbia (Belgrade vineyard area) and Eastern Serbia (Mlava vineyard area). Leaf extracts were characterized mostly with phenolics acids, flavonols and flavan-3-ols. Ellagic acid and rutin were the most abundant components, found in the concentration up to 770mg/kg and 450mg/kg of dry weight, respectively. Total phenolic content was in the range from 27.5 to 76.0g GAE/kg of dry weight while the radical scavenging activity ranged from 0.429 to 0.867mmol TE/kg of dry weight. The most common element in all samples was K (content ranging from 2.30g/kg to 6.77g/kg of dry weight), followed by Ca, Na, and B. A variation in the chemical composition was shown to be convenient way to differentiate among the grape leaves of diverse varietal origin. Clear separation was demonstrated between objects of different geographical origin by Principal Component Analysis. Serbian variety ‘Petra’, an interspecies hybrid with atypical composition, was detected as an outlier in comparison to other samples.
The removal of the bisphenol A (BPA) from sulphate-rich wastewater has been investigated using an electro-Fenton oxidation system with metal-oxide carbon nanostructured anode. The process produces ...highly oxidizing species, including hydroxyl radicals on the anode surface and bulk solution via an electrochemically monitored Fenton reaction. The focus of this research is the detection of BPA intermediates and the prediction of the BPA degradation mechanism during the electro-Fenton process using the SnO2-MWCNT nanostructured anode. In accordance to detected reactive oxygen species, BPA intermediates, and their respective peak area profiles, two primary degradation pathways can be defined. Whether direct cleavage of BPA precedes hydroxylation, oxidation, and dealkylation, or vice versa, the resulting products consist of catechols, dicatechols, quinones, aldehydes, carboxylic acids, and ultimately carbon dioxide and water. To ensure a comprehensive understanding, the impact of applied current, catalyst concentration, and treatment duration on degradation and mineralization efficiency, as well as degradation kinetics, was investigated. The degradation of BPA was found to follow pseudo-first-order reaction kinetics. The results showed that the degradation of BPA was attributed to the co-action of electro-Fenton oxidation and electrochemical oxidation. This study confirms the eco-friendly nature of the electro-Fenton process by demonstrating the toxicity of intermediaries formed during BPA treatment.
•BPA degradation was studied via electro-Fenton using SnO2-MWCNT nanostructured anode.•BPA intermediates have been identified and two reaction pathways have been proposed.•Toxicity predictions have confirmed the formation of non-toxic intermediates.•BPA oxidation by OH∙ follows pseudo-first-order kinetics.
The aim of this study was to determine the levels of Zn, Cu, and Fe in three canned fish species marketed Serbia to see if they meet recommended daily intake requirements or exceed safety limits. We ...collected a total of 207 samples of canned tuna, sardine, and mackerel, in oil or tomato sauce and analysed them with inductively coupled plasma mass spectrometry (ICP-MS) after acid digestion. The highest levels were obtained for Zn (15.1 mg kg
) and Cu (1.37 mg kg
) in sardine in oil and tomato sauce, respectively, and for Fe (18.98 mg kg
) in mackerel in tomato sauce. Our results keep within the ranges reported by several national food databases and available literature data, with a few exceptions. Our findings also single out canned sardines as the richest source of the three essential elements combined. The estimated daily intake (EDI) of the three essential elements, however, was subpar, and ranged between 0.14 % and 0.72 % of the recommended dietary allowance (RDA) for Zn, Cu, and Fe.
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