Green biocatalyst for decolorization of azo dyes from industrial wastewater: Coriolopsis trogii 2SMKN laccase immobilized on recycled brewer's spent grain.

This study presents an innovative approach for the reuse and recycling of waste material, brewer's spent grain (BSG) for creating a novel green biocatalyst. The same BSG was utilized in several consecutive steps: initially, it served as a substrate for the cultivation and production of laccase by a novel isolated fungal strain, Coriolopsis trogii 2SMKN, then, it was reused as a carrier for laccase immobilization, aiding in the process of azo dye decolorization and finally, reused as recycled BSG for the second successful laccase immobilization for six guaiacol oxidation, contributing to a zero-waste strategy. The novel fungal strain produced laccase with a maximum activity of 171.4 U/g after 6 days of solid-state fermentation using BSG as a substrate. The obtained laccase exhibited excellent performance in the decolorization of azo dyes, both as a free and immobilized, at high temperatures, without addition of harmful mediators, achieving maximum decolorization efficiencies of 99.0%, 71.2%, and 61.0% for Orange G (OG), Congo Red, and Eriochrome Black T (EBT), respectively. The immobilized laccase on BSG was successfully reused across five cycles of azo dye decolorization process. Notably, new green biocatalyst outperformed commercial laccase from Aspergillus spp. in the decolorization of OG and EBT. GC-MS and LC-MS revealed azo-dye degradation products and decomposition pathway. This analysis was complemented by antimicrobial and phytotoxicity tests, which confirmed the non-toxic nature of the degradation products, indicating the potential for safe environmental disposal.

Entropy-weighted water quality index, hydrogeochemistry, and Monte Carlo simulation of source-specific health risks of groundwater in the Morava River plain (Serbia).

Population growth, urbanization, industry, floods, and agriculture globally degrade groundwater in river plains, necessitating action for its quality assessment and management. Hence, a comprehensive methodology, including hydrogeochemical facies (Piper, Gibbs), irrigation indices (SAR, Wilcox), entropy-weighted water quality index (EWQI), positive matrix factorization (PMF), and Monte Carlo simulation of source-specific health risks was used in this study to analyze groundwater in the Morava river plain (Serbia). The results revealed a prevalent Ca-Mg-HCO3 groundwater type, influenced by water-rock interactions. Although groundwater was found suitable for irrigation, only 66.7 % of the samples were considered drinkable. Agricultural activities, natural processes, and municipal wastewater were identified as primary pollution sources. The incremental lifetime cancer risk (ILCR) and hazard index (HI) threshold exceedance for adults and children ranged from 8.5 % to 39 % of the samples, with arsenic identified as the most risk-contributing contaminant. These findings provide valuable insights for researchers studying groundwater vulnerability in river plains.

Spatial Variability of Rare Earth Elements in Groundwater in the Vicinity of a Coal-Fired Power Plant and Associated Health Risk.

This study investigated the occurrence and distribution of rare earth elements (REEs), including 14 lanthanoids, scandium (Sc), and yttrium (Y), in groundwater around a large coal-fired thermal power plant (TPP). The ICP-MS technique was used to analyze 16 REEs in groundwater samples collected from monitoring wells. REE concentrations ranged from 59.9 to 758 ng/L, with an average of 290 ng/L. The most abundant was Sc, followed by La, accounting for 54.2% and 21.4% of the total REE concentration, respectively. Geospatial analysis revealed the REE enrichment at several hotspots near the TPP. The highest REE concentrations were observed near the TPP and ash landfill, decreasing with the distance from the plant and the landfill. REE fractionation ratios and anomalies suggested the Light REE dominance, comprising over 78% of the total REEs. Correlation and principal component analyses indicated similar behavior and sources for most REEs. Health risk assessment found hazard indices (HI) of 1.36 × 10-3 and 1.98 × 10-3 for adults and children, respectively, which are far below the permissible limit (HI = 1). Likewise, incremental lifetime cancer risks (ILCR) were all below 1 × 10-6. Nevertheless, ongoing ash disposal and potential accumulation in the environment could elevate the REE exposure over time.

Ecological and Health Risks Attributed to Rare Earth Elements in Coal Fly Ash.

The occurrence and distribution of yttrium and rare earth elements (REYs), along with major elements and heavy metal(loid)s (HMs) in coal fly ash (CFA) from five coal-fired power plants (CFPPs), were analyzed, and the REY-associated ecological and health risks were assessed. The individual REYs in CFA were abundant in the following order: Ce > La > Nd > Y > Pr > Gd > Sm > Dy > Er > Yb > Eu > Ho > Tb > Tm > Lu. The total REY content ranged from 135 to 362 mg/kg, averaging 302 mg/kg. The mean light-to-heavy REY ratio was 4.1, indicating prevalent light REY enrichment in CFA. Significantly positive correlations between the REYs suggested that they coexist and share similar origins in CFA. REYs were estimated to pose low to moderate ecological risks, with risk index (RI) values ranging from 66 to 245. The hazard index (HI) and target cancer risk (TCR) of REYs from CFA, estimated to be higher for children (HIc = 0.15, TCRc = 8.4 × 10-16) than for adults (HIa = 0.017, TCRa = 3.6 × 10-16), were well below the safety limits (HI = 1, TCR = 1.0 × 10-6). However, the danger to human health posed by HMs in the same CFA samples (HIc = 5.74, TCRc = 2.6 × 10-4, TCRa = 1.1 × 10-4) exceeded the safe thresholds (excl. HIa = 0.63). The mean RI and HI attributed to REYs in CFA were 14% and 2.6%, respectively, of the total risks that include HMs.

Multivariate Assessment and Risk Ranking of Pesticide Residues in Citrus Fruits.

Pesticides are extensively used in the cultivation and postharvest protection of citrus fruits, therefore continuous monitoring and health risk assessments of their residues are required. This study aimed to investigate the occurrence of pesticide residues on citrus fruits and to evaluate the acute and chronic risk for adults and children. The risk ranking of twenty-three detected pesticides was carried out according to a matrix ranking scheme. Multiple residues were detected in 83% of 76 analyzed samples. In addition, 28% contained pesticides at or above maximum residue levels (MRLs). The most frequently detected pesticides were imazalil, azoxystrobin, and dimethomorph. According to the risk ranking method, imazalil was classified in the high-risk group, followed by prochloraz, chlorpyrifos, azinphos-methyl, tebufenpyrad, and fenpiroximate, which were considered to pose a medium risk. The majority of detected pesticides (74%) posed a low risk. The health risk assessment indicated that imazalil and thiabendazole contribute to acute (HQa) and chronic (HQc) dietary risk, respectively. The HQc was negligible for the general population, while the HQa of imazalil and thiabendazole exceeded the acceptable level in the worst-case scenario. Cumulative chronic/acute risk (HIc/HIa) assessment showed that chronic risk was acceptable in all samples for children and adults, while the acute risk was unacceptable in 5.3% of citrus fruits for adults and 26% of citrus fruits for children. Sensitivity analyses indicated that the ingestion rate and individual body weight were the most influential risk factors.

Influence of Ultrasonic and Chemical Pretreatments on Quality Attributes of Dried Pepper (Capsicum annuum).

This study investigates the effects of ultrasound, in combination with chemical pretreatments, on the quality attributes (total phenolic and carotenoid content, antioxidant activity (2,2-Diphenyl-1-picrylhydrazyl assay (DPPH)), ferric-reducing ability (FRAP), CIE L* a* b* color, non-enzymatic browning, rehydration ratio, textural and morphological properties) of red pepper subjected to drying (hot air drying or freeze drying). The fractional factorial design was used to assess the impact of factors. The global Derringer desirability function was used to determine the optimal conditions for the best quality attributes of dried pepper. The drying method influenced total phenolic content, a* (redness), and initial rehydration ratio; pretreatment time significantly affected FRAP antiradical activity, a*, chroma and non-browning index, while pH-value had a significant effect on the texture of dried pepper. Non-enzymatic browning was reduced to 72.6%, while the DPPH antioxidant capacity of freeze-dried peppers was enhanced from 4.2% to 71.9%. Ultrasonic pretreatment led to changes in the pepper morphology, while potassium metabisulfite (KMS) was a more effective additive than citric acid.

Spatial distribution and source apportionment of DTPA-extractable metals in soils surrounding the largest Serbian steel production plant.

Despite presenting a practical approach for the characterization of the environmental risk of potentially toxic elements (PTEs) derived from steel production facilities, the analysis of the spatial distribution of bioavailable PTEs concentrations in the soil is frequently overlooked in the management of polluted sites. In this study, the diethylenetriaminepentaacetic acid (DTPA)-extractable forms of PTEs were investigated in soils surrounding the largest Serbian steel production plant. The correlation and geostatistical analysis indicated their pronounced variability suggesting the anthropogenic origin of most investigated elements, apparently from the steel production facility. The detailed visualization of variables and observations derived by self-organizing maps (SOMs) revealed the homologies in PTEs' distribution patterns, implying the common origin of some elements. These observations were confirmed by principal component analysis (PCA) and positive matrix factorization (PMF). The аpplied approach supports a comprehensive assessment of contaminated sites' ecological and health risks and provides a basis for soil remediation.

Deep Eutectic Solvent Based Reversed-Phase Dispersive Liquid-Liquid Microextraction and High-Performance Liquid Chromatography for the Determination of Free Tryptophan in Cold-Pressed Oils.

A fast and straightforward reversed-phase dispersive liquid-liquid microextraction (RP-DLLME) using a deep eutectic solvent (DES) procedure to determine free tryptophan in vegetable oils was developed. The influence of eight variables affecting the RP-DLLME efficiency has been studied by a multivariate approach. A Plackett-Burman design for screening the most influential variables followed by a central composite response surface methodology led to an optimum RP-DLLME setup for a 1 g oil sample: 9 mL hexane as the diluting solvent, vortex extraction with 0.45 mL of DES (choline chloride-urea) at 40 °C, without addition of salt, and centrifugation at 6000 rpm for 4.0 min. The reconstituted extract was directly injected into a high-performance liquid chromatography (HPLC) system working in the diode array mode. At the studied concentration levels, the obtained method detection limits (MDL) was 11 mg/kg, linearity in matrix-matched standards was R2 ≥ 0.997, relative standard deviations (RSD) was 7.8%, and average recovery was 93%. The combined use of the recently developed DES -based RP-DLLME and HPLC provides an innovative, efficient, cost-effective, and more sustainable method for the extraction and quantification of free tryptophan in oily food matrices. The method was employed to analyze cold-pressed oils from nine vegetables (Brazil nut, almond, cashew, hazelnut, peanut, pumpkin, sesame, sunflower, and walnut) for the first time. The results showed that free tryptophan was present in the range of 11-38 mg/100 g. This article is important for its contributions to the field of food analysis, and for its development of a new and efficient method for the determination of free tryptophan in complex matrices, which has the potential to be applied to other analytes and sample types.

Speciation of Hexavalent Chromium in Aqueous Solutions Using a Magnetic Silica-Coated Amino-Modified Glycidyl Methacrylate Polymer Nanocomposite.

A new magnetic amino-functionalized polymeric sorbent based on glycidyl methacrylate was synthesized and used in the separation of chromium Cr(VI) oxyanions sorption from aqueous solutions in a static batch system. The kinetic and isothermal parameters of the sorption process were determined. The experimental data were best fitted by a pseudo-second-order model with R2 = 0.994 and χ2 = 0.004. The sorption process of Cr(VI) removal by amino-functionalized sorbent was controlled by both intraparticle diffusion and liquid film diffusion. The equilibrium results showed that the sorption process is best described by the Freundlich model, followed closely by the Sips isotherm model, with a maximum sorption capacity of 64 mg/g. Quantum chemical modeling revealed that the sorption sites on the sorbent surface are fragments with diethylenetriamine and aminopropyl silane groups that coated the magnetic nanoparticles. The calculations showed that Cr(VI) oxyanions (Cr2O72-, CrO42- and HCrO4-) bind to both sorption sites, with diethylenetriamine centers slightly favored. The X-ray photoelectron spectroscopy (XPS) spectra demonstrate that the chromium bound to the sorbent in the form of Cr(III), indicating that the Cr(VI) can be converted on the surface of the sorbent to a less harmful form Cr(III) due to the sorbent's chemical composition.

Dispersive liquid-liquid microextraction and Monte Carlo simulation of margin of safety for octocrylene, EHMC, 2ES, and homosalate in sunscreens.

Dispersive liquid-liquid microextraction (DLLME) using a floating organic drop has been optimized and used for the sample preparation of four commonly used ultraviolet filter (UVF) substances in sunscreens. Plackett-Burman experimental design was used to screen 10 variables in DLLME. The most significant variables were then optimized by using a response surface method with a Box-Behnken design. DLLME followed by an optimized HPLC identified octocrylene, 2-ethylhexyl-4-methoxycinnamate, ethylhexyl salicylate, and homosalate as the frequently found UVFs in commercial sunscreens. The systemic exposure dosage and margin of safety (MoS) for the identified UVFs were estimated using in-use concentrations and application patterns. The average systemic exposure dosage values for octocrylene, 2-ethylhexyl-4-methoxycinnamate, ethylhexyl salicylate, and homosalate were 0.52, 0.61, 0.020, and 0.079 mg/kg body weight per day, respectively. Whereas the average MoS values for individual UVFs ranging from 296 to 3160 were all significantly higher than the limit value of 100, the combined exposure risks were slightly above the limit. The probabilistic health risk assessment using Monte Carlo simulation revealed that the combined MoS values were (mean, 10‰, 90‰) 342, 119, and 441, respectively. Regarding the usage of sunscreen cosmetics containing the UVFs studied, these results indicate a safety concern for those who apply multiple UVF products.

Accumulation of heavy metal(loid)s and polycyclic aromatic hydrocarbons in the sediment of the Prahovo Port (Danube) and associated risks.

The current study investigated the concentrations, possible sources, toxicity, and ecological risk of eight heavy metal(loid)s (As, Cd, Cr, Cu, Hg, Ni, Pb, Zn) and sixteen priority polycyclic aromatic hydrocarbons (PAHs) in surface sediments in the port of Prahovo (Danube, Serbia). Among the examined HMs, the most abundant was Cu (38.3 mg/kg), followed by Zn. The Σ16PAHs concentrations ranged from 25 to 112.5 µg/kg, with 4-ring PAHs (17.3 µg/kg) being the most dominant in the study area. The mean and maximum values of HMs and PAHs obtained in this study were below the national regulatory limits and within environmental criteria. Particularly significant correlations between As, Cd, Cr, Ni, Pb, Zn, 5-, 6-ring PAHs, as well as between Pb and Hg, indicated their similar anthropogenic sources, pathways, and adsorption mechanisms. These findings were confirmed by cluster analysis and principal component analysis. Diagnostic ratios demonstrated that contamination in inner port stations was characterized by pyrogenic sources, while PAHs of petrogenic origin prevailed in samples near the port entrance. The mean ERM quotient (mERMq), toxic risk index (TRI), and toxic equivalent quotient (TEQ) were also calculated to assess the toxicity of the investigated HMs and PAHs in sediments. Positive matrix factorization suggested four potential sources as the main components of sediment contamination, whereas the risk assessment indicated a low or relatively insignificant risk of adverse biological effects from the combined toxicity of HMs and PAHs for the entire study area.

Impact of Crosslinking on the Characteristics of Pectin Monolith Cryogels.

In this research, the pectin monoliths were prepared via the sol-gel process through different routes of crosslinking and additional freeze-drying. The crosslinking reaction was induced by the use of calcium ions in aqueous solutions and in alcohol/water solutions. The resulting pectin monoliths obtained by freeze-drying were macroporous with open cells, limited specific surface area, moderate mechanical stability and moderate biodegradation rate. The presence of alcohol in crosslinking solution significantly changed the morphology of final pectin monoliths, which was evidenced by the reduction of their pore size for one order. The specific surface area of pectin monoliths obtained through the calcium-water-alcohol route was 25.7 m2/g, the Young compressive modulus was 0.52 MPa, and the biodegradation rate was 45% after 30 days of immersion in compost media. Considering that pectin can be obtained from food waste, and its physical properties could be tailored by different crosslinking routes, the pectin monoliths could find wide application in the pharmaceutical, agricultural, medical and food industries, providing sustainable development concepts.

Calcium-pyro-hydrochar derived from the spent mushroom substrate as a functional sorbent of Pb2+ and Cd2+ from aqueous solutions.

A calcium-pyro-hydrochar (Ca-PHC) can be distinguished as a novel sorbent of Pb2+ and Cd2+ from an aqueous solution. It was obtained using hydrothermal treatment of the spent mushroom substrate (SMS), followed by a CaCl2·5H2O activation and pyrolysis. The characterisation of chars before and after modifications was done by scanning electron microscope (SEM), Brunauer-Emmett-Teller (BET) and Fourier transform infrared (FTIR). Batch experiments were performed to examine Ca-PHC's sorption properties and binding mechanisms to selected metal ions. The maximum sorption capacities of Ca-PHC for Pb2+ and Cd2+ were 297 mg g-1, and 131 mg g-1, respectively. The obtained results demonstrated that the sorption of Pb2+ and Cd2+ by Ca-PHC follows a pseudo-second kinetic model and Freundlich isotherm. The binding of the selected metals onto Ca-PHC was enabled by the ion-exchange mechanism, surface complexation, mineral precipitation and cation-π interaction. Thermodynamic parameters indicate that metal ions binding by Ca-PHC are spontaneous and endothermic. Due to the high adsorption capacities, the obtained Ca-PHC has good potential for application in industrial wastewater treatment. In addition, the demonstrated use of SMS highlights another possibility of applying this specific biomass relevant to sustainable and economical waste management in the growing mushroom industry.

Novel Biocomposite Films Based on High Methoxyl Pectin Reinforced with Zeolite Y for Food Packaging Applications.

Pectin is a natural biopolymer with broad applications in the food industry and it is suitable to prepare edible films to prolong food shelf-life. However, the main limitation of pectin-based films is their poor mechanical and barrier properties. Zeolite Y is a hydrophobic clay that can be used as film reinforcement material to improve its physicochemical and mechanical properties. In this work, the influence of high methoxyl citrus and apple pectin on physicochemical properties of biopolymer films modified with zeolite Y (0.05-0.2 wt%) was investigated. The films were characterized by FTIR, TGA, WAXD, mechanical analysis, and water vapor permeability analysis, and a potential film application is presented. The WAXD and FTIR analysis demonstrated that the strongest interaction between pectin chains and zeolite Y occurred when citrus high methylated pectin was used. Adding 0.2 wt% of zeolite Y into citrus high methylated pectin matrix enhanced the tensile strength by 66%, thermal stability by 13%, and water vapor barrier by 54%. In addition, fruit shelf-life test was performed, where strawberries were sealed in film. It was shown that sealed strawberries maintained a better color and healthy appearance than the control treatment after 7 days at 10 °C. This study enabled the development of biocomposite films with improved properties for potential application in food packaging.

Removal of Nickel Ions from Aqueous Solutions by 2-Hydroxyethyl Acrylate/Itaconic Acid Hydrogels Optimized with Response Surface Methodology.

The adsorption of Ni2+ ions from water solutions by using hydrogels based on 2-hydroxyethyl acrylate (HEA) and itaconic acid (IA) was studied. Hydrogel synthesis was optimized with response surface methodology (RSM). The hydrogel with the best adsorption capacity towards Ni2+ ions was chosen for further experiments. The hydrogel was characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and atomic force microscopy (AFM) analysis before and after the adsorption of Ni2+ ions. Batch equilibrium experiments were conducted to investigate the influence of solution pH, hydrogel weight, ionic strength, adsorption time, temperature and initial concentration of nickel ions on the adsorption. Time-dependent adsorption fitted the best to the pseudo-second-order kinetic model. A thermodynamic study revealed that the adsorption was an exothermic and non-spontaneous process. Five isotherm models were studied, and the best fit was obtained with the Redlich-Peterson model. Consecutive adsorption/desorption studies indicated that the HEA/IA hydrogel can be efficiently used as a sorbent for the removal of Ni2+ ions from the water solution. This study develops a potential adsorbent for the effective removal of trace nickel ions.

Spatial distribution, radiological risk assessment and positive matrix factorization of gamma-emitting radionuclides in the sediment of the Boka Kotorska Bay.

Surface sediment from the Boka Kotorska Bay (Adriatic Sea) was analyzed for the content of technogenic cesium (137Cs) and naturally occurring (40K, 226Ra, 232Th, 238U) radionuclides. The activity concentrations of the radionuclides have been correlated with the major elements (Si, Al, Ca, Fe, K, Mg, Ti, P, Mn) content of sediment samples. The spatial interpolation identified primordial radioactivity more pronounced in the inland of the bay. Correlation and hierarchical cluster analyses clearly distinguished 226Ra, 232Th, and 238U from 137Cs. In addition, a strong association between primordial radionuclides and most major elements was found. Positive matrix factorization apportioned technogenic and natural radionuclides sources, while Si and Ca were separated from other elements. Radiological hazard parameters (Raeq, D, AEDE, Hin, Hex, AGDE, AUI) that include the doses and indices, and the excess lifetime cancer risk indicate that the risk in the studied area due to gamma radiation is within the acceptable level.

The characterization and pollution status of the surface sediment in the Boka Kotorska Bay, Montenegro.

Surface sediments collected from twelve stations in the Boka Kotorska Bay were analyzed for the level and distribution of twenty-six elements and ten oxides, grain sizes, organic matter, and carbonate content. Potentially toxic elements (Al, Fe, Mn, Cr, Zn, Ni, Cu, Pb, As, Co, U) were determined to assess the contamination status and potential environmental risk according to the single-element indices (enrichment factor (EF), geoaccumulation index (Igeo), contamination factor (CF)), and combined index (pollution load index (PLI)). The single-element indices EF and CF revealed that the surface marine sediment was moderately polluted with Pb, Cu, and Cr, while Igeo indicated moderate pollution with Ni > Cr > Zn > Cu > As and moderate to heavy pollution with Pb, as a result of the anthropogenic factors. The method of the combined effect of toxic elements, PLI, showed the highest pollution rate at the shipyard location in the Bay of Tivat. Pearson's correlation coefficient (r), principal component analysis (PCA), and cluster analysis (CA) were applied to highlight similarities and differences in the distribution of the investigated elements in the Bay, confirming the claim obtained by the pollution indices. The sediment contamination with most heavy metals, such as Cr, Zn, Ni, Cu, Pb, and As, has been identified in the Tivat Bay area.

Spatial and temporal distribution of pollution indices in marine surface sediments-a chemometric approach.

Concentrations of As, Cd, Cr, Cu, Hg, Mn, Ni, Pb, Zn, and Fe measured at forty locations in the Boka Kotorska Bay were used to monitor the spatial and temporal quality of sediment and to assess surface sediment contamination over the last 15 years. This ecological geochemistry assessment was made using two classes of pollution indices: single indices concerning the investigated elements (contamination factor (Cf)) and integrated indices concerning the locations (pollution load index (PLI), potential ecological risk index (RI), mean effects range median quotient (MERMQ), toxic risk index (TRI), contamination severity index (CSI)). The distribution of all indices was geostatistically mapped and several hotspots were identified. Based on the indices applied in the risk assessment, the mean contribution of individual metal species to the total risk was determined and presented in the following order: Cd > Hg > As > Pb > Ni > Cu > Cr > Zn. This study revealed that Cd and Hg were at the top of the risk list among the examined elements. The temporal distribution of Hg has shown a decreasing trend during the period 2005-2019, while the presence of Cd in the Bay environment is of major concern. The results revealed that the most polluted part of the investigated area was Tivat bay within the Boka Kotorska Bay. Multivariate statistical analysis of pollution indices resulted in multicollinearity, which enabled the use of a reduced number of indices with an acceptable risk estimation.

Characterization of PM2.5 sources in a Belgrade suburban area: a multi-scale receptor-oriented approach.

Designated as the most harmful for health, PM2.5 aerosol fraction was a subject of our study. It was collected for all four seasons during 2014/15 in the suburban area of Belgrade (Serbia) and analysed for Al, Si, P, S, Cl, K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Br, As, Ba and Pb elements and for NH4+, NO3- and SO42- ions by particle-induced X-ray emission and ion chromatography techniques, respectively. Obtained concentrations have been treated by a combination of several receptor-oriented models to reveal source contributions to the suburban PM2.5 at different spatial scales. Applied positive matrix factorization analysis indicated five main groups of emission sources: biomass burning (14.5%), traffic (3.9%), regional combustion/secondary sulphates (28.8%), local combustion/secondary nitrates (29.7%) and soil (5.4%). Local heating units had been pointed out as dominant contributors by long-range transport and ground-wind circulation analyses. Air masses circulating over the Balkan Peninsula denoted regional emissions as responsible for the high concentrations of secondary sulphates. Local and long-range transport analyses combined suggested that the BB and the LC/NO3 originated from the wider urban area. Several Saharan dust episodes were detected as well. Presented results might be a basis for the development of air pollution mitigation strategies in the continental Balkan area, considered one of the most polluted and under-investigated European regions.

Theoretical modeling of sorption of metal ions on amino-functionalized macroporous copolymer in aqueous solution.

With regard to the harmful effects of heavy metals on human health and the environment, the demand for synthesis and investigation of macromolecules with large capacity of harmful substances sorption is ever greater. Quantum-chemical methods may be applied in structural modeling, prediction, and characterization of such molecules and reactions. Sorption of metal ions (Cu2+, Cd2+, Co2+, and Ni2+) to triethylenetetramine-functionalized copolymer poly(GMA-co-EGDMA)-teta was successfully modeled by quantum chemical calculations, at the B3LYP//6-311++G**/lanl2dz level. Optimized structures of metal complexes were used for calculation of real binding energy of metal ion within the complex (ΔEr). Solvent and hydrolyzation effects were essential for obtaining the objective values. Solvent effect was included in ΔEr by using the total solvation energy for reaction of formation of tetaOH complex (ΔEs1, the first approach) or by using dehydration energy of free metal ion (ΔEs2, the second approach). Experimental results were confirmed in our theoretical analyses (using the second approach). Graphical abstract Theoretical modeling of divalent metal ions sorption on triethylenetetramine-functionalized copolymer poly(GMA-co-EGDMA)-teta.