Mobility and sorption assessment of selected pesticides in alluvial aquifer.

The objective of the paper was to use transport model of selected pesticides (carbendazim, acetamiprid and imidacloprid) in determination of linear sorption coefficients in alluvial aquifer. For constructing transport model, results of a field experiment at the location of Kovin-Dubovac drainage system in Serbia were used in order to set hydraulic parameters (hydraulic conductivity, aquifer layer thickness of the observed area, effective porosity etc.). The field experiment consisted of a tracer test during which concentrations of non-reactive tracer (Cl-) and selected pesticides (carbendazim, acetamiprid and imidacloprid) were monitored. For better characterization of hydraulic parameters, a pumping test was conducted at the observed well and results were used in designing transport model. Simulation model was constructed with Lizza groundwater flow software and W.O.D.A. (Well Outline and Design Aid) solver. Obtained linear sorption coefficients in the sand and gravel water-bearing layer were 0.14 mL g-1 for carbendazim and 0.11 mL g-1 for acetamiprid and imidacloprid. Results from this study are a unique insight into mobility of observed pesticides in the alluvial groundwater in natural conditions and can be used in contamination assessment for drinking water wells.

The photocatalytic degradation of carbofuran and Furadan 35-ST: the influence of inert ingredients.

A comparative study on photocatalytic degradation of the pesticide carbofuran and its commercial product Furadan 35-ST in an aqueous suspension of ZnO, irradiated by long-wave light (315-400 nm), is presented in this study. In order to assess the effects of inert ingredients present in the commercial product Furadan 35-ST, non-competitive and competitive adsorption and kinetic studies of carbofuran degradation processes were conducted. A higher photochemical degradation rate was found for pure carbofuran in comparison to a two-component system, carbofuran and single addition of ingredients at appropriate concentrations, and the commercial product Furadan 35-ST. The overall effect of inert ingredients was evaluated from a competitive study using the model system of Furadan 35-ST. The results of a mineralization study, obtained by ion chromatography (IC) and total organic carbon (TOC) analyses, revealed the formation of acetate, oxalate, and formate ions. Photodegradation products of carbofuran, three of them detected for the first time, were identified based on high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) and gas chromatography-mass spectrometry (GC-MS) results, and their photodegradation pathways were proposed.

Occurrence and behavior of selected pharmaceuticals during riverbank filtration in The Republic of Serbia.

The objectives of the research are to determine the occurrence of pharmaceuticals in surface water and groundwater in the Republic of Serbia and to identify significant effects of river-water purification through riverbank filtration, concerning oxic conditions and hydrogeological conditions of alluvial aquifers in Serbia. Between 2009 and 2015, a total of 19 studied pharmaceuticals and metabolites were analyzed in 184 samples, 10 were detected in surface water, and 8 in groundwater. Carbamazepine and metamizole metabolites N-acetyl-4-amino-antipyrine (4-AAA) and N-formyl-4-amino-antipyrine (4-FAA) have the highest frequency of occurrence in surface water (57.3-68.8 %) and in groundwater (19.5-43.9 %), respectively. Highest detected concentrations were for 4-AAA (520 ng/L) and 4-FAA (248 ng/L) in surface water as well as in groundwater (4-AAA 128 ng/L and 4-FAA 150 ng/L). Results showed that riverbank filtration sites with different hydrogeological and oxic conditions could significantly remove investigated pharmaceuticals. Percentage of removal during riverbank filtration was determined for carbamazepine (65.4 %), trimethoprim (100 %), 4-AAA (91.2 %), and 4-FAA (70 %) for all investigated locations. Based on the available data for three specific locations (Danube River alluvion, Sava River alluvion, and Velika Morava River alluvion), results showed that besides oxic conditions, residence time of groundwater in alluvial aquifer and ratio of infiltrated water from river to the well play very important role in the quality of groundwater. These results are extremely important for better understanding of self-purification potential of alluvial aquifers and protection from potential impacts of anthropogenic pollution to the groundwater sources in the Republic of Serbia.

Mathematical modeling of cross-linking monomer elution from resin-based dental composites.

Elution of potentially toxic substances, including monomers, from resin-based dental composites may affect the biocompatibility of these materials in clinical conditions. In addition to the amounts of eluted monomers, mathematical modeling of elution kinetics reveals composite restorations as potential chronic sources of leachable monomers. The aim of this work was to experimentally quantify elution of main cross-linking monomers from four commercial composites and offer a mathematical model of elution kinetics. Composite samples (n = 7 per group) of Filtek Supreme XT (3M ESPE), Tetric EvoCeram (Ivoclar Vivadent), Admira (Voco), and Filtek Z250 (3M ESPE) were prepared in 2-mm thick Teflon moulds and cured with halogen or light-emitting diode light. Monomer elution in ethanol and water was analyzed using high-performance liquid chromatography up to 28 days postimmersion. The mathematical model was expressed as a sum of two exponential regression functions representing the first-order kinetics law. Elution kinetics in all cases followed the same mathematical model though differences in rate constants as well as the extent of monomer elution were material-, LCU-, medium-dependent. The proposed mechanisms of elution indicate fast elution from surface and subsurface layers and up to 100 times slower monomer extraction from the bulk polymer.

Methods for monitoring of pesticide residues in water: current status and recent trends.

An overview of analytical methods currently used for the determination of pesticide residues in water samples is presented. As liquid chromatography and gas chromatography, coupled to mass spectrometry, are considered to be the most appropriate techniques for determination of pesticides in environmental waters, the most recent developments and applications in this field are discussed, as well as the extraction procedures employed for analyte isolation and preconcentration.

Pharmaceutical residues in the Danube River Basin in Serbia - a two-year survey.

Pharmaceuticals are emerging contaminants with damaging effects to the environment and human health. Their presence in surface and especially groundwaters is regarded as detrimental, as they can ultimately reach drinking water. The aim of this work was to monitor pharmaceutical contamination of the Danube River and its tributaries in Serbia, and to assess the potential of their passing through all natural filtrations and reaching the groundwater. A total of 70 surface and groundwater samples was collected at 38 sampling sites at the Danube in Serbia. They were taken in five sampling campaigns performed in summer and autumn of 2009 and winter, spring and autumn of 2010. Samples were analyzed using a previously developed method which includes solid-phase extraction followed by liquid chromatography-tandem mass spectrometry.

Chemometrically assisted development and validation of LC-UV and LC-MS methods for simultaneous determination of torasemide and its impurities.

Complete evaluation of chromatographic behavior and establishment of optimal experimental conditions for determination of torasemide and its four impurities are determined by experimental design. Fractional factorial and 3(n) full factorial design were employed for efficient and rapid optimization of liquid chromatography-ultraviolet and liquid chromatography-mass spectrometry (LC-MS) methods. Separation is achieved on a Zorbax SB C(18) analytical column (250 x 4.6 mm, 5 µm) with mobile phase consisting of acetonitrile and 10 mM ammonium formate (pH 2.5 with formic acid) in gradient mode. The flow rate is 1 mL min(-1), the temperature of the column is 25 °C and UV detection is performed at 290 nm. The efficiency of ionization in electrospray ionization is higher than in atmospheric pressure chemical ionization mode; therefore, it is further used for analysis of torasemide and its impurities. Both methods meet all validation criteria. The calibration curves show high linearity with the coefficients of correlation (r) greater than 0.9982. The obtained recovery values (95.78-104.92%) and relative standard deviation values (0.12-5.56%) indicate good accuracy and precision. Lower limit of detection (LOD) and limit of quantitation (LOQ) values are obtained with the LC-MS method, indicating higher sensitivity of the proposed method.

Monomer elution from nanohybrid and ormocer-based composites cured with different light sources.

OBJECTIVES: To study monomer elution from four resin-based composites (RBCs) cured with different light sources. METHODS: Twenty-eight premolars were randomly allocated to four groups. Standardized cavities were prepared and restored with a nanohybrid (Filtek Supreme XT or Tetric EvoCeram), an ormocer (Admira) or a microhybrid RBC (Filtek Z250) which served as control. Buccal restorations were cured with a halogen and oral restorations with an LED light-curing unit. Elution of diurethane dimethacrylate (UDMA), Bisphenol A diglycidylether methacrylate (BisGMA), triethylene glycol dimethacrylate (TEGDMA) and 2-hydroxyethyl methacrylate (HEMA) was analyzed using high-performance liquid chromatography (HPLC) 1h to 28 days post-immersion in 75% ethanol. Data were analyzed using multivariate and repeated measures analysis of variance (α = 0.05). RESULTS: The greatest elution of UDMA and BisGMA occurred from Tetric EvoCeram and the least from Filtek Z250 (p < 0.05). LED and halogen light-curing units gave similar results for all RBCs (p > 0.05) except Tetric EvoCeram which showed greater elution for the LED unit (p < 0.05). TEGDMA was below the limit of quantification. HEMA eluted in similar concentrations from Filtek Supreme and Tetric EvoCeram (p > 0.05). SIGNIFICANCE: The two nanohybrid RBCs eluted more cross-linking monomers than the ormocer and the control microhybrid RBC. Continuous elution over 28 days indicates that RBCs act as a chronic source of monomers in clinical conditions. Light source may affect monomer elution since differences were found for one out of four RBCs. Mathematical models for elution kinetics of UDMA and BisGMA indicated two elution mechanisms.

Determination of pesticides in surface and ground waters by liquid chromatography-electrospray-tandem mass spectrometry.

The sensitive multiresidual analytical method for simultaneous analysis of 14 most commonly used agricultural pesticides in Serbia was developed and optimized. The selected insecticides, fungicides and herbicides belong to seven chemical classes (organophosphates, neonicotinoids, carbamates, diacylhydrazines, benzimidazoles, triazines and phenylureas). The method was based on solid-phase extraction followed by liquid chromatography-tandem mass spectrometry. The following parameters that may affect the SPE procedure efficiency were optimized: the sorbent type in combination with different elution solvents, the sample pH and the sample volume. For each pesticide, MS(n) analysis was performed and distinctive ions and transitions were selected for identification and quantification, as well as for confirmation purposes. External matrix-matched calibration method was used to eliminate variable matrix effect and ensure precise quantification. Good recoveries (72-129%), and low limits of detection (0.4-5.5 ng L(-1)) and quantification (1.1-18.2 ng L(-1)) were achieved for all selected pesticides. The developed and optimized method was successfully applied in the analysis of several river waters, as well as ground waters in Serbia, influenced by agriculture. The most frequently detected pesticide was carbendazim. Dimethoate, carbofuran and propazine were also found in the investigated samples.

Determination of carbendazim residues in fruit juices by liquid chromatography-tandem mass spectrometry.

In this paper a rapid optimized method for routine analysis of carbendazim residues in fruit juices is reported. The procedure is based on matrix solid-phase dispersion (MSPD) with diatomaceous earth and analysis of the extract by liquid chromatography-tandem mass spectrometry, with electrospray ionization (LC-ESI-MS/MS). In the method optimization, finding of the optimal pH for the extraction of carbendazim from juice was particularly critical. Significant matrix effects were observed, but could be eliminated using matrix-matched standards. High recoveries (82-102%), good repeatability (RSD