Steroid-based tracing of sewage-sourced pollution of river water and wastewater treatment efficiency: Dissolved and suspended water phase distribution.

In this work, the environmental distribution of steroid compounds and the level of sewage-derived contamination were assessed using sterol ratios in the confluence area of two major rivers in the Serbian capital, where raw sewage is discharged without any treatment. Special attention was paid to steroids partitioning between the dissolved and suspended phases of river and wastewater samples, since steroids tend to easily bind to particulate matter. The efficiency of sterol removal in two wastewater treatment plants in Serbia was also evaluated. Human/animal sterols coprostanol and cholesterol, and phytosterol ß-sitosterol were the dominant compounds in all water samples. The sterol abundance pattern in river water was different from that in raw sewage, indicating a more pronounced biogenic input, as well as greater impact of wastewater discharges on the composition of the suspended phase. Severe contamination of the investigated area was determined, with the Danube being more contaminated than the Sava River due to different hydrodynamic conditions leading to significantly higher sterol levels in the suspended particulate matter. It was also shown that the greater part of human/animal sterols and phytosterols present in river water samples (83.0 ±â€¯11.9 % and 87.1 ±â€¯15.2 %) and wastewater samples (92.1 ±â€¯6.8 % and 95.0 ±â€¯5.7 %) was bound to suspended material compared to the dissolved phase, emphasizing the need to consider and analyze both water phases in the tracing of steroid-based environmental pollution in order to obtain a realistic picture of steroid contamination and their fate in the aquatic environment. A high removal rate (>98 %) of coprostanol and cholesterol during wastewater treatment was determined and only the coprostanol/(coprostanol + cholestanol) ratio was found to be sensitive enough to be affected by an improvement in the quality of treated wastewater.

Emerging contaminants in sediment core from the Iron Gate I Reservoir on the Danube River.

The Iron Gate I Reservoir is the largest impoundment on the Danube River. It retains >50% of the incoming total suspended solids load and the associated organic contaminants. In the sediment core of the Iron Gate I Reservoir we report the presence and fate of four classes of emerging contaminants (pharmaceuticals, pesticides, steroids and perfluorinated compounds), predominantly not covered by the EU monitoring programs, but considered as future candidates. Based on contaminant's partitioning behavior in the water/sediment system and the suspected ecotoxicological potential asserted from the literature data, the risk of recorded concentrations for sediment-dwelling organisms was discussed. The high anticipated risk was associated with antibiotics sulfamethoxazole and erythromycin, and pesticides linuron and carbendazim (banned in the EU, but still approved for use in the investigated area) and malathion. This indicated the need for better control of release of these compounds into the river, and implied their inclusion in future regular monitoring. Higher concentrations of pharmaceuticals and most pesticides and sterols were recorded in the fragment of allochthonous coarser sediment, assumed to have entered the reservoir during a high discharge event. Only one perfluorinated compound was recorded in the upper part of the sediment core. The vertical concentration profiles of pesticides propazine and malathion indicated their uniform source, most likely atmospheric transport and deposition of particles deriving from agricultural land.

Nutrient Composition of Three Mangulica Pork Cuts from Serbia.

The purpose of this study was to analyze and evaluate the levels of essential elements (Mn, Fe, Cu, Zn, and Se) and proximate composition (moisture, protein, fat, and ash) of three pork cuts (loin, hind leg, and shoulder) from free-range Mangulica pigs from Serbia. Essential elements were determined by inductively coupled plasma mass spectrometry (ICP-MS). Shoulder contained the highest levels of essential elements (Mn, 0.192 mg kg-1; Fe, 19.550 mg kg-1; Cu, 1.490 mg kg-1; Zn, 44.470 mg kg-1; and Se, 0.130 mg kg-1). The shoulder and hind leg cut differed significantly from the loin in Mn, Fe, Cu, and Zn levels. This study showed that Mangulica pork is a rich source of Fe and Zn, and these elements showed significant correlations for a range of tissue combinations. The highest levels of protein (21.15 g/100 g) and fat (10.60 g/100 g) were established in loin, and the highest moisture level occurred in shoulder (72.02 g/100 g). Statistically, significant differences were established only between loin and shoulder in protein and fat contents.

Development and validation of a stability-indicating LC-UV and LC-MS/MS methods for quantitative analysis of anisomycin and identification of degradation products

ABSTRACT Multifunctional drug anisomycin was subjected to forced degradation in accordance with International Conference on Harmonisation (ICH) guidelines for the first time. The drug was exposed to the recommended stress conditions of hydrolysis (acidic, alkaline and neutral), oxidation, thermal stress and photolysis, in order to investigate its stability. Optimized LC-MS/MS method was validated as recommended by ICH Q2(R1) guideline with respect to the specificity, accuracy, precision, limits of detection and quantitation, linearity and robustness. Anisomycin exhibited high instability under alkaline and thermal (neutral hydrolysis) conditions. It showed moderate stability under acidic, neutral, oxidative, thermal (acidic hydrolysis) and photolytic conditions, with the lowest degradation level observed in the case of light and oxidation stress. Formation of the same degradation product, identified as deacetylanisomycin, was observed under all applied stress conditions.

Solid-phase extraction of multi-class pharmaceuticals from environmental water samples onto modified multi-walled carbon nanotubes followed by LC-MS/MS.

In this paper, pristine and chemically treated multi-walled carbon nanotubes (MWCNTs) were employed as solid-phase extraction sorbents for the isolation and enrichment of multi-class pharmaceuticals from the surface water and groundwater, prior to liquid chromatography-tandem mass spectrometry analysis. Thirteen pharmaceuticals that belong to different therapeutical classes (erythromycin, azithromycin, sulfamethoxazole, diazepam, lorazepam, carbamazepine, metoprolol, bisoprolol, enalapril, cilazapril, simvastatin, clopidogrel, diclofenac) and two metabolites of metamizole (4-acetylaminoantipyrine and 4-formylaminoantipyrine) were selected for this study. The influence of chemical treatment on MWCNT surface characteristics and extraction efficiency was studied, and it was shown that HCl treatment of MWCNT leads to a decrease in the amount of surface oxygen groups and at the same time favorably affects the efficiency toward extraction of selected pharmaceuticals. After the optimization of the SPE procedure, the following conditions were chosen: 50 mg of HCl-treated MCWNT as a sorbent, 100 mL of water sample at pH 6, and 15 mL of the methanol-dichloromethane mixture (1:1, v/v) as eluent. Under optimal conditions, high recoveries (79-119%), as well as low detection (0.2 to 103 ng L-1) and quantitation (0.5-345 ng L-1) limits, were obtained. The optimized method was applied to the analysis of five surface water and two groundwater samples, and three pharmaceuticals were detected, the antiepileptic drug carbamazepine and two metabolites of antipyretic metamizole.

Mineral composition and toxic element levels of muscle, liver and kidney of intensive (Swedish Landrace) and extensive (Mangulica) pigs from Serbia.

Mineral composition (Fe, Zn, Cu, Mn, Se, Cr, Co, Ni, Na, K, Mg, Ca) and toxic element levels (Cd, Pb, Hg, As) of soil, feed and tissue (muscle, liver and kidney) from intensive (Swedish Landrace, housed indoors, fed a known diet, 4 years) and extensive (Mangulica, free-roaming, non-specified diet, 7-8 months) pigs were determined by inductively coupled plasma mass spectrometry (ICP-MS). Controlled nutrition produced pigs with higher concentrations of most minerals (muscle: Mn, Se, K, Mg; liver: Zn, Cu, Mn, Se, Cr, Ca; kidney: Zn, Cu, Mn, Se, K, Mg), but for Fe the opposite trend was found. Long-term free-ranging pigs have a higher risk of contamination by toxic elements (Cd exceeded the maximum residue level in kidney). Principal component analysis and cluster analysis were used to assess the effect of different pig breed/lifestyle (pig type) on element composition of muscle, liver and kidney of pigs. Multivariate data analysis showed good discriminating capabilities.

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.

Sorption of selected pharmaceuticals and pesticides on different river sediments.

In the present work, the sorption ability of 17 pharmaceutical compounds, two metabolites, and 15 pesticides (34 target compounds in total) onto four different river sediments was investigated separately. Selected compounds present the most frequently prescribed pharmaceuticals in human and animal medicine and the most frequently used pesticides in agriculture. Their presence into the surface, ground, and waste waters was confirmed into the numerous papers in literature, as well as their presence into the river sediments (for some of them). However, investigations of their sorption onto the river sediments, as major natural protection from potential pollution of ground water by them is missing. Sorption in this study was investigated onto river sediments taken from rivers in the Republic of Serbia, where only less than 10 % of total generated waste water passes through mainly basic treatment processes. Experiments were based on batch equilibrium procedures and obtained solutions were analyzed by previously developed and validated sensitive high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) analytical methods. All results were modeled by Freundlich isotherms. Obtained results have shown that Kf coefficient values are in correlation with organic carbon content. Kd sorption coefficient values were relatively low and ranged in wide ranges for almost all compounds and sediments. That implicates on the conclusion that capacities of the investigated sorbents are not large for those compounds.

Alkali modified hydrochar of grape pomace as a perspective adsorbent of Pb(2+) from aqueous solution.

Hydrochar produced via hydrothermal carbonization of grape pomace was considered as novel sorbent of Pb(2+) from aqueous solution. In order to enhance the adsorption capacity, hydrochar was chemically modified using 2 M KOH solution. Both materials were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy and X-ray diffraction technique. Batch experiments were performed to examine the effect of sorbent dosage, pH and contact time. Obtained results showed that the KOH treatment increased the sorption capacity of hydrochar from 27.8 mg g(-1) up to 137 mg g(-1) at pH 5. Adsorption of lead on either of the materials was achieved through ion-exchange mechanism, chemisorption and Pb(2+)-π interaction. The Sips isotherm model gave the best fit with the experimental data obtained for Pb(2+) sorption using activated hydrochar. The adsorption kinetic followed a pseudo second-order model. Thermodynamic parameters implied that the Pb(2+) binding for hydrochar surface was spontaneous and exothermic process. Findings from this work suggest that the hydrothermal carbonization is a promising route for production of efficient Pb (2+) sorbents for wastewater treatment.

Sterol ratios as a tool for sewage pollution assessment of river sediments in Serbia.

In this work, source pollution tracing of the sediments of the Danube River and its tributaries in Serbia was performed using sterol ratios. Improved liquid chromatography-tandem mass spectrometry method, which enabled complete chromatographic separation of four analytes with identical fragmentation reactions (epicoprostanol, coprostanol, epicholestanol and cholestanol), was applied for the determination of steroid compounds (hormones, human/animal and plant sterols). A widespread occurrence of sterols was identified in all analyzed samples, whereas the only detected hormones were mestranol and 17α-estradiol. A human-sourced sewage marker coprostanol was detected at the highest concentration (up to 1939 ng g(-1)). The ratios between the key sterol biomarkers, as well as the percentage of coprostanol relative to the total sterol amount, were applied with the aim of selecting the most reliable for distinction between human-sourced pollution and the sterols originated from the natural sources in river sediments. The coprostanol/(cholesterol + cholestanol) and coprostanol/epicoprostanol ratios do not distinguish between human and natural sources of sterols in the river sediments in Serbia. The most reliable sterol ratios for the sewage pollution assessment of river sediments in the studied area were found to be coprostanol/(coprostanol + cholestanol), coprostanol/cholesterol and epicoprostanol/coprostanol. For the majority of sediments, human-derived pollution was determined. Two sediment samples were identified as influenced by a combination of human and natural biogenic sources.

Determination of pharmaceuticals and pesticides in river sediments and corresponding surface and ground water in the Danube River and tributaries in Serbia.

The aim of this study was the development of analytical methods for the simultaneous determination of 25 selected pharmaceuticals, metabolites, and pesticides, belonging to the various chemical classes, in river sediments and their corresponding surface and ground water with the purpose of monitoring the contamination levels. The methods were based on the solid-phase extraction as the sample preparation method for water samples, and the ultrasonic solvent extraction for the sediment samples, followed by the liquid chromatography-tandem mass spectrometry. High recoveries were achieved for extraction from both water and sediment samples for the majority of analytes. Low limits of detection were achieved for all investigated compounds in the water sample (1-5 ng L(-1)) as well as in the sediment (1-3 ng g(-1)). Applicability of the developed methods was demonstrated by determination of pharmaceutical and pesticide residues in 30 surface water, 44 groundwater, and 5 sediment samples from the Danube River Basin in Serbia. Sixty percent of target compounds were detected in environmental samples. The most frequently detected analytes in river sediments were the pesticides dimethoate and atrazine, while carbamazepine and metamizole metabolites 4-AAA and 4-FAA were the most frequently found in water samples.

Trace analysis of selected hormones and sterols in river sediments by liquid chromatography-atmospheric pressure chemical ionization-tandem mass spectrometry.

In this paper, development and optimization of new LC-MS method for determination of twenty selected hormones, human/animal and plant sterols in river sediments were described. Sediment samples were prepared using ultrasonic extraction and clean up with silica gel/anhydrous sodium sulphate cartridge. Extracts were analyzed by liquid chromatography-linear ion trap-tandem mass spectrometry, with atmospheric pressure chemical ionization. The optimized extraction parameters were extraction solvent (methanol), weight of the sediment (2 g) and time of ultrasonic extraction (3× 10 min). Successful chromatographic separation of hormones (estriol and estrone, 17α- and 17ß-estradiol) and four human/animal sterols (epicoprostanol, coprostanol, α-cholestanol and ß-cholestanol) that have identical fragmentation reactions was achieved. The developed and optimized method provided high recoveries (73-118%), low limits of detection (0.8-18 ng g(-1)) and quantification (2.5-60 ng g(-1)) with the RSDs generally lower than 20%. Applicability of the developed method was confirmed by analysis of six river sediment samples. A widespread occurrence of human/animal and plant sterols was found. The only detected hormone was mestranol in just one sediment sample.

Cardiovascular drugs in environmental waters and wastewaters: method optimization and real sample analysis.

A sensitive method for determination of the eight most prescribed drugs used in combined cardiovascular therapy in Serbia was developed and optimized. The method was based on SPE followed by LC/ion trap-MS/MS with positive electrospray ionization. Parameters that affect the SPE were optimized, such as the eluent, sample pH, and sample volume. Good recoveries from groundwater (87.6-120.9%) as well as wastewater (84.5-106.6%) were achieved with this method, except in the case of atorvastatin (26.1 and 45.2%, respectively). The method was applied in the analysis of four river water samples collected in Serbia, as well as nine corresponding groundwater samples. Residues of the P-blockers metoprolol and bisoprolol as well as the anticoagulant clopidogrel were detected for the first time in river water. Groundwater samples did not contain drug residues. Influents and effluents of two wastewater treatment plants showed the predominant presence of metoprolol and enalapril. The removal rate of metoprolol was generally low, whereas enalapril was eliminated with the highest efficiency. Atorvastatin was detected in influents and completely removed in the treatment.

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.

Release behaviour of carbamazepine-loaded poly(ε-caprolactone)/poly(ethylene oxide) microspheres.

Poly(ε-caprolactone) (PCL), a biodegradable and biocompatible aliphatic polyester has a great potential as a drug carrying material in controlled drug delivery/release systems. The most simple and economical way to tailor the release profile of active substances from biodegradable polymer matrix is by the addition of the second polymeric component in the polymer matrix, i.e. by blending. This study describes the preparation and characterization of a carbamazepine-loaded microspheres by the use of PCL blended with poly(ethylene oxide) as a drug carrying material. By the use of two-component hydrophilic/hydrophobic polymer blend as a microspheres' matrix material, release profile of the drug can be modified and dictated. The microspheres prepared by classical oil-in-water emulsion solvent evaporation technique were characterized with respect to particle size and morphology, polymer matrix composition, encapsulation efficiency, physical state of the drug and in vitro release behaviour. It was presented that the release profile can be modified by the presence and the amount of hydrophilic component in the starting formulation of microspheres.

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.

Photocatalytic degradation of metoprolol tartrate in suspensions of two TiO2-based photocatalysts with different surface area. Identification of intermediates and proposal of degradation pathways.

This study investigates the efficiency of the photocatalytic degradation of metoprolol tartrate (MET), a widely used ß(1)-blocker, in TiO(2) suspensions of Wackherr's "Oxyde de titane standard" and Degussa P25. The study encompasses transformation kinetics and efficiency, identification of intermediates and reaction pathways. In the investigated range of initial concentrations (0.01-0.1 mM), the photocatalytic degradation of MET in the first stage of the reaction followed approximately a pseudo-first order kinetics. The TiO(2) Wackherr induced a significantly faster MET degradation compared to TiO(2) Degussa P25 when relatively high substrate concentrations were used. By examining the effect of ethanol as a scavenger of hydroxyl radicals (OH), it was shown that the reaction with OH played the main role in the photocatalytic degradation of MET. After 240 min of irradiation the reaction intermediates were almost completely mineralized to CO(2) and H(2)O, while the nitrogen was predominantly present as NH(4)(+). Reaction intermediates were studied in detail and a number of them were identified using LC-MS/MS (ESI+), which allowed the proposal of a tentative pathway for the photocatalytic transformation of MET as a function of the TiO(2) specimen.