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.
This paper presents a case study of a massive fish mortality during a Cylindrospermopsis raciborskii bloom in Aleksandrovac Lake, Serbia in mid-December 2012. According to a preliminary investigation of the samples taken on November 6 before the fish mortalities and to extended analyses of samples taken on November 15, no values of significant physicochemical parameters emerged to explain the cause(s) of the fish mortality. No industrial pollutants were apparent at this location, and results excluded the likelihood of bacterial infections. Even after freezing, the dissolved oxygen concentration in the water was sufficient for fish survival. High concentrations of chlorophyll a and phaeophytin occurred in the lake, and phytoplankton bloom samples were lethal in Artemia salina bioassays. A bloom of the cyanobacterium C. raciborskii was recorded during November. Although the A. salina bioassays indicated the presence of toxic compounds in the cyanobacterial cells, the cyanotoxins, microcystins, cylindrospermopsin and saxitoxin were not detected.
In this work, a total of 38 pesticides was monitored in the Danube River Basin in Serbia during ten sampling campaigns in 2009, 2010, and 2011. The quantification of analytes was performed using procedures based on solid‐phase extraction (SPE) followed by LC–MS/MS or GC–MS. In general, low pesticide levels were found, except for the samples collected during May–June of 2010 and June of 2011. During this period, pesticide application is high and rainfall was described as extremely above normal or above normal, leading to very pronounced runoff and very high detected pesticide levels. At the sampling site Smederevo (the Danube River), high concentrations of terbuthylazine (200 ng L−1) and metolachlor (150 ng L−1) were found. In the Danube tributary Morava, high concentrations of carbendazim (269 ng L−1), atrazine (188 ng L−1), terbuthylazine (180 ng L−1), and acetochlor (110 ng L−1) were detected, while in the tributary Tisa only terbuthylazine was present at high levels (130 ng L−1). In other sampling campaigns, pesticides were present at low concentrations. The most frequently found pesticide was carbendazim, probably due to slow degradation rate in environment.
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.
Groundwater constitutes the largest reservoir of freshwater in the world (excluding glaciers and ice caps); thus it is major source of potable, agricultural and industrial water. According to the International Groundwater Resources Assessment Centre (IGRAC) [1], groundwater provides almost 50% of all drinking water worldwide, about 40% of water for irrigated agriculture and about 30% of water supply required for industry. Similar to the majority European countries, the contribution of groundwater to the water supply in Serbia is around 70%, of which more than 50% comes from alluvial aquifers [2]. These valuable resources are under increasing pressure due to different human activities (including population-and wealth growth) and climate change [1]. The water supply in the northern part of Serbia, Province of Vojvodina, depends only on groundwater resources [3]. Municipal and industrial water supplies in Vojvodina rely entirely on groundwater abstractions from the three types of aquifers: alluvial aquifers, the
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