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In this study, analysis of variance (ANOVA), cluster analysis (CA) and principal component analysis (PCA) were employed in order to evaluate the concentration profile of organic contaminants found in three main river from central Transylvania, Romania. Samples were collected from nine sampling stations, in two different sampling campaigns (wet season and dry season). Water samples were extracted using solid-phase extraction and analyzed using gas chromatography coupled with mass spectrometry (GC/MS). Twelve organic pollutants belonging to different classes were used for further interpretations. ANOVA highlighted compounds which distinguished Olt River from Mures River, and compounds that are influenced by increased river flow from the wet season. CA was applied to group the sampling stations. Three clusters were obtained, according to their organic load. PCA extracted five principal components explaining 87.330% from data set variability. Based on these results, a future monitoring study may be optimized by reducing the sampling points and compounds to those that are representative for each river, thereby reducing costs, without any information loss.

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The Prut River, the second longest tributary of the Danube river, was investigated for a wide range of anthropogenic organic pollutants to fill the data gap on environmental contamination in eastern European surface waters. In this study, the occurrence of a wide range of organic pollutants was measured along the transboundary Prut River, between Sculeni and Branza in 2010-2012. Using two different analytical methods, gas chromatography coupled to mass spectrometry and liquid chromatography coupled to high-resolution mass spectrometry, over 300 compounds were screened for and 88 compounds were determined in the Prut River. In general, the chemicals occurred at low levels. At the last sampling site upstream of the confluence with the Danube river at Branza, the highest average concentrations (≥ 100 ng L) were determined for the artificial sweetener acesulfame, the pharmaceuticals metformin, 4-acetamidoantipyrene, and 4,4,5,8-tetramethylchroman-2-ol, the antioxidants 2,4-di-tert-butylphenol, 3-tert-butyl-4-hydroxyanisol, and 3,5-di-tert-butyl-4-hydroxy-toluene, the personal care products HHCB (galaxolide), 4-phenyl-benzophenone, and octyl dimethyl-p-aminobenzoic acid, the industrial chemical diphenylsulfone, and the sterol cholesterol. Low concentrations of agricultural pesticides occurred in the catchment. At Branza, the total accumulated load of all measured compounds was calculated to be almost 19 kg day. In comparison to the Rhine River, the loads in the Prut, determined with same LC-HRMS method for the same set of analytes, were two orders of magnitude lower. Discharge of wastewater without proper treatment from the city of Iasi in the Jijia catchment (Romania) as well as from the city of Cahul (Moldova) revealed a distinct increase in concentrations and loads in the Prut at Frasinesti and Branza. Thus, an implementation of wastewater treatment capacities in the Prut River basin would considerably reduce the loads of micropollutants from urban point sources.

Background, aim, and scope Pharmaceutically active substances are a class of emerging contaminants, which has led to increasing concern about potential environmental risks. After excretion, substantial amounts of unchanged pharmaceuticals and their metabolites are discharged into domestic wastewaters. The absence of data on the environmental exposure in Eastern Europe is significant, since use patterns and volumes differ from country to country. In Romania, the majority of wastewater, from highly populated cities and industrial complex zones, is still discharged into surface waters without proper treatment or after inefficient treatment. In respect to this, it is important to determine the environmental occurrence and behavior of pharmaceuticals and personal care products (PPCPs) in wastewaters and surface waters. The objective of the present study was to investigate the occurrence of selected PPCPs during the transport in the Somes River by mass flow analysis before and after upgrading a municipal wastewater treatment plant (WWTP) in Cluj-Napoca, which serves 350,000 inhabitants and is the largest plant discharging into the Somes River. The concentrations of PPCPs at Cluj-Napoca can be correlated with the high population and a high number of hospitals located in the catchment area leading to higher mass flows. The results of this study are expected to provide information, with respect to the Romanian conditions, for environmental scientists, WWTP operators, and legal authorities. The data should support the improvement of existing WWTPs and implementation of new ones where necessary and, therefore, minimize the input of contaminants into ambient waters. Materials and methods The PPCPs were selected on the basis of consumption at the regional scale, reported aquatic toxicity, and the suitability of the gas chromatography/mass spectrometry (GC/MS) method for the determination of the compounds at trace levels. The studied PPCPs, caffeine (stimulant), carbamazepine (antiepileptic), pentoxifylline (anticoagulant), cyclophosphamide (cytostatic), ibuprofen (analgesic), and galaxolide (musk fragrance), were determined in samples of the Somes River. The analytes were enriched by solid-phase extraction and subsequently determined by GC/MS. Caffeine, pentoxifylline, and galaxolide were determined underivatized, whereas the acidic pharmaceuticals carbamazepine, cyclophosphamide, and ibuprofen were determined after derivatization with N-methyl-N-(trimethylsilyl)-trifluoroacetamide. Results and discussion The concentrations in the Somes River varied from below 10 ng/L up to 10 μg/L. A substantial decrease of the exposure in the Somes River could be observed due to the upgrade of the municipal WWTP in Cluj-Napoca. The loads in the river stretch between Cluj-Napoca and Dej (Somes Mic) varied strongly:Environ Sci Pollut Res (2009) 16 (Suppl 1):S46-S54

The mass flows of selected pharmaceuticals and personal care products (PPCPs) were studied in the aqueous compartment of the river Somes in Romania. PPCPs were measured in wastewater treatment effluents and in the receiving river water. The analytical method for the determination of PPCPs in river water was based on solid phase extraction and GC-ITMS. Carbamazepine, pentoxyfylline, ibuprofen, diazepam, galaxolide, tonalide and triclosan were determined in wastewater effluents with individual concentrations ranging from 15 to 774 ng L(-1). Caffeine was measured at concentrations up to 42 560 ng L(-1). Due to the high contamination of WWTP effluents, the receiving river was also polluted. The most abundant PPCPs measured in the Somes were caffeine, galaxolide, carbamazepine and triclosan. They were present at all the 15 sampling sites along the Somes, the concentrations ranging from 10 to 400 ng L(-1). The concentrations in the effluents of the different wastewater treatment plants (WWTPs) varied considerably and the differences are due to different elimination efficiencies of the studied PPCPs during sewage treatment. Only one of 5 WWTPs studied, the WWTP in Cluj-Napoca, was working properly, and therefore technical measures have to be taken for upgrading the WWTPs and reducing the environmental load of micropollutants. This study is the first overview of PPCPs along on Romanian part of river Somes.

In order to investigate the minor volatile compounds of traditional homemade fruit brandies from Romania (Transylvania region), as a result of their assortment and provenience, a number of 26 samples (18 plum brandies samples from 3 different counties, 4 samples of apple brandy and 4 samples of pear brandy) were analyzed using liquid-liquid extraction and gas-chromatography coupled with mass-spectrometry (GC-MS) technique. The GC-MS chromatograms of the hexane extracts led to the identification of 34 compounds (9 terpenes, 14 fatty acids esters, 3 free fatty acids, 4 carboxylic acid esters, 1 hydrocarbon, 1 aldehyde and 1 acetal). The most abundant compounds were the fatty acid esters. Chemometric analysis (Principal Component Analysis-PCA) was applied to discriminate the differences between the volatiles’ fingerprint. Considering the plum brandy samples, significant differences have been observed according to their provenience region. Based on relative abundance of determined compounds important differences among samples from different counties can be seen.. Ethyl hexadecanoate was the main factor for this discrimination. When compared the three types of fruit brandies, significant differences were noticed for their content in ethyl esters of hexanoic, benzoic and hexadecanoic acids. For some plum brandies, according to their fingerprint, possible adulteration with apple brandy can be noted, based on their similar volatiles’ pattern. The pear brandy was strongly delimitated by the other two types of brandies. The PCA data showed a good discrimination according to the region of provenience of the plum brandies in parallel with the composition specificity of the three analyzed fruit brandies.