High sensitive multiresidue analysis of pharmaceuticals and antifungals in surface water using U-HPLC-Q-Exactive Orbitrap HRMS. Application to the Danube river basin on the Romanian territory

<p>The occurrence of 67 pharmaceutical and antifungal residues in the Danube river on the Romanian territory was studied by using solid-phase extraction (SPE) and LC-Q Exactive Orbitrap high resolution MS in both full scan (FS) MS and targeted MS/MS modes. A single-laboratory validation procedure was carried out for the determination of 67 compounds in FSMS mode evaluating selectivity, sensitivity, linearity, precision and accuracy. The method showed satisfactory analytical performance. The evaluation of the recovery concluded that 75% of the compounds show recoveries between 85 and 115% and 10% of the compounds show recoveries between 85% and 65%. The level of detection was lower than 5ngl^-1 for 66% of the compounds, between 5 and 10ngl^-1 for 22% and between 10 and 25ngl^-1 for 14% of the compounds. The coefficients of determination R² were higher than 0.99 for 79% of the compounds, over a linearity range of 2.5-50ngl^-1. Targeted MS/MS analysis, performed in addition to the full scan acquisition was used for confirmatory purpose.Twenty samples of Danube water and three of the main tributaries were collected in May, July, August and October 2014. Analysis of the selected water samples revealed the occurrence of 23 compounds such as diclofenac, carbamazepine, sulfamethoxazole, tylosin, indomethacin, ketoprofen, piroxicam, together with antifungals like thiabendazole, and carbendazim. Carbamazepine was detected in 17 samples, the maximum concentration being 40ngl^-1. The highest concentration reached was 166ngl^-1 for diclofenac.</p

Quantitative modelling to estimate the transfer of pharmaceuticals through the food production system

Use of pharmaceuticals in animal production may cause an indirect route of contamination of food products of animal origin. This study aimed to assess, through mathematical modelling, the transfer of pharmaceuticals from contaminated soil, through plant uptake, into the dairy food production chain. The scenarios, model parameters, and values refer to contaminants in emission slurry production, storage time, immission into soil, plant uptake, bioaccumulation in the animal's body, and transfer to meat and milk. Modelling results confirm the possibility of contamination of dairy cow's meat and milk due the ingestion of contaminated feed by the cattle. The estimated concentration of pharmaceutical residues obtained for meat ranged from 0 to 6 ng kg-1 for oxytetracycline, from 0.011 to 0.181 µg kg-1 for sulfamethoxazole, and from 4.70 to 11.86 µg kg-1 for ketoconazole. The estimated concentrations for milk were: zero for oxytetracycline, lower than 40 ng L-1 for sulfamethoxazole, and from 0.98 to 2.48 µg L-1 for ketoconazole. Results obtained for the three selected pharmaceuticals indicate a minor risk for human health. This study showed that supply chain modelling could be an effective tool in assessing the indirect contamination of feedstuff and animal products by residues of pharmaceuticals. The model can easily be adjusted to other contaminants and supply chain and, in this way, present a valuable tool to underpin decision making

Quantitative modelling to estimate the transfer of pharmaceuticals through the food production system

Use of pharmaceuticals in animal production may cause an indirect route of contamination of food products of animal origin. This study aimed to assess, through mathematical modelling, the transfer of pharmaceuticals from contaminated soil, through plant uptake, into the dairy food production chain. The scenarios, model parameters, and values refer to contaminants in emission slurry production, storage time, immission into soil, plant uptake, bioaccumulation in the animal's body, and transfer to meat and milk. Modelling results confirm the possibility of contamination of dairy cow's meat and milk due the ingestion of contaminated feed by the cattle. The estimated concentration of pharmaceutical residues obtained for meat ranged from 0 to 6 ng kg-1 for oxytetracycline, from 0.011 to 0.181 µg kg-1 for sulfamethoxazole, and from 4.70 to 11.86 µg kg-1 for ketoconazole. The estimated concentrations for milk were: zero for oxytetracycline, lower than 40 ng L-1 for sulfamethoxazole, and from 0.98 to 2.48 µg L-1 for ketoconazole. Results obtained for the three selected pharmaceuticals indicate a minor risk for human health. This study showed that supply chain modelling could be an effective tool in assessing the indirect contamination of feedstuff and animal products by residues of pharmaceuticals. The model can easily be adjusted to other contaminants and supply chain and, in this way, present a valuable tool to underpin decision making

Distribuição espacial, sazonal e estrutura populacional do caranguejo Aratus pisonii (H. Milne Edwards) (Crustacea, Decapoda, Sesarmidae) do manguezal de Itacuruçá, Rio de Janeiro, Brasil Spatial and seasonal distribution and population structure of the crab Aratus pisonii (H. Milne Edwards) (Crustacea, Decapoda, Sesarmidae) in Itacuruçá mangrove, Rio de Janeiro, Brazil

Este trabalho teve por objetivo analisar a distribuição espacial e sazonal e a estrutura populacional do caranguejo arborícula Aratuspisonii (H. Milne Edwards, 1837). O trabalho foi realizado através de coletas mensais de junho de 2000 a maio de 2001, para estudo da estrutura populacional e coletas sazonais de janeiro a outubro de 2002 para o estudo da distribuição espacial e sazonal, dividiu-se o manguezal em três áreas. Para a distribuição espacial e sazonal foram capturados 694 indivíduos sendo 45% na área 1, 36% na área 2 e 19% na área 3. O número de indivíduos apresentou diferença significativa na distribuição espacial entre as áreas 2 e 3. Para o estudo da estrutura populacional foi capturado um total de 742 caranguejos, sendo 59% machos, 32,7% fêmeas e 8,3% fêmeas ovígeras. A razãosexual obtida foi de 1: 0,69 (macho:fêmea) e a largura da carapaça variou de 9,6 a 25,0 mm em machos e de 5,5 a 24,9 mm em fêmeas. A distribuição da freqüência em classes de tamanho foi unimodal e os machos foram mais freqüentes entre as classes de 19,1 a 21,0 mm LC, enquanto as fêmeas entre 17,1 a 19,0 mm LC. A razão sexual ao longo de cada classe de tamanho demonstrou predominância de machos em quase todas as classes, exceto entre as classes de 5,1 a 7,0 e 7,1 a 9,0 mm de LC.<br>This work was performed by monthly sampling from June 2000 to May 2001 for population structure studies and by seasonal sampling from January to October 2002 for space and seasonal distribution studies, dividing the mangrove in three different areas. On the space-seasonal distribution study, 694 crabs were caught, where 45% was captured in area 1,36% in area 2 and 19% in area 3. There were significant differences between the number of individuals between area 2 and 3. For the population structure study a total of 742 crabs were captured, being 59% male, 32.7% female and 8.3% ovigerous females. The sex ratio was 1:0.69 (male:female), and the carapace width ranged from 9.6 to 25.0 mm CW in males and from 5.5 to 24.9 mm CW in females. The size class distribution was unimodal and the males were more frequent between 19.1 to 21.0 mm CW, while females between 17.1 to 19 mm CW. The sex ratio along each size class showed the male predominance in almost all classes except between the classes of 5.1 to 7.0 and 7.1 to 9.0 mm CW

Decentralization and the development of nationalized party systems in new democracies: evidence from Latin America

The extent to which a party system is nationalized—with nationalization being defined as the degree to which major political parties obtain similar vote shares throughout the national territory—has considerable consequences for political representation, public policy making, and even the survival of democracy. Yet, so far there is little empirical evidence about the conditions that promote or inhibit the development of nationalized party systems in new democracies. Using electoral data from 89 elections in 16 Latin American democracies, this article provides a systematic analysis of the effect of decentralization on party system nationalization. The results show that political decentralization and fiscal decentralization inhibit the development of nationalized party systems, thus suggesting that a trade-off exists between decentralized governance and party system nationalization. These results are robust when controlling for ethnolinguistic fractionalization and characteristics of the electoral system