Determination of Pharmaceuticals in Coastal Systems Using Solid Phase Extraction (SPE) Followed by Ultra Performance Liquid Chromatography – tandem Mass Spectrometry (UPLC-MS/MS)

This paper describes the optimization and validation of an analytical method for the determination of 83 pharmaceutically active compounds (PhACs) in aqueous samples using solid-phase extraction (SPE) followed by ultra performance liquid chromatography-triple quadrupole mass spectrometry (UPLC-QqQ-MS/MS). First, several experiments were conducted to optimize different SPE extraction parameters such as pH, elution solvents, and Na2EDTA addition. Extraction recovery percentages were between 17 and 146%, being higher than 70% for 47 target analytes. The effect of salinity in the extraction efficiency proved to be negligible ( 90%), and the precision of the method, calculated as the relative standard deviation (RSD) of replicate extractions and analyses, was less than 20%. The optimized method was successfully applied to the analysis of real water samples in estuarine and coastal systems from SW Spain (Cadiz Bay and Huelva Estuary). 49 out of 83 target compounds were found in 75% of samples. Ibuprofen, atenolol, gemfibrozil and caffeine were the most commonly detected substances, reaching concentrations up to 195 ng L-1

High resolution mass spectrometry (HRMS) determination of drugs in wastewater and wastewater based epidemiology in Cadiz Bay (Spain)

Multi-residue methods for the determination of the myriad of compounds of emerging concern (CECs) entering in the environment are key elements for further assessment on their distribution and fate. Here, we have developed an analytical protocol for the simultaneous analysis of 195 prescription, over-the-counter, and illicit drugs by using a combination of solid phase extraction (SPE) and determination by liquid chromatography coupled to high resolution mass spectrometry (LC-HRMS). The method was applied to the analysis of influent sewage samples from 3 wastewater treatment plants (WWTPs) from Cadiz Bay (SW Spain), enabling the quantification of more than 100 pharmaceuticals, 19 of them at average concentrations higher than 1 μg L−1, including caffeine (92 μg L−1), paracetamol (72 μg L−1), and ibuprofen (56 μg L−1), as well as several illicit drugs (e.g., cocaine). Wastewater based epidemiology (WBE) was applied for 27 of the detected compounds to establish their consumption in the sampling area, which has been never attempted before. Caffeine, naproxen, and salicylic acid stood out because of their high consumption (638, 51, and 20 g d−1·1000pop−1, respectively). Regarding illicit drugs, cocaine showed the highest frequency of detection and we estimated an average consumption of 3683 mg d−1·1000pop−1 in Cadiz Bay. The combination of new HRMS methods, capable of discriminating thousands of chemicals, and WBE will allow for a more comprehensive characterization of chemical substances and their consumption in urban environments in the near future.The authors thank the staff from JF, CA and PR WWTPs for their assistance during sampling. This research was funded by Junta de Andalucía (ref. FEDER-UCA18-107036) through the FEDER Andalucía 2014-20 program

Removal of emerging pollutants in conventional and microalgae based biotechnology urban wastewater treatment plants

Wastewater treatment plants (WWTPs) reduce portion of the input of pharmaceuticals in aquatic systems, but there is no data available about the elimination of emerging contaminants with microalgae technology. The aim of this work was to determine the average mass flows and concentrations of pharmaceuticals in influents and effluents from two sewages treatment plants using conventional and microalgae based biotechnologies and to compare the removal of pharmaceuticals using both depuration technologies. Only between 20 to 60% of five pharmaceuticals groups is reduce in both WWTP using conventional technologies consisting of a pretreatment, primary settling and secondary treatment by aerobic biological reactor. Using microalgae based biotechnologies efficiency of removal pharmaceuticals is higher than conventional technologies and it increase by using DAF (Dissolve Air Flotation) technology to separate algae biomass

Synthetic surfactants in Swiss sewage sludges: Analytical challenges, concentrations and per capita loads

Surfactants are high-production-volume chemicals that are among the most abundant organic pollutants in municipal wastewater. In this study, sewage sludge samples of 36 Swiss wastewater treatment plants (WWTPs), serving 32% of the country's population, were analyzed for major surfactant classes by liquid chromatography mass spectrometry (LC-MS). The analyses required a variety of complementary approaches due to different analytical challenges, including matrix effects (which can affect adduction formation) and the lack of reference standards. The most abundant contaminants were linear alkylbenzene sulfonates (LAS; weighted mean [WM] concentration of 3700 mu g g(-1) dry weight), followed by secondary alkane sulfonates (SAS; 190 mu g g(-1)). Alcohol polyethoxylates (AGO; 8.3 mu g g(-1)), nonylphenol polyethoxylates (NPEO; 16 mu g g(-1)), nonylphenol (NP; 3.1 mu g g(-1)), nonylphenol ethoxy carboxylates (NPEC; 0.35 mu g g(-1)) and ten-octylphenol (tert-OP, 1.8 mu g g(-1)) were present at much lower concentrations. This concentration pattern agrees with the production volumes of the surfactants and their fates in WWTPs. Branched AEO homologues dominated over linear homologues, probably due to higher persistence. Sludge concentrations of LAS, SAS, and NP were positively correlated with the residence time in the anaerobic digester. Derivation of the per capita loads successfully revealed potential industrial/commercial emission sources. Comparison of recent versus historic data showed a decrease in NPEO and NP levels by one or two orders of magnitude since their ban in the 1980s. By contrast, LAS still exhibit similar concentrations compared to 30 years ago

Multi-omic approach to evaluate the response of gilt-head sea bream (Sparus aurata) exposed to the UV filter sulisobenzone

Sulisobenzone (BP-4) is one of the benzophenone type UVfiltersmost frequently detected in aquatic ecosystems. As a suspected endocrine disrupting compound, scarce information is available yet about other molecular effects and its mechanismof action. Here, we used an integrated transcriptomic and metabolomic approach to improve the current understanding on the toxicity of BP-4 towards aquatic species. Gilt-head sea bream individualswere exposed at environmentally relevant concentrations (10 μg L-1) for 22 days. Transcriptomic analysis revealed 371 differentially expressed genes in liver while metabolomic analysis identified 123 differentially modulated features in plasma and 118 in liver. Integration of transcriptomic and metabolomic data showed disruption of the energy metabolism(>10 pathways related to the metabolismof amino acids and carbohydrateswere impacted) and lipid metabolism (5 glycerophospholipids and the expression of 3 enzymes were affected), suggesting oxidative stress.We also observed, for the first time in vivo and at environmental relevant concentrations, the disruption of several enzymes involved in the steroid and thyroid hormones biosynthesis. DNA and RNA synthesis was also impacted by changes in the purine and pyrimidine metabolisms. Overall, the multiomic workflow presented here increases the evidence on suspected effects of BP-4 exposure and identifies additional modes of action of the compounds that could have been overlooked by using single omic approaches. ©2021 The Authors. Published by Elsevier B.V.This research was supported by the Spanish Ministry of Economy, Industry and Competitiveness (MINECO) (CTM2015-70731-R) and the FPI fellowship (BES-2016-078593). The authors also would like to acknowledge the Laboratory of Aquaculture at the Faculty of Marine and Environmental Sciences (University of Cádiz), Thibaut Dumas and David Rosain (UMR HydroSciences, Université Montpellier, France) for their support

Structural control of the non-ionic surfactant alcohol ethoxylates (AEOs) on transport in natural soils

Surfactants, after use, enter the environment through diffuse and point sources such as irrigation with treated and non-treated waste water and urban and industrial wastewater discharges. For the group of non-ionic synthetic surfactant alcohol ethoxylates (AEOs), most of the available information is restricted to the levels and fate in aquatic systems, whereas current knowledge of their behavior in soils is very limited. Here we characterize the behavior of different homologs (C12-C18) and ethoxymers (E03, E06, and E08) of the AEOs through batch experiments and under unsaturated flow conditions during infiltration experiments. Experiments used two different agricultural soils from a region irrigated with reclaimed water (Guadalete River basin, SW Spain). In parallel, water flow and chemical transport were modelled using the HYDRUS-1D software package, calibrated using the infiltration experimental data. Estimates of water flow and reactive transport of all surfactants were in good agreement between infiltration experiments and simulations. The sorption process followed a Freundlich isotherm for most of the target compounds. A systematic comparison between sorption data obtained from batch and infiltration experiments revealed that the sorption coefficient (K-d) was generally lower in infiltration experiments, performed under environmental flow conditions, than in batch experiments in the absence of flow, whereas the exponent (beta) did not show significant differences. For the low clay and organic carbon content of the soils used, no clear dependence of K-d on them was observed. Our work thus highlights the need to use reactive transport parameterization inferred under realistic conditions to assess the risk associated with alcohol ethoxylates in subsurface environments. (C) 2020 The Authors. Published by Elsevier Ltd

Fast 4D elastic group-wise image registration. Convolutional interpolation revisited

Background and Objective:This paper proposes a new and highly efficient implementation of 3D+t groupwise registration based on the free-form deformation paradigm. Methods:Deformation is posed as a cascade of 1D convolutions, achieving great reduction in execution time for evaluation of transformations and gradients. Results:The proposed method has been applied to 4D cardiac MRI and 4D thoracic CT monomodal datasets. Results show an average runtime reduction above 90%, both in CPU and GPU executions, compared with the classical tensor product formulation. Conclusions:Our implementation, although fully developed for the metric sum of squared differences, can be extended to other metrics and its adaptation to multiresolution strategies is straightforward. Therefore, it can be extremely useful to speed up image registration procedures in different applications where high dimensional data are involved.MEC-TEC2017-82408-

Un viaje al Cosmos en 52 semanas

230 p.Este libro se plantea como una serie de artículos que dibujan un recorrido por el Universo, desde lo más cercano a lo más distante. Constituye una herramienta útil y actualizada para los interesados en la astronomía, y combina el conocimiento básico con los resultados científicos más novedosos. La astrofísica constituye una ciencia viva y en permanente avance por ello nos encontramos con un Plutón que ya no es considerado planeta; con nuevos datos sobre la posible presencia de agua en Marte; con géiseres en Encelado, un pequeño satélite de Saturno que se creía geológicamente inactivo; con una miríada de nuevos planetas girando alrededor de otras estrellas; con, quizá, un nuevo tipo de agujero negro y fascinantes resultados sobre las explosiones cortas de rayos gamma, uno de los eventos más energéticos del Universo y, hasta hace poco, también uno de los más desconocidos; con la mision COROT, y otras, como BepiColombo, que ya se encuentran en su fase de desarrollo instrumental.Peer reviewe

Amphilimus- vs. zotarolimus-eluting stents in patients with diabetes mellitus and coronary artery disease: the SUGAR trial

Aim: Patients with diabetes mellitus are at high risk of adverse events after percutaneous revascularization, with no differences in outcomes between most contemporary drug-eluting stents. The Cre8 EVO stent releases a formulation of sirolimus with an amphiphilic carrier from laser-dug wells, and has shown clinical benefits in diabetes. We aimed to compare Cre8 EVO stents to Resolute Onyx stents (a contemporary polymer-based zotarolimus-eluting stent) in patients with diabetes. Methods and results: We did an investigator-initiated, randomized, controlled, assessor-blinded trial at 23 sites in Spain. Eligible patients had diabetes and required percutaneous coronary intervention. A total of 1175 patients were randomly assigned (1:1) to receive Cre8 EVO or Resolute Onyx stents. The primary endpoint was target-lesion failure, defined as a composite of cardiac death, target-vessel myocardial infarction, and clinically indicated target-lesion revascularization at 1-year follow-up. The trial had a non-inferiority design with a 4% margin for the primary endpoint. A superiority analysis was planned if non-inferiority was confirmed. There were 106 primary events, 42 (7.2%) in the Cre8 EVO group and 64 (10.9%) in the Resolute Onyx group [hazard ratio (HR) 0.65, 95% confidence interval (CI) 0.44 to 0.96; pnon-inferiority <0.001; psuperiority = 0.030]. Among the secondary endpoints, Cre8 EVO stents had significantly lower rate than Resolute Onyx stents of target-vessel failure (7.5% vs 11.1%, HR 0.67, 95% CI 0.46 to 0.99; p = 0.042). Probable or definite stent thrombosis and all-cause death were not significantly different between groups. Conclusions: In patients with diabetes, Cre8 EVO stents were non-inferior to Resolute Onyx stents with regard to target-lesion failure composite outcome. An exploratory analysis for superiority at 1 year suggests that the Cre8 EVO stents might be superior to Resolute Onyx stents with regard to the same outcome

Aplicación de la metodología aprendizaje-servicio en la asignatura "Clínica jurídica de acción social" de la Facultad de Derecho

Memoria ID-149. Ayudas de la Universidad de Salamanca para la innovación docente, curso 2019-2020