A los ojos rectorales

La decisión de editar la revista Rued@ (Revista Universidad, Ética y derechos) por parte de las Defensorías Universitarias constituye una herramienta de enorme conveniencia que, al unísono, permite materializar dos importantes objetivos: poner en valor el excelente trabajo que desempeñan estos órganos, imprescindibles en el democrático funcionamiento de nuestro sistema universitario, y, desde el conocimiento sobre su labor, afianzar su mantenimiento en el actual modelo universitario español. Mi agradecimiento, pues, a la directora de la Rued@, la Prof.ª Dr.ª María Acale Sánchez, Defensora de la Universidad de Cádiz, por la invitación a participar en este foro y por impulsar, desde el principio, la creación y puesta en marcha de este nuevo medio de expresión, especializado, donde convergen la acción de nuestras Defensorías, necesitadas de este tipo de puntos de encuentros para intercambiar ideas, experiencias y conocimientos

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

Microbial community composition of anoxic marine sediments in the Bay of Cádiz (Spain)

The composition of the microbial community inhabiting the anoxic coastal sediments of the Bay of Cádiz (southern Spain) was investigated using a molecular approach consisting of PCR cloning and denaturing gradient gel electrophoresis (DGGE), based on 16S rRNA sequences. The total cell count was 1-5 × 108 cells/g sediment and, as determined by catalyzed reporter deposition-fluorescent in situ hybridization (CARD-FISH), the proportion of Bacteria to Archaea was about 70:30. The analysis of 16S-rRNA gene sequences revealed a wide spectrum of microorganisms, which could be grouped into 111 operational taxonomic units (OTUs). Many of the OTUs showed high phylogenetic similarity to microorganisms living in marine sediments of diverse geographic origin. The phylogenetic groups that were predominantly detected were Firmicutes, Deltaproteobacteria, and Gammaproteobacteria, accounting for 23, 15, and 14% of the clones, respectively. Diversity in the domain Archaea was significantly lower than in the domain Bacteria. The majority of the archaeal OTUs belonged to the Crenarchaeota phylum. Since most of the sequences could not be identified precisely at the genus/species level, the functional roles of the microorganisms in the ecosystem could not be inferred. However, seven OTUs affiliated with the Delta- and Epsilonproteobacteria were identified down to the genus level, with all of the identified genera known to occur in sulfate-rich marine environmentsThis work was partially supported by grant REN2001-2980-C02-02 from the Spanish Ministry of Education and Science to J.L.S. We express our gratitude to PETRESA for funding under contract FGUAM 01130

Variaciones estacionales de tensioactivos aniónicos en sedimentos estuáricos del río Guadalete (Cádiz, España)

The presence and longitudinal and temporal distributions of the two main anionic surfactants, linear alkylbenzene sulfonates (LAS) and alkyl ethoxysulfates (AES), were monitored in surface sediments from the Guadalete estuary, located in the north of the Bay of Cadiz (SW of Spain). Seasonal samplings were performed for two years at three different stations; one of them located up-stream near the discharge outlet of a wastewater treatment plant (WWTP). A control station was also sampled in a tidal channel within the boundaries of a natural park adjacent to the estuary. LAS and AES concentration values ranged from 196 to 2864 ng g-1 and from 147 to 557 ng g-1, respectively, the lowest values corresponding to the control station and the highest ones found near the WWTP outlet. A general decrease in the concentrations of both surfactants was found in summer, when degradation processes are faster, whereas the highest concentrations were detected during the wet months, when temperature decreases and rainwater exceeds the WWTP capacity, so untreated wastewater is discharged directly into the river. Due to differential sorption and degradation processes, the relative distribution of LAS homologues in sediments showed higher percentages for those having longer alkyl chains, whereas AES homologues with an even carbon unit number in the alkyl chain and AES ethoxymers with fewer ethylene groups were predominant. No hazard for aquatic organisms was foreseen at the concentrations found for both surfactants along the estuary.Se ha realizado un seguimiento de la presencia y las distribuciones temporal y longitudinal de los dos tensioactivos aniónicos más usados -sulfonato de alquilbenceno lineal (LAS) y alquil etoxisulfatos (AES)- en sedimentos superficiales del estuario del río Guadalete, localizado al norte de la Bahía de Cádiz (SO de España). Para ello se llevaron a cabo muestreos estacionales durante dos años en tres estaciones diferentes, una de ellas localizada río arriba y en las inmediaciones de la zona de descarga de una estación depuradora de aguas residuales (EDAR). También se muestreó una estación control en un caño mareal situado dentro de los límites de un parque natural cercano al estuario. El rango de concentraciones de LAS y AES encontrado estuvo comprendido entre 196 y 2864 ng g-1 y entre 147 y 557 ng g-1 respectivamente, correspondiendo los valores más bajos a la estación control y los más altos a aquella situada cerca de la descarga de la EDAR. En términos generales, se detectó un descenso en las concentraciones de ambos tensioactivos durante el verano, cuando los procesos degradativos alcanzan mayor velocidad, mientras que las concentraciones más altas correspondieron a los meses con mayores precipitaciones, cuando se registra un descenso en la temperatura y tienen lugar descargas de agua residual sin tratar a causa de la saturación de la EDAR. Debido a procesos de adsorción y degradación diferencial, la distribución relativa de homólogos de LAS en el sedimento mostró un porcentaje mayor para aquellos con mayor longitud de cadena alquílica, mientras que los homólogos de AES con número par de carbonos en dicha cadena y los etoxímeros con menor número de grupo etoxilados fueron predominantes. No se detectó ningún riesgo para los organismos acuáticos teniendo en cuenta las concentraciones encontradas en el estuario para ambos tensioactivos

Distribution of anionic and nonionic surfactants in a sewage-impacted Mediterranean coastal lagoon: Inputs and seasonal variations

In this work we have monitored the seasonal inputs, occurrence and distribution of the world’s most widely used surfactants (linear alkylbenzene sulfonates, LAS, nonylphenol polyethoxylates, NPEOs, and alcohol polyethoxylates, AEOs) in Mar Menor lagoon (SE Spain) and its main tributary (El Albujón) for the first time. Concentration of target compounds was determined in both surface waters and sediments after solid phase extraction and pressurized liquid extraction, respectively, followed by liquid chromatography-mass spectrometry (LC-MS). There were significant differences in surfactant fluxes from El Albujón towards Mar Menor depending on the season and the day of the week, with maximum estimated annual inputs being detected for LAS (406 kg) and their metabolites, sulfophenyl carboxylic acids (482 kg). Average concentrations of surfactants in the lagoon were between 44 and 1665 µg/kg in sediment, and between 0.3 and 63 µg/L in water. These levels were significantly higher for samples collected near the shore than for those measured inside the lagoon itself. Overall, the occurrence and distribution of surfactants in the system could be explained due to a combination of different sources (surface and groundwater inputs, treated and untreated wastewater effluents, towns, ports, etc.) and simultaneous in-situ physicochemical and biological processes, with an special emphasis on degradation during warmer months.En prensa3,258

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

Determination and occurrence of secondary alkane sulfonates (SAS) in aquatic environments

A new methodology has been developed for the determination of secondary alkane sulfonates (SAS), an anionic surfactant, in environmental matrices. Sediment and sludge samples were extracted using pressurized liquid extraction and sonication, whereas wastewater and surface water samples were processed using solid-phase extraction. Extraction recoveries were acceptable for both aqueous (78-120%) and solid samples (83-100%). Determination of SAS was carried out by high or ultra performance liquid chromatography e mass spectrometry using ion trap and time-of-flight detectors. The methodology was applied to samples from Guadalete River (SW Spain), where SAS concentrations below 1 mg L 1 were measured in surface water, and from 72 to 9737 mg kg 1 in sediments. Differential partitioning was observed for SAS homologues as those having a longer hydrocarbon chain which preferentially sorbed onto particulate matter. A preliminary environmental risk assessment also showed that SAS measured levels were not harmful to the aquatic community in the sampling area