Development and Validation of a Multi-Pollutant Method for the Analysis of Polycyclic Aromatic Hydrocarbons, Synthetic Musk Compounds and Plasticizers in Atmospheric Particulate Matter (PM₂.₅)

[Abstract] Exposure to atmospheric particulate matter (PM) associated pollutants is a global concern due to the risk posed in human health after inhalation. In this study, a simple and sensitive multi-residue method is developed for the analysis of 50 organic pollutants, comprising 18 polycyclic aromatic hydrocarbons (PAHs), 12 phthalate esters (PAEs), 12 organophosphorus flame retardants (OPFRs), 6 synthetic musk compounds (SMCs) and 2 bisphenols in PM₂.₅ samples. The method consists of three cycles of ultrasonic assisted solvent extraction and vortex (UASE + vortex), followed by a vortex-assisted dispersive solid phase extraction (d-SPE) clean-up and a final determination step by using programmed temperature vaporization-gas chromatography-tandem mass spectrometry (PTV-GC-MS/MS). Experimental conditions concerning clean-up adsorbents (alumina, silica gel and Florisil®) and filters (glass fibre, PTFE and nylon), as well as PTV-GC-MS/MS conditions were studied. In addition, the use of SRM (selected reaction monitoring) mode in MS-MS, as well as matrix-matched calibration together with labelled subrogate standards, resulted in successfully validation results for most of the compounds due to the high sensitivity, minimization of matrix effects and recovering losses compensation. The proposed method was validated in terms of linearity, limits of detection and quantification (LODs and LOQs), analytical recoveries by analysing a spiked composite sample (PM₂.₅) at three spiking levels and intra-day and inter-day precision. Moreover, an urban particulate matter standard reference material (SRM 1648a) was analysed to assess PAHs determination accuracy. Furthermore, applicability of the method was proved by analysing 12 PM₂.₅ samples from an industrial area. Among all studied pollutants, bisphenol A (BPA) was the most predominant with an average concentration of 5000 pg m⁻³, followed by bis(2-ethylhexyl) phthalate (DEHP) and diisobutyl phthtalate (DiBP) with 1990 pg m⁻³ and 632 pg m⁻³, respectively. Concerning OPFRs, average concentrations between 345 – 253 pg m⁻³ were found for triphenyl phosphine oxide (TPPO), tris(chloropropyl) phosphate (TCPP), tri-iso-butyl phosphate (TiBP) and tris(2-butoxyethyl) phosphate (TBOEP). Finally, the highest PAHs levels were found for 5-6 ring-number PAHs (Σ5-6 rings PAHs) with an average concentration of 2680 pg m⁻³, while only 2 SMCs were quantitated accounting for 17.5 pg m⁻³ by average.This work was supported by the Ministerio de Ciencia, Innovación y Universidades (MCIU), Agencia Estatal de Investigación (AEI) and Fondo Europeo de Desarrollo Regional (FEDER) (Programa Estatal de I+D+i Orientada a los Retos de la Sociedad, ref: RTI 2018-101116-B-I00) and the Xunta de Galicia (Programa de Consolidación y Estructuración de Unidades de Investigación Competitivas ref: ED431C 2017/28-2017-2020). Joel Sánchez-Piñero acknowledges the Xunta de Galicia and the European Union (European Social Fund - ESF) for a predoctoral grant (ED481A-2018/164). The Laboratorio de Medio Ambiente de Galicia (LMAG) of the Subdirección Xeral de Meteoroloxía e Cambio Climático (Xunta de Galicia) is also acknowledged for providing the samples used in the present research workXunta de Galicia; ED431C 2017/28-2017-2020Xunta de Galicia; ED481A-2018/16

Modelado, diseño y construcción de un sistema activo de control de estabilidad de bajo costo para cohetes experimentales tipo aficionado

This paper presents the modeling, design and construction of a Rocket amateur of low cost, using an active control system through a mobile nozzle to achieve greater stability. Here describes the methods and procedures used in the experiment, developing the analysis, simulation and implementation of a prototype control for achieve a flight path.Este artículo presenta el modelado, diseño y construcción de un cohete tipo aficionado de bajo costo, empleando un sistema de control activo por medio de una tobera móvil para lograr una mayor estabilidad. Se plantean los métodos y procedimientos utilizados en el experimento, desarrollando el análisis, simulación e implementación de un prototipo de control para lograr una trayectoria de vuelo

Impact of ovarian endometrioma and surgery on reproductive outcomes: a single-center Spanish cohort study

Anti-Müllerian hormone (AMH) and antral follicular count (AFC) decrease in women with ovarian endometrioma (OMA) and in vitro fertilization (IVF). In addition, these parameters drop even further when women with OMA undergo surgery. In this study, the primary aim was to compare the reproductive variables in IVF-treated women with and without endometriosis. The secondary aim was to explore if the reproductive variables were modified by endometrioma surgery. In this retrospective study, 244 women undergoing IVF were enrolled at the Hospital Universitario La Paz (Madrid, Spain). Women were categorized as OMA not surgically treated (OMA; n = 124), OMA with surgery (OMA + S; n = 55), and women with infertility issues not related to OMA (control; n = 65). Demographic and clinical variables, including age, body mass index (BMI), and reproductive (AMH, AFC, number of extracted oocytes, and transferred embryos) and obstetrical data (biochemical pregnancy and fetal heart rate at 6 weeks) were collected. Adjusted logistic regression models were built to evaluate reproductive and pregnancy outcomes. The models showed that women with OMA (with and without surgery) had significantly decreased levels of AMH and AFC and numbers of cycles and C + D embryos. Women with OMA + S had similar rates of pregnancy to women in the control group. However, women with OMA had lower biochemical pregnancy than controls (aOR = 0.08 [0.01; 0.50]; p-value = 0.025). OMA surgery seems to improve pregnancy outcomes, at least until 6 weeks of gestation. However, it is important to counsel the patients about surgery expectations due to the fact that endometrioma itself reduces the quality of oocytesThis research was funded by Health National Project from Instituto de Salud Carlos III (Spain; Ref. PI-20-01368

Molecular dynamics simulation of surface phenomena due to high electronic excitation ion irradiation in amorphous silica

We studied by means of an atomistic model based on molecular dynamics the thermal evolution of surface atoms in amorphous silica under high electronic excitation produced by irradiation with swift heavy ions. The model was validated with the total and differential yields measured in sputtering experiments with different ions and ion energies showing a very good quantitative prediction capability. Three mechanisms are behind the evolution of the surface region: (1) an ejection mechanism of atoms and clusters with kinetic energy exceeding their binding energy to the sample surface, which explains the experimentally observed angular distributions of emitted atoms, and the correlation of the total sputtering yield with the electronic stopping power and the incidence angle. (2) A collective mechanism of the atoms in the ion track originated by the initial atom motion outwards the track region subsequently followed by the return to the resulting low-density region in the track center. The collective mechanism describes the energy dissipation of bulk atoms and the changes in density, residual stress, defect formation and optical properties. (3) A flow mechanism resulting from the accumulation and subsequent evolution of surface atoms unable to escape. This mechanism is responsible for the crater rim formation.Open Access funding provided thanks to the CRUE-CSIC agreement with Springer Nature. This work was funded by the projects Radiafus-5 (PID2019-105325RB-C32) of Spanish Ministry of Science, Technofusion (S2018/EMT-4437) of Madrid Regional Government and Eurofusion (EH150531176). The authors acknowledge the computer resources and technical assistance provided by the Centro de Supercomputación y Visualización de Madrid (CeSViMa) CESVIMA-MAGERIT. AP acknowledges the support of FONDECYT under grants 3190123. EMB thanks support from grant ANPCyT PICTO-UUMM-2019-00048. JK was supported by the Beatriz Galindo Program (BEAGAL18/00130) from the Ministerio de Educación y Formación Profesional of Spain

Diagnostic effectiveness of anti-citrullinated peptides antibodies of second and third generations for rheumatoid arthritis

Introduction: Rheumatoid arthritis is an autoimmune disease characterized by the presence of antibodies against citrullinated peptides, which are one of the indicators for the diagnosis of a disease.  The usefulness of different methods for the determination of these antibodies in the diagnosis of Cuban patients with rheumatoid arthritis is necessary to be established.Objective: To establish the diagnostic effectiveness of the second (anti-CCP2) and third (anti-CCP3) generation assays for the determination these antibodies against citrullinated peptides in Cuban patients with rheumatoid arthritis.Material and method: 101 patients with rheumatoid arthritis, 58 patients with other rheumatic and inflammatory diseases, and 43 healthy persons participated in the study. The diagnostic efficiency of rheumatoid factor (RF), anti-CCP2 and anti-CCP3 antibodies were determined using ELISA test, by calculating sensitivity, specificity, and positive and negative predictive values.Results: The anti-CCP2 assay showed a better balance of sensitivity (48.5 %) and specificity (98.0 %).  The lower sensibility was observed for RF (40.3%) when the specificity was set at 98 %. Specificity increased to 100% when anti-CCP2 and RF assays were used. All autoantibodies showed association with C-reactive protein and correlation with erythrocyte sedimentation rate. Only anti-CCP2 antibodies showed no correlation with the DAS28 clinical indicator.Conclusions: Anti-CCP2 antibodies are the ones of greater effectiveness in the diagnosis of Cuban patients with rheumatoid arthritis. RF identification allows to identify seronegative anti-CCP2 patients; therefore, the combination of both immunoassays leads to an improvement in the diagnostic effectiveness.  Keywords: Rheumatoid arthritis, cyclic citrullinated peptide, antibodies, anti-CCP2, anti-CCP3, diagnosis.</p

Occurrence of organotin compounds in waters of the spanish coast under the European Water Framework Directive

Organotin compounds (OTCs), such as tributyltin (TBT), are persistent organic pollutants that are present in water samples (surface water, river water, sea water, waste water, etc.) because of anthropogenic activities (antifouling agents in ship paints, biocides in polymers, etc.). The toxicity and endocrine disruption potential of these chemicals have been demonstrated even at very low levels (<1 ng L−1) (Devos et al. 2012). Due to the extensive presence of OTCs in all environmental media as well as their adverse effects on human health and biota, quantitative and qualitative determination of those com-pounds in complex environmental matrices has become a matter of great concern, mainly butyl and phenyl-substituted. Also, these compounds are included in the list of priority substances according to the EU Directive 2013/39/EU amending Directives 2000/60/EC and 2008/105/EC as regards priority substances in the field of water policy. This directive specifies annual average environmental quality standard (AA-EQS) of 0.2 ng L−1 TBT and a maximum allowable environmental quality standard (MAC-EQS) of 1.5 ng L−1 TBT for all surface waters. Samples were collected in two semiconfined coastal areas, one of them an area with high industrial and port activities (Ría de Vigo) and the other one with high touristic and agricultural activity (Mar Menor).The sampling campaigns were performed in spring and autumn of 2015. The levels of MBT, DBT, TBT, MPhT, DPhT and TPhT in the seawater samples were analyzed by HS-SPME-GC–QqQMS/ MS method (Moscoso-Pérez et al. 2015). MPhT, DPhT and TPhT were not detected in any sample at levels higher than LOQ. For butylated compounds, MBT, DBT and TBT were detected in 100% of the analyzed samples in the Mar Menor. In the Vigo estuary, MBT has been detected in 83.3% of the samples, the DBT in 75% and the TBT in 88%. The TBT is present in 92% of the total of 39 analyzed samples, being detected in 100% of the samples of the Mar Menor and in 88% of the samples of the Ría de Vigo. These levels are similar than those detected in other locations, and lower than the detected in ports near the coast of Gijón characterized by a great maritime traffic (Centineo et al. 2004).Program of Consolidation and Structuring of Units of Competitive Investigation of the University System of Galicia (Xunta de Galicia) potentially cofinanced by ERDF in the frame of the operative Program of Galicia 2007-2013 (reference: GRC2013-047) and by the Ministry of Economy and Competitiveness (IMPACTA, project reference: CTM2013-48194-C3-2-R, and ARPA-ACUA, project reference: CTM2016-77945-C3-3-R)

Influence of renal dysfunction on the differential behaviour of procalcitonin for the diagnosis of postoperative infection in cardiac surgery

Producción CientíficaBackground: procalcitonin is a valuable marker in the diagnosis of bacterial infections; however, the impairment of renal function can influence its diagnostic precision. The objective of this study is to evaluate the differential behaviour of procalcitonin, as well as its usefulness in the diagnosis of postoperative pulmonary infection after cardiac surgery, depending on the presence or absence of impaired renal function. Materials and methods: A total of 805 adult patients undergoing cardiac surgery with extracorporeal circulation (CBP) were prospectively recruited, comparing the behaviour of biomarkers between the groups with and without postoperative pneumonia and according to the presence or absence of renal dysfunction. Results: Pulmonary infection was diagnosed in 42 patients (5.21%). In total, 228 patients (28.32%) presented postoperative renal dysfunction. Procalcitonin was significantly higher in infected patients, even in the presence of renal dysfunction. The optimal procalcitonin threshold differed markedly in patients with renal dysfunction compared to patients without renal dysfunction (1 vs. 0.78 ng/mL p < 0.05). The diagnostic accuracy of procalcitonin increased significantly when the procalcitonin threshold was adapted to renal function. Conclusions: Procalcitonin is an accurate marker of postoperative infection in cardiac surgery, even in the presence of renal dysfunction. Renal function is an important determinant of procalcitonin levels and, therefore, its diagnostic thresholds must be adapted in the presence of renal dysfunction.Instituto de Salud Carlos III - (grant COV20/00491, PI18/01238, CIBERINFEC CB21/13/00051)Junta de Castilla y León - (grant VA321P18, GRS 1922/A/19, GRS 2057/A/19)Junta de Castilla y León, Consejería de Educación - (grant VA256P20)Fundación Ramón Areces - (grant CIVP19A5953)Instituto de Salud Carlos III y Fondo Europeo de Desarrollo Regional (FEDER)/Fondo Social Europeo - (grant CM20/00138

Temas Socio-Jurídicos. Volumen 6 No. 18 Enero 1988

La edición de la Revista Temas Socio-jurídicos, número 18 de la Facultad de Derecho de la Universidad Autónoma de Bucaramanga, rinde un homenaje a la obra de don Andrés Bello, en especial al código civil, al cumplirse el primer centenario de su adopción por la República unitaria, verificada por la ley 57 del 15 de abril de 1887.The edition of the Socio-legal Issues Magazine, number 18 of the Faculty of Law of the Autonomous University of Bucaramanga, pays homage to the work of Mr. Andrés Bello, especially the civil code, on the first centenary of its adoption by the unitary Republic, verified by Law 57 of April 15, 1887

Filtros suavizadores en imágenes sintéticas de resonancia magnética cerebral: un estudio comparativo

This paper presents the evaluation of two computational techniques for smoothing noise that might be present in synthetic images or numerical phantoms of magnetic resonance (MRI). The images that will serve as the databases (DB) during the course of this evaluation are available freely on the Internet and are reported in specialized literature as synthetic images called BrainWeb. The images that belong to this DB were contaminated with Rician noise, this being the most frequent type of noise in real MRI images. Also, the techniques that are usually considered to minimize the impact of Rician noise on the quality of BrainWeb images are matched with the Gaussian filter (GF) and an anisotropic diffusion filter, based on the gradient of the image (GADF). Each of these filters has 2 parameters that control their operation and, therefore, undergo a rigorous tuning process to identify the optimal values that guarantee the best performance of both the GF and the GADF. The peak of the signal-to-noise ratio (PSNR) and the computation time are considered as key elements to analyze the behavior of each of the filtering techniques applied. The results indicate that: a) both filters generate PSNR values comparable to each other. b) The GF requires a significantly shorter computation time to soften the Rician noise present in the considered DB. Keywords: Synthetic Cerebral images, Magnetic resonance, Rician noise, Gaussian filter, Anisotropic diffusion filter, PSNR.Este artículo presenta la evaluación de dos técnicas computacionales para el suavizado de ruido, que puede estar presente en imágenes sintéticas o phantoms numéricos de resonancia magnética (MRI). Las imágenes que servirán como bases de datos (DB) para el desarrollo de la mencionada evaluación están disponibles, de manera libre, en la Internet y se reportan, en la literatura especializada, como imágenes sintéticas denominadas BrainWeb. Las imágenes pertenecientes a esta DB fueron contaminadas con ruido Riciano debido a que este es el tipo de ruido más frecuente en imágenes de MRI reales. Por otra parte, las técnicas consideradas para minimizar el impacto de este ruido, en la calidad de las imágenes de la BrainWeb, se hacen coincidir con el filtro Gausiano (GF) y un filtro de difusión anisotrópica, basado en el gradiente de la imagen (GADF). Cada uno de estos filtros posee 2 parámetros que controlan su funcionamiento y, por ende, deben someterse a un proceso de entonación riguroso para identificar los valores óptimos que garanticen el mejor desempeño tanto del GF como del GADF. El pico de la relación señal a ruido (PSNR) y el tiempo de cómputo son considerados como elementos clave para analizar el comportamiento de cada una de las técnicas de filtrado aplicadas. Los resultados indican que: a) Ambos filtros generan valores de PSNR comparables entre sí. b) El GF requiere de un tiempo de cómputo, significativamente, menor para suavizar el ruido Riciano presente en la DB considerada. Palabras clave: Imágenes sintéticas cerebrales, Resonancia magnética, Ruido Riciano, Filtro Gausiano, Filtro de difusión anisotrópica, PSNR

Un modelo de aprendizaje colaborativo para la Edad Moderna: el recurso a las TICS y su aplicación a un entorno de docencia virtual II

Depto. de Historia Moderna y ContemporáneaFac. de Geografía e HistoriaFALSEsubmitte