Técnicas cromatográficas utilizadas en monitorización ambiental

Máster en Enxeñaría AmbientalO Máster de Enxeñería Ambiental impártese na Escola Técnica Superior de Enxeñería (ETSE) da Universidade de Santiago de Compostela, cuns 30 estudantes anuais de nova matrícula. Consta de 90 créditos ECTS e realízase nun período de 18 meses. No primeiro ano (60 ECTS) impártense cinco módulos, que se distribúen dende setembro a xullo. No segundo ano (30 ECTS), nos dous primeiros meses impártense as clases teóricas do módulo seis e o resto dos meses dedícanse ao Proxecto Fin de Máster. Os módulos impartidos nos dous anos de Máster son os que se indican a continuación: Primeiro ano: Módulo I: Fundamentos. Módulo II: Tratamento de Augas Módulo III: Monitorización e Redución da Contaminación Atmosférica Instrumentación e Monitorización Ambiental(IMA) Medio Ambiente e Redución de Emisións Técnicas de Análise Territorial Laboratorio de Modelización Módulo IV: Recuperación de Solos e Xestión de Residuos Módulo V: Prácticas externas Segundo ano: Módulo VI: Xestión Ambiental. Módulo VII: Proxecto Fin de Máster. A materia de Instrumentación e Monitorización Ambiental (IMA) é unha materia obrigatoria de 3 créditos ECTS do Módulo III (Monitorización e redución da contaminación atmosférica). Os contidos impartidos en IMA introducen o alumno nas diferentes técnicas instrumentais empregadas na monitorización ambiental, dende a etapa de mostraxe ata a análise das mostras no laboratorio. O número de horas presenciais é 28, das cales 9 se empregan para o estudo da cromatografía. No primeiro tema da materia estúdase a colección e tratamento da mostra previamente á análise. No segundo tema trátanse os métodos espectroscópicos, fundamentais para realizar un número moi elevado de análises. E por fin, no tema 3 trátanse os métodos cromatográficos, xa que unha vez que temos preparada a mostra e antes de realizar unha cuantificación dun composto, por exemplo utilizando métodos espectroscópicos, frecuentemente é necesario levar a cabo unha separación cromatográfica de dito composto para evitar a presenza doutras sustancias que interfiren na determinación. Así, as técnicas cromatográficas son un grupo de potentes ferramentas de separación, identificación e determinación de compostos químicos en mesturas complexas. Polo tanto son fundamentais nos laboratorios de análise, xa que a maior parte das mostras que chegan a eles son mostras complexas, xa sexa no ámbito clínico, industrial ou medioambiental. Tralo tema de cromatografía trátanse os sensores (tema 4) e os sensores remotos (tema 5). En ámbolos dous casos, o obxectivo é realizar as medicións do modo máis sinxelo posible, a ser posible sen separación previa. Por último, nos temas finais do curso tamén se tratarán algunhas aplicacións da cromatografía relacionadas coa análise de contaminantes en chemineas e nas medidas da calidade de aire.Universidade de Santiago de Compostela. Servizo de Normalización Lingüístic

Cloud point extraction and ICP-MS for titanium speciation in water samples

An analytical method for the separation and determination of titanium dioxide nanoparticles in water samples has been developed. The separation was performed by Cloud Point Extraction (CPE) with Triton X-114. Titanium dioxide nanoparticles and ionic titanium were analysed in the surfactant rich phase and surfactant poor phase respectively, by inductively coupled plasma-mass spectrometry (ICP-MS). Parameters related to the CPE procedure such as Triton X-114 and NaCl concentrations were evaluated. Optimum concentrations of 0.03% (w/v) and 2.5 mM of Triton X-114 and NaCl respectively, were selected to develop this study. The TiO2 nanoparticles extracted were digested using HNO3 and H2O2 in an ultrasonic bath for 10 min at 60°C and analysed by ICP-MS. The analytical characteristics of the method (calibration, limits of detection and quantification, precision and recovery) were evaluated. The LOD and LOQ for Ti determination in the surfactant rich phase were 0.13 and 0.45 µg L−1, respectively. Finally, the method was applied for the determination of TiO2 nanoparticles in swimming pool water samplesThe authors wish to thank the Spanish Ministerio de Ciencia, Innovación y Universidades (Project number RTI2018-099222-B-100), the European Union (programme Interreg Atlantic Area, Project number EAPA_590/2018), and Xunta de Galicia (Grupo de Referencia Competitiva ED431C2018/19 for financial support. This research was partially supported by the Consellería de Educación Program for the Development of Strategic Grouping in Materials - AEMAT at the University of Santiago de Compostela under grant No. ED431E2018/08, Xunta de Galicia. These programs are co-funded by FEDER (UE).S

Analysis of brain regional distribution of aluminium in rats via oral and intraperitoneal administration

In the present work, accumulation and distribution of aluminium in the rat brain following both intraperitoneal and oral administration were studied. Electrothermal atomic absorption spectrometry was used to determine aluminium concentration in different brain areas (cerebellum, ventral midbrain, cortex, hippocampus, and striatum). Most of the brain areas showed accumulation of aluminium, but a greater and more significant increase was noted in the group receiving aluminium via intraperitoneal administration. Aluminium distribution was also dependent on the administration route.S

Bioaccumulation of titanium dioxide nanoparticles in green (Ulva sp.) and red (Palmaria palmata) seaweed

A bioaccumulation study in red (Palmaria palmata) and green (Ulva sp.) seaweed has been carried out after exposure to different concentrations of citrate-coated titanium dioxide nanoparticles (5 and 25 nm) for 28 days. The concentration of total titanium and the number and size of accumulated nanoparticles in the seaweeds has been determined throughout the study by inductively coupled plasma mass spectrometry (ICP-MS) and single particle-ICP-MS (SP-ICP-MS), respectively. Ammonia was used as a reaction gas to minimize the effect of the interferences in the 48Ti determination by ICP-MS. Titanium concentrations measured in Ulva sp. were higher than those found in Palmaria palmata for the same exposure conditions. The maximum concentration of titanium (61.96 ± 15.49 μg g−1) was found in Ulva sp. after 28 days of exposure to 1.0 mg L−1 of 5 nm TiO2NPs. The concentration and sizes of TiO2NPs determined by SP-ICP-MS in alkaline seaweed extracts were similar for both seaweeds exposed to 5 and 25 nm TiO2NPs, which indicates that probably the element is accumulated in Ulva sp. mainly as ionic titanium or nanoparticles smaller than the limit of detection in size (27 nm). The implementation of TiO2NPs in Ulva sp. was confirmed by electron microscopy (TEM/STEM) in combination with energy dispersive X-Ray analysis (EDX)The authors wish to thank the fnancial support of Ministerio de Economía y Competitividad (project INNOVANANO, reference RT2018-099222-B-100), European Union (INTERREG Atlantic Area, project NANOCULTURE, reference EAPA590/2018), and Xunta de Galicia (Grupo de Referencia Competitiva, grant number ED431C 2022/29)S

Effectiveness, safety/tolerability of OBV/PTV/r ± DSV in patients with HCV genotype 1 or 4 with/without HIV-1 co-infection, chronic kidney disease (CKD) stage IIIb-V and dialysis in Spanish clinical practice - Vie-KinD study

Limited data are available on the effectiveness and tolerability of direct-acting antivirals (DAAs) therapies in the real world for HCV-infected patients with comorbidities. This study aimed to describe the effectiveness of OBV/PTV/r ± DSV (3D/2D regimen) with or without ribavirin (RBV) in HCV or HCV/HIV co-infected patients with GT1/GT4 and CKD (IIIb-V stages), including those under hemodialysis and peritoneal dialysis in routine clinical practice in Spain in 2015.Non-interventional, retrospective, multicenter data collection study in 31 Spanish sites. Socio-demographic, clinical variables, study treatment characteristics, effectiveness and tolerability data were collected from medical records.Data from 135 patients with a mean age (SD) of 58.3 (11.4) years were analyzed: 92.6% GT1 (81.6% GT1b and 17.6% GT1a) and 7.4% GT4, 14 (10.4%) HIV/HCV co-infected, 19.0% with fibrosis F3 and 28.1% F4 by FibroScan®, 52.6% were previously treated with pegIFN and RBV. 11.1%, 14.8% and 74.1% of patients had CKD stage IIIb, IV and V respectively. 68.9% of patients were on hemodialysis; 8.9% on peritoneal dialysis and 38.5% had history of renal transplant. A total of 125 (96.2%) of 135 patients were treated with 3D, 10 (7.4%) with 2D and 30.4% received RBV. The overall intention-to-treat (ITT) sustained virologic response at week 12 (SVR12) was 92.6% (125/135) and the overall modified-ITT (mITT) SVR12 was 99.2% (125/126). The SVR12 rates (ITT) per sub-groups were: HCV mono-infected (91.7%), HCV/HIV co-infected (100%), GT1 (92.0%), GT4 (100%), CKD stage IIIb (86.7%), stage IV (95%) and stage V (93%). Among the 10 non-SVR there was only 1 virologic failure (0.7%); 4 patients had missing data due lost to follow up (3.0%) and 5 patients discontinued 3D/2D regimen (3.7%): 4 due to severe adverse events (including 3 deaths) and 1 patient´s decision.These results have shown that 3D/2D regimens are effective and tolerable in patients with advanced CKD including those in dialysis with GT 1 or 4 chronic HCV mono-infection and HIV/HCV coinfection in a real-life cohort. The overall SVR12 rates were 92.6% (ITT) and 99.2% (mITT) without clinically relevant changes in eGFR until 12 weeks post-treatment. These results are consistent with those reported in clinical trials

Introdución á monitorización ambiental

Máster en Enxeñaría AmbientalNesta unidade faise en primeiro lugar unha introdución á monitorización ambiental para pasar, en segundo lugar, a explicar o proceso de mostraxe ambiental. A etapa de mostraxe é unha das primeiras etapas do proceso analítico e unha das máis importantes. Unha etapa de mostraxe mal planificada levará á obtención de resultados erróneos no proceso analítico.Universidade de Santiago de Compostela. Servizo de Normalización Lingüístic

Study Design on the Presence of Metals in Moisturisers, and Compliance with Regulation (EC) No. 1223/2009 of the European Parliament and of the Council of the European Union, on Cosmetic Products

Metals are present in cosmetics due to deliberate addition by the manufacturers, contamination of raw materials, and/or contamination during their manufacture or storage. The objective of this work was to explore the metal content in the most-consumed moisturising creams on the Spanish market, to verify their degree of compliance with Regulation (EC) No. 1223/2009 of the European Parliament and of the Council of the European Union, regarding the presence of metals in cosmetics. The moisturisers were digested (microwave-assisted acid digestion) and analysed by inductively coupled plasma-mass spectrometry (ICP-MS), for metal assessment. The ICP-MS measurements were successfully validated (RSDs lower than 5% and analytical recoveries within the 91–110% range). Metals banned in cosmetics were found at very low concentrations in some of the moisturisers, as inevitable traces of pollutants. This was the case with beryllium (found in only two samples, at concentrations lower than 0.10 µg g−1), cadmium (found at 0.075 µg g−1 in one sample), mercury (found in four samples at concentrations within the 0.10–0.18 µg g−1 range), and lead (also found in four samples at concentrations from 0.03 to 0.44 µg g−1). Furthermore, nickel (0.16–0.56 µg g−1, six samples), chromium (0.09–0.30 µg g−1, three samples), and cobalt (lower than 0.13 µg g−1, two samples) were also found in the analysed creams

Metal Content in Textile and (Nano)Textile Products

Metals, metallic compounds, and, recently, metallic nanoparticles appear in textiles due to impurities from raw materials, contamination during the manufacturing process, and/or their deliberate addition. However, the presence of lead, cadmium, chromium (VI), arsenic, mercury, and dioctyltin in textile products is regulated in Europe (Regulation 1907/2006). Metal determination in fabrics was performed by inductively coupled plasma-mass spectrometry (ICP-MS) after microwave-assisted acid digestion. The ICP-MS procedure has been successfully validated; relative standard deviations were up to 3% and analytical recoveries were within the 90–107% range. The developed method was applied to several commercial textiles, and special attention has been focused on textiles with nanofinishing (fabrics prepared with metallic nanoparticles for providing certain functionalities). Arsenic content (in textile T4) and lead content (in subsamples T1-1, T1-2, and T3-3) were found to exceed the maximum limits established by the European Regulation 1907/2006. Although impregnation of yarns with mercury compounds is not allowed, mercury was quantified in fabrics T1-2, T5, and T6. Further speciation studies for determining hexavalent chromium species in sample T9 are necessary (hexavalent chromium is the only species of chromium regulated). Some textile products commercialised in Europe included in this study do not comply with European regulation 1907/2006

Ultrasonication followed by enzymatic hydrolysis as a sample pre-treatment for the determination of Ag nanoparticles in edible seaweed by SP-ICP-MS

Seaweed can bioaccumulate nanomaterials that would be transferred to the trophic chain. This work describes the optimization of a method for the separation of silver nanoparticles (AgNPs) from seaweed using an ultrasound-assisted enzymatic hydrolysis method and ulterior determination by single particle inductively coupled plasma mass spectrometry (SP-ICP-MS). The following parameters affecting the isolation of AgNPs were optimized using a Palmaria palmata (red seaweed) sample previously exposed to AgNPs: type of sonication (bath vs. ultrasonic probe), ultrasound amplitude, sonication time, sonication mode (pulsed vs. continuous sonication), concentration of the enzymes mixture (Macerozyme R-10®), and enzymatic hydrolysis time. The stability of AgNPs during extraction was tested by transmission electron microscopy (TEM) and using a standard of 15 nm of polyvinylpyrrolidone (PVP)-coated AgNPs analyzed by SP-ICP-MS. The analytical performance was evaluated with good results. For total Ag determination, the limits of detection and quantification were 2.2 and 7.7 ng g−1, respectively; and for AgNPs determination, the limits of detection in size and number were 14 nm and 4.34 × 107 part g−1, respectively. Besides, the matrix effect, the repeatability and the analytical recovery were also studied. Finally, the method was applied to the analysis of several red (Palmaria palmata) and green (Ulva sp.) seaweed samplesThe authors wish to acknowledge the financial support of Ministerio de Economía y Competitividad (project INNOVANANO, reference RT2018-099222-B-100), European Union (INTERREG Atlantic Area, project NANOCULTURE, reference EAPA590/2018), and Xunta de Galicia (Grupo de Referencia Competitiva, grant number ED431C2018/19)S

spICP-MS characterisation of released silver nanoparticles from (nano)textile products

The low limits of detection and information regarding the concentration and size distribution of nanoparticles provided by single particle inductively coupled plasma mass spectrometry (spICP-MS) has been taken in advance for assessing released silver nanoparticles from (nano)textiles (nanosilver textiles). The releasing procedure consisted of using orbital-horizontal shaking (100 rpm, 20 °C, 30 min) and ultrapure water (10 mL) as an extractant, and it was found to guarantee silver nanoparticles stability (silver nanoparticle concentration and size distribution). Stability of released silver nanoparticles was further investigated at several filtration (0.22, 0.45 and 5.0 μm) and centrifugation conditions, stages required for fluff removal after extraction and just before spICP-MS determinations. Filtration using 5.0 μm filters was found to not affect silver nanoparticles concentrations and size distributions. The extractive procedure plus spICP-MS has shown a limit of detection and a limit of quantification for silver nanoparticle number concentration of 4.59 × 104 and 1.53 × 105 silver nanoparticles per gram of textile, respectively, whereas a limit of detection in size of 12 nm was obtained. Repeatability of the overall procedure was 14% (silver nanoparticle concentration) and 6% (mean silver nanoparticle size). Similarly, analytical recovery assays using standard silver nanoparticles of 20, 40, and 60 nm led to recoveries within the 102–113% range. The high degree of fixation of the AgNPs to the fabric and the softness of the extraction process to guarantee the integrity of the nanoparticles has led to a non-quantitative extraction (extraction percentages between 0.3 and 9.0% depending on the textile sample). However, the methodology developed has proven to be highly efficient for the characterization of the extracted AgNPs, and robust since the stability of the released AgNPs during the extraction procedureThe authors wish to acknowledge the financial support of the Ministerio de Economía y Competitividad (projects INNOVANANO, reference RT2018–099222-B-100), and the Xunta de Galicia (Grupo de Referencia Competitiva, grant number ED431C2018/19). I. Rujido-Santos thanks the Xunta de Galicia and the European Social Fund (FSE) for a pre-doctoral grant (ref. ED481A-2018/127)S