Ozonation, photocatalysis and photocatalytic ozonation of diuron. Intermediates identification

Authors thank economic support received from Gobierno de Extremadura and CICYT of Spain through Projects GRU10012 and CTQ2012-35789-C02-01, respectively. Mr. Rafael Rodríguez Solís also thanks Gobierno de Extremadura, Consejería de Empleo, Empresa e Innovación, and FSE Funds for his Ph.D. grant (PD12058).Aqueous 3-(3,4-dichlorophenyl)-1,1-dimethylurea (diuron) has been oxidized by ozonation, photocatalysis and photocatalytic ozonation. Diuron degradation takes place via radical pathway through hydroxyl radicals in those systems involving ozone. Diuron elimination in photocatalytic ozonation is not enhanced if compared to single ozonation; however, TOC removal was significantly improved. Specifically, 80% TOC removal in 2 h was reached in photocatalytic ozonation while single ozonation just led to 25% TOC reduction. Photocatalysis required 9 h to reach 25% TOC reduction. Ten transformation by-products generated during the application of the three technologies were tentatively identified by liquid chromatography–quadrupole time-of-flight mass spectrometry (LC–QTOF–MS/MS). Single ozonation and photocatalytic ozonation led to the formation and complete elimination of all by-products. Low weight carboxylic acids evolution suggests that high TOC removal in photocatalytic ozonation is linked to its capacity to oxidize small oxygenated compounds and release of inorganic chloride and nitrate. Toxicity evolution to Vibrio fischeri in photocatalytic ozonation displayed an increase in inhibition at the initial stages (>90% of inhibition), followed by a decrease of this parameter as the reaction progressed. The final treated sample shows a lower toxicity than the initial one (55% vs 20%).Gobierno de Extremadura GRU10012CICYT of Spain CTQ2012-35789-C02-01Gobierno de Extremadura, Consejería de Empleo, Empresa e InnovaciónFSE Funds PD1205

Simulated solar driven photolytic ozonation for the oxidation of aqueous recalcitrant-to-ozone tritosulfuron. Transformation products and toxicity

The authors are grateful to Junta de Extremadura (Project IB16022), co-financed by the European Funds for Regional Development, for economically supporting this work. Moreover, it is also acknowledged the ‘Servicio de Análisis Elemental y Molecular (SAEM)’ of ‘Servicios de Apoyo a la Investigación de la Universidad de Extremadura (SAIUex)’ for the helping with the intermediate products analyses.This work reports the combination of ozone and solar radiation as an advanced oxidation process to remove the herbicide tritosufuron (TSF) in water. Firstly, the recalcitrance of TSF has been assessed, obtaining an ozonation second order rate constant of 5–154 M−1 min−1 in the range of pH from 5 to 8; while the rate constant with HOradical dot was found to be (1.8–3.1)·109 M−1 s−1. Secondly, the simultaneous application of simulated solar radiation in between 300 and 800 nm and ozone resulted positive in the oxidation rate of TSF. Mineralization extent was also higher. Less effective oxidation was achieved after limiting the radiation to the range 360–800 nm or 390–800 nm; also completely inappropriate for mineralization. Thirdly, the detected transformation products (TPs) demonstrated the vulnerability of TSF molecule to be attacked by HOradical dot in the sulfonylurea bridge. The combination of ozone and radiation of 300–800 nm led to the most effective removal of the TPs. Finally, after the photolytic ozonation treatment toxicity was also evaluated in terms of phytotoxicity towards the germination and root elongation of Lactuca Sativa seeds, and toxicity by immobilization tests of Daphnia Magna.Junta de Extremadura (Project IB16022)European Funds for Regional Developmen

Photocatalytic ozonation of pyridine-based herbicides by N-doped titania

The authors thank the economic support received from Gobierno de Extremadura and CICYT of Spain through Projects GRU10012 and CTQ2012-35789-C02-01, respectively. Mr. Rafael Rodríguez Solís thanks Gobierno de Extremadura, Consejería de Empleo, Empresa e Innovación, and FSE Funds for his Ph.D. grant (PD12058).BACKGROUND: A mixture of three pyridine herbicides in water (clopyralid, triclopyr and picloram) has been treated with photocatalytic processes, involving oxygen or ozone. Nitrogen doped and undoped titania were used in the process. Toxicity evolution during photocatalytic ozonation was monitored considering BOD, Daphnia parvula and fitotoxicity trials. RESULTS: N doped titania with an optimized photoactivity was tested in photocatalytic ozonation, leading to nearly 95% mineralization in 180 min. This catalyst was characterized by SEM, TEM, XRD and XPS techniques (13.5 nm crystal size, anatase phase, 1% N, and formation of O-Ti-N linkage). No loss of photocatalytic activity was observed after five consecutive runs. Although no toxicity from the parent compounds was observed, this parameter increased during the early stages of the oxidation process. When parent compounds were totally degraded and dechlorination was completed, toxicity decayed again to negligible values. CONCLUSION: N doping improves bare titania photoactivity through an optimum amount of N. Photocatalysis/ozone showed better behavior than photocatalysis/oxygen in herbicide removal and mineralization, and no significant loss of activity was observed after five runs. Toxicity initially increased due to toxic byproducts formation; however, it decreased after their abatement.Gobierno de Extremadura GRU10012CICYT of Spain CTQ2012-35789-C02-01Gobierno de ExtremaduraFSE Funds (PD12058

Simulated solar photo-assisted decomposition of peroxymonosulfate. Radiation filtering and operational variables influence on the oxidation of aqueous bezafibrate

This work investigates the potential of the combination of peroxymonosulfate (PMS) and simulated solar radiation (λ > 300 nm) to remove bezafibrate from aqueous solution. Different solar light filters indicate a higher removal efficiency as the wavelength range used moves to the more energetic region of the solar spectrum. The system PMS/Daylight (300–800 nm) eliminates bezafibrate (1 mg L−1) in less than 30 min under the best conditions used in this study (CPMS = 4·10−4 M) with no pH control (acidic pH). The efficiency of the process significantly improves under alkaline conditions (pH = 10), likely due to a higher PMS photolysis rate. Experiments conducted at different initial concentration of PMS and bezafibrate suggest first order regarding PMS and different from 1 in the case of bezafibrate. Intermediates generated at the beginning of the process have been tentatively identified to propose a hypothetical reaction pathway and to estimate their toxicity

Photocatalytic ozonation of 4-chloro-2-methylphenoxyacetic acid and its reaction intermediate 4-chloro-2-methyl phenol

This work has been supported by the CICYT of Spain (Project CTQ2012-39789-C02-01). Mr. Rafael Rodríguez Solís thanks the Gobierno de Extremadura, Consejería de Empleo, Empresa e Innovación and FSE Funds for his Ph.D. grant (PD12058).Aqueous 4-chloro-2-methylphenoxyacetic acid (MCPA) has been treated by the systems UVA/TiO2/N2, O3, TiO2/O3, UVA/O3, UVA/TiO2/O2, and UVA/TiO2/O3. Under the conditions investigated (T = 20 °C, pH = 4.5, Qgas = 30 L/h, V = 1 L, CO3= 5 ppm, CMCPA = 5 ppm, CTiO2= 0.5 g/L), MCPA is removed in less than 30 min. Photocatalytic ozonation is the most efficient process both in terms of MCPA removal rate (100% conversion in less than 15 min) and mineralization extent (60% after 3 h and 25 °C). 4-Chloro-2-methyl phenol (CMP) is detected in those systems combining TiO2 and UVA radiation. The presence of ozone involves the complete depletion of CMP following its generation. The direct rate constant between CMP and ozone corroborates the high reactivity observed (7.2 ± 0.3 × 104 (M s)−1, 4.4 ± 0.2 × 105 (M s)−1, and 2.9 ± 0.7 × 106 (M s)−1 at pHs 4, 7 and 10, respectively). Identified intermediates detected in the UVA/TiO2/O3 applied to MCPA correspond to oxygenated species derived from the parent compound after loss of some substitution groups. No significant toxicity of intermediates is observed in BOD5, Daphnia parvula, and Culex pipiens larvae tests.CICYT of Spain (Project CTQ2012-39789-C02-01)Gobierno de ExtremaduraFSE Funds (PD12058

Synergism between peroxymonosulfate and LaCoO3-TiO2 photocatalysis for oxidation of herbicides. Operational variables and catalyst characterization assessment

Authors thank economic support received from Junta de Extremadura, CICYT of Spain and FEDER funds through Projects GR15033 and CTQ2015/64944-R, respectively. Mr Rafael Rodríguez Solís also acknowledges Gobierno de Extremadura, Consejería de Empleo Empresa e Innovación, and FSE Funds for his PhD grant (PD12058). Catalyst characterization was provided by Facility of Analysis and Characterization of Solids and Surfaces of SAIUEx (financed by University of Extremadura, Junta de Extremadura, MICINN, FEDER and FSE).BACKGROUND. This paper reports the use of novel coupled LaCoO3-TiO2 as photocatalyst with double route of peroxymonosulfate (PMS) activation. First, as a photocatalyst due to titania; and second, through PMS heterogeneous decomposition onto LaCoO3 particles. Thus, photocatalytical activity was tested for removing a mixture of four herbicides of different recalcitrance (metazachlor, tembotrione, tritosulfuron and ethofumesate). RESULTS. The presence of light and PMS highly enhanced herbicides removal rate: 3.5–5 times increases were obtained with UVA light. Oxidant concentration, catalyst load, pH and temperature were assessed. Herbicides were completely oxidized depending on their recalcitrant nature and the operational variables. 55% TOC conversion was reached using Oxone® 5 × 10−4 mol L−1. Phytotoxicity assays denoted no inhibition after 180 min of photocatalytic treatment (∼80% initial inhibition). Solid properties of Co/Ti = 0.1:1 ratio were studied by means of SEM (LaCoO3 aggregates linked to a variety of shapes and sizes of TiO2), XRF (6.1% of LaCoO3), XPS (superficial Co3+, La3+ and Ti4+), XRD (anatase, rutile and rhombohedral LaCoO3) and UV–vis diffuse reflectance (visible range absorption and bandgap of 2.88 eV for TiO2). CONCLUSION. Catalysts based on LaCoO3-TiO2 combined with peroxymonosulfate seem to be suitable for removing organic pollutants, with a moderate conversion of TOC and elimination of toxicity.Junta de Extremadura GR15033CICYT of Spain CTQ2015/64944-RFEDER foundsGobierno de ExtremaduraFSE Funds (PD12058)University of ExtremaduraJunta de ExtremaduraMICINNFS

Efecto de la fuente de nitrógeno en la distribución de asimilados y composición de savia en ajipa (Pachyrhizus ahipa (Wedd.) Parodi)

7 páginas, 4 figuras, 1 tabla y 17 referencias. Trabajo presentado en el VI Simposium Nacional - II Ibérico sobre nutrición mineral de las plantas, Sevilla, del 12 al 15 de Noviembre de 1996. Entidades colaboradoras Junta de Andalucía, Universidad de Sevilla, Consejo Superior de Investigaciones Científicas, Sociedad Española de Fisiología Vegetal, El Monte, Caja de Huelva y Sevilla y Gat Fertiliquidos. Editores Científicos: Rafael Sarmiento Solís, Eduardo O. Leidi Montes y Antonio Troncoso de Arce. (Instituto de Recursos Naturales y Agrobiología de Sevilla).[EN]:Ahipa (Pachyrhizus ahipa (Wedd.) Parodi) is a legume root crop of Andean origin which accumulates carbohydrates of industrial interest in its tuberous roots and rotenone in leaves and seeds. The aim of this work was the study of lhe effect of N source (nitrate vs symbiotic N2, fixation) on growth, assimilate partitioning and xylem sap composition. The treatments consisted in: (a) plants inoculated with an specific Rhizobium strain irrigated wilh a N free nutrient solution (T-N2); and (b) non inoculated plants irrigated with a nutrient solution contai ning 4 mM NO3K (T-NO3). Main differences in growth and assimilate allocation were observed between plants grown in different treatments: N2,-fixing plants showed an increased earliness and reduced tuberous root growth in comparison with NO3-fed plants . Dry matter allocation into leaves and shoots was higher in NO -fed plants lhan in N2-fixing plants. Nitrogen concentration in leaves, stems and roots was higher in N2-fixing plants than in NO3-fed plants. At early growth stages, main xylem sap nitrogenous solutes were amino acids and amides. At flowering, N2-fixing plants showed high concentratÍon ofureides (allantoin+allantoic acid) and the amino acid L-canavanine[ES]:La ajipa (PachyrhiZlls ahipa (Wedd) Parodi), leguminosa de origen andino, se caracteriza por la acumulación de hidratos de carbono de interés industrial en sus raíces tuberosas y la presencia de rotenona en hojas y semillas. En este trabajo hemos estudiado el efecto de la nutrición nitrogenada (fijación simbiótica de N2 ó N mineral) sobre el crecimiento, partición de asimilados y composición de savia de xilema. Los tratamientos consistieron en: (a) plantas inoculadas con una cepa especifica de Rhizobium spp. (T-N2) y (b) plantas no inoculadas (T-NO3). Las planta se cultivaron en perlita/vermiculit y se regaron con solución de Hewitt sin N (T-N2) o 4 mM NO3K (T-NO3). Se observaron importantes diferencias debidas a la fuente de N: las plantas T-N, presentaron una mayor precocidad en la floración y fructificación y un menor desarrollo de la raíz tuberosa en comparación con las plantas T-NO2. La acumulación de materia seca en hojas y tallos de las plantas también fue superior en las plantas T-NO3. La concentración de N en hojas, tallos y raices fue superior en la plantas T-N2. En estadios tempranos de crecimiento, los componentes principales de savia de xilema, en ambos tratamientos. eran aminoácidos y amidas. En floración, las plantas T-N2, presentaban altas concentraciones de ureidos (alantoina+ácido alantoico) y el principal aminoácido transportado era L-canavanina.Sección de Nutrición Mineral de la Sociedad Española de Fisiología Vegetal y Instituto de Recursos Naturales y Agrobiología de Sevilla, CSIC.Peer reviewe

Retos de la lactancia materna en el siglo XXI

La lactancia materna exclusiva durante seis meses y complementaria hasta los dos años de vida es una recomendación de la Organización Mundial de la Salud, por las propiedades de la leche materna y sus múltiples beneficios para la madre, el bebé, las familias y la nación. Autoridades mundiales e instancias legales han establecido diversas iniciativas con el fin de promover y aumentar la práctica de lactancia, sin embargo, existen muchas barreras biológicas, culturales, sociales, comunitarias, institucionales y políticas que la han dificultado. Existen muchas investigaciones; sin evidencia científica y políticas actuales que respaldan la lactancia materna, sin embargo, cada día va en descenso. Es necesario educar y comunicar a la comunidad, profesionales de la salud y tomadores de decisiones sobre este tema, que aparentemente solo es relevante para las mujeres en un periodo específico de su vida, pero que en realidad es trascendental para toda la sociedad por su impacto en la economía, en la política y salud pública

Novel isoreticular UiO-66-NH2 frameworks by N-cycloalkyl functionalization of the 2-aminoterephtalate linker with enhanced solar photocatalytic degradation of acetaminophen

Supplementary data to this article can be found online at https://doi.org/10.1016/j.cej.2023.141889.This work reports for the first time the functionalization of the 2-aminoterephtalate linker of UiO-66-NH2 with cyclopentyl or cyclohexyl rings. The resulting materials displayed reduced bandgaps with enhanced separation of the photogenerated charges due to the inductive electron effect of the cycloalkyl substituent. These functionalized materials displayed higher photocatalytic performance towards the solar abatement of acetaminophen than UiO-66-NH2. The photocatalytic activation mechanism was proposed based on the band alignment and scavenger tests, suggesting the major contribution of holes and superoxide radicals. In particular, UiO-66-NH-C5 exhibited high stability under reaction with low activity loss after reusing. The acetaminophen degradation pathway was also studied indicating that the ACE molecules were coupled to dimers and trimers that were further oxidized. The small bandgap, the band structure, and the photocatalytic performance resulting from the cycloalkyl functionalization of UiO-66-NH2 make it a promising approach to designing novel photocatalysts for solar abatement of emerging contaminants.Spanish State Research Agency (PID2019-106186RB-I00/AEI/10.13039/501100011033 and PID2019- 105479RB-I00 MCIN/AEI/10.13039/501100011033)Spanish Ministry of Science, Innovation, and Universities for his postdoctoral contract (Juan de la Cierva Formaci ́on, Ref. FJC2018- 035513-I)Support provided by the external services of the Autonomous University of Madrid (SIdI) and the Uni- versity of Extremadura (SAIUEx)Funding for open access charge: Universidad de Granada/CBU

Implementación de Vehículos de Recuperación en el Batallón de Infantería Mecanizada

Se ha detectado la necesidad de dotar a las unidades de entidad Batallón de Infantería Mecanizada (BIMZ), las cuales operan con el Vehículo de Combate de Infantería (VCI) “Pizarro”, de vehículos encargados para su recuperación. Estos vehículos, junto con sus herramientas y armamento, tienen que tener la capacidad de llevar a cabo tanto recuperaciones como traslados o reparaciones in situ, de forma segura y eficaz, con el objetivo de mantener la operatividad de la unidad a la que apoyan, constituyendo un elemento fundamental en la conducción de las operaciones. El motivo por el cual se lleva a cabo este trabajo es que en la actualidad no existen esta clase de vehículos en los Batallones de Infantería Mecanizada en base a VCI “Pizarro”, como si ocurre en otros batallones, como el Batallón de Infantería de Carros de Combate (BICC), que cuentan con vehículos de recuperación con la misma plataforma/barcaza que el Leopardo 2E.La problemática actual es que cuando hay alguna contingencia de este tipo, al no existir un vehículo de recuperación o traslado de los VCI,s, esta tarea suele realizarse con otro vehículo de las mismas características, perdiendo capacidad de combate y reduciendo la potencia de fuego de la unidad, o bien con vehículos que no están adaptados completamente al terreno (vehículos de ruedas). En este sentido, este Trabajo trata de ofrecer una solución a la recuperación de vehículos en el BIMZ.<br /