Equilibrium, kinetics and breakthrough curves of acetaminophen adsorption onto activated carbons from microwave-assisted FeCl3-activation of lignin

Activated carbons have been prepared by chemical activation of lignin with FeCl3 using microwave (MW) heating. The use of MW significantly reduced the activation time compared to conventional heating. Microwave power, impregnation ratio (R: mass ratio of FeCl3 to lignin precursor) and MW holding time have been studied as variables affecting the development of porous texture. The optimum conditions were found at 800 W, R = 5 and 30 min MW heating time. Under those conditions an essentially microporous activated carbon was obtained, with BET surface area higher than 1150 m2·g−1 and acidic surface, whose pH at the point of zero charge was 4.2. This activated carbon was tested for the adsorption of acetaminophen, as model emerging contaminant, from aqueous phase. The adsorption isotherms, obtained at 20, 40 and 60 °C, fitted well to Redlich–Peterson model. The maximum acetaminophen adsorption reached about 300 mg·g−1 at 60 °C. Values of 35.5 kJ·mol−1 and 238.3 J·mol−1·K−1 were obtained for the enthalpy and entropy of adsorption, respectively. Those positive values are indicative of an endothermic process and increased randomness at the solid/solution interface upon adsorption. The adsorption kinetics was better described by pseudo-second order driving force model. Breakthrough curves were also obtained at different adsorption temperatures, flow rates and acetaminophen inlet concentrations. They fitted well to a logistic-type equation representative of the Bohart-Adams, Thomas and Yoon-Nelson models. Adsorbent regeneration with hot water (80 °C) revealed easy and complete desorption thus providing a promising view of the potential application of this activated carbonThe authors acknowledge the financial support from the State Research Agency (PID2019-106186RB-I00/AEI/10.13039/501100011033, Spain). M. Penas-Garzón thanks Spanish MECD for FPU16/00576 gran

The structural and electronic properties of nanostructured Ce1–x–yZrxTbyO2 ternary oxides: Unusual concentration of Tb3+ and metal_oxygen_metal interactions

10 pages, 12 figures, 1 table.Ceria-based ternary oxides are widely used in many areas of chemistry, physics, and materials science. Synchrotron-based time-resolved x-ray diffraction, x-ray absorption near-edge spectroscopy (XANES), Raman spectroscopy, and density-functional calculations were used to study the structural and electronic properties of Ce–Zr–Tb oxide nanoparticles. The nanoparticles were synthesized following a novel microemulsion method and had sizes in the range of 4–7 nm. The Ce1–x–yZrxTbyO2 ternary systems exhibit a complex behavior that cannot be predicted as a simple extrapolation of the properties of Ce1–xZrxO2, Ce1–xTbxO2, or the individual oxides (CeO2, ZrO2, and TbO2). The doping of ceria with Zr and Tb induces a decrease in the unit cell, but there are large positive deviations with respect to the cell parameters predicted by Vegard's rule for ideal solid solutions. The presence of Zr and Tb generates strain in the ceria lattice through the creation of crystal imperfections and O vacancies. The O K-edge and Tb LIII-edge XANES spectra for the Ce1–x–yZrxTbyO2 nanoparticles point to the existence of distinctive electronic properties. In Ce1–x–yZrxTbyO2 there is an unexpected high concentration of Tb3+, which is not seen in TbO2 or Ce1–xTbxO2 and enhances the chemical reactivity of the ternary oxide. Tb_O_Zr interactions produce a stabilization of the Tb(4f,5d) states that is responsible for the high concentration of Tb3+ cations. The behavior of Ce1–x–yZrxTbyO2 illustrates how important can be metal_oxygen_metal interactions for determining the structural, electronic, and chemical properties of a ternary oxide.The research carried out at the Chemistry Department of Brookhaven National Laboratory was financed through Contract No. DE-AC02-98CH10886 with the US Department of Energy (Division of Chemical Sciences). The NSLS is supported by the Divisions of Materials and Chemical Sciences of DOE. Work at the “Instituto de Catálisis y Petroleoquímica (CSIC)” was done with financial support from CICYT (Project No. MAT2000-1467).Peer reviewe

A Light Calibration System for the ProtoDUNE-DP Detector

A LED-based fiber calibration system for the ProtoDUNE-Dual Phase (DP) photon detection system (PDS) has been designed and validated. ProtoDUNE-DP is a 6x6x6 m3 liquid argon time-projection-chamber currently being installed at the Neutrino Platform at CERN. The PDS is based on 36 8-inch photomultiplier tubes (PMTs) and will allow triggering on cosmic rays. The system serves as prototype for the PDS of the final DUNE DP far detector in which the PDS also has the function to allow the 3D event reconstruction on non-beam physics. For this purpose an equalized PMT response is desirable to allow using the same threshold definition for all PMT groups, simplifying the determination of the trigger efficiency. The light calibration system described in this paper is developed to provide this and to monitor the PMT performance in-situ.Comment: 15 pages, 5 figure

Performances of multi-gap timing RPCs for relativistic ions in the range Z=1-6

We present the performance of Multi-gap timing RPCs under irradiation by fully stripped relativistic ions (gamma*beta=2.7, Z=1-6). A time resolution of 80 ps at high efficiency has been obtained by just using standard `off the shelf' 4-gap timing RPCs from the new HADES ToF wall. The resolution worsened to 100 ps for ~ 1 kHz/cm2 proton flux and for ~ 100 Hz/cm2 Carbon flux. The chambers were operated at a standard field of E=100 kV/cm and showed a high stability during the experiment, supporting the fact that RPCs are a convenient choice when accommodating a very broad range of ionizing particles is needed. The data provides insight in the region of very highly ionizing particles (up to x 36 mips) and can be used to constrain the existing avalanche and Space-Charge models far from the usual `mip valley'. The implications of these results for the general case of detection based on secondary processes (n, gamma) resulting in highly ionizing particles with characteristic energy distributions will be discussed, together with the nature of the time-charge correlation curve.Comment: 31 pages, 19 figures, submitted to JINS

Performance of a TMD to mitigate wind-induced interference effects between two industrial chimneys

This is the final version. Available on open access from MDPI via the DOI in this record. The present paper studies the performance of a tuned mass damper (TMD) installed in a 183 m tall chimney located at the edge of the wake shed by another chimney. Numerical and experimental results are available. For the simulations, wind action is considered by solving several 2D flow problems on a selected number of horizontal planes, in the transverse direction to the stacks. On such planes, Navier-Stokes equations are solved to estimate the fluid action at different positions of the chimneys and standard interpolation techniques are applied in the vertical direction. An Arbitrary Lagrangian-Eulerian (ALE) approach is used to consider the moving domain, and a fractional-step scheme is used to solve the fluid field. For the structural modelling, chimneys are meshed using 3D beam finite elements. The time integration procedure used for the structural dynamics is based on the standard second order Bossak method. For each period of time, the fluid problem is solved, the aeroelastic analysis is carried out and the geometry of the fluid mesh of each plane is updated according to the structural movements. With this procedure and model updating techniques, the response of the leeward chimney is evaluated for different scenarios, revealing an interesting dependence of the TMD performance on the wind speed and direction.International Committee on Industrial Chimney

Metronidazole photodegradation under solar light with UiO-66-NH2 photocatalyst: Mechanisms, pathway, and toxicity assessment

Metronidazole is a nitroimidazole antibiotic that is increasingly detected in aquatic bodies. Therefore, there is an urgent need to research methodologies to remove this and other antibiotics. One of the alternatives is the application of solar photocatalysis, which requires the use of an efficient photocatalyst. In this work, UiO-66-NH2 was synthesized by a facile solvothermal method and evaluated for the degradation of metronidazole under simulated solar light. The effects of catalyst dosage, initial pH, and metronidazole concentration were discussed, establishing the best operation conditions. In addition, the stability and reproducibility of UiO-66-NH2 activity were also verified. The quenching reaction showed that holes and superoxide radicals coexisted as the main active species, being responsible for the metronidazole degradation. The pathway of metronidazole photodegradation was proposed by means of density functional theory calculations and LC/ESI-MS analysis. It is noteworthy that this study detected for the first time C6H11N3O4, C4H6N2O3, and C4H8N2O4 as metronidazole photodegradation byproducts. ECOSAR toxicity analysis showed that all byproducts were less toxic than the original metronidazole, supporting the potential feasibility of this method for treating water polluted with this antibioticThis work was supported by the National State Research Agency of Spain (project number: PID2019–106186RB-I00/AEI/10.13039/ 501100011033). Yilan Wang acknowledges the financial support provided by China Scholarship Council (CSC No. 201908610198). The authors sincerely acknowledged support from the external services of the Autonomous University of Madrid (SIdI

Adsorption of emerging pollutants on lignin-based activated carbon: Analysis of adsorption mechanism via characterization, kinetics and equilibrium studies

Lignin has been employed as a precursor to synthesize activated carbons with the aim of lignin-biomass revalorization. The properties of these activated carbons were compared, and the best adsorbent was employed to remove two emerging pollutants from water, acetaminophen and acetamiprid. The adsorption mechanisms of pharmaceutical and pesticide compounds were analyzed, modeled and interpreted via statistical physics models. In particular, adsorption kinetics and isotherms of acetaminophen and acetamiprid at temperatures between 20 and 60 ◦C were quantified experimentally. Equilibrium data were fitted to different statistical physics-based isotherm models to establish the corresponding adsorption mechanism. A double layer adsorption model with one type of functional group was the best to correlate and explain the removal of these organic molecules. Steric parameters for the adsorption of these organic compounds were also calculated thus determining that their adsorption was multi-molecular. At tested operating conditions, acetaminophen adsorption was endothermic, while acetamiprid removal was exothermic. Physical adsorption forces were expected to be responsible for the removal of both compounds. This study reports new insights on the adsorption mechanisms of relevant emerging pollutants commonly found in water worldwid

TiO2:Cex onto Al Clays for Photocatalytic Solar Water Disinfection

A novel methodology was employed to prepare new nanocomposites with photocatalytic properties based on Ce-doped TiO2 nanoparticles arranged over a layered silicate. The catalysts were porous materials formed by exfoliated silicate layers surrounded by anatase nanoparticles. In this way, the anatase was doped by different amounts of Ce, yielding to catalysts with light absorption properties on the visible region. The photocatalytic behavior was tested for different reactions: adsorption and photocatalysis, showing outstanding and promising results for the removal of bacteria by using solar light as an energy source. The influence of the physicochemical properties of the catalyst and the reaction parameters will be studied in detail to manage new catalysts for the disinfection of drinking water

Role of Na+ transporters HKT1;1 and HKT1;2 in tomato salt tolerance. I. Function loss of cheesmaniae alleles in roots and aerial parts

We wish to thank Elena Sanchez Romero (EEZ-CSIC) for her technical assistance, the Scientific Instrumentation Service at EEZ-CSIC, Granada, for their ICP-OES mineral analysis and Michael O'Shea for proofreading the manuscript. The study was funded by grant AGL201782452-C2-1R (A.B.) and grant AGL2017-82452-C2-2R (M.J.A.), both from the Spanish Ministerio de Ciencia e Innovacion/Agencia Estatal de Investigacion, MCIN/AEI/10.13039/501100011033, and FEDER "Una manera de hacer Europa", as well as grant ACCESP2018 (J.A.T.) from the University of Granada. J.E. was supported by a JAE Intro-CSIC grant, JAEINT_19_00566.We analyzed the physiological impact of function loss on cheesmaniae alleles at the HKT1;1 and HKT1;2 loci in the roots and aerial parts of tomato plants in order to determine the relative contributions of each locus in the different tissues to plant Na+/K+ homeostasis and subsequently to tomato salt tolerance. We generated different reciprocal rootstock/scion combinations with non-silenced, single RNAi-silenced lines for ScHKT1;1 and ScHKT1;2, as well as a silenced line at both loci from a near isogenic line (NIL14), homozygous for the Solanum cheesmaniae haplotype containing both HKT1 loci and subjected to salinity under natural greenhouse conditions. Our results show that salt treatment reduced vegetative growth and altered the Na+/K+ ratio in leaves and flowers; negatively affecting fruit production, particularly in graft combinations containing single silenced ScHKT1;2- and double silenced ScHKT1;1/ScHKT1;2 lines when used as scion. We concluded that the removal of Na+ from the xylem by ScHKT1;2 in the aerial part of the plant can have an even greater impact than that on Na+ homeostasis at the root level under saline conditions. Also, ScHKT1;1 function loss in rootstock greatly reduced the Na+/K+ ratio in leaf and flower tissues, minimized yield loss under salinity. Our results suggest that, in addition to xylem Na+ unloading, ScHKT1;2 could also be involved in Na+ uploading into the phloem, thus promoting Na+ recirculation from aerial parts to the roots. This recirculation of Na+ to the roots through the phloem could be further favoured by ScHKT1;1 silencing at these roots.Spanish Ministerio de Ciencia e Innovacion/Agencia Estatal de Investigacion AGL2017-82452-C2-1R AGL2017-82452-C2-2RFEDER "Una manera de hacer Europa" MCIN/AEI/10.13039/501100011033University of Granada ACCESP2018JAE Intro-CSIC grant JAEINT_19_0056