Isotope analysis of water by means of near-infrared dual-wavelength diode laser spectroscopy

A novel diode laser spectrometer was developed using dual-wavelength multiplexing, ensuring ideal conditions for high-precision and simultaneous measurements of the 2H/1H, 17O/16O, and 18O/16O isotope ratios in water. A 1.4-µm diode laser probed a H16OH/HO2H line pair near 7198 cm-1, while a similar laser observed H16OH, H17OH, and H18OH ro-vibrational lines around 7183 cm-1, or a H16OH/H18OH line pair near 7200 cm–1. The 1-σ standard deviation is 0.2‰ for 18O/16O, and 0.5‰ for the 2H/1H and 17O/16O isotope ratios. Preliminary experiments with repeated injections of a natural abundance sample point to an accuracy of about 1‰ for all three isotope ratios in natural samples.

Modeling metal influence on the gate opening in ZIF-8 materials

Zeolitic imidazolate frameworks (ZIFs) undergo pressure-induced phase transitions that are peculiar to each ZIF. The phase transition is associated with the rotation of the imidazolate, and it is accompanied by an increase of their pore openings, affecting ZIFs performance in separation processes. This phenomenon is known as the gate opening or the swing effect. Here we report the metal dependence of the ambient pressure and high pressure (HP) phases of ZIF-8(M) with M = Mg, Fe, and Zn, determined by using periodic Kohn-Sham density functional models. We show that the substitution of Zn with Mg or Fe has a big influence on the gate opening energy, which significantly decreases, an opposite trend than what was previously reported upon functionalization of the linker. The lowest energy phase of ZIF-8(Fe) is different than for ZIF-8(Mg) and ZIF-8(Zn), and its structure is significantly closer to the HP phase. Multireference wave function methods have been used to study the electronic structure of ZIF-8(Fe), confirming the metal center to be high spin (S = 2) divalent iron in antiferromagnetic coupling. The high-spin nature of the iron species coupled with a band gap in the visible light range makes ZIF-8(Fe) an interesting material for catalysis and photocatalysis

Thermal Treatment Effect on CO and NO Adsorption on Fe(II) and Fe(III) Species in Fe3O-Based MIL-Type Metal-Organic Frameworks: A Density Functional Theory Study

The properties of metal-organic frameworks (MOFs) based on triiron oxo-centered (Fe3O) metal nodes are often related to the efficiency of the removal of the solvent molecules and the counteranion chemisorbed on the Fe3O unit by postsynthetic thermal treatment. Temperature, time, and the reaction environment play a significant role in modifying key features of the materials, that is, the number of open metal sites and the reduction of Fe(III) centers to Fe(II). IR spectroscopy allows the inspection of these postsynthetic modifications by using carbon monoxide (CO) and nitric oxide (NO) as probe molecules. However, the reference data sets are based on spectra recorded for iron zeolites and oxides, whose structures are different from the Fe3O one. We used density functional theory to study how the adsorption enthalpy and the vibrational bands of CO and NO are modified upon dehydration and reduction of Fe3O metal nodes. We obtained a set of theoretical spectra that can model the modification observed in previously reported experimental spectra. Several CO and NO bands were previously assigned to heterogeneous Fe(II) and Fe(III) sites, suggesting a large defectivity of the materials. On the basis of the calculations, we propose an alternative assignment of these bands by considering only crystallographic iron sites. These findings affect the common description of Fe3O-based MOFs as highly defective materials. We expect these results to be of interest to the large community of scientists working on Fe(II)- and Fe(III)-based MOFs and related materials

Comparing the reaction profiles of single iron catalytic sites in enzymes and in reticular frameworks for methane-to-methanol oxidation

The design of synthetic inorganic catalysts mimicking the first coordination spheres of enzymatic cofactors often results in lower yields and selectivity than their biological counterparts. In this study, we exploit Kohn-Sham density functional methods to compare the reaction profiles of four single iron-based catalysts for the direct oxidation of methane to methanol: two biomimetic models based on two enzymes (cytochrome P450 and taurine dioxygenase [TauD]) and two synthetic reticular frameworks (iron-BEA zeolite and tri-iron oxo-center-based metal-organic framework). Both the biomimetic and inorganic catalysts show almost zero selectivity toward methanol for methane conversions >1% at ambient temperature. This study highlights that iron's first coordination shell can influence selectivity toward methanol but to a limited extent. In the absence of methanol protection strategies, high selectivity can be reached only by mimicking the reaction microenvironment of enzymes beyond the first coordination shell of iron

Use of microbial fuel cells for soil remediation. A preliminary study on DDE

DDE (2,2-bis (p-chlorophenyl)-1,1-dichloroetylene) is a very persistent and bioaccumulative pesticide and its residues are continuously found in the environment. Among the green remediation strategies for soil recovery, terrestrial Microbial Fuel Cells (MFC) are arousing great interest in scientific community. MFCs transform energy stored in the chemical bonds of organic compounds into electrical energy thanks to exo-electrogen microorganisms naturally occurring in soil, which catalyse oxidation and reduction reactions in the area between two graphite electrodes. This work reports preliminary data on the use of MFCs for promoting soil decontamination from DDE. Several experimental conditions (e.g. addition of compost and open/closed circuit) were applied for assessing how to improve MFC performance in favouring DDE removal. MFCs promoted a significant DDE removal (39%) after 2 months, while at the same time any pesticide decrease was observed in the batch condition. Compost addition stimulated microbial activity and improved MFC performance for a longer time

Stabilization of a p-u sensor mounted on a vehicle for measuring the acoustic impedance of road surfaces

The knowledge of the acoustic impedance of a material allows for the calculation of its acoustic absorption. Impedance can also be linked to structural and physical proprieties of materials. However, while the impedance of pavement samples in laboratory conditions can usually be measured with high accuracy using devices such as the impedance tube, complete in-situ evaluation results are less accurate than the laboratory results and is so time consuming that a full scale implementation of in-situ evaluations is practically impossible. Such a system could provide information on the homogeneity and the correct laying of an installation, which is proven to be directly linked to its acoustic emission properties. The present work studies the development of a measurement instrument which can be fastened through holding elements to a moving laboratory (i.e., a vehicle). This device overcomes the issues that afflict traditional in-situ measurements, such as the impossibility to perform a continuous spatial characterization of a given pavement in order to yield a direct evaluation of the surface’s quality. The instrumentation has been uncoupled from the vehicle’s frame with a system including a Proportional Integral Derivative (PID) controller, studied to maintain the system at a fixed distance from the ground and to reduce damping. The stabilization of this device and the measurement system itself are evaluated and compared to the traditional one

Branching ratios for the beta decay of 21Na

We have measured the beta-decay branching ratio for the transition from 21Na to the first excited state of 21Ne. A recently published test of the standard model, which was based on a measurement of the beta-nu correlation in the decay of 21Na, depended on this branching ratio. However, until now only relatively imprecise (and, in some cases, contradictory) values existed for it. Our new result, 4.74(4)%, reduces but does not remove the reported discrepancy with the standard model.Comment: Revtex4, 2 fig

Novel laser-based techniques for monitoring of volcanoes

An overview of novel laser techniques suitable for volcanic monitoring, based on different kinds of infrared laser sources, is presented. Their main advantages and drawbacks are discussed focusing on the achievable sensitivity and precision levels in analysis of gaseous species. Some of the most recent experimental results obtained in laboratory development as well as in field tests of home-built laser spectrometers are reported. New perspectives in optical devices aimed at geochemical and geophysical applications are also considered

Asymptotic normalization coefficient of ^{8}B from breakup reactions and the S_{17} astrophysical factor

We show that asymptotic normalization coefficients (ANC) can be extracted from one nucleon breakup reactions of loosely bound nuclei at 30-300 MeV/u. In particular, the breakup of ^{8}B is described in terms of an extended Glauber model. The 8B ANC extracted for the ground state of this nucleus from breakup data at several energies and on different targets, C^2 = 0.450+/-0.039} fm^-1, leads to the astrophysical factor S_{17}(0)= 17.4+/-1.5 eVb for the key reaction for solar neutrino production 7Be(p,gamma)8B. The procedure described here is more general, providing an indirect method to determine reaction rates of astrophysical interest with beams of loosely bound radioactive nuclei.Comment: 4 pages, RevTex, 3 figures revised version to appear in Phys Rev Let

Efecto de las variables de operación en la resistencia a la corrosión en recubrimientos de aleaciones de Zinc Níquel con adiciones de partículas de CSi y Al2O3 y aditivo

El recubrimiento metálico de zinc aleado con otros metales como el níquel, tiene muy buena resistencia contra la corrosión. Se encontró que las microestructuras de los recubrimientos son de granos más finos con partículas y que la morfología depende de espesores de los recubrimientos. El tipo de partículas y la cantidad de las mismas en solución modifican su incorporación a la aleación aumentando la dureza y el contenido de níquel en la aleación. Se hicieron fotomicrografías en microscopio electrónico y óptico (en muestras vistas en corte con partículas). Se realizaron los diagramas de difracción de rayos X en muestras con recubrimiento de la aleación de Zn-Ni con y sin partículas sobre acero. Los depósitos se realizaron a partir de soluciones concentradas en ambos componentes, Zn y Ni a corriente constante, y a tiempos de deposición en aumento de 5 a 30 minutos, con el agregado de partículas a la solución. Se encontró que la microestructura cambia notablemente con el agregado de CSi o de Al2O3 a la aleación de Zn-Ni. Además con el agregado de partículas al recubrimiento, aumenta el porcentaje de Ni en el Zn-Ni, lo cual está relacionado con una mayor resistencia contra la corrosión. Los diagramas de difracción muestran que con el agregado de partículas de CSi se destaca una presencia importante de orientaciones preferenciales (330) en la fase γ, los cuales se incrementan con el tiempo de deposición. Asociado al incremento de textura en orientaciones (330), se incrementan además las tensiones residuales compresivas en los depósitos de Zn-Ni. Con el agregado de partículas de alúmina predomina el desarrollo de una fuerte textura asociada con las orientaciones (110) de la fase η, las cuales son predominantes a tiempos de deposición intermedios (t aprox. 10 minutos) y disminuyen notablemente a tiempos superiores. Sin el agregado de partículas y con el agregado de partículas de CSi o de Al2O3 , las orientaciones (101) asociadas a la fase Zn no muestran un desarrollo de textura u orientación preferencial. Las texturas medidas para muestras de varios micrones de espesor tienen valores con intensidades de texturas menores que en un espesor mayor en 10 micrones. Asimismo se encontró que para ese espesor de 10 micrones el material presenta mayor resistencia a la corrosión. Se midió la resistencia de Transferencia de Carga del material RTC en ohm por Impedancia en muestras de igual espesor en el espesor óptimo de 10 micrones es RTC para muestras producidas a 8Adm-2 durante 10 minutos de electrólisis. Los valores de RTC medidos son: RTC ZnNi + Al2O3 > RTC ZnNi + CSi > RTC ZnNi sólo. Se midió RTC en función del espesor y se encontró que hay un espesor óptimo de 10 micrones a partir del cual aumenta el valor de RTC y disminuye la densidad de corriente de corrosión. En los ensayos de Niebla salina en muestras de igual espesor, se encontró que el porcentaje del área con corrosión blanca es menor para el Zn Ni con Al 2 O 3 respecto del área afectada en los otros casos. El principal aporte del trabajo está relacionado con el cambio de la microestructura y de texturas, según las partículas adicionadas al recubrimiento. Se debe tener en cuenta que en el material, en el caso de la adición de micropartículas de CSi o de Al2O3 se produce el cambio del porcentaje de níquel en la aleación, la dureza y del cambio de texturas.The metallic coating of zinc alloyed with other metals such as nickel, has very good corrosion resistance. It was found that the type and quantity of particles, increases the hardness and the nickel content in the alloy. Photomicrographs were made in electronic and optical microscope (in samples with particle, sectional views). It has investigated the dependence of the percentage of Ni in the alloy and the addition of both types of particles, the applied current density , and composition of particles in the solution (20 to 60 g/l ). It has been found that the Ni contents is between 11 to 17 %, for applied current densities between 8 and 30 Adm-2. The microhardness values in the Zn-Ni are from 200 Hv and their values are increased to 400-500 Hv (Vickers) in the presence of particles. We have measured the resistance of the material in ohm by Impedance, being the ZnNi in the presence of particles: RTC ZnNi + Al2O3 > RTC ZnNi + CSi > RTC ZnNi. The RTC value is according to the thickness coatings and we have found that there is an optimum thickness of 10 microns in which the value of RTC is increases and de corrosion current density decreases. In salt spray tests on samples with the same thickness, it was found that the area with white rust is lower for Zn Ni with Al2O3 on the affected area in other cases.Fil:Mahmud, Z. Instituto Nacional de Tecnología Industrial (INTI). Procesos SuperficialesFil:Pina, J. Instituto Nacional de Tecnología Industrial (INTI). Procesos SuperficialesFil:Gagliardi, J. Instituto Nacional de Tecnología Industrial (INTI). Procesos SuperficialesFil:Amelotti, F. Instituto Nacional de Tecnología Industrial (INTI). Procesos SuperficialesFil:Gassa, L. Universidad Nacional de La Plata (UNLP). Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y AplicadasFil:Míngolo, N. Comisión Nacional de Energía Atómica (CNEA)Fil:Gordillo, G. Universidad de Buenos Aires (UBA). Facultad de Ciencias Exactas y Naturales. Departamento de Química Inorgánica, Analítica y Química Físic