Dimensional crossover of correlated anion disorder in oxynitride perovskites

A simple crossover from two-dimensional to three-dimensional correlated disorder of O and N atoms on a cubic lattice has been discovered within the Ba1xSrxTaO2N series of perovskite oxynitrides. The crossover is driven by lattice expansion as x decreases, and provides a rapid increase in entropy due to a change from subextensive to extensive configurational entropy regimes.We thank STFC, UK for support for H. J. and provision of ISIS beamtime, and EPSRC for additional support. This work was also supported by the Ministerio de Economia y Competitividad (MINECO), Spain through Project MAT2017-86616-R, the Severo Ochoa Program SEV-2015-0496, and Fellowship support to AB (MAT2011-24757). We thank the ALBA synchrotron for the provision of beamtime and Prof. Rosa Palacin, Dr Carlos Frontera (ICMAB-CSIC) and Dr F. Fauth (ALBA) for assistance with data collection.Peer reviewe

Biogeochemistry of Plane Trees as a Tool to Detect Atmospheric Pollution

The plane tree, which is a valuable tool to detect atmospheric pollution, is one of the most common trees in European cities. Soil and leaf samplings were carried out in Barcelona and its environs (NE Spain) to establish the soil-plant relationship.Dry and ashed leaves and soils were analyzed by Instrumental Neutron Activation Analysis and Inductively Coupled Plasma-Optical Emission Spectroscopy (ICP/OES) at the ACTLABS laboratories in Ontario, Canada. Given that diesel is the main fuel used in vehicles in Europe, we sought to establish the role of diesel in atmospheric pollution. Diesel samples were obtained from service stations and analyzed after preconcentration using ICP/MS at the geochemistry laboratories of the University of Barcelona. The average content of diesel oil shows high values of Pb, Cu, Cr, Ag, Cd and Mn. High values of Pb, Cu, Au, Hg and Sb in leaves and soils were detected downtown and along main roadsoutside the city, whereas low levels of these elements were observed in rural areas

Multibiomarker approach to fipronil exposure in the fish Dicentrarchus labrax under two temperature regimes

Fipronil is a phenylpyrazole insecticide widely used to control pests in agriculture even though evidence of harmful side effects in non-target species has been reported. A comprehensive study on the effects of dietary administration of Regent®800WG (80 % fipronil) in European sea bass juveniles was carried out under two temperature regimes: a) natural conditions, and b) 3 °C above the natural temperature (an increase predicted for the NW Mediterranean by the end of this century). Fipronil was added to the fish food (10 mg fipronil /Kg feed) and the effects were studied at several time points including right before administration, 7 and 14 days after daily fipronil feed and one-week after the insecticide withdrawal from the diet (depuration period). A wide array of physiological and metabolic biomarkers including feeding rate, general condition indices, plasma and epidermal mucus metabolites, immune response, osmoregulation, detoxification and oxidative-stress markers and digestive enzymes were assessed. General linear models and principal component analyses indicated that regardless of water temperature, fipronil resulted in a significant alteration of several of the above listed biomarkers. Among them, glucose and lactate levels increased in plasma and decreased in epidermal mucus as indicators of a stress response. Similarly, a depletion in catalase activity and higher lipid peroxidation in liver of fipronil-exposed fish were also indicative of an oxidative-stress condition. Fipronil induced a time dependent inhibition of Cytochrome P450-related activities and an increase of phase II glutathione-S-transferase. Moreover, fipronil administration was able to reduce the hypo-osmoregulatory capability as shown by the increase of plasmatic osmolality and altered several digestive enzymes including trypsin, lipase, alpha amylase and maltase. Finally, analyses in bile and muscle confirmed the rapid clearance of fipronil but the persistence of the metabolite fipronil-sulfone in bile even after the 7-day depuration period. Altogether, the results reveal a notable impact of this compound on the physiological condition of the European sea bass. The results should be considered in future environmental risk assessment studies since fipronil could be hazardous to fish species, particularly those inhabiting estuarine ecosystems exposed to the discharge of agriculture runoffs where this pesticide is mainly used

Processes controlling the fate of chloroethenes emanating from dnapl aged sources in river-aquifer contexts

This work dealt with the physical and biogeochemical processes that favored the natural attenuation of chloroethene plumes of aged sources located close to influent rivers in the presence of co-contaminants, such as nitrate and sulfate. Two working hypotheses were proposed: i) Reductive dechlorination is increased in areas where the river-aquifer relationship results in the groundwater dilution of electron acceptors, the reduction potential of which exceeds that of specific chloroethenes; ii) zones where silts predominate or where textural changes occur are zones in which biodegradation place preferentially takes place. A field site on a Quaternary alluvial aquifer at Torelló, Catalonia (Spain) was selected to validate these hypotheses. This aquifer is adjacent to an influent river and its redox conditions favor reductive dechlorination. The main findings showed that the low concentrations of nitrate and sulfate due to dilution caused by the input of surface water diminish the competition for electrons between microorganisms that reduce co-contaminants and chloroethenes. Under these conditions, the most bioavailable electron acceptors were PCE and metabolites, which meant that their biodegradation was favored. This led to the possibility of devising remediation strategies based on bioenhancing natural attenuation. The artificial recharge with water that is low in nitrates and sulfates may favor dechlorinating microorganisms if the redox conditions in the mixing water are sufficiently maintained as reducing and if there are nutrients, electron donors and carbon sources necessary for these microorganisms

Pharmacogenetics of Immunosuppressants in Solid Organ Transplantation: Time to Implement in the Clinic

Our aim in this chapter is to present the state of the art, including our own group research, in the field of immunosuppressant pharmacogenetics in the four main types of solid organ transplantation: kidney, heart, lung, and liver. The main focus will be on those findings in the field that have been widely investigated and then in those that are close to clinical implementation, mainly CYP3A5 genotyping for the adjustment of the initial tacrolimus dose. This recommendation will be discussed in more detail, explaining its clinical potential as well as its limitations. To end, a short opinion about the feasibility of implementation in the health systems as well as discussion about private companies selling pharmacogenetic tests will be presented

A new intermediate intercalate in superconducting sodium-doped hafnium nitride chloride

Anew phase has been observed during the sodiumintercalation of hafnium nitride chloride as intermediate between the host β-HfNCl and the already reported Na 0.29 HfNCl with Tc of 24 K; the new intermediate shows interlayer spacings ranging from 9.48 to 9.67 A°, corresponds to a second stage intercalate of HfNCl and is superconducting with a critical temperature of 20 K.Beltran Porter, Daniel, [email protected]

Temporal hydrochemical and microbial variations in microcosm experiments from sites contaminated with chloromethanes under biostimulation with lactic acid

The objective of our research is to identify the sequence of degradation processes leading to microbial speciation of microorganisms involved in degradation of CT and CF under natural attenuation and lactic acid biostimulation conditions. To this end, a comparative study of two types of microcosm experiments was carried out to analyze two scenarios: natural attenuation and lactic acid biostimulation. Experiments were carried out with water and sediment from a field site located at a petrochemical complex whose hydrochemical background inhibited the natural attenuation of carbon tetrachloride and chloroform. A significant result of our work was that these experiments allowed us to identify the CT abiotic degradation processes, among which the abiotic degradation induced by the biogenic activity of Dechlorosoma suillum should be noted. Although this is an abiotic degradation, the metabolism of this microorganism generates green rust precipitates, which in turn favor the abiotic reductive dechlorination of CT. Other relevant result was the identification of the biotic reductive dechlorination of CF by a bacterium of the Clostridiales order. This result presented the particularity that an apparent absence of isotopic fractionation was observed because a mixture of chloroform of different origins was produced. Our research showed that these processes were more efficient, in terms of faster degradation rates, when biostimulation with lactic acid was carried out. This biostimulation could therefore be an efficient remediation strategy at sites contaminated by chloromethanes, especially in cases where a complex pollution history results in a rich hydrochemical background that makes it difficult natural attenuation

Engineering Polar Oxynitrides: Hexagonal Perovskite BaWON2

Non-centrosymmetric polar compounds have important technological properties. Reported perovskite oxy- nitrides show centrosymmetric structures, and for some of them high permittivities have been observed and ascribed to local dipoles induced by partial order of nitride and oxide. Reported here is the first hexagonal perovskite oxynitride BaWON2, which shows a polar 6H polytype. Synchrotron X-ray and neutron powder diffraction, and annular bright-field in scan- ning transmission electron microscopy indicate that it crystal- izes in the non-centrosymmetric space group P63mc, with a total order of nitride and oxide at two distinct coordination environments in cubic and hexagonal packed BaX3 layers. A synergetic second-order Jahn-Teller effect, supported by first principle calculations, anion order, and electrostatic repulsions between W6+ cations, induce large distortions at two inequiva- lent face-sharing octahedra that lead to long-range ordered dipoles and spontaneous polarization along the c axis. The new oxynitride is a semiconductor with a band gap of 1.1 eV and a large permittivity