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AbstractThe ethylene glycol oxidation reaction on nickel and ruthenium modified palladium nanocatalysts was investigated with electrochemical, spectroelectrochemical, and chromatographic methods. These carbon‐supported materials, prepared by a revisited polyol approach, exhibited high activity towards the ethylene glycol electrooxidation in alkaline medium. Electrolysis coupled with high performance liquid chromatography/mass spectrometry (HPLC‐MS) and in situ Fourier transform infrared spectroscopy (FTIRS) measurements allowed us to determine the different compounds electrogenerated in the oxidative conversion of this two‐carbon molecule. High value‐added products such as oxalate, glyoxylate, and glycolate were identified in all electrolytic solutions, whereas glyoxylate was selectively formed at the Ru45@Pd55/C electrode surface. In situ FTIRS results also showed a decrease in the pH value in the thin layer near the electrode as a consequence of OH− consumption during the spectroelectrochemical experiments.

In the present study, we explored the temperature evolution and hydrogen desorption properties of the Mg50Ni50 alloy through both numerical simulation and experimental analyses. Desorption kinetics characterization was carried out using the volumetric method, specifically employing a Sievert's-type apparatus to investigate solid-gas reactions. The experiments covered a temperature range from 313 K to 353 K, with an initial hydrogen pressure of 12 bar. Simultaneously, a mathematical approach was employed to numerically investigate the temperature evolution within the hydride bed. Using COMSOL Multiphysics as a simulator, a numerical simulation was conducted based on experimental data. The study examined the impact of cooling temperature on hydride temperature evolution. Results revealed that hydrogen desorption kinetics of the amorphous Mg50Ni50 alloy are more significant compared to those of Mg2Ni compounds. Moreover, the effect of the warming temperature on the equilibrium pressure can also be observed in the hydrogen desorption isotherm curves. The experimental study of the Mg50Ni50 alloy provided activation energy data, along with determination of hydride formation enthalpy and entropy. On the other hand, we showed that the hydride temperature is maximum at the hydride-hydrogen interface within the hydride center.

Abstract. Flooding in the Amazon basin is frequently attributed to modes of large-scale climate variability, but little attention is paid to how these modes influence the timing and duration of floods despite their importance to early warning systems and the significant impacts that these flood characteristics can have on communities. In this study, river discharge data from the Global Flood Awareness System (GloFAS 2.1) and observed data at 58 gauging stations are used to examine whether positive or negative phases of several Pacific and Atlantic indices significantly alter the characteristics of river flows throughout the Amazon basin (1979–2015). Results show significant changes in both flood magnitude and duration, particularly in the north-eastern Amazon for negative El Niño–Southern Oscillation (ENSO) phases when the sea surface temperature (SST) anomaly is positioned in the central tropical Pacific. This response is not identified for the eastern Pacific index, highlighting how the response can differ between ENSO types. Although flood magnitude and duration were found to be highly correlated, the impacts of large-scale climate variability on these characteristics are non-linear; some increases in annual flood maxima coincide with decreases in flood duration. The impact of flood timing, however, does not follow any notable pattern for all indices analysed. Finally, observed and simulated changes are found to be much more highly correlated for negative ENSO phases compared to the positive phase, meaning that GloFAS struggles to accurately simulate the differences in flood characteristics between El Niño and neutral years. These results have important implications for both the social and physical sectors working towards the improvement of early warning action systems for floods.

Climate change is expected to increase temperature and decrease summer precipitation in Central Europe. Little is known about how warming and drought will affect phenological patterns of oaks, which are considered to possess excellent adaptability to these climatic changes. Here, we investigated bud burst and intra-annual shoot growth of Quercus robur, Q. petraea and Q. pubescens grown on two different forest soils and exposed to air warming and drought. Phenological development was assessed over the course of three growing seasons. Warming advanced bud burst by 1–3 days °C−1 and led to an earlier start of intra-annual shoot growth. Despite this phenological shift, total time span of annual growth and shoot biomass were not affected. Drought changed the frequency and intensity of intra-annual shoot growth and advanced bud burst in the subsequent spring of a severe summer drought by 1–2 days. After re-wetting, shoot growth recovered within a few days, demonstrating the superior drought tolerance of this tree genus. Our findings show that phenological patterns of oaks are modified by warming and drought but also suggest that ontogenetic factors and/or limitations of water and nutrients counteract warming effects on the biomass and the entire span of annual shoot growth. PLoS ONE, 9 (2) ISSN:1932-6203

If femoral blood is not available at autopsy, toxicological analyses, in particular blood ethanol measurements, are carried out on cardiac blood. This is known to be subject to major redistribution. We aimed to determine whether subclavian blood can be equated with a peripheral blood sample and could be used if femoral blood is not available. The study was based on 50 medicolegal autopsies in which we compared ethanol concentrations between subclavian blood, the different heart blood compartments (right and left cardiac blood), and femoral blood. Mechanisms that could lead to variations in concentration, i.e., postmortem redistribution and/or endogenous production, were also taken into account in interpreting the results. Ethanol concentrations were determined by headspace gas chromatography with a flame ionization detector. In each case, we recorded the circumstances of death, resuscitation attempts if any, degree of putrefaction, chest or abdominal trauma, and/or inhalation of gastric fluid in the airways. Ethanol concentrations in subclavian blood were found to be close to those in peripheral blood (p = 0.948) and were not influenced by the degree of putrefaction (r = 0.017, p = 0.904), gastric ethanol concentration (r = -0.011, p = 0.940), inhalation of gastric contents in the airways (p = 0.461), or cardiac resuscitation attempts (p = 0.368). We discuss the possible explanations for these findings and stress the value of sampling subclavian blood when femoral blood is not obtainable at autopsy.

Dans les latitudes tempérées élevées, les ongulés donnent généralement naissance dans une fenêtre temporelle étroite lorsque les conditions sont optimales pour la survie de la progéniture au printemps ou au début de l'été, et utilisent une photopériode changeante pour les conceptions temporelles afin d'anticiper ces conditions. Cependant, dans les basses latitudes tropicales, la variation de la durée du jour est minime et la variation des précipitations rend le cycle saisonnier moins prévisible. Néanmoins, plusieurs espèces d'ongulés conservent des pics de naissance étroits dans de telles conditions, tandis que d'autres montrent que les naissances se propagent assez largement tout au long de l'année. Nous avons étudié comment la variation des précipitations d'une année à l'autre et d'une année à l'autre a influencé le moment de la reproduction de quatre espèces d'ongulés montrant ces modèles contrastés dans la région de Masai Mara au Kenya. Les quatre espèces présentaient des pics de naissance au cours de la période optimale putative au début de la saison humide. Pour le hartebeest et l'impala, le pic de naissance est diffus et la progéniture naît tout au long de l'année. En revanche, le topi et le phacochère ont montré une concentration saisonnière étroite de naissances, avec des conceptions supprimées une fois que les précipitations mensuelles sont tombées en dessous d'un seuil. Les fortes précipitations de la saison précédente et les fortes pluies précoces de l'année en cours ont amélioré la survie au stade juvénile de toutes les espèces, à l'exception de l'impala. Nos résultats révèlent comment la variation des précipitations affectant la croissance des graminées et donc la nutrition des herbivores peut régir la phénologie reproductive des ongulés dans les latitudes tropicales où la variation de la longueur du jour est minime. Le mécanisme sous-jacent semble être la suppression des conceptions une fois que les gains nutritionnels deviennent insuffisants. En réagissant de manière proximale à la variation des précipitations au cours de l'année, les ongulés de la savane tropicale sont moins susceptibles d'être affectés négativement par les conséquences du réchauffement climatique sur la phénologie de la végétation que les ongulés du Nord montrant un contrôle photopériodique plus rigide sur le moment de la reproduction. En latitudes templadas altas, los ungulados generalmente dan a luz dentro de una ventana de tiempo estrecha cuando las condiciones son óptimas para la supervivencia de la descendencia en primavera o principios del verano, y utilizan conceptos cambiantes de fotoperíodo a tiempo para anticipar estas condiciones. Sin embargo, en latitudes tropicales bajas, la variación de la duración del día es mínima, y la variación de las precipitaciones hace que el ciclo estacional sea menos predecible. Sin embargo, varias especies de ungulados conservan picos de nacimiento estrechos en tales condiciones, mientras que otras muestran nacimientos muy extendidos a lo largo del año. Investigamos cómo la variación interanual de las precipitaciones influyó en el tiempo reproductivo de cuatro especies de ungulados que muestran estos patrones contrastantes en la región de Masai Mara en Kenia. Las cuatro especies exhibieron picos de nacimiento durante el periodo óptimo putativo en la estación húmeda temprana. Para hartebeest e impala, el pico de nacimiento era difuso y las crías nacían durante todo el año. Por el contrario, topi y jabalí mostraron una estrecha concentración estacional de nacimientos, con concepciones suprimidas una vez que las precipitaciones mensuales cayeron por debajo de un nivel umbral. Las altas precipitaciones en la temporada anterior y las altas lluvias tempranas en el año en curso mejoraron la supervivencia en la etapa juvenil para todas las especies, excepto los impalas. Nuestros hallazgos revelan cómo la variación de la precipitación que afecta el crecimiento de la hierba y, por lo tanto, la nutrición de los herbívoros, puede gobernar la fenología reproductiva de los ungulados en latitudes tropicales donde la variación de la duración del día es mínima. El mecanismo subyacente parece ser la supresión de las concepciones una vez que las ganancias nutricionales se vuelven insuficientes. Al responder proximalmente a la variación de las precipitaciones dentro del año, es menos probable que los ungulados de la sabana tropical se vean afectados negativamente por las consecuencias del calentamiento global para la fenología de la vegetación que los ungulados del norte que muestran un control fotoperiódico más rígido sobre el tiempo reproductivo. In high temperate latitudes, ungulates generally give birth within a narrow time window when conditions are optimal for offspring survival in spring or early summer, and use changing photoperiod to time conceptions so as to anticipate these conditions. However, in low tropical latitudes day length variation is minimal, and rainfall variation makes the seasonal cycle less predictable. Nevertheless, several ungulate species retain narrow birth peaks under such conditions, while others show births spread quite widely through the year. We investigated how within-year and between-year variation in rainfall influenced the reproductive timing of four ungulate species showing these contrasting patterns in the Masai Mara region of Kenya. All four species exhibited birth peaks during the putative optimal period in the early wet season. For hartebeest and impala, the birth peak was diffuse and offspring were born throughout the year. In contrast, topi and warthog showed a narrow seasonal concentration of births, with conceptions suppressed once monthly rainfall fell below a threshold level. High rainfall in the previous season and high early rains in the current year enhanced survival into the juvenile stage for all the species except impala. Our findings reveal how rainfall variation affecting grass growth and hence herbivore nutrition can govern the reproductive phenology of ungulates in tropical latitudes where day length variation is minimal. The underlying mechanism seems to be the suppression of conceptions once nutritional gains become insufficient. Through responding proximally to within-year variation in rainfall, tropical savanna ungulates are less likely to be affected adversely by the consequences of global warming for vegetation phenology than northern ungulates showing more rigid photoperiodic control over reproductive timing. في خطوط العرض المعتدلة العالية، تلد ذوات الحوافر عمومًا في غضون فترة زمنية ضيقة عندما تكون الظروف مثالية لبقاء النسل في الربيع أو أوائل الصيف، وتستخدم تغيير الفترة الضوئية إلى مفاهيم زمنية لتوقع هذه الظروف. ومع ذلك، في خطوط العرض الاستوائية المنخفضة، يكون تباين طول اليوم ضئيلًا، ويجعل تباين هطول الأمطار الدورة الموسمية أقل قابلية للتنبؤ. ومع ذلك، فإن العديد من الأنواع ذوات الحوافر تحتفظ بقمم ولادة ضيقة في ظل هذه الظروف، في حين أن البعض الآخر يظهر أن الولادات تنتشر على نطاق واسع خلال العام. لقد حققنا في كيفية تأثير التباين في هطول الأمطار خلال العام وبين الأعوام على التوقيت التكاثري لأربعة أنواع من ذوات الحوافر تظهر هذه الأنماط المتناقضة في منطقة ماساي مارا في كينيا. أظهرت جميع الأنواع الأربعة قمم ولادة خلال الفترة المثلى المفترضة في موسم الأمطار المبكر. بالنسبة لحيوان النحل والامبالا، كانت ذروة الولادة منتشرة وولدت ذرية على مدار العام. على النقيض من ذلك، أظهر التوبي والخنزير الحربي تركيزًا موسميًا ضيقًا للولادات، مع قمع المفاهيم بمجرد انخفاض هطول الأمطار الشهري إلى ما دون مستوى العتبة. عزز ارتفاع هطول الأمطار في الموسم السابق وارتفاع الأمطار المبكرة في العام الحالي البقاء على قيد الحياة في مرحلة الشباب لجميع الأنواع باستثناء الإمبالا. تكشف النتائج التي توصلنا إليها كيف أن تباين هطول الأمطار الذي يؤثر على نمو العشب وبالتالي تغذية الحيوانات العاشبة يمكن أن يحكم الفينولوجيا الإنجابية لذوات الحوافر في خطوط العرض الاستوائية حيث يكون تباين طول اليوم ضئيلًا. يبدو أن الآلية الأساسية هي قمع المفاهيم بمجرد أن تصبح المكاسب الغذائية غير كافية. من خلال الاستجابة القريبة من التباين في هطول الأمطار خلال العام، فإن ذوات الحوافر في السافانا الاستوائية أقل عرضة للتأثر سلبًا بعواقب الاحترار العالمي على فينولوجيا الغطاء النباتي من ذوات الحوافر الشمالية التي تظهر تحكمًا دوريًا ضوئيًا أكثر صرامة في توقيت التكاثر.