Observing the in situ chiral modification of Ni nanoparticles using scanning transmission X-ray microspectroscopy

Enantioselective heterogeneous hydrogenation of Cdouble bond; length as m-dashO bonds is of great potential importance in the synthesis of chirally pure products for the pharmaceutical and fine chemical industries. One of the most widely studied examples of such a reaction is the hydrogenation of β-ketoesters and β-diketoesters over Ni-based catalysts in the presence of a chiral modifier. Here we use scanning transmission X-ray microscopy combined with near-edge X-ray absorption fine structure spectroscopy (STXM/NEXAFS) to investigate the adsorption of the chiral modifier, namely (R,R)-tartaric acid, onto individual nickel nanoparticles. The C K-edge spectra strongly suggest that tartaric acid deposited onto the nanoparticle surfaces from aqueous solutions undergoes a keto-enol tautomerisation. Furthermore, we are able to interrogate the Ni L2,3-edge resonances of individual metal nanoparticles which, combined with X-ray diffraction (XRD) patterns showed them to consist of a pure nickel phase rather than the more thermodynamically stable bulk nickel oxide. Importantly, there appears to be no “particle size effect” on the adsorption mode of the tartaric acid in the particle size range ~ 90–~ 300 nm.

Polymer protected gold nanoparticles: synthesis, characterization and application in catalysis

This review discusses the stabilization of gold nanoparticles (AuNPs) by nonionic, anionic, cationic and amphoteric polymers. The protocols used for synthesis of AuNPs in aqueous and organic solvents are described. Size, shape and morphology of AuNPs are characterized by various physicochemical methods. Application aspects of polymer-protected AuNPs in catalysis are outlined.

Effective separation of Am(III) and Eu(III) from HNO3 Q1 Q2 solutions using CyMe4-BTPhen-functionalized silica-coated magnetic nanoparticles

It has been shown that CyMe4-BTPhen-functionalized silica-coated maghemite (c-Fe2O3) magnetic nanoparticles (MNPs) are capable of quantitative separation of Am(III) from Eu(III) from HNO3 solutions. These MNPs also show a small but significant selectivity for Am(III) over Cm(III) with a separation factor of around 2 in 4 M HNO3. The water molecule in the cavity of the BTPhen may also play an important part in the selectivity.

Revisiting asymmetry for the decaying phases of El Niño and La Niña

This study investigated the relationship between the asymmetry in the duration of El Ni?o and La Ni?a and the length of their decaying phases. The results suggested that the duration asymmetry comes from the long decaying ENSO cases rather than the short decaying ones. The evolutions of short decaying El Ni?o and La Ni?a are approximately a mirror image with a rapid decline in the following summer for the warm and cold events. However, a robust asymmetry was found in long decaying cases, with a prolonged and re-intensified La Ni?a in the following winter. The asymmetry for long decaying cases starts from the westward extension of the zonal wind anomalies in a mature winter, and is further contributed to by the air-sea interaction over the tropical Pacific in the following seasons.

Remarkable dynamics of nanoparticles in the urban atmosphere

Nanoparticles emitted from road traffic are the largest source of respiratory exposure for the general public living in urban areas. It has been suggested that adverse health effects of airborne particles may scale with airborne particle number, which if correct, focuses attention on the nanoparticle (less than 100 nm) size range which dominates the number count in urban areas. Urban measurements of particle size distributions have tended to show a broadly similar pattern dominated by a mode centred on 20–30 nm diameter emitted by diesel engine exhaust. In this paper we report the results of measurements of particle number concentration and size distribution made in a major London park as well as on the BT Tower, 160 m aloft. These measurements taken during the REPARTEE project (Regents Park and BT Tower experiment) show a remarkable shift in particle size distributions with major losses of the smallest particle class as particles are advected away from the traffic source. In the Park, the traffic related mode at 20–30 nm diameter is much reduced with a new mode at <10 nm. Size distribution measurements also revealed higher number concentrations of sub-50 nm particles at the BT Tower during days affected by higher turbulence as determined by Doppler Lidar measurements and are indicative of loss of nanoparticles from air aged during less turbulent conditions. These results are suggestive of nanoparticle loss by evaporation, rather than coagulation processes. The results have major implications for understanding the impacts of traffic-generated particulate matter on human health.

Effective separation of Am(III) and Eu(III) from HNO3 solutions using CyMe4-BTPhen-functionalized silica-coated magnetic nanoparticles

It has been shown that CyMe4-BTPhen-functionalized silica-coated maghemite (c-Fe2O3) magnetic nanoparticles (MNPs) are capable of quantitative separation of Am(III) from Eu(III) from HNO3 solutions. These MNPs also show a small but significant selectivity for Am(III) over Cm(III) with a separation factor of around 2 in 4 M HNO3. The water molecule in the cavity of the BTPhen may also play an important part in the selectivity.

A new understanding of El Niño's impact over East Asia: dominance of the ENSO combination mode

Previous studies have shown that the Indo-Pacific atmospheric response to ENSO comprises two dominant modes of variability: a meridionally quasi-symmetric response (independent from the annual cycle) and an anti-symmetric response (arising from the nonlinear atmospheric interaction between ENSO variability and the annual cycle), referred to as the combination mode (C-Mode). This study demonstrates that the direct El Niño signal over the tropics is confined to the equatorial region and has no significant impact on the atmospheric response over East Asia. The El Niño-associated equatorial anomalies can be expanded towards off-equatorial regions by the C-Mode through ENSO’s interaction with the annual cycle. The C-Mode is the prime driver for the development of an anomalous low-level anticyclone over the western North Pacific (WNP) during the El Niño decay phase, which usually transports more moisture to East Asia and thereby causes more precipitation over southern China. We use an Atmospheric General Circulation Model that well reproduces the WNP anticyclonic anomalies when both El Niño sea surface temperature (SST) anomalies as well as the SST annual cycle are prescribed as boundary conditions. However, no significant WNP anticyclonic circulation anomaly appears during the El Niño decay phase when excluding the SST annual cycle. Our analyses of observational data and model experiments suggest that the annual cycle plays a key role in the East Asian climate anomalies associated with El Niño through their nonlinear atmospheric interaction. Hence, a realistic simulation of the annual cycle is crucial in order to correctly capture the ENSO-associated climate anomalies over East Asia.

Impact of different El Niño types on the El Niño/IOD relationship

Previous studies reported that positive phases of the Indian Ocean Dipole (IOD) tend to accompany El Niño during boreal autumn. Here we show that the El Niño/IOD relationship can be better understood when considering the two different El Niño flavors. Eastern-Pacific (EP) El Niño events exhibit a strong correlation with the IOD dependent on their magnitude. In contrast, the relationship between Central-Pacific (CP) El Niño events and the IOD depends mainly on the zonal location of the sea surface temperature anomalies rather than their magnitude. CP El Niño events lying further west than normal are not accompanied by significant anomalous easterlies over the eastern Indian Ocean along the Java/Sumatra coast, which is unfavorable for the local Bjerknes feedback and correspondingly for an IOD development. The El Niño/IOD relationship has experienced substantial changes due to the recent decadal El Niño regime shift, which has important implications for seasonal prediction.

Intensified anticyclonic anomaly over the western North Pacific during El Niño decaying summer under a weakened Atlantic thermohaline circulation

It has been well documented that there is an anticyclonic anomaly over the western North Pacific (WNPAC, hereafter) during El Niño decaying summer. This El Niño-WNPAC relationship is greatly useful for the seasonal prediction of summer climate in the WNP and East Asia. In this study, we investigate the modification of the El Niño-WNPAC relationship induced by a weakened Atlantic thermohaline circulation (THC) in a water-hosing experiment. The results suggest that the WNPAC during the El Niño decaying summer, as well as the associated precipitation anomaly over the WNP, is intensified under the weakened THC. On the one hand, this intensification is in response to the increased amplitude and frequency of El Niño events in the water-hosing experiment. On the other hand, this intensification is also because of greater climatological humidity over the western to central North Pacific under the weakened THC. We suggest that the increase of climatological humidity over the western to central North Pacific during summer under the weakened THC is favorable for enhanced interannual variability of precipitation, and therefore favorable for the intensification of the WNPAC during El Niño decaying summer. This study suggests a possible modulation of the El Niño–Southern Oscillation-WNP summer monsoon relationship by the low-frequency fluctuation of Atlantic sea surface temperature. The results offer an explanation for the observed modification of the multidecadal fluctuation of El Niño-WNPAC relationship by the Atlantic multidecadal oscillation.

The partial oxidation of methane over Pd/Al2O3 catalyst nanoparticles studied in-situ by near ambient-pressure x-ray photoelectron spectroscopy

Near ambient-pressure X-ray photoelectron spectroscopy (NAP-XPS) is used to study the chemical state of methane oxidation catalysts in-situ. Al2O3{supported Pd catalysts are prepared with different particle sizes ranging from 4 nm to 10 nm. These catalysts were exposed to conditions similar to those used in the partial oxidation of methane (POM) to syn-gas and simultaneously monitored by NAP-XPS and mass spectrometry. NAP-XPS data show changes in the oxidation state of the palladium as the temperature in- creases, from metallic Pd0 to PdO, and back to Pd0. Mass spectrometry shows an increase in CO production whilst the Pd is in the oxide phase, and the metal is reduced back under presence of newly formed H2. A particle size effect is observed, such that CH4 conversion starts at lower temperatures with larger sized particles from 6 nm to 10 nm. We find that all nanoparticles begin CH4 conversion at lower temperatures than polycrystalline Pd foil.

Response of El Niño sea surface temperature variability to greenhouse warming

The destructive environmental and socio-economic impacts of the El Niño/Southern Oscillation1, 2 (ENSO) demand an improved understanding of how ENSO will change under future greenhouse warming. Robust projected changes in certain aspects of ENSO have been recently established3, 4, 5. However, there is as yet no consensus on the change in the magnitude of the associated sea surface temperature (SST) variability6, 7, 8, commonly used to represent ENSO amplitude1, 6, despite its strong effects on marine ecosystems and rainfall worldwide1, 2, 3, 4, 9. Here we show that the response of ENSO SST amplitude is time-varying, with an increasing trend in ENSO amplitude before 2040, followed by a decreasing trend thereafter. We attribute the previous lack of consensus to an expectation that the trend in ENSO amplitude over the entire twenty-first century is unidirectional, and to unrealistic model dynamics of tropical Pacific SST variability. We examine these complex processes across 22 models in the Coupled Model Intercomparison Project phase 5 (CMIP5) database10, forced under historical and greenhouse warming conditions. The nine most realistic models identified show a strong consensus on the time-varying response and reveal that the non-unidirectional behaviour is linked to a longitudinal difference in the surface warming rate across the Indo-Pacific basin. Our results carry important implications for climate projections and climate adaptation pathways.

The impact of westerly wind bursts and ocean initial state on the development, and diversity of El Niño events

Westerly wind bursts (WWBs) that occur in the western tropical Pacific are believed to play an important role in the development of El Niño events. Here, following the study of Lengaigne et al. (Clim Dyn 23(6):601–620, 2004), we conduct numerical simulations in which we reexamine the response of the climate system to an observed wind burst added to a coupled general circulation model. Two sets of twin ensemble experiments are conducted (each set has control and perturbed experiments). In the first set, the initial ocean heat content of the system is higher than the model climatology (recharged), while in the second set it is nearly normal (neutral). For the recharged state, in the absence of WWBs, a moderate El Niño with a maximum warming in the central Pacific (CP) develops in about a year. In contrast, for the neutral state, there develops a weak La Niña. However, when the WWB is imposed, the situation dramatically changes: the recharged state slides into an El Niño with a maximum warming in the eastern Pacific, while the neutral set produces a weak CP El Niño instead of previous La Niña conditions. The different response of the system to the exact same perturbations is controlled by the initial state of the ocean and the subsequent ocean–atmosphere interactions involving the interplay between the eastward shift of the warm pool and the warming of the eastern equatorial Pacific. Consequently, the observed diversity of El Niño, including the occurrence of extreme events, may depend on stochastic atmospheric processes, modulating El Niño properties within a broad continuum.

Increasing frequency of extreme El Niño events due to greenhouse warming

El Niño events are a prominent feature of climate variability with global climatic impacts. The 1997/98 episode, often referred to as ‘the climate event of the twentieth century’1, 2, and the 1982/83 extreme El Niño3, featured a pronounced eastward extension of the west Pacific warm pool and development of atmospheric convection, and hence a huge rainfall increase, in the usually cold and dry equatorial eastern Pacific. Such a massive reorganization of atmospheric convection, which we define as an extreme El Niño, severely disrupted global weather patterns, affecting ecosystems4, 5, agriculture6, tropical cyclones, drought, bushfires, floods and other extreme weather events worldwide3, 7, 8, 9. Potential future changes in such extreme El Niño occurrences could have profound socio-economic consequences. Here we present climate modelling evidence for a doubling in the occurrences in the future in response to greenhouse warming. We estimate the change by aggregating results from climate models in the Coupled Model Intercomparison Project phases 3 (CMIP3; ref. 10) and 5 (CMIP5; ref. 11) multi-model databases, and a perturbed physics ensemble12. The increased frequency arises from a projected surface warming over the eastern equatorial Pacific that occurs faster than in the surrounding ocean waters13, 14, facilitating more occurrences of atmospheric convection in the eastern equatorial region.

El Niño 2015/2016: impact analysis of past El Niños

This is a DfID (Department for International Development) commissioned report on the impact of historical El Niño events on low- and middle-income countries across Africa and elsewhere. The report identifies El Niño events in the past 35 years and highlights regions and countries vulnerable to their impacts. The impacts on rainfall and temperature are broken down by season and country as the El Niño develops, peaks and decays and are represented in at-a-glance Impact Tables. The Impact Tables also include an extensive review of literature (e.g., peer-reviewed, grey literature and media reports) to identify potential socio-economic impacts in vulnerable sectors such as water, infrastructure, energy and health. The risk of such impacts are graded as high, medium or potential depending on the meteorological signal and the robustness of evidence available.

El Niño 2015/2016 impact analysis, monthly outlook November 2015

During the summer and autumn 2015, El Niño conditions in the east and central Pacific have strengthened, disrupting weather patterns throughout the tropics and into the mid-latitudes. For example, rainfall during this summer’s Indian monsoon was approximately 15% below normal. The continued strong El Niño conditions have the potential to trigger damaging impacts (e.g., droughts, famines, floods), particularly in less-developed tropical countries, which would require a swift and effective humanitarian response to mitigate damage to life and property (e.g., health, migration, infrastructure). This analysis uses key climatic variables (temperature, soil moisture and precipitation) as measures to monitor the ongoing risk of these potentially damaging impacts. The previous 2015-2016 El Niño Impact Analysis was based on observations over the past 35 years and produced Impact Tables showing the likelihood and severity of the impacts on temperature and rainfall by season. The current report is an extension of this work providing information from seasonal forecast models to give a more detailed monthly outlook of the potential near-term impacts of the current El Niño conditions by region. This information has been added to the Impact Tables in the form of a monthly outlook column. This monthly outlook is an indication of the average likely conditions for that month and region and is not a definite prediction of weather impacts.