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The East Asian summer monsoon is unique among summer monsoon systems in its complex seasonality, exhibiting distinct intraseasonal stages. Previous studies have alluded to the downstream influence of the westerlies flowing around the Tibetan Plateau as key to its existence. We explore this hypothesis using an atmospheric general circulation model that simulates the intraseasonal stages with fidelity. Without a Tibetan Plateau, East Asia exhibits only one primary convective stage typical of other monsoons. As the plateau is introduced, the distinct rainfall stages—spring, pre-mei-yu, mei-yu, and midsummer—emerge, and rainfall becomes more intense overall. This emergence coincides with a pronounced modulation of the westerlies around the plateau and extratropical northerlies penetrating northeastern China. The northerlies meridionally constrain the moist southerly flow originating from the tropics, leading to a band of lower-tropospheric convergence and humidity front that produces the rainband. The northward migration of the westerlies away from the northern edge of the plateau leads to a weakening of the extratropical northerlies, which, coupled with stronger monsoonal southerlies, leads to the northward migration of the rainband. When the peak westerlies migrate north of the plateau during the midsummer stage, the extratropical northerlies disappear, leaving only the monsoon low-level circulation that penetrates northeastern China; the rainband disappears, leaving isolated convective rainfall over northeastern China. In short, East Asian rainfall seasonality results from the interaction of two seasonally evolving circulations—the monsoonal southerlies that strengthen and extend northward, and the midlatitude northerlies that weaken and eventually disappear—as summer progresses.

The East Asian summer monsoon is unique among summer monsoon systems in its complex seasonality, exhibiting distinct intraseasonal stages. Previous studies have alluded to the downstream influence of the westerlies flowing around the Tibetan Plateau as key to its existence. We explore this hypothesis using an atmospheric general circulation model that simulates the intraseasonal stages with fidelity. Without a Tibetan Plateau, East Asia exhibits only one primary convective stage typical of other monsoons. As the plateau is introduced, the distinct rainfall stages—spring, pre-mei-yu, mei-yu, and midsummer—emerge, and rainfall becomes more intense overall. This emergence coincides with a pronounced modulation of the westerlies around the plateau and extratropical northerlies penetrating northeastern China. The northerlies meridionally constrain the moist southerly flow originating from the tropics, leading to a band of lower-tropospheric convergence and humidity front that produces the rainband. The northward migration of the westerlies away from the northern edge of the plateau leads to a weakening of the extratropical northerlies, which, coupled with stronger monsoonal southerlies, leads to the northward migration of the rainband. When the peak westerlies migrate north of the plateau during the midsummer stage, the extratropical northerlies disappear, leaving only the monsoon low-level circulation that penetrates northeastern China; the rainband disappears, leaving isolated convective rainfall over northeastern China. In short, East Asian rainfall seasonality results from the interaction of two seasonally evolving circulations—the monsoonal southerlies that strengthen and extend northward, and the midlatitude northerlies that weaken and eventually disappear—as summer progresses.

We present a general simulation approach for fluid-solid interactions based on the fully Eulerian reference map technique. The approach permits the modelling of one or more finitely deformable continuum solid bodies interacting with a fluid and with each other. A key advantage of this approach is its ease of use, as the solid and fluid are discretized on the same fixed grid, which greatly simplifies the coupling between the phases. We use the method to study a number of illustrative examples involving an incompressible Navier-Stokes fluid interacting with multiple neo-Hookean solids. Our method has several useful features including the ability to model solids with sharp corners and the ability to model actuated solids. The latter permits the simulation of active media such as swimmers, which we demonstrate. The method is validated favourably in the flag-flapping geometry, for which a number of experimental, numerical and analytical studies have been performed. We extend the flapping analysis beyond the thin-flag limit, revealing an additional destabilization mechanism to induce flapping.

Understanding interactions at the interfaces of carbon with ionic liquids (ILs) is crucially beneficial for the diagnostics and performance improvement of electrochemical devices containing carbon as active materials or conductive additives in electrodes and ILs as solvents or additives in electrolytes. The interfacial interactions of three typical imidazolium-based ILs, 1-alkyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (AMImTFSI) ILs having ethyl (C2), butyl (C4) and octyl (C8) chains in their cations, with highly oriented pyrolytic graphite (HOPG) were studied in-situ by electrochemical scanning tunneling microscopy (EC-STM). The etching of HOPG surface and the exfoliation of graphite/graphene flakes as well as cation intercalation were observed at the HOPG/C2MImTFSI interface. The etching also takes place in C4MImTFSI at −1.5 V vs Pt but only at step edges with a much slower rate, whereas C8MIm+ cations adsorbs strongly on the HOPG surface under similar conditions with no observable etching or intercalation. The EC-STM observations can be explained by the increase in van der Waals interaction between the cations and the graphite surface with increasing length of alkyl chains.

In the version of this Article originally published, the author Baran Eren was mistakenly affiliated with the Harbin Institute of Technology, China; it has now been corrected to Materials Science Division, Lawrence Berkeley National Laboratory, Berkeley, CA, USA.

Bimetallic and multi-component catalysts typically exhibit composition-dependent activity and selectivity, and when optimized often outperform single-component catalysts. Here we used ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) and in situ and ex situ transmission electron microscopy (TEM) to elucidate the origin of composition dependence observed in the catalytic activities of monodisperse CoPd bimetallic nanocatalysts for CO oxidation. We found that the catalysis process induced a reconstruction of the catalysts, leaving CoOx on the nanoparticle surface. The synergy between Pd and CoOx coexisting on the surface promotes the catalytic activity of the bimetallic catalysts. This synergistic effect can be optimized by tuning the Co/Pd ratios in the nanoparticle synthesis, and it reaches a maximum at compositions near Co0.24Pd0.76, which achieves complete CO conversion at the lowest temperature. Our combined AP-XPS and TEM studies provide direct observation of the surface evolution of the bimetallic nanoparticles under catalytic conditions and show how this evolution correlates with catalytic properties.

On orbital timescales, higher summer insolation is thought to strengthen the continental monsoon while weakening the maritime monsoon in the Northern hemisphere. Through simulations using the Community Earth System Model, we evaluated the relative influence of perihelion precession and high obliquity in the early Holocene during the Asian summer monsoon. The major finding was that precession dominates the atmospheric heating change over the Tibetan Plateau–Himalayas and Maritime Continent, whereas obliquity is responsible for the heating change over the equatorial Indian Ocean. Thus, precession and obliquity can play contrasting roles in driving the monsoons on orbital timescales. In late spring–early summer, interior Asian continental heating drives the South and East Asian monsoons. The broad-scale monsoonal circulation further expands zonally in July–August, corresponding to the development of summer monsoons in West Africa and the subtropical Western North Pacific (WNP) as well as a sizable increase in convection over the equatorial Indian Ocean. Tropical and oceanic heating becomes crucial in late summer. Over South Asia–Indian Ocean (50°E−110°E), the precession maximum intensifies the monsoonal Hadley cell (heating with an inland/highland origin), which is opposite to the meridional circulation change induced by high obliquity (heating with a tropical origin). The existence of the Tibetan Plateau–Himalayas intensifies the precessional impact. During the late-summer phase of the monsoon season, the effect of obliquity on tropical heating can be substantial. In addition to competing with Asian continental heating, obliquity-enhanced heating over the equatorial Indian Ocean also has a Walker-type circulation impact, resulting in suppression of precession-enhanced heating over the Maritime Continent.

The interfaces between electrode and electrolyte play a vital role in various electrochemical systems. However, the understanding of such embedded interfaces and interfacial processes is still limited partly because of the short of proper characterizations tools, especially in-situ/operando techniques. In the past decade, substantial effort has been devoted in the development of in-situ/operando techniques to investigate the solid/liquid interfaces. One successful approach is the combination of in-situ liquid cells and soft x-ray absorption spectroscopy (sXAS). In this review, we showcased several recent examples using such liquid-cell-based in-situ/operando sXAS method to study different aspects of the electrode/electrolyte interface under reaction conditions, including the adsorption and deposition of solute species on electrode surface, morphological and chemical changes of electrode surface, and potential-dependent orientations of interfacial solvent molecules. These examples demonstrated capability of such in-situ/operando sXAS techniques in providing element- and chemical-sensitive interfacial information. This in-situ/operando sXAS technique also opens the way to the investigation of various solid/liquid interfaces in other important heterogeneous reactions.

Thin films of n-type γ-Cu3V2O8 are prepared with high phase purity via reactive co-sputtering deposition. Complementary X-ray spectroscopic methods are used to reveal that the valence band maximum consists of O 2p states, while the conduction band minimum is primarily composed of Cu 3d states. Therefore, γ-Cu3V2O8 is classified as a charge transfer insulator, in which the 1.80 eV indirect band gap corresponds to the O 2p → Cu 3d transition. Through photoelectrochemical measurements, the surface of γ-Cu3V2O8 photoanodes is found to display intrinsic activity for catalyzing water oxidation that is stable with time. The combination of a small optical band gap, suitable valence band energy, and excellent photoelectrochemical stability suggests that γ-Cu3V2O8 could be a promising photoanode material. However, it is found that the charge extraction efficiency from these semiconductor photoanodes is strongly limited by a short (20-40 nm) hole diffusion length. Characterization of the electronic structure and transport properties of γ-Cu3V2O8 photoanodes suggests strategies for improving energy conversion efficiency and provides fundamental insights that can be used for understanding and evaluating function in a broader class of emerging ternary metal oxides.

Ambient-pressure X-ray photoelectron spectroscopy (XPS) was used to investigate the reactions of CO, H2, and their mixtures on Co foils. We found that CO adsorbs molecularly on the clean Co surface and desorbs intact in vacuum with increasing rate until ∼90°C where all CO desorbs in seconds. In equilibrium with 100 mTorr gas, CO dissociates above 120°C, leaving carbide species on the surface but no oxides, because CO efficiently reduces the oxides at temperatures ∼100°C lower than H2. Water as impurities or produced by reaction of CO and H2 efficiently oxidizes Co even at room temperature. Under 97:3 CO/H2 mixture and with increasing temperatures, the Co surface becomes more oxidized and covered by hydroxyl groups until ∼150°C where surface starts to get reduced, accompanied by carbide accumulation indicative of CO dissociation. A similar trend was observed for 9:1 and 1:1 mixtures, but surface reduction begins at higher temperatures. (Figure Presented).

The early Holocene climatic optimum is associated with perihelion precession and high obliquity, though most studies emphasize the former over the latter. Asian monsoon proxy records only decisively show the precessional impact. To explore the obliquity effect, four climate simulations are conducted by fixing orbital parameters of present-day (0K), early Holocene (11K), the lowest obliquity (31K), and 11K's precession and eccentricity with 31K's obliquity (11Kp31Ko). We show that high obliquity significantly augments the precessional impact by shifting the Asian monsoon farther north than present. By contrast, the present-day monsoon seasonality can still be identified in the simulations with low obliquity. We argue that the upper tropospheric (South Asian) and lower tropospheric (North Pacific) high-pressure systems are affected by the subtropical atmospheric heating changes responding to obliquity. As a consequence, associated with the changes in meridional gradients of geopotential height and temperature made by the heating, midlatitude transient eddies and monsoon-midlatitude interactions are modulated.

Orbital forcing exerts a strong influence on global monsoon systems, with higher summer insolation leading to stronger summer monsoons in the Northern Hemisphere. However, the associated regional and seasonal changes, particularly the interaction between regional monsoon systems, remain unclear. Simulations using the Community Earth System Model demonstrate that the western North Pacific (WNP) summer monsoon responds to orbital forcing opposite to that of other major Northern Hemisphere monsoon systems. Compared with its current climate state, the simulated WNP monsoon and associated lower-tropospheric trough is absent in the early Holocene when the precession-modulated Northern Hemisphere summer insolation is higher, whereas the summer monsoons in South and East Asia are stronger and shift farther northward. We attribute the weaker WNP monsoon to the stronger diabatic heating of the summer Asian monsoon—in particular over the southern Tibetan Plateau and Maritime Continent—that in turn strengthens the North Pacific subtropical high through atmospheric teleconnections. By contrast, the impact of the midlatitude circulation changes on the WNP monsoon is weaker when the solar insolation is higher. Prior to the present WNP monsoon onset, the upper-tropospheric East Asian jet stream weakens and shifts northward; the monsoon onset is highly affected by the jet-induced high potential vorticity intrusion. In the instance of the extreme perihelion-summer, the WNP monsoon is suppressed despite a stronger midlatitude precursor than present-day, and the midlatitude circulation response to the enhanced South Asian precipitation is considerable. These conditions indicate internal monsoon interactions of an orbital scale, implying a potential mechanistic control of the WNP monsoon.

The summer rainfall climate of East Asia underwent large and abrupt changes during past climates, in response to precessional forcing, glacial-interglacial cycles as well as abrupt changes to the North Atlantic during the Last Glacial. However, current interpretations of said changes are typically formulated in terms of modulation of summer monsoon intensity, and do not account for the known complexity in the seasonal evolution of East Asian rainfall, which exhibits sharp transition from the Spring regime to the Meiyu, and then again from the Meiyu to the Summer regime. We explore the interpretation that East Asian rainfall climate undergoes a modulation of its seasonality during said paleoclimate changes. Following previous suggestions we focus on role of the westerly jet over Asia, namely that its latitude relative to Tibet is critical in determining the stepwise transitions in East Asian rainfall seasons. In support of this linkage, we show from observational data that the interannual co-variation of June (July-August) rainfall and upper tropospheric zonal winds show properties consistent with an altered timing of the transition to the Meiyu (Summer), and with more northward-shifted westerlies for earlier transitions.We similarly suggest that East Asian paleoclimate changes resulted from an altered timing in the northward evolution of the jet and hence the seasonal transitions, in particular the transition of the jet from south of the Plateau to the north that determines the seasonal transition from Spring rains to the Meiyu. In an extreme scenario - which we speculate the climate system tended towards during stadial (cold) phases of D/O stadials and periods of low Northern Hemisphere summer insolation - the jet does not jump north of the Plateau, essentially keeping East Asia in prolonged Spring conditions.We argue that this hypothesis provides a viable explanation for a key paleoproxy signature of D/O stadials over East Asia, namely the heavier mean δ18O of precipitation as recorded in speleothem records. The southward jet position prevents the low-level monsoonal flow - which is isotopically light - from penetrating into the interior of East Asia; as such, precipitation there will be heavier, consistent with speleothem records. This hypothesis can also explain other key evidences of East Asian paleoclimate changes, in particular the occurrence of dusty conditions during North Atlantic stadials, and the southward migration of the Holocene optimal rainfall.

We develop computational methods for the simulation of osmotic swelling phenomena relevant to microscopic vesicles containing transformable solute molecules. We introduce stochastic immersed boundary methods (SIBMs) that can capture osmotically driven fluid transport through semipermeable elastic membranes subject to thermal fluctuations. We also develop numerical methods to handle within SIBMs an elastic shell model for a neo-Hookean material. Our extended SIBM allows for capturing osmotic swelling phenomena driven by concentration changes and interactions between a discrete collection of confined particles while accounting for the thermal fluctuations of the semipermeable membrane and the hydrodynamic transport of solvent. We use our computational methods to investigate osmotic phenomena in regimes that go beyond the classical Van't Hoff theory. We develop statistical mechanics theories for osmotic swelling of vesicles when there are significant interactions between particles that can transform over time. We validate our theoretical results against detailed computational simulations. Our methods are expected to be useful for a wide class of applications allowing for the simulation of osmotically driven flows, thermally fluctuating semipermeable elastic structures, and solute interactions.

Lithium-sulfur batteries have a theoretical specific energy that is a factor of five greater than that of current lithium-ion batteries, but suffer from consequences of the solubility of lithium polysulfide reaction intermediates that form as the batteries are charged and discharged. These species can react with each other and diffuse out of the cathode, causing battery capacity to fade and ultimately, cell failure. In spite of work that has spanned four decades, fingerprints of polysulfides have not yet been established, precluding a systematic study of lithium-sulfur chemistry. Herein we demonstrate the use of principal component analysis of X-ray absorption spectroscopy (XAS) to obtain fingerprints of lithium polysulfides. This approach enables interpretation of spectral data without any assumptions regarding the origin of the observed spectral features or knowledge of the stability of the polysulfide species of interest.We show that in poly(ethylene oxide)-based solid electrolytes containing polysulfides made by chemically reacting Li2S and elemental sulfur, Li2S2 and Li2S6 spontaneously disproportionate to give binary Li2S/Li2S4 and Li2S4/Li 2S8 mixtures, respectively, while Li2S 4 and Li2S8 exist as single molecular species. XAS fingerprints of Li2S4 and Li2S8 are thus presented. © 2014 The Electrochemical Society.

In nature, animals must contend with the presence of noise, which may limit their ability to detect prey, attract mates and escape predators. Sources of noise vary and may originate from natural (e.g. animal sounds, water) or anthropogenic (e.g. traffic, construction) sources. The vibratory sensory modality has long been overlooked in the study of anthropogenic effects on wildlife. Human-induced environmental changes may introduce noise sources as well as artificial substrates that alter vibratory noise profiles, leading to maladaptive behavioural responses. We conducted field measurements of vibratory noise on various substrate types (natural and artificial) used by animals in human-developed habitats. Next, we conducted laboratory experiments on how vibratory noise affects the prey detection ability of the European garden spider, Araneus diadematus. We tested whether changes in vibratory noise profiles consistent with anthropogenic alterations of vibratory habitats are sufficient to alter the spider's sensitivity to prey cues. We found that overall noise amplitude on artificial substrates was lower and less variable across contexts compared with natural substrates. In experiments with different noise levels, we observed that garden spiders showed noise-dependent changes in sensitivity to prey-mimicking cues, with response thresholds lowest at intermediate noise levels. Experimental levels of intermediate noise consistent with field measurements on natural substrates suggest that spiders' predatory performance is higher when webs are constructed on natural substrates. This suggests that human-introduced substrates may interfere with spiders' predatory performance. As human activities and habitat alteration are widespread, our findings highlight the need to consider the vibratory sensory channel in assessing anthropogenic impacts on wildlife. © 2014 The Association for the Study of Animal Behaviour.