Quartz crystal microbalance monitoring of density changes in mesoporous TiO2 phytate films during redox and ion exchange processes

Nanofilm deposits of TiO2 nanoparticle phytates are formed on gold electrode surfaces by 'directed assembly' methods. Alternate exposure of a 3-mercapto-propionic acid modified gold surface to (i) a TiO2 sol and (ii) an aqueous phytic acid solution (pH 3) results in layer-by-layer formation of a mesoporous film. Ru(NH3)(6)(3+) is shown to strongly adsorb/accumulate into the mesoporous structure whilst remaining electrochemically active. Scanning the electrode potential into a sufficiently negative potential range allows the Ru(NH3)(6)(3+) complex to be reduced to Ru(NH3)(6)(2+) which undergoes immediate desorption. When applied to a gold coated quartz crystal microbalance (QCM) sensor, electrochemically driven adsorption and desorption processes in the mesoporous structure become directly detectable as a frequency response, which corresponds directly to a mass or density change in the membrane. The frequency response (at least for thin films) is proportional to the thickness of the mass-responsive film, which suggests good mechanical coupling between electrode and film. Based on this observation, a method for the amplified QCM detection of small mass/density changes is proposed by conducting measurements in rigid mesoporous structures. (C) 2003 Elsevier Science B.V. All rights reserved.

The distinct contributions of age of acquisition and word frequency in auditory word perception

We report two studies of the distinct effects that a word's age of acquisition (AoA) and frequency have on the mental lexicon. In the first study, a purely statistical analysis, we show that AoA and frequency are related in different ways to the phonological form and imageability of different words. In the second study, three groups of participants (34 seven-year-olds, 30 ten-year-olds, and 17 adults) took part in an auditory lexical decision task, with stimuli varying in AoA, frequency, length, neighbourhood density, and imageability. The principal result is that the influence of these different variables changes as a function of AoA: Neighbourhood density effects are apparent for early and late AoA words, but not for intermediate AoA, whereas imageability effects are apparent for intermediate AoA words but not for early or late AoA. These results are discussed from the perspective that AoA affects a word's representation, but frequency affects processing biases.

Decreased frequency of North Atlantic polar lows associated with future climate warming

Every winter, the high-latitude oceans are struck by severe storms that are considerably smaller than the weather-dominating synoptic depressions1. Accompanied by strong winds and heavy precipitation, these often explosively developing mesoscale cyclones—termed polar lows1—constitute a threat to offshore activities such as shipping or oil and gas exploitation. Yet owing to their small scale, polar lows are poorly represented in the observational and global reanalysis data2 often used for climatological investigations of atmospheric features and cannot be assessed in coarse-resolution global simulations of possible future climates. Here we show that in a future anthropogenically warmed climate, the frequency of polar lows is projected to decline. We used a series of regional climate model simulations to downscale a set of global climate change scenarios3 from the Intergovernmental Panel of Climate Change. In this process, we first simulated the formation of polar low systems in the North Atlantic and then counted the individual cases. A previous study4 using NCEP/NCAR re-analysis data5 revealed that polar low frequency from 1948 to 2005 did not systematically change. Now, in projections for the end of the twenty-first century, we found a significantly lower number of polar lows and a northward shift of their mean genesis region in response to elevated atmospheric greenhouse gas concentration. This change can be related to changes in the North Atlantic sea surface temperature and mid-troposphere temperature; the latter is found to rise faster than the former so that the resulting stability is increased, hindering the formation or intensification of polar lows. Our results provide a rare example of a climate change effect in which a type of extreme weather is likely to decrease, rather than increase.

Relationship between dietary-induced changes in intestinal commensal microflora and duodenojejunal myoelectric activity monitored by radiotelemetry in the rat in vivo

Interdigestive intestinal motility, and especially phase III of the migrating myoelectric/motor complex (MMC), is responsible for intestinal clearance and plays an important role in prevention of bacterial overgrowth and translocation in the gut. Yet previous results from gnotobiotic rats have shown that intestinal microflora can themselves affect the characteristics of the myoelectric activity of the gut during the interdigestive state. Given that the composition of the intestinal microflora can be altered by dietary manipulations, we investigated the effect of supplementation of the diet with synbiotics on intestinal microflora structure and the duodenojejunal myoelectric activity in the rat. To reduce animal distress caused by restraint and handling, which can itself affect GI motility, we applied radiotelemetry for duodenojejunal EMG recordings in conscious, freely moving rats. Thirty 16-month-old Spraque-Dawley rats were used. The diet for 15 rats (E group) was supplemented with chicory inulin, Lactobacillus rhamnosus and Bifidobacterium lactis. The remaining 15 rats were fed control diet without supplements (C group). Three rats from each group were implanted with three bipolar electrodes positioned at 2, 14 and 28 cm distal to the pylorus. After recovery, two 6 h recordings of duodenojejunal EMG were carried out on each operated rat. Subsequently, group C rats received feed supplements and group E rats received only control diet for 1 week, and an additional two 6 h recordings were carried out on each of these rats. Non-operated C and E rats were killed and samples of GI tract were collected for microbiological analyses. Supplementation of the diet with the pro- and prebiotics mixture increased the number of bifidobacteria, whereas it decreased the number of enterobacteria in jejunum, ileum, caecum and colon. In both caecum and colon, the dietary supplementation increased the number of total anaerobes and lactobacilli. Treatment with synbiotics increased occurrence of phase III of the MMC at all three levels of the small intestine. The propagation velocity of phase III in the whole recording segment was also increased from 3.7 +/- 0.2 to 4.4 +/- 0.2 cm min(-1) by dietary treatment. Treatment with synbiotics increased the frequency of response potentials of the propagated phase III of the MMC at both levels of the jejunum, but not in the duodenum. In both parts of the jejunum, the supplementation of the diet significantly decreased the duration of phase II of the MMC, while it did not change the duration of phase I and phase III. Using the telemetry technique it was demonstrated that changes in the gastrointestinal microflora exhibited an intestinal motility response and, more importantly, that such changes can be initiated by the addition of synbiotics to the diet.

The signature of ENSO in the Northern Hemisphere midlatitude seasonal mean flow and high-frequency intraseasonal variability

The impact of pronounced positive and negative sea surface temperature (STT) anomalies in the tropical Pacific associated with the El Niño/Southern Oscillation (ENSO) phenomenon on the atmospheric circulation in the Northern Hemisphere extratropics during the boreal winter season is investigated. This includes both the impact on the seasonal mean flow and on the intraseasonal variability on synoptic time scales. Moreover, the interaction between the transient fluctuations on these times scales and the mean circulation is examined. Both data from an ensemble of five simulations with the ECHAM3 atmospheric general circulation model at a horizontal resolution of T42 each covering the period from 1979 through 1992 and operational analyses from ECMWF for the corresponding period are examined. In each of the simulations observed SSTs for the period of investigation are given as lower boundary forcing, but different atmospheric initial conditions are prescribed. The simulations with ECHAM3 reveal a distinct impact of the pronounced SST-anomalies in the tropical Pacific on the atmospheric circulation in the Northern Hemisphere extratropics during El Niño as well as during La Niña events. These changes in the atmospheric circulation, which are found to be highly significant in the Pacific/North American as well as in the Atlantic/European region, are consistent with the essential results obtained from the analyses. The pronounced SST-anomalies in the tropical Pacific lead to changes in the mean circulation, which are characterized by typical circulation patterns. These changes in the mean circulation are accompanied by marked variations of the activity of the transient fluctuations on synoptic time scales, that are changes in both the kinetic energy on these time scales and the atmospheric transports of momentum and heat accomplished by the short baroclinic waves. The synoptic disturbances, on the other hand, play also an important role in controlling the changes in the mean circulation associated with the ENSO phenomenon. They maintain these typical circulation patterns via barotropic, but counteract them via baroclinic processes. The hypothesis of an impact of the ENSO phenomenon in the Atlantic/European region can be supported. As the determining factor the intensification (reduction) of the Aleutian low and the simultaneous reduction (intensification) of the Icelandic low during El Niño and during La Niña events respectively, is identified. The changes in the intensity of the Aleutian low during the ENSO-events are accompanied by an alteration of the transport of momentum caused by the short baroclinic waves over the North American continent in such a way that the changes in the intensity of the Icelandic low during El Niño as well as during La Niña events are maintained.

Will greenhouse gas-induced warming over the next 50 years lead to higher frequency and greater intensity of hurricanes?

The use of a high resolution atmospheric model at T106 resolution, for studying the influence of greenhouse warming on tropical storm climatology, is investigated. The same method for identifying the storms has been used as in a previous study by Bengtsson et al. The sea surface temperature anomalies have been taken from a previous transient climate change experiment, obtained with a low resolution ocean-atmosphere coupled model. The global distribution of the storms, at the time when the CO2 concentration in the atmosphere had doubled, agrees in geographical position and seasonal variability with that of the present climate, but the number of storms is significantly reduced, particularly at the Southern Hemisphere. The main reason to this, appear to be connected to changes in the large scale circulation, such as a weaker Hadley circulation and stronger upper air westerlies. The low level vorticity in the hurricane genesis regions is generally reduced compared to the present climate, while the vertical tropospheric wind shear is somewhat increased. Most tropical storm regions indicate reduced surface windspeeds and a slightly weaker hydrological cycle.

Geochemical changes recorded in Lynch's Crater, Northeastern Australia, over the past 50 ka

There are many geochemical reconstructions of environmental change in the mid and high latitudes but relatively few in the tropical latitudes, despite their considerable potential for reconstructing environmental processes that cannot be identified using more traditional proxies. Here we present one reconstruction of environmental change for the tropics. This reconstruction covers the past 50 ka using a suite of geochemical data from the high-resolution sequence of Lynch's Crater in northeast Queensland, Australia, a region highly sensitive to El Niño-Southern Oscillation (ENSO) activity. The 23 major oxides and trace elements measured could be summarised by extracting three axes using principal components analysis (accounting for 72% of the variability). The data indicate that the greatest variability in the geochemical data accounted for erosional activity within the catchment that was associated with past changes in the frequency of ENSO activity (though this was less sensitive during wetter periods, probably as a result of buffering by high vegetation cover). The remaining variability was largely explained by elements that form complexes with organic compounds (e.g., humic acids) and those that are important nutrients for specific vegetation types (and therefore a measure of vegetation distribution). For more detailed reconstructions, further work is required to disentangle the complex controls of elements within sedimentary sequences.

European storminess and associated circulation weather types: future changes deduced from a multi-model ensemble of GCM simulations

A range of possible changes in the frequency and characteristics of European wind storms under future climate conditions was investigated on the basis of a multi-model ensemble of 9 coupled global climate model (GCM) simulations for the 20th and 21st centuries following the IPCC SRES A1B scenario. A multi-model approach allowed an estimation of the (un)certainties of the climate change signals. General changes in large-scale atmospheric flow were analysed, the occurrence of wind storms was quantified, and atmospheric features associated with wind storm events were considered. Identified storm days were investigated according to atmospheric circulation, associated pressure patterns, cyclone tracks and wind speed patterns. Validation against reanalysis data revealed that the GCMs are in general capable of realistically reproducing characteristics of European circulation weather types (CWTs) and wind storms. Results are given with respect to frequency of occurrence, storm-associated flow conditions, cyclone tracks and specific wind speed patterns. Under anthropogenic climate change conditions (SRES A1B scenario), increased frequency of westerly flow during winter is detected over the central European investigation area. In the ensemble mean, the number of detected wind storm days increases between 19 and 33% for 2 different measures of storminess, only 1 GCM revealed less storm days. The increased number of storm days detected in most models is disproportionately high compared to the related CWT changes. The mean intensity of cyclones associated with storm days in the ensemble mean increases by about 10 (±10)% in the Eastern Atlantic, near the British Isles and in the North Sea. Accordingly, wind speeds associated with storm events increase significantly by about 5 (±5)% over large parts of central Europe, mainly on days with westerly flow. The basic conclusions of this work remain valid if different ensemble contructions are considered, leaving out an outlier model or including multiple runs of one particular model.

Statistical uncertainty of changes in winter storms over the North Atlantic and Europe in an ensemble of transient climate simulations

Winter storms are among the most important natural hazards affecting Europe. We quantify changes in storm frequency and intensity over the North Atlantic and Europe under future climate scenarios in terms of return periods (RPs) considering uncertainties due to both sampling and methodology. RPs of North Atlantic storms' minimum central pressure (CP) and maximum vorticity (VOR) remain unchanged by 2100 for both the A1B and A2 scenarios compared to the present climate. Whereas shortened RPs for VOR of all intensities are detected for the area between British Isles/North-Sea/western Europe as early as 2040. However, the changes in storm VOR RP may be unrealistically large: a present day 50 (20) year event becomes approximately a 9 (5.5) year event in both A1B and A2 scenarios by 2100. The detected shortened RPs of storms implies a higher risk of occurrence of damaging wind events over Europe.

Ultralow-frequency modulation of whistler-mode wave growth

Measurements from ground-based magnetometers and riometers at auroral latitudes have demonstrated that energetic (~30-300keV) electron precipitation can be modulated in the presence of magnetic field oscillations at ultra-low frequencies. It has previously been proposed that an ultra-low frequency (ULF) wave would modulate field and plasma properties near the equatorial plane, thus modifying the growth rates of whistler-mode waves. In turn, the resulting whistler-mode waves would mediate the pitch-angle scattering of electrons resulting in ionospheric precipitation. In this paper, we investigate this hypothesis by quantifying the changes to the linear growth rate expected due to a slow change in the local magnetic field strength for parameters typical of the equatorial region around 6.6RE radial distance. To constrain our study, we determine the largest possible ULF wave amplitudes from measurements of the magnetic field at geosynchronous orbit. Using nearly ten years of observations from two satellites, we demonstrate that the variation in magnetic field strength due to oscillations at 2mHz does not exceed ±10% of the background field. Modifications to the plasma density and temperature anisotropy are estimated using idealised models. For low temperature anisotropy, there is little change in the whistler-mode growth rates even for the largest ULF wave amplitude. Only for large temperature anisotropies can whistler-mode growth rates be modulated sufficiently to account for the changes in electron precipitation measured by riometers at auroral latitudes.

Analysis of frequency and intensity of European winter storm events from a multi-model perspective, at synoptic and regional scales

This study focuses on the analysis of winter (October-November-December-January-February-March; ONDJFM) storm events and their changes due to increased anthropogenic greenhouse gas concentrations over Europe. In order to assess uncertainties that are due to model formulation, 4 regional climate models (RCMs) with 5 high resolution experiments, and 4 global general circulation models (GCMs) are considered. Firstly, cyclone systems as synoptic scale processes in winter are investigated, as they are a principal cause of the occurrence of extreme, damage-causing wind speeds. This is achieved by use of an objective cyclone identification and tracking algorithm applied to GCMs. Secondly, changes in extreme near-surface wind speeds are analysed. Based on percentile thresholds, the studied extreme wind speed indices allow a consistent analysis over Europe that takes systematic deviations of the models into account. Relative changes in both intensity and frequency of extreme winds and their related uncertainties are assessed and related to changing patterns of extreme cyclones. A common feature of all investigated GCMs is a reduced track density over central Europe under climate change conditions, if all systems are considered. If only extreme (i.e. the strongest 5%) cyclones are taken into account, an increasing cyclone activity for western parts of central Europe is apparent; however, the climate change signal reveals a reduced spatial coherency when compared to all systems, which exposes partially contrary results. With respect to extreme wind speeds, significant positive changes in intensity and frequency are obtained over at least 3 and 20% of the European domain under study (35–72°N and 15°W–43°E), respectively. Location and extension of the affected areas (up to 60 and 50% of the domain for intensity and frequency, respectively), as well as levels of changes (up to +15 and +200% for intensity and frequency, respectively) are shown to be highly dependent on the driving GCM, whereas differences between RCMs when driven by the same GCM are relatively small.

Future changes in atmospheric rivers and their implications for winter flooding in Britain

Within the warm conveyor belt of extra-tropical cyclones, atmospheric rivers (ARs) are the key synoptic features which deliver the majority of poleward water vapour transport, and are associated with episodes of heavy and prolonged rainfall. ARs are responsible for many of the largest winter floods in the mid-latitudes resulting in major socioeconomic losses; for example, the loss from United Kingdom (UK) flooding in summer/winter 2012 is estimated to be about $1.6 billion in damages. Given the well-established link between ARs and peak river flows for the present day, assessing how ARs could respond under future climate projections is of importance in gauging future impacts from flooding. We show that North Atlantic ARs are projected to become stronger and more numerous in the future scenarios of multiple simulations from five state-of-the-art global climate models (GCMs) in the fifth Climate Model Intercomparison Project (CMIP5). The increased water vapour transport in projected ARs implies a greater risk of higher rainfall totals and therefore larger winter floods in Britain, with increased AR frequency leading to more flood episodes. In the high emissions scenario (RCP8.5) for 2074–2099 there is an approximate doubling of AR frequency in the five GCMs. Our results suggest that the projected change in ARs is predominantly a thermodynamic response to warming resulting from anthropogenic radiative forcing.

The resting-state neurovascular coupling relationship: rapid changes in spontaneous neural activity in the somatosensory cortex are associated with haemodynamic fluctuations that resemble stimulus-evoked haemodynamics

Although promise exists for patterns of resting-state blood oxygen level-dependent (BOLD) functional magnetic resonance imaging (fMRI) brain connectivity to be used as biomarkers of early brain pathology, a full understanding of the nature of the relationship between neural activity and spontaneous fMRI BOLD fluctuations is required before such data can be correctly interpreted. To investigate this issue, we combined electrophysiological recordings of rapid changes in multi-laminar local field potentials from the somatosensory cortex of anaesthetized rats with concurrent two-dimensional optical imaging spectroscopy measurements of resting-state haemodynamics that underlie fluctuations in the BOLD fMRI signal. After neural ‘events’ were identified, their time points served to indicate the start of an epoch in the accompanying haemodynamic fluctuations. Multiple epochs for both neural ‘events’ and the accompanying haemodynamic fluctuations were averaged. We found that the averaged epochs of resting-state haemodynamic fluctuations taken after neural ‘events’ closely resembled the temporal profile of stimulus-evoked cortical haemodynamics. Furthermore, we were able to demonstrate that averaged epochs of resting-state haemodynamic fluctuations resembling the temporal profile of stimulus-evoked haemodynamics could also be found after peaks in neural activity filtered into specific electroencephalographic frequency bands (theta, alpha, beta, and gamma). This technique allows investigation of resting-state neurovascular coupling using methodologies that are directly comparable to that developed for investigating stimulus-evoked neurovascular responses.

Simulation of late-twenty-first-century changes in wintertime atmospheric circulation over Europe due to anthropogenic causes

Evidence is presented, based on an ensemble of climate change scenarios performed with a global general circulation model of the atmosphere with high horizontal resolution over Europe, to suggest that the end-of-century anthropogenic climate change over the North Atlantic--European region strongly projects onto the positive phase of the North Atlantic Oscillation during wintertime. It is reflected in a doubling of the residence frequency of the climate system in the associated circulation regime, in agreement with the nonlinear climate perspective. The strong increase in the amplitude of the response, compared to coarse-resolution coupled model studies, suggests that improved model representation of regional climate is needed to achieve more reliable projections of anthropogenic climate change on European climate.

First look at changes in flood hazard in the inter-sectoral impact model intercomparison project ensemble

Climate change due to anthropogenic greenhouse gas emissions is expected to increase the frequency and intensity of precipitation events, which is likely to affect the probability of flooding into the future. In this paper we use river flow simulations from nine global hydrology and land surface models to explore uncertainties in the potential impacts of climate change on flood hazard at global scale. As an indicator of flood hazard we looked at changes in the 30-y return level of 5-d average peak flows under representative concentration pathway RCP8.5 at the end of this century. Not everywhere does climate change result in an increase in flood hazard: decreases in the magnitude and frequency of the 30-y return level of river flow occur at roughly one-third (20-45%) of the global land grid points, particularly in areas where the hydro-graph is dominated by the snowmelt flood peak in spring. In most model experiments, however, an increase in flooding frequency was found in more than half of the grid points. The current 30-y flood peak is projected to occur in more than 1 in 5 y across 5-30% of land grid points. The large-scale patterns of change are remarkably consistent among impact models and even the driving climate models, but at local scale and in individual river basins there can be disagreement even on the sign of change, indicating large modeling uncertainty which needs to be taken into account in local adaptation studies.