Regional climate impacts of a possible future grand solar minimum

Any reduction in global mean near-surface temperature due to a future decline in solar activity is likely to be a small fraction of projected anthropogenic warming. However, variability in ultraviolet solar irradiance is linked to modulation of the Arctic and North Atlantic Oscillations, suggesting the potential for larger regional surface climate effects. Here, we explore possible impacts through two experiments designed to bracket uncertainty in ultraviolet irradiance in a scenario in which future solar activity decreases to Maunder Minimum-like conditions by 2050. Both experiments show regional structure in the wintertime response, resembling the North Atlantic Oscillation, with enhanced relative cooling over northern Eurasia and the eastern United States. For a high-end decline in solar ultraviolet irradiance, the impact on winter northern European surface temperatures over the late twenty-first century could be a significant fraction of the difference in climate change between plausible AR5 scenarios of greenhouse gas concentrations.

Separating the influence of projected changes in air temperature and wind on patterns of sea level change and ocean heat content

We present ocean model sensitivity experiments aimed at separating the influence of the projected changes in the “thermal” (near-surface air temperature) and “wind” (near-surface winds) forcing on the patterns of sea level and ocean heat content. In the North Atlantic, the distribution of sea level change is more due to the “thermal” forcing, whereas it is more due to the “wind” forcing in the North Pacific; in the Southern Ocean, the “thermal” and “wind” forcing have a comparable influence. In the ocean adjacent to Antarctica the “thermal” forcing leads to an inflow of warmer waters on the continental shelves, which is somewhat attenuated by the “wind” forcing. The structure of the vertically integrated heat uptake is set by different processes at low and high latitudes: at low latitudes it is dominated by the heat transport convergence, whereas at high latitudes it represents a small residual of changes in the surface flux and advection of heat. The structure of the horizontally integrated heat content tendency is set by the increase of downward heat flux by the mean circulation and comparable decrease of upward heat flux by the subgrid-scale processes; the upward eddy heat flux decreases and increases by almost the same magnitude in response to, respectively, the “thermal” and “wind” forcing. Regionally, the surface heat loss and deep convection weaken in the Labrador Sea, but intensify in the Greenland Sea in the region of sea ice retreat. The enhanced heat flux anomaly in the subpolar Atlantic is mainly caused by the “thermal” forcing.

The solsticial pause on Mars: 2 modelling and investigation of causes

The martian solsticial pause, presented in a companion paper (Lewis et al., this issue), was investigated further through a series of model runs using the UK version of the LMD/UK Mars Global Climate Model. It was found that the pause could not be adequately reproduced if radiatively active water ice clouds were omitted from the model. When clouds were used, along with a realistic time-dependent dust opacity distribution, a substantial minimum in near-surface transient eddy activity formed around solstice in both hemispheres. The net effect of the clouds in the model is, by altering the thermal structure of the atmosphere, to decrease the vertical shear of the westerly jet near the surface around solstice, and thus reduce baroclinic growth rates. A similar effect was seen under conditions of large dust loading, implying that northern midlatitude eddy activity will tend to become suppressed after a period of intense flushing storm formation around the northern cap edge. Suppression of baroclinic eddy generation by the barotropic component of the flow and via diabatic eddy dissipation were also investigated as possible mechanisms leading to the formation of the solsticial pause but were found not to make major contributions. Zonal variations in topography were found to be important, as their presence results in weakened transient eddies around winter solstice in both hemispheres, through modification of the near-surface flow. The zonal topographic asymmetry appears to be the primary reason for the weakness of eddy activity in the southern hemisphere relative to the northern hemisphere, and the ultimate cause of the solsticial pause in both hemispheres. The meridional topographic gradient was found to exert a much weaker influence on near-surface transient eddies.

Seasonal surface urban energy balance and wintertime stability simulated using three land-surface models in the high-latitude city Helsinki

The performance of three urban land surface models, run in offline mode, with their default external parameters, is evaluated for two distinctly different sites in Helsinki: Torni and Kumpula. The former is a dense city centre site with 22% vegetation, while the latter is a suburban site with over 50% vegetation. At both locations the models are compared against sensible and latent heat fluxes measured using the eddy covariance technique, along with snow depth observations. The cold climate experienced by the city causes strong seasonal variations that include snow cover and stable atmospheric conditions. Most of the time the three models are able to account for the differences between the study areas as well as the seasonal and diurnal variability of the energy balance components. However, the performances are not systematic across the modelled components, season and surface type. The net all-wave radiation is well simulated, with the greatest uncertainties related to snowmelt timing, when the fraction of snow cover has a key role, particularly in determining the surface albedo. For the turbulent fluxes, more variation between the models is seen which can partly be explained by the different methods in their calculation and partly by surface parameter values. For the sensible heat flux, simulation of wintertime values was the main problem, which also leads to issues in predicting near-surface stabilities particularly at the dense city centre site. All models have the most difficulties in simulating latent heat flux. This study particularly emphasizes that improvements are needed in the parameterization of anthropogenic heat flux and thermal parameters in winter, snow cover in spring and evapotranspiration in order to improve the surface energy balance modelling in cold climate cities.

Impact of Laptev Sea flaw polynyas on the atmospheric boundary layer and ice production using idealized mesoscale simulations

The interaction between polynyas and the atmospheric boundary layer is examined in the Laptev Sea using the regional, non-hydrostatic Consortium for Small-scale Modelling (COSMO) atmosphere model. A thermodynamic sea-ice model is used to consider the response of sea-ice surface temperature to idealized atmospheric forcing. The idealized regimes represent atmospheric conditions that are typical for the Laptev Sea region. Cold wintertime conditions are investigated with sea-ice–ocean temperature differences of up to 40 K. The Laptev Sea flaw polynyas strongly modify the atmospheric boundary layer. Convectively mixed layers reach heights of up to 1200 m above the polynyas with temperature anomalies of more than 5 K. Horizontal transport of heat expands to areas more than 500 km downstream of the polynyas. Strong wind regimes lead to a more shallow mixed layer with strong near-surface modifications, while weaker wind regimes show a deeper, well-mixed convective boundary layer. Shallow mesoscale circulations occur in the vicinity of ice-free and thin-ice covered polynyas. They are forced by large turbulent and radiative heat fluxes from the surface of up to 789 W m−2, strong low-level thermally induced convergence and cold air flow from the orographic structure of the Taimyr Peninsula in the western Laptev Sea region. Based on the surface energy balance we derive potential sea-ice production rates between 8 and 25 cm d−1. These production rates are mainly determined by whether the polynyas are ice-free or covered by thin ice and by the wind strength.

Vanadium Pentoxide Nanostructures: An Effective Control of Morphology and Crystal Structure in Hydrothermal Conditions

A systematic study was made of the synthesis of V(2)O(5)center dot nH(2)O nanostructures, whose morphologies, crystal structure, and amount of water molecules between the layered structures were regulated by strictly controlling the hydrothermal treatment variables. The synthesis involved a direct hydrothermal reaction between V(2)O(5) and H(2)O(2), without the addition of organic surfactant or inorganic ions. The experimental results indicate that high purity nanostructures can be obtained using this simple and clean synthetic route. Oil the basis of a study of hydrothermal treatment variables such as reaction temperature and time, X-ray diffraction (XRD) and scanning transmission electron microscopy (STEM) revealed that it was possible to obtain nanoribbons of the V(2)O(5)center dot nH(2)O monoclinic phase and nanowires or nanorods of the V(2)O(5)center dot nH(2)O orthorhombic phase. Thermal gravimetric analysis (TGA) shows also that the water content in the Structure call be controlled at appropriate hydrothermal conditions. Concerning the oxidation state of the vanadium atoms of as-obtained samples, a mixed-valence state composed of V(4+) and V(5+) was observed ill the V(2)O(5)center dot nH(2)O monoclinic phase, while the valence of the vanadium atoms was preferentially 5+ in the V(2)O(5)center dot nH(2)O orthorhombic phase. The X-ray absorption near-edge structure (XANES) results also indicated that the local structure of vanadium possessed a higher degree of symmetry in the V(2)O(5)center dot nH(2)O monoclinic phase.

Ethanol steam reforming for production of hydrogen on magnesium aluminate-supported cobalt catalysts promoted by noble metals

The performance of noble metal (Pt, Ru, Ir)-promoted Co/MgAl(2)O(4) catalysts for the steam reforming of ethanol was investigated. The catalysts were characterized by energy-dispersive X-ray spectroscopy, Xray diffraction, UV-vis diffuse reflectance spectroscopy, temperature-programmed reduction, temperature-programmed oxidation and X-ray absorption near edge structure (XANES). The results showed that the formation of inactive cobalt aluminate was suppressed by the presence of a MgAl(2)O(4) spinel phase. The effects of the noble metals included a marked lowering of the reduction temperatures of the cobalt surface species interacting with the support. It was seen that the addition of noble metal stabilized the Co sites in the reduced state throughout the reaction. Catalytic performance was enhanced in the promoted catalysts, particularly CoRu/MgAl(2)O(4), which showed the highest selectivity for H(2) production. (C) 2009 Elsevier B.V. All rights reserved.

Investigation of the CO tolerance mechanism at several Pt-based bimetallic anode electrocatalysts in a PEM fuel cell

The electrocatalysis of CO tolerance of Pt/C, PtRu/C, PtFe/C, PtMo/C, and PtW/C at a PEM fuel cell anode has been investigated using single cell polarization and online electrochemical mass spectrometry (EMS) measurements, and cyclic voltammetry, X-ray diffraction (XRD), in situ X-ray absorption near edge structure (XANES) analyses of the electrocatalysts. For all bimetallic electrocatalysts, which presented higher CO tolerance, EMS results have shown that the production of CO(2) start at lower hydrogen electrode overpotentials as compared to Pt/C, confirming the occurrence of the so-called bifunctional mechanism. On the other hand, XANES results indicate an increase in the Pt 5d-band vacancies for the bimetallic catalysts, particulary for PtFe/C, this leading to a weakening of the Pt-CO bond, helping to increase the CO tolerance (the so-called electronic effect). For PtMo/C and PtRu/C supplied with H(2)/CO, the formation of CO(2) is observed even when the cell is at open circuit, confirming some elimination of CO by a chemical process, most probably the water gas shift reaction. (C) 2008 Elsevier Ltd. All rights reserved.

Effects of adding La and Ce to hydrotalcite-type Ni/Mg/Al catalyst precursors on ethanol steam reforming reactions

Catalyst precursors composed of Ni/Mg/Al oxides with added La and Ce were tested in ethanol steam reforming (ESR) reactions. La and Ce were added by anion-exchange. The oxides were characterized by X-ray photoelectron spectroscopy (XPS) and X-ray absorption near-edge structure (XANES) analysis. The catalyst precursors consist of a mixture of oxides, with the nickel in the form of NiO strongly interacting with the support Mg/Al. The XPS analysis showed a lanthanum-support interaction, but no interaction of Ce species with the support. The reaction data obtained with the active catalysts showed that the addition of Ce and La resulted in better H(2) production at 550 degrees C. The CeNi catalyst provided the higher ethanol conversion, with lower acetaldehyde production, possibly clue to a favoring of water adsorption on the weakly interacting clusters of CeO(2) on the surface. (C) 2010 Elsevier B.V. All rights reserved.

CuO and CuO-ZnO catalysts supported on CeO(2) and CeO(2)-LaO(3) for low temperature water-gas shift reaction

This paper describes an investigation on CuO and CuO-ZnO catalysts supported on CeO(2) and CeO(2)-La(2)O(3) oxides, which were designed for the low temperature water-gas shift reaction (WGSR). Bulk catalysts were prepared by co-precipitation of metal nitrates and characterized by energy-dispersive spectroscopy (EDS), X-ray diffraction (XRD), surface area (by the BET method), X-ray photoelectron spectroscopy (XPS), and in situ X-ray absorption near edge structure (XANES). The catalysts` activities were tested in the forward WGSR, and the CuO/CeO(2) catalyst presented the best catalytic performance. The reasons for this are twofold: (1) the presence of Zn inhibits the interaction between Cu and Ce ions, and (2) lanthanum oxide forms a solid solution with cerium oxide, which will cause a decrease in the surface area of the catalysts. Also the CuO/CeO(2) catalyst presented the highest Cu content on the surface, which could influence its catalytic behavior. Additionally, the Cu and Cu(1+) species could influence the catalytic activity via a reduction-oxidation mechanism, corroborating to the best catalytic performance of the Cu/Ce catalyst. (c) 2010 Elsevier B.V. All rights reserved.

Methane conversion reactions on Ni catalysts promoted with Rh: Influence of support

Ni catalysts supported on gamma-Al(2)O(3) and Mg(Al)O were prepared with and without Rh as a promoter and tested in the reforming of methane in the presence of excess methane, simulating a model biogas. The effects of adding synthetic air on the methane conversion and the formation of carbon were assessed. The catalysts were characterized by X-ray spectroscopy (EDS), surface area (BET), X-ray diffraction (XRD), Temperature-programmed reduction (TPR), X-ray absorption near-edge structure (XANES) and XPD. The results showed that in catalysts without Rh, the Ni interacts strongly with the supports, showing high reduction temperatures in TPR tests. The addition of Rh increased the amount of reducible Ni and facilitated the reduction of the species interacting strongly with the support. In the catalytic tests, the samples promoted with Rh suffered higher carbon deposition. The in situ XPD suggested that on the support gamma-Al(2)O(3), the presence of Rh probably led to a segregation of Ni species with time on stream, leading to carbon deposition. On the support MgAlO, the presence of Rh improved the dispersion of Ni, by reducing the Ni(0) crystallite size, suggesting that in this case the carbon deposition was due to a favoring of CH(4) decomposition by Rh. (C) 2011 Elsevier B.V. All rights reserved.

Synchrotron microComputed tomography of the mature bovine dentinoenamel junction

The mature dentinoenamel junction (DEJ) is viewed by some investigators and the current authors, not as a fossilized, sharp transition between enamel and dentin, but as a relatively broad structural transition zone including the mantle dentin and the inner aprismatic enamel. In this study, the DEJ structure in bovine incisors was studied with synchrotron microComputed Tomography (microCT) using small cubes cut parallel to the tooth surface. The reconstructions revealed a zone of highly variable punctate contrast between bulk dentin and enamel; the mean linear attenuation coefficients and their standard deviations demonstrated that this zone averaged less mineral than dentin or enamel but had more highly variable structure than either. The region with the punctuate contrast is, therefore, the mantle dentin. The thickness of the mantle dentin seen in a typical data set was about 30 mu m, and the mantle dentin-enamel interface deviated +/- 15 mu m from the average plane over a distance of 520 mu m. In the highest resolution data (similar to 1.5 mu m isotropic voxels, volume elements), tubules in the dentin could be discerned in the vicinity of the DEJ. Contrast sensitivity was high enough to detect differences in mineral content between near-surface and near-DEJ volumes of the enamel. Reconstructions before and after two cubes were compressed to failure revealed cracks formed only in the enamel and did not propagate across the mantle dentin, regardless of whether loading was parallel to or perpendicular to the DEJ. (C) 2007 Elsevier B.V. All rights reserved.

Electronic structure of Pb1-xLaxTiO3 ferroelectric materials from Ti 2p and O 1s soft x-ray absorption spectroscopy

The electronic structure of Pb1-xLaxTiO3 (PLT) compounds for x ranging from 0 to 30 at. % of La is investigated by means of soft x-ray absorption near edge structure (XANES) at the Ti L-3,L-2 and O K edges. The greatest modification in the structure of the Ti 2p XANES spectra of the PLT compounds is observed in the region of the high energy peak of the L-3 edge (e(g) states), which exhibits a splitting in the undoped sample. As the amount of lanthanum increases, this splitting becomes less pronounced. This modification is interpreted as a decrease in the degree of disorder of titanium atoms, which is correlated to the substitution of Pb by La atoms. The structural changes observed at the low energy peaks of the O K-edge XANES spectra of the PLT compounds may be interpreted in terms of hybridization between O 2p, Ti 3d, and Pb 6p orbitals. A decrease in the degree of hybridization observed as Pb atoms are replaced by La atoms may be related to the differences in the ferroelectric properties observed between x=0.0 and x=0.30 compounds. (c) 2006 American Institute of Physics.

Effect of presence of an acid catalyst on structure and properties of iron-doped siloxane-polyoxyethylene nanocomposites prepared by sol-gel

In this work we investigate the effect of hydrochloric acid (HC) addition on the structure and thermal and magnetic properties of iron-doped siloxane-polyoxyethylene (POE) hybrids prepared by the sol-gel route. X-ray powder diffraction (XRD) and X-ray absorption near edge structure (XANES) results reveal the dominance of ferrihydrite nanoparticles and a mixture of this phase with FeCl4- species in the hybrid prepared without and with HCl, respectively. Thermal analysis reveals the existence of two crystalline polymeric phases in the hybrid prepared with HCl whereas hybrids prepared without HCl are amorphous. The 105 and 60 Angstrom sized ferrihydrite nanoparticles were detected by SAXS analysis of the composite prepared without and with HCl, respectively. The magnetic results suggest that in both samples antiferromagnetic nanoparticles coexist with small clusters/isolated ions. In the sample without HCl addition, larger particles dominate the magnetic behavior, while the opposite occurs for the sample prepared using HCl catalyst. (C) 2004 Elsevier B.V. All rights reserved.

Relationship between Crystal Shape, Photoluminescence, and Local Structure in SrTiO3 Synthesized by Microwave-Assisted Hydrothermal Method

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)