Copper deposition on TiO2 from copper(II)hexafluoroacetylacetonate

The authors have studied the adsorption of CuII(hfac)2 on the surface of a model oxide system, TiO2(110), and probed the molecular stability with respect to thermal cycling, using atomic scale imaging by scanning tunneling microscopy supported by x-ray photoemission spectroscopy. They find that at 473 K, the adsorbed metal-organic molecules begin to dissociate and release Cu atoms which aggregate and form Cu nanoparticles. These Cu nanoparticles ripen over time and the size (height) distribution develops into a bimodal distribution. Unlike other organometallic systems, which show a bimodal distribution due to enhanced nucleation or growth at surface step edges, the nanoparticles do not preferentially form at steps. The reduced mobility of the Cu islands may be related to the co-adsorbed ligands that remain in very small clusters on the surface.

The effects of explicit versus parameterized convection on the MJO in a large-domain high-resolution tropical case study. Part I: Characterization of large-scale organization and propagation

High-resolution simulations over a large tropical domain (∼20◦S–20◦N and 42◦E–180◦E) using both explicit and parameterized convection are analyzed and compared to observations during a 10-day case study of an active Madden-Julian Oscillation (MJO) event. The parameterized convection model simulations at both 40 km and 12 km grid spacing have a very weak MJO signal and little eastward propagation. A 4 km explicit convection simulation using Smagorinsky subgrid mixing in the vertical and horizontal dimensions exhibits the best MJO strength and propagation speed. 12 km explicit convection simulations also perform much better than the 12 km parameterized convection run, suggesting that the convection scheme, rather than horizontal resolution, is key for these MJO simulations. Interestingly, a 4 km explicit convection simulation using the conventional boundary layer scheme for vertical subgrid mixing (but still using Smagorinsky horizontal mixing) completely loses the large-scale MJO organization, showing that relatively high resolution with explicit convection does not guarantee a good MJO simulation. Models with a good MJO representation have a more realistic relationship between lower-free-tropospheric moisture and precipitation, supporting the idea that moisture-convection feedback is a key process for MJO propagation. There is also increased generation of available potential energy and conversion of that energy into kinetic energy in models with a more realistic MJO, which is related to larger zonal variance in convective heating and vertical velocity, larger zonal temperature variance around 200 hPa, and larger correlations between temperature and ascent (and between temperature and diabatic heating) between 500–400 hPa.

Oppositely charged polyelectrolytes: complex formation and effects of chain asymmetry

The formation of complexes in solutions of oppositely charged polyions has been studied by Monte Carlo simulations. The amount as well as the length, and thus, the absolute charge of one of the polyions have been varied. There is an increasing tendency to form large clusters as the excess of one kind of polyion decreases. When all polyions have the same length, this tendency reaches a maximum near, but off, equivalent amounts of the two types of polyions. When one kind of polyion is made shorter, the propensity to form large clusters decreases and the fluctuations in cluster charge increases. Simple free-energy expressions have been formulated on the basis of a set of simple rules that help rationalize the observations. By calculating cluster distributions in both grand canonical and canonical ensembles, it has been possible to show the extent of finite-size effects in the simulations.

Complex formation in solutions of oppositely charged polyelectrolytes at different polyion compositions and salt content

The formation of complexes in solutions containing positively charged polyions (polycations) and a variable amount of negatively charged polyions (polyanions) has been investigated by Monte Carlo simulations. The polyions were described as flexible chains of charged hard spheres interacting through a screened Coulomb potential. The systems were analyzed in terms of cluster compositions, structure factors, and radial distribution functions. At 50% charge equivalence or less, complexes involving two polycations and one polyanion were frequent, while closer to charge equivalence, larger clusters were formed. Small and neutral complexes dominated the solution at charge equivalence in a monodisperse system, while larger clusters again dominated the solution when the polyions were made polydisperse. The cluster composition and solution structure were also examined as functions of added salt by varying the electrostatic screening length. The observed formation of clusters could be rationalized by a few simple rules.

Climate warming–related strengthening of the tropical hydrological cycle

The authors estimate climate warming–related twenty-first-century changes of moisture transports from the descending into the ascending regions in the tropics. Unlike previous studies that employ time and space averaging, here homogeneous high horizontal and vertical resolution data from an Intergovernmental Panel on Climate Change Fourth Assessment Report (IPCC AR4) climate model are used. This allows for estimating changes in much greater detail (e.g., the estimation of the distribution of ascending and descending regions, changes in the vertical profile, and separating changes of the inward and outward transports). Low-level inward and midlevel outward moisture transports of the convective regions in the tropics are found to increase in a simulated anthropogenically warmed climate as compared to a simulated twentieth-century atmosphere, indicating an intensification of the hydrological cycle. Since an increase of absolute inward transport exceeds the absolute increase of outward transport, the resulting budget is positive, meaning that more water is projected to converge in the moist tropics. The intensification is found mainly to be due to the higher amount of water in the atmosphere, while the contribution of weakening wind counteracts this response marginally. In addition the changing statistical properties of the vertical profile of the moisture transport are investigated and the importance of the substantial outflow of moisture from the moist tropics at midlevels is demonstrated.

Measuring variation in potato roots in both field and glasshouse: the search for useful yield predictors and a simple screen for root traits

Aims Potatoes have an inadequate rooting system for efficient acquisition of water and minerals and use disproportionate amounts of irrigation and fertilizer. This research determines whether significant variation in rooting characteristics of potato exists, which characters correlate with final yield and whether a simple screen for rooting traits could be developed. Methods Twenty-eight genotypes of Solanum tuberosum groups Tuberosum and Phureja were grown in the field; eight replicate blocks to final harvest, while entire root systems were excavated from four blocks. Root classes were categorised and measured. The same measurements were made on these genotypes in the glasshouse, 2 weeks post emergence. Results In the field, total root length varied from 40 m to 112 m per plant. Final yield was correlated negatively with basal root specific root length and weakly but positively with total root weight. Solanum tuberosum group Phureja genotypes had more numerous roots and proportionally more basal than stolon roots compared with Solanum tuberosum, group Tuberosum genotypes. There were significant correlations between glasshouse and field measurements. Conclusions Our data demonstrate that variability in rooting traits amongst commercially available potato genotypes exists and a robust glasshouse screen has been developed. By measuring potato roots as described in this study, it is now possible to assess rooting traits of large populations of potato genotypes.

The influence of anthropogenic landscape changes on weather in south Florida

Using identical observed meteorology for lateral boundary conditions, the Regional Atmospheric Modeling System was integrated for July-August 1973 for south Florida. Three experiments were performed-one using the observed 1973 landscape, another the 1993 landscape, and the third the 1900 landscape, when the region was close to its natural state. Over the 2-month period, there was a 9% decrease in rainfall averaged over south Florida with the 1973 landscape and an 11% decrease with the 1993 landscape, as compared with the model results when the 1900 landscape is used. The limited available observations of trends in summer rainfall over this region are consistent with these trends.

Towards global drought early warning capability: expanding international cooperation for the development of a framework for global drought monitoring and forecasting

Drought is a global problem that has far-reaching impacts and especially 47 on vulnerable populations in developing regions. This paper highlights the need for a Global Drought Early Warning System (GDEWS), the elements that constitute its underlying framework (GDEWF) and the recent progress made towards its development. Many countries lack drought monitoring systems, as well as the capacity to respond via appropriate political, institutional and technological frameworks, and these have inhibited the development of integrated drought management plans or early warning systems. The GDEWS will provide a source of drought tools and products via the GDEWF for countries and regions to develop tailored drought early warning systems for their own users. A key goal of a GDEWS is to maximize the lead time for early warning, allowing drought managers and disaster coordinators more time to put mitigation measures in place to reduce the vulnerability to drought. To address this, the GDEWF will take both a top-down approach to provide global real-time drought monitoring and seasonal forecasting, and a bottom-up approach that builds upon existing national and regional systems to provide continental to global coverage. A number of challenges must be overcome, however, before a GDEWS can become a reality, including the lack of in-situ measurement networks and modest seasonal forecast skill in many regions, and the lack of infrastructure to translate data into useable information. A set of international partners, through a series of recent workshops and evolving collaborations, has made progress towards meeting these challenges and developing a global system.

Standardized test to evaluate numerical weather prediction algorithms

In order to assist in comparing the computational techniques used in different models, the authors propose a standardized set of one-dimensional numerical experiments that could be completed for each model. The results of these experiments, with a simplified form of the computational representation for advection, diffusion, pressure gradient term, Coriolis term, and filter used in the models, should be reported in the peer-reviewed literature. Specific recommendations are described in this paper.

Realism of rainfall in a very high-resolution regional climate model

The realistic representation of rainfall on the local scale in climate models remains a key challenge. Realism encompasses the full spatial and temporal structure of rainfall, and is a key indicator of model skill in representing the underlying processes. In particular, if rainfall is more realistic in a climate model, there is greater confidence in its projections of future change. In this study, the realism of rainfall in a very high-resolution (1.5 km) regional climate model (RCM) is compared to a coarser-resolution 12-km RCM. This is the first time a convection-permitting model has been run for an extended period (1989–2008) over a region of the United Kingdom, allowing the characteristics of rainfall to be evaluated in a climatological sense. In particular, the duration and spatial extent of hourly rainfall across the southern United Kingdom is examined, with a key focus on heavy rainfall. Rainfall in the 1.5-km RCM is found to be much more realistic than in the 12-km RCM. In the 12-km RCM, heavy rain events are not heavy enough, and tend to be too persistent and widespread. While the 1.5-km model does have a tendency for heavy rain to be too intense, it still gives a much better representation of its duration and spatial extent. Long-standing problems in climate models, such as the tendency for too much persistent light rain and errors in the diurnal cycle, are also considerably reduced in the 1.5-km RCM. Biases in the 12-km RCM appear to be linked to deficiencies in the representation of convection.

Concentrations of free amino acids and sugars in nine potato varieties: effects of storage and relationship with acrylamide formation

Acrylamide forms during cooking and processing predominately from the reaction of free asparagine and reducing sugars in the Maillard reaction. The identification of low free asparagine and reducing sugar varieties of crops is therefore an important target. In this study, nine varieties of potato (French fry varieties Maris Piper (from two suppliers), Pentland Dell, King Edward, Daisy, and Markies; and chipping varieties Lady Claire, Lady Rosetta, Saturna, and Hermes) grown in the United Kingdom in 2009 were analyzed at monthly intervals through storage from November 2009 to July 2010. Acrylamide formation was measured in heated flour and chips fried in oil. Analysis of variance revealed significant interactions between varieties nested within type (French fry and chipping) and storage time for most free amino acids, glucose, fructose, and acrylamide formation. Acrylamide formed in chips correlated significantly with acrylamide formed in flour and with chip color. There were significant correlations between glucose or total reducing sugar concentration and acrylamide formation in both variety types, but with fructose the correlation was much stronger for chipping than for French fry varieties. Conversely, there were significant correlations with acrylamide formation for both total free amino acid and free asparagine concentration in the French fry but not chipping varieties. The study showed the potential of variety selection for preventing unacceptable levels of acrylamide formation in potato products and the variety-dependent effect of long-term storage on acrylamide risk. It also highlighted the complex relationship between precursor concentration and acrylamide risk in potatoes.

Tetragonal and helical morphologies from polyferrocenylsilane block polyelectrolytes via ionic self-assembly

The use of ionic self-assembly, a facile noncovalent approach, to access non-conventional block copolymer morphologies, including tetragonal and helical structures, from a combination of polyferrocenylsilane diblock copolymer polyelectrolytes and AOT-based surfactants, is described.

Is missing orographic gravity wave drag near 60°S the cause of the stratospheric zonal wind biases in chemistry–climate models?

Nearly all chemistry–climate models (CCMs) have a systematic bias of a delayed springtime breakdown of the Southern Hemisphere (SH) stratospheric polar vortex, implying insufficient stratospheric wave drag. In this study the Canadian Middle Atmosphere Model (CMAM) and the CMAM Data Assimilation System (CMAM-DAS) are used to investigate the cause of this bias. Zonal wind analysis increments from CMAMDAS reveal systematic negative values in the stratosphere near 608S in winter and early spring. These are interpreted as indicating a bias in the model physics, namely, missing gravity wave drag (GWD). The negative analysis increments remain at a nearly constant height during winter and descend as the vortex weakens, much like orographic GWD. This region is also where current orographic GWD parameterizations have a gap in wave drag, which is suggested to be unrealistic because of missing effects in those parameterizations. These findings motivate a pair of free-runningCMAMsimulations to assess the impact of extra orographicGWDat 608S. The control simulation exhibits the cold-pole bias and delayed vortex breakdown seen in the CCMs. In the simulation with extra GWD, the cold-pole bias is significantly reduced and the vortex breaks down earlier. Changes in resolved wave drag in the stratosphere also occur in response to the extra GWD, which reduce stratospheric SH polar-cap temperature biases in late spring and early summer. Reducing the dynamical biases, however, results in degraded Antarctic column ozone. This suggests that CCMs that obtain realistic column ozone in the presence of an overly strong and persistent vortex may be doing so through compensating errors.

Dynamics of the lower stratospheric circulation response to ENSO

A robust feature of the observed response to El Nin˜o–Southern Oscillation (ENSO) is an altered circulation in the lower stratosphere. When sea surface temperatures (SSTs) in the tropical Pacific are warmer there is enhanced upwelling and cooling in the tropical lower stratosphere and downwelling and warming in the midlatitudes, while the opposite is true of cooler SSTs. The midlatitude lower stratospheric response to ENSO is larger in the Southern Hemisphere (SH) than in the Northern Hemisphere (NH). In this study the dynamical version of the Canadian Middle Atmosphere Model (CMAM) is used to simulate 25 realizations of the atmospheric response to the 1982/83 El Nin˜o and the 1973/74 La Nin˜ a. This version ofCMAMis a comprehensive high-top general circulation model that does not include interactive chemistry. The observed lower stratospheric response to ENSO is well reproduced by the simulations, allowing them to be used to investigate the mechanisms involved. Both the observed and simulated responses maximize in December–March and so this study focuses on understanding the mechanisms involved in that season. The response in tropical upwelling is predominantly driven by anomalous transient synoptic-scale wave drag in the SH subtropical lower stratosphere, which is also responsible for the compensating SH midlatitude response. This altered wave drag stems from an altered upward flux of wave activity from the troposphere into the lower stratosphere between 208 and 408S. The altered flux of wave activity can be divided into two distinct components. In the Pacific, the acceleration of the zonal wind in the subtropics from the warmer tropical SSTs results in a region between the midlatitude and subtropical jets where there is an enhanced source of low phase speed eddies. At other longitudes, an equatorward shift of the midlatitude jet from the extratropical tropospheric response to El Nin˜o results in an enhanced source of waves of higher phase speeds in the subtropics. The altered resolved wave drag is only apparent in the SH and the difference between the two hemispheres can be related to the difference in the climatological jet structures in this season and the projection of the wind anomalies associated with ENSO onto those structures.