Spectro-electrochemical and DFT studies of a planar Cu(II)–phenolate complex active in the aerobic oxidation of primary alcohols

A square-planar compound [Cu(pyrimol)Cl] (pyrimol = 4-methyl-2-N-(2-pyridylmethylene)aminophenolate) abbreviated as CuL–Cl) is described as a biomimetic model of the enzyme galactose oxidase (GOase). This copper(II) compound is capable of stoichiometric aerobic oxidation of activated primary alcohols in acetonitrile/water to the corresponding aldehydes. It can be obtained either from Hpyrimol (HL) or its reduced/hydrogenated form Hpyramol (4-methyl-2-N-(2-pyridylmethyl)aminophenol; H2L) readily converting to pyrimol (L-) on coordination to the copper(II) ion. Crystalline CuL–Cl and its bromide derivative exhibit a perfect square-planar geometry with Cu–O(phenolate) bond lengths of 1.944(2) and 1.938(2) Å. The cyclic voltammogram of CuL–Cl exhibits an irreversible anodic wave at +0.50 and +0.57 V versus ferrocene/ferrocenium (Fc/Fc+) in dry dichloromethane and acetonitrile, respectively, corresponding to oxidation of the phenolate ligand to the corresponding phenoxyl radical. In the strongly donating acetonitrile the oxidation path involves reversible solvent coordination at the Cu(II) centre. The presence of the dominant CuII–L. chromophore in the electrochemically and chemically oxidised species is evident from a new fairly intense electronic absorption at 400–480 nm ascribed to a several electronic transitions having a mixed pi-pi(L.) intraligand and Cu–Cl -> L. charge transfer character. The EPR signal of CuL–Cl disappears on oxidation due to strong intramolecular antiferromagnetic exchange coupling between the phenoxyl radical ligand (L.) and the copper(II) centre, giving rise to a singlet ground state (S = 0). The key step in the mechanism of the primary alcohol oxidation by CuL–Cl is probably the alpha-hydrogen abstraction from the equatorially bound alcoholate by the phenoxyl moiety in the oxidised pyrimol ligand, Cu–L., through a five-membered cyclic transition state.

Objective detection of sting jets in low-resolution datasets

Sting jets are transient coherent mesoscale strong wind features that can cause damaging surface wind gusts in extratropical cyclones. Currently, we have only limited knowledge of their climatological characteristics. Numerical weather prediction models require enough resolution to represent slantwise motions with horizontal scales of tens of kilometres and vertical scales of just a few hundred metres to represent sting jets. Hence, the climatological characteristics of sting jets and the associated extratropical cyclones can not be determined by searching for sting jets in low-resolution datasets such as reanalyses. A diagnostic is presented and evaluated for the detection in low-resolution datasets of atmospheric regions from which sting jets may originate. Previous studies have shown that conditional symmetric instability (CSI) is present in all storms studied with sting jets, while other, rapidly developing storms of a similar character but no CSI do not develop sting jets. Therefore, we assume that the release of CSI is needed for sting jets to develop. While this instability will not be released in a physically realistic way in low-resolution models (and hence sting jets are unlikely to occur), it is hypothesized that the signature of this instability (combined with other criteria that restrict analysis to moist mid-tropospheric regions in the neighbourhood of a secondary cold front) can be used to identify cyclones in which sting jets occurred in reality. The diagnostic is evaluated, and appropriate parameter thresholds defined, by applying it to three case studies simulated using two resolutions (with CSI-release resolved in only the higher-resolution simulation).

Near real-time flood detection in urban and rural areas using high resolution Synthetic Aperture Radar images

A near real-time flood detection algorithm giving a synoptic overview of the extent of flooding in both urban and rural areas, and capable of working during night-time and day-time even if cloud was present, could be a useful tool for operational flood relief management. The paper describes an automatic algorithm using high resolution Synthetic Aperture Radar (SAR) satellite data that builds on existing approaches, including the use of image segmentation techniques prior to object classification to cope with the very large number of pixels in these scenes. Flood detection in urban areas is guided by the flood extent derived in adjacent rural areas. The algorithm assumes that high resolution topographic height data are available for at least the urban areas of the scene, in order that a SAR simulator may be used to estimate areas of radar shadow and layover. The algorithm proved capable of detecting flooding in rural areas using TerraSAR-X with good accuracy, classifying 89% of flooded pixels correctly, with an associated false positive rate of 6%. Of the urban water pixels visible to TerraSAR-X, 75% were correctly detected, with a false positive rate of 24%. If all urban water pixels were considered, including those in shadow and layover regions, these figures fell to 57% and 18% respectively.

How to quantify the resolution of surface climate by circulation types: an example for Alpine precipitation

A novel approach is presented for the evaluation of circulation type classifications (CTCs) in terms of their capability to predict surface climate variations. The approach is analogous to that for probabilistic meteorological forecasts and is based on the Brier skill score. This score is shown to take a particularly simple form in the context of CTCs and to quantify the resolution of a climate variable by the classifications. The sampling uncertainty of the skill can be estimated by means of nonparametric bootstrap resampling. The evaluation approach is applied for a systematic intercomparison of 71 CTCs (objective and manual, from COST Action 733) with respect to their ability to resolve daily precipitation in the Alpine region. For essentially all CTCs, the Brier skill score is found to be higher for weak and moderate compared to intense precipitation, for winter compared to summer, and over the north and west of the Alps compared to the south and east. Moreover, CTCs with a higher number of types exhibit better skill than CTCs with few types. Among CTCs with comparable type number, the best automatic classifications are found to outperform the best manual classifications. It is not possible to single out one ‘best’ classification for Alpine precipitation, but there is a small group showing particularly high skill.

Kinetic multi-layer model of gas-particle interactions in aerosols and clouds (KM-GAP): linking condensation, evaporation and chemical reactions of organics, oxidants and water

We present a novel kinetic multi-layer model for gas-particle interactions in aerosols and clouds (KM-GAP) that treats explicitly all steps of mass transport and chemical reaction of semi-volatile species partitioning between gas phase, particle surface and particle bulk. KM-GAP is based on the PRA model framework (Pöschl-Rudich-Ammann, 2007), and it includes gas phase diffusion, reversible adsorption, surface reactions, bulk diffusion and reaction, as well as condensation, evaporation and heat transfer. The size change of atmospheric particles and the temporal evolution and spatial profile of the concentration of individual chemical species can be modelled along with gas uptake and accommodation coefficients. Depending on the complexity of the investigated system, unlimited numbers of semi-volatile species, chemical reactions, and physical processes can be treated, and the model shall help to bridge gaps in the understanding and quantification of multiphase chemistry and microphysics in atmo- spheric aerosols and clouds. In this study we demonstrate how KM-GAP can be used to analyze, interpret and design experimental investigations of changes in particle size and chemical composition in response to condensation, evaporation, and chemical reaction. For the condensational growth of water droplets, our kinetic model results provide a direct link between laboratory observations and molecular dynamic simulations, confirming that the accommodation coefficient of water at 270 K is close to unity. Literature data on the evaporation of dioctyl phthalate as a function of particle size and time can be reproduced, and the model results suggest that changes in the experimental conditions like aerosol particle concentration and chamber geometry may influence the evaporation kinetics and can be optimized for eðcient probing of specific physical effects and parameters. With regard to oxidative aging of organic aerosol particles, we illustrate how the formation and evaporation of volatile reaction products like nonanal can cause a decrease in the size of oleic acid particles exposed to ozone.

A 3D cloud-construction algorithm for the EarthCARE satellite mission

This article presents and assesses an algorithm that constructs 3D distributions of cloud from passive satellite imagery and collocated 2D nadir profiles of cloud properties inferred synergistically from lidar, cloud radar and imager data. It effectively widens the active–passive retrieved cross-section (RXS) of cloud properties, thereby enabling computation of radiative fluxes and radiances that can be compared with measured values in an attempt to perform radiative closure experiments that aim to assess the RXS. For this introductory study, A-train data were used to verify the scene-construction algorithm and only 1D radiative transfer calculations were performed. The construction algorithm fills off-RXS recipient pixels by computing sums of squared differences (a cost function F) between their spectral radiances and those of potential donor pixels/columns on the RXS. Of the RXS pixels with F lower than a certain value, the one with the smallest Euclidean distance to the recipient pixel is designated as the donor, and its retrieved cloud properties and other attributes such as 1D radiative heating rates are consigned to the recipient. It is shown that both the RXS itself and Moderate Resolution Imaging Spectroradiometer (MODIS) imagery can be reconstructed extremely well using just visible and thermal infrared channels. Suitable donors usually lie within 10 km of the recipient. RXSs and their associated radiative heating profiles are reconstructed best for extensive planar clouds and less reliably for broken convective clouds. Domain-average 1D broadband radiative fluxes at the top of theatmosphere(TOA)for (21 km)2 domains constructed from MODIS, CloudSat andCloud–Aerosol Lidar and Infrared Pathfinder Satellite Observations (CALIPSO) data agree well with coincidental values derived from Clouds and the Earth’s Radiant Energy System (CERES) radiances: differences betweenmodelled and measured reflected shortwave fluxes are within±10Wm−2 for∼35% of the several hundred domains constructed for eight orbits. Correspondingly, for outgoing longwave radiation∼65% are within ±10Wm−2.

The impact of resolution on the adjustment and decadal variability of the Atlantic Meridional Overturning Circulation in a coupled climate model

Variations in the Atlantic Meridional Overturning Circulation (MOC) exert an important influence on climate, particularly on decadal time scales. Simulation of the MOC in coupled climate models is compromised, to a degree that is unknown, by their lack of fidelity in resolving some of the key processes involved. There is an overarching need to increase the resolution and fidelity of climate models, but also to assess how increases in resolution influence the simulation of key phenomena such as the MOC. In this study we investigate the impact of significantly increasing the (ocean and atmosphere) resolution of a coupled climate model on the simulation of MOC variability by comparing high and low resolution versions of the same model. In both versions, decadal variability of the MOC is closely linked to density anomalies that propagate from the Labrador Sea southward along the deep western boundary. We demonstrate that the MOC adjustment proceeds more rapidly in the higher resolution model due the increased speed of western boundary waves. However, the response of the Atlantic Sea Surface Temperatures (SSTs) to MOC variations is relatively robust - in pattern if not in magnitude - across the two resolutions. The MOC also excites a coupled ocean-atmosphere response in the tropical Atlantic in both model versions. In the higher resolution model, but not the lower resolution model, there is evidence of a significant response in the extratropical atmosphere over the North Atlantic 6 years after a maximum in the MOC. In both models there is evidence of a weak negative feedback on deep density anomalies in the Labrador Sea, and hence on the MOC (with a time scale of approximately ten years). Our results highlight the need for further work to understand the decadal variability of the MOC and its simulation in climate models.

Upper-ocean heat budget and ocean eddy transport in the south-east Pacific in a high-resolution coupled model

We present an analysis of the oceanic heat advection and its variability in the upper 500 m in the southeastern tropical Pacific (100W–75W, 25S–10S) as simulated by the global coupled model HiGEM, which has one of the highest resolutions currently used in long-term integrations. The simulated climatology represents a temperature advection field arising from transient small-scale (<450 km) features, with structures and transport that appear consistent with estimates based on available observational data for the mooring at 20S, 85W. The transient structures are very persistent (>4 months), and in specific locations they generate an important contribution to the local upper-ocean heat budget, characterised by scales of a few hundred kilometres, and periods of over a year. The contribution from such structures to the local, long-term oceanic heat budget however can be of either sign, or vanishing, depending on the location; and, although there appears some organisation in preferential areas of activity, the average over the entire region is small. While several different mechanisms may be responsible for the temperature advection by transients, we find that a significant, and possibly dominant, component is associated with vortices embedded in the large-scale, climatological salinity gradient associated with the fresh intrusion of mid-latitude intermediate water which penetrates north-westward beneath the tropical thermocline