Forecast, measurement, and modeling of an unprecedented polar ozone filament event over Mauna Loa Observatory, Hawaii

In mid-March 2005 the northern lower stratospheric polar vortex experienced a severe stretching episode, bringing a large polar filament far south of Alaska toward Hawaii. This meridional intrusion of rare extent, coinciding with the polar vortex final warming and breakdown, was followed by a zonal stretching in the wake of the easterly propagating subtropical main flow. This caused polar air to remain over Hawaii for several days before diluting into the subtropics. After being successfully forecasted to pass over Hawaii by the high-resolution potential vorticity advection model Modèle Isentrope du transport Méso-échelle de l'Ozone Stratosphérique par Advection (MIMOSA), the filament was observed on isentropic surfaces between 415 K and 455 K (17–20 km) by the Jet Propulsion Laboratory stratospheric ozone lidar measurements at Mauna Loa Observatory, Hawaii, between 16 and 19 March 2005. It was materialized as a thin layer of enhanced ozone peaking at 1.6 ppmv in a region where the climatological values usually average 1.0 ppmv. These values were compared to those obtained by the three-dimensional Chemistry-Transport Model MIMOSA-CHIM. Agreement between lidar and model was excellent, particularly in the similar appearance of the ozone peak near 435 K (18.5 km) on 16 March, and the persistence of this layer at higher isentropic levels for the following three days. Passive ozone, also modeled by MIMOSA-CHIM, was at about 3–4 ppmv inside the filament while above Hawaii. A detailed history of the modeled chemistry inside the filament suggests that the air mass was still polar ozone–depleted when passing over Hawaii. The filament quickly separated from the main vortex after its Hawaiian overpass. It never reconnected and, in less than 10 days, dispersed entirely in the subtropics

Simultaneous lidar and EOS MLS measurements, and modeling, of a rare polar ozone filament event over Mauna Loa Observatory, Hawaii

In mid-March 2005, a rare lower stratospheric polar vortex filamentation event was observed simultaneously by the JPL lidar at Mauna Loa Observatory, Hawaii, and by the EOS MLS instrument onboard the Aura satellite. The event coincided with the beginning of the spring 2005 final warming. On 16 March, the filament was observed by lidar around 0600 UT between 415 K and 455 K, and by MLS six hours earlier. It was seen on both the lidar and MLS profiles as a layer of enhanced ozone, peaking at 1.7 ppmv in a region where the climatological values are usually around or below 1 ppmv. Ozone profiles measured by lidar and MLS were compared to profiles from the Chemical Transport Model MIMOSA-CHIM. The agreement between lidar, MLS, and the model is excellent considering the difference in the sampling techniques. MLS was also able to identify the filament at another location north of Hawaii.

Lower-stratospheric radiative damping and polar-night jet oscillation events

The effect of stratospheric radiative damping time scales on stratospheric variability and on stratosphere–troposphere coupling is investigated in a simplified global circulation model by modifying the vertical profile of radiative damping in the stratosphere while holding it fixed in the troposphere. Perpetual-January conditions are imposed, with sinusoidal topography of zonal wavenumber 1 or 2. The depth and duration of the simulated sudden stratospheric warmings closely track the lower-stratospheric radiative time scales. Simulations with the most realistic profiles of radiative damping exhibit extended time-scale recoveries analogous to polar-night jet oscillation (PJO) events, which are observed to follow sufficiently deep stratospheric warmings. These events are characterized by weak lower-stratospheric winds and enhanced stability near the tropopause, which persist for up to 3 months following the initial warming. They are obtained with both wave-1 and wave-2 topography. Planetary-scale Eliassen–Palm (EP) fluxes entering the vortex are also suppressed, which is in agreement with observed PJO events. Consistent with previous studies, the tropospheric jets shift equatorward in response to the warmings. The duration of the shift is closely correlated with the period of enhanced stability. The magnitude of the shift in these runs, however, is sensitive only to the zonal wavenumber of the topography. Although the shift is sustained primarily by synoptic-scale eddies, the net effect of the topographic form drag and the planetary-scale fluxes is not negligible; they damp the surface wind response but enhance the vertical shear. The tropospheric response may also reduce the generation of planetary waves, further extending the stratospheric dynamical time scales.

Pairwise assembly of organopalladium(II) units with cyanurato(3-) and trithiocyanurato(3-) ligands: formation of chiral Pd12, Pd10 and Pd9 cage-molecules

The o-palladated, chloro-bridged dimers [Pd{2-phenylpyridine(-H)}-μ-Cl]2 and [Pd{N,N-dimethylbenzylamine(-H)}-μ-Cl]2 react with cyanuric acid in the presence of base to afford closed, chiral cage-molecules in which twelve organo-Pd(II) centers, located in pairs at the vertices of an octahedron, are linked by four tetrahedrally-arranged cyanurato(3-) ligands. Incomplete (Pd10) cages, having structures derived from the corresponding Pd12 cages by replacing one pair of organopalladium centers with two protons, have also been isolated. Reaction of [Pd{2-phenylpyridine(-H)}-μ-Cl]2 with trithiocyanuric acid gives an entirely different and more open type of cage-complex, comprising only nine organopalladium centers and three thiocyanurato(3-) ligands: cage-closure in this latter system appears to be inhibited by steric crowding of the thiocarbonyl groups.

Polar cap patch segmentation of the tongue of ionization in the morning convection cell

Two types of poleward moving plasma concentration enhancements (PMPCEs) were observed during a sequence of pulsed reconnection events, both in the morning convection cell: Type L (low density) was associated with a cusp flow channel and seems likely to have been produced by ionization associated with particle precipitation, while Type H (high density) appeared to originate from the segmentation of the tongue of ionization by the processes which produced the Type L events. As a result, the Type L and Type H PMPCEs were interspersed, producing a complex density structure which underlines the importance of cusp flow channels as a mechanism for segmenting and structuring electron density in the cusp and shows the necessity of differentiating between at least two classes of electron density patches.

An optically transparent thin-layer electrochemical cell for the study of vibrational circular dichroism of chiral redox-active molecules

An optically transparent thin-layer electrochemical (OTTLE) cell with a locally extended optical path has been developed in order to perform vibrational circular dichroism (VCD) spectroscopy on chiral molecules prepared in specific oxidation states by means of electrochemical reduction or oxidation. The new design of the electrochemical cell successfully addresses the technical challenges involved in achieving sufficient infrared absorption. The VCD-OTTLE cell proves to be a valuable tool for the investigation of chiral redox-active molecules.

On the role of the ocean in projected atmospheric stability changes in the Atlantic polar low region

The occurrence of destructive mesoscale ‘polar low’ cyclones in the subpolar North Atlantic is projected to decline under anthropogenic change, due to an increase in atmospheric static stability. This letter reports on the role of changes in ocean circulation in shaping the atmospheric stability. In particular, the Atlantic Meridional Overturning Circulation (AMOC) is projected to weaken in response to anthropogenic forcing, leading to a local minimum in warming in this region. The reduced warming is restricted to the lower troposphere, hence contributing to the increase in static stability. Linear correlation analysis of the CMIP3 climate model ensemble suggests that around half of the model uncertainty in the projected stability response arises from the varied response of the AMOC between models.

Comparative effect of dairy fatty acids on cell adhesion molecules, nitric oxide and relative gene expression in healthy and diabetic human aortic endothelial cells

Dairy intake, despite its high saturated fatty acid (SFA) content, is associated with a lower risk of cardiovascular disease and diabetes. This in vitro study determined the effect of individual fatty acids (FA) found in dairy, and FA mixtures representative of a high SFA and a low SFA dairy lipid on markers of endothelial function in healthy and type II diabetic aortic endothelial cells.

Automated identification and tracking of polar-cap plasma patches at solar minimum

A method of automatically identifying and tracking polar-cap plasma patches, utilising data inversion and feature-tracking methods, is presented. A well-established and widely used 4-D ionospheric imaging algorithm, the Multi-Instrument Data Assimilation System (MIDAS), inverts slant total electron content (TEC) data from ground-based Global Navigation Satellite System (GNSS) receivers to produce images of the free electron distribution in the polar-cap ionosphere. These are integrated to form vertical TEC maps. A flexible feature-tracking algorithm, TRACK, previously used extensively in meteorological storm-tracking studies is used to identify and track maxima in the resulting 2-D data fields. Various criteria are used to discriminate between genuine patches and "false-positive" maxima such as the continuously moving day-side maximum, which results from the Earth's rotation rather than plasma motion. Results for a 12-month period at solar minimum, when extensive validation data are available, are presented. The method identifies 71 separate structures consistent with patch motion during this time. The limitations of solar minimum and the consequent small number of patches make climatological inferences difficult, but the feasibility of the method for patches larger than approximately 500 km in scale is demonstrated and a larger study incorporating other parts of the solar cycle is warranted. Possible further optimisation of discrimination criteria, particularly regarding the definition of a patch in terms of its plasma concentration enhancement over the surrounding background, may improve results.

Landscape evolution and ice-sheet behaviour in a semi-arid polar environment: James Ross Island, NE Antarctic Peninsula

This study of landscape evolution presents both new modern and palaeo process-landform data, and analyses the behaviour of the Antarctic Peninsula Ice Sheet through the Last Glacial Maximum (LGM), the Holocene and to the present day. Six sediment-landform assemblages are described and interpreted for Ulu Peninsula, James Ross Island, NE Antarctic Peninsula: (1) the Glacier Ice and Snow Assemblage; (2) the Glacigenic Assemblage, which relates to LGM sediments and comprises both erratic-poor and erratic-rich drift, deposited by cold-based and wet-based ice and ice streams respectively; (3) the Boulder Train Assemblage, deposited during a Mid-Holocene glacier readvance; (4) the Ice-cored Moraine Assemblage, found in front of small cirque glaciers; (5) the Paraglacial Assemblage including scree, pebble-boulder lags, and littoral and fluvial processes; and (6) the Periglacial Assemblage including rock glaciers, protalus ramparts, blockfields, solifluction lobes and extensive patterned ground. The interplay between glacial, paraglacial and periglacial processes in this semi-arid polar environment is important in understanding polygenetic landforms. Crucially, cold-based ice was capable of sediment and landform genesis and modification. This landsystem model can aid the interpretation of past environments, but also provides new data to aid the reconstruction of the last ice sheet to overrun James Ross Island.

Dimer formation by symbiotic donor–acceptor interaction between two molecules of a specially designed dioxomolybdenum(VI) complex containing both donor and acceptor centers – A structural, spectroscopic and DFT study

This work presents a model study for the formation of a dimeric dioxomolybdenum(VI) complex [MoO2L]2, generated by simultaneous satisfaction of acceptor and donor character existing in the corresponding monomeric Mo(VI) complex MoO2L. This mononuclear complex is specially designed to contain a coordinatively unsaturated Mo(VI) acceptor centre and a free donor group, (e.g. –NH2 group) strategically placed in the ligand skeleton [H2L = 2-hydroxyacetophenonehydrazone of 2-aminobenzoylhydrazine]. Apart from the dimer [MoO2L]2, complexes of the type MoO2L·B (where B = CH3OH, γ-picoline and imidazole) are also reported. All the complexes are characterized by elemental analysis, spectroscopic (UV–Vis, IR, 1H NMR) techniques and cyclic voltammetry. Single crystal X-ray structures of [MoO2L]2 (1), MoO2L·CH3OH (2), and MoO2L.(γ-pic) (3) have been determined and discussed. DFT calculation on these complexes corroborates experimental data and provides clue for the facile formation of this type of dimer not reported previously. The process of dimer formation may also be viewed as an interaction between two molecules of a specially designed complex acting as a monodentate ligand. This work is expected to open up a new field of design and synthesis of dimeric complexes through the process of symbiotic donor–acceptor (acid–base) interaction between two molecules of a specially designed monomer.

Can polar lows be objectively identified and tracked in the ECMWF operational analysis and the ERA-Interim reanalysis?

Polar lows are maritime meso-cyclones associated with intense surface wind speeds and oceanic heat fluxes at high latitudes. The ability of the ERA-Interim (ERAI) reanalysis to represent polar lows in the North Atlantic is assessed by comparing ERAI and the ECMWF operational analysis for the period 2008-2011. First, the representation of a set of satellite observed polar lows over the Norwegian and Barents Seas in the operational analysis and ERAI is analysed. Then, the possibility of directly identifying and tracking the polar lows in the operational analysis and ERAI is explored using a tracking algorithm based on 850 hPa vorticity with objective identification criteria on cyclone dynamical intensity and atmospheric static stability. All but one of the satellite observed polar lows with a lifetime of at least 6 hours have an 850 hPa vorticity signature of a co-located mesocyclone in both the operational analysis and ERAI for most of their life cycles. However, the operational analysis has vorticity structures that better resemble the observed cloud patterns and stronger surface wind speed intensities compared to those in ERAI. By applying the objective identification criteria, about 55% of the satellite observed polar lows are identified and tracked in ERAI, while this fraction increases to about 70% in the operational analysis. Particularly in ERAI, the remaining observed polar lows are mainly not identified because they have too weak wind speed and vorticity intensity compared to the tested criteria. The implications of the tendency of ERAI to underestimate the polar low dynamical intensity for future studies of polar lows is discussed.

Tripodal molecules for the promotion of phosphoester hydrolysis

A series of low molecular weight tripodal amide/histidine-containing compounds (1–2) have been synthesised and shown to increase the rate of bis-(p-nitrophenyl) phosphate (BNPP) and soman (GD) breakdown in buffered aqueous solution.

The ocean's role in polar climate change: asymmetric Arctic and Antarctic responses to greenhouse gas and ozone forcing

In recent decades, the Arctic has been warming and sea ice disappearing. By contrast, the Southern Ocean around Antarctica has been (mainly) cooling and sea-ice extent growing. We argue here that interhemispheric asymmetries in the mean ocean circulation, with sinking in the northern North Atlantic and upwelling around Antarctica, strongly influence the sea-surface temperature (SST) response to anthropogenic greenhouse gas (GHG) forcing, accelerating warming in the Arctic while delaying it in the Antarctic. Furthermore, while the amplitude of GHG forcing has been similar at the poles, significant ozone depletion only occurs over Antarctica. We suggest that the initial response of SST around Antarctica to ozone depletion is one of cooling and only later adds to the GHG-induced warming trend as upwelling of sub-surface warm water associated with stronger surface westerlies impacts surface properties. We organize our discussion around ‘climate response functions’ (CRFs), i.e. the response of the climate to ‘step’ changes in anthropogenic forcing in which GHG and/or ozone-hole forcing is abruptly turned on and the transient response of the climate revealed and studied. Convolutions of known or postulated GHG and ozone-hole forcing functions with their respective CRFs then yield the transient forced SST response (implied by linear response theory), providing a context for discussion of the differing warming/cooling trends in the Arctic and Antarctic. We speculate that the period through which we are now passing may be one in which the delayed warming of SST associated with GHG forcing around Antarctica is largely cancelled by the cooling effects associated with the ozone hole. By mid-century, however, ozone-hole effects may instead be adding to GHG warming around Antarctica but with diminished amplitude as the ozone hole heals. The Arctic, meanwhile, responding to GHG forcing but in a manner amplified by ocean heat transport, may continue to warm at an accelerating rate.

Adsorption of organic molecules at the TiO2(110) surface: the effect of van der Waals interactions

Understanding the interaction of organic molecules with TiO2 surfaces is important for a wide range of technological applications. While density functional theory (DFT) calculations can provide valuable insight about these interactions, traditional DFT approaches with local exchange-correlation functionals suffer from a poor description of non-bonding van der Waals (vdW) interactions. We examine here the contribution of vdW forces to the interaction of small organic molecules (methane, methanol, formic acid and glycine) with the TiO2 (110) surface, based on DFT calculations with the optB88-vdW functional. The adsorption geometries and energies at different configurations were also obtained in the standard generalized gradient approximation (GGA-PBE) for comparison. We find that the optB88-vdW consistently gives shorter surface adsorbate-to-surface distances and slightly stronger interactions than PBE for the weak (physisorbed) modes of adsorption. In the case of strongly adsorbed (chemisorbed) molecules both functionals give similar results for the adsorption geometries, and also similar values of the relative energies between different chemisorption modes for each molecule. In particular both functionals predict that dissociative adsorption is more favourable than molecular adsorption for methanol, formic acid and glycine, in general agreement with experiment. The dissociation energies obtained from both functionals are also very similar, indicating that vdW interactions do not affect the thermodynamics of surface deprotonation. However, the optB88-vdW always predicts stronger adsorption than PBE. The comparison of the methanol adsorption energies with values obtained from a Redhead analysis of temperature programmed desorption data suggests that optB88-vdW significantly overestimates the adsorption strength, although we warn about the uncertainties involved in such comparisons.