Ibergirhynchia contraria (F. A. Roemer, 1850), an Early Carboniferous seep-related rhynchonellide brachiopod from the Harz Mountains, Germany - A possible successor to Dzieduszyckia?

A new genus Ibergirhynchia, a member of the rhynchonellide superfamily Dimerelloidea, is described for the species Terebratula contraria Roemer, 1850, from Early Carboniferous deposits of the Harz Mountains, Germany. Ibergirhynchia contraria is from a monospecific brachiopod limestone that formed on top of the drowned Devonian Iberg Reef which persisted as a seamount during Famennian and Early Carboniferous times. Ibergirhynchia contraria is considered a cold seep-related brachiopod based on this locality. Such seep associations have been observed for Mesozoic representatives of the rhynchonellide superfamily Dimerelloidea. Ibergirhynchia is considered the first Paleozoic representative of the family Rhynchonellinidae. Ibergirhynchia resembles Dzieduszyckia externally and may be derived from this dimerelloid.

Interactions between mass balance, atmospheric circulation, and recent climate change on the Djankuat Glacier, Caucasus Mountains, Russia

This paper reports recent changes in the mass balance record from the Djankuat Glacier, central greater Caucasus, Russia, and investigates possible relationships between the components of mass balance, local climate, and distant atmospheric forcing. The results clearly show that a strong warming signal has emerged in the central greater Caucasus, particularly since the 1993/1994 mass balance year, and this has led to a significant increase in the summer ablation of Djankuat. At the same time, there has been no compensating consistent increase in winter precipitation and accumulation leading to the strong net loss of mass and increase in glacier runoff. Interannual variability in ablation and accumulation is partly associated with certain major patterns of Northern Hemisphere climatic variability. The positive phase of the North Pacific (NP) teleconnection pattern forces negative geopotential height and temperature anomalies over the Caucasus in summer and results in reduced summer melt, such as in the early 1990s, when positive NP extremes resulted in a temporary decline in ablation rates. The positive phase of the NP is related to El Nino-Southern Oscillation, and it is possible that a teleconnection between the tropical Pacific sea surface temperatures and summer air temperatures in the Caucasus is bridged through the NP pattern. More recently, the NP pattern was predominantly negative, and this distant moderating forcing on summer ablation in the Caucasus was absent. Statistically significant correlations are observed between accumulation and the Scandinavian (SCA) teleconnection pattern. The frequent occurrence of the positive SCA phase at the beginning of accumulation season results in lower than average snowfall and reduced accumulation. The relationship between the North Atlantic Oscillation (NAO), Arctic Oscillation, and accumulation is weak, although positive precipitation anomalies in the winter months are associated with the negative phase of the NAO. A stronger positive correlation is observed between accumulation on Djankuat and geopotential height over the Bay of Biscay unrelated to the established modes of the Northern Hemisphere climatic variability. These results imply that the mass balance of Djankuat is sensitive to the natural variability in the climate system. Distant forcing, however, explains only 16% of the variance in the ablation record and cannot fully explain the recent increase in ablation and negative mass balance.

Late-20th-century changes in glacier extent in the Caucasus Mountains, Russia/Georgia

Glaciers occupy an area of similar to 1600 km(2) in the Caucasus Mountains. There is widespread evidence of retreat since the Little Ice Age, but an up-to-date regional assessment of glacier change is lacking. In this paper, satellite imagery (Landsat Thematic Mapper and Enhanced Thematic Mapper Plus) is used to obtain the terminus position of 113 glaciers in the central Caucasus in 1985 and 2000, using a manual delineation process based on a false-colour composite (bands 5, 4, 3). Measurements reveal that 94% of the glaciers have retreated, 4% exhibited no overall change and 2% advanced. The mean retreat rate equates to similar to 8 m a(-1), and maximum retreat rates approach similar to 38 m a(-1). The largest (>10 km(2)) glaciers retreated twice as much (similar to 12 m a(-1)) as the smallest (<1 km(2)) glaciers (similar to 6 m a(-1)), and glaciers at lower elevations generally retreated greater distances. Supraglacial debris cover has increased in association with glacier retreat, and the surface area of bare ice has reduced by similar to 10% between 1985 and 2000. Results are compared to declassified Corona imagery from the 1960s and 1970s and detailed field measurements and mass-balance data for Djankuat glacier, central Caucasus. It is concluded that the decrease in glacier area appears to be primarily driven by increasing temperatures since the 1970s and especially since the mid-1990s. Continued retreat could lead to considerable changes in glacier runoff, with implications for regional water resources.

Recent glacier retreat in the Caucasus Mountains, Russia, and associated increase in supraglacial debris cover and supra-/proglacial lake development

This paper reports changes in supraglacial debris cover and supra-/proglacial lake development associated with recent glacier retreat (1985-2000) in the central Caucasus Mountains, Russia. Satellite imagery (Landsat TM and ETM+) was used to map the surface area and supraglacial debris cover on six neighbouring glaciers in the Adylsu valley through a process of manual digitizing on a false-colour composite of bands 5, 4, 3 (red, green, blue). The distribution and surface area of supraglacial and proglacial lakes was digitized for a larger area, which extended to the whole Landsat scene. We also compare our satellite interpretations to field observations in the Adylsu valley. Supraglacial debris cover ranges from < 5% to > 25% on individual glaciers, but glacier retreat between 1985 and 2000 resulted in a 3-6% increase in the proportion of each glacier covered by debris. The only exception to this trend was a very small glacier where debris cover did not change significantly and remote mapping proved more difficult. The increase in debris cover is characterized by a progressive upglacier migration, which we suggest is being driven by focused ablation (and therefore glacier thinning) at the up-glacier limit of the debris cover, resulting in the progressive exposure of englacial debris. Glacier retreat has also been accompanied by an increase in the number of proglacial and supraglacial lakes in our study area, from 16 in 1985 to 24 in 2000, representing a 57% increase in their cumulative surface area. These lakes appear to be impounded by relatively recently lateral and terminal moraines and by debris deposits on the surface of the glacier. The changes in glacier surface characteristics reported here are likely to exert a profound influence on glacier mass balance and their future response to climate change. They may also increase the likelihood of glacier-related hazards (lake outbursts, debris slides), and future monitoring is recommended.

Evidence for long-term regional changes in precipitation on the East Coast Mountains in Mauritius

Global climate change and its impacts are being increasingly studied and precipitation trends are one of the measures of quantifying climate change especially in the tropics. This study uses daily rainfall data to determine if there are changes in the long-term trends in rainfall variability in the East Coast Mountains of Mauritius during the last few decades, and to investigate the factors influencing the trends in the inter-annual to inter-decadal rainfall variability. Statistical modelling has been used to investigate the trends in total seasonal rainfall, the number of rain days and the mean amount of rain per rainy days and the local, regional and large-scale factors that affect them on inter-annual to inter-decadal time scales. The strongest inter-decadal trend was found in the number of rain days for both rainfall seasons, and the other variables were found to have weak or insignificant trends. Both local factors, such as the surrounding sea surface temperatures and large-scale phenomena such as Indian Monsoon and the El Niño Southern Oscillation were found to influence rainfall patterns.

Dicopper(II) complexes of a new di-para-xylyldioxatetraazamacrocycle and cascade species with dicarboxylate anions: thermodynamics and structural properties

The new dioxatetraazamacrocycle (L-1) was synthesized by a 2 + 2 condensation and characterized. Stability constants of its copper(II) complexes were determined by spectrophotometry in DMSO at 298.2 K in 0. 10 mol dm(-3) KClO4. Mainly dinuclear complexes are formed and the presence of mononuclear species is dependent on the counterion (Cl- or ClO4-). The association constants of the dinuclear copper(II) complexes with dicarboxylate anions [oxalate (oxa(2-)), malonate (mal(2-)), succinate (suc(2-)), and glutarate (glu(2-))] were also determined by spectrophotometry at 298.2 K in DMSO, and it was found that values decrease with an increase of the alkyl chain between the carboxylate groups. X-Band EPR spectra of the dicopper(II) complexes and of their cascade species in frozen DMSO exhibit dipole-dipole coupling, and their simulation, together with their UV-vis spectra, showed that the copper centres of the complexes in solution had square pyramidal geometries though with different distortions. From the experimental data, it was also possible to predict the Cu...Cu distances, the minimum being found at 6.4 angstrom for the (Cu2LCl4)-Cl-1 complex and then successively this distance slightly increases when the chloride anions are replaced by dicarboxylate anions, from 6.6 angstrom for oxa(2-) to 7.8 for glu(2-). The crystal structures of the dinuclear copper cascade species with oxa(2-) and suc(2-) were determined and showed one anion bridging both copper centres and Cu...Cu distances of 5.485(7) angstrom and 6.442(8) angstrom, respectively.

Cascade dicopper architectures of a dibenzodioxatetraazamacrocycle

The dibenzodioxatetraazamacrocycle [26]pbz(2)N(4)O(2) was characterised by single crystal X-ray diffraction and the protonation constants of this compound and the stability constants of its copper(II) and lead(II) complexes were determined by potentiometry in water at 298.2 K in 0.10 mol dm(-3) in KNO3. Mono- and dinuclear complexes were found for both metal ions, the dinuclear complexes being the main species in the 5-7.5 pH range for copper(II) and 7.5-8.5 for lead(II). As expected the values of the stability constants for the copper(II) complexes are lower than those for related macrocycles containing only nitrogen atoms. The presence of mono- and dinuclear copper complexes was also confirmed by electrospray ionization mass spectrometry. These results suggest that the symmetric macrocyclic cavity of [26]pbZ(2)N(4)O(2) has enough space for the coordination of two metal ions. Additionally, NMR spectroscopy showed that the dinuclear complex of lead(II) has high symmetry. The equilibrium constants of the dinuclear copper(II) complexes and dicarboxylate anions (oxalate, malonate and succinate) were also determined in 0.10 mol dm-3 aqueous KNO3 solution. Only species containing one anion, Cu(2)H(h)LA((2+h)), were found, strongly suggesting that the anion bridges the two copper(II) ions. The binding constants of the cascade species formed by [Cu-2[26]pbZ(2)N(4)O(2)(H2O)(4+) with dicarboxylate anions decrease with the increase in length of the alkyl chain of the anion, a fact which was attributed to a higher conformational energy necessary for the rearrangement of the macrocycle to accommodate the larger anions bridging the two copper(II) centres. The variation of the magnetic susceptibility with temperature Of [Cu-2(H-2[26]pbz(2)N(4)O(2))(oxa)(3)]-4H(2)O and [Cu-2([26]pbz(2)N(4)O(2))(suc)Cl-2] were measured and the two complexes showed different behaviour. (c) 2007 Elsevier Ltd. All rights reserved.

Geodetic mass balance of Azarova glacier, Kodar Mountains, eastern Siberia, and its links to observed and projected climatic change

The Kodar Mountains in eastern Siberia accommodate 30 small, cold-based glaciers with a combined surface area of about 19 km2. Very little is known about these glaciers, with the first survey conducted in the late 1950s. In this paper, we use terrestrial photogrammetry to calculate changes in surface area, elevation, volume and geodetic mass balance of the Azarova Glacier between 1979 and 2007 and relate these to meteorological data from nearby Chara weather station (1938-2007). The glacier surface area declined by 20±6.9% and surface lowered on average by 20±1.8 m (mean thinning: 0.71 m a-1) resulting in a strongly negative cumulative and average mass balance of -18±1.6 m w.e. and -640±60 mm w.e.a-1 respectively. The July-August air temperature increased at a rate of 0.036oC a-1 between 1979 and 2007 and the 1980-2007 period was, on average, around 1oC warmer than 1938-1979. The regional climate projections for A2 and B2 CO2 emission scenarios developed using PRECIS regional climate model indicate that summer temperatures will increase in 2071–2100 by 2.6-4.7°C and 4.9-6.2°C respectively in comparison with 1961–1990. The annual total of solid precipitation will increase by 20% under B2 scenario but decline by 3% under A2 scenario. The length of the ablation season will extend from July–August to June-September. The Azarova Glacier exhibits high sensitivity to climatic warming due to its low elevation, exposure to comparatively high summer temperatures, and the absence of a compensating impact of cold season precipitation. Further summer warming and decline of solid precipitation projected under the A2 scenario will force Azarova to retreat further while impacts of an increase in solid precipitation projected under the B2 scenario require further investigation.

Organocatalytic enantioselective construction of nitrocyclohexanes containing multiple chiral centres via a cascade reaction

The stereoselective construction of complex molecules with multiple stereogenicity in a single step represents an extremely useful, but challenging approach to complexity in chemical synthesis. The development of organocatalytic cascade processes has proven useful in these studies, but reports where four or more stereocentres are created in a single step from just two achiral reagents are rare. Herein we report the development of a novel asymmetric domino Michael-Michael reaction between nitrohex-4-enoates and nitro-olefins to generate cyclohexanes of high complexity, including one with a quaternary centre, and one with five contiguous stereocentres. This methodology provides access to a range of useful nitrocyclohexane derivatives, including a novel class of a-lycorane-like structures.

The relationship between the North American summer monsoon, the Rocky Mountains and the North Pacific subtropical anticyclone in HadAM3

In this study the relationship between the North American monsoon, the Californian sea surface temperature (SST) cold pool, the Rocky Mountains and the North Pacific subtropical anticyclone is investigated using the Hadley Centre's atmospheric climate model, HadAM3. In 1996 Hoskins hypothesized that heating in the North American monsoon might be important for the maintenance of the summertime North Pacific subtropical anticyclone, since the monsoon heating may induce descent to the north-west of the monsoon in the descending eastern flank of the subtropical anticyclone. This descent is further enhanced by radiative cooling and is associated with equatorward surface winds parallel to the western coast of North America. These equatorward winds induce oceanic upwelling of cold water and contribute to the formation of the Californian SST cold pool, which may feed back on the anticyclone by further suppressing convection and inducing descent. More recently, Rodwell and Hoskins also investigated the global summer monsoon–subtropical anticyclone relationship. They examined the role that mountains play in impeding the progress of the low-level mid-latitude westerlies, either deflecting the westerlies northwards where they ascend along the sloping mid-latitude isentropes or deflecting them southwards forcing them to descend along the isentropes. In particular, the introduction of the Rockies into a primitive-equation model adiabatically induces descent in the eastern descending flank of the North Pacific subtropical anticyclone. These hypothesized mechanisms have been investigated using HadAM3, focusing on the possible suppression of convection by the Californian SST cold pool, the response of the North Pacific subtropical anticyclone to the strength of the North American monsoon and the ‘blocking’ of the mid-latitude westerlies by the Rocky Mountains. The role of the Rockies is examined by integrating the model with modified orography for the Rocky Mountains. Changing the height of the Rockies alters the circulation in a way consistent with the mechanism outlined above. Higher Rocky mountains force the westerlies southwards, inducing descent in the eastern flank of the subtropical anticyclone as the air descends along the sloping isentropes. The relationship between the North American monsoon and the North Pacific subtropical anticyclone is investigated by suppressing the monsoon in HadAM3. The suppression of the monsoon is accomplished by increasing the surface albedo over Mexico, which induces anomalous ascent on the eastward flank of the subtropical anticyclone and anomalous polewards surface winds along the western coast of the North American continent, also providing support for the above hypothesis. The removal of the Californian SST cold pool, however, has a statistically insignificant effect on the model, suggesting that in this model the feedback of the SST cold pool on the eastern flank of the anticyclone is weak.