An Assessment of the Recent Past and Future Climate Change, Glacier Retreat, and Runoff in the Caucasus Region Using Dynamical and Statistical Downscaling and HBV-ETH Hydrological Model

The paper discusses the observed and projected warming in the Caucasus region and its implications for glacier melt and runoff. A strong positive trend in summer air temperatures of 0.05 degrees C a(-1) is observed in the high-altitude areas providing for a strong glacier melt and continuous decline in glacier mass balance. A warming of 4-7 degrees C and 3-5 degrees C is projected for the summer months in 2071-2100 under the A2 and B2 emission scenarios respectively, suggesting that enhanced glacier melt can be expected. The expected changes in winter precipitation will not compensate for the summer melt and glacier retreat is likely to continue. However, a projected small increase in both winter and summer precipitation combined with the enhanced glacier melt will result in increased summer runoff in the currently glaciated region of the Caucasus (independent of whether the region is glaciated at the end of the twenty-first century) by more than 50% compared with the baseline period.

Long-term change, interannual and intra-seasonal variability in climate and glacier mass balance in the Central Greater Caucasus, Russia

Long-term trends, interannual and intra-seasonal variability in the mass-balance record from Djankuat glacier, central Greater Caucasus, Russia, are related to local climate change, synoptic and large-scale anomalies in atmospheric circulation. A clear warming signal emerged in the central Greater Caucasus in the early 1990s, leading to a strong increase in ablation. In the absence of a compensating change in winter accumulation, the net mass balance of Djankuat has declined. The highest value of seasonal ablation on record was registered in the summer of 2000. At the beginning of the 21st century these trends reversed. Ablation was below average even in the summer of 2003, which was unusually warm in western Europe. Precipitation and winter accumulation were high, allowing for a partial recovery of net mass balance. The interannual variability in the components of mass balance is weakly related to the North Atlantic Oscillation (NAO) and the Scandinavian teleconnection patterns, but there is a clear link with the large-scale circulation anomalies represented by the Rossby pattern. Five synoptic categories have been identified for the ablation season of 2005, revealing a strong separation between components of radiation budget, air temperature and daily melt. Air temperature is the main control over melt. The highest values of daily ablation are related to the strongly positive NAO which forces high net radiation, and to the warm and moist advection from the Black Sea.

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.

Pb-210-Ra-226 and Ra-228-Th-232 systematics in young arc lavas: implications for magma degassing and ascent rates

New data show that island arc rocks have (Pb-210/Ra-226)(o) ratios which range from as low as 0.24 up to 2.88. In contrast, (Ra-22S/Th-232) appears always within error of I suggesting that the large Ra-226-excesses observed in arc rocks were generated more than 30 years ago. This places a maximum estimate on melt ascent velocities of around 4000 m/year and provides further confidence that the Ra-226 excesses reflect deep (source) processes rather than shallow level alteration or seawater contamination. Conversely, partial melting must have occurred more than 30 years prior to eruption. The Pb-210 deficits are most readily explained by protracted magma degassing. Using published numerical models, the data suggest that degassing occurred continuously for periods up to several decades just prior to eruption but no link with eruption periodicity was found. Longer periods are required if degassing is discontinuous, less than 100% efficient or if magma is recharged or stored after degassing. The long durations suggest much of this degassing occurs at depth with implications for the formation of hydrothermal and copper-porphyry systems. A suite of lavas erupted in 1985-1986 from Sangeang Api volcano in the Sunda arc are characterised by deficits of Pb-210 relative to Ra-226 from which 6-8 years of continuous Rn-222 degassing would be inferred from recent numerical models. These data also form a linear (Pb-210)/Pb-(Ra-226)/Pb array which might be interpreted as a 71-year isochron. However, the array passes through the origin suggesting displacement downwards from the equiline in response to degassing and so the slope of the array is inferred not to have any age significance. Simple modelling shows that the range of (Ra-226)/Pb ratios requires thousands of years to develop consistent with differentiation occurring in response to cooling at the base of the crust. Thus, degassing post-dated, and was not responsible for magma differentiation. The formation, migration and extraction of gas bubbles must be extremely efficient in mafic magma whereas the higher viscosity of more siliceous magmas retards the process and can lead to Pb-210 excesses. A possible negative correlation between (Pb-210/Ra-226)(o) and SO2 emission rate requires further testing but may have implications for future eruptions. (C) 2004 Elsevier B.V. All rights reserved.

Characterisation of amorphous and nanocrystalline molecular materials by total scattering

The use of high-energy X-ray total scattering coupled with pair distribution function analysis produces unique structural fingerprints from amorphous and nanostructured phases of the pharmaceuticals carbamazepine and indomethacin. The advantages of such facility-based experiments over laboratory-based ones are discussed and the technique is illustrated with the characterisation of a melt-quenched sample of carbamazepine as a nanocrystalline (4.5 nm domain diameter) version of form III.

The three-dimensional vortical nature of atmospheric and oceanic turbulent flows

Using a novel numerical method at unprecedented resolution, we demonstrate that structures of small to intermediate scale in rotating, stratified flows are intrinsically three-dimensional. Such flows are characterized by vortices (spinning volumes of fluid), regions of large vorticity gradients, and filamentary structures at all scales. It is found that such structures have predominantly three-dimensional dynamics below a horizontal scale LLR, where LR is the so-called Rossby radius of deformation, equal to the characteristic vertical scale of the fluid H divided by the ratio of the rotational and buoyancy frequencies f/N. The breakdown of two-dimensional dynamics at these scales is attributed to the so-called "tall-column instability" [D. G. Dritschel and M. de la Torre Juárez, J. Fluid. Mech. 328, 129 (1996)], which is active on columnar vortices that are tall after scaling by f/N, or, equivalently, that are narrow compared with LR. Moreover, this instability eventually leads to a simple relationship between typical vertical and horizontal scales: for each vertical wave number (apart from the vertically averaged, barotropic component of the flow) the average horizontal wave number is equal to f/N times the vertical wave number. The practical implication is that three-dimensional modeling is essential to capture the behavior of rotating, stratified fluids. Two-dimensional models are not valid for scales below LR. ©1999 American Institute of Physics.

Diurnal cycle of land surface temperature in a desert encroachment zone as observed from satellites

Climate variability in the African Soudano-Sahel savanna zone has attracted much attention because of the persistence of anomalously low rainfall. Past efforts to monitor the climate of this region have focused on rainfall and vegetation conditions, while land surface temperature (LST) has received less attention. Remote sensing of LST is feasible and possible at global scale. Most remotely sensed estimates of LST are based on the National Oceanic and Atmospheric Administration (NOAA) Advanced Very High Resolution Radiometer (AVHRR) that are limited in their ability to capture the full diurnal cycle. Although more frequent observations are available from past geostationary satellites, their spatial resolution is coarser than that of polar orbiting satellites. In this study, the improved capabilities of the Spinning Enhanced Visible and Infrared Imager (SEVIRI) on the METEOSAT Second Generation (MSG) instrument are used to remotely sense the LST in the African Soudano-Sahel savanna zone at a resolution of 3 km and 15 minutes. In support of the Radiative Atmospheric Divergence using the ARM Mobile Facility (AMF), GERB and AMMA Stations (RADAGAST) project, African Monsoon Multidisciplinary Analyses (AMMA) project and the Department of Energy's Atmospheric Radiation Measurement (ARM) program, the ARM Mobile Facility was deployed during 2006 in this climatically sensitive region, thereby providing a unique opportunity to evaluate remotely sensed algorithms for deriving LST.

The radiative effect of a fir canopy on a snowpack

Models of snow processes in areas of possible large-scale change need to be site independent and physically based. Here, the accumulation and ablation of the seasonal snow cover beneath a fir canopy has been simulated with a new physically based snow-soil vegetation-atmosphere transfer scheme (Snow-SVAT) called SNOWCAN. The model was formulated by coupling a canopy optical and thermal radiation model to a physically based multilayer snow model. Simple representations of other forest effects were included. These include the reduction of wind speed and hence turbulent transfer beneath the canopy, sublimation of intercepted snow, and deposition of debris on the surface. This paper tests this new modeling approach fully at a fir site within Reynolds Creek Experimental Watershed, Idaho. Model parameters were determined at an open site and subsequently applied to the fir site. SNOWCAN was evaluated using measurements of snow depth, subcanopy solar and thermal radiation, and snowpack profiles of temperature, density, and grain size. Simulations showed good agreement with observations (e.g., fir site snow depth was estimated over the season with r(2) = 0.96), generally to within measurement error. However, the simulated temperature profiles were less accurate after a melt-freeze event, when the temperature discrepancy resulted from underestimation of the rate of liquid water flow and/or the rate of refreeze. This indicates both that the general modeling approach is applicable and that a still more complete representation of liquid water in the snowpack will be important.

The structure of crystallisable copolymers of L-lactide, epsilon-caprolactone and glycolide

We apply a new X-ray scattering approach to the study of melt-spun filaments of tri-block and random terpolymers prepared from lactide, caprolactone and glycolide. Both terpolymers contain random sequences, in both cases the overall fraction of lactide units is similar to 0.7 and C-13 and H-1 NMR shows the lactide sequence length to be similar to 9-10. A novel representation of the X-ray fibre pattern as series of spherical harmonic functions considerably facilitates the comparison of the scattering from the minority crystalline phase with hot drawn fibres prepared from the poly(L-lactide) homopolymer. Although the fibres exhibit rather disordered structures we show that the crystal structure is equivalent to that displayed by poly(L-lactide) for both the block and random terpolymers. There are variations in the development of a two-phase structure which reflect the differences in the chain architectures. There is evidence that the random terpolymer includes non-lactide units in to the crystal interfaces to achieve a well defined two-phase structure. (c) 2005 Published by Elsevier Ltd.

Impact of land cover changes on the South African climate

The Joint UK Land Environmental Simulator (JULES) was run offline to investigate the sensitivity of land surface type changes over South Africa. Sensitivity tests were made in idealised experiments where the actual land surface cover is replaced by a single homogeneous surface type. The vegetation surface types on which some of the experiments were made are static. Experimental tests were evaluated against the control. The model results show among others that the change of the surface cover results in changes of other variables such as soil moisture, albedo, net radiation and etc. These changes are also visible in the spin up process. The model shows different surfaces spinning up at different cycles. Because JULES is the land surface model of Unified Model, the results could be more physically meaningful if it is coupled to the Unified Model.

A novel approach to processing high-performance polymers that exploits entropically driven ring-opening polymerization

Blends of the poly(ether sulfone) derived from 4,4'-biphenol and 4,4'-dichlorodiphenylsulfone (Radel-R(TM)) with its homologous macrocyclic oligomers show greatly lowered melt viscosities relative to that of the parent polymer, potentially enabling more facile production and fabrication of fiber-reinforced composite materials. The macrocycles can then undergo entropically driven ring-opening polymerization in situ. The required blends can be obtained easily in one step, by carrying out polycondensations at concentrations lower than those usually used for polymer synthesis.

Fractionated crystallization and fractionated melting of confined PEO microdomains in PB-b-PEO and PE-b-PEO diblock copolymers

The confined crystallization of poly(ethylene oxide) (PEO) in predominantly spherical microdomains formed by several diblock copolymers was studied and compared. Two polybutadiene-b-poly(ethylene oxide) diblock copolymers were prepared by sequential anionic polymerization (with approximately 90 and 80 wt % polybutadiene (PB)). These were compared to equivalent samples after catalytic hydrogenation that produced double crystalline polyethylene-b-poly(ethylene oxide) diblock copolymers. Both systems are segregated into microdomains as indicated by small-angle X-ray scattering (SAXS) experiments performed in the melt and at lower temperatures. However, the PB-b-PEO systems exhibited a higher degree of order in the melt. A predominantly spherical morphology of PEO in a PB or a PE matrix was observed by both SAXS and transmission electron microscopy, although a possibly mixed morphology (spheres and cylinders) was formed when the PEO composition was close to the cylinder-sphere domain transitional composition as indicated by SAXS. Differential scanning calorimetry experiments showed that a fractionated crystallization process for the PEO occurred in all samples, indicating that the PE cannot nucleate PEO in these diblock copolymers. A novel result was the observation of a subsequent fractionated melting that reflected the crystallization process. Sequential isothermal crystallization experiments allowed us to thermally separate at least three different crystallization and melting peaks for the PEO microdomains. The lowest melting point fraction was the most important in terms of quantity and corresponded to the crystallization of isolated PEO spheres (or cylinders) that were either superficially or homogeneously nucleated. This was confirmed by Avrami index values of approximately 1. The isothermal crystallization results indicate that the PE matrix restricts the crystallization of the covalently bonded PEO to a higher degree compared to PB.

Crystal and molecular structure of the thioether-analogue of PEEK from X-ray powder data and diffraction-modelling

Analysis of X-ray powder data for the melt-crystallisable aromatic poly(thioether thioether ketone) [-S-Ar-S-Ar-CO-Ar](n), ('PTTK', Ar= 1,4-phenylene), reveals that it adopts a crystal structure very different from that established for its ether-analogue PEEK. Molecular modelling and diffraction-simulation studies of PTTK show that the structure of this polymer is analogous to that of melt-crystallised poly(thioetherketone) [-SAr-CO-Ar](n) in which the carbonyl linkages in symmetry-related chains are aligned anti-parallel to one another. and that these bridging units are crystallographically interchangeable. The final model for the crystal structure of PTTK is thus disordered, in the monoclinic space group 121a (two chains per unit cell), with cell dimensions a = 7.83, b = 6.06, c = 10.35 angstrom, beta = 93.47 degrees. (c) 2005 Elsevier Ltd. All rights reserved.

Enthalpy-driven ring-opening polymerization of highly strained macrocyclic biaryl-ether-ketones

Highly strained macrocyclic ether-ketones obtained by nickel-catalyzed cyclization of linear precursor oligomers undergo ring-opening polyinerization via ether exchange in the presence of nucleophilic initiators such as fluoride or phenoxide anions. Strain enthapies of these macrocycles, from DSC analyses of their exothermic ring-opening polymerization are in the range 50-90 kJ mol(-1). Melt-phase polymerization generally affords slightly cross-linked materials, but solution-phase polymerization at high macrocycle concentrations gives fully soluble, high molar mass polymers with inherent viscosities of up to 1.78 dL g(-1). Sequence-analysis of the resulting polymers by C-13 NMR shows that alternating or random monomer sequences may be obtained, depending on whether one or both aromatic rings adjacent to the ether linkages are activated toward nucleophilic attack.

Microfabrication of high-performance aromatic polymers as nanotubes or fibrils by in situ ring-opening polymerisation of macrocyclic precursors

Melt-phase nucleophilic ring-opening polymerisation of macrocyclic aromatic ethers and thioethers at high temperatures within the cylindrical pores of an anodic-alumina membrane, followed by dissolution of the template, enables replication of the membrane's internal pore structure and so affords high-performance aromatic polymers with well-defined fibrillar or tubular morphologies.