Highly Fluorous Tetraarylborate Anions : Versatile Counterions for Homogeneous Catalysis in Novel Reaction Media

The recycling of homogeneous catalysts is highly desirable from both an environmental and an economical point of view. However, the fact that catalysts and products are distributed homogeneously throughout the reaction mixture hampers catalyst separation. An elegant approach facilitating catalyst recovery is its immobilisation in a liquid support. Three solvent systems that have shown promise in this respect are fluorous biphasic solvent systems, supercritical carbon dioxide and ionic liquids. This thesis addresses the development of highly fluorous tetraarylborate anions which can be employed as such, or in combination with fluorous ligands, to enhance the solubility and performance of ionic catalysts in perfluorinated solvents and supercritical carbon dioxide. Furthermore, these anions have been used in the design of ionic liquids with unprecedented physical properties

Rapid loss of firn pore space accelerates 21st century Greenland mass loss

Mass loss from the two major ice sheets and their contribution to global sea level rise is accelerating. In Antarctica, mass loss is dominated by increased flow velocities of outlet glaciers, following the thinning or disintegration of coastal ice shelves into which they flow. In contrast, ∼55% of post‒1992 Greenland ice sheet (GrIS) mass loss is accounted for by surface processes, notably increased meltwater runoff. A subtle process in the surface mass balance of the GrIS is the retention and refreezing of meltwater, currently preventing ∼40% of the meltwater to reach the ocean. Here we force a high‒resolution atmosphere/snow model with a mid‒range warming scenario (RCP4.5, 1970–2100), to show that rapid loss of firn pore space, by >50% at the end of the 21st century, quickly reduces this refreezing buffer. As a result, GrIS surface mass loss accelerates throughout the 21st century and its contribution to global sea level rise increases to 1.7 ±0.5 mm yr−1, more than four times the current value

Melting trends over the Greenland ice sheet (1958–2009) from spaceborne microwave data and regional climate models

To study near-surface melt changes over the Greenland ice sheet (GrIS) since 1979, melt extent estimates from two regional climate models were compared with those obtained from spaceborne microwave brightness temperatures using two different remote sensing algorithms. The results from the two models were consistent with those obtained with the remote sensing algorithms at both daily and yearly time scales, encouraging the use of the models for analyzing melting trends before the satellite era (1958–1979), when forcing data is available. Differences between satellite-derived and model-simulated results still occur and are used here to identify (i) biases in the snow models (notably in the albedo parametrization, in the thickness of a snow layer, in the maximum liquid water content within the snowpack and in the snowfall impacting the bare ice appearance in summer) and (ii) limitations in the use of passive microwave data for snowmelt detection at the edge of the ice sheet due to mixed pixel effect (e.g., tundra or rock nearby the ice sheet). The results from models and spaceborne microwave sensors confirm a significant (p-value = 0.01) increase in GrIS surface melting since 1979. The melt extent recorded over the last years (1998, 2003, 2005 and 2007) is unprecedented in the last 50 yr with the cumulated melt area in the 2000's being, on the average, twice that of the 1980's

В. Б. Антонович у листах, спогадах та працях Д. І. Багалія

The previous interglacial (Eemian, 130–114 kyr BP) had a mean sea level highstand 4 to 7 m above the current level, and, according to climate proxies, a 2 to 6 K warmer Arctic summer climate. Greenland ice cores extending back into the Eemian show a reduced depletion in δ18O of about 3‰ for this period, which suggests a significant warming of several degrees over the Greenland ice sheet. Since the depletion in δ18O depends, among other factors, on the condensation temperature of the precipitation, we analyze climatological processes other than mean temperature changes that influence condensation temperature, using output of the regional climate model RACMO2. This model is driven by ERA-40 reanalysis and ECHO-G GCM boundaries for present-day, preindustrial and Eemian climate. The processes that affect the condensation temperature of the precipitation are analyzed using 6-hourly model output. Our results show that changes in precipitation seasonality can cause significant changes of up to 2 K in the condensation temperature that are unrelated to changes in mean temperature

Isolation and characterization of Alicycliphilus denitrificans strain BC, which grows on benzene with chlorate as the electron acceptor

A bacterium, strain BC, was isolated from a benzene-degrading chlorate-reducing enrichment culture. Strain BC degrades benzene in conjunction with chlorate reduction. Cells of strain BC are short rods that are 0.6 microm wide and 1 to 2 microm long, are motile, and stain gram negative. Strain BC grows on benzene and some other aromatic compounds with oxygen or in the absence of oxygen with chlorate as the electron acceptor. Strain BC is a denitrifying bacterium, but it is not able to grow on benzene with nitrate. The closest cultured relative is Alicycliphilus denitrificans type strain K601, a cyclohexanol-degrading nitrate-reducing betaproteobacterium. Chlorate reductase (0.4 U/mg protein) and chlorite dismutase (5.7 U/mg protein) activities in cell extracts of strain BC were determined. Gene sequences encoding a known chlorite dismutase (cld) were not detected in strain BC by using the PCR primers described in previous studies. As physiological and biochemical data indicated that there was oxygenation of benzene during growth with chlorate, a strategy was developed to detect genes encoding monooxygenase and dioxygenase enzymes potentially involved in benzene degradation in strain BC. Using primer sets designed to amplify members of distinct evolutionary branches in the catabolic families involved in benzene biodegradation, two oxygenase genes putatively encoding the enzymes performing the initial successive monooxygenations (BC-BMOa) and the cleavage of catechol (BC-C23O) were detected. Our findings suggest that oxygen formed by dismutation of chlorite can be used to attack organic molecules by means of oxygenases, as exemplified with benzene. Thus, aerobic pathways can be employed under conditions in which no external oxygen is supplie

Comparison of the meteorology and surface energy balance at Storbreen and Midtdalsbreen, two glaciers in southern Norway

We compare 5 years of meteorological records from automatic weather stations (AWSs) on Storbreen and Midtdalsbreen, two glaciers in southern Norway, located approximately 120 km apart. The records are obtained from identical AWSs with an altitude difference of 120 m and cover the period September 2001 to September 2006. Air temperature at the AWS locations is found to be highly correlated, even with the seasonal cycle removed. The most striking difference between the two sites is the difference in wind climate. Midtdalsbreen is much more under influence of the large-scale circulation with wind speeds on average a factor 1.75 higher. On Storbreen, weaker katabatic winds are dominant. The main melt season is from May to September at both locations. During the melt season, incoming and net solar radiation are larger on Midtdalsbreen, whereas incoming and net longwave radiation are larger on Storbreen, primarily caused by thicker clouds on the latter. The turbulent fluxes are a factor 1.7 larger on Midtdalsbreen, mainly due to the higher wind speeds. Inter-daily fluctuations in the surface energy fluxes are very similar at the AWS sites. On average, melt energy is a factor 1.3 larger on Midtdalsbreen, a result of both larger net radiation and larger turbulent fluxes. The relative contribution of net radiation to surface melt is larger on Storbreen (76%) than on Midtdalsbreen (66%). As winter snow depth at the two locations is comparable in most years, the larger amount of melt energy results in an earlier disappearance of the snowpack on Midtdalsbreen and 70% more ice melt than on Storbreen. We compare the relative and absolute values of the energy fluxes on Storbreen and Midtdalsbreen with reported values for glaciers at similar latitudes. Furthermore, a comparison is made with meteorological variables measured at two nearby weather stations, showing that on-site measurements are essential for an accurate calculation of the surface energy balance and melt rate