Highly stereoselective decarboxylation of (+)-1-Bromo-1-chloro-2,2,2-trifluoropropanoic acid gives (+)-1-Bromo-1-chloro-2,2,2-trifluoroethane ((+)-Halothane) with retention of configuration

The absolute configuration of the title acid (2) has been determined to be S by X-ray crystallography. Thus, decarboxylation of 2 produces (S)-(+)-halothane with 99% retention of configuration. This behavior is compared to other stereoselective decarboxylation reactions of ?-haloacids from the literature that also give high degrees of retention of configuration when in the form of their quaternary ammonium salts, which contain one proton. The proton of the ammonium salt is necessary to protonate the anionic intermediate formed from decarboxylation. In the absence of this relatively acidic proton, we had previously found that using triethylene glycol (TEG) as both solvent and proton source for the decarboxylation reaction of acid 2 caused poor stereoselectivity. This was in contrast to 1,2,2,2-tetrafluoro-1-methoxypropionic acid (6), which showed a high degree of retention of configuration in TEG. To rationalize this differing behavior we report DFT studies at PCM-B3LYP/6-31++G** level of theory (the results were additionally confirmed with 6-311++G** and aug-cc-pVDZ basis sets). The energy barrier to inversion of configuration of the anionic reaction intermediate of acid 2 (11) is 10.23 kcal/mol. However, we find that the anionic intermediate from acid 6 (10) would rather undergo ?-elimination instead of inversion of configuration. Thus the planar transition state required for inversion of configuration is never reached, regardless of the rate of proton transfer to the anion.

(Table 1) Iceberg characteristics and start and end date and location of iceberg buoys in the Weddell Sea

The drift of 52 icebergs tagged with GPS buoys in the Weddell Sea since 1999 has been investigated with respect to prevalent drift tracks, sea ice/iceberg interaction, and freshwater fluxes. Buoys were deployed on small- to medium-sized icebergs (edge lengths ? 5 km) in the southwestern and eastern Weddell Sea. The basin-scale iceberg drift of this size class was established. In the western Weddell Sea, icebergs followed a northward course with little deviation and mean daily drift rates up to 9.5 ± 7.3 km/d. To the west of 40°W the drift of iceberg and sea ice was coherent. In the highly consolidated perennial sea ice cover of 95% the sea ice exerted a steering influence on the icebergs and was thus responsible for the coherence of the drift tracks. The northward drift of buoys to the east of 40°W was interrupted by large deviations due to the passage of low-pressure systems. Mean daily drift rates in this area were 11.5 ± 7.2 km/d. A lower threshold of 86% sea ice concentration for coherent sea ice/iceberg movement was determined by examining the sea ice concentration derived from Special Sensor Microwave Imager (SSM/I) and Advanced Microwave Scanning Radiometer for EOS (AMSR-E) satellite data. The length scale of coherent movement was estimated to be at least 200 km, about half the value found for the Arctic Ocean but twice as large as previously suggested. The freshwater fluxes estimated from three iceberg export scenarios deduced from the iceberg drift pattern were highly variable. Assuming a transit time in the Weddell Sea of 1 year, the iceberg meltwater input of 31 Gt which is about a third of the basal meltwater input from the Filchner Ronne Ice Shelf but spreads across the entire Weddell Sea. Iceberg meltwater export of 14.2 × 103 m3 s?1, if all icebergs are exported, is in the lower range of freshwater export by sea ice.

Evaluation of long chain 1,14-alkyl diols in marine sediments as indicators for upwelling and temperature

Long chain alkyl diols form a group of lipids occurring widely in marine environments. Recent studies have suggested several palaeoclimatological applications for proxies based on their distributions, but also revealed uncertainties about their applicability. Here we evaluate the use of long chain 1,14-alkyl diol indices for reconstruction of temperature and upwelling conditions by comparing index values, obtained from a comprehensive set of marine surface sediments, with environmental factors like sea surface temperature (SST), salinity and nutrient concentrations. Previous cultivation efforts indicated a strong effect of temperature on the degree of saturation and the chain length distribution of long chain 1,14-alkyl diols in Proboscia spp., quantified in the diol saturation index (DSI) and diol chain length index (DCI), respectively. However, values of these indices in surface sediments show no relationship with annual mean SST of the overlying water. It remains unknown what determines the DSI, although our data suggests that it may be affected by diagenesis, while the relationship between temperature and DCI may be different for different Proboscia species. In addition, contributions of algae other than Proboscia diatoms may affect both indices, although our data provide no direct evidence for additional long chain 1,14-alkyl diol sources. Two other indices using the abundance of 1,14-diols vs. 1,13-diols and C30 1,15-diols have previously been applied as indicators for upwelling intensity at different locations. The geographical distribution of their values supports the use of 1,14 diols vs. 1,13 diols [C28 + C30 1,14-diols]/[(C28 + C30 1,13-diols) + (C28 + C30 1,14-diols)] as a general indicator for high nutrient or upwelling conditions.

(Table 1) Geochemical composition of surface waters obtained aboard the R/V Rift along the Volga-Caspian canal

The Volga River discharge consists of the waters transferred by fast currents through channels and the waters which are passing through the shallow areas of the delta overgrown by cane. Using the hydrochemical data, it is possible to track distribution of the waters modified by 'biofilters' of macrophytes in the delta shallows starting from the external edge of the delta. The main distinctive features of these waters are the high content of dissolved oxygen, the abnormally high values of the pH, and the low content of dissolved inorganic carbon (both total and as CO2). These waters extend in the shape of 1 to 3-km-wide strips at a distance of 20-40 km from the outer border of the delta. The analysis of the data obtained during the expeditions run by the Institute of Oceanology of the Russian Academy of Sciences in 2003-2009, along with archived and published data, show that such 'modified' waters occur almost constantly along the outer edge of the Volga River delta.

Delta 66Zn ratios and age of carbonates from ODP Site 138-849 (Table 1)

The carbonate fraction of sediment core ODP 849, leg 138, located in the eastern equatorial Pacific, mostly consisting of coccoliths, was separated and analyzed for its Zn isotopic composition. The overall variation in Zn isotopic composition, as determined by multiple-collector, magnetic-sector, inductively coupled plasma mass spectrometry, was found to be on the order of 1? (expressed in delta66Zn, where deltaxZn=[(xZn/64Zn)sample/(xZn/64Zn)standard -1]*10**3 and x=66, 67 or 68) over the last 175 ka. The analytical precision was 0.04 per mil and the overall reproducibility was usually better than 0.07 per mil. The Zn isotopic composition signal exhibits several marked peaks and a high-frequency variability. A periodogram of the delta66Zn signal showed two periodicities of 35.2 and 21.2 ka. We suggest that the latter is caused by the precession of the Earth's axis of rotation. The periodogram exhibits a minimum at 41.1 ka, thus showing that the Zn isotopic composition is independent of the obliquity in the eastern equatorial Pacific. The range of delta66Zn values observed for the carbonate fraction of ODP 849 overlaps with the range observed for Fe-Mn nodules in the world's oceans, which suggests that seawater/carbonate Zn isotope fractionation is weak. We therefore assume that most of the Zn isotope variability is a result of the selective entrainment of the light isotopes by organic matter in the surface ocean. The ODP 849 delta66Zn record seems to follow the changes in the insolation cycles. Changes in the late summer/fall equatorial insolation modulate the intensity of the equatorial upwelling, hence the mixing between deep and surface waters. We propose that during decreased summer/fall equatorial insolation, when a steep thermocline can develop (El Niño-like conditions), the surface waters cannot be replenished by deep waters and become depleted in the lighter Zn isotopes by biological activity, thus resulting in the progressive increase of the delta66Zn values of the carbonate shells presumably in equilibrium with surface seawater.

Stable oxygen and carbon isotope ratios of foraminifera from Oligocene to Miocene sediments of DSDP Hole 39-354 from Ceara Rise, West Altlantic (Table 1)

The oxygen- and carbon-isotope compositions of planktic and benthic foraminifera and calcareous nannofossils from Middle Oligocene-Early Miocene Equatorial Atlantic sediments (DSDP Site 354) indicate two important paleoceanographic changes, in the Late Oligocene (foraminiferal Zone P.21) and in the Early Miocene (foraminiferal Zone N.5). The first change, reflected by a delta18O increase of 1.45? in Globigerina venezuelana, affected only intermediate pelagic and not surface, deep or bottom waters. The second change affected surface and intermediate waters, whereas deep and bottom waters showed only minor fluctuations. In the case of the former the isotope effect of the moderate ice accumulation on the Antarctic continent is amplified in the Equatorial Atlantic by changes in the circulation pattern. The latter paleoceanographic change, reflected by a significant increase in 18O in both planktic and benthic forms (about 1.0? and 0.5?, respectively), may have been caused by ice volume increase and temperature decrease. Both oxygen- and carbon-isotope compositions indicate a marked depth-habitat stratification for planktic foraminifera and calcareous nannofossils. Three different dwelling groups are recognized: shallow Globigerinoides, Globoquadrina dehiscens, Globorotalia mayeri and nannofossils; intermediate Globigerina venezuelana; and deep Catapsydrax dissimilis. The comparison of foraminifera and calcareous nannofossils suggests that the isotopic compositions of nannofossils are generally controlled by the same parameters which control the isotopic composition of shallow-dwelling foraminifera, but the former are more enriched in 18O.

(Table 1) Physical properties of sediments at DSDP Holes 69-504 and 69-505

Values of physical properties measured in the upper sections of sediment cores recovered at Sites 504 and 505 exhibit a remarkable similarity. Below a depth of 145 m Site 504 sediments appear to have undergone changes which are reflected in physical property values. This alteration may have been due to high temperatures in the sediment. In most of Site 505, and in Site 504 above 145 m, seismic velocity averages 1.51 km/s, wet bulk density 1.32 g/cm**3, porosity 80%, and thermal conductivity 0.80% W/m °K. Below 145 m at Site 504 and 210 m at Site 505, mean density increases to 1.40 g/cm**3, porosity decreases to 67%, seismic velocity increases to 1.53 km/s, and thermal conductivity increases to values in excess of 1.0 W/m °K. A good correlation between independent measurements of water content and thermal resistivity supports the existence of small but regular variation in the measured parameters on the scale of 10 m and less.

Table 1 : AMS-14C data used for the reconstruction of the Wismar Bay shoreline displacement curve

The Baltic coast of Mecklenburg-Vorpommern is located in the transition Zone between the region of Fennoscandian Uplift and the Central European Depression. In relation to the eustatic sea-level rise, the northeast coast shows a slower inundation, while for the southwestern area a faster transgression is indicated, which can be attributed to crustal movements. To determine the spatial and temporal differences since the onset of the Littorina Transgression, three relative sea-level curves have been established along a transect parallel to the gradient of upliftlsubsidence. The Wismar Bay area is one endpoint of the transect demonstrating today 10 Abb., 2 Tab. a relative sea-level rise of 1.4 mm/a. To determine the relative sea-level curve for the Wismar Bay, two sites were investigated on Rustwerder Spit (Poel) and Redentin. They provided reliable depth-age data, while the stratigraphy was additionally supported by lithological/geochemical, pollen, diatom and macrofossil data. Additional evidence was provided by archaeological submarine surveys and excavations. Comparing the new relative sea-level curve with a curve from the Vorpommern coast, it can be shown that for the period from 4000 cal BC until present, the differences between the two curves are caused by a constant neotectonic movement, while for the older periods an increasing isostatic component must be taken into account.