Geochemistry of neritic carbonates of ODP Hole 134-831B

Drilling at Bougainville Guyot (Ocean Drilling Program Site 831), New Hebrides Island Arc during Leg 134 revealed that 727.5 m of carbonate overlies an andesite basement. The carbonate cap at Site 831 consists of 20 m of pelagic carbonate overlying 707.5 m of neritic carbonates. The neritic section consists of ~230 m of largely unaltered aragonite sediment that overlies ~497 m of totally calcitized limestone. The deeper portion of the calcitized interval has been pervasively altered by diagenesis. Prior to this study the age distribution of sediments at Bougainville Guyot was poorly known because age diagnostic fossils are sparsely and discontinuously distributed in the sequence. We have used Sr isotopes to provide temporal constraints on the deposition of carbonates at Site 831; these constraints are critical in reconstructing the vertical movement of Bougainville Guyot before its collision with the New Hebrides Island Arc. Overall, the chronostratigraphy of Bougainville Guyot can be subdivided into three intervals: (1) a Pleistocene interval (102.4 to 391.11 meters below sea floor [mbsf]); (2) a Miocene interval (410.31 to 669.53 mbsf); and (3) an Oligocene interval (678.83 to 727.50 mbsf). Strontium isotopic ages of samples increase with increasing depth in the carbonate sequence, except near the bottom of the sequence, where several samples exhibit a consistent reversed age vs. depth trend. Such age reversals are most likely the product of post-depositional rock-water interaction. Preliminary stable isotope data are consistent with diagenetic alteration in the marine and meteoric environments. Several abrupt decreases in d87Sr, and hence age, of sediments are recognized in the carbonate cap at Bougainville Guyot. These disconformities are most likely the product of subaerial exposure in response to relative sea-level fall. Indeed, Sr-isotope ages indicate that 2 to 9 m.y. of sediment deposition is missing across these d87Sr disconformities.

Wave height (regular and irregular waves) reduction in 2m water depth over a 40-m-long salt marsh test section in a large scale laboratory flume

Coastal communities around the world face increasing risk from flooding as a result of rising sea level, increasing storminess, and land subsidence. Salt marshes can act as natural buffer zones, providing protection from waves during storms. However, the effectiveness of marshes in protecting the coastline during extreme events when water levels and waves are highest is poorly understood. Here, we experimentally assess wave dissipation under storm surge conditions in a 300-m-long wave flume that contains a transplanted section of natural salt marsh. We find that the presence of marsh vegetation causes considerable wave attenuation, even when water levels and waves are high. From a comparison with experiments without vegetation, we estimate that up to 60% of observed wave reduction is attributed to vegetation. We also find that although waves progressively flatten and break vegetation stems and thereby reduce dissipation, the marsh substrate remained remarkably stable and resistant to surface erosion under all conditions.The effectiveness of storm wave dissipation and the resilience of tidal marshes even at extreme conditions suggest that salt marsh ecosystems can be a valuable component of coastal protection schemes.

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.

Hyperspectral downwelling irradiance during POLARSTERN cruise ANT-XXVI/1

A Monte Carlo based radiative transfer model has been developed for calculating the availability of solar radiation within the top 100 m of the ocean. The model is optimized for simulations of spatial high resolution downwelling irradiance Ed fluctuations that arise from the lensing effect of waves at the water surface. In a first step the accuracy of simulation results has been verified by measurements of the oceanic underwater light field and through intercomparison with an established radiative transfer model. Secondly the potential depth-impact of nonlinear shaped single waves, from capillary to swell waves, is assessed by considering the most favorable conditions for light focusing, i.e. monochromatic light at 490 nm, very clear oceanic water with a low chlorophyll a content of 0.1 mg/m**3 and high sun elevation. Finally light fields below irregular wave profiles accounting for realistic sea states were simulated. Our simulation results suggest that under open ocean conditions light flashes with 50% irradiance enhancements can appear down to 35 m depth, and light variability in the range of ±10% compared to the mean Ed is still possible in 100 m depth.