Recognition of cyclic, acyclic, exocyclic, and spiro Acetals via structurally diagnostic ion/molecule reactions with the (CH3)(2)N-C+=O acylium ion

Reactions of the model acylium ion (CH3)(2)N-C+=O with acyclic, exocyclic, and Spiro acetals of the general formula (RO)-O-1-(CRR4)-R-3-OR2-upole mass spectrometry. Characteristic intrinsic reactivities were observed for each of these classes of acetals. The two most Characteristic intrinsic reactivities were observed for each of these classes of acetals. The two most common reactions observed were hydride and alkoxy anion [(RO-)-O-1 and (RO-)-O-2] abstraction. Other specific reactions were also observed: (a) a secondary polar [4(+) + 2] cycloaddition for acetals bearing alpha,beta-unsaturated R-3 or R-4 substituents and (b) OH- abstraction for exocyclic and spiro acetals. These structurally diagnostic reactions, in conjunction with others observed previously for cyclic acetals, are shown to reveal the class of the acetal molecule and its ring type and substituents and to permit their recognition and distinction from other classes of isomeric molecules.

The Southern Brazilian shelf: general characteristics, quaternary evolution and sediment distribution

Extending from latitude 34ºS to 22ºS the Southern Brazilian shelf constitutes the only part of the Brazilian shelf with a subtropical to temperate environment. The studies on the different geological aspects of the area began in the 1960's and have recently been reassessed after studies related to the determination of the Economic Exclusive Zone. In terms of morphology, the Southern Brazilian shelf may be divided into three sectors, the São Paulo Bight, the Florianópolis-Mostardas Sector and the Rio Grande Cone, characterized by conspicuous differences in terms of geological determining factors, bathymetry, declivities and the presence of canyons and channels. Despite the existence of hundreds of radiocarbon datings the sea level changes curve of southern Brazil during the Last Glacial Cycle is still a matter of debate. A recent controversy on the Middle and late Holocene sea level changes curve raised the question of the amplitude of the oscillations which occurred in the period. Also, a few but relatively consistent radiocarbon datings suggest the occurrence of a high sea level during Isotope Stage 3. In terms of sedimentary cover the Southern Brazilian shelf exhibits a very strong hydrodynamic control, both latitudinal and bathymetrical. The sector southward from 25ºS is characterized by the influence of the plume of water carrying sediments originating from the Río de La Plata. Actually its presence is conspicuous up to 28ºS, with the area between this latitude and 25ºS constituting a transitional zone. In terms of bathymetry the outer shelf is marked by the "floor-polisher" effect of the Brazil Current, which is responsible for the maintenance of a relict facies in areas deeper than 100 meters.

30 million years of Permian volcanism recorded in the Choiyoi igneous province (W Argentina) and their source for younger ash fall deposits in the Parana Basin: SHRIMP U-Pb zircon geochronology evidence

We present four SHRIMP U-Pb zircon ages for the Choiyoi igneous province from the San Rafael Block, central-western Argentina. Dated samples come from the Yacimiento Los Reyunos Formation (281.4 +/- 2.5 Ma) of the Cochico Group (Lower Choiyoi section: andesitic breccias, dacitic to rhyolitic ignimbrites and continental conglomerates). Agua de los Burros Formation (264.8 +/- 2.3 Ma and 264.5 +/- 3.0 Ma) and Cerro Carrizalito Formation (251.9 +/- 2.7 Ma Upper Choiyoi section: rhyolitic ignimbrites and pyroclastic flows) spanning the entire Permian succession of the Choiyoi igneous province. A single ziron from the El Imperial Formation, that is overlain unconformably by the Choiyoi succession, yielded an early Permian age (297.2 +/- 5.3 Ma). while the main detrital zircon population indicated an Ordovician age (453.7 +/- 8.1 Ma). The new data establishes a more precise Permian age (Artinskian-Lopingian) for the section studied spanning 30 Ma of volcanic activity. Volcanological observations for the Choiyoi succession support the occurrence of explosive eruptions of plinian to ultraplinian magnitudes, capable of injecting enormous volumes of tephra in the troposphere-stratosphere. The new SHRIMP ages indicate contemporaneity between the Choyoi succession and the upper part of the Parana Basin late Paleozoic section, from the Irad up to the Rio do Rasto formations, encompassing about 24 Ma. Geochemical data show a general congruence in compositional and tectonic settings between the volcanics and Parana Basin Permian ash fall derived layers of bentonites. Thickness and granulometry of ash fall layers broadly fit into the depletion curve versus distance from the remote source vent of ultraplinian eruptions. Thus, we consider that the Choiyoi igneous province was the source of ash fall deposits in the upper Permian section of the Parana Basin. Data presented here allow a more consistent correlation between tectono-volcanic Permian events along the paleo-Pacific margin of southwestern Gondwana and the geological evolution of neighboring Paleozoic foreland basins in South America and Africa. (C) 2010 International Association for Gondwana Research. Published by Elsevier B.V. All rights reserved.