C−H Bond Activation by Iridium(III) and Iridium(IV) Oxo Complexes

Oxidation of an iridium(III) oxo precursor enabled the structural, spectroscopic, and quantum-chemical characterization of the first well-defined iridium(IV) oxo complex. Side-by-side examination of the proton-coupled electron transfer thermochemistry revealed similar driving forces for the isostructural oxo complexes in two redox states due to compensating contributions from H+ and e− transfer. However, C−H activation of dihydroanthracene revealed significant hydrogen tunneling for the distinctly more basic iridium(III) oxo complex. Our findings complement the growing body of data that relate tunneling to ground state properties as predictors for the selectivity of C−H bond activation.</p

Tectono‐Stratigraphic Evolution of the Kerguelen Large Igneous Province: The Conjugate William’s Ridge‐Broken Ridge Rifted Margins

AbstractExtensive investigation of continental rift systems has been fundamental for advancing the understanding of extensional tectonics and modes of formation of new ocean basins. However, current rift classification schemes do not account for conjugate end members formed by Large Igneous Province crust, referring to thick mafic crust, sometimes including continental fragments. Here, we investigate the rifting of William's Ridge (Kerguelen Plateau) and Broken Ridge, components of the Kerguelen Large Igneous Province now situated in the Southeast Indian Ocean, and incorporate these end members into the deformation migration concept for rifted margins. We use multichannel seismic reflection profiles and data from scientific drill cores acquired on both conjugate margins to propose, for the first time, a combined tectono‐stratigraphic framework. We interpret seismic patterns, tectonic features, and magnetic anomaly picks to determine an across‐strike structural domain classification. This interpretation considers the rift system overall to be “magma‐poor” despite being located proximal to the Kerguelen plume but suggests that syn‐rift interaction between the Kerguelen mantle plume and the lithospheric structure of William's Ridge and Broken Ridge has controlled the along‐strike segmentation of both conjugates. We integrate seismic reflection and bathymetric data to test the hypothesis of predominantly transform motion, between the Australian and Antarctic plates, in Late Cretaceous and Paleogene time.</jats:p

The evolving paleobathymetry of the circum-Antarctic Southern Ocean since 34 Ma – A key to understanding past cryosphere-ocean developments

The Southern Ocean is a key player in the climate, ocean and atmospheric system. As the only direct connection between all three major oceans since the opening of the Southern Ocean gateways, the development of the Southern Ocean and its relationship with the Antarctic cryosphere has influenced the climate of the entire planet. Although the depths of the ocean floor have been recognized as an important factor in climate and paleoclimate models, appropriate paleobathymetric models including a detailed analysis of the sediment cover are not available. Here, we utilize more than 40 years of seismic reflection data acquisition along the margins of Antarctica and its conjugate margins, along with multiple drilling campaigns by the International Ocean Discovery Program (IODP) and its predecessor programs. We combine and update the seismic stratigraphy across the regions of the Southern Ocean and calculate ocean-wide paleobathymetry grids via a backstripping method. We present a suite of high-resolution paleobathymetric grids from the Eocene-Oligocene Boundary to modern times. The grids reveal the development of the Southern Ocean from isolated basins to an interconnected ocean affected by the onset and vigor of an Antarctic Circumpolar Current, as well as the glacial sedimentation and erosion of the Antarctic continent. The ocean-wide comparison through time exposes patterns of ice sheet development such as switching of glacial outlets and the change from wet-based to dry-based ice sheets. Ocean currents and bottom-water production interact with the sedimentation along the continental shelf and slope and profit from the opening of the ocean gateways

IODP workshop: developing scientific drilling proposals for the Argentina Passive Volcanic Continental Margin (APVCM) – basin evolution, deep biosphere, hydrates, sediment dynamics and ocean evolution

The Argentine margin contains important sedimentological, paleontological and chemical records of regional and local tectonic evolution, sea level, climate evolution and ocean circulation since the opening of the South Atlantic in the Late Jurassic–Early Cretaceous as well as the present-day results of post-depositional chemical and biological alteration. Despite its important location, which underlies the exchange of southern- and northern-sourced water masses, the Argentine margin has not been investigated in detail using scientific drilling techniques, perhaps because the margin has the reputation of being erosional. However, a number of papers published since 2009 have reported new high-resolution and/or multichannel seismic surveys, often combined with multi-beam bathymetric data, which show the common occurrence of layered sediments and prominent sediment drifts on the Argentine and adjacent Uruguayan margins. There has also been significant progress in studying the climatic records in surficial and near-surface sediments recovered in sediment cores from the Argentine margin. Encouraged by these recent results, our 3.5-day IODP (International Ocean Discovery Program) workshop in Buenos Aires (8–11 September 2015) focused on opportunities for scientific drilling on the Atlantic margin of Argentina, which lies beneath a key portion of the global ocean conveyor belt of thermohaline circulation. Significant opportunities exist to study the tectonic evolution, paleoceanography and stratigraphy, sedimentology, and biosphere and geochemistry of this margin.Facultad de Ciencias Naturales y Muse

WSClean : an implementation of a fast, generic wide-field imager for radio astronomy

This article has been accepted for publication in Monthly Notices of the Royal Astronomical Society. © 2014 The Authors. Published by Oxford University Press on behalf of the Royal Astronomical Society.Astronomical widefield imaging of interferometric radio data is computationally expensive, especially for the large data volumes created by modern non-coplanar many-element arrays. We present a new widefield interferometric imager that uses the w-stacking algorithm and can make use of the w-snapshot algorithm. The performance dependencies of CASA's w-projection and our new imager are analysed and analytical functions are derived that describe the required computing cost for both imagers. On data from the Murchison Widefield Array, we find our new method to be an order of magnitude faster than w-projection, as well as being capable of full-sky imaging at full resolution and with correct polarisation correction. We predict the computing costs for several other arrays and estimate that our imager is a factor of 2-12 faster, depending on the array configuration. We estimate the computing cost for imaging the low-frequency Square-Kilometre Array observations to be 60 PetaFLOPS with current techniques. We find that combining w-stacking with the w-snapshot algorithm does not significantly improve computing requirements over pure w-stacking. The source code of our new imager is publicly released.Peer reviewedFinal Published versio

WSCLEAN: an implementation of a fast, generic wide-field imager for radio astronomy

Astronomical wide-field imaging of interferometric radio data is computationally expensive, especially for the large data volumes created by modern non-coplanar many-element arrays. We present a new wide-field interferometric imager that uses the w-stacking algorithm and can make use of the w-snapshot algorithm. The performance dependences of CASA's w-projection and our new imager are analysed and analytical functions are derived that describe the required computing cost for both imagers. On data from the Murchison Widefield Array, we find our new method to be an order of magnitude faster than w-projection, as well as being capable of full-sky imaging at full resolution and with correct polarization correction. We predict the computing costs for several other arrays and estimate that our imager is a factor of 2-12 faster, depending on the array configuration. We estimate the computing cost for imaging the lowfrequency Square Kilometre Array observations to be 60 PetaFLOPS with current techniques. We find that combining w-stacking with the w-snapshot algorithm does not significantly improve computing requirements over pure w-stacking. The source code of our new imager is publicly released