Self-control tames the coupling of reactive radicals

Highly reactive or unstable chemical reagents are challenging to prepare, store, and safely handle, so chemists frequently generate them in situ from convenient precursors. In an ideal case, the rate of release of the reagent would be matched to the rate of its “capture” in the desired chemical reaction, thereby preventing the reagent from accumulating and minimizing any opportunity for decomposition. However, this synchronization is rarely achieved or even attempted: The rate of release is usually dictated by the conditions of the reaction (1), rather than being regulated by capture of the reagent. In this issue, Tellis et al. (2) on page 433 and Zuo et al. (3) on page 437 independently report the use of iridium photocatalysis (4, 5) to supply highly reactive radical coupling partners (R⋅) to a nickel-catalyzed carbon-carbon bond-forming process (see the figure). Intriguingly, the two points of contact between the iridium and nickel cycles enforce autoregulated release of the radical, ensuring its efficient capture by nickel rather than its decomposition via other pathways

Velocity-conductivity relations for cratonic lithosphere and their application : example of Southern Africa

Author Posting. © American Geophysical Union, 2013. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Geochemistry, Geophysics, Geosystems 14 (2013): 806–827, doi:10.1002/ggge.20075.Seismic velocity is a function of bulk vibrational properties of the media, whereas electrical resistivity is most often a function of transport properties of an interconnected minor phase. In the absence of a minor conducting phase then the two should be inter-relatable primarily due to their sensitivity to temperature variation. We develop expressions between shear wave velocity and resistivity for varying temperature, composition, and water content based on knowledge from two kimberlite fields: Jagersfontein (Kaapvaal Craton) and Gibeon (Rehoboth Terrane). We test the expressions through comparison between a new high-resolution regional seismic model, derived from surface wave inversion of earthquake data from Africa and the surrounding regions, and a new electrical image from magnetotelluric (MT) data recorded in SAMTEX (Southern African Magnetotelluric Experiment). The data-defined robust linear regression between the two is found to be statistically identical to the laboratory-defined expression for 40 wt ppm water in olivine. Cluster analysis defines five clusters that are all geographically distinct and tectonically relate to (i) fast, cold, and variably wet Kaapvaal Craton, (ii) fast and wet central Botswana, (iii) slow, warm, and wet Rehoboth Terrane, (iv) moderately fast, cold, and very dry southernmost Angola Craton, and (v) slow, warm, and somewhat dry Damara Belt. From the linear regression expression and the MT image we obtain predicted seismic velocity at 100 km and compare it with that from seismic observations. The differences between the two demonstrate that the linear relationship between Vs and resistivity is appropriate for over 80% of Southern Africa. Finally, using the regressions for varying water content, we infer water content in olivine across Southern Africa.We wish to again acknowledge the three main funding agencies, the U.S. National Science Foundation’s Continental Dynamics Program (grant EAR0455242 to RLE), the South African Department of Science and Technology (grant to South African Council for Geoscience), and Science Foundation Ireland (grant 05/RGP/GEO001 to AGJ), for their support. Industry support for SAMTEX from De Beers Group Services, BHP Billiton and Rio Tinto Mining and Exploration resulted in a program far more extensive than originally conceived. S.F. has been supported by the NERC New Investigator grant NE/G000859/1. M.M. wishes to thank Science Foundation Ireland (grant 08/RFP/GEO1693 SAMTEX to AGJ) for support. J.F. wishes to thank Enterprise Ireland (grant Topo-Med to AGJ), Science Foundation Ireland (grant 10/IN.1/I3022 IRETHERMto AGJ), and the JAE-DOC Programme from Spanish CSIC, cofunded by FSE for support.2013-10-0

Robust magnetotelluric inversion

Author Posting. © The Author(s), 2014. This article is posted here by permission of The Royal Astronomical Society for personal use, not for redistribution. The definitive version was published in Geophysical Journal International 196 (2014): 1365-1374, doi:10.1093/gji/ggt484.A robust magnetotelluric (MT) inversion algorithm has been developed on the basis of quantile-quantile (q-q) plotting with confidence band and statistical modelling of inversion residuals for the MT response function (apparent resistivity and phase). Once outliers in the inversion residuals are detected in the q-q plot with the confidence band and the statistical modelling with the Akaike information criterion, they are excluded from the inversion data set and a subsequent inversion is implemented with the culled data set. The exclusion of outliers and the subsequent inversion is repeated until the q-q plot is substantially linear within the confidence band, outliers predicted by the statistical modelling are unchanged from the prior inversion, and the misfit statistic is unchanged at a target level. The robust inversion algorithm was applied to synthetic data generated from a simple 2-D model and observational data from a 2-D transect in southern Africa. Outliers in the synthetic data, which come from extreme values added to the synthetic responses, produced spurious features in inversion models, but were detected by the robust algorithm and excluded to retrieve the true model. An application of the robust inversion algorithm to the field data demonstrates that the method is useful for data clean-up of outliers, which could include model as well as data inconsistency (for example, inability to fit a 2-D model to a 3-D data set), during inversion and for objectively obtaining a robust and optimal model. The present statistical method is available irrespective of the dimensionality of target structures (hence 2-D and 3-D structures) and of isotropy or anisotropy, and can operate as an external process to any inversion algorithm without modifications to the inversion program.TM was supported by the scientific program of TAIGA (trans-crustal advection and in-situ reaction of global sub-seafloor aquifer) sponsored by the MEXT of Japan, and is supported by the NIPR project KP-7. ADC is supported by US National Science Foundation (NSF) grant EAR1015185

Lithospheric structure of an Archean craton and adjacent mobile belt revealed from 2-D and 3-D inversion of magnetotelluric data : example from southern Congo craton in northern Namibia

Author Posting. © American Geophysical Union, 2013. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Journal of Geophysical Research: Solid Earth 118 (2013): 4378–4397, doi:10.1002/jgrb.50258.Archean cratons, and the stitching Proterozoic orogenic belts on their flanks, form an integral part of the Southern Africa tectonic landscape. Of these, virtually nothing is known of the position and thickness of the southern boundary of the composite Congo craton and the Neoproterozoic Pan-African orogenic belt due to thick sedimentary cover. We present the first lithospheric-scale geophysical study of that cryptic boundary and define its geometry at depth. Our results are derived from two-dimensional (2-D) and three-dimensional (3-D) inversion of magnetotelluric data acquired along four semiparallel profiles crossing the Kalahari craton across the Damara-Ghanzi-Chobe belts (DGC) and extending into the Congo craton. Two-dimensional and three-dimensional electrical resistivity models show significant lateral variation in the crust and upper mantle across strike from the younger DGC orogen to the older adjacent cratons. We find Damara belt lithosphere to be more conductive and significantly thinner than that of the adjacent Congo craton. The Congo craton is characterized by very thick (to depths of  250 km) and resistive (i.e., cold) lithosphere. Resistive upper crustal features are interpreted as caused by igneous intrusions emplaced during Pan-African magmatism. Graphite-bearing calcite marbles and sulfides are widespread in the Damara belt and account for the high crustal conductivity in the Central Zone. The resistivity models provide new constraints on the southern extent of the greater Congo craton and suggest that the current boundary drawn on geological maps needs revision and that the craton should be extended further south.The SAMTEX consortiummembers (Dublin Institute for Advanced Studies, Woods Hole Oceanographic Institution, Council for Geoscience (South Africa), De Beers Group Services, The University of the Witwatersrand, Geological Survey of Namibia, Geological Survey of Botswana, Rio Tinto Mining and Exploration, BHP Billiton, Council for Scientific and Industrial Research (South Africa), and ABB Sweden) are thanked for their funding and logistical support during the four phases of data acquisition. This work is also supported by research grants from the National Science Foundation (EAR-0309584 and EAR-0455242 through the Continental Dynamics Program to R. L. Evans), the Department of Science and Technology, South Africa, and Science Foundation of Ireland (grant 05/RFP/ GEO001to A. G. Jones).2014-02-0

The radial velocity curve of HD153919 (4U1700-37) revisited

We have re-analysed all available high-resolution ultraviolet IUE spectra of the high-mass X-ray binary HD153919/4U1700-37. The radial velocity semi-amplitude of 20.6 +/- 1.0 km/s and orbital eccentricity of 0.22 +/- 0.04 agree very well with the values obtained earlier from optical spectra. They disagree with earlier conclusions for the same data reduced by Heap & Corcoran (1992) and by Stickland & Lloyd (1993).Comment: 6 pages, latex, figure included, Astronomy & Astrophysics, in pres

Area selection for diamonds using magnetotellurics : examples from southern Africa

Author Posting. © Elsevier B.V., 2009. This is the author's version of the work. It is posted here by permission of Elsevier B.V. for personal use, not for redistribution. The definitive version was published in Lithos 112 (2009): 83-92, doi:10.1016/j.lithos.2009.06.011.Southern Africa, particularly the Kaapvaal Craton, is one of the world’s best natural laboratories for studying the lithospheric mantle given the wealth of xenolith and seismic data that exist for it. The Southern African Magnetotelluric Experiment (SAMTEX) was launched to complement these databases and provide further constraints on physical parameters and conditions by obtaining information about electrical conductivity variations laterally and with depth. Initially it was planned to acquire magnetotelluric data on profiles spatially coincident with the Kaapvaal Seismic Experiment, however with the addition of seven more partners to the original four through the course of the experiment, SAMTEX was enlarged from two to four phases of acquisition, and extended to cover much of Botswana and Namibia. The complete SAMTEX dataset now comprises MT data from over 675 distinct locations in an area of over one million square kilometres, making SAMTEX the largest regional-scale MT experiment conducted to date. Preliminary images of electrical resistivity and electrical resistivity anisotropy at 100 km and 200 km, constructed through approximate one-dimensional methods, map resistive regions spatially correlated with the Kaapvaal, Zimbabwe and Angola Cratons, and more conductive regions spatially associated with the neighbouring mobile belts and the Rehoboth Terrain. Known diamondiferous kimberlites occur primarily on the boundaries between the resistive or isotropic regions and conductive or anisotropic regions. Comparisons between the resistivity image maps and seismic velocities from models constructed through surface wave and body wave tomography show spatial correlations between high velocity regions that are resistive, and low velocity regions that are conductive. In particular, the electrical resistivity of the sub-continental lithospheric mantle of the Kaapvaal Craton is determined by its bulk parameters, so is controlled by a bulk matrix property, namely temperature, and to a lesser degree by iron content and composition, and is not controlled by contributions from interconnected conducting minor phases, such as graphite, sulphides, iron oxides, hydrous minerals, etc. This makes quantitative correlations between velocity and resistivity valid, and a robust regression between the two gives an approximate relationship of Vs [m/s] = 0.045*log(resistivity [ohm.m]).We especially thank our academic funding sponsors; the Continental Dynamics programme of the U.S. National Science Foundation, the South African Department of Science and Technology, and Science Foundation Ireland

'They’ve Got Their Wine Bars, We’ve Got Our Pubs’: Housing, diversity and community in two south London neighbourhoods

This chapter explores how housing policies and the nature of housing stock have conditioned residential geographies and diversity patterns in two south London neighbourhoods, Bermondsey and Camberwell. The key drivers are policy changes to social housing allocation and the post-industrial reconfiguration of urban space expressed in processes of gentrification and the redevelopment of riverside docklands into expensive housing units. These developments have challenged existing narratives of community, but they have also shifted the focus of analytical enquiry towards emerging us-them divides based on class and generation. Within the context of diversity and social cohesion, both neighbourhoods are characterized by a comparatively unproblematic day-to-day muddling along with difference, but also a generally declining level of civic engagement and neighbourhood cohesion, expressed by a sense of ‘living together apart

Volumetric, relaxometric and diffusometric correlates of psychotic experiences in a non-clinical sample of young adults

BACKGROUND: Grey matter (GM) abnormalities are robust features of schizophrenia and of people at ultra high-risk for psychosis. However the extent to which neuroanatomical alterations are evident in non-clinical subjects with isolated psychotic experiences is less clear. METHODS: Individuals (mean age 20 years) with (n = 123) or without (n = 125) psychotic experiences (PEs) were identified from a population-based cohort. All underwent T1-weighted structural, diffusion and quantitative T1 relaxometry MRI, to characterise GM macrostructure, microstructure and myelination respectively. Differences in quantitative GM structure were assessed using voxel-based morphometry (VBM). Binary and ordinal models of PEs were tested. Correlations between socioeconomic and other risk factors for psychosis with cortical GM measures were also computed. RESULTS: GM volume in the left supra-marginal gyrus was reduced in individuals with PEs relative to those with no PEs. The greater the severity of PEs, the greater the reduction in T1 relaxation rate (R1) across left temporoparietal and right pre-frontal cortices. In these regions, R1 was positively correlated with maternal education and inversely correlated with general psychopathology. CONCLUSIONS: PEs in non-clinical subjects were associated with regional reductions in grey-matter volume reduction and T1 relaxation rate. The alterations in T1 relaxation rate were also linked to the level of general psychopathology. Follow up of these subjects should clarify whether these alterations predict the later development of an ultra high-risk state or a psychotic disorder

Electrical lithosphere beneath the Kaapvaal craton, southern Africa

Author Posting. © American Geophysical Union, 2011. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Journal of Geophysical Research 116 (2011): B04105, doi:10.1029/2010JB007883.A regional-scale magnetotelluric (MT) experiment across the southern African Kaapvaal craton and surrounding terranes, called the Southern African Magnetotelluric Experiment (SAMTEX), has revealed complex structure in the lithospheric mantle. Large variations in maximum resistivity at depths to 200–250 km relate directly to age and tectonic provenance of surface structures. Within the central portions of the Kaapvaal craton are regions of resistive lithosphere about 230 km thick, in agreement with estimates from xenolith thermobarometry and seismic surface wave tomography, but thinner than inferred from seismic body wave tomography. The MT data are unable to discriminate between a completely dry or slightly “damp” (a few hundred parts per million of water) structure within the transitional region at the base of the lithosphere. However, the structure of the uppermost ∼150 km of lithosphere is consistent with enhanced, but still low, conductivities reported for hydrous olivine and orthopyroxene at levels of water reported for Kaapvaal xenoliths. The electrical lithosphere around the Kimberley and Premier diamond mines is thinner than the maximum craton thickness found between Kimberley and Johannesburg/Pretoria. The mantle beneath the Bushveld Complex is highly conducting at depths around 60 km. Possible explanations for these high conductivities include graphite or sulphide and/or iron metals associated with the Bushveld magmatic event. We suggest that one of these conductive phases (most likely melt-related sulphides) could electrically connect iron-rich garnets in a garnet-rich eclogitic composition associated with a relict subduction slab.In addition to the funding and logistical support provided by SAMTEX consortium members, this work is also supported by research grants from the National Science Foundation (EAR‐0309584 and EAR‐0455242 through the Continental Dynamics Program), the Department of Science and Technology, South Africa, and Science Foundation of Ireland (grant 05/RFP/ GEO001)

Recent developments on the ALICE central Trigger processor

The ALI CE Central Trigger Processor has been constructed and tested, and will shortly be installed in the experimental area. In this review, we introduce the new developments in hardware and software, present a measurement of the minimum propagation time, and illustrate various trigger applications