ESC Publications - Cambridge Univesity
Not a member yet
4214 research outputs found
Sort by
Rotor-synchronized acquisition of quadrupolar satellite-transition NMR spectra: practical aspects and double-quantum filtration
No full textThe very broad resonances of quadrupolar (spin I > 1/2) nuclei are resolved by magic angle spinning (MAS) into a large number of spinning sidebands, each of which often remains anisotropically broadened. The quadrupolar interaction can be removed to a first-order approximation if the MAS NMR spectrum is acquired in a rotor-synchronized fashion, aliasing the spinning sidebands onto a centreband and thereby increasing the signal-to-noise ratio in the resulting, possibly second-order broadened, spectrum. We discuss the practical aspects of this rotor-synchronization in the direct (t2) time domain, demonstrating that the audiofrequency filters in the receiver section of the spectrometer have a significant impact on the precise timings needed in the experiment. We also introduce a novel double-quantum filtered rotor-synchronized experiment for half-integer spin quadrupolar (spin I = 3/2, 5/2, etc.) nuclei that makes use of central-transition-selective inversion pulses to both excite and reconvert double-quantum coherences and yields a simplified spectrum containing only the ST1 (mI = ± 1/2 ↔ ± 3/2) satellite-transition lineshapes. For spin I = 5/2 nuclei, such as 17O and 27Al, this spectrum may exhibit a significant resolution increase over the conventional central-transition spectrum
Cool-water carbonate sedimentology and eustasy; Pleistocene upper slope environments, Great Australian Bight (Site 1127, ODP LEG 182)
No full textThe southern Australian shelf is the largest area of the globe composed of cool-water carbonates and provides the basis for the development of actualistic models of such sediments. Ocean Drilling Program Leg 182 drilling of the sedimentary succession provides essential information to also decipher the dynamics of this depositional system. Sediment samples and geophysical logs from a core drilled on the Eucla Plateau off the coast of southern Australia (Site 1127) have been used to study sedimentary cyclicity in an 800-m-thick cool-water carbonate Pleistocene wedge. This periplatform succession is dominated by bioclastic packstone and wackestone with minor intercalations of bioclastic grainstone. Fluctuations of stable oxygen-isotope values in bulk carbonate samples parallel global climatic and related sea-level fluctuations as predicted in the SPECMAP-curve. The sea-level-controlled sedimentary cycles of the slope succession are several tens of meters thick. Lowstand deposits are relatively fine grained and include abundant sponge spicules, whereas highstand deposits are coarser grained and contain abundant high-Mg calcite bioclasts. Aragonite content makes up to 36% of the cool-water carbonates. Aragonite originates from tunicate spicules. Primary, sea-level-controlled carbonate mineralogical and textural changes are likely to promote facies-dependent differential diagenesis during later burial stages of such successions
Inversion of travel-time data under a statistical model for seismic velocities and layer interfaces
No full textWe invert large-aperture seismic reflection and refraction
data from a geologically complex area on the northeast Atlantic margin to jointly estimate seismic velocities
and depths of major interfaces. Our approach combines this geophysical data information with prior information on seismic compressional velocities and the structural interpretation of seismic sections. We constrain
expected seismic velocities in the prior model using information from well logs from a nearby area.
The layered structure and prior positions of the interfaces
follow information from the seismic section obtained
by processing the short offsets. Instead of using
a conventional regularization technique to smooth the
interface-velocity model, we describe the spatial correlation of interfaces and velocities with a geostatistical model, using a multivariate Gaussian probability density function. We impose a covariance function on the velocity field in each layer and on each interface in the model to control the smoothness of the solution.
The inversion is performed by minimizing an objective
function with two terms, one term measuring
traveltime residuals and the other measuring the fit to
the statistical model. We calculate the posterior uncertainties and evaluate the relative influence of data and the prior model on estimated interface depths and seismic velocities. The method results in the estimation of
velocity and interface geometry beneath a basaltic sill
system down to 7 km depth. This method aims to enhance
the interpretation process by combining multidisciplinary
information in a quantitative model-based
approach
Top-down pre-cooled natural ventilation
No full textThis paper studies the summertime regime of precooled natural ventilation of an auditorium or other occupied open-plan space equipped with a high-level vent and a low-level vent. A chiller unit is connected to the high-level vent to provide precooling. Fresh air from the exterior comes into the room through the high-level vent passing through the precooling system. Precooled air then produces negative (downward) buoyancy, which overcomes positive (upward) buoyancy produced by the occupants, and displaces original air in the room downwards and out through the low-level vent. This leads to an equilibrium in which a steady downflow is maintained, and in which the room becomes thermally uniform at a temperature below that of the exterior. A quantitative model is developed to describe these conditions and successfully tested with analogue laboratory experiments. The model shows that for a given room geometry and chiller, there is a maximum heat load which can be accommodated while maintaining ventilation and thermal comfort through downward ventilation. We show how effective and energy-efficient ventilation may be achieved through coordinated adjustment of the vent area and the amount of cooling.
Practical application: Top-down precooled natural ventilation can be an effective and energy efficient technique for providing thermal and ventilation comfort in a wide range of modern buildings during high summer or in warm climates. The present work describes how the system works, and how it may be controlled to achieve satisfactory results in terms of comfort and energy efficiency
Determination of the uranium valence state in brannerite using EELS, XPS, and EDX
No full textIn this study, the valence states of uranium in synthetic and natural brannerite samples were studied using a combination of transmission electron microscopy-electron energy loss spectroscopy, scanning electron microscopy-energy dispersive X-ray analysis (SEM-EDX), and X-ray photoelectron spectroscopy (XPS) techniques. We used a set of five (UO2, CaUO4, SrCa2UO6, UTi2O6, and Y0.5U0.5Ti2O6) U standard samples, including two synthetic brannerites, to calibrate the EELS branching ratio, M5/(M4 + M5), against the number of f electrons. The EELS data were collected at liquid nitrogen temperature in order to minimise the effects of electron beam reduction of U6+ and U5+. Test samples consisted of three additional synthetic brannerites (Th0.7U0.3Ti2O6, Ca0.2U0.8Ti2O6, and Th0.55U0.3- Ca0.15Ti2O6) and three natural brannerites from different localities. The natural brannerite samples are all completely amorphous, due to cumulative alpha decay events over geological time periods (24-508 Ma). Our U valence calibration results are in reasonable agreement with previous work, suggesting possibly a non-linear relationship between the branching ratio and the number of f electrons (and hence the average valence state) of U in solids. We found excellent agreement between the nominal valence states of U and the average valence states determined directly by EELS and estimated by EDX analysis (with assumptions regarding stoichiometry) in two of the three synthetic brannerite test samples. The average U oxidation states of the five synthetic brannerite samples, as derived from XPS analyses, are also in good agreement with those determined by other techniques. The average valence states of U in three amorphous (metamict) natural brannerite samples with alpha decay doses ranging from 3.6×1016 to 6.9×1017 α/mg were found to be 4.4, 4.7, and 4.8, consistent with the presence of U5+ and/or U6+ as well as U4+ in these samples. These results are in general agreement with previous wet chemical analyses of natural brannerite. However, the average valence states inferred by SEM-EDX for two of the natural brannerite samples do not show satisfactory agreement with the EELS determined valence. This may be due to the occurrence of OH- groups, cation vacancies, anion vacancies, or excess oxygen in the radiation-damaged structure of natural brannerite
Tectonic control of the Tejo river fluvial incision during the late Cenozoic, in Ródão - central Portugal (Atlantic Iberian border)
No full textStaircases of strath terraces and strongly incised valleys are the most typical landscape features of Portuguese rivers. This paper examines the incision achieved during the late Cenozoic in an area crossed by the Tejo river between the border with Spain and the small town of Gavião. In the more upstream reach of this area, the Tejo crosses the Ródão tectonic depression, where four levels of terraces are distinguished. During the late Cenozoic fluvial incision stage, the Ródão depression underwent less uplift than the adjacent areas along the river. This is reflected by the greater thicknesses and spatial extent of the terraces; terrace genesis was promoted by impoundment of alluvium behind a quartzitic ridge and the local presence of a soft substratum. Outside this tectonic depression, the Tejo has a narrow valley incised in the Hercynian basement, with some straight reaches that probably correspond to NE–SW and NNW–SSE faults, the terraces being nearly absent. Geomorphological evidence of tectonic displacements affecting the Ródão dissected terrace remnants is described. Geochronological dating of the two younger and lower terrace levels of this depression suggests a time-averaged incision rate for the Tejo in the Ródão area, of ca. 1.0 m/ka over the last 60 thousand years. A clear discrepancy exists between this rate and the 0.1 m/ka estimated for the longer period since the end of the Pliocene. Although episodes of valley incision may be conditioned by climate and base-level changes, they may also have been controlled by local factors such as movement of small fault-bounded blocks, lithology and structure. Regional crustal uplift is considered to be the main control of the episodes of valley incision identified for this large, long-lived river. A model is proposed in which successive regional uplift events—tectonic phases—essentially determined the long periods of rapid river downcutting that were punctuated by short periods of lateral erosion and later by some aggradation, producing strath terraces
Grid computing and molecular simulations: the vision of the eMinerals Project
No full textThis paper discusses a number of aspects of using grid computing methods in support of molecular simulations, with examples drawn from the eMinerals project. A number of components for a useful grid infrastructure are discussed, including the integration of compute and data grids, automatic metadata capture from simulation studies, interoperability of data between simulation codes, management of data and data accessibility, management of jobs and workflow, and tools to support collaboration. Use of a grid infrastructure also brings certain challenges, which are discussed. These include making use of boundless computing resources, the necessary changes, and the need to be able to manage experimentation
What status for the Quaternary?
No full textThe status of the Quaternary, long regarded as a geological period effectively coincident with the main climatic deterioration of the current Ice Age, has recently been questioned as a formal stratigraphic unit. We argue here that it should be retained as a formal period of geological time. Furthermore, we consider that its beginning should be placed at the Gauss-Matuyama magnetic chron boundary at about 2.6 Ma, rather than at its current position at about 1.8 Ma. The Quaternary would be formally subdivided into the Pleistocene and Holocene epochs
Gold mineralization within the Witwatersrand Basin, South Africa: evidence for a modified placer origin of the deposit, and the role of the Vredefort impact event
No full textThe chemical composition of gold within the Archaean metasedimentary rocks of the Witwatersrand Supergroup displays significant heterogeneity at the micro-, meso-and regional scales. A detailed electron microbeam analytical and petrological study of the main auriferous horizons in the Central Rand Group throughout the Witwatersrand Basin indicates that gold has been remobilized late in the paragenetic sequence over distances of less than centimetres. Contemporaneous chlorite formation was strongly rock-buffered. Gold mobilization occurred under fluid-poor conditions at temperatures that did not exceed 350 °C. Widespread circulation of mineralizing fluids within the Central Rand Group is not supported by the gold and chlorite chemical data. Brittle deformation that affects most of the paragenetic sequence of the Central Rand Group late in its post-depositional history is followed by sequences of mineral growth and dissolution that appear throughout the Central Rand Group and have consistent textural relationships with gold. The consistent location within the paragenetic sequence, the wide regional and stratigraphic extent of the brittle deformation, together with mineral chemical and petrological data suggest that the Vredefort Impact Event (2.02 Ga) was the cause of this late deformation, and that post-impact fluid-poor metamorphism resulted in crystallization of a significant proportion of the gold on and within mineral grains that were deformed during this event
Reconstruction of sea-surface temperatures from assemblages of planktonic foraminifera: multi-technique approach based on geographically constrained calibration data sets and its application to glacial Atlantic and Pacific Oceans
No full textWe present a conceptual framework for a new approach to environmental calibration of planktonic foraminifer census counts. This approach is based on simultaneous application of a variety of transfer function techniques, which are trained on geographically constrained calibration data sets. It serves to minimise bias associated with the presence of cryptic species of planktonic foraminifera and provides an objective tool for assessing reliability of environmental estimates in fossil samples, allowing identification of adverse effects of no-analog faunas and technique-specific bias. We have compiled new calibration data sets for the North (N=862) and South (N=321) Atlantic and the Pacific Ocean (N=1111). We show evidence that these data sets offer adequate coverage of the Sea-Surface Temperature (SST) and faunal variation range and that they are not affected by the presence of pre-Holocene samples and/or calcite dissolution. We have applied four transfer function techniques, including Artificial Neural Networks, Revised Analog Method and SIMMAX (with and without distance weighting) on faunal counts in a Last Glacial Maximum (LGM) data set for the Atlantic Ocean (748 samples in 167 cores; based on the GLAMAP-2000 compilation) and a new data set for the Pacific Ocean (265 samples in 82 cores) and show that three of these techniques provide adequate degree of independence for the advantage of a multi-technique approach to be realised. The application of our new approach to the glacial Pacific lends support to the contraction and perhaps even a cooling of the Western Pacific Warm Pool and a substantial (>3 °C) cooling of the eastern equatorial Pacific and the eastern boundary currents. Our results do not provide conclusive evidence for LGM warming anywhere in the Pacific. The Atlantic reconstruction shows a number of robust patterns, including substantial cooling of eastern boundary currents with considerable advection of subpolar waters into the Benguela Current, a cooling of the equatorial Atlantic by not, vert, similar5 °C, and steep SST gradients in the mid-latitude North Atlantic. The transfer function techniques generally agree that subtropical gyre areas in both hemispheres did not change significantly since the LGM, although the ANN technique produced glacial SST in the southern gyre 1–2 °C warmer than today. We have revisited the issue of sea-ice occurrence in the Nordic Seas and using the distribution of subpolar species of planktonic foraminifera in glacial samples, we conclude that the Norwegian Sea must have been ice-free during the summer