889 resultados para Twin coronet porphyrins
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For certain observing types, such as those that are remotely sensed, the observation errors are correlated and these correlations are state- and time-dependent. In this work, we develop a method for diagnosing and incorporating spatially correlated and time-dependent observation error in an ensemble data assimilation system. The method combines an ensemble transform Kalman filter with a method that uses statistical averages of background and analysis innovations to provide an estimate of the observation error covariance matrix. To evaluate the performance of the method, we perform identical twin experiments using the Lorenz ’96 and Kuramoto-Sivashinsky models. Using our approach, a good approximation to the true observation error covariance can be recovered in cases where the initial estimate of the error covariance is incorrect. Spatial observation error covariances where the length scale of the true covariance changes slowly in time can also be captured. We find that using the estimated correlated observation error in the assimilation improves the analysis.
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Using data from the EISCAT (European Incoherent Scatter) VHF and CUTLASS (Co-operative UK Twin- Located Auroral Sounding System) HF radars, we study the formation of ionospheric polar cap patches and their relationship to the magnetopause reconnection pulses identified in the companion paper by Lockwood et al. (2005). It is shown that the poleward-moving, high-concentration plasma patches observed in the ionosphere by EISCAT on 23 November 1999, as reported by Davies et al. (2002), were often associated with corresponding reconnection rate pulses. However, not all such pulses generated a patch and only within a limited MLT range (11:00–12:00 MLT) did a patch result from a reconnection pulse. Three proposed mechanisms for the production of patches, and of the concentration minima that separate them, are analysed and evaluated: (1) concentration enhancement within the patches by cusp/cleft precipitation; (2) plasma depletion in the minima between the patches by fast plasma flows; and (3) intermittent injection of photoionisation-enhanced plasma into the polar cap. We devise a test to distinguish between the effects of these mechanisms. Some of the events repeat too frequently to apply the test. Others have sufficiently long repeat periods and mechanism (3) is shown to be the only explanation of three of the longer-lived patches seen on this day. However, effect (2) also appears to contribute to some events. We conclude that plasma concentration gradients on the edges of the larger patches arise mainly from local time variations in the subauroral plasma, via the mechanism proposed by Lockwood et al. (2000).
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We report high-resolution observations of the southward-IMF cusp/cleft ionosphere made on December 16th 1998 by the EISCAT (European incoherent scatter) Svalbard radar (ESR), and compare them with observations of dayside auroral luminosity, as seen at a wavelength of 630 nm by a meridian scanning photometer at Ny Alesund, and of plasma flows, as seen by the CUTLASS (co-operative UK twin location auroral sounding system) Finland HF radar. The optical data reveal a series of poleward-moving transient red-line (630 nm) enhancements, events that have been associated with bursts in the rate of magnetopause reconnection generating new open flux. The combined observations at this time have strong similarities to predictions of the effects of soft electron precipitation modulated by pulsed reconnection, as made by Davis and Lockwood (1996); however, the effects of rapid zonal flow in the ionosphere, caused by the magnetic curvature force on the newly opened field lines, are found to be a significant additional factor. In particular, it is shown how enhanced plasma loss rates induced by the rapid convection can explain two outstanding anomalies of the 630 nm transients, namely how minima in luminosity form between the poleward-moving events and how events can re-brighten as they move poleward. The observations show how cusp/cleft aurora and transient poleward-moving auroral forms appear in the ESR data and the conditions which cause enhanced 630 nm emission in the transients: they are an important first step in enabling the ESR to identify these features away from the winter solstice when supporting auroral observations are not available.
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The generation of flow and current vortices in the dayside auroral ionosphere has been predicted for two processes ocurring at the dayside magnetopause. The first of these mechanisms is time-dependent magnetic reconnection, in “flux transfer events” (FTEs); the second is the action of solar wind dynamic pressure changes. The ionospheric flow signature of an FTE should be a twin vortex, with the mean flow velocity in the central region of the pattern equal to the velocity of the pattern as a whole. On the other hand, a pulse of enhanced or reduced dynamic pressure is also expected to produce a twin vortex, but with the central plasma flow being generally different in speed from, and almost orthogonal to, the motion of the whole pattern. In this paper, we make use of this distinction to discuss recent observations of vortical flow patterns in the dayside auroral ionosphere in terms of one or other of the proposed mechanisms. We conclude that some of the observations reported are consistent only with the predicted signature of FTEs. We then evaluate the dimensions of the open flux tubes required to explain some recent simultaneous radar and auroral observations and infer that they are typically 300 km in north–south extent but up to 2000 km in longitudinal extent (i.e., roughly 5 hours of MLT). Hence these observations suggest that recent theories of FTEs which invoke time-varying reconnection at an elongated neutral line may be correct. We also present some simultaneous observations of the interplanetary magnetic field (IMF) and solar wind dynamic pressure (observed using the IMP8 satellite) and the ionospheric flow (observed using the EISCAT radar) which are also only consistent with the FTE model. We estimate that for continuously southward IMF (
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The terrestrial magnetopause suffered considerable sudden changes in its location on 9–10 September 1978. These magnetopause motions were accompanied by disturbances of the geomagnetic field on the ground. We present a study of the magnetopause motions and the ground magnetic signatures using, for the latter, 10 s averaged data from 14 high latitude ground magnetometer stations. Observations in the solar wind (from IMP 8) are employed and the motions of the magnetopause are monitored directly by the spacecraft ISEE 1 and 2. With these coordinated observations we are able to show that it is the sudden changes in the solar wind dynamic pressure that are responsible for the disturbances seen on the ground. At some ground stations we see evidence of a “ringing” of the magnetospheric cavity, while at others only the initial impulse is evident. We note that at some stations field perturbations closely match the hypothesized ground signatures of flux transfer events. In accordance with more recent work in the area (e.g. Potemra et al., 1989, J. geophys. Res., in press), we argue that causes other than impulsive reeonnection may produce the twin ionospheric flow vortex originally proposed as a flux transfer even signature.
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The effects of flux transfer events (FTE) on the dayside auroral ionosphere are studied, using a simple twin-vortex model of induced ionospheric plasma flow. It is shown that the predicted and observed velocities of these flows are sufficient to drive nonthermal plasma in the F region, not only within the newly opened flux tube of the FTE, but also on the closed, or "old" open, field lines around it. In fact, with the expected poleward neutral wind, the plasma is more highly nonthermal on the flanks of, but outside, the open flux tube: EISCAT observations indicate that plasma is indeed driven into nonthermal distributions in these regions. The nonthermal plasma is thereby subject to additional upforce due to the resulting ion temperature anisotropy and transient expansion due to Joule heating and also to ion accelerations associated with the FTE field aligned current system. Any upflows produced on closed field lines in the vicinity of the FTE are effectively bunched-up in the "wake" of the FTE. Observations from the AMPTE-UKS satellite at the magnetopause reveal ion upflows of energy ∼100 eV flowing out from the ionosphere on closed field lines which are only found in the wake of the FTE. Such flows are also only found shortly after two, out of all the FTEs observed by AMPTE-UKS. The outflow from the ionosphere is two orders of magnitude greater than predicted for the "classical" polar wind. It is shown that such ionospheric ion flows are only expected in association with FTEs on the magnetopause which are well removed from the sub-solar point-either towards dusk or, as in the UKS example discussed here, towards dawn. It is suggested that such ionospheric ions will only be observed if the center of the FTE open flux tube passes very close to the satellite. Consequently, we conclude the ion upflows presented here are probably driven by the second of two possible source FTEs and are observed at the satellite with a lag after the FTE which is less than their time-of-flight.
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One of the prerequisites for achieving skill in decadal climate prediction is to initialize and predict the circulation in the Atlantic Ocean successfully. The RAPID array measures the Atlantic Meridional Overturning Circulation (MOC) at 26°N. Here we develop a method to include these observations in the Met Office Decadal Prediction System (DePreSys). The proposed method uses covariances of overturning transport anomalies at 26°N with ocean temperature and salinity anomalies throughout the ocean to create the density structure necessary to reproduce the observed transport anomaly. Assimilating transport alone in this way effectively reproduces the observed transport anomalies at 26°N and is better than using basin-wide temperature and salinity observations alone. However, when the transport observations are combined with in situ temperature and salinity observations in the analysis, the transport is not currently reproduced so well. The reasons for this are investigated using pseudo-observations in a twin experiment framework. Sensitivity experiments show that the MOC on monthly time-scales, at least in the HadCM3 model, is modulated by a mechanism where non-local density anomalies appear to be more important for transport variability at 26°N than local density gradients.
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In general, particle filters need large numbers of model runs in order to avoid filter degeneracy in high-dimensional systems. The recently proposed, fully nonlinear equivalent-weights particle filter overcomes this requirement by replacing the standard model transition density with two different proposal transition densities. The first proposal density is used to relax all particles towards the high-probability regions of state space as defined by the observations. The crucial second proposal density is then used to ensure that the majority of particles have equivalent weights at observation time. Here, the performance of the scheme in a high, 65 500 dimensional, simplified ocean model is explored. The success of the equivalent-weights particle filter in matching the true model state is shown using the mean of just 32 particles in twin experiments. It is of particular significance that this remains true even as the number and spatial variability of the observations are changed. The results from rank histograms are less easy to interpret and can be influenced considerably by the parameter values used. This article also explores the sensitivity of the performance of the scheme to the chosen parameter values and the effect of using different model error parameters in the truth compared with the ensemble model runs.
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Operational forecasting centres are currently developing data assimilation systems for coupled atmosphere-ocean models. Strongly coupled assimilation, in which a single assimilation system is applied to a coupled model, presents significant technical and scientific challenges. Hence weakly coupled assimilation systems are being developed as a first step, in which the coupled model is used to compare the current state estimate with observations, but corrections to the atmosphere and ocean initial conditions are then calculated independently. In this paper we provide a comprehensive description of the different coupled assimilation methodologies in the context of four dimensional variational assimilation (4D-Var) and use an idealised framework to assess the expected benefits of moving towards coupled data assimilation. We implement an incremental 4D-Var system within an idealised single column atmosphere-ocean model. The system has the capability to run both strongly and weakly coupled assimilations as well as uncoupled atmosphere or ocean only assimilations, thus allowing a systematic comparison of the different strategies for treating the coupled data assimilation problem. We present results from a series of identical twin experiments devised to investigate the behaviour and sensitivities of the different approaches. Overall, our study demonstrates the potential benefits that may be expected from coupled data assimilation. When compared to uncoupled initialisation, coupled assimilation is able to produce more balanced initial analysis fields, thus reducing initialisation shock and its impact on the subsequent forecast. Single observation experiments demonstrate how coupled assimilation systems are able to pass information between the atmosphere and ocean and therefore use near-surface data to greater effect. We show that much of this benefit may also be gained from a weakly coupled assimilation system, but that this can be sensitive to the parameters used in the assimilation.
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Tracking the formation and full evolution of polar cap ionization patches in the polar ionosphere, we directly observe the full Dungey convection cycle for southward interplanetary magnetic field (IMF) conditions. This enables us to study how the Dungey cycle influences the patches’ evolution. The patches were initially segmented from the dayside storm enhanced density plume at the equatorward edge of the cusp, by the expansion and contraction of the polar cap boundary due to pulsed dayside magnetopause reconnection, as indicated by in situ Time History of Events and Macroscale Interactions during Substorms(THEMIS) observations. Convection led to the patches entering the polar cap and being transported antisunward, while being continuously monitored by the globally distributed arrays of GPS receivers and Super Dual Auroral Radar Network radars. Changes in convection over time resulted in the patches following a range of trajectories, each of which differed somewhat from the classical twin-cell convection streamlines. Pulsed nightside reconnection, occurring as part of the magnetospheric substorm cycle, modulated the exit of the patches from the polar cap, as confirmed by coordinated observations of the magnetometer at Tromsø and European Incoherent Scatter Tromsø UHF radar. After exiting the polar cap, the patches broke up into a number of plasma blobs and returned sunward in the auroral return flow of the dawn and/or dusk convection cell. The full circulation time was about 3 h.
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Metal-organic frameworks (MOFs) can be exceptionally good catalytic materials thanks to the presence of active metal centres and a porous structure that is advantageous for molecular adsorption and confinement. We present here a first-principles investigation of the electronic structure of a family of MOFs based on porphyrins connected through phenyl-carboxyl ligands and AlOH species, in order to assess their suitability for the photocatalysis of fuel production reactions using sunlight. We consider structures with protonated porphyrins and those with the protons exchanged with late 3d metal cations (Fe2+, Co2+, Ni2+, Cu2+, Zn2+), a process that we find to be thermodynamically favorable from aqueous solution for all these metals. Our band structure calculations, based on an accurate screened hybrid functional, reveal that the bandgaps are in a favorable range (2.0 to 2.6 eV) for efficient adsorption of solar light. Furthermore, by approximating the vacuum level to the pore center potential, we provide the alignment of the MOFs’ band edges with the redox potentials for water splitting and carbon dioxide reduction, and show that the structures studied here have band edges positions suitable for these reactions at neutral pH.
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Electrical methods of geophysical survey are known to produce results that are hard to predict at different times of the year, and under differing weather conditions. This is a problem which can lead to misinterpretation of archaeological features under investigation. The dynamic relationship between a ‘natural’ soil matrix and an archaeological feature is a complex one, which greatly affects the success of the feature’s detection when using active electrical methods of geophysical survey. This study has monitored the gradual variation of measured resistivity over a selection of study areas. By targeting difficult to find, and often ‘missing’ electrical anomalies of known archaeological features, this study has increased the understanding of both the detection and interpretation capabilities of such geophysical surveys. A 16 month time-lapse study over 4 archaeological features has taken place to investigate the aforementioned detection problem across different soils and environments. In addition to the commonly used Twin-Probe earth resistance survey, electrical resistivity imaging (ERI) and quadrature electro-magnetic induction (EMI) were also utilised to explore the problem. Statistical analyses have provided a novel interpretation, which has yielded new insights into how the detection of archaeological features is influenced by the relationship between the target feature and the surrounding ‘natural’ soils. The study has highlighted both the complexity and previous misconceptions around the predictability of the electrical methods. The analysis has confirmed that each site provides an individual and nuanced situation, the variation clearly relating to the composition of the soils (particularly pore size) and the local weather history. The wide range of reasons behind survey success at each specific study site has been revealed. The outcomes have shown that a simplistic model of seasonality is not universally applicable to the electrical detection of archaeological features. This has led to the development of a method for quantifying survey success, enabling a deeper understanding of the unique way in which each site is affected by the interaction of local environmental and geological conditions.
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Observations from the Heliospheric Imager (HI) instruments aboard the twin STEREO spacecraft have enabled the compilation of several catalogues of coronal mass ejections (CMEs), each characterizing the propagation of CMEs through the inner heliosphere. Three such catalogues are the Rutherford Appleton Laboratory (RAL)-HI event list, the Solar Stormwatch CME catalogue, and, presented here, the J-tracker catalogue. Each catalogue uses a different method to characterize the location of CME fronts in the HI images: manual identification by an expert, the statistical reduction of the manual identifications of many citizen scientists, and an automated algorithm. We provide a quantitative comparison of the differences between these catalogues and techniques, using 51 CMEs common to each catalogue. The time-elongation profiles of these CME fronts are compared, as are the estimates of the CME kinematics derived from application of three widely used single-spacecraft-fitting techniques. The J-tracker and RAL-HI profiles are most similar, while the Solar Stormwatch profiles display a small systematic offset. Evidence is presented that these differences arise because the RAL-HI and J-tracker profiles follow the sunward edge of CME density enhancements, while Solar Stormwatch profiles track closer to the antisunward (leading) edge. We demonstrate that the method used to produce the time-elongation profile typically introduces more variability into the kinematic estimates than differences between the various single-spacecraft-fitting techniques. This has implications for the repeatability and robustness of these types of analyses, arguably especially so in the context of space weather forecasting, where it could make the results strongly dependent on the methods used by the forecaster.
Examining the relationships between Holocene climate change, hydrology, and human society in Ireland
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This thesis explores human-environment interactions during the Mid-Late Holocene in raised bogs in central Ireland. The raised bogs of central Ireland are widely-recognised for their considerable palaeoenvironmental and archaeological resources: research over the past few decades has established the potential for such sites to preserve sensitive records of Holocene climatic variability expressed as changes in bog surface wetness (BSW); meanwhile archaeological investigations over the past century have uncovered hundreds of peatland archaeological features dating from the Neolithic through to the Post-Medieval period including wooden trackways, platforms, and deposits of high-status metalwork. Previous studies have attempted to explore the relationship between records of past environmental change and the occurrence of peatland archaeological sites reaching varying conclusions. More recently, environmentally-deterministic models of human-environment interaction in Irish raised bogs at the regional scale have been explicitly tested leading to the conclusion that there is no relationship between BSW and past human activity. These relationships are examined in more detail on a site-by-site basis in this thesis. To that end, testate amoebae-derived BSW records from nine milled former raised bogs in central Ireland were produced from sites with known and dated archaeological records. Relationships between BSW records and environmental conditions within the study area were explored through both the development of a new central Ireland testate amoebae transfer function and through comparisons between recent BSW records and instrumental weather data. Compilation of BSW records from the nine fossil study sites show evidence both for climate forcing, particularly during 3200-2400 cal BP, as well as considerable inter-site variability. Considerable inter-site variability was also evident in the archaeological records of the same sites. Whilst comparisons between BSW and archaeological records do not show a consistent linear relationship, examination of records on a site-by-site basis were shown to reveal interpretatively important contingent relationships. It is concluded therefore, that future research on human-environment interactions should focus on individual sites and should utilise theoretical approaches from the humanities in order to avoid the twin pitfalls of masking important local patterns of change, and of environmental determinism.
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David Arnold who retired this year as the Professor of Asian and Global History at the University of Warwick remains one of the most prolific historians of colonial medicine and modern South Asia. A founding member of the subaltern studies collective, he is considered widely as a pioneer in the histories of colonial medicine, environment, penology, hunger and famines within South Asian studies and beyond. In this interview he recalls his formative inspirations, ideological motivations and reflects critically on his earlier works, explaining various shifts as well as map- ping the possible course of future work. He talks at length about his forthcoming works on everyday technology, food and monsoon Asia. Finally, he shares with us his desire of initiating work on an ambitious project about the twin themes of poison and poverty in South Asian his- tory, beginning with the Bengal famine in the late eighteenth century and ending with the Bhopal gas tragedy of the early 1980s. This conversation provides insights into the ways in which the field of medical history in modern South Asia has been shaped over the past three decades through interactions with broader discussions on agency, resistance, power, everydayness, subal- tern studies, global and spatial histories. It hints further at the newer directions which are being opened up by such persisting intellectual entanglements.