Sulphide sinking in magma conduits: Evidence from mafic–ultramafic plugs on Rum and the wider North Atlantic Igneous Province

This is the final version of the article. Available from the publisher via the DOI in this record.Ni–Cu–PGE (platinum group element) sulphide mineralization is commonly found in magmatic conduit systems. In many cases the trigger for formation of an immiscible sulphide liquid involves assimilation of S-bearing crustal rocks. Conceptually, the fluid dynamics of sulphide liquid droplets within such conduits is essentially a balance between gravitational sinking and upwards entrainment. Thus, crustal contamination signatures may be present in sulphides preserved both up- and down-flow from the point of interaction with the contaminant. We examine a suite of ultramafic volcanic plugs on the Isle of Rum, Scotland, to decipher controls on sulphide accumulation in near-surface magma conduits intruded into a variable sedimentary stratigraphy. The whole-rock compositions of the plugs broadly overlap with the compositions of ultramafic units within the Rum Layered Complex, although subtle differences between each plug highlight their individuality. Interstitial base metal sulphide minerals occur in all ultramafic plugs on Rum. Sulphide minerals have magmatic δ34S (ranging from –1·3 to +2·1‰) and S/Se ratios (mean = 2299), and demonstrate that the conduit magmas were already S-saturated. However, two plugs in NW Rum contain substantially coarser (sometimes net-textured) sulphides with unusually light δ34S (–14·7 to +0·3‰) and elevated S/Se ratios (mean = 4457), not represented by the immediate host-rocks. Based on the Hebrides Basin sedimentary stratigraphy, it is likely that the volcanic con duits would have intruded through a package of Jurassic mudrocks with characteristically light δ34S (–33·8 to –14·7‰). We propose that a secondary crustal S contamination event took place at a level above that currently exposed, and that these sulphides sank back to their present position. Modelling suggests that upon the cessation of active magma transport, sulphide liquids could have sunk back through the conduit over a distance of several hundreds of metres, over a period of a few days. This sulphide ‘withdrawal’ process may be observed in other vertical or steeply inclined magma conduits globally; for example, in the macrodykes of East Greenland. Sulphide liquid sinking within a non-active conduit or during magma ‘suck-back’ may help to explain crustal S-isotopic compositions in magma conduits that appear to lack appropriate lithologies to support this contamination, either locally or deeper in the system.Sulphur isotope analyses were funded by NERC Isotope Geosciences Facilities grant, IP-1356-1112. H.S.R.H. acknowledges the financial support of the Natural Environment Research Council (NERC) for her PhD studentship (NE/J50029X) and funding of open access publication. This is a contribution to the TeaSe (Te and Se Cycling and Supply) research consortium supported by NERC award NE/M011615/1 to Cardiff University and the University of Leicester

Chemical Modification of Polaronic States in Anatase TiO2(101)

Two polymorphs of TiO2, anatase and rutile, are employed in photocatalytic applications. It is broadly accepted that anatase is the more catalytically active and subsequently finds wider commercial use. In this work, we focus on the Ti3+ polaronic states of anatase TiO2(101), which lie at ∼1.0 eV binding energy and are known to increase catalytic performance. Using UV-photoemission and two-photon photoemission spectroscopies, we demonstrate the capability to tune the excited state resonance of polarons by controlling the chemical environment. Anatase TiO2(101) contains subsurface polarons which undergo sub-band-gap photoexcitation to states ∼2.0 eV above the Fermi level. Formic acid adsorption dramatically influences the polaronic states, increasing the binding energy by ∼0.3 eV. Moreover, the photoexcitation oscillator strength changes significantly, resonating with states ∼3.0 eV above the Fermi level. We show that this behavior is likely due to the surface migration of subsurface oxygen vacancies

Developing and validating a cardiovascular risk score for patients in the community with prior cardiovascular disease

OBJECTIVE: Patients with atherosclerotic cardiovascular disease (CVD) vary significantly in their risk of future CVD events; yet few clinical scores are available to aid assessment of risk. We sought to develop a score for use in primary care that estimates short-term CVD risk in these patients. METHODS: Adults aged <80 years with prior CVD were identified from a New Zealand primary care cohort study (PREDICT), and linked to national mortality, hospitalisation and dispensing databases. A Cox model with an outcome of myocardial infarction, stroke or CVD death within 2 years was developed. External validation was performed in a cohort from the UK. RESULTS: 24 927 patients, 63% men, 63% European, median age 65 years (IQR 58-72 years), experienced 1480 CVD events within 2 years after a CVD risk assessment. A risk score including ethnicity, comorbidities, body mass index, creatine creatinine and treatment, in addition to established risk factors used in primary prevention, predicted a median 2-year CVD risk of 5.0% (IQR 3.5%-8.3%). A plot of actual against predicted event rates showed very good calibration throughout the risk range. The score performed well in the UK cohort but overestimated risk for those at highest risk, who were predominantly patients defined as having heart failure. CONCLUSIONS: The PREDICT-CVD secondary prevention score uses routine measurements from clinical practice that enable it to be implemented in a primary care setting. The score will facilitate risk communication between primary care practitioners and patients with prior CVD, particularly as a resource to show the benefit of risk factor modification

On Convergence and Threshold Properties of Discrete Lotka-Volterra Population Protocols

In this work we focus on a natural class of population protocols whose dynamics are modelled by the discrete version of Lotka-Volterra equations. In such protocols, when an agent $a$ of type (species) $i$ interacts with an agent $b$ of type (species) $j$ with $a$ as the initiator, then $b$'s type becomes $i$ with probability $P\_{ij}$. In such an interaction, we think of $a$ as the predator, $b$ as the prey, and the type of the prey is either converted to that of the predator or stays as is. Such protocols capture the dynamics of some opinion spreading models and generalize the well-known Rock-Paper-Scissors discrete dynamics. We consider the pairwise interactions among agents that are scheduled uniformly at random. We start by considering the convergence time and show that any Lotka-Volterra-type protocol on an $n$-agent population converges to some absorbing state in time polynomial in $n$, w.h.p., when any pair of agents is allowed to interact. By contrast, when the interaction graph is a star, even the Rock-Paper-Scissors protocol requires exponential time to converge. We then study threshold effects exhibited by Lotka-Volterra-type protocols with 3 and more species under interactions between any pair of agents. We start by presenting a simple 4-type protocol in which the probability difference of reaching the two possible absorbing states is strongly amplified by the ratio of the initial populations of the two other types, which are transient, but "control" convergence. We then prove that the Rock-Paper-Scissors protocol reaches each of its three possible absorbing states with almost equal probability, starting from any configuration satisfying some sub-linear lower bound on the initial size of each species. That is, Rock-Paper-Scissors is a realization of a "coin-flip consensus" in a distributed system. Some of our techniques may be of independent value

Revealing lithium-silicide phase transformations in nano-structured silicon-based lithium ion batteries via in situ NMR spectroscopy.

Nano-structured silicon anodes are attractive alternatives to graphitic carbons in rechargeable Li-ion batteries, owing to their extremely high capacities. Despite their advantages, numerous issues remain to be addressed, the most basic being to understand the complex kinetics and thermodynamics that control the reactions and structural rearrangements. Elucidating this necessitates real-time in situ metrologies, which are highly challenging, if the whole electrode structure is studied at an atomistic level for multiple cycles under realistic cycling conditions. Here we report that Si nanowires grown on a conducting carbon-fibre support provide a robust model battery system that can be studied by (7)Li in situ NMR spectroscopy. The method allows the (de)alloying reactions of the amorphous silicides to be followed in the 2nd cycle and beyond. In combination with density-functional theory calculations, the results provide insight into the amorphous and amorphous-to-crystalline lithium-silicide transformations, particularly those at low voltages, which are highly relevant to practical cycling strategies.K.O acknowledges a research fellowship from Japanese Society for the Promotion of Science (JSPS). E.S acknowledges support by a Marie Curie Intra European Fellowship within the 7th European Community Framework Programme and thanks Churchill College (Cambridge, UK) for a non-stipendiary Raymond and Beverly Sackler Research fellowship. C.J.K and A.E.F acknowledge a research studentship from the Cambridge Nano Science and Technology Doctoral Training Centre (NanoDTC). A.J.M acknowledges the support from the Winton Programme for the Physics of Sustainability. S.H acknowledges funding from ERC grant InsituNANO (project number 279342). C.P.G and C.D thank the Royal Society, and C.P.G thanks European Research Council (ERC). C.P.G. acknowledges support from the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies of the U.S. Department of Energy, under Contract DE-AC02-05CH11231, subcontract 6952000.This is the accepted manuscript. The final version is available from Nature Communications at http://www.nature.com/ncomms/2014/140203/ncomms4217/full/ncomms4217.html

In the interests of time: Improving HIV allocative efficiency modelling via optimal time-varying allocations

Introduction: International investment in the response to HIV and AIDS has plateaued and its future level is uncertain. With many countries committed to ending the epidemic, it is essential to allocate available resources efficiently over different response periods to maximize impact. The objective of this study is to propose a technique to determine the optimal allocation of funds over time across a set of HIV programmes to achieve desirable health outcomes. Methods: We developed a technique to determine the optimal time-varying allocation of funds (1) when the future annual HIV budget is pre-defined and (2) when the total budget over a period is pre-defined, but the year-on-year budget is to be optimally determined. We use this methodology with Optima, an HIV transmission model that uses non-linear relationships between programme spending and associated programmatic outcomes to quantify the expected epidemiological impact of spending.We apply these methods to data collected from Zambia to determine the optimal distribution of resources to fund the right programmes, for the right people, at the right time. Results and discussion: Considering realistic implementation and ethical constraints, we estimate that the optimal time-varying redistribution of the 2014 Zambian HIV budget between 2015 and 2025 will lead to a 7.6% (7.3% to 7.8%) decrease in cumulative new HIV infections compared with a baseline scenario where programme allocations remain at 2014 levels. This compares to a 5.1% (4.6% to 5.6%) reduction in new infections using an optimal allocation with constant programme spending that recommends unrealistic programmatic changes. Contrasting priorities for programme funding arise when assessing outcomes for a five-year funding period over 5-, 10- and 20-year time horizons. Conclusions: Countries increasingly face the need to do more with the resources available. The methodology presented here can aid decision-makers in planning as to when to expand or contract programmes and to which coverage levels to maximize impact

Mapping the UK renal psychosocial workforce : the first comprehensive workforce survey

Background: Emerging evidence of psychosocial problems in CKD patients has led to an acceptance that a focus on the emotional wellbeing of the patient should be included in the provision of comprehensive CKD care. It is unclear if an increased attention for psychosocial needs in guidelines and policy documents has led to a rise in psychosocial staffing levels or change in composition of staff since the last workforce mapping in 2002. This paper offers a critical analysis and in-depth discussion of findings and their implications, in addition to providing an international perspective and exposing gaps in current knowledge. Methods: Data on psychosocial staffing levels was taken from a survey based on the Scottish Renal Association’s (SRA) staffing survey that was sent to all units in England, Wales and Northern-Ireland in 2016. In addition, data from a psychosocial staffing survey designed by and distributed via psychosocial professional groups was used. This data was then completed with Freedom of Information (FOI) requests and collated to describe the current renal psychosocial workforce in all 84 UK renal units. This was compared to results from the last renal workforce mapping in 2002. Results: The results from this mapping show great variability in models of service provision, significant exceeding of benchmarks for staffing levels, and a change in staffing patterns over the past 15 years. Adult psychology services have increased in number, but provision remains low due to increased patient numbers, whereas adult social work and paediatric services have decreased. Conclusion: A lack in the provision of renal psychosocial services has been identified, together with the absence of a general service provision model. These findings provide a valuable benchmark for units, a context from which to review and monitor provision alongside patient need. Along with recommendations, this paper forms a foundation for future research and workforce planning. Research into best practice models of service provision and the psychosocial needs of CKD patients lies at the heart of the answers to many identified questions

Regions identity between the genome of vertebrates and non-retroviral families of insect viruses

<p>Abstract</p> <p>Background</p> <p>The scope of our understanding of the evolutionary history between viruses and animals is limited. The fact that the recent availability of many complete insect virus genomes and vertebrate genomes as well as the ability to screen these sequences makes it possible to gain a new perspective insight into the evolutionary interaction between insect viruses and vertebrates. This study is to determine the possibility of existence of sequence identity between the genomes of insect viruses and vertebrates, attempt to explain this phenomenon in term of genetic mobile element, and try to investigate the evolutionary relationship between these short regions of identity among these species.</p> <p>Results</p> <p>Some of studied insect viruses contain variable numbers of short regions of sequence identity to the genomes of vertebrate with nucleotide sequence length from 28 bp to 124 bp. They are found to locate in multiple sites of the vertebrate genomes. The ontology of animal genes with identical regions involves in several processes including chromatin remodeling, regulation of apoptosis, signaling pathway, nerve system development and some enzyme-like catalysis. Phylogenetic analysis reveals that at least some short regions of sequence identity in the genomes of vertebrate are derived the ancestral of insect viruses.</p> <p>Conclusion</p> <p>Short regions of sequence identity were found in the vertebrates and insect viruses. These sequences played an important role not only in the long-term evolution of vertebrates, but also in promotion of insect virus. This typical win-win strategy may come from natural selection.</p