Nature of band-gap states in V-doped TiO2 revealed by resonant photoemission

Band-gap states in V-doped TiO2 have been studied by photoemission spectroscopy over a range of photon energies encompassing the Ti 3p and V 3p core thresholds. The states show resonant enhancement at photon energies significantly higher than found for Ti 3d states introduced into TiO2 by oxygen deficiency or alkalimetal adsorbates. This demonstrates that the gap states relate to electrons trapped on dopant V cations rather than host Ti cations

Annually resolved patterns of summer temperature over the Northern Hemisphere since AD 1400 from a tree-ring-density network

The development of annually-resolved estimates of summer temperature patterns over the mid-to-high latitudes of the Northern Hemisphere land masses is described. The estimates were derived from a calibration of an extensive network of tree-ring density chronologies, with data extending back as far as 1400 (though with greatly reduced spatial coverage prior to 1600). The chronology data were first gridded onto a 5° longitude by 5° latitude grid, followed by a local calibration and verification of each grid box series against observed April-to-September mean temperatures. It was demonstrated that calibration by simple linear regression of individual grid boxes in isolation (i.e., without using any non-local proxy or temperature information) yields a spatial reconstruction with suppressed variance when averaged over large areas. The local calibration was adapted, therefore, to ensure that the magnitude of sub-continental, regional-scale variations is realistically maintained, while still achieving significant skill at the grid-box scale. A second version of the reconstructed grids was also generated, by incorporating additional variations on century time scales that may have been removed by the original standardisation of the tree-ring density chronologies. The spatial extent of both versions (with and without the additional low-frequency variability) was extended using principal component regression, for all locations where a verification correlation of 0.4 or above was achieved. These reconstructions of summer temperature have significant skill, with an overall space-time correlation of around 0.7 for both the calibration and verification against observed temperatures

The mechanisms of North Atlantic CO2 uptake in a large Earth System Model ensemble

The oceans currently take up around a quarter of the carbon dioxide (CO2) emitted by human activity. While stored in the ocean, this CO2 is not influencing Earth's radiation budget; the ocean CO2 sink therefore plays an important role in mitigating global warming. CO2 uptake by the oceans is heterogeneous, with the subpolar North Atlantic being the strongest CO2 sink region. Observations over the last 2 decades have indicated that CO2 uptake by the subpolar North Atlantic sink can vary rapidly. Given the importance of this sink and its apparent variability, it is critical that we understand the mechanisms behind its operation. Here we explore the combined natural and anthropogenic subpolar North Atlantic CO2 uptake across a large ensemble of Earth System Model simulations, and find that models show a peak in sink strength around the middle of the century after which CO2 uptake begins to decline. We identify different drivers of change on interannual and multidecadal timescales. Short-term variability appears to be driven by fluctuations in regional seawater temperature and alkalinity, whereas the longer-term evolution throughout the coming century is largely occurring through a counterintuitive response to rising atmospheric CO2 concentrations. At high atmospheric CO2 concentrations the contrasting Revelle factors between the low latitude water and the subpolar gyre, combined with the transport of surface waters from the low latitudes to the subpolar gyre, means that the subpolar CO2 uptake capacity is largely satisfied from its southern boundary rather than through air-sea CO2 flux. Our findings indicate that: (i) we can explain the mechanisms of subpolar North Atlantic CO2 uptake variability across a broad range of Earth System Models; (ii) a focus on understanding the mechanisms behind contemporary variability may not directly tell us about how the sink will change in the future; (iii) to identify long-term change in the North Atlantic CO2 sink we should focus observational resources on monitoring lower latitude as well as the subpolar seawater CO2; (iv) recent observations of a weakening subpolar North Atlantic CO2 sink may suggest that the sink strength has peaked and is in long-term decline.This work was supported by the EU FP7 Collaborative Project CarboOcean (Grant Agreement Number 264879), the Joint DECC/Defra Met Office Hadley Centre Climate Programme (GA01101), and the NERC directed research programme RAGNARoCC (NE/K002473/1)

Using digital technology to protect health in prolonged poor air quality episodes: a case study of the AirRater App during the Australian 2019–20 fires

In the southern hemisphere summer of 2019–20, Australia experienced its most severe bushfire season on record. Smoke from fires affected 80% of the population, with large and prolonged exceedances of the Australian National Air Quality Standard for fine particulate matter (PM2.5) recorded in all major population centers. We examined if AirRater, a free smartphone app that reports air quality and tracks user symptoms in near real‐time, assisted those populations to reduce their smoke exposure and protect their health. We distributed an online survey to over 13,000 AirRater users to assess how they used this information during the 2019-20 bushfire season, and why it was helpful to aid decision‐making in reducing personal smoke exposure. We received responses from 1732 users (13.3%). Respondents reported the app was highly useful, supporting informed decision‐making regarding daily activities during the smoke‐affected period. Commonly reported activities supported by information provided through the app were staying inside (76%), rescheduling or planning outdoor activities (64%), changing locations to less affected areas (29%) and informing decisions on medication use (15%). Innovative and easy‐to‐use smartphone apps such as AirRater, that provide individual‐level and location‐specific data, can enable users to reduce their exposure to environmental hazards and therefore protect their health

Smoke pollution must be part of the savanna fire management equation: a case study from Darwin, Australia

Savanna fire management is a topic of global debate, with early dry season burning promoted as a large-scale emissions reduction opportunity. To date, discussions have centred on carbon abatement efficacy, biodiversity and cultural benefits and/or risks. Here we use a case study of Darwin, Australia to highlight smoke pollution as another critical consideration. Smoke pollution from savanna fires is a major public health issue, yet absent so far from discussions of program design. Here, we assess the likely impacts of increased early dry season burning on smoke pollution in Darwin between 2004 and 2019, spanning the introduction and expansion of carbon abatement programs. We found increased smoke pollution in the early dry season but little change in the late dry season, contributing to a net annual increase in air quality standard exceedances. Geospatial analysis suggests this relates to increased burning in the path of early dry season trade winds. This study highlights the complex health trade-offs involved with any large-scale prescribed burning, including for carbon abatement

Effects of serum proteins on corrosion behavior of ISO 5832–9 alloy modified by titania coatings

Stainless steel ISO 5832–9 type is often used to perform implants which operate in protein-containing physiological environments. The interaction between proteins and surface of the implant may affect its corrosive properties. The aim of this work was to study the effect of selected serum proteins (albumin and γ-globulins) on the corrosion of ISO 5832–9 alloy (trade name M30NW) which surface was modified by titania coatings. These coatings were obtained by sol– gel method and heated at temperatures of 400 and 800 °C. To evaluate the effect of the proteins, the corrosion tests were performed with and without the addition of proteins with concentration of 1 g L−1 to the physiological saline solution (0.9 % NaCl, pH 7.4) at 37 °C. The tests were carried out within 7 days. The following electrochemical methods were used: open circuit potential, linear polarization resistance, and electrochemical impedance spectroscopy. In addition, surface analysis by optical microscopy and X-ray photoelectron spectroscopy (XPS) method was done at the end of weekly corrosion tests. The results of corrosion tests showed that M30NW alloy both uncoated and modified with titania coatings exhibits a very good corrosion resistance during weekly exposition to corrosion medium. The best corrosion resistance in 0.9 % NaCl solution is shown by alloy samples modified by titania coating annealed at 400 °C. The serumproteins have no significant effect onto corrosion of investigated biomedical steel. The XPS results confirmed the presence of proteins on the alloy surface after 7 days of immersion in proteincontaining solutions.The investigations were supported by the National Science Centre project No. N N507 501339. The authors gratefully acknowledge Dr. Janusz Sobczak and Dr. hab. Wojciech Lisowski from Institute of Physical Chemistry of PAS for XPS surface analyses

New insights into atypical Alzheimer's disease in the era of biomarkers

Most patients with Alzheimer's disease present with amnestic problems; however, a substantial proportion, over-represented in young-onset cases, have atypical phenotypes including predominant visual, language, executive, behavioural, or motor dysfunction. In the past, these individuals often received a late diagnosis; however, availability of CSF and PET biomarkers of Alzheimer's disease pathologies and incorporation of atypical forms of Alzheimer's disease into new diagnostic criteria increasingly allows them to be more confidently diagnosed early in their illness. This early diagnosis in turn allows patients to be offered tailored information, appropriate care and support, and individualised treatment plans. These advances will provide improved access to clinical trials, which often exclude atypical phenotypes. Research into atypical Alzheimer's disease has revealed previously unrecognised neuropathological heterogeneity across the Alzheimer's disease spectrum. Neuroimaging, genetic, biomarker, and basic science studies are providing key insights into the factors that might drive selective vulnerability of differing brain networks, with potential mechanistic implications for understanding typical late-onset Alzheimer's disease

A new rhynchocephalian from the late jurassic of Germany with a dentition that is unique amongst tetrapods.

Rhynchocephalians, the sister group of squamates (lizards and snakes), are only represented by the single genus Sphenodon today. This taxon is often considered to represent a very conservative lineage. However, rhynchocephalians were common during the late Triassic to latest Jurassic periods, but rapidly declined afterwards, which is generally attributed to their supposedly adaptive inferiority to squamates and/or Mesozoic mammals, which radiated at that time. New finds of Mesozoic rhynchocephalians can thus provide important new information on the evolutionary history of the group. A new fossil relative of Sphenodon from the latest Jurassic of southern Germany, Oenosaurus muehlheimensis gen. et sp. nov., presents a dentition that is unique amongst tetrapods. The dentition of this taxon consists of massive, continuously growing tooth plates, probably indicating a crushing dentition, thus representing a previously unknown trophic adaptation in rhynchocephalians. The evolution of the extraordinary dentition of Oenosaurus from the already highly specialized Zahnanlage generally present in derived rhynchocephalians demonstrates an unexpected evolutionary plasticity of these animals. Together with other lines of evidence, this seriously casts doubts on the assumption that rhynchocephalians are a conservative and adaptively inferior lineage. Furthermore, the new taxon underlines the high morphological and ecological diversity of rhynchocephalians in the latest Jurassic of Europe, just before the decline of this lineage on this continent. Thus, selection pressure by radiating squamates or Mesozoic mammals alone might not be sufficient to explain the demise of the clade in the Late Mesozoic, and climate change in the course of the fragmentation of the supercontinent of Pangaea might have played a major role

An 11th century a.d. burnt granary at La Gravette, south-western France : preliminary archaeobotanical results

International audienceA thick layer of carbonised seeds was encountered in an 11th century a.d. room situated in the seigneurial part of the village of La Gravette. This paper presents the first results of charcoal and seed analyses which give information on the food products stored in the granary and on their arrangement there. Triticum aestivum/durum/turgidum was by far the most important stored crop, while Avena sp., then Hordeum vulgare, Secale cereale, Triticum monococcum and Vitis vinifera were secondary. Weeds were poorly represented. Charcoals were dominated by deciduous Quercus sp., and 11 additional wood taxa were recorded, including especially Fagus sylvatica, Fraxinus sp., Rosaceae, Corylus avellana, Acer campestre and Ulmus sp. According to the charcoal distribution, Quercus and Fagus were probably building materials while most of other taxa would have been used for basketry, wattling or joinery work. In the western part of the granary, naked wheat was stored in bulk. In the eastern part, various crops (at least naked wheat, barley, rye, oat and grape) were stored in small amounts, most of which were probably separated by light wooden structures. The cereal crops had largely been processed and cleaned. The stored products probably represent taxes paid to the lord who owned the granary

Reducing bias in auditory duration reproduction by integrating the reproduced signal

Duration estimation is known to be far from veridical and to differ for sensory estimates and motor reproduction. To investigate how these differential estimates are integrated for estimating or reproducing a duration and to examine sensorimotor biases in duration comparison and reproduction tasks, we compared estimation biases and variances among three different duration estimation tasks: perceptual comparison, motor reproduction, and auditory reproduction (i.e. a combined perceptual-motor task). We found consistent overestimation in both motor and perceptual-motor auditory reproduction tasks, and the least overestimation in the comparison task. More interestingly, compared to pure motor reproduction, the overestimation bias was reduced in the auditory reproduction task, due to the additional reproduced auditory signal. We further manipulated the signal-to-noise ratio (SNR) in the feedback/comparison tones to examine the changes in estimation biases and variances. Considering perceptual and motor biases as two independent components, we applied the reliability-based model, which successfully predicted the biases in auditory reproduction. Our findings thus provide behavioral evidence of how the brain combines motor and perceptual information together to reduce duration estimation biases and improve estimation reliability