Manipulation of Fischer Tropsch Catalysts for Controlled Selectivity: Investigating the role of a Manganese Dopant

Cobalt-based Fischer-Tropsch (FT) catalysts are widely used to convert syngas to long-chain hydrocarbons. Recently, significant increases in alcohol selectivity have been reported with high manganese doping. In this work, commercially relevant catalyst extrusions have been studied by synchrotron X-ray Diffraction Computed Tomography (XRD-CT) during catalyst activation and operation to understand the evolution of crystalline phases of cobalt nanoparticles supported on TiO2 with various manganese doping levels (up to 10 wt. %). Data processing pipelines have been developed to assist in the Rietveld refinement of large quantities of diffraction data to provide quantitative metrics for the spatially and temporally resolved diffraction results. A high pressure cell and testing methodology have been developed to conduct operando studies at relevant pressures (25 bar) and temperatures on an imaging beamline, with the potential to operate multiple samples simultaneously to maximise runtime and operation utilisation while removing inter-run variability. Since a large proportion of the Mn dopant tends to be highly disperse, a series of model catalyst systems were developed to evaluate different catalyst-dopant interactions and doping levels. A modified salt-mediated hydrothermal synthesis was used to produce Co3O4 nanoparticles which either comprised a Co-Mn spinel solid solution, manganese surface coated Co3O4 particles or physical mixtures of Co3O4 and Mn3O4. These systems were produced with various Co:Mn ratios to correspond to the commercially relevant extrusions, before being supported on TiO2. The resulting catalysts were characterised via XRD and STEM and tested for FT activity and selectivity to understand what type of interaction, and what ratios of Co:Mn, are required to produce significant quantities of alcohol products under typical FT conditions. The % Mn requirements for alcohol selectivity in the commercially relevant catalysts correspond to the model systems where the cobalt and manganese were closely interacting. The development of the model systems also provides effective reference materials for comparison of characterisation results with the commercial catalyst samples

Smoking and looked-after children: a mixed-methods study of policy, practice, and perceptions relating to tobacco use in residential units

Despite the implementation of smoke-free policies by local authorities and a statutory requirement to promote the health and well-being of looked-after children and young people in England, rates of tobacco use by this population are substantially higher than in the general youth population. A mixed-methods study, comprising a survey of residential care officers in 15 local authority-operated residential units and semi-structured, face-to-face interviews with residential carers in three local authority-operated residential units, was conducted in the East Midlands. Survey data were descriptively analysed; and interview data were transcribed and analysed using thematic framework analysis. Forty-two care officers (18% response rate) completed the survey, and 14 participated in the interviews. Despite reporting substantial awareness of smoke-free policies, a lack of adherence and enforcement became apparent, and levels of reported training in relation to smoking and smoking cessation were low (21%). Potential problems relating to wider tobacco-related harms, such as exploitative relationships; a reliance on tacit knowledge; and pessimistic attitudes towards LAC quitting smoking, were indicated. The findings highlight the need for the development of comprehensive strategies to promote adherence to and enforcement of local smoke-free policy within residential units for looked-after children and young people, and to ensure appropriate support pathways are in place for this population

The influence of lateral advection on the residual estuarine circulation : a numerical modeling study of the Hudson River Estuary

Author Posting. © American Meteorological Society, 2009. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Physical Oceanography 39 (2009): 107-124, doi:10.1175/2008JPO3952.1.In most estuarine systems it is assumed that the dominant along-channel momentum balance is between the integrated pressure gradient and bed stress. Scaling the amplitude of the estuarine circulation based on this balance has been shown to have predictive skill. However, a number of authors recently highlighted important nonlinear processes that contribute to the subtidal dynamics at leading order. In this study, a previously validated numerical model of the Hudson River estuary is used to examine the forces driving the residual estuarine circulation and to test the predictive skill of two linear scaling relationships. Results demonstrate that the nonlinear advective acceleration terms contribute to the subtidal along-channel momentum balance at leading order. The contribution of these nonlinear terms is driven largely by secondary lateral flows. Under a range of forcing conditions in the model runs, the advective acceleration terms nearly always act in concert with the baroclinic pressure gradient, reinforcing the residual circulation. Despite the strong contribution of the nonlinear advective terms to the subtidal dynamical balance, a linear scaling accurately predicts the strength of the observed residual circulation in the model. However, this result is largely fortuitous, as this scaling does not account for two processes that are fundamental to the estuarine circulation. The skill of this scaling results because of the compensatory relationship between the contribution of the advective acceleration terms and the suppression of turbulence due to density stratification. Both of these processes, neither of which is accounted for in the linear scaling, increase the residual estuarine circulation but have an opposite dependence on tidal amplitude and, consequently, strength of stratification.This research was supported by the Beacon Institute for Rivers and Estuaries—Woods Hole Oceanographic Institution postdoctoral fellowship program, as well as NSF Grants OCE-0452054 and OCE-0451740

Sincerity, Hypocrisy, and Conspiracy Theory in the Occupied Palestinian Territory.

Concerns about lying and sincerity in politics are common in most societies, as are concerns about conspiracy theories. But in the occupied Palestinian territory, these concerns give rise to particular kinds of effects because of the conditions of Israeli occupation. Political theorists often interpret opacity claims and conspiracy theories as responses to social disorder. In occupied Palestine, disorder and instability are standard. Opacity claims and conspiracy theories therefore require a different kind of analysis. Through an examination of the semiotic ideology of sincerity, especially as it has emerged in the conflict between Fatah and Hamas, this article argues that opacity claims act as a form of nationalist pedagogy, at once reinforcing the basic principles of sincerity of action and word, and encouraging a wariness of political spin

Synthesis of global satellite observations of magmatic and volcanic deformation: implications for volcano monitoring & the lateral extent of magmatic domains

Global Synthetic Aperture Radar (SAR) measurements made over the past decades provide insights into the lateral extent of magmatic domains, and capture volcanic process on scales useful for volcano monitoring. Satellite-based SAR imagery has great potential for monitoring topographic change, the distribution of eruptive products and surface displacements (InSAR) at subaerial volcanoes. However, there are challenges in applying it routinely, as would be required for the reliable operational assessment of hazard. The deformation detectable depends upon satellite repeat time and swath widths, relative to the spatial and temporal scales of volcanological processes. We describe the characteristics of InSAR-measured volcano deformation over the past two decades, highlighting both the technique’s capabilities and its limitations as a monitoring tool. To achieve this, we draw on two global datasets of volcano deformation: the Smithsonian Institution Volcanoes of the World database and the Centre for the Observation and Modelling of Earthquakes, Volcanoes and Tectonics volcano deformation catalogue, as well as compiling some measurement characteristics and interpretations from the primary literature. We find that a higher proportion of InSAR observations capture non-eruptive and non-magmatic processes than those from ground-based instrument networks, and that both transient ( 5 years) deformation episodes are under-represented. However, satellite radar is already used to assess the development of extended periods of unrest and long-lasting eruptions, and improved spatial resolution and coverage have resulted in the detection of previously unrecognised deformation at both ends of the spatial scale (~ 10 to > 1000 km²). ‘Baseline’ records of past InSAR measurements, including ‘null’ results, are fundamental for any future interpretation of interferograms in terms of hazard‚ both by providing information about past deformation at an individual volcano, and for assessing the characteristics of deformation that are likely to be detectable (and undetectable) using InSAR. More than half of all InSAR deformation signals attributed to magmatic processes have sources in the shallow crust (< 5 km depth). While the depth distribution of InSAR-derived deformation sources is affected by measurement limitations, their lateral distribution provides information about the extent of active magmatic domains. Deformation is common (24% of all potentially magmatic events) at loci ≥5 km away from the nearest active volcanic vent. This demonstrates that laterally extensive active magmatic domains are not exceptional, but can comprise the shallowest part of trans-crustal magmatic systems in a range of volcanic settings

First observations of Weddell seals foraging in sponges in Erebus Bay, Antarctica

Attaching cameras to marine mammals allows for first-hand observation of underwater behaviours that may otherwise go unseen. While studying the foraging behaviour of 26 lactating Weddell seals (Leptonychotes weddellii) in Erebus Bay during the austral spring of 2018 and 2019, we witnessed three adults and one pup investigating the cavities of Rossellidae glass sponges, with one seal visibly chewing when she removed her head from the sponge. To our knowledge, this is the first report of such behaviour. While the prey item was not identifiable, some Trematomus fish (a known Weddell seal prey) use glass sponges for shelter and in which to lay their eggs. Three of the four sponge foraging observations occurred around 13:00 (NZDT). Two of the three sponge foraging adults had higher-than-average reproductive rates, and the greatest number of previous pups of any seal in our study population, each having ten pups in 12 years. This is far higher than the study population average of three previous pups (± 2.6 SD). This novel foraging strategy may have evolved in response to changes in prey availability, and could offer an evolutionary advantage to some individuals that exploit prey resources that others may not. Our observations offer new insight into the foraging behaviours of one of the world’s most studied marine mammals. Further research on the social aspects of Weddell seal behaviour may increase our understanding of the extent and mechanisms of behavioural transfer between conspecifics. Research into the specific foraging behaviour of especially successful or experienced breeders is also warranted

Synthesizing multi-sensor, multi-satellite, multi-decadal datasets for global volcano monitoring

Owing to practical limitations less than half of Earth's 1400 subaerial volcanoes have no ground monitoring and few are monitored consistently. Earth-observing satellite missions provide global and frequent measurements of volcanic activity that are closing these gaps in coverage. We compare databases of global, satellite-detections of ground deformation (1992–2016), SO₂ emissions (1978–2016), and thermal features (2000–2016) that together include 306 volcanoes. Each database has limitations in terms of spatial and temporal resolution but each technique contributed 45–86 unique detections of activity that were not detected by other techniques. Integration of these three databases shows that satellites detected ~10² volcanic activities per year before the year 2000 and ~103 activities per year after the year 2000. We find that most of the 54 erupting volcanoes without satellite-detections are associated with low volcano explosivity index eruptions and note that many of these eruptions (71%, 97/135) occurred in the earliest decades of remote sensing (pre-2000) when detection thresholds were high. From 1978 to 2016 we conduct a preliminary analysis of the timing between the onset of satellite-detections of deformation (N = 154 episodes, N = 71 volcanoes), thermal features (N = 16,544 episodes, N = 99 volcanoes), and SO₂ emissions (N = 1495 episodes, N = 116 volcanoes) to eruption start dates. We analyze these data in two ways: first, including all satellite-detected volcanic activities associated with an eruption; and second, by considering only the first satellite-detected activity related to eruption. In both scenarios, we find that deformation is dominantly pre-eruptive (47% and 57%) whereas available databases of thermal features and SO₂ emissions utilizing mainly low-resolution sensors are dominantly co-eruptive (88% and 76% for thermal features, 97% and 96% for SO₂ emissions)

Asymmetric tidal mixing due to the horizontal density gradient

Author Posting. © American Meteorological Society, 2008. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Physical Oceanography 38 (2008): 418-434, doi:10.1175/2007JPO3372.1.Stratification and turbulent mixing exhibit a flood–ebb tidal asymmetry in estuaries and continental shelf regions affected by horizontal density gradients. The authors use a large-eddy simulation (LES) model to investigate the penetration of a tidally driven bottom boundary layer into stratified water in the presence of a horizontal density gradient. Turbulence in the bottom boundary layer is driven by bottom stress during flood tides, with low-gradient (Ri) and flux (Rf) Richardson numbers, but by localized shear during ebb tides, with Ri = ¼ and Rf = 0.2 in the upper half of the boundary layer. If the water column is unstratified initially, the LES model reproduces periodic stratification associated with tidal straining. The model results show that the energetics criterion based on the competition between tidal straining and tidal stirring provides a good prediction for the onset of periodic stratification, but the tidally averaged horizontal Richardson number Rix has a threshold value of about 0.2, which is lower than the 3 suggested in a recent study. Although the tidal straining leads to negative buoyancy flux on flood tides, the authors find that for typical values of the horizontal density gradient and tidal currents in estuaries and shelf regions, buoyancy production is much smaller than shear production in generating turbulent kinetic energy.This work is supported by Grants OCE-0451699 and OCE-0451740 from the National Science Foundation

Testing for Associations between Loci and Environmental Gradients Using Latent Factor Mixed Models

Adaptation to local environments often occurs through natural selection acting on a large number of loci, each having a weak phenotypic effect. One way to detect these loci is to identify genetic polymorphisms that exhibit high correlation with environmental variables used as proxies for ecological pressures. Here, we propose new algorithms based on population genetics, ecological modeling, and statistical learning techniques to screen genomes for signatures of local adaptation. Implemented in the computer program "latent factor mixed model" (LFMM), these algorithms employ an approach in which population structure is introduced using unobserved variables. These fast and computationally efficient algorithms detect correlations between environmental and genetic variation while simultaneously inferring background levels of population structure. Comparing these new algorithms with related methods provides evidence that LFMM can efficiently estimate random effects due to population history and isolation-by-distance patterns when computing gene-environment correlations, and decrease the number of false-positive associations in genome scans. We then apply these models to plant and human genetic data, identifying several genes with functions related to development that exhibit strong correlations with climatic gradients.Comment: 29 pages with 8 pages of Supplementary Material (V2 revised presentation and results part