An investigation of the nature and reactivity of the carbonaceous species deposited on mordenite by reaction with methanol

An investigation of the nature of the carbonaceous species deposited upon mordenite by reaction with methanol has been undertaken. The nature of the species has been shown to be a strong function of both temperature and time on stream. Upon reaction at 300 degrees C a range of alkyl and aromatic species, consistent with the development of an active hydrocarbon pool, are evident and time on stream studies have shown that these are developed within 5 min. Upon reaction at 500 degrees C, a narrower range of hydrogen deficient aromatic species is evident. Thermal volatilisation analysis (TVA), not previously applied to the study of coked zeolites, is shown to be complementary to the more commonly applied C analysis, C-13 MAS NMR and TGA techniques

High Stellar FUV/NUV Ratio and Oxygen Contents in the Atmospheres of Potentially Habitable Planets

Recent observations of several planet-hosting M dwarfs show that most have FUV/NUV flux ratios 1000 times greater than that of the Sun. Here we show that the atmospheric oxygen contents (O2 and O3) of potentially habitable planets in this type of UV environment could be 2~3 orders of magnitude greater than those of their counterparts around Sun-like stars as a result of decreased photolysis of O3, H2O2, and HO2. Thus detectable levels of atmospheric oxygen, in combination with the existence of H2O and CO2, may not be the most promising biosignatures on planets around stars with high FUV/NUV ratios such as the observed M dwarfs

Plume mapping and isotopic characterisation of anthropogenic methane sources

Methane stable isotope analysis, coupled with mole fraction measurement, has been used to link isotopic signature to methane emissions from landfill sites, coal mines and gas leaks in the United Kingdom. A mobile Picarro G2301 CRDS (Cavity Ring-Down Spectroscopy) analyser was installed on a vehicle, together with an anemometer and GPS receiver, to measure atmospheric methane mole fractions and their relative location while driving at speeds up to 80 kph. In targeted areas, when the methane plume was intercepted, air samples were collected in Tedlar bags, for delta C-13-CH4 isotopic analysis by CF-GC-IRMS (Continuous Flow Gas Chromatography-Isotope Ratio Mass Spectrometry). This method provides high precision isotopic values, determining delta C-13-CH4 to +/- 0.05 per mil. The bulk signature of the methane plume into the atmosphere from the whole source area was obtained by Keeling plot analysis, and a delta C-13 -CH4 signature, with the relative uncertainty, allocated to each methane source investigated. Both landfill and natural gas emissions in SE England have tightly constrained isotopic signatures. The averaged delta C-13-CH4 for landfill sites is -58 +/- 3%o. The delta C-13-CH4 signature for gas leaks is also fairly constant around -36 +/- 2 parts per thousand, a value characteristic of homogenised North Sea supply. In contrast, signatures for coal mines in N. England and Wales fall in a range of -51.2 +/- 0.3 parts per thousand to 30.9 +/- 1.4 parts per thousand, but can be tightly constrained by region. The study demonstrates that CRDS-based mobile methane measurement coupled with off-line high precision isotopic analysis of plume samples is an efficient way of characterising methane sources. It shows that iiotopic measurements allow type identification, and possible location of previously unknown methane sources. In modelling studies this measurement provides an independent constraint to determine the contributions of different sources to the regional methane budget and in the verification of inventory source distribution. (C) 2015 Elsevier Ltd. All rights reserved

Atmospheric nitrogen oxides (NO and NO2) at Dome C, East Antarctica, during the OPALE campaign

Mixing ratios of the atmospheric nitrogen oxides NO and NO2 were measured as part of the OPALE (Oxidant Production in Antarctic Lands & Export) campaign at Dome C, East Antarctica (75.1 degrees S, 123.3 degrees E, 3233 m), during December 2011 to January 2012. Profiles of NOx mixing ratios of the lower 100m of the atmosphere confirm that, in contrast to the South Pole, air chemistry at Dome C is strongly influenced by large diurnal cycles in solar irradiance and a sudden collapse of the atmospheric boundary layer in the early evening. Depth profiles of mixing ratios in firn air suggest that the upper snowpack at Dome C holds a significant reservoir of photolytically produced NO2 and is a sink of gas-phase ozone (O-3). First-time observations of bromine oxide (BrO) at Dome C show that mixing ratios of BrO near the ground are low, certainly less than 5 pptv, with higher levels in the free troposphere. Assuming steady state, observed mixing ratios of BrO and RO2 radicals are too low to explain the large NO2 : NO ratios found in ambient air, possibly indicating the existence of an unknown process contributing to the atmospheric chemistry of reactive nitrogen above the Antarctic Plateau. During 2011-2012, NOx mixing ratios and flux were larger than in 2009-2010, consistent with also larger surface O-3 mixing ratios resulting from increased net O-3 production. Large NOx mixing ratios at Dome C arise from a combination of continuous sunlight, shallow mixing height and significant NOx emissions by surface snow (F-NOx). During 23 December 2011-12 January 2012, median F-NOx was twice that during the same period in 20092010 due to significantly larger atmospheric turbulence and a slightly stronger snowpack source. A tripling of F-NOx in December 2011 was largely due to changes in snowpack source strength caused primarily by changes in NO3- concentrations in the snow skin layer, and only to a secondary order by decrease of total column O-3 and associated increase in NO3- photolysis rates. A source of uncertainty in model estimates of F-NOx is the quantum yield of NO3- photolysis in natural snow, which may change over time as the snow ages

Tracer Measurements in Growing Sea Ice Support Convective Gravity Drainage Parameterizations

Gravity drainage is the dominant process redistributing solutes in growing sea ice. Modeling gravity drainage is therefore necessary to predict physical and biogeochemical variables in sea ice. We evaluate seven gravity drainage parameterizations, spanning the range of approaches in the literature, using tracer measurements in a sea ice growth experiment. Artificial sea ice is grown to around 17 cm thickness in a new experimental facility, the Roland von Glasow air‐sea‐ice chamber. We use NaCl (present in the water initially) and rhodamine (injected into the water after 10 cm of sea ice growth) as independent tracers of brine dynamics. We measure vertical profiles of bulk salinity in situ, as well as bulk salinity and rhodamine in discrete samples taken at the end of the experiment. Convective parameterizations that diagnose gravity drainage using Rayleigh numbers outperform a simpler convective parameterization and diffusive parameterizations when compared to observations. This study is the first to numerically model solutes decoupled from salinity using convective gravity drainage parameterizations. Our results show that (1) convective, Rayleigh number‐based parameterizations are our most accurate and precise tool for predicting sea ice bulk salinity; and (2) these parameterizations can be generalized to brine dynamics parameterizations, and hence can predict the dynamics of any solute in growing sea ic

High fidelity simulations of ion trajectories in miniature ion traps using the boundary-element method

In this paper we present numerical modeling results for endcap and linear ion traps, used for experiments at the National Physical Laboratory in the UK and Innsbruck University respectively. The secular frequencies for Strontium-88 and Calcium-40 ions were calculated from ion trajectories, simulated using boundary-element and finite-difference numerical methods. The results were compared against experimental measurements. Both numerical methods showed high accuracy with boundary-element method being more accurate. Such simulations can be useful tools for designing new traps and trap arrays. They can also be used for obtaining precise trapping parameters for desired ion control when no analytical approach is possible as well as for investigating the ion heating rates due to thermal electronic noise.Comment: 6 pages, 5 figures, changes made to the text according to the editor's and referee's comment

Does digital video enhance student learning in field-based experiments and develop graduate attributes beyond the classroom?

This is an Accepted Manuscript of an article published by Taylor & Francis in Journal of Geography in Higher Education on 02/05/2016, available online: http://www.tandfonline.com/doi/full/10.1080/03098265.2016.1141186?src=recsysThe connection between fieldwork and development of graduate attributes is explored in this paper. Digital technologies present opportunities to potentially enhance the learning experience of students undertaking fieldwork, and develop core digital attributes and competencies required by Higher Education Institutions (HEIs) and employers. This paper reports the success of adopting digital video capture in technology-rich field experiments that form part of final year undergraduate courses in Physical Geography at an HEI in New Zealand. Student perceptions were obtained via a range of approaches. Results suggest that deployment of digital video reinforces student learning and connects with core graduate attributes

Quantum calculations of Coulomb reorientation for sub-barrier fusion

Classical mechanics and Time Dependent Hartree-Fock (TDHF) calculations of heavy ions collisions are performed to study the rotation of a deformed nucleus in the Coulomb field of its partner. This reorientation is shown to be independent on charges and relative energy of the partners. It only depends upon the deformations and inertias. TDHF calculations predict an increase by 30% of the induced rotation due to quantum effects while the nuclear contribution seems negligible. This reorientation modifies strongly the fusion cross-section around the barrier for light deformed nuclei on heavy collision partners. For such nuclei a hindrance of the sub-barrier fusion is predicted.Comment: accepted for publication in Physical Review Lette

Catalytic Isohypsic-Redox Sequences for the Rapid Generation of C_sp3-Containing Heterocycles

Cross‐coupling reactions catalyzed by transition metals are among the most influential in modern synthetic chemistry. The vast majority of transition metal catalyzed cross‐couplings rely on a catalytic cycle involving alternating oxidation and reduction of the metal center and are generally limited to forging just one type of new bond per reaction (e.g. the biaryl linkage formed during a Suzuki cross‐coupling). Here we present an Isohypsic–Redox Sequence (IRS) that uses one metal to effect two catalytic cycles, thereby generating multiple new types of bonds from a single catalyst source. We show that the IRS strategy is amenable to several widely used transformations including the Suzuki–Miyaura coupling, Buchwald–Hartwig amination, and Wacker oxidation. Furthermore, each of these reactions generates value‐added heterocycles with significant sp3‐C (3‐dimensional) content. Our results provide a general framework for generating complex products by using a single metal to fulfill multiple roles. By uniting different combinations of reactions in the isohypsic and redox phases of the process, this type of catalytic multiple bond‐forming platform has the potential for wide applicability in the efficient synthesis of functional organic molecules

Contextual factors among indiscriminate or larger attacks on food or water supplies, 1946-2015

This research updates previous inventories of malicious attacks on food and water to include data from 1946 through mid-2015. A systematic search of news reports, databases and previous inventories of poisoning events was undertaken. Incidents that threatened or were intended to achieve direct harm to humans, and that were either relatively large (number of victims > 4 or indiscriminate in intent or realisation were included. Agents could be chemical, biological or radio-nuclear. Reports of candidate incidents were subjected to systematic inclusion and exclusion criteria as well as validity analysis (not always clearly undertaken in previous inventories of such attacks). We summarise contextual aspects of the attacks that may be important for scenario prioritisation, modelling and defensive preparedness. Opportunity is key to most realised attacks, particularly access to dangerous agents. The most common motives and relative success rate in causing harm were very different between food and water attacks. The likelihood that people were made ill or died also varied by food/water mode, and according to motive and opportunity for delivery of the hazardous agent. Deaths and illness associated with attacks during food manufacture and prior to sale have been fewer than those in some other contexts. Valuable opportunities for food defence improvements are identified in other contexts, especially food prepared in private or community settings