The application of inelastic neutron scattering to investigate the interaction of methyl propanoate with silica

A modern industrial route for the manufacture of methyl methacrylate involves the reaction of methyl propanoate and formaldehyde over a silica-supported Cs catalyst. Although the process has been successfully commercialised, little is known about the surface interactions responsible for the forward chemistry. This work concentrates upon the interaction of methyl propanoate over a representative silica. A combination of infrared spectroscopy, inelastic neutron scattering, DFT calculations, X-ray diffraction and temperature-programmed desorption is used to deduce how the ester interacts with the silica surface

Options for managing alkaline steel slag leachate: A life cycle assessment

Management of steel slag (a major by-product of the steel industry) includes the treatment of highly alkaline leachate (pH > 11.5) from rainwater infiltration of slag deposits to prevent adverse impact upon surface or ground waters. This study aims to compare different treatment options for steel slag leachate through a life cycle assessment (LCA). Five options were compared: active treatment by acid dosing (A-H2SO4), active treatment by carbon dioxide dosing (A-CO2), active treatment by calcium chloride dosing (A-CaCl2), passive treatment by cascade and reedbeds with pumping (P-P), and passive treatment by cascade and reedbeds in a gravity-driven configuration (P-G). The functional unit was 1 m3 of treated leachate with pH < 9, considering 24 h and 365 days of operating, maintenance operations every year, and service life of 20 years. Inventory data were obtained from project designers, commercial suppliers, laboratory data and field tests. The environmental impacts were calculated in OpenLCA using the ELCD database and ILCD 2011 method, covering twelve impact categories. The A-CaCl2 option scored worse than all other treatments for all considered environmental impact categories. Regarding human toxicity, A-CaCl2 impact was 1260 times higher than the lowest impact option (A-CO2) for carcinogenics and 53 times higher for non-carcinogenics (A-H2SO4). For climate change, the lowest impact was calculated for P-G < P-P < A-H2SO4 < A-CO2 < A-CaCl2, while for particulate matter/respiratory inorganics, the options ranked as follows P-G < P-P < A-CO2 < A-H2SO4 < A-CaCl2. The major contributor to these impact categories was the Solvay process to produce CaCl2. Higher uncertainty was associated with the categories particulate matter formation, climate change and human toxicity, as they are driven by indirect emissions from electricity and chemicals production. Both passive treatment options had better environmental performance than the active treatment options. Potential design measures to enhance environmental performance of the treatments regarding metal removal and recovery are discussed and could inform operational management at active and legacy steel slag disposal sites

Mechanism of Vanadium Leaching during Surface Weathering of Basic Oxygen Furnace Steel Slag Blocks: A Microfocus X-ray Absorption Spectroscopy and Electron Microscopy Study

© 2017 American Chemical Society. Basic oxygen furnace (BOF) steelmaking slag is enriched in potentially toxic V which may become mobilized in high pH leachate during weathering. BOF slag was weathered under aerated and air-excluded conditions for 6 months prior to SEM/EDS and μXANES analysis to determine V host phases and speciation in both primary and secondary phases. Leached blocks show development of an altered region in which free lime and dicalcium silicate phases were absent and Ca-Si-H was precipitated (CaCO 3 was also present under aerated conditions). μXANES analyses show that V was released to solution as V(V) during dicalcium silicate dissolution and some V was incorporated into neo-formed Ca-Si-H. Higher V concentrations were observed in leachate under aerated conditions than in the air-excluded leaching experiment. Aqueous V concentrations were controlled by Ca 3 (VO 4 ) 2 solubility, which demonstrate an inverse relationship between Ca and V concentrations. Under air-excluded conditions Ca concentrations were controlled by dicalcium silicate dissolution and Ca-Si-H precipitation, leading to relatively high Ca and correspondingly low V concentrations. Formation of CaCO 3 under aerated conditions provided a sink for aqueous Ca, allowing higher V concentrations limited by kinetic dissolution rates of dicalcium silicate. Thus, V release may be slowed by the precipitation of secondary phases in the altered region, improving the prospects for slag reuse

Cutaneous hypersensitivity reactions to freshwater cyanobacteria – human volunteer studies

BACKGROUND: Pruritic skin rashes associated with exposure to freshwater cyanobacteria are infrequently reported in the medical and scientific literature, mostly as anecdotal and case reports. Diagnostic dermatological investigations in humans are also infrequently described. We sought to conduct a pilot volunteer study to explore the potential for cyanobacteria to elicit hypersensitivity reactions. METHODS: A consecutive series of adult patients presenting for diagnostic skin patch testing at a hospital outpatient clinic were invited to participate. A convenience sample of volunteers matched for age and sex was also enrolled. Patches containing aqueous suspensions of various cyanobacteria at three concentrations were applied for 48 hours; dermatological assessment was made 48 hours and 96 hours after application. RESULTS: 20 outpatients and 19 reference subjects were recruited into the study. A single outpatient produced unequivocal reactions to several cyanobacteria suspensions; this subject was also the only one of the outpatient group with a diagnosis of atopic dermatitis. No subjects in the reference group developed clinically detectable skin reactions to cyanobacteria. CONCLUSION: This preliminary clinical study demonstrates that hypersensitivity reactions to cyanobacteria appear to be infrequent in both the general and dermatological outpatient populations. As cyanobacteria are widely distributed in aquatic environments, a better appreciation of risk factors, particularly with respect to allergic predisposition, may help to refine health advice given to people engaging in recreational activities where nuisance cyanobacteria are a problem

“He's Still the Winner in My Mind”: Maintaining the Collective Identity in Sport through Social Creativity and Group Affirmation

Social Creativity and Group Affirmation are two strategies by which individuals that identify with a sporting activity, team, group or individual may protect that sense of identification in light of negative events. This paper explores the use of such strategies through examining reactions to doping allegations surrounding Lance Armstrong to explain how members of two brand communities (one based on the brand of Armstrong as cyclist and the other on the brand of Armstrong as cancer survivor) maintain a sense of allegiance. Through undertaking a netnographic approach, six strategies were identified by members of these communities, three of which could be identified as Social Creativity Strategies (Lance Armstrong as “superhuman”, the notion of cycling as a ‘level playing field’, Armstrong as scapegoat) and three as Group Affirmation (Armstrong as a continuing inspiration, the Armstrong legacy, and denial). The two brand communities demonstrated differing patterns of maintenance, with those within the cycling community focusing more upon Social Creativity strategies, whereas those members of the Armstrong as cancer survivor brand tended to focus upon Group Affirmation strategies

Treating patients as persons : a capabilities approach to support delivery of person-centered care

Peer reviewedPublisher PD

Toward a simulation approach for alkene ring-closing metathesis : scope and limitations of a model for RCM

A published model for revealing solvent effects on the ring-closing metathesis (RCM) reaction of di-Et diallylmalonate 7 has been evaluated over a wider range of conditions, to assess its suitability for new applications. Unfortunately, the model is too flexible and the published rate consts. do not agree with exptl. studies in the literature. However, by fixing the values of important rate consts. and restricting the concn. ranges studied, useful conclusions can be drawn about the relative rates of RCM of different substrates, precatalyst concn. can be simulated accurately and the effect of precatalyst loading can be anticipated. Progress has also been made toward applying the model to precatalyst evaluation, but further modifications to the model are necessary to achieve much broader aims

Primary irritant and delayed-contact hypersensitivity reactions to the freshwater cyanobacterium Cylindrospermopsis raciborskii and its associated toxin cylindrospermopsin

BACKGROUND: Freshwater cyanobacteria are common inhabitants of recreational waterbodies throughout the world; some cyanobacteria can dominate the phytoplankton and form blooms, many of which are toxic. Numerous reports in the literature describe pruritic skin rashes after recreational or occupational exposure to cyanobacteria, but there has been little research conducted on the cutaneous effects of cyanobacteria. Using the mouse ear swelling test (MEST), we sought to determine whether three toxin-producing cyanobacteria isolates and the purified cyanotoxin cylindrospermopsin produced delayed-contact hypersensitivity reactions. METHODS: Between 8 and 10 female Balb/c mice in each experiment had test material applied to depilated abdominal skin during the induction phase and 10 or 11 control mice had vehicle only applied to abdominal skin. For challenge (day 10) and rechallenge (day 17), test material was applied to a randomly-allocated test ear; vehicle was applied to the other ear as a control. Ear thickness in anaesthetised mice was measured with a micrometer gauge at 24 and 48 hours after challenge and rechallenge. Ear swelling greater than 20% in one or more test mice is considered a positive response. Histopathology examination of ear tissues was conducted by independent examiners. RESULTS: Purified cylindrospermopsin (2 of 9 test mice vs. 0 of 5 control mice; p = 0.51) and the cylindrospermopsin-producing cyanobacterium C. raciborskii (8 of 10 test mice vs. 0 of 10 control mice; p = 0.001) were both shown to produce hypersensitivity reactions. Irritant reactions were seen on abdominal skin at induction. Two other toxic cyanobacteria (Microcystis aeruginosa and Anabaena circinalis) did not generate any responses using this model. Histopathology examinations to determine positive and negative reactions in ear tissues showed excellent agreement beyond chance between both examiners (κ = 0.83). CONCLUSION: The irritant properties and cutaneous sensitising potential of cylindrospermopsin indicate that these toxicological endpoints should be considered by public health advisors and reservoir managers when setting guidelines for recreational exposure to cyanobacteria

On the reliability of inflaton potential reconstruction

If primordial scalar and tensor perturbation spectra can be inferred from observations of the cosmic background radiation and large-scale structure, then one might hope to reconstruct a unique single-field inflaton potential capable of generating the observed spectra. In this paper we examine conditions under which such a potential can be reliably reconstructed. For it to be possible at all, the spectra must be well fit by a Taylor series expansion. A complete reconstruction requires a statistically-significant tensor mode to be measured in the microwave background. We find that the observational uncertainties dominate the theoretical error from use of the slow-roll approximation, and conclude that the reconstruction procedure will never insidiously lead to an irrelevant potential.Comment: 16 page LaTeX file with eight postscript figures embedded with epsf; no special macros neede

Mobilisation of arsenic from bauxite residue (red mud) affected soils: effect of pH and redox conditions

The tailings dam breach at the Ajka alumina plant, western Hungary in 2010 introduced ~1 million m3 of red mud suspension into the surrounding area. Red mud (fine fraction bauxite residue) has a characteristically alkaline pH and contains several potentially toxic elements, including arsenic. Aerobic and anaerobic batch experiments were prepared using soils from near Ajka in order to investigate the effects of red mud addition on soil biogeochemistry and arsenic mobility in soil–water experiments representative of land affected by the red mud spill. XAS analysis showed that As was present in the red mud as As(V) in the form of arsenate. The remobilisation of red mud associated arsenate was highly pH dependent and the addition of phosphate to red mud suspensions greatly enhanced As release to solution. In aerobic batch experiments, where red mud was mixed with soils, As release to solution was highly dependent on pH. Carbonation of these alkaline solutions by dissolution of atmospheric CO2 reduced pH, which resulted in a decrease of aqueous As concentrations over time. However, this did not result in complete removal of aqueous As in any of the experiments. Carbonation did not occur in anaerobic experiments and pH remained high. Aqueous As concentrations initially increased in all the anaerobic red mud amended experiments, and then remained relatively constant as the systems became more reducing, both XANES and HPLC–ICP-MS showed that no As reduction processes occurred and that only As(V) species were present. These experiments show that there is the potential for increased As mobility in soil–water systems affected by red mud addition under both aerobic and anaerobic conditions