12 resultados para Alkaline earths

em CentAUR: Central Archive University of Reading - UK


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The Earth’s global atmospheric electric circuit depends on the upper and lower atmospheric boundaries formed by the ionosphere and the planetary surface. Thunderstorms and electrified rain clouds drive a DC current (∼1 kA) around the circuit, with the current carried by molecular cluster ions; lightning phenomena drive the AC global circuit. The Earth’s near-surface conductivity ranges from 10−7 S m−1 (for poorly conducting rocks) to 10−2 S m−1 (for clay or wet limestone), with a mean value of 3.2 S m−1 for the ocean. Air conductivity inside a thundercloud, and in fair weather regions, depends on location (especially geomagnetic latitude), aerosol pollution and height, and varies from ∼10−14 S m−1 just above the surface to 10−7 S m−1 in the ionosphere at ∼80 km altitude. Ionospheric conductivity is a tensor quantity due to the geomagnetic field, and is determined by parameters such as electron density and electron–neutral particle collision frequency. In the current source regions, point discharge (coronal) currents play an important role below electrified clouds; the solar wind-magnetosphere dynamo and the unipolar dynamo due to the terrestrial rotating dipole moment also apply atmospheric potential differences. Detailed measurements made near the Earth’s surface show that Ohm’s law relates the vertical electric field and current density to air conductivity. Stratospheric balloon measurements launched from Antarctica confirm that the downward current density is ∼1 pA m−2 under fair weather conditions. Fortuitously, a Solar Energetic Particle (SEP) event arrived at Earth during one such balloon flight, changing the observed atmospheric conductivity and electric fields markedly. Recent modelling considers lightning discharge effects on the ionosphere’s electric potential (∼+250 kV with respect to the Earth’s surface) and hence on the fair weather potential gradient (typically ∼130 V m−1 close to the Earth’s surface. We conclude that cloud-to-ground (CG) lightning discharges make only a small contribution to the ionospheric potential, and that sprites (namely, upward lightning above energetic thunderstorms) only affect the global circuit in a miniscule way. We also investigate the effects of mesoscale convective systems on the global circuit.

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The oxidation of glucose is a complex process usually requiring catalytically active electrode surfaces or enzyme modified electrodes. In this study the effect of high intensity microwave radiation on the oxidation of glucose in alkaline solution at Au, Cu, and Ni electrodes is reported. Calibration experiments with the Fe(CN)(6)(3-/4-) redox system in aqueous 0.1 M NaOH indicate that strong thermal effects occur at both 50 and 500 mu m diameter electrodes with temperatures reaching 380 K. Extreme mass transport effects with mass transport coefficients of k(mt) > 0.01 m s(-1) (or k(mt) > 1.0 cm s(-1)) are observed at 50 mu m diameter electrodes in the presence of microwaves. The electrocatalytic oxidation of glucose at 500 mu m diameter Au, Cu, or Ni electrodes immersed in 0.1 M NaOH and in the presence of microwave radiation is shown to be dominated by kinetic control. The magnitude of glucose oxidation currents at Cu electrodes is shown to depend on the thickness of a pre-formed oxide layer. At 50 mu m diameter Au, Cu, or Ni electrodes microwave enhanced current densities are generally higher, but only at Au electrodes is a significantly increased rate for the electrocatalytic oxidation of glucose to gluconolactone observed. This rate enhancement appears to be independent of temperature but microwave intensity dependent, and therefore non-thermal in nature. Voltammetric currents observed at Ni electrodes in the presence of microwaves show the best correlation with glucose concentration and are therefore analytically most useful.

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The oxidation of glucose is a complex process usually requiring catalytically active electrode surfaces or enzyme-modified electrodes. In this study the effect of high intensity microwave radiation on the oxidation of glucose in alkaline solution at Au, Cu, and Ni electrodes is reported. Calibration experiments with the Fe(CN)63–/4– redox system in aqueous 0.1 M NaOH indicate that strong thermal effects occur at both 50 and 500 µm diameter electrodes with temperatures reaching 380 K. Extreme mass transport effects with mass transport coefficients of kmt > 0.01 m s–1(or kmt > 1.0 cm s–1) are observed at 50 µm diameter electrodes in the presence of microwaves. The electrocatalytic oxidation of glucose at 500 µm diameter Au, Cu, or Ni electrodes immersed in 0.1 M NaOH and in the presence of microwave radiation is shown to be dominated by kinetic control. The magnitude of glucose oxidation currents at Cu electrodes is shown to depend on the thickness of a pre-formed oxide layer. At 50 µm diameter Au, Cu, or Ni electrodes microwave enhanced current densities are generally higher, but only at Au electrodes is a significantly increased rate for the electrocatalytic oxidation of glucose to gluconolactone observed. This rate enhancement appears to be independent of temperature but microwave intensity dependent, and therefore non-thermal in nature. Voltammetric currents observed at Ni electrodes in the presence of microwaves show the best correlation with glucose concentration and are therefore analytically most useful.

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Fluorophos and colourimetric procedures for alkaline phosphatase (ALP) testing were compared using milk with raw milk additions, purified bovine ALP additions and heat treatments. Repeatability was between 0.9% and 10.1% for Fluorophos, 3.5% and 46.1% for the Aschaffenburg and Mullen (A&M) procedure and 4.4% and 8.8% for the Scharer rapid test. Linearity (R-2) using raw milk addition was 0.96 between Fluorophos and the Scharer procedure. Between the Fluorophos and the A&M procedures, R-2 values were 0.98, 0.99 and 0.98 for raw milk additions, bovine ALP additions and heat treatments respectively. Fluorophos showed greater sensitivity and was both faster and simpler to perform.

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The rigid [6]ferrocenophane, L-1, was synthesised by condensation of 1,1'-ferrocene dicarbaldehyde with trans-1,2-diaminocyclohexane in high dilution at r.t. followed by reduction. When other experimental conditions were employed, the [6,6,6]ferrocenephane (L-2) was also obtained. Both compounds were characterised by single crystal X-ray crystallography. The protonation of L-1 and its metal complexation were evaluated by the effect on the electron-transfer process of the ferrocene (fc) unit of L-1 using cyclic voltammetry (CV) and square wave voltammetry (SWV) in anhydrous CH3CN solution and in 0.1 M (Bu4NPF6)-Bu-n as the supporting electrolyte. The electrochemical process of L-1 between 300 and 900 mV is complicated by amine oxidation. On the other hand, an anodic shift from the fc/fc(+) wave of L-1 of 249, 225, 81 and 61 mV was observed by formation of Zn2+, Ni2+, Pd2+ and Cu2+ complexes, respectively. Whereas Mg2+ and Ca2+ only have with L-1 weak interactions and they promote the acid-base equilibrium of L-1. This reveals that L-1 is an interesting molecular redox sensor for detection of Zn2+ and Ni2+, although the kinetics of the Zn2+ complex formation is much faster than that of the Ni2+ one. The X-ray crystal structure of [(PdLCl2)-Cl-1] was determined and showed a square-planar environment with Pd(II) and Fe(II) centres separated by 3.781(1) angstrom. The experimental anodic shifts were elucidated by DFT calculations on the [(MLCl2)-Cl-1] series and they are related to the nature of the HOMO of these complexes and a four-electron, two-orbital interaction.

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Water vapour modulates energy flows in Earth's climate system through transfer of latent heat by evaporation and condensation and by modifying the flows of radiative energy both in the longwave and shortwave portions of the electromagnetic spectrum. This article summarizes the role of water vapour in Earth's energy flows with particular emphasis on (1) the powerful thermodynamic constraint of the Clausius Clapeyron equation, (2) dynamical controls on humidity above the boundary layer (or free-troposphere), (3) uncertainty in continuum absorption in the relatively transparent "window" regions of the radiative spectrum and (4) implications for changes in the atmospheric hydrological cycle.

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The Earth’s climate, as well as planetary climates in general, is broadly regulated by three fundamental parameters: the total solar irradiance, the planetary albedo and the planetary emissivity. Observations from series of different satellites during the last three decades indicate that these three quantities are generally very stable. The total solar irradiation of some 1,361 W/m2 at 1 A.U. varies within 1 W/m2 during the 11-year solar cycle (Fröhlich 2012). The albedo is close to 29 % with minute changes from year to year but with marked zonal differences (Stevens and Schwartz 2012). The only exception to the overall stability is a minor decrease in the planetary emissivity (the ratio between the radiation to space and the radiation from the surface of the Earth). This is a consequence of the increase in atmospheric greenhouse gas amounts making the atmosphere gradually more opaque to long-wave terrestrial radiation. As a consequence, radiation processes are slightly out of balance as less heat is leaving the Earth in the form of thermal radiation than the amount of heat from the incoming solar radiation. Present space-based systems cannot yet measure this imbalance, but the effect can be inferred from the increase in heat in the oceans where most of the heat accumulates. Minor amounts of heat are used to melt ice and to warm the atmosphere and the surface of the Earth.

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Rising sea level is perhaps the most severe consequence of climate warming, as much of the world’s population and infrastructure is located near current sea level (Lemke et al. 2007). A major rise of a metre or more would cause serious problems. Such possibilities have been suggested by Hansen and Sato (2011) who pointed out that sea level was several metres higher than now during the Holsteinian and Eemian interglacials (about 250,000 and 120,000 years ago, respectively), even though the global temperature was then only slightly higher than it is nowadays. It is consequently of the utmost importance to determine whether such a sea level rise could occur and, if so, how fast it might happen. Sea level undergoes considerable changes due to natural processes such as the wind, ocean currents and tidal motions. On longer time scales, the sea level is influenced by steric effects (sea water expansion caused by temperature and salinity changes of the ocean) and by eustatic effects caused by changes in ocean mass. Changes in the Earth’s cryosphere, such as the retreat or expansion of glaciers and land ice areas, have been the dominant cause of sea level change during the Earth’s recent history. During the glacial cycles of the last million years, the sea level varied by a large amount, of the order of 100 m. If the Earth’s cryosphere were to disappear completely, the sea level would rise by some 65 m. The scientific papers in the present volume address the different aspects of the Earth’s cryosphere and how the different changes in the cryosphere affect sea level change. It represents the outcome of the first workshop held within the new ISSI Earth Science Programme. The workshop took place from 22 to 26 March, 2010, in Bern, Switzerland, with the objective of providing an in-depth insight into the future of mountain glaciers and the large land ice areas of Antarctica and Greenland, which are exposed to natural and anthropogenic climate influences, and their effects on sea level change. The participants of the workshop are experts in different fields including meteorology, climatology, oceanography, glaciology and geodesy; they use advanced space-based observational studies and state-of-the-art numerical modelling.

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Transient and equilibrium sensitivity of Earth's climate has been calculated using global temperature, forcing and heating rate data for the period 1970–2010. We have assumed increased long-wave radiative forcing in the period due to the increase of the long-lived greenhouse gases. By assuming the change in aerosol forcing in the period to be zero, we calculate what we consider to be lower bounds to these sensitivities, as the magnitude of the negative aerosol forcing is unlikely to have diminished in this period. The radiation imbalance necessary to calculate equilibrium sensitivity is estimated from the rate of ocean heat accumulation as 0.37±0.03W m^−2 (all uncertainty estimates are 1−σ). With these data, we obtain best estimates for transient climate sensitivity 0.39±0.07K (W m^−2)^−1 and equilibrium climate sensitivity 0.54±0.14K (W m^−2)^−1, equivalent to 1.5±0.3 and 2.0±0.5K (3.7W m^−2)^−1, respectively. The latter quantity is equal to the lower bound of the ‘likely’ range for this quantity given by the 2007 IPCC Assessment Report. The uncertainty attached to the lower-bound equilibrium sensitivity permits us to state, within the assumptions of this analysis, that the equilibrium sensitivity is greater than 0.31K (W m^−2)^−1, equivalent to 1.16K(3.7W m^−2)^−1, at the 95% confidence level.

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Recent paleoclimate studies provide strong evidence for an association between cosmogenic isotope production and Earth’s climate throughout the holecene. These isotopes are generated by the bombardment of Earth’s atmosphere by galactic cosmic rays, the fluxes of which vary in approximately inverse proportion to the total open magnetic flux of the Sun. This paper discusses how results from the Ulysses spacecraft allow us to quantify the open solar flux from observations of near-Earth interplanetary space and to study its long-term variations using the homogeneous record of geomagnetic activity. A study of the results and of their accuracy is presented. The two proposed mechanisms that could lead to the open solar flux being a good proxy for solar-induced climate change are discussed: the first is the modulation of the production of some types of cloud by the air ions produced by cosmic rays; the second is a variation in the total or spectral solar irradiance, in association with changes in the open flux. Some implications for our understanding of anthropogenic climate change are discussed.

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Measurements of the ionospheric E region during total solar eclipses in the period 1932-1999 have been used to investigate the fraction of Extreme Ultra Violet and soft X-ray radiation, phi, that is emitted from the limb corona and chromosphere. The relative apparent sizes of the Moon and the Sun are different for each eclipse, and techniques are presented which correct the measurements and, therefore, allow direct comparisons between different eclipses. The results show that the fraction of ionising radiation emitted by the limb corona has a clear solar cycle variation and that the underlying trend shows this fraction has been increasing since 1932. Data from the SOHO spacecraft are used to study the effects of short-term variability and it is shown that the observed long-term rise in phi has a negligible probability of being a chance occurrence.

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Changes in land management practices may have significant implications for soil microbial communities important in organic P turnover. Soil bacteria can increase plant P availability by excreting phosphatase enzymes which catalyze the hydrolysis of ester-phosphate bonds. Examining the diversity and abundance of alkaline phosphatase gene harboring bacteria may provide valuable insight into alkaline phosphatase production in soils. This study examined the effect of 20 years of no input organic (ORG), organic with composted manure (ORG + M), conventional (CONV) and restored prairie (PRA) management on soil P bioavailability, alkaline phosphatase activity (ALP), and abundance and diversity of ALP gene (phoD) harboring bacteria in soils from the northern Great Plains of Canada. Management system influenced bioavailable P (P < 0.001), but not total P, with the lowest concentrations in the ORG systems and the highest in PRA. Higher rates of ALP were observed in the ORG and ORG + M treatments with a significant negative correlation between bioavailable P and ALP in 2011 (r2 = 0.71; P = 0.03) and 2012 (r2 = 0.51; P = 0.02), suggesting that ALP activity increased under P limiting conditions. The phoD gene abundance was also highest in ORG and ORG + M resulting in a significant positive relationship between bacterial phoD abundance and ALP activity (r2 = 0.71; P = 0.009). Analysis of phoD bacterial community fingerprints showed a higher number of species in CONV compared to ORG and ORG + M, contrary to what was expected considering greater ALP activity under ORG management. In 2012, banding profiles of ORG + M showed fewer phoD bacterial species following the second manure application, although ALP activity is higher than in 2011. This indicates that a few species may be producing more ALP and that quantitative gene analysis was a better indicator of activity than the number of species present.