Effects of pressure on aqueous chemical equilibria at subzero temperatures with applications to Europa

Pressure plays a critical role in controlling aqueous geochemical processes in deep oceans and deep ice. The putative ocean of Europa could have pressures of 1200 bars or higher on the seafloor, a pressure not dissimilar to the deepest ocean basin on Earth (the Mariana Trench at 1100 bars of pressure). At such high pressures, chemical thermodynamic relations need to explicitly consider pressure. A number of papers have addressed the role of pressure on equilibrium constants, activity coefficients, and the activity of water. None of these models deal, however, with processes at subzero temperatures, which may be important in cold environments on Earth and other planetary bodies. The objectives of this work were to (1) incorporate a pressure dependence into an existing geochemical model parameterized for subzero temperatures (FREZCHEM), (2) validate the model, and (3) simulate pressure-dependent processes on Europa. As part of objective 1, we examined two models for quantifying the volumetric properties of liquid water at subzero temperatures: one model is based on the measured properties of supercooled water, and the other model is based on the properties of liquid water in equilibrium with ice.The relative effect of pressure on solution properties falls in the order: equilibrium constants(K) > activity coefficients (γ) > activity of water (a_w). The errors (%) in our model associated with these properties, however, fall in the order: γ > K > a_w. The transposition between K and γ is due to a more accurate model for estimating K than for estimating γ. Only activity coefficients are likely to be significantly in error. However, even in this case, the errors are likely to be only in the range of 2 to 5% up to 1000 bars of pressure. Evidence based on the pressure/temperature melting of ice and salt solution densities argue in favor of the equilibrium water model, which depends on extrapolations, for characterizing the properties of liquid water in electrolyte solutions at subzero temperatures, rather than the supercooled water model. Model-derived estimates of mixed salt solution densities and chemical equilibria as a function of pressure are in reasonably good agreement with experimental measurements.To demonstrate the usefulness of this low-temperature, high-pressure model, we examined two hypothetical cases for Europa. Case 1 dealt with the ice cover of Europa, where we asked the question: How far above the putative ocean in the ice layer could we expect to find thermodynamically stable brine pockets that could serve as habitats for life? For a hypothetical nonconvecting 20 km icy shell, this potential life zone only extends 2.8 km into the icy shell before the eutectic is reached. For the case of a nonconvecting icy shell, the cold surface of Europa precludes stable aqueous phases (habitats for life) anywhere near the surface. Case 2 compared chemical equilibria at 1 bar (based on previous work) with a more realistic 1460 bars of pressure at the base of a 100 km Europan ocean. A pressure of 1460 bars, compared to 1 bar, caused a 12 K decrease in the temperature at which ice first formed and a 11 K increase in the temperature at which MgSO₄·12H₂O first formed. Remarkably, there was only a 1.2 K decrease in the eutectic temperatures between 1 and 1460 bars of pressure. Chemical systems and their response to pressure depend, ultimately, on the volumetric properties of individual constituents, which makes every system response highly individualistic.     

Energetic Charged Particles Above Thunderclouds

The French government has committed to launch the satellite TARANIS to study transient coupling processes between the Earth’s atmosphere and near-Earth space. The prime objective of TARANIS is to detect energetic charged particles and hard radiation emanating from thunderclouds. The British Nobel prize winner C.T.R. Wilson predicted lightning discharges from the top of thunderclouds into space almost a century ago. However, new experiments have only recently confirmed energetic discharge processes which transfer energy from the top of thunderclouds into the upper atmosphere and near-Earth space; they are now denoted as transient luminous events, terrestrial gamma-ray flashes and relativistic electron beams. This meeting report builds on the current state of scientific knowledge on the physics of plasmas in the laboratory and naturally occurring plasmas in the Earth’s atmosphere to propose areas of future research. The report specifically reflects presentations delivered by the members of a novel Franco-British collaboration during a meeting at the French Embassy in London held in November 2011. The scientific subjects of the report tackle ionization processes leading to electrical discharge processes, observations of transient luminous events, electromagnetic emissions, energetic charged particles and their impact on the Earth’s atmosphere. The importance of future research in this area for science and society, and towards spacecraft protection, is emphasized.     

Solar modulation in surface atmospheric electricity

The solar wind modulates the flux of galactic cosmic rays impinging on Earth inversely with solar activity. Cosmic ray ionisation is the major source of air's electrical conductivity over the oceans and well above the continents. Differential solar modulation of the cosmic ray energy spectrum modifies the cosmic ray ionisation at different latitudes, varying the total atmospheric columnar conductance. This redistributes current flow in the global atmospheric electrical circuit, including the local vertical current density and the related surface potential gradient. Surface vertical current density and potential gradient measurements made independently at Lerwick Observatory, Shetland, from 1978 to 1985 are compared with modelled changes in cosmic ray ionisation arising from solar activity changes. Both the lower troposphere atmospheric electricity quantities are significantly increased at cosmic ray maximum (solar minimum), with a proportional change greater than that of the cosmic ray change.     

Land cover classification by an artificial neural network with ancillary information

Abstract

Remote sensing is an important source of land cover data required by many GIS users. Land cover data are typically derived from remotely–sensed data through the application of a conventional statistical classification. Such classification techniques are not, however, always appropriate, particularly as they may make untenable assumptions about the data and their output is hard, comprising only the code of the most likely class of membership. Whilst some deviation from the assumptions may be tolerated and a fuzzy output may be derived, making more information on class membership properties available, alternative classification procedures are sometimes required. Artificial neural networks are an attractive alternative to the statistical classifiers and here one is used to derive a fuzzy classification output from a remotely–sensed data set that may be post–processed with ancillary data available in a GIS to increase the accuracy with which land cover may be mapped. With the aid ancillary information on soil type and prior knowledge of class occurrence the accuracy of an artificial neural network classification was increased by 29–93 to 77–37 per cent. An artificial neural network can therefore be used generate a fuzzy classification output that may be used with other data sets in a GIS, which may not have been available to the producer of the classification, to increase the accuracy with which land cover may be classified.     

Evolution of the Australian lithosphere

The evolution of the Australian plate can be interpreted in a plate‐tectonic paradigm in which lithospheric growth occurred via vertical and horizontal accretion. The lithospheric roots of Archaean lithosphere developed contemporaneously with the overlying crust. Vertical accretion of the Archaean lithosphere is probably related to the arrival of large plumes, although horizontal lithospheric accretion was also important to crustal growth. The Proterozoic was an era of major crustal growth in which the components of the North Australian, West Australian and South Australian cratons were formed and amalgamated during a series of accretionary events and continent‐continent collisions, interspersed with periods of lithospheric extension. During Phanerozoic accretionary tectonism, approximately 30% of the Australian crust was added to the eastern margin of the continent in a predominantly supra‐subduction environment. Widespread plume‐driven rifting during the breakup of Gondwana may have contributed to the destruction of Archaean lithospheric roots (as a result of lithospheric stretching). However, lithospheric growth occurred at the same time due to mafic underplating along the eastern margin of the plate. Northward drift of Australia during the Tertiary led to the development of a complex accretionary margin at the leading edge of the plate (Papua New Guinea).