A molal-based model for strong acid chemistry at low temperatures (<200 to 298 K)

Geochemical processes occurring in cold environments on Earth, Mars, and Europa have elicited considerable interest in the application of geochemical models to subzero temperatures. Few existing geochemical models explicitly include acid chemistry and those that do are largely restricted to temperatures ≥0°C or rely on the mole-fraction scale rather than the more common molal scale. This paper describes (1) use of the Clegg mole-fraction acid models to develop a molal-based model for hydrochloric, nitric, and sulfuric acids at low temperatures; (2) incorporation of acid chemistry and nitrate minerals into the FREZCHEM model; (3) validation and limitations of the derived acid model; and (4) simulation of hypothetical acidic brines for Europa.The Clegg mole-fraction acid models were used to estimate activities of water and mean ionic activity coefficients that serve as the database for estimating molal Pitzer-equation parameters for HCl (188 to 298 K), HNO₃ (228 to 298 K), and H₂SO₄ (208 to 298 K). Model eutectics for HNO₃ and H₂SO₄ agree with experimental measurements to within ± 0.2°C. In agreement with previous work, the experimental freezing point depression (fpd) data for pure HCl at subzero temperatures were judged to be flawed and unreliable. Three alternatives are discussed for handling HCl chemistry at subzero temperatures. In addition to defining the solubility of solid-phase acids, this work also adds three new nitrate minerals and six new acid salts to the FREZCHEM model and refines equilibria among water ice, liquid water, and water vapor over the temperature range from 180 to 298 K. The final system is parameterized for Na-K-Mg-Ca-H-Cl-SO₄-NO₃-OH-HCO₃-CO₃-CO₂-H₂O.Simulations of hypothetical MgSO₄-H₂SO₄-H₂O and Na₂SO₄-MgSO₄-H₂SO₄-H₂O brines for Europa demonstrate how freezing can convert a predominantly salt solution into a predominantly acid solution at subzero temperatures. This result has consequences for the effects of salinity, acidity, and temperature as limiting factors for potential life on Europa. Strong acidity would limit life-forms to highly acidophilic organisms.     

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.     

Formation of U-depleted rhyolite from a basanite at El Hierro, Canary Islands

Phonolite and trachyte are the felsic magmas of the alkaline magma suites, which characterize the Canary Islands. The October 2011 submarine eruption off El Hierro, the westernmost island, nevertheless, produced a small volume of rhyolitic magma. The rhyolite occurred as highly vesicular, white coloured pumices enveloped in and mingled with darker coloured basanitic pumice. The basanitic pumice is relatively crystal poor with a few euhedral olivines (mostly Fo_77–79), clinopyroxenes and Fe-rich spinels, whereas very rare olivine of same composition is found together with equally rare Fe-sulphide and FeTi-rich oxides in the rhyolite. The Fe–Mg exchange equilibrium in the oxides permits to calculate an equilibrium temperature of 970–890 °C for the rhyolite, in agreement with quartz-melt equilibrium at ca. 930 °C. A striking mineralogical feature of the rhyolite is the presence of rounded to contorted grains of milky quartz, which are xenocrysts incorporated and partly dissolved into the magma. Analyses of residual volatile concentrations in the glasses show that the rhyolite melt was highly degassed, whereas the basanitic glass still has important halogen concentrations. Trace element patterns of the mafic glasses and their elevated incompatible element concentrations are typical of the western Canary Island basanites. In contrast, the trace element composition of the rhyolite shows surprisingly low concentrations for all elements except the most incompatible ones (e.g. Rb, Ba, K and Th). All other measured LILE, HFSE and REE have significantly lower concentration than the basanitic counterpart that can be explained by fractionation of accessory phases (1 % apatite, 1 % sphene and 0.1 % zircon). Surprisingly, low U concentration is presumably related to elevated oxygen fugacity in the rhyolite, causing U to be in a hexavalent state, and fluxing of F-rich gas leading to volatilization of UF₆, known to emanate at low temperature. The results suggest that a gas-rich basanitic melt remobilized a small volume of stagnant rhyolitic melt formed by incorporation of approximately 10 % quartz-rich sediment into a late differentiate of trachytic composition. Sediments at the interface of an old oceanic crust adjacent to a continental shield and younger volcanic island are likely to act as magma traps were sediment assimilation may alter the mantle-derived magma composition. Quartz assimilation thus explains the production of rhyolite magma in a volcanic island characterized by an alkaline magma series from primitive basanites to trachytes.     

Changes in Nutrient Biogeochemistry in Response to the Regression of Zostera noltii Meadows in the Arcachon Bay (France)

From 1989 to 2007, a severe decline in Zostera noltii meadows was reported in the Arcachon Bay, with an accelerated regression after 2005. We investigated the inter-annual variability of the biogeochemistry of the sediment in an area affected by seagrass decline. In late summer and in winter of the years 2006, 2010, and 2011, sediment cores were collected at low tide on vegetated and adjacent non-vegetated sediments located in the eastern part of the Arcachon Bay. The geochemical analyses of sediment solid-phase organic carbon, reactive P and Fe, and the pore water concentrations of Fe²⁺, DIP, and NH₄ ⁺ are presented. The changes in the chemistry of sediment and pore water between 2006 and 2010 are interpreted as a consequence of the decrease in the Z. noltii biomass between 2006 and 2010. The absence of significant seasonal variations in biomass throughout the growth period (March–September) in 2011 is most likely related to the regression of Z. noltii meadow that strongly affects the study area. In contrast to the healthy meadow in 2006, the declining meadow favored the dissolution of sedimentary particulate phosphorus in winter. In late summer, the low biomass of seagrass resulted in a net release of ammonium in the pore water of the upper 20 cm of sediment. This study clearly shows that seagrass decay may enhance nutrient release in sediments, resulting in a significant supply of phosphorus to the water column of a magnitude comparable to annual inputs to the lagoon from the rivers and the tidal pump.     

The marine controlled source electromagnetic response of a steel borehole casing: applications for the NEPTUNE Canada gas hydrate observatory

Gas hydrates are a potential energy resource, a possible factor in climate change and an exploration geohazard. The University of Toronto has deployed a permanent seafloor time‐domain controlled source electromagnetic (CSEM) system offshore Vancouver Island, within the framework of the NEPTUNE Canada underwater cabled observatory. Hydrates are known to be present in the area and due to their electrically resistive nature can be monitored by 5 permanent electric field receivers. However, two cased boreholes may be drilled near the CSEM site in the near future. To understand any potential distortions of the electric fields due to the metal, we model the marine electromagnetic response of a conductive steel borehole casing. First, we consider the commonly used canonical model consisting of a 100 Ωm, 100 m thick resistive hydrocarbon layer embedded at a depth of 1000 m in a 1 Ωm conductive host medium, with the addition of a typical steel production casing extending from the seafloor to the resistive zone. Results show that in both the frequency and time domains the distortion produced by the casing occurs at smaller transmitter‐receiver offsets than the offsets required to detect the resistive layer. Second, we consider the experimentally determined model of the offshore Vancouver Island hydrate zone, consisting of a 5.5 Ωm, 36 m thick hydrate layer overlying a 0.7 Ωm sedimentary half‐space, with the addition of two borehole casings extending 300 m into the seafloor. In this case, results show that the distortion produced by casings located within a 100 m safety zone of the CSEM system will be measured at 4 of the 5 receivers. We conclude that the boreholes must be positioned at least 200 m away from the CSEM array so as to minimize the effects of the casings.     

A review of the LATEX project: mesoscale to submesoscale processes in a coastal environment

The main objective of the LAgrangian Transport EXperiment (LATEX) project was to study the influence of coastal mesoscale and submesoscale physical processes on circulation dynamics, cross-shelf exchanges, and biogeochemistry in the western continental shelf of the Gulf of Lion, Northwestern Mediterranean Sea. LATEX was a five-year multidisciplinary project based on the combined analysis of numerical model simulations and multi-platform field experiments. The model component included a ten-year realistic 3D numerical simulation, with a 1 km horizontal resolution over the gulf, nested in a coarser 3 km resolution model. The in situ component involved four cruises, including a large-scale multidisciplinary campaign with two research vessels in 2010. This review concentrates on the physics results of LATEX, addressing three main subjects: (1) the investigation of the mesoscale to submesoscale processes. The eddies are elliptic, baroclinic, and anticyclonic; the strong thermal and saline front is density compensated. Their generation processes are studied; (2) the development of sampling strategies for their direct observations. LATEX has implemented an adaptive strategy Lagrangian tool, with a reference software available on the web, to perform offshore campaigns in a Lagrangian framework; (3) the quantification of horizontal mixing and cross-shelf exchanges. Lateral diffusivity coefficients, calculated in various ways including a novel technique, are in the range classically encountered for their associated scales. Cross-shelf fluxes have been calculated, after retrieving the near-inertial oscillation contribution. Further perspectives are discussed, especially for the ongoing challenge of studying submesoscale features remotely and from in situ data.     

Investigating suspended particulate matter in coastal waters using the fractal theory

Ocean Dynamics - Suspended particulate matters (SPM) in coastal waters were investigated with an approach combining suspended particulate matter concentrations (SPMCs) measured by an optical...