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.     

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...     

Hydrodynamic time parameters response to meteorological and physical forcings: toward a stagnation risk assessment device in coastal areas

Ocean Dynamics - Identifying zones of stagnation and deposition of terrigenous matter or contaminants induced by human activity is a key issue in coastal areas. In this paper, circulation processes...     

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.     

Calcification depth and spatial distribution of Thoracosphaera heimii cysts: Implications for palaeoceanographic reconstructions

For the optimal use in palaeoceanographic studies of the stable oxygen isotopic signal and elemental composition of the calcareous photosynthetic dinoflagellate Thoracosphaera heimii, it is essential to gain detailed information about its calcification depth and spatial distribution. We therefore studied the vertical and horizontal distribution patterns of T. heimii in the upper water column (0–200 m) along three transects: an inshore–offshore gradient off Cape Blanc (CB), a south–north transect from CB to the Portuguese coast and a north–south transect off Tanzania. We compared concentrations of living cysts (cells with cell content) with chlorophyll-a, salinity and temperature measurements at the sampling depth. In order to explore the seasonal variability in cyst production, three transect off CB were sampled at three different times of the year.Living T. heimii cysts were found in the upper 160 m of the water column with highest concentrations in the photic zone indicating that the calcification of T. heimii occurs in the upper part of the water column. Maximal abundances of living cysts were found relatively often in or just above the deep chlorophyll maximum (DCM), the depth of which varies regionally from about 20–40 m off CB to about 80 m off Tanzania and along the transect from CB to the Portuguese Coast. However, there was no significant correlation at the 95% confidence level between the cyst concentrations and temperature, salinity and chlorophyll-a concentrations at the sampling depths observed.In both the Atlantic and Indian Oceans, the highest abundances of T. heimii were observed in regions where the upper water masses contained relatively low nutrient concentrations that are influenced only sporadically, or not at all, by enhanced photic zone mixing related to the presence of upwelling cells or river outflow plumes at or close to the sampling sites. The seasonal production of cysts by T. heimii appears to be negatively related to the presence of upwelling filaments across the sampling sites. Our study suggests that turbulence of the upper water masses is a major environmental factor influencing T. heimii production.     

40Ar/ 39Ar dating of Penninic Front tectonic displacement (W Alps) during the Lower Oligocene (31–34 Ma)

Direct absolute dating of the Penninic Frontal Thrust tectonic motion is achieved using the ⁴⁰Ar/³⁹Ar technique in the Pelvoux Crystalline Massif (Western Alps). The dated phengites were formed syn-kinematically in shear zones. They underline the brittle-ductile stretching lineation, pressure-shadow fibres and slickensides consistent with underthrusting of the European continental slab below the propagating Penninic Thrust. Chlorite–phengite thermobarometry yields 10–15 km and T ∼280 °C, while ⁴⁰Ar/³⁹Ar phengite ages mainly range between 34 and 30 Ma, with one younger age at 27 Ma. This Early Oligocene age range matches a major tectonic rearrangement of the Alpine chain. Preservation of prograde ⁴⁰Ar/³⁹Ar ages is ascribed to passive exhumation of the Pelvoux shear zone network, sandwiched between more external thrusts and the Penninic Front reactivated as an E-dipping detachment fault. Partial resetting in the Low Temperature part of argon spectra below 24 Ma is ascribed to brittle deformation and alteration of phengites.     

Does upward seepage of river water and storm water runoff determine water quality of urban drainage systems in lowland areas? A case study for the Rhine–Meuse delta

The water quality of urban drainage ditches in lowlands in the Rhine‐Meuse delta was analysed with principal component analysis (PCA) during a dry period and a rain storm, and related to the seepage of polluted river water and effective impervious area (EIA). This was done in order to test the hypothesis that seepage of river water and storm water runoff from impervious areas strongly determine the water quality of urban drainage systems along large lowland rivers. Our analysis revealed that upward seepage of groundwater originating from rivers Rhine and Meuse was positively correlated with nitrate, potassium, sodium and chloride and negatively correlated with alkalinity, calcium, magnesium and iron. EIA was correlated with very few environmental variables (i.e. phosphate, pH and iron in the dry period and iron during the rain storm). Nickel and zinc concentrations generally exceeded the maximum allowable concentrations (MAC), while lead and phosphorus concentrations were just above the nutrient standards and MAC in a few locations during the rain storm. To optimize water quality in urban water systems, attention should be paid to all sources of pollution and not only to EIA. The impact of local groundwater seepage originating from large rivers in lowlands on the chemistry of urban water systems is often underestimated and should be taken into account when assessing water quality and improving water quality status. Copyright © 2009 John Wiley & Sons, Ltd.