Kinetics of brucite dissolution at 25°C in the presence of organic and inorganic ligands and divalent metals

Brucite (Mg(OH)₂) dissolution rate was measured at 25°C in a mixed-flow reactor at various pH (5 to 11) and ionic strengths (0.01 to 0.03 M) as a function of the concentration of 15 organic and 5 inorganic ligands and 8 divalent metals. At neutral and weakly alkaline pH, the dissolution is promoted by the addition of the following ligands ranked by decreasing effectiveness: EDTA ≥ H₂PO₄⁻ > catechol ≥ HCO₃⁻ > ascorbate > citrate > oxalate > acetate ∼ lactate and it is inhibited by boric acid. At pH >10.5, it decreases in the presence of PO₄³⁻, CO₃²⁻, F⁻, oxine, salicylate, lactate, acetate, 4-hydroxybenzoate, SO₄²⁻ and B(OH)₄⁻ with orthophosphate and borate being the strongest and the weakest inhibitor, respectively. Xylose (up to 0.1 M), glycine (up to 0.05 M), formate (up to 0.3 M) and fulvic and humic acids (up to 40 mg/L DOC) have no effect on brucite dissolution kinetics. Fluorine inhibits dissolution both in neutral and alkaline solutions. From F sorption experiments in batch and flow-through reactors and the analysis of reacted surfaces using X-ray Photoelectron Spectroscopy (XPS), it is shown that fluorine adsorption is followed by its incorporation in brucite lattice likely via isomorphic substitution with OH. The effect of eight divalent metals (Sr, Ba, Ca, Pb, Mn, Fe, Co and Ni) studied at pH 4.9 and 0.01 M concentration revealed brucite dissolution rates to be correlated with the water molecule exchange rates in the first hydration sphere of the corresponding cation.The effect of investigated ligands on brucite dissolution rate can be modelled within the framework of the surface coordination approach taking into account the adsorption of ligands on dissolution-active sites and the molecular structure of the surface complexes they form. The higher the value of the ligand sorption constant, the stronger will be its catalyzing or inhibiting effect. As for Fe and Al oxides, bi- or multidentate mononuclear surface complexes, that labilize Mg-O bonds and water coordination to Mg atoms at the surface, enhance brucite dissolution whereas bi- or polynuclear surface complexes tend to inhibit dissolution by bridging two or more metal centers and extending the cross-linking at the solid surface. Overall, results of this study demonstrate that very high concentrations of organic ligands (0.01-0.1 M) are necessary to enhance or inhibit brucite dissolution. As a result, the effect of extracellular organic products on the weathering rate of Mg-bearing minerals is expected to be weak.     

Isotopic composition of dissolved inorganic carbon in subsurface sediments of gas hydrate-bearing mud volcanoes, Lake Baikal: implications for methane and carbonate origin

We report on the isotopic composition of dissolved inorganic carbon (DIC) in pore-water samples recovered by gravity coring from near-bottom sediments at gas hydrate-bearing mud volcanoes/gas flares (Malenky, Peschanka, Peschanka 2, Goloustnoe, and Irkutsk) in the Southern Basin of Lake Baikal. The δ¹³C values of DIC become heavier with increasing subbottom depth, and vary between ?9.5 and +21.4‰ PDB. Enrichment of DIC in ¹³C indicates active methane generation in anaerobic environments near the lake bottom. These data confirm our previous assumption that crystallization of carbonates (siderites) in subsurface sediments is a result of methane generation. Types of methanogenesis (microbial methyl-type fermentation versus CO₂-reduction) were revealed by determining the offset of δ¹³C between dissolved CH₄ and CO₂, and also by using δ¹³C and δD values of dissolved methane present in the pore waters. Results show that both mechanisms are most likely responsible for methane generation at the investigated locations.     

What causes the spread of model projections of ocean dynamic sea-level change in response to greenhouse gas forcing?

Sea levels of different atmosphere–ocean general circulation models (AOGCMs) respond to climate change forcing in different ways, representing a crucial uncertainty in climate change research. We isolate the role of the ocean dynamics in setting the spatial pattern of dynamic sea-level (ζ) change by forcing several AOGCMs with prescribed identical heat, momentum (wind) and freshwater flux perturbations. This method produces a ζ projection spread comparable in magnitude to the spread that results from greenhouse gas forcing, indicating that the differences in ocean model formulation are the cause, rather than diversity in surface flux change. The heat flux change drives most of the global pattern of ζ change, while the momentum and water flux changes cause locally confined features. North Atlantic heat uptake causes large temperature and salinity driven density changes, altering local ocean transport and ζ. The spread between AOGCMs here is caused largely by differences in their regional transport adjustment, which redistributes heat that was already in the ocean prior to perturbation. The geographic details of the ζ change in the North Atlantic are diverse across models, but the underlying dynamic change is similar. In contrast, the heat absorbed by the Southern Ocean does not strongly alter the vertically coherent circulation. The Arctic ζ change is dissimilar across models, owing to differences in passive heat uptake and circulation change. Only the Arctic is strongly affected by nonlinear interactions between the three air-sea flux changes, and these are model specific.

     

东昆仑南缘早三叠世洪水川组的源区特征:来自碎屑组成、重矿物和岩石地球化学的证据

分布于东昆仑南缘的早三叠世洪水川组系一套由砾岩、砂岩、页岩和鲕粒灰岩等浅海相和河流相沉积物构成的弧前盆地沉积组合.砂岩碎屑组成、重矿物组合、岩石地球化学和古水流综合研究结果表明,洪水川组砂岩物源主要来自于北侧的岛弧带,同时南侧的阿尼玛卿蛇绿混杂带也为其形成提供了部分物源;源区主要出露长英质岩石、变质岩和硅质岩.     

Endogenic heat from Enceladus' south polar fractures: New observations, and models of conductive surface heating

Linear features dubbed “tiger stripes” in the south polar region of Enceladus have anomalously high heat fluxes and are the apparent source of the observed plume. Several explanations for the observed activity have been proposed, including venting from a subsurface reservoir of liquid water, sublimation of surface ice, dissociation of clathrates, and shear heating. Thermal modeling presented in this work, coupled with observations from the Cassini Composite Infrared Spectrometer (CIRS) instrument, seeks to elucidate the underlying physical mechanism by constraining vent temperatures and thermal emission sources, using a model in which the observed thermal signature results primarily from conductive heating of the surface by warm subsurface fractures. The fractures feed surface vents, which may themselves contribute to the observed thermal emission. Model variables include vent temperature, presence of a surface insulating layer, vent width, time-variable heat input, and heat sources other than the central vent. Results indicate that CIRS spectra are best fitted with a model in which the surface is heated by narrow vents at temperatures as high as 223 K. Although equally good fits can be obtained for vent temperatures in the range of 130 to 155 K if the vents are wider (180 m and 22 m respectively) and dominate the emission spectrum, these models are probably less realistic because vents with these temperatures and widths cannot supply the observed H₂O vapor flux. The lack of emission angle dependence of the thermal emission when July 2005 and November 2006 CIRS observations are compared also argues against thermal emission being dominated by the vents themselves. Thus, results favor high-temperature models, possibly venting from a subsurface liquid water reservoir. However, a fracture filled with liquid water near the surface would produce significantly higher radiances than were detected unless masked by a thermally insulating surface layer. Models that best match the CIRS data are characterized by small fractions of the surface at high temperatures, which strengthens the case for the vents and/or their conductively-heated margins being the primary heat source. Models where the thermal emission is dominated by conductive heating of the surface from below by a laterally-extensive buried heat source cannot reproduce the observed spectrum. Models with a 10 cm thick upper insulating layer produce a poor match to the CIRS spectra, suggesting high thermal inertias near the tiger stripes. Finally, tiger stripe thermal emission measured by CIRS varied by less than 15% over the 16 month period from July 2005 to November 2006.     

Steric Sea-Level Change and its Impact on the Gravity Field caused by Global Climate Change

It is sometimes assumed that steric sea-level variations do not produce a gravity signal as no net mass change, thus no change of ocean bottom pressure is associated with it. Analyzing the output of two CO₂ emission scenarios over a period of 2000 years in terms of steric sea-level changes, we try to quantify the gravitational effect of steric sea-level variations. The first scenario, computed with version 2.6 of the Earth System Climate Model developed at the University of Victoria, Canada (UVic ESCM), is implemented with a linear CO₂ increase of 1% of the initial concentration of 365 ppm and shows a globally averaged steric effect of 5.2 m after 2000 years. In the second scenario, computed with UVic ESCM version 2.7, the CO₂ concentration increases quasi-exponentially to a level of 3011 ppm and is hold fixed afterwards. The corresponding globally averaged steric effect in the first 2000 years is 2.3 m. We show, due to the (vertical) redistribution of ocean water masses (expansion or contraction), the steric effect results also in a small change in the Earth’s gravity field compared to usually larger changes associated with net mass changes. Maximum effects for computation points located on the initial ocean surface can be found in scenario 1, with the effect on gravitational attraction and potential ranging from 0.0 to −0.7·10⁻⁵ m s⁻² and −3·10⁻³ to 6·10⁻³ m² s⁻², respectively. As expected, the effect is not zero but negligible for practical applications.     

Slip Sequences in Laboratory Experiments Resulting from Inhomogeneous Shear as Analogs of Earthquakes Associated with a Fault Edge

Faults are intrinsically heterogeneous with common occurrences of jogs, edges and steps. We therefore explore experimentally and theoretically how fault edges may affect earthquake and slip dynamics. In the presented experiments and accompanying theoretical model, shear loads are applied to the edge of one of two flat blocks in frictional contact that form a fault analog. We show that slip occurs via a sequence of rapid rupture events that initiate from the loading edge and are arrested after propagating a finite distance. Each successive event extends the slip size, transfers the applied shear across the block, and causes progressively larger changes of the contact area along the contact surface. Resulting from this sequence of events, a hard asperity is dynamically formed near the loaded edge. The contact area beyond this asperity is largely reduced. These sequences of rapid events culminate in slow slip events that precede a major, unarrested slip event along the entire contact surface. We suggest that the 1998 M5.0 Sendai and 1995 off-Etorofu earthquake sequences may correspond to this scenario. Our work demonstrates, qualitatively, how the simplest deviation from uniform shear loading may significantly affect both earthquake nucleation processes and how fault complexity develops.     

Changing seas in the Early–Middle Miocene of Central Europe: a Mediterranean approach to Paratethyan stratigraphy

The Miocene palaeogeographic evolution of the Paratethys Sea is still poorly constrained. Here, we use modern Mediterranean biochronology to provide an up‐to‐date overview of changing seas in Central Europe. Instead of a Paratethys that waxed and waned with fluctuating global sea levels, we show that the development of different seas was mainly controlled by tectonic phases. The Early Miocene “Ottnangian Sea” (~18 Ma) was connected to the Mediterranean via the Rhône valley, while the “Karpatian Sea” (~16.5 Ma) was initiated by a tectonically induced marine transgression through the Trans‐Tethyan gateway. In most Central European basins, the establishment of the “Badenian Sea” (<15.2 Ma), triggered by subduction‐related processes in the Pannonian and Carpathian domain, is significantly younger (by ~1 Myr) than usually estimated. The updated palaeogeographic reconstructions provide a better understanding of the concepts of basin dynamics, land–sea distribution and palaeoenvironmental change in the Miocene of Central Europe.     

Subvisible CO2 ice clouds detected in the mesosphere of Mars

The formation of CO₂ ice clouds in the upper atmosphere of Mars has been suggested in the past on the basis of a few temperature profiles exhibiting portions colder than CO₂ frost point. However, the corresponding clouds were never observed. In this paper, we discuss the detection of the highest clouds ever observed on Mars by the SPICAM ultraviolet spectrometer on board Mars Express spacecraft. Analyzing stellar occultations, we detected several mesospheric detached layers at about 100 km in the southern winter subtropical latitudes, and found that clouds formed where simultaneous temperature measurements indicated that CO₂ was highly supersaturated and probably condensing. Further analysis of the spectra reveals a cloud opacity in the subvisible range and ice crystals smaller than 100 nm in radius. These layers are therefore similar in nature as the noctilucent clouds which appear on Earth in the polar mesosphere. We interpret these phenomena as CO₂ ice clouds forming inside supersaturated pockets of air created by upward propagating thermal waves. This detection of clouds in such an ultrararefied and supercold atmosphere raises important questions about the martian middle-atmosphere dynamics and microphysics. In particular, the presence of condensates at such high altitudes begs the question of the origin of the condensation nuclei.     

Synthetic stellar and SSP libraries as templates for Gaia simulations

ESA’s Gaia mission will collect low resolution spectroscopy in the optical range for ～10⁹ objects. Complete and up-to-date libraries of synthetic stellar spectra are needed to built algorithms aimed to automatically derive the classification and the parametrization of this huge amount of data. In addition, libraries of stellar spectra are one of the main ingredients of stellar population synthesis models, aiming to derive the properties of unresolved stellar populations from their integrated light. We present (a) the newly computed libraries of synthetic spectra built by the Gaia community, covering the whole optical range (300–1100 nm) at medium-high resolution of (0.3 nm) for stars spanning the most different types, from M to O, from A-peculiar to Emission lines to White Dwarfs, and (b) the implementation of those libraries in our SSP code (Tantalo in The Initial Mass Function 50 Years Later, 327:235 2005), exploring different stellar evolution models.