The surface chemistry of multi-oxide silicates

The surface chemistry of natural wollastonite, diopside, enstatite, forsterite, and albite in aqueous solutions was characterized using both electrokinetic techniques and surface titrations performed for 20 min in batch reactors. Titrations performed in such reactors allow determination of both proton consumption and metal release from the mineral surface as a function of pH. The compositions, based on aqueous solution analysis, of all investigated surfaces vary dramatically with solution pH. Ca and Mg are preferentially released from the surfaces of all investigated divalent metal silicates at pH less than ∼8.5-10 but preferentially retained relative to silica at higher pH. As such, the surfaces of these minerals are Si-rich and divalent metal poor except in strongly alkaline solutions. The preferential removal of divalent cations from these surfaces is coupled to proton consumption. The number of protons consumed by the preferential removal of each divalent cation is pH independent but depends on the identity of the mineral; ∼1.5 protons are consumed by the preferential removal of each Ca atom from wollastonite, ∼3 protons are consumed by the preferential removal of each Mg or Ca atom from diopside or enstatite, and ∼4 protons are consumed by the preferential removal of each Mg from forsterite. These observations are interpreted to stem from the creation of additional ‘internal’ adsorption sites by the preferential removal of divalent metal cations which can be coupled to the condensation of partially detached Si. Similarly, Na and Al are preferentially removed from the albite surface at 2 > pH > 11; mass balance calculations suggest that three protons are consumed by the preferential removal of each Al atom from this surface over this entire pH range. Electrokinetic measurements on fresh mineral powders yield an isoelectric point (pH_IEP) 2.6, 4.4, 3.0, 4.5, and <1, for wollastonite, diopside, enstatite, forsterite, and albite, respectively, consistent with the predominance of SiO₂ in the surface layer of all of these multi-oxide silicates at acidic pH. Taken together, these observations suggest fundamental differences between the surface chemistry of simple versus multi-oxide minerals including (1) a dependency of the number and identity of multi-oxide silicate surface sites on the aqueous solution composition, and (2) the dominant role of metal-proton exchange reactions on the reactivity of multi-oxide mineral surfaces including their dissolution rate variation with aqueous solution composition.     

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.     

Methane with Abnormally High δ13C and δD Values from the Coastal Hot Springs in Lake Baikal

Lithology and Mineral Resources - We studied the composition and isotopic characteristics (δ13C and δD) of hydrocarbon gases from the Kotelnikovsky, Zmeiny, and Goryachnisky hot springs...     

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.     

Numerical simulation of artificial ground freezing in a fluid-saturated rock mass with account for filtration and mechanical processes

This study is devoted to the numerical simulation of the artificial ground freezing process in a fluid-saturated rock mass of the potassium salt deposit. A coupled model of nonstationary thermal conductivity, filtration and thermo-poroelasticity, which takes into account dependence of the physical properties on temperature and pressure, is proposed on the basis of the accepted hypotheses. The considered area is a cylinder with a depth of 256 meters and diameter of 26.5 meters and includes 13 layers with different thermophysical and filtration properties. Numerical simulation was carried out by the finite-element method. It has been shown that substantial ice wall formation occurs non-uniformly along the layers. This can be connected with geometry of the freezing wells and with difference in physical properties. The average width of the ice wall in each layer was calculated. It was demonstrated that two toroidal convective cells induced by thermogravitational convection were created from the very beginning of the freezing process. The effect of the constant seepage flow on the ice wall formation was investigated. It was shown that the presence of the slow flow lead to the delay in ice wall closure. In case of the flow with a velocity of more than 30 mm per day, closure of the ice wall was not observed at all in the foreseeable time.     

Paleogeographic evolution of the Southern Pannonian Basin: 40Ar/39Ar age constraints on the Miocene continental series of Northern Croatia

The Pannonian Basin, originating during the Early Miocene, is a large extensional basin incorporated between Alpine, Carpathian and Dinaride fold-thrust belts. Back-arc extensional tectonics triggered deposition of up to 500-m-thick continental fluvio-lacustrine deposits distributed in numerous sub-basins of the Southern Pannonian Basin. Extensive andesitic and dacitic volcanism accompanied the syn-rift deposition and caused a number of pyroclastic intercalations. Here, we analyze two volcanic ash layers located at the base and top of the continental series. The lowermost ash from Mt. Kalnik yielded an ⁴⁰Ar/³⁹Ar age of 18.07?±?0.07?Ma. This indicates that the marine-continental transition in the Slovenia-Zagorje Basin, coinciding with the onset of rifting tectonics in the Southern Pannonian Basin, occurs roughly at the Eggenburgian/Ottnangian boundary of the regional Paratethys time scale. This age proves the synchronicity of initial rifting in the Southern Pannonian Basin with the beginning of sedimentation in the Dinaride Lake System. Beside geodynamic evolution, the two regions also share a biotic evolutionary history: both belong to the same ecoregion, which we designate here as the Illyrian Bioprovince. The youngest volcanic ash level is sampled at the Glina and Karlovac sub-depressions, and both sites yield the same ⁴⁰Ar/³⁹Ar age of 15.91?±?0.06 and 16.03?±?0.06?Ma, respectively. This indicates that lacustrine sedimentation in the Southern Pannonian Basin continued at least until the earliest Badenian. The present results provide not only important bench marks on duration of initial synrift in the Pannonian Basin System, but also deliver substantial backbone data for paleogeographic reconstructions in Central and Southeastern Europe around the Early–Middle Miocene transition.