Experimental investigation of the effects of temperature and ionic strength on Mo isotope fractionation during adsorption to manganese oxides

The Mo stable isotope system is being applied to study changes in ocean redox. Such applications implicitly assume that Mo isotope fractionation in aqueous systems is relatively insensitive to frequently changing environmental variables such as temperature (T) and ionic strength (I). A major driver of fractionation is the adsorption of Mo to Mn oxyhydroxide surfaces [Barling J. and Anbar A. D. (2004) Molybdenum isotope fractionation during adsorption by manganese oxides. Earth Planet. Sci. Lett.217(3-4), 315-329]. Here, we report the results of experiments that determine the extent to which Mo isotope fractionation during adsorption of Mo to the Mn oxyhydroxide mineral birnessite is sensitive to T and I. The results are compared to new predictions from quantum chemical computations. We measured fractionation from 1 to 50 °C at I = 0.1 m and found that Δ^97/95Mo_{dissolved-adsorbed} varies from 1.9‰ to 1.6‰ over this temperature range. Experiments were also performed at 25 °C in synthetic seawater (I = 0.7); fractionation at this condition was the same within analytical error as in low ionic strength experiments. These findings confirm that the Mo isotope fractionation during adsorption to Mn oxyhydroxides is relatively insensitive to variations and T and I over environmentally relevant ranges. To relate these findings to potential mechanisms of Mo isotope fractionation, we also report results for density functional theory computations of the fractionation between and various possible structures of molybdic acid as a function of temperature. Because no plausible species fractionates from with a magnitude matching the experiments, we are left with three possibilities to explain the fractionation: (1) solvation effects on the vibrational frequencies of aqueous species considered thus far are significant, such that our calculations in vacuo yield inaccurate fractionations; (2) a trace aqueous species not yet considered fractionates from and then adsorbs to birnessite; or (3) a surface complex not present in solution forms on birnessite in which Mo is not tetrahedrally coordinated. Our findings help validate assumptions underlying paleoceanographic applications of the Mo isotope system and also lead us closer to understanding the mechanism of isotope fractionation during adsorption of Mo to Mn oxyhydroxides.     

The iron-isotope fractionation dictated by the carboxylic functional: An ab-initio investigation

The ground-state geometries, electronic energies and vibrational properties of carboxylic complexes of iron were investigated both in vacuo and under the effect of a reaction field, to determine thermodynamic properties of iron-acetates and the role of the carboxylic functional on the isotopic imprinting of this metal in metalorganic complexation. The electronic energy, zero point corrections and thermal corrections of these substances at variational state were investigated at the DFT/B3LYP level of theory with different basis set expansions and the effect of the reaction field on the variational structures was investigated through the Polarized Continuun Model. Thermochemical cycle calculations, combined with solvation energy calculations and appropriate scaling from absolute to conventional properties allowed to compute the Gibbs free energy of formation from the elements of the investigated aqueous species and to select the best procedure to be applied in the successive vibrational analysis. The best compliance with the few existing thermodynamic data for these substances was obtained by coupling the gas phase calculations at DFT/B3LYP level with the [6-31G(d,p)]-[6-31G+(d,p)] (for cations and neutral molecules - anions; respectively) with solvation calculations adopting atomic radii optimized for the HF/6-31G(d) level of theory (UAHF). A vibrational analysis conducted on ⁵⁴Fe, ⁵⁶Fe, ⁵⁷Fe and ⁵⁸Fe gaseous isotopomers yielded reduced partition function ratios which increased not only with the nominal valence of the central cation, as expected, but, more importantly, with the extent of the complexation operated by the organic functional. Coupling thermodynamic data with separative effects it was shown that this last is controlled, as expected, by the relative bond strength of the complex in both aggregation states. Through the Integral Equation Formalism of the Polarized Continuum Model (IEFPCM) the effect of the ionic strength of the solution and of a T-dependent permittivity on the energy and separative effects of the solvated metalorganic complexes were analyzed in detail. The solvent effect in the standard state (hypothetical one-molal solution referred to infinite dilution; T = 298.15 K, P = 1 bar) is a limited reduction of the separative effects of all the isotopomeric couples. With an increase in T (and the concomitant decrease in the dielectric constant of the solvent) this effect diminishes progressively.     

Thermodynamic model for arsenic speciation in sulfidic waters: A novel use of ab initio computations

Recent discoveries demonstrate that the chemistry of arsenic in sulfidic waters is much more complex that previously believed. One implication is that all earlier thermodynamic data on stabilities of As thioanions require revision. Previously used experimental approaches for determining As thioanion stabilities may be inadequate to deal with the full range of complexity. Here we use computational as well as empirical information to construct a provisional model for equilibrium As thioanion distributions in sulfidic waters. Whereas previous authors have argued for either As(III) or As(V) thioanions, the new model predicts that both are important and can occur simultaneously under commonly encountered pH and ΣS^−II conditions. At the order of magnitude level, the model reasonably predicts the solubility of As₂S₃ in sulfidic solutions, provides tentative peak assignments for published Raman spectroscopic data and plausibly accounts for how sulfide modifies the bacterial toxicity of As. The model yields a thermodynamic justification for how sulfide, which is usually regarded as a reducing agent, can counter-intuitively drive oxidation of As(III) to As(V), as has been observed both in the laboratory and in the field. Despite its uncertain accuracy, the model serves as a useful source of new, testable hypotheses about As geochemistry and highlights crucial experimental data needs.     

Exurbia from the bottom-up: Confronting empirical challenges to characterizing a complex system

We describe empirical results from a multi-disciplinary project that support modeling complex processes of land-use and land-cover change in exurban parts of Southeastern Michigan. Based on two different conceptual models, one describing the evolution of urban form as a consequence of residential preferences and the other describing land-cover changes in an exurban township as a consequence of residential preferences, local policies, and a diversity of development types, we describe a variety of empirical data collected to support the mechanisms that we encoded in computational agent-based models. We used multiple methods, including social surveys, remote sensing, and statistical analysis of spatial data, to collect data that could be used to validate the structure of our models, calibrate their specific parameters, and evaluate their output. The data were used to investigate this system in the context of several themes from complexity science, including have (a) macro-level patterns; (b) autonomous decision making entities (i.e., agents); (c) heterogeneity among those entities; (d) social and spatial interactions that operate across multiple scales and (e) nonlinear feedback mechanisms. The results point to the importance of collecting data on agents and their interactions when producing agent-based models, the general validity of our conceptual models, and some changes that we needed to make to these models following data analysis. The calibrated models have been and are being used to evaluate landscape dynamics and the effects of various policy interventions on urban land-cover patterns.     

The posthumous tectonics and mechanism of exhumation of granitic plutons: The case of the Transbaikal region and the Tien Shan

The study of granitic plutons of the Baikal Highland and the Tien Shan has made it possible to establish new features of their posthumous (after incorporation into the consolidated Earth’s crust) structural reworking and to understand the implications of the cataclastic flow for the exhumation of the crystalline basement in the studied regions. It is shown that granitic plutons undergo appreciable structural transformation at the stages of tectonic reactivation that is significantly separated in time from the moment of formation of plutons as geological bodies. The 3D cataclastic deformation is the main mode of structural reworking of granitic plutons, while the cataclastic flow is the main form of their mobility. Newly recognized slice structures characterize the volumetric deformation of granites.     

Late Precambrian rifting in the geological history of the western slope of the South Urals

The rift-related geodynamic setting of the Late Precambrian geological evolution on the western slope of the South Urals is reconstructed on the basis of localization of lithotectonic complexes of this age, their formation conditions, and the geochemistry of rocks. The Early Riphean stage comprises accumulation of coarse-clastic rocks intercalating with alkaline volcanic rocks of the Navysh Complex, which is a constituent of the Ai Formation, and emplacement of doleritic and picritic intrusions of the Shuida Complex and melanocratic dolerite and gabbrodolerite of the Yusha Complex. The Middle Riphean stage is characterized by wide-spread coarse-clastic terrigenous rocks of the Mashak Formation that intercalate with volcanic rocks of the bimodal basalt-rhyolite association, the Berdyaush pluton of rapakivi granite, the Kusa-Kopan layered intrusive complex, the Lapyshta Complex of dolerites and picrites, and numerous occurrences of gabbrodolerites. The terrigenous rocks of the Vendian stage include conglomerate, gravelstone, and sandstone of the Asha Group, while igneous rocks comprise alkaline volcanics of the Arsha Complex, alkali gabbroids of the Miseli Complex, and melanocratic syenite of the Avashla Complex. The geological evolution of the region is distinguished by local (failed or aborted) rifting. The occurrence of lithotectonic complexes is controlled by dynamic conditions of rifting. A certain inheritance in the evolution may be traced for the Early and Middle Riphean and partly for the Late Riphean and Vendian.     

Crystalline basement and fold complex of the Volga-Ural, Pericaspian, and Fore-Caucasus petroliferous basins

3D models of apparent magnetization and density of rocks allow us to provide insights into the deep structure of the Volga-Ural, Pericaspian, and Fore-Caucasus petroliferous basins. In the Volga-Ural Basin, some Riphean rifts reveal close spatial relations to Paleoproterozoic linear zones, presumably of the rift nature as well. The structure of the Paleoproterozoic Toropets-Serdobsk Belt is interpreted in detail. Rocks with petrophysical properties inherent to basic volcanics are established in the pre-Paleozoic basement of the marginal zone of the Pericaspian Basin. These rocks locally spread beyond the boundary escarpment and may be regarded as a part of the Riphean plume-related basaltic province. It is shown that the Pericaspian Basin was formed on the place of a triple junction of Riphean rifts: the Sarpa and Central Pericaspian oceanic branches and the continental branch of the Pachelma Aulacogen. The drastically different petrophysical properties of the basement beneath Baltica and the Astrakhan Arch indicate that this arch is an element of the large terrane that was attached to Baltica in the Vendian. The suture along which the Astrachan Terrane is conjugated with the basement of the central and southern segments of the Karpinsky Ridge is traced beneath the Paleozoic complex. A system of northwest-verging thrust faults formed during the collision between Scythia and Eurasia is mapped in the basement of the junction zone between the Karpinsky Ridge and Scythian Platform (Terrane). According to geological data, this event took place in the Early Paleozoic.     

Lateral protrusions in the structure of the Earth’s lithosphere

The factual material and modeling results concerning the geology of specific structural elements defined as lateral protrusions, or flowing layers, are considered. The formation of such structural elements is a fundamental phenomenon that controls many features of the structural evolution and geodynamics of platform basement and foldbelts. A lateral protrusion, or flowing layer, is a spatially constrained, nearly horizontal geological body with attributes of 3D tectonic flow (rheid deformation) and lateral transport of rock masses. Flowing layers are large lateral protrusions that play important role in the structure of the continental and oceanic lithosphere. They embody the internal mobility of huge rock bodies and confirm the possibility of their lateral redistribution at different depths of the continental lithosphere. The lateral displacement of rocks within such assemblies may occur in the regime of cold deformation, heating, metamorphism, and ductile flow of rocks under subsolidus conditions or in the process of their partial melting.     

Geochronology of Pliocene volcanism in the Dzhavakheti Highland (the Lesser Caucasus). Part 1: Western part of the Dzhavakheti Highland

Isotopic-geochronological study of the Pliocene magmatic activity in western part of the Dzhavakheti Highland (northwestern region of the Lesser Caucasus) is carried out. The results obtained imply that the Pliocene magmatic activity lasted in this part of the highland approximately 2 million years from 3.75 to 1.75–1.55 Ma. As is established, the studied volcanic rocks correspond in composition mostly to K-Na subalkaline and more abundant normal basalts. Time constraints of main phases in development of basic volcanism within the study region are figured out. We assume that individual pulses of silicic to moderately silicic volcanism presumably took place in the Dzhavakheti Highland about 3.2 and 2.5 Ma ago.     

On the global stratotype section and point of the Triassic base

A unique succession of volcanogenic deposits with representative paleontological remains characterizing the Permian-Triassic boundary interval in the North Siberian platform and Taimyr is described. The succession is suitable for selecting a standard for the Triassic base in nonmarine deposits. Abundant and diverse fossils occurring in the succession evidence that volcanism responsible for origin of the plateau basalt province in Siberia was not a brief epoch of paroxysmal eruptions, which eliminated everything alive. Throughout the formation history of relevant plateau basalts, the organic world of the plateau and around existed and gradually evolved.