Accurate Determination of Barium Isotopic Compositions in Sequentially Leached Phases from Carbonates by Double Spike-Thermal Ionization Mass Spectrometry (DS-TIMS).

Recent studies have proposed barium isotopes as a novel proxy for studying primary productivity in paleo-oceangraphical studies and elements cycling through the critical zone. Pristine marine carbonates are generally assumed to preserve Ba isotope compositions of ancient seawater. However, Ba incorporated in or adsorbed on detrital minerals such as clays in impure carbonates may limit the accurate application of the Ba isotope proxy for paleo-ocean environmental reconstruction purposes. We present here a sequential extraction procedure and show that a considerable range of Ba concentrations can be associated with the four operationally defined sequential leaching fractions (water-soluble, exchangeable, carbonate, and oxidizable fractions). Chemical separation of Ba from these leachates is achieved with a recovery of >98.6% by our modified ion exchange procedure. Potential instrumental mass bias effects and barium isotope fractionation during the chemical separation are corrected using a carefully optimized 130Ba-135Ba double-spike method. A long-term reproducibility better than ±0.03‰ (2SD) for δ137/134Ba has been achieved by using the double spike-thermal ionization mass spectrometry (DS-TIMS) in this study. We demonstrate that significant variations of δ137/134Ba in the analyzed leachates suggest a considerable Ba isotope fractionation between carbonate mineral phase and noncarbonate phases of marine carbonate rocks. The barium isotope distribution in a set of standard reference materials and natural geological samples under various geological settings has been presented. When utilizing Ba isotopes as a proxy for primary productivity and the biogeochemical cycling of Ba, our new findings from sequential Ba extraction as well as our modified precise DS-TIMS analytical setup should be taken into account.

Silicon Isotope Geochemistry: Fractionation Linked to Silicon Complexations and Its Geological Applications.

The fundamental advances in silicon isotope geochemistry have been systematically demonstrated in this work. Firstly, the continuous modifications in analytical approaches and the silicon isotope variations in major reservoirs and geological processes have been briefly introduced. Secondly, the silicon isotope fractionation linked to silicon complexation/coordination and thermodynamic conditions have been extensively stressed, including silicate minerals with variable structures and chemical compositions, silica precipitation and diagenesis, chemical weathering of crustal surface silicate rocks, biological uptake, global oceanic Si cycle, etc. Finally, the relevant geological implications for meteorites and planetary core formation, ore deposits formation, hydrothermal fluids activities, and silicon cycling in hydrosphere have been summarized. Compared to the thermodynamic isotope fractionation of silicon associated with high-temperature processes, that in low-temperature geological processes is much more significant (e.g., chemical weathering, biogenic/non-biogenic precipitation, biological uptake, adsorption, etc.). The equilibrium silicon isotope fractionation during the mantle-core differentiation resulted in the observed heavy isotope composition of the bulk silicate Earth (BSE). The equilibrium fractionation of silicon isotopes among silicate minerals are sensitive to the Si-O bond length, Si coordination numbers (CN), the polymerization degrees of silicate unites, and the electronegativity of cations in minerals. The preferential enrichment of different speciation of dissoluble Si (DSi) (e.g., silicic acid H4SiO4° (H4) and H3SiO4- (H3)) in silica precipitation and diagenesis, and chemical weathering, lead to predominately positive Si isotope signatures in continental surface waters, in which the dynamic fractionation of silicon isotope could be well described by the Rayleigh fractionation model. The role of complexation in biological fractionations of silicon isotopes is more complicated, likely involving several enzymatic processes and active transport proteins. The integrated understanding greatly strengthens the potential of δ30Si proxy for reconstructing the paleo terrestrial and oceanic environments, and exploring the meteorites and planetary core formation, as well as constraining ore deposits and hydrothermal fluid activity.

Matrix Effects Originating from Coexisting Minerals and Accurate Determination of Stable Silver Isotopes in Silver Deposits.

Except for extensive studies in core formation and volatile-element depletion processes using radiogenic Ag isotopes (i.e., the Pd-Ag chronometer), recent research has revealed that the mass fractionation of silver isotopes is in principle controlled by physicochemical processes (e.g., evaporation, diffusion, chemical exchange, etc.) during magmatic emplacement and hydrothermal alteration. As these geologic processes only produce very minor variations of δ109Ag from -0.5 to +1.1‰, more accurate and precise measurements are required. In this work, a robust linear relationship between instrumental mass discrimination of Ag and Pd isotopes was obtained at the Ag/Pd molar ratio of 1:20. In Au-Ag ore deposits, silver minerals have complex paragenetic relationships with other minerals (e.g., chalcopyrite, sphalerite, galena, pyrite, etc.). It is difficult to remove such abundant impurities completely because the other metals are tens to thousands of times richer than silver. Both quantitative evaluation of matrix effects and modification of chemical chromatography were carried out to deal with the problems. Isobaric inferences (e.g., 65Cu40Ar+ to 105Pd, 208Pb2+ to 104Pd, and 67Zn40Ar+ to 107Ag+) and space charge effects dramatically shift the measured δ109Ag values. The selection of alternative Pd isotope pairs is effective in eliminating spectral matrix effects so as to ensure accurate analysis under the largest possible ranges for metal impurities, which are Cu/Ag ≤ 50:1, Fe/Ag ≤ 600:1, Pb/Ag ≤ 10:1, and Zn/Ag ≤ 1:1, respectively. With the modified procedure, we reported silver isotope compositions (δ109Ag) in geological standard materials and typical Au-Ag ore deposit samples varying from -0.029 to +0.689 ‰ with external reproducibility of ±0.009-0.084 ‰. A systemic survey of δ109Ag (or ε109Ag) variations in rocks, ore deposits, and environmental materials in nature is discussed.

Adsorption Behavior of Metasilicate on N-Methyl d-Glucamine Functional Groups and Associated Silicon Isotope Fractionation.

Significant isotope fractionation of silicon provides a powerful geochemical tracer for biological and physicochemical processes in terrestrial and marine environments. The exact mechanism involved in silicon uptake as part of the biological process is not well known. The silicon uptake in biological processes is investigated using silicate adsorption onto the N-methylglucamine functional group (sugarlike structure, abbreviated as L) of Amberlite IRA-743 resin as an analogue of the formation of silicate-sugar complexes in plants. This study provides new evidence that certain sugars can react readily with basic silicic acid to form sugar-silicate chelating complexes, and the equilibrium adsorption behavior of silicate can be well described by the Langmuir isotherm with a Gibbs free energy (ΔG) of -11.94 ± 0.21 kJ·mol(-1) at 293 K. The adsorption kinetics corresponds well to a first-order kinetic model in which the adsorption rate constant ka of 1.25 × 10(-4) s(-1) and the desorption rate constant kd of 4.00 × 10(-6) s(-1) are obtained at 293 K. Both ka and kd increase with increasing temperature. The bonding configurations of silicate-sugar complexes imply the principal coordination complex of hexacoordinated silicon (silicon/L = 1:3) in the liquid phase and the dominant tetracoordinated silicon in the solid phase. Similar to those of many natural processes, the biological uptake via the sugar-silicate chelating complexes favors the preferential enrichment of light Si isotopes into solids, and the Rayleigh model controls the dynamic isotope fractionation with an estimated silicon isotope fractionation factor (i.e., αsolid-solution = [Formula: see text]) of 0.9971. This study advanced the fundamental understanding of the dynamic isotope fractionation of silicon during silicon cycling from the lithosphere to the biosphere and hydrosphere in surficial processes.

Seawater barium and sulfide removal improved marine habitability for the Cambrian Explosion of early animals.

An increase in atmospheric pO2 has been proposed as a trigger for the Cambrian Explosion at ∼539-514 Ma but the mechanistic linkage remains unclear. To gain insights into marine habitability for the Cambrian Explosion, we analysed excess Ba contents (Baexcess) and isotope compositions (δ138Baexcess) of ∼521-Myr-old metalliferous black shales in South China. The δ138Baexcess values vary within a large range and show a negative logarithmic correlation with Baexcess, suggesting a major (>99%) drawdown of oceanic Ba inventory via barite precipitation. Spatial variations in Baexcess and δ138Baexcess indicate that Ba removal was driven by sulfate availability that was ultimately derived from the upwelling of deep seawaters. Global oceanic oxygenation across the Ediacaran-Cambrian transition may have increased the sulfate reservoir via oxidation of sulfide and concurrently decreased the Ba reservoir by barite precipitation. The removal of both H2S and Ba that are deleterious to animals could have improved marine habitability for early animals.