{"title":"Osmium Transport and Enrichment From the Lithosphere to the Hydrosphere: New Perspectives From Hydrothermal Experiments and Geochemical Modeling","authors":"Haibo Yan, Xing Ding, Junfeng Liu, Xianglin Tu, Weidong Sun, I-Ming Chou","doi":"10.1029/2023JB028261","DOIUrl":null,"url":null,"abstract":"<p>Metal complexation and speciation is the primary process responsible for metal transport and circulation in hydrothermal systems, during which stable and soluble metal complexes play a pivotal role. Here, we investigate the speciation of Os and the thermodynamic stability of Os(IV)-Cl complexes in chloride-bearing solutions at temperatures ranging from 150 to 600°C and pressure of 100 MPa through hydrolysis experiments. The results show that the dominant species of Os is OsCl<sub>6</sub><sup>2−</sup> at temperatures between 150 and 450°C and 100 MPa, gradually converting into Os(IV)-OH-Cl and Os(II)-Cl complexes over 450°C. The equilibrium constant (ln <i>K</i>) (<i>K</i> = [HCl]<sup>4</sup> ⨯ [Cl<sup>−</sup>]<sup>2</sup>/[OsCl<sub>6</sub><sup>2−</sup>]) between OsCl<sub>6</sub><sup>2−</sup> and water molecule is determined as ln <i>K</i> = (50.43 ± 4.633) − (54223 ± 2525.6)/<i>T</i>, and Δ<sub><i>r</i></sub><i>H</i><sub><i>m</i></sub><sup><i>Θ</i></sup> and Δ<sub><i>r</i></sub><i>S</i><sub><i>m</i></sub><sup><i>Θ</i></sup> are inferred to be (450.8 ± 21.00) kJ · mol<sup>−1</sup> and (419.3 ± 38.52) J · mol<sup>−1</sup> · K<sup>−1</sup>. Furthermore, the formation constant (ln <i>β</i>) of OsCl<sub>6</sub><sup>2−</sup> exhibits a change from −0.097 to −0.104 as temperatures increase from 150 to 400°C, while the change values in standard Gibbs free energy (Δ<sub><i>r</i></sub><i>G</i><sub><i>m</i></sub><sup><i>Θ</i></sup>) for the hydrolysis reactions decrease with rising temperature, suggesting a temperature-dependent thermodynamic stability of OsCl<sub>6</sub><sup>2−</sup>. Geochemical modeling further demonstrates that high solubility of OsCl<sub>6</sub><sup>2−</sup> could exist in low-temperature and acidic fluids (≤300°C and pH < 5), or relatively high-temperature and acidic-neutral fluids (>300°C and pH < 7), primarily influenced by the Cl concentration. Acidic and near-neutral fluids with high Cl concentration venting in the mid-ocean ridge, back-arc, and sediment-hosted systems contribute more to dissolving and transporting Os from the lithosphere to the hydrosphere, thereby impacting the global ocean dissolved Os budget.</p>","PeriodicalId":15864,"journal":{"name":"Journal of Geophysical Research: Solid Earth","volume":null,"pages":null},"PeriodicalIF":3.9000,"publicationDate":"2024-07-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Geophysical Research: Solid Earth","FirstCategoryId":"89","ListUrlMain":"https://onlinelibrary.wiley.com/doi/10.1029/2023JB028261","RegionNum":2,"RegionCategory":"地球科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"GEOCHEMISTRY & GEOPHYSICS","Score":null,"Total":0}
引用次数: 0
Abstract
Metal complexation and speciation is the primary process responsible for metal transport and circulation in hydrothermal systems, during which stable and soluble metal complexes play a pivotal role. Here, we investigate the speciation of Os and the thermodynamic stability of Os(IV)-Cl complexes in chloride-bearing solutions at temperatures ranging from 150 to 600°C and pressure of 100 MPa through hydrolysis experiments. The results show that the dominant species of Os is OsCl62− at temperatures between 150 and 450°C and 100 MPa, gradually converting into Os(IV)-OH-Cl and Os(II)-Cl complexes over 450°C. The equilibrium constant (ln K) (K = [HCl]4 ⨯ [Cl−]2/[OsCl62−]) between OsCl62− and water molecule is determined as ln K = (50.43 ± 4.633) − (54223 ± 2525.6)/T, and ΔrHmΘ and ΔrSmΘ are inferred to be (450.8 ± 21.00) kJ · mol−1 and (419.3 ± 38.52) J · mol−1 · K−1. Furthermore, the formation constant (ln β) of OsCl62− exhibits a change from −0.097 to −0.104 as temperatures increase from 150 to 400°C, while the change values in standard Gibbs free energy (ΔrGmΘ) for the hydrolysis reactions decrease with rising temperature, suggesting a temperature-dependent thermodynamic stability of OsCl62−. Geochemical modeling further demonstrates that high solubility of OsCl62− could exist in low-temperature and acidic fluids (≤300°C and pH < 5), or relatively high-temperature and acidic-neutral fluids (>300°C and pH < 7), primarily influenced by the Cl concentration. Acidic and near-neutral fluids with high Cl concentration venting in the mid-ocean ridge, back-arc, and sediment-hosted systems contribute more to dissolving and transporting Os from the lithosphere to the hydrosphere, thereby impacting the global ocean dissolved Os budget.
期刊介绍:
The Journal of Geophysical Research: Solid Earth serves as the premier publication for the breadth of solid Earth geophysics including (in alphabetical order): electromagnetic methods; exploration geophysics; geodesy and gravity; geodynamics, rheology, and plate kinematics; geomagnetism and paleomagnetism; hydrogeophysics; Instruments, techniques, and models; solid Earth interactions with the cryosphere, atmosphere, oceans, and climate; marine geology and geophysics; natural and anthropogenic hazards; near surface geophysics; petrology, geochemistry, and mineralogy; planet Earth physics and chemistry; rock mechanics and deformation; seismology; tectonophysics; and volcanology.
JGR: Solid Earth has long distinguished itself as the venue for publication of Research Articles backed solidly by data and as well as presenting theoretical and numerical developments with broad applications. Research Articles published in JGR: Solid Earth have had long-term impacts in their fields.
JGR: Solid Earth provides a venue for special issues and special themes based on conferences, workshops, and community initiatives. JGR: Solid Earth also publishes Commentaries on research and emerging trends in the field; these are commissioned by the editors, and suggestion are welcome.