scholarly journals The trisulfur radical ion S3•− controls platinum transport by hydrothermal fluids

2021 ◽  
Vol 118 (34) ◽  
pp. e2109768118
Author(s):  
Gleb S. Pokrovski ◽  
Maria A. Kokh ◽  
Elsa Desmaele ◽  
Clément Laskar ◽  
Elena F. Bazarkina ◽  
...  
Keyword(s):  
Elevated Temperatures ◽  
High Capacity ◽  
Selective Extraction ◽  
Hydrothermal Fluids ◽  
Thermodynamic Simulations ◽  
Poorly Soluble ◽  
Chloride Sulfate ◽  
Economic Concentration ◽  
Shallow Crust

Platinum group elements (PGE) are considered to be very poorly soluble in aqueous fluids in most natural hydrothermal–magmatic contexts and industrial processes. Here, we combined in situ X-ray absorption spectroscopy and solubility experiments with atomistic and thermodynamic simulations to demonstrate that the trisulfur radical ion S3•− forms very stable and soluble complexes with both PtII and PtIV in sulfur-bearing aqueous solution at elevated temperatures (∼300 °C). These Pt-bearing species enable (re)mobilization, transfer, and focused precipitation of platinum up to 10,000 times more efficiently than any other common inorganic ligand, such as hydroxide, chloride, sulfate, or sulfide. Our results imply a far more important contribution of sulfur-bearing hydrothermal fluids to PGE transfer and accumulation in the Earth’s crust than believed previously. This discovery challenges traditional models of PGE economic concentration from silicate and sulfide melts and provides new possibilities for resource prospecting in hydrothermal shallow crust settings. The exceptionally high capacity of the S3•− ion to bind platinum may also offer new routes for PGE selective extraction from ore and hydrothermal synthesis of noble metal nanomaterials.

scholarly journals Sulfur radical species form gold deposits on Earth

2015 ◽  
Vol 112 (44) ◽  
pp. 13484-13489 ◽  
Author(s):  
Gleb S. Pokrovski ◽  
Maria A. Kokh ◽  
Damien Guillaume ◽  
Anastassia Y. Borisova ◽  
Pascal Gisquet ◽  
...  
Keyword(s):  
Elevated Temperatures ◽  
Gold Deposits ◽  
Key Factors ◽  
Radical Species ◽  
X Ray ◽  
Thermodynamic Simulations ◽  
X Ray Absorption ◽  
Source Concentration ◽  
Sulfur Radical

Current models of the formation and distribution of gold deposits on Earth are based on the long-standing paradigm that hydrogen sulfide and chloride are the ligands responsible for gold mobilization and precipitation by fluids across the lithosphere. Here we challenge this view by demonstrating, using in situ X-ray absorption spectroscopy and solubility measurements, coupled with molecular dynamics and thermodynamic simulations, that sulfur radical species, such as the trisulfur ion S3−, form very stable and soluble complexes with Au+ in aqueous solution at elevated temperatures (>250 °C) and pressures (>100 bar). These species enable extraction, transport, and focused precipitation of gold by sulfur-rich fluids 10–100 times more efficiently than sulfide and chloride only. As a result, S3− exerts an important control on the source, concentration, and distribution of gold in its major economic deposits from magmatic, hydrothermal, and metamorphic settings. The growth and decay of S3− during the fluid generation and evolution is one of the key factors that determine the fate of gold in the lithosphere.

Electron and ion irradiation-induced dissolution of mechanical twins in the intermetalic U3Si: An in situ HVEM study

1989 ◽  
Vol 47 ◽  
pp. 652-653
Author(s):  
Charles W. Allen ◽  
Robert C. Birtcher
Keyword(s):  
Elevated Temperatures ◽  
Ion Irradiation ◽  
Ion Beam ◽  
National Laboratory ◽  
Argonne National Laboratory ◽  
Heavy Ion ◽  
High Energy ◽  
Mechanical Twinning ◽  
In Situ Experiments

The uranium silicides, including U3Si, are under study as candidate low enrichment nuclear fuels. Ion beam simulations of the in-reactor behavior of such materials are performed because a similar damage structure can be produced in hours by energetic heavy ions which requires years in actual reactor tests. This contribution treats one aspect of the microstructural behavior of U3Si under high energy electron irradiation and low dose energetic heavy ion irradiation and is based on in situ experiments, performed at the HVEM-Tandem User Facility at Argonne National Laboratory. This Facility interfaces a 2 MV Tandem ion accelerator and a 0.6 MV ion implanter to a 1.2 MeV AEI high voltage electron microscope, which allows a wide variety of in situ ion beam experiments to be performed with simultaneous irradiation and electron microscopy or diffraction.At elevated temperatures, U3Si exhibits the ordered AuCu3 structure. On cooling below 1058 K, the intermetallic transforms, evidently martensitically, to a body-centered tetragonal structure (alternatively, the structure may be described as face-centered tetragonal, which would be fcc except for a 1 pet tetragonal distortion). Mechanical twinning accompanies the transformation; however, diferences between electron diffraction patterns from twinned and non-twinned martensite plates could not be distinguished.

The threshold energy for atom displacement in fcc metals

1990 ◽  
Vol 48 (4) ◽  
pp. 530-531
Author(s):  
Wilfried Sigle ◽  
Matthias Hohenstein ◽  
Alfred Seeger
Keyword(s):  
Growth Rate ◽  
Elevated Temperatures ◽  
Threshold Energy ◽  
Dislocation Loops ◽  
Absolute Minimum ◽  
Voltage Electron ◽  
Atom Displacement ◽  
Electron Microscopes ◽  
Fcc Metal

Prolonged electron irradiation of metals at elevated temperatures usually leads to the formation of large interstitial-type dislocation loops. The growth rate of the loops is proportional to the total cross-section for atom displacement,which is implicitly connected with the threshold energy for atom displacement, Ed . Thus, by measuring the growth rate as a function of the electron energy and the orientation of the specimen with respect to the electron beam, the anisotropy of Ed can be determined rather precisely. We have performed such experiments in situ in high-voltage electron microscopes on Ag and Au at 473K as a function of the orientation and on Au as a function of temperature at several fixed orientations.Whereas in Ag minima of Ed are found close to <100>,<110>, and <210> (13-18eV), (Fig.1) atom displacement in Au requires least energy along <100>(15-19eV) (Fig.2). Au is thus the first fcc metal in which the absolute minimum of the threshold energy has been established not to lie in or close to the <110> direction.

In Situ Polymerized Protic Ionogels for Fuel Cells at Elevated Temperatures

2021 ◽  
Author(s):  
Mengdou Zou ◽  
Jie Luo ◽  
Xurui Wang ◽  
Shuai Tan ◽  
Caihong Wang ◽  
...  
Keyword(s):  
Fuel Cells ◽  
Elevated Temperatures

scholarly journals Ultraviolet Absorption Cross-Sections of Ammonia at Elevated Temperatures for Nonintrusive Quantitative Detection in Combustion Environments

2021 ◽  
pp. 000370282199044
Author(s):  
Wubin Weng ◽  
Shen Li ◽  
Marcus Aldén ◽  
Zhongshan Li
Keyword(s):  
Cross Section ◽  
Cross Sections ◽  
Absorption Cross Section ◽  
Elevated Temperatures ◽  
Uv Absorption ◽  
Energy Utilization ◽  
Quantitative Detection ◽  
Absorption Cross ◽  
Hot Gas

Ammonia (NH3) is regarded as an important nitrogen oxides (NOx) precursor and also as an effective reductant for NOx removal in energy utilization through combustion, and it has recently become an attractive non-carbon alternative fuel. To have a better understanding of thermochemical properties of NH3, accurate in situ detection of NH3 in high temperature environments is desirable. Ultraviolet (UV) absorption spectroscopy is a feasible technique. To achieve quantitative measurements, spectrally resolved UV absorption cross-sections of NH3 in hot gas environments at different temperatures from 295 K to 590 K were experimentally measured for the first time. Based on the experimental results, vibrational constants of NH3 were determined and used for the calculation of the absorption cross-section of NH3 at high temperatures above 590 K using the PGOPHER software. The investigated UV spectra covered the range of wavelengths from 190 nm to 230 nm, where spectral structures of the [Formula: see text] transition of NH3 in the umbrella bending mode, v2, were recognized. The absorption cross-section was found to decrease at higher temperatures. For example, the absorption cross-section peak of the (6, 0) vibrational band of NH3 decreases from ∼2 × 10−17 to ∼0.5 × 10−17 cm2/molecule with the increase of temperature from 295 K to 1570 K. Using the obtained absorption cross-section, in situ nonintrusive quantification of NH3 in different hot gas environments was achieved with a detection limit varying from below 10 parts per million (ppm) to around 200 ppm as temperature increased from 295 K to 1570 K. The quantitative measurement was applied to an experimental investigation of NH3 combustion process. The concentrations of NH3 and nitric oxide (NO) in the post flame zone of NH3–methane (CH4)–air premixed flames at different equivalence ratios were measured.

scholarly journals Rapid alteration of fractured volcanic conduits beneath Mt Unzen

2021 ◽  
Vol 83 (5) ◽  
Author(s):  
Tim I. Yilmaz ◽  
Fabian B. Wadsworth ◽  
H. Albert Gilg ◽  
Kai-Uwe Hess ◽  
Jackie E. Kendrick ◽  
...  
Keyword(s):  
Country Rock ◽  
Geophysical Methods ◽  
Hydrothermal Fluids ◽  
Deep Drilling ◽  
Stress Regime ◽  
Argillic Alteration ◽  
Carbon And Oxygen Isotope ◽  
Propylitic Alteration ◽  
Indirect Information

AbstractThe nature of sub-volcanic alteration is usually only observable after erosion and exhumation at old inactive volcanoes, via geochemical changes in hydrothermal fluids sampled at the surface, via relatively low-resolution geophysical methods or can be inferred from erupted products. These methods are spatially or temporally removed from the real subsurface and thus provide only indirect information. In contrast, the ICDP deep drilling of the Mt Unzen volcano subsurface affords a snapshot into the in situ interaction between the dacitic dykes that fed dome-forming eruptions and the sub-volcanic hydrothermal system, where the most recent lava dome eruption occurred between 1990 and 1995. Here, we analyse drill core samples from hole USDP-4, constraining their degree and type of alteration. We identify and characterize two clay alteration stages: (1) an unusual argillic alteration infill of fractured or partially dissolved plagioclase and hornblende phenocryst domains with kaolinite and Reichweite 1 illite (70)-smectite and (2) propylitic alteration of amphibole and biotite phenocrysts with the fracture-hosted precipitation of chlorite, sulfide and carbonate minerals. These observations imply that the early clay-forming fluid was acidic and probably had a magmatic component, which is indicated for the fluids related to the second chlorite-carbonate stage by our stable carbon and oxygen isotope data. The porosity in the dyke samples is dominantly fracture-hosted, and fracture-filling mineralization is common, suggesting that the dykes were fractured during magma transport, emplacement and cooling, and that subsequent permeable circulation of hydrothermal fluids led to pore clogging and potential partial sealing of the pore network on a timescale of ~ 9 years from cessation of the last eruption. These observations, in concert with evidence that intermediate, crystal-bearing magmas are susceptible to fracturing during ascent and emplacement, lead us to suggest that arc volcanoes enclosed in highly fractured country rock are susceptible to rapid hydrothermal circulation and alteration, with implications for the development of fluid flow, mineralization, stress regime and volcanic edifice structural stability. We explore these possibilities in the context of alteration at other similar volcanoes.

scholarly journals In situ XRD and operando spectra-electrochemical investigation of tetragonal WO3-x nanowire networks for electrochromic supercapacitors

2021 ◽  
Vol 13 (1) ◽  
Author(s):  
Shen Wang ◽  
Hongbo Xu ◽  
Tingting Hao ◽  
Peiyuan Wang ◽  
Xiang Zhang ◽  
...  
Keyword(s):  
Reaction Mechanism ◽  
Electronic Device ◽  
High Capacity ◽  
Optical Modulation ◽  
Function Evaluation ◽  
Dual Function ◽  
Electrochemical Performances ◽  
Electrochemical Cycling ◽  
Nanowire Networks

AbstractElectrochromic supercapacitors (ESCs) are appealing for smart electronic device applications due to their advantages of dual-function integration. Unfortunately, the synchronous dual-function evaluation and the essential reaction mechanism are ambiguous. Herein, we constructed a 3D WO3-x nanowire networks/fluorine-doped tin oxide (WO3-x NWNs/FTO) bifunctional electrode for ESCs by a solvothermal self-crystal seeding method. The synchronous correspondence relationship between the optical and electrochemical performances of the WO3-x NWNs/FTO electrode was explored using an operando spectra-electrochemical characterization method. It reveals an excellent areal capacity of 57.57 mF cm−2 with a high corresponding optical modulation (ΔT) of 85.05% and high optical-electrochemical cycling stability. Furthermore, the synergistic reaction mechanism between the Al3+ ion intercalation behavior and the surface pseudocapacitance reaction during electrochemical cycling is revealed utilizing in situ X-ray diffraction. Based on these results, an ESC device was constructed by pairing WO3-x/FTO as the cathode with V2O5 nanoflowers/FTO (V2O5 NFs/FTO) as the anode, which simultaneously deliver high capacity and large optical modulation. Moreover, the energy storage level of the ESC device could be visually monitored by rapid and reversible color transitions in real time. This work provides a promising pathway to developing multi-functional integrated smart supercapacitors.

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