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Significance of pH and iron-sulfur chemistry for molybdenum sequestration under sulfidic conditions
Abstract
Molybdenum (Mo), a redox-sensitive trace metal, plays an important role in recording ancient oxygenation and deoxygenation events as a paleoredox proxy. The mobility and reactivity of Mo in aqueous conditions are closely tied to the chemistry of reduced sulfur and iron species. However, our current knowledge on the formation, structure, stability, and condensation pathways of FeMoS clusters in aqueous settings remains limited, which has driven the current study. In this study, we conducted systematic experiments investigating the interactions between dissolved Mo (initially introduced as molybdate, MoO42–, or tetrathiomolybdate, MoS42–), ferrous iron (Fe2+), and sulfide (ΣH2Saq) in variously defined abiotic sulfidic systems to determine the external conditions (i.e., pH, and reactant concentrations and ratios) necessary for the formation of solid-phase Fe-Mo sulfides. Solution samples of each system were monitored using ultraviolet-visible spectroscopy (UV–vis) to track the degree of thiolation of dissolved Mo species. Precipitates were analyzed using X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) to determine their elemental compositions and valences, and structure (i.e., crystalline or amorphous), respectively. All FeMoS precipitates were amorphous and contained 76–90% Mo(IV) and 10–24% Mo(V) with a trend toward lower Mo(IV):Mo(V) ratios with increasing pH. The degree of Mo thiolation, which was strongly dependentmore »
- Authors:
-
- University of Texas at El Paso, TX (United States); Arizona State University, Tempe, AZ (United States)
- Virginia Polytechnic Institute and State University (Virginia Tech), Blacksburg, VA (United States)
- Arizona State University, Tempe, AZ (United States)
- Publication Date:
- Research Org.:
- Univ. of Texas at El Paso, TX (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 2204410
- Grant/Contract Number:
- SC0021995
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Chemical Geology
- Additional Journal Information:
- Journal Volume: 638; Journal ID: ISSN 0009-2541
- Publisher:
- Elsevier
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 58 GEOSCIENCES; Molybdenum sequestration; Paleoredox proxy; Molybdate; Thiomolybdate; Mixed-metal-sulfide formation
Citation Formats
Phillips, Rachel, Singerling, Sheryl, Leng, Weinan, and Xu, Jie. Significance of pH and iron-sulfur chemistry for molybdenum sequestration under sulfidic conditions. United States: N. p., 2023.
Web. doi:10.1016/j.chemgeo.2023.121702.
Phillips, Rachel, Singerling, Sheryl, Leng, Weinan, & Xu, Jie. Significance of pH and iron-sulfur chemistry for molybdenum sequestration under sulfidic conditions. United States. https://doi.org/10.1016/j.chemgeo.2023.121702
Phillips, Rachel, Singerling, Sheryl, Leng, Weinan, and Xu, Jie. Fri .
"Significance of pH and iron-sulfur chemistry for molybdenum sequestration under sulfidic conditions". United States. https://doi.org/10.1016/j.chemgeo.2023.121702.
@article{osti_2204410,
title = {Significance of pH and iron-sulfur chemistry for molybdenum sequestration under sulfidic conditions},
author = {Phillips, Rachel and Singerling, Sheryl and Leng, Weinan and Xu, Jie},
abstractNote = {Molybdenum (Mo), a redox-sensitive trace metal, plays an important role in recording ancient oxygenation and deoxygenation events as a paleoredox proxy. The mobility and reactivity of Mo in aqueous conditions are closely tied to the chemistry of reduced sulfur and iron species. However, our current knowledge on the formation, structure, stability, and condensation pathways of FeMoS clusters in aqueous settings remains limited, which has driven the current study. In this study, we conducted systematic experiments investigating the interactions between dissolved Mo (initially introduced as molybdate, MoO42–, or tetrathiomolybdate, MoS42–), ferrous iron (Fe2+), and sulfide (ΣH2Saq) in variously defined abiotic sulfidic systems to determine the external conditions (i.e., pH, and reactant concentrations and ratios) necessary for the formation of solid-phase Fe-Mo sulfides. Solution samples of each system were monitored using ultraviolet-visible spectroscopy (UV–vis) to track the degree of thiolation of dissolved Mo species. Precipitates were analyzed using X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) to determine their elemental compositions and valences, and structure (i.e., crystalline or amorphous), respectively. All FeMoS precipitates were amorphous and contained 76–90% Mo(IV) and 10–24% Mo(V) with a trend toward lower Mo(IV):Mo(V) ratios with increasing pH. The degree of Mo thiolation, which was strongly dependent on solution pH and Fe2+ concentrations, greatly affected the amount of Mo sequestered (i.e., an increased degree of Mo thiolation in solution led to an increased amount of Mo in the final FeMoS precipitate). Furthermore, these findings suggest that changes in pH and Fe2+ concentrations may be responsible for the sulfide-independent variations in Mo behavior observed in euxinic basins.},
doi = {10.1016/j.chemgeo.2023.121702},
journal = {Chemical Geology},
number = ,
volume = 638,
place = {United States},
year = {Fri Sep 01 00:00:00 EDT 2023},
month = {Fri Sep 01 00:00:00 EDT 2023}
}
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