Weathering-induced Sb isotope fractionation during leaching of stibnite and formation of secondary Sb minerals

Publikation: Beitrag in FachzeitschriftArtikelForschungPeer-Review

Autoren

Externe Organisationen

  • Friedrich-Schiller-Universität Jena
  • Slovak Academy of Sciences
  • Naturhistorisches Museum Prag
  • Technische Universität Wien (TUW)
  • Universität Wien
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OriginalspracheEnglisch
Aufsatznummer122253
Seitenumfang13
FachzeitschriftChemical geology
Jahrgang662
Frühes Online-Datum25 Juni 2024
PublikationsstatusVeröffentlicht - 5 Sept. 2024

Abstract

In this work, we investigated the extent of antimony (Sb) isotopic fractionation during weathering of stibnite at supergene conditions. Antimony isotope data have been obtained from secondary Sb minerals collected from Pezinok, Dobšiná (both Slovakia) and Allchar (North Macedonia) deposits and mine tailings. The Sb isotope compositions of sulfides and secondary Sb minerals formed on the primary stibnite [Sb2S3] or in mine tailings grains were compared with each other. Furthermore, we experimentally investigated Sb isotope fractionation during stibnite leaching with different acids. Our study reveals a large isotopic range for δ123Sb (from −0.50 to +0.69 ‰) for secondary Sb minerals. They are either isotopically indistinguishable or isotopically lighter than the primary stibnite. Isotopically indistinguishable weathering products likely formed by quantitative Sb transfer from stibnite to the secondary minerals, such as brandholzite [Mg(H2O)6[Sb(OH)6]2] from Pezinok. Isotopic fractionation towards lighter δ123Sb was observed for adsorption of Sb onto iron oxides. Distinctly isotopically lighter δ123Sb was observed in secondary Sb minerals tripuhyite [FeSbO4], chapmanite [Fe3+2Sb3+(Si2O5)O3(OH)], hydroxyferroromeite [Fe2Sb2O6(OH)], and stibiconite [Sb3O6OH] that either replace stibnite or formed in mine tailings from the pore solutions. These secondary minerals were likely generated by partial precipitation of Sb from aqueous solutions produced by dissolution of stibnite. In the leaching experiments with HCl and oxalic acid, Sb was leached without significant isotope effects during the first 2–3 days, followed by a drop of the dissolved Sb concentration associated with Sb isotope fractionation towards high δ123Sb in the leachate (by up to 0.5 ‰) after 4–7 days. We interpret these observations to be related to the precipitation of secondary Sb oxides with low δ123Sb, resulting in an isotopically heavy dissolved Sb pool. These findings are in agreement with previous results of isotopically heavy groundwater and mine drainage water with δ123Sb > +0.36 ‰ that may suggest that the ‘truly’ dissolved (operationally defined as <0.45 μm) Sb fraction in general may be isotopically heavy.

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Weathering-induced Sb isotope fractionation during leaching of stibnite and formation of secondary Sb minerals. / Kaufmann, Andreas B.; Lazarov, Marina; Horn, Ingo et al.
in: Chemical geology, Jahrgang 662, 122253, 05.09.2024.

Publikation: Beitrag in FachzeitschriftArtikelForschungPeer-Review

Kaufmann AB, Lazarov M, Horn I, Števko M, Ðorđević T, Kiefer S et al. Weathering-induced Sb isotope fractionation during leaching of stibnite and formation of secondary Sb minerals. Chemical geology. 2024 Sep 5;662:122253. Epub 2024 Jun 25. doi: 10.1016/j.chemgeo.2024.122253
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title = "Weathering-induced Sb isotope fractionation during leaching of stibnite and formation of secondary Sb minerals",
abstract = "In this work, we investigated the extent of antimony (Sb) isotopic fractionation during weathering of stibnite at supergene conditions. Antimony isotope data have been obtained from secondary Sb minerals collected from Pezinok, Dob{\v s}in{\'a} (both Slovakia) and Allchar (North Macedonia) deposits and mine tailings. The Sb isotope compositions of sulfides and secondary Sb minerals formed on the primary stibnite [Sb2S3] or in mine tailings grains were compared with each other. Furthermore, we experimentally investigated Sb isotope fractionation during stibnite leaching with different acids. Our study reveals a large isotopic range for δ123Sb (from −0.50 to +0.69 ‰) for secondary Sb minerals. They are either isotopically indistinguishable or isotopically lighter than the primary stibnite. Isotopically indistinguishable weathering products likely formed by quantitative Sb transfer from stibnite to the secondary minerals, such as brandholzite [Mg(H2O)6[Sb(OH)6]2] from Pezinok. Isotopic fractionation towards lighter δ123Sb was observed for adsorption of Sb onto iron oxides. Distinctly isotopically lighter δ123Sb was observed in secondary Sb minerals tripuhyite [FeSbO4], chapmanite [Fe3+2Sb3+(Si2O5)O3(OH)], hydroxyferroromeite [Fe2Sb2O6(OH)], and stibiconite [Sb3O6OH] that either replace stibnite or formed in mine tailings from the pore solutions. These secondary minerals were likely generated by partial precipitation of Sb from aqueous solutions produced by dissolution of stibnite. In the leaching experiments with HCl and oxalic acid, Sb was leached without significant isotope effects during the first 2–3 days, followed by a drop of the dissolved Sb concentration associated with Sb isotope fractionation towards high δ123Sb in the leachate (by up to 0.5 ‰) after 4–7 days. We interpret these observations to be related to the precipitation of secondary Sb oxides with low δ123Sb, resulting in an isotopically heavy dissolved Sb pool. These findings are in agreement with previous results of isotopically heavy groundwater and mine drainage water with δ123Sb > +0.36 ‰ that may suggest that the {\textquoteleft}truly{\textquoteright} dissolved (operationally defined as <0.45 μm) Sb fraction in general may be isotopically heavy.",
keywords = "Fractionation, Oxidative leaching, Sb isotopes, Secondary minerals, Stibnite, Weathering",
author = "Kaufmann, {Andreas B.} and Marina Lazarov and Ingo Horn and Martin {\v S}tevko and Tamara {\DH}or{\d}evi{\'c} and Stefan Kiefer and Stefan Weyer and Juraj Majzlan",
note = "Publisher Copyright: {\textcopyright} 2024 The Authors",
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doi = "10.1016/j.chemgeo.2024.122253",
language = "English",
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Download

TY - JOUR

T1 - Weathering-induced Sb isotope fractionation during leaching of stibnite and formation of secondary Sb minerals

AU - Kaufmann, Andreas B.

AU - Lazarov, Marina

AU - Horn, Ingo

AU - Števko, Martin

AU - Ðorđević, Tamara

AU - Kiefer, Stefan

AU - Weyer, Stefan

AU - Majzlan, Juraj

N1 - Publisher Copyright: © 2024 The Authors

PY - 2024/9/5

Y1 - 2024/9/5

N2 - In this work, we investigated the extent of antimony (Sb) isotopic fractionation during weathering of stibnite at supergene conditions. Antimony isotope data have been obtained from secondary Sb minerals collected from Pezinok, Dobšiná (both Slovakia) and Allchar (North Macedonia) deposits and mine tailings. The Sb isotope compositions of sulfides and secondary Sb minerals formed on the primary stibnite [Sb2S3] or in mine tailings grains were compared with each other. Furthermore, we experimentally investigated Sb isotope fractionation during stibnite leaching with different acids. Our study reveals a large isotopic range for δ123Sb (from −0.50 to +0.69 ‰) for secondary Sb minerals. They are either isotopically indistinguishable or isotopically lighter than the primary stibnite. Isotopically indistinguishable weathering products likely formed by quantitative Sb transfer from stibnite to the secondary minerals, such as brandholzite [Mg(H2O)6[Sb(OH)6]2] from Pezinok. Isotopic fractionation towards lighter δ123Sb was observed for adsorption of Sb onto iron oxides. Distinctly isotopically lighter δ123Sb was observed in secondary Sb minerals tripuhyite [FeSbO4], chapmanite [Fe3+2Sb3+(Si2O5)O3(OH)], hydroxyferroromeite [Fe2Sb2O6(OH)], and stibiconite [Sb3O6OH] that either replace stibnite or formed in mine tailings from the pore solutions. These secondary minerals were likely generated by partial precipitation of Sb from aqueous solutions produced by dissolution of stibnite. In the leaching experiments with HCl and oxalic acid, Sb was leached without significant isotope effects during the first 2–3 days, followed by a drop of the dissolved Sb concentration associated with Sb isotope fractionation towards high δ123Sb in the leachate (by up to 0.5 ‰) after 4–7 days. We interpret these observations to be related to the precipitation of secondary Sb oxides with low δ123Sb, resulting in an isotopically heavy dissolved Sb pool. These findings are in agreement with previous results of isotopically heavy groundwater and mine drainage water with δ123Sb > +0.36 ‰ that may suggest that the ‘truly’ dissolved (operationally defined as <0.45 μm) Sb fraction in general may be isotopically heavy.

AB - In this work, we investigated the extent of antimony (Sb) isotopic fractionation during weathering of stibnite at supergene conditions. Antimony isotope data have been obtained from secondary Sb minerals collected from Pezinok, Dobšiná (both Slovakia) and Allchar (North Macedonia) deposits and mine tailings. The Sb isotope compositions of sulfides and secondary Sb minerals formed on the primary stibnite [Sb2S3] or in mine tailings grains were compared with each other. Furthermore, we experimentally investigated Sb isotope fractionation during stibnite leaching with different acids. Our study reveals a large isotopic range for δ123Sb (from −0.50 to +0.69 ‰) for secondary Sb minerals. They are either isotopically indistinguishable or isotopically lighter than the primary stibnite. Isotopically indistinguishable weathering products likely formed by quantitative Sb transfer from stibnite to the secondary minerals, such as brandholzite [Mg(H2O)6[Sb(OH)6]2] from Pezinok. Isotopic fractionation towards lighter δ123Sb was observed for adsorption of Sb onto iron oxides. Distinctly isotopically lighter δ123Sb was observed in secondary Sb minerals tripuhyite [FeSbO4], chapmanite [Fe3+2Sb3+(Si2O5)O3(OH)], hydroxyferroromeite [Fe2Sb2O6(OH)], and stibiconite [Sb3O6OH] that either replace stibnite or formed in mine tailings from the pore solutions. These secondary minerals were likely generated by partial precipitation of Sb from aqueous solutions produced by dissolution of stibnite. In the leaching experiments with HCl and oxalic acid, Sb was leached without significant isotope effects during the first 2–3 days, followed by a drop of the dissolved Sb concentration associated with Sb isotope fractionation towards high δ123Sb in the leachate (by up to 0.5 ‰) after 4–7 days. We interpret these observations to be related to the precipitation of secondary Sb oxides with low δ123Sb, resulting in an isotopically heavy dissolved Sb pool. These findings are in agreement with previous results of isotopically heavy groundwater and mine drainage water with δ123Sb > +0.36 ‰ that may suggest that the ‘truly’ dissolved (operationally defined as <0.45 μm) Sb fraction in general may be isotopically heavy.

KW - Fractionation

KW - Oxidative leaching

KW - Sb isotopes

KW - Secondary minerals

KW - Stibnite

KW - Weathering

UR - http://www.scopus.com/inward/record.url?scp=85197097791&partnerID=8YFLogxK

U2 - 10.1016/j.chemgeo.2024.122253

DO - 10.1016/j.chemgeo.2024.122253

M3 - Article

AN - SCOPUS:85197097791

VL - 662

JO - Chemical geology

JF - Chemical geology

SN - 0009-2541

M1 - 122253

ER -

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