Oxidation mechanism of pyrite in a thiosulfate solution: electrochemical impedance (EIS) and in situ Raman spectroscopy

Ammoniacal thiosulfate has been used lately as an alternative lixiviant for leaching gold from sulfides ores which are not amenable for cyanidation. However, the oxidation of the sulfide minerals generates products that inhibit the dissolution of gold and can promote the degradation of the leaching...

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Autores:
Vásquez Arroyave, Ferley Alejandro
Calderón Gutiérrez, Jorge Andrés
Bedoya Lora, Franky Esteban
Tamayo Sepúlveda, Jose Adrián
Tipo de recurso:
Article of investigation
Fecha de publicación:
2023
Institución:
Universidad de Antioquia
Repositorio:
Repositorio UdeA
Idioma:
eng
OAI Identifier:
oai:bibliotecadigital.udea.edu.co:10495/46095
Acceso en línea:
https://hdl.handle.net/10495/46095
Palabra clave:
Ferric hydroxides
Thiosulfates
Sulfur Compounds
Tiosulfatos
Compuestos de Azufre
Iron oxides
Óxido de hierro
Oxidation of pyrite
http://aims.fao.org/aos/agrovoc/c_2f72fa26
http://id.loc.gov/authorities/subjects/sh85047852
http://id.nlm.nih.gov/mesh/D013885
http://id.nlm.nih.gov/mesh/D013457
ODS 6: Agua limpia y saneamiento. Garantizar la disponibilidad y la gestión sostenible del agua y el saneamiento para todos
ODS 9: Industria, innovación e infraestructura. Construir infraestructuras resilientes, promover la industrialización inclusiva y sostenible y fomentar la innovación
ODS 12: Producción y consumo responsables. Garantizar modalidades de consumo y producción sostenibles
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dc.title.eng.fl_str_mv Oxidation mechanism of pyrite in a thiosulfate solution: electrochemical impedance (EIS) and in situ Raman spectroscopy
title Oxidation mechanism of pyrite in a thiosulfate solution: electrochemical impedance (EIS) and in situ Raman spectroscopy
spellingShingle Oxidation mechanism of pyrite in a thiosulfate solution: electrochemical impedance (EIS) and in situ Raman spectroscopy
Ferric hydroxides
Thiosulfates
Sulfur Compounds
Tiosulfatos
Compuestos de Azufre
Iron oxides
Óxido de hierro
Oxidation of pyrite
http://aims.fao.org/aos/agrovoc/c_2f72fa26
http://id.loc.gov/authorities/subjects/sh85047852
http://id.nlm.nih.gov/mesh/D013885
http://id.nlm.nih.gov/mesh/D013457
ODS 6: Agua limpia y saneamiento. Garantizar la disponibilidad y la gestión sostenible del agua y el saneamiento para todos
ODS 9: Industria, innovación e infraestructura. Construir infraestructuras resilientes, promover la industrialización inclusiva y sostenible y fomentar la innovación
ODS 12: Producción y consumo responsables. Garantizar modalidades de consumo y producción sostenibles
title_short Oxidation mechanism of pyrite in a thiosulfate solution: electrochemical impedance (EIS) and in situ Raman spectroscopy
title_full Oxidation mechanism of pyrite in a thiosulfate solution: electrochemical impedance (EIS) and in situ Raman spectroscopy
title_fullStr Oxidation mechanism of pyrite in a thiosulfate solution: electrochemical impedance (EIS) and in situ Raman spectroscopy
title_full_unstemmed Oxidation mechanism of pyrite in a thiosulfate solution: electrochemical impedance (EIS) and in situ Raman spectroscopy
title_sort Oxidation mechanism of pyrite in a thiosulfate solution: electrochemical impedance (EIS) and in situ Raman spectroscopy
dc.creator.fl_str_mv Vásquez Arroyave, Ferley Alejandro
Calderón Gutiérrez, Jorge Andrés
Bedoya Lora, Franky Esteban
Tamayo Sepúlveda, Jose Adrián
dc.contributor.author.none.fl_str_mv Vásquez Arroyave, Ferley Alejandro
Calderón Gutiérrez, Jorge Andrés
Bedoya Lora, Franky Esteban
Tamayo Sepúlveda, Jose Adrián
dc.contributor.researchgroup.none.fl_str_mv Centro de Investigación Innovación y Desarrollo de Materiales (CIDEMAT)
dc.subject.lcsh.none.fl_str_mv Ferric hydroxides
topic Ferric hydroxides
Thiosulfates
Sulfur Compounds
Tiosulfatos
Compuestos de Azufre
Iron oxides
Óxido de hierro
Oxidation of pyrite
http://aims.fao.org/aos/agrovoc/c_2f72fa26
http://id.loc.gov/authorities/subjects/sh85047852
http://id.nlm.nih.gov/mesh/D013885
http://id.nlm.nih.gov/mesh/D013457
ODS 6: Agua limpia y saneamiento. Garantizar la disponibilidad y la gestión sostenible del agua y el saneamiento para todos
ODS 9: Industria, innovación e infraestructura. Construir infraestructuras resilientes, promover la industrialización inclusiva y sostenible y fomentar la innovación
ODS 12: Producción y consumo responsables. Garantizar modalidades de consumo y producción sostenibles
dc.subject.mesh.none.fl_str_mv Thiosulfates
Sulfur Compounds
dc.subject.decs.none.fl_str_mv Tiosulfatos
Compuestos de Azufre
dc.subject.agrovoc.none.fl_str_mv Iron oxides
Óxido de hierro
dc.subject.proposal.eng.fl_str_mv Oxidation of pyrite
dc.subject.agrovocuri.none.fl_str_mv http://aims.fao.org/aos/agrovoc/c_2f72fa26
dc.subject.lcshuri.none.fl_str_mv http://id.loc.gov/authorities/subjects/sh85047852
dc.subject.meshuri.none.fl_str_mv http://id.nlm.nih.gov/mesh/D013885
http://id.nlm.nih.gov/mesh/D013457
dc.subject.ods.none.fl_str_mv ODS 6: Agua limpia y saneamiento. Garantizar la disponibilidad y la gestión sostenible del agua y el saneamiento para todos
ODS 9: Industria, innovación e infraestructura. Construir infraestructuras resilientes, promover la industrialización inclusiva y sostenible y fomentar la innovación
ODS 12: Producción y consumo responsables. Garantizar modalidades de consumo y producción sostenibles
description Ammoniacal thiosulfate has been used lately as an alternative lixiviant for leaching gold from sulfides ores which are not amenable for cyanidation. However, the oxidation of the sulfide minerals generates products that inhibit the dissolution of gold and can promote the degradation of the leaching solution. The complexity of the ammoniacal thiosulfate leaching system has prevented the unification and clarification of the mechanisms of oxidation of sulfide ores used for gold extraction. In this study, a method combining polarization curves, Electrochemical impedance spectroscopy (EIS), and in situ Raman spectroscopy was implemented to investigate the oxidation process of high-purity pyrite. Pyrite samples were dispersed in carbon paste electrode (CPE-Py). The polarization curves of CPE-Py exhibited an increase in current values for overpotentials greater than 0.1 V, indicating the initiation of mineral oxidation processes. Subsequently, a maximum current was observed initially, followed by subsequent decrease, indicating the occurrence of passivation processes on the electrode surface. Hydrodynamic polarization curves demonstrated that the overpotential at which the passivation process occurs is independent of mass transport, suggesting that the passivation products were formed through solid-state transformation. Impedance spectra revealed that at overpotentials below 0.1 V, a partially resolved capacitive semicircle was observed, which was associated with the resistance encountered when charge was transferred between the solution and the surface layer interface. This resistance decreased as the polarization overpotential increased, implying a decrease in charge transfer kinetics. At higher overpotentials (0.3 V-0.4 V), a second capacitive semicircle appeared, linked to the oxidation of one or several species present in the mineral. In situ Raman spectroscopy was utilized to identify the oxidation species of pyrite in ammonia-thiosulfate ((NH4)2S2O3) leaching solution at a pH = 10.2. The composition of the species varied depending on the applied anodic potential. At low anodic potentials (0.1 V), Fe(OH)2 and thiosulfate (S2O32-) were formed, while at high anodic potentials (0.4 V), iron products such as Fe3O4 and γ-FeOOH, as well as sulfide species including thiosulfate, tetrathionates and sulfates (S2O32-, S4O6-2 and SO42-) were formed.
publishDate 2023
dc.date.issued.none.fl_str_mv 2023
dc.date.accessioned.none.fl_str_mv 2025-05-26T03:19:02Z
dc.type.none.fl_str_mv Artículo de investigación
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dc.identifier.citation.none.fl_str_mv J. A. Tamayo, F. A. Vásquez, F. Bedoya, and J. A. Calderón, "Oxidation mechanism of pyrite in a thiosulfate solution: Electrochemical Impedance (EIS) and In Situ Raman Spectroscopy", Heliyon, vol. 9, no. 11, 2023, doi: 10.1016/j.heliyon.2023.e21809.
dc.identifier.uri.none.fl_str_mv https://hdl.handle.net/10495/46095
dc.identifier.doi.none.fl_str_mv 10.1016/j.heliyon.2023.e21809
dc.identifier.eissn.none.fl_str_mv 2405-8440
identifier_str_mv J. A. Tamayo, F. A. Vásquez, F. Bedoya, and J. A. Calderón, "Oxidation mechanism of pyrite in a thiosulfate solution: Electrochemical Impedance (EIS) and In Situ Raman Spectroscopy", Heliyon, vol. 9, no. 11, 2023, doi: 10.1016/j.heliyon.2023.e21809.
10.1016/j.heliyon.2023.e21809
2405-8440
url https://hdl.handle.net/10495/46095
dc.language.iso.none.fl_str_mv eng
language eng
dc.relation.ispartofjournalabbrev.none.fl_str_mv Heliyon
dc.relation.citationendpage.none.fl_str_mv 13
dc.relation.citationissue.none.fl_str_mv 11
dc.relation.citationstartpage.none.fl_str_mv 1
dc.relation.citationvolume.none.fl_str_mv 9
dc.relation.ispartofjournal.none.fl_str_mv Heliyon
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spelling Vásquez Arroyave, Ferley AlejandroCalderón Gutiérrez, Jorge AndrésBedoya Lora, Franky EstebanTamayo Sepúlveda, Jose AdriánCentro de Investigación Innovación y Desarrollo de Materiales (CIDEMAT)2025-05-26T03:19:02Z2023J. A. Tamayo, F. A. Vásquez, F. Bedoya, and J. A. Calderón, "Oxidation mechanism of pyrite in a thiosulfate solution: Electrochemical Impedance (EIS) and In Situ Raman Spectroscopy", Heliyon, vol. 9, no. 11, 2023, doi: 10.1016/j.heliyon.2023.e21809.https://hdl.handle.net/10495/4609510.1016/j.heliyon.2023.e218092405-8440Ammoniacal thiosulfate has been used lately as an alternative lixiviant for leaching gold from sulfides ores which are not amenable for cyanidation. However, the oxidation of the sulfide minerals generates products that inhibit the dissolution of gold and can promote the degradation of the leaching solution. The complexity of the ammoniacal thiosulfate leaching system has prevented the unification and clarification of the mechanisms of oxidation of sulfide ores used for gold extraction. In this study, a method combining polarization curves, Electrochemical impedance spectroscopy (EIS), and in situ Raman spectroscopy was implemented to investigate the oxidation process of high-purity pyrite. Pyrite samples were dispersed in carbon paste electrode (CPE-Py). The polarization curves of CPE-Py exhibited an increase in current values for overpotentials greater than 0.1 V, indicating the initiation of mineral oxidation processes. Subsequently, a maximum current was observed initially, followed by subsequent decrease, indicating the occurrence of passivation processes on the electrode surface. Hydrodynamic polarization curves demonstrated that the overpotential at which the passivation process occurs is independent of mass transport, suggesting that the passivation products were formed through solid-state transformation. Impedance spectra revealed that at overpotentials below 0.1 V, a partially resolved capacitive semicircle was observed, which was associated with the resistance encountered when charge was transferred between the solution and the surface layer interface. This resistance decreased as the polarization overpotential increased, implying a decrease in charge transfer kinetics. At higher overpotentials (0.3 V-0.4 V), a second capacitive semicircle appeared, linked to the oxidation of one or several species present in the mineral. In situ Raman spectroscopy was utilized to identify the oxidation species of pyrite in ammonia-thiosulfate ((NH4)2S2O3) leaching solution at a pH = 10.2. The composition of the species varied depending on the applied anodic potential. At low anodic potentials (0.1 V), Fe(OH)2 and thiosulfate (S2O32-) were formed, while at high anodic potentials (0.4 V), iron products such as Fe3O4 and γ-FeOOH, as well as sulfide species including thiosulfate, tetrathionates and sulfates (S2O32-, S4O6-2 and SO42-) were formed.Universidad de Antioquia. Vicerrectoría de investigación. Comité para el Desarrollo de la Investigación - CODIColombia. Ministerio de Ciencia, Tecnología e Innovación - MinCienciasInstituto Tecnológico Metropolitano - ITMCOL000792713 páginasapplication/pdfengElsevierLondres, Inglaterrahttp://creativecommons.org/licenses/by-nc-nd/4.0/info:eu-repo/semantics/openAccessAttribution-NonCommercial-NoDerivatives 4.0 Internationalhttp://purl.org/coar/access_right/c_abf2https://pubmed.ncbi.nlm.nih.gov/38027955/Ferric hydroxidesThiosulfatesSulfur CompoundsTiosulfatosCompuestos de AzufreIron oxidesÓxido de hierroOxidation of pyritehttp://aims.fao.org/aos/agrovoc/c_2f72fa26http://id.loc.gov/authorities/subjects/sh85047852http://id.nlm.nih.gov/mesh/D013885http://id.nlm.nih.gov/mesh/D013457ODS 6: Agua limpia y saneamiento. Garantizar la disponibilidad y la gestión sostenible del agua y el saneamiento para todosODS 9: Industria, innovación e infraestructura. Construir infraestructuras resilientes, promover la industrialización inclusiva y sostenible y fomentar la innovaciónODS 12: Producción y consumo responsables. 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