Polymetallic nanoparticles in pyrite from massive and stockwork ores of VMS deposits of the Iberian Pyrite Belt

This paper reports the first-ever study on nanoscale mineralogy in pyrite from the volcanogenic massive sulfide (VMS) deposits of the Iberian Pyrite Belt, southwestern Iberian Peninsula. It targeted colloform-textured grains formed at low temperature in the distal part of a polymetallic (Pb-Zn) mass...

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Autores: González-Jiménez, José María, Yesares, Lola, Piña, Rubén, Sáez, Reinaldo, Ruíz de Almodóvar, Gerardo, Nieto, Fernando, Tenorio, Sergio
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2022
País:España
Institución:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/358106
Acceso en línea:http://hdl.handle.net/10261/358106
Access Level:acceso abierto
Palabra clave:Arsenian pyrite
Gold
Iberian Pyrite Belt (IPB)
Trace metals
volcanogenic massive sulfides (VMS)
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repository_id_str
dc.title.none.fl_str_mv Polymetallic nanoparticles in pyrite from massive and stockwork ores of VMS deposits of the Iberian Pyrite Belt
title Polymetallic nanoparticles in pyrite from massive and stockwork ores of VMS deposits of the Iberian Pyrite Belt
spellingShingle Polymetallic nanoparticles in pyrite from massive and stockwork ores of VMS deposits of the Iberian Pyrite Belt
González-Jiménez, José María
Arsenian pyrite
Gold
Iberian Pyrite Belt (IPB)
Trace metals
volcanogenic massive sulfides (VMS)
title_short Polymetallic nanoparticles in pyrite from massive and stockwork ores of VMS deposits of the Iberian Pyrite Belt
title_full Polymetallic nanoparticles in pyrite from massive and stockwork ores of VMS deposits of the Iberian Pyrite Belt
title_fullStr Polymetallic nanoparticles in pyrite from massive and stockwork ores of VMS deposits of the Iberian Pyrite Belt
title_full_unstemmed Polymetallic nanoparticles in pyrite from massive and stockwork ores of VMS deposits of the Iberian Pyrite Belt
title_sort Polymetallic nanoparticles in pyrite from massive and stockwork ores of VMS deposits of the Iberian Pyrite Belt
dc.creator.none.fl_str_mv González-Jiménez, José María
Yesares, Lola
Piña, Rubén
Sáez, Reinaldo
Ruíz de Almodóvar, Gerardo
Nieto, Fernando
Tenorio, Sergio
author González-Jiménez, José María
author_facet González-Jiménez, José María
Yesares, Lola
Piña, Rubén
Sáez, Reinaldo
Ruíz de Almodóvar, Gerardo
Nieto, Fernando
Tenorio, Sergio
author_role author
author2 Yesares, Lola
Piña, Rubén
Sáez, Reinaldo
Ruíz de Almodóvar, Gerardo
Nieto, Fernando
Tenorio, Sergio
author2_role author
author
author
author
author
author
dc.contributor.none.fl_str_mv Ministerio de Ciencia e Innovación (España)
European Research Council
Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]
dc.subject.none.fl_str_mv Arsenian pyrite
Gold
Iberian Pyrite Belt (IPB)
Trace metals
volcanogenic massive sulfides (VMS)
topic Arsenian pyrite
Gold
Iberian Pyrite Belt (IPB)
Trace metals
volcanogenic massive sulfides (VMS)
description This paper reports the first-ever study on nanoscale mineralogy in pyrite from the volcanogenic massive sulfide (VMS) deposits of the Iberian Pyrite Belt, southwestern Iberian Peninsula. It targeted colloform-textured grains formed at low temperature in the distal part of a polymetallic (Pb-Zn) massive sulfide lens hosted in felsic volcanoclastic rocks from the Masa Valverde deposit, and euhedral-textured grains (re)-deposited by higher temperature fluids in the Co-Au rich stockwork hosted in black shales of the Filón Norte orebody of the Tharsis deposit. The results acquired by a combination of techniques for mineral microanalysis and characterization (i.e., reflected light, FE-SEM, EPMA, LA-ICP-MS, HRTEM-STEM and TEM-EDS) show that trace amounts of metals (Au, Ag, As, Pb, Sb, Cu, Co) are incorporated as both lattice-bound and into nanoparticles (NPs). The mode of occurrence is strongly related with the evolutionary history of the mineralization. In the colloform pyrite collected from the massive sulfide lens, a rhythmic banding/oscillatory zonation with up to 3 wt% As, 5,000 ppm Pb, 1,070 ppm Sb and 750 ppm Cu is defined by the coexistence of several nano-sized layers (5 to 100 nm) and NPs (<100 nm) containing all these metals. The NPs include galena [PbS], tetrahedrite [(Cu,Fe)SbS)] and arsenopyrite [FeAsS] that exhibit euhedral and less frequently anhedral (i.e., droplet-like) morphologies being both randomly and preferentially oriented with respect to As-rich pyrite bands they are usually associated with. These features suggest formation of the NPs via direct deposition from the hydrothermal fluid(s) or low-temperature melts entrained in them as well as exsolution of trace elements originally dissolved in the As-rich pyrite structure. Additionally, some of these NPs are connected to late fractures disrupting the chemical zoning in colloform pyrite documenting a third genetic type of NPs related to late infiltration of fluids post-dating pyrite formation. In contrast, euhedral pyrite from the stockwork form well-developed homogeneous grains with discrete porous areas relatively depleted in Fe (45.20 wt%), and As (8,800 ppm) but enriched in Co (5,900 ppm). At the nanoscale, Co-enriched domains show patchy zoning defined by irregular distribution of Co– and As-rich bands of 200–500 nm in thickness. These nanometer Co– and As-rich bands are often disrupted by micron-to-nano-sized polycrystalline Au-Ag-Hg particles that fill voids in porous areas. Contact morphology anatomy between Co-rich pyrite and inclusions suggests that the Au-Ag-Hg particles are negative crystals occupying spaces originated in pyrite by coupled dissolution-reprecipitation reaction. Likewise, HRTEM observations along such pyrite-inclusion contacts show the existence of polycrystalline matrices in both pyrite and Au-Ag-Hg inclusions, the former consisting of nano-sized domains of arsenian pyrite and/or arsenopyrite in As-free pyrite and the Au-Ag-Hg inclusions made up of multiple crystal domains including nano-crystallites of Au/Ag or electrum. Recognition of crystalline nanodomains and NPs in these polycrystalline matrices raises the possibility that Au NPs or nanomelts already present in the hydrothermal fluid catalyzed the formation of these heterogeneous crystals.
publishDate 2022
dc.date.none.fl_str_mv 2022
2024
2024
2024
dc.type.none.fl_str_mv info:eu-repo/semantics/article
http://purl.org/coar/resource_type/c_6501
Publisher's version
info:eu-repo/semantics/publishedVersion
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10261/358106
url http://hdl.handle.net/10261/358106
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv #PLACEHOLDER_PARENT_METADATA_VALUE#
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PID2019-111715GB-I00
http://dx.doi.org/10.1016/j.oregeorev.2022.104875
Sí
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.publisher.none.fl_str_mv Elsevier BV
publisher.none.fl_str_mv Elsevier BV
dc.source.none.fl_str_mv reponame:DIGITAL.CSIC. Repositorio Institucional del CSIC
instname:Consejo Superior de Investigaciones Científicas (CSIC)
instname_str Consejo Superior de Investigaciones Científicas (CSIC)
reponame_str DIGITAL.CSIC. Repositorio Institucional del CSIC
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spelling Polymetallic nanoparticles in pyrite from massive and stockwork ores of VMS deposits of the Iberian Pyrite BeltGonzález-Jiménez, José MaríaYesares, LolaPiña, RubénSáez, ReinaldoRuíz de Almodóvar, GerardoNieto, FernandoTenorio, SergioArsenian pyriteGoldIberian Pyrite Belt (IPB)Trace metalsvolcanogenic massive sulfides (VMS)This paper reports the first-ever study on nanoscale mineralogy in pyrite from the volcanogenic massive sulfide (VMS) deposits of the Iberian Pyrite Belt, southwestern Iberian Peninsula. It targeted colloform-textured grains formed at low temperature in the distal part of a polymetallic (Pb-Zn) massive sulfide lens hosted in felsic volcanoclastic rocks from the Masa Valverde deposit, and euhedral-textured grains (re)-deposited by higher temperature fluids in the Co-Au rich stockwork hosted in black shales of the Filón Norte orebody of the Tharsis deposit. The results acquired by a combination of techniques for mineral microanalysis and characterization (i.e., reflected light, FE-SEM, EPMA, LA-ICP-MS, HRTEM-STEM and TEM-EDS) show that trace amounts of metals (Au, Ag, As, Pb, Sb, Cu, Co) are incorporated as both lattice-bound and into nanoparticles (NPs). The mode of occurrence is strongly related with the evolutionary history of the mineralization. In the colloform pyrite collected from the massive sulfide lens, a rhythmic banding/oscillatory zonation with up to 3 wt% As, 5,000 ppm Pb, 1,070 ppm Sb and 750 ppm Cu is defined by the coexistence of several nano-sized layers (5 to 100 nm) and NPs (<100 nm) containing all these metals. The NPs include galena [PbS], tetrahedrite [(Cu,Fe)SbS)] and arsenopyrite [FeAsS] that exhibit euhedral and less frequently anhedral (i.e., droplet-like) morphologies being both randomly and preferentially oriented with respect to As-rich pyrite bands they are usually associated with. These features suggest formation of the NPs via direct deposition from the hydrothermal fluid(s) or low-temperature melts entrained in them as well as exsolution of trace elements originally dissolved in the As-rich pyrite structure. Additionally, some of these NPs are connected to late fractures disrupting the chemical zoning in colloform pyrite documenting a third genetic type of NPs related to late infiltration of fluids post-dating pyrite formation. In contrast, euhedral pyrite from the stockwork form well-developed homogeneous grains with discrete porous areas relatively depleted in Fe (45.20 wt%), and As (8,800 ppm) but enriched in Co (5,900 ppm). At the nanoscale, Co-enriched domains show patchy zoning defined by irregular distribution of Co– and As-rich bands of 200–500 nm in thickness. These nanometer Co– and As-rich bands are often disrupted by micron-to-nano-sized polycrystalline Au-Ag-Hg particles that fill voids in porous areas. Contact morphology anatomy between Co-rich pyrite and inclusions suggests that the Au-Ag-Hg particles are negative crystals occupying spaces originated in pyrite by coupled dissolution-reprecipitation reaction. Likewise, HRTEM observations along such pyrite-inclusion contacts show the existence of polycrystalline matrices in both pyrite and Au-Ag-Hg inclusions, the former consisting of nano-sized domains of arsenian pyrite and/or arsenopyrite in As-free pyrite and the Au-Ag-Hg inclusions made up of multiple crystal domains including nano-crystallites of Au/Ag or electrum. Recognition of crystalline nanodomains and NPs in these polycrystalline matrices raises the possibility that Au NPs or nanomelts already present in the hydrothermal fluid catalyzed the formation of these heterogeneous crystals.The Spanish project CGL2016-79204-R provided funding for field emission gun–environmental scanning electron microscopy (FEG-ESEM) and electron microprobe microanalyses (EMPA)/laser ablation–inductively coupled plasma–mass spectrometry (LA-ICP-MS) analyses of sulfides, respectively, while the PID2019-111715 GB-I00 and 18/IF/6347 project financed FIB-HRTEM analyses. Research grants, infrastructures, and human resources leading to this research have benefited from funding by the European Social Fund and the European Regional Development Fund.Elsevier BVMinisterio de Ciencia e Innovación (España)European Research CouncilConsejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]2024202420222024info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Publisher's versioninfo:eu-repo/semantics/publishedVersionhttp://hdl.handle.net/10261/358106reponame:DIGITAL.CSIC. Repositorio Institucional del CSICinstname:Consejo Superior de Investigaciones Científicas (CSIC)Inglés#PLACEHOLDER_PARENT_METADATA_VALUE#info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PID2019-111715GB-I00http://dx.doi.org/10.1016/j.oregeorev.2022.104875Síinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/3581062026-05-22T06:33:51Z
score 15,81155

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