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Compositional Systematics of Sphalerites from Western Bergslagen, Sweden Huvud- Och Spårelementsystematik I Zinkblände Från Västra Bergslagen, Sverige

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Compositional Systematics of Sphalerites from Western Bergslagen, Sweden Huvud- Och Spårelementsystematik I Zinkblände Från Västra Bergslagen, Sverige Examensarbete vid Institutionen för geovetenskaper Degree Project at the Department of Earth Sciences ISSN 1650-6553 Nr 370 Compositional Systematics of Sphalerites from Western Bergslagen, Sweden Huvud- och spårelementsystematik i zinkblände från västra Bergslagen, Sverige Aristeidis Kritikos INSTITUTIONEN FÖR GEOVETENSKAPER DEPARTMENT OF EARTH SCIENCES Examensarbete vid Institutionen för geovetenskaper Degree Project at the Department of Earth Sciences ISSN 1650-6553 Nr 370 Compositional Systematics of Sphalerites from Western Bergslagen, Sweden Huvud- och spårelementsystematik i zinkblände från västra Bergslagen, Sverige Aristeidis Kritikos ISSN 1650-6553 Copyright © Aristeidis Kritikos Published at Department of Earth Sciences, Uppsala University (www.geo.uu.se), Uppsala, 2016 Abstract Compositional Systematics of Sphalerites from Western Bergslagen, Sweden Aristeidis Kritikos Sphalerite is, apart from being the main global source of zinc (Zn), also one of the main source for the critical elements indium (In), gallium (Ga) and germanium (Ge), which can be extracted as by-products during Zn mining. In the westernmost part of the Palaeoproterozoic Bergslagen ore province, Sweden, In-anomalies have been reported from sulphide mineralizations. These In-anomalies can be attributed to either pre-ore formation crustal processes manifested by the local (Svecofennian, c. 1.87-1.89 Ga) syn-volcanic mineralisations, or to epigenetic metasomatic events primarily related to younger (c. 1.80- 1.79 Ga) granitoids. In this study, sphalerite samples from 19 different mineralisations in westernmost Bergslagen were examined by both electron probe microanalyzer (EPMA) and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), in order to firstly, measure trace element concentrations, and especially those of the critical element In, Ga and Ge, and secondly, to apply this information to gain new information on the trace element inventory and incorporation mechanisms of sphalerite. The dataset also allows for testing the ore-formation process models, not least in cases of elevated In- contents. Utilization of these two analytical methods also provided the opportunity for a direct spot-to- spot comparison of their performance in detecting trace element concentrations in sphalerite. The results verify the In-enrichment of the area, whereas Ga and Ge only follow crustal abundancies. The concentrations of the other trace elements vary significantly, even at a sample scale. The compositional variation shows several patterns between certain elements, suggesting that their incorporation in the sphalerite lattice was allowed via substitution mechanisms (e.g. In3++(Cu+,Ag+)↔2Zn2+; Fe2++Cd2++Mn2+↔3Zn2+; Cu++Mn2++In3+↔3Zn2+). In contrast, some measured high Cd, Ag and Pb concentrations are attributed to nano (or micro) inclusions of primarily galena. Other elements such as As, Sn, Sb, Se, Au, Tl, Ni, Te and Mo yielded, in almost all the samples, concentrations below the detection limit for both analytical methods. Discrimination methods based on trace element concentrations and distribution of the In-enriched mineralizations suggest that the In- anomalies are most likely related to Svecofennian volcanic to subvolcanic hydrothermal processes, forming mineralisations that were later modified during the Svecokarelian orogeny. Finally, the direct comparison of EPMA results to that of LA-ICP-MS, showed the significantly better performance of the latter method in detecting trace-level concentrations, provided that a proper calibration procedure has been followed. Keywords: Western Bergslagen, sphalerite, critical elements, trace elements, substitution mechanisms, EPMA, LA-ICP-MS. Degree Project E1 in Earth Science, 1GV025, 30 credits Supervisors: Karin Högdahl and Erik Jonsson Department of Earth Sciences, Uppsala University, Villavägen 16, SE-752 36 Uppsala (www.geo.uu.se) ISSN 1650-6553, Examensarbete vid Institutionen för geovetenskaper, No. 370, 2016 The whole document is available at www.diva-portal.org Populärvetenskaplig sammanfattning Huvud-och spårelementsystematik i zinkblände från västra Bergslagen, Sverige Aristeidis Kritikos Sulfidmineralet zinkblände är, förutom att vara den huvudsakliga globala källan för zink (Zn), också ett av de viktigaste värdmineralen för de kritiska metallerna indium (In), gallium (Ga) och germanium (Ge), vilka kan utvinnas som viktiga biprodukter vid zinkbrytning. I den västligaste delen av malmprovinsen Bergslagen i Mellansverige har In-anomalier rapporterats från flera mineraliseringar. Dessa lokala In-anrikningar kan tillskrivas antingen processer verksamma innan och under den vulkaniska aktiviteten, eller senare geologiska händelser relaterade till yngre graniter. I denna studie har zinkblände från 19 olika mineraliseringar i västra Bergslagen karakteriserats med två olika system för mikrokemisk analys; elektronmikrosond (EPMA) och laserablativ induktivt kopplad plasma-masspektrometri (LA-ICP-MS). Detta har gjorts för att mäta spårelementhalter, och särskilt då för de kritiska metallerna In, Ga och Ge. Genom att använda dessa två metoder parallellt gavs också möjligheten till direkta jämförelser mellan dem vad gäller deras kapacitet för spårelementanalys av zinkblände. Resultaten verifierar att detta område är anomalt In-anrikat, medan halterna av Ga och Ge är låga och endast följer genomsnittshalterna för kontinental jordskorpa. Halterna av de övriga spårelementen varierar avsevärt, även på individuell provskala, och visar i flera fall systematiska mönster mellan vissa element. Dessa mönster tyder på att deras införlivande i zinkbländestrukturen gått via flera specifika utbytes-(substitutions-)mekanismer (t.ex. In3++ (Cu+, Ag+) ↔2Zn2+; Fe2+ + Cd2++ Mn2+ ↔3Zn2+, Cu++ Mn2++ In3+ ↔3Zn2+). Däremot kan förhöjda halter av Cd, Ag och Pd tillskrivas nano- (eller mikro-) inneslutningar av framförallt blyglans. Andra element, som As, Sn, Sb, Se, Au, TI, Ni, Te och Mo uppvisade halter under detektionsgränserna för båda analysmetoderna i nästan alla undersökta prov. Bildningsmässiga (genetiska) diskrimineringsmetoder baserade på spårelementhalter kombinerat med de geologiska och spatiella relationerna för de In-anrikade mineraliseringarna tyder på att de senare bildades genom svekofenniska vulkanisk-hydrotermala processer och därefter modifierats under svekokarelsk bergskedjebildning. Slutligen, i den direkta jämförelsen av EPMA gentemot LA-ICP-MS, visade den senare metoden signifikant bättre kapacitet för spårämnesanalys, förutsatt att ett korrekt kalibreringsprotokoll har följts. Nyckelord: Västra Bergslagen, zinkblände, kritiska metaller, spårelement, substitutionsmekanismer, EPMA, LA-ICP-MS. Examensarbete E1 i geovetenskap, 1GV025, 30 hp Handledare: Karin Högdahl och Erik Jonsson Institutionen för geovetenskaper, Uppsala universitet, Villavägen 16, 752 36 Uppsala (www.geo.uu.se) ISSN 1650-6553, Examensarbete vid Institutionen för geovetenskaper, Nr 370, 2016 Hela publikationen finns tillgänglig på www.diva-portal.org Table of Contents 1. Introduction and background ............................................................................................. 1 1.1 Critical elements for energy saving devices .................................................................................. 2 1.2 Sphalerite ...................................................................................................................................... 3 2. Geological setting of the Bergslagen ore province ............................................................ 5 2.1 Volcanic evolution ........................................................................................................................ 9 2.2 Metallogenesis of Bergslagen ..................................................................................................... 10 3. Methodology ....................................................................................................................... 11 3.1 Sample preparation ..................................................................................................................... 13 3.2 Reflected light microscopy ......................................................................................................... 13 3.3 Electron Microprobe Analysis .................................................................................................... 14 3.3.1 EPMA analytical setup ...................................................................................... 15 3.4 LA-ICP-MS ................................................................................................................................. 16 3.4.1 LA-ICP-MS analytical setup .............................................................................. 17 4. Studied mineralizations ..................................................................................................... 18 4.1 Långban ....................................................................................................................................... 20 4.2 Lahäll .......................................................................................................................................... 21 4.3 Myssfallet .................................................................................................................................... 22 4.4 Myssberget/Mysstjärnen ............................................................................................................. 23 4.5 Näset ..........................................................................................................................................
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