LA-ICP-MS analyses of minor and trace elements and bulk Ge isotopes in zoned Ge-rich sphalerites from the Noailhac – Saint-Salvy deposit (France): Insights into incorporation mechanisms and ore deposition processes

Belissont, Rémi; Boiron, Marie-Christine; Luais, Béatrice; Cathelineau, ‪Michel

doi:10.1016/j.gca.2013.10.052

Cited by 248 publications

(143 citation statements)

References 53 publications

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“…We used two separate analytical protocols for sulfates/silicates and sulfides/sulfosalts, respectively. For alunite, barite and dickite, the collected analytes were 27 Al, 31 P, 44 Ca, 49 Ti, 53 Cr, 55 Mn, 57 Fe, 65 Cu, 66 Zn, 71 Ga, 72 Ge, 75 As, 77 Se, 85 Rb, 88 Sr, 98 Mo, 107 Ag, 115 In, 118 Sn, 121 Sb, 137 Ba, 139 La, 140 Ce, 197 Au, 208 Pb, 209 Bi, 232 Th and 238 U. The internal standard isotopes used for data reduction were 27 Al (alunite and dickite) and 137 Ba (barite), based on contents confirmed previously by WDS.…”

Section: La-icp-ms Spot Analysesmentioning

confidence: 99%

“…NIST-SRM-610 [51] was used as a bracketing external standard, and GSE-1G and GSD-1G [52] were analyzed as secondary standards to evaluate accuracy. For enargite, sphalerite, pyrite and galena, the collected analytes were 51 V, 52 Cr, 55 Mn, 57 Fe, 59 Co, 60 Ni, 65 Cu, 66 Zn, 71 Ga, 72 Ge, 75 As, 77 Se, 95 Mo, 107 Ag, 114 Cd, 115 In, 118 Sn, 121 Sb, 125 Te, 197 Au, 202 Hg, 205 Tl, 208 Pb and 209 Bi. USGS Mass-1 [53] was used as a bracketing external standard, and NIST-SRM-610, GSE-1G and GSD-1G were used as secondary standards.…”

Section: La-icp-ms Spot Analysesmentioning

confidence: 99%

“…However, a high activity of Cu or Ag may still promote the formation of Ge-bearing Cu or Ag sulfides at lower sulfur activities [9]. The precise nature of Ge incorporation into sphalerite is less clear, and potentially more complex, than that of In and Ga [10,69,74,75,107,108]. It is, therefore, difficult to assess possible physicochemical controls on Ge enrichment in these ores.…”

Section: In-ga ± Ge Mineralization In Intermediate-sulfidation Sphalementioning

confidence: 99%

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Mineralogical Distribution of Germanium, Gallium and Indium at the Mt Carlton High-Sulfidation Epithermal Deposit, NE Australia, and Comparison with Similar Deposits Worldwide

et al. 2017

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Germanium, gallium and indium are in high demand due to their growing usage in high-tech and green-tech applications. However, the mineralogy and the mechanisms of concentration of these critical elements in different types of hydrothermal ore deposits remain poorly constrained. We investigated the mineralogical distribution of Ge, Ga and In at the Mt Carlton high-sulfidation epithermal deposit in NE Australia, using electron probe microanalysis and laser ablation inductively-coupled plasma mass spectrometry. Parageneses from which selected minerals were analyzed include: Stage 1 acid sulfate alteration (alunite), Stage 2A high-sulfidation enargite mineralization (enargite, argyrodite, sphalerite, pyrite, barite), Stage 2B intermediate-sulfidation sphalerite mineralization (sphalerite, pyrite, galena) and Stage 3 hydrothermal void fill (dickite). Moderate to locally high concentrations of Ga were measured in Stage 1 alunite (up to 339 ppm) and in Stage 3 dickite (up to 150 ppm). The Stage 2A ores show enrichment in Ge, which is primarily associated with argyrodite (up to 6.95 wt % Ge) and Ge-bearing enargite (up to 2189 ppm Ge). Co-existing sphalerite has comparatively low Ge content (up to 143 ppm), while Ga (up to 1181 ppm) and In (up to 571 ppm) are higher. Sphalerite in Stage 2B contains up to 611 ppm Ge, 2829 ppm Ga and 2169 ppm In, and locally exhibits fine colloform bands of an uncharacterized Zn-In mineral with compositions close to CuZn 2 (In,Ga)S 4 . Barite, pyrite and galena which occur in association with Stage 2 mineralization were found to play negligible roles as carriers of Ge, Ga and In at Mt Carlton. Analyzed reference samples of enargite from seven similar deposits worldwide have average Ge concentrations ranging from 12 to 717 ppm (maximum 2679 ppm). The deposits from which samples showed high enrichment in critical elements in this study are all hosted in stratigraphic sequences that locally contain carbonaceous sedimentary rocks. In addition to magmatic-hydrothermal processes, such rocks could potentially be important for the concentration of critical elements in high-sulfidation epithermal deposits.

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Section: La-icp-ms Spot Analysesmentioning

confidence: 99%

Section: La-icp-ms Spot Analysesmentioning

confidence: 99%

Section: In-ga ± Ge Mineralization In Intermediate-sulfidation Sphalementioning

confidence: 99%

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Mineralogical Distribution of Germanium, Gallium and Indium at the Mt Carlton High-Sulfidation Epithermal Deposit, NE Australia, and Comparison with Similar Deposits Worldwide

et al. 2017

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“…Scales in counts-per-second. Measured isotopes: 56 Fe, 69 Ga, 75 As, 59 Co, 60 Ni, 109 Ag, 2095 Bi, 182 W.…”

Section: What Is Being Analyzed?mentioning

confidence: 99%

Trace Element Analysis of Minerals in Magmatic-Hydrothermal Ores by Laser Ablation Inductively-Coupled Plasma Mass Spectrometry: Approaches and Opportunities

et al. 2016

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Laser ablation inductively-coupled plasma mass spectrometry (LA-ICP-MS) has rapidly established itself as the method of choice for generation of multi-element datasets for specific minerals, with broad applications in Earth science. Variation in absolute concentrations of different trace elements within common, widely distributed phases, such as pyrite, iron-oxides (magnetite and hematite), and key accessory minerals, such as apatite and titanite, can be particularly valuable for understanding processes of ore formation, and when trace element distributions vary systematically within a mineral system, for a vector approach in mineral exploration. LA-ICP-MS trace element data can assist in element deportment and geometallurgical studies, providing proof of which minerals host key elements of economic relevance, or elements that are deleterious to various metallurgical processes. This contribution reviews recent advances in LA-ICP-MS methodology, reference standards, the application of the method to new mineral matrices, outstanding analytical uncertainties that impact on the quality and usefulness of trace element data, and future applications of the technique. We illustrate how data interpretation is highly dependent on an adequate understanding of prevailing mineral textures, geological history, and in some cases, crystal structure.

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“…Some authors (e.g., [3][4][5]) have favoured incorporation of Ge 4+ into the sphalerite structure, implying either coupled substitution or vacancies to achieve charge compensation. For example, [5,6] invoke the 3Zn 2+ ↔ Ge 4+ + 2Ag + substitution for the incorporation of Ge (up to 1200 ppm) in Ag-rich (max 1000 ppm) sphalerite from a French vein-type deposit, based on a coarse correlation between Ge and Ag.…”

Section: Introductionmentioning

confidence: 99%

Distribution and Substitution Mechanism of Ge in a Ge-(Fe)-Bearing Sphalerite

et al. 2015

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Abstract:The distribution and substitution mechanism of Ge in the Ge-rich sphalerite from the Tres Marias Zn deposit, Mexico, was studied using a combination of techniques at μm-to atomic scales. Trace element mapping by Laser Ablation Inductively Coupled 118Mass Spectrometry shows that Ge is enriched in the same bands as Fe, and that Ge-rich sphalerite also contains measurable levels of several other minor elements, including As, Pb and Tl. Micron-to nanoscale heterogeneity in the sample, both textural and compositional, is revealed by investigation using Focused Ion Beam-Scanning Electron Microscopy (FIB-SEM) combined with Synchrotron X-ray Fluorescence mapping and High-Resolution Transmission Electron Microscopy imaging of FIB-prepared samples. Results show that Ge is preferentially incorporated within Fe-rich sphalerite with textural complexity finer than that of the microbeam used for the X-ray Absorption Near Edge Structure (XANES) measurements. Such heterogeneity, expressed as intergrowths between 3C sphalerite and 2H wurtzite on [11 0] zones, could be the result of either a primary growth process, or alternatively, polystage crystallization, in which early Fe-Ge-rich sphalerite is partially replaced by Fe-Ge-poor wurtzite. FIB-SEM imaging shows evidence for replacement supporting the latter. Transformation of sphalerite into wurtzite is promoted by (111)* twinning or lattice-scale defects, leading to a heterogeneous ZnS sample, in which the dominant component, sphalerite, can host up to ~20% wurtzite. Ge K-edge XANES spectra for this sphalerite are identical to those of the germanite and argyrodite standards and the synthetic chalcogenide glasses GeS2 and GeSe2, indicating the Ge formally exists in the tetravalent form in this sphalerite. Fe K-edge XANES spectra for the same sample indicate that Fe is present mainly as Fe 2+, and Cu K-edge XANES spectra are characteristic for Cu + . Since there is no evidence for coupled substitution involving a monovalent element, we propose that Ge ) with vacancies in the structure to compensate for charge balance. This study shows the utility of synchrotron radiation combined with electron beam micro-analysis in investigating low-level concentrations of minor metals in common sulfides.

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LA-ICP-MS analyses of minor and trace elements and bulk Ge isotopes in zoned Ge-rich sphalerites from the Noailhac – Saint-Salvy deposit (France): Insights into incorporation mechanisms and ore deposition processes

Cited by 248 publications

References 53 publications

Mineralogical Distribution of Germanium, Gallium and Indium at the Mt Carlton High-Sulfidation Epithermal Deposit, NE Australia, and Comparison with Similar Deposits Worldwide

Mineralogical Distribution of Germanium, Gallium and Indium at the Mt Carlton High-Sulfidation Epithermal Deposit, NE Australia, and Comparison with Similar Deposits Worldwide

Trace Element Analysis of Minerals in Magmatic-Hydrothermal Ores by Laser Ablation Inductively-Coupled Plasma Mass Spectrometry: Approaches and Opportunities

Distribution and Substitution Mechanism of Ge in a Ge-(Fe)-Bearing Sphalerite

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