Trace and minor element variations and sulfur isotopes in crystalline and colloform ZnS: Incorporation mechanisms and implications for their genesis

Pfaff, Katharina; Koenig, Alan E.; Wenzel, Thomas J.; Ridley, I.; Hildebrandt, Ludwig H.; Leach, D. L.; Markl, Gregor

doi:10.1016/j.chemgeo.2011.04.018

Cited by 34 publications

(45 citation statements)

References 57 publications

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“…A lack of correlation between Fe content and sphalerite color has been observed in studies of MVT deposits (Roedder and Dwornik, 1968;Viets et al, 1992;Peevler et al, 2003;Pfaff et al, 2011) and postorogenic vein mineralization (Harms and Heckmann, 2004). In vein-hosted layered sphalerite of MVT deposits in SW Wisconsin, sphalerite with higher Fe concentration tends to be darker (McLimans et al, 1980).…”

Section: Relationship Between Color and Chemical Compositionmentioning

confidence: 92%

“…A number of processes have been proposed to account for the chemical variability of sphalerite, including both external (e.g., change in composition of the mineralizing fluid) and internal (e.g., differential kinetic absorption at the mineral-fluid interface) processes (Di Benedetto et al, 2005, and references therein). Isotopic ratios, especially of sulfur, are of particular benefit for assessing putative sources in the genesis of hydrothermal deposits, and have extensively been applied to the Irish ore field (e.g., Anderson et al, 1998;Blakeman et al, 2002;Wilkinson et al, 2005a;Barrie et al, 2009) and to some MVT deposits (e.g., Kuhlemann et al, 2001;Peevler et al, 2003;Pfaff et al, 2011). Therefore, combining chemistry and isotopes measured on layered sphalerite may help to assess whether the chemical composition of sulfides records fluid origin the Navan ore deposit.…”

Section: Introductionmentioning

confidence: 98%

“…The minor to trace element distribution and compositional zoning in sphalerite in low-to medium-temperature hydrothermal systems has been subject to numerous studies (e.g., Roedder and Dwornik, 1968;McLimans et al, 1980;Viets et al, 1992;Kuhlemann and Zeeh, 1995;Fowler and L'Heureux, 1996;Katsev et al, 2001;Di Benedetto et al, 2005;Pfaff et al, 2011;Ye et al, 2011). A number of processes have been proposed to account for the chemical variability of sphalerite, including both external (e.g., change in composition of the mineralizing fluid) and internal (e.g., differential kinetic absorption at the mineral-fluid interface) processes (Di Benedetto et al, 2005, and references therein).…”

Section: Introductionmentioning

confidence: 99%

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Minor Elements in Layered Sphalerite as a Record of Fluid Origin, Mixing, and Crystallization in the Navan Zn-Pb Ore Deposit, Ireland

et al. 2014

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This study tests the utility of the minor to trace element composition of sphalerite to discriminate between possible sources of ore-forming fluids, and to constrain processes involved in ore genesis of the world-class Irish-type Navan Zn-Pb orebody, Ireland. Detailed petrography and electron microprobe microanalyses were performed on layered sphalerite previously analyzed for Zn, Fe, and S isotope compositions. Layered sphalerite displays a wide range of chemical composition at both sample and crystal scales. The color, style, and scale of layering show variations with chemical composition, but none of these correlations are consistent between samples. However, there are strong intersample correlations between chemical and S-Fe-Zn isotope compositions at the millimeter scale. Sphalerite precipitated from deep, hydrothermal fluids with 34 S-enriched sulfide is enriched in Cd, Sb, Cu, and Ag, whereas Fe and As are enriched in sphalerite precipitated from shallow, bacteriogenic brines with isotopically light S. Significant chemical variations also occur at the micrometer scale in sphalerite regardless of its genetic affinity. These variations are interpreted as being due to variations in temperature, pH, and sulfur activity following the arrival at the site of deposition of pulses of hydrothermal fluids at specific stages of sphalerite growth. Therefore the chemistry of sphalerite, coupled with its texture, appears to be a powerful tool to elucidate fluid typing and ore genesis. The results support the hypothesis that layered sphalerite forms by rapid crystallization due to mixing of two fluids of contrasting physicochemical properties, a process required for the formation of Irish-type and some other hydrothermal deposits including, most notably, Mississippi Valley-type (MVT) deposits. The existence of layered sphalerite, coupled with its texture and chemical composition, may therefore provide useful insight for the mineral exploration industry in Ireland and elsewhere.

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Section: Relationship Between Color and Chemical Compositionmentioning

confidence: 92%

Section: Introductionmentioning

confidence: 98%

Section: Introductionmentioning

confidence: 99%

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Minor Elements in Layered Sphalerite as a Record of Fluid Origin, Mixing, and Crystallization in the Navan Zn-Pb Ore Deposit, Ireland

et al. 2014

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“…However, the technical grade of argon gas used contained enough oxygen (1000 ppm) to partially oxidize Ge(II)I 2 (coordination number 3) into Ge(IV)I 4 (coordination number 6) and GeO 2 , as revealed by later XRD (X-ray Diffraction) analysis. The renierite ((Cu,Zn) 11 (Ge,As) 2 Fe 4 S 16 ) standard was a natural mineral sample (given by The Royal Museum for Central Africa in Tervuren, Belgium). Renierite is a copper sulphide from the tennantite-tetrahedrite family and contains 7% Ge (Ge content determined by an electron microprobe).…”

Section: Sphalerite Samplesmentioning

confidence: 99%

Characterization of Germanium Speciation in Sphalerite (ZnS) from Central and Eastern Tennessee, USA, by X-ray Absorption Spectroscopy

et al. 2017

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X-ray absorption near edge structure (XANES) spectroscopy was used on zoned sphalerites (ZnS) from two world-class Mississippi Valley Type deposits, the Central and Eastern Tennessee Mining district, USA, in order to investigate germanium oxidation states. Due to the low germanium concentrations of these samples, it was necessary to perform the X-ray absorption spectroscopy (XAS) in fluorescence mode. The overlapping of the Zn Kβ and Ge Kα emission lines meant that a high energy-resolution was required. This was achieved using crystal analysers and allowed a bandwidth of 1.3 eV to be obtained. Experimental spectra were compared to XANES calculations and three configurations of germanium incorporation into sphalerite were identified. The first two, the most prevalent, show germanium (II) and (IV) surrounded by sulphur atoms in tetrahedral coordination, suggesting the replacement of Zn by Ge. In the third configuration, germanium (IV) is surrounded by oxygen atoms. This third configuration is unexpected for a zinc sulphide mineral and it resembles that of argutite (GeO 2 ).

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“…Sphalerite is a minor mineral in the deposit, and is likely the source of elevated Zn (100s of ppm), as well as Cd and In in till overlying the deposit. Cadmium and In are known to occur in sphalerite (Cook et al 2009;Pfaff et al 2011). The source of elevated Pb (100-400 ppm) contents in till is likely galena, which was observed in the mineralized zones by Nast and Williams-Jones (1991).…”

Section: Source Of High Metal Contents In Tillmentioning

confidence: 99%

Till geochemical signatures associated with the Sisson W-Mo deposit, New Brunswick, Canada

McClenaghan

Seaman²,

Parkhill³

et al. 2014

atgeol

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A till composition study was carried out around the Sisson W-Mo deposit, New Brunswick, Canada, one of the largest W deposits in the world, to test modern analytical methods for W in till and document glacial dispersal from a significant W source. The <0.063 mm fraction of till defines glacial dispersal down ice of the deposit and use of this fraction is recommended for W-Mo exploration in the region. Metal-rich till overlying the deposit contains up to 816 ppm W and 63 ppm Mo. One km down ice, till contains 75 ppm W and 8 ppm Mo, and till in background areas contains a maximum of 7 ppm W, and 2 ppm Mo. Indicator elements for the deposit include W and Mo, and pathfinder elements include Ag, As, Bi, Cd, Cu, In, Pb, Te, and Zn. This list of elements is more extensive than previously identified for the Sisson deposit or identified in other published till geochemical studies because of the polymetallic nature of the Sisson deposit and the broad suite of elements that can now be determined using modern analytical techniques. Lithium meta/tetraborate fusion inductively coupled plasma-mass spectrometry was used to determine the total concentration of W in till and is a fast and cost effective method as compared to those reported in the older literature. Glacial dispersal of W and Mo from the Sisson deposit is detectable at a regional scale at least 14 km down ice (southeast) using surface till sampling. A 2 km till sample spacing should be sufficient to detect glacial dispersal from a W-Mo deposit of this size. RÉSUMÉUne étude de composition du till a été réalisée autour du dépôt de Sisson, composé de tungstène et de molybdène et situé au Nouveau-Brunswick, au Canada. Il s'agit de l'un des plus importants dépôts de tungstène au monde. L' étude a été réalisée pour mettre à l' essai les méthodes modernes d'analyse du tungstène contenu dans le till et pour obtenir des données sur la dispersion glaciaire d'une importante source de tungstène. La fraction inférieure à 0,063 mm du till dé-finit la dispersion glaciaire du dépôt sous la glace et on recommande l'utilisation de cette fraction pour l' exploration du tungstène-molybdène dans la région. Le till riche en métal sus-jacent au dépôt contient jusqu'à 816 ppm de tungstène et 63 ppm de molybdène. À un kilomètre sous la glace, le till contient 75 ppm de tungstène et 8 ppm de molybdène, tandis que la partie inférieure du till contient tout au plus 7 ppm de tungstène et 2 ppm de molybdène. Parmi les élé-ments indicateurs du dépôt, on trouve du tungstène et du molybdène, et les indicateurs géochimiques comprennent notamment l'argent, l'arsenic, le bismuth, le cadmium, le cuivre, l'indium, le plomb, le tellure et le zinc. Puisque le dépôt de Sisson est de nature polymétallique et qu'il est maintenant possible de définir une vaste gamme d' éléments grâce aux techniques modernes d'analyse, la liste d' éléments est plus longue que celle précédemment établie pour le dépôt de Sisson ou que ce qui a été publié dans d'autres études géochimiques du till. Pour déterminer la conc...

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Trace and minor element variations and sulfur isotopes in crystalline and colloform ZnS: Incorporation mechanisms and implications for their genesis

Cited by 34 publications

References 57 publications

Minor Elements in Layered Sphalerite as a Record of Fluid Origin, Mixing, and Crystallization in the Navan Zn-Pb Ore Deposit, Ireland

Minor Elements in Layered Sphalerite as a Record of Fluid Origin, Mixing, and Crystallization in the Navan Zn-Pb Ore Deposit, Ireland

Characterization of Germanium Speciation in Sphalerite (ZnS) from Central and Eastern Tennessee, USA, by X-ray Absorption Spectroscopy

Till geochemical signatures associated with the Sisson W-Mo deposit, New Brunswick, Canada

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