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Minerals
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Distribution and Segregation of Trace Elements in Hydrothermal Systems
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Distribution and Segregation of Trace Elements in Hydrothermal Systems

A special issue of Minerals (ISSN 2075-163X). This special issue belongs to the section "Mineral Geochemistry and Geochronology".

Deadline for manuscript submissions: closed (30 November 2020) | Viewed by 8708

Special Issue Editors

Dr. Vladimir Tauson

E-Mail Website
Guest Editor
A. P. Vinogradov Institute of Geochemistry, Russian Academy of Sciences, 664033 Irkutsk, Russia
Interests: mineral geochemistry; physical chemistry; experiment; ore deposits; hydrothermal processes
Special Issues, Collections and Topics in MDPI journals
Dr. Sergey Lipko

E-Mail Website
Co-Guest Editor
A. P. Vinogradov Institute of Geochemistry, Russian Academy of Sciences, 664033 Irkutsk, Russia
Interests: mineral analytics; experiment; scanning probe microscopy; electron microscopy; X-ray photoelectron spectroscopy
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

Despite the comprehensive development of computer modeling of natural systems, many important questions remain unsolved. We still fail to reliably explain the ratios of trace elements (TE) observed in minerals even in widespread minerals of hydrothermal, sedimentary–hydrothermal, and other ore-forming systems. Little attention has been given to TE fractionation into real mineral crystal bearing different structural imperfections (defects). The role of mineral surfaces in trace element uptake at high P and T parameters also remains debatable. The segregation of TE may occur at the defect sites following solid solution decomposition under temperature decrease, but it also can result from crystal surface interaction with impurity. The adequate understanding of the distribution and speciation of TE is also important for the analysiss of ore samples and recovery processing of ore mineral resources. This Special Issue will focus on the regularities of TE behavior in hydrothermal systems, including but not limited to topics such as prediction of TE contents in hydrothermal minerals crystallized from aqua-salt solutions; restoration of paleofluid composition in respect of TE using the minerals of variable composition; analysis of TE entrapment by real mineral crystals containing structural imperfections; experimental and theoretical grounds for ultralow-content element distribution; and partitioning of highly incompatible elements between minerals and solutions (fluids).

Dr. Vladimir Tauson
Dr. Sergey Lipko
Guest Editors

Manuscript Submission Information

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Keywords

  • trace elements
  • distribution
  • segregation
  • co-crystallization
  • crystal imperfections
  • structural defects
  • mineral surface
  • hydrothermal systems

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Published Papers (3 papers)

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Research

24 pages, 4365 KiB  
Article
Partitioning and Surficial Segregation of Trace Elements in Iron Oxides in Hydrothermal Fluid Systems
by Nikolay Smagunov, Vladimir Tauson, Sergey Lipko, Dmitriy Babkin, Taisa Pastushkova, Olga Belozerova and Nikolay Bryansky
Minerals 2021, 11(1), 57; https://doi.org/10.3390/min11010057 - 10 Jan 2021
Cited by 7 | Viewed by 2605
Abstract
Partitioning experiments were done by hydrothermal synthesis of crystals containing trace elements (TEs) by internal sampling of fluid at the temperature of 450 °C and pressure of 1 kbar. The crystal phases obtained were magnetite, hematite, and Ni-spinel, which were studied using X-ray [...] Read more.
Partitioning experiments were done by hydrothermal synthesis of crystals containing trace elements (TEs) by internal sampling of fluid at the temperature of 450 °C and pressure of 1 kbar. The crystal phases obtained were magnetite, hematite, and Ni-spinel, which were studied using X-ray diffraction (XRD), X-ray electron probe microanalysis (EPMA), laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), atomic absorption spectrometry (AAS), and atomic force microscopy (AFM). The solutions from the sampler’s fluid probes were analysed by AAS for TEs included elements of the iron group plus aluminium. The highest co-crystallisation coefficients of TE and Fe between mineral and fluid (DTE/Fe) in magnetite were measured for V, Al, Ni and Cr (in decreasing order of n units in value), a lower value was observed for Co (2 × 10−1), and still lower values for Ti, Zn, and Mn (n × 10−2–10−3). In hematite, DTE/Fe values were highest for Al and V (order of n units in value), while lower values characterised Ti, Cr, and Co (n × 10−1–10−3), and the lowest values were exhibited by Cu, Mn, and Zn (n × 10−5). Copper was confirmed to be the most incompatible with all minerals studied; however, Cu had a high content on crystal surfaces. This surficial segregation contributes to the average TE concentration even when a thin layer of nonautonomous phase (NAP) is enriched in the element of interest. The accumulation of TEs on the surface of crystals increased bulk content 1–2 orders of magnitude above the content of structurally-bound elements even in coarse crystals. The inverse problem—evaluation of TE/Fe ratios in fluids involved in the formation of magnetite-containing deposits—revealed that the most abundant metals in fluids were Fe followed by Mn, Zn, and Cu, which comprised 10 to 30% of the total iron content. Full article
(This article belongs to the Special Issue Distribution and Segregation of Trace Elements in Hydrothermal Systems)
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13 pages, 432 KiB  
Article
Gold Partitioning in a Model Multiphase Mineral-Hydrothermal Fluid System: Distribution Coefficients, Speciation and Segregation
by Sergey Lipko, Vladimir Tauson and Valeriy Bychinskii
Minerals 2020, 10(10), 890; https://doi.org/10.3390/min10100890 - 7 Oct 2020
Cited by 7 | Viewed by 2605
Abstract
The characteristics of Au partitioning in a multiphase, multicomponent hydrothermal system at 450 °C and 1 kbar pressure were obtained using experimental and computational physicochemical modelling and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) analysis. Sphalerite and magnetite contained 0.1–0.16 ± 0.02 [...] Read more.
The characteristics of Au partitioning in a multiphase, multicomponent hydrothermal system at 450 °C and 1 kbar pressure were obtained using experimental and computational physicochemical modelling and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) analysis. Sphalerite and magnetite contained 0.1–0.16 ± 0.02 µg/g Au and coexisted with galena and bornite which contained up to 73 ± 5 and 42 ± 10 µg/g Au, respectively. Bornite and chalcopyrite were the most effective Au scavengers with cocrystallization coefficients Au/Fe and Au/Cu in mineral-fluid system n–n × 10−2. Sphalerite and magnetite were the weakest Au absorbers, although Fe impurity in sphalerite facilitated Au uptake. Using the phase composition correlation principle, Au solubility in minerals was estimated (µg/g Au): low-Fe sphalerite = 0.7, high-Fe sphalerite = 5, magnetite = 1, pyrite = 3, pyrite-Mn = 7, pyrite-Cu = 10, pyrrhotite = 21, chalcopyrite = 110, bornite = 140 and galena = 240. The sequence reflected increasing metallicity of chemical bonds. Gold segregation occurred at crystal defects, and on surfaces, and influenced Au distribution due to its segregation at crystal interblock boundaries enriched in Cu-containing submicron phases. The LA-ICP-MS analysis of bulk and surficial gold admixtures revealed elevated Au content in surficial crystal layers, especially for bornite and galena, indicating the presence of a superficial nonautonomous phase (NAP) and dualism in the distribution of gold. Thermodynamic calculations showed that changes in experimental conditions, primarily in sulfur regime, increased the content of the main gold species (AuCl2− and AuHS0) and decreased the content of FeCl20, the prevailing form of iron in the fluid phase. The elevation of S2 and H2S fugacity affected Au partitioning and cocrystallization coefficients. Using Au content in pyrite, chalcopyrite, magnetite and bornite from volcanic-sedimentary, skarn-hosted and magmatic-hydrothermal sulfide deposits, the ranges of metal ratios in fluids were estimated: Au/Fe = n × 10−4−n × 10−7 and Au/Cu = n × 10−4−n × 10−6. Pyrite and magnetite were crystallized from solutions enriched in Au compared to chalcopyrite and bornite. The presence of NAP, and associated dualism in distribution coefficients, strongly influenced Au partitioning, but this effect does not fully explain the high gold fractionation into mineral precipitates in low-temperature geothermal systems. Full article
(This article belongs to the Special Issue Distribution and Segregation of Trace Elements in Hydrothermal Systems)
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19 pages, 4781 KiB  
Article
Indium and Antimony Distribution in a Sphalerite from the “Burgstaetter Gangzug” of the Upper Harz Mountains Pb-Zn Mineralization
by Thomas Schirmer, Wilfried Ließmann, Chandra Macauley and Peter Felfer
Minerals 2020, 10(9), 791; https://doi.org/10.3390/min10090791 - 8 Sep 2020
Cited by 6 | Viewed by 2990
Abstract
The sphalerite from the Burgstaetter Gangzug, a vein system of the Upper Harz Mountain nearby the town of Clausthal-Zellerfeld, exhibits a very interesting and partly complementary incorporation pattern of Cu, In and Sb, which has not yet been reported for natural sphalerite. A [...] Read more.
The sphalerite from the Burgstaetter Gangzug, a vein system of the Upper Harz Mountain nearby the town of Clausthal-Zellerfeld, exhibits a very interesting and partly complementary incorporation pattern of Cu, In and Sb, which has not yet been reported for natural sphalerite. A sphalerite specimen was characterized with electron probe micro-analysis (EPMA) and atom probe tomography (APT). Based on the EPMA results and a multilinear regression, a relation expressed as Cu = 0.98In + 1.81Sb + 0.03 can be calculated to describe the correlation between the elements. This indicates, that the incorporation mechanisms of In and Sb in the structure differ substantially. Indium is incorporated with the ratio Cu:In = 1:1 like in roquesite (CuInS2), supporting the coupled substitution mechanism 2Zn2+ → Cu+ + In3+. In contrast, Sb is incorporated with a ratio of Cu:Sb = 1.81:1. APT, which has a much higher spatial resolution indicates a ratio of Cu: Sb = 2.28: 1 in the entire captured volume, which is similar to the ratio calculated by EPMA, yet with inhomogeneities at the nanometer-scale. Analysis of the solute distribution shows two distinct sizes of clusters that are rich in Cu, Sb and Ag. Full article
(This article belongs to the Special Issue Distribution and Segregation of Trace Elements in Hydrothermal Systems)
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