Mineralogical thallium geochemistry and isotope variations from igneous, metamorphic, and metasomatic systems

Shelby T. Rader, Frank K. Mazdab, Mark D Barton

Research output: Contribution to journalArticle

4 Citations (Scopus)

Abstract

This study presents new thallium (Tl) concentration and isotopic composition data for potassium feldspar (K-feldspar), micas, sulfides, and other minerals using solution multi-collector inductively-coupled plasma mass spectrometry (MC-ICP-MS). The samples studied represent a diverse set of igneous, metamorphic, and metasomatic rock types. Purified separates of minerals anticipated to be Tl-bearing were analyzed; in many cases coexisting minerals were measured to examine the distribution of Tl and its isotopes between coexisting phases. This study is the first of its kind to document mineralogical controls on Tl chemical and isotopic fractionation. Thallium contents in rock-forming minerals and common sulfides vary from below detection limit (here, approximately 0.2 ppm Tl in the mineral utilizing an IsoProbe MC-ICP-MS) to 3200 ppm. In this present study, mica and feldspar samples can reach Tl concentrations well over 20 ppm, compared to only 0.7 ppm in average crust. In contrast, only 14 of 38 common sulfide samples contain Tl at levels above the detection limit. Measured Tl isotope ratios, reported as ε205Tl relative to the NIST 997 standard solution, range from −12.1 ± 0.6 to +18.0 ±1.4 (2σ). Most samples analyzed fall within the published range of ε205Tl (−20 to +15) (Nielsen et al., 2017). Although most sulfides show limited Tl enrichment, they display the highest ε205Tl values among coexisting minerals, with Fe-rich micas having the lowest ε205Tl values. The patterns in enrichment are best interpreted to reflect crystal chemical differences and the incompatible, dominantly lithophile nature of Tl. In turn, isotopic fractionation also reflects control by the bonding environment as well as redox conditions. The preferential distribution of Tl into micas and K-feldspar found here is consistent with the similarity in charge and ionic radius of Tl+ and K+. The higher ε205Tl values in sulfides agree with previous observations and theoretical studies showing the tendency of covalent bonds, high bond strengths, and high oxidation states to favor heavy isotopes. This work highlights important areas for future research regarding the natural weathering of Tl-bearing substrates, understanding regional cycling of Tl, and potential bioremediation of Tl contamination.

Original languageEnglish (US)
Pages (from-to)42-65
Number of pages24
JournalGeochimica et Cosmochimica Acta
Volume243
DOIs
StatePublished - Dec 15 2018

Fingerprint

thallium
Geochemistry
Thallium
Isotopes
geochemistry
isotope
Sulfides
Minerals
sulfide
feldspar
Bearings (structural)
mineral
Inductively coupled plasma mass spectrometry
isotopic fractionation
Fractionation
mass spectrometry
Rocks
metasomatic rock
plasma
Covalent bonds

Keywords

  • Inter-mineral Tl partitioning
  • Metasomatism
  • Mineralogical thallium
  • Solution multi-collector inductively-coupled plasma mass spectrometry (MC-ICP-MS)

ASJC Scopus subject areas

  • Geochemistry and Petrology

Cite this

Mineralogical thallium geochemistry and isotope variations from igneous, metamorphic, and metasomatic systems. / Rader, Shelby T.; Mazdab, Frank K.; Barton, Mark D.

In: Geochimica et Cosmochimica Acta, Vol. 243, 15.12.2018, p. 42-65.

Research output: Contribution to journalArticle

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N2 - This study presents new thallium (Tl) concentration and isotopic composition data for potassium feldspar (K-feldspar), micas, sulfides, and other minerals using solution multi-collector inductively-coupled plasma mass spectrometry (MC-ICP-MS). The samples studied represent a diverse set of igneous, metamorphic, and metasomatic rock types. Purified separates of minerals anticipated to be Tl-bearing were analyzed; in many cases coexisting minerals were measured to examine the distribution of Tl and its isotopes between coexisting phases. This study is the first of its kind to document mineralogical controls on Tl chemical and isotopic fractionation. Thallium contents in rock-forming minerals and common sulfides vary from below detection limit (here, approximately 0.2 ppm Tl in the mineral utilizing an IsoProbe MC-ICP-MS) to 3200 ppm. In this present study, mica and feldspar samples can reach Tl concentrations well over 20 ppm, compared to only 0.7 ppm in average crust. In contrast, only 14 of 38 common sulfide samples contain Tl at levels above the detection limit. Measured Tl isotope ratios, reported as ε205Tl relative to the NIST 997 standard solution, range from −12.1 ± 0.6 to +18.0 ±1.4 (2σ). Most samples analyzed fall within the published range of ε205Tl (−20 to +15) (Nielsen et al., 2017). Although most sulfides show limited Tl enrichment, they display the highest ε205Tl values among coexisting minerals, with Fe-rich micas having the lowest ε205Tl values. The patterns in enrichment are best interpreted to reflect crystal chemical differences and the incompatible, dominantly lithophile nature of Tl. In turn, isotopic fractionation also reflects control by the bonding environment as well as redox conditions. The preferential distribution of Tl into micas and K-feldspar found here is consistent with the similarity in charge and ionic radius of Tl+ and K+. The higher ε205Tl values in sulfides agree with previous observations and theoretical studies showing the tendency of covalent bonds, high bond strengths, and high oxidation states to favor heavy isotopes. This work highlights important areas for future research regarding the natural weathering of Tl-bearing substrates, understanding regional cycling of Tl, and potential bioremediation of Tl contamination.

AB - This study presents new thallium (Tl) concentration and isotopic composition data for potassium feldspar (K-feldspar), micas, sulfides, and other minerals using solution multi-collector inductively-coupled plasma mass spectrometry (MC-ICP-MS). The samples studied represent a diverse set of igneous, metamorphic, and metasomatic rock types. Purified separates of minerals anticipated to be Tl-bearing were analyzed; in many cases coexisting minerals were measured to examine the distribution of Tl and its isotopes between coexisting phases. This study is the first of its kind to document mineralogical controls on Tl chemical and isotopic fractionation. Thallium contents in rock-forming minerals and common sulfides vary from below detection limit (here, approximately 0.2 ppm Tl in the mineral utilizing an IsoProbe MC-ICP-MS) to 3200 ppm. In this present study, mica and feldspar samples can reach Tl concentrations well over 20 ppm, compared to only 0.7 ppm in average crust. In contrast, only 14 of 38 common sulfide samples contain Tl at levels above the detection limit. Measured Tl isotope ratios, reported as ε205Tl relative to the NIST 997 standard solution, range from −12.1 ± 0.6 to +18.0 ±1.4 (2σ). Most samples analyzed fall within the published range of ε205Tl (−20 to +15) (Nielsen et al., 2017). Although most sulfides show limited Tl enrichment, they display the highest ε205Tl values among coexisting minerals, with Fe-rich micas having the lowest ε205Tl values. The patterns in enrichment are best interpreted to reflect crystal chemical differences and the incompatible, dominantly lithophile nature of Tl. In turn, isotopic fractionation also reflects control by the bonding environment as well as redox conditions. The preferential distribution of Tl into micas and K-feldspar found here is consistent with the similarity in charge and ionic radius of Tl+ and K+. The higher ε205Tl values in sulfides agree with previous observations and theoretical studies showing the tendency of covalent bonds, high bond strengths, and high oxidation states to favor heavy isotopes. This work highlights important areas for future research regarding the natural weathering of Tl-bearing substrates, understanding regional cycling of Tl, and potential bioremediation of Tl contamination.

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