The sulfur speciation in S-bearing minerals: New constraints by a combination of electron microprobe analysis and DFT calculations with special reference to sodalite-group minerals

Hettmann, Kai; Wenzel, Thomas J.; Marks, Michael A.W.; Markl, Gregor

doi:10.2138/am.2012.4031

Cited by 28 publications

(27 citation statements)

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“…For data reduction, a PhiRhoZet correction was applied (Armstrong 1991). For reliable quantitative S measurements, it is necessary to determine the exact position of the S Kα peak as it changes with the speciation of S (Hettmann et al 2012). The S Kα 1,2 peak for sulphide (ZnS) lies at 2307.9 ± 0.36 eV (3σ) and for sulphate (BaSO 4 ) at 2309.1 ± 0.69 eV (3σ).…”

Section: Methodology Electron Probe Microanalysis (Epma)mentioning

confidence: 99%

“…Cationic sublattice vibrations at 175 cm −1 Mikuła et al (2015) 263 Na-O with Al/Si-tetrahedra bending Hettmann et al (2012) v 2 of S − 3 Ledé et al (2007) 294 Symmetric Al/Si-tetrahedra bending 463 ClNa 4 -tetrahedra stretching Hettmann et al (2012) Si-O bending, SiO 4 vibration Angell (1973) and Dutta and Del Barco (1985) v T-O- T Gesing et al (2010) 965 Asymmetric strong Si and weak Al-tetrahedra stretching Hettmann et al (2012) 987 Symmetric Al/Si-tetrahedra stretching/A 1 stretching frequency of v 1 of sodalite framework 2 6 3 2 9 4 4 1 0 4 9 7 5 3 4 5 6 1 5 9 1 7 3 5 9 6 5 1 0 1 0 1 0 5 8 1 1 2 2 6 0 8 9 8 7 4 6 3 From top to bottom: 4 4 1 4 5 0 Fig. 10 Raman spectra of sodalite samples differing in their S content and optical properties.…”

Section: Assigned To/comments References 166mentioning

confidence: 99%

“…An overview of other sodalite-group minerals (SGM) is given in Table 1. The metal site, M, typically contains mono-to divalent elements such as Ca, K, Li, Na, Sr, Mn and Zn (Deer et al 1996;Williams et al 2010;Hettmann et al 2012). The T site contains tetrahedrally coordinated elements such as Al, Si, B and Be (Kotel'nikov et al 2005;Williams et al 2010;Kaliwoda et al 2011).…”

Section: Introductionmentioning

confidence: 99%

“…The T site contains tetrahedrally coordinated elements such as Al, Si, B and Be (Kotel'nikov et al 2005;Williams et al 2010;Kaliwoda et al 2011). Considerable variations occur on the extra framework-site, X, where anions or molecules such as Cl − , Br − , I − , S 2− , SO 4 2− CO 3 2− and OH − are present (Fleet 2005;Kotel'nikov et al 2005;Bellatreccia et al 2009;Williams et al 2010;Balassone et al 2012;Hettmann et al 2012). Minerals of the sodalite group typically crystallize in SiO 2 -undersaturated and alkaline magmas and their associated hydrothermal systems (Hogarth and Griffin 1976;Deer et al 1996;Di Muro et al 2004;Krumrei et al 2007).…”

Section: Introductionmentioning

confidence: 99%

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Luminescence and tenebrescence of natural sodalites: a chemical and structural study

2016

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Section: Methodology Electron Probe Microanalysis (Epma)mentioning

confidence: 99%

Section: Assigned To/comments References 166mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Luminescence and tenebrescence of natural sodalites: a chemical and structural study

2016

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“…Nevertheless, the presence of primary methane-dominated and water-free fluid inclusions, as found in most agpaites (e.g., Krumrei et al 2007), and low sulfate/sulphide ratios found in sodalite from naujaites, again indicate relatively reduced conditions (Hettmann et al 2012). The high amount of Fe 3 + in clinopyroxene of the agpaitic rocks does not contradict these observations, since the Fe 2 + /Fe 3 + ratio in silicate melts depends not only on oxygen fugacity, but is largely influenced by peralkalinity, the presence of water and other factors (Botcharnikov et al 2005;Giuli et al 2012;Markl et al 2010).…”

Section: Redox Conditionsmentioning

confidence: 98%

The Ilímaussaq Alkaline Complex, South Greenland

Marks

Markl

2015

Springer Geology

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The Ilímaussaq complex in South Greenland is a well-studied multiphase alkaline to peralkaline intrusion of Mesoproterozoic age. Most of the Ilímaussaq rocks are extremely enriched in alkalis, iron, halogens, high-field-strength elements (HFSE) and other rare elements, forming one of the most differentiated peralkaline rock suites known.The major factors causing the extreme differentiation trends are low oxygen fugacity and silica activity as well as very low water activity in the melts. These inhibit the early exsolution of aqueous NaCl-bearing fluids and facilitate the enrichment of alkalis and halogens in the melts, thereby increasing the solubility of HFSE. The unusually long crystallization interval of these rocks and the suspected continuous transition from melt to fluid results in extensive (auto)metasomatism and hydrothermal overprint. Primary mineral assemblages are therefore partially resorbed in most rock units and replaced by secondary minerals to various extents.The Ilímaussaq complex is a well-known example of magmatic layering in peralkaline plutonic rocks. Recent investigations of mineral chemical trends in the layered rocks permit better understanding of their formation. The mechanism of crystal mats formation in the cooling magma causing crowding effects during settling of the layering-forming minerals is believed to govern the formation of the Ilímaussaq layered sequence.Despite more than 100 years of research and hundreds of publications on Ilí-maussaq, important aspects on the origin of some Ilímaussaq rocks, the architecture and deep structure of the complex and the significance of hydrocarbons and bitumens present in the peralkaline rocks remain unclear. Thus, plenty of room for further studies on these unusual rocks exists and interdisciplinary research is needed to better understand the genesis of this unique magmatic complex.

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A Raman study of chalcogen species in sodalite‐group minerals from the volcanic rocks of Latium (Italy)

Ventura

Capitelli

Sbroscia

et al. 2019

J Raman Spectroscopy

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Sodalite‐group minerals are silicates belonging to the zeolite group hosting in their cages a variety of cations and anions. Four mineral species of the sodalite‐group are known in nature, the main difference being connected to the identity of the chemical species in the cages, particularly the sulfur molecular arrangements. Notably, the sodalite‐group minerals show different colours; lazurite, in particular, is the main constituent of the well‐known lapis lazuli, a material used throughout the human history as a precious stone or as a blue pigment for artworks. In this paper, we exploit Raman and Fourier‐transform infrared (FTIR) spectroscopy to highlight an existing connection between the chalcogen species entrapped within the samples originated from the volcanic region of Latium (Italy) and their final colour. We show that Raman spectroscopy is a very valuable tool in characterizing the extraframework content in these minerals. Further, our analysis demonstrates how the blue hue of the sodalite species is related to the S3−/SO42− relative content. We finally show how most specimen are also rich in CO2, a feature addressed by combination with FTIR spectroscopy. These findings have a particular interest not only in geology, but also in Cultural Heritage studies.

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The sulfur speciation in S-bearing minerals: New constraints by a combination of electron microprobe analysis and DFT calculations with special reference to sodalite-group minerals

Cited by 28 publications

References 41 publications

Luminescence and tenebrescence of natural sodalites: a chemical and structural study

Luminescence and tenebrescence of natural sodalites: a chemical and structural study

The Ilímaussaq Alkaline Complex, South Greenland

A Raman study of chalcogen species in sodalite‐group minerals from the volcanic rocks of Latium (Italy)

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