Sulfur-bearing monazite-(Ce) from the Eureka carbonatite, Namibia: oxidation state, substitution mechanism, and formation conditions

Sam Broom-Fendley, Martin Smith, Marcelo Andrade, Santanu Ray, David Banks, Edward Loye, Daniel Atencio, Jonathan Pickles, Frances Wall

Research output: Contribution to journalArticle

Abstract

Sulfur-bearing monazite-(Ce) occurs in silicified carbonatite at Eureka, Namibia, forming rims up to ~0.5 mm thick on earlier-formed monazite-(Ce) megacrysts. We present X-ray photoelectron spectroscopy (XPS) data demonstrating that sulfur is predominantly accommodated in monazite-(Ce) as sulfate, via a clino-anhydrite-type coupled substitution mechanism. Minor sulfide and sulfite peaks in the XPS spectra, however, also indicate that more complex substitution mechanisms incorporating S2- and S4+ are possible. Incorporation of S6+ through clino-anhydrite-type substitution results in an excess of M2+ cations, which previous workers have suggested is accommodated by auxiliary substitution of OH- for O2-. However, Raman data show no indication of OH-, and instead we suggest charge imbalance is accommodated through F- substituting for O2-. The accommodation of S in the monazite-(Ce) results in considerable structural distortion that may account for relatively high contents of ions with radii beyond those normally found in monazite-(Ce), such as the heavy rare earth elements (REE), Mo, Zr and V. In contrast to S-bearing monazite-(Ce) in other carbonatites, S-bearing monazite-(Ce) at Eureka formed via a dissolution-precipitation mechanism during prolonged weathering, with S derived from an aeolian source. While large S-bearing monazite-(Ce) grains are likely to be rare in the geological record, formation of secondary S-bearing monazite-(Ce) in these conditions may be a feasible mineral for dating palaeo-weathering horizons.
Original languageEnglish
JournalMineralogical Magazine
DOIs
Publication statusPublished - 11 Dec 2019

Bibliographical note

This is an Open Access article, distributed under the terms of the Creative Commons Attribution licence (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted re-use, distribution, and reproduction in any medium, provided the original work is properly cited.

Keywords

  • Sulfur-bearing monazite-(Ce)
  • Redox
  • Carbonatite
  • Silcrete
  • Calcrete
  • Weathering

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