The parisite–(Ce) enigma: challenges in the identification of fluorcarbonate minerals

Zeug, Manuela; Nasdala, Lutz; Ende, Martin; Habler, Gerlinde; Hauzenberger, Christoph; Chanmuang, N Chutimun; Škoda, Radek; Topa, Dan; Wildner, Manfred; Wirth, Richard

doi:10.1007/s00710-020-00723-x

Cited by 13 publications

(10 citation statements)

References 63 publications

(111 reference statements)

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“…This has been done previously in the literature, as for instance, to observe Nd 3+ in parisite–(Ce). [ 65 ] In that case, under 532 excitation (Figure 5 in that paper), additional unassigned emission bands were observed at approximately 16,800, 15,400, and 14,200 cm −1 (595, 649, and 704 nm), which according to the data in Table 1 correspond to the emissions of Sm 3+ . Figure S8 shows the emission spectra of a crystal of apatite excited with the argon laser lines at 488 and 514.5 nm which reveal a strong Sm 3 + 4 G 5/2 – 6 H 9/2 emission at approximately 650 nm under 488 nm excitation and the Nd 3 + 4 F 5/2 – 4 I 9/2 emission at approximately 800 nm under 514.5 nm excitation.…”

Section: Discussionmentioning

confidence: 76%

Probing luminescence of rare earth ions in natural pink fluorites using Raman microscopes

Hagemann

Ayoubipour

Delgado

et al. 2022

J Raman Spectroscopy

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It is well-known that many natural fluorite crystals contain rare earth ions. In this work, a series of pink fluorites is studied to demonstrate that the use of Raman microscopes allows to obtain high resolution emission spectra of trivalent rare earth ions. These emission spectra allow in principle to distinguish differences of the local environment related to the charge compensation necessary when the divalent Ca ion is replaced by a trivalent rare earth ion. The pink fluorites from the Alps have grown under hydrothermal conditions, which results in the incorporation of oxygen into the fluorite. In one sample from Juchlistock (Bern, Switzerland), a trigonal Eu 3+ -oxygen center is clearly identified. Interestingly, a pink fluorite from China (Huanggang Mine, Inner Mongolia, China) shows a quite different emission spectrum from those of the Alps. In this sample, the emission bands have much lower relative intensity compared with the intensity of the CaF 2 Raman peak, indicating a much lower content of Er 3+ and Ho 3+ which emit around 520-560 nm. Literature examples show that Raman measurements of differently colored fluorite crystals can also present sharp rare earth spectra. By extension, it is thus possible to observe and identify emission spectra of rare earth ions in other mineral crystals using Raman microspectroscopy and avoid misassignments of the corresponding observed Raman spectra.

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Section: Discussionmentioning

confidence: 76%

Probing luminescence of rare earth ions in natural pink fluorites using Raman microscopes

Hagemann

Ayoubipour

Delgado

et al. 2022

J Raman Spectroscopy

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“…Some studies have reported the measurement of F in cerianite by EPMA 12 ; however, potential interferences should be considered. The EPMA analyses of the synthetic F‐free CePO 4 showed an apparent 1.1 wt.% F. The apparent concentrations are due to the interference from the 2nd order of the Mz line of Ce on the fluorine Kα line 48 . After the correction for interference, the estimated 0.22 wt.% F concentrations in supergene cerianite were indistinguishable from the detection limit of 0.16–0.18 wt.% of the method (Table 2), and we concluded that our supergene cerianite has negligible F content.…”

Section: Discussionmentioning

confidence: 97%

Raman spectroscopic study of non‐stoichiometry in cerianite from critical zone

Zhukova

Stepanov

Malyutina

et al. 2023

J Raman Spectroscopy

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Cerianite (CeO2) is one of the key minerals controlling the behavior of rare earth elements (REE) in supergene environment, yet little is known about the composition and structure of the mineral. We present Raman spectroscopy and compositional data on regolith cerianite from carbonatite‐related supergene REE deposits. Cerianite showed a low content of impurities, distinguishing from high‐temperature environments, where the mineral is characterized by elevated concentrations of lanthanides other than Ce. The Raman spectra are characterized by the shift of the dominant peak located at 464–465 cm−1 in stoichiometric CeO2 to the lower wavenumbers of 450–455 cm−1, the widening of this peak with the increasing shift, and the presence of additional peaks at 225–230, 284, and 604–613 cm−1. The independence of the main spectral characteristics from the laser wavelength (tested by three lasers: 488, 532, and 633 nm) suggests that the features are genuine and not produced by REE luminescence. The anhydrous composition of supergene cerianite is indicated by the absence of Raman bands in the water‐bearing region of the spectra (2700–3200 cm−1). The spectral features of supergene cerianite, combined with the compositional data, suggest non‐stoichiometry in the mineral and the presence of Ce3+ with oxygen vacancies in the mineral structure. Our observations demonstrate the efficiency of Raman spectroscopy for the identification of the non‐stoichiometric composition of cerianite and its common occurrence in the critical zone.

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“…The range of δ 34 S values is close to that of magmatic fluids, namely 0‰ -5‰, similar with tin deposits in Brazilian Rondonia. However, in the context of the study area, the value of δ 34 S is slightly more enriched, possibly influenced by an igneous sulphide reservoir that has a value range of -2 ‰ to + 35 ‰ [40]. Kelabat granite is the closest surrounding rock, it may be a stable isotope source of S for the sulphide mineralizing-hydrothermal fluid.…”

Section: Characteristics and Composition Of Hydrothermal Fluidmentioning

confidence: 91%

The Occurrence of Primary REE Minerals and Their Para genesis within S-Type Granite and Quartz Vein, South Bangka, Bangka Belitung Islands, Indonesia

2022

JEEE

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Primary rare earth element (REE) minerals known as carbonate and phosphate were identified in some localities. The carbonate type consists mainly of parasite, allanite, and bastnaesite, while REE phosphate group comprises mainly monazite and xenotime. They are accompanied by thorite and zircon. REE-bearing quartz vein is associated with cassiterite, pyrite, chalcopyrite, sphalerite, and tourmaline. The hydrothermal fluid that plays a role in REE mineral precipitation is subdivided into three stages: early (> 316oC - 316oC), medium (< 316oC – 210oC), and late (<210oC190oC). The δ18O range which is 12, 7 ‰ – 13 ‰, and the δ34S range are 3, 9 ‰ – 5, 5 ‰ indicate that the origin of hydrothermal fluid comes from mixing fluids of both meteoric and magmatic sources, and also influenced by metamorphic waters. While the source of sulphur is granitic and sedimentary rocks. REE phosphate is thought to have formed in the early magmatic crystallization stage except for monazite formed in the medium magmatic-hydrothermal and late hydrothermal stages. Primary REE carbonate may have formed in a medium hydrothermal-magmatic stage except for parasite and allanite, they may have formed in late-stage hydrothermal. Chalcopyrite and sphalerite seem to be associated with REE minerals in the medium and late hydrothermal stages

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The parisite–(Ce) enigma: challenges in the identification of fluorcarbonate minerals

Cited by 13 publications

References 63 publications

Probing luminescence of rare earth ions in natural pink fluorites using Raman microscopes

Probing luminescence of rare earth ions in natural pink fluorites using Raman microscopes

Raman spectroscopic study of non‐stoichiometry in cerianite from critical zone

The Occurrence of Primary REE Minerals and Their Para genesis within S-Type Granite and Quartz Vein, South Bangka, Bangka Belitung Islands, Indonesia

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