Ti-Nb Mineralization of Late Carbonatites and Role of Fluids in Its Formation: Petyayan-Vara Rare-Earth Carbonatites (Vuoriyarvi Massif, Russia)
Abstract
:1. Introduction
2. Geological Setting of the Petyayan-Vara Rocks
- (1)
- Fine-grained dolomitic carbonatites and silicocarbonatites with microcline and/or phlogopite (hereinafter called titaniferous carbonatites), locally enriched with apatite (carbonatites with K-Al-Si-Ti-Fe ± P specialization);
- (2)
- Medium-grained dolomitic carbonatites with barite, strontianite, and ancylite-(Ce) (Ce,La)Sr(CO3)2(OH)×H2O ± bastnaesite-(Ce) (Ce,La)(CO3)F (carbonatites with Ba-REE-Sr specialization); and
- (3)
- Breccias of dolomitic carbonatites with cement consisting of fine-grained quartz and hydroxylbastnaesite-(Ce) (Ce,La)(CO3)(OH) (carbonatites with REE-Si specialization).
3. Research Material and Analytical Methods
4. Results
4.1. Titanium Minerals
4.2. Niobium Minerals
5. Discussion
- (1)
- (2)
- Fluorcalciopyrochlore is naturally substituted by varieties, whereas in the A-site (1) Ca and Na contents decrease, (2) cations become minor up to xenopyrochlores (А-vacancy > 1 a.p.f.u), and (3) Ba, Sr, REE, Th, U, Pb, and H2O become the dominant cations. In the B-site, a decreasing trend in Nb content isomorphically substituted by Ti and Fe occurs. Y-site is characterized by F decreasing until it disappears, and OH-groups occur in this position. Different authors have linked this chemical specific feature of pyrochlores with magmatic [51], hydrothemal [27,28,31,49,52,53,54], or supergene [55,56] processes. The “hydrothermal” point of view prevails.
- (3)
- In pyrochlores that are most reasonably referred to supergenous [17,49,56,57], the same chemical features are the most manifested. Ba, Sr, REE, Th, U, Pb, H2O, and rarely K remain the dominant cations in the A-site, but in general, the occupancy rate of this position drops to the lowest level, down to zero. Ca and/or Na tend to disappear. No fluorine-varieties are detected among supergenous pyrochlore. They differ from “hydrothermal” pyrochlores with the B-site completely filled with niobium. With a vacant A-site, it makes supergenous pyrochlores become the richest in niobium: 75 wt % vs. 50 wt % in other varieties.
6. Conclusions and Perspectives
Author Contributions
Funding
Acknowledgments
Conflicts of Interest
References
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Components | U-Th (1) 1 | Ca-F (1) | Ca-F (2) | Ca-F (2) | Pb (1) | Pb (1) | Pb (2) | Pb (2) |
---|---|---|---|---|---|---|---|---|
BaO | b.d.l. | b.d.l. | b.d.l. | b.d.l. | b.d.l. | b.d.l. | b.d.l. | b.d.l. |
K2O | b.d.l. | b.d.l. | 0.06 | 0.04 | b.d.l. | b.d.l. | b.d.l. | b.d.l. |
Na2O | b.d.l. | 4.66 | 6.84 | 6.73 | 0.36 | b.d.l. | b.d.l. | b.d.l. |
SrO | 4.09 | 1.41 | 1.19 | 1.25 | 1.42 | 1.80 | 2.00 | 3.13 |
CaO | 5.88 | 15.48 | 16.49 | 16.25 | 4.02 | 1.05 | 1.17 | 1.51 |
PbO | b.d.l. | b.d.l. | b.d.l. | b.d.l. | 32.14 | 31.10 | 26.81 | 25.41 |
UO2 | 3.18 | b.d.l. | b.d.l. | b.d.l. | b.d.l. | b.d.l. | b.d.l. | b.d.l. |
ThO | 9.71 | b.d.l. | b.d.l. | b.d.l. | b.d.l. | b.d.l. | b.d.l. | b.d.l. |
Y2O3 | b.d.l. | 0.72 | 0.43 | 0.42 | b.d.l. | b.d.l. | b.d.l. | b.d.l. |
La2O3 | 0.42 | b.d.l. | 0.40 | 0.51 | b.d.l. | 2.20 | 2.92 | 2.55 |
Ce2O3 | 2.47 | 0.66 | 0.74 | 0.93 | 0.54 | 4.21 | 5.75 | 5.29 |
Nd2O3 | 0.44 | b.d.l. | 0.19 | 0.20 | b.d.l. | 0.33 | 0.51 | 0.21 |
Sm2O3 | b.d.l. | b.d.l. | 0.20 | 0.22 | b.d.l. | b.d.l. | b.d.l. | b.d.l. |
SiO2 | 3.42 | b.d.l. | 0.12 | 0.26 | 0.47 | 0.16 | 0.26 | 0.60 |
TiO2 | 8.94 | 4.95 | 4.74 | 5.12 | 2.72 | 3.33 | 3.21 | 2.22 |
Fe2O3 | 3.24 | 0.39 | 0.11 | 0.17 | 0.71 | 0.57 | 0.73 | 0.61 |
ZrO2 | b.d.l. | b.d.l. | 0.30 | 0.48 | b.d.l. | b.d.l. | b.d.l. | b.d.l. |
Nb2O5 | 41.74 | 57.49 | 64.39 | 64.60 | 42.00 | 44.09 | 46.11 | 48.73 |
Ta2O5 | b.d.l. | b.d.l. | 0.17 | 0.10 | b.d.l. | b.d.l. | b.d.l. | b.d.l. |
F | b.d.l. | 3.80 | 2.84 | 2.85 | b.d.l. | b.d.l. | b.d.l. | b.d.l. |
Total | 83.53 | 89.56 | 99.21 | 100.13 | 84.38 | 88.84 | 89.47 | 90.26 |
F=O | 0.00 | 1.60 | 1.20 | 1.20 | 0.00 | 0.00 | 0.00 | 0.00 |
Total | 83.53 | 87.96 | 98.01 | 98.93 | 84.38 | 88.84 | 89.47 | 90.26 |
Formula calculated to 2 B-site cations | ||||||||
Ba | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
K | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
Na | 0.00 | 0.60 | 0.80 | 0.77 | 0.06 | 0.00 | 0.00 | 0.00 |
Sr | 0.15 | 0.05 | 0.04 | 0.04 | 0.07 | 0.09 | 0.10 | 0.15 |
Ca | 0.40 | 1.10 | 1.07 | 1.03 | 0.39 | 0.10 | 0.10 | 0.13 |
Pb | 0.00 | 0.00 | 0.00 | 0.00 | 0.78 | 0.73 | 0.60 | 0.55 |
U | 0.04 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
Th | 0.14 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
Y | 0.00 | 0.03 | 0.01 | 0.01 | 0.00 | 0.00 | 0.00 | 0.00 |
La | 0.01 | 0.00 | 0.01 | 0.01 | 0.00 | 0.07 | 0.09 | 0.08 |
Ce | 0.06 | 0.02 | 0.02 | 0.02 | 0.02 | 0.13 | 0.17 | 0.16 |
Nd | 0.01 | 0.00 | 0.00 | 0.00 | 0.00 | 0.01 | 0.02 | 0.01 |
Sm | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
Σ cat (A) | 0.81 | 1.80 | 1.96 | 1.90 | 1.33 | 1.13 | 1.08 | 1.07 |
Vac (A) | 1.19 | 0.20 | 0.04 | 0.10 | 0.67 | 0.87 | 0.92 | 0.93 |
Si | 0.22 | 0.00 | 0.01 | 0.02 | 0.04 | 0.01 | 0.02 | 0.05 |
Ti | 0.42 | 0.25 | 0.22 | 0.23 | 0.19 | 0.22 | 0.20 | 0.13 |
Fe | 0.17 | 0.02 | 0.01 | 0.01 | 0.05 | 0.04 | 0.05 | 0.04 |
Zr | 0.00 | 0.00 | 0.01 | 0.01 | 0.00 | 0.00 | 0.00 | 0.00 |
Nb | 1.19 | 1.73 | 1.76 | 1.73 | 1.72 | 1.73 | 1.73 | 1.78 |
Ta | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
Σ cat (B) | 2.00 | 2.00 | 2.00 | 2.00 | 2.00 | 2.00 | 2.00 | 2.00 |
F | 0.00 | 0.80 | 0.54 | 0.53 | 0.00 | 0.00 | 0.00 | 0.00 |
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Kozlov, E.; Fomina, E.; Sidorov, M.; Shilovskikh, V. Ti-Nb Mineralization of Late Carbonatites and Role of Fluids in Its Formation: Petyayan-Vara Rare-Earth Carbonatites (Vuoriyarvi Massif, Russia). Geosciences 2018, 8, 281. https://doi.org/10.3390/geosciences8080281
Kozlov E, Fomina E, Sidorov M, Shilovskikh V. Ti-Nb Mineralization of Late Carbonatites and Role of Fluids in Its Formation: Petyayan-Vara Rare-Earth Carbonatites (Vuoriyarvi Massif, Russia). Geosciences. 2018; 8(8):281. https://doi.org/10.3390/geosciences8080281
Chicago/Turabian StyleKozlov, Evgeniy, Ekaterina Fomina, Mikhail Sidorov, and Vladimir Shilovskikh. 2018. "Ti-Nb Mineralization of Late Carbonatites and Role of Fluids in Its Formation: Petyayan-Vara Rare-Earth Carbonatites (Vuoriyarvi Massif, Russia)" Geosciences 8, no. 8: 281. https://doi.org/10.3390/geosciences8080281