The Effect of Mn Substitution on Natural Sphalerites by Means of Raman Spectroscopy: A Case Study of the Săcărâmb Au–Ag–Te Ore Deposit, Apuseni Mountains, Romania
Abstract
:1. Introduction
2. Geological Setting
3. Materials and Methods
4. Results
4.1. Mineral Paragenesis and Chemistry of Sphalerite
4.2. Raman Spectroscopy and Band Assignments
5. Discussion
5.1. Vibrational Characteristics of Mn-Substituted Sphalerite
5.2. Implications for Metallogenesis of the Săcărâmb Ore Deposit
- Stage I is a high-temperature stage between 400 and 500 °C, dominated by common sulfides disseminated in the altered andesitic neck.
- Stage II is characterized by temperatures between 350 and 400 °C; it is a more complex stage with the presence of sulfosalts and the development of vein systems,
- Stage III is a Mn-rich stage; it is considered the main ore formation stage with temperatures between 200 and 300 °C, and alabandite as the main sulfide mineral, forming veins of up to 10 cm in diameter. In this stage, sphalerite crystals with the highest Mn content were identified.
- Stage IV is a telluride- and sulfosalt-rich stage with lower temperatures between 150 and 230 °C, as presented by Dincă [20]. Sphalerite in this stage has a high Mn concentration as in stage III; however, Fe and Cd are present in the composition.
- Stage V, the oxide and As-Sb stage, is the final mineralization stage in which glauch-type ore is present with Mn oxides, realgar, orpiment, stibnite, and native Au. The formation temperature is between 100 and 150 °C.
6. Conclusions
- Natural sphalerites of (M = Mn, Fe), where x is in the range of 0.07 ≤ x ≤ 0.25, were analyzed by means of SEM-EDS and Raman spectroscopy. The sphalerite samples contain an extensive amount of Mn (between 0 and 14.10 wt.%), which is the largest concentration of Mn in sphalerites from Romanian territory.
- New Raman spectra of natural Mn-rich sphalerites are presented for the first time. The results obtained in the present study provide Mn estimation by determining the positions of the 330 and 300 cm−1 Raman bands. Accordingly, two linear equations were obtained. In this regard, the present study has revealed the usefulness of Raman spectroscopy for (semi)quantitative measurements of Mn concentration in natural sphalerites.
- This systematic peak-position shift towards lower wavenumbers with increasing Mn content is mainly linked to the smaller ionic radius of Mn2+ and polyhedral distortions in tetrahedral sites (MnS4) where the symmetry reduces from Td to D2d.
- In this study, three genetic types of sphalerites were identified: from ferroan to manganoferroan , as well as mangan-rich compositions.
- Mn-sphalerites are strongly connected to the presence of alabandite in mineralized assemblages.
- The formation of several types of sphalerites in the Săcărâmb Au–Ag–Te ore deposit was caused by the succession of different types of hydrothermal fluids and the interaction between the fluids and the host material (host rocks and earlier mineralized stages).
Author Contributions
Funding
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
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Sector/Sample Type | Samples | Mn | Fe | Cd | Cu | Zn | S | SUM | Calculated Formula | (Mn,Fe)-S (cm−1) | LO Zn-S (cm−1) | ||
---|---|---|---|---|---|---|---|---|---|---|---|---|---|
Core sample | SGD_11_2 | n.d. | 4.72 | n.d. | n.d. | 63.11 | 32.18 | 100 | 0 | 299 | 330 | 350 | |
Core sample | SGD_11_1 | n.d. | 9.48 | n.d. | n.d. | 58.48 | 32.05 | 100 | 0 | 299 | 330 | 351 | |
Core sample | 5_SGD_10_2 | 0.75 | 4 | 0.03 | n.d. | 65.42 | 29.8 | 100 | 0.01 | 300 | 331 | 350 | |
Core sample | 5_SGD_10_1 | 0.98 | 2.79 | 0.14 | n.d. | 63.13 | 32.97 | 100 | 0.02 | 300 | 331 | 348 | |
Core sample | 5_SGD_10_3 | 1.22 | 3.50 | 0.72 | n.d. | 63.85 | 30.71 | 100 | 0.02 | 299 | 330 | 348 | |
Sector 3 | 2_S3H2_2 | 3.49 | 5.4 | n.d. | n.d. | 59.81 | 31.3 | 100 | 0.06 | 298 | 327 | 350 | |
Sector 3 | 2_S3H2_1 | 7.22 | 2.23 | n.d. | n.d. | 58.1 | 32.44 | 100 | 0.13 | 297 | 326 | 349 | |
Sector 2 | 8_SGD_22a_1 | 7.55 | 0.24 | 0.4 | n.d. | 59.81 | 32 | 100 | 0.13 | 297 | 328 | 350 | |
Sector 3 | 2_S3H2_3 | 7.92 | 3.57 | n.d. | n.d. | 53.37 | 35.14 | 100 | 0.14 | 298 | 328 | 350 | |
Sector 3 | 4_S3K5_1 | 9.55 | 0.56 | 0.13 | n.d. | 53.28 | 36.48 | 100 | 0.16 | 298 | 327 | 348 | |
Sector 3 | S3I1_1_1 | 10.22 | 0.46 | n.d. | n.d. | 52.96 | 36.36 | 100 | 0.17 | 298 | 329 | 351 | |
Sector 3 | S3E4_1_4c | 12.29 | n.d. | 0.16 | n.d. | 54.92 | 32.63 | 100 | 0.21 | 298 | 330 | 352 | |
Sector 2 | SG1_1_3 | 13.11 | 0.05 | 0.28 | 0.16 | 53.50 | 32.90 | 100 | 0.23 | 297 | 328 | 350 | |
Sector 3 | S3E4_1_4b | 13.74 | n.d. | 0.49 | n.d. | 53.96 | 31.81 | 100 | 0.24 | 295, 307 sh | 328 | 349 | |
Sector 3 | S3E4_1_4 | 14.10 | 0.24 | 0.03 | n.d. | 54.23 | 31.40 | 100 | 0.25 | 295, 307 sh | 326 | 350 |
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Dincă, G.; Apopei, A.I.; Szabo, R.; Maftei, A.E. The Effect of Mn Substitution on Natural Sphalerites by Means of Raman Spectroscopy: A Case Study of the Săcărâmb Au–Ag–Te Ore Deposit, Apuseni Mountains, Romania. Minerals 2022, 12, 885. https://doi.org/10.3390/min12070885
Dincă G, Apopei AI, Szabo R, Maftei AE. The Effect of Mn Substitution on Natural Sphalerites by Means of Raman Spectroscopy: A Case Study of the Săcărâmb Au–Ag–Te Ore Deposit, Apuseni Mountains, Romania. Minerals. 2022; 12(7):885. https://doi.org/10.3390/min12070885
Chicago/Turabian StyleDincă, George, Andrei Ionuț Apopei, Robert Szabo, and Andreea Elena Maftei. 2022. "The Effect of Mn Substitution on Natural Sphalerites by Means of Raman Spectroscopy: A Case Study of the Săcărâmb Au–Ag–Te Ore Deposit, Apuseni Mountains, Romania" Minerals 12, no. 7: 885. https://doi.org/10.3390/min12070885