Factors Controlling the Gallium Preference in High-Al Chromitites
Abstract
:1. Introduction
2. Materials and Methods
2.1. Mineral Analysis
2.2. Whole Rock Analysis
3. A Brief Outline of Characteristics for the Studied Chromitites
4. Results
4.1. Compositional Variations in Chromite
4.2. Distribution of Trace Elements in Chromitites
5. Discussion
5.1. Factors Controlling the Spinel Chemistry
5.1.1. Magmatic Versus Post-Magmatic Processes
5.1.2. Spinel Structure
5.1.3. Applications to Natural Spinels
6. Conclusions
- (1)
- The lower Ga contents in high-Cr chromitites (11 to 23 ppm) compared to high-Al ones (27–49 ppm) suggest that the composition of the parent magma may be a major factor controlling the preference of Ga in high-Al chromitites.
- (2)
- The positive trend between the Fe3+/(Al + Cr + Fe3+) atomic ratio and Ga content for large chromite deposits may suggest the effect of the redox conditions on the Ga distribution in chromitites.
- (3)
- Plot of the Cr/(Cr + Al) atomic ratios versus Ga content exhibits differences in terms of the slope of correlation lines for the different occurrences, suggesting that, in addition to the composition of parent magmas, other factors such as temperature, pressure or redox conditions may affect the observed deviation from linearity for small metamorphosed chromitite bodies.
- (4)
- The depletion of Ga and Al, and elevated Mn, Co, Zn and Fe contents in certain small chromitite occurrences, transformed during post-magmatic metamorphism, suggest potential change of the Ga content in Cr-spinel during sub-solidus reactions.
- (5)
- Assuming that low-Cr spinel is characterized by the highest value of the inversion parameter (x) at higher than 650 °C, then the high Al content in spinels may be a driving force for the degree of inversion in the structure that facilitate the substitution of Al3+ for Ga3+ at magmatic conditions.
Author Contributions
Funding
Acknowledgments
Conflicts of Interest
References
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Vourinos | Pindos | Skyros | |||||||||||||
wt% | Vour. 1 | Vour. 2 | Vour. 3 | Vour. 4 | Vour. 5 | Pi.1. | Pi.2 | Pi. 3 | Pi. 4 | Pi. 5 | Pi.6 | Pi.7 | Sky. 1 | Sky. 2 | Sky. 3 |
TiO2 | 0.3 | 0.2 | 0.2 | 0.1 | 0.2 | 0.2 | 0.3 | 0.2 | 0.2 | 0.1 | 0.2 | 0.1 | 0.2 | 0.2 | 0.2 |
Al2O3 | 11.4 | 9.4 | 9.8 | 23.9 | 11.3 | 26.2 | 27.2 | 32.9 | 34.5 | 16.5 | 15.5 | 8.2 | 20.11 | 24.5 | 22.1 |
Cr2O3 | 59.7 | 63.2 | 61.3 | 44.8 | 60.4 | 41.5 | 39.5 | 35.9 | 34.8 | 52.8 | 52.1 | 61.4 | 48.8 | 45.3 | 47.1 |
MgO | 13.6 | 12.1 | 13.6 | 16.2 | 12.4 | 14.5 | 13.6 | 16.4 | 16.7 | 12.4 | 10.1 | 11.7 | 13.9 | 15.7 | 10.2 |
FeO | 13.1 | 14.1 | 12.7 | 11.1 | 14.6 | 13.5 | 15.7 | 12.3 | 12.5 | 15.6 | 18.7 | 14.9 | 13.6 | 11.8 | 19.7 |
Fe2O3 | 1.7 | 0.1 | 2.1 | 4.2 | .5 | 3.4 | 3.1 | 2.3 | 2.6 | 2.9 | 2.7 | 2.8 | 2.2 | 2.3 | 0.3 |
MnO | 0.3 | 0.2 | 0.2 | 0.2 | 0.2 | 0.3 | n.d. | 0.1 | n.d. | 0.2 | 0.3 | 0.3 | 0.1 | 0.1 | 0.2 |
NiO | 0.2 | 0.1 | n.d. | n.d. | 0.2 | 0.3 | n.d. | 0.2 | n.d. | 0.2 | 0.1 | 0.2 | 0.1 | 0.2 | 0.2 |
Total | 100.3 | 99.5 | 99.9 | 100.5 | 99.8 | 99.9 | 99.4 | 100.1 | 101.2 | 100.7 | 99.7 | 99.6 | 99.01 | 100.1 | 100 |
Cr/(Cr+Al) | 0.77 | 0.81 | 0.81 | 0.56 | 0.78 | 0.52 | 0.49 | 0.42 | 0.4 | 0.70 | 0.69 | 0.81 | 0.62 | 0.55 | 0.58 |
Mg/(Mg+Fe2+) | 0.65 | 0.62 | 0.66 | 0.72 | 0.60 | 0.65 | 0.61 | 0.71 | 0.72 | 0.59 | 0.49 | 0.58 | 0.64 | 0.69 | 0.51 |
Fe3+/(Cr+Al+Fe3+) | 0.031 | 0.000 | 0.025 | 0.036 | 0.0055 | 0.038 | 0.036 | 0.025 | 0.027 | 0.0413 | 0.028 | 0.036 | 0.027 | 0.026 | 0.0033 |
Numbers of Cations on the Basis of 32 Oxygens | |||||||||||||||
Ti | 0.019 | 0.039 | 0.040 | 0.018 | 0.039 | 0.036 | 0.054 | 0.035 | 0.014 | 0.019 | 0.039 | 0.020 | 0.037 | 0.036 | 0.038 |
Al | 3.426 | 2.889 | 2.997 | 6.736 | 3.451 | 7.415 | 7.758 | 8.966 | 9.241 | 4.650 | 4.728 | 2.555 | 5.896 | 6.922 | 6.532 |
Cr | 12.037 | 13.031 | 12.523 | 8.471 | 12.383 | 7.891 | 7.558 | 6.563 | 6.254 | 10.645 | 10.662 | 12.835 | 9.602 | 8.586 | 9.340 |
Mg | 5.170 | 4.703 | 5.250 | 5.774 | 4.790 | 5.210 | 4.906 | 5.652 | 5.658 | 4.712 | 3.896 | 4.611 | 5.156 | 5.610 | 3.813 |
Fe2+ | 2.744 | 3.271 | 2.744 | 2.203 | 3.164 | 2.706 | 3.149 | 2.326 | 2.377 | 3.222 | 4.056 | 3.300 | 2.840 | 2.367 | 4.142 |
Fe3+ | 0.498 | 0.001 | 0.400 | 0.757 | 0.087 | 0.620 | 0.575 | 0.401 | 0.436 | 0.659 | 0.533 | 0.570 | 0.427 | 0.420 | 0.053 |
Mn | 0.065 | 0.044 | 0.045 | 0.040 | 0.044 | 0.061 | 0.000 | 0.020 | 0.000 | 0.043 | 0.065 | 0.067 | 0.021 | 0.020 | 0.042 |
Ni | 0.157 | 0.021 | 0.000 | 0.000 | 0.042 | 0.058 | 0.000 | 0.037 | 0.000 | 0.041 | 0.020 | 0.042 | 0.020 | 0.039 | 0.040 |
Rhodope Massif | Urals Kempirsai | ||||||||||||||
Skyros | Greece | Bulgaria | |||||||||||||
Goliamo | Northern Part | Southern Part | |||||||||||||
wt% | Sky. 4 | Sky. 5 | Soufli 1 | Soufli 2 | Gomati | Broucevci | Jacovitsa | Pletena | Kamenyane 1 | Kamenyane 2 | Batamshinsk | Main Ore Field | |||
TiO2 | 0.1 | 0.2 | n.d. | 0.2 | 0.2 | 0.4 | 0.2 | 0.5 | 0.4 | 0.3 | 0.3 | 0.3 | 0.1 | 0.2 | |
Al2O3 | 11.2 | 12.6 | 15.8 | 19.6 | 30.8 | 27.9 | 5.5 | 10.4 | 4.5 | 1.2 | 24.4 | 23.3 | 9.3 | 9.8 | |
Cr2O3 | 59.1 | 58.1 | 53.9 | 47.8 | 35.5 | 37.3 | 58.8 | 49.8 | 33.2 | 24.9 | 46.6 | 47.1 | 61.3 | 60.2 | |
MgO | 13.8 | 14.4 | 13.4 | 14.1 | 15.3 | 16.6 | 10.2 | 8.2 | 11.9 | 7.2 | 14.3 | 14.2 | 15.5 | 15.2 | |
FeO | 12.1 | 11.5 | 13.4 | 13.5 | 13.9 | 10.4 | 16.2 | 20.7 | 13.6 | 20.2 | 14.1 | 14.1 | 9.9 | 10.3 | |
Fe2O3 | 2.4 | 2.2 | 3.1 | 5.0 | 5.1 | 6.0 | 7.2 | 9.5 | 35.1 | 45.6 | 0.3 | 0.8 | 4.5 | 4.3 | |
MnO | 0.2 | 0.2 | 0.2 | 0.2 | n.d. | 0.2 | 0.6 | 0.5 | n.d. | 0.2 | n.d. | n.d. | n.d. | n.d. | |
NiO | 0.2 | 0.2 | n.d. | 0.2 | n.d. | 0.2 | 0.2 | 0.2 | 0.3 | 0.4 | 0.2 | 0.2 | 0.1 | 0.3 | |
Total | 99.1 | 99.7 | 100.2 | 99.8 | 100.3 | 99.1 | 99.1 | 100 | 99.2 | 99.9 | 100.4 | 99.9 | 100.8 | 100.3 | |
Cr/(Cr+Al) | 0.75 | 0.79 | 0.70 | 0.63 | 0.44 | 0.47 | 0.88 | 0.74 | 0.83 | 0.94 | 0.56 | 0.58 | 0.82 | 0.80 | |
Mg/(Mg+Fe2+) | 0.68 | 0.69 | 0.62 | 0.65 | 0.66 | 0.72 | 0.52 | 0.37 | 0.52 | 0.38 | 0.64 | 0.65 | 0.74 | 0.73 | |
Fe3+/(Cr+Al+Fe3+) | 0.03 | 0.026 | 0.036 | 0.059 | 0.057 | 0.068 | 0.093 | 0.123 | 0.455 | 0.62 | 0.0015 | 0.009 | 0.053 | 0.052 | |
Numbers of cations on the basis of 32 oxygens | |||||||||||||||
Ti | 0.019 | 0.038 | 0.019 | 0.036 | 0.035 | 0.035 | 0.041 | 0.102 | 0.082 | 0.062 | 0.054 | 0.054 | 0.019 | 0.038 | |
Al | 3.414 | 3.813 | 4.636 | 5.591 | 8.475 | 7.828 | 1.767 | 3.277 | 1.452 | 0.386 | 6.987 | 6.,675 | 2.787 | 2.947 | |
Cr | 12.066 | 11.695 | 10.745 | 9.396 | 6.553 | 7.021 | 12.670 | 10.582 | 7.168 | 5.648 | 8.880 | 9.070 | 12.323 | 12.143 | |
Mg | 5.321 | 5.512 | 5.036 | 5.231 | 5.324 | 5.890 | 4.143 | 3.291 | 4.858 | 3.088 | 5.137 | 5.151 | 5.874 | 5.780 | |
Fe2+ | 2.613 | 2.442 | 2.940 | 2.805 | 2.711 | 2.067 | 3.715 | 4.653 | 3.114 | 4.839 | 2.879 | 2.864 | 2.125 | 2.197 | |
Fe3+ | 0.480 | 0.414 | 0.580 | 0.940 | 0.901 | 1.079 | 1.481 | 1.936 | 7.215 | 9,844 | 0.024 | 0.146 | 0.852 | 0.833 | |
Mn | 0.044 | 0.044 | 0.043 | 0.000 | 0.000 | 0.040 | 0.138 | 0.115 | 0.000 | 0.046 | 0.000 | 0.000 | 0.000 | 0.000 | |
Ni | 0.041 | 0.041 | 0.000 | 0.000 | 0.000 | 0.038 | 0.044 | 0.044 | 0.114 | 0.088 | 0.039 | 0.038 | 0.020 | 0.062 |
Location | SEM/EDS | Trace Element (ppm) | wt% | ppb | ||||||
---|---|---|---|---|---|---|---|---|---|---|
Cr/(Cr+Al) | Mg/(Mg+Fe2+) | Ni | Co | V | Zn | Ga | Fe | ΣPGE * | Pd/Ir * | |
Vourinos 1 | 0.77 | 0.65 | 2000 | 240 | 500 | 260 | 14 | 8.1 | 140 | 0.06 |
Vourinos 2 | 0.81 | 0.62 | 1580 | 210 | 560 | 550 | 15 | 7.9 | 135 | 0.35 |
Vourinos 3 | 0.81 | 0.66 | 1900 | 200 | 400 | 300 | 13 | 8.72 | 92 | 0.55 |
Vourinos 4 | 0.56 | 0.72 | 1800 | 170 | 780 | 360 | 27 | 9.2 | 30 | 0.54 |
Vourinos 5 | 0.78 | 0.61 | 1800 | 180 | 620 | 280 | 14 | 7.76 | 109 | 0.63 |
Pindos 1 | 0.52 | 0.63 | 1300 | 140 | 600 | 400 | 23 | 7.84 | 51 | 1.0 |
Pindos 2 | 0.48 | 0.6 | 1500 | 260 | 710 | 410 | 32 | 9.77 | 143 | 1.0 |
Pindos 3 | 0.42 | 0.71 | 1500 | 260 | 710 | 520 | 34 | 7.8 | 117 | 6.33 |
Pindos 4 | 0.4 | 0.72 | 1630 | 240 | 580 | 460 | 32 | 7.3 | 6123 | 34.2 |
Pindos5 | 0.67 | 0.57 | 750 | 270 | 760 | 520 | 16 | 9.7 | 3875 | 12.2 |
Pindos 6 | 0.69 | 0.49 | 720 | 240 | 760 | 620 | 23 | 10.1 | 2098 | 7.2 |
Pindos 7 | 0.81 | 0.58 | 1450 | 290 | 560 | 490 | 17 | 10.2 | 181 | 0.22 |
Skyros 1 | 0.61 | 0.64 | 1300 | 250 | 1200 | 540 | 34 | 10.9 | 2300 | 0.08 |
Skyros 2 | 0.55 | 0.69 | 1600 | 200 | 1000 | 400 | 36 | 9.45 | 464 | 0.7 |
Skyros 3 | 0.58 | 0.51 | 1500 | 240 | 870 | 450 | 40 | 9.6 | 251 | 0.67 |
Skyros 4 | 0.75 | 0.69 | 1250 | 220 | 640 | 420 | 14 | 10.7 | 145 | 0.33 |
Skyros 5 | 0.79 | 0.69 | 1200 | 200 | 620 | 400 | 11 | 10.1 | 145 | 0.1 |
Othrys (n = 4) | 0.54 | 0.69 | 1400 | 210 | 960 | 370 | 33 | 9.8 | 91 | 0.36 |
Rhodope Massif | ||||||||||
Greece | ||||||||||
Soufli1 | 0.70 | 0.62 | 1700 | 230 | 380 | 580 | 16 | 13.2 | 150 | 0.2 |
Soufli2 | 0.63 | 0.65 | 1150 | 220 | 460 | 280 | 12 | 10.6 | 82 | 1.0 |
Gomati | 0.49 | 0.67 | 1030 | 130 | 730 | 280 | 24 | 9.6 | 104 | 0.25 |
Bulgaria | ||||||||||
Broucevci | 0.47 | 0.72 | 1300 | 230 | 790 | 420 | 45 | 11 | 60 | 0.92 |
Jacovitsa | 0.88 | 0.52 | 2250 | 310 | 240 | 760 | 9 | 13.9 | 197 | 0.46 |
Pletena | 0.74 | 0.37 | 890 | 290 | 330 | 1030 | 13 | 17.9 | 563 | 0.07 |
Goliamo Kamenyane 1 | 0.83 | 0.52 | 1550 | 80 | 1000 | 450 | 12 | 11.6 | 87 | 0.14 |
Goliamo Kamenyane 2 | 0.94 | 0.38 | 2260 | 970 | 370 | 4030 | 6 | 64.3 | 40 | 1.93 |
Kemprsai (Urals) | ||||||||||
Northern | 0.80 | 0.73 | 1600 | 210 | 160 | 160 | 14 | 9.1 | ||
Batamshinsk | 0.82 | 0.74 | 1600 | 230 | 200 | 190 | 16 | 9.5 | ||
Southern | 0.56 | 0.58 | 1500 | 240 | 680 | 480 | 48 | 12.6 | ||
XL Let Kazakhstan | 0.64 | 0.65 | 1700 | 230 | 730 | 340 | 49 | 10.1 |
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Eliopoulos, I.-P.D.; Eliopoulos, G.D. Factors Controlling the Gallium Preference in High-Al Chromitites. Minerals 2019, 9, 623. https://doi.org/10.3390/min9100623
Eliopoulos I-PD, Eliopoulos GD. Factors Controlling the Gallium Preference in High-Al Chromitites. Minerals. 2019; 9(10):623. https://doi.org/10.3390/min9100623
Chicago/Turabian StyleEliopoulos, Ioannis-Porfyrios D., and George D. Eliopoulos. 2019. "Factors Controlling the Gallium Preference in High-Al Chromitites" Minerals 9, no. 10: 623. https://doi.org/10.3390/min9100623