Alteration and Non-Formula Elements Uptake of Zircon from Um Ara Granite, South Eastern Desert, Egypt
Abstract
:1. Introduction
2. Geological and Mineralogical Background
3. Sample Preparation and Analytical Procedures
4. Results
4.1. Textural Observations
4.2. Major and Trace Elements Composition
4.3. REE Pattern of Zircon
5. Discussion
5.1. Zircon Alteration
5.2. Timing of ‘Non-Formula’ Element Uptake in Um Ara Zircon
- (i)
- An early stage of hydrothermal activity took place between 603 and 530 Ma ago. The granitic rocks in the Um Ara area formed during this period, following intense mountain-building. Zircon crystals extracted from these granites have been dated to 603 ± 14 Ma, confirming this timeframe [16]. The intrusion of these granites seems to be influenced by deep shear zones and faulting in the Earth’s crust. These shear zones acted as pathways for rare metal-bearing hydrothermal fluids. The granites contain various accessory minerals, like columbite, ilmenite, zircon, xenotime, thorite, monazite, and apatite. These minerals behave differently when they are altered by fluids. Some zircon crystals have compositions close to ideal stoichiometry, while others show signs of alteration. Normally, elements like uranium, thorium, and REEs would not be easily incorporated into zircon crystals, especially at low temperatures. So, it is likely that something changed the zircon crystals (metamictization) to allow them to accommodate these elements. This event likely involved the release of hot fluids during the final stages of magma cooling and crystallization, leading to Na- and K-metasomatism within the granite [14]. However, this phase was insufficient to alter zircon and other refractory minerals (xenotime, thorite, monazite, and apatite) due to their inherent resistance to alteration.
- (ii)
- Late-stage hydrothermal event (ca. 20 Ma), linked to the main rifting phase of the Red Sea. The prolonged metamictization of the refractory minerals could have eventually weakened them, rendering them susceptible to modification by this later hydrothermal event. This event may have led to the uptake of non-formula elements in the zircon, as supported by previous studies on metamict zircon crystals from the Gabel Hamradom in the Egyptian Eastern Desert. The time of this hydrothermal event is determined to be around 17.9 + 6.9 − 7.4 to 22.2 + 5.4 − 4.8 Ma [6].
- (iii)
- Surficial weathering event that led to the alteration of the Um Ara granites. Low-temperature alteration by oxic groundwater may have contributed to further uptake of non-formula elements in the zircon. The 230Th/234U ages of 50,000 to 159,000 years for uranophane from the Um Ara granites match up with periods of heavy rainfall (pluvial periods) known as the Kubbaniyan and Nabtian that occurred in the Egyptian Eastern Desert [56]. A similar low-temperature weathering event has been suggested as a mechanism for element uptake in metamict zircons [57,58].
6. Conclusions
- Initial zircon crystallization occurred around 603 Ma in the Um Ara granitic source, accompanied by the formation of other U- and Th-bearing minerals such as xenotime, thorite, monazite, and apatite.
- Long-term metamictization of the primary zircon crystals, as well as the associated U- and Th-bearing minerals, resulted in the formation of fractures and cracks within these minerals. These fractures and cracks facilitated the subsequent alteration processes by allowing fluid circulation and chemical changes.
- A major hydrothermal event, contemporaneous with the rifting of the Red Sea around 20 Ma, led to fluid-rock interaction and the release of Zr, Si, U, Th, Hf, Fe, Al, Ca, Ti, P, As, and REEs from the metamicted zircon and associated U- and Th-bearing minerals. As the hydrothermal alteration progressed, voids or altered remnants were left behind within the zircon grains. The enrichment of the hydrothermal fluids with non-formula elements, such as REEs, P, Al, Ca, Fe, and Ti, facilitated their incorporation into the modified zircon crystal structure, filling the voids and altered zones.
- Subsequent pluvial periods in the Kubbaniyan and Nabtian periods (around 50,000–159,000 years ago) may have allowed further uptake of non-formula elements during low-temperature alteration. The shear zones within the Um Ara granites facilitated the mobilization and transport of non-formula element-bearing fluids, likely as carbonate and fluoride complexes.
- Subsequent pluvial periods in the Kubbaniyan and Nabtian periods (around 50,000–159,000 years ago) may have had a limited role in incorporating additional elements into zircon. The shear zones within the Um Ara granites facilitated the mobilization and transport of non-formula element-bearing fluids, likely as carbonate and fluoride complexes.
Funding
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
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Element | Emission Line | Std. | Analyzer Crystal | Limit of Quantification (LOQ) (wt.%) |
---|---|---|---|---|
Si | Kα1 | Wollastonite | PETH | 0.066 |
Zr | Lα1 | Zr oxide | PETJ | 0.042 |
U | Mα1 | UO2 | PETH | 0.081 |
Th | Mα1 | ThO2 | PETH | 0.102 |
Hf | Lα1 | HfO2 | LIFH | 0.033 |
Pb | Mα1 | PbVGe oxides | PETH | 0.015 |
Fe | Kα1 | Fe2O3 | LIFH | 0.033 |
Al | Kα1 | Y-garnet | TAP | 0.027 |
Ca | Kα1 | Wollastonite | PETJ | 0.051 |
Mg | Kα1 | MgO | TAP | 0.051 |
Ti | Kα1 | Ilmenite | PETJ | 0.024 |
P | Kα1 | LaPO4 | TAP | 0.081 |
Y | Lα1 | Y-garnet | TAP | 0.039 |
As | Lα1 | Cal-STD | LIF | 0.039 |
La | Lα1 | LaPO4 | LIF | 0.045 |
Ce | Lα1 | CePO4 | LIFH | 0.069 |
Nd | Lβ1 | NdPO4 | LIFH | 0.036 |
Sm | Lβ1 | SmPO4 | LIFH | 0.057 |
Eu | Lβ1 | EuPO4 | LIFH | 0.036 |
Gd | Lβ1 | GdPO4 | LIF | 0.075 |
Tb | Lβ1 | TbPO4 | LIFH | 0.036 |
Dy | Lβ1 | DyPO4 | LIFH | 0.075 |
Ho | Lβ1 | HoPO4 | LIFH | 0.018 |
Er | Lβ1 | ErPO4 | LIFH | 0.018 |
Tm | Lα1 | TmPO4 | LIFH | 0.018 |
Yb | Lα1 | YbPO4 | LIFH | 0.039 |
Lu | Lα1 | LuPO4 | LIFH | 0.021 |
Mineral Type | Less Altered Zircon | Altered Zircon | Uranophane | |||||||
---|---|---|---|---|---|---|---|---|---|---|
Sample | SP1 (N* = 1) | SP2-1 (N* = 2) | SP2-2 (N* = 8) | SP3-1 (N* = 7) | SP3-2 (N* = 8) | SP4-1 (N* = 8) | SP5 (N* = 8) | SP4-2B (N* = 8) | U1 (N = 3) | U3 (N = 3) |
Oxides (wt.%) | ||||||||||
SiO2 | 32.853 | 32.846 | 30.518 | 30.913 | 28.44 | 26.48 | 25.84 | 26.66 | 14.327 | 13.696 |
ZrO2 | 66.273 | 64.848 | 63.184 | 62.605 | 50.04 | 41.08 | 39.2 | 36.52 | 0.037 | 0.006 |
UO2 | 0.083 | 0.118 | 0.085 | 0.013 | 2.195 | 3.166 | 2.262 | 5.518 | 66.685 | 60.288 |
ThO2 | 0.103 | 0.05 | - | 0.038 | 1.035 | 8.685 | 6.73 | 8.01 | - | - |
HfO2 | - | 0.075 | 1.716 | 1.275 | 3.342 | 2.931 | 6.257 | 2.905 | 0.157 | - |
PbO | - | - | - | 0.092 | - | - | 0.104 | - | - | |
FeO | 0.152 | 0.145 | 0.035 | 0.625 | 0.992 | 1.086 | 2.035 | 1.662 | 0.219 | 0.284 |
Al2O3 | - | - | 0.029 | - | 0.813 | 2.062 | 1.768 | 3.224 | 0.15 | 0.289 |
CaO | 0.057 | 0.043 | - | 0.051 | 1.368 | 1.597 | 1.416 | 1.426 | 6.764 | 6.143 |
MgO | - | - | - | - | 0.059 | 0.055 | - | 0.074 | 0.029 | 0.069 |
TiO2 | - | - | 0.053 | 0.064 | 0.026 | - | - | - | 0.014 | - |
P2O5 | - | - | - | - | 0.248 | 0.417 | 0.39 | 0.128 | - | - |
Y2O3 | - | - | - | - | 0.518 | - | 0.564 | - | - | - |
As2O3 | - | - | - | - | 0.06 | 0.061 | 0.22 | 0.128 | 0.034 | 0.055 |
La2O3 | - | - | 0.046 | 0.047 | 0.07 | 0.15 | 0.25 | 0.054 | - | 0.056 |
Ce2O3 | - | - | 0.079 | 0.07 | 0.103 | 1.024 | 0.941 | 0.856 | 0.183 | - |
Nd2O3 | - | - | 0.106 | 0.126 | 0.04 | 0.039 | 0.037 | 0.036 | 0.118 | 0.06 |
Sm2O3 | - | - | 0.059 | 0.075 | 0.063 | 0.184 | 0.144 | 0.066 | - | - |
EU2O3 | - | - | 0.056 | 0.091 | 0.04 | 0.037 | 0.038 | 0.045 | - | - |
Gd2O3 | - | - | 0.198 | 0.175 | 0.081 | 0.164 | 0.11 | 0.078 | - | - |
Tb2O3 | - | - | 0.037 | 0.037 | 0.037 | 0.039 | 0.037 | 0.039 | - | 0.089 |
Dy2O3 | - | - | 0.077 | 0.162 | 0.288 | 0.328 | 0.177 | 0.241 | - | - |
Ho2O3 | - | - | 0.175 | 0.104 | 0.082 | 0.02 | 0.018 | 0.018 | - | - |
Er2O3 | - | - | 0.02 | 0.02 | 0.356 | 0.053 | 0.413 | 0.076 | - | - |
Tm2O3 | - | - | 0.062 | 0.023 | 0.193 | 0.018 | 0.037 | 0.072 | - | 0.035 |
Yb2O3 | - | - | 0.26 | 0.078 | 0.489 | 0.393 | 0.395 | 0.044 | - | - |
Lu2O3 | - | - | 0.112 | 0.033 | 0.182 | 0.089 | 0.03 | 0.021 | - | 0.075 |
Total | 99.52 | 98.13 | 96.91 | 96.56 | 91.25 | 90.16 | 89.31 | 88.01 | 88.72 | 81.15 |
Structural formula | Based on O = 4 | Based on O = 7 | ||||||||
Si | 1.007 | 1.017 | 0.982 | 0.991 | 0.991 | 0.976 | 0.969 | 1.000 | 1.508 | 1.549 |
Al | - | - | 0.001 | - | 0.033 | 0.090 | 0.078 | 0.142 | 0.019 | 0.039 |
P | - | - | - | - | 0.007 | 0.013 | 0.012 | 0.004 | - | - |
As | - | - | - | - | 0.001 | 0.001 | 0.005 | 0.003 | 0.002 | 0.004 |
T-site | 1.007 | 1.017 | 0.982 | 0.991 | 1.033 | 1.080 | 1.064 | 1.150 | ||
Zr | 0.990 | 0.979 | 0.991 | 0.979 | 0.850 | 0.738 | 0.717 | 0.668 | 0.002 | 0.000 |
U | 0.001 | 0.001 | 0.001 | 0.000 | 0.017 | 0.026 | 0.019 | 0.046 | 1.562 | 1.517 |
Th | 0.001 | 0.000 | - | 0.000 | 0.008 | 0.073 | 0.057 | 0.068 | - | - |
Hf | - | 0.001 | 0.016 | 0.012 | 0.033 | 0.031 | 0.067 | 0.031 | 0.005 | - |
Pb | - | - | - | - | 0.001 | 0.000 | - | 0.001 | - | - |
Fe | 0.004 | 0.004 | 0.001 | 0.017 | 0.029 | 0.034 | 0.064 | 0.052 | 0.019 | 0.027 |
Ca | 0.001 | 0.001 | - | 0.002 | 0.051 | 0.063 | 0.057 | 0.057 | 0.763 | 0.744 |
Mg | - | - | - | - | 0.003 | 0.001 | - | 0.004 | 0.005 | 0.012 |
Ti | - | - | 0.001 | 0.002 | 0.000 | - | - | - | 0.001 | - |
Y | - | - | - | 0.000 | 0.010 | - | 0.011 | - | - | - |
La | - | - | 0.000 | 0.000 | 0.001 | 0.002 | 0.004 | 0.000 | - | 0.002 |
Ce | - | - | 0.001 | 0.001 | 0.001 | 0.014 | 0.013 | 0.012 | 0.007 | - |
Nd | - | - | 0.001 | 0.001 | 0.000 | 0.000 | 0.000 | 0.001 | 0.004 | 0.002 |
Sm | - | - | 0.001 | 0.001 | 0.000 | 0.002 | 0.002 | 0.001 | - | - |
Eu | - | - | 0.001 | 0.000 | 0.000 | 0.000 | 0.000 | 0.000 | - | - |
Gd | - | - | 0.002 | 0.001 | 0.000 | 0.002 | 0.001 | 0.001 | - | - |
Tb | - | - | 0.000 | 0.000 | 0.000 | 0.000 | 0.000 | 0.000 | - | 0.003 |
Dy | - | - | 0.000 | 0.000 | 0.003 | 0.004 | 0.002 | 0.003 | - | - |
Ho | - | - | 0.002 | 0.002 | 0.001 | 0.000 | 0.000 | 0.000 | - | - |
Er | - | - | 0.000 | 0.000 | 0.004 | 0.001 | 0.005 | 0.001 | - | - |
Tm | - | - | 0.001 | 0.000 | 0.002 | 0.000 | 0.000 | 0.001 | - | 0.001 |
Yb | - | - | 0.003 | 0.001 | 0.005 | 0.004 | 0.005 | 0.000 | - | - |
Lu | - | - | 0.001 | 0.001 | 0.002 | 0.001 | 0.000 | 0.000 | - | 0.003 |
A-Site | 0.996 | 0.986 | 1.022 | 1.019 | 1.023 | 0.996 | 1.025 | 0.948 | ||
Total | 2.002 | 2.003 | 2.004 | 2.010 | 2.056 | 2.076 | 2.089 | 2.098 | 3.896 | 3.904 |
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Abd El-Naby, H.H. Alteration and Non-Formula Elements Uptake of Zircon from Um Ara Granite, South Eastern Desert, Egypt. Minerals 2024, 14, 834. https://doi.org/10.3390/min14080834
Abd El-Naby HH. Alteration and Non-Formula Elements Uptake of Zircon from Um Ara Granite, South Eastern Desert, Egypt. Minerals. 2024; 14(8):834. https://doi.org/10.3390/min14080834
Chicago/Turabian StyleAbd El-Naby, Hamdy H. 2024. "Alteration and Non-Formula Elements Uptake of Zircon from Um Ara Granite, South Eastern Desert, Egypt" Minerals 14, no. 8: 834. https://doi.org/10.3390/min14080834