p-Type II–VI compounds doped by rare-earth elements

Abstract The grossular-andradite solid solutions in garnet from skarn deposits in relation to hydrothermal processes and physicochemical conditions of ore formation remain controversial. Here we investigate garnet occurring in association with calcic and magnesian skarn rocks in the Cuihongshan polymetallic skarn deposit of NE China. The calcic skarn rocks contain three types of garnets. (1) Prograde type I Al-rich anisotropic garnets display polysynthetic twinning and a compositional range of Grs18–80Adr10–75. This type of garnet shows markedly low rare earth element (REE) contents (3.27–78.26 ppm) and is strongly depleted in light rare earth elements (LREE, 0.57–44.65 ppm) relative to heavy rare earth elements (HREE, 2.31–59.19 ppm). They also display a significantly negative Eu anomaly (Eu/Eu* of 0.03–0.90). (2) Fe-rich retrograde type II garnets are anisotropic with oscillatory zoning and own wide compositional variations (Grs1–47Adr30–95) with flat REE (13.73–377.08 ppm) patterns. (3) Fe-rich retrograde type III isotropic garnets display oscillatory zoning and morphological transition from planar dodecahedral {110} crystal faces to {211} crystal faces in the margin. Types III garnets exhibit relatively narrow compositional variations of Grs0.1–12Adr85–97 with LREE-enrichment (0.80–51.87 ppm), flat HREE patterns (0.15–2.46 ppm) and strong positive Eu anomalies (Eu/Eu* of 0.93–27.07 with almost all >1). The magnesian skarn rocks contain euhedral isotropic type IV Mn-rich garnet veins with a composition of Grs10–23Sps48–62Alm14–29. All calcic garnets contain considerable Sn and W contents. Type II garnet containing intermediate compositions of andradite and grossular shows the highest Sn contents (64.36–2778.92 ppm), albeit the lowest W range (1.11–468.44 ppm). Birefringence of garnet is probably caused by strain from lattice mismatch at a twinning boundary or ion substitution near intermediate compositions of grossular-andradite. The fine-scale, sharp, and straight garnet zones are probably caused by self-organization, but the compositional variations of zones from core to rim are probably caused by external factors. The zoning is likely driven by external factors such as composition of the hydrothermal fluid. REE concentrations are probably influenced by the relative proportion and temperature of the system. Moreover, the LREE-HREE fractionation of garnet can be attributed to relative compositions of grossular-andradite system. The W and Sn concentrations in garnet can be used as indicators for the exploration of W-Sn skarn deposits.

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Trace and Rare Earth Elements, and Sr Isotopic Compositions of Fluorite from the Shihuiyao Rare Metal Deposit, Inner Mongolia: Implication for Its Origin

Minerals ◽

10.3390/min10100882 ◽

2020 ◽

Vol 10 (10) ◽

pp. 882

Author(s):

Zhen-Peng Duan ◽

Shao-Yong Jiang ◽

Hui-Min Su ◽

Xin-You Zhu ◽

Tao Zou ◽

...

Keyword(s):

Rare Earth ◽

Rare Earth Elements ◽

Inner Mongolia ◽

Mining Area ◽

Rare Metal ◽

Type I ◽

Type Ii ◽

Type Iii ◽

Hydrothermal Stage ◽

Magmatic Stage

Abundant fluorites occur in the Shihuiyao rare metal (Nb-Ta-Rb) deposit in Inner Mongolia of NE China, and they can be classified by their occurrence into three types. Type I occurs disseminated in greisen pockets of albitized granite. Type II occurs in the skarn zone between granite and carbonate host rocks, and it can be subdivided into different subtypes according to color, namely dark purple (II-D), magenta (II-M), green (II-G), light purple (II-P), and white (II-W). Type III are the fluorite-bearing veins in the silty mudstones. On the basis of petrography of the fluorites and their high contents of HFSEs (high field strength elements) and LILEs (large ion lithophile elements), strong negative Eu anomalies, and tetrad effects, we suggest that Type I fluorites crystallized in a late-magmatic stage with all the components derived from the granite. The high Y/Ho ratios suggest that the Type II fluorites crystallized in the early- or late-hydrothermal stage. The rare earth elements (REEs) characterized by various Eu anomalies of the Type II fluorites indicate a mixed origin for ore-forming metals from granite-related fluids and limestones, and the oxygen fugacity increased during fluid migration and cooling. Compared to the Type II fluorites, the similar trace element contents of the Type III suggest a similar origin, and remarkable positive Eu anomalies represent a more oxidizing environment. The Sr isotopic composition (87Sr/86Sr)i = 0.710861) of the Type I fluorites may represent that of the granite-derived fluids, whereas the (87Sr/86Sr)i ratios of the Type II (0.710168–0.710380) and Type III (0.709018) fluorites are lower than that of the Type I fluorites but higher than those of the Late Permian-Early Triassic seawater, suggesting a binary mixed Sr source, i.e., granite-derived fluids and marine limestones. Nevertheless, the proportion of limestone-derived Sr in the mixture forming the Type III fluorites is much higher than that of Type II. The rare metal Nb and Ta get into the granite-derived F-rich fluids by complexing with F and precipitate in the form of columbite-group minerals after the Type I fluorites crystallize. Most of Nb and Ta may have deposited as columbite-group minerals during the magmatic stage, resulting in no Nb-Ta mineralization in the hydrothermal stage when the Type II and III fluorites formed. Hence, the Type I fluorites in the Shihuiyao mining area can be used as an important exploration tool for the Nb-Ta mineralization.

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Zircon Genesis and Geochronology for the Zhangbaoshan Super-Large Rubidium Deposit in the Eastern Tianshan, NW China: Implication to Magmatic-Hydrothermal Evolution and Mineralization Processes

Frontiers in Earth Science ◽

10.3389/feart.2021.682720 ◽

2021 ◽

Vol 9 ◽

Author(s):

Jun Zhi ◽

Ruxiong Lei ◽

Boyang Chen ◽

M. N. Muhtar ◽

Zhijie Feng ◽

...

Keyword(s):

Rare Earth ◽

Rare Earth Elements ◽

Oscillatory Zoning ◽

Magmatic Zircon ◽

Type I ◽

Early Triassic ◽

Type Ii ◽

Eastern Tianshan ◽

Hydrothermal Stage ◽

Highly Evolved

The Zhangbaoshan (ZBS) super-large Rubidium deposit, located in the Eastern Tianshan, is a typical granite-type Rb deposit. The ZBS deposit is mainly hosted in the highly evolved Baishitouquan (BST) pluton enriched in F and Rb, which exhibits five lithological zones from the bottom to the top: leucogranite (zone-a), amazonite-bearing granite (zone-b), amazonite granite (zone-c), topaz-bearing amazonite granite (zone-d) and topaz albite granite (zone-e), as well as minor small lodes of amazonite pegmatite. Two types of zircon were identified from the BST pluton. Type-I zircons mainly occur in the zone–a, are characterized by obvious oscillatory zoning, high Zr contents (47.4–67.3 wt% ZrO2) and Zr/Hf ratios (21.72–58.23), low trace element concentrations, and heavy rare earth elements (HREE)–enriched patterns with prominent positive Ce anomalies (Ce/Ce* = 1.21–385) and strong negative Eu anomalies (Eu/Eu* = 0.008–0.551), indicative of early magmatic zircon. Type–II zircons mainly occur in the upper zones (zone-c to zone-e), exhibit porous and dark Cathodoluminescence images, inhomogeneous internal structure, plenty of mineral inclusions, low Zr (38.7–51.0 wt% ZrO2) and Zr/Hf ratios (3.35–11.00), high Hf (34,094–85,754 ppm), Th (718–4,980 ppm), U (3,540–32,901 ppm), Ta (86.7–398 ppm), Y (1,630–28,890 ppm) and rare earth elements (REEs) (3,910–30,165 ppm), as well as slightly HREE–enriched patterns and significant M–type tetrad patterns with t3 values (quantification factor of tetrad effect) of 1.51–1.69. It is suggested that the type–II zircons are crystallized from a deuteric F–rich fluid coexisted with the highly evolved residual magma during the transition from the magmatic to the F–rich hydrothermal stage of the BST pluton. The F–rich fluid exsolution during the magmatic–hydrothermal transition is one of the most important factors controlling the modification of highly evolved granite and related Rb enrichment and mineralization. The type–I zircon samples from zone–a yield concordant ages of 250 ± 2.5 Ma and 250.5 ± 1.7 Ma, respectively, indicating that the BST pluton was emplaced in the Early Triassic. The type–II zircons from zone–c to zone–e yield lower intercept U–Pb ages between 238 and 257 Ma, which may represent the age of F–rich fluid–melt interaction during the transition from the magmatic to the hydrothermal stage. The mineralization of the ZBS super–large Rb deposit should have occurred shortly after emplacement of the BST pluton in the Early Triassic. Combined with available data, it is suggested that the Triassic is an important period for granitic magmatism and rare metal metallogeny in the Eastern Tianshan.

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Characteristics of genetic mineralogy of pyrite and quartz and their indicating significance in the Gaosongshan Gold Deposit, Heilongjiang Province, NE China

Earth Sciences Research Journal ◽

10.15446/esrj.v22n4.57512 ◽

2018 ◽

Vol 22 (4) ◽

pp. 301-318

Author(s):

Huiqing Geng ◽

Xuexiang Gu ◽

Yongmei Zhang

Keyword(s):

Trace Elements ◽

Rare Earth ◽

Rare Earth Elements ◽

Gold Deposit ◽

Volcanic Rocks ◽

Forming Process ◽

Quartz Veins ◽

Epithermal Gold Deposit ◽

Basic Volcanic ◽

P Type

The Gaosongshan epithermal gold deposit in Heilongjiang, Northeast China, is hosted by the Lower Cretaceous intermediate-basic volcanic rocks. Three auriferous quartz veins including eleven gold orebodies were all discovered in tectonoclastic zones. Genetic mineralogy study including the thermoelectricity, rare earth elements and trace elements of pyrite and rare earth elements of quartz were carried out. Thermoelectric conductive type of pyrite is mainly N-P type. Calculating the thermoelectric parameters XNP and denudation percentage γ of pyrites from orebodies 1-I, 2-II and 2-IV, suggests that gold orebodies are all eroded to their middle-lower parts. The variable range of Co concentrations (51.3-264.0ppm) and Ni concentrations (68.9-258.0ppm) and Co: Ni ratio (0.31-1.90), together with relatively small Sr/Ba ratio in ore-bearing pyrites (0.11-0.50), supports a hydrothermal origin of mineralization at Gaosongshan gold deposit. Compared with volcanic rocks, the chondrite-normalized REE patterns of ore-bearing pyrites and quartz are all LREE enriched with similar ΣLREE/ΣHREE ratio ranging from 7.37-13.68 in ore-bearing pyrites, 4.74-15.37 in ore-bearing quartz and no Ce anomalies. δEu values in ore-bearing pyrites and quartz are 0.65-1.66 (average=0.93) and 0.66-1.62 (average=1.03), respectively. δEu values of volcanic rocks are 0.861.07 (average 0.94), suggesting no obvious negative Eu anomalies. Similar REE characteristics of ore-bearing pyrites and quartz and volcanic rocks, together with previous oxygen and hydrogen isotope studies of quartz, suggest that the ore-forming fluids of the Gaosongshan gold deposit were mainly magmatic origin which was associated with andesitic magma and was partly mixed with atmospheric water. Comparing trace elements characteristics of ore-bearing pyrites with volcanic rocks, together with previous S isotopic studies, it is concluded that the ore-forming materials were derived from the surrounding rocks. Slight changes of Y/Ho (23.8027.28), Zr/Hf (35.4147.83), Nb/Ta (10.9618.52) in ore-bearing pyrites indicate that the ore-forming fluid system is relatively stable during the ore-forming process.

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