Enrichment Characteristics and Mechanisms of Lithium, Gallium, and Rare Earth Elements (REY) within Late Permian Coal-Bearing Strata in Wanfu Mine, Xian’an Coalfield, Guangxi Province, Southwest China
by
,
Degao Zhang
1,2,3,
Xiaoyun Yan
1,2,3,*,
Baoqing Li
4,
Jie Sun
1,
Li Zhang
1,
Xiangcheng Jin
5,
Xiaotao Xu
1,
Shaobo Di
1 and
Shaoqing Huang
1 1
General Prospecting Institute of China National Administration of Coal Geology, Beijing 100039, China
2
China National Administration of Coal Geology, Beijing 100038, China
3
Key Laboratory of Transparent Mine Geology and Digital Twin Technology, National Mine Safety Administration, Beijing 100039, China
4
Key Laboratory of Tectonics and Petroleum Resources, China University of Geosciences, Ministry of Education, Wuhan 430074, China
5
College of Geoscience and Survey Engineering, China University of Mining and Technology, Beijing 100083, China
*
Author to whom correspondence should be addressed.
Minerals 2024, 14(9), 853; https://doi.org/10.3390/min14090853
Submission received: 25 April 2024
/
Revised: 10 August 2024
/
Accepted: 12 August 2024
/
Published: 23 August 2024
(This article belongs to the Special Issue Critical Metal Minerals in Coal)
Abstract
:The study of lithium (Li), gallium (Ga), and rare earth elements (REY) within coal-bearing strata represents a cutting-edge concern in coal geology, ore deposit studies, and metallurgy research. With the rapid advancement of technology and emerging industries, the global demand for Li-Ga-REY has significantly escalated. Several countries worldwide are facing immense pressure due to shortages in Li-Ga-REY resources. Coal-associated Li-Ga-REY depositions have emerged as a pivotal direction for augmenting Li-Ga-REY reserves. To ascertain the enrichment distribution patterns and genetic mechanisms of Li-Ga-REY within the coal-bearing strata of the late Permian Heshan Formation in Wanfu mine, Xian’an Coalfield, Guangxi Province, this study carried out comprehensive testing and analysis on Li-Ga-REY enriched in the mineralized layers within the strata. The Heshan Formation in Wanfu mine presents four layers of Li-Ga-REY-enriched mineralization, labeled from bottom to top as mineralized layers I, II, III, and IV, corresponding to coal seams K5, K4, K3, and K2. These critical metals are predominantly hosted within clay minerals (kaolinite, illite/smectite, and chlorite). The enrichment of critical metals within the Heshan Formation is closely related to terrigenous detrital materials from the Daxin paleocontinent, volcanic detrital materials induced by the Emeishan mantle plume and the Yuenan magmatic arc. The accumulation of Li-Ga-REY and other critical elements within the mineralized layers is the result of inputs from terrestrial and volcanic detrital sources, interactions between peatification and diagenesis stages, and occasionally the input of metal-enriched fluids. In the mineralized layers I, II, and III, the content of lithium oxide (Li2O) surpasses the boundary grade, and the levels of REY, Ga, and (Nb,Ta)2O5 are close to boundary grades, indicating promising exploration prospects. The Wanfu mine in the Xian’an Coalfield can be considered a primary target zone for the exploration and development of coal-associated critical metal resources in Guangxi.
1. Introduction
Critical elements resources are dominated by rare metals (such as Li, Rb, and Zr), sparse metals (such as Ga, Ge, and Re), and rare earth elements (REY) [1,2]. Due to their unique material properties, critical elements play an irreplaceable role in emerging industries, including new materials, new energy, national defense, and military industries [3,4]. With the increasing shortage of conventional ore resources and the rapid growth of global demand, there is an urgent need to find and develop new resources for these elements. As a special sedimentary organic rock, coal can be enriched in critical elements and form large or super-large ore deposits under some specific geological conditions [5]. Therefore, the critical metal resources in coal-bearing strata can serve as an important supplement to conventional ore resources. The critical metal deposits discovered in coal-bearing strata include coal-Ge, coal-Ga-Al, and coal-REE [6,7,8].
The coal-bearing strata of the Heshan Formation in Late Permian Guangxi are mainly distributed in central and southwest Guangxi, including the Heshan, Xianyin, Fusui, Yishan, Binlin, Qianjiang, Xincheng and Baiwang coalfields [9]. Some studies have shown that critical elements are also enriched in some coal-bearing strata of the Heshan Formation in the Late Permian in Guangxi, such as the abnormal enrichment of V-Se-Mo-Re-U in the Late Permian coal measures in the Yishan coalfield. Dai et al. [10] and Shao et al. [11] found the enrichment of V-Se-Mo-U in the Late Permian coal measures in the Heshan Coalfield. Dai et al. [12], Liao Jialong et al. [9], and Zhang et al. [13] discovered the accumulation and mineralization of Li-Ga-REY in the late Permian coal measures in the Fusi and Xian’an coalfields. However, there are divergences about their occurrence states and material sources. On this basis, this paper takes the Li-Ga-REY-enriched mineralized layers in the Late Permian Heshan Formation in Wanfu mine, Xian’an Coalfield, as the research object to investigate critical elements and enrichment causes in coal-bearing strata, aiming to promote the exploration of critical metal depositions in the coal-bearing strata in Guangxi Province.
2. Geological Setting
The Wanfu mine, Xian’an Coalfield, Guangxi Province, is located on the western flank of the Xian’an syncline in the eastern part of the Youjiang Basin (Figure 1). Its central region consists of Middle Triassic argillaceous sandstone interbedded with mudstone, and Lower Triassic formations are composed of limestone, dolomite, calcareous sandstone, argillaceous sandstone, marl, and oolitic limestone [14]. The peripheral zones contain Upper Permian limestone, carbonaceous mudstone, coal, bauxite, and Middle–Lower Permian carbonate rocks. Additionally, exposures of the Devonian and Carboniferous systems are also presented in the region.
Among them, the Late Permian Heshan Formation is the major coal-bearing stratum exhibiting littoral or marine–continental transitional facies. The coal-bearing stratum of the Heshan Formation is mainly composed of carbonate rock, carbonaceous mudstone, mudstone, marl and coal seam, and partial siltstone. Local parts have intercalations of medium–thick bedded argillaceous limestone, dolomite, or dolomitic limestone. Heshan Formation is in parallel unconformity contact with the lower Maokou Formation and in conformity contact with the overlying Dalong Formation (Figure 2) [15,16]. At the turn of the Middle and late Permian, influenced by the convergence of the Gondwana plate and Laua plate, the global sea level dropped, and the Emeishan basalt erupted, resulting in significant changes in the distribution pattern of sedimentary facies of the Heshan Formation, forming a composite of rifted basin and terrigenous clastic basin. The source regions of the Late Permian coal-bearing rock series in Guangxi are the Yunkai Upland, the Neozoic Upland, and the Jiangnan Upland, which had been formed.
3. Samples and Analytical Procedures
A total of fifty-one non-coal samples were collected from 9502 drill cores in the Wanfu mine, Xian’an Coalfield, Guangxi Province. In order to avoid contamination and oxidation, the samples collected from each ply were immediately stored in clean and uncontaminated plastic bags.
The trace element concentrations in the samples were determined by Agilent 7700e inductively coupled plasma mass spectrometry (ICP-MS, Agilent, Santa Clara, CA, USA). All samples were ashed at 900 °C. The high-temperature ashes (HTAs) were then analyzed by X-ray fluorescence spectrometry (XRF, ZSX Primus II, Rigaku, Tokyo, Japan) in order to determine the concentrations of major elements.
In order to identify the mineral assemblages in the study sample, a low-temperature oxygen-plasma asher (EMITECH K1050X, East Sussex, UK) was used to remove the organic matter from the coal. The coal low-temperature ash (LTA) and non-coal samples were analyzed using a Bruker D8 Advance XRD (Bruker, Leipzing, Germany). The sample was placed into a glass holder and gently pressed with a glass slide to minimize preferred orientation effects. A Bruker D8 Advance diffractometer was employed to obtain X-ray powder diffractograms with Ni-filtered Cu-Kα radiation operated at 150 Kv and 40 mA from 5.0 to 90° with a step size of 0.02°.
After coating selected polished pellets with carbon, this study conducted mineral phase and element distribution analysis on them using a scanning electron microscope equipped with an energy-dispersive X-ray spectrometer (SEM-EDS, FEI QuantaTM 650 FEG, Eugene, OR, USA). A double polarizing microscope was employed to examine thin sections petrographically using microscopic techniques.
4. Results
4.1. Mineralogy
4.1.1. Minerals in Samples
The main crystalline phases in the samples identified by XRD are listed in Table 1. The mineral assemblages in the samples are kaolinite, illite, quartz, calcite, pyrite, albite (Table 1), and trace amounts of anatase, bassanite, chlorite, dolomite, diaspore, and anhydrite (Figure 3). Melanterite only exists in the sample ZK9502-14 (Table 1). The types of mineral assemblage of the four mineralized layers exhibit significant differences (Table 1). The minerals in the mineralized layer I (ZK9502-02,03,04,05,06) consist mainly of illite, calcite, pyrite, cookeite, and, to a lesser extent, albite and diaspore, along with trace amounts of kaolinite, dolomite, bassanite, rutile, and anatase. The minerals in the mineralized layer II (ZK9502-18) consist mainly of kaolinite, and, to a lesser extent, pyrite, along with trace amounts of calcite, dolomite, and anatase. The minerals in the mineralized layer III (ZK9502-16,42,17,43) consist mainly of kaolinite and quartz, and, to a lesser extent, clinochlore, illite, and calcite, along with trace amounts of pyrite, diaspore, bassanite, and anatase. The minerals in the mineralized layer IV (ZK9502-12,13,14) consist mainly of kaolinite, quartz, calcite, pyrite, and, to a lesser extent, dolomite, along with trace amounts of bassanite, anatase, and melanterite.
4.1.2. Mode of Occurrence of Minerals
Illite primarily occurs as layers along the bedding planes (Figure 4A), and to a lesser extent, in association with kaolinite, occurring as a fine-grained mixture of the two minerals.
Calcite is the dominant mineral in the studied samples; calcite is found as fracture and cavity infillings (Figure 4A,B)
Quartz occurs as independent subhedral to euhedual crystals, indicating that the quartz is of detrital origin (Figure 4A,B and Figure 5A,B).
Pyrite primarily occurs as single euhedral crystals or framboidal pyrite aggregates (Figure 4A,B and Figure 5B,D).
Albite mainly occurs as dispersed particles with irregular corroded borders (Figure 5A), indicating the alteration of albite. Diaspore is also found in some samples and primarily occurs as dispersed particles embedded within a clay minerals matrix (Figure 4C), indicating a detrital origin.
Jarosite, as an iron sulphate mineral, was found in the studied samples using SEM. Rao and Gluskoter [17] reported jarosite is most likely derived from the oxidation of pyrite during storage in the lab. The jarosite was scattered in the corroded pyrite matrix or as the outer part of the corroded pyrite (Figure 5D). Furthermore, the existence of melanterite could also be another piece of evidence for the oxidation of pyrite [18,19].
4.2. Geochemistry
4.2.1. Major Element Oxides
Table 2 provides the concentrations of major element oxides in bench samples. The major element oxides in mineralized layers I, II, III, and IV are SiO2 and Al2O3, which are probably affiliated with clay minerals and feldspars in the samples. The constant elements in the floor and roof of the mineralized layers mainly include CaO and SiO2, which are consistent with the co-occurrences of calcite–quartz.
The ratio of SiO2/Al2O3 increases sequentially from mineralized layers I to IV, which largely results from the quartz- and Na-bearing feldspars in mineralized layers III and IV. Moreover, the low SiO2/Al2O3 ratio in mineralized layer I can be attributed to the presence of diaspore.
4.2.2. Trace Elements
The trace element contents of the mineralized layer bench samples collected from the ZK9502 drill hole are listed in Table 2. Figure 6 compares the trace element values of the mineralized layers determined in this study with the average values of the world clay data reported by Grigoriev et al. [20]. The concentration coefficients (CC) of <0.5, 0.5–2, 2.0–5.0, 5.0–10, 10–100, and >100 indicate depleted, similarity, slight enrichment, enrichment, significant enrichment, and unusual enrichment, respectively [21].
Lithium is significantly enriched in mineralized layer I, with a CC of >10. The trace elements with a CC of 5–10 include Cr, Nb, Eu, Gd, Er, and U. Other slightly enriched trace elements include V, Co, Ni, Cu, Ga, Y, Zr, La, Ce, Pr, Nd, Sm, Tb, Dy, Ho, Tm, Yb, Lu, Hf, Ta, Tl, and Pb, with CC of 2–5. Only trace elements have a CC of <0.5, which are Rb, Sr, and Ba. Meanwhile, the remaining elements, Be, Sc Zn, Cs, and Th, with CC of 0.5–2, have concentrations close to the corresponding averages of the upper continental crust (Figure 3).
As shown in Figure 6, compared with the average values of the world clay data, Li, Cr, Cu, Nb, and Er are enriched (5 < CC < 10) in mineralized layer II. V, Co, Ni, Ga, Zr, REY (except Eu and Er), Hf, Ta, Pb, and U are slightly enriched (2 < CC< 5). Be, Sc, Zn, La, and Th (0.5 < CC < 2) are close to the average values of the world clay. Rb, Sr, Cs, and Ba are depleted (CC < 0.5).
In mineralized layer III, compared with the average values of the world clay, Li is significantly enriched (10 < CC < 100). U is enriched (5 < CC < 10). Cr, Zr, Nb, Er, Yb, Lu Hf, Ta, Pb, and Th are slightly enriched (2 < CC< 5). Co, Cu, Zn, Rb, Cs, and Ba are depleted (CC < 0.5). The remaining elements are close to the average values of the world clay (0.5 < CC < 2) (Figure 6).
In mineralized layer IV, compared with the average values of the world clay, Li, V, Sr, Dy, Ho, Er, Yb, Lu, Pb, and U are slightly enriched (2 < CC < 5). Cr, Co, Ni, Cu, Zn, Rb, and Ba are depleted (CC < 0.5). The remaining elements are close to the average values of the world clay (0.5 < CC < 2) (Figure 6).
The concentration of lithium (Li) ranges from 33 to 133 μg/g, with an average value of 88 μg/g. The concentration of Ga is between 13 and 20 μg/g and is 17 μg/g on average. REY have a concentration ranging from 230 to 355 μg/g and an average value of 295 μg/g. Additionally, the concentration of U varies from 12 to 24 μg/g, with a mean value of 19 μg/g.
4.2.3. Rare Earth Element and Yttrium (REY)
The total REY concentrations in mineralized layers I, II, III, and IV are 895, 551, 249, and 295 μg/g, respectively (Table 2).
The REY enrichment in mineralized layers I and II belong to the H-REY type (LaN/LuN <1; Figure 7) and M-REY type (LaN/SmN < 1 and GdN/LuN > 1), with no or slightly positive Eu anomalies (Figure 7). In mineralized layers III and IV, REY enrichment exhibits the H-REY type (LaN/LuN < 1; Figure 7) and M-REY type (LaN/SmN < 1, GdN/LuN > 1), accompanied by varying degREYs of negative Eu anomalies, indicating the input of detrital material with a chondrite-like composition [22,23].
5. Discussion
5.1. Sediment Source Region
The ratio of Al2O3/TiO2 in sedimentary rocks generally corresponds to the lithology of the source rock, which is effective for determining the properties of source rocks [24]. Girty et al. (1996) suggested that a Al2O3/TiO2 ratio between 3 and 8 indicated a predominantly mafic igneous rock, a ratio from 8 to 21 implied a chiefly intermediate igneous rock, and a ratio between 21 and 70 mainly represented a felsic igneous rock [25].
The ratios of Al2O3/TiO2 in the samples in mineralized layers I and II indicate that the sediment source region is mainly characterized by intermediate igneous rocks, while the ratios of Al2O3/TiO2 in the samples in mineralized layers III and IV denote that the sediment source region has the characteristic of felsic igneous rocks (Figure 8). Previous studies demonstrated that the dominant source region of sediment in the late Permian coal-bearing strata in Guangxi Province, China was the detrital material derived from weathering residues located immediately above the Maokou Formation limestone [26,27,28]. These residues primarily consist of terrigenous felsic detrital materials. Hence, the terrigenous materials for the mineralized layers in the Wanfu mine stem from the continental detrital material of the Daxin upland. Additionally, volcanic detrital material induced by the Emeishan mantle plume and the northern magmatic arc also significantly influences the composition of these strata [29,30].
According to the La/Sc-Th/Co diagram proposed by Cullers (2000) [31], most sample points are in the felsic igneous rock region, with a few points from mineralized layers I and II falling outside the region (Figure 9). Therefore, the mineralized layers in the Heshan Formation in Guangxi mainly originate from intermediate and felsic igneous rocks.
5.2. Volcanic Ash
By plotting the samples of coal-bearing Li ore layers I, II, III, and IV from Wanfu mine, Xian’an Coalfield in Guangxi onto the Nb/Y-Zr/TiO2 provenance discrimination diagram (Figure 10), it can be observed that the sample points mainly fall within the fields of coarse-grained andesite, coarse-grained rock, andesite, and rhyolite, which partially overlap with the late-stage felsic igneous rocks in the Emeishan large igneous province. From this, it is inferred that the late-stage felsic igneous rock in the Emeishan large igneous province may be one of the sources of Li ore layers I, II, III, and IV in the Wanfu mine, Xian’an Coalfield, Guangxi [32,33,34].
Additionally, Zhang et al. [35] conducted a thorough analysis using zircon U-Pb dating, zircon trace elements Th/Nb-Hf/Th and Th/U-Nb/Hf tectonic discrimination diagrams, and rare earth elements. This analysis suggests that the lithium mineralization layers in the Heshan Formation of Guangxi are primarily derived from intermediate to felsic igneous rocks related to the Emeishan large igneous province and the Permian magmatic arc of the Paleo-Tethys.
Figure 9.
Plot of La/Sc-Th/Co in the samples in mineralized layers I, II, III, and IV in the coal-bearing strata from the Wanfu mine, Xian’an coalfield, Guangxi Province.
Figure 9.
Plot of La/Sc-Th/Co in the samples in mineralized layers I, II, III, and IV in the coal-bearing strata from the Wanfu mine, Xian’an coalfield, Guangxi Province.
5.3. Hydrothermal Fluids
Previous studies have indicated that the differentiation of Eu in surface environments is challenging due to the stringent requirements for high reducing conditions (stronger than SO42−-H2S) and elevated temperatures (>250 °C) [36]. Typically, Eu anomalies are inherited from the source rock [37]. For instance, detrital material derived from the Emeishan basalt in the Late Permian coals of the Qiannan region exhibits a positive Eu anomaly in its upper crust-normalized rare earth element distribution [38,39]. Geochemical indicators such as Al2O3/TiO2-Th/Sc diagrams, Zr/TiO2-Nb/Y diagrams, and the vertical distribution of Al2O3/TiO2 collectively suggest that the detrital material in mineralized layer I of borehole ZK9502 has an intermediate to acidic composition. Consequently, a negative Eu anomaly is expected in this layer. However, conversely, a slightly positive Eu anomaly (1.06–1.13) is observed.
Positive Eu anomalies are commonly associated with high-temperature hydrothermal fluids affecting coal deposits and mafic volcanic ash, as well as being inherited from sediment source rocks with a mafic-dominated composition [40,41,42]. The sediment source region of mineralized layer I was mainly characterized by intermediate–felsic igneous composition, and, therefore, the minor positive Eu anomaly in this layer may be attributed to the influence of hydrothermal fluids. Furthermore, the consistency of the positive Eu anomaly in mineralized layer I suggests that the input of hydrothermal fluids may have occurred during the syn- to early-diagenetic stages when hydrothermal fluids could more easily permeate the mineralized layer.
6. Conclusions
Four Li-Ga-REY enriched mineralized layers are developed in the coal-bearing strata in Wanfu mine, Xian’an Coalfield, Guangxi Province. Mineralized layers I, II, III, and IV correspond to the coal layers K5, K4, K3, and K2 in the coal-bearing strata of the Heshan Group, respectively. The enrichment mineralization of Li, Ga, and REY in the mineralized layers stems from the combination of intermediate–felsic-dominated composition sediment source inputs, intermediate–felsic volcanic ash inputs, and hydrothermal fluids occurring during the syn- to early-diagenetic stages.
Author Contributions
Conceptualization, D.Z., X.Y. and B.L.; methodology, X.Y.; software, B.L.; J.S. and L.Z. collected the samples; X.Y., X.J., X.X., S.D. and S.H. conducted the experiments; D.Z., X.Y. and X.J., writing—original manuscript; B.L. and J.S. revised the manuscript. All authors have read and agreed to the published version of the manuscript.
Funding
This research was supported by The National Key R&D Program of China (2021YFC2902005), the National Natural Science Foundation of China (No.42102211, 42272207), and the China Coal Geological Administration Carbon Neutral Special Project (ZMKJ-2021-ZX03).
Data Availability Statement
Data are contained within the article.
Acknowledgments
The authors would like to give their sincere thanks to the Guangxi Bureau of Coal Geology for assistance during sampling and to Fuqiang Zhang (Guangxi Bureau of Coal Geology) for his great help in the analysis of data.
Conflicts of Interest
The authors declare no conflicts of interest.
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Figure 1.
Regional geological map of the Wanfu mining, Xian’an coalfield, Guangxi Province.
Figure 2.
Sampling location map of borehole ZK9502 in the Wanfu mine, Xian’an coalfield, Guangxi Province.
Figure 2.
Sampling location map of borehole ZK9502 in the Wanfu mine, Xian’an coalfield, Guangxi Province.
Figure 3.
Minerals in ZK9502-03.
Figure 4.
SEM backscattered electron images of minerals in samples. (A) Layers of illite along the bedding planes and particle quartz in sample ZK9502-02; (B) calcite, quartz, and pyrite in sample ZK9502-02; (C) diaspore in sample ZK9502-03; (D) EDS spectrum of diaspore in (C) in sample ZK9502-03.
Figure 4.
SEM backscattered electron images of minerals in samples. (A) Layers of illite along the bedding planes and particle quartz in sample ZK9502-02; (B) calcite, quartz, and pyrite in sample ZK9502-02; (C) diaspore in sample ZK9502-03; (D) EDS spectrum of diaspore in (C) in sample ZK9502-03.
Figure 5.
SEM backscattered electron images of minerals in samples. (A) Calcite, quartz, and albite in sample ZK9502-02; (B) calcite, pyrite, quartz, and albite in sample ZK9502-02; (C) EDS spectrum of natrojarosite in (D) in sample ZJ-5-14; (D) pyrite and natrojarosite in sample ZK9502-02.
Figure 5.
SEM backscattered electron images of minerals in samples. (A) Calcite, quartz, and albite in sample ZK9502-02; (B) calcite, pyrite, quartz, and albite in sample ZK9502-02; (C) EDS spectrum of natrojarosite in (D) in sample ZJ-5-14; (D) pyrite and natrojarosite in sample ZK9502-02.
Figure 6.
Concentration coefficients of trace elements of mineralized layers I, II, III, and IV in coal-bearing series from Wanfu mine, Xian’an coalfield, Guangxi Province.
Figure 6.
Concentration coefficients of trace elements of mineralized layers I, II, III, and IV in coal-bearing series from Wanfu mine, Xian’an coalfield, Guangxi Province.
Figure 7.
REY distribution patterns of mineralized layers I (A), II (B), III (C), and IV (D) in coal-bearing series from Wanfu mine, Xian’an coalfield, Guangxi Province. REY are normalized to Upper Continental Crust (UCC) [22].
Figure 7.
REY distribution patterns of mineralized layers I (A), II (B), III (C), and IV (D) in coal-bearing series from Wanfu mine, Xian’an coalfield, Guangxi Province. REY are normalized to Upper Continental Crust (UCC) [22].
Figure 8.
Plot of TiO2 vs. Al2O3 in the samples from the mineralized layers I, II, III, and IV in the coal-bearing strata from the Wanfu mine, Xian’an coalfield, Guangxi Province.
Figure 8.
Plot of TiO2 vs. Al2O3 in the samples from the mineralized layers I, II, III, and IV in the coal-bearing strata from the Wanfu mine, Xian’an coalfield, Guangxi Province.
Figure 10.
Plot of Nb/Y-Zr/TiO2 in the samples from the mineralized layers I, II, III, and IV in the coal-bearing strata from the Wanfu mine, Xian’an coalfield, Guangxi Province.
Figure 10.
Plot of Nb/Y-Zr/TiO2 in the samples from the mineralized layers I, II, III, and IV in the coal-bearing strata from the Wanfu mine, Xian’an coalfield, Guangxi Province.
Table 1.
Quantitative mineralogical composition of study samples (wt. %) determined using XRD.
| Sample | Illite | Kaolinite | Clinochlore | Cookeite | Quartz | Calcite | Dolomite | Siderite | Pyrite | Albite | Anatase | Rutile | Diaspore | Bassanite | Melanterite |
|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
| ZK9502-01 | 95.10 | 1.10 | 3.70 | ||||||||||||
| ZK9502-02 | 37.00 | 2.90 | 20.50 | 1.70 | 28.70 | 0.90 | 4.70 | 3.70 | |||||||
| ZK9502-03 | 44.00 | 12.00 | 1.20 | 18.00 | 2.50 | 0.30 | 20.40 | 1.60 | |||||||
| ZK9502-04 | 41.30 | 34.60 | 17.20 | 5.90 | 1.10 | ||||||||||
| ZK9502-05 | 68.00 | 15.20 | 3.50 | 6.40 | 4.10 | 2.80 | |||||||||
| ZK9502-06 | 53.70 | 35.60 | 1.40 | 6.50 | 2.00 | 0.80 | |||||||||
| ZK9502-07 | 77.10 | 11.40 | 1.70 | 6.70 | 1.80 | 1.30 | |||||||||
| ZK9502-08 | 75.90 | 7.90 | 2.90 | 1.50 | 6.80 | 3.30 | 1.70 | ||||||||
| ZK9502-09 | 95.50 | 4.50 | |||||||||||||
| ZK9502-10 | 68.10 | 5.90 | 3.50 | 22.50 | |||||||||||
| ZK9502-11 | 3.10 | 51.10 | 27.30 | 8.70 | 2.70 | 7.30 | |||||||||
| ZK9502-12 | 39.90 | 47.90 | 2.70 | 6.60 | 0.50 | 2.50 | |||||||||
| ZK9502-13 | 44.60 | 33.50 | 10.40 | 4.30 | 4.30 | 1.90 | 1.10 | ||||||||
| ZK9502-14 | 6.20 | 16.40 | 55.00 | 14.70 | 2.40 | 5.30 | |||||||||
| ZK9502-15 | 3.20 | 8.50 | 42.20 | 3.90 | 7.20 | 8.60 | 23.20 | 0.90 | 2.20 | ||||||
| ZK9502-16 | 12.50 | 79.90 | 2.40 | 1.00 | 3.10 | 0.50 | 0.70 | ||||||||
| ZK9502-17 | 90.00 | 5.20 | 1.10 | 0.80 | 1.00 | 1.90 | |||||||||
| ZK9502-18 | 87.50 | 1.30 | 1.00 | 7.70 | 2.50 | ||||||||||
| ZK9502-19 | 95.60 | 3.00 | 1.30 | ||||||||||||
| ZK9502-20 | 10.50 | 75.60 | 10.90 | 1.80 | 1.10 | ||||||||||
| ZK9502-21 | 11.00 | 57.60 | 31.30 | ||||||||||||
| ZK9502-22 | 19.50 | 72.60 | 2.70 | 0.70 | 4.50 | ||||||||||
| ZK9502-23 | 9.10 | 86.70 | 4.00 | 0.20 | |||||||||||
| ZK9502-24 | 6.20 | 91.60 | 1.20 | 1.00 | |||||||||||
| ZK9502-25 | 12.10 | 84.60 | 1.60 | 1.80 | |||||||||||
| ZK9502-26 | 9.40 | 88.40 | 2.10 | ||||||||||||
| ZK9502-27 | 16.40 | 80.50 | 3.10 | ||||||||||||
| ZK9502-28 | 38.30 | 53.90 | 1.80 | 1.50 | 4.50 | ||||||||||
| ZK9502-29 | 15.50 | 74.80 | 6.00 | 3.70 | |||||||||||
| ZK9502-30 | 24.90 | 22.60 | 39.00 | 6.20 | 1.30 | 6.10 | |||||||||
| ZK9502-31 | 7.20 | 88.60 | 4.30 | ||||||||||||
| ZK9502-32 | 8.20 | 86.20 | 5.60 | ||||||||||||
| ZK9502-33 | 1.40 | 95.90 | 2.70 | ||||||||||||
| ZK9502-34 | 14.20 | 14.10 | 55.60 | 2.10 | 1.80 | 12.20 | |||||||||
| ZK9502-35 | 16.20 | 17.50 | 44.30 | 2.90 | 2.20 | 14.20 | 2.70 | ||||||||
| ZK9502-36 | 7.10 | 24.10 | 57.30 | 5.90 | 2.50 | 3.10 | |||||||||
| ZK9502-37 | 30.30 | 66.60 | 3.10 | ||||||||||||
| ZK9502-38 | 2.90 | 90.70 | 6.40 | ||||||||||||
| ZK9502-39 | 2.70 | 22.00 | 65.20 | 7.60 | 2.50 | ||||||||||
| ZK9502-40 | 4.70 | 90.90 | 4.40 | ||||||||||||
| ZK9502-41 | 9.40 | 5.20 | 4.40 | 76.50 | 4.00 | 0.50 | |||||||||
| ZK9502-42 | 85.70 | 6.80 | 2.50 | 1.90 | 0.90 | 2.20 | |||||||||
| ZK9502-43 | 38.20 | 57.00 | 4.10 | 0.60 | 0.10 | ||||||||||
| ZK9502-44 | 6.90 | 23.40 | 64.10 | 5.10 | 0.50 | ||||||||||
| ZK9502-45 | 6.10 | 92.60 | 1.30 | ||||||||||||
| ZK9502-46 | 5.40 | 4.10 | 79.10 | 9.90 | 1.50 | ||||||||||
| ZK9502-47 | 68.00 | 31.70 | 0.30 | ||||||||||||
| ZK9502-48 | 97.10 | 1.40 | 1.50 | ||||||||||||
| ZK9502-49 | 7.70 | 81.70 | 3.50 | 7.20 | |||||||||||
| ZK9502-50 | 3.60 | 32.70 | 49.30 | 2.50 | 0.90 | 10.90 | |||||||||
| ZK9502-51 | 9.50 | 78.20 | 6.30 | 0.30 | 5.70 |
Table 2.
The percentage of major element oxides (%) and trace element concentrations in the study samples (μg/g).
Table 2.
The percentage of major element oxides (%) and trace element concentrations in the study samples (μg/g).
| Sample | SiO2 | TiO2 | Al2O3 | Fe2O3 | MnO | MgO | CaO | Na2O | K2O | P2O5 | Li | Be | Sc | V | Cr | Co | Ni | Cu | Zn | Ga | Rb | Sr | Zr | Nb |
|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
| ZK9502-01 | 0.25 | 0.06 | 0.63 | 1.60 | 0.12 | 1.20 | 50.00 | 0.05 | 0.08 | 0.01 | 5.4 | 0.77 | 1.0 | 54 | 54 | 2.8 | 22 | 5.2 | 39 | 2 | 3.4 | 847 | 21 | 2.8 |
| ZK9502-02 | 11.00 | 0.71 | 10.00 | 18.00 | 0.04 | 0.64 | 7.60 | 0.30 | 0.72 | 0.01 | 357 | 2.6 | 12 | 255 | 177 | 8.6 | 61 | 29 | 43 | 22 | 25 | 222 | 433 | 25 |
| ZK9502-03 | 17.00 | 2.90 | 32.00 | 19.00 | 0.03 | 0.30 | 1.10 | 0.38 | 1.40 | 0.01 | 1194 | 5.6 | 23 | 414 | 520 | 9.8 | 42 | 54 | 34 | 52 | 44 | 36 | 703 | 97 |
| ZK9502-04 | 28.00 | 2.70 | 30.00 | 14.00 | 0.03 | 0.44 | 0.56 | 0.52 | 1.60 | 0.02 | 3853 | 7.2 | 24 | 690 | 660 | 108 | 316 | 157 | 57 | 29 | 48 | 39 | 635 | 83 |
| ZK9502-05 | 34.00 | 2.40 | 30.00 | 11.00 | 0.02 | 0.64 | 0.75 | 0.97 | 2.70 | 0.02 | 2052 | 6.2 | 21 | 1133 | 1039 | 79 | 322 | 126 | 76 | 31 | 91 | 53 | 577 | 75 |
| ZK9502-06 | 26.00 | 1.50 | 22.00 | 9.80 | 0.04 | 0.65 | 15.00 | 1.10 | 1.70 | 0.02 | 739 | 4.1 | 24 | 683 | 839 | 80 | 374 | 77 | 84 | 27 | 60 | 211 | 369 | 49 |
| ZK9502-07 | 32.00 | 2.50 | 24.00 | 11.00 | <dl | 0.94 | 7.80 | 0.30 | 4.10 | 0.02 | 19 | 1.4 | 23 | 389 | 499 | 36 | 138 | 73 | 53 | 35 | 137 | 100 | 539 | 72 |
| ZK9502-08 | 33.00 | 2.50 | 25.00 | 11.00 | <dl | 1.20 | 4.00 | 0.36 | 3.90 | 0.02 | 16 | 1.7 | 26 | 441 | 557 | 36 | 160 | 82 | 62 | 38 | 143 | 66 | 603 | 79 |
| ZK9502-09 | <dl | 0.02 | 0.41 | 0.12 | 0.01 | 1.40 | 49.00 | 0.06 | 0.11 | 0.01 | 11 | 0.11 | 0.61 | 33 | 47 | 3.1 | 16 | 1.3 | 21 | 0.27 | 1.3 | 345 | 6.3 | 0.57 |
| ZK9502-10 | 52.00 | 0.21 | 10.00 | 2.10 | 0.24 | 1.90 | 12.00 | 1.20 | 0.59 | 0.03 | 36 | 1.5 | 6.1 | 69 | 23 | 8.2 | 15 | 9.6 | 45 | 11 | 26 | 1135 | 110 | 7.3 |
| ZK9502-11 | 62.00 | 0.30 | 14.00 | 2.50 | 0.09 | 1.80 | 1.70 | 2.10 | 0.69 | 0.07 | 44 | 2.1 | 7.6 | 86 | 40 | 5.3 | 11 | 7.8 | 45 | 16 | 36 | 581 | 165 | 10 |
| ZK9502-12 | 41.00 | 0.35 | 14.00 | 3.20 | 0.04 | 0.62 | 2.10 | 1.00 | 0.64 | 0.02 | 126 | 1.9 | 10 | 79 | 27 | 7.6 | 13 | 11 | 37 | 18 | 27 | 629 | 235 | 13 |
| ZK9502-13 | 40.00 | 0.45 | 17.00 | 2.80 | 0.03 | 1.20 | 4.50 | 0.82 | 0.73 | 0.02 | 140 | 1.9 | 11 | 96 | 37 | 6.8 | 17 | 10 | 39 | 19 | 30 | 695 | 233 | 13 |
| ZK9502-14 | 28.00 | 0.26 | 11.00 | 1.80 | 0.05 | 3.90 | 23.00 | 1.00 | 0.54 | 0.01 | 33 | 1.7 | 8.6 | 139 | 87 | 7.3 | 24 | 7.2 | 36 | 13 | 19 | 2059 | 148 | 9.3 |
| ZK9502-15 | 46.00 | 0.40 | 17.00 | 3.80 | 0.05 | 1.50 | 2.20 | 1.80 | 1.40 | 0.02 | 34 | 3.0 | 13 | 229 | 141 | 5.2 | 44 | 18 | 107 | 21 | 65 | 1219 | 425 | 24 |
| ZK9502-16 | 34.00 | 0.75 | 26.00 | 3.30 | 0.01 | 0.38 | 0.92 | 0.50 | 0.72 | 0.01 | 426 | 4.2 | 13 | 265 | 346 | 7.2 | 55 | 19 | 59 | 28 | 22 | 225 | 493 | 49 |
| ZK9502-17 | 37.00 | 0.94 | 32.00 | 1.40 | 0.01 | 0.19 | 0.22 | 0.19 | 0.30 | 0.01 | 925 | 4.8 | 10 | 178 | 314 | 7.3 | 52 | 13 | 40 | 26 | 8 | 94 | 580 | 48 |
| ZK9502-18 | 22.00 | 2.30 | 19.00 | 7.30 | <dl | 0.30 | 0.67 | 0.18 | 0.19 | 0.01 | 450 | 5.0 | 27 | 484 | 757 | 70 | 225 | 215 | 69 | 40 | 4.6 | 55 | 680 | 98 |
| ZK9502-19 | 1.00 | 0.08 | 1.50 | 8.50 | 0.05 | 1.40 | 67.00 | 0.11 | 0.20 | 0.01 | 6.9 | 0.48 | 4.9 | 23 | 38 | 4 | 21 | 3.6 | 11 | 1.2 | 0.73 | 584 | 11 | 1.2 |
| ZK9502-20 | 15.00 | 0.13 | 3.30 | 1.80 | 0.05 | 2.90 | 36.00 | 0.76 | 0.27 | 0.05 | 7.9 | 0.87 | 3.9 | 17 | 214 | 4.4 | 15 | 16 | 39 | 5.5 | 8.5 | 1063 | 90 | 3.1 |
| ZK9502-21 | 15.00 | 0.03 | 0.97 | 0.56 | 0.06 | 6.70 | 36.00 | 0.22 | 0.11 | 0.03 | 7.1 | 0.75 | 1.7 | 17 | 228 | 2.3 | 31 | 109 | 15 | 1.3 | 2.3 | 1187 | 27 | 1.2 |
| ZK9502-22 | 26.00 | 0.10 | 2.70 | 1.20 | 0.03 | 1.40 | 35.00 | 0.76 | 0.23 | 0.02 | 6.8 | 0.70 | 2.9 | 47 | 336 | 3.7 | 21 | 10 | 23 | 2.7 | 6.1 | 1638 | 33 | 2.6 |
| ZK9502-23 | 11.00 | 0.05 | 1.30 | 0.37 | 0.01 | 1.50 | 44.00 | 0.21 | 0.12 | 0.01 | 4.6 | 0.28 | 2.6 | 54 | 112 | 2.8 | 22 | 11 | 12 | 1.5 | 4.1 | 2011 | 15 | 1 |
| ZK9502-24 | 8.70 | 0.06 | 1.70 | 0.53 | 0.02 | 0.95 | 44.00 | 0.29 | 0.14 | 0.01 | 6.6 | 0.76 | 2.9 | 28 | 76 | 3.2 | 18 | 5.2 | 13 | 2 | 3.6 | 2685 | 24 | 1.6 |
| ZK9502-42 | 39.00 | 1.10 | 37.00 | 2.70 | 0.02 | 0.23 | 1.40 | 0.28 | 0.26 | 0.01 | 1147 | 5.8 | 13 | 123 | 175 | 5.4 | 40 | 13 | 21 | 33 | 5.4 | 140 | 505 | 48 |
| ZK9502-43 | 72.00 | 0.47 | 14.00 | 1.50 | <dl | 0.19 | 2.20 | 0.31 | 0.26 | 0.01 | 980 | 5.9 | 14 | 122 | 184 | 5.6 | 41 | 13 | 22 | 37 | 5.6 | 145 | 428 | 48 |
| Sample | Cs | Ba | La | Ce | Pr | Nd | Sm | Eu | Gd | Tb | Dy | Y | Ho | Er | Tm | Yb | Lu | Hf | Ta | Tl | Pb | Th | U | |
| ZK9502-01 | 0.66 | 12 | 19 | 32 | 3 | 11 | 2.1 | 0.55 | 2.5 | 0.3 | 1.9 | 29 | 0.37 | 0.96 | 0.12 | 0.67 | 0.09 | 0.61 | 0.22 | 0.74 | 2.9 | 1 | 4.7 | |
| ZK9502-02 | 6.4 | 75 | 35 | 103 | 11 | 50 | 11 | 2.8 | 12 | 2.3 | 15 | 119 | 3.3 | 9.7 | 1.2 | 7.2 | 1.1 | 8.5 | 1.7 | 8 | 15 | 7.4 | 35 | |
| ZK9502-03 | 9.9 | 137 | 35 | 110 | 9.2 | 36 | 9.3 | 2.3 | 10 | 1.8 | 13 | 74 | 3 | 9.3 | 1.3 | 8.2 | 1.3 | 18 | 6.3 | 7 | 50 | 27 | 32 | |
| ZK9502-04 | 12 | 160 | 175 | 417 | 53 | 223 | 46 | 9.1 | 42 | 5.5 | 28 | 125 | 5 | 12 | 1.7 | 10 | 1.5 | 17 | 5.5 | 1.8 | 72 | 26 | 28 | |
| ZK9502-05 | 17 | 314 | 333 | 326 | 90 | 360 | 64 | 12 | 56 | 6.9 | 33 | 147 | 5.8 | 14 | 1.7 | 9.7 | 1.4 | 15 | 4.9 | 1.3 | 58 | 27 | 30 | |
| ZK9502-06 | 11 | 210 | 311 | 185 | 70 | 274 | 43 | 9.1 | 42 | 5.4 | 28 | 132 | 5.1 | 12 | 1.6 | 9.3 | 1.3 | 10 | 3.3 | 2.5 | 39 | 18 | 20 | |
| ZK9502-07 | 19 | 388 | 75 | 149 | 19 | 76 | 15 | 2.8 | 13 | 2.1 | 12 | 62 | 2.4 | 7.2 | 1 | 6.6 | 0.97 | 13 | 4.6 | 2.9 | 33 | 19 | 12 | |
| ZK9502-08 | 18 | 420 | 79 | 175 | 21 | 84 | 17 | 3.3 | 15 | 2.3 | 13 | 69 | 2.7 | 7.9 | 1.2 | 7.4 | 1.1 | 15 | 5.2 | 45 | 21 | 13 | ||
| ZK9502-09 | 0.17 | 6.1 | 1.7 | 2.4 | 0.45 | 1.7 | 0.34 | 0.07 | 0.3 | 0.04 | 0.24 | 2.1 | 0.05 | 0.14 | 0.02 | 0.12 | 0.02 | 0.18 | 0.05 | 1.8 | 0.28 | 2.3 | ||
| ZK9502-10 | 5.6 | 195 | 20 | 50 | 4.8 | 18 | 4.5 | 0.8 | 4.6 | 0.72 | 4.5 | 25 | 0.88 | 2.7 | 0.4 | 2.6 | 0.39 | 3.6 | 0.77 | 25 | 12 | 18 | ||
| ZK9502-11 | 11 | 213 | 37 | 75 | 8.3 | 29 | 6.1 | 0.75 | 5.7 | 0.91 | 5.4 | 32 | 1.1 | 3.4 | 0.49 | 3.3 | 0.5 | 5.1 | 1.1 | 28 | 18 | 19 | ||
| ZK9502-12 | 11 | 88 | 39 | 87 | 10 | 41 | 9.1 | 1.2 | 9 | 1.6 | 10 | 71 | 2.2 | 6.9 | 1 | 6.6 | 1 | 5.6 | 0.99 | 36 | 15 | 22 | ||
| ZK9502-13 | 12 | 67 | 31 | 69 | 8.4 | 31 | 7.3 | 0.89 | 7 | 1.2 | 7.7 | 51 | 1.6 | 5 | 0.8 | 5.2 | 0.79 | 6.6 | 1.3 | 40 | 19 | 24 | ||
| ZK9502-14 | 7.5 | 73 | 67 | 101 | 12 | 48 | 11 | 1.8 | 11 | 2 | 12 | 66 | 2.5 | 7.5 | 1.1 | 7 | 0.99 | 4.3 | 0.82 | 26 | 12 | 11 | ||
| ZK9502-15 | 20 | 204 | 30 | 68 | 8.2 | 30 | 6.9 | 0.84 | 6.4 | 1.2 | 7.6 | 42 | 1.6 | 5.1 | 0.78 | 5.2 | 0.79 | 11 | 1.7 | 40 | 23 | 55 | ||
| ZK9502-16 | 7.5 | 61 | 54 | 117 | 13 | 52 | 11 | 1.5 | 10 | 1.9 | 11 | 72 | 2.4 | 7.6 | 1.1 | 7.3 | 1.1 | 12 | 3.5 | 49 | 28 | 51 | ||
| ZK9502-17 | 5.3 | 25 | 48 | 97 | 10 | 40 | 7.9 | 0.95 | 6.6 | 1.1 | 6.5 | 36 | 1.3 | 4 | 0.6 | 3.9 | 0.56 | 16 | 2.6 | 39 | 31 | 24 | ||
| ZK9502-18 | 4.2 | 31 | 91 | 177 | 25 | 98 | 21 | 4.6 | 18 | 3 | 18 | 65 | 3.5 | 10 | 1.5 | 9.8 | 1.5 | 18 | 6 | 50 | 24 | 10 | ||
| ZK9502-19 | 0.18 | 8.4 | 24 | 21 | 8.3 | 38 | 10 | 3 | 16 | 2.7 | 16 | 122 | 3.4 | 9.6 | 1.2 | 6 | 0.83 | 0.37 | 0.11 | 2.1 | 0.4 | 4.9 | ||
| ZK9502-20 | 2.2 | 103 | 8.9 | 18 | 2.5 | 11 | 3 | 0.71 | 3.3 | 0.61 | 3.6 | 23 | 0.8 | 2.3 | 0.38 | 2.3 | 0.35 | 2.1 | 0.2 | 5.3 | 2.4 | 2.7 | ||
| ZK9502-21 | 0.39 | 21 | 3 | 5.7 | 0.7 | 2.8 | 0.74 | 0.17 | 0.93 | 0.18 | 1.1 | 9.8 | 0.27 | 0.76 | 0.13 | 0.79 | 0.12 | 0.52 | 0.08 | 2.1 | 0.93 | 3.4 | ||
| ZK9502-22 | 1.1 | 45 | 8.9 | 15 | 1.9 | 7.3 | 1.6 | 0.28 | 1.5 | 0.26 | 1.4 | 11 | 0.32 | 0.9 | 0.14 | 0.86 | 0.13 | 0.69 | 0.15 | 5.6 | 2.4 | 5.9 | ||
| ZK9502-23 | 0.7 | 26 | 9.2 | 12 | 1.4 | 5.5 | 1.1 | 0.23 | 1.2 | 0.19 | 1 | 9.2 | 0.22 | 0.58 | 0.09 | 0.52 | 0.07 | 0.42 | 0.09 | 4.2 | 1.5 | 7.8 | ||
| ZK9502-24 | 0.94 | 47 | 14 | 21 | 2.5 | 9.8 | 2.5 | 0.53 | 3.8 | 0.77 | 5.3 | 50 | 1.4 | 3.9 | 0.65 | 3.9 | 0.59 | 0.63 | 0.11 | 4.2 | 2.1 | 6.3 | ||
| ZK9502-42 | 5.7 | 24 | 29 | 60 | 6.5 | 24 | 4.8 | 0.61 | 4.3 | 0.86 | 5.1 | 31 | 1.1 | 3.2 | 0.53 | 3.3 | 0.49 | 12 | 3.1 | 52 | 35 | 23 | ||
| ZK9502-43 | 5.8 | 22 | 29 | 61 | 6.7 | 24 | 4.9 | 0.63 | 4.4 | 0.89 | 5.3 | 34 | 1.2 | 3.3 | 0.56 | 3.5 | 0.53 | 13 | 3 | 55 | 33 | 22 |
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Zhang, D.; Yan, X.; Li, B.; Sun, J.; Zhang, L.; Jin, X.; Xu, X.; Di, S.; Huang, S. Enrichment Characteristics and Mechanisms of Lithium, Gallium, and Rare Earth Elements (REY) within Late Permian Coal-Bearing Strata in Wanfu Mine, Xian’an Coalfield, Guangxi Province, Southwest China. Minerals 2024, 14, 853. https://doi.org/10.3390/min14090853
AMA Style
Zhang D, Yan X, Li B, Sun J, Zhang L, Jin X, Xu X, Di S, Huang S. Enrichment Characteristics and Mechanisms of Lithium, Gallium, and Rare Earth Elements (REY) within Late Permian Coal-Bearing Strata in Wanfu Mine, Xian’an Coalfield, Guangxi Province, Southwest China. Minerals. 2024; 14(9):853. https://doi.org/10.3390/min14090853
Chicago/Turabian StyleZhang, Degao, Xiaoyun Yan, Baoqing Li, Jie Sun, Li Zhang, Xiangcheng Jin, Xiaotao Xu, Shaobo Di, and Shaoqing Huang. 2024. "Enrichment Characteristics and Mechanisms of Lithium, Gallium, and Rare Earth Elements (REY) within Late Permian Coal-Bearing Strata in Wanfu Mine, Xian’an Coalfield, Guangxi Province, Southwest China" Minerals 14, no. 9: 853. https://doi.org/10.3390/min14090853
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