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GEOLOGY, ECOLOGY, AND LANDSCAPES 2022, VOL. 6, NO. 4, 286–298 INWASCON https://doi.org/10.1080/24749508.2021.1923263 RESEARCH ARTICLE Geochemical patterns and metallogenic material source of the Naoyangping-Damogou zinc-fluorite deposits in Pingli County, China a,b c Claude Ernest Moussounda Kounga and Ahmed Amara Konaté a b School of Earth Resources, China University of Geosciences, Wuhan, China; Resources Developing & Management Dept., Baosteel Resources (Shanghai) Holdings Co., Ltd., Shanghai, China; Laboratoire De Recherche Appliquée En Géoscience Et Environnement, Institut Supérieur Des Mines Et Géologie De Boké, Baralandé Boké, Guinea ABSTRACT ARTICLE HISTORY Received 15 October 2020 The Naoyangping-Damogou Zinc-fluorite deposits in Pingli County, China, are usually asso- Accepted 24 April 2021 ciated with limestone and trachyte rocks. The ore bodies are in closed genetic relationship with fault structures. The results of this study show that the source of the ore-forming elements of KEYWORDS the Naoyangping-Damogou zinc-fluorite deposits does not have the characteristics of a deep Geochemistry; zinc-fluorite source; it can be found in the infiltration of meteoric waters along the fractures on alkali deposits; trace elements; trachyte and argillite boundary, water-rock interaction and leaching of ore-forming elements in naoyangping-damogou; rocks. The ore-forming elements migrated into favorable position by the precipitation. The pingli county results of this work can be used as supportive information during additional geological surveys in the study area. 1. Introduction Richardson & Holland, 1979; Subías & Fernández- Nıeto, 1995; Williams-Jones et al., 2000). Fluorite North Daba Mountain is an important component of deposits occur as lenses and veins in many localities the South Qinling orogen (Wang et al., 2009; Y.P. in the North Daba Mountain. Based on the structural Dong et al., 2011; Zhang et al., 2004, 2001). Scientific feature and occurrence, it was suggested that fluorite works have revealed remarkable magmatic-tectonic mineralization has a hydrothermal origin. hydrothermal mineralization in the North Daba The aim of this study is to compare petrochemical Mountain region in alkaline rocks or intermediate data to some isotopic data from Chinese Geological rocks including niobium-tantalum ore (Jia et al., Survey of Shanxi Province, in order to clarify the role 2004; S.B. Deng et al., 2003), a magmatic-related of rainwater in the genesis of sphalerite and fluorite hydrothermal zinc-fluorite deposit (Wei et al., 2009), mineralization hosted by the Zhuxi group limestone of titanomagnetite deposits in diabase dikes (Li, 2012; Late-Triassic age. In addition, this study reports for L. Liu et al., 2012), and witherite and barite deposits the first time the REE distribution and patterns of host that are related to volcanics and hydrothermal waters rocks and sphalerite ore, as well as fluid inclusion (J.J. Liu et al., 2010; Lü et al., 2004). Therefore, analysis of fluorite from different localities of research on the region’s typical deposits has an impor- Naoyangping-Damogou area to discuss its origin. tant significance in regional prospecting for possible discovery of additional deposits. Pre-investigation and detailed studies on the Naoyangping-Damogou zinc- 2. Ore deposit geology fluorite deposit have been conducted for geological 2.1 Geological features of the prospecting several times since the 1989s and 2009s, Naoyangping-Damogou ore field although researches on the genetic mechanism of the deposit and on the regional metallogenic background North Daba Mountains is a main component of the are limited. South Qinling orogen, confined by Ankang fault in the Fluorite of varied color and habit occurs in a wide North and by Chengkou-Fangxian fault in the South. range of ore deposits, from low-temperature and mod- Debates on the magmatic evolution, formation age erate salinity epithermal veins and replacements to and tectonic setting about the alkali volcanic rocks high-temperature and high-salinity magmatic deposits still exist due to lack of comparison and systematical such as greisens, skarns, porphyries, and pegmatite research of distribution of alkali volcanic rocks that systems (e.g., Bühn et al., 2002; Coniglio et al., 2000; does not allow a general frame of regional magmatic Gagnon et al., 2003; Galindo et al., 1994; Goldring & evolution. The lack of study on mineralization age and Greenwood, 1990; Hill et al., 2000; Kesler, 1977; ore-forming elements of zinc-fluorite deposit CONTACT Ahmed Amara Konaté firstname.lastname@example.org Laboratoire De Recherche Appliquée En Géoscience Et Environnement, Institut Supérieur Des Mines Et Géologie De Boké, BP 84, Baralandé Boké, Guinea © 2021 The Author(s). Published by Informa UK Limited, trading as Taylor & Francis Group on behalf of the International Water, Air & Soil Conservation Society(INWASCON). This is an Open Access article distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. GEOLOGY, ECOLOGY, AND LANDSCAPES 287 constrains the breakthrough of mineral deposit The quartz content is null or very low (<<5%). The exploration. rock is light in color, generally grey and grayish- Naoyangping-Damogou zinc-fluorite deposit is yellow. The rock exhibits porphyritic texture with located to the south-east wing of Pingli anticlinorium, phenocrysts of glassy feldspar and a criptocrystalline where the anticlinorium is the core strata of Wudang matrix. In this ssection,the rock shows a trachyte tex- Rock Group Yaoping Rock Formation. The wing part ture, i.e., alkali feldspar microcrysts oriented along of strata is steeper with the dip angle varying from 42° length with a nearly parallel arrangement. Massive to 70° and shows a development of secondary reverse structure is dominating, although a vesiculated struc- antiformal syncline. The mining area rocks are mainly ture can also be observed. composed of sedimentary rocks from the Middle Silurian Zhuxi group. Lithology is mainly argillite, Trachyte breccia sandy slate, with intercalate flaggy sandstone and Trachyte breccia compositions are in general relatively limestone (Shaanxi Province, Bureau of Geology and complex. It is not only a wall-rock breccia, but often it Mineral Exploration and Development Bureau of the includes fragments from different, also single- first Geological Brigade, Shaanxi Province, 2012). component, and underground sources. Fragments Local outcrops of marble were observed with silicified are included in a matrix of fine rock crumbs and alteration. A little area also displays outcrops of the powder. Breccia fragments are angular to rounded in Lower Silurian Meiziya group, which is distributed in shape. the east margin of the mining area. Within the mining area it is developed, a fracture Trachyte porphyry zone where anticlines of various size can be found. It is mostly composed of K-feldspar group minerals; According to its distribution, orientation of tectonic the rock exhibits porphyritic texture with K-felspar structures can be divided into four groups including and quartz phenocrysts, and a criptocrystalline matrix. nearly EW direction, NW-SE direction, NWW-SEE Based on field evidences, basic and alkaline rock direction and NE-SW direction. Among them, NW- veins show a discontinuous distribution. Among SE direction is mainly the ore-controlling fracture them, trachyte rocks and mineralization have close zone in the mining area. Magmatic rocks in the relationships all within the mining area. mining area are well-developed and can be divided mainly into two categories according to the content 2.2 Characteristics of main vein orebodies of SiO2 (Wang, 2007): (1) basic-ultrabasic rocks mostly represented by, pyroxenites, and (2) intermedi- In this study, fluorite deposits from eight localities in ate acid-acid rocks represented by trachytes. the Naoyangping-Damogou area, including K1, K2 The basic-ultrabasic rocks (pyroxenites) are distrib- (Zn), K2 (CaF2), K3, K4, K5, KH7 and K8 areas are uted in the western part of the ore field and crop out in investigated (Figure 1). K1, K2 (Zn), K4, K5 and KH7 irregular bands mainly including clinopyroxene rich form the main body of sphalerite ore and K2, K3 and rocks types and pyroclastic rocks types. There are K8 represent the main body of fluorite ore. In the mainly composed of dark green pyroxene porphyrite. southern part of K2 ore body, a fluorite mineralization The schistosity is developed and exhibits pyroxene has been discovered (Shaanxi Province, Bureau of (augite) phenocrysts, with tabular and columnar crys- Geology and Mineral Exploration and Development, tals. The metamorphism and alteration are strong. The Bureau of the first Geological Brigade, Shaanxi alteration includes uralitization of pyroxene and dif- Province, 2012). These ore bodies occur without fuse replacement of microcrystalline matrix by sericite exception in a faulted-fracture zone within NE-SE and chlorite. In the mining area, basic subvolcanic direction. The orebody morphology and scale are rocks are distributed in a small zone, mainly occurring strictly controlled by the fault fracture zone. at the west part of Naoyangping. Moreover, in the Zhuxi Group system, there are lenticular and banded. 2.1.1 The K1 orebody (Damogou) Clinopyroxene rocks in Langao-Pingli are dominated Damogou (K1) represents the main body of sphalerite by microcrystalline olivine-bearing pyroxenite. ore in the mining area. The orebody is hosted in the Trachytes are represented in the study area. They Middle Silurian Zhuxi Formation slate rock and alkali are Alkali trachyte, trachyte breccia, and trachyte trachyte rock fault contact zone. The explored orebody porphyry. is 384 m in length. Orebody average thickness is about 3.42 m and is stable in Damogou. The average Zn Alkali trachyte grade is about 10.57% and CaF2 grade is about The most abundant minerals are K-feldspars (mainly 11.95%. The dips of orebody vary from 71° to 64°. orthoclase, with minor microcline). Subordinate The orebody outcrops extend from 1142 m to minerals are plagioclase, hornblende, biotite and 1212 m above the sea level. The industrial ore type is pyroxene. dominated by primary sulfide ores, associated with 288 C. E. MOUSSOUNDA KOUNGA AND A. A. KONATÉC Figure 1. Geological sketch map of the Naoyangping-Damogou zinc-fluorite deposits 1: Middle Silurian Zhuxi Group (S zh), 2: Lower Silurian Meiziya Group (S m), 3: Alkali trachyte rock, 4: Basic pyroxenite rock, 5: Limestone bands, 6: Mineralization alteration zone, 7: Zinc orebody, 8: Fluorite orebody, 9: Stratum boundary, 10: Attitude of rock, 11: Fault, 12: Open pit mining pits. a fluorite resource. A few outcrops of oxidized ore ore bodies range from 989 to 1049 m above the sea appear discontinuous, with very low amounts of Zn level. The main orebody is about 320 m in length. and Pb. Their SE side’s dip angle vary from 20° to 34°, the Sphalerite mainly shows allotriomorphic to auto- biggest value is about 48° in the NW side. On the morphic granular texture, cataclased and followed by whole, orebody dip angle change direction steepening metasomatic replacement. The ore structures are to the north-west. The dip of orebody is about 71°- mainly disseminated, massive and brecciated; they 42°. The fluorite grade is of about 41.98% on average. are followed by vein structures. Lead and zinc contents are very low. The Pb and Zn grades vary from 0.00% to 0.01% and 0.00% to 0.02%, respectively. The dominant lithological units in the 2.1.2 The K3 orebody (Naoyangping) Naoyangping area are represented by quaternary, Naoyangping (K3) constitutes the main body of fluor - Middle Silurian Zhuxi Group and alkaline rocks. ite ore in the study area. Mineralization was controlled by F1 secondary fracture zones and is closely related to faults (Figure 1). The fracture zone is about 400 m in 3. Materials and analytical methods length and 12 m in width. Fluorite mineralizations found in this area occurs mainly in fault zone. Representative samples of magmatic rocks, lime- Generally ore bodies are NW-trending and limited stones, fluorites and sphalerite ores from different by F1 fault in the southern part. The outcrops of all localities in the study area, including Naoyangping GEOLOGY, ECOLOGY, AND LANDSCAPES 289 and Damogou areas were collected and crushed. The accelerating voltage was 15kv, the beam current was samples were separated by handpickingunder 10nA, and the laser spot size was set to 1 µm. a binocular microscope. Samples were subjected to petrographic, mineralogical, geochemical and fluid 4. Results inclusion investigations. Twenty fluorite samples from different localities of the 4.1 Occurrence of fluorite Naoyangping-Damogou area were collected and Fluorite deposits in the Naoyangping-Damogou area crushed. Samples were separated by hand picking occurs mainly as veins ranging in thickness from few under a binocular microscope. Thin sections were pre- centimeters up to 10.87 m. The host rocks are magmatic pared for these samples (8 samples) and investigated rocks such as pyroxenite, alkali trachyte and limestone. under the optical microscope to investigate the texture The color of the fluorite varies from grayish-white to of the fluorite. A Nikon Research microscope with purple, followed by white, grey and green. It shows attached camera was used to examine the prepared thin a vitreous luster. Fluorite grains are uniform and about sections at State Key Laboratory of Continental 2–23 mm in size. The fluorite is mainly euhedral (idio- Dynamics of Northwest University, Department of morphic)-hypidiomorphic granular, cataclastic and Geology of Xi’an. cryptocrystalline in texture (Figure 2). The fluorite Fluid inclusion studies were performed on doubly occurs in fluorite-only veins and in hydrothermal quartz polished fluorite samples taken from the mineraliza- veins, quartz carbonate veins along the host rock folia- tion area. The microthermometric measurements tion and fissures. Fluorite also wraps fragments of sur- were carried out using a Linkam TH600 heating and rounding rocks. The fluorite is manly dominated by cooling stages of the State Key Laboratory of massive structure, and followed by disseminated, brec- Continental Dynamics of Northwest University, ciated, zoned (zonal pattern) and structures (Figure 2). Department of Geology, Xi’an, China following the method described in Ouyang et al. (2014). The heating rate during the phase transitions was controlled 4.2 Ore Petrography –1 manually in the range of 5 to 15°C min . Repeated Petrographic examinations of fluorites from the studied measurements indicated that the reproducibility of the localities indicate that they show variations. The fluor - temperature determinations was better than ± 0.5°C. ites were classified into four categories based on the The homogenization temperatures (Th) of fluid field geology and the alteration zone of the ore deposit, inclusions were measured in eight (8) fluorite samples. including fluorite alkali trachyte ore-type and fluorite Salinities were calculated using the equation of limestone ore-type. Two types of fluorites also are dis- Bodnar (1993) and Hall et al. (1988) for the low- and tinguished at Naoyangping-Damogou area: white and medium-to high-salinity NaCl-H O system, purple fluorite. In general, the fluorite ore deposit in the respectively. Naoyangping area (K3) typically belongs to the hydro- To analyze the REEs in the magmatic, limestone thermally-altered rock, with low grades of fluorite ore. rocks and Sphalerite ore, the twenty powdered sam- The major common gangue minerals in the studied ples were determined by ICP-MS technique by using ores include mainly quartz (silica), followed by clayey electron microprobe analysis of the State Key minerals, chlorite, sericite, feldspar, calcite (Figure 3). Laboratory of Continental Dynamics of Northwest University, Department of Geology, Xi’an (China). Nineteen magmatic rocks samples from the 4.3 Ore mineralogy Naoyangping-Damogou area were analyzed for The fluorite contents as well as gangue minerals, major-oxide trace elements contents of magmatic which calculated based on XRD and chemical (nor- rocks were analyzed by ICP-ES technique at State mative calculations) analyses. Key Laboratory of Continental Dynamics of The semi-quantitative mineralogical composition of Northwest University of Xi’an. Fluorite, which is the fluorite samples from Naoyangping-Damogou area is main constituent in the study samples, was identified 40% for fluorite, 19% for ferrodolomite, 15% for plagio- in the X-ray powder diffraction patterns by its char- clase, 10% for quartz, 5% for pyrite and K-feldspar, 4% acteristic strong reflection. In addition to fluorite, for muscovite/sericite, 2% for calcite and small amount common gangue minerals such as mainly quartz for phlogopite and chlorite. Traces of zircon and apatite (silica) and followed by clayey mineral, chlorite, ser- were detected in some of the analyzed samples. icite, feldspar, calcite, etc., were also detected in the XRD patterns of studied deposits (Figure 3). Measurement of mineral chemical composition was 4.4 Major oxides conducted at the State Key Laboratory of Continental Dynamics of Northwest University of Xi’an by using Nineteen magmatic rock samples were analyzed for the EPMA-1600 electron microprobe. The major oxide elements. Distribution of major trace 290 C. E. MOUSSOUNDA KOUNGA AND A. A. KONATÉC Figure 2. Structure and texture of the Naoyangping fluorite ore. A: Massive pyrite with semi- euhedral granular texture, B: Fluorite veins stricture, C: Pyrite euhedral-semi euhedral granular structure, D: Fluorite-plagioclase pseudomorph (metasomatic pseudo- morph structure), E: Fluorite encapsulated (wrapped) gangue minerals, and F: Fluorite cataclastic texture. elements in magmatic rocks was analyzed by using 4.5.1 Rare earth elements in magmatic rocks ICP-ES technique and the results are shown in Table The ∑REE of magmatic rocks such as alkali-pyroxenite 1. CaO in the table is that allocated for calcite, while Ca from different localities of the study area ranges is that for CaF . Fluorine controlled the allocation of between 403.39ppm and 476.41ppm, with an average Ca for fluorite and the rest of Ca is for calcite. SiO of 438.79 ppm. Chondrite-normalized (Boynton, contents range between 38.07% and 67.57% with an 1984) REE patterns for ultra-basic pyroxenite and average of 52.82%. Relatively high SiO contents in alkali trachyte rocks from different localities are many of the studied samples are due to the high quartz shown in Figures 10a and Figure 10d. The Eu anomaly content. CaO % varies between 0.07% and 24.87% is calculated as Eu/Eu* = EuN/(SmN.GdN) and Ce with an average of 12.47%. Relatively high CaO con- anomaly is calculated as tents in some of the samples are due to the occurrence Ce/Ce* = (3Ce/Ce )/(2La/La +Nd/Nd ). The REE N N N of calcite in such samples. Other oxides such as Al O , patterns show similar general trends with some excep- 2 3 TiO , TFe O , MnO, MgO, K O, Na O, and P O tions. Chondrite-normalized REE patterns for mag- 2 2 3 2 2 2 5 occur as traces. Exceptions occur in some samples matic rocks such as the ultra-basic pyroxenite rocks where some oxides are present in considerably high (Figure 4a) show LREE enrichment relative to HREE content, such as samples that show relatively high Al as shown by (La/Sm) ratios that vary from 6.1 to 2 N O , TFe O , Na O and K O contents due to the occur- 10.7. Significant positive Eu anomalies are pro- 3 2 3 2 2 rence of orthoclase. nounced, with Eu/Eu* from 0.91 to 1.02 and an aver- age of 0.94. Significant Ce anomalies have been observed in the analyzed samples (Ce/Ce* ranges 4.5 Rare earth elements from 0.96 to 0.99 with an average of 0.98). Trace element distributions in magmatic rocks, in 4.5.2 Rare earth elements in alkali trachyte rocks limestone and sphalerite ore from different localities The ∑REE of alkali trachyte rocks ranges between of Naoyangping-Damogou area are shown in Table 2 153.09ppm and 692.20ppm with an average of and Table 3 respectively. We compare LA-ICP-MS 379.91ppm. Chondrite-normalized REE patterns for (Magmatic rocks) and LA-ICP-MS (Limestone and alkali trachyte rocks (Figure 4b) from different local- sphalerite ore) using Sr, Y, and the lanthanides, ities exhibit LREE enrichment relative to HREE as which are also detectable in most fluorite grains shown by (La/Yb) ratios that vary from 16.85 to (Ismail et al., 2014; Mao et al., 2015). 30.64 with an average of 20.60. Significant negative GEOLOGY, ECOLOGY, AND LANDSCAPES 291 Figure 3. The gangue minerals composition of the Naoyangping fluorite ores.A: pyrite-quartz- felsic minerals with pyrite dispersed in felsic minerals gangue, B: pyrite-muscovite sericite, with pyrite dispersed in sericite gangue, C: pyrite- dolomite within pyrite dispersed in dolomite gangue, D: fluorite-pyrite within enclosed in fluorite, E: Purple fluorite which show an uneven distribution of color, F: fluorite-quartz-felsic minerals within fluorite and felsic minerals contact, G: Fluorite- muscovite-sericite within fluorite and sericite contact zone, H: Fluorite- Dolomite within fluorite and dolomite contact zone, and I:fluorite- pyrite within fluorite and pyrite contact zone. Table 1. Major oxide concentrations (Wt. %) in the analyzed magmatic rocks samples of the Naoyangping-Damogou area. Sample No. Sample Name SiO2 TiO2 Al2O3 TFe2O3 MnO MgO CaO Na2O K2O P2O5 LOI Total (%) XTWL01 Trachyte 58.50 1.11 22.43 4.25 0.10 1.80 0.66 1.57 7.62 0.18 1.42 99.64 XTWL03 Trachyte 62.87 0.82 19.47 2.74 0.07 0.60 0.19 5.97 4.50 0.07 3.21 100.51 XTWL04 Diabase 65.89 1.04 16.63 3.61 0.08 0.73 0.29 6.27 3.92 0.11 0.89 99.46 XTWL05 Diabase xenoliths 40.72 5.12 10.75 14.18 0.22 6.98 14.92 3.29 0.10 0.77 2.74 99.79 XTWL06 Trachyte 40.32 5.61 11.94 14.67 0.24 6.96 12.94 3.40 0.17 0.90 2.99 100.14 XTWL07 Felsic Mylonite 67.57 0.75 15.11 3.41 0.09 0.05 0.52 5.95 4.30 0.08 1.57 99.40 XTWL-105 Diabase 38.72 4.74 10.04 12.59 0.19 5.96 17.25 3.14 0.10 0.75 6.10 99.58 XTWL-106 Diabase 38.07 4.95 10.25 13.34 0.20 6.23 16.78 3.49 0.11 0.76 5.57 99.75 XTWL-107 Trachyte 59.38 1.06 17.22 4.00 0.09 0.64 2.41 3.31 8.21 0.22 2.97 99.51 XTWL-108 Trachyte 56.46 1.16 17.52 4.28 0.06 0.61 3.48 4.50 7.48 0.30 3.51 99.36 XTWL-1010 Trachyte 53.93 0.40 7.48 3.49 0.23 0.76 24.87 1.42 1.88 0.13 4.55 99.14 XTWL-1011 Trachyte 50.72 0.42 7.60 2.95 0.21 1.12 23.63 2.20 1.51 0.17 8.60 99.13 XTWL-1012 Volcanic bomb 60.09 0.91 18.00 3.31 0.14 0.54 1.90 6.88 5.53 0.11 2.05 99.46 XTWL-1013 Volcanic cement 62.90 0.94 18.41 3.54 0.17 0.46 0.20 6.36 5.60 0.13 0.82 99.53 H01 Trachyte 66.64 0.94 15.65 3.65 0.05 0.13 0.20 5.06 5.83 0.10 1.57 99.82 H02 Trachyte 53.74 1.07 22.61 5.45 0.15 1.32 0.54 2.59 8.17 0.13 4.16 99.93 H05 Trachyte 58.47 1.06 17.81 6.46 0.09 0.57 0.07 3.72 7.63 0.08 3.57 99.53 H06 Trachyte 57.11 1.05 21.71 4.34 0.10 1.72 0.76 1.57 7.83 0.17 3.26 99.62 H07 Trachyte 66.32 1.01 16.66 3.50 0.08 0.66 0.20 6.36 3.95 0.11 0.86 99.71 292 C. E. MOUSSOUNDA KOUNGA AND A. A. KONATÉC Table 2. Trace element concentrations (Wt. %) in the analyzed magmatic rocks of the mining area. Sample XTWL- XTWL- XTWL- XTWL- No. 105 106 Y05 Y06 1012 1013 Y01 Y03 Y04 Name Diabase Diabase Diabase Trachyte Volcanic bomb Cement Trachyte Trachyte Diabase Li 8.12 9.20 11.84 10.53 5.96 7.10 6.96 36.56 11.97 Be 2.47 2.31 1.45 2.67 5.79 12.96 3.07 3.60 5.96 Sc 27.92 28.22 26.47 26.76 4.34 3.34 2.92 4.04 8.17 V 520.54 516.13 489.64 444.25 15.09 16.08 12.26 60.46 30.14 Cr 40.02 22.13 93.23 25.47 2.83 9.24 8.14 9.55 12.73 Co 49.34 49.52 45.44 47.54 0.59 0.76 0.38 1.08 0.66 Ni 68.18 66.17 105.63 86.05 5.01 6.28 9.19 17.70 29.46 Cu 174.54 260.95 144.92 164.69 1.45 1.80 9.92 2.69 2.86 Zn 121.05 127.81 139.21 146.89 132.13 65.74 40.94 116.63 140.65 Ga 27.30 28.33 27.48 31.88 34.98 30.37 25.32 31.57 40.50 Rb 2.37 1.68 1.33 1.12 103.17 112.36 68.96 123.12 56.68 Sr 2713.09 3022.56 1681.96 3692.69 56.21 35.55 87.83 115.95 27.50 Y 31.50 32.30 33.62 34.91 36.01 31.89 21.61 29.19 48.06 Zr 465.54 473.91 472.23 502.65 479.38 530.87 641.51 504.29 1536.12 Nb 114.77 119.13 112.77 121.26 136.82 153.23 195.32 181.25 319.68 Cd 0.18 0.19 0.27 1.17 0.21 0.12 0.11 0.28 0.55 In 0.12 0.12 0.15 0.14 0.12 0.09 0.12 0.14 0.22 Cs 0.07 0.08 0.07 0.07 0.48 0.50 1.95 3.56 0.87 Ba 163.86 155.28 141.96 119.49 382.95 386.93 126.08 1796.51 327.66 La 84.45 84.29 95.68 95.88 87.19 98.06 131.39 111.86 174.56 Ce 169.84 171.84 196.58 198.93 169.39 170.84 207.10 218.33 286.70 Pr 20.92 21.33 23.55 23.93 20.64 21.15 25.78 24.05 36.24 Nd 79.76 80.35 96.14 98.23 67.27 72.89 87.54 85.76 126.89 Sm 14.22 14.28 17.01 17.61 10.86 10.92 12.21 12.89 19.00 Eu 4.49 4.47 4.84 5.03 2.11 1.90 1.08 1.92 3.33 Gd 12.15 12.20 14.70 15.43 9.43 8.44 8.84 10.18 14.74 Tb 1.71 1.74 1.96 2.06 1.61 1.35 1.09 1.47 2.22 Dy 8.01 8.24 9.25 9.80 8.55 7.28 5.26 7.57 11.63 Ho 1.47 1.49 1.68 1.76 1.74 1.55 1.11 1.53 2.39 Er 3.37 3.36 3.83 4.01 4.38 4.17 3.14 4.09 6.51 Tm 0.40 0.42 0.47 0.49 0.60 0.58 0.46 0.58 0.95 Yb 2.29 2.30 2.67 2.86 3.71 3.59 3.08 3.72 6.13 Lu 0.31 0.32 0.37 0.83 0.54 0.55 0.48 0.56 0.91 Hf 11.05 11.34 12.55 13.43 11.78 13.16 15.38 12.07 40.28 Ta 7.24 7.52 8.16 8.84 9.37 10.56 13.69 13.27 22.27 Pb 6.51 6.26 56.88 122.79 7.08 7.50 24.46 51.16 50.35 Bi 0.03 0.03 0.17 0.11 0.01 0.03 0.08 0.05 0.10 Th 10.98 11.09 12.92 13.53 13.53 12.44 19.57 19.23 27.40 U 2.46 2.51 2.91 2.93 1.97 2.13 1.87 4.05 6.51 Eu anomalies are pronounced, with Eu/Eu* from 0.30 Damogou K1 orebody. REE concentrations range to 0.62 and with an average of 0.52. Significant Ce between 481.85ppm and 603.72ppm with an average anomalies have been observed in the analyzed samples of 535.19ppm. Chondrite-normalized REE patterns of (Ce/Ce* ranges from 0.82 to 0.95 with an average the sphalerite are shown in Figure 10d. They both have of 0.93). enrichment LREE distribution patterns while the ∑LREE/∑HREE values range from 12.52 to 13.95, with an average of 13.09. La/Yb ratios range from 4.5.3 Rare earth elements in limestone and 18.75 to 31.21 with an average of 23.28. LREE and sphalerite ore HREE indicate relatively negative difference degree of The ∑REE of limestone rocks from the different local- fractionation by (La/Sm) ratios that vary from 3.73 ities of the study area ranges from 32.39ppm to to 17.45 and (Gd/Yb) ratios that vary from 1.21 to 89.28ppm with an average of 61.50ppm. Chondrite- 5.75. Significant negative Eu anomalies are pro- normalized REE patterns of limestone rocks (Figure nounced with Eu/Eu* ratios range from 0.46 to 0.59 4c) are enriched in LREE. The ∑LREE/∑HREE rratio with an average of 0.52. Ce anomalies have been values ranges from 3.39 to 12.78 with an average of observed in the analyzed samples (Ce/Ce* ranges 10.81. The La/Yb ratios range from 4.00 to 41.87 with from 0.99 to 1.00 with an average of 1.00). an average of 18.80. Significant negative anomalies as shown by (La/Sm) ratios that vary from 8.41 to 10.23 indicate the order of difference of degree of fractiona- 4.6 Fluid inclusion petrography and tion. Eu anomalies ratios range from 0.87 to 2.12 with microthermometry an average of 1.30. Those of Ce anomalies range between 0.80 and 1.77 with an average of 1.13. Fluid inclusions were studied in fluorite (Figure 5). All samples of sphalerite ore in the mining area Four types of fluid inclusions were identified in our were collected in the open pit bottom of the samples based on their phase composition at room GEOLOGY, ECOLOGY, AND LANDSCAPES 293 Table 3. Trace elements concentrations (Wt. %) in the analyzed limestone rock and Sphalerite ore from Damogou (K1). Sample XTWL XTWL XTWL XTWL No. -101 -102 -103 -104 Y08 Pd01 K01 K03 K03 Lime- Lime- Lime- Lime- Lime- Sphale- Sphale- Name stone stone stone stone stone Calcite rite rite Sphalerite Li 5.84 0.80 3.96 0.76 0.68 0.38 1.61 1.23 1.14 Be 0.19 0.25 0.54 0.87 0.29 0.001 0.23 0.30 0.30 Sc 4.69 1.32 1.95 0.78 1.13 3.72 1.53 2.47 2.30 V 100.7 7.20 15.83 3.76 8.71 1.41 5.42 7.89 3.27 Cr 7.86 4.50 10.22 3.75 8.20 6.93 3.34 17.43 2.46 Co 10.39 1.71 5.28 9.14 17.50 0.41 13.44 14.81 14.58 Ni 13.13 2.48 7.23 14.07 30.59 22.91 1.12 1.90 1.03 Cu 50.41 3.18 4.62 3.65 9.52 1.60 110.3 229.6 269.7 Zn 36.61 6.08 13.00 10.00 25.94 796.6 163,198 174,867 177,703 Ga 6.14 1.30 2.90 3.61 4.69 0.53 10.70 16.65 16.36 Rb 15.67 6.25 28.03 3.13 2.04 0.18 43.47 11.46 41.37 Sr 2282 501.5 2135 422.1 591.9 2551 65.48 122.5 18.75 Y 5.92 7.29 7.91 9.19 11.86 10.96 35.97 40.51 44.28 Zr 64.19 16.31 41.50 17.66 21.64 1.32 314.9 438.5 463.4 Nb 13.34 5.63 15.82 8.42 9.79 1.47 70.41 78.25 102.5 Cd 0.13 0.031 0.053 0.029 0.14 1.48 238.0 261.7 246.6 In 0.041 0.005 0.010 0.010 0.013 0.17 1.48 2.62 3.83 Cs 2.99 0.24 1.81 0.042 0.040 0.016 0.30 0.33 0.25 Ba 1081 33.08 106.0 24.75 26.33 7.12 193.4 52.28 185.9 La 24.28 8.46 15.61 13.50 15.74 5.12 134.1 106.3 116.0 Ce 35.72 13.25 26.08 36.08 51.39 11.10 266.8 214.0 231.7 Pr 4.13 1.49 2.71 2.22 2.72 1.32 30.25 23.53 25.69 Nd 14.50 5.28 9.09 7.65 10.23 5.02 109.2 85.89 92.39 Sm 2.38 1.01 1.52 1.38 1.99 1.37 19.31 14.06 14.39 Eu 1.62 0.35 0.46 0.41 0.54 1.08 3.75 2.41 2.14 Gd 2.21 1.08 1.47 1.52 2.29 1.80 19.00 13.97 13.93 Tb 0.30 0.18 0.23 0.25 0.34 0.41 2.29 1.76 1.78 Dy 1.37 0.98 1.19 1.32 1.81 2.50 9.59 8.67 9.21 Ho 0.25 0.22 0.26 0.28 0.37 0.45 1.52 1.62 1.79 Er 0.59 0.54 0.66 0.72 0.92 1.04 3.96 4.61 5.21 Tm 0.071 0.071 0.083 0.092 0.12 0.14 0.49 0.60 0.70 Yb 0.42 0.44 0.56 0.55 0.73 0.92 3.08 3.84 4.44 Lu 0.058 0.067 0.082 0.078 0.095 0.12 0.46 0.57 0.66 Hf 1.48 0.34 0.88 0.36 0.52 0.037 6.99 9.33 9.99 Ta 0.80 0.31 0.91 0.53 0.59 0.078 4.55 6.05 6.65 Pb 4.34 5.83 12.65 49.24 114.8 31.74 5.35 3.87 7.58 Bi 0.009 0.026 0.064 0.27 0.58 0.076 0.058 0.053 0.037 Th 1.41 0.83 2.26 1.07 1.20 0.081 7.51 10.06 10.09 U 0.45 0.59 0.29 0.39 0.73 0.031 1.63 3.19 2.42 temperature and according also to the classifications Homogenization temperatures of all these fluids in of Nash and Theodore (1971) and Roedder. The result Naoyangping-Damogou are mostly in the range 289°C of petrographic observations indicates that the inclu- to 340°C. Most of the inclusions have freezing point sions are mainly of gas-liquid two-phase, pure gas values ranging from −0.3°C to −0.8°C. All these inclu- phase, pure liquid phase, and CO -H O three-phase sions show low salinity, which ranges from 0.53 wt. % 2 2 daughter mineral-bearing type (Figure 6). −1.33 wt. % NaCl . eqv Microthermometry of fluid inclusions in fluorite from Damogou area reveals that the homogenization 5. Discussion temperatures range from 295°C to 340°C with sali- nities from 0.53% to 1.33%NaCl and the homoge- The data obtained by cross plot of the Naoyangping- eqv. neous temperatures of fluid inclusions in fluorite from Damogou fluorites on a Tb/Ca versus Tb/La variation Naoyangping area range from 289°C to 329°C with diagram (after Moller et al., 1976) (Figure 7) are compa- high salinities (Table 4). Liquid-rich two-phase inclu- tible with a structurally controlled, sedimentary- sions are common in the grain boundary or present as hydrothermal origin. The relative positions of fluorite- trails penetrating crystal boundaries, suggesting rich samples on the Tb/Ca vs.Tb/La diagram are consis- a secondary origin (Figure 6A and Figure 6B). The tent with this late crystallization environment. According primary fluid inclusions are usually 5–10 mm in size to Dolnicek and Slobodnik (2001), fluorite of hydrother- and are spherical to semi-spherical in shape (Figure mal origin is homogeneous without any growth zones. 6C and Figure 6D). The Damogou inclusions are Primitive mantle trace elements diagram of the dominated by fluids that show low salinities. Naoyangping-Damogou area are illustrated in 294 C. E. MOUSSOUNDA KOUNGA AND A. A. KONATÉC Figure 4. Chondrite-normalized REE patterns of the ultra-basic pyroxenite, alkali trachyte, limestone rocks and sphalerite ore of the Naoyangping-Damogou zinc-fluorite deposits. (a) The Chondrite-normalized REE pattern of the ultra-basic pyroxenite rocks. (b) The Chondrite-normalized REE pattern of the Naoyangping- Damogou alkali trachyte rocks. (c) The Chondrite-normalized REE pattern of the Naoyangping-Damogou Limestone rocks. (d) The Chondrite-normalized REE pattern of the Naoyangping-Damogou sphalerite ore. Figure 5. Different type of the Naoyangping-Damogou fluid inclusions. A and B secondary inclusions, C and D are primary inclusions. A: Damogou K1 orebody 1085 middle section fluorite system of secondary inclusions; B: Naoyangping K3-PD10 fluorite system of secondary inclusions, C: Damogou K1 orebody 1136 middle section system of vapor-rich inclusions, and D: Damogou K1 orebody 1136 middle section system of pure liquid inclusions. Figure16a-d. From them, it can be discovered that the Primitive mantle trace elements spider diagram of trace elements contents of ultra-basic pyroxenite alkaline trachyte and sphalerite ore are shown in Figures (Figure 8a) samples are similar, whereas two samples 8b and Figure 8d, respectively. A comparison of those had significantly higher Pb content, much likely two diagrams shows a certain similarity. Sr values are caused by the late hydrothermal alteration of the area. significantly depleted and the trace elements in the GEOLOGY, ECOLOGY, AND LANDSCAPES 295 Figure 6. Morphology of the Naoyangping-Damogou fluid inclusions. A, B and C: secondary fluid inclusions; D: pure gas fluid inclusions, and E: inclusions containing daughter crystal F: daughter crystal. Table 4. Microthermometric data of fluid inclusions from the Naoyangping-Damogou study area. Sample Sampling Samples lithology Type of fluid Freezing Range of Density of o o No. location characteristics inclusions Range of Th ( C) point ( C) salinity fluid LT01 K1-1085 middle- Purple Gas-liquid two- 295 ~ 335 300 ~ 320 −0.3~ −0.8 0.53 ~ 1.33 0.658 ~ 0.663 stage fluorite phase (Damogou) LT03 K1-1136 middle- White Gas-liquid two- stage fluorite phase LT04 K1-1136 middle- White Gas-liquid two- stage fluorite phase LT05 K1-open pit White Gas-liquid two- 310 ~ 340 fluorite phase LT06 K1-open pit White Gas-liquid two- fluorite phase LT09 K3-PD10 Purple Gas-liquid two- 289 ~ 329 289 ~ 329 fluorite phase (Naoyangping) LT10 K3-PD10 Purple Gas-liquid two- fluorite phase LT11 K3-PD10 Purple Gas-liquid two- fluorite phase whole curve are approximately the same. This may be interpreted as an indication that the material sources of alkaline trachyte and sphalerite ore are analogous. It also shows that in the mining area the ore-forming elements of sphalerite ore and alkaline trachyte are closely related. The Figure 9 display δD and δ O characteristics of the fluid inclusion water in Naoyangping-Damogou zinc-fluorite deposits obtained by the Geological Survey Institute of Shaanxi province. On the same diagram, it is shown that the hydrogen and oxygen compositions of the studied samples are located between meteoric water line and kaolinite weathering line, which is just below the field of regional primary magmatic waters. Thus, it is not easy to determine the source of hydrothermal ore-forming solutions of this deposit. Isotopic data indicate that most probably they Figure 7. Plot of the Naoyangping-Damogou fluorites on a Tb/ derived from magmatic water with mixed rainwater. Ca versus Tb/La variation diagram (After: .Moller et al., 1976). This result clearly shows that the Naoyangping- Trends are taken from Geological Survey of Shaanxi Province (2009) Damogou area hydrothermal ore-forming solution 296 C. E. MOUSSOUNDA KOUNGA AND A. A. KONATÉC Figure 8. Primitive mantle trace elements diagram of the Naoyangping-Damogou area of each lithology. (a) Primitive mantle trace elements spider diagram of ultra-basic pyroxenite rocks. (b) Primitive mantle trace elements spider diagram alkaline trachyte rocks. (c) Primitive mantle trace elements spider diagram of limestone. (d) Primitive mantle trace elements spider diagram of Sphalerite. mainly originated from the intraformational-evolution (Figure 10) shows that the source of sulfur in the ore of rainwater. Sulphur isotopic determinations for pyrite deposits is not characteristic of a deep source. The most and sphalerite from Damogou area (see histogram in probable source of sulfur in ore-forming fluid can be Figure 10) display δ S values concentrated in the range the alkali trachyte or the thermo-chemical sulfate between 13‰ and 15‰, and the sphalerite ore deposit reduction in sedimentary rocks (Zeng, 2013). are characterized by enrichment in heavy sulfur δ S. Sulfur isotopic characteristics in Sphalerite are 6. Conclusion significantly different from that in the mantle source of sulfur (0‰). Additionally, the same histogram As one of the ore deposit types in the south-east wing of Pingli Anticlinorium of the North Daba Mountain, Figure 10. Histogram of the isotopic determination of Pyrite and Sphalerite from Damogou area (After Geological Survey of Figure 9. δD and δ O characteristics of the fluid inclusion Shaanxi Province, 2009). water at Naoyangping -Damogou zinc-fluorite deposit (After Geological Survey of Shaanxi Province, 2009). 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Geology Ecology and Landscapes – Taylor & Francis
Published: Oct 2, 2022
Keywords: Geochemistry; zinc-fluorite deposits; trace elements; naoyangping-damogou; pingli county
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