Figure
1.
(a), (b) Geotectonic map of the study area; (c) geological map of the Chifeng-Chaoyang region showing distribution of the gold deposits (Wang et al., 2016).
| Citation: | Fan Yang, Xuejiao Pang, Bin Li, Jingsheng Chen, Jilong Han, Miao Liu, Zhongzhu Yang, Yan Wang, Yi Shi. Geological, Fluid Inclusion, H-O-S-Pb Isotope Constraints on the Genesis of the Erdaogou Gold Deposit, Liaoning Province. Journal of Earth Science, 2021, 32(1): 103-115. doi: 10.1007/s12583-020-1068-5
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Chifeng-Chaoyang region is located in a special tectonic location, which is the conjuncture of the North China Craton (NCC) and Xingmeng orogenic belt (XOB) (eastern segment of Central Asian Orogenic Belt (CAOB)), and belongs to the transitional zone between NCC and XOB (Figs. 1a, 1b). Under the influence of CAOB, the northern margin of the NCC experienced intense tectonic-magmatic-volcanic activities in Paleozoic and Mesozoic, which made the area the important non-ferrous metal mineral bases in China, with a large number of gold deposits (Fig. 1c). Bounded by the Chifeng-Kaiyuan fault, the southern side of the fault produces medium-large gold deposits such as Jinchanggouliang, Erdaogou, Honghuagou, Anjiaying and Paishanlou. In the north, there are gold deposits such as Zhuanshanzi and Gongbeidi.
Erdaogou gold deposit is located in Longtan Township, Beipiao City, Liaoning Province, bordering Jinchangguliang Town, Aohan Banner, Inner Mongolia. Since it was put into production in the 1980s, the proven reserves have exceeded 35 t and the mined reserves have exceeded 20 t. The average grade of the industrial ore body is 10.5 g/t, accompanied by elements such as Ag-Cu-Pb-Zn. The deposit has attracted the attention of many scholars, who have studied the ore geology (Xu, 2007), geochronology (Miao et al., 2003; Pang, 1997), isotope analyses (Fu, 2012; Pang, 1998; Guo, 1994), and fluid inclusion geochemistry (Fu, 2012; Pang and Qiu, 1994). But the genesis of the Erdaogou gold deposit is still controversial, and there are mainly the following viewpoints: magmatic hydrothermal (Wang et al., 1989), epithermal hydrothermal (Yang, 2019; Pang, 1997; Pang and Qiu, 1994), and orogenic (Sun, 2013). In this paper, we describe the geological characteristics and metallogenic types of Erdaogou deposit through detailed field geological survey and petrographic observation. On this basis, we use fluid inclusion, stability and radioisotope composition to better constrain the source of ore-forming fluids and metals. The new comprehensive data above enables us to gain a better understanding of the genesis of the Erdaogou deposit. Furthermore, our study also provides a basis for the determination of metallotectonic background.
The study area is located in the northern part of the NCC and south of the XOB, which is closely related to the evolution of paleo-Asian Ocean (Jahn, 2004; Şengör et al., 1993). The XOB formed during the final closure of the Paleo-Asian Ocean and amalgamation of the NCC along the Solonker suture zone before Triassic (Xiao et al., 2009). During the Jurassic Period (165–135 Ma), NCC underwent strong contraction and deformation due to the formation of XOB (Zhang et al., 2008). In addition, the Early Jurassic basin experienced strong contraction, inversion and erosion from the middle to early Late Jurassic (Meng, 2003). However, the tectonics of NCC changed from contraction to extension at ca. 130–100 Ma (Kusky et al., 2007), contemporaneous with the development of metamorphic core complexes (Yang et al., 2007), intense magmatism and large-scale gold metallogenesis (Mao et al., 2007). The Mesozoic intrusive rocks developed and invaded into the Archean and Paleozoic strata (Fig. 1c). The Precambrian strata are mainly the Archean Jianping Group, which is a set of hornblende gneiss series dominated by hornblende gneiss and anorthosite hornblende gneiss (Liu et al., 2011). Mesoproterozoic strata include Changzhougou, Chuanlinggou, Tuanshanzi, Dahongyu and Gaoyuzhuang Formation, which is mainly a set of sedimentary formations. Mesozoic−Cenozoic strata are widely developed, mainly including Xinglonggou, Beipiao, Haifanggou, Tiaojishan, Tuchengzi, Zhangjiakou, Yixian, Jiufotang, Shahai Formation and Quaternary sediment.
The tectonic pattern in study area is dominated by faults striking EW, NW and NEE (Fig. 1c), the Chifeng-Kaiyuan deep fault has evolved among which the Late Archean to the Cenozoic and it is mainly divided into four stages: generation stage, development stage, active stage and damage stage. The NW-trending faults controlled the distribution of the deposits.
The main strata exposed in the mining areas are the metamorphic rocks of Jianping Group in the Archean and the volcanic rocks of the Tiaojishan Formation of Jurassic in the Mesozoic (Fig. 2). The metamorphic rocks of Xiaotazigou Formation of Jianping Group with the largest distribution area are mainly biotite gneiss mixed with amphibolite, granulite and biotite amphibole plagioclase gneisses, which is a set of submarine eruptive volcanic rocks rich in femic and formed by later metamorphic deformation. Volcanic rocks of the Tiaojishan Formation are widely distributed in the mining areas and their lithology is complex. They are mainly composed of a set of dacitic-rhyolitic lava, tuff and volcanic breccia (Yang et al., 2019).
Granite intrusions are relatively developed in the mining areas, which invaded into the metamorphic rocks of the Jianping Group and the volcanic rocks of the Tiaojishan Formation. The main rock masses are Jinchanggouliang and Xiduimiangou. The rock mass of Jinchanggouliang is gneissic granite and intruded into the Jianping Group of Archean. The Xiduimiangou rock mass intruded into the Jianping Group of Archean and the Tiaojishan Formation of Jurassic. The rock mass is divided into central phase and marginal phase, with the central phase being quartz-monzonite porphyry and the marginal phase being quartz monzonite. In addition, the diorite porphyry, syenite porphyry, rhyolite porphyry, lamprophyre and other dykes are relatively developed.
Fault structures in the mining areas are well developed, mainly extending in NE and EW direction. Erdaogou gold deposit is located at the intersection of NE Jianping-Mahugou fault and NW Beipiao-Jinchanggouliang fault. In addition, NE, EW and NW secondary faults are also developed in the mining areas. The form, size and occurrence of gold ore bodies are strictly controlled by secondary fault structures.
Erdaogou gold deposit is located in the east of Xiduimiangou rock mass (Fig. 2), and the surrounding rocks are mainly rhyolitic volcanic rock, quartz monzonite and quartz diorite. There are more than 60 numbered veins, most of which are more than 500 m in length, and 4 of which are more than 1 000 m in length. Among them, No. 16 vein is the longest (2 860 m), and 25 of which are 500–1 000 m in length. Medium-size veins account for about half. The veins can be divided into three groups according to the strike. The first group of veins (NNE- striking and NWW-dipping) is mainly located west of No. 101 vein. The second group of veins (EW-striking and N-dipping) is mainly located west of No. 101 vein. In the third group, the veins strike NW, and the veins at the NE side of the Dongduimiangou-Loushang fault dip to NE, while the veins at the SE side dip to SE. The ore veins in the mining areas are steeply inclined, with the inclination between 70º and 80º.
There are mainly two types of ore body, one is gold-bearing quartz vein type (Figs. 3a, 3b), and the other is tectonic alteration rock type (Fig. 3c). Gold-bearing quartz types in this deposit, which are quartz-pyrite veins and quartz- polymetallic sulfide veins. Tectonic alteration rock type ores are mainly pyrite sericite ores (Fig. 3d). The ore structure mainly consists of massive structure (Figs. 3f, 3h), brecciform structure (Fig. 3a), disseminated structure (Figs. 3e, 3i) and banded structure (Fig. 3g). The ore structure mainly consists of metasomatic relict structure, metasomatic false appearance structure, corona structure, droplet-like structure, cataclastic structure (Fig. 4e), metasomatic resorption structure (Fig. 4c) and including structure (Fig. 4d). The ore minerals are mainly pyrite (Figs. 4a–4e), chalcopyrite (Figs. 4a–4c), and the secondary minerals are sphalerite, galena (Figs. 4a–4d), chalcocite, bornite, arsenopyrite, and tetrahedrite, etc., while the gold minerals are native gold (Fig. 4f), native silver, and electrum. Gangue minerals are mainly quartz, followed by chlorite, sericite, K-feldspar and carbonate minerals. The alteration in the surrounding rock of the ore body is relatively developed, and the alteration zone is generally 5–10 m thick. The alteration types include potassic alteration, sericite-quartz alteration, chloritization, sericitization, adularization and carbonation.
Combined with field geology, ore structure, mineral symbiosis combination, cross-cutting relationship, the deposit ore-forming process is divided into the following three stages (Fig. 5), quartz-pyrite stage (stage Ⅰ), quartz-polymetallic sulfide stage (stage Ⅱ), quartz-carbonate stage (stage Ⅲ).
Fluid inclusion and laser Raman analysis experimental samples were selected from typical ore samples of different stages Ⅰ, Ⅱ, and Ⅲ from the middle 8 to the middle 19 of Erdaogou gold mine for testing, including milky and off-white quartz in stage Ⅰ, smoky gray and off-white quartz in stage Ⅱ, and white quartz in stage Ⅲ. These samples were firstly ground into double-faced sectioning thin sections about 0.2 mm thick in the chamber, soaked in alcohol for about 24 h and then washed and dried with clean water. Based on the petrography of fluid inclusions, representative inclusions at different stages were selected for micrometric measuring temperature and laser Raman spectroscopy. The microscopic measurement of mineral fluid inclusions and the laser Raman component test of the single fluid inclusions were carried out in the Geological Fluid Laboratory, College of Earth Sciences, Jilin University, and the Analysis and Test Center, Beijing Institute of Geology, Nuclear Industry, respectively. The inclusions were observed using Carl Zeiss Axiolab microscope (10×50) from Germany. The temperature measuring instrument is UK Linkamthms-600 cold and hot platform. Before the test, artificial 25% CO2-H2O and pure H2O inclusions (international standard) were used for systematic calibration. The temperature control range of the instrument is 195–600 ºC, and the temperature measurement precision is ±0.1 ºC when the temperature is less than 31 ºC, ±1 ºC when the temperature is between 31 ºC and 300 ºC, and ±2 ºC when the temperature is greater than 300 ºC. Specific analysis process can be seen from Wang et al. (2013). The laser Raman probe analysis test experiment was completed on the RM2000 laser Raman probe produced by Renishaw company in the UK. The Ar ion laser was used, the wavelength was 514 nm, the measured light spectrum counting time was 30 s, the scanning frequency was once, the scanning range was 1 000–4 000 cm-1, and the spectral resolution was 2 cm-1. Specific analysis process can be seen in related articles (Wang et al., 2013).
Seven quartz samples used for H-O isotope analysis were taken from quartz-sulfide veins. The sample was tested on the Finnigan MAT253 gas isotope mass spectrometer at the laboratory of stable isotopes, Beijing Institute of Geology, Nuclear Industry. The BrF5 method was used to analyze the oxygen isotope of quartz, and the analysis accuracy was better than 0.2‰. According to the average uniform temperature (T) of fluid inclusions in each ore-forming stage, the approximate value of δ18OH2O with quartz equilibrium fluid was obtained by Clayton et al.'s (1972) oxygen isotope separation equilibrium equation between quartz and water (1 000lnα=3.38×106/T2– 3.40). Hydrogen isotope analysis directly obtained the water in the inclusions by explosion method (Coleman et al., 1982), and replaced the hydrogen in the effluent by zinc reduction method, with analysis accuracy better than 1‰. The experimental results of hydrogen and oxygen isotopes are given according to the standard mean ocean water (SMOW). Specific experimental procedures, instrument parameters and standard samples can be referred to Liu et al. (2013).
Eight sulfide samples for sulfur and lead isotopic analyses were taken from sulfide-bearing veins. Most of these sulfides are symbiotic and are the products of hydrothermal metallogenic stage. The test sample was broken and screened to 60–80 meshes, and the corresponding single mineral was selected under binoculars to ensure its purity of more than 99%. Then the single mineral sample was washed with distilled water and dried at low temperature, and then the pure single mineral sample was ground to 200-mesh in an agate bowl for testing. Sulfur isotope test process, the single sulfide mineral mixed with cuprous oxide according to certain proportion, under the vacuum state to reflect oxide and sulfur dioxide gas, heat collected by freezing method, and then use the Delta Ⅴ Plus type gas isotope mass spectrometer analysis, sulfur isotopic composition of measurement results on the basis of the CDT, analysis precision is better than that of ±0.2‰. Lead isotope testing, single sulfide mineral in the Teflon crucible with HF acid to dissolve, reoccupy HCl chloride, fluoride can be converted to and then gets the acid was used to extract the sample, and purification of lead sample with anion exchange with ISOPROBE-T lead isotope analysis, thermal surface ionization mass spectrometer for 1 mu g lead 208Pb/206Pb, the analysis accuracy is better than 0.05‰. The above sulfur and lead isotope analysis was completed at the Laboratory of Stable Isotopes, Beijing Institute of Geology, Nuclear Industry. Specific experimental procedures, instrument parameters and standard samples can be referred to Liu et al. (2013).
The main minerals observed in fluid inclusions (Fls) are quartz of stage Ⅰ, II and III. According to Lu (2008), we selected the Fls of primary origin with random isolated distribution or cluster distribution in quartz for temperature measurement, to ensure the validity of the data and reflect the ore-forming fluid in Fls. Two compositional types of fluid inclusions (Fig. 6) were identified based on their phases at room temperature, their observed phase transitions during heating and freezing runs, and from laser Raman spectroscopy. Type I is aqueous (H2O-NaCl; W-type) and type II is aqueous-carbonic (CO2-H2O-NaCl; C-type).
The W-type Fls are present in stage Ⅰ, II and III of quartz, and they account for 80% of the total fluid inclusion population. These fluid inclusions are two-phase inclusions composed of liquid water (LH2O) and vapor water (VH2O) at room temperature. Most of them are elliptic, oblong and irregular in shape, with sizes between 2–14 μm and most of them between 3–9 μm. The vapor-liquid ratio is generally low (less than 30%), most of which are between 10%–25%.
C-type fluid inclusions usually develop in quartz of stage Ⅱ and are often associated with W-type Fls. It is mainly composed of liquid water, liquid CO2 and vapor CO2 (LH2O+LCO2+VCO2).
The CO2 volumetric proportions of the inclusions at room temperature vary between 15% and 30%. Most of them are elliptic and irregular in shape, with sizes between 2–12 μm and most of them between 3–10 μm. They occur mainly in the form of isolated individual inclusions or clusters inclusions arranged at random.
The microscopic temperature of W- and C-type fluid inclusions in quartz minerals was measured. The microscopic temperature data and calculation parameters of the single inclusion in different symbiotic stages are shown in Table 1 and graphically illustrated in Fig. 7.
| Stage | Type | Tm-CO2(℃) | Tm-cla(℃) | Th-CO2(℃) | Tm-ice(℃) | Th(℃) | Salinity(wt.% NaCl equiv.) | CO2 density(g/cm3) | Estimated pressures(MPa) |
| I | W | -7.6– -4.9 | 334–395 | 7.72–11.23 | 91.34–108.81 | ||||
| II | W | -20.7– -1.3 | 214–333 | 2.24–23.18 | |||||
| C | -61.2– -57.6 | 8.5–9.9 | 20.6–30.1 | 268–364 | 0.20–2.96 | 0.59–0.78 | 56.56–91.61 | ||
| III | W | -3.2– -0.2 | 172–272 | 0.35–5.25 | 35.21–71.16 |
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For quartz-pyrite stage (stage Ⅰ), only W-type fluid inclusions were observed in quartz. Their final ice melting temperatures (Tm-ice) range from -7.6 to -4.9 ºC, and their salinities range from 7.72 wt.% to 11.23 wt.% NaCl equiv. The inclusions yielded relatively high homogenization temperatures (Tm-hot) of 334–395 ºC, densities of 0.67–0.74 g/cm3, and pressure of 91.34–108.81 MPa.
Quartz from the quartz-polymetallic sulfide stage (stage Ⅱ) contains W-and C-type Fls. The W-type Fls yield an ice melting temperatures (Tm-ice) of -20.7– -1.3 ºC, and salinities of 2.24 wt.%–23.18 wt.% NaCl equiv. The Fls are homogenized to liquid phase at temperatures of 214–333 ºC, and corresponding densities of 0.69–1.00 g/cm3.The melting temperature of solid CO2 of C-type inclusions is between -61.2 and -57.6 ºC, which is lower than the triple point temperature of pure CO2 (-56.6 ºC). The melting temperature of the clathrate (Tm-cla) is between 8.5 and 9.9 ºC, and the salinity of the inclusion is between 0.20 wt.% and 2.96 wt.% NaCl equiv. The homogeneous temperatures (Th-CO2) of CO2 are between 20.6 and 30.1 ºC with the calculated densities of CO2 ranging from 0.59 to 0.78 g/cm3. The Fls are completely homogenized to liquid at temperatures (Tm-hot) of 268 to 364 ºC with the pressure of 56.56–91.61 MPa.
Only W-type fluid inclusions were observed in quartz of quartz-calcite stage (stage Ⅲ). Their final ice melting temperatures (Tm-ice) range from -3.2 to -2 ºC, and their salinities range from 0.35 wt.% to 5.25 wt.% NaCl equiv. The inclusions yielded relatively high homogenization temperatures (Tm-hot) of 172–272 ºC, densities of 0.76–0.93 g/cm3, and pressure of 35.21–71.16 MPa.
In order to determine the composition of the fluid inclusions, representative fluid inclusions were selected for laser Raman analysis. The results are shown in Fig. 8. The W-type inclusions from stage Ⅰ to III consist mainly of H2O but contain minor CO2. The C-type inclusions of stage Ⅱ contain a vapor phase of CO2 and a liquid phase with a large amount of water.
The sulfur isotope analysis results of sulfide in Erdaogou deposit are shown in Table 2 and Fig. 9. Eight sulfide samples (pyrite and galena) from Erdaogou give the δ34SV-CDT values of -2.2‰ to 2.3‰. The δ34SV-CDT values of pyrite separates range from -0.6‰ to 0.2‰, averaging of -0.15‰ (n=4). Galena grains yield δ34SV-CDT values of -2.2‰ to -1.3‰, with an average of -1.65‰ (n=4). Lead isotope data are shown in Table 3 and Fig. 10. The 208Pb/204Pb, 207Pb/204Pb and 206Pb/204Pb values of 8 sulfide samples are between 36.991–37.960, 15.318–15.660 and 17.065–17.458, respectively.
| Sample No. | Mineral | δ34SV-CDT (%) | Data sources |
| EDG16 | Pyrite | 2.3 | |
| EDG6 | Pyrite | -0.2 | |
| EDG2 | Pyrite | -0.7 | |
| EDG-S-1 | Pyrite | -0.2 | |
| EDG-S-2 | Pyrite | 0.9 | |
| EDG-S-3 | Pyrite | -0.1 | Sun et al., 2013 |
| EDG-S-4 | Pyrite | -0.6 | |
| EDG-S-5 | Pyrite | 0.3 | |
| EDG-1-1a | Pyrite | 0.2 | |
| EDG-1-1b | Galena | -2.2 | |
| EDG-1-1c | Galena | -1.8 | |
| EDG-1-10 | Pyrite | -0.6 | This study |
| EDG-1-13a | Galena | -1.3 | |
| EDG-1-13b | Galena | -1.3 | |
| EDG-1-15 | Pyrite | 0.1 | |
| EDG-3-8 | Pyrite | -0.3 |
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| Sample No. | Mineral | 206Pb/204Pb | 2σ | 207Pb/204Pb | 2σ | 208Pb/204Pb | 2σ | μ | ω | Data sources |
| EDG14 | Pyrite | 17.28 | 0.002 | 15.403 | 0.001 | 37.394 | 0.003 | 9.22 | 36.68 | Hou et al., 2011 |
| EDG16 | Pyrite | 17.205 | 0.002 | 15.408 | 0.002 | 37.353 | 0.004 | 9.25 | 37.02 | |
| EDG6 | Pyrite | 17.211 | 0.002 | 15.399 | 0.001 | 37.341 | 0.004 | 9.23 | 36.83 | |
| EDG2 | Pyrite | 17.074 | 0.002 | 15.398 | 0.002 | 37.246 | 0.004 | 9.25 | 37.26 | |
| EDG-1-1a | Pyrite | 17.233 | 0.002 | 15.461 | 0.002 | 37.52 | 0.005 | 9.35 | 38.15 | This study |
| EDG-1-1b | Galena | 17.214 | 0.003 | 15.426 | 0.003 | 37.417 | 0.008 | 9.28 | 37.44 | |
| EDG-1-1c | Galena | 17.242 | 0.003 | 15.456 | 0.002 | 37.513 | 0.005 | 9.34 | 38.01 | |
| EDG-1-10 | Pyrite | 17.172 | 0.003 | 15.458 | 0.003 | 37.489 | 0.005 | 9.36 | 38.38 | |
| EDG-1-13a | Galena | 17.218 | 0.007 | 15.416 | 0.004 | 37.39 | 0.013 | 9.26 | 37.19 | |
| EDG-1-13b | Galena | 17.239 | 0.004 | 15.409 | 0.003 | 37.38 | 0.008 | 9.24 | 36.94 | |
| EDG-1-15 | Pyrite | 17.200 | 0.003 | 15.473 | 0.004 | 37.545 | 0.013 | 9.38 | 38.61 | |
| EDG-3-8 | Pyrite | 17.228 | 0.003 | 15.476 | 0.003 | 37.561 | 0.007 | 9.38 | 38.53 |
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Hydrogen and oxygen isotope compositions of quartz-polymetallic sulfide stage (stage Ⅱ) are shown in Table 4 and Fig. 11. The measured δ18Oquzrtz(SMOW) of stage Ⅱ range from 9.68‰ to 17.2‰ whereas the δDH2O values range from -110.9‰ to -71‰. The calculation formula of Clayton et al. (1972) was used to recalculate the values of δ18OH2O between 3.2‰ and 11.8‰.
| Sample No. | Stage | Mineral | Th (ºC) | 18OV-SMOW‰ | δ18OH2O‰ | δDH2O‰ | Data sources |
| EDG-1-10 | Stage Ⅱ | Quartz | 290 | 17.0 | 11.6 | -91.1 | |
| EDG-1-13 | Quartz | 290 | 15.1 | 9.7 | -86.7 | ||
| EDG-1-15 | Quartz | 290 | 16.8 | 11.4 | -84.6 | ||
| EDG-5-1a | Quartz | 290 | 17.0 | 11.6 | -81.6 | ||
| EDG-5-1b | Quartz | 290 | 17.3 | 11.9 | -74.6 | ||
| EDG-3-8 | Quartz | 290 | 16.6 | 11.2 | -78.7 | ||
| EDG14 | Quartz | 14.7 | 7.9 | -110.9 | Hou et al., 2011 | ||
| EDG16 | Quartz | 14.2 | 7.4 | -100.7 | |||
| EDG6 | Quartz | 14.3 | 7.5 | -97.8 | |||
| 93-54 | Quartz | 270 | 15.7 | 7.6 | -72 | Pang, 1998 | |
| 93-57 | Quartz | 285 | 11.5 | 4.0 | -84 | ||
| 93-61 | Quartz | 300 | 14.3 | 7.4 | -81 | ||
| 93-66 | quartz | 294 | 13.2 | 6.1 | -71 | ||
| 93-15 | quartz | 242 | 12.5 | 3.2 | -85 | ||
| V58-3-1 | quartz | 320 | 10.3 | 4.1 | -96.7 | Wei, 2001 | |
| V58-3-3 | quartz | 300 | 9.7 | 6.9 | -93.3 |
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Detailed field observation of Erdaogou gold deposit and the exploration results show that the majority of mineralization is controlled by NE, EW and NW trending faults with lesser amounts located within quartz-monzonite porphyry and quartz monzonite and volcanic rocks of the Tiaojishan Formation. Ore types include massive, disseminated, brecciated, veinlet- reticulated, and quartz-sulfide veins. The host rock underwent obvious hydrothermal alteration. The alteration types include potassic alteration, sericite-quartz alteration, chloritization, sericitization, adularization and carbonation. The sulfide assemblage is dominated by pyrite and contains a small amount of galena and sphalerite. The alteration characteristics and mineralogical characteristics of Erdaogou deposit are similar to those of low-sulfidation epithermal hydrothermal deposits in other areas.
Stable sulfur isotopes provide useful tools for constraining the origin of sulfur (Ohmoto, 1986). The lack of typical sulfate minerals in Erdaogou deposit indicates that δ34S values of sulfide can represent the sulfur isotope ratios of the most ores (Wang et al., 2020). The narrow range of δ34S compositions (Fig. 9) of sulfides in Erdaogou deposit indicates that the formation of sulfides under stable chemical and physical conditions comes from a relatively homogeneous source (Ohmoto and Goldhaber, 1997; Ohmoto and Rye, 1979). The values range from -2.2‰ to 2.3‰, with an average of -0.9‰. This is consistent with sulfide from magma and magma-related sources, whose isotopic composition ranges from -3‰ to 1‰ (Guo et al., 2019; Ohmoto and Rye, 1979). This indicates that the sulfur and its associated metals in the deposit are magmatic origin and may be the products of magmatic volatilization or subvolcanic rock leaching (Akaryali and Akbulut, 2016).
Since U and Th in sulphide minerals are negligible and lead concentrations are high, the isotopic composition of lead in sulphide can represent the source of lead (Zartman and Doe, 1981). The lead isotope ratio in Erdaogou deposit indicates that there are two possible sources of lead, one is the single homogeneous lead source, the other is heterogeneous source of multiple isotopes. The calculated μ and ω values of pyrite and galena samples are of 9.24–9.38, 36.94–38.61, respectively. The μ values is between the mantle (8–9) and the average crustal value of 9.74 (Doe and Zartman, 1979). The ω values are close to the average crustal value (36.84). The lead isotope data are located between the lower crust and mantle evolution lines in the Pb isotopic tectonic discrimination diagram and are closer to the mantle evolution line (Fig. 10) (Zartman and Doe, 1981). These suggest that lead is a mixture, possibly derived from a mixture of lower crust and possible mantle components.
The hydrogen and oxygen isotope values of Erdaogou deposit indicate that magmatic fluid may be involved in the hydrothermal system. However, the metallogenic system of Erdaogou deposit cannot be simply considered to be related to the specific magmatic events. Studies have shown that, especially under the condition of low water/rock ratio, isotope ratios similar to Erdaogou deposit can also be obtained through the long-term interaction between atmospheric water and igneous surrounding rocks, particularly at low water/rock ratios (Taylor, 1997), and/or modified through boiling (Ashrafpour et al., 2012; Alderton and Fallick, 2000), mixing with magma water, or any combinations of these processes can obtain the above hydrogen and oxygen isotopic composition (Fig. 11). At epithermal temperatures, boiling causes 16O and H to be fractionated into the vapor phase, thus increasing the δ18O and δD values of the hydrothermal fluids (Alderton and Fallick, 2000). Therefore, enrichment of 18O may be at least partly attributable to the boiling process. Mixing with magmatic water could also explain the δ18O and δD value shifts, however, any magmatic fluid must have a relatively low salinity, consistent with the dilute fluids in Erdaogou deposit (Audétat et al., 2008).
In hydrothermal solutions, gold mainly migrates in the form of gold bisulfide complexes such as Au(HS)2− or Au(HS)0 (Mikucki, 1998; Gammons et al., 1994). In near-neutral to weakly alkaline ore-forming fluids at a pressure of 200 MPa and temperatures of 200–400 ºC, Au(HS)2− and Au(HS)0 are the primary Au-transporting complexes (Benning and Seward, 1996). Gold is commonly accompanied by Au-hosting sulfides. In the Erdaogou deposit, these are namely pyrite and galena. The gold bisulfide was therefore the most likely species for gold transport.
Petrographic studies of fluid inclusions show that different types of fluid inclusions (W-, C-) exist in the quartz veins of Erdaogou gold deposit at different metallogenic stages. According to the composition, temperature, salinity and related mineralization of hydrothermal fluid, the properties of hydrothermal fluid can be inverted, the evolution model can be established, and the mineralization process can be revealed.
In the early stage of mineralization (stage Ⅰ), a small amount of pyrite and quartz were precipitated together. The fluid inclusions in the quartz crystals of stage Ⅰ were mainly W-type, with high homogenization temperature (334–395 ºC) and medium salinity (7.72 wt.%–11.23 wt.% NaCl equiv.). The W-type fluid inclusions in the quartz-polymetallic sulfide stage (stage Ⅱ) are homogenized at 214–333 ºC, with medium salinity (2.24 wt.%–23.18 wt% NaCl equiv.), and C-type inclusions yielded homogenization temperatures from 268 to 364 ºC, with the salinities of 0.20 wt.%–2.96 wt.% NaCl equiv. Coexisting vapor-and liquid-rich W Fls with variable vapor-to-liquid ratios are potential indicators of boiling in the early and main stages (Simmons et al., 2005; White and Hedenquist, 1995). At the same time, W-type inclusions have different densities but similar temperature. The complete homogenization temperature of C-type inclusions is similar to that of W-type inclusions, all of which indicate that fluid boiling play an important mechanism responsible for gold and sulfide deposition in Erdaogou hydrothermal systems. Fluid boiling can cause the escape of volatile components such as CO2. The decrease of CO2 content in the fluid will lead to the increase of pH value of the fluid and the decrease of PCO2 will lead to the decomposition of gold-bearing complex and the reduction of gold solubility. The decrease of temperature and pressure will lead to the massive precipitation of gold and other sulfide in this stage. At this stage, a large amount of pyrite and a small amount of galena, sphalerite and other sulfide were precipitated out of the fluid. W-type fluid inclusions in quartz of quartz-calcite stage (stage Ⅲ) have much lower homogenization temperatures of 172–272 ºC, with salinities of 0.35 wt.% to 5.25 wt.% NaCl equiv. As the temperature and pressure of the fluid system decrease, quartz and calcite are gradually separated from the fluid.
Therefore, the hydrothermal fluid in Erdaogou deposit has the characteristics of high-medium temperature and medium salinity in the early stage, and the temperature and salinity gradually decrease from the main metallogenic stage to the late quartz-calcite stage (Fig. 12). Lithologic observation and laser Raman study of fluid inclusions indicate that the ore-forming fluid in the early stage and main stage of mineralization belongs to the CO2-H2O-NaCl system with medium high temper-ature and low salinity, and the fluid in the late stage of mineralization evolves into the H2O-NaCl system with low temperature and low salinity.
Metallogenic fluid pressure and temperature decrease, fluid mixing and boiling, fluid/rock interaction and phase separation all lead to metal precipitation (Ramboz et al., 1982). Modeling studies have shown that fluid boiling and mixing are the most efficient processes in hydrothermal systems and can lead to the deposition of ore and gangue minerals (Hedenquist and Lowenstern, 1994).
The homogenization temperatures of fluid inclusions from stage Ⅰ to stage Ⅲ in the Erdaogou deposit are in the range of 334–395, 214–364 and 172–272 ºC, showing relatively significant variations. However, the decrease in salinity from stage Ⅰ to stage Ⅲ was not obvious. These results indicate that the apparent temperature variation is more likely to cause precipitation of the ore. The isotopes of hydrogen and oxygen indicate that fluid boiling or mixing may occur during the evolution of the hydrothermal system of Erdaogou gold deposit and lead to the precipitation of gold-bearing fluid. Abundant calcite veins, calcite-quartz symbiosis, and brecciform structures may be further evidence of boiling (Simmons et al., 2000; Simmons and Christenson, 1994). Fluid boiling can cause the escape of volatile components such as CO2 and H2S, CO2 reduction caused by the increase of solution pH value, leading to complex decomposition of Au and solubility decrease of Au, the interaction of the two and the decrease of temperature led to the massive precipitation of gold and other sulfide in this stage.
Low-sulfidation epithermal deposits are thought to be formed by the near-neutral pH dilute fluids in which deep circulating groundwater mixes with magma components (Corbett and Leach, 1998). The gangue assemblages of Erdaogou deposit are mainly quartz-sericite-adularia, and the ore minerals are characterized by a large amount of pyrite and a small amount of galena and sphalerite. The metallogenic hydrothermal fluid is characterized by weak acid to weak alkalinity (pH=5.69–7.20) (Pang and Qiu, 1996), which is consistent with sericite and quartz commonly found in the Erdaogou gold deposit, indicating the formation of a near-neutral pH fluids (Heinrich et al., 2004). In addition, pyrite-arsenopyrite-sphalerite assemblage is commonly developed in hydrothermal deposits with low sulfide temperature. In addition, the temperature and salinity of the quartz-polymetallic sulfide stage are similar to that of the typical epithermal hydrothermal deposits elsewhere.
(1) The hydrothermal metallogenic process of Erdaogou gold deposit can be divided into three stages, i.e., quartz-pyrite stage (stage Ⅰ), quartz-polymetallic sulfide stage (stage Ⅱ) and quartz-calcite stage (stage Ⅲ).
(2) The results of sulfur and lead isotopes reveal that the ore-forming components come from the mixture of crust and mantle. Oxygen and hydrogen isotope data at Erdaogou indicate that magmatic fluid and meteoric water may both be involved in the hydrothermal system.
(3) The major types of fluid inclusions are aqueous type (W-type) and aqueous-carbonic type (C-type) inclusions. The ore-forming fluid is CO2-H2O-NaCl system which has the characteristics of medium-low temperatures, moderate salinities and low densities. Based on the geological characteristics of the deposit, fluid inclusion and isotopic results, it is considered that the temperature decrease, fluid boiling are the key factors that lead to the ore precipitation and the genetic type of Erdaogou gold deposit is low-sulfidation epithermal deposit.
ACKNOWLEDGMENTS: This research was supported by the National Key Development Project (No. 2018YFC0603804), China Geological Survey (No. DD20190042) and Opening Foundation of Key Laboratory of Mineral Resources Evaluation in Northeast Asia, Ministry of Natural Resources. We thank the reviewers and the editors for constructive comments. The final publication is available at Springer via https://doi.org/10.1007/s12583-020-1068-5.| Akaryali, E. , Akbulut, K. , 2016. Constraints of C-O-S Isotope Compositions and the Origin of the Ünlüpınar Volcanic-Hosted Epithermal Pb-Zn±Au Deposit, Gümüşhane, NE Turkey. Journal of Asian Earth Sciences, 117: 119-134. https://doi.org/10.1016/j.jseaes.2015.12.012 |
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Figures(12) / Tables(4)
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Fan Yang, Xuejiao Pang, Bin Li, Jingsheng Chen, Jilong Han, Miao Liu, Zhongzhu Yang, Yan Wang, Yi Shi. Geological, Fluid Inclusion, H-O-S-Pb Isotope Constraints on the Genesis of the Erdaogou Gold Deposit, Liaoning Province. Journal of Earth Science, 2021, 32(1): 103-115. doi: 10.1007/s12583-020-1068-5
| Stage | Type | Tm-CO2(℃) | Tm-cla(℃) | Th-CO2(℃) | Tm-ice(℃) | Th(℃) | Salinity(wt.% NaCl equiv.) | CO2 density(g/cm3) | Estimated pressures(MPa) |
| I | W | -7.6– -4.9 | 334–395 | 7.72–11.23 | 91.34–108.81 | ||||
| II | W | -20.7– -1.3 | 214–333 | 2.24–23.18 | |||||
| C | -61.2– -57.6 | 8.5–9.9 | 20.6–30.1 | 268–364 | 0.20–2.96 | 0.59–0.78 | 56.56–91.61 | ||
| III | W | -3.2– -0.2 | 172–272 | 0.35–5.25 | 35.21–71.16 |
DownLoad:
CSV
| Sample No. | Mineral | δ34SV-CDT (%) | Data sources |
| EDG16 | Pyrite | 2.3 | |
| EDG6 | Pyrite | -0.2 | |
| EDG2 | Pyrite | -0.7 | |
| EDG-S-1 | Pyrite | -0.2 | |
| EDG-S-2 | Pyrite | 0.9 | |
| EDG-S-3 | Pyrite | -0.1 | Sun et al., 2013 |
| EDG-S-4 | Pyrite | -0.6 | |
| EDG-S-5 | Pyrite | 0.3 | |
| EDG-1-1a | Pyrite | 0.2 | |
| EDG-1-1b | Galena | -2.2 | |
| EDG-1-1c | Galena | -1.8 | |
| EDG-1-10 | Pyrite | -0.6 | This study |
| EDG-1-13a | Galena | -1.3 | |
| EDG-1-13b | Galena | -1.3 | |
| EDG-1-15 | Pyrite | 0.1 | |
| EDG-3-8 | Pyrite | -0.3 |
DownLoad:
CSV
| Sample No. | Mineral | 206Pb/204Pb | 2σ | 207Pb/204Pb | 2σ | 208Pb/204Pb | 2σ | μ | ω | Data sources |
| EDG14 | Pyrite | 17.28 | 0.002 | 15.403 | 0.001 | 37.394 | 0.003 | 9.22 | 36.68 | Hou et al., 2011 |
| EDG16 | Pyrite | 17.205 | 0.002 | 15.408 | 0.002 | 37.353 | 0.004 | 9.25 | 37.02 | |
| EDG6 | Pyrite | 17.211 | 0.002 | 15.399 | 0.001 | 37.341 | 0.004 | 9.23 | 36.83 | |
| EDG2 | Pyrite | 17.074 | 0.002 | 15.398 | 0.002 | 37.246 | 0.004 | 9.25 | 37.26 | |
| EDG-1-1a | Pyrite | 17.233 | 0.002 | 15.461 | 0.002 | 37.52 | 0.005 | 9.35 | 38.15 | This study |
| EDG-1-1b | Galena | 17.214 | 0.003 | 15.426 | 0.003 | 37.417 | 0.008 | 9.28 | 37.44 | |
| EDG-1-1c | Galena | 17.242 | 0.003 | 15.456 | 0.002 | 37.513 | 0.005 | 9.34 | 38.01 | |
| EDG-1-10 | Pyrite | 17.172 | 0.003 | 15.458 | 0.003 | 37.489 | 0.005 | 9.36 | 38.38 | |
| EDG-1-13a | Galena | 17.218 | 0.007 | 15.416 | 0.004 | 37.39 | 0.013 | 9.26 | 37.19 | |
| EDG-1-13b | Galena | 17.239 | 0.004 | 15.409 | 0.003 | 37.38 | 0.008 | 9.24 | 36.94 | |
| EDG-1-15 | Pyrite | 17.200 | 0.003 | 15.473 | 0.004 | 37.545 | 0.013 | 9.38 | 38.61 | |
| EDG-3-8 | Pyrite | 17.228 | 0.003 | 15.476 | 0.003 | 37.561 | 0.007 | 9.38 | 38.53 |
DownLoad:
CSV
| Sample No. | Stage | Mineral | Th (ºC) | 18OV-SMOW‰ | δ18OH2O‰ | δDH2O‰ | Data sources |
| EDG-1-10 | Stage Ⅱ | Quartz | 290 | 17.0 | 11.6 | -91.1 | |
| EDG-1-13 | Quartz | 290 | 15.1 | 9.7 | -86.7 | ||
| EDG-1-15 | Quartz | 290 | 16.8 | 11.4 | -84.6 | ||
| EDG-5-1a | Quartz | 290 | 17.0 | 11.6 | -81.6 | ||
| EDG-5-1b | Quartz | 290 | 17.3 | 11.9 | -74.6 | ||
| EDG-3-8 | Quartz | 290 | 16.6 | 11.2 | -78.7 | ||
| EDG14 | Quartz | 14.7 | 7.9 | -110.9 | Hou et al., 2011 | ||
| EDG16 | Quartz | 14.2 | 7.4 | -100.7 | |||
| EDG6 | Quartz | 14.3 | 7.5 | -97.8 | |||
| 93-54 | Quartz | 270 | 15.7 | 7.6 | -72 | Pang, 1998 | |
| 93-57 | Quartz | 285 | 11.5 | 4.0 | -84 | ||
| 93-61 | Quartz | 300 | 14.3 | 7.4 | -81 | ||
| 93-66 | quartz | 294 | 13.2 | 6.1 | -71 | ||
| 93-15 | quartz | 242 | 12.5 | 3.2 | -85 | ||
| V58-3-1 | quartz | 320 | 10.3 | 4.1 | -96.7 | Wei, 2001 | |
| V58-3-3 | quartz | 300 | 9.7 | 6.9 | -93.3 |
DownLoad:
CSV
| Stage | Type | Tm-CO2(℃) | Tm-cla(℃) | Th-CO2(℃) | Tm-ice(℃) | Th(℃) | Salinity(wt.% NaCl equiv.) | CO2 density(g/cm3) | Estimated pressures(MPa) |
| I | W | -7.6– -4.9 | 334–395 | 7.72–11.23 | 91.34–108.81 | ||||
| II | W | -20.7– -1.3 | 214–333 | 2.24–23.18 | |||||
| C | -61.2– -57.6 | 8.5–9.9 | 20.6–30.1 | 268–364 | 0.20–2.96 | 0.59–0.78 | 56.56–91.61 | ||
| III | W | -3.2– -0.2 | 172–272 | 0.35–5.25 | 35.21–71.16 |
| Sample No. | Mineral | δ34SV-CDT (%) | Data sources |
| EDG16 | Pyrite | 2.3 | |
| EDG6 | Pyrite | -0.2 | |
| EDG2 | Pyrite | -0.7 | |
| EDG-S-1 | Pyrite | -0.2 | |
| EDG-S-2 | Pyrite | 0.9 | |
| EDG-S-3 | Pyrite | -0.1 | Sun et al., 2013 |
| EDG-S-4 | Pyrite | -0.6 | |
| EDG-S-5 | Pyrite | 0.3 | |
| EDG-1-1a | Pyrite | 0.2 | |
| EDG-1-1b | Galena | -2.2 | |
| EDG-1-1c | Galena | -1.8 | |
| EDG-1-10 | Pyrite | -0.6 | This study |
| EDG-1-13a | Galena | -1.3 | |
| EDG-1-13b | Galena | -1.3 | |
| EDG-1-15 | Pyrite | 0.1 | |
| EDG-3-8 | Pyrite | -0.3 |
| Sample No. | Mineral | 206Pb/204Pb | 2σ | 207Pb/204Pb | 2σ | 208Pb/204Pb | 2σ | μ | ω | Data sources |
| EDG14 | Pyrite | 17.28 | 0.002 | 15.403 | 0.001 | 37.394 | 0.003 | 9.22 | 36.68 | Hou et al., 2011 |
| EDG16 | Pyrite | 17.205 | 0.002 | 15.408 | 0.002 | 37.353 | 0.004 | 9.25 | 37.02 | |
| EDG6 | Pyrite | 17.211 | 0.002 | 15.399 | 0.001 | 37.341 | 0.004 | 9.23 | 36.83 | |
| EDG2 | Pyrite | 17.074 | 0.002 | 15.398 | 0.002 | 37.246 | 0.004 | 9.25 | 37.26 | |
| EDG-1-1a | Pyrite | 17.233 | 0.002 | 15.461 | 0.002 | 37.52 | 0.005 | 9.35 | 38.15 | This study |
| EDG-1-1b | Galena | 17.214 | 0.003 | 15.426 | 0.003 | 37.417 | 0.008 | 9.28 | 37.44 | |
| EDG-1-1c | Galena | 17.242 | 0.003 | 15.456 | 0.002 | 37.513 | 0.005 | 9.34 | 38.01 | |
| EDG-1-10 | Pyrite | 17.172 | 0.003 | 15.458 | 0.003 | 37.489 | 0.005 | 9.36 | 38.38 | |
| EDG-1-13a | Galena | 17.218 | 0.007 | 15.416 | 0.004 | 37.39 | 0.013 | 9.26 | 37.19 | |
| EDG-1-13b | Galena | 17.239 | 0.004 | 15.409 | 0.003 | 37.38 | 0.008 | 9.24 | 36.94 | |
| EDG-1-15 | Pyrite | 17.200 | 0.003 | 15.473 | 0.004 | 37.545 | 0.013 | 9.38 | 38.61 | |
| EDG-3-8 | Pyrite | 17.228 | 0.003 | 15.476 | 0.003 | 37.561 | 0.007 | 9.38 | 38.53 |
| Sample No. | Stage | Mineral | Th (ºC) | 18OV-SMOW‰ | δ18OH2O‰ | δDH2O‰ | Data sources |
| EDG-1-10 | Stage Ⅱ | Quartz | 290 | 17.0 | 11.6 | -91.1 | |
| EDG-1-13 | Quartz | 290 | 15.1 | 9.7 | -86.7 | ||
| EDG-1-15 | Quartz | 290 | 16.8 | 11.4 | -84.6 | ||
| EDG-5-1a | Quartz | 290 | 17.0 | 11.6 | -81.6 | ||
| EDG-5-1b | Quartz | 290 | 17.3 | 11.9 | -74.6 | ||
| EDG-3-8 | Quartz | 290 | 16.6 | 11.2 | -78.7 | ||
| EDG14 | Quartz | 14.7 | 7.9 | -110.9 | Hou et al., 2011 | ||
| EDG16 | Quartz | 14.2 | 7.4 | -100.7 | |||
| EDG6 | Quartz | 14.3 | 7.5 | -97.8 | |||
| 93-54 | Quartz | 270 | 15.7 | 7.6 | -72 | Pang, 1998 | |
| 93-57 | Quartz | 285 | 11.5 | 4.0 | -84 | ||
| 93-61 | Quartz | 300 | 14.3 | 7.4 | -81 | ||
| 93-66 | quartz | 294 | 13.2 | 6.1 | -71 | ||
| 93-15 | quartz | 242 | 12.5 | 3.2 | -85 | ||
| V58-3-1 | quartz | 320 | 10.3 | 4.1 | -96.7 | Wei, 2001 | |
| V58-3-3 | quartz | 300 | 9.7 | 6.9 | -93.3 |
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