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Article

Characteristics and Metallogenic Significance of Fe-Mn Carbonate Minerals in the Erdaokan Ag Deposit, Heilongjiang Province, Northeast China: Constraints from Sm-Nd Geochronology and Trace Elements

by
Yuanjiang Yang
1,
Chenglu Li
1,
Zeyu Wang
2,3,*,
Huajuan Gu
1,
Wenpeng Yang
1,
Maowen Yuan
4,
Anzong Fu
1,
Bo Zheng
1,
Zhaoxun Cheng
1 and
Baoshan Liu
2,3
1
Natural Resources Survey Institute of Heilongjiang Province, Harbin 150036, China
2
Shenyang Geological Survey Center, China Geological Survey, Shenyang 110034, China
3
Northeast Geological S&T Innovation Center of China Geological Survey, Shenyang 110034, China
4
School of Earth Science and Resources, China University of Geosciences, Beijing 100083, China
*
Author to whom correspondence should be addressed.
Minerals 2024, 14(7), 655; https://doi.org/10.3390/min14070655
Submission received: 5 June 2024 / Revised: 20 June 2024 / Accepted: 21 June 2024 / Published: 26 June 2024
(This article belongs to the Special Issue Rare Metal and Related Deposits: Geology, Geochemistry and Mineralization)
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Abstract

:
Fe-Mn carbonate is the dominant mineral in the Erdaokan Ag deposit, which represents the first large independent silver deposit during the Late Triassic Period in the Duobaoshan Cu-Mo-Au mineralization concentrated area of Heilongjiang Province, NE China. The Fe-Mn carbonates in the deposit frequently co-exist with Ag minerals. Thus, the presence of Fe-Mn carbonates plays a crucial role in the ore-formation process, making their analysis essential for obtaining valuable metallogenic information about the Erdaokan deposit. Through microexamination, SEM and EDS analysis, a clear relationship between Fe-Mn carbonate minerals and Ag minerals was established. Furthermore, electron probe microanalysis, LA-ICP-MS, and Sr-Nd isotope tests were conducted to analyze Fe-Mn carbonates for significant metallogenic insights. The distribution pattern of trace elements and rare-earth elements in Fe-Mn carbonates is similar, characterized by Zr depletion (below 0.131 ppm), enrichment of light rare-earth elements, a noticeable deficit of Eu (δEu = 0.06–0.63), and an average Y/Ho value of 34.29, indicating the involvement of upper mantle-derived deep magma in the formation of ore-forming materials. The samples had a Sm-Nd isochron age of 233.7 ± 1.2 Ma, suggesting that the Erdaokan Ag deposit was formed during the Late Triassic Period. This study highlights the significance of Fe-Mn carbonate as a valuable mineral indicator for regional silver prospecting purposes, and confirms the Late Triassic Period as another important metallogenic stage in the Duobaoshan Cu-Mo-Au mineralization concentrated area.

1. Introduction

The Duobaoshan Cu-Mo-Au mineralization concentrated area, situated in the eastern part of the Xing’an–Mongolia orogenic belt, represents a region that has undergone superimposed transformations associated with the Paleo-Asian Ocean, Mongol-Okhotsk Ocean, and Pacific Ocean tectonic domains. This area is characterized by numerous ore deposits exhibiting rich mineral species and complex types, making it a focal point for research on ore prospecting and metallogenic theory in Northeast China. During the Caledonian period, the region was influenced by the subduction of the ancient Asian Ocean (480–470 Ma), resulting in the formation of porphyry-type deposits such as the Duobaoshan copper deposit [1,2,3] and the Tongshan copper deposit [4]. During the Indonesian and early Yanshanian periods, the region was influenced by the subduction of the Mongolian Okhotsk Ocean, resulting in the formation of a skarn-type Xiaodubaoshan copper deposit [5] and a hydrothermal Erdaokan silver deposit [6,7], both of which were formed between 240 and 230 Ma, and the skarn-type Sankuanggou iron deposit [8], which was formed between 180 and 170 Ma. Since the middle–late Yanshan period, the region has been mainly affected by the subduction of the Pacific Plate. Epithermal-type deposits such as Zhengguang gold deposits [9], Yongxin gold deposits [10], Sandaowanzi gold deposits [11], and Shangmachang gold deposits [12] were generated between 150 and 100 Ma. Among these deposits, the Erdaokan Ag deposit stands out as a recently discovered large-scale independent silver deposit from the Late Triassic Period [6,7]. Its unique formation age renders it an important research site for understanding the metallogenic mechanisms within both the Duobaoshan Cu-Mo-Au mineralization concentrated area and the CAOB (Central Asian Orogenic Belt). Although some mineralogical studies have been conducted on this deposit, there remains uncertainty regarding its precise origin and the formation processes of the ore-forming fluid [13,14,15].
Fe-Mn carbonates, commonly encountered in deposits, serve as indicators for the nature, environment, and evolution of ore-forming fluids [16,17,18,19,20,21,22,23,24,25]. In our study, Fe-Mn carbonate is a pervasive mineral within the Erdaokan deposit and occurs abundantly in the ore. Microscopically, there is a conspicuous symbiotic relationship between Ag and Fe-Mn carbonate. Therefore, it is imperative to conduct a comprehensive analysis of the mineral composition and elemental distribution characteristics of Fe-Mn carbonates to gain profound insights into the specific ore-forming processes associated with the Erdaokan deposit.
Based on a comprehensive geological investigation of the Erdaokan deposit, this study employed various analytical techniques, including electron probe microanalysis (EPMA), scanning electron microscopy (SEM), energy-dispersive spectrometry (EDS), and laser ablation–inductively coupled plasma–mass spectrometry (LA-ICP-MS), to trace the origin of ore-forming fluids. Additionally, Sm-Nd isotope testing was utilized to obtain the metallogenic age of the Erdaokan deposit. Building upon these experimental findings, we have refined the metallogenic model for the Erdaokan silver deposit to better reflect its actual formation process. The findings confirm that the Late Triassic Period was a significant period for ore-formation in the Duobaoshan Cu-Mo-Au mineralized area, and highlight Fe-Mn carbonate as a promising exploration indicator in this region. Fe-Mn carbonate and Ag minerals such as pyrargyrite and argentite, have an intimate symbiotic relationship, and these findings provide valuable insights into ore-forming element migration, and offer new guidance for prospecting strategies in the Duobaoshan Cu-Mo-Au mineralization concentrated area.

2. Geological Setting

2.1. Regional Geology

The Erdaokan silver deposit belongs to the Duobaoshan Cu-Mo-Au mineralization concentrated area, which is one of the most significant metallogenic regions in Northeast China. It is situated in the eastern part of the Central Asian orogenic belt, and is northeast of the Greater Khingan mountains (Figure 1a). The Greater Khingan mountains, an extensive accretionary orogenic belt connecting Siberia and North China Craton [26,27], are linked to the Pacific Plate in the east and the Mongol-Okhotsk plate in the west. From northwest to southeast, there are four blocks: the Erguna block, the Xing’an block, the Songnen–Zhangguangcailing block, and the Jiamusi block (Figure 1b). This region exhibits a Paleozoic (Ordovician–Silurian, Carboniferous, Permian) arc basin system, along with magmatic arcs and Mesozoic volcano-sedimentary superposition basins. The geological evolution of this area can be divided into two stages: during the Paleozoic period, it was influenced by the Paleo–Asian Marine tectonic system; from the late Paleozoic to the early Mesozoic period, it experienced microcontinent amalgamation, leading to the final closure of the Paleo–Asian Ocean [28]. In addition to these influences, during the Mesozoic, NE–SW trending fault systems formed due to the Circum–Pacific tectonic system, and the Okhotsk tectonic system in Mongolia resulted in the formation of various epithermal and porphyry deposits, such as the Duobaoshan Cu deposit [1,2,3], Tongshan Cu deposit [4], Sankuanggou Fe deposit [8], Zhengguang Au deposit [9], Yongxin Au deposit [10], Sandaowanzi Au deposit [11], Shangmachang Au deposit [12], and Erdaokan Ag deposit [6,7].

2.2. Deposit Geology

The Erdaokan deposit represents a recent discovery of a large-scale silver (Ag) deposit. The geological units in the area predominantly comprise the Lower Devonian Niqiuhe Formation, which is characterized by the deposition of clastic sedimentary rocks ranging from fine to coarse in shallow marine sedimentary facies during the transgression period. These formations exhibit distinct sericitization and chloritization, highlighting their significance as host rocks for the Ag deposit. Moreover, the mining area encompasses several volcanic formations, including rhyolite and andesite from the Upper Triassic Qingshuihe Formation. Intrusive rocks, such as Middle to Upper Triassic of porphyritic diabase, diorite, and dacite occur as veins, closely associated with the mineralization process.
In the mining area, two Ag ore bodies (Figure 2a) were discovered, exhibiting a steep occurrence of ore (Figure 2b). The first ore body, named I AgB, has a controlling length of 556.27 m and a maximum dip controlling depth of 273.35 m. It possesses a maximum true thickness of 26.75 m, an average true thickness of 6.23 m. The second ore body, referred to as II AgB, spans across a controlling length of 689.39 m with a maximum dip controlling depth of up to 231.64 m. It has a maximum thickness of 40.29 m and an average thickness of approximately 10.20 m. Furthermore, its inferred economic resource quantity of the deposit is estimated to be 1777 t of silver metal content. The highest recorded grade for silver was found to be 25,516.00 g/t, with an average grade of 431.10 g/t. Additionally, the associated Mn ore reserve in Erdaokan deposit amounts to 90.0 × 104 t with an average grade of 11.75%, while the associated Pb metal quantity in Erdaokan deposit is 1.68 × 104 t with an average grade of 0.75%. Moreover, the associated Zn metal quantity in Erdaokan deposit is 0.16 × 104 t with an average grade of 1.15%.
The Erdaokan Ag deposit predominantly contains pyrargyrite, stephanite, and argentite as its primary silver minerals. Additional silver-bearing minerals include galenite, pyrite, sphalerite, and a small amount of tetrahedrite [13,14,15]. The total content of silver minerals accounts for 0.074%. Carbonate minerals within the deposit mainly consist of Mn siderite, Fe rhodochrosite, and ankerite. The Fe-Mn carbonates make up 59.06% of the total carbonate present in the deposit. They are distributed in a banded manner (Figure 3a) or nodular manner in the ore (Figure 3b,c), often intersected by quartz veins (Figure 3d) and replaced by siliceous material (Figure 3b–d). Under microscopic examination, rhombic twin structures can be observed (Figure 3e), along with oscillatory zoning patterns (Figure 3e–h), semi-automorphic rhombic aggregates (Figure 3f,g), and residual structures (Figure 3h); Ag and Fe-Mn carbonate minerals have a close symbiotic relationship (Figure 3i). The deposit also contains trace amounts of arsenopyrite and covellite. Additionally, magnetic oxides, including magnetite and hematite (Figure 3a), along with minor quantities of pyrolusite and ferromanganese, can be found. Quartz is the main gangue mineral, followed by feldspar and minor amounts of pyroxene, calcite, muscovite, and hematite.
The alteration in the Erdaokan deposit exhibits distinct spatial zoning, which can be divided into three stages (Figure 4): the sheet-like precipitation of quartz–sulfide minerals, the formation of galenite–sphalerite–Fe–Mn carbonate assemblages, and the occurrence of pyrite–arsenopyrite–carbonate aggregates. In the first stage, well-formed quartz, pyrite, and a small amount of arsenopyrite precipitated with some quartz-filled voids within the pyrite and arsenopyrite. The second stage represents the primary mineralization period characterized by the development of galenite, sphalerite, and copper sulfides. Silver acanthite and pyrargyrite were also observed within the lattice structure of the galenite, sphalerite, and pyrite. Additionally, Fe-Mn carbonates, along with magnetite asphalt calcite hematite, appeared later in this stage. In the third stage, disseminated or vein-like aggregates consisting predominantly of pyrite and arsenopyrite were observed along with abundant calcite precipitation.

3. Materials and Methods

Based on the observation and analysis of rock specimens and microscope samples in this area, this study employed electron probe microanalysis (EPMA), scanning electron microscopy (SEM), and LA-ICP-MS testing to investigate the morphology, distribution patterns, coexistence relationships, elemental distribution, and elemental composition characteristics of minerals at a micro scale. Subsequently, the origin of Fe-Mn carbonate minerals was inferred. Additionally, Sm-Nd isotope analysis was conducted to determine the formation time of Fe-Mn carbonates and to compare it with the deposit’s age. These findings will contribute to establishing the ore-forming process of the Erdaokan Ag deposit. Detailed sampling and experimental information are provided below.
The A-B exploration line controls the main ore body, and the drill holes were sequentially numbered as 1, 2, 3, 4, 5, and 6, as shown in Figure 2a. The test samples for EPMA and LA-ICP-MS analysis were collected from four specific drill holes (ZK284-1, ZK284-2, Zk284-4, ZK284-5), with their sampling locations indicated by yellow stars in Figure 2b. A total of thirty testing points were examined using EPMA, while nineteen testing points were analyzed using LA-ICP-MS. Additionally, Sm-Nd isotope samples were obtained from six distinct drill holes (ZK266-2, ZK268-3, ZK274-6, ZK276-2, ZK278-6, and ZK328-9), corresponding to numbers 7, 8, 9, 10, 11, and 12 in Figure 2a.
The EPMA and LA-ICP-MS were conducted at Wuhan Spectrum Analysis Technology Co., Ltd. The EPMA was performed using a JXA-8230 instrument (JEOL Ltd., Tokyo, Japan) with an acceleration voltage of 15 kV, current of 20 nA, and a beam spot diameter of 5 μm. Prior to the experiment, the sample underwent carbon film coating. A total of 30 Fe-Mn carbonate samples were measured using EPMA (Figure 5a). The LA-ICP-MS analyses were carried out using GeoLas HD and Agilent 7900 instruments. The laser energy used was 80 mJ, with a frequency of 5 Hz and a laser beam diameter of 44 µm. For specific analysis conditions and procedures, please refer to the literature [30]. NIST610, BHVO-2G, BIR-1G, and BCR-2G international standard substances were used as trace element calibration standards for this study. ICP MS DATACAL 10.8 software was employed for data processing. A total of 19 measurement points were utilized, and the test minerals and their corresponding locations can be observed in Figure 3f,g and Figure 5a,b. For microscopic morphology observation and elemental composition analysis of minerals, we used an FEI Quanta650 scanning electron microscope (SEM) operating at an acceleration voltage range between 200 and 300 Kv, with magnification of up to 6 × 106 in combination with a Bruker QUANTAX EDS X-ray diffractometer. Sm-Nd isotope analysis was conducted at Nantai Geological Testing and Research Institute in Nanjing using an ISOPROBE-T thermal ionization mass spectrometer for Sm-Nd isochron age measurement. The Nd standard sample (143Nd/144Nd = 0.511860 ± 0.000008, 2σ, n = 8) complied with the US La Jolla Nd isotope standard. A correction factor based on 146Nd/144Nd = 0.7219 was applied to account for mass fractionation. Details regarding the procedure and methodology can be found in references [31,32].

4. Results

4.1. Microscopic Analysis of Fe-Mn Carbonate Minerals

The Fe-Mn carbonates constitute 59.06% of the total carbonate content in the deposit, which is consistent with EPMA results indicating that Fe and Mn are the primary components of the carbonate minerals (Figure 6a–d). Atomic absorption spectroscopy analysis of 774 whole rock samples from the Erdaokan Ag deposit revealed a positive correlation between Ag and Mn concentrations (Figure 7). Microscopic observations demonstrated that pyrargyrite was distributed within the Fe-Mn carbonate minerals (Figure 5b and Figure 8a,b), while SEM analysis identified argentite as crystals < 20 μm distribution within these minerals (Figure 8c). Furthermore, EDS mapping confirmed widespread distribution of Ag in areas where Fe and Mn were present, highlighting a close relationship between Ag and Fe-Mn carbonate minerals (Figure 8d).
The EDS image analysis reveals the presence of zoning structures in the Fe-Mn carbonate (Figure 9a), characterized by a gradual transition in the concentrations of Fe and Mn (Figure 9b,c). In the Fe-Mn carbonates, Ca content surpasses that of Mg (Figure 9d,e), while Si is predominantly absent (Figure 9f). Notably, there is a decrease in Mn content from core to rim, accompanied by an increase in both Fe and Mg content. Furthermore, higher concentrations of Ca are observed at the core compared to its outer regions, exhibiting a rhythmic pattern.

4.2. Analysis of Major and Trace Elements

The major element data obtained by EPMA are presented in Table 1. The composition of Fe-Mn carbonates primarily consists of Fe, Mn, and O, with minor amounts of Ca and Mg, as well as trace amounts of Si (Figure 6a–d, Figure 10a), furthermore, the FeO and MnO content in Fe-Mn carbonate shows continuous transitional changes (Figure 10b). The content of FeO + MnO exhibits a negative correlation with CaO (Figure 11a), while no relationship is observed between CaO and SrO (Figure 11b). The carbonate equivalents for these elements are as follows: MnCO3 = 2.88%–97.53%, FeCO3 = 1.34%–92.39%, CaCO3 = 0.30%–11.26%, MgCO3 = 0.02%–8.03%. Notably, there is a negative correlation between MnO and FeO (Figure 11c), suggesting the possibility of isomorphic replacement between Mn and Fe.
The trace elements data obtained by LA-ICP-MS are presented in Table 2. Phosphorus ranges from 15.22 to 46.14 ppm, while K ranges from 0.75 to 14.56 ppm, indicating an overall deficit in these elements. Sr content varies from 0.02 to 12.20 ppm, whereas Ti content ranges from 0.03 to 8.95 ppm. It should be noted that the values for Zr and Nb fall below the detection limit of the instrument used in this study. The similar radii of Mn2+, Fe2+, and Mg2+ (0.083 nm, 0.083 nm, and 0.072 nm, respectively) facilitate replacement reactions among them, contributing to their comparable distribution patterns observed in siderite, Mn siderite, Fe rhodochrosite, and rhodochrosite samples as shown by the spidergram of trace elements normalized to the primitive mantle (Figure 12a–c). These Fe-Mn carbonate samples exhibit deficits in large ion lithophile elements, such as K and Sr, as well as high field strength elements including Zr, Ti, and Nb.
Fe-Mn carbonate minerals exhibit a ∑REE ranging from 0.88 to 67.06 ppm, with LREE content ranging from 0.75 to 66.55 ppm and HREE content ranging from 0.12 to 6.24 ppm for rare-earth elements (REE). The LREE/HREE ratio ranges from 1.72 to 194.47, the (La:Yb)N ranges from 1.24 to 1112.90, the (Sm:Nd)N is mostly <1 and ranges from 0.21 to 1.59, the (La:Sm)N ranges from 0.86 to 41.68, and them(Gd:Yb)N ranges from 0.31 to 9.10. When standardized using chondritic values, rhodochrosite exhibits significantly higher ΣREE than siderite (Figure 12d–f), while siderite, Mn siderite, and Fe rhodochrosite show similar distribution patterns. Fe-Mn carbonates display a right-skewed curve for REE enrichment, indicating preferential enrichment of LREE over HREE. The δEu values range between 0.06 and 0.63, suggesting the presence of a notable negative Eu anomaly. The substitution of Eu2+ for Ca2+ is impeded by the lower mass concentration of Ca2+ in the Fe-Mn carbonates of the Erdaokan Ag deposit, thereby resulting in the observed negative Eu anomaly.

4.3. Dating Analysis of Fe-Mn Carbonate Minerals

The Sm and Nd contents, as well as the isotopic compositions in the Fe-Mn carbonate mineral from the Erdaokan Ag deposit, are presented in Table 3. The results indicate that the Sm and Nd contents meet the requirements for isotope dating. Specifically, the Sm content ranges from 0.2115 to 0.9604 ppm, while the Nd content ranges from 0.7859 to 0.9827 ppm. Moreover, the values of 147Sm/144Nd vary between 0.0815 and 0.7169, with corresponding values of 143Nd/144Nd ranging from 0.512374 to 0.513346 being observed as well (Table 3). Importantly, a reliable Sm-Nd isochron age of approximately 233.7 ± 1.2 Ma has been determined for these samples (Figure 13a), which is further supported by a small weighted mean square deviation (MSWD = 1.5).
The high concentrations of Sm and Nd in Fe-Mn carbonates ensure precise and reliable determination of Sm-Nd isochron ages. Figure 13b demonstrates no correlation between 1/Nd and 143Nd/144Nd in Fe-Mn carbonate samples, excluding the possibility of an isotope mixing line [34]. This Sm-Nd isochron age of the Fe-Mn carbonate mineral confirms that the main period of Erdaokan Ag deposit mineralization occurred during the Late Triassic Period (233.7 ± 1.2 Ma).

5. Discussion

5.1. Analysis of Fluid Source in Erdaokan Deposit

The main carbonates in the Erdaokan deposit are Fe-Mn carbonates (Figure 10a). Fe-Mn carbonate commonly occurs in the later stage of carbonate magma evolution, being closely associated with low-temperature hydrothermal deposits. Fe-Mn carbonate can be classified into two forms of isomorphism: Fe siderite and Mn rhodochrosite. The Fe and Mn content in the Fe-Mn carbonate of the Erdaokan deposit exhibits continuous transitional changes (Figure 10b), indicating that the formation of Fe-Mn carbonates in this deposit is a continuous process. Therefore, it can be inferred that these Fe-Mn carbonates originate from the same fluid source. A negative correlation between CaO and (FeO + MnO) is observed (Figure 11a), suggesting that Ca may replace Fe and Mn within the lattice structure of the Fe-Mn carbonate due to water–rock reactions involving Ca during deep-seated hydrothermal activity interacting with limestone from the Niqiuhe Formation [35]. The distribution of trace elements in Fe-Mn carbonate is comparable to that of limestone in the Niqiuhe formation. Both exhibit a shortage of Zr, Nb, and Ti, indicating that some of the limestone from the Niqiuhe formation contributed to the creation of Fe-Mn carbonates [33].
The distribution of trace elements in Fe-Mn carbonates exhibits a strong correlation with the main mineralization sulfides, such as pyrite, chalcopyrite, sphalerite, and bitumen in the mining area (Figure 12a–c). The δ34S values of galena range from −0.97‰ to +3.8‰, indicating the presence of deep magmas in the ore-forming fluid [13]. Furthermore, the LREE/HREE ratio is between 1.72 and 194.47, while (La:Yb)N is between 1.24 and 1112.90, indicating that LREE has a higher fractionation degree than HREE. Note that the material source has the primary characteristics of a deep source [33]. The patterns of trace elements (Figure 12a,c) and rare-earth elements (Figure 12d,f) suggest a close relationship between Fe-Mn carbonate and deep magmatic–hydrothermal processes [14]. Furthermore, the depletion of Zr in Fe-Mn carbonates suggests the involvement of upper-mantle material in the hydrothermal system. Therefore, it can be inferred that the ore-forming fluid consists primarily of deep-source magma with a minor contribution from upper-mantle materials. The absence of barite in the Erdaokan Ag ore indicates that sulfur content is not significantly high within the ore-forming system, and that redox conditions do not play a key controlling role in ore-formation [36].
The formation of magnetite is observed as a result of late thermal action on Fe-Mn carbonate minerals [37]. The correlation between CaO and SrO in Fe-Mn carbonates was found to be insignificant (Figure 11b), indicating that the displacement of Ca by Sr mainly occurs during the high-temperature stage of magma crystallization [38]. This suggests that there is no apparent substitution between these two elements, and mineralization took place during the medium- to low-temperature stage. The negative Eu anomaly (0.06–0.63) is indicative of carbonate crystallization from a low-temperature fluid (<200 °C) [39]. Fluid inclusions within quartz veins indicate an average deposit formation temperature of 152.1 °C [13], implying characteristics of low-temperature mineralization. Overall, it can be stated that the Erdaokan Ag deposit exhibits medium- to low-temperature mineralization.
The distribution pattern of rare-earth elements (REE) in Fe-Mn carbonates reflects their formation by the same fluid, indicating a close relationship between Fe-Mn carbonate and deep magmatic–hydrothermal processes [13,15]. This is consistent with the distribution patterns observed in metal sulfides and bitumen (Figure 12d,f). Additionally, it should be noted that rhodochrosite exhibits higher REE content than siderite (Figure 12d,e).
Postma (1981) [40] demonstrated that Mn has a higher affinity for carbonate, leading to the formation of carbonate rocks and the enrichment of REE. Consequently, it is hypothesized that the sequential occurrence of fluid phases involves the initial formation of Mn siderite followed by Fe rhodochrosite. In EPMA’s EDS mapping (Figure 9b,c), Mn is observed in the core region of Fe-Mn carbonate, while Fe predominantly resides in its rim. This observation further supports the notion that Mn siderite forms prior to Fe rhodochrosite. Previous investigations have indicated that modern seawater exhibits a Y/Ho ratio greater than 44, whereas hydrothermal seabed and chondrite samples typically fall within the range of 24–34 [16,20,41]. The average Y/Ho ratio in Fe-Mn carbonates from the Erdaokan deposit mining area was determined as 34.29, which aligns with values observed in hydrothermal vents and chondritic meteorites. These findings suggest a deep magmatic–hydrothermal origin for these Fe-Mn carbonates.

5.2. Sm-Nd Isotopes and Metallogenic Age Indication

The Sm-Nd isotopic system has been widely employed to determine the metallogenic geological age of hydrothermal deposits. Commonly used minerals for Sm-Nd isotope dating include fluorite, calcite, tourmaline, scheelite, and sulfide metal minerals [42,43,44,45,46,47,48]. However, the Sm-Nd systematics of Fe-Mn carbonate minerals formed through hydrothermal processes have received less attention [49]. In the Erdaokan Ag deposit, Fe-Mn carbonate is abundant throughout the entire mineralization stage and occurs mainly in the galena–sphalerite–Fe–Mn carbonate stage, which represents the primary silver metallogenic phase. Therefore, determining its formation age is crucial for constraining the overall mineralization age. Due to their high Sm/Nd ratios, Fe-Mn carbonate minerals in the Erdaokan deposit are suitable for Sm-Nd isotope dating. The obtained results indicate a mineralization age of 233.7 ± 1.2 Ma for Fe-Mn carbonate minerals, which aligns well with both bitumen (234.6 ± 1.2 Ma) [14] and sulfide Rb-Sr (232.9 ± 2.3 Ma) [15] data from the same deposit area. These findings further confirm that the ore-forming event at Erdaokan occurred during the Late Triassic Period.
A significant number of Cu-Au deposits have been discovered in the Duobaoshan Cu-Mo-Au mineralization concentrated area, where the Erdaokan silver deposit is located. Unlike the Triassic formations of Duobaoshan and Tongshan deposits, which primarily formed during the Ordovician [4,8,50,51], the Sankuanggou Fe deposit mainly originated in the Jurassic Period [8,52,53]. Similarly, the Sandaowanzi gold deposit and Yongxin gold deposit were predominantly formed during the Cretaceous Period [10,12,54,55,56]. Recent studies have revealed some Triassic diagenetic events in the Duobaoshan Cu-Mo-Au mineralization concentrated area [2,5,57], reporting that magmatic rocks with ages ranging from 244 ± 2 Ma to 214 ± 3 Ma are present in this region. These rock types include tonalite and granodiorite, as well as porphyritic-like granodiorite. This evidence suggests that Triassic magmatic activity within this concentration area aligns closely with the metallogenic age of Erdaokan deposit. The Mengdehe gold deposit situated south of this region was formed during the Late Triassic Period (209.6 ± 3.1 Ma) [58], coinciding with metallogenesis within the Erdaokan silver deposit’s time frame. Collectively, these findings establish a newly recognized metallogenic age for the Duobaoshan Cu-Mo-Au mineralization concentrated area involving Triassic diagenetic and metallogenic events. It should be noted that there is a distinct difference between Erdaokan’s metallogenic age and that of large Ag-Pb-Zn deposits such as Shuangjianzishan (135.0 ± 0.6 Ma) [59], Erentaolegai (139 ± 2.3 Ma) [60], Jiawula (133 ± 0.66 Ma) [61], and Chagan Buragen (138 ± 1 Ma) [62] found southwest of the Greater Khingan metallogenic belt, thus emphasizing Erdaokan’s crucial indicative significance within the Duobaoshan Cu-Mo-Au mineralization concentrated area.

5.3. Metallogenic Model of Erdaokan Silver Deposit and Favorable Conditions for Ag Enrichment

In summary, the Duobaoshan Cu-Mo-Au mineralization concentrated area experienced significant magmatic activity during the Middle to Late Triassic Period due to the superposition of the Okhotsk Ocean tectonic domain [5,63,64,65,66]. The upward migration of deep-seated magma carrying Ag and other ore-forming materials in the Erdaokan area resulted in the formation of a medium- to low-temperature magmatic hydrothermal deposits with weak structures (Figure 14). Moreover, interaction between the ascending fluid and surrounding rocks was observed. Late-stage magmatic hydrothermal activity caused the heating of limestone from the Niqiuhe Formation, which was exposed in the Erdaokan mining area, and this led to its transformation into structures with high specific surface area [67,68]. This transformation facilitated adsorption and enrichment of Ag, Mn, and other ore minerals within the hydrothermal system. Additionally, magnetite and hematite were commonly found in peripheral areas of Fe-Mn carbonate minerals in this mining region, indicating significant thermal alteration subsequent to mineralization. Such thermal alteration likely contributed to further enhancement of Ag deposition. These findings provide an explanation for the supernormal enrichment of Ag (highest grade: 25,516.00 g/t) at the Erdaokan deposit, while offering new insights into prospecting strategies within this ore cluster area.

6. Conclusions

  • Fe-Mn carbonate is a pervasive mineral in the Erdaokan Ag deposit, primarily formed during the galenite–sphalerite–Fe–Mn carbonate stage. Through microscopic analysis and EPMA, pyrargyrite was found to coexist with Fe-Mn carbonate, while argentite is finely disseminated within Fe-Mn carbonates. Consequently, the presence of Fe-Mn carbonation has great potential as an indicator for prospecting regional Ag deposits, and provides a novel avenue for comprehending mineral deposit information.
  • The Fe-Mn carbonates can be classified into manganese siderite and iron rhodochrosite, representing the two extremes of isomorphism. These Fe-Mn carbonates are primarily distributed in banded or nodular forms within the ore, often intersected by quartz veins. Microscopically, the Fe-Mn carbonates exhibit semi-idiomorphic rhomboid morphology, semi-idiomorphic rhomboid assemblage, rhomboid twinning, and residual structures resulting from quartz metasomatism. The concentrations of Fe and Mn show continuous variations, and display a similar distribution pattern to that of rare-earth trace elements.
  • The Fe-Mn carbonates in the Erdaokan Ag deposit exhibit a similar distribution pattern of trace elements and REE, indicating a pronounced resemblance to the pyrite pattern observed in the deposit. Furthermore, these carbonates display a depletion of Zr, an enrichment of light rare-earth elements, a noticeable deficit of Eu, and an average Y/Ho value of 34.29. These findings suggest that the ore-forming materials originated from deep magma sources with involvement from upper-mantle materials.
  • The Sm-Nd isotopic isochron age of the Fe-Mn carbonate monomineral has been determined to be 233.7 ± 1.2 Ma (MSWD = 1.5), indicating that the formation of the Erdaokan Ag deposit occurred during the Late Triassic Period in a magmatic hydrothermal environment characterized by moderate to low temperatures. This study further reinforces the significance of the Late Triassic Period as an additional metallogenic stage in the Duobaoshan Cu-Mo-Au mineralization concentrated area.

Author Contributions

Conceptualization, Y.Y. and C.L.; methodology, Z.W.; validation, H.G. and W.Y.; formal analysis, M.Y.; investigation, A.F., B.Z. and B.L.; software, Z.C. and B.L. All authors have read and agreed to the published version of the manuscript.

Funding

This research was Supported by Heilongjiang Provincial Key R&D Program Project (No. GA21A204), Heilongjiang Provincial Natural Science Foundation of China (No. LH2023D025), Scientific Research Project of Heilongjiang Provincial Bureau of Geology and Mineral Resources (No. HKY202301) and National Natural Science Foundation of China (No. 41872038).

Data Availability Statement

The data were used for the research described in this article.

Acknowledgments

The authors wish to acknowledge Zhenjiang Liu, Xuefei Liu and Yi Cao of China University of Geosciences (Beijing) for their contribution to improving the quality of this article.

Conflicts of Interest

The authors declare no conflicts of interest. The funders had no role in the design of this study, nor in the collection, analyses, or interpretation of the data, nor in the writing of the manuscript, nor in the decision to publish the results.

References

  1. Liu, J.; Wu, G.; Li, Y.; Zhu, M.T.; Zhong, W. Re-Os sulfide (chalcopyrite, pyrite and molybdenite) systematicand fluid inclusion study of the Duobaoshan porphyry Cu (Mo) deposit, Heilongjiang Province, China. J. Asian Earth Sci. 2012, 49, 300–312. [Google Scholar] [CrossRef]
  2. Zeng, Q.D.; Liu, J.M.; Chu, S.X.; Wang, Y.B.; Sun, Y.; Duan, X.X.; Zhou, L.L.; Qu, W.J. Re-Os and U-Pb geochronology of the Duobaoshan porphyry Cu-Mo-(Au) deposit, northeast China, and its geological significance. J. Asian Earth Sci. 2014, 79, 895–909. [Google Scholar] [CrossRef]
  3. Gao, R.Z.; Xue, C.J.; Lu, X.B.; Zhao, X.B.; Yang, Y.S.; Li, C.C. Genesis of the Zhengguang gold deposit in the Duobaoshan ore field, Heilongjiang Province, NE China: Constraints from geology, geochronology and S-Pb isotopic Compositions. Ore Geol. Rev. 2017, 84, 202–217. [Google Scholar] [CrossRef]
  4. Hao, Y.J.; Ren, Y.S.; Duan, M.X.; Tong, K.Y.; Chen, C.; Li, C. Re-Os Isotopic Dating of the Molybdenite from the Tongshan Porphyry Cu-Mo Deposit in Heilongjiang Province, NE China. Acta Geol. Sin. (Engl. Ed.) 2014, 88 (Suppl. S2), 522–523. [Google Scholar]
  5. Hao, Y.J.; Ren, Y.S.; Duan, M.X.; Zhao, H.L.; Tong, K.Y.; Sun, Z.M. Tectonic setting of Triassic magmatic and metallogenic event in the Duobaoshan mineralization area of Heilongjiang Province, NE China. Geol. J. 2017, 52, 67–91. [Google Scholar] [CrossRef]
  6. Bao, X.B.; Yin, G.L.; Yu, X.Z. Geological characteristics of Erdaokancun Silver Polymetallic Deposit, Nenjiang County, Heilongjiang Province and its prospecting indicators. Gold 2019, 7, 20–23, (In Chinese with English abstract). [Google Scholar]
  7. Xu, W.X.; Li, C.L.; Bao, X.B.; Yuan, M.W. Geological characteristics and genesis analysis of the first Triassic silver deposit discovered in Northeast of Da Hinggan Mountains. Miner. Resour. Geol. 2019, 33, 434–441, (In Chinese with English abstract). [Google Scholar]
  8. Chu, S.X.; Zeng, Q.D.; Liu, J.M.; Wang, Y.B. Early–Middle Jurassic magmatism and skarn-porphyry mineralization in NE China: Geochronological and geochemical constraints from the Sankuanggou skarn Fe-Cu-(Mo) deposit, and tectonic implications. J. Geochem. Explor. 2019, 200, 84–103. [Google Scholar] [CrossRef]
  9. Wang, L.; Qin, K.Z.; Cao, M.J.; Danišík, M.; Evans, N.J.; Li, G.M.; Song, G.X.; Pang, X.Y. Thermal history of an Early Paleozoic epithermal deposit: Constraints from 40Ar/39Ar and (U-Th)/He thermochronology at Zhengguang, eastern Central Asian Orogenic Belt. Ore Geol. Rev. 2020, 126, 103791. [Google Scholar] [CrossRef]
  10. Li, C.L.; Li, L.; Yuan, M.W.; Alam, M.; Li, S.R.; Santosh, M.; Deng, C.Z.; Liu, H.; Xu, G.Z. Study on pyrite thermoelectricity, ore-forming fluiAll authors have been informed and agreed.ds and H-O-Rb-Sr isotopes of the Yongxin gold deposit, Central Asian Orogenic Belt: Implications for ore genesis and exploration. Ore Geol. Rev. 2020, 121, 103568. [Google Scholar] [CrossRef]
  11. Gao, S.; Xu, H.; Zang, Y.Q.; Yang, L.J.; Yang, B.; Wang, T. Late Mesozoic magmatism and metallogeny in NE China: The Sandaowanzi-Beidagou example. Int. Geol. Rev. 2017, 59, 1413–1438. [Google Scholar] [CrossRef]
  12. Gao, S.; Xu, H.; Zang, Y.Q.; Wang, T. Mineralogy, ore-forming fluids and geochronology of the Shangmachang and Beidagou gold deposits, Heilongjiang province, NE China. J. Geochem. Explor. 2018, 188, 137–155. [Google Scholar] [CrossRef]
  13. Yuan, M.W.; Li, L.; Li, S.R. Mineralogy, fluid inclusions and S-Pb-H-O isotopes of the Erdaokan Ag-Pb-Zn deposit, Duobaoshan metallogenic belt, NE China: Implications for ore genesis. Ore Geol. Rev. 2019, 113, 103074. [Google Scholar] [CrossRef]
  14. Yuan, M.W.; Li, L.; Li, S.R.; Santosh, M.; Li, C.L.; Alam, M.; Hou, Z.Q. Bitumen Sm-Nd, pyrite Rb-Sr and zircon U-Pb isotopes constrain timing of ore formation and hydrocarbon deposition in the Erdaokan Ag-Pb-Zn deposit, NE China. Ore Geol. Rev. 2021, 134, 104161. [Google Scholar] [CrossRef]
  15. Yuan, M.W.; Li, L.; Li, C.L.; Li, S.R.; Santosh, M.; Alam, M.; Hou, Z.Q. The genesis of bitumen and its relationship with mineralization in the Erdaokan Ag-Pb-Zn deposit from the Great Xing’an Range, northeastern China. Ore Geol. Rev. 2021, 139, 104464. [Google Scholar] [CrossRef]
  16. Yang, Z.; Jiang, M.J.; Zhao, S.R.; Ding, Z.J.; He, M.C. Stable isotopes and halogen geochemistry of the Huayuan carbonate-hosted Pb-Zn ore district, South China: Implications for the salt source of ore-forming fluids. Acta Geol. Sin. (Engl. Ed.) 2022, 96, 506–516. [Google Scholar] [CrossRef]
  17. Xiong, S.F.; Gong, Y.J.; Yao, S.Z.; Shen, C.B.; Ge, X.; Jiang, S.Y. Nature and evolution of the ore-forming fluids from Nanmushu carbonate-hosted Zn-Pb deposit in the Mayuan district, Shaanxi Province, Southwest China. Geofluids 2017, 2017, 2410504. [Google Scholar] [CrossRef]
  18. Xu, Y.W.; Mao, G.Z.; Geng, H.Y.; He, T.L.; Xu, Q.L.; Meng, Y.K.; Cao, M.P.; Yang, F.J.; An, P.R.; Song, L.G.; et al. Ore-forming materials and fluids and ore-controlling factors of the Liaoshang gold deposit in Jiaodong Peninsula, NE China. Ore Geol. Rev. 2023, 154, 105330. [Google Scholar] [CrossRef]
  19. Myint, A.Z.; Wagner, T.; Fusswinkel, T. Calcite trace element geochemistry of Au deposits in the Singu-Tabeikkyin Gold District, Myanmar: Implications for the sources of ore-forming fluids. Ore Geol. Rev. 2022, 145, 104892. [Google Scholar] [CrossRef]
  20. Bau, M.; Dulski, P. Distribution of yttrium and rare–earth elements in the Penge and Kuruman iron-formations, Transvaal Supergroup, South Africa. Precambrian Res. 1996, 79, 37–55. [Google Scholar] [CrossRef]
  21. Bau, M. Controls on the fractionation of isovalent trace elements in magmatic and aqueous systems: Evidence form Y/Ho, Zr/Hf, and lanthanide tetrad effect. Contrib. Mineral. Petrol. 1996, 123, 323–333. [Google Scholar] [CrossRef]
  22. Jiang, S.Y.; Chen, X.; Chen, Y.Q.; Jiang, Y.H.; Dai, B.Z.; Ni, P. Geochemistry and genetic model for the giant magnesite deposits in the eastern Liaoning Province, China. Acta Petrol. Sin. 2004, 20, 765–772. [Google Scholar]
  23. Planavsky, N.; Bekker, A.; Rouxel, O.J.; Kamber, B.; Hofmann, A.; Knudsen, A.; Lyons, T.W. Rare Earth Element and yttrium compositions of Archean and Paleoproterozoic Fe formations revisited: New perspectives on the significance and mechanisms of deposition. Geochim. Cosmochim. Acta 2010, 74, 6387–6405. [Google Scholar] [CrossRef]
  24. Presley, B.J.; Kaplan, I.R. Changes in dissolved sulfate, calcium and carbonate from interstitial water of near-shore sediments. Geochim. Cosmochim. Acta 1968, 32, 1037–1048. [Google Scholar] [CrossRef]
  25. Chen, F.G.; Pufahl, K.P.; Wang, Q.F.; Matheson, E.J.; Shabaga, B.M.; Zhang, Q.Z.; Zeng, Y.S.; Le, X.W.; Ruan, D.; Zhao, Y.T. A new model for the genesis of Carboniferous Mn Ores, Longtou deposit, South China Block. Econ. Geol. 2022, 117, 107–125. [Google Scholar] [CrossRef]
  26. Wang, F.; Zhou, X.H.; Zhang, L.C.; Ying, J.F.; Zhang, Y.T.; Wu, F.Y.; Zhu, R.X. Late Mesozoic volcanism in the Great Xing’an Range (NE China): Timing and implications for the dynamic setting of NE Asia. Earth Planet. Sci. Lett. 2006, 251, 179–198. [Google Scholar] [CrossRef]
  27. Fan, W.M.; Guo, F.; Wang, Y.J.; Lin, G. Late Mesozoic calc-alkaline volcanism of post-orogenic extension in the northern Da Hinggan Mountains, northeastern China. J. Volcanol. Geotherm. Res. 2003, 121, 115–135. [Google Scholar] [CrossRef]
  28. Wu, H.Y.; Zhang, L.C.; Wan, B.; Chen, Z.G.; Xiang, P.; Pirajno, F.; Du, A.D.; Qu, W.J. Re-Os 40Ar/39Ar ages of the Jiguanshan porphyry Mo deposit, Xilamulun metallogenic belt, NE China, constraints on mineralization events. Miner. Depos. 2011, 46, 171–185. [Google Scholar] [CrossRef]
  29. Deng, C.Z.; Li, C.L.; Rong, Y.M.; Chen, D.; Zhou, T.; Wang, X.Y.; Chen, H.Y.; Lehmann, B.; Yin, R.S. Different metal sources in the evolution of an epithermal ore system: Evidence from mercury isotopes associated with the Erdaokan epithermal Ag-Pb-Zn deposit, NE China. Gondwana Res. 2021, 95, 1–9. [Google Scholar] [CrossRef]
  30. Liu, Y.S.; Hu, Z.C.; GAO, S.; Günther, D.; Xu, J.; Gao, C.G.; Chen, H.H. In situ analysis of major and trace elements of anhydrous minerals by LA-ICP-MS without applying an internal standard. Chem. Geol. 2008, 257, 34–43. [Google Scholar] [CrossRef]
  31. Yang, Y.H.; Wu, F.Y.; Yang, J.H.; Chew, D.M.; Xie, L.W.; Chu, Z.Y.; Zhang, Y.B.; Huang, C. Sr and Nd isotopic compositions of apatite reference materials used in U-Th-Pb geochronology. Chem. Geol. 2014, 385, 35–55. [Google Scholar] [CrossRef]
  32. Yang, Y.H.; Wu, F.Y.; Li, Q.L.; Rojas-Agramonte, Y.; Yang, J.H.; Li, Y.; Ma, Q.; Xie, L.W.; Huang, C.; Fan, H.R.; et al. In situ U–Th–Pb dating and Sr-Nd isotope analysis of bastnäsite by LA-(MC)-ICP-MS. Geostand. Geoanal. Res. 2019, 43, 543–565. [Google Scholar] [CrossRef]
  33. Dong, J.; Yuan, M.W.; Li, C.L. Geochemical characteristics of hydrothermal rhodochrosite in Erdaokan Ag-Pb-Zn deposit Duobaoshan metallogenic belt, Heilongjiang province and its indications. J. Jilin Univ. Earth Sci. Ed. 2022, 52, 855–865, (In Chinese with English abstract). [Google Scholar]
  34. Faure, G. Principle of Isotope Geology; John Wiley and Sons Inc.: Hoboken, NJ, USA, 1986. [Google Scholar]
  35. Peter, S.M. Relation between depositional environment and the elemental composition of early diagenetic siderite. Geology 1989, 17, 704–706. [Google Scholar]
  36. Kelley, K.D.; Leach, D.L.; Johnson, C.A.; Clark, J.L.; Fayek, M.; Slack, J.F.; Anderson, V.M.; Ayuso, R.A.; Ridley, W.I. Textural, compositional, and sulfur isotope variations of sulfide minerals in the Red Dog Zn-Pb-Ag deposits, Brooks Range, Alaska: Implications for ore formation. Econ. Geol. 2004, 99, 1509–1532. [Google Scholar] [CrossRef]
  37. Kang, N.; Schmidt, M.W.; Poli, S.; Franzolin, E.; Connolly, J.A.D. Melting of siderite to 20 GPa and thermodynamic properties of FeCO3-melt. Chem. Geol. 2015, 400, 34–43. [Google Scholar] [CrossRef]
  38. Wall, F.; Le Bas, M.J.; Srivastave, R.K. Calcite and carbocernaite exsolution and cotectic textures in a Sr, REE–rich carbonatite dyke from Rajasthan, India. Mineral. Mag. 1993, 57, 495–513. [Google Scholar] [CrossRef]
  39. Gamyanin, G.N.; Vikent’eva, O.V.; Prokof’ev, V.Y.; Bortnikov, N.S. Arkachan: A new Gold–Bismuth–Siderite–Sulfide type of deposits in the West Verkhoyansky Tin District, Yakutia. Geol. Ore Depos. 2015, 57, 465–495. [Google Scholar] [CrossRef]
  40. Postma, D. Formation of siderite and vivianite and the pore-water composition of a recent bog sediment in Denmark. Chem. Geol. 1981, 31, 225–244. [Google Scholar] [CrossRef]
  41. Bolhar, R.; Kamber, B.S.; Moorbath, S.; Fedo, C.N.; Whitehouse, M.J. Characterisation of early Archaean chemical sediments by trace element signatures. Earth Planet. Sci. Lett. 2004, 222, 43–60. [Google Scholar] [CrossRef]
  42. Chesley, J.T.; Halliday, A.N.; Scrivener, R.C. Samarium–neodymium direct dating of fluorite mineralization. Science 1991, 252, 949–995. [Google Scholar] [CrossRef]
  43. Chesley, J.T.; Halliday, A.N.; Kyser, T.K.; Spry, P.G. Direct dating of Mississippi Valley-type mineralizations: Use of Sm-Nd in fluorite. Econ. Geol. 1994, 89, 1192–1199. [Google Scholar] [CrossRef]
  44. Jiang, S.Y.; John, F.S.; Martin, R.P. Sm-Nd dating of the giant Sullivan Pb-Zn-Ag deposit, British Columbia. Geology 2000, 28, 751–754. [Google Scholar] [CrossRef]
  45. Peng, J.T.; Hu, R.Z.; Burnard, P.G. Samarium-neodymium isotope systematics of hydrothermal calcites from the Xikuangshan antimony deposit (Hunan, China): The potential of calcite as a geochronometer. Chem. Geol. 2003, 200, 129–136. [Google Scholar] [CrossRef]
  46. Oberthür, T.; Melcher, F.; Henjes, K.F.; Gerdes, A.; Stein, H.; Zimmerman, A.E.; Ghorfi, M. Hercynian age of the cobalt-nickel-arsenide–(gold) ores, Bou Azzer, Anti-Atlas, Morocco: Re-Os, Sm-Nd, and U-Pb age determinations. Econ. Geol. 2009, 104, 1065–1079. [Google Scholar] [CrossRef]
  47. Su, W.; Hu, R.; Xia, B.; Xia, Y.; Liu, Y. Calcite Sm-Nd isochron age of the Shuiyindong Carlin-type gold deposit, Guizhou, China. Chem. Geol. 2009, 258, 269–274. [Google Scholar] [CrossRef]
  48. Henjes, K.F.; Prochaska, W.; Niedermayr, A.; Sullivan, N.; Baxter, E. Sm-Nd dating of hydrothermal carbonate formation: An example from the Breitenau magnesite deposit (Styria, Austria). Chem. Geol. 2014, 387, 184–201. [Google Scholar] [CrossRef]
  49. Krupenin, M.T.; Kuznetsov, A.B.; Chervyakovskaya, M.V.; Gulyaeva, T.Y.; Konstantinova, G.V. The Source of Ore Fluids and Sm-Nd Age of Siderite from the Largest Bakal Deposit, Southern Urals. Geol. Ore Depos. 2021, 63, 324–340. [Google Scholar] [CrossRef]
  50. Zeng, H.; Zhao, Y.Y.; Fu, J.J.; Li, Y. Features of sulfide and plumbum isotopes of the copper deposits in Duobaoshan deposit cluster in Heilongjiang Province, China. Acta Geol. Sin. (Engl. Ed.) 2014, 88, 643–644. [Google Scholar] [CrossRef]
  51. Hu, X.L.; Yao, S.Z.; Ding, Z.J.; He, M.C. Early Paleozoic magmatism and metallogeny in Northeast China: A record from the Tongshan porphyry Cu deposit. Miner. Depos. 2016, 52, 85–103. [Google Scholar] [CrossRef]
  52. Hao, Y.J.; Ren, Y.S.; Duan, M.X.; Tong, K.Y.; Chen, C.; Yang, Q.; Li, C. Metallogenic events and tectonic setting of the Duobaoshan ore field in Heilongjiang Province, NE China. J. Asian Earth Sci. 2015, 97, 442–458. [Google Scholar] [CrossRef]
  53. Deng, K.; Li, Q.; Chen, Y.J.; Zhang, C.; Zhu, X.F.; Xu, Q.W. Geochronology, geochemistry and Sr-Nd-Pb-Hf isotopes of the Early Jurassic granodiorite from the Sankuanggou intrusion, Heilongjiang Province, Northeastern China: Petrogenesis and geodynamic implications. Lithos 2018, 296, 113–128. [Google Scholar] [CrossRef]
  54. Yu, R.T.; Li, B.L.; Sun, F.Y.; Li, Z.H.; Li, H.W.; Shi, Y.F. Geochronology, geochemistry and Hf isotopes of andesites in the Sandaowanzi gold deposit (Great Xing’an Range, NE China): Implications for petrogenesis, tectonic setting, and mineralization. Acta Geochim. 2021, 40, 251–270. [Google Scholar] [CrossRef]
  55. Zhai, D.G.; Liu, J.J.; Ripley, E.M.; Wang, J.P. Geochronological and He-Ar-S isotopic constraints on the origin of the Sandaowanzi gold-telluride deposit, northeastern China. Lithos 2015, 212, 338–352. [Google Scholar] [CrossRef]
  56. Zhao, Z.H.; Sun, J.G.; Li, G.H.; Xu, W.X.; Lu, C.L.; Guo, Y.; Liu, J.; Zhang, X. Zircon U-Pb geochronology and Sr-Nd-Pb-Hf isotopic constraints on the timing and origin of the Early Cretaceous igneous rocks in the Yongxin gold deposit in the Lesser Xing’an Range, NE China. Geol. J. 2020, 55, 2684–2703. [Google Scholar] [CrossRef]
  57. Zhao, C.; Qin, K.Z.; Song, G.X.; Li, G.M. Switch of geodynamic setting from the Paleo-Asian Ocean to the Mongol-Okhotsk Ocean: Evidence from granitoids in the Duobaoshan ore field, Heilongjiang Province, Northeast China. Lithos 2019, 336, 202–220. [Google Scholar] [CrossRef]
  58. Li, C.L.; Deng, C.Z.; Li, S.R.; Yuan, M.W.; Yang, Y.J. Geochronology and genesis of the newly discovered Mengdehe orogenic-type Au deposit in the Xing’an-Mongolia orogenic Belt, NE China. Ore Geol. Rev. 2021, 133, 104083. [Google Scholar] [CrossRef]
  59. Zhai, D.G.; Williams–Jones, A.E.; Liu, J.; David, S.; Voudouris, P.C.; Tombros, S.; Li, K.; Li, P.; Sun, H. The genesis of the giant Shuangjianzishan epithermal Ag-Pb-Zn deposit, Inner Mongolia, Northeastern China. Econ. Geol. 2020, 115, 101–128. [Google Scholar] [CrossRef]
  60. Xu, L.Q.; Liu, C.; Deng, J.F.; Li, N.; Dai, M.; Bai, L.B. Geochemical characteristics and ziron U-Pb SHRIMP age of igneous rocks in Erentaolegai silver deposit, Inner Mongolia. Acta Petrol. Sin. 2014, 30, 3203–3212, (In Chinese with English abstract). [Google Scholar]
  61. Niu, S.D.; Li, S.R.; Huizenga, J.M.; Santosh, M.; Zhang, D.H.; Li, Z.D.; Tang, L. 40Ar/39Ar geochronology fluid inclusions and ore-grade distribution of the Jiawula Ag-Pb-Zn deposit NE China: Implications for deposit genesis and exploration. Geol. J. 2019, 55, 1115–1127. [Google Scholar] [CrossRef]
  62. Li, T.G.; Wu, G.; Liu, J.; Wang, G.R.; Hu, Y.Q.; Zhang, Y.F.; Luo, D.F.; Mao, Z.H.; Xu, B. Geochronology fluid inclusions and isotopic characteristics of the Chaganbulagen Pb-Zn-Ag deposit, Inner Mongolia, China. Lithos 2016, 261, 340–355. [Google Scholar] [CrossRef]
  63. Li, Y.; Xu, W.L.; Wang, F.; Pei, F.P.; Tang, J.; Zhao, S. Triassic volcanism along the eastern margin of the Xing’an Massig, NE China: Constraints on the spatial-emporal extent of the Mongol-khotsk tectonic regime. Gondwana Res. 2017, 48, 205–223. [Google Scholar] [CrossRef]
  64. Li, Y.; Xu, W.L.; Tang, J.; Pei, F.P.; Wang, F.; Sun, C.Y. Geochronology and geochemistry of Mesozoic intrusive rocks in the Xing’an Massif of NE China: Implications for the evolution and spatial extent of the Mongol-khotsk tectonic regime. Lithos 2018, 304, 57–73. [Google Scholar] [CrossRef]
  65. Zhou, J.B.; Cao, J.L.; Wilde, S.A.; Zhao, G.C.; Zhang, J.J.; Wang, B. Paleo-Pacific subduction-accretion: Evidence from Geochemical and U-Pb zircon dating of the Nadanhada accretionary complex, NE China. Tectonics 2014, 33, 2444–2466. [Google Scholar] [CrossRef]
  66. Aouizerat, A.; Xiao, W.J.; Schulmann, K.; Jerabek, P.; Monie, P.; Zhou, J.B.; Zhang, J.J.; Ao, S.J.; Li, R.; Li, Y.C. Structures, Strain Analyses, and 40Ar/39Ar Ages of Blueschist-Bearing Heilongjiang Complex (NE China): Implications for the Mesozoic Tectonic Evolution of NE China. Geol. J. 2018, 160, 1–30. [Google Scholar] [CrossRef]
  67. Ptáček, P.; Bartoníčková, E.; Ṧvec, J. The kinetics and mechanism of thermal decomposition of SrCO3 polymorphs. Ceram. Int. 2015, 41, 115–126. [Google Scholar] [CrossRef]
  68. Xie, J.J.; Chen, T.; Xing, B.B.; Liu, H.B.; Xie, Q.Q.; Li, H.W.; Wu, Y.C. The thermochemical activity of dolomite occurred in dolomite-palygorskite. Appl. Clay Sci. 2016, 119, 42–48. [Google Scholar] [CrossRef]
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Figure 1. Geological map of Duobaoshan Cu-Mo-Au mineralization concentrated area: (a) schematic map of the Central Asian orogenic belt; (b) the tectonic map of Northeast China; (c) geology and mineral map of Duobaoshan Cu-Mo-Au mineralization concentrated area (modified after reference [29]).
Figure 1. Geological map of Duobaoshan Cu-Mo-Au mineralization concentrated area: (a) schematic map of the Central Asian orogenic belt; (b) the tectonic map of Northeast China; (c) geology and mineral map of Duobaoshan Cu-Mo-Au mineralization concentrated area (modified after reference [29]).
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Figure 2. Geological map and prospecting line profile map of the Erdaokan deposit: (a) geological map depicting the Erdaokan deposit; (b) prospecting line profile map illustrating line 284 (The section in Figure 2b corresponds to the A–B section in Figure 2a).
Figure 2. Geological map and prospecting line profile map of the Erdaokan deposit: (a) geological map depicting the Erdaokan deposit; (b) prospecting line profile map illustrating line 284 (The section in Figure 2b corresponds to the A–B section in Figure 2a).
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Figure 3. Ore and microscopic images: (a) Fe-Mn carbonate minerals (fcm) are observed to be distributed in a banded manner within the ore, which is subsequently replaced by magnetite (mag); (b,c) nodular distribution of Fe-Mn carbonate minerals can be observed in the ore; (d) Quartz (qtz) veins intersect with Fe-Mn carbonate minerals; (e) rhombohedral lattice structure of Fe-Mn carbonate minerals is evident; (f,g) hemidiomorphic rhomboid assembly can be observed; (h) residual texture of Fe-Mn carbonate minerals is present; (i) the presence of Ag is closely associated with the occurrence of Fe-Mn carbonate minerals. (The red circles indicate the location of in-situ laser testing points, (e–h) are under crossed polars images).
Figure 3. Ore and microscopic images: (a) Fe-Mn carbonate minerals (fcm) are observed to be distributed in a banded manner within the ore, which is subsequently replaced by magnetite (mag); (b,c) nodular distribution of Fe-Mn carbonate minerals can be observed in the ore; (d) Quartz (qtz) veins intersect with Fe-Mn carbonate minerals; (e) rhombohedral lattice structure of Fe-Mn carbonate minerals is evident; (f,g) hemidiomorphic rhomboid assembly can be observed; (h) residual texture of Fe-Mn carbonate minerals is present; (i) the presence of Ag is closely associated with the occurrence of Fe-Mn carbonate minerals. (The red circles indicate the location of in-situ laser testing points, (e–h) are under crossed polars images).
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Figure 4. The sequence diagram depicting the hydrothermal mineralization period of the Erdaokan Ag deposit.
Figure 4. The sequence diagram depicting the hydrothermal mineralization period of the Erdaokan Ag deposit.
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Figure 5. Microscopic image of Fe-Mn carbonate minerals: (a) hemidiomorphic ring band structure; (b) pyrargyrite (pyr) coexisting with Fe-Mn carbonate minerals. (The yellow circle indicates a portion of the location for in-situ electron probe testing, while the red circle represents the location of in-situ laser testing; Figure 5a,b are under crossed polars images).
Figure 5. Microscopic image of Fe-Mn carbonate minerals: (a) hemidiomorphic ring band structure; (b) pyrargyrite (pyr) coexisting with Fe-Mn carbonate minerals. (The yellow circle indicates a portion of the location for in-situ electron probe testing, while the red circle represents the location of in-situ laser testing; Figure 5a,b are under crossed polars images).
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Figure 6. X-ray spectrum of Fe-Mn carbonate: (a,b) samples from ZK284-1; (c) samples from ZK284-4; (d) samples from ZK284-5.
Figure 6. X-ray spectrum of Fe-Mn carbonate: (a,b) samples from ZK284-1; (c) samples from ZK284-4; (d) samples from ZK284-5.
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Figure 7. The content relating to Ag and Mn in whole rock samples.
Figure 7. The content relating to Ag and Mn in whole rock samples.
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Minerals 14 00655 g008
Figure 8. Microscopic images depicting Fe-Mn carbonate minerals: (a,b) Images illustrating the presence of pyrargyrite (pyr) within Fe-Mn carbonate minerals; (c) Image demonstrating the distribution of argentite (arg) in Fe-Mn carbonate; (d) Elemental mapping showcasing the distribution of Fe, Mn, Ag, Si, and Zn ((a,b) are under crossed polars images).
Figure 8. Microscopic images depicting Fe-Mn carbonate minerals: (a,b) Images illustrating the presence of pyrargyrite (pyr) within Fe-Mn carbonate minerals; (c) Image demonstrating the distribution of argentite (arg) in Fe-Mn carbonate; (d) Elemental mapping showcasing the distribution of Fe, Mn, Ag, Si, and Zn ((a,b) are under crossed polars images).
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Minerals 14 00655 g009
Figure 9. Characterization of Fe-Mn carbonate: (a) high-angle annular dark-field (HAADF) image of Fe-Mn carbonate mineral; (b–f) elemental mapping depicting the spatial distribution of Mn, Fe, Mg, Ca, and Si within this particular sample of Fe-Mn carbonate mineral.
Figure 9. Characterization of Fe-Mn carbonate: (a) high-angle annular dark-field (HAADF) image of Fe-Mn carbonate mineral; (b–f) elemental mapping depicting the spatial distribution of Mn, Fe, Mg, Ca, and Si within this particular sample of Fe-Mn carbonate mineral.
Minerals 14 00655 g009
Minerals 14 00655 g010
Figure 10. The correlation between the concentrations of MnO, FeO, MgO, and CaO in Fe-Mn carbonate: (a) The correlation between the concentration of (FeO + MnO) − CaO − MgO; (b) The correlation between the concentrations of MgO − MnO − FeO.
Figure 10. The correlation between the concentrations of MnO, FeO, MgO, and CaO in Fe-Mn carbonate: (a) The correlation between the concentration of (FeO + MnO) − CaO − MgO; (b) The correlation between the concentrations of MgO − MnO − FeO.
Minerals 14 00655 g010
Minerals 14 00655 g011
Figure 11. The content correlation of MnO, FeO, CaO, and SrO in Fe-Mn carbonate: (a) FeO + MnO vs. CaO; (b) SrO vs. CaO; (c) FeO vs. MnO.
Figure 11. The content correlation of MnO, FeO, CaO, and SrO in Fe-Mn carbonate: (a) FeO + MnO vs. CaO; (b) SrO vs. CaO; (c) FeO vs. MnO.
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Minerals 14 00655 g012
Figure 12. Partitioning of trace elements and rare earth elements is as follows: (a) siderite trace element; (b) rhodochrosite trace element; (c) Fe rhodochrosite and Mn siderite trace element; (d) siderite rare earth element; (e) rhodochrosite rare earth element; (f) Mn siderite-Fe rhodochrosite rare earth element (The data on bitumen is cited [14], the data on pyrite, sphalerite, and tetrahedrite have been cited [15], the rhombosite data, represented by the green lines, are referenced in citation [33]).
Figure 12. Partitioning of trace elements and rare earth elements is as follows: (a) siderite trace element; (b) rhodochrosite trace element; (c) Fe rhodochrosite and Mn siderite trace element; (d) siderite rare earth element; (e) rhodochrosite rare earth element; (f) Mn siderite-Fe rhodochrosite rare earth element (The data on bitumen is cited [14], the data on pyrite, sphalerite, and tetrahedrite have been cited [15], the rhombosite data, represented by the green lines, are referenced in citation [33]).
Minerals 14 00655 g012
Minerals 14 00655 g013
Figure 13. Sm-Nd isochron diagrams for the Erdaokan deposit: (a) Sm-Nd isotopic diagram of Fe-Mn carbonate minerals (The numbers in Figure 13 are consistent with the samples in Table 3); (b) 1/Nd-143Nd/144Nd diagram of Fe-Mn carbonate.
Figure 13. Sm-Nd isochron diagrams for the Erdaokan deposit: (a) Sm-Nd isotopic diagram of Fe-Mn carbonate minerals (The numbers in Figure 13 are consistent with the samples in Table 3); (b) 1/Nd-143Nd/144Nd diagram of Fe-Mn carbonate.
Minerals 14 00655 g013
Minerals 14 00655 g014
Figure 14. Geotectonic location and model illustration of the Erdaokan deposit: (a) schematic diagram depicting the geotectonic location of the Duobaoshan Cu-Mo-Au mineralization concentrated area; (b) schematic model illustrating the metallogenic process of the Erdaokan deposit.
Figure 14. Geotectonic location and model illustration of the Erdaokan deposit: (a) schematic diagram depicting the geotectonic location of the Duobaoshan Cu-Mo-Au mineralization concentrated area; (b) schematic model illustrating the metallogenic process of the Erdaokan deposit.
Minerals 14 00655 g014
Table 1. Key constituents of Fe-Mn carbonate minerals with a weight percentage of 10−2.
Table 1. Key constituents of Fe-Mn carbonate minerals with a weight percentage of 10−2.
MnOFeOMgOCaOBaOSrOSiO2Al2O3ZnOTotalMnCO3FeCO3MgCO3CaCO3
Spot1ZK284-125.7028.431.112.880.050.141.430.110.0759.9142.9047.451.854.81
Spot2ZK284-127.2527.900.404.270.040.050.000.010.0759.9845.4246.510.677.12
Spot3ZK284-137.0519.300.552.01-0.100.050.040.0159.1162.6932.660.933.40
Spot4ZK284-134.5321.500.502.140.010.110.00--58.7958.7236.570.853.64
Spot5ZK284-123.5732.100.572.52--0.02--58.7740.1054.610.984.28
Spot6ZK284-121.4136.880.571.100.030.02---60.0235.6861.450.951.84
Spot7ZK284-111.1440.394.732.65----0.0458.9518.9068.528.034.49
Spot8ZK284-19.0940.733.065.36---0.06-58.3015.5969.865.259.20
Spot9ZK284-258.360.800.040.52-0.01--0.1159.8497.531.340.060.87
Spot10ZK284-255.253.250.010.180.05---0.0358.7694.025.520.020.30
Spot11ZK284-251.424.990.282.42-0.10-0.02-59.2486.818.430.474.08
Spot12ZK284-250.085.980.183.45-0.05-0.01-59.7583.8110.010.305.78
Spot13ZK284-248.445.880.135.370.020.040.05-0.0860.0080.749.800.228.94
Spot14ZK284-247.439.540.173.430.040.010.00-0.1260.7478.0915.700.285.64
Spot15ZK284-446.729.750.083.48----0.1560.1877.6416.200.135.79
Spot16ZK284-444.467.510.256.65--0.09-0.0458.9975.3712.740.4211.26
Spot17ZK284-443.2111.550.323.590.04-0.050.05-58.7973.4919.640.556.10
Spot18ZK284-437.8120.260.441.69--0.03-0.0760.2962.7133.600.732.80
Spot19ZK284-432.1424.640.241.430.100.030.06--58.6554.8042.020.422.44
Spot20ZK284-430.3622.623.012.95-0.070.060.04-59.1051.3738.275.094.99
Spot21ZK284-421.4834.091.712.10-0.04-0.000.1859.6036.0357.202.883.52
Spot22ZK284-416.1638.921.042.860.02-0.800.080.2060.0626.9064.801.724.76
Spot23ZK284-415.9140.281.422.100.020.030.540.06-60.3626.3666.742.353.49
Spot24ZK284-412.1045.800.911.310.09-0.340.09-60.6319.9675.541.502.15
Spot25ZK284-55.3048.601.524.18---0.020.1359.748.8781.352.547.00
Spot26ZK284-54.3949.642.042.900.23-0.460.06-59.717.3583.133.414.85
Spot27ZK284-53.4653.851.790.490.05---0.1359.775.7990.102.990.83
Spot28ZK284-53.0656.280.350.850.20-0.060.090.0360.915.0292.390.571.40
Spot29ZK284-51.7353.470.711.69--0.060.040.4958.192.9791.901.222.90
Spot30ZK284-51.7051.400.165.640.07-0.020.100.0459.122.8886.930.279.54
The contents of MnCO3, FeCO3, MgCO3, and CaCO3 were determined by extrapolating from the measured contents of MnO, FeO, MgO, and CaO. “-” denotes values below the detection limit of the instrument.
Table 2. The LA-ICP-MS data obtained from Fe-Mn carbonate samples.
Table 2. The LA-ICP-MS data obtained from Fe-Mn carbonate samples.
Spot1Spot2Spot3Spot4Spot5Spot6Spot7Spot8Spot9Spot10Spot11Spot12Spot13Spot14Spot15Spot16Spot17Spot18Spot19
ZK284-1ZK284-1ZK284-2ZK284-2ZK284-2ZK284-2ZK284-2ZK284-2ZK284-4ZK284-4ZK284-4ZK284-4ZK284-4ZK284-4ZK284-4ZK284-5ZK284-5ZK284-5ZK284-5
P45.1321.5432.9015.8618.6030.5315.2224.7322.7532.0324.2330.0824.0428.6640.7043.8537.8019.2946.14
K0.841.617.865.3914.360.754.061.801.2414.560.953.234.826.282.545.374.162.372.56
Ti0.070.070.770.330.240.451.140.130.070.130.420.390.580.120.720.308.950.032.72
Zn271.19316.2439.0610.304.707.4669.613.927.7936.0233.0140.8933.1936.0835.5332.97333.4343.40136.20
Rb0.010.010.060.020.150.030.020.020.020.050.010.010.020.020.080.090.020.020.03
Sr4.543.837.360.430.840.965.070.370.021.050.813.921.320.602.110.8912.200.787.26
Y0.350.624.288.008.286.515.813.663.180.770.501.211.440.450.7412.322.334.784.15
Zr0.030.100.120.07-0.110.07-0.020.090.070.130.050.080.080.110.040.070.05
Nb-------0.020.010.01-0.010.01--0.010.09-0.02
Ba3.342.330.820.100.330.301.140.050.020.340.031.510.390.010.060.401.750.092.16
La0.260.332.324.054.755.165.746.010.477.9216.5023.9215.4516.9128.431.903.833.757.55
Ce0.310.513.719.428.718.469.929.780.859.6220.6029.2025.1021.4730.744.848.0610.0215.89
Pr0.020.050.411.100.930.931.070.860.110.711.302.081.871.271.980.670.861.191.45
Nd0.110.142.385.624.713.223.443.490.552.103.895.185.073.484.913.753.674.985.35
Sm0.050.060.511.011.040.510.530.370.190.280.270.800.490.490.431.390.800.890.82
Eu-0.010.040.100.020.060.050.090.03-0.030.03-0.040.060.070.040.090.11
Gd0.010.060.710.891.180.750.690.470.290.060.110.210.200.130.241.350.470.481.00
Tb0.010.010.100.130.130.100.120.060.060.010.030.030.020.020.020.260.080.120.17
Dy0.050.050.750.791.060.670.770.430.340.070.050.090.190.020.131.670.330.680.79
Ho0.010.020.160.200.200.170.190.130.070.02-0.03-0.020.030.380.090.210.15
Er-0.060.370.470.490.430.380.320.160.030.020.040.130.060.041.270.330.620.41
Tm-0.010.040.050.070.060.060.040.05--0.010.01-0.010.160.030.040.05
Yb0.040.020.280.300.280.430.340.300.070.080.010.050.02-0.031.000.260.510.40
Lu--0.030.040.060.060.070.070.01----0.010.010.150.040.120.05
Hf0.010.010.01-0.010.01-0.01-0.02-0.020.02-----0.02
Ta----0.39----0.01-0.01-------
Th------0.01----0.010.010.010.010.020.06-0.40
U---0.010.01------0.01-0.01--0.15--
Y/Ho38.9339.2427.5140.5840.8439.5531.3128.1344.2048.19201.8842.73-29.9621.6332.4527.0923.2827.28
ΣREE0.881.3211.8124.1523.6320.9923.3522.413.2520.9042.8061.6648.5443.9267.0618.8518.8923.6834.19
LREE0.751.119.3721.2920.1518.3420.7420.592.2020.6442.5861.2047.9743.6666.5512.6117.2620.9231.18
HREE0.120.222.452.863.472.662.611.821.050.260.220.460.570.260.516.241.622.763.02
LREE:HREE6.065.143.837.455.806.907.9411.312.1078.60194.47132.2384.77171.44131.202.0210.637.5810.34
δEu0.370.400.210.310.060.290.250.630.40-0.480.15-0.320.560.160.190.360.39
(La:Sm)N3.673.432.852.512.876.346.8610.191.6117.7138.8918.9020.0221.5141.680.863.022.655.82
(La:Yb)N5.0112.385.619.2411.518.1711.2413.324.5768.871112.90317.34552.57-755.281.289.974.9812.86
(Sm:Nd)N1.251.360.660.560.680.490.470.331.040.410.210.470.300.440.271.140.670.550.47
(Gd:Yb)N0.312.492.072.433.421.421.611.243.330.619.103.378.63-7.761.101.480.762.04
The element content unit is (ppm), “-“ indicates that the measured value falls below the detection limit of the instrument.
Table 3. Isotopic analysis of Sm-Nd in Fe-Mn carbonate minerals.
Table 3. Isotopic analysis of Sm-Nd in Fe-Mn carbonate minerals.
Sm (ppm)Nd (ppm)Testing Error147Sm/144Nd143Nd/144Nd
Sample1ZK266-20.78150.98270.0000090.48020.512988
Sample2ZK268-30.96040.81030.0000080.71690.513346
Sample3ZK274-60.46830.78590.0000070.36470.512805
Sample4ZK276-20.13270.97160.0000090.08150.512374
Sample5ZK278-60.36240.85120.0000060.25620.512641
Sample6ZK328-90.21150.97610.0000070.13080.512452
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Yang, Y.; Li, C.; Wang, Z.; Gu, H.; Yang, W.; Yuan, M.; Fu, A.; Zheng, B.; Cheng, Z.; Liu, B. Characteristics and Metallogenic Significance of Fe-Mn Carbonate Minerals in the Erdaokan Ag Deposit, Heilongjiang Province, Northeast China: Constraints from Sm-Nd Geochronology and Trace Elements. Minerals 2024, 14, 655. https://doi.org/10.3390/min14070655

AMA Style

Yang Y, Li C, Wang Z, Gu H, Yang W, Yuan M, Fu A, Zheng B, Cheng Z, Liu B. Characteristics and Metallogenic Significance of Fe-Mn Carbonate Minerals in the Erdaokan Ag Deposit, Heilongjiang Province, Northeast China: Constraints from Sm-Nd Geochronology and Trace Elements. Minerals. 2024; 14(7):655. https://doi.org/10.3390/min14070655

Chicago/Turabian Style

Yang, Yuanjiang, Chenglu Li, Zeyu Wang, Huajuan Gu, Wenpeng Yang, Maowen Yuan, Anzong Fu, Bo Zheng, Zhaoxun Cheng, and Baoshan Liu. 2024. "Characteristics and Metallogenic Significance of Fe-Mn Carbonate Minerals in the Erdaokan Ag Deposit, Heilongjiang Province, Northeast China: Constraints from Sm-Nd Geochronology and Trace Elements" Minerals 14, no. 7: 655. https://doi.org/10.3390/min14070655

APA Style

Yang, Y., Li, C., Wang, Z., Gu, H., Yang, W., Yuan, M., Fu, A., Zheng, B., Cheng, Z., & Liu, B. (2024). Characteristics and Metallogenic Significance of Fe-Mn Carbonate Minerals in the Erdaokan Ag Deposit, Heilongjiang Province, Northeast China: Constraints from Sm-Nd Geochronology and Trace Elements. Minerals, 14(7), 655. https://doi.org/10.3390/min14070655

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