Abstract
The Mississippi Valley–type (MVT) deposits reached their maximum abundance during the final assembly of Pangea. The intense orogenic activity during this assembly in relatively low latitudes created abundant opportunities for the migration of sedimentary brines into the interior carbonate platforms landward of the orogenic belts, leading to the formation of MVT deposits. Thus, dating the MVT deposits can potentially aid in the reconstruction of the plate tectonic evolution during the assembly of Pangea. The Yangtze Craton hosts significant carbonate-hosted Zn–Pb deposits (> 60 Mt Pb + Zn metals), accounting for 30% of China’s Zn–Pb resources. However, determining the timing of zinc and lead mineralization in these reservoirs is challenging. This study employs LA-ICP-MS U–Pb geochronology on calcites to date Zn–Pb deposits hosted in Lower Cambrian limestone in the Huayuan orefield. Three generations of calcite formation were dated: the first recorded the pre-ore deposition of Lower Cambrian limestone at 517 ± 10 Ma, the second marked a hydrothermal event linked to stratiform sphalerite ore formation at 501.4 ± 8.4 Ma, and the third was associated with discordant breccia-hosted Zn–Pb mineralization at 397.5 ± 9.6 Ma. Our results indicate that Paleozoic carbonate-hosted Pb–Zn mineralization in the Yangtze Craton is linked to (1) the final assembly of Gondwana in the late Cambrian-early Ordovician (520–480 Ma); and (2) the intracontinental orogeny response to Jiangnan Uplift (420–400 Ma). This study highlights the temporal relationship between low temperature carbonate-hosted mineralization and orogenic events that are consistent with classic MVT models worldwide. It also contributes geochronological data for the reconstruction of plate-tectonic evolution during Pangea assembly. Furthermore, it demonstrates the potential of in situ U–Pb calcite geochronology to date ore deposits lacking syn-ore minerals suitable for traditional dating methods.
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Introduction
Low temperature carbonate-hosted Pb–Zn deposits such as Mississippi Valley-Type (MVT) deposits are a diverse group of epigenetic-replacement ores predominantly found in platform carbonate sequences1,2. They form primarily in orogenic forelands3,4 or extensional basin settings5,6 during regional contractional orogenic events2,6,7,8,9,10, with significant control exerted by faults1,2,7,8. Thus, Mississippi Valley–type deposits (MVT) are believed to be the products of large-scale migration of basinal brines (200–250 °C; 10–35 wt%) driven by orogeny1,4. For example, during the assembly of Pangea, various factors converged to create optimal conditions for low temperature carbonate-hosted Pb–Zn mineralization, including extensive orogenic activity that prepared the ground for these deposits districts through far-field deformation of the craton, emphasizing the role of tectonics in low temperature carbonate-hosted Pb–Zn deposits formation1,2,7. Therefore, determining the precise mineralization age is crucial for establishing the link between low temperature carbonate-hosted Pb–Zn mineralization and regional contractional events. Furthermore, dating these deposits can potentially aid in the reconstruction of the plate tectonic evolution.
Low temperature carbonate-hosted Pb–Zn mineralization along the Yangtze Craton margin occurred primarily during two significant periods: 500–470 Ma11,12,13 and 430–400 Ma12,13,14,15. However, the temporal relationship between these two mineralization events and specific regional tectonics process remains obscure. This ambiguity arises from the complex interplay of prolonged and multiple regional compressional tectonics that have influenced carbonate-hosted Zn–Pb mineralization over time6,16,17,18. The overlapping tectonic events complicate the accurate dating of mineralization, resulting in ongoing debates about the chronology and mechanisms of these deposits.
Despite advances in dating techniques, accurately determining the age of low temperature carbonate-hosted deposits remains complex due to the absence of suitable U-rich minerals, necessitating reliance on alternative dating methods like Rb–Sr and Sm–Nd isochron dating15,19,20,21,22,23. These methods often yield mixed ages due to potential contamination by inclusions of carbonate, clays, or volcanic ash that could impart differing 87Sr/86Sr ratios24. Additionally, they frequently fail to differentiate between various geodynamic settings and multiple mineralization stages2,21,25,26,27.
Recent LA-ICP-MS advances in U–Pb dating of carbonate have improved the accuracy of timing low-temperature geological events. Despite the challenges of calcite’s low uranium content and open-system behavior, this method has proven effective in diverse geological contexts, including diagenesis, fluid migration, brittle deformation, and ore formation29,30,31,32,33,34,34,35,36. The technique has notably determined precise ages for Yukon’s Carlin-type Au deposits37, advanced understanding of petroleum migration in the Tarim Basin38, and offered new insights into low-temperature carbonate-hosted deposit formation6,11,27.
We present the calcite U–Pb ages for the Early Cambrian carbonate-hosted deposits (Limei and Danaopo) of the Huayuan orefield (ca. 20 Mt contained Pb + Zn @ 4%) in the central Yangtze Craton margin (Fig. 1; modified from Zhang et al.28). We are investigating: (1) whether Huayuan Pb–Zn mineralization corresponds to the two low-temperature carbonate-hosted Pb–Zn events (500–470 Ma and 430–400 Ma) on the Yangtze Craton margin, and (2) the relationship between these mineralization events and regional compressional tectonics. This relationship remains unclear due to the lack of detailed petrographic and mineralogical analysis, therefore fails to constrain the multiple stages of Pb–Zn mineralization. Large errors and variations of ages within a single deposit also commonly occur, which might reflect a narrow range of Rb/Sr ratios or partial or total resetting of the isotopic systems by post-mineralization hydrothermal fluids24. Our in situ U–Pb ages from calcites associated with the Zn–Pb mineralization from two individual deposits (Limei and Danaopo) within the Huayuan carbonate-hosted Zn–Pb orefield (Fig. 1), combined with in situ calcite trace elements and sphalerite Rb–Sr age data, provide robust timing constraints on carbonate-hosted Zn–Pb mineralization in the Huayuan orefield. This study aims to accurately date the low-temperature carbonate-hosted Pb–Zn mineralization at the Huayuan orefield and clarify its relationship with regional tectonic processes along the Yangtze Craton margin. By providing precise U–Pb ages for calcite, we address uncertainties about the timing of mineralization events and their association with major compressional tectonics, thereby enhancing the understanding of history of the plate tectonic evolution in this region.
(a) Tectonic map of South China. The green dashed box (top left) indicates the area shown in Fig. 1b (modified from Zhang et al.28 Created with CorelDRAW 2024: https://www.coreldraw.com/en/). Abbreviations: NCC = North China Craton, QDOB = Qinling-Dabie Orogenic Belt, YC = Yangtze Craton, JOB = Jiangnan Orogenic Belt, CB = Cathaysia Block, SGFB = Songpan Ganzê Fold Belt, YA = Yidun Arc, SOB = Sanjiang Orogenic Belt; (b) Simplified tectonic map of the Yangtze Craton and adjacent orogenic belts with metamorphic complexes, showing the distribution of carbonate-hosted Pb–Zn deposits around the Yangtze Craton.
Geological setting
Regional geology
The Huayuan carbonate-hosted Zn–Pb orefield is located along the central margin of the Yangtze Craton, bounded by the Jiangnan Orogen to the southeast (Fig. 1). The amalgamation of the Yangtze and Cathaysia Blocks around 980–820 Ma formed the Jiangnan orogenic belt and the Proto-South China continent39,40. This event initiated the Nanhua rift basin around 820 Ma, which ceased around 760 Ma40,41,42. Subsequently, stable neritic-slope conditions from ca. 760 to 460 Ma supported the deposition of widespread carbonate platforms along with carbonaceous, siliceous, and muddy rocks. Despite this stability, intermittent hydrothermal and minor magmatic activities occurred in the Nanhua basin during the Cambrian43,44,45,46. The Early Paleozoic Caledonian intracontinental orogeny between ca. 460–420 Ma transformed the basin into a foreland basin40,41,47.
The southeastern Yangtze Craton exhibits a complex geological structure, comprising a Meso-Neoarchean crystalline basement of Kongling Group gneiss and amphibolite, a Proterozoic metamorphic basement containing Banxi Group sandstone, silty slate, and sedimentary tuff, and sedimentary covers from the Sinian to Quaternary periods, consisting of clastic and carbonate rocks48,49,50. The Yangtze Craton likely remained at low latitudes from the Neoproterozoic to the Mesozoic, creating favorable conditions for extensive carbonate and evaporite deposition49.
The Huayuan lead–zinc orebodies are mostly hosted in Upper Neoproterozoic-Lower Permian deformed carbonaceous strata51 (Fig. 1), controlled by folds, faults, and lithological contacts52. The main ore-bearing dolomitic carbonates were deposited in the Ediacaran–Early Cambrian, Late Devonian, and Early Carboniferous. In the central and northern Yangtze Craton, gypsum-dominated evaporites are mostly linked with Upper Neoproterozoic and Cambrian carbonate layers and are ore-bearing53. These sulfates were likely the sulfur source for the Huayuan mineralization28. Minor magmatism was reported in the region but was interpreted to be ore-unrelated52.
Northwestward orogenic transpression has formed the NE-/NNE-trending fold-and-thrust structures, strike-slip faults, and secondary normal faults in the central Yangtze Craton54,55. These faults are considered important for localizing the Pb–Zn ore fluids51. There are three major carbonated-hosted Pb–Zn ore fields on the Yangtze Craton margin (Fig. 1b): the Upper Yangtze Pb–Zn province, Mayuan Pb–Zn ore-field, and Huayuan ore-field26. At the northern margin, the Mayuan Zn–Pb ore-field is defined by strata-bound and stratiform ores situated within breccias and dissolution-replacement features in Upper Neoproterozoic Dengying dolostone formation11,26,56. An epigenetic model proposes that the Mayuan Zn–Pb deposits are linked to the closure of the Proto-Tethys. This is supported by U–Pb geochronology of carbonate minerals, which dates the mineralization events at 473.4 ± 2.7 Ma and 368.7 ± 3.1 Ma11.
At the SW margin of the Yangtze Craton, the Sichuan–Yunnan–Guizhou Triangle (SYGT) of Zn–Pb deposits are hosted within the late Neoproterozoic, Devonian, Carboniferous, and Permian carbonates57 (Fig. 1b) and contains ~ 400 carbonate-hosted Pb–Zn deposits with > 26 Mt of metal resources57.
Previous geochronological studies on these Pb–Zn deposits (sphalerite Rb–Sr and calcite Sm–Nd) yielded two groups of ages ranging from ca. 362–411 Ma15,58,59,60,61 and ca. 192–226 Ma19,62,63,64,65, respectively. These carbonate-hosted Pb–Zn deposits were closely associated with the intracontinental deformation of the Late Triassic orogeny, in response to the closure of the Paleo-Tethys Ocean19. The locations of these Pb–Zn deposits in the SYGT are invariably governed by an intracontinental oblique strike-slip structural system, resulting from collisional processes between the Yangtze and Indosinian blocks during the Late Triassic66.
The Huayuan Pb–Zn orefield is hosted within the Lower Cambrian Qingxudong platform-facies algal limestone at the center of the Yangtze Craton28 (Fig. 1b). Sulfur-lead isotopic analyses demonstrate that interactions between metal-rich brines from the Niutitang Formation’s black shale and H2S-rich fluids from the Qingxudong algal limestone, through thermochemical sulfate reduction (TSR), play a crucial role in the precipitation of Huayuan Zn–Pb ores28,67. Calcite C-O isotope analysis indicates that the carbon was derived from the dissolution of Qingxudong Formation algal limestone, while the oxygen originated from interactions between wall rocks and basinal brine68. Previous sphalerite Rb–Sr and calcite U–Pb dating indicate that the formation of sphalerite at Huayuan occurred mainly between 510–495 Ma, 410 Ma, and 460 Ma12,14,27. The relationship between this wide range of mineralization processes and orogenic events is still disputed.
Local geology of the Huayuan orefield
The Huayuan orefield is bounded by the Huayuan-Zhangjiajie wrench fault to the west and the Jishou-Guzhang fault to the east (Fig. 2a). The dominant structures in the Huayuan area are the NNE-/NE-axial folds and NE-trending wrench faults, with Pb–Zn mineralization occurring mainly within the subsidiary normal faults52. These features were likely formed by the oblique North China-Yangtze collision and the preceding Craton rotation69, which reactivated the Yangtze-Cathaysia suture zone54, or by the Paleo-Pacific subduction70.
(a) Geologic map and (b) generalized stratigraphic columns of the Huayuan Pb–Zn orefield; (c) geological profile of the Danaopo deposit, showing the strata and orebodies (modified after Zhang et al.28 This figure was created with CorelDRAW 2024: https://www.coreldraw.com/en/).
Exposed strata in the Huayuan orefield include the Upper Neoproterozoic Doushantuo and Dengying Formations shales and Cambrian carbonate sequences (Fig. 2b). The Cambrian strata consist of the Lower Cambrian calcareous silty shale of the Niutitang Formation and Shipai Formation, the Lower Cambrian Limestone (the lower member) and dolomite (the upper member) of the Qingxudong Formation, the Middle Cambrian argillaceous dolomite of the Gaotai Formation, and the Upper Cambrian sandy dolomite of the Loushanguan Formation52. The lower limestone member of the Qingxudong Formation consists of four layers (Fig. 2b), including (from bottom up) two layers of interbedded fine- and coarse-grained limestone (50–100 m) and a third layer of 8–215 m fine-grained algal limestone (main ore-bearing layer) (Fig. 2b, c). The uppermost layer is approximately 21–74 m thick and composed of intrasparite and oolitic limestone, which hosts the Pb–Zn ore. It is primarily composed of micritic calcite (Cal-0) and contains numerous algal decay and intergranular pores, making it susceptible to metasomatism due to its fragility and chemical reactivity. The upper limestone member of the Qingxudong Formation (21–108 m) is host to the Hg ore belt to the south of the Zn–Pb orefield71.
The epigenetic Zn–Pb ores in the Huayuan orefield are confined by NE-trending faults and reef mounds52. The ores form primarily as open-space filling of voids, breccia cement, and replacement of the host limestone. These ores are layered/laminated in nature and of low to medium grade (~ 4 wt% Pb + Zn), with multiple generations of sulfides, carbonates, and barites, as well as minor fluorites28. The Lower Cambrian Niutitang Formation contains a significant amount of bitumen and is interpreted to be a source of hydrocarbons and other metals in the Huayuan district67,72.
The Guzhang anticline comprises Neoproterozoic Banxi Group rocks at its core and Cambrian strata on its limbs that gently dipping (5°–12°). The NE-trending Huayuan-Zhangjiajie (F1), Lianghe-Changle (F3), and NNE-trending Malichang (F2) faults are associated with Pb–Zn ore deposits (Fig. 2c). Drilling and geophysical surveys have not reported any igneous rock occurrences. Some researchers52 attribute the formation of these NE-trending faults to the early Paleozoic orogeny.
The Limei and Danaopo deposits are representative deposits in Huayuan orefield. The Limei deposit contains both stratabound and discordant orebodies, whereas the Danaopo deposit only contains discordant orebodies. Stratabound ore fills open space in bedded algal-bearing and porous limestone. The stratiform ores consist dominantly of pale-yellow sphalerite and calcite, with a minor amount of barite and dolomite. The discordant breccia-hosted orebodies are structurally controlled by NE-trending faults. This type of ore consists primarily of brown-yellow sphalerite with minor galena, pyrite, and marcasite. Non-metallic minerals consist primarily of calcite with traces of barite, fluorite, and dolomite.
Sample selection and analytical methods
Sample selection
Three samples of ore-bearing calcites from layered/stratabound and discordant orebodies from Limei (LM) and Danaopo (DNP) deposits in Huayuan district were selected for in situ U–Pb calcite dating. Seven samples of brown sphalerite in discordant breccia-hosted ores from the Limei (LM) deposit were selected for Rb–Sr isochron dating. Sampling focused on hydrothermal calcite coeval with Pb/Zn mineralization, with some samples selected with calcite pre-dating the sulfide assemblage to establish a temporal framework for the mineralization process. Dating the pre-sulfide calcite allows for determining the timing of hydrothermal events before the main ore-forming stage. This helps to understand the sequence of geological events leading to mineralization and provides insights into the conditions and processes influencing ore formation. This approach enhances the understanding of the geological history and improves the accuracy of the mineralization model.
Cathodoluminescence
Before performing the calcite U–Pb dating analysis, a detailed examination of the polished thin sections was carried out using microscopy and cathodoluminescence (CL) to identify evidence of multiple generations of calcite. The optical CL photomicrography was conducted at the Southwest Petroleum University using an Axioscope 5 microscope equipped with a CLF-2 CL system. The electron source for the low-vacuum CLF-2 system was operated at 13 kV with an approximate current of 345 mA.
Calcite trace elements
Trace elements analysis was carried out using a Thermo Scientific quadrupole iCap TQ ICP-MS and ASI Resolution LR 193 nm ArF excimer LA system at the Micro-Origin and Spectrum Laboratory (Sichuan Chuangyuan Weipu Analytical Technology Co. Ltd.). The detailed analytical methods and procedures used are described in Online Appendix 1.
Calcite U–Pb dating
In-situ U–Pb dating of calcite was performed at the Micro-Origin and Spectrum Laboratory (Sichuan Chuangyuan Weipu Analytical Technology Co. Ltd.) using a Thermo Scientific quadrupole iCap TQ ICP-MS combined with an ASI Resolution LR 193 nm ArF excimer laser ablation (LA) system, following established standard procedures73,74,75. The laser operated with He carrier gas at 320 mL/min, 0.99 L/min Ar nebulizer gas, and 5 mL/min N2 for enhanced sensitivity. The iCap TQ was optimized for sensitivity and low oxide rates (less than 1% using NIST 612). A 50 um line is ablated with repetition rate of 10 Hz, at 3 J/cm2, and scan speed at 3 um/s. The sensitivity is achieved with > 900k cps for U which is equilibrant to > 24k cps/ppm. Also, the background of the LA-ICPMS was below 10 cps (usually less than 5 cps) for 207Pb to achieve high SNR for low (less than 0.1 ppm, 238U) content carbonate samples. ICP conditions were: coolant gas at 14 L/min, RF power at 1550 W, auxiliary gas at 0.8 L/min, and nebulizer gas at 0.99 L/min. Only masses 206, 207, 208, 232, and 238 were measured due to high Hg interference from Ar gas. Laser timing parameters were: 2 s surface cleaning, 7 s washout, 15 s background, 20 s ablation, 6 s washout, 15 Hz repetition rate, and 3.0 J/cm2 fluence with 120 µm spots. NIST 614 glass was used to bracket carbonate references and unknowns every five intervals, correcting for 207Pb/206Pb and 238U/206Pb ratios without down-hole fractionation correction. The calibration process utilized internal standards AHX-1d (238.2 ± 0.9 Ma)76 for ensuring stability and high uranium content, and PTKD-2 (151–157 Ma)73 for monitoring purposes due to its variable age and low uranium content. For LD-5, which contains low levels of common lead, the upper intercept had to be fixed based on the SK model (72 Ma corresponding to 0.84 ppm common lead). The LD-5 calcite standard produced a U–Pb Tera-Wasserburg concordia lower intercept age of 72.71 ± 0.38 Ma (MSWD = 1.4), anchored to a 207Pb/206Pb ratio of 0.8573.
Sphalerite Rb–Sr dating
Rb–Sr isotope analysis was carried out at the laboratory of Tianjin Center, China Geological Survey. The Sr isotope ratios were measured by Thermo Fisher Scientific Triton TIMS (USA). Inductively coupled plasma mass spectrometry (ICP-MS, Agilent 7900, USA). The detailed analytical methods and procedures used are described in Online Appendix 1.
Analytical results
Mineral Paragenesis
All deposits in the Huayuan ore-field exhibit similar mineral parageneses, characterized by primary sulfide phases of sphalerite and galena, with minor pyrite, and gangue minerals of dolomite and calcite. Barite and fluorite are also locally abundant. Petrographic studies have identified three post-sedimentary hydrothermal stages (S1-S3; Fig. 3) associated with two types of Zn–Pb ores: (1) layered, laminated, or stratabound (Figs. 4a–c, 5a), and (2) discordant orebodies (Figs. 4e–f, 5d).
Summary of mineral paragenesis for the Limei and Danaopo deposits in the Huayuan Pb–Zn orefield.
(a–d) Photographs of the Limei pale-yellow sphalerite (Sp1) from stratiform ore samples, showing sphalerite-calcite veins in the limestone micro-fracture/suture. The sulfide ore is characterized by having calcite phenocrysts in centimeter-scale veins, and sphalerite at the bottom of the hydrothermal calcite-limestone interface. (e–g) Photographs of the Danaopo yellow–brown nodular-cockade-type sphalerite (Sp2) from discordant breccia-hosted ore samples: (e) Sp2-calcite-barite veins cutting limestone; (f) Sp2-pyrite-calcite-barite veins cutting limestone; (g) Sp2-Py2-calcite-Brt2 vein in limestone.
(a) Photographs of the pale-yellow sphalerite (Sp1)-calcite (Cal-2) veins and the areas of LA-MC-ICP-MS calcite U–Pb isotope analyses and U–Pb ages for (b) pre-ore calcite (Cal-1); (c) pale-yellow sphalerite (Sp1)-related calcite (Cal-2); (d) photographs of the yellow–brown sphalerite (Sp2)-pyrite (Py2)-calcite (Cal-3) veins; (e) the areas of LA-MC-ICP-MS calcite U–Pb isotope analyses and U–Pb ages for yellow–brown sphalerite (Sp2)-related calcite (Cal-3); (f–h) cathodoluminescence (CL) images of pre-ore calcite (Cal-1) and syn-ore calcite (Cal-2; Cal-3) crystals from the Limei and Danaopo deposits.
Pre-ore Calcite (Cal-1) Stage (S1): The initial stage (S1) involves pre-ore calcite (Cal-1), occurring as grayish cloudy, prismatic crystals along the limestone with a clear boundary to the ore-bearing vein (Fig. 5b). The Cal-1 phase predates the ore stage and is found in both Limei and Danaopo deposits (Fig. 5b, e). The hosted limestone and pre-ore calcite (Cal-1) are commonly dull red to almost non-luminescent under cathodoluminescence (CL) (Fig. 5f).
Pale Yellow Sphalerite (Sp1)-Calcite (Cal-2) Stage (S2): Stage 2 (S2) features pale-yellow sphalerite (Sp1) as the exclusive sulfide phase, occurring as coarse-grained (> 500 μm) subhedral crystals (Fig. 4), primarily coexisting with calcite (Cal-2) and trace euhedral tabular barite (Brt1). These veins (< 3 cm wide) were emplaced along micro-sutures/fractures in limestone, mainly forming stratiform ores in the Limei deposit. The sphalerite is present at the hydrothermal calcite-limestone interface. Cal-2 in these veins occurs as euhedral to anhedral crystals and clear veined aggregates (Fig. 5b, c). The syn-ore calcite (Cal-2) is relatively homogeneous, with high CL intensity, displaying a bright orange luminescence (Fig. 5f–h).
Brown Sphalerite (Sp2)-Galena-Pyrite-Calcite (Cal-3) Stage (S3): Stage 3 (S3) is characterized by discordant breccia-hosted veins (> 5 cm wide) that crosscut the limestone, mainly occurring in the Danaopo deposit. Sulfide ores comprise nodular/cockade sphalerite (Sp2; Fig. 4e, f), appearing as brown (Sp2B; Fig. 4f), coarse-grained subhedral to euhedral crystals (> 500 μm), intergrown with galena and minor pyrite (Py2; Fig. 4g). Non-metallic minerals include primarily calcite (Figs. 4, 5d–e) and, to a lesser extent, barite and fluorite. Pyrite occurs as euhedral grains (5 to > 50 μm; Fig. 4f) along the boundary between the calcite-sulfide vein and the limestone (Fig. 4f). Brown sphalerite is situated between the pyrite and gangue minerals (Figs. 4f, 5e). Barite appears as euhedral tabular grains or fine-grained aggregates. Cal-3 is characterized by clear, massive, breccia, and veined aggregates and euhedral to anhedral coarse-grained crystals (Fig. 5d, e). The syn-ore calcite (Cal-3) also exhibits a relatively homogeneous composition, high CL intensity, and bright orange luminescence (Fig. 5f–h).
Calcite trace elements
Trace element contents of carbonates from the Huayuan orefield are listed in Online Appendix 2. Ore-bearing limestone (Cal-0) has an average of 3210 ppm Mg, 296 ppm Sr, 255 ppm Mn, 354 ppm Fe, 2.29 ppm Pb, and 0.11 ppm U. Cal-1 preserved similar contents of Mg (3399 ppm) and Sr (319 ppm) and lower Mn (113 ppm), Fe (70.4 ppm), Pb (0.44 ppm), and U (0.08 ppm). Cal-2 and Cal-3 yield higher Sr (940–1354 ppm) and lower Mg (1752–2169 ppm), Fe (51.7–142.9 ppm), and U (0.01–0.04 ppm).
Figure 6 shows the chondrite-normalized rare earth elements (REE) patterns for these carbonates. Slightly light rare-earth (LREE) enrichment can be observed in all calcite. Qingxudong limestone (Cal-0) yields a mediant total REE contents, with slightly negative Eu anomalies (Eu/Eu* values of 0.70; Eu/Eu* = Eu/((Sm + Nd)/2)). Cal-1 is characterized by a lower total REE contents, with no Eu anomalies. In contrast, Cal-2 preserved a higher total REE contents, with slightly negative Eu anomalies (Eu/Eu* values of 0.94). Cal-3 displays a similar total REE contents as the ore-bearing limestone (Cal-0), with positive Eu anomalies (Eu/Eu* values of 1.90).
Calcite U–Pb dating
Three in situ calcite U–Pb lower intercept ages and one sphalerite Rb–Sr isochron age (Fig. 7) are summarized in the following section. The data are presented according to the paragenetic relationship between carbonate and sulfide minerals. The complete LA-ICP-MS and Rb–Sr results are given in Online Appendix 3 and Online Appendix 4. All of these ages (517.0 ± 10.0 Ma to 397.5 ± 9.6 Ma; 2σ; 95% confidence interval) fall within a relatively narrow range and overlap or postdate the early Cambrian depositional age of the host rocks (ca. 543–513 Ma).
Tera-Wasserburg concordia diagrams of (A) pre-ore calcite (Cal-1); (B) pale-yellow sphalerite (Sp1)-related calcite (Cal-2); (C) Rb–Sr isochron diagram for brown sphalerite (Sp2); (D) Tera-Wasserburg concordia diagram of yellow–brown sphalerite (Sp2)-related calcite (Cal-3).
The pre-ore Cal-1 phase within LM-02 yielded lower intercept ages of 517.0 ± 10.0 Ma (MSWD = 0.9, Fig. 7a), representing the oldest of the dated samples. Calcite 2 (Cal-2) phase within sample LM-04 yielded a lower intercept age of 501.4 ± 8.4 Ma (MSWD = 1.4, Fig. 7b). In contrast, U–Pb isotope analyses of Cal-3 phase yielded the younger lower intercept ages of 397.5 ± 9.6 Ma (MSWD = 1.7, Fig. 7d).
Rb and Sr concentrations and isotopic compositions of seven brown sphalerite samples from discordant breccia-hosted ores are presented in Online Appendix 4. The Rb and Sr concentrations range from 0.2996 to 0.3791 ppm and from 4.0765 to 38.4308 ppm, respectively. The 87Rb/86Sr ratios range from 0.0227 to 0.2696. Measured 87Sr/86Sr ratios vary from 0.70500 ± 0.00006 (2σ) to 0.71063 ± 0.00014 (2σ). The data define a Rb–Sr isochron age of 414 ± 16 Ma (MSWD = 1.0) with an initial 87Sr/86Sr ratio of 0.709422 ± 0.000022 (Fig. 7c). This result provides a precise age constraint on main-ore stage sulfide precipitation.
In summary, calcite U–Pb and sphalerite Rb–Sr ages of 517.0 ± 10.0 Ma, 501.4 ± 8.4 Ma, 414 ± 16 Ma and 397.5 ± 9.6 Ma were obtained in Huayuan Pb–Zn orefield.
Discussion
Ore fluid origins
The initial 87Sr/86Sr ratio of brown sphalerite (0.7094) in the Limei deposit is significantly higher than the 87Sr/86Sr ratio of the mantle (0.7035)79. It is also slightly higher than the paleo-seawater value at 418 Ma (0.7088)80, the ore-bearing Lower Cambrian Qingxudong carbonates (~ 0.7089)71, or that of the upper dolomite strata (~ 0.7092)81. Therefore, the high 87Sr/86Sr of Huayuan sulfide possibly derived from the more radiogenic underlying strata. The underlying strata, shales and black shales of the Cambrian Balang (~ 0.8273) and Niutitang Formations (~ 0.7182) are characterized by significantly more radiogenic 87Sr/86Sr ratios71. Similarly, the Sr isotope analysis of ore-related calcite suggests that ore fluids of Huayuan derived from underlying strata82. The S isotope and sulfide geochemistry concluded that Huayuan ore-fluids have a mixed origin between metal-rich brines (underlying basal Niutitang Fm. black shale) and H2S-rich fluid28 (ore-bearing Qingxudong Fm.). Therefore, the Sr isotope signature of the Huayuan sphalerite may reflect interaction of hydrothermal fluids derived from the underlying strata (with higher 87Sr/86Sr ratios) with the ore-bearing limestone or coeval seawater (with lower 87Sr/86Sr ratios). This is supported by higher Sr contents of Cal-2 and Cal-3, and different REE patterns (Fig. 6) between syn-ore calcite (Cal-2, Cal-3) and ore-bearing limestone (Cal-0). The higher total REE of Cal-2 reveals an input of enriched REE contents from underlying strata (Niutitang Fm.77).
The indistinguishable total REE content between Cal-3 and Cal-0, coupled with the positive Eu anomalies observed in Cal-3 (Fig. 6), suggests increased fluid-rock interaction under high-temperature conditions during the formation of discordant breccia-hosted ores83. As the ore-bearing strata are carbonates, these fluid-rock interactions can lower the fluid pH84, leading to the formation of acidic fluids. Thus the high temperatures acidic fluids can enhance the mobility of Eu2+, and preferentially substitutes for Ca2+ over trivalent REEs85, resulting in positive Eu anomalies in mineral precipitates86,87,88. Positive Eu anomalies have been documented by Ren and Li89 in the Neoproterozoic Doushantuo cap carbonates of the Yangtze Craton. They propose that these carbonates were formed in an extensive anoxic Ediacaran ocean in the shallow-to-deep water columns, with a high-temperature (140 °C and 236°C27,28) hydrothermal input for REEs90,91. We suggest that the positive Eu anomaly observed in the Huayuan Cal-3 may be inherited from the Neoproterozoic Doushantuo cap carbonates.
In summary, we infer that ore-forming fluids from Neoproterozoic Doushantuo brine reservoirs, leached Zn and Pb from Proterozoic basement rocks (evidence from Pb isotope67,92). These brines migrated upward through reactivated syn-rift fault systems and underwent extensive fluid-rock interactions with the Qingxudong Formation limestone, leading to the formation of Cal-3-bearing breccia-hosted ores and redistribute REEs and result in positive Eu anomalies88.
Mineralization ages and geological significance
The U–Pb isotope ages presented here provide constraints on the timing of ore formation in the Huayuan area. The age of the host rock (Qingxudong Formation) is Cambrian series 2, which should be younger than ~ 521 Ma. Furthermore, the Niutitang Formation, located below the Qingxudong Formation, contains many volcanic tuffs. The zircon U–Pb dating of these tuffs ranges from 524.2 to 518.0 Ma43,93,94. Our pre-ore calcite (Cal-1) yields a U–Pb age of 517 Ma, which is slightly younger than the host rock. MVT ores typically form near age of host rock (e.g., Irish Canning basin95, Irish Midlands25) to tens to hundreds of million years younger1. Thus, we suggest that pre-ore calcite (Cal-1) formed shortly after host rock deposition and recrystallized from it.
Petrographical evidence of the calcites and sulfides indicates that pale-yellow sphalerite (Sp1) was synchronous with Cal-2, whereas yellow–brown sphalerite (Sp2) was synchronous with Cal-3 (Figs. 4, 6d–e). The isotope ages of the syn-ore calcite and sphalerite reveal a two-stage metallogenic process: (1) ~ 500 Ma and (2) ~ 414 to 400 Ma.
Recent studies show many Yangtze Craton carbonate-hosted Pb–Zn deposits have isotope ages concentrated in the period of ca. 500–470 Ma. For instance, a sphalerite Rb–Sr isochron age of ca. 507 Ma was reported for the Bingdongshan Pb–Zn deposit13. Rb–Sr isochron dating of the Dagoudong Zn–Pb deposit yielded an age of 489.6 ± 5.9 Ma12 (South Huayuan). In situ LA-ICP-MS U–Pb dating of associated carbonates within the Jiulingzi carbonate-hosted Zn–Pb deposit (northern margin of the Yangtze Craton) defined an ore formation age of 473.4 ± 2.7 Ma11.
The closure of the Kuunga Ocean during Cambrian-Ordovician period (530–480 Ma) resulted in the final assembly of Gondwana96,98. The detrital zircon population from Neoproterozoic-Ordovician in Hainan Island and the Northampton Complex in the Western Australian margin of Gondwana supports an amalgamation of South China-India with Western Australia along the Kuunga suture97. In the late Neoproterozoic-Cambrian, the South China Craton was situated off northeast India97,99,100,101 (Fig. 8a). The Ordovician–Silurian strata in South China contain ca. 490 Ma exotic zircons102 that were likely derived from the Bhimphedian (530–470 Ma) and Ross-Delamerian (520–480 Ma) orogens within eastern Gondwana103.
(a) Simplified reconstruction of Gondwana showing the ___location of South China96,97. sPCMs = southern Prince Charles Mountains. IC = Indochina. (b) A series of sketches showing the amalgamation of the South China Craton and the Western Australia Craton during the late Cambrian-early Ordovician (520–480 Ma); (c) development of the late Ordovician-early Silurian (460–400 Ma) Orogeny.
Notably, ca. 520–480 Ma metamorphic events have been documented for this orogen in South China97 (Fig. 8b). In addition, paleomagnetic data indicate that the Yangtze region was within 25° of the equator during the Ediacaran and Cambrian periods19,104. The presence of 530–510 Ma juvenile detrital zircons in the early Cambrian foreland basin along the western Yangtze margin suggests a collision with an arc in the Proto-Tethys Ocean near the Arabian-Indian Gondwana margin101.
The age of Cal-2 (related pale-yellow Sp1; 501.4 ± 8.4 Ma) in Huayuan is consistent with the timing of these orogens. Geochronological data, thus reveal a temporal relationship between the Huayuan early Pb–Zn mineralization and the assembly of Gondwana in the Late Cambrian–Early Ordovician.
During the Late Ordovician to Early Devonian period (Fig. 8b; 460–400 Ma), an intracontinental orogeny occurred in the South China Craton as a response to the closure of the Proto-Tethys Ocean or the subduction of the Proto-Pacific Ocean40,97,105. This has been related to the co-genetic Alice Springs orogenic belt in central Australia105 (460–400 Ma). The strong uplift of the Jiangnan region54 (Fig. 8c, 420–410 Ma) represents the peak of the intracontinental orogeny in South China, associated with magmatism that is dated at 430–400 Ma106. The main ore deposition age in the Huayuan orefield (~ 400 Ma) is temporally associated with this Silurian-Devonian orogeny event (Fig. 9).
Ages of typical carbonate-hosted Pb–Zn deposits in the Yangtze Craton margin and regional tectonic revolution.
Many carbonate-hosted Zn–Pb deposits in the Yangtze Craton were temporally constrained to 430–400 Ma. The sphalerite Rb–Sr isochron dating suggests the Bingdongshan and Aozigang Zn–Pb deposits were formed at 434–431 Ma and 409 ± 9.7 Ma, respectively12,13. Sphalerite Rb–Sr isochron age of ~ 410 Ma was reported for the Shizishan and Rouxianshan Zn–Pb deposits in Huayuan12,14. From a global perspective, a significant spike in MVT mineralization occurred during the Late Silurian to Jurassic7 (~ 430 to 200 Ma). Therefore, our in situ calcite data indicate that Huayuan secondary Zn mineralization belongs to this late Silurian to early Devonian MVT metallogenic event that represents the peak of contemporaneous orogeny.
Conclusions
This study employs LA-ICP-MS U–Pb geochronology on calcites to accurately determine the ages of carbonate-hosted Zn–Pb mineralization in the Huayuan orefield, Central Yangtze Craton. Two distinct mineralization events are identified: (1) early stratiform pale-yellow sphalerite ore formation at 501.4 ± 8.4 Ma, and (2) late discordant breccia-hosted brown sphalerite and galena mineralization at 397.5 ± 9.6 Ma.
These findings align with known Pb–Zn mineralization events along the Yangtze Craton margin, specifically during the 500–470 Ma and 430–400 Ma periods. The early mineralization (~ 500 Ma) is associated with the final assembly of Gondwana during the Late Cambrian to Early Ordovician, while the later mineralization phase (~ 400 Ma) corresponds to the intracontinental orogeny related to the Jiangnan Uplift.
This study highlights the effectiveness of in situ U–Pb calcite dating in establishing precise age constraints for ore deposits, particularly in cases where traditional methods fall short. The temporal correlation between the Huayuan mineralization and regional orogenic events enhances our understanding of the geological history of the Yangtze Craton and provides a robust framework for exploring similar deposits globally.
Future research should focus on integrating geochronological data with detailed petrographic and geochemical analyses to further elucidate complex mineralization processes. Refining these techniques and expanding their application across various geological settings will contribute to more efficient and targeted mineral exploration strategies.
Data availability
All data generated or analysed during this study are included in this published article (and its Supplementary Information files).
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Acknowledgements
Editor-in-Chief Prof. Rafal Marszalek, handling editor Prof. Patrick Meister, and two reviewers are thanked for their constructive comments and suggestions, which helped improve this paper. The study benefited from the financial support provided by the National Natural Science Foundation of China (42073001 and 42372105), the Science and Technology Innovation Program of Hunan Province (2021RC4055), Major Scientific and Technological Research Project on Natural Resources in Hunan Province (2022-02) and the Science and Technology Plan Project of the Department of Natural Resources of Hunan Province (2019-07, 2017-04)
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B.L. designed the research and provided samples; B.L. and W.D.Z. interpreted the results; W.D.Z. wrote the manuscript with suggestions from all co-authors; B.L. is the supervisor and contributed significantly to analysis and manuscript preparation; J.X.Z., P.L., Y.X.F. and J.P.F edited the manuscript; Y.X. measured the samples.
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Li, B., Zhang, WD., Zhao, JX. et al. U–Pb geochronology of carbonate-hosted Pb–Zn ores reveals plate-tectonic evolution of eastern Asia during the early Paleozoic. Sci Rep 14, 25313 (2024). https://doi.org/10.1038/s41598-024-76170-x
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DOI: https://doi.org/10.1038/s41598-024-76170-x
