| Citation: | Lingtong Xu, Wenchao Yu, Song Jin, Guo Hua, Pengfei Ma, Yuansheng Du, Cailong Zhang. Transition from the Sedimentary Manganese Deposit to Supergene Manganese Ore in Eastern Hebei, North China: Evidences from Mineralogy and Geochemistry. Journal of Earth Science, 2025, 36(1): 11-28. doi: 10.1007/s12583-023-1856-9
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Original sedimentary manganese (Mn) deposits and supergene Mn ores are important Mn resources in China. However, the geochemical information from Chinese supergene Mn ores is scarce, and the relationship between sedimentary Mn deposits and supergene Mn ores is ambiguous. In this study, we collected the original Mn-bearing dolomitic sandstones (ZK20-3 drillcore) and supergene Mn ores (Longmen Section) from eastern Hebei, North China for systematic petrographic, mineralogical and geochemical analyses. Our new data help us to figure out the transformation from original Mn-bearing deposits to supergene ores. The main minerals of original Mn-bearing dolomitic sandstones are quartz and feldspar, with minor muscovite, dolomite, rhodochrosite, ankerite, and kutnohorite. Supergene Mn-oxide ores only emerged in the middle part of the Longmen (LM) Section, and mainly contain quartz, pyrolusite, cryptomelane, todorokite and occasional dolomite. The possible transformation sequence of Mn minerals is: kutnohorite/rhodochrosite → pyrolusite (I) → cryptomelane (todorokite) → todorokite (cryptomelane) → pyrolusite (II). For Mn-oxide ores, Fe, Na and Si are enriched but Al, Ca, Mg and K are depleted with the enrichment of Mn. For original and supergene ores, the total rare earth element + ytterbium (∑REY) contents range from 105.68 × 10-6 to 250.56 × 10-6 and from 18.08 × 10-6 to 176.60 × 10-6, respectively. Original Mn ores have similar slightly LREE-enriched patterns, but the purer Mn-oxide ore shows a HREE-enriched pattern. In the middle part of the LM Section, positive Ce anomalies in Mn-oxide ores indicate the precipitation of Ce-bearing minerals. It implies the existence of geochemical barriers, which changed pH and Eh values due to the long-time influence of groundwater.
Manganese (Mn) is the second abundant transition metal element in the continental crust after iron (Yu et al., 2020). As a kind of redox-sensitive element, manganese is soluble as Mn2+ but precipitates as oxides or hydroxides when oxidized to a higher valence state in an aqueous system (Roy, 2006). Due to its redox-related property, the migration and precipitation of manganese in the subaerial environment are considered as important indicators for Earth's oxidation (Hummer et al., 2022; Yu et al., 2021, 2020; Johnson et al., 2016). For example, the existence of pyrolusite, vernadite, and todorokite in marine sediments could directly indicate an oxic environment (Sensarma et al., 2021; Fang et al., 2020). And the formation of Mn carbonates generally reflects the oxygenation of surface seawater in a redox-stratified basin due to the enrichment of Mn is related to their oxide precursors (Yu et al., 2020; Roy, 2006). Furthermore, cryptomelane often emerged as supergene oxidized products (Yan et al., 2006).
Compared with original Mn-bearing deposits, studies on the geochemistry of supergene Mn ores are relatively poor at present. After exposing to the surface, the original Mn-bearing rocks will suffer compositional variations that related to primary mineral dissolution and secondary mineral generation due to weathering (Li et al., 2020; Pack et al., 2000). The major rock-forming mineral dissolution and Mn enrichment are important processes during the formation of supergene Mn ores, which are accompanied by the adsorption of economic metals such as Cu, Co, and Ni (Hao and Peng, 1998). The weathering intensity and oxidation depth of ore beds are controlled by climate, geobiology, tectonism, lithology, and regional hydrology (Zhou et al., 2020; Li et al., 2007). Among these factors, tectonism and climate are regarded as dominant ones. In addition, groundwater and well-developed drainage systems are necessary for the development of weathering profiles (Pracejus et al., 1988). Therefore, supergene Mn deposits with different weathering degrees formed under various environments, most of which have higher grades than that of their precursors because of the activation and redistribution of Mn. Some typical supergene Mn deposits (e.g., Groote Eylandt, Australia) have been systematically studied (Pracejus and Bolton, 1992; Pracejus et al., 1990, 1988). These studies focus on the paragenetic association of minerals (e.g., Mn (oxyhydr-)oxides minerals) and formation models (Evdokimov and Pharoe, 2021; Dash et al., 2020; Carmichael et al., 2017; Pack et al., 2000; Ostwald, 1992). The main conclusions of these studies are: (1) supergene high-valence (+4) Mn (oxyhydr-)oxides can transform from any previous Mn-bearing minerals; (2) supergene Mn (oxyhydr-)oxides generally form via precipitation from Mn-rich fluids, replacement of original Mn-bearing minerals, direct in-situ oxidation, weathering and lateritization; (3) the common supergene Mn-oxides are todorokite, nsutite, romanechite, lithiophorite, cryptomelane and pyrolusite, especially the last two.
Two types of Mn ore deposits were found in the North China Craton (NCC): the sedimentary and supergene Mn deposits (Fan et al., 1999). The former has been studied preliminarily (Jin et al., 2022, 2020; Fang et al., 2020), but achievements in the formation of supergene Mn ores are still insufficient. The sedimentary Mn deposits are mainly hosted in the Mesoproterozoic strata such as the Gaoyuzhuang, Tieling, and Xiamaling formations (Jin et al., 2020). The Gaoyuzhuang Formation contains the largest reserve (> 90 %) of the sedimentary-type Mn ores (Fu et al., 2014). In Qianxi and Xinglong metallogenetic zones of eastern Hebei, the 2nd Member of the Gaoyuzhuang Formation is dominated by original and supergene ores, respectively. Therefore, two types of samples from different metallogenetic zones (the original Mn ores in the Qinjiayu deposit (ZK20-3), Qianxi County and the supergene Mn ores in the Longmen (LM) Section, Xinglong County) were collected in this study, aiming to understand the specific petrological, mineralogical and geochemical transition from original ores to supergene ones.
As the largest and oldest craton in eastern Eurasia (Wan et al., 2020), the North China Craton (NCC) is mainly composed of Archean metamorphic basement and Proterozoic sedimentary strata (Figure 1a; Jin et al., 2022, 2020; Guo et al., 2013). The NCC was involved in the assembly and breakup of the Columbia Supercontinent evidenced by three Paleoproterozoic orogenic belts (i.e., the ~1.95 Ga Khondalite belt, the ~1.90 Ga Jiao-Liao-Ji belt and the ~1.85 Ga Trans-North China Orogen; Dong et al., 2023; Li et al., 2022; Lv et al., 2021) and a series of intra-cratonic rift basins, including the Yanliao Basin (~1.8–1.3 Ga; Lyu et al., 2022). Developed at the margin of the eastern NCC, the Yanliao Basin can be divided into southern and northern branches and preserves the complete Mesoproterozoic stratigraphic successions with a depocenter around the Jixian area, Tianjin (Deng et al., 2021; Fang et al., 2020). The extension and filling time of southern branch was generally considered to be earlier than that of northern branch based on the stratigraphic correlation and the distribution of 1.70–1.67 Ga magmatic events (Lyu et al., 2022; Deng et al., 2021).
The Mesoproterozoic sedimentary record in the Yanliao Basin is continuous and can be divided into Jixian Group and Xiamaling Formation in ascending order. At the bottom of the Jixian Group, the age of the Gaoyuzhuang Formation was well constrained by previous geochronological works, yielding a sedimentary age between ~1.6 to 1.54 Ga (Tang et al., 2016; Tian et al., 2015). A large-scale transgression occurred in the Yanliao Basin during this period, which reached the Wutai oldland in the west and Shanhaiguan oldland in the east (Figure 1b; Pan et al., 2013; Huang, 2006). Subsequently, thick and continuous carbonate deposits were formed in the epicontinental sea environment (Pan et al., 2013). The Gaoyuzhuang Formation can be subdivided into four members (from bottom to top): the 1st Member, quartz arenite that gives way to cherty dolomicrite intercalated with clayey dolomicrite; the 2nd Member, thin Mn-rich dolomitic sandstone interbedded with shale and Mn-rich dolostone; the 3rd Member, dolomitic micrite and muddy dolomicrite with cherty concretions; and the 4th Member, stromatolitic dolostone and dolomicrite with cherty concretions (Figure 2; Jin et al., 2020; Guo et al., 2013; Mei, 2007).
This study is based on two types of sample sets from the ZK20-3 drillcore and weathered LM outcrop section. The ZK20-3 drillcore (coordinate: 40º9′24″N, 118º12′18″E) is located in the west of Qinjiayu Village, Qianxi County, eastern Hebei Province (Figure 1c). This drillcore is completely constituted of the Gaoyuzhuang Formation, Mn-bearing dolomitic sandstones interbedded with shales can be found at depth of 430–462 m (the bottom of the 2nd Member) (Figure 2). Eight Mn-bearing dolomitic sandstones and three shales were collected at 2.5 m intervals within the Mn ore layer.
The LM Section (coordinate: 40º14′24″N, 117º21′31″E) is located ~100 km west of Qinjiayu Village, in Xinglong County, southwest of Chengde City (Figure 1c). It consists of the 2nd Member of the Gaoyuzhuang Formation (Figure 2), with Mn-oxide ores in the middle part (with a thickness of ~1 m) and Mn-bearing dolomitic sandstones interbedded with shales (with a thickness of ~3.1 m) in the middle-upper part, and the rest are Mn-bearing dolomitic sandstones. Mn-bearing layers in the LM Section and ZK20-3 drillcore are comparable, because they are found in the similar position in the 2nd Member of the Gaoyuzhuang Formation and the thicknesses of Mn-ore layers are nearly consistent (12.8 m for ZK20-3 vs. 12.0 m for LM Section). Six weathered shales, four supergene Mn-oxide ores, and 33 weathered dolomitic sandstones were collected from the bottom to the top. The Mn-oxide ores can be separated into three types: impure oxide ore with detritus and carbonates (LM-23), impure oxide ores with detritus but minor carbonates (LM-24, LM-25), and purer oxide ore with minor detritus and carbonates (LM-26).
Petrographic studies were made on 37 thin sections in polarized and reflected light by a CARL ZEISS AXIO SCOPE A1 microscope at the China University of Geosciences (Wuhan).
Thin sections were observed to investigate mineral morphology and microstructure, and to analyze internal components of Mn-bearing rocks under a HITACHI-SU8010 field emission scanning electron microscope (FESEM) at the State Key Laboratory of Biogeology and Environmental Geology (BGEG), China University of Geoscience (Wuhan). To manifest the relative contents and distribution of various elements, element mapping of energy dispersive X-ray spectrometry (EDS) analysis was also employed with analytical conditions under 30 kV for the accelerating voltage and 5 nA for the beam current.
The XRD analysis was performed using a TD-3500 X-ray diffraction instrument in the State Key Laboratory of Biogeology and Environmental Geology (BGEG), China University of Geosciences (Wuhan) with smooth-faced powders that were compressed in the holders. This machine carried out a continuous scan with a speed of 5°/min at 30 kV and 20 mA under an angle range from 5° to 65°. The main mineral compositions and corresponding semi-quantified contents have been obtained by the data-processing software Jade 6.0. In total 54 samples were examined.
Bulk rock elements analyses were carried out by the ALS Chemex Laboratory (Guangzhou, China). Each sample was ground to powder finer than 200 mesh and dried before chemical analyses. Major element content was analyzed using a PANalytical PW2424 X-Ray fluorescence (XRF) unit with a detection limit of 100 ppm and a relative error of less than ±5%. Dried powdered samples were placed in platinum crucibles with lithium tetraborate-lithium metaborate-lithium nitrate mixed fluxes and melted at 1 050 ºC in a high-precision fusion machine after confirming samples and fluxes were fully mixed. Then pour the melts into platinum molds to form cooling melt-films for analysis. At the same time, the other set of samples was accurately weighted and burned in a muffle furnace at 1 000 ºC. The weight difference between the sample before and after burning is the loss on ignition (LOI).
Trace element, rare earth element and yttrium (REY) contents were analyzed using an inductively coupled plasma mass spectrometer (ICP-MS) and an inductively coupled plasma atomic emission spectrometer (ICP-AES). Weighting samples in two copies, the one was digested with perchloric acid, nitric acid, and hydrofluoric acid. After drying, bring to volume by dilute hydrochloric acid and then using ICP-MS for analysis. Evenly mixed the other one with lithium tetraborate or lithium metaborate flux and melted in a furnace above 1 025 ºC. After cooling, the molten liquid was treated with nitric acid, hydrochloric acid, and hydrofluoric acid. This was followed by analyzing with ICP-AES which has a relative error of less than ±10%. Finally, selecting reasonable values according to the element properties and the digestion effect.
The mass change between protolith and altered rock was calculated by the following equation (MacLean and Barrett, 1993).
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ΔM=wid⋅wjpwjd−wip |
(1) |
In this equation, wip and wid are the mass fractions of the mobile element in protolith and altered rock, respectively. wjp is the mass fraction of the immobile element in the protolith; wjd is the mass fraction of the immobile element in the altered rock. The immobile element also called the monitor element is a relative concept that refers to the element with no or less mobility than other elements in a geological process. In this study, Ti was selected as the monitor element.
The freshly-obtained dark gray Mn-bearing dolomitic sandstones are located at the bottom of ZK20-3 (Figure 2). Some of them contain horizontal beddings which consisted of grey and dark gray laminae (Figure 3d). Microscale observations show that the main components of dark gray laminae are carbonates, dipped in manganese and organic matter. But the grey laminae contain more terrigenous detrital minerals such as quartz, feldspar, and muscovite (Figures 4a, 4b). Euhedral pyrites also were observed (Figures 5a, 5b). In the LM Section, the thin stratified layers present apparent weathering traces and have a lighter color (Figures 3a, 3b, 3c). The Mn-bearing minerals in weathered rocks enriched as the band or clump (Figures 4c, 4d, 4e); Different weathering stages represented by mineral contact boundary can be found in some samples (Figure 4f). Thin Mn-oxide crusts and the yellowish-brown mottles caused by weathering of carbonates are observed on the weathered rock surface (Figure 3e). Mn-oxide ores are agglomerate with a rough and porous surface, and the clay-like material is replaced by Mn-oxides (Figure 3f). Only Mn-oxides and little quartz are present under the microscope (Figures 4f, 5e, 5f).
XRD analysis results are given in Table S1. Typical XRD patterns of original dolomitic sandstones and Mn-oxide ores are shown in Figure 6. XRD analyses of the eleven original rocks in the lower part of ZK20-3 indicate that minerals in original Mn-bearing dolomitic sandstones are mainly quartz and feldspar, with a substantial amount of muscovite, dolomite, and rhodochrosite. A small quantity of ankerite and kutnohorite was also identified. The other three shale samples are chiefly composed of quartz and feldspar, with a handful of muscovite. For the LM Section, XRD analyses show that there is no major change in the mineral assembly for weathered dolomitic sandstones apart from the middle part where Mn accumulated. Whereas with the contents of quartz and feldspar decrease, the contents of dolomite increase. In the middle part, quartz and dolomite both decrease or even disappear. Manganese oxide minerals such as todorokite, cryptomelane, and pyrolusite emerged as the main component. There is a mineralogical similarity between shale samples from the LM Section and drillcore except for the existence of kaolinite in the LM Section. However, it is worth noting that the occurrence of substantial calcite (LM-12, LM-23, LM-38) may be related to calcite veins (Table S1).
Major oxide concentrations of studied samples were plotted on two geochemical profiles to indicate their variation trends and correlations, as shown in Figures 7a, 7b. Results of geochemical analyses in Table S2 show that the main compositions of eight original dolomitic sandstones are 27.23 wt.%–40.77 wt.% SiO2 and 10.26 wt.%–14.62 wt.% Mn3O4. The contents of Al2O3 and CaO are also high with ranges of 5.26 wt.%–8.81 wt.% and 5.56 wt.%–12.15 wt.%, respectively. They contain moderate concentrations of MgO (3.98 wt.%–6.68 wt.% with a mean of 5.38 wt.%), K2O (3.64 wt.%–6.19 wt.% with a mean of 4.91 wt.%), and TFe2O3 (3.37 wt.%–4.20 wt.% with a mean of 3.85 wt.%), but low and consistent concentrations of TiO2 (0.20 wt.%–0.32 wt.% with a mean of 0.26 wt.%). The contents of Na2O are negligible (< 0.1 wt.%, Figure 7a and Table S2). All shales in drillcore contain SiO2 > 60 wt.% (60.05 wt.%– 63.05 wt.%), Al2O3 > 12 wt.% (12.14 wt.%–13.90 wt.%), and Mn3O4 < 1.5 wt.% (1.17 wt.%–1.44 wt.%). They have higher concentrations of K2O (8.47 wt.%–10.10 wt.%) but lower contents of TFe2O3 (3.30 wt.%–3.75 wt.%), CaO (1.14 wt.%– 2.01 wt.%), MgO (1.60 wt.%–2.18 wt.%), TiO2 (0.43 wt.%–0.48 wt.%) and Na2O (0.08 wt.%– 0.09 wt.%). Bivariate plots for 11 samples from ZK20-3 show strong negative correlation in Mn3O4-Al2O3 (n = 11, r = -0.97, p(α) < 0.01), whereas Mn3O4-CaO (n = 11, r = +0.94, p(α) < 0.01) and Mn3O4-MgO (n = 11, r = +0.95, p(α) < 0.01) show strong positive correlations (Figures 8a, 8b, 8c).
Compared with original rocks, supergene rocks from the LM Section have variable concentrations of oxides (Table S2 and Figure 7b). The contents of prominent chemical constituents vary from 0.03 wt.% to 84.29 wt.% for Mn3O4, 1.74 wt.% to 69.32 wt.% for SiO2, 0.27 wt.% to 14.18 wt.% for Al2O3, 0.13 wt.% to 18.35 wt.% for CaO, and 0.05 wt.% to 9.76 wt.% for MgO. The concentrations of Mn3O4 are remarkably elevated in the middle section with decreased contents of SiO2, Al2O3, CaO, MgO, and K2O. All weathered dolomitic sandstones contain almost consistent concentrations of TFe2O3, but lower and variable concentrations of alkali elements K and Na. The content of TiO2 shows small fluctuations which are coincident with Al2O3. However, the element contents of weathered shales are relatively stable. Apparent hyperbolic trends were detected in Mn3O4 versus Al2O3, CaO, and MgO for weathered samples (Figures 8a, 8b, 8c). Values of Mn/Fe ratio significantly increase in Mn-oxide ores with a range from 12.71 to 299.33 (Table S2).
Trace element concentrations in all samples are given in Table S3. All of them were normalized by the Upper Continental Crust (UCC) (Figure 9; McLennan, 2001). Most samples contain lower contents of V, Cr, Co, Ni, Cu, Rb, Sr, Zr, Nb, Ba, Hf, Th, Pb, and Zn, but higher contents of As and U compared to the UCC. For Mn-oxide ores, Sr, As and U are enriched but other trace elements have lower contents than that of the remaining samples. The remaining samples, however, show similar UCC-normalized patterns with apparent Sr depletion and As enrichment. It is worth mentioning that the contents of Co, Ni, Cu, Pb, and Zn in partially weathered samples are higher than that of original rocks (Figure 9).
Original rocks (∑REY = 105.68 × 10-6 to 250.56 × 10-6, avg. = 149.71 × 10-6) have a higher mean content of ∑REY than supergene rocks (∑REY = 18.08 × 10-6 to 176.70 × 10-6, avg. = 114.06 × 10-6) (Table S4). The lowest ∑REY concentration was recorded in Sample LM-26, which has the highest Mn content (Mn3O4 = 84.29 wt.%). And a strong positive correlation was found between ∑REY and SiO2 + Al2O3 + K2O (n = 54, r = +0.79, p(α) < 0.01; Figure 10). Shale-normalized REY patterns (REYSN) of the studied samples (relative to PAAS, Post Archean Australian Shale; Taylor and McLennan, 1985) are present in Figure 11. Original rocks and weathered shales have a similar trend that enriched in LREE ((Pr/Yb)SN = 1.10 – 1.69 and 1.01 – 1.76, respectively) (Figures 11a, 11b). Supergene Mn-bearing dolomitic sandstones show relatively flat patterns ((Pr/Yb)SN = 0.82 – 1.28, avg. = 1.09) or LREE-enriched ((Pr/Yb)SN = 1.34 – 1.86, avg. = 1.61) patterns (Figure 11c). A strong HREE-enriched pattern is exhibited in the purer Mn-oxide ore (LM-26; (Pr/Yb)SN = 0.14) (Figure 11f). But the rest impure Mn-oxide ores (LM-23, LM-24 and LM-25) have similar REY patterns with slight HREE depletion (Figure 11d and Table S4).
Ce anomalies may be influenced by its neighbor La, thus La anomalies were calculated in the following way (Lawrence et al., 2006).
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δLa=La/La∗=[La/(Pr×(Pr/Nd)2)]SN |
(2) |
If there are positive La anomalies, then Ce anomalies were calculated by
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δCe=Ce/Ce∗=[Ce/(Pr2/Nd)]SN |
(3) |
Otherwise, Ce anomalies were calculated by
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δCe=Ce/Ce∗=[Ce/(La×Pr)1/2]SN |
(4) |
The subscript "SN" represents the concentration of samples normalized by PAAS.
In ZK20-3, most original Mn-bearing dolomitic sandstones show slightly positive Ce anomalies and all shales present no anomalies (Figure 7a). For supergene samples from the LM Section, all shales and Mn-bearing dolomitic sandstones from the upper section show slightly negative Ce anomalies. In the middle part, Mn-oxide ores except for LM-26 (with negative Ce anomaly) have slightly positive Ce anomalies. And there are no apparent anomalies of Ce in the rest samples (Figure 7b). All shales and weathered dolomitic sandstones (depleted in manganese) have slightly negative Eu anomalies, which however, is more apparent in Sample LM-26. The anomalies of Y only appear in Mn-oxides and are positive (Figures 7, 11 and Table S4).
Average geochemical compositions of eight original Mn-bearing dolomitic sandstones and three shales were used as the starting points for mass balance calculations. Ti was chosen as the monitor element due to its more stable nature during weathering and diagenesis process. Results are displayed in Table S5 and Figure 7c. There is a strong positive correlation between Al2O3 and TiO2 (n = 54, r = +0.98, p(α) < 0.01; Figure 8f). And two sets of samples have similar lithologies and components. Furthermore, the normalized patterns of trace and rare earth elements are parallel between original and weathered rocks except for Mn ores. Thereby, it is reasonable to consider that samples from the drillcore represent the protoliths of weathered rocks in the LM Section. Two stages of Mn depletion and enrichment from the top to the bottom are observed, and the enrichment degree even reaches seven times higher at the middle part of the deposit. The mass change for Fe (except for shales) and Na have a similar trend with manganese but at a lower level. Al and K have the same tendency of depletion except for three samples that reveal enrichment. Variations of Ca and Mg are similar and unstable in weathering process, but most of them show enrichment, especially at the bottom. The enrichment of Si mainly occurs in the middle and bottom of the section and reaches 18.76%.
As indicated by XRD analyses and microscopic observation, manganese in original dolomitic sandstones is disseminated in the matrix with the valence of bivalence (Figures 4a, 4b and Figures 5a, 5b). But it was meliorated as aggregates with vermicular orientation accompanied by the dissolution of feldspars or produced as corrugated strips in the slightly weathered samples (Figure 4c). Although carbonates still exist in weathered samples, Mn-oxides (pyrolusite, cryptomelane, todorokite) and clay minerals have formed (Figures 5c, 5d, 6 and Table S1). Pyrolusite and cryptomelane occur together frequently in supergene deposits. Pyrolusite is one of the most stable Mn-oxide phases in the oxygen-rich supergene environment and also is the early-stage production of violently altered carbonates (Varentsov, 1996; Hao and Guan, 1995). But cryptomelane, which can be considered as the evidence of secondary oxidation of Mn-oxides will replace it when there is a high content of potassium in solutions. In humic acid-riched solutions, however, cryptomelane will be decomposed and reprecipitated as pyrolusite (Dash et al., 2020; Yan et al., 2006).
The mineral paragenesis of Mn-bearing minerals in weathered samples can be reconstructed by the thin section observation. Pyrolusite exists as aggregates or fills in pores that caused by carbonate dissolution (Figures 5c, 5d). But the strongly weathered sample is almost entirely composed of different stage pyrolusite (Figures 4f, 5e, 5f). The surface of early-stage pyrolusite is rough and porous. In contrast, the surface of late-stage pyrolusite is smoother and quartz grains as well as microfractures can be found within it. This phenomenon may be caused by the heterogeneity of lithology and microenvironment during weathering (Lang et al., 2007; Yan et al., 2006). These features indicate that the supergene Mn ores in this area are chiefly formed in two ways (Hao and Peng, 1998): (1) The solutions directly reacted with the original rocks. Manganese ores formed in this way often contain more impurities and are accompanied by residual original minerals, and the level of mineral crystallization is low; (2) Mn2+ ions in the solutions were oxidized during migration and filled in pores and fissures. Manganese ores formed in this way generally have high levels of crystallization, high grades, and fewer impurities. In the about ~1 m interval at the Middle LM Section, Mn-oxides emerged from bottom to top in the following order: pyrolusite (LM-23), todorokite (LM-24), and cryptomelane (LM-25). But the topmost Mn-oxide ore (LM-26), in turn, contains only pyrolusite. The previous study in karstic Mn ores in the Úrkút Mn deposit, Hungary concluded that the sequence of oxidizing transformation of fine-layered rhodochrosite-clayey ore is: carbonate → manganite → pyrolusite (I) → cryptomelane → todorokite → pyrolusite (II) (Varentsov, 1996). Among them, manganite is the unstable initial supergene production of Mn carbonates (Fan et al., 1992). However, Vafeas et al. (2018) suggested that cryptomelane formed behind todorokite based on the study of supergene Mn-oxides at the Sebilo manganese mine in the Kalahari Manganese Field, South Africa. So we give the sequence of oxidizing transformation of Mn-bearing dolomitic sandstones in the LM Section as kutnohorite/rhodochrosite → pyrolusite (I) → cryptomelane (todorokite) → todorokite (cryptomelane) → pyrolusite (II).
In the LM Section, with the increase of Mn, the contents of Ca, Mg, K, Si, and Al in weathered dolomitic sandstones decrease (Figure 7b). However, Fe and Na are slightly enriched (Figure 7c). Fe and Mn have similar geochemical behaviors due to their close chemical properties, but the migratory capacity of manganese is six times greater than that of iron (Plavshudin and Shvets, 1970). The enrichment of Na may be caused by the absorption of clay minerals (Chi and Wang, 1993). K and Al are almost deficient in the whole section and have a similar tendency (Figure 7c), reflecting that K and Al are basically preserved in feldspar and carried away by leaching fluids. The abnormal enrichment of Mn and Fe but depletion of Al in the middle part of the LM Section probably ascribes to the variation in pH values due to the migration of fluids. When meteoric waters pass through regions with dense vegetation, the pH values could be changed from 6.0–5.5 to 4.5–3.7 (Varentsov, 1996). However, pH values will be gradually increased with the dissolution of carbonate minerals during the vertical migration of fluids, especially at the rock-soil interface (Wang et al., 2022). Although there is no rock-soil interface in the LM Section, the middle section with the highest degree of weathering may act in a similar role. Furthermore, the oxidized precipitation of Mn and Fe needs sufficient oxygen. Relevant studies indicated that the groundwater table can act as an important redox barrier to promote the oxidized precipitation of redox-sensitive elements (Zhou et al., 2020). And fluctuations of the groundwater table between wet and dry seasons result in the development of oxic fronts in the lower saprolite (Li et al., 2020). Indeed, there are apparent positive Ce anomalies in the middle section (Figure 7b) and the weathering degree there is the highest (Figures 3a, 3b, 3c). These evidences support the deduction that the middle part of the LM Section was located around the groundwater table during the weathering process. When Mn-bearing acid solutions migrated to the middle section, the variation of pH values and enhanced oxidation would result in the precipitation of Mn-oxides or hydroxides (Yan et al., 2006; Varentsov, 1996).
Fresh and weathered dolomitic sandstone samples show significant Sr depletion and As enrichment. It reflects the affinity between fresh and weathered samples (Figure 9). Whereas, Mn-oxide ores are enriched in Sr, As, and U. The distribution of redox-sensitive element U is usually related to Fe-Mn-oxides during weathering (Koppi et al., 1996). Sr and As can form stable oxides or salts in the oxidation zone (Zhu, 1998), so they accumulate with the precipitation of Mn-oxides. Furthermore, Cu, Co, Ni, Pb, Zn, and Mn may form isomorphic compounds (Hao and Peng, 1998), thus some weathered samples have relatively higher contents in comparison with original rocks. However, compared to hydrogenetic Mn nodules or crusts, the contents of Cu, Co, Ni, Pb, and Zn in Mn-oxide ores are much lower. It may be owing to the rapid precipitation of Mn-oxides, resulting in a short adsorption time for trace elements. Besides, the small pore sizes of pyrolusite hinder these elements from entering crystal structures (Lang et al., 2007; Yan et al., 2006). Hence, the type of Mn-oxides is one of the determinants for the enrichment of these economic trace elements during the formation of supergene Mn deposits.
Except for Mn-oxide ores and Mn-depleted dolomitic sandstones, the rest samples from the LM Section have similar REY patterns to that from the drillcore (for samples that have the same lithology), which further confirm the affinity between fresh and weathered samples (Figures 11a, 11b, 11c). REY patterns in impure Mn-oxide ores LM-23, LM-24, and LM-25 are consistent, with slightly HREE-depleted patterns and positive Y anomalies (LM-23, containing terrigenous detritus and carbonates; LM-24 and LM-25, containing terrigenous detritus but tiny carbonates). These patterns are different from Mn-oxides formed by weathering of Mn-bearing carbonates in Nikopol of Ukraine, Guangxi, and Anhui of South China, which have MREE-enriched patterns (Figure 11d; Sasmaz et al., 2020; Li et al., 2015; Xie et al., 2006). It is likely caused by the discrepancies in primary components, since manganese deposits in Ukraine and South China preserved significant hydrothermal information, which are different from the terrigenous-dominated Mn ores preserved in the Gaoyuzhuang Formation (Jin et al., 2020). The REY content of LM-23 is only slightly higher than that of LM-24 and LM-25, but much higher in comparison with sample LM-26 (the purer Mn-oxide ore only with minor terrigenous detritus). It reflects that the contents of REY in carbonates are extremely low and most of them are preserved in terrigenous clasts, as proved by the positive correlation of ∑REY-SiO2 + Al2O3 + K2O (Figure 10). In addition to the lower REY content, sample LM-26 shows a different REY pattern from other Mn-oxide ores with obvious HREE enrichment and negative anomalies of Ce and Eu and higher positive Y anomaly, which is similar to that of hydrothermal Mn deposits except for Eu anomalies (Figure 11f; Bau et al., 2014, 1996). In general, with the increasing contents of Mn-oxides, REY patterns changed from HREE-depleted to HREE-enriched. The reason for such a change is probably related to the rapid precipitation of Mn-oxides, as mentioned earlier. Compared with LREE, HREE (include Y) preferentially forms complexes with carbonates and organic matters during weathering (Li et al., 2020; Huang and Wang, 2002). Consequently, weathering solutions are enriched in HREE and the rapidly precipitated Mn-oxides inherit the characteristics of weathering solutions due to the non-equilibrium state exchange of elements between Mn-oxides and solutions. This process is similar to the formation of hydrothermal Mn-oxides in the ocean, which inherit the characteristics of seawater except for Eu anomalies (Bau et al., 2014). And similar patterns (HREE-enriched) are also found in supergene ores in the Kalahari and Postmasburg Mn deposits, South Africa (Varentsov and Kuleshov, 2019). The redox potential of Mn4+/Mn2+ is similar to that of Ce4+/Ce3+ (Xie et al., 2023), and Mn-oxide can adsorb and catalyze Ce (Zhou et al., 2024; Li et al., 2020). But the initial positive Ce anomaly does not appear in the top Mn-oxide ore (LM-26) which contains the most Mn-oxide and shows negative Ce anomaly (Figure 7b). It implies the existence of the alkaline barrier and the oxidation of Ce needs higher pH values than that of Mn under a similar redox condition (Glasby and Schulz, 1999).
Based on discussions of mineralogy and geochemistry variations above, we could find that in the LM Section, the degree of weathering at the middle part is higher than that of the upper section (Figures 3a, 3b). It is contradictory to the fact that the upper part of one section should be more weathered in the same environment without difference in lithology. The reason for this is likely to be linked with regional hydrology. The deeper part of the LM Section has been around the groundwater table with the change of elevation, and the long-term effect of groundwater caused the more weathered situation. Afterward, the crust was rapidly uplifted and formed the present landform. Subsequently, the whole section began to be synchronously weathered and the second stage of weathering occurred. However, the time of uplift and weathering for the Mn-bearing deposit of the Gaoyuzhuang Formation is still unknown.
The NCC suffered a long and complicated tectonic evolution. The Late Mesozoic Yanshanian Movement and the Cenozoic Himalayan Movement led to the uplift of the Paleo-Mesoproterozoic strata in the NCC. Subsequently, the foundation of modern topography formed (Wang et al., 2018; Jia et al., 2004). The Yanshanian Movement is one of the most important tectonic events in the geological history of China. But before that, it had gone through the Early Mesozoic Indosinian Movement which resulted in the collision and convergence of North China and the South China blocks, and the earliest deformation of the strata in the NCC (Mei, 2010; Li S Z et al., 2009). The subsequent Yanshanian Movement established the modern tectonic framework and topography of China (Wang et al., 2018; Zhang et al., 2013). Tectonic activities during the Yanshanian Period are mainly compressional deformations accompanied by large-scale magma intrusion and volcanic activities (Zhu et al., 2021; Wang et al., 2018). The Xinglong thrust tectonics in the central Yanshan belt which is characterized by both cover sequences and basement being involved in the contraction deformations are formed by Yanshanian Movement (Zhu et al., 2021; Yang et al., 2006). Yang et al. (2006) confirmed that the Yanshan belt uplifted between ~158 and ~137 Ma based on in-situ U-Pb ages and Hf isotopic data of detrital zircons, and suggested that it was related to the subduction of the oceanic plate beneath the northern margin of the NCC. During the transition period from Paleogene to Neogene, the Himalayan Movement was intense and resulted in a large-scale uplift and depression of the crust in the Yanshan region in response to the collision of Indian, Pacific, and Eurasian plates (Zhang et al., 2015; Jia et al., 2004). In addition, apatite (U-Th)/He and apatite fission-track data indicate that the Qinling and Taihang Mountains also experienced a rapid exhumation during the Late Oligocene and Early Miocene (Yu et al., 2022).
During Middle–Late Jurassic, the paleoclimate in eastern Hebei, North China was moist and warm, and coexisted with seasonal semiaridity and aridity, evidenced by plant fossils preserved in the Tiaojishan Formation (Tian et al., 2014). And mud cracks, gypsums, and salt pseudomorphs preserved in the Tuchengzi Formation, western Liaoning, China, indicating a hot and dry environment in the Jurassic–Cretaceous transition time (Zheng et al., 2001). Furthermore, the presence of aeolian deposits discovered in Early Cretaceous strata suggests the degradation under a severely hot and arid environment, which may result in the extinction of the Yanliao Biota (Xu et al., 2017). If the LM Section was exposed and remained above the surface for a long time during this stage because of the Yanshanian Movement, then its degree of weathering should be higher because the moist and hot paleoclimates favor the formation of supergene Mn-oxides in weathering crusts (e.g., supergene tetravalent Mn-oxides in Australia, Ostwald, 1992).
Reconstruction of Paleogene continental paleoclimate in East Asia is deficient but abundant in North America and Europe (Quan et al., 2012). In Northeast China, the high temperature with a decreasing tendency and dry climate prevailed the most of the Eocene time (~42–38 Ma), whereas the Early–Middle Oligocene (~38–30.3 Ma) was characterized by several cycles of dryness and humidity along with a slight turn back in temperature (Xia et al., 2020). It is in line with the conclusion that two cooling events arose in the Early and Middle Eocene and the mean annual temperature (MAT) rebounded in the late Middle Eocene proposed by Quan et al. (2012). The paleoclimate in eastern China changed significantly in the Neogene. The arid and semiarid climate during the Paleogene was replaced by a humid and semihumid environment due to factors including the Paratethys retreat, the South China Sea expansion, and the building of Qinling and Taihang mountains (Yu et al., 2022). The Miocene climate in North China was warmer and wetter than today. The temperature was at a high level with minor fluctuations during the Early to Middle Miocene but declined in the Late Miocene (Li J F et al., 2009). It is consistent with the pattern of global temperature change during the Miocene (Kürschner et al., 2008). The warm and wet climate is favorable for the formation of supergene Mn-oxide deposits (Deng and Li, 2017). During the Quaternary, the climate alternated between warm-moist and cold-dry environments (Jin and Liu, 2002). Furthermore, several Cenozoic weathering crusts have been found in North China (Wu et al., 2000). From the perspective of paleoclimatic evolution, it is more possible that the prolonged exposure of the Gaoyuzhuang Formation initiated from the Himalayan Period. Otherwise, the degree of weathering would be higher under long-term favorable weathering conditions, especially in the Jurassic–Cretaceous Period (Figure 12).
(1) Original Mn-bearing dolomitic sandstones in the Mesoproterozoic Gaoyuzhuang Formation mainly contain quartz and feldspar with a substantial amount of muscovite, dolomite and rhodochrosite and a small quantity of ankerite and kutnohorite. However, supergene Mn-oxide ores mainly consisted of pyrolusite, cryptomelane, and todorokite. The possible sequence of Mn mineral transformation is: kutnohorite/rhodochrosite → pyrolusite (I) → cryptomelane (todorokite) → todorokite (cryptomelane) → pyrolusite (II). In the middle part of the LM Section, elements such as Al, Ca, Mg and K are depleted but Mn, Fe, Si and Na are enriched with the secondary enrichment of Mn. However, most elements (Mn, Fe, Si, Ca, Mg, Na) are enriched except Al and K at the basal section.
(2) The HREE-depleted REY patterns of impure Mn-oxides are consistent with original ores. However, the level is lower than that of the latter. On the contrary, the purer Mn-oxide ore is strongly enriched in HREE. These features are different from supergene Mn ores in other regions, but analogs also can be found. Compared with original ores, supergene Mn-oxide ores have lower ∑REY contents, especially LREE.
(3) The formation of supergene Mn ores in the LM Section resulted from multiple tectonic movements. Among these, the Yanshanian and Himalayan movements played important roles. The prolonged exposure of the LM Section likely occurred in the Himalayan Period, and the middle section was affected by groundwater for a long time before the present landscape formed. Hence, it shows two-stage weathering and the middle part is more weathered than the top.
ACKNOWLEDGMENTS: This study was supported by the National Key R & D Program of China (No. 2022YFF0800200), the NSFC (Nos. U1812402 and 42072131), Most Special Fund (No. MSFGPMR33) from the State Key Laboratory of GPMR, the CUG Scholar Scientific Research Funds (No. 2022036), the NSF of Hebei Province (No. D2021334001), Research Project of Talent Engineering Training of Hebei Province (No. B2020005007), Research Project of Postdoctoral Scientific Research Station of HBGMR (No. 454-0602-YBN-Z9E4), Natural Science Foundation of Hebei Province (No. D2021334001), and the Central Government Guides Local Funds for Scientific and Technological Development (No. 236Z7608G). The final publication is available at Springer viahttps://doi.org/10.1007/s12583-023-1856-9.| Bau, M., Koschinsky, A., Dulski, P., et al., 1996. Comparison of the Partitioning Behaviours of Yttrium, Rare Earth Elements, and Titanium between Hydrogenetic Marine Ferromanganese Crusts and Seawater. Geochimica et Cosmochimica Acta, 60(10): 1709–1725. https://doi.org/10.1016/0016-7037(96)00063-4 |
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Lingtong Xu, Wenchao Yu, Song Jin, Guo Hua, Pengfei Ma, Yuansheng Du, Cailong Zhang. Transition from the Sedimentary Manganese Deposit to Supergene Manganese Ore in Eastern Hebei, North China: Evidences from Mineralogy and Geochemistry. Journal of Earth Science, 2025, 36(1): 11-28. doi: 10.1007/s12583-023-1856-9
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