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Article

Paleoenvironment of Mesoproterozoic Gaoyuzhuang and Wumishan Formations, North China: New Insights from Geochemistry and Carbon and Oxygen Isotopes of Dolostones

by
Feng Ma
1,2,
Tingxin Li
1,2,
Yun Zhou
3,
Jin Cai
3 and
Yongfeng Cai
3,*
1
Institute of Hydrogeology and Environmental Geology, Chinese Academy of Geological Sciences, Shijiazhuang 050061, China
2
Technology Innovation Center for Geothermal & Hot Dry Rock Exploration and Development, Minstry of Natural Resources, Shijiazhuang 050061, China
3
Guangxi Key Laboratory of Hidden Metallic Ore Deposits Exploration & Collaborative Innovation Center for Exploration of Nonferrous Metal Deposits and Efficient Utilization of Resources in Guangxi, Guilin University of Technology, Guilin 541004, China
*
Author to whom correspondence should be addressed.
Minerals 2022, 12(9), 1111; https://doi.org/10.3390/min12091111
Submission received: 30 April 2022 / Revised: 27 August 2022 / Accepted: 29 August 2022 / Published: 31 August 2022
(This article belongs to the Special Issue Diagenesis and Geochemistry of Carbonates)
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Abstract

:
The Mesoproterozoic Gaoyuzhuang and Wumishan Formations are major geothermal reservoirs in the Hebei Province, North China. Compared to the exploration of geothermal resources and heat-controlling structures, carbon and oxygen isotopic records of the two formations are limited. Here, we present integrated field, petrological, geochemical, carbon, and oxygen isotopic data of carbonate rocks from the Gaoyuzhuang and Wumishan Formations. The Wumishan Formation is characterized by higher CaO and MgO contents and lower SiO2 contents than the Gaoyuzhuang Formation, indicating that the source of the Wumishan Formation likely contains less terrigenous clastic materials. The two formations have low total rare earth element contents, similar to marine carbonate rocks. They show different Eu and Ce anomalies, Al/(Al + Fe + Mn) and Fe/Ti ratios, and (Co + Ni + Cu) contents. They generally show similar carbon isotopic compositions, whereas the carbonate rocks of the middle-upper Gaoyuzhuang Formation show lower δ18O values than the samples from the Wumishan and lower Gaoyuzhuang Formations. These data suggest that the two formations have experienced different transgressive–regressive cycles and that their sedimentary environments varied and were unstable in different sedimentary periods. The middle-upper Gaoyuzhuang Formation was likely affected by hydrothermal fluids, whereas the Wumishan Formation is composed of normal seawater deposits. Integrated evidence reveals that both of the Mesoproterozoic Gaoyuzhuang and Wumishan Formations were deposited in rift environments caused by the breakup of the Columbia/Nuna supercontinent.

1. Introduction

Carbonate rock records are abundant in depositional and original information (e.g., seawater temperature, salinity, carbonate system, nutrients) and are thus an ideal indicator to reveal the conditions of the paleoenvironment. Oxygen isotopes are considered to be an effective proxy for reconstructing the paleotemperature [1] and have been used to calculate the paleotemperature of Paleozoic carbonate rocks from Svalbard and Newfoundland [2]. The stable isotope composition of seawater is easily affected by salinity variations because light C and O isotopes are preferentially evaporated [3]. Keith and Weber (1964) further proposed an equation to calculate the paleosalinity according to the carbon and oxygen isotopes of the carbonate rocks that have developed since the Jurassic period [4]. Sea level changes have been recorded in the rare earth elements (REE) and yttrium (Y) concentrations as well as the carbon and oxygen isotopes found in Carboniferous–Triassic carbonate rocks [5]. The strontium and carbon isotopes in Early Cambrian carbonate rocks have been used to constrain the contribution of the paleoenvironment to the Redlichiid–Olenellid Extinction Carbon Isotope Excursion (ROECE) [6]. The geochemical indices of different elements (e.g., V/Cr, Ni/Co, Ni/V, U/Th, (Cu + Mo)/Zn) have been used to interpret the palaeoredox conditions in Jurassic sediments [7]. However, these proxies may be more or less altered by strong diagenesis [8], which is also referred to as the so-called “age effect” [9]. In order to reduce the “age effect”, a re-evaluation of the calibration of elemental and isotopic proxies is proposed [10,11,12].
It is worth noting that petrographic and carbon and oxygen isotopic evidence shows that Precambrian dolomites are different from Phanerozoic dolomites [13]; thus, using ancient dolostones archives as proxies of their paleoenvironment is still contentiously debated [14,15,16]. Nevertheless, recent studies have shown that carbonate rocks can provide faithful recordings of the paleoenvironmental conditions in the early oceans [17,18]. Insusceptible proxies, such as the Cr, Pb, and Nd isotopes of carbonate rocks, seem to have eluded being influenced by post-depositional processes and have preserved signatures that are close to their original conditions [19]. Statistical learning studies on Archean carbonate diagenesis have shown that the diagenetic processes that cause the re-crystallization of dolomite and the consequent textural changes do not affect the distribution of major and trace elements [20]. The geochemical and stable isotope compositions (e.g., REE, Y, 13C, 18O, 98Mo) in Proterozoic carbonate rocks have been used to describe paleoenvironments and depositional conditions [21,22]. Therefore, geochemical and isotopic proxies can be used to reveal paleoenvironment reconstructions of Precambrian carbonates after evaluating their robustness.
The Mesoproterozoic Gaoyuzhuang and Wumishan Formations in the eastern North China Craton are characterized by huge geothermal reserves [23,24]. Previous studies have mainly focused on the hydrochemical composition of geothermal fluids [25,26], fractures in the dolostones [27], the exploration and development of geothermal resources [23], numerical models of the coupled fluid flow and heat transfer processes in the geothermal fields [28], the heat-controlling structures in the geothermal area [29], and the hydrothermal origin of the chert bands and nodules in the dolostones [30]. However, less attention has been paid to isotopic compositions of carbon and oxygen, which are important to the reconstruction of the paleoenvironment of the two formations. This study presents detailed field, petrological, bulk-rock geochemical, and carbon and oxygen isotopic data of the dolostones from the Gaoyuzhuang and Wumishan Formations. These new data sets are used to discuss the depositional environment and hydrothermal processes of the Gaoyuzhuang and Wumishan Formations, which are crucial to unraveling the Mesoproterozoic paleoenvironment of the North China Craton.

2. Geologic Setting

The study area is located in the eastern portion of the North China Craton (Figure 1a). The North China Craton is one of the oldest cratons in China, as evidenced by its Archean–Paleoproterozoic crystalline basement [31]. The craton has undergone strong modifications since the Mesozoic age and experienced at least two lithospheric extension and thinning events during the Yanshanian and Himalayan periods [31,32]. Numerous active fractures, strong seismic activity, and the uplifting of mountainous areas and the sinking of plains in the craton suggest that the lithosphere is still active [25]. The eastern North China Craton was part of the Circum-Pacific tectonic domain during the Cenozoic age [33].
The strata in the area are mainly Archean, Mesoproterozoic (including the Changcheng Group and Jixian Group), early Paleozoic (Cambrian and Ordovician), and Cenozoic (Quaternary) [34]. The Gaoyuzhuang Formation in the upper Changcheng Group mainly consists of gray dolostone, stromatolite-bearing dolostone, and argillaceous dolostone. The gray dolostone in the lower part of the formation is mainly composed of dolomite and experienced silicification. The stromatolite-bearing dolostone in the middle part underwent pyritization, and the stromatolite is columnar, whereas the stromatolite-bearing dolostone in the upper part contains numerous massive stromatolites and a few siliceous bands. The Wumishan Formation in the middle Jixian Group is mainly composed of dolostone and argillaceous dolostone. The dolomites in the argillaceous dolostone are mainly composed of pelitic crystal (75%) and muddy crystal (15%). The dolomites in the stromatolite-bearing dolostone mainly consist of pelitic crystal and organic matter. The detailed lithologies of the strata are shown in Figure 2.
The sedimentation of various deposits occurred in different depth zones and show different sedimentary facies. During the early sedimentary period of the Gaoyuzhuang Formation, sediments were characterized by terrigenous detritus and gravel detritus, representing a supratidal zone and intertidal zone [35]. Sediments from the middle of the sedimentary period mainly consist of manganiferous detritus and flourishing stromatolites [35]. This indicates deeper water in the sedimentary environment, representing an intertidal zone and subtidal zone [35]. At the end of the sedimentary period, the water became shallow, and sediments were mainly composed of fine crystalline algal dolostone, reflecting a supratidal zone and intertidal zone [35]. As for the Wumishan Formation, sediments from the early sedimentary period contain a few oncolites, representing a subtidal zone [36]. Sediments from the middle sedimentary period are characterized by pelitic crystals and silicification, reflecting an intertidal zone [36]. At the end of the sedimentary period, sediments were mainly comprised of argillaceous and sandy detritus, representing a supratidal zone [36].

3. Materials and Methods

3.1. Sampling Strategy and Field Investigated

The massive Paleo–Mesoproterozoic volcanic sedimentary series, iron-enriched and marine sulfide sediments, and micropaleontological and macroalgae fossils in the North China Craton provide a robust means of stratigraphic correlation [37,38]. The biostratigraphical information of our samples follows the pattern of the Proterozoic Changcheng and Jixian groups (including the Gaoyuzhuang and Wumimshan Formations) of the North China Craton (Figure 2; [35,36,37]).
Fieldwork was conducted on the outcrops of the Mesoproterozoic Gaoyuzhuang and Wumimshan Formations in the eastern North China Craton, in the Tuonan, Langyashan, and Qiyu areas (Figure 1b). Rock samples were collected from the different parts of the Gaoyuzhuang and Wumimshan Formations. Only fresh samples were selected for thin-section and element and isotope analyses. Six (sample numbers GS01-GS06), nine (GZ01-GZ09), and seven (GX01-GX07) samples were taken from the upper, middle, and lower portions of the Gaoyuzhuang Formation, respectively. Seven (WS01-WS07), seven (WZ01-WZ07), and nine (WX01-WX09) samples were taken from the upper, middle, and lower portions of the Wumimshan Formation, respectively (Figure 2). The above 45 samples were used for carbon and oxygen isotopic analyses, and 8 samples from the Gaoyuzhuang Formation and 7 samples from the Wumimshan Formation were selected for major and trace element analyses (Table 1). Detailed rock-type information is listed in Table 2.

3.2. Geochemical and Isotopic Analyses

The 45 rock samples were sawed into slabs, and the central fresh parts were selected for microsectioning and for analyses of the major and trace element compositions. Afterwards, the rocks were crushed in a steel mortar and ground in a steel mill. Only fresh samples were selected for pulverizing to 200-mesh and for elemental and isotopic analyses. The major oxides in whole rocks were analyzed at the Guangxi Key Laboratory of Hidden Metallic Ore Deposits Exploration, Guilin University of Technology, via wavelength X-ray fluorescence spectrometry using a Rigaku ZSX Primus II spectrometer with the relative standard deviations of <5%. Glass discs were made by melting dehydrated sample powders. The calibration lines used for quantification were produced by the bivariate regression of the data from 36 reference materials encompassing a large range of silicate compositions [39]. The trace element concentrations were measured using an inductively coupled plasma mass spectrometer (ICP-MS). The specified sample preparation and analytical methods are based on [40]. An internal standard solution containing the single element Rh was used to monitor signal drift while counting. A set of Chinese national rock standards, e.g., GSD-1A, GSD-2A, GSD-4A, GBW07127, and GBW07130, were chosen for the calibration. Analytical precision was typically better than 5%. The REEs and trace elements of the rocks were normalized according to the North American Shale Composite (NASC) in order to better reveal their geological implications. The normalization values for the NASC are from references [41,42,43]. Carbon and oxygen isotopes were measured using an MAT 253 mass spectrometer coupled to a Kiel IV carbonate device. The laboratory temperature was 25 °C ± 0.1 °C. The relative standard deviations (1SD) of the measurements (δ13C and δ18O, VPDB) were <0.030‰ and 0.080‰, respectively.

4. Results

4.1. Petrographic and Mineralogical of Dolostones

The cherty dolostone samples from the Gaoyuzhuang Formation are dark gray, fine-grained, and middle-thin-bedded (Figure 3a). The dolomites are mostly micritic and anhedral. The micro-sedimentary beddings are well-developed (Figure 4a). The gray dolostones are medium–coarse-grained and are characterized by numerous joints (Figure 3b). The dolomites have different textures, such as micritic textures and fine-grained textures (Figure 4b). They are mostly subhedral and euhedral. Dark micritic dolomite lumps are sporadically distributed among the fine-grained dolomites (Figure 4b). The interbedded argillaceous dolostones are fine-grained and thinly laminated (Figure 3c). The dolomites are mostly anhedral and micritic. Veins of different calcite complexes cross through the dolomite (Figure 4c).
The dolostone samples from the upper Wumimshan Formation are middle-bedded and are associated with marble and bioclastics (Figure 3d). The main mineral in dolostones is dolomite, which is a micritic, powdery crystal. The grain sizes of the dolomite crystals are ~10 μm. The crystals are mainly anhedral and subhedral and show steady light extinction. They are densely packed with each other and show microscopic stratification (Figure 4d). The fine-grained dolostone samples are white-gray and dark gray and show obvious stratification (Figure 3e). They have experienced intense tectonic stress, as evidenced by well-developed cleavage recording typical cleavage domains and microlithons (Figure 4e). The argillaceous dolostones from the lower Wumimshan Formation are laminated and interbedded with gray dolostones (Figure 3f). The dolomites in these samples are mostly micritic and anhedral (Figure 4f). Fractures can be observed among the micritic dolomites, and they are mostly filled by calcites (Figure 4f).
Most of the dolomite samples are fine-grained, subhedral to euhedral, and display planar textures (Figure 4). Some samples from the Gaoyuzhuang Formation show fabric-retention dolomitization with well-preserved dissolution pores (Figure 4b), whereas the dolomitization of the Wumimshan Formation is generally fabric-destructive and contains rare bioclastics (Figure 4f). Coarse-grained dolostone, recrystallized from fine-grained matrix dolostone, can be occasionally observed in the Gaoyuzhuang Formation (Figure 4a). In contrast, neither the early marine cements nor the dolomicrites from the Wumimshan Formation show evident recrystallization (Figure 4d,f).

4.2. Major and Trace Elements

The main chemical compositions of the carbonate rocks in the Gaoyuzhuang Formation are as follows: CaO (24.15–33.97%, average = 30.71%), MgO (16.50–23.40%, average = 21.02%), and SiO2 (0.27–25.36%, average = 8.37%), with a small number of chemical compositions comprising TiO2 (<0.03%), Fe2O3T (total Fe2O3, 0.04-0.75%, average = 0.34%), Al2O3 (0.22–0.70%, average = 0.46%), K2O (0.001–0.36%, average = 0.13%), and Na2O (0.05–0.55%, average = 0.20%) (Table 1; Figure 5). Some of the dolostone samples have a high MnO content (>0.1%, Table 1). This is consistent with the field observation that they contain manganese nodules (Figure 3a). The chemical compositions of most of the carbonate rocks in the Wumishan Formation are characterized by generally higher CaO (29.56–33.87%, average = 32.98%) and MgO (20.60–23.43%, average = 22.65%) contents and lower SiO2 (0.23–9.86%, average = 1.70%), TiO2 (<0.01%), Fe2O3T (<0.01%), Al2O3 (0.19–0.33%, average = 0.25%), K2O (<0.01%), Na2O (0.07–0.15%, average = 0.09%), and MnO (<0.02%) contents than the carbonate rocks in the Gaoyuzhuang Formation (Table 1; Figure 5).
The dolostones from both the Gaoyuzhuang and Wumishan Formations have low total rare earth element contents (ΣREE), with contents of 4.97–30.71 ppm (average = 15.3 ppm) and 1.23–2.61 ppm (average = 1.72 ppm), respectively. The Gaoyuzhuang dolostones have (La/Yb)n and (Gd/Yb)n ratios of 1.20–5.00 and 1.00–2.55, respectively, whereas the Wumishan dolostones have lower (La/Yb)n (0.72–3.97) and (Gd/Yb)n (0.61–2.60) ratios. Their LREE/HREE ratios are 7.42–16.53 and 4.84–10.47, respectively, which are all higher than 1, indicating that the LREEs are relatively enriched. Their ΣREE positively correlate with the LREE/HREE ratios (Figure 6). This also indicates that the LREEs were relatively enriched during the sedimentation of these samples.
Most of the samples from the Gaoyuzhuang Formation exhibit positive Eu anomalies with δEu values [δEu = Eu/sqrt(Sm × Gd)] of 1.12–2.73 and no obvious Ce anomalies, with δCe values [δCe = Ce/sqrt(La × Pr)] of 0.88–0.98 on REE-normalized plots (Figure 7a). The samples from the Wumishan Formation exhibit different Eu anomalies. Some of them show negative Eu anomalies with δEu values of 0.33–0.64, and the others show positive Eu anomalies (δEu = 1.36–2.39). Their δCe values mainly range from 0.61 to 0.88, indicating that they have negative Ce anomalies (Figure 7a). All of the samples generally show lower REE and trace element contents than those of the North American Shale Composite (NASC) (Figure 7; 41–43).

4.3. Carbon and Oxygen Isotopes

The carbon and oxygen isotope data of the carbonate rocks in the Gaoyuzhuang and Wumishan Formations are shown in Table 2. The δ13C and δ18O values of the Gaoyuzhuang dolostones range from −2.7 to 0.8‰ (average = −0.5‰) and from −10.2 to −4.5‰ (average = −7.0‰), respectively. The Wumishan dolostones show higher δ13C and δ18O values that range from −1.2 to 1.1‰ (average = 0.1‰) and from −5.5 to −1.6‰ (average = −3.2‰), respectively.

5. Interpretation and Discussion

Three samples from the Gaoyuzhuang Formation and one sample from the Wumishan Formation show high SiO2 contents of 12.82–25.36% and 9.86%, respectively (Table 1). This indicates that they may contain terrigenous clastic materials that are either derived from the weathering of ancient bedrocks in the peripheral areas or from the dissolution and precipitation of silica caused by microbial action. Microscopic petrographical studies show that there is some detrital quartz in the rock samples (Figure 4a,e). This further indicates that some terrigenous clastics were admixed in the sources. The other samples have high CaO and MgO contents and low SiO2 contents (Table 1), indicating that there are no obvious clay minerals that have been mixed into their sources. Previous studies have shown that Mg/Ca ratios can be used to reveal the degree of dolomitization [19]. The Mg/Ca ratios for all of the samples from different parts of the Gaoyuzhuang and Wumishan Formations are very similar, indicating that dolomitization was not an important post-depositional process in the sedimentary pile [19]. In addition, all of the samples have low total rare earth element contents (ΣREE < 35 ppm) (Table 1) that are similar to those of marine carbonate rocks (ΣREE < 100 ppm; [44]). Therefore, they can be used to discuss the sedimentary environment of the carbonate rocks collected in the present study.
Previous studies of Paleozoic and Proterozoic carbonate rocks have shown that δ18O is a sensitive proxy of diagenetic processes [8,9]. It is generally believed that the δ13C and δ18O values of well-preserved, non-evaporitic Precambrian carbonate rocks range from −2 to +2‰ and from −10 to −2‰, respectively, whereas δ18O lower than −10‰ may have been affected by diagenesis [8,45]. The δ13C values of most samples from the Gaoyuzhuang and Wumishan Formations show slight fluctuations, ranging from −1.2 to 1.1‰ and −1.9 to 0.8‰, respectively (Table 2). The Wumishan Formation has δ18O values ranging from −5.5 to −1.6‰, whereas the δ18O results of the Gaoyuzhuang Formation reveal moderate partitioning from −10.2 to −4.5‰, with lower δ18O values mostly occurring in the middle-upper Gaoyuzhuang Formation (Table 2). This indicates that most of the carbonate samples, except the samples from the middle-upper Gaoyuzhuang Formation, preserve original sedimentary features.
The relatively constant δ18O values (Table 2) do not reflect the different diagenetic facies of the Wumishan Formation and the lower Gaoyuzhuang Formation [46]. However, the values of the middle-upper Gaoyuzhuang Formation are depleted in 18O with respect to those measured in the earlier diagenetic lower Gaoyuzhuang Formation (Table 2). This suggests a hydrothermal fluid-dominated system during dolomitization [46]. The mentioned depletion in 18O may be related to an increase in temperature [47]. In contrast, the δ13C values of the Gaoyuzhuang and Wumishan Formations match those of the Cambrian limestones where HCO3− may have been buffered by the carbonates [46].
In addition, there is no obvious linear relationship between the δ13C and δ18O values (Figure 8). All of the above evidence indicates that the isotopic compositions of carbon and oxygen for most of the samples from the Wumishan Formation and the lower Gaoyuzhuang Formation were not modified by alterations and thus can represent primary values from the time of deposition [1,48]. Only occasional covariation of the samples from the middle-upper Gaoyuzhuang Formation was observed between δ13C and δ18O (Figure 8). It has been claimed that such a covariation can indicate depositional or diagenetic processes; however, only the δ18O profile is likely to have been affected if the latter occurred [49].
Furthermore, in the section of carbonate deposits, a progressive increase in crystal size could be caused by the recrystallization of carbonate minerals [50]. Samples from the Gaoyuzhuang and Wumishan Formations are mainly fine-grained and show planar textures (Figure 4). This indicates that the mineral features of carbonate rocks in the two formations are inconsistent with the typical effects of “significant recrystallization” [50].
Taking the above into account, the δ13C and δ18O values of the Wumishan Formation and the lower Gaoyuzhuang Formation can be used as isotope tracers to reconstruct their depositional environment, but it is necessary to avoid using the δ18O values of the middle-upper Gaoyuzhuang Formation due to the impact of hydrothermal processes.

5.1. Sea-Level Fluctuations

Carbon isotopes can be used to discuss sea-level fluctuations [51]. The burial rate of organic carbon is influenced by sea-level fluctuations [52,53]. Generally, the burial rate of organic carbon increases and the oxidation area of ancient land decreases as the sea level rises. This leads to reduced amounts of organic carbon sourced from weathering and denudation being introduced into the ocean, thus increasing the 13C values of seawater. Conversely, when the sea level falls, the burial rate of organic carbon decreases, and the continental area becomes larger. This results in a large amount of 12C being introduced into the seawater that further fractionates with carbonate, thus reducing the δ13C value of marine carbonate. In addition, the burial rate of organic carbon is also influenced by the number of algae. Algae adapts to various water conditions, and photosynthesis is a necessary condition for their survival. Photosynthesis consumes large amounts of 12C from the CO2 and HCO3− in seawater. Therefore, δ13C values are high in periods where algae activities are flourishing, and low δ13C values are observed in periods with scarce algae activity [54].
Low uptake of organic carbon and bioproductivity during the deposition of the lower Gaoyuzhuang Formation resulted in low carbonate δ13C values (Figure 9; Table 2). The δ13C values show different variations in the middle Gaoyuzhuang Formation (Figure 9; Table 2), indicating that there were fluctuations in the sea level. Stromatolite-bearing dolostones are common in the upper Gaoyuzhuang Formation (Figure 9). Stromatolite is formed by the biological action of blue-green algae [55]. Thus, the stromatolite-bearing dolostones occurring in the upper Gaoyuzhuang Formation indicate that there was a rich algae population producing organic carbon, increasing the δ13C values (Figure 9; Table 2).
The rocks from the lower part of the Wumishan Formation have relatively high δ13C values (>0.1‰; Figure 10; Table 2). This indicates that sea-level rise occurred during the sedimentation period of the lower Wumishan Formation. The middle Wumishan Formation commonly shows low δ13C values (Figure 10; Table 2), indicating a shallow water depth caused by decreases in the sea level. The upper Wumishan Formation is characterized by widespread stromatolite-bearing dolostones and high δ13C values (mostly greater than 0.2‰; Figure 10; Table 2), indicating that algae experienced strong biological action during the sedimentary stage of the upper Wumishan Formation. Thin silty clastics intervals in the upper Wumishan Formation (Figure 3d) may represent a drop in sea level [56]. The silty clastics and bioclastics at these intervals may have been deposited as a function of sea-level-driven reciprocal sedimentation [56]. A small number of samples from the upper Wumishan Formation show negative δ13C values (Table 2), which may have recorded a short-term drop in sea level.
According to the above discussion, the sedimentation of both the Gaoyuzhuang and Wumishan Formations experienced different transgressive–regressive cycles, and their sedimentary environments varied and were unstable during different sedimentary stages.

5.2. Hydrothermal Process

Rare earth elements (REEs) are efficient indicators that can be used to identify hydrothermal sediments and normal seawater sediments [44,57,58]. Hydrothermal sediments are characterized by negative Ce anomalies, positive Eu anomalies, and HREE enrichment, whereas normal seawater sediments are characterized by low HREE contents and negative Eu anomalies or no Eu depletion [56,59]. The samples from the Gaoyuzhuang Formation show obvious positive Eu anomalies (Figure 7) that are similar to those of hydrothermal sediments. Some of the samples from the Wumishan Formation show negative Eu anomalies (Figure 7) and have low HREE contents (Table 1). This is similar to what has been found in normal seawater sediments. Fe and Mn enrichment in sedimentary rocks is mainly related to hydrothermal processes, while Al enrichment is largely related to the mixing of terrigenous clastic materials. Adachi et al. (1986) and Boström et al. (1973) proposed that the ratios of Al/(Al + Fe + Mn), Fe/Ti, and (Fe + Mn)/Ti can be used to identify the source of hot-water and normal seawater sediments [60,61]. Hot-water sediments are characterized by Al/(Al + Fe + Mn) < 0.35, Fe/Ti > 20, and (Fe + Mn)/Ti > 25. Most of the samples from the Gaoyuzhuang Formation have Fe/Ti ratios of 42–180 and (Fe + Mn)/Ti ratios of 57–404 (Table 2). The samples from the Wumishan Formation show lower Fe/Ti (0.38–1.17) and (Fe + Mn)/Ti (2.57–15.8) ratios. This indicates that the rocks of the Gaoyuzhuang Formation were affected by hot waters, whereas the Wumishan Formation is mainly composed of normal seawater sediments. Both the Gaoyuzhuang and Wumishan Formations have Al/(Al + Fe + Mn) ratios greater than 0.35, indicating that terrigenous clastic materials are mixed into their sources. The Al/(Al + Fe + Mn) ratios of the Wumishan Formation (0.92–0.97) are higher than those of the Gaoyuzhuang Formation (0.36–0.78) (Table 2), suggesting that more terrigenous clastic materials are mixed into the source of the Wumishan Formation. To the typical features of the lower Wumishan Formation belongs a microcrystalline fabric (Figure 4f) with occurrences of argillaceous and siliciclastic components (Figure 3f), further suggesting a mixture of terrigenous clastic materials. The (Co + Ni + Cu) × 10 – Fe − Mn diagram shows that the trace element contents/ratios of the rocks of Gaoyuzhuang Formation are likely similar to trace element composition of hydrothermal deposits (HTD) and Red Sea hot brine deposits (RSHBD) (Figure 11a; [60,62,63,64]). This further supports that the Gaoyuzhuang Formation was likely affected by hydrothermal fluids. Boström et al. (1983) and Spry et al. (1990) proposed that the Fe/Ti versus Al/(Al + Fe + Mn) plot can be used to distinguish the degree of the hydrothermal source and terrigenous material mixing [65,66]. It shows that 20–60% of the hydrothermal fluid is contained in the source of the Gaoyuzhuang Formation and that there is no obvious hydrothermal fluid that has been mixed into the source of the Wumishan Formation (Figure 11b). The rocks from the Gaoyuzhuang Formation, especially from the middle-upper Gaoyuzhuang Formation, show obviously lower δ18O values than the Wumishan Formation (Figure 8; Table 2). The likely reason is that hydrothermal processes may have affected the δ18O values of the Gaoyuzhuang Formation.
Hydrothermal processes are mainly controlled by crust–mantle interaction and the type, stability, and persistence of the heat source. It can be developed in different periods and in the different tectonic settings responsible for crustal evolution, such as in the mid-oceanic ridge, back-arc and inter-arc basins, rifts, fault basins, etc. [67,68]. Tian et al. (2015) proposed that the sedimentary age of the Gaoyuzhuang Formation is the early Mesoproterozoic (1600~1550 Ma) period according to the identification of a ~1577 Ma tuff in the lower Gaoyuzhuang Formation [69]. The sedimentary age of the Wumishan Formation was constrained at 1485 Ma according to the zircon SHRIMP U-Pb age of bentonite [70]. Numerous studies have shown that the Late Paleoproterozoic to Mesoproterozoic (1.8-1.3 Ga) period was important for the breakup of the Columbia/Nuna supercontinent [31,71,72,73,74]. This suggests that both the Gaoyuzhuang and Wumishan Formations were deposited in rift settings caused by the breakup of the Columbia/Nuna supercontinent. Previous studies have shown that the basement rocks of the study area are mainly composed of Archean–Proterozoic gneiss, amphibolite, and granulite, among others [75,76]. These rocks record well-developed joints and fractures due to intense deformation and metamorphism and thus have excellent water permeability and show good groundwater convection in the vertical direction. This is convenient for the rapid migration of deep heat to the Gaoyuzhuang and Wumishan Formations. Therefore, the long and intense hydrothermal fluid activities caused by the breakup of the Columbia/Nuna supercontinent are crucial to the geothermal reservoir in the area.

6. Conclusions

Based on detailed field observations, petrography, whole-rock element geochemistry, and the carbon and oxygen isotopes of the carbonate rocks in the Gaoyuzhuang and Wumishan Formations, the following conclusions can be drawn:
(1)
Fluctuating δ13C values were recorded in the carbonate rocks from both the Gaoyuzhuang and Wumishan Formations. This indicates the occurrence of marine transgressions and regressions resulting in sea-level rises and falls. The oxygen isotopic data show that they have been influenced by diagenesis to some degree. Thus, the use of δ18O values as tracer isotopes to reveal the paleotemperature should be considered carefully, but these values still offer a feasible proxy for tracing regional emergence, rainwater and freshwater infiltration, and glaciation. This is the case for the Gaoyuzhuang Formation in particular.
(2)
Carbon isotopes are easily influenced by biological action. Most of the stromatolite-bearing dolostones from both the Gaoyuzhuang and Wumishan Formations show high δ13C values. This suggests that algae activity resulted in an uptake of organic carbon, which increased the δ13C values of carbon dissolved in seawater.
(3)
Most of the samples from the Gaoyuzhuang Formation exhibit positive Eu anomalies and no obvious Ce anomalies. Some of the samples from the Wumishan Formation show negative Eu anomalies and weakly negative Ce anomalies. This indicates that the rocks of the Gaoyuzhuang Formation were affected by hot waters, whereas the Wumishan Formation is mainly composed of normal seawater sediments.
(4)
Both of the Mesoproterozoic formations, the Gaoyuzhuang and Wumishan Formations, were deposited in rift settings that resulted from the breakup of the Columbia/Nuna supercontinent. The breakup of the supercontinent resulted in widespread and long-term hydrothermal fluid activities and formed an excellent geothermal reservoir in the area.

Author Contributions

Conceptualization, F.M. and Y.C.; methodology, T.L., Y.Z. and J.C.; software, T.L.; validation, F.M.; formal analysis, Y.C.; investigation, F.M. and Y.C.; resources, F.M. and Y.C.; data curation, T.L., Y.Z. and J.C.; writing—original draft preparation, F.M. and Y.C.; writing—review and editing, F.M. and Y.C.; visualization, Y.Z.; supervision, Y.C.; project administration, F.M. and Y.C.; funding acquisition, F.M. All authors have read and agreed to the published version of the manuscript.

Funding

This research was funded by the National Key R&D Program of China (2019YFB1504101), the National Natural Science Foundation of China (41602271 and 42072259), and the Guangxi Natural Science Foundation Program (2020GXNSFGA297003 and 2022GXNSFAA035620).

Data Availability Statement

Not applicable.

Acknowledgments

We thank Yichao Ma, Kai Zhao, Fenglei Liu, and Yue Qin for their help with the geochemical and isotopic analysis and fieldwork. We appreciate the Editor and two anonymous reviewers for their constructive and critical comments that significantly helped to improve the manuscript.

Conflicts of Interest

The authors declare no conflict of interest.

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Figure 1. (a) Tectonic location of the study area in China. (b) Geologic map of the eastern North China Craton showing the main structures and strata.
Figure 1. (a) Tectonic location of the study area in China. (b) Geologic map of the eastern North China Craton showing the main structures and strata.
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Figure 2. Lithological column of the study area.
Figure 2. Lithological column of the study area.
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Figure 3. Field photos of the carbonate rocks from the Gaoyuzhuang (a–c) and Wumishan Formations (d–f). (a) Finely laminated early diagenetic dolostone showing columnar stromatolites (blue arrows). The length of the pen is 14 cm. (b) Lime dolostone from the upper part and fine-grained dolostone from the lower part showing numerous small calcite veins (blue arrows) and vertical joints (yellow arrows). The width of the hammer is 17 cm. (c) The fine-grained dolostone in the upper part is gray-white and has partial marbleization. Argillaceous dolostone in the middle part showing laminated and cracked structures. The lime dolostone from the lower part is dark gray and contains small calcite veins (blue arrows). Vertical joints (yellow arrows) are common in different types of dolostone. Rock occurrence is 165°∠14°. The length of the hammer is 29 cm. (d) Marbleized dolostone showing bedding features (white arrows), chert nodules (blue arrows), and karrens (yellow arrows) and interbedding with laminated marble and bioclastics. The length of the hammer is 29 cm. (e) Interbedded fine-grained dolostone and lamellar dolostone showing obviously different colors and cracked structures and containing vertical joints (yellow arrows). The height of the boy is 175 cm. (f) Dark gray dolostone showing numerous irregular calcite veins (blue arrows). Argillaceous clastics (white arrows) showing laminated structures and paralleling to stratification plane. The length of the hammer is 29 cm.
Figure 3. Field photos of the carbonate rocks from the Gaoyuzhuang (a–c) and Wumishan Formations (d–f). (a) Finely laminated early diagenetic dolostone showing columnar stromatolites (blue arrows). The length of the pen is 14 cm. (b) Lime dolostone from the upper part and fine-grained dolostone from the lower part showing numerous small calcite veins (blue arrows) and vertical joints (yellow arrows). The width of the hammer is 17 cm. (c) The fine-grained dolostone in the upper part is gray-white and has partial marbleization. Argillaceous dolostone in the middle part showing laminated and cracked structures. The lime dolostone from the lower part is dark gray and contains small calcite veins (blue arrows). Vertical joints (yellow arrows) are common in different types of dolostone. Rock occurrence is 165°∠14°. The length of the hammer is 29 cm. (d) Marbleized dolostone showing bedding features (white arrows), chert nodules (blue arrows), and karrens (yellow arrows) and interbedding with laminated marble and bioclastics. The length of the hammer is 29 cm. (e) Interbedded fine-grained dolostone and lamellar dolostone showing obviously different colors and cracked structures and containing vertical joints (yellow arrows). The height of the boy is 175 cm. (f) Dark gray dolostone showing numerous irregular calcite veins (blue arrows). Argillaceous clastics (white arrows) showing laminated structures and paralleling to stratification plane. The length of the hammer is 29 cm.
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Figure 4. Photomicrographs of the carbonate rocks from the Gaoyuzhuang (a–c) and Wumishan Formations (d–f). (a) Well-developed micro-sedimentary beddings (blue arrows) in the lamellar stromatolite dolostone in the upper Gaoyuzhuang Formation. (b) Micritic (blue arrows) and fine-grained textures in the fine-grained dolostone from the middle Gaoyuzhuang Formation. (c) Calcite within the lime dolostone from the lower Gaoyuzhuang Formation. Dolomites are mostly anhedral and micritic and cut by different calcite vein complexes (blue arrows). (d) Dolomites in the upper Wumishan Formation are densely packed with each other and show microscopic stratification (blue arrows). (e) Well-developed cleavages in the middle Wumishan Formation showing typical cleavage domains (blue arrows) and microlithons (yellow arrows). (f) Uncemented dissolution and partially cemented fractures with calcite cement deposits (blue arrows) of the fine-grained dolostone in the lower Wumishan Formation.
Figure 4. Photomicrographs of the carbonate rocks from the Gaoyuzhuang (a–c) and Wumishan Formations (d–f). (a) Well-developed micro-sedimentary beddings (blue arrows) in the lamellar stromatolite dolostone in the upper Gaoyuzhuang Formation. (b) Micritic (blue arrows) and fine-grained textures in the fine-grained dolostone from the middle Gaoyuzhuang Formation. (c) Calcite within the lime dolostone from the lower Gaoyuzhuang Formation. Dolomites are mostly anhedral and micritic and cut by different calcite vein complexes (blue arrows). (d) Dolomites in the upper Wumishan Formation are densely packed with each other and show microscopic stratification (blue arrows). (e) Well-developed cleavages in the middle Wumishan Formation showing typical cleavage domains (blue arrows) and microlithons (yellow arrows). (f) Uncemented dissolution and partially cemented fractures with calcite cement deposits (blue arrows) of the fine-grained dolostone in the lower Wumishan Formation.
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Figure 5. Plots of (a) MgO versus SiO2, (b) MgO versus TiO2, (c) MgO versus Al2O3, (d) MgO versus FeOT, (e) MgO versus CaO, (f) MgO versus Na2O, (g) MgO versus P2O5, and (h) MgO versus MnO for the carbonate rocks from the Gaoyuzhuang and Wumishan Formations.
Figure 5. Plots of (a) MgO versus SiO2, (b) MgO versus TiO2, (c) MgO versus Al2O3, (d) MgO versus FeOT, (e) MgO versus CaO, (f) MgO versus Na2O, (g) MgO versus P2O5, and (h) MgO versus MnO for the carbonate rocks from the Gaoyuzhuang and Wumishan Formations.
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Figure 6. Plots of (a) ΣREE versus ΣLREE/ΣHREE and (b) ΣLREE versus ΣHREE for the carbonate rocks from the Gaoyuzhuang and Wumishan Formations.
Figure 6. Plots of (a) ΣREE versus ΣLREE/ΣHREE and (b) ΣLREE versus ΣHREE for the carbonate rocks from the Gaoyuzhuang and Wumishan Formations.
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Figure 7. (a) NASC-normalized REE patterns and (b) NASC-normalized spider diagrams of incompatible elements for the carbonate rocks from the Gaoyuzhuang and Wumishan Formations.
Figure 7. (a) NASC-normalized REE patterns and (b) NASC-normalized spider diagrams of incompatible elements for the carbonate rocks from the Gaoyuzhuang and Wumishan Formations.
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Figure 8. Plot of δ13C versus δ18O values for the carbonate rocks from the Gaoyuzhuang and Wumishan Formations.
Figure 8. Plot of δ13C versus δ18O values for the carbonate rocks from the Gaoyuzhuang and Wumishan Formations.
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Figure 9. Vertical δ13C and δ18O profiles of the carbonate rocks from the Gaoyuzhuang Formation.
Figure 9. Vertical δ13C and δ18O profiles of the carbonate rocks from the Gaoyuzhuang Formation.
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Figure 10. Vertical δ13C and δ18O profiles for the carbonate rocks from the Wumishan Formation.
Figure 10. Vertical δ13C and δ18O profiles for the carbonate rocks from the Wumishan Formation.
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Minerals 12 01111 g011 550
Figure 11. Plots of (a) (Co + Ni + Cu) × 10 – Fe − Mn and (b) Fe/Ti versus Al/(Al + Fe + Mn) for the carbonate rocks from the Gaoyuzhuang and Wumishan Formations. Abbreviations: RSHBD = Red Sea hot brine deposits, HGN = hydrogenous nodules, HTD = hydrothermal deposits, EPRD = East Pacific Rise deposits, EPR = East Pacific Rise, RS = Red Sea, TS = terrigenous sediments, PS = pelagic sediments.
Figure 11. Plots of (a) (Co + Ni + Cu) × 10 – Fe − Mn and (b) Fe/Ti versus Al/(Al + Fe + Mn) for the carbonate rocks from the Gaoyuzhuang and Wumishan Formations. Abbreviations: RSHBD = Red Sea hot brine deposits, HGN = hydrogenous nodules, HTD = hydrothermal deposits, EPRD = East Pacific Rise deposits, EPR = East Pacific Rise, RS = Red Sea, TS = terrigenous sediments, PS = pelagic sediments.
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Table
Table 1. Major element (wt.%) and trace element (ppm) compositions of the carbonate rocks in the Gaoyuzhuang and Wumimshan Formations.
Table 1. Major element (wt.%) and trace element (ppm) compositions of the carbonate rocks in the Gaoyuzhuang and Wumimshan Formations.
FormationGaoyuzhuang FormationWumishan Formation
MemberUpperMiddleLowerUpperMiddleLower
SampleGS01GS03GZ01GZ04GZ08GX02GX05GX07WS01WS04WZ01WZ03WX02WX04WX07
GPS39°07′52.2′′ N, 115°03′17.6′′ E39°07′41.3′′ N, 115°03′34.7′′ E39°08′58.1′′ N, 115°02′53.5′′ E39°08′32.2′′ N, 115°02′58.3′′ E39°08′04.5′′ N, 115°03′08.8′′ E39°09′50.4′′ N, 115°01′01.6′′ E39°09′21.1′′ N, 115°01′21.7′′ E39°09′13.9′′ N, 115°01′37.2′′ E39°03′10.2′′ N, 115°08′53.7′′ E39°02′55.6′′ N, 115°09′13.3′′ E39°06′42.6′′ N, 115°04′23.7′′ E39°06′31.1′′ N, 115°04′43.5′′ E39°07′11.2′′ N, 115°04′06.7′′ E39°07′02.8′′ N, 115°04′15.3′′ E39°01′11.2′′ N, 115°03′36.8′′ E
SiO22.3824.350.270.3012.821.000.4925.360.230.310.390.460.359.860.27
TiO20.010.010.030.0010.010.0010.0020.0010.0010.0010.0030.0020.0010.0020.001
Al2O30.640.700.570.230.650.290.220.400.190.240.270.330.280.220.21
MgO21.3616.5022.4922.7623.4022.3922.1417.1522.9922.9122.6722.8323.4320.6023.09
Fe2O3T0.750.630.290.040.440.080.310.150.0010.0010.0010.0010.0010.0010.001
K2O0.360.290.170.050.040.030.0010.060.0010.0010.010.030.0010.0020.001
Na2O0.110.060.400.070.270.060.050.550.070.070.080.080.150.070.13
CaO31.2524.1532.7233.3233.9732.7032.7224.8333.6033.0833.6233.8733.6529.5633.52
MnO0.090.100.020.010.140.020.120.170.010.010.010.010.010.010.01
P2O50.020.030.020.010.030.010.020.020.010.010.010.010.010.010.02
V10.147.648.551.343.081.191.602.591.240.730.547.740.931.191.68
Cr28.074.988.232.743.542.944.282.342.823.421.563.413.622.492.07
Co9.144.094.234.285.576.193.943.254.653.463.653.945.263.554.66
Ni13.467.258.758.948.3910.739.397.138.647.377.789.1011.997.898.76
Cu5.371.391.881.850.260.941.111.530.630.471.054.040.762.501.16
Zn13.599.051.116.379.198.557.535.341.202.454.892.81-0.093.900.78
Ga36.101.771.291.0936.451.160.434.560.100.160.410.340.230.190.34
Rb9.865.413.451.861.410.890.592.450.570.620.770.870.390.540.55
Sr95.1158.531.3109.6272.241.0150.284.523.937.147.843.940.215.531.3
Y4.064.832.591.122.460.801.231.590.260.310.680.420.480.290.42
Zr14.057.4610.575.955.584.145.0320.371.472.065.446.216.013.082.82
Nb1.750.530.520.170.380.160.180.190.270.320.120.150.070.070.06
Cs0.290.060.130.070.050.020.010.330.000.010.030.020.030.010.00
Ba106236.2823.7030.80108836.568.561312.603.428.064.964.563.788.17
La5.076.872.241.224.551.343.702.830.370.640.430.510.430.440.30
Ce9.3212.163.902.069.002.236.665.350.681.120.550.690.510.790.40
Pr1.081.450.480.231.030.230.750.590.090.160.070.100.060.080.08
Nd3.905.601.870.763.790.792.332.090.220.390.210.270.200.250.23
Sm0.771.230.330.150.680.150.360.400.050.060.030.050.030.060.00
Eu0.480.280.050.050.580.040.090.110.020.020.010.010.000.010.01
Gd0.911.130.330.180.790.130.330.310.040.040.050.080.030.050.05
Tb0.140.170.060.030.090.030.040.050.030.030.010.020.010.010.01
Dy0.540.830.310.090.470.110.230.230.040.050.050.050.040.040.06
Ho0.140.150.070.030.080.020.040.050.020.020.010.010.010.010.01
Er0.280.410.190.080.230.070.100.120.030.050.050.030.030.040.04
Tm0.060.060.030.020.030.010.020.020.020.020.010.010.000.000.01
Yb0.210.320.180.070.170.040.070.080.010.020.030.030.020.040.04
Lu0.050.040.030.010.020.010.010.010.010.000.000.000.000.000.00
Hf0.440.170.210.110.140.120.080.360.060.040.040.100.110.080.11
Ta0.890.060.140.050.080.070.070.040.630.660.120.080.060.090.05
Th0.630.520.450.150.320.110.100.150.070.070.080.080.030.040.04
U0.220.280.240.080.180.080.060.130.100.050.050.440.040.150.25
Table
Table 2. Carbon and oxygen isotope compositions of the carbonate rocks in the Gaoyuzhuang and Wumimshan Formations.
Table 2. Carbon and oxygen isotope compositions of the carbonate rocks in the Gaoyuzhuang and Wumimshan Formations.
FormationMemberSamplesRock Typeδ13C(‰)δ18O(‰)
Gaoyuzhuang FormationUpperGS01stromatolite-bearing dolostone0.78−7.34
GS02stromatolite-bearing dolostone0.17−6.79
GS03chert banding dolostone−0.09−8.42
GS04stromatolite-bearing dolostone0.44−9.48
GS05stromatolite-bearing dolostone0.08−10.15
GS06stromatolite-bearing dolostone0.63−6.97
MiddleGZ01argillaceous dolostone−0.79−8.63
GZ02argillaceous dolostone−0.46−5.77
GZ03argillaceous dolostone−1.02−9.26
GZ04gray dolostone−0.29−7.53
GZ05gray dolostone−0.86−5.69
GZ06gray dolostone−2.66−8.85
GZ07gray dolostone−1.86−9.58
GZ08fine-grained dolostone−1.15−4.68
GZ09fine-grained dolostone0.09−7.42
LowerGX01dark gray dolostone−0.07−5.32
GX02dark gray dolostone−0.78−6.13
GX03dark gray dolostone−1.64−5.24
GX04dark gray dolostone−0.77−5.48
GX05dark gray dolostone−0.81−5.39
GX06dark gray dolostone0.18−4.98
GX07argillaceous dolostone−0.14−4.53
Wumishan FormationUpperWS01chert-bearing dolostone0.18−3.15
WS02chert-bearing dolostone0.24−4.27
WS03chert-bearing dolostone0.42−3.88
WS04stromatolite-bearing dolostone−0.67−3.93
WS05stromatolite-bearing dolostone1.21−2.82
WS06stromatolite-bearing dolostone0.23−2.57
WS07argillaceous dolostone0.88−4.79
MiddleWZ01fine-grained dolostone−0.78−2.66
WZ02fine-grained dolostone−1.15−1.62
WZ03gray dolostone−0.11−2.11
WZ04gray dolostone−0.32−2.17
WZ05gray dolostone−1.13−2.38
WZ06gray dolostone0.32−4.51
WZ07fine-grained dolostone−1.05−2.13
LowerWX01chert-bearing dolostone1.06−5.49
WX02chert-bearing dolostone0.28−2.41
WX03chert-bearing dolostone0.11−2.98
WX04argillaceous dolostone0.21−4.62
WX05argillaceous dolostone0.09−2.74
WX06dark gray dolostone0.64−3.22
WX07dark gray dolostone0.54−4.12
WX08dark gray dolostone0.34−3.21
WX09dark gray dolostone0.27−2.39
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Ma, F.; Li, T.; Zhou, Y.; Cai, J.; Cai, Y. Paleoenvironment of Mesoproterozoic Gaoyuzhuang and Wumishan Formations, North China: New Insights from Geochemistry and Carbon and Oxygen Isotopes of Dolostones. Minerals 2022, 12, 1111. https://doi.org/10.3390/min12091111

AMA Style

Ma F, Li T, Zhou Y, Cai J, Cai Y. Paleoenvironment of Mesoproterozoic Gaoyuzhuang and Wumishan Formations, North China: New Insights from Geochemistry and Carbon and Oxygen Isotopes of Dolostones. Minerals. 2022; 12(9):1111. https://doi.org/10.3390/min12091111

Chicago/Turabian Style

Ma, Feng, Tingxin Li, Yun Zhou, Jin Cai, and Yongfeng Cai. 2022. "Paleoenvironment of Mesoproterozoic Gaoyuzhuang and Wumishan Formations, North China: New Insights from Geochemistry and Carbon and Oxygen Isotopes of Dolostones" Minerals 12, no. 9: 1111. https://doi.org/10.3390/min12091111

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