Implications of the Precambrian Non-stromatolitic Carbonate Succession Making up the Third Member of Mesoproterozoic Gaoyuzhuang Formation in Yanshan Area of North China

A particular non-stromatolitic carbonate succession making up the third member of the Mesoproterozoic Gaoyuzhuang （高于庄） Formation might demonstrate that a stromatolite decline of the Mesoproterozoic occurring at ca. 1 450 Ma besides other three events of the Proterozoic, respectively, occurred at ca. 2 000 Ma, ca. 1 000 Ma, and ca. 675 Ma. The forming duration of this non-stromatolitic carbonate succession can be generally correlative to that of a similar depositional succession in North America, i.e. a non-stromatolitic carbonate succession made up by the Helena Formation of the Belt Supergroup, which suggests that the stromatolite decline occurring at ca. 1 450 Ma may be a global event. This information endows the non-stromatolitic carbonate succession making up the third member of the Gaoyuzhuang Formation in the Yanshan （燕山） area with important significance for the further understanding of Precambrian sedimentology. The Mesoproterozoic Gaoyuzhuang Formation in Yanshan area is a set of more than 1 000 m thick carbonate strata that can be divided into four members （or subformations）. The first member （or the Guandi （官地） subformation） is marked by a set of stromatolitic dolomites overlying a set of transgressive sandstones; the second member （or the Sangshu＇an （桑树鞍） subformation） is a set of manganese dolomites with a few stromatolites; the third member （or the Zhangjiayu （张家峪） subformation） is chiefly made up of leiolite and laminite limestones and is characterized by the development of molar-tooth structures in leiolite limestone; the fourth member （or the Huanxiusi （环秀寺） subformation） is composed of a set of dolomites of stromatolitic reefs or lithoherms. Sequence-stratigraphic divisions at two sections, i.e. the Jixian （蓟县） Section in Tianjin （天津） and the Qiangou （千沟） Section of Yanqing （延庆） County in Beijing （北京）, demonstrate that a particularly non-stromatolitic succession making up the third member of the Mesoproterozoic Gaoyuzhuang Formation is developed in the Yanshan area of North China, in which lots of grotesque matground structures （wrinkle structures and palimpsest ripples） are developed in beds of leiolite limestone at the Qiangou Section and lots,of molar-tooth structures are developed in beds of leiolite limestone at the Jixian Section. The time scale of the Gaoyuzhuang Formation is deduced as 200 Ma （from 1 600 Ma to 1 400 Ma）. The duration of an obvious hiatus between the Gaoyuzhuang Formation and the underlying Dahongyu （大红） Formation is deduced as 50 Ma to 100 Ma, thus the forming duration of the Gaoyuzhuang Formation is thought as 100 Ma （1 500 Ma to 1 400 Ma）. Furthermore, the age of the subface of the third member of the Gaoyuzhuang Formation that is just in the mid position of the Gaoyuzhuang Formation can be deduced as about 1 450 Ma, which is the basis to infer a stromatolite decline of the Mesoproterozoic occurring at ca. 1 450 Ma. Importantly, several features of both the molar-tooth structure and the stromatolite, such as the particular forming environment, the important facies-indicative meaning, and the episodic distribution in the earth history, might express the evolutionary periodicity of the surface environment of the earth and can provide meaningful clues for the understanding of the Precambrian world, although their origin and forming mechanism is highly contentious. Therefore, like other three stromatolitic declines, respectively, occurring at ca. 675 Ma, ca. 1 000 Ma, and ca. 2 000 Ma, the identification of the stromatolite decline occurring at ca. 1 450 Ma during the Golden Age of stromatolites （2 800 Ma to 1 000 Ma） has important meaning for the further understanding of the evolving carbonate world of the Precambrian.

Origin of Molar-Tooth Structure Based on Sequence-Stratigraphic Position and Macroscopic Features: Example from Mesoproterozoic Gaoyuzhuang Formation at Jixian Section, Tianjin, North China

Both the macroscopic feature and the sequence-stratigraphic position of the molar-tooth structure developed in the third member of the Gaoyuzhuang （高于庄） Formation at the Jixian （蓟县） Section in Tianjin （天津） can provide some useful information about its origin and can reveal some problems to be further researched in the future. The Mesoproterozoic Gaoyuzhuang Formation is a set of 1 600 m thick carbonate strata. This formation can be divided into four members. The first member is mainly made up of stromatolitic dolomites; the second is marked by a set of manganese dolomites; the third is mainly composed of lamina limestones with the development of molar-tooth strcutures; the fourth is a set of stromatolitic-lithoherm dolomites. According to lithofacies and its succession, several types of meter-scale cycles can be discerned in the Gaoyuzhuang Formation： the L-M type, the subtidal type and the peritidal type. There is a regularly vertical stacking pattern for meter-scale cycles in the third-order sequence. Therefore, the Mesoproterozoic Gaoyuzhuang Formation can be divided into 13 third-order sequences （SQ1 to SQ13 ） and can further be grouped into 4 second-order sequences. The third member is marked by lamina limestones and can be grouped into three third-order sequences （SQ9 to SQ11 ）. The molar-tooth structure is developed in the middle part of the third sequence, i.e. SQH , in the third member. Several features of this kind of molar-tooth structure reflect some features of carbonate sedimentation in the Precambrian, such as the particular configuration, abundant organic matter, and easy silication. Stromatolites are chiefly formed in a shallow tidal-flat environment; lamina are mainly formed in the shallow ramp and molar-tooth structures are mainly generated in a relatively more deep-water environment from the middle to the deep ramp. Therefore, similar to stromatolite and lamina, the molartooth structure might also be a kind of bio-sedimentation structure. This suggestion is based on macroscopic observation and the sedimentary-facies analysis of the molar-tooth structures from the sequencestratigraphic position. These features of Precambrian sedimentation also reveal the problem of Precambrian carbonate sedimentation. With more detailed study, a more practical solution for these problems may be obtained in the future.

Sedimentary Features and Implications for the Precambrian Non-stromatolitic Carbonate Succession:A Case Study of the Mesoproterozoic Gaoyuzhuang Formation at the Qiangou Section in Yanqing County of Beijing

In the long Precambrian period, stromatolitic carbonate successions were very common. However, the non-stromatolitic carbonate succession that is marked by subtidal deposits shows a sharp contrast to the stromatolitic carbonate succession. Both the non-stromatolitic and the stromatolitic carbonate successions are important clues for the further understanding of the evolving carbonate world of the Precambrian. The Mesoproterozoic Gaoyuzhuang Formation at the Qiangou section in northwestern suburb of Beijing is a set of more than 1000 m-thick carbonate strata that can be divided into four members （or subformations）, in which a non-stromatolitic carbonate succession marked by the scarcity of stromatolites makes up the third member of the formation. This non-stromatolitic carbonate succession can further be subdivided into three third-order sequences that are marked by the regular succession of sedimentary facies. In third-order sequences, a lot of subtidal carbonate meter-scale cycles made up of medium-bedded leiolite limestones and thin-bedded marls constitute their transgressive system tracts （TSTs） and the early high-stand system tracts （EHSTs）, a lot of meter- scale cycles made up by thin-bedded limestones and marls constitute their condensed sections （CSs）, and thick-bedded to massive dolomitic limestones or lime dolomites make up the late high-stand system tracts （LHSTs）. The particularly non-stromatolitic carbonate succession making up the third member of the Mesoproterozoic Gaoyuzhuang Formation at the Qiangou section might be the representative of the non-stromatolitic carbonate succession of the Precambrian because of its special lithological features and particular sedimentary structures, and its general sedimentary features are helpful and meaningful for the further understanding of the evolution rules of the sophisticate and evolving carbonate world of the Precambrian. The time scale of the Gaoyuzhuang Formation is deduced as that from 1600 Ma to 1400 Ma; thus, the non-stromatolitic sedimentary succession making up the third member of the Gaoyuzhuang Formation may demonstrate a stromatolite decline event occurring at ca. 1450 Ma of the Proterozoic besides other three events that occurred respectively at ca. 2000 Ma, ca. 1000 Ma and ca. 675 Ma. The forming duration of this non-stromatolitic sedimentary succession of the third member of the Gaoyuzhuang Formation can be generally correlated with a similar sedimentary succession in North America, i.e. a non-stromatolitic sedimentary succession of the Helena Formation of the Belt Supergroup, which suggests that the stromatolite decline occurring at ca. 1450 Ma might be a global event. Therefore, the non-stromatolitic sedimentary succession discussed in the paper provides an important example for further understanding of carbonate sedimentology in the Precambrian.

Molar Tooth Structure:a Contribution from the Mesoproterozoic Gaoyuzhuang Formation,Tianjin City,North China

Molar-tooth(MT) structure is an enigmatic sedimentary structure consisting of variously-shaped cracks and voids filled with a characteristically uniform,equant calcite microspar.It is globally distributed but temporally restricted to rocks from Neoarchean to Neoproterozoic age.The origin of MT structures has been debated for more than a century and the topic continues to be highly contentious.Some features of MT structure occurring in micritic limestones of the Mesoproterozoic Gaoyuzhuang Formation(ca.1500 Ma to ca.1400 Ma),Jixian section,Tianjin City,North China show that:1) there is a definite interface or lining,rich in organic material and pyrite,between the MT crack-filling calcite microspar and the micritic host rock,which is also rich in organic matter;2) the micritic host rocks are notable for the absence of stromatolites and microbial laminites;3) distinctive conglomeratic lag deposits made up of intraclasts of MT microspar result from storm reworking of the MT structures;4) the MT structure is associated with possible algal megafossils such as Chuaria;5) the MT microspar is made up of the larger calcite crystal and the MT crack is marked by the diversity of configurations;6) both the TOC content and the carbon-isotopic value(δ^(13)C_(PDB)) among the host rock, the MT microspar and the possible algae fossil are obviously different.For the forming mechanism of the Gaoyuzhuang MT structure,these features can still indicate that:A) the MT microspar was formed by rapid precipitation and lithification;B) the MT microspar precipitated directly within the cracks; C) the decomposition of organic matter within the host micrite might be the chief mechanism producing gas bubbles;D) microscale gas-sediment interaction led to the generation of the MT cracks and the precipitation of microspar therein;E) the MT cracks might represent the track of migration and expansion of gas bubbles,and that the recrystallization of host micrites cannot be eliminated during forming process of the MT microspar;F) the MT structure is occurred in early diagenetic period;and G) the formation of MT microspars is a complex diagenetic process.Therefore,model of the microbially-induced gas-bubble expansion and migration is the best interpretation for the formation of the MT structure.Effectively,MT structures are a type of sedimentary structure that is formed in the early diagenetic period and is related to microbial activities and organic matter degradation.

Trace and rare earth elemental geochemistry of carbonate succession in the Middle Gaoyuzhuang Formation,Pingquan Section:Implications for Early Mesoproterozoic ocean redox conditions

The concentrations of redox-sensitive trace elements,such as uranium(U),vanadium(V),molybdenum(Mo),cobalt(Co),chromium(Cr) and rare earth elements(REE+Y) were determined in a given carbonate succession in the Gaoyuzhuang Formation(～1.56 Ga),which spans depths from outer shelf to intertidal,to explore the Early Mesoproterozoic ocean redox conditions.The values of the Zr-normalized redox-sensitive trace element concentrations and some relevant ratios show obvious changes from bottom to top in the succession.Samples from the outer shelf setting(M1 interval) demonstrate significantly enhanced values in Zr-normalized redox-sensitive trace element concentrations and relevant ratios(the peaks of Mo/U,V/Cr and Ni/Co ratios larger than 8,4.25,and 7,respectively).Authigenic framboidal pyrites were also found within oncolite-like carbonate concretions and surrounding host rocks in this interval.These all indicate a euxinic state in the outer shelf environment.Less enrichment of Zr-normalized redox-sensitive elemental abundances and a mild decrease in the values of geochemical ratios were present in the inner shelf environment(M2 interval)(the V/Cr and Ni/Co ratios fall into a range of 2.5 4.25 and 4 5,respectively),suggesting dysoxic conditions dominant in the inner shelf setting.Samples from the shallower subtidal and intertidal settings(M3 and M4 intervals) are mostly invariable with much lower values of Zr-normalized redox-sensitive elements and relevant ratios,with the V/Cr and Ni/Co ratios typically near or less than 2 and 5 respectively,indicative of oxic conditions in the high energy subtidal/intertidal zones.A remarkable negative Ce anomaly exhibited in the shale-normalized REE+Y diagram in the M4 interval may provide evidence in support of the hypothesis.Taken together,our results suggest a relatively shallow chemocline in the Early Mesoproterozoic ocean:the transitions between euxinic,dysoxic and oxic may occur in quiet-water outer shelf and highenergy subtidal zone,respectively.The presence of euxinic ocean bottom waters is compatible with low concentrations of seawater sulfate and reduced levels of atmospheric oxygen during this period.The extreme environmental conditions induced by these anoxic oceans could have been responsible for the delayed oxygenation of the biosphere and hindered the evolution of multicellular life.

The Mesoproterozoic Oxygenation Event

The accumulation of oxygen is one of the most important characteristics that distinguish Earth from other planets in the solar system,which is also considered to be the key factor influencing the birth and evolution of complex life forms.The oxygenation process of the Earth surface has long been viewed to be episodic with two critical intervals occurring in the early Paleoproterozoic(2.45-2.10 Ga)and the late Neoproterozoic(0.80-0.54 Ga),with a 1.3-billion-year-long low oxygen period in between.Recently,increasing independent works carried out by different scientific teams in the Yanliao Basin,North China are demonstrating that the atmospheric oxygen concentrations had reached>4%PAL(present atmospheric levels)at least during 1.59-1.56,1.44-1.43,and 1.40-1.36 Ga.These estimated values are higher than the previously recommended values of<0.1-1%PAL.Such a scenario discovered in the Yanliao Basin is consistent with the synchronously deposited strata in Australia and Siberia,pointing to a Mesoproterozoic oxygenation event(1.59-1.36 Ga)between the two major oxygenation intervals during the Proterozoic.This Mesoproterozoic oxygenation event is coupled with the break-up of the Columbia(Nuna)supercontinent,the formation of organic-rich shales and Fe-Mn deposits,and the early innovation of eukaryotic algae,indicating that the geological and biological co-evolutionary processes control the Earth surface system.