Genetic Mechanism and Environment Implications of Siderites in the Lopingian Coal-Bearing Series, Western Guizhou of China: Constrained by Whole-Rock and In Situ Geochemistry

A large number of siderites have been found in the Lopingian (Late Permian) coal-bearing series in western Guizhou, which occurs in various microscopic morphologies and has potential insights into the sedimentary and diagenetic environments. An integrated set of analyses, such as microscopic observation; X-ray diffraction; whole-rock major and trace element, carbon, and oxygen isotope; and in situ major and trace element, has been carried out to unravel the genetic mechanism of the siderites and their environmental implications. According to the microscopic morphology, the siderites can be generally divided into three types and six subtypes, including gelatinous siderites (I), microcrystal-silty siderite [II; microlite siderites (II1), powder crystal siderites (II2)], and spheroidal siderite [III, petal-like siderite (III1), radiating fibrous siderite (III2) and concentric siderite (III3)]. Whole-rock geochemical results show that the iron source for the formation of the siderites was mainly from extensive weathering of the Emeishan high-titanium basalts in hot climate conditions. The carbon and oxygen isotopic results indicate that the origin of CO2 in type I siderites is derived from the dehydroxylation of organic matter. The CO2 in types II1 and II2 siderites is mainly derived from deposited organic matter and marine carbonate rocks, respectively. The CO2 source of type III siderites is sedimentary organic matter and marine carbonate rocks and is affected by different fluids during diagenesis. The whole-rock and in situ geochemical characteristics further point to that type I siderites were formed in the synsedimentary period most strongly affected by seawater. Redox proxies, such as V/Sc, V/(V+Ni), and δ Ce, constrained their formation in a stable and weakly reduced condition. Type II siderites could have been developed in saltwater. Among them, type II1 siderites were formed in the early diagenetic stage, whereas type II2 siderites originated from recrystallization of type II1 siderites and accompanied by metasomatism with calcites under diagenetic fluids of weak reduction to weak oxidation conditions. Type III siderites were formed under the influence of multistage diagenetic fluids. Among them, type III1 siderites formed by the growth of powder crystal siderites (II2) under diagenetic fluids with a weak reducing condition. Type III2 siderites formed by growth around microlite siderites under weak reducing diagenetic fluids. Type III3 siderites formed by concentric growth in diagenetic fluids with weak reduction to weak oxidation conditions and relatively active conditions.

A persistently low level of atmospheric oxygen in Earth’s middle age

Resolving how Earth surface redox conditions evolved through the Proterozoic Eon is fundamental to understanding how biogeochemical cycles have changed through time. The redox sensitivity of cerium relative to other rare earth elements and its uptake in carbonate minerals make the Ce anomaly (Ce/Ce*) a particularly useful proxy for capturing redox conditions in the local marine environment. Here, we report Ce/Ce* data in marine carbonate rocks through 3.5 billion years of Earth’s history, focusing in particular on the mid-Proterozoic Eon (i.e., 1.8 – 0.8 Ga). To better understand the role of atmospheric oxygenation, we use Ce/Ce* data to estimate the partial pressure of atmospheric oxygen (pO2) through this time. Our thermodynamics-based modeling supports a major rise in atmospheric oxygen level in the aftermath of the Great Oxidation Event (~ 2.4 Ga), followed by invariant pO2 of about 1% of present atmospheric level through most of the Proterozoic Eon (2.4 to 0.65 Ga).

The Shibantan Lagerstätte: insights into the Proterozoic–Phanerozoic transition

The Shibantan Lagerstätte (551–543 Ma) in the Yangtse Gorges area in South China is one of the best-known examples of terminal Ediacaran fossil assemblages preserved in marine carbonate rocks. Taxonomically dominated by benthic organisms, the Shibantan Lagerstätte preserves various photoautotrophs, biomineralizing tubular fossils, Ediacara-type macrofossils (including rangeomorphs, arboreomorphs, erniettomorphs, palaeopascichnids, a possible dickinsoniomorph, the mobile bilaterian Yilingia and soft-bodied tubular fossils), abundant ichnofossils and a number of problematic and dubious fossils. Shibantan fossils provide intriguing insights into ecological interactions among mobile bilaterians, sessile benthic Ediacara-type organisms and microbial mats, thus offering important data to test various hypotheses accounting for the decline of the Ediacara biota and the concurrent expansion of bilaterian bioturbation and mobility across the Proterozoic–Phanerozoic transition.

Stable Isotope (S, Mg, B) Constraints on the Origin of the Early Precambrian Zhaoanzhuang Serpentine-Magnetite Deposit, Southern North China Craton

The origin of the Zhaoanzhuang serpentine-magnetite deposit in the southern North China Craton (NCC) is highly disputed, with some investigators having proposed an ultramafic origin, whereas others favor a chemical sedimentary origin. These discrepancies are largely due to the difficulty in determining the protolithic characteristics of the highly metamorphosed rocks. Sulfur, magnesium, and boron isotope geochemistry combined with detailed petrography was carried out in this study to constrain the original composition of the Zhaoanzhuang iron orebodies. Anhydrite is present as coarse crystals intergrown with magnetite, indicating that the anhydrite formed simultaneously with the magnetite during metamorphism rather than as a product of later hydrothermal alteration. The anhydrite has a narrow range of positive δ34S values from +19.8 to +22.5‰ with a mean value of +21.1‰. These values are significantly higher than that of typical magmatic sulfur (δ34S = 0 ± 5‰) and deviate away from primary igneous anhydrite towards mantle-sulfur isotopic values, but they are similar to those of marine evaporitic anhydrite and gypsum (~+21‰). The sulfur isotopic compositions of several samples show obvious signs of mass-independent sulfur fractionation (Δ33S = −0.47‰ to +0.90‰), suggesting that they were influenced by an external sulfur source through a photochemical reaction at low oxygen concentrations, which is consistent with the Neoarchean-Paleoproterozoic atmosphere. Coarse-grained tourmaline from the tourmaline-rich interlayers of the orebodies occurs closely with Mg-rich minerals such as phlogopite, talc, and diopside, indicating that it has a metamorphic origin. The δ11B values of the tourmaline range from −0.2‰ to +3.6‰ with a mean value of +2.0‰, which is much positive relative to that of magmatic tourmaline but is consistent with that of carbonate-derived tourmaline. The magnesium isotopic analyses of the serpentine–magnetite ores and the magnesium-rich wall rocks revealed a wide range of very negative δ26Mg values from −1.20‰ to −0.34‰ with an average value of −0.80‰. The value is higher than that of ultramafic rocks (δ26Mg = −0.25‰) and exhibits minor Mg isotopic fractionation. However, these values are consistent with those of marine carbonate rocks, which have lower δ26Mg values and larger Mg isotopic variations (δ26Mg = −0.45‰ to −4.5‰). Collectively, the S–Mg–B isotopic characteristics of the Zhaoanzhuang iron orebodies clearly indicate a chemical sedimentary origin. The protoliths of these orebodies most likely reflect a series of Fe–Si–Mg-rich marine carbonate rocks with a considerable evaporite component, indicating a carbonate-rich superior-type banded iron formation precipitated in an evaporitic shallow marine sedimentary environment.