B. G. Pokrovskii

Carbon, oxygen, strontium, and sulfur isotopic compositions in late Precambrian rocks of the Patom Complex, central Siberia: Communication 1. results, isotope stratigraphy, and dating problems

Results of the study of isotopic compositions of C, O, S, and Sr in late Precambrian sections of the Patom Complex and its analogues are presented. Total scatter in δ13C values is more than 21‰ (from −13.5 to 8.1‰). The sections strongly differ in thickness, but they have similar carbon isotope curves with two dramatic drops in δ13C from extremely high (>4‰) to extremely low (<−8‰) values. The lower negative excursion is associated with the glacial horizon (Dzhemkukan and Nichatka formations), while the upper excursion spans the entire Zhuya Group, which is as thick as 800–1000 m on the carbonate shelf (Nikol’skoe and Chencha formations along the Zhuya and Lena Rivers) and only 250–350 m at the carbonate platform (Torgo Formation, Chara River). Steady extremely high δ13C values (from 7 to 8‰) are typical of the glacial horizon underlying the Mariinsk Formation, as well as the Barakun and Valyukhta formations and their analogues, which separate negative excursions. The minimum 87Sr/86Sr ratios in limestones of the Kumukulakh (0.70725), Barakun (0.70727), Valyukhta (0.70769), Nikol’skoe (0.707904), Chencha (0.70786) and Torgo (0.70799) formations suggest the accumulation of sediments 660–580 Ma ago. Correspondingly, glacial diamictites of the Nichatka and Dzhemkukan (Bol’shoi Patom) formations can be correlated with the early stage of the Marinoan glaciation (635–665 Ma); the Zhuya Formation, with transgression that terminates the late stage of the same glaciation or the Gaskiers glaciation (580 Ma). Problems related to the genesis of carbonate rocks with extremely high and low δ13C values will be considered in the second communication.

Carbon, oxygen, strontium, and sulfur isotopic compositions in late Precambrian rocks of the Patom Complex, central Siberia: Communication 2. Nature of carbonates with ultralow and ultrahigh δ13C values

The Patom Complex is characterized by a unique association of carbonate rocks with ultralow (≤8‰) and ultrahigh (>6‰) δ13C values. The thickness, stable isotopic composition along the strike, and lithological and geochemical parameters suggest that these rocks could not form as a result of short-term local events or epigenetic processes. Ultralow δ13C values (less than −8‰) in carbonate rocks of the Zhuya Group, which substantially exceed all the known negative C isotope anomalies in thickness (up to 1000 m) and amplitude (δ13C = −10 ± 2‰), point to sedimentation under conditions of extreme “contamination” of water column by oxidized isotopically light organic (hereafter, light) carbon. The decisive role in this contamination belonged to melting and oxidation of huge volumes of methane hydrates accumulated in sediments during the powerful and prolonged Early Vendian glacial epoch. The accumulation of δ13C-depleted carbonates was preceded by the deposition of carbonates with anomalously high δ13C values. These carbonates formed at high rates of the burial of organic matter and methane in sediments during periods when the sedimentation basin consumed carbon dioxide from the atmosphere and organic carbon was conserved in sediments.

Isotopic signatures of deposition and transformation of Lower Cambrian saliferous rocks in the Irkutsk amphitheater: Communication 2. Strontium isotopic composition

Rb-Sr data were obtained for different Lower Cambrian rocks from boreholes Bel’sk and Zhigalovo drilled in the Irkutsk amphitheater. Shales in the lower part and insoluble residue of marls throughout the entire (up to 2 km thick) sequence define the first transformation stage of silicate rocks dated at 580 Ma with a large uncertainty. Sulfate and carbonate rocks are the main Sr carriers in the Lower Cambrian rocks. Owing to a negligible amount of silicate impurities in them, the input of radiogenic Sr exerted no significant influence on the Rb-Sr isotope system. However, almost all carbonate and sulfate rocks studied are contaminated by radiogenic Sr relative to its initial isotopic composition in the sedimentation basin. Hence, the rocks experienced epigenetic (probably, repeated) recrystallization and one or several stages of dissolution.

The late Cenomanian paleoecological event (OAE 2) in the eastern Caucasus basin of Northern Peri-Tethys

The Cretaceous sections of the eastern Caucasus contain rich in organic matter (OM) sediments corresponding to the late Cenomanian Oceanic Anoxic Event 2. They are marked by positive δ13C and negative δ18O isotopic anomalies, which are characteristic for this level in many areas of the world. The sediments exhibit distinct cyclic patterns reflected in an alternation of black OM-rich and gray more calcareous layers. The rocks are enriched with many chemical elements, although concentrations of some of them (Mo, Se) are lower than in typical sediments of anoxic basins. It is inferred that anoxic environments in the paleobasin were unstable and locally developed. Nannofossil assemblages from OAE 2 sediments are dominated by the highly resistant eurytropic taxon Watznaueria accompanied by common cool-water Eprolithus and rare warm-water Rhagodiscus representatives, which implies the development of environments unfavorable for the normal marine nannoflora and short-term cooling in the basin during OAE 2. The OM-rich sediments were deposited against the background of the rapid eustatic transgression due to a significant increase in productivity of phytoplankton in the paleobasin. The OAE 2 duration is estimated to be approximately 400 ka.

Isotopic signatures of deposition and transformation of Lower Cambrian saliferous rocks in the Irkutsk Amphitheater: Communication 3. Carbon and oxygen isotopic compositions in carbonates

In previous communications based on the study of sulfur and strontium, we showed that Lower Cambrian rocks of the Irkutsk Amphitheater underwent a significant epigenetic transformation. All postsedimentary alterations of rocks are related to the influence of water solutions that provoke the direct (physical) dissolution of material and its chemical transformation. In particular, an appreciable portion of anhydrites disappeared from the section due to reduction. Probably, these processes took place several times in the past and they are continuing at present. A similar conclusion was deduced from the strontium isotopic composition of carbonate rocks. Their strontium isotopic composition is usually shifted relative to the primary composition, although the prevalence of sulfate and carbonate rocks in the section promotes the stability of strontium isotopic composition with respect to secondary alterations. The carbon isotope system is even more stable due to the abundance of carbonate rocks in the section. This circumstance is probably responsible for the incapacity of isotope data to serve as obvious evidence of the epigenetic transformation of carbonates. The major elements of the evolution of carbon isotope signature could be retained since the sedimentation stage.

Oxygen Isotopic Composition in Riphean Mudstones of the Yudoma–Maya Trough: Implication for Isotopic Dating

In Riphean mudstones of the Yudoma–Maya Trough (southeastern Siberian Platform), which underwent deep catagenetic and metagenetic transformations, δ18O values range from 11.2 to 18.9‰ (δ18Oaver= 14.4‰), which are 5–7‰ lower than those in similar Cenozoic rocks. The isotopic shift is caused by postsedimentary alterations at temperatures up to 200°C under the influence of a moderate influx of metamorphogenic solutions and relative geochemical insulation of rock formations from each other. Within separate formations, we have revealed a distinct positive correlation between δ18O and SiO2 , which is typical for thermodynamically ordered metamorphic rocks composed of minerals in isotopic equilibrium.

Isotope and chemical composition of gases from mud volcanoes in the Taman Peninsula and problem of their genesis

Variations in the carbon isotope composition in gases and waters of mud volcanoes in the Taman Peninsula are studied. The δ13C values in CH4 and CO2 vary from −59.5 to −44.0‰ (δ13Cav = −52.4 ± 5.4‰) and from −17.8 to +22.8‰ (δ13Cav = +6.9 ± 9.3‰), respectively. In waters from most mud volcanoes of the peninsula, this parameter ranges from +3.3 to +33.1‰, although locally lower values are also recorded (up to −12‰. Fractionation of carbon isotopes in the CO2-HCO3 system corresponds to the isotope equilibrium under Earth’s surface temperatures. The growth of carbon dioxide concentration in the gaseous phase and increase in the HCO3 ion concentration in their water phase is accompanied by the enrichment of the latter with the heavy 13C isotope. The δ13CTDIC value in the water-soluble carbon depends on the occurrence time of water on the Earth’s surface (exchange with atmospheric CO2, methane oxidation, precipitation of carbonates, and other processes), in addition to its primary composition. In this connection, fluctuations in δ13CTDIC values in mud volcanoes with stagnant waters may amount to 10–20‰. In the clayey pulp, concentrations of carbonate matter recalculated to CaCO3 varies from 1–4 to 36–50 wt %. The δ13C value in the latter ranges from −3.6 to +8.4‰. Carbonate matter of the clayey pulp represents a mixture of sedimentogenic and authigenic carbonates. Therefore, it is usually unbalanced in terms of the carbon isotope composition with the water-soluble CO2 forms.

Siderite microconcretions in the glauconite-bearing clayey-silty rocks of the Khaipakh Formation (Middle Riphean, Olenek Uplift)

Siderite microconcretions in the glauconite-bearing clayey-silty rock member of the lower sub-formation of the Khaipakh Formation (Middle Riphean, Olenek Uplift) are scrutinized for the first time. In two Khorbusuonka River sections located with a spacing of 12 km, the microconcretions occur as lenses and interlayers. Together with glauconitites, they serve as a distinct marker horizon of this stratigraphic interval. Their structures, morphologies, diffraction characteristics, chemical compositions, and isotope data are considered. They were examined comprehensively with modern investigation methods (X-ray diffraction, scanning electron microscopy with the application of local microprobe analysis, and others). Structural-morphological types of microconcretions are identified. Calculation of the chemical composition of carbonates based on numerous microprobe analyses made it possible to reveal different degrees of mineral heterogeneity in each type in terms of the distribution of macro- and microlevel isomorphous trace-elements and to refine the character of their secondary alterations at different stages of lithogenesis. The results of oxygen and hydrogen isotopic studies are presented for algal dolomites and limestones from the Middle and Lower Riphean sections in the Olenek Uplift (Debengda, Arymass, and Kyutingda formations). They demonstrated that siderites are similar to limestones and dolomites in terms of the oxygen isotopic composition (δ18O = 17.6–24.8, δ18Oav = 20.0 ± 2.4‰), but are marked by low δ13C values (from −6.3 to −12.0‰ (δ13Cav = −8.6 ± 2.1‰), suggesting the formation of microconcretions during early diagenesis. Siderite microconcretions were formed in the clayey-silty sediment slightly after glauconite, whose grains could serve as crystallization centers and (or) be entrapped during the growth of separate microcrystals. The role of catalyzers during the formation of both glauconite and siderite was played by bacterial communities, whose poorly preserved remnants have been detected not only in the studied member of the lower Khaipakh subformation, but also above and below the section. Separate types of microconcretion could be formed during the replacement of oncolites by siderite.

Isotopic-geochemical peculiarities of gases in mud volcanoes of eastern Georgia

Isotopic-geochemical study revealed the presence of mantle He (3He/4He up to 223 × 10−8) in gases from mud volcanoes of eastern Georgia. This fact confirms that the Middle Kura basin fill encloses an intrusive body previously distinguished from geophysical data. Wide variations in the carbon isotopic composition δ13C of CH4 and CO2 and the chemical composition of gas and water at a temporally constant 3He/4He ratio indicate their relation with crustal processes. Unusual direct correlations of the 3He/4He ratio with the contents of He and CH4 and the 40Ar/36Ar ratio can be explained by the generation of gas in the Cenozoic sequence of the Middle Kura basin.

Gas seeps in the North Caspian water area

Seismoacoustic profiling and sonar survey of the North Caspian water area revealed in some areas signs of intense release of methane from the sedimentary sequence. This fact was also supported by submarine videorecording data. Such sites are characterized by hummocky and ridgy morphologies, which accommodate local cone-shaped bodies (up to 1.3–1.5 m high) overgrown with algae, Balanus, and shelly material. Based on dredging data, these rises are composed of hard sandstones and shells. They can cover the seafloor or make up separate interlayers in the bottom sediments down to a depth of 2.7 m. Mineralogical studies demonstrated that the coarse-grained sediments are cemented with Mg-calcite, with δ13C reaching −32.6‰. They also include microcrystalline barite and globular iron sulfides. The results of investigation suggest that the local activation of authigenic mineral formation is related to gas discharge sources.