Geochemistry of О, Н, C,S, and Sr isotopes in the water and sediments of the Aral basin

The paper presents original authors' data on the O, H, C, S, and Sr isotopic composition of water and sediments from the basins into which the Aral Sea split after its catastrophic shoaling: Chernyshev Bay (CB), the basin of the Great Aral in the north, Lake Tshchebas (LT), and Minor Sea (MS). The data indicate that the δ¹⁸О, δD, δ¹³C, and δ³⁴S of the water correlate with the mineralization (S) of the basins (as of 2014): for CB, S = 135.6‰, δ¹⁸О = 4.8 ± 0.1‰, δD = 5 ± 2‰, δ¹³C (dissolved inorganic carbon, DIC) = 3.5 ± 0.1‰, δ³⁴S = 14.5‰; for LT, S = 83.8‰, δ¹⁸О = 2.0 ± 0.1‰, δD =–13.5 ± 1.5‰, δ¹³C = 2.0 ± 0.1‰, δ³⁴S = 14.2‰; and for MS, S = 9.2‰, δ¹⁸О =–2.0 ± 0.1‰, δD =–29 ± 1‰, δ¹³C =–0.5 ± 0.5‰, δ³⁴S = 13.1‰. The oxygen and hydrogen isotopic composition of the groundwaters are similar to those in MS and principally different from the artesian waters fed by atmospheric precipitation. The mineralization, δ¹³С, and δ³⁴S of the groundwaters broadly vary, reflecting interaction with the host rocks. The average δ¹³С values of the shell and detrital carbonates sampled at the modern dried off zones of the basins are similar: 0.8 ± 0.8‰ for CB, 0.8 ± 1.4‰ for LT, and –0.4 ± 0.3‰ for MS. The oxygen isotopic composition of the carbonates varies much more broadly, and the average values are as follows: 34.2 ± 0.2‰ for CB, 32.0 ± 2.2‰ for LT, and 28.2 ± 0.9‰ for MS. These values correlate with the δ¹⁸O of the water of the corresponding basins. The carbonate cement of the Late Eocene sandstone of the Chengan Formation, which makes up the wave-cut terrace at CB, has anomalously low δ¹³С up to –38.5‰, suggesting origin near a submarine methane seep. The δ³⁴S of the mirabilite and gypsum (11.0 to 16.6‰) from the bottom sediments and young dried off zone also decrease from CB to MS in response to increasing content of sulfates brought by the Syr-Darya River (δ³⁴S = 9.1 to 9.9‰) and weakening sulfate reduction. The ⁸⁷Sr/⁸⁶Sr ratio in the water and carbonates of the Aral basins do not differ, within the analytical error, and is 0.70914 ± 0.00003 on average. This value indicate that the dominant Sr source of the Aral Sea is Mesozoic–Cenozoic carbonate rocks. The Rb–Sr systems of the silicate component of the bottom silt (which is likely dominated by eolian sediments) of MS and LT plot on the Т = 160 ± 5 Ma, I₀ = 0.7091 ± 0.0001, pseudochron. The Rb–Sr systems of CB are less ordered, and the silt is likely a mixture of eolian and alluvial sediments.     

Isotopic compositions of C,O, Sr,and S and problem of ages of the Katera and Uakit Groups,western Transbaikal region

The age of the Katera Group, which occupies a large area in the western North Muya Range and occurs 100–150 km east of the Uakit Group, is a debatable issue. Based on geological correlations with reference sections of the Baikal Group and Patom Complex, the Katera and Uakit groups were previously considered nearly coeval units and assigned to Late Precambrian (Khomentovskii and Postnikov, 2002; Salop, 1964). This was supported partly by the Sm–Nd model datings (Rytsk et al., 2007, 2009, 2011). Finds of the Paleozoic flora substantiated the revision of age of the Uakit Group and its assignment to the Late Devonian–Early Carboniferous (Gordienko et al., 2010; Minina, 2003, 2012, 2014). We have established that Sr and C isotopic compositions in carbonates of these groups differ drastically, as suggested by their different ages. Sediments of the Nyandoni Formation (Katera Group), which contains carbonates characterized by minimum values of ⁸⁷Sr/⁸⁶Sr = 0.7056 and maximum values of δ¹³C = 4.9‰, were accumulated in the first half of Late Riphean (800–850 Ma ago), whereas the overlying Barguzin Formation (⁸⁷Sr/⁸⁶Sr_min = 0.70715, δ¹³C_max= 10.5‰) was deposited at the end of Late Riphean (700–750 Ma). Judging from the isotope data, the Nerunda Formation (Uakit Group), which contains carbonates with characteristics matching the most rigorous criteria of fitness for the chemostratigraphic correlation (Sr content up to 4390 μg/g, Mn/Sr < 0.1, δ¹⁸O = 23.0 ± 1.8‰), was deposited at the end of Vendian ~550–540 Ma ago). The sequence includes thick typical carbonate horizons with very contrast carbon isotopic compositions: the lower unit has anomalous high δ¹³C values (5.8 ± 1.0‰); the upper unit, by anomalous low δ¹³C values (–5.2 ± 0.5‰]). Their Sr isotopic composition is relatively homogeneous (⁸⁷Sr/⁸⁶Sr = 0.7084 ± 0.0001) that is typical of the Late Vendian ocean. The S isotopic composition of pyrites from the Nyandoni Formation (Katera Group) (δ³⁴S = 14.1 ± 6.8‰) and pyrites from the Mukhtunny Formation (Uakit Group) (δ³⁴S = 0.7 ± 1.4‰) does not contradict the C and Sr isotopic stratigraphic data.     

Isotopic evidence for postsedimentary transformation of rocks of the Lower Cambrian Angara Formation in the Irkutsk Amphitheater

The section of the Angara Formation (upper portion of Lower Cambrian) is composed of a complex combination of dolomites, anhydrites, marlstones, and salinastones. The occurrence of solution breccia, various types of metasomatism, and other indications testify to the substantial postsedimentary reworking of these rocks. Sulfate reduction, one of the most important processes of reworking, is clearly expressed in the sulfur isotopic composition. The ⁸⁷Sr/⁸⁶Sr ratio in carbonate and sulfate materials is more stable owing to the relatively high Sr content in these rocks. Nevertheless, most sulfate and carbonate rocks are contaminated with the radiogenic Sr. The carbon isotope ratio in carbonates is close to the “normal” value despite the evaporitic character of sedimentation basins and the possible participation of organic carbon, which is a product of the oxidation of hydrocarbons by sulfates, in the transformation of carbonates. The Rb-Sr analysis of the clayey component of marlstones and the K-Ar analysis of mudstones from the lower portion of the Lower Cambrian-Vendian section indicate that the rocks were mainly transformed during a time span corresponding to the Caledonian folding dramatically manifested at the platform margin.     

Traces of brine and hydrocarbon migration in carbon,oxygen, and sulfur isotopic compositions of reservoir rocks in the Talakan petroleum field,Southwestern Yakutia

Dolomites from the productive Osa horizon (upper subformation of the Lower Cambrian Bilir Formation) in the Talakan petroleum field show a prominent 1–2‰ decrease in δ¹⁸O (from 23–24 to 21–22‰), which presumably marks a zone of relatively high water/rock ratios. Productive boreholes are characterized by moderate δ³⁴S values (from 25.1 to 30.6‰) and negative correlation between δ³⁴S in anhydrite and δ¹⁸O in associated dolomite, which points to a partial sulfate reduction during catagenesis. In nonproductive borehole, δ³⁴S values increase significantly (from 31.4 to 35.6‰) and show positive correlation with δ¹⁸O in dolomite. Rocks recovered by nonproductive borehole possibly recrystallized during early diagenesis, and, correspondingly lost their permeability and capacity to form pores. Limestones and dolomites of the Osa horizon have a carbon isotopic composition within the range of normal marine carbonates (δ¹³C = 0 ± 1 ‰), which does not indicate a significant role of organic matter in postsedimentary recrystallization of carbonate sediments. A positive δ¹³C excursion up to 4.5‰ recorded in the lower subformation of the Bilir Formation presumably occurred at the sedimentation stage under conditions of high rates of bioproductivity and organic matter burial in sediments.     

Changes to depositional palaeoenvironments within the Qikou depression (Bohaiwan Basin,China): carbon and oxygen isotopes in lacustrine carbonates of the Palaeogene Shahejie Formation

This paper reports the carbon and oxygen isotope compositions of lacustrine carbonate sediments from the Palaeogene Shahejie Formation, Qikou depression, Bohaiwan Basin, with the aim of determining the palaeoenvironmental conditions in the region. Results from Es₂, the second member of the Shahejie Formation, showed values of δ¹³C and δ¹⁸O from –1.2‰ to +2.4‰ (average +0.6‰) and from –6.8‰ to –4.7‰ (average –5.7‰), respectively, suggesting a relatively hot climate attending deposition. The slightly closed nature of the lake, which contains brackish water, resulted in higher carbonate δ¹³C and δ¹⁸O values than in a meteoric environment. The values of δ¹³C and δ¹⁸O preserved within the carbonates of the overlying lower Shahejie I (Es₁) varied between +1.3‰ and +4.9‰ (average +3.2‰) and from ?4.4‰ to ?1.8‰ (average ?3.1‰), respectively, indicating that the climate became colder at that time. Subsequently, a marine transgression caused the salinity of the lake water to increase. The values of δ¹³C and δ¹⁸O were controlled by salinity. The high δ¹³C values were also influenced by the rapid burial of the lake organisms and by algal photosynthesis. Values of δ¹³C and δ¹⁸O from carbonates in upper Es₁ ranged from ?8.0‰ to +11.0‰ (average +10.1‰) and from ?5.0‰ to ?1.5‰ (average ?3.4‰), respectively, indicating a slight increase in the temperature over time. In the closed and reducing environment, extremes in δ¹³C values resulted from biochemical fermentation. The positive δ¹³C excursion recorded in the carbonates of the Shahejie Formation in the Qikou depression indicates that the palaeoclimate underwent a significant transformation during the Eocene and the Oligocene.     

Carbon and Oxygen Isotope Compositions of Some Upper Cretaceous–Paleocene Sequences in Argentina and Chile

The Cretaceous-Paleocene (K-T) transition has been recorded in sedimentary carbonate rocks in northwestern Argentina and southern Chile. In the Yacoraite Basin, Argentina, this transition has been preserved in a 2 m thick marly layer, at the base of the Tunal Formation, which overlies lacustrine/marine carbonates of the Yacoraite Formation (Cabra Corral dam). The K-T transition is also preserved at Maimara, where Tertiary sandstones overlie a 50 m thick limestone bed of the Yacoraite Formation. In the Magellan Basin, Chile, glauconitic sandstones with calcitic cement and limestone concretions of the Maastrichtian Punta Rocallosa Formation are overlain by sandstones, claystones, and limestones of the Chorillo Chico Formation. The K-T transition is preserved in the lower portion of the Chorillo Chico Formation.

Carbonates of the Yacoraite Formation display bulk-rock δ¹³C values from +1 to +2‰ PDB, with a negative incursion (?4‰ PDB) at the K-T transition. δ¹³C values in the Tunal Formation marls vary from ?3 to ?1‰ PDB. At Rocallosa Point, δ¹³C values in limestone strata, calcite cement, and limestone concretions vary from ?4 to ?33 ‰ PDB, and the lowest value in the Chorillo Chico Formation apparently marks the K-T transition. The δ¹⁸O fluctuations in the Yacoraite and Magellan carbonate rocks suggest a temperature drop at the K-T transition, followed by a temperature rise.

High ⁸⁷Sr/⁸⁶Sr ratios (0.7140-0.7156) characterize the studied profiles of the Yacoraite Formation, documenting an important ⁸⁷Sr-enriched source of Sr to the water from which these carbonates precipitated. At the Magellan basin, ⁸⁷Sr/⁸⁶Sr ratios are closer to the expected values for the global Late Cretaceous-Paleocene ocean.     

Carbon,oxygen and strontium isotope geochemistry of Proterozoic carbonate rocks of the Vindhyan Basin,central India

Carbon, oxygen and strontium isotope compositions of carbonate rocks of the Proterozoic Vindhyan Supergroup, central India suggest that they can be correlated with the isotope evolution curves of marine carbonates during the latter Proterozoic. The carbonate rocks of the Lower Vindhyan Supergroup from eastern Son Valley and central Vindhyan sections show δ¹³C values of ∼0‰ (V-PDB) and those from Rajasthan section are enriched up to +2.8‰. In contrast, the carbonate rocks of the Upper Vindhyan succession record both positive and negative shifts in δ¹³C compositions. In the central Vindhyan section, the carbonates exhibit positive δ¹³C values up to +5.7‰ and those from Rajasthan show negative values down to –5.2‰. The δ¹⁸O values of most of the carbonate rocks from the Vindhyan Supergroup show a narrow range between –10 and –5‰ (V-PDB) and are similar to the ‘best preserved’ ¹⁸O compositions of the Proterozoic carbonate rocks. In the central Vindhyan and eastern Son Valley sections, carbonates from the Lower Vindhyan exhibit best-preserved ⁸⁷Sr/⁸⁶Sr compositions of 0.7059±6, which are lower compared to those from Rajasthan (0.7068±4). The carbonates with positive δ¹³C values from Upper Vindhyan are characterized by lower ⁸⁷Sr/⁸⁶Sr values (0.7068±2) than those with negative δ¹³C values (0.7082±6). A comparison of C and Sr isotope data of carbonate rocks of the Vindhyan Supergroup with isotope evolution curves of the latter Proterozoic along with available geochronological data suggest that the Lower Vindhyan sediments were deposited during the Mesoproterozoic Eon and those from the Upper Vindhyan represent a Neoproterozoic interval of deposition.     

C, О, S,and Sr Isotope Geochemistry and Chemostratigraphy of Ordovician Sediments in the Moyero River Section,Northern Siberian Platform

The ⁸⁷Sr/⁸⁶Sr ratio in gypsum and limestones of the Ordovician section of the Moyero River decreases from the bottom upward from 0.7091?0.7095 in the Irbukli Formation (Nyaian Regional Stage, ~Lower Ordovician Tremadocian Stage) to 0.7080 in the upper part of the Dzherom Formation (Dolborian Regional Stage, ~Upper Ordovician Katian Stage), which is well consistent with biostratigraphic subdivision of the section and existing concept concerning the strontium isotope evolution of the World Ocean. The most characteristic feature of the carbon isotope curve is decrease of δ¹³С values in carbonates from weakly positive values (0.5…1.1‰) in the Irbukli Formation (Nyaian Regional Stage) to sharply negative values (–5.4...–5.8‰) in the middle part of the Kochakan Formation (top of the Kimaian Regional Stage, ~end of the Dapingian–base of the Darriwilian Stage). Increase of δ¹⁸О from 20?22‰ to 26?28‰, the negative correlation of δ¹³С and δ¹⁸О, and decrease of δ³⁴S in gypsum from 30?32‰ to 22?24‰ in this interval indicate that the ¹³С depletion of carbonates was not related to the sulfate reduction and oxidation of organic matter during diagenesis and that the negative δ¹³С excursion was of primary nature. The presence of negative δ¹³С anomalies at this stratigraphic level in Ordovician sections of the South and North America (Buggish et al., 2003; Edwards and Saltzman, 2014; McLaughlin et al., 2016) indicates the global or subglobal distribution of this event, which was possibly related to the emergence of the oldest ground vegetation. Against the general decrease of δ¹³С, the lower part of the section reveals three low-amplitude (1?2‰) positive excursions, the position of which in general confirms the existing correlation scheme of the Moyero River section with the international scale. The upper part of the section is characterized by the alternation of low-δ¹³С intervals (from–2 to–3‰) and brief positive excursions with amplitude of 0.5?1.3‰. The positive δ¹³С excursion terminating the Ordovician section of the Moyero River correlates with the δ¹³С excursion in the middle Katian Stage, while the δ¹³С excursion in the lower part of the Baksian Regional Stage correlates with the excursion marking the Katian–Sandbian boundary.     

C-and Sr-isotope chemostratigraphy as a tool for verifying age of Riphean deposits in the Kama-Belaya aulacogen,the east European platform

The Kyrpy Group of the East European platform is regarded by tradition as correlative with the Lower Riphean Burzyan Group of the Bashkirian meganticlinorium in the southern Urals. Age and correlation of the Kyrpy Group remain problematic, however, because of a limited geochronological information and controversial interpretation of paleontological materials. Data of C-and Sr-isotope chemostratigraphy contribute much to the problem solution. In the Kyrpy Group of the Kama-Belaya aulacogen, the Kaltasy Formation carbonates 1300 to 2400 m thick (boreholes 133 and 203 of the Azino-Pal’nikovo and Bedryazh areas) show ⁸⁷Sr/⁸⁶Sr ratios ranging around 0.7040 and narrow diapasons of δ¹³C values: about 0.5‰ (V-PDB) in shallow-water facies and-2.0‰ (V-PDB) in sediments of deeper origin. Despite the facies dependence of carbon isotope composition, δ¹³C variations not greater than ±1.0‰ are depicted in chemostratigraphic profiles of carbonate rocks characterizing separate stratigraphic intervals up to 800 m thick in the above borehole sections. Low ⁸⁷Sr/⁸⁶Sr ratios and almost invariant δ¹³C values in carbonates of the Kaltasy Formation are obviously contrasting with these parameters in the Middle and Upper Riphean deposits, being comparable with isotopic characteristics of the Lower Riphean sediments (Mesoproterozoic deposits older than 1300 Ma). Consequently, the results obtained evidence in favor of the Early Riphean age of the Kaltasy Formation and the Kyrpy Group as a whole.     

Isotope geochemistry (O, C, S, Sr) and Rb-Sr age of carbonatites in central Tuva

The Rb-Sr isochron age of igneous ankerite-calcite and siderite carbonatites in central Tuva is estimated at 118 ± 9 Ma. The following ranges of initial values of O, C, Sr, and sulfide and S isotopic compositions were established: δ¹⁸O_carb = +(8.8?14.7)‰, δ¹³C_carb = ?(3.6?4.9)‰, δ¹⁸O_quartz = +(11.6?13.7)‰, δ³⁴S_pyrite = +(0.3?1.1)‰, and (⁸⁷Sr/⁸⁶Sr)_i =0.7042?0.7048 for ankerite-calcite carbonatite and δ¹⁸O_sid = +(9.2?12.4)‰, δ¹³C_sid = ?(3.9?5.9)‰, δ¹⁸O_quartz = +(11.2?11.4)‰, δ³⁴S_pyrite = ?(4.4–1.8)‰, δ³⁴S_sulfate = +(8.6?14.5)‰, and (⁸⁷Sr/⁸⁶Sr)_i = 0.7042?0.7045 for siderite carbonatite. The obtained isotopic characteristics indicate that both varieties of carbonatites are cognate and their mantle source is comparable with the sources of Late Mesozoic carbonatites in the western Transbaikal region and Mongolia. The revealed heterogeneity of isotopic compositions of carbonatites is caused by their contamination with country rocks, replacement with hydrothermal celestine, and supergene alteration.     

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.     

Formation of magnesite and siderite deposits in the Southern Urals—evidence of inclusion fluid chemistry

World-class deposits of magnesite and siderite occur in Riphean strata of the Southern Urals, Russia. Field evidence, inclusion fluid chemistry, and stable isotope data presented in this study clearly proof that the replacement and precipitation processes leading to the formation of the epigenetic dolomite, magnesite and hydrothermal siderite were genetically related to evaporitic fluids affecting already lithified rocks. There is, however, a systematic succession of events leading to the formation of magnesite in a first stage. After burial and diagenesis the same brines were modified to hot and reducing hydrothermal fluids and were the source for the formation of hydrothermal siderite. The magnesites of the Satka Formation as well as the magnesites and the siderites of the Bakal Formation exhibit low Na/Br (106 to 222) and Cl/Br (162 to 280) ratios plotting on the seawater evaporation trend, indicating that the fluids acquired their salinity by evaporation processes of seawater. Temperature calculations based on cation exchange thermometers indicate a formation temperature of the magnesites of?~?130 °C. Considering the fractionation at this temperature stable isotope evidence shows that the magnesite forming brines had δ¹⁸O_SMOW values of?~?+1 ‰ thus indicating a seawater origin of the original fluid. Furthermore it proves that these fluids were not yet affected by appreciable fluid-rock interaction, which again implies magnesite formation in relatively high crustal levels. In contrast to the magnesites, the siderite mineralization was caused by hydrothermal fluids that underwent more intense reactions with their host rocks in deeper crustal levels compared to the magnesite. The values of ⁸⁷Sr ^/86Sr in the siderites are substantially higher compared to the host rock slates. They also exceed the ⁸⁷Sr ^/86Sr ratios of the magnesites and the host rock limestones indicating these slates as the source of iron as a consequence of water-rock interaction. The siderites were formed at temperatures of?~?250 °C indicating a relatively heavy fluid in equilibrium with siderite of 13 ‰ δ¹⁸O_SMOW, which is in the range of diagenetic/metamorphic fluids and reflects the?±?complete equilibration with the host rocks. Carbon isotope evidence shows that the fluid forming the siderites underwent a much higher interaction with the host rocks resulting in a lowering of the δ¹³C numbers (?3,3 to ?3,7 ‰). The light carbon was most probably derived from decaying hydrocarbons in the Riphean sediments. In a very early stage after sedimentation of the Satka Formation (~1,550 Ma) magnesite was formed by seepage reflux of evaporitic bittern brines at the stage of riftogenic activity in the region (1,380–1,350 Ma). Sedimentation of the Bakal Formation (~1,430 Ma) and intrusion of diabase dykes (1,386?±?1,4 Ma) followed. Diagenetic/epigenetic mobilization of these buried fluids at?~?1,100 Ma resulted in the formation of hydrothermal siderite bodies.     

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‰ (δ¹³C_av = ?52.4 ± 5.4‰) and from ?17.8 to +22.8‰ (δ¹³C_av = +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 δ¹³C_TDIC 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 δ¹³C_TDIC 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.     

Geochemistry of C,O, and Sr isotopes and chemostratigraphy of neoproterozoic rocks in the northern Yenisei Ridge

Isotopic compositions of C, O, and Sr in carbonates, as well as Rb-Sr systems in the silicate material from Upper Precambrian and Lower Cambrian rocks exposed by the Chapa River in the northern Yenisei Ridge, are studied. The Late Precambrian part of the section includes the following formations (from the bottom to top): Lopatinskaya (hereafter, Lopatino), Vandadykskaya (hereafter, Vandadyk) or Kar’ernaya, Chivida, Suvorovskaya (hereafter, Suvorovo), Pod”emskaya (hereafter, Podyom), and Nemchanka. They are characterized by alternation of horizons with anomalously high and low δ¹³C values (such alternation is typical of the ∼700–550 Ma interval). The lower, relatively thin (20 m), positive excursion (δ¹³C up to 4.3‰) was established in dolomites from the lower subformation of the Vandadyk (Kar’ernaya) Formation (hereafter, lower Vandadyk subformation). The upper positive excursion (δ¹³C = 2.2 ± 0.6‰) was recorded in the 3-km-thick Nemchanka Formation enriched in terrigenous rocks. The lower negative excursion stands out as uniform, moderately low δ¹³C values (−2 ± 1‰) and significant thickness. It comprises the upper part of the Vandadyk Formation, as well as Chivida and Podyom formations. The upper negative excursion is related to a thin (∼20 m) marker carbonate horizon of the upper Nemchanka subformation, in which δ¹³C values fall down to −8.3‰. The lower part of the Lebyazhinskaya (hereafter, Lebyazhino) Formation, which overlies the Nemchanka Formation, shows a step-by-step increase in δ¹³C from −2.2 to 2.5‰ typical of the Vendianto-Cambrian (Nemakit-Daldyn Horizon/Stage) transitional sequences. The absence of relationships between the carbon and oxygen isotope compositions and other parameters of postsedimentary alterations suggests that the excursions characterized above could form at the sedimentation stage and coincide in general with δ¹³C fluctuations in seawater. The value of ⁸⁷Sr/⁸⁶Sr = 0.7076−0.7078 in limestones of the Podyom Formation points to their early Ediacaran age. Values of ⁸⁷Sr/⁸⁶Sr = 0.70841 and 0.70845 in dolomites of the lower Lebyazhino subformation correspond to the Early Cambrian. The Rb-Sr systems of the clay material from the Vandadyk and Chivida formations are approximated by a straight line, parameters of which correspond to the age of 695 ± 20 Ma (⁸⁷Sr/⁸⁶Sr₀ = 0.7200 ± 0.0013) and probably characterize the epigenetic stage of older sedimentary rocks, which were subjected to very rapid exhumation and “polar” sulfuric acid weathering in the course of glacioeustatic regression.     

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 (13C 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.     

Geochemistry and isotope geochemistry of the Monfalcone thermal waters (northern Italy): inference on the deep geothermal reservoir

Geochemical investigations were carried out to define the origin of the low- to moderate-temperature thermal waters feeding the Monfalcone springs in northern Italy. Chemical data indicate that waters approach the composition of seawater. Mixing processes with cold low-salinity waters are highlighted. The δ¹⁸O and δD values are in the range ?5.0 to ?6.4 ‰, and ?33 to ?40 ‰, respectively, suggesting the dilution of the saline reservoir by karst-type freshwaters. A surplus of Ca²⁺ and Sr²⁺ ions with respect to a conservative mixing is ascribed to diagenetic reactions of the thermal waters with Cretaceous carbonates at depth. The measured Sr isotopic composition (⁸⁷Sr/⁸⁶Sr ratio) ranges between 0.70803 and 0.70814; after correction for the surplus Sr, a ⁸⁷Sr/⁸⁶Sr ratio indicating Miocene paleo-seawater is obtained. The dissolved gases indicate long-lasting gas–water interactions with a deep-originated gas phase of crustal origin, dominated by CO₂ and marked by a water TDIC isotopic composition in the range ?5.9 to?8.8 and helium signature with 0.08?<?R/Ra?<?0.27, which is a typical range for the crust. A possible scenario for the Monfalcone thermal reservoir consists of Miocene marine paleowaters which infiltrated through the karstic voids formed within the prevalently Cretaceous carbonates during the upper Eocene emersion of the platform, and which were entrapped by the progressive burial by terrigenous sediments.     

Carbon and oxygen stable isotopes in the middle-upper miocene and lower pliocene carbonates of the Eastern Paratethys (Kerch-Taman Region): Palaeoenvironments and post-sedimentation changes

C and O isotope composition of Middle-Upper Miocene and Lower Pliocene carbonates from Kerch-Taman Region (Eastern Paratethys) have been studied in order to reconstruct palaeoenvironmental variability and post-sedimentation changes. The δ¹³C and δ¹⁸О values of the Upper Sarmatian to Lower Pliocene organogenic carbonates reflect the desalinization of paleobasins, global Late Miocene Cooling, and increase in seasonal temperature fluctuations. Isotopic composition of the Middle Sarmatian organogenic carbonates was strongly influenced by evaporation processes, high bioproductivity, and local submarine methane emissions. Warm climate and low bioproductivity together with unstable hydrological regime during the Late Chokrakian and the Karaganian times influenced the isotope composition of primary carbonates. Calcite shell of Spiratella sp. (δ¹³C =–0.4‰ and δ¹⁸О =–0.4‰) from Tarkhanian sediments was formed in warm marine environment. Dolomitization prevails over other secondary mineralization in the studied carbonate rocks. Two groups of secondary dolomites that are characterized by negative and positive δ¹³C values have been recognized. Lowe δ¹³C values (up to–31.4‰) in dolomites indicate the influence of both dissolved inorganic carbon (DIC) from oxidized organic matter (С_org) and methane. Dolomites with positive δ¹³C values (7.0 and 7.8‰) associat with migration of CO₂- and CH₄-containing saline groundwater.     

Physical and chemical growth conditions of Ordovician organogenic deep-water dolomite concretions: implications for the δ18O of Early Palaeozoic sea water

The estimated depth of formation of authigenic dolomite concretions in the Middle Ordovician Cloridorme Formation, Quebec, ranges from < 1 m to 150–200 m below sea floor (mbsf) (mostly between < 1 and 25 mbsf), based on centre‐to‐margin variations in minus‐cement porosity (80–90% to 45–75%). Formation depths are > 350 mbsf (25–17% porosity) in the Lower Ordovician Levis Formation. Outward‐decreasing δ¹³C_VPDB values (10·2–0·8‰) suggest precipitation in the methane generation zone with an increasing contribution of light carbonate derived by advection from thermocatalytic reactions at depth. Anomalously low δ¹⁸O_VPDB values (centre‐to‐margin variations of ?0·4 to ?7·5‰) give reasonable temperatures for the concretion centres only if the δ¹⁸O of Ordovician sea water was negative (?6‰) and the bottom water was warm (> 15 °C). The 3–5‰ lower values for the concretion margins compared with the centres can be explained if, in addition, volcanic‐ash alteration, organic‐matter decomposition and/or advection of ¹⁸O‐depleted water lowered the δ¹⁸O of the pore water further by 2·0–4·0‰ during the first 25–200 m of burial. Reasonable growth temperatures for the margins of 17–20 °C are compatible with a lowering of the isotopic ratios by 1 to < 1·3‰ as a temperature effect. The systematic concentric isotope zonation of the concretions suggests that the well‐ordered near‐stoichiometric dolomite is a primary feature and not the result of recrystallization. Diagenetic dolomite beds of the Cloridorme Formation appear to have formed by coalescence of concretions, as shown by randomly sampled traverses that indicate formation at different subsurface depths. Growth of the Cloridorme dolomites was probably limited by calcium availability, at least 50% of which was derived from connate water, and the remainder by diffusion from sea water. Dolomite precipitation was favoured over calcite by very high sedimentation rates, the abundance of marine organic matter in the host sediment and a correspondingly thin sulphate reduction zone. Deep‐seated concretion growth in the Levis Formation required either internal sources for the participating ions (carbonate dissolution event) or porewater advection along faults.     

The vanadium isotopic composition of L ordinary chondrites

Stable isotopic data of meteorites are critical for understanding the evolution of terrestrial planets. In this study, we report high-precision vanadium (V) isotopic compositions of 11 unequilibrated and equilibrated L chondrites. Our samples show an average δ⁵¹V of ??1.25‰?±?0.38‰ (2SD, n?=?11), which is ~?0.5‰ lighter than that of the bulk silicate Earth constrained by mantle peridotites. Isotopic fractionation in type 3 ordinary chondrites vary from ??1.76‰ to ??1.29‰, whereas the δ⁵¹V of equilibrated chondrites vary from ??1.37‰ to ??1.08‰. δ⁵¹V of L chondrites do not correlate with thermal metamorphism, shock stage, or weathering degree. Future studies are required to explore the reason for V isotope variation in the solar system.     

Strontium and oxygen isotopic systems in waters of mud volcanoes of the Taman Peninsula

Ten of eleven analyzed water samples from mud volcanoes of the Taman Peninsula are characterized by ⁸⁷Sr/⁸⁶Sr ratio within 0.70734–0.70957, which overlaps the values typical of the Mesozoic and Cenozoic sedimentary carbonates, but sharply differs from the value in the clayey sediments of the Maikop Group (0.7157 ± 0.0022). These data indicate that the strontium isotopic composition is mainly defined by carbonate reservoirs, with relatively little effect of elision solutions, input of which is noticeable only in the water of Gladkovsky Volcano (⁸⁷Sr/⁸⁶Sr = 0.71076). The high δ¹⁸O in mud volcanic waters (up to 14.2‰) can also be attributed to ionic exchange with sedimentary carbonates at temperatures around 150°C.