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.     

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.     

西沙群岛西科1井中新统-上新统白云岩微观特征及成因

西科1井白云岩主要分布于上中新统黄流组, 在上新统莺歌海组二段和中中新统梅山组有零星分布; 主要的白云岩层段一般发育在褐色铁质矿物浸染的古暴露面之下.根据岩石铸体薄片观察、阴极发光及扫描电镜测试分析, 西科1井白云岩中白云石总体上呈微晶及细粉晶双峰态结构, 微晶白云石为灰岩基质经选择性白云石化的结果, 呈平直晶面半自形晶, 主要为泥微晶基质白云石化的结果; 粉晶-细晶白云石呈平直晶面自形晶, 为胶结物白云石或过度白云化结果, 过度白云化雾心亮边白云石的"亮边"与胶结物白云石成分一致, 阴极发光下二者显示同样的光性特征.微量元素测试及碳氧同位素测试表明: 白云岩一般具有低铁、低锰含量, δ18O_PDB均为正值, 变化于2.293‰~5.072‰之间, δ13C_PDB变化于1.214‰~3.051‰之间; 西科1井白云岩与西琛1井白云岩具有相似的层位分布特征和碳、氧同位素特征, 可能反映着相同或相似的成因.回流渗透模式可能适用于西沙地区白云岩, 频繁的海平面升降、环礁内蒸发环境及与中新世末期构造运动有关的热流体上涌促进了西沙地区白云岩的形成, 高渗透性礁相碳酸盐岩沉积为高Mg/Ca比值的蒸发水回流渗透提供了运移通道.      

Carbonate Rocks from the Riphean–Vendian Boundary Deposits of the Anabar Uplift: Isotope (<Superscript>87</Superscript>Sr/<Superscript>86</Superscript>Sr, δ<Superscript>13</Superscript>C, δ<Superscript>18</Superscript>O) Systematics and Chemostratigraphic Consequences

New ⁸⁷Sr/⁸⁶Sr, δ¹³C, and δ¹⁸О chemostratigraphic data were obtained for carbonate rocks of the Lower Riphean Yusmastakh and the Vendian Starorechenskaya formations. The δ¹³С values in dolomites of the Yusmastakh Formation varies from–0.6 to–0.1‰ and in dolomites and dolomitic limestones of the Starorechenskaya Formation, from–1.2 to–0.4‰ PDB, and δ¹⁸О values, from 24.4 to 26.4‰ and from 25.3 to 27.6‰ SMOW, respectively. The Rb–Sr systematics of carbonate rocks was studied using the refined method of stepwise dissolution of samples in acetic acid, including chemical removal of up to one-third of the ground sample by preliminary acid leaching and subsequent partial dissolution of the rest of the sample. Owing to this procedure, secondary carbonate material is removed, which enables one to improve the quality of the Sr-chemostratigraphic data obtained. The initial ⁸⁷Sr/⁸⁶Sr ratios in carbonate rocks of the Yusmastakh (0.70468–0.70519) and Starorechenskaya (0.70832–0.70883) formations evidence the Riphean–Vendian boundary in the Precambrian sequence of the Anabar Uplift.     

Massive dolomitization of a late Miocene carbonate platform: a case of mixed evaporative brines with meteoric water,Nijar, Spain

Late Miocene platform carbonates from Nijar, Spain, have been extensively dolomitized. Limestones are present in the most landward parts of the platform, in stratigraphically lower units and topographically highest outcrops, suggesting that dolomitizing fluids were derived from the adjacent Nijar Basin. The dolomite crystals range from <10 to ≈100 μm existing as both replacements and cements. Na, Cl and SO₄ concentrations in the dolomites range from 200 to 1700 p.p.m., 250–650 p.p.m., and 600–7000 p.p.m., respectively, comparable with other Tertiary and modern brine dolomite values, and also overlapping values from mixing-zone dolomites. Sr concentrations range between 50 and 300 p.p.m., and the molar Sr/Ca ratios of dolomitizing fluids are estimated to range between 7× seawater brine to freshwater ratios. The δ¹⁸O and δ¹³C of the dolomites range from ?1·0 to +4·2‰ PDB, and ?4·0 to +2·0‰ PDB, respectively. ⁸⁷Sr/⁸⁶Sr values (0·70899–0·70928) of the dolomites range from late Miocene seawater to values greater than modern seawater. Mixtures of freshwater with seawater and evaporative brines probably precipitated the Nijar dolomites. Modelled covariations of molar Sr/Ca vs. δ¹⁸O and Na/Ca vs. δ¹⁸O from these mixtures are consistent with those of the proposed Nijar dolomitizing fluids. Complete or partial dolomite recrystallization is ruled out by well preserved CL zoning, nonstoichiometry and quantitative water–rock interaction modelling of covariations of Na vs. Sr and δ¹⁸O vs. δ¹³C. The possibility of multiple dolomitization events induced by evaporative brines, seawater and freshwater, respectively, is consistent with mineral-mineral mixing modelling. The basin-derived dolomitizing brines probably mixed with freshwater in the Nijar Basin or mixed with fresh groundwater in the platform, and were genetically related either to deposition of the Yesares gypsum or the Feos gypsum. Dolomitization occurred during either the middle Messinian or the early upper Messinian. Nijar dolomitization models may be applicable to dolomitization of other late Miocene platform carbonates of the western Mediterranean. Moreover, the Nijar models may offer an analogue for more ancient evaporite-absent platform carbonates fringing evaporite basins.     

Primary dolomite in the Late Triassic Travenanzes Formation,Dolomites, Northern Italy: Facies control and possible bacterial influence

In the late Carnian (Late Triassic), a carbonate‐clastic depositional system including a distal alluvial plain, flood basin and sabkha, tidal flat and shallow carbonate lagoon was established in the Dolomites (Northern Italy). The flood basin was a muddy supratidal environment where marine carbonates and continental siliciclastics interfingered. A dolomite phase made of sub‐micrometre euhedral crystals with a mosaic microstructure of nanometre‐scale domains was identified in stromatolitic laminae of the flood basin embedded in clay. This dolomite is interpreted here as primary and has a nearly stoichiometric composition, as opposed to younger early diagenetic (not primary) dolomite phases, which are commonly calcian. This primary dolomite was shielded from later diagenetic transformation by the clay. The stable isotopic composition of dolomite was analyzed along a depositional transect. The δ¹³C values range between ca ?6‰ and +4‰, with the most ¹³C‐depleted values in dolomites of the distal alluvial plain and flood basin, and the most ¹³C‐enriched in dolomites of the tidal flat and lagoon. Uniform δ¹⁸O values ranging between 0‰ and +3‰ were found in all sedimentary facies. It is hypothesized that the primary dolomite with mosaic microstructure nucleated on extracellular polymeric substances secreted by sulphate reducing bacteria. A multi‐step process involving sabkha and reflux dolomitization led to partial replacement and overgrowth of the primary dolomite, but replacement and overgrowth were facies‐dependent. Dolomites of the landward, clay‐rich portion of the sedimentary system were only moderately overgrown during late dolomitization steps, and partly retain an isotopic signature consistent with bacterial sulphate reduction with δ¹³C as low as ?6‰. In contrast, dolomites of the marine, clay‐free part of the system were probably transformed through sabkha and reflux diagenetic processes into calcian varieties, and exhibit δ¹³C values of ca +3‰. Major shifts of δ¹³C values strictly follow the lateral migration of facies and thus mark transgressions and regressions.     

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.     

Characteristics and Dolomitization of Upper Cambrian to Lower Ordovician Dolomite from Outcrop in Keping Uplift, Western Tarim Basin, Northwest China

Late Cambrian to Early Ordovician sedimentary rocks in the western Tarim Basin, Northwest China, are composed of shallow-marine platform carbonates. The Keping Uplift is located in the northwest region of this basin. On the basis of petrographic and geochemical features, four matrix replacement dolomites and one type of cement dolomite are identified. Matrix replacement dolomites include (1) micritic dolomites (MD1); (2) fine–coarse euhedral floating dolomites (MD2); (3) fine–coarse euhedral dolomites (MD3); and (4) medium–very coarse anhedral mosaic dolomites (MD4). Dolomite cement occurs in minor amounts as coarse saddle dolomite cement (CD1) that mostly fills vugs and fractures in the matrix dolomites. These matrix dolomites have δ18O values of ?9.7‰ to ?3.0‰ VPDB (Vienna Pee Dee Belemnite); δ13C values of ?0.8‰ to 3.5‰ VPDB; 87Sr/86Sr ratios of 0.708516 to 0.709643; Sr concentrations of 50 to 257 ppm; Fe contents of 425 to 16878 ppm; and Mn contents of 28 to 144 ppm. Petrographic and geochemical data suggest that the matrix replacement dolomites were likely formed by normal and evaporative seawater in early stages prior to chemical compaction at shallow burial depths. Compared with matrix dolomites, dolomite cement yields lower δ18O values (?12.9‰ to ?9.1‰ VPDB); slightly lower δ13C values (?1.6‰–0.6‰ VPDB); higher 87Sr/86Sr ratios (0.709165–0.709764); and high homogenization temperature (Th) values (98°C–225°C) and salinities (6 wt%–24 wt% NaCl equivalent). Limited data from dolomite cement shows a low Sr concentration (58.6 ppm) and high Fe and Mn contents (1233 and 1250 ppm, respectively). These data imply that the dolomite cement precipitated from higher temperature hydrothermal salinity fluids. These fluids could be related to widespread igneous activities in the Tarim Basin occurring during Permian time when the host dolostones were deeply buried. Faults likely acted as important conduits that channeled dolomitizing fluids from the underlying strata into the basal carbonates, leading to intense dolomitization. Therefore, dolomitization, in the Keping Uplift area is likely related to evaporated seawater via seepage reflux in addition to burial processes and hydrothermal fluids.     

Stable isotope evidence for the origin of diagenetic carbonate minerals from the Lower Jurassic Inmar Formation, southern Israel

The oxygen isotope compositions of diagenetic carbonate minerals from the Lower Jurassic Inmar Formation, southern Israel, have been used to identify porewater types during diagenesis. Changes in porewater composition can be related to major geological events within southern Israel. In particular, saline brines played an important role in late (Pliocene-Pleistocene) dolomitization of these rocks. Diagenetic carbonates included early siderite (δ¹⁸O_SMOW=+24.4 to +26.5‰δ¹³C_PDB=?1.1 to +0.8‰), late dolomite, ferroan dolomite and ankerite (δ¹⁸O_SMOW=+18.4 to +25.8‰; δ¹³C_PDB=?2.1 to +0.2‰), and calcite (δ¹⁸O_SMOW=+21.3 to +32.6‰; δ¹³C_PDB=?4.2 to + 3.2‰). The petrographic and isotopic results suggest that siderite formed early in the diagenetic history at shallow depths. The dolomitic phases formed at greater depths late in diagenesis. Crystallization of secondary calcite spans early to late diagenesis, consistent with its large range in isotopic values. A strong negative correlation exists between burial depth (temperature) and the oxygen isotopic compositions of the dolomitic cements. In addition, the δ¹⁸O values of the dolomitic phases in the northern Negev and Judea Mountains are in isotopic equilibrium with present formation waters. This behaviour suggests that formation of secondary dolomite post-dates the tectonic activity responsible for the present relief of southern Israel (Upper Miocene to Pliocene) and that the dolomite crystallized from present formation waters. Such is not the case in the Central Negev. In that locality, present formation waters have much lower salinities and δ¹⁸O values, indicating invasion of freshwater, and are out of isotopic equilibrium with secondary dolomite. Recharge of the Inmar Formation by meteoric water in the Central Negev occurred in the Pleistocene, and halted formation of dolomite.     

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.     

Evidence for high temperature and 18O‐enriched fluids in the Arab‐D of the Ghawar Field,Saudi Arabia

Using the clumped isotope method, the temperature of dolomite and calcite formation and the oxygen isotopic composition (δ¹⁸O_w) of the diagenetic fluids have been determined in a core taken from the Arab‐D of the Ghawar field, the largest oil reservoir in the world. These analyses show that while the dolomites and limestones throughout the major zones of the reservoir recrystallized at temperatures between ca 80°C and 100°C, the carbonates near the top of the reservoir formed at significantly lower temperatures (20 to 30°C). Although the δ¹⁸O values of the diagenetic fluids show large variations ranging from ca <0‰ to ca +8‰, the variations exhibit consistent downhole changes, with the highest values being associated with the portion of the reservoir with the highest permeability and porosity. Within the limestones, dolomites and dolomites associated with the zone of high permeability, there are statistically significant different trends between the δ¹⁸O_w values and recrystallization temperature. These relationships have different intercepts suggesting that fluids with varying δ¹⁸O_w values were involved in the formation of dolomite and limestone compared to the formation of dolomite associated with the zone of high permeability. These new data obtained using the clumped isotope technique show how dolomitization and recrystallization by deep‐seated brines with elevated δ¹⁸O_w values influence the δ¹⁸O values of carbonates, possibly leading to erroneous interpretations unless temperatures can be adequately constrained.     

Carbon and oxygen isotopes in the Frasnian–Famennian section of the Kuznetsk basin (southern West Siberia)

The first detailed isotope-geochemical study of carbonate deposits has been performed in the Lower Famennian stratotype section of the northwestern Kuznetsk Basin (Kosoy Utyos), which was localized in the middle latitudes of the Northern Hemisphere in the Late Devonian. The δ¹³C_carb, δ¹³C_org, and δ¹⁸O variation curves were constructed for the section deposits. Geochemical and petrographic studies of carbonates allowed allocation of samples that underwent postsedimentation alteration and exclude them from further interpretation. Compared with coeval sections in the other world's regions, the Kosoy Utyos section is characterized by higher δ¹³C_carb values, up to 5.4‰, whereas the maximum value in subequatorial area sections is 4‰. The isotope shift amplitude of the studied section reaches 4.6‰, which is 1.5‰ higher than those in other regions. The δ¹⁸O values are 3‰ lower than the ones of the world's coeval sections. The results obtained show that δ¹³C and δ¹⁸O variation trends differ from those of coeval subequatorial sections. The high shift amplitude and maximum δ¹³C_carb values in the Kosoy Utyos section are due to the shallow-water carbonate sedimentation environments on the Siberian continental shelf and, probably, the lower temperatures of waters in the middle latitudes as compared with the subequatorial areas.     

Recrystallization of dolomite: evidence from the Monterey Formation (Miocene), California

Dolomites from the upper calcareous-siliceous member of the Miocene Monterey Formation exposed west of Santa Barbara, California, were analysed for geochemical, isotopic and crystallographic variation. The data clearly document the progressive recrystallization of dolomite during burial diagenesis in marine pore fluids. Recrystallization is recognized by the following compositional and crystallographic variations. Dolomites have decreasing δ¹⁸O and δ¹³C compositions, decreasing Sr contents and increasing Mg contents with increasing burial depths and temperatures from east to west in the study area. δ¹⁸O values vary from 5·3‰ in the east to − 5·5‰ PDB in the west and are interpreted to reflect the greater extent and higher temperature of dolomite recrystallization in the west. δ¹³C values correlate with δ¹⁸O and decrease from 13·6‰ in the east to − 8·7‰ PDB in the west. Sr concentrations correlate positively with δ¹⁸O values and decrease from a mean of 750 ppm in the east to a mean of 250 ppm in the west. Mol% MgCO₃ values inversely correlate with δ¹⁸O values and increase from a minimum of 41·0 in the east to a maximum of 51·4 in the west. Rietveld refinements of powder X-ray diffraction data indicate that the more recrystallized dolomites have more contracted unit cells and increased cation ordering. The fraction of the Ca sites in the dolomites that are occupied by Ca atoms increases slightly with the approach to stoichiometry. The fraction of the Mg sites occupied by Mg atoms strongly correlates with mol% MgCO₃. Even in early diagenetic, non-stoichiometric dolomites, there is little substitution of Mg in Ca sites. During recrystallization, the amount of Mg substituting for Ca in Ca sites decreases even further. Most of the disorder in the least recrystallized, non-stoichiometric dolomites is related to substitution of excess Ca on Mg sites.     

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,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.     

Origin and Accumulation of Natural Gases in the Upper Paleozoic Strata of the Ordos Basin in Central China

The natural gases in the Upper Paleozoic strata of the Ordos basin are characterized by relatively heavy C isotope of gaseous alkanes with δ 13C1 and δ13C2 values ranging mainly from ?35‰ to ?30‰ and ?27‰ to ?22‰, respectively, high δ13C excursions (round 10) between ethane and methane and predominant methane in hydrocarbon gases with most C1/(C1-C5) ratios in excess of 0.95, suggesting an origin of coal-derived gas. The gases exhibit different carbon isotopic profiles for C1-C4 alkanes with those of the natural gases found in the Lower Paleozoic of this basin, and believed to be originated from Carboniferous-Permian coal measures. The occurrence of regionally pervasive gas accumulation is distinct in the gently southward-dipping Shanbei slope of the central basin. It is noted that molecular and isotopic composition changes of the gases in various gas reservoirs are associated with the thermal maturities of gas source rocks. The abundances and δ13C values of methane generally decline northwards and from the basin center to its margins, and the effects of hydrocarbon migration on compositional modification seem insignificant. However, C isotopes of autogenetic calcites in the vertical and lateral section of reservoirs show a regular variation, and are as a whole depleted upwards and towards basin margins. Combination with gas maturity gradient, the analysis could be considered to be a useful tool for gas migration.     

Geochemical peculiarities of the formation of the Novoshirokinskii gold-polymetallic deposit,Eastern Transbaikalia,Russia

The fluid inclusions in minerals and isotope composition of sulfur in sulfides and carbon and oxygen in carbonates are studied for the Novoshirokinskii gold-polymetallic deposit. The ore-forming fluids are characterized by the following physico-chemical and isotope-geochemical parameters: temperature of 290–100°C, salinity of 13–2.5 wt % NaCl-equiv., δ¹⁸O from +8 to 0‰, δ¹³C of 2.5 ± 0.5‰, and δ³⁴S of 10.5 ± 1.0‰. It is concluded that the Late Proterozoic-Early Cambrian carbonaceous-terrigenous and carbonate rocks were involved in the Late Jurassic ore-magmatic system.     

Multistage hydrothermal dolomites in the Middle Devonian (Givetian) carbonates from the Guilin area, South China

Pervasive dolomites occur preferentially in the stromatoporoid biostromal (or reefal) facies in the basal Devonian (Givetian) carbonate rocks in the Guilin area, South China. The amount of dolomites, however, decreases sharply in the overlying Frasnian carbonate rocks. Dolostones are dominated by replacement dolomites with minor dolomite cements. Replacement dolomites include: (1) fine to medium, planar‐e floating dolomite rhombs (Rd1); (2) medium to coarse, planar‐s patchy/mosaic dolomites (Rd2); and (3) medium to very coarse non‐planar anhedral mosaic dolomites (Rd3). They post‐date early submarine cements and overlap with stylolites. Two types of dolomite cements were identified: planar coarse euhedral dolomite cements (Cd1) and non‐planar (saddle) dolomite cements (Cd2); they post‐date replacement dolomites and predate late‐stage calcite cements that line mouldic vugs and fractures. The replacement dolomites have δ¹⁸O values from ?13·7 to ?9·7‰ VPDB, δ¹³C values from ?2·7 to + 1·5‰ VPDB and ⁸⁷Sr/⁸⁶Sr ratios from 0·7082 to 0·7114. Fluid inclusion data of Rd3 dolomites yield homogenization temperatures (T_h) of 136–149 °C and salinities of 7·2–11·2 wt% NaCl equivalent. These data suggest that the replacive dolomitization could have occurred from slightly modified sea water and/or saline basinal fluids at relatively high temperatures, probably related to hydrothermal activities during the latest Givetian–middle Fammenian and Early Carboniferous times. Compared with replacement dolomites, Cd2 cements yield lower δ¹⁸O values (?14·2 to ?9·3‰ VPDB), lower δ¹³C values (?3·0 to ?0·7‰ VPDB), higher ⁸⁷Sr/⁸⁶Sr ratios (≈ 0·7100) and higher T_h values (171–209 °C), which correspond to trapping temperatures (T_r) between 260 and 300 °C after pressure corrections. These data suggest that the dolomite cements precipitated from higher temperature hydrothermal fluids, derived from underlying siliciclastic deposits, and were associated with more intense hydrothermal events during Permian–Early Triassic time, when the host dolostones were deeply buried. The petrographic similarities between some replacement dolomites and Cd2 dolomite cements and the partial overlap in ⁸⁷Sr/⁸⁶Sr and δ¹⁸O values suggest neomorphism of early formed replacement dolomites that were exposed to later dolomitizing fluids. However, the dolomitization was finally stopped through invasion of meteoric water as a result of basin uplift induced by the Indosinian Orogeny from the early Middle Triassic, as indicated by the decrease in salinities in the dolomite cements in veins (5·1–0·4 wt% NaCl equivalent). Calcite cements generally yield the lowest δ¹⁸O values (?18·5 to ?14·3‰ VPDB), variable δ¹³C values (?11·3 to ?1·2‰ VPDB) and high T_h values (145–170 °C) and low salinities (0–0·2 wt% NaCl equivalent), indicating an origin of high‐temperature, dilute fluids recharged by meteoric water in the course of basin uplift during the Indosinian Orogeny. Faults were probably important conduits that channelled dolomitizing fluids from the deeply buried siliciclastic sediments into the basal carbonates, leading to intense dolomitization (i.e. Rd3, Cd1 and Cd2).     

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.     

Physicochemical model for the generation of the isotopic composition of the carbonate travertine produced by the Tokhana spring,mount Elbrus area,northern Caucasus

The isotopic composition of calcite from travertine deposits of the Tokhana-Verkhnii hot spring in the Elbrus area shows broad variations in δ¹³C and δ¹⁸O (from +3.8 to +16.3‰ and from +24.6 to +28.1‰, respectively). The δ¹³C and δ¹⁸O values increase toward the sole of the travertine dome. The isotopically heaviest carbonates (δ¹³C of up to +16.3‰) were found near the bottom of the dome and composed ancient travertine, which are now not washed by mineral water. The scatter of the δ¹³C values of the fresh sample is slightly narrower: from +3.8 to +10‰. Calculations indicate that all carbonates of the Tokhana dome were not in equilibrium with spontaneous carbon dioxide released by the spring (\(\delta ^{13} C_{CO_2 } \) = ?8‰). To explain the generation of isotopically heavy travertine, a physicochemical model was developed for precipitation of Ca carbonates during the gradual degassing of the mineral water. The character of variations in the calculated δ¹³C values (from +5.5 to +13‰) is in good agreement with the tendency in the variations of the δ¹³C in the carbonate samples. The calculated and measured pH values are also consistent. Our results demonstrate that the isotopic composition of large travertine masses can be heterogeneous, and this should be taken into account during paleoclimatic and paleohydrogeological reconstruction.