The nature and origin of sideritic ironstone bands in the Tertiary Lowmead and Duaringa Basins,Queensland

Sideritic ironstones in Tertiary lacustrine oil shale from the Lowmead and Duaringa Basins in Queensland, contain two distinctive types of siderite in the ironstone bands: sphaerosiderite in the mudstone and coal, and finely crystalline siderite in the lamosite. The petrological evidence indicates that the siderite in the ironstone bands formed eogenetically by growing displacively within the soft sediment. Chemically the siderite is very pure though the sphaerosiderite sometimes shows compositional zoning. Stable oxygen and carbon isotope analyses of the siderite show a wide range of values from ‐12.8‰ to ‐2.4 %₀ δ¹⁸O (PDB) and ‐5.5‰ to +12.9‰ δ¹³C (PDB) for the Lowmead Basin; and ‐9.6‰ to ‐1.2‰ δ¹⁸O (PDB) and ‐18.6‰ to +16.4‰ δ¹³C (PDB) for the Duaringa Basin. The oxygen isotope data indicate that the siderite formed in freshwater environments but not in isotopic equilibrium with the formation waters. Kinetic factors offer the most plausible explanation for the anomalously light δ¹⁸O values of many of the siderites. The carbon isotope data show that the carbonate for the formation of the siderite originated predominantly from methanogenic fermentation processes but there was also the varying influence of bacterial oxidation processes. The different petrological and isotopic characteristics of the ironstones broadly reflect variations in their depositional environments and the variable eogenetic conditions in which the siderite formed. There is no suitable single model to explain the genesis of all the different types of ironstones other than that a synsedimentary iron‐enrichment process is involved.     

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.     

Palaeoproterozoic magnesite: lithological and isotopic evidence for playa/sabkha environments

Magnesite forms a series of 1‐ to 15‐m‐thick beds within the ≈2·0 Ga (Palaeoproterozoic) Tulomozerskaya Formation, NW Fennoscandian Shield, Russia. Drillcore material together with natural exposures reveal that the 680‐m‐thick formation is composed of a stromatolite–dolomite–‘red bed’ sequence formed in a complex combination of shallow‐marine and non‐marine, evaporitic environments. Dolomite‐collapse breccia, stromatolitic and micritic dolostones and sparry allochemical dolostones are the principal rocks hosting the magnesite beds. All dolomite lithologies are marked by δ¹³C values from +7·1‰ to +11·6‰ (V‐PDB) and δ¹⁸O ranging from 17·4‰ to 26·3‰ (V‐SMOW). Magnesite occurs in different forms: finely laminated micritic; stromatolitic magnesite; and structureless micritic, crystalline and coarsely crystalline magnesite. All varieties exhibit anomalously high δ¹³C values ranging from +9·0‰ to +11·6‰ and δ¹⁸O values of 20·0–25·7‰. Laminated and structureless micritic magnesite forms as a secondary phase replacing dolomite during early diagenesis, and replaced dolomite before the major phase of burial. Crystalline and coarsely crystalline magnesite replacing micritic magnesite formed late in the diagenetic/metamorphic history. Magnesite apparently precipitated from sea water‐derived brine, diluted by meteoric fluids. Magnesitization was accomplished under evaporitic conditions (sabkha to playa lake environment) proposed to be similar to the Coorong or Lake Walyungup coastal playa magnesite. Magnesite and host dolostones formed in evaporative and partly restricted environments; consequently, extremely high δ¹³C values reflect a combined contribution from both global and local carbon reservoirs. A ¹³C‐rich global carbon reservoir (δ¹³C at around +5‰) is related to the perturbation of the carbon cycle at 2·0 Ga, whereas the local enhancement in ¹³C (up to +12‰) is associated with evaporative and restricted environments with high bioproductivity.     

The oxygen and carbon isotope composition of Carboniferous fossil components: sea-water effects

The aragonitic molluscs and lime-mud of the Pennsylvanian Buckhorn asphalt (Deese Group) of southern Oklahoma precipitated calcium carbonate in oxygen and carbon isotopic equilibrium with ambient sea-water. In addition, δ¹⁸O values indicate that the pelecypods precipitated their shells during the warmer months of the year. The coiled nautiloids probably precipitated their shells in the warm surface water and throughout the year. For the orthocone nautiloids, the δ¹⁸O values suggest that they precipitated their shells in deeper/cooler water. The low-Mg calcite brachiopods of the Mississippian Lake Valley Formation of New Mexico precipitated shells in oxygen and carbon isotopic equilibrium with ambient sea-water. The δ¹⁸O and δ¹³C values of the Buckhorn and Lake Valley faunas, in conjunction with other published results, suggest that Carboniferous sea-water was, on a average, depleted in δ¹⁸O by 1·5 ± 2‰, PDB, relative to Recent sea-water. However, the δ¹³C value of +2.6 ± 2‰, PDB, for average Carboniferous sea-water is similar to that of Recent ocean water. Early diagenetic alteration of metastable carbonates probably occurs in a meteoric-sea-water mixing zone. In this zone the oxygen and carbon isotopic compositions of these components are increased by about 2-4‰, PDB over their marine composition.     

Changes in carbon and oxygen isotope composition during limestone diagenesis

The calcite fossils of the Derbyhaven Beds, Isle of Man, have δ¹³C values (+ 1·8 PDB) similar to modern, shallow-water marine skeletons, but the δ¹⁸O values (?6·1 PDB) are much lighter than modern skeletons. The light oxygen values indicate either re-equilibration with isotopically light water before cementation started, or Carboniferous sea water with δ¹⁸O of ?6‰. Aragonite dissolution was followed by precipitation of zoned calcite cement. In this cement, up to six intracrystalline zones, recognized in stained thin sections, show isotopic variation. Carbon varies from + 3-8 to + 1-2‰. and oxygen from ? 2-6 to ? 12-4‰. with decreasing age of the cement. This trend is attributed to increasing temperature and to isotopic evolution of the pore waters during burial. The zoned calcite is sequentially followed by dolomite and kaolinite cements which continue the trend towards light isotopic values. This trend is continued with younger, fault-controlled dolomite, and is terminated by vein-filling calcite and dolomite. The younger calcite, interpreted as a near-surface precipitate from meteoric waters, is unrelated to the older sequence of carbonates and has distinctly different carbon isotope ratios: δ¹³C ? 6-8‰.     

Carbon isotope heterogeneity in metamorphic diamond from the Kokchetav UHP dolomite marble,northern Kazakhstan

We analysed isotopic compositions of metamorphic microdiamond secondary ion mass spectrometry. Typical microdiamonds in this dolomite marble show star-shaped morphologies (S-type) consisting of single-crystal cores and polycrystalline rims. Four S-type microdiamonds and two R-type microdiamonds (single crystals with rugged surfaces) were analysed using a 5 μm diameter ion beam. S-type microdiamonds have heterogeneous carbon isotopic compositions even in a single grain. Analysis of a typical S-type microdiamond (no. xx01-1-13) revealed clear difference in δ¹³C between core and rim. The rim shows lighter isotopic compositions ranging from??17.2‰ to??26.9‰, whereas the core is much heavier, with δ¹³C ranging from??9.3‰ to??13.0‰. The δ¹³C values of R-type microdiamonds fall into narrow ranges from??8.3‰ to??14.9‰ for no. xx01-1-10 and from??8.3‰ to??15.3‰ for no. xx01-1-16. These δ¹³C values are similar to those of the S-type microdiamond cores. The R-type probably formed at the same stage as the core of the S-type, whereas rim growth at a second stage did not occur or occurred very weakly in R-type microdiamonds. These carbon isotopic data support the two-stage growth of microdiamonds in the Kokchetav ultrahigh-pressure host rock. To explain the second stage growth of S-type microdiamonds, we postulate a simple fluid infiltration of light carbon from neighbouring gneisses into the dolomite marble.     

Stable carbon isotopes in selected granitic,mafic, and ultramafic igneous rocks

Noncarbonate (combustion) and carbonate (acid decomposition) carbon were separately analyzed in 18 granitic rocks from a group of related Tertiary intrusions near Crested Butte, Colorado, and 14 mafic and ultramafic rocks from various localities in the western United States. Among the granites, carbonate carbon ranges from nil to 0.76 per cent with δC¹³-values from ?5.6 to ? 9.0‰ (vs PDB); noncarbonate carbon varies from 32–360 ppm with δC¹³-values from ?19.7 to ?26.6‰, The mafic and ultramafic rocks have carbonate carbon contents ranging from 53 ppm to about 2 per cent with δC¹³-values from + 2.9 to ?10.3‰; noncarbonate carbon varies from 26 to 150 ppm with δC¹³-values of ?22.2 to ? 27.l‰ For these samples, carbonate carbon ranges from 12.0 to 29.4‰ heavier than coexisting noncarbonate carbon. This consistent difference between δC¹³ of carbonate and noncarbonate carbon may be an isotopic fractionation effect. Because the specific indigenous form of noncarbonate (combustion) carbon is in doubt, conclusive interpretations regarding isotopic equilibration and fractionation cannot be made.These results have bearing on the assessment of the isotopic composition of mantle carbon and consequently are germane to the question of the origin (source) and history of crustal carbon. If mantle carbon is isotopically similar to noncarbonate (combustion) carbon, i.e. δC¹³-values from ?19.7 to ? 27.1‰, then a simple mantle degassing source for crustal carbon is improbable. Such a result would indicate an additional source of crustal carbon such as from a primitive atmosphere or extra-terrestrial accretion.     

Isotopic constraints on growth conditions of multiphase calcite–pyrite–barite concretions in Carboniferous mudstones

Carbonate concretions in the Lower Carboniferous Caton Shale Formation contain diagenetic pyrite, calcite and barite in the concretion matrix or in different generations of septarian fissures. Pyrite was formed by sulphate reduction throughout the sediment before concretionary growth, then continued to form mainly in the concretion centres. The septarian calcites show a continuous isotopic trend from δ¹³C=?28·7‰ PDB and δ¹⁸O=?1·6‰ PDB through to δ¹³C=?6·9‰ PDB and δ¹⁸O=?14·6‰ PDB. This trend arises from (1) a carbonate source initially from sulphate reduction, to which was added increasing contributions of methanogenic carbonate; and (2) burial/temperature effects or the addition of isotopically light oxygen from meteoric water. The concretionary matrix carbonates must have at least partially predated the earliest septarian cements, and thus used the same carbonate sources. Consequently, their isotopic composition (δ¹³C=?12·0 to ?10·1‰ PDB and δ¹⁸O=?5·7 to ?5·6‰ PDB) can only result from mixing a carbonate cement derived from sulphate reduction with cements containing increasing proportions of carbonate from methanogenesis and, directly or indirectly, also from skeletal carbonate. Concretionary growth was therefore pervasive, with cements being added progressively throughout the concretion body during growth. The concretions contain barite in the concretion matrix and in septarian fissures. Barite in the earlier matrix phase has an isotopic composition (δ³⁴S=+24·8‰ CDT and δ¹⁸O=+16·4‰ SMOW), indicating formation from near‐surface, sulphate‐depleted porewaters. Barites in the later septarian phase have unusual isotopic compositions (δ³⁴S=+6 to +11‰ CDT and δ¹⁸O=+8 to +11‰ SMOW), which require the late addition of isotopically light sulphate to the porewaters, either from anoxic sulphide oxidation (using ferric iron) or from sulphate dissolved in meteoric water. Carbon isotope and biomarker data indicate that oil trapped within septarian fissures was derived from the maturation of kerogen in the enclosing sediments.     

Isotopic composition (δ<Superscript>13</Superscript>C and δ<Superscript>18</Superscript>O) and genesis of carbonates from the famennian manganiferous formation of Pai-Khoi

The results of isotope-geochemical studies of carbonates of different mineral types from manganese and host rocks of the Famennian manganiferous formation of Pai-Khoi are reported. Kutnahorite ores are characterized by δ¹³C values from–6.6 to 1.3‰ and δ¹⁸O from 20.0 to 27.4‰. Rhodonite–rhodochrosite rocks of the Silovayakha ore occurrence have δ¹³C from–5.2 to–2.9 and δ¹⁸O from 25.4 to 24.3‰. Mineralogically similar rocks of the Nadeiyakha ore occurrence show the lighter carbon and oxygen isotopic compositions: δ¹³C from–16.4 to–13.1 and δ¹⁸O from 24.8 to 22.5‰. Similar isotopic compositions were also obtained for rhodochrosite–kutnahorite rocks of this ore occurrence: δ¹³C from–13.0 to–10.4‰ and δ¹⁸O from 24.6 to 21.7‰. Siderorodochrosite ores differ in the lighter oxygen and carbon isotopic compositions: δ¹⁸O from 18.7 to 17.6‰ and δ¹³C from–10.2 to–9.3‰, respectively. In terms of the carbon and oxygen isotopic compositions, host rocks in general correspond to marine sedimentary carbonates. Geological-mineralogical and isotope data indicate that the formation of the manganese carbonates was related to the hydrothermal ore-bearing fluids with the light isotopic composition of oxygen and carbon dissolved in CO₂. The isotopic features indicate an authigenic formation of manganese carbonates under different isotopegeochemical conditions.     

Carbon and Oxygen Isotopic Characteristics of REE—Fluorocarbonate Minerals and Their Genetic Implications,Bayan Obo Deposit,Inner Mongloia,China

REE－fluorocarbonates as major REE minerals in the Bayan Obo deposit,the largest REE deposit in the world,were analyzed for their stable isotopic compositions,The δ^13 C and δ^18 O values of huanghoite,cebaite and bastnaesite from late-stage veins vary in the ranges of 7.8--4.0‰ and 6.7-9.4‰,respectively,These data are relatively similar to those of bastnaesites from banded ores:δ^13C-5.6--5.2‰ andδ^18O3.6-5.5‰.The REE fluorocarbonates from both late-staege veins and banded ores are characterized by lower δ^13 C and δ^18O values,especially the δ^18O values of bastnaesites from banded ores.Compared with them,the disseminated bastnaesits the dolomite-type ores possess rather highδ^13 C and δ^18O values,i.e.,-2.1-0.4‰ and 8.6-12.9‰ respectively.The high values are typical of the sedimentary host dolomite rocks as well as of the dolomite-type-ores.The carbon and oxygen isotopic characteristics of REE fluorocarbonate minerals provide new evidence for the hypothesis on the origin of Bayan Obo deposit-epigenetic hydrothermal metasomatism.     

Origin of Paleofluids in Dabashan Foreland Thrust Belt:Geochemical Evidence of 13C,18O and 87Sr/86Sr in Veins and Host Rocks

In the last ten years, with important discoveries from oil and gas exploration in the Dabashan foreland depression belt in the borderland between Shanxi and Sichuan provinces, the relationship between the formation and evolution of, and hydrocarbon accumulation in, this foreland thrust belt from the viewpoint of basin and oil and gas exploration has been studied. At the same time, there has been little research on the origin of fluids within the belt. Based on geochemical system analysis including Z values denoting salinity and research on δ13C, δ18O and 87Sr/86Sr isotopes in the host rocks and veins, the origin of paleofluids in the foreland thrust belt is considered. There are four principal kinds of paleofluid, including deep mantle-derived, sedimentary, mixed and meteoric. For the deep mantle-derived fluid, the δ13C is generally less than ?5.0‰PDB, δ18O less than -10.0‰PDB, Z value less than 110 and 87Sr/86Sr less than 0.70600; the sedimentary fluid is mainly marine carbonate-derived, with the δ13C generally more than ?2.0‰PDB, δ18O less than ?10.0‰PDB, Z value more than 120 and 87Sr/86Sr ranging from 0.70800 to 0.71000; the mixed fluid consists mainly of marine carbonate fluid (including possibly a little mantle-derived fluid or meteoric water), with the δ13C generally ranging from ?2.0‰ to ?8.0‰PDB, δ18O from ?10.0‰ to ?18.0‰ PDB, Z value from 105 to 120 and 87Sr/86Sr from 0.70800 to 0.71000; the atmospheric fluid consists mainly of meteoric water, with the δ13C generally ranging from 0.0‰ to ?10.0‰PDB, δ18O less than ?8.0‰PDB, Z value less than 110 and 87Sr/86Sr more than 0.71000. The Chengkou fault belt encompasses the most complex origins, including all four types of paleofluid; the Zhenba and Pingba fault belts and stable areas contain a simple paleofluid mainly of sedimentary type; the Jimingsi fault belt contains mainly sedimentary and mixed fluids, both consisting of sedimentary fluid and meteoric water. Jurassic rocks of the foreland depression belt contain mainly meteoric fluid.     

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.     

南海台西南区碳酸盐岩矿物学和稳定同位素组成特征——天然气水合物存在的主要证据之一

南海台西南区是中国南海中天然气水合物赋存的最有利场所。研究表明,该区的碳酸盐岩主要以结壳、烟囱的形式出现,结壳的裂隙或孔洞中常常充填有淡黄-白色的文石晶体。碳酸盐岩中自生碳酸盐矿物主要为文石、高镁方解石,少量白云石、铁白云石和菱铁矿。扫描电子显微镜(SEM)分析表明,文石主要呈针状、长柱状、放射束状,高镁方解石呈颗粒状。碳酸盐岩的碳同位素δ13C值主要在-56·878‰~-32·829‰PDB之间,大多数小于-40‰PDB,显示了生物甲烷成因碳源的特征;氧同位素δ18O值在2·1875‰~5·045‰PDB之间,主要在4‰PDB以上,这种较重的氧同位素比值表明,天然气水合物分解产生的富18O水体可能是碳酸盐岩沉淀的流体源。矿物学和碳氧稳定同位素研究表明,南海台西南区的碳酸盐岩为细菌性甲烷成因碳酸盐岩,可能与天然气水合物有关,显示了该区水合物存在的可能性很大。     

The Paleozoic Ozbak-Kuh carbonate-hosted Pb-Zn deposit of East Central Iran: Isotope (C,O, S,Pb) geochemistry and ore genesis

Lead and zinc mineralization occurs in dolostones of the Middle Devonian Sibzar Formation at Ozbak-Kuh, which is located 150 km north of Tabas city in East Central Iran. The ore is composed of galena, sphalerite and calcite, with subordinate dolomite and bitumen. Wall-rock alterations include carbonate recrystallization and dolomitization. Microscopic studies reveal that the host rock is replaced by galena and sphalerite. The Pb–Zn mineralization is epigenetic and stratabound. The δ¹³C values of hydrothermal calcite samples fall in the narrow range between ?0.3‰ and 0.8‰. The δ¹⁸O values in calcite display a wider range, between ?14.5‰ and ?11.9‰. The δ¹³C and δ¹⁸O values overlap with the oxygen and carbon isotopic compositions of Paleozoic seawater, indicating the possible important participation of Paleozoic seawater in the ore-forming fluid. The δ¹⁸O signature corresponds to a spread in temperature of about 70 °C in the ore-bearing fluid. The δ¹³C values indicate that the organic materials within the host rocks did not contribute significantly in the hydrothermal fluid. The δ³⁴S values of galena and sphalerite samples occupy the ranges of 12.2‰–16.0‰ and 12.1–16.8‰, respectively. These values reveal that the seawater sulfate is the most probable source of sulfur. The reduced sulfur was most likely supplied through thermochemical sulfate reduction. The sulfur isotope ratios of co-precipitated sphalerite–galena pairs suggest that deposition of the sulfide minerals took place under chemical disequilibrium conditions. The ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb, and ²⁰⁸Pb/²⁰⁴Pb ratios of the galena samples represent average values of 18.08, 15.66, and 38.50, respectively. These ratios indicate that galena Pb likely originated from an orogenic source in which supracrustal rocks with high ²³⁸U/²⁰⁴Pb and ²³²Th/²⁰⁴Pb ratios are dominant. The average lead isotope model age portrays Cambrian age. This model age is not coeval with the host rocks, which are of middle Devonian age. It is probable that the pre-Middle Devonian model age shows the derivation of Pb from older sources either from host rocks of Cambrian age or from deposits previously formed in these rock units. The Pb isotopic composition of galena accords with the occurrence of an orogenic activity from Late Neoproterozoic to Lower Cambrian in Central Iran. The proposed genetic model considers the fact that mineralization formed in fractured and brecciated host rocks along shear zones and faults from metal-bearing connate waters that were discharged due to deformational dewatering of sediments.     

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.     

The Talgan massive sulfide deposit, the southern Urals, Russia, as an example of subseafloor ore deposition from magmatic fluid

The sequence of orebody formation at the Talgan massive sulfide deposit; morphology of sulfide orebodies; mineralogy, texture, and structure of ore; chemical composition of minerals; and fluid inclusions and relationships between stable isotopes (S, C, O) in sulfides from ores and carbonate rocks are discussed. The deposit is localized in the Uzel’ga ore field of the northern Magnitogorsk Megazone. The sulfide ore is hosted in the upper felsic sequence of the Middle Devonian Karamalytash Formation, composed of basalt, basaltic andesite, and rhyodacite. Orebodies are irregular lenses lying conformably with host rocks. Pyrite, chalcopyrite, sphalerite, and fahlore are the major ore minerals; galena, bornite, and hematite are of subordinate abundance. Sulfide mineralization bears attributes of deposition under subseafloor conditions. The carbonate and rhyolite interlayers at the roofs of orebodies and the supraore limestone sequence served as screens. Zoning typical of massive sulfide deposits was not established. The study of fluid inclusions has shown that the temperature of the hydrothermal solution varied from 375 to 110°C. δ³⁴S‰ ranges from ?2.4 to +3.2‰ in pyrite, from ?1.2 to +2.8‰ in chalcopyrite, and from ?3.5 to +3.0‰ in sphalerite (CDT). These parameters correspond to an isotopic composition of magmatic sulfur without a notable percentage of sulfate sulfur. δ¹³C and δ¹⁸O of carbonates vary from ?18.1 to +5.9‰ (PDB) and from +13.7 to +27.8‰ (SMOW), respectively. The carbon and oxygen isotopic compositions of carbonates from ores and host rocks markedly deviate from the field of marine carbonates; a deep source of carbon is suggested. The results obtained show that the main mass of polysulfide ore at the Talgan deposit was formed beneath the floor of a paleoocean. The ore-forming system was short-lived and its functioning did not give rise to the formation of zonal orebodies. Magmatic fluid played the leading role in mineral formation.     

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.     

Stable isotopic compositions of Recent freshwater cyanobacterial carbonates from the British Isles: local and regional environmental controls

Recent (<50 years old) freshwater cyanobacterial carbonates from diverse environments (streams, lakes, waterfalls) throughout Britain and Ireland were analysed for their stable carbon and oxygen isotope compositions. The mean δ¹⁸O value of ?5–9‰ PDB for river and stream data represents calcite precipitation in equilibrium with the mean oxygen isotopic composition of precipitation in central Britain (?7–5‰SMOW) assuming a mean water temperature of 9°C. The mean δ¹⁸O of lake data, ?4–5‰ PDB, is statistically different, reflecting the effects of residence time and/or variations in the oxygen isotopic composition of rainfall. Carbon isotopes have wide variations in both fluviatile and lake data sets (+ 3 to ?12‰ PDB). These variations are principally controlled in the fluviatile samples by contribution of isotopically light ‘soil zone’ carbon relative to isotopically heavier carbon from limestone aquifer rock dissolution. Lake samples have the heaviest carbon isotope values, reflecting a trend toward isotopic equilibrium between atmospheric CO₂ and aqueous HCO^?₃. We infer that isotopic compositions of ancient cyanobacterial carbonates should also record environmental information, although the effects of stabilization and diagenesis on primary δ¹⁸O values will need careful consideration. Primary carbon isotope compositions should be well preserved, although in marine samples values will be buffered by the isotopic composition of aqueous marine bicarbonate.     

Ordovician low- to intermediate-Mg calcite marine cements from Sweden: marine alteration and implications for oxygen isotopes in Ordovician seawater

Petrography demonstrates the presence of three types of fibrous calcite cement in buildup deposits of the Kullsberg Limestone (middle Caradoc), central Sweden. Translucent fibrous calcite has intrinsic blue luminescence (CL) indicative of pure calcite. This cement has 2–5 mol% MgCO₃, low Mn and Fe (≤ 100 p.p.m.), and is considered to be slightly altered to unaltered, primary low- to intermediate-Mg calcite. Grey turbid fibrous calcite has variable but generally low MgCO₃ content (most analyses <2 mol%) and variable CL response, with Mn and Fe concentrations up to 1200 and 500 p.p.m., respectively. The heterogeneous characteristics of this variety of fibrous calcite are caused by diagenetic alteration of a translucent fibrous calcite precursor. Light-brown turbid fibrous calcite has low MgCO₃ (near 1 mol%) and variable Mn (up to 800 p.p.m.) and Fe (up to 500 p.p.m.) concentrations, with an abundance of bright luminescent patches, which formed during alteration caused by reducing diagenetic fluids. The δ¹³C and δ¹⁸O values of all fibrous calcite form a tight field (δ¹³C=1·7 to 3·1‰ PDB, δ¹⁸O= ? 2·6 to ? 4·1‰ PDB) compared with fibrous calcite isotope values from other units. Fibrous calcite δ¹⁸O values are larger than adjacent meteoric or burial cements, which have δ¹⁸O δ ? 8‰ PDB. Consequently, most diagenetic alteration of Kullsberg fibrous calcite is interpreted to have occurred in the marine diagenetic realm. First-generation equant and bladed calcite cements, which pre-date fibrous calcite, are interpreted as unaltered, low-Mg calcite marine cements based on δ¹³C and δ¹⁸O data (δ¹³C = 2·3 to 2·7‰ PDB, δ¹⁸O= ? 2·8 to ? 3·5‰ PDB). Unlike fibrous cement, which reflects global sea water chemistry, first-generation equant and bladed calcite are indicators of localized modification of seawater chemistry in restricted settings. Kullsberg abiotic marine cements have larger δ¹⁸O values than most Caradoc marine precipitates from equatorial Laurentia. Positive Kullsberg δ¹⁸O values are attributed to lower seawater temperatures and/or slightly elevated salinity on the Baltic platform relative to seawater from which other marine precipitates formed.     

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.