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.     

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.     

http://www.sciencedirect.com/science/article/pii/S1674987113001114

The Deccan Syneclise is considered to have significant hydrocarbon potential.However,significant hydrocarbon discoveries,particularly for Mesozoic sequences,have not been established through conventional exploration due to the thick basalt cover over Mesozoic sedimentary rocks.In this study,near-surface geochemical data are used to understand the petroleum system and also investigate type of source for hydrocarbons generation of the study area.Soil samples were collected from favorable areas identified by integrated geophysical studies.The compositional and isotopic signatures of adsorbed gaseous hydrocarbons(methane through butane) were used as surface indicators of petroleum micro-seepages.An analysis of 75 near-surface soil-gas samples was carried out for light hydrocarbons(C1-C4) and their carbon isotopes from the western part of Tapti graben,Deccan Syneclise,India.The geochemical results reveal sites or clusters of sites containing anomalously high concentrations of light hydrocarbon gases.High concentrations of adsorbed thermogenic methane(C_1 = 518 ppb) and ethane plus higher hydrocarbons(ΣC_(2+) = 977 ppb) were observed.Statistical analysis shows that samples from 13% of the samples contain anomalously high concentrations of light hydrocarbons in the soil-gas constituents.This seepage suggests largest magnitude of soil gas anomalies might be generated/source from Mesozoic sedimentary rocks,beneath Deccan Traps.The carbon isotopic composition of methane,ethane and propane ranges are from-22.5‰ to-30.2‰ PDB,-18.0‰to 27.1‰ PDB and 16.9‰-32.1‰ PDB respectively,which are in thermogenic source.Surface soil sample represents the intersection of a migration conduit from the deep subsurface to the surface connected to sub-trappean Mesozoic sedimentary rocks.Prominent hydrocarbon concentrations were associated with dykes,lineaments and presented on thinner basaltic cover in the study area,which probably acts as channel for the micro-seepage of hydrocarbons.     

Sulphur and carbon isotopic composition of power supply coals in the Pannonian Basin, Hungary

The present work is an attempt to establish the stable isotope database for Mesozoic to Tertiary coals from the Pannonian Basin, Hungary. Maceral composition, proximate analysis, sulphur form, sulphur isotopes (organic and pyritic), and carbon isotopes were determined. This database supports the assessment of the environmental risks associated with energy generation, the characterization of the formation and the distribution of sulphur in the coals used.The maceral composition, the sulphur composition, the C, S isotopic signatures, and some of the geological evidences published earlier show that the majority of these coals were deposited in freshwater and brackish water environments, despite the relatively high average sulphur content. However, the Upper Cretaceous, Eocene, and Lower Miocene formations also contain coal seams of marine origin, as indicated by their maceral composition and sulphur and carbon chemistry.The majority of the sulphur in these coals occurs in the organic form. All studied sulphur phases are relatively rich in ³⁴S isotopes (δ³⁴S_organic = + 12.74‰, δ³⁴S_pyrite = + 10.06‰, on average). This indicates that marine bacterial sulphate reduction played a minor role in their formation, in the sense that isotopic fractionation was limited. It seems that the interstitial spaces of the peat closed rapidly during early diagenesis due to a regime of high depositional rate, leading to a relative enrichment of the heavy sulphur isotopes.     

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.     

Origin of siderite mineralisation in Petrova and Trgovska Gora Mts., NW Dinarides

The Petrova and Trgovska Gora Mts. (Gora=Mountain) are Variscan basement units incorporated into the northwestern Dinarides during the Alpine orogeny. They host numerous siderite-quartz-polysulphide, siderite-chalcopyrite, siderite-galena and barite veins, as well as stratabound hydrothermal-replacement ankerite bodies within carbonates in non-metamorphosed, flysch-like Permo-Carboniferous sequences. The deposits have been mined for Cu, Pb, Ag and Fe ores since Medieval times. Fluid inclusion studies of quartz from siderite-polysulphide-quartz and barite veins of both regions have shown the presence of primary aqueous NaCl?CaCl₂±MgCl₂?H₂O±CO₂ inclusions. The quartz-sulphide stage of both regions show variable salinities; 2.7–26.2 wt% NaCl eq. for the Trgovska Gora region and 3.4–23.4 wt% NaCl eq. for the Petrova gora region, and similar homogenisation temperatures (100–230°C). Finally, barite is precipitated from low salinity-low temperature solutions (3.7–15.8 wt % NaCl equ. and 115–145°C). P-t conditions estimated via isochore construction yield formation temperatures between 180–250°C for the quartz-sulphide stage and 160–180°C for the barite stage, using a maximum lithostatic pressure of 1 kbar (cc. 3 km of overburden). The sulphur isotope composition of barite from both deposits indicates the involvement of Permian seawater in ore fluids. This is supported by the elevated bromium content of the fluid inclusion leachates (120–660 ppm in quartz, 420–960 ppm in barite) with respect to the seawater, indicating evaporated seawater as the major portion of the ore-forming fluids. Variable sulphur isotope compositions of galena, pyrite and chalcopyrite, between ?3.2 and +2.7‰, are interpreted as a product of incomplete thermal reduction of the Permian marine sulphate mixed with organically- and pyrite-bound sulphur from the host sedimentary rocks. Ore-forming fluids are interpreted as deep-circulating fluids derived primarily from evaporated Permian seawater and later modified by interaction with the Variscan basement rocks. ⁴⁰Ar/³⁹Ar data of the detrital mica from the host rocks yielded the Variscan age overprinted by an Early Permian tectonothermal event dated at 266–274 Ma. These ages are interpreted as those reflecting hydrothermal activity correlated with an incipient intracontinental rifting in the Tethyan domain. Nevertheless, 75 Ma recorded at a fine-grained sericite sample from the alteration zone is interpreted as a result of later resetting of white mica during Campanian opening/closure of the Sava back arc in the neighbouring Sava suture zone (Ustaszewski et al. 2008).     

The use of environmental markers to identify groundwater salinization sources in a Neogene basin, Kert aquifer case, NE Morocco

Environmental isotopes data of oxygen and hydrogen of natural water and sulphur and oxygen of dissolved sulphate as well as characteristics of d-excess are used to illustrate the salinity origin in Kert aquifer NE Morocco. In this study, 14 groundwater samples and surface water of the Kert River were collected in the Kert plain during December 2008, and were combined with previously collected hydrochemical data. The isotope compositions of these waters range from ?5.74 to ?4.51 ‰ for oxygen and from ?40.8 to ?34.1 ‰ for hydrogen. In Kert River these values are ?6.47 ‰ for oxygen and ?47.56 ‰ for hydrogen. All the samples with a slope <8 do not fall on the meteoric water line indicating a light evaporation. Water has low and different d-excess values (ranging from +1.37 to +9.82 ‰), reflecting different climatic conditions. Based on the nitrate concentration water in the Kert aquifer comes from the modern precipitation. The isotope compositions range from ?2.2 to +16 ‰ for sulphur and from +5.02 to +13.86 ‰ for oxygen. In Kert River these values are ?4.6 and +5.3 ‰ for sulphur and oxygen, respectively. There are fairly constant difference between oxygen of water and the oxygen of sulphate suggesting a dominant control of this latter in sulphate sources. At least three major sulphate sources were identified by the isotope data from sulphate in these waters: (1) dissolved marine sulphate from the underlying upper Miocene unit; (2) dissolved sulphate from Kert River; (3) sulphate derived from oxidation of sulphur compounds in the metamorphic massif of Temsamane. The latter has a dilution role. The isotopic variations of these waters and sulphate concentration therein reflect mixing of these sources in the aquifer.     

The origin of sulphur in gypsum and dissolved sulphate in the Central Namib Desert,Namibia

This study investigates the sulphur source of gypsum sulphate and dissolved groundwater sulphate in the Central Namib Desert, home to one of Africa's most extensive gypsum (CaSO₄·2H₂O) accumulations. It investigates previously suggested sulphate precursors such as bedrock sulphides and decompositional marine biogenic H₂S and studies the importance of other potential sources in order to determine the origin of gypsum and dissolved sulphate in the region. An attempt has been made to sample all possible sulphur sources, pathways and types of gypsum accumulations in the Central Namib Desert. We have subjected those samples to sulphur isotopic analyses and have compiled existing results. In addition, ionic ratios of Cl/SO₄ are used to determine the presence of non-sea-salt (NSS) sulphur in groundwater and to investigate processes affecting groundwater sulphate. In contrast to previous work, this study proposes that the sulphur cycle, and the formation of gypsum, in the Namib Desert appears to be dominated by the deposition of atmospheric sulphates of phytoplanktonic origin, part of the primary marine production of the Benguela upwelling cells. The aerosol sulphates are subjected to terrestrial storage within the gypsum deposits on the hyper-arid gravel plain and are traceable in groundwater including coastal sabkhas. The hypothesis of decompositional marine biogenic H₂S or bedrock sulphide sources, as considered previously for the Namib Desert, cannot account for the widespread accumulation of gypsum in the region. The study area in the Central Namib Desert, between the Kuiseb and Omaruru rivers, features extensive gypsum accumulations in a ca. 50–70 km wide band, parallel to the shore. They consist of surficial or shallow pedogenic gypsum crusts in the desert pavement, hydromorphic playa or sabkha gypsum, as thin isolated pockets on bedrock ridges and as discrete masses of gypsum selenite along some faults. The sulphur isotopic values (δ³⁴S ‰CDT) of these occurrences are between δ³⁴S +13.0 and +18.8‰, with lower values in proximity to sulphuric ore bodies (δ³⁴S +3.1 and +3.4‰). Damaran bedrock sulphides have a wide range from δ³⁴S −4.1 to +13.8‰ but seem to be significant sources on a local scale at the most. Dissolved sulphate at playas, sabkhas, springs, boreholes and ephemeral rivers have an overall range between δ³⁴S +9.8 and +20.8‰. However, they do not show a systematic geographical trend. The Kalahari waters have lower values, between δ³⁴S +5.9 and +12.3‰. Authigenic gypsum from submarine sediments in the upwelling zone of the Benguela Current between Oranjemund and Walvis Bay ranges between δ³⁴S −34.6 to −4.6‰. A single dry atmospheric deposition sample produced a value of δ³⁴S +15.9‰. These sulphur isotopic results, complemented by meteorological, hydrological and geological information, suggest that sulphate in the Namib Desert is mainly derived from NSS sulphur, in particular oxidation products of marine dimethyl sulphide CH₃SCH₃ (DMS). The hyper-arid conditions prevailing along the Namibian coast since Miocene times favour the overall preservation of the sulphate minerals. However, sporadic and relatively wetter periods have promoted gypsum formation: the segregation of sulphates from the more soluble halite, and the gradual seaward redistribution of sulphate. This study suggests that the extreme productivity of the Benguela Current contributes towards the sulphur budget in the adjacent Namib Desert.     

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.     

Sulphur isotope distribution in the Pb-Zn-deposit Bleiberg (Carinthia,Austria)

The sulphur isotope composition of 233 sulphides and 40 sulphates has been investigated and evaluated in combination with 29 earlier published data. The total variation of δ³⁴S values for the sulphides and the sulphates ranges from ?40 up to ?1 ‰ and from +7 up to +20 ‰, respectively. For the mineral species the variations are (with number of samples in brackets): galena (96) ?32 up to ?2 ‰, sphalerite (141) ?30 up to ?4 ‰, marcasite (16) ?27 up to ?1 ‰, pyrite (10) ?26 up to ?13 ‰, molybedenite (3) ?40 up to ?29 ‰, anhydrite and gypsum (8) +15 up to +20 ‰, coelestine (1) +19 ‰, and barite (33) +7 up to +18 ‰. The frequency distribution of the δ³⁴S values corresponds with the complexity of the ore forming processes which resulted in six strata-bound ore mineralizations. The sulphate values clearly show that the sulphate sulphur originates from sea water sulphate. The sulphides are formed by bacteriogeneric processes from seawater sulphate, and their sulphur isotope composition depends on the lithofacies of the sediments as well as on the following diagenetic processes.     

Mantle-derived fluids in the basement of the Deccan Trap: evidence from stable carbon and oxygen isotopes of carbonates from the Killari borehole basement, Maharashtra, India

We report here for the first time geochemical, mineralogical and stable carbon and oxygen isotopic data on the crystalline basement rocks of the 1993 Killari earthquake region of Maharashtra (India), which is covered by a thick suite of Deccan volcanics. Our results revealed the hitherto unknown amphibolite–granulite nature of the 2.5?Ga basement, which contains 2.00–2.28?wt% of CO₂. The stable carbon (δ¹³C) and oxygen (δ¹⁸O) isotopic measurements on carbonates separated from two basement samples KIL-13 (440.5?m depth) and KIL-20 (499.6?m depth) collected from the KLR-1 borehole drilled in the epicentral region showed the respective values of ?6.23 and ?6.22‰ versus PDB for δ¹³C and 7.94 and 8.11‰ versus SMOW for δ¹⁸O. The samples plot in the primary igneous carbonatite field, indicating the mantle origin of the carbonates, derived through the process of mantle metasomatism from the deep mantle carbon reservoir. This would suggest large-scale crust-mantle thermal fluid interaction beneath the Killari seismogenic region, which is characterized by massive upwarping of the high-velocity mafic crust and retrograde metamorphism.     

Isotope Data on Barite and Celestite Deposits Related to Three Mesozoic Evaporitic Sequences of the Neuquén Basin,Argentina

Stratabound barite and celestite deposits, related mainly to three evaporitic sequences, occur in the Mesozoic Neuquen Retroarc Basin, developed to the east of the Andean Cordillera of western Argentina. This basin is filled with Jurassic and Cretaceous marine to continental sediments that unconformably overlie basement rocks of Paleozoic to Triassic age.

Celestite deposits formed by initial precipitation from seawater, with later crystallization during diagenesis and recrystallization related to Eocene intrusive activity. This is supported by evidence of evaporitic associations, textures, and Sr and S-isotope data. The barite deposits were deposited in a near-shore environment and could have formed as a result of interaction between barium absorbed in clay minerals (derived from weathering of basement rocks) and hypersaline seawater. This genetic model is supported by evidence such as the stratabound setting, textures, and Sr and S-isotope data.

Carbon and oxygen-isotopic compositions of carbonates, which are interbedded with celestites, are in the range expected for marine carbonates. Lead-isotopic compositions of galenas from bedded and vein barite deposits of Upper Jurassic and Lower Cretaceous ages are consistent with Pb remobilization from a source located at high levels of the upper crust, possibly the basement rocks.     

Sulphur cycling in organic-rich marine sediments from a Scottish fjord

In this study, the biogeochemical transformations of sulphur in organic‐rich marine sediments in a Scottish fjord are investigated by a combination of pore water and sediment geochemistry with sulphide diffusive gradient thin‐film probes and sulphate isotopic data (δ³⁴S and δ¹⁸O). Particular attention is paid to sulphur cycling in the upper sediment profile where sulphate reduction occurs but free sulphide is below the detection limits of conventional pore water geochemical analysis but quantifiable by sulphide diffusive gradient thin film. In the uppermost part of the sediment core, δ¹⁸O sulphate decreased from near‐sea water values to +7‰, indicating that anoxic sulphide oxidation dominated during this interval. Sulphate δ³⁴S remained unchanged as there was no net sulphate reduction (i.e. reduction was balanced by re‐oxidation). Below 4 cm depth, there was a slight increase in sulphate δ³⁴S from 20‰ to 23‰ associated with minor accumulation of iron sulphide. The δ¹⁸O of the sulphate also increased, to around +10‰ at 10 cm depth, as a result of the isotopic exchange of sulphate–oxygen with pore water and/or sulphur disproportionation reactions mediated during sulphur cycling. These processes continued to increase the δ¹⁸O of the sulphate to 14‰ at 20 cm depth with no further change in the δ³⁴S of the sulphate. Below 20 cm depth, free sulphide is detectable in pore waters and both the δ³⁴S of the sulphate and sulphide increase with depth with an offset controlled by kinetic fractionation during bacterial sulphate reduction. The δ³⁴S of the sedimentary organic fraction shifted towards lower, more bacteriogenic, values with depth in the profile, without any increase in the size of this sulphur pool. Thus, the organic sulphur fraction was open to interaction with bacteriogenic sulphide without the occurrence of net addition. Therefore, caution should be exercised when using sulphur isotopic compositions to infer simple net addition of bacteriogenic sulphide to the organic sulphur fraction.     

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.     

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.     

Diagenetic controls on the isotopic composition of carbonate‐associated sulphate in the Permian Capitan Reef Complex,West Texas

Late Palaeozoic‐age strata from the Capitan Reef in west Texas show facies‐dependent heterogeneity in the sulphur isotopic composition of carbonate‐associated sulphate, which is trace sulphate incorporated into carbonate minerals that is often used to reconstruct the sulphur isotopic composition of ancient seawater. However, diagenetic pore fluid processes may influence the sulphur isotopic composition of carbonate‐associated sulphate. These processes variously modify the sulphur isotopic composition of incorporated sulphate from syndepositional seawater in shelf crest, outer shelf, shelf margin and slope depositional settings. This study used a new multicollector inductively‐coupled plasma mass spectrometry technique to determine the sulphur isotopic composition of samples of individual depositional and diagenetic textures. Carbonate rocks representing peritidal facies in the Yates and Tansill formations preserve the sulphur isotopic composition of Guadalupian seawater sulphate despite alteration of the carbon and oxygen isotopic compositions by meteoric and dolomitizing diagenetic processes. However, sulphur isotopic data indicate that limestones deposited in reef and slope facies in the Capitan and Bell Canyon formations largely incorporate sulphate from anoxic marine‐phreatic pore fluids isotopically modified from seawater by microbial sulphate reduction, despite generally preserving the carbon and oxygen isotopic compositions of Permian seawater. Some early and all late meteoric calcite cements have carbonate‐associated sulphate with a sulphur isotopic composition distinct from that of Permian seawater. Detailed petrographic and sedimentary context for carbonate‐associated sulphate analyses will allow for improved reconstructions of ancient seawater composition and diagenetic conditions in ancient carbonate platforms. The results of this study indicate that carbonate rocks that diagenetically stabilize in high‐energy environments without pore fluid sulphate gradients can provide a robust archive of ancient seawater's sulphur isotopic composition.     

Rare earth element and stable isotope (O, S) geochemistry of barite from the Bijgan deposit, Markazi Province, Iran

The Bijgan barite deposit, which is located northeast of Delijan in Markazi Province of Iran, occurs as a small lenticular body at the uppermost part of an Eocene volcano-sedimentary rock unit. The presence of fossiliferous and carbonaceous strata suggests that the host rocks were deposited in a quiet marine sedimentary environment. Barite, calcite, iron oxides and carbonaceous clay materials are found as massive patches as well as thin layers in the deposit. Barite is marked by very low concentrations of Sr (1–2%) and total amounts of rare earth elements (REEs) (6.25–17.39?ppm). Chondrite-normalized REE patterns of barite indicate a fractionation of light REEs (LREEs) from La to Sm, similar to those for barite of different origins from elsewhere. The La_CN/Lu_CN ratios and chondrite-normalized REE patterns reveal that barite in the Bijgan deposit is enriched in LREE relative to heavy rare earth elements (HREEs). The similarity between the Ce/La ratios in the barite samples and those found in deep-sea barite supports a marine origin for barite. Lanthanum and Gd exhibit positive anomalies, which are common features of marine chemical sediments. Cerium shows a negative anomaly in most samples that was inherited from the negative Ce anomaly of hydrothermal fluid that mixed with seawater at the time of barite precipitation. The δ¹⁸O values of barites show a narrow range of 9.1–11.4‰, which is close to or slightly lower than that of contemporaneous seawater at the end of the Eocene. This suggests a contribution of oxygen from seawater in the barite-forming solution. The δ³⁴S values of barites (9.5–15.3‰) are lower than that of contemporaneous seawater, which suggests a contribution of magmatic sulfur to the ore-forming solution. The oxygen and sulfur isotope ratios indicate that submarine hydrothermal vent fluids are a good analog for solutions that precipitated barite, due to similarities in the isotopic composition of the sulfates. The available data including tectonic setting, host rock characteristics, REE geochemistry, and oxygen and sulfur isotopic compositions support a submarine hydrothermal origin for the Bijgan barite deposit. At the seafloor, barite deposition occurred where ascending Ba-bearing hydrothermal fluids encountered seawater. Sulfate was derived from the sulfate-bearing marine waters, and, to a lesser extent, by oxidized H₂S, which was derived from magmatic hydrothermal fluids.     

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.     

The isotopic composition of strontium in non-marine carbonate rocks: the Flagstaff Formation of Utah*

The isotopic composition of strontium in surface water in continental basins is determined primarily by the geology of the basin and to a lesser extent by climatic conditions. Consequently, the ⁸⁷Sr/⁸⁶Sr ratios of brines in such basins can change only as a result of changes in the geology or climate. This principle of isotope geology was studied by analysis of a suite of non-marine carbonate rocks from the Flagstaff Formation (Palaeocene-Eocene) of Utah. The samples were collected from a section in Fairview Canyon of Sanpete County. They include both limestone and dolomite and were selected to have low non-carbonate residues. The concentrations of strontium in calcites averages 383 ± 128 p.p.m., while those of dolomites increase from 354 ± 74 p.p.m. in the lower 43 m of section to a maximum of 2259 p.p.m. higher up. The increase in the strontium content of dolomite is interpreted as evidence for a change from steady-state to progressively more evaporitic conditions. Two dolomites have isotopic compositions of oxygen expressed as δ¹⁸O = -2.75‰ (relative to the PDB standard) and are enriched in ¹⁸O relative to two calcites whose average δ¹⁸O value is -9.9‰. The ⁸⁷Sr/⁸⁶Sr ratios of the carbonate minerals range from 0.70890 to 0.71260. These values are clearly greater than the ⁸⁷Sr/⁸⁶Sr ratio of marine carbonates of Early Eocene age which is 0.70744. The variation of the ⁸⁷Sr/⁸⁶Sr ratio in this section of the Flagstaff Formation is real and reflects the occurrence of geological events which changed the isotopic composition of Sr entering Lake Flagstaff. The non-carbonate fractions of six carbonate rocks and one sandstone fit a straight line on the strontium mixing diagram in co-ordinates of initial ⁸⁷Sr/⁸⁶Sr and 1/Sr concentration. These results suggest that the isotopic composition of strontium in Lake Flagstaff may have been modulated by periodic input of volcanogenic detritus of felsic composition.     

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.