Dolomitization by penesaline sea water in Early Jurassic peritidal platform carbonates, Gibraltar, western Mediterranean

Peritidal carbonates of the Lower Jurassic (Liassic) Gibraltar Limestone Formation, which form the main mass of the Rock of Gibraltar, are replaced by fine and medium crystalline dolomites. Replacement occurs as massive bedded or laminated dolomites in the lower 100 m of an ≈460‐m‐thick platform succession. The fine crystalline dolomite has δ¹⁸Ο values either similar to, or slightly higher than, those expected from Early Jurassic marine dolomite, and δ¹³C values together with ⁸⁷Sr/⁸⁶Sr ratios that overlap with sea‐water values for that time, indicating that the dolomitizing fluid was Early Jurassic sea water. Absence of massive evaporitic minerals and/or evaporite solution‐collapse breccias in these carbonate rocks indicates that the salinity of sea water during dolomitization was below that of gypsum precipitation. The occurrence of peritidal facies, a restricted microbiota and rare gypsum pseudomorphs are also consistent with penesaline conditions (salinity 72–199‰). The medium crystalline dolomite has some δ¹⁸Ο and δ¹³C values and ⁸⁷Sr/⁸⁶Sr ratios similar to those of Early Jurassic marine dolomites, which indicates that ambient sea water was again a likely dolomitizing fluid. However, the spread of δ¹⁸Ο, δ¹³C and ⁸⁷Sr/⁸⁶Sr values indicates that dolomitization occurred at slightly increased temperatures as a result of shallow (≈500 m) burial or that dolomitization was multistage. These data support the hypothesis that penesaline sea water can produce massive dolomitization in thick peritidal carbonates in the absence of evaporite precipitation. Taking earlier models into consideration, it appears that replacement dolomites can be produced by sea water or modified sea water with a wide range of salinities (normal, penesaline to hypersaline), provided that there is a driving mechanism for fluid migration. The Gibraltar dolomites confirm other reports of significant Early Jurassic dolomitization in the western Tethys carbonate platforms.     

Testing the preservation potential of early diagenetic dolomites as geochemical archives

Early marine diagenetic dolomite is a rather thermodynamically-stable carbonate phase and has potential to act as an archive of marine porewater properties. However, the variety of early to late diagenetic dolomite phases that can coexist within a single sample can result in extensive complexity. Here, the archive potential of early marine dolomites exposed to extreme post-depositional processes is tested using various types of analyses, including: petrography, fluid inclusion data, stable δ¹³C and δ¹⁸O isotopes, ⁸⁷Sr/⁸⁶Sr ratios, and U-Pb age dating of various dolomite phases. In this example, a Triassic carbonate platform was dissected and overprinted (diagenetic temperatures of 50 to 430°C) in a strike-slip zone in Southern Spain. Eight episodes of dolomitization, a dolostone cataclasite and late stage meteoric/vadose cementation were recognized. The following processes were found to be diagenetically relevant: (i) protolith deposition and fabric-preservation, and marine dolomitization of precursor aragonite and calcite during the Middle–Late Triassic; (ii) intermediate burial and formation of zebra saddle dolomite and precipitation of various dolomite cements in a Proto-Atlantic opening stress regime (T ca 250°C) during the Early–Middle Jurassic; (iii) dolomite cement precipitation during early Alpine tectonism, rapid burial to ca 15 km, and high-grade anchizone overprint during Alpine tectonic evolution in the Early Eocene to Early Miocene; (iv) brecciation of dolostones to cataclasite during the onset of the Carboneras Fault Zone activity during the Middle Miocene; and (v) late-stage regression and subsequent meteoric overprint. Data shown here document that, under favourable conditions, early diagenetic marine dolomites and their archive data may resist petrographic and geochemical resetting over time intervals of 10⁸ or more years. Evidence for this preservation includes preserved Late Triassic seawater δ¹³C_DIC values and primary fluid inclusion data. Data also indicate that oversimplified statements based on bulk data from other petrographically-complex dolomite archives must be considered with caution.     

Sedimentology and chemostratigraphy of the Bwipe Neoproterozoic cap dolostones (Ghana,Volta Basin): A record of microbial activity in a peritidal environment

Neoproterozoic glacial and post-glacial sediments from the Volta Basin (West Africa) form a stratigraphic ‘Triad’ of tillites, carbonates and cherts. The carbonates that cap the tillites were studied in detail at Bwipe (Ghana), in the western part of the basin. They are made of finely-laminated dolostones with well-preserved sedimentary features, suggesting that dolomite formation was penecontemporaneous of deposition in a warm, arid peritidal environment, with microbial activity. Rare-earth element distribution display seawater-like patterns. Redox-sensitive trace elements indicate suboxic conditions. High Ba/Al ratios can be related to high organic productivity. δ¹³C values are nearly constant at −3.7‰ and δ¹⁸O_PDB are about −6‰. ⁸⁷Sr/⁸⁶Sr ratios range between 0.7061 and 0.7073. The δ¹³C signatures are nearly similar to those of coeval cap dolostones from the northern part of the Basin. The dolostones change upwards to limestones with secondary textures, as well as more negative δ¹³C and higher ⁸⁷Sr/⁸⁶Sr ratio. Therefore, only the dolostones witness the post-glacial conditions in seawater. It is proposed that, due to a bloom of microbial productivity following ice thaw, organic matter likely accumulated at the water–sediment interface and was consumed by sulphate-reducing bacteria, leading to the precipitation of δ¹³C-negative dolomite. This microbially mediated model is supported by present-day field evidence from hypersaline lagoons in Brazil and by previously published culture experiments. It is consistent with the sedimentological and geochemical data from the Ghana cap dolostones and can be applied to other Neoproterozoic cap dolostones worldwide.     

Formation of modern dolomite in hypersaline pans of the Western Cape,South Africa

Authigenic calcite and dolomite and biogenic aragonite occur in Holocene pan sediments in a Mediterranean‐type climate on the western coastal plain of South Africa. Sediment was analysed from a Late Pleistocene coastal pan at Yzerfontein and four Holocene inland pans ranging from brackish to hypersaline. The pans are between 0·08 and 0·14 km² in size. The δ¹⁸O_PDB values of carbonate minerals in the pan sediments range from ?2·41 to 5·56‰ and indicate precipitation from evaporative waters. Covariance of total organic content and percentage carbonate minerals, and the δ¹³C_PDB values of pan carbonate minerals (?8·85 to ?1·54‰) suggest that organic matter degradation is a significant source of carbonate ions. The precipitation of the carbonate minerals, especially dolomite, appears to be mediated by sulphate‐reducing bacteria in the black sulphidic mud zone found in the brine‐type hypersaline pans. The knobbly, sub‐spherical texture of the carbonate minerals suggests that the precipitation of the carbonate minerals, particularly dolomite, is related to microbial processes. The ⁸⁷Sr/⁸⁶Sr ratios of pan carbonate minerals (0·7108 to 0·7116) are slightly higher than modern sea water and indicate a predominantly sea water (marine aerosol) source for calcium (Ca²⁺) ions with relatively minor amounts of Ca²⁺ derived from the chemical weathering of bedrock.     

Dolomitization by hypersaline reflux into dense groundwaters as revealed by vertical trends in strontium and oxygen isotopes: Upper Muschelkalk,Switzerland

The Trigonodus Dolomit is the dolomitized portion of the homoclinal ramp sediments of the Middle Triassic Upper Muschelkalk in the south‐east Central European Basin. Various dolomitizing mechanisms, followed by recrystallization, have been previously invoked to explain the low δ¹⁸O, high ⁸⁷Sr/⁸⁶Sr, extensive spatial distribution and early nature of the replacive matrix dolomites. This study re‐evaluates the origin, timing and characteristics of the dolomitizing fluids by examining petrographic and isotopic trends in the Trigonodus Dolomit at 11 boreholes in northern Switzerland. In each borehole the ca 30 m thick unit displays the same vertical trends with increasing depth: crystal size increase, change from anhedral to euhedral textures, ultraviolet‐fluorescence decrease, δ¹⁸O_VPDB decrease from ?1·0‰ at the top to ?6·7‰ at the base and an ⁸⁷Sr/⁸⁶Sr increase from 0·7080 at the top to 0·7117 at the base. Thus, dolomites at the top of the unit record isotopic values similar to Middle Triassic seawater (δ¹⁸O_VSMOW = 0‰; ⁸⁷Sr/⁸⁶Sr = 0·70775) while dolomites at the base record values similar to meteoric groundwaters from the nearby Vindelician High (δ¹⁸O_VSMOW = ?4·0‰; ⁸⁷Sr/⁸⁶Sr = >0·712). According to water–rock interaction modelling, a single dolomitizing or recrystallizing fluid cannot have produced the observed isotopic trends. Instead, the combined isotopic, geochemical and petrographic data can be explained by dolomitization via seepage‐reflux of hypersaline brines into dense, horizontally‐advecting groundwaters that already had negative δ¹⁸O and high ⁸⁷Sr/⁸⁶Sr values. Evidence for the early groundwaters is found in meteoric calcite cements that preceded dolomitization and in fully recrystallized dolomites with isotopic characteristics identical to the groundwaters following matrix dolomitization. This study demonstrates that early groundwaters can play a decisive role in the formation and recrystallization of massive dolomites and that the isotopic and textural signatures of pre‐existing groundwaters can be preserved during seepage‐reflux dolomitization in low‐angle carbonate ramps.     

Dolomitization of the Middle Devonian Winnipegosis carbonates in south-central Saskatchewan, Canada

The Middle Devonian Winnipegosis carbonate unit in south‐central Saskatchewan is partially to completely dolomitized. Two major types of replacive dolomite are distinguished. Microcrystalline to finely crystalline dolomite (type 1) displays nonplanar‐a to planar‐s textures, mimetically replaces the precursor limestone, accounts for about four‐fifths of dolomite phases volumetrically, and mainly occurs in the Winnipegosis mounds and the Lower Winnipegosis Member directly underlying the mounds. Medium crystalline dolomite (type 2) shows planar‐s to planar‐e textures, commonly occurs in the Lower Winnipegosis and Brightholme members, and decreases upward in abundance. The ⁸⁷Sr/⁸⁶Sr ratios of type 1 dolomite (0·70795 to 0·70807) fall within the estimated Sr‐isotopic range for Middle Devonian marine carbonates. Stratigraphic, petrographic and geochemical data constrain the formation of type 1 dolomite to hypersaline sea water in a near‐surface environment, after marine cementation and sub‐aerial diagenesis and prior to precipitation of the Middle Devonian Leofnard salts. Movement of dolomitizing fluids could be driven by density differences and elevation head. The shift to lower δ¹⁸O values of type 1 dolomite [?7·4 to ?5·1‰ Vienna Pee Dee Belemnite (VPDB)] is interpreted as the result of recrystallization at elevated temperatures during burial. Type 2 dolomite has higher ⁸⁷Sr/⁸⁶Sr ratios (0·70809–0·70928), suggesting that the dolomite probably formed from basinal fluids with an increased richness in the radiogenic Sr isotope. In type 2 dolomite, Sr²⁺ concentrations are lower, and Fe²⁺ and Mn²⁺ concentrations are higher, compared with the associated limestone and type 1 dolomite. Type 2 dolomite is interpreted as having been formed from upward‐migrating basinal fluids during latest Devonian and Carboniferous period.     

Methane‐related microbial gypsum calcitization in stromatolites of a marine evaporative setting (Münder Formation,Upper Jurassic,Hils Syncline,north Germany)

Fossil stromatolites may reveal information about their hydrochemical palaeoenvironment, provided that assignment to a specific microbial community and a corresponding biogeochemical mechanism of formation can be made. Tithonian stromatolites of the Münder Formation at Thüste, north Germany, have traditionally been considered as formed by intertidal cyanobacterial communities. However, thin sections of the stromatolites show elongated angular traces of former gypsum crystals in a dense arrangement, but no algal or cyanobacterial filament traces. Moreover, high Fe²⁺ and Mn²⁺ contents, oxygen‐isotope and sulphur‐isotope ratios of carbonate‐bound sulphates, and sulphurized hydrocarbon biomarkers of the stromatolitic carbonate indicate that CaCO₃ precipitation occurred near the oxic–anoxic interface as a result of intensive bacterial sulphur cycling rather than photosynthetic activity. Furthermore, anaerobic oxidation of methane by Archaea may have driven CaCO₃ precipitation in deeper parts of the biofilm community, as reflected by high concentrations of squalane with a strongly negative δ¹³C in conjunction with evaporite pseudomorphs showing extremely low δ¹³C_Carb ratios. Consequently, the Thüste stromatolites are now interpreted as having initially formed by gypsum impregnation of biofilms. Subsequently, early Mg‐calcitic calcitization within the biofilms occurred because of combined bacterial iron, manganese and sulphate reduction, with an increasing contribution of anaerobic oxidation of methane with depth. This model plausibly explains the prominent preservation of signals derived from oxygen‐independent metabolic pathways, whereas virtually no geochemical record exists for an aerobic community that may, nevertheless, have prevailed at the stromatolite surface. Photic‐zone stromatolites with a prominent signal of anaerobic oxidation of methane may be common in, and indicative of, oxygen‐depleted sulphate‐bearing environments with high rates of methane production, conditions that possibly were fulfilled at the Archaean to Proterozoic transition.     

Anomalous unradiogenic 87Sr//86Sr ratios in ultrahigh‐pressure crustal carbonates – evidence for fluid infiltration during deep subduction?

Marbles from Changpu (Dabie Shan, eastern China), subducted to 4.4 GPa, have ⁸⁷Sr/⁸⁶Sr values < 0.7040. These low ⁸⁷Sr/⁸⁶Sr values, which would imply a sedimentation age > 2 Ga if considered as primary signature, reflect fluid–rock interaction with a fluid from a low‐⁸⁷Sr/⁸⁶Sr source. The introduction of low‐⁸⁷Sr/⁸⁶Sr was paralleled by introduction of Mg and loss of Si, K and Na in such a way that carbonates from the purest marbles have the least evolved Sr isotopic composition. Introduction of Mg is also indicated by the distribution of calcite and dolomite. Calcite forms inclusions in garnet, whereas dolomite is restricted to the matrix. These chemical changes, inferred from the mineralogy, in combination with textural evidence require a mobile metamorphic fluid. P–T–X constraints for fluid generation and for permeability increase related to mineral reactions and phase transitions suggest that the marbles acquired their anomalous Sr‐isotopic composition during subduction below 60 km. The marbles with the least radiogenic Sr isotopic composition demonstrate that crustal rocks may lose their isotopic fingerprint during deep subduction.     

Strontium-isotope stratigraphy as a constraint on the age of condensed levels: examples from the Jurassic of the Subbetic Zone (southern Spain)

Condensed levels are often characterized by reworked fossils that may lead to incorrect age assessments. Strontium‐isotope stratigraphy is an important chronostratigraphic tool that can be used to verify the biostratigraphic information from condensed beds. This paper describes a study of the ⁸⁷Sr/⁸⁶Sr isotope ratios of 56 belemnite samples collected from 28 stratigraphic sections of the boundary between the Upper Member of the Gavilán Formation and the Zegrí Formation (Pliensbachian, Subbetic Zone). The petrographic and geochemical data (δ¹⁸O, δ¹³C, concentrations of Fe, Mn and Mg, and the Sr/Mn ratio) suggest that the belemnites have preserved their original marine geochemical composition. After plotting the samples in diagrams of ⁸⁷Sr/⁸⁶Sr values against time according to their biostratigraphic age, four different groups (A, B, C and D) were obtained with respect to the reference curve. In groups A and B, the age deduced from the Sr‐isotope ratio is in total or partial agreement, respectively, with the biostratigraphic age; therefore the ⁸⁷Sr/⁸⁶Sr ratio is a good method for the dating, correlation and assessment of biostratigraphic results. In groups C and D, the SIS age and the biostratigraphic age do not coincide. A graphic procedure is presented as a suitable methodology to constrain the age of the samples showing an SIS age that differs from the relative age deduced (by biostratigraphy or stratigraphic correlation) for the bed they were collected in. These situations are interpreted as being the result of reworking of the belemnites (group C) or ammonites (group D) that are included in condensed levels. These condensed levels formed during the maximum flooding event that led to the drowning of the Gavilán carbonate platform. The methodology supplied in this paper represents a valuable tool in identifying reworking processes, improving correlation and constraining biochronostratigraphic results. The values of ⁸⁷Sr/⁸⁶Sr represent a new contribution to the data set of ⁸⁷Sr/⁸⁶Sr ratios for the Pliensbachian.     

The role and impact of freshwater–seawater mixing zones in the maturation of regional dolomite bodies within the proto Floridan Aquifer, USA

Palaeogene dolostones from the sub‐surface of Florida are ideal for the study of dolomite maturation because they record the early stages of a secondary dolomite overprint without destruction by later diagenetic overprints. Two distinct dolomite textures occur in the dolostones of the Upper Eocene Ocala and Lower Oligocene Suwannee limestones in west‐central Florida: a porous and permeable sucrosic dolomite and a less porous and relatively impermeable indurated non‐sucrosic dolomite. In both textures, the initial matrix dolomite is dully luminescent, whereas the secondary overprint is dominantly luminescent cement in the Suwannee and only neomorphic luminescent dolomite in the Ocala. The abundance of luminescent dolomite ranges from 2% to 38%, which translates to 1·6 km³ of material in the Suwannee and 13·5 km³ in the Ocala. Extrapolated trace‐element contents (Sr and Na) and δ¹⁸O values for the matrix and luminescent end‐members indicate a marine origin for the matrix dolomite in both units, and a freshwater–seawater mixing‐zone origin for the secondary luminescent dolomites. The δ¹⁸O values indicate that a saline, middle mixing‐zone environment overprinted the Suwannee but a more dilute mixing zone affected the Ocala. Fluid–fluid mixing models constrained by modern Floridan aquifer hydrochemistry and extrapolated ⁸⁷Sr/⁸⁶Sr values of the luminescent phases indicate that the mixing zones operated during the Late Miocene to Pliocene in the Ocala and affected the Suwannee in the Pliocene. The luminescent Suwannee mixing‐zone cement reduced porosity up to threefold and permeability up to 100‐fold, which converted many sucrosic dolomites to indurated dolomites. By contrast, the neomorphic luminescent Ocala dolomite did not have an appreciable impact on the maturations. Although freshwater–seawater mixing zones were not the sites of the initial dolomitization, the mixing‐zone environment did dramatically overprint and mature the regionally widespread dolomites of the Ocala and Suwannee limestones. This maturation occurred shortly after formation of the proto‐Floridan aquifer; the timing suggests the matrix dolomites were ‘ripe’ for alteration and that the only prerequisite for mixing‐zone dolomite is pre‐existing dolomite substrates to reduce kinetic barriers. In contrast to recent claims, the results of this study demonstrate that mixing zones can be effective in forming regionally significant amounts of secondary dolomite and influencing the petrophysical maturation of dolomite bodies.     

Characteristics of Breccias and C-O-Sr-S Isotope Geochemistry of the Duocaima Pb-Zn Deposit in Tuotuohe, Qinghai Province: Implications for the Ore-forming Process

The Duocaima carbonate-hosted Pb-Zn deposit is a newly found large deposit in the southern area of Qinghai Province.In this paper, the characteristics, genesis, significance to Pb-Zn mineralization of the widely developed breccias, and the ore-forming process have been carefully studied based on geological documentation of drilling holes, microscopic observations of petrography and microstructure and some stable isotope measurements.Based on the compositions of the clast and matrix, the breccias can be classified into three types: limestone clasts cemented by marl; limestone clasts with fine-grained calcareous materials; and limestone clasts cemented by hydrothermal calcite.The mineralization in the first type of breccia is weak, whereas it is strong in the latter two types of breccias.According to the locations of occurrence and structural characteristics of the breccias along with the relationship between the breccias and mineralization, part of the limestone clasts that are cemented by marl and outcrop in the contact zone between the Wudaoliang Formation(Nw) and the underlying Jiushidaoban Formation(Pj) are attributed to synsedimentary fault-genetic breccia, whereas the last of the limestone clasts that are cemented by marl and developed in the Jiushidaoban Formation(Pj) are attributed to the breccia generated by karst cave collapse; the limestone clasts with fine-grained calcareous materials and the limestone clasts cemented by hydrothermal calcite are attributed to breccia formed by hydrothermal dissolution.The breccia formed by karst collapse had consistently evolved for a long period of time, while the breccias with other origins were formed around the period of mineralization(i.e., about or slightly later than 20–16 Ma).The breccia generated by karst cave collapse and hydrothermal dissolution are somewhat related; the formation of the breccia from karst cave collapse provided open space for the later mineralization and reaction between hydrothermal fluids and host rocks, and the subsequent strong dissolution by hydrothermal fluids transformed some of the breccia formed earlier by karst cave collapse.Meanwhile, carbonate host rocks with breccias and brecciaed mineralization can be a potential sign of Mississippi Valley Type(MVT) deposits and important indicators for regional mineral exploration.The δ13CV-PDB, δ18OVSMOW, and 87Sr/86 Sr values of hydrothermal calcite in the Duocaima deposit range from 4.3‰ to 7.1‰, 14.9‰ to 20.1‰, and 0.707494 to 0.708185, respectively; the δ13CV-PDB, δ18OV-SMOW, and 87Sr/86 Sr values of the host limestones of the Jiushidaoban Formation range from 3.6‰ to 5.3‰, 18.0‰ to 20.5‰, and 0.707372 to 0.707945, respectively.The δ13CV-PDB and 87Sr/86 Sr values of hydrothermal calcite and limestone are similar, indicating single sources of C and Sr in this deposit, with the likely source being the limestone of the Jiushidaoban Formation.The minor scattering of the δ18OV-SMOW values suggests that different O isotope fluids underwent the isotope exchange reaction.The C-O-Sr isotope characteristics indicate that the host limestones experienced a dissolution and precipitation process during mineralization, which is beneficial to improving the porosity of host rocks and promoting the precipitation of metal sulfides.The δ34SV-CDT value of the breccia-type mineralization sulfides ranges from-30.4‰ to-0.3‰; that is, the δ34SV-CDT value is negative with considerable variation, illustrating that during the breccia-type mineralization process, the bacteriogenic reduction of sulfates provided the vast majority of sulfur, whereas the thermochemical reduction of sulfates was relatively unimportant.The brecciation that occurred as a result of karst cave collapse was mainly generated by the dissolution of groundwater; however, the brecciation related to hydrothermal dissolution and mineralization processes were caused by mixing of different fluids.     

Stable isotopes reveal ecological differences amongst now‐extinct proboscideans from the Cincinnati region,USA

The mobility and dietary preferences of now‐extinct proboscideans have not been comprehensively examined in the central USA. We used stable carbon (δ¹³C), oxygen (δ¹⁸O) and strontium (⁸⁷Sr/⁸⁶Sr) isotopic signatures in molar enamel to investigate the foraging ecology of four mastodons (Mammut americanum) and eight mammoths (Mammuthus spp.) from southwestern Ohio and northwestern Kentucky. We tested two hypotheses: (i) these individuals were nomadic migrants that were passing through the region when they died; and (ii) mammoths and mastodons foraged in different environments. Unexpectedly, our results suggest that 11 of the 12 sampled individuals were regional residents. With the exception of one mastodon, ⁸⁷Sr/⁸⁶Sr ratios for proboscideans and regional water samples were statistically indistinguishable; slightly lower ratios for waters suggest glacial loess has an impact on modern samples. Amongst the individuals identified as residents, ⁸⁷Sr/⁸⁶Sr ratios indicate that mammoths and mastodons foraged in discrete geographical areas, and δ¹³C values imply dietary differences between the genera, which is consistent with our expectations. Oxygen isotope values may be able to distinguish animals that lived during the Last Glacial Maximum (LGM) from those that lived more recently. Three mammoths and one mastodon yielded δ¹⁸O values that are similar to modern regional precipitation and surface water, but too high for estimated drinking water during the LGM. We propose that these individuals lived during a relatively warm period following the LGM. Compellingly, the mammoth with the highest δ¹⁸O value also has the lowest δ¹³C value, suggesting that this individual was alive after regional vegetation shifted from open parkland to deciduous forest dominated by C₃ species. Our results demonstrate that a wealth of information can be gleaned from fossil museum specimens and lay a foundation for future work on the foraging ecology of proboscideans and other extinct megafauna from the Midwest USA.     

Application of carbon isotope chemostratigraphy to the Renison dolomites,Tasmania: A Neoproterozoic age

This study uses carbon isotope chemostratigraphy to propose an age for the Success Creek Group and Crimson Creek Formation in the absence of any direct radiometric dates, palaeomagnetic or reliable palaeontological data. The δ¹³C values were determined for the least‐altered dolomite samples. Suitable samples were selected on the basis of grainsize, cathodoluminescence petrography, most enriched δ¹⁸O values (> ‐2%o) low Mn/Sr ratios and low Fe and Mn concentrations. The average least‐altered, most ¹³C‐enriched dolomicrite samples in the youngest (No. 1) dolomite horizon are + 4.6%o. This is typical of Neoproterozoic (but not Cambrian) carbonates. The δ¹³C values of all dolomite samples in the succession are significantly positive (up to + 7.5%o) and the excursion characteristic of the Proterozoic/Cambrian boundary has not been observed. The lack of negative δ¹³C values in all dolomite samples studied also suggests an absence of correlatives of Sturtian and Varanger tillites in the dolomite successions. The δ¹³C values in all three dolomite horizons suggest a Neoproterozoic age between about 820 to 570 Ma (Cryogenian to Neoproterozoic III) on the current global compilation carbon isotope curves. This age for the Success Creek Group and Crimson Creek Formation, inferred from carbon isotope chemostratigraphy, can be substantiated by other evidence. The age of the Renison dolomites is constrained by K‐Ar dates of 708 ± 6 Ma from detrital muscovite in the underlying Oonah Formation and 588 ± 8 and 600 ± 8 Ma from doleritic rock in a lithostratigraphic equivalent of the Crimson Creek Formation from the Smithton Basin. Furthermore, acritarchs and the stromatolite Baicalia cf. B. burra also suggest a Neoproterozoic rather than Cambrian age.     

Deducing the source and composition of rare earth mineralising fluids in carbonatites: insights from isotopic (C,O, <Superscript>87</Superscript>Sr/<Superscript>86</Superscript>Sr) data from Kangankunde,Malawi

Carbonatites host some of the largest and highest grade rare earth element (REE) deposits but the composition and source of their REE-mineralising fluids remains enigmatic. Using C, O and ⁸⁷Sr/⁸⁶Sr isotope data together with major and trace element compositions for the REE-rich Kangankunde carbonatite (Malawi), we show that the commonly observed, dark brown, Fe-rich carbonatite that hosts REE minerals in many carbonatites is decoupled from the REE mineral assemblage. REE-rich ferroan dolomite carbonatites, containing 8–15 wt% REE₂O₃, comprise assemblages of monazite-(Ce), strontianite and baryte forming hexagonal pseudomorphs after probable burbankite. The ⁸⁷Sr/⁸⁶Sr values (0.70302–0.70307) affirm a carbonatitic origin for these pseudomorph-forming fluids. Carbon and oxygen isotope ratios of strontianite, representing the REE mineral assemblage, indicate equilibrium between these assemblages and a carbonatite-derived, deuteric fluid between 250 and 400 °C (δ¹⁸O + 3 to + 5‰_VSMOW and δ¹³C ? 3.5 to ? 3.2‰_VPDB). In contrast, dolomite in the same samples has similar δ¹³C values but much higher δ¹⁸O, corresponding to increasing degrees of exchange with low-temperature fluids (< 125 °C), causing exsolution of Fe oxides resulting in the dark colour of these rocks. REE-rich quartz rocks, which occur outside of the intrusion, have similar δ¹⁸O and ⁸⁷Sr/⁸⁶Sr to those of the main complex, indicating both are carbonatite-derived and, locally, REE mineralisation can extend up to 1.5 km away from the intrusion. Early, REE-poor apatite-bearing dolomite carbonatite (beforsite: δ¹⁸O + 7.7 to + 10.3‰ and δ¹³C ?5.2 to ?6.0‰; ⁸⁷Sr/⁸⁶Sr 0.70296–0.70298) is not directly linked with the REE mineralisation.     

白云岩成岩相与地球化学特征--以鄂尔多斯盆地中东部马家沟组马五5-马五1亚段为例

白云岩成岩相研究对恢复其成岩环境具有重要意义。以鄂尔多斯盆地中东部马家沟组马五₅-马五₁亚段为例,利用岩芯及岩石薄片研究了白云岩的成岩相类型及岩相特征,并根据氧、碳稳定同位素、锶同位素以及主、微量元素等分析了各类成岩相的地球化学特征。结果显示,鄂尔多斯盆地中东部马五₅-马五₁亚段白云岩成岩相主要包括近地表环境下的膏盐溶蚀角砾相、活跃回流渗透云化相和隐伏回流渗透云化相,以及表生淡水环境下的风化岩溶角砾相等四类,其中受淡水或混合水影响的近地表环境下的膏盐溶蚀角砾相、活跃回流渗透云化相及隐伏回流渗透云化相白云岩样品具有相对奥陶纪海水"负偏"的δ18O和δ13C值,相对高Mn或低Fe含量,中等-强阴极发光,高于同期海水的87Sr/86Sr值以及相对较低的Al和Ti含量;而表生淡水环境下的风化岩溶角砾相白云岩样品因受表生期淡水以及大量陆源碎屑物的影响,呈现出低于同期海水的δ18O和δ13C值,相对高Mn和过高Fe含量,弱或无阴极发光,明显高于同期海水的87Sr/86Sr值以及明显较高Al和Ti含量。研究结果表明,氧、碳稳定同位素、锶同位素及主、微量元素等地化数据是识别白云岩成岩相的有效指标。     

Zebra dolomitization as a result of focused fluid flow in the Rocky Mountains Fold and Thrust Belt, Canada

Discordant zebra dolomite bodies occur locally in the Middle Cambrian Cathedral and Eldon Formations of the Main Ranges of the Canadian Rocky Mountains Fold and Thrust Belt. They are characterized by alternating dark grey (a) and white (b) bands, forming an ‘abba’ diagenetic cyclicity. These bands developed parallel to both bedding and cleavage. Dark grey (a) bands consist of fine (< 300 μm) non-planar crystalline impure dolomite. The white (b) bands are composed of coarse (up to several millimetres) milky-white pure saddle dolomites (b1) which are often covered by pore-lining zoned dolomite (b2). The b phases often possess a saddle-shaped morphology. In contrast to the replacement origin of the a dolomite, the zoned b2 dolomite rims are interpreted as a cement formed in open cavities. The b1 dolomite is interpreted as the result of recrystallization with diagenetic leaching of non-carbonate components. All the zebra dolomites studied are (nearly) stoichiometric and are characterized by enriched Na and depleted Sr concentrations. Fe and Mn concentrations in these dolomites differ depending on the sample locality. Fluid inclusion data indicate that the dolomites formed from relatively hot (T_H = 130–200 °C), saline (20–23 wt% CaCl₂ eq.) fluids. A diagenetic high temperature origin is also supported by depleted δ¹⁸O values (−20 to −14‰ VPDB). A contribution of ⁸⁷Sr-enriched fluids is reflected in the ⁸⁷Sr/⁸⁶Sr values (0·7091–0·7123). Zebra dolomite development is explained by focused fluid flow, which exploited areas of structural weaknesses (e.g. basin-platform, rim areas, faults, etc.). Expulsion of hot basinal brines in a tectonically active regime generated overpressures, which explains the development of secondary porosity during zebra dolomitization as well as the intra-zebra fracturing at decimetre to micrometre scale.     

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

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

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).     

Geochemical fingerprints of dolomitization in Bahamian carbonates: Evidence from sulphur,calcium, magnesium and clumped isotopes

In an effort to constrain the mechanism of dolomitization in Neogene dolomites in the Bahamas and improve understanding of the use of chemostratigraphic tracers in shallow‐water carbonate sediments the δ³⁴S, Δ₄₇, δ¹³C, δ¹⁸O, δ^44/40Ca and δ²⁶Mg values and Sr concentrations have been measured in dolomitized intervals from the Clino core, drilled on the margin of Great Bahama Bank and two other cores (Unda and San Salvador) in the Bahamas. The Unda and San Salvador cores have massively dolomitized intervals that have carbonate associated sulphate δ³⁴S values similar to those found in contemporaneous seawater and δ^44/40Ca, δ²⁶Mg values, Sr contents and Δ₄₇ temperatures (25 to 30°C) indicating relatively shallow dolomitization in a fluid‐buffered system. In contrast, dolomitized intervals in the Clino core have elevated values of carbonate associated sulphate δ³⁴S values indicating dolomitization in a more sediment‐buffered diagenetic system where bacterial sulphate reduction enriches the residual in ³⁴S, consistent with high sediment Sr concentrations and low δ^44/40Ca and high δ²⁶Mg values. Only dolomites associated with hardgrounds in the Clino core have carbonate associated δ³⁴S values similar to seawater, indicating continuous flushing of the upper layers of the sediment by seawater during sedimentary hiatuses. This interpretation is supported by changes to more positive δ^44/40Ca values at hardground surfaces. All dolomites, whether they formed in an open fluid‐buffered or closed sediment‐buffered diagenetic system have similar δ²⁶Mg values suggesting that the HMC transformed to dolomite. The clumped isotope derived temperatures in the dolomitized intervals in Clino yield temperatures that are higher than normal, possibly indicating a kinetic isotope effect on dolomite Δ₄₇ values associated with carbonate formation through bacterial sulphate reduction. The findings of this study highlight the utility of applying multiple geochemical proxies to disentangle the diagenetic history of shallow‐water carbonate sediments and caution against simple interpretations of stratigraphic variability in these geochemical proxies as indicating changes in the global geochemical cycling of these elements in seawater.     

Isotope hydrology of the Chalk River Laboratories site,Ontario, Canada

This paper presents results of hydrochemical and isotopic analyses of groundwater (fracture water) and porewater, and physical property and water content measurements of bedrock core at the Chalk River Laboratories (CRL) site in Ontario. Density and water contents were determined and water-loss porosity values were calculated for core samples. Average and standard deviations of density and water-loss porosity of 50 core samples from four boreholes are 2.73 ± 12 g/cc and 1.32 ± 1.24 percent. Respective median values are 2.68 and 0.83 indicating a positive skewness in the distributions. Groundwater samples from four deep boreholes were analyzed for strontium (⁸⁷Sr/⁸⁶Sr) and uranium (²³⁴U/²³⁸U) isotope ratios. Oxygen and hydrogen isotope analyses and selected solute concentrations determined by CRL are included for comparison. Groundwater from borehole CRG-1 in a zone between approximately +60 and −240 m elevation is relatively depleted in δ¹⁸O and δ²H perhaps reflecting a slug of water recharged during colder climatic conditions. Porewater was extracted from core samples by centrifugation and analyzed for major dissolved ions and for strontium and uranium isotopes. On average, the extracted water contains 15 times larger concentration of solutes than the groundwater. ²³⁴U/²³⁸U and correlation of ⁸⁷Sr/⁸⁶Sr with Rb/Sr values indicate that the porewater may be substantially older than the groundwater. Results of this study show that the Precambrian gneisses at Chalk River are similar in physical properties and hydrochemical aspects to crystalline rocks being considered for the construction of nuclear waste repositories in other regions.