Formation of carbonate concretions in surface sediments of two mud mounds,offshore Costa Rica: a stable isotope study

The surface sediments of two mud mounds (“Mound 11” and “Mound 12”) offshore southwest Costa Rica contain abundant authigenic carbonate concretions dominated by high-Mg calcite (14–20 mol-% MgCO₃). Pore fluid geochemical profiles (sulfate, sulfide, methane, alkalinity, Ca and Mg) indicate recent carbonate precipitation within the zone of anaerobic oxidation of methane (AOM) at variable depths. The current location of the authigenic carbonate concretions is, however, not related to the present location of the AOM zone, suggesting mineral precipitation under past geochemical conditions as well as changes in the flow rates of upward migrating fluids. Stable oxygen and carbon isotope analysis of authigenic carbonate concretions yielded δ¹⁸O_carbonate values ranging between 34.0 and 37.7 ‰ Vienna standard mean ocean water (VSMOW) and δ¹³C_carbonate values from ?52.2 to ?14.2 ‰ Vienna Pee Dee belemnite (VPDB). Assuming that no temperature changes occurred during mineral formation, the authigenic carbonate concretions have been formed at in situ temperature of 4–5 °C. The δ¹⁸O_carbonate values suggest mineral formation from seawater-derived pore fluid (δ¹⁸O_porefluid = 0 ‰ VSMOW) for Mound 12 carbonate concretions but also the presence of an emanating diagenetic fluid (δ¹⁸O_porefluid ≈5 ‰) in Mound 11. A positive correlation between δ¹³C_carbonate and δ¹⁸O_carbonate is observed, indicating the admixing of two different sources of dissolved carbon and oxygen in the sediments of the two mounds. The carbon of these sources are (1) marine bicarbonate (δ¹³C_porefluid ≈0 ‰) and (2) bicarbonate which formed during the AOM (δ¹³C_porefluid ≈?70 ‰). Furthermore, the δ¹⁸O_porefluid composition, with values up to +4.7 ‰ Vienna standard mean ocean water (VSMOW), is interpreted to be affected by the presence of emanating, freshened and boron-enriched fluids. Earlier, it has been shown that the origin of ¹⁸O-enriched fluids are deep diagenetic processes as it was indicated by the presence of methane with thermogenic signature (δ¹³C_CH4 = ?38 ‰). A combination of present geochemical data with geophysical observations indicates that Mounds 11 and 12 represent a single fluid system interconnected by deep-seated fault(s).     

Cold-seep-driven carbonate deposits at the Central American forearc: contrasting evolution and timing in escarpment and mound settings

Continuous surface cores of cold-seep carbonates were recovered offshore Pacific Nicaragua and Costa Rica from 800 to 1,500-m water depths (Meteor 66/3) in order to decipher their evolution and methane enriched fluid emanation in contrasting geological settings. Cores from the mounds Iguana, Perezoso, Baula V and from the Jaco Scarp escarpment were used for a multi-method approach. For both settings aragonite was revealed as dominant authigenic carbonate phase in vein fillings and matrix cementation, followed by Mg-calcite as second most abundant. This common precipitation process of CaCO₃ polymorphs could be ascribed as indirectly driven by chemical changes of the advecting pore water due to anaerobic oxidation of methane. A more direct influence of seep-related microbial activity on the authigenic mineral assemblage in both settings is probably reflected by the observed minor amounts of dolomite and a dolomite-like CaMg carbonate (MgCO₃ ~ 42 %). δ¹³C data of Jaco Scarp samples are significantly lower (?43 to ?56 ‰ PDB) than for mound samples (?22 to ?36 ‰ PDB), indicating differences in fluid composition and origin. Noteworthy, δ¹⁸O values of Scarp samples correlate most closely with the ocean signature at their time of formation. Documenting the archive potential, a high resolution case study of a mound core implies at least 40 changes in fluid supply within a time interval of approximately 14 ky. As most striking difference, the age data indicate a late-stage downward-progressing cementation front for all three mound cap structures (approx. 2–5 cm/ky), but a significantly faster upward carbonate buildup in the bulging sediments on top of the scarp environment (approx. 120 cm/ky). The latter data set leads to the hypothesis of chemoherm carbonate emplacement in accord with reported sedimentation rates until decompression of the advective fluid system, probably caused by the Jaco Scarp landslide and dating this to approximately 13,000 years ago.     

The structure and genesis of limestones at the boundary between the Abalak and Bazhenov formations in Central West Siberia

In the central West-Siberian basin, fractured and cavernous carbonate rocks that are often oilbearing, which are referred to as correlation layer 1 (CL1), are frequently present at the top of the Abalak formation and/or at the bottom of the Bazhenov formation. They are sporadically distributed over the profile and the area; their genesis is still not completely clear. The structural features and oil-bearing capacity of carbonate rocks have been studied, as well at the distributions of carbon and oxygen stable isotopes from bulk rocks and calcite filling fractures in the CL1 layer that was penetrated by six wells. The spherolitic microstructure of limestones together with the carbon and oxygen isotope distributions (δ¹³C =–14 to–26‰ VPDB; δ¹⁸O = 0 to–5‰ VPDB) indicate the precipitation of carbonate material due to microbial activity on the surface and/or in the upper part of sediments at high methane concentrations. The fractures and caverns in limestones are frequently oil-bearing; they contain coarse crystals of calcite, pyrite, quartz, and, more rarely, barite. This degree of mineralization and the isotope composition of calcite oxygen (up to–18‰ VPDB) indicate that calcite precipitates at elevated temperature (up to 120°C) from the hydrothermal fluids that could migrate from underlying strata.     

Variations of the Ca/Ca ratio in seawater during the past 24 million years: evidence from δCa and δO values of Miocene phosphates

The Ca isotope variation of 11 Miocene and Pleistocene, authigenic, marine phosphates is rather small compared to the corresponding variation in δ¹⁸O values. The δ⁴⁴Ca values are not correlated with the δ¹⁸O values and, therefore, they are not temperature controlled. It is likely that the δ⁴⁴Ca values of the phosphorites reflect the variation in the δ⁴⁴Ca values of paleo-seawater but, in contrast to Sr, not the isotopic composition of seawater itself. Furthermore, Ca and Sr isotopic compositions are decoupled with decreasing stratigraphic age of the phosphate peloids with Sr isotopic compositions changing to more radiogenic values while Ca isotopic compositions remain rather stable. All samples have δ⁴⁴Ca values below present-day seawater values, suggesting that phosphate formation discriminates against heavy Ca isotopes.Phosphorites and carbonaceous sediments have a similar Ca isotopic variation during the Miocene. A systematic and more or less constant shift between marine carbonates and phosphates is observed: the phosphate samples are slightly less enriched in ⁴⁰Ca compared to carbonates. This shift has been related to a mineral-dependent kinetic mass fractionation during precipitation from seawater. The rather stable δ⁴⁴Ca value for the 19 to 9 Ma old phosphorites points to a constant δ⁴⁴Ca fractionation of about 1.1 between seawater and phosphorites during the past and suggests steady-state conditions for the Mid-Miocene seawater (sedimentation flux equals erosion flux).     

Isotopic evidence for the incorporation of methane-derived carbon into foraminifera from modern methane seeps, Hydrate Ridge, Northeast Pacific

The presence of modern methane seeps at Hydrate Ridge, offshore Oregon, provide an opportunity to study the influence of methane seeps on the ecology and geochemistry of living foraminifera. A series of cores were collected from the southern summit of Hydrate Ridge in 2002. Samples were preserved and stained to determine the δ¹³C composition of three species of live (stained) and dead benthic foraminifera: Uvigerina peregrina, Cibicidoides mckannai, and Globobulimina auriculata. Specimens were examined under light and Scanning Electron Microscopy (SEM) and exhibit no evidence of diagenesis or authigenic carbonate precipitation. Individual living foraminifera from seep sites recorded δ¹³C values from −0.4‰ to −21.2‰, indicating the isotopic influence of high methane concentrations. Average δ¹³C values (calculated from single specimens) range from −1.28 to −5.64‰ at seep sites, and −0.81 to −0.85‰ at a control (off seep) site.Two distinct seep environments, distinguished by the presence of microbial mats or clam fields, were studied to determine environmental influences on δ¹³C values. Individual foraminifera from microbial mat sites exhibited more depleted δ¹³C values than those from clam field sites. We interpret these differences as an effect of food source and/or symbiotic microbes on foraminiferal carbon isotopic values, acting to magnify the negative δ¹³C values recorded via the DIC pool. No statistical difference was found between δ¹³C values of live vs. dead specimens. This suggests that authigenic carbonate precipitation did not play a dominant role in the observed isotopic compositions. However, a few dead specimens with extremely negative δ¹³C composition (<-12‰) do indicate potential evidence for an authigenic influence on the recorded δ¹³C composition.     

Extraordinary C enrichment of diether lipids at the Lost City Hydrothermal Field indicates a carbon-limited ecosystem

Active and inactive carbonate chimneys from the Lost City Hydrothermal Field contain up to 0.6% organic carbon with diverse lipid assemblages. The δ¹³C values of total organic carbon range from −21.5‰ vs. VPDB at an extinct carbonate chimney to −2.8‰ at a 70 °C, actively venting carbonate chimney. Samples collected at locations with total organic carbon with δ¹³C > −15‰ also contained high abundances of isoprenoidal and nonisoprenoidal diether lipids. Samples with TOC more depleted in ¹³C lacked or contained lower amounts of these diethers.Isoprenoidal diethers, including sn-2 hydroxyarchaeol, sn-3 hydroxyarchaeol, and putative dihydroxyarchaeol, are likely to derive from methanogenic archaea. These compounds have δ¹³C values ranging from −2.9 to +6.7‰ vs. VPDB. Nonisoprenoidal diethers and monoethers are presumably derived from bacteria, and have structures similar to those produced by sulfate-reducing bacteria in culture and at cold seeps. In samples that also contained abundant hydroxyarchaeols, these diethers have δ¹³C values between −11.8 and +3.6‰. In samples without abundant hydroxyarchaeols, the nonisoprenoidal diethers were typically more depleted in ¹³C, with δ¹³C as low as −28.7‰ in chimneys and −45‰ in fissures.The diethers at Lost City are probably derived from hydrogen-consuming methanogens and bacteria. High hydrogen concentrations favor methanogenesis over methanotrophy and allow the concurrent growth of methanogens and sulfate-reducing bacteria. The unusual enrichment of ¹³C in lipids can be attributed to nearly complete consumption of bioavailable carbon in vent fluids. Under carbon-limited conditions, the isotope effects that usually lead to ¹³C-depletion in organic material cannot be expressed. Consequently, metabolic products such as lipids and methane have δ¹³C values typical of abiotic carbon.     

Authigenic carbonate burial in the Late Devonian–Early Mississippian Bakken Formation (Williston Basin,USA)

Late Devonian (Famennian) marine successions globally are typified by organic-rich black shales deposited in anoxic and euxinic waters and the cessation of shelf carbonate sedimentation. This global ‘carbonate crisis’, known as the Hangenberg Event, coincides with a major extinction of reef-building metazoans and perturbations to the global carbon cycle, evidenced by positive carbon-isotope excursions of up to 4‰. It has been suggested that authigenic carbonate, formed as cements in sedimentary pore spaces during early burial diagenesis, is a significant mass fraction of the total global carbon burial flux, particularly during periods of low oxygen concentration. Because some authigenic carbonate could have originated from remineralization of organic carbon in sediments, it is possible for this reservoir to be isotopically depleted and thereby drive changes in the carbon isotopic composition of seawater. This study presents bulk isotopic and elemental analyses from fine-grained siliciclastics of the Late Devonian–Early Mississippian Bakken Formation (Williston Basin, USA) to assess the volume and isotopic composition of carbonates in these sediments. Carbonate in the Bakken black shales occurs primarily as microscopic disseminated dolomite rhombs and calcite cements that, together, comprise a significant mass-fraction (ca 9%). The elemental composition of the shales is indicative of a dynamic anoxic to sulphidic palaeoenvironment, likely supported by a fluctuating chemocline. Despite forming in an environment favourable to remineralization of organic matter and the precipitation of isotopically depleted authigenic carbonates, the majority of carbon isotope measurements of disseminated carbonate fall between −3‰ and +3‰, with systematically more depleted carbonates in the deeper-water portions of the basin. Thus, although there is evidence for a significant total mass-fraction of carbonate with contribution from remineralized organic matter, Bakken authigenic carbonates suggest that Famennian black shales are unlikely to be sufficiently ¹³C-depleted relative to water column dissolved inorganic carbon to serve as a major lever on seawater isotopic composition.     

Isotope and chemical composition of gases from mud volcanoes in the Taman Peninsula and problem of their genesis

Variations in the carbon isotope composition in gases and waters of mud volcanoes in the Taman Peninsula are studied. The δ¹³C values in CH₄ and CO₂ vary from ?59.5 to ?44.0‰ (δ¹³C_av = ?52.4 ± 5.4‰) and from ?17.8 to +22.8‰ (δ¹³C_av = +6.9 ± 9.3‰), respectively. In waters from most mud volcanoes of the peninsula, this parameter ranges from +3.3 to +33.1‰, although locally lower values are also recorded (up to ?12‰. Fractionation of carbon isotopes in the CO₂-HCO₃ system corresponds to the isotope equilibrium under Earth’s surface temperatures. The growth of carbon dioxide concentration in the gaseous phase and increase in the HCO₃ ion concentration in their water phase is accompanied by the enrichment of the latter with the heavy ¹³C isotope. The δ¹³C_TDIC value in the water-soluble carbon depends on the occurrence time of water on the Earth’s surface (exchange with atmospheric CO₂, methane oxidation, precipitation of carbonates, and other processes), in addition to its primary composition. In this connection, fluctuations in δ¹³C_TDIC values in mud volcanoes with stagnant waters may amount to 10–20‰. In the clayey pulp, concentrations of carbonate matter recalculated to CaCO₃ varies from 1–4 to 36–50 wt %. The δ¹³C value in the latter ranges from ?3.6 to +8.4‰. Carbonate matter of the clayey pulp represents a mixture of sedimentogenic and authigenic carbonates. Therefore, it is usually unbalanced in terms of the carbon isotope composition with the water-soluble CO₂ forms.     

Authigenic Carbonate Formation in the Ocean

Oceanic authigenic carbonates are classified according to the origin of carbonate carbon source using a complex methodology that includes methods of sedimentary petrography, mineralogy, isotope geochemistry, and microbiology. Mg-calcite (proto-dolomite) and aragonite predominate among the authigenic carbonates. All authigenic carbonates are depleted in heavy carbon isotope ¹³ and enriched in heavy oxygen isotope ¹⁸O (in PDB system), indicating biological fractionation of isotopes during the carbonate formation. Results obtained show that authigenic carbonate formation is a biogeochemical (microbial) process, which involves carbon from ancient sedimentary rocks, abiogenic methane, and bicarbonate-ion of hydrothermal fluids into the modern carbon cycle.     

Formation of 18O-depleted dolomite within a marine evaporitic sequence, Triassic Reichenhall Formation, Austria

Dark grey, bituminous dolostones interbedded with marine-derived anhydrite horizons occur in the Triassic Reichenhall Formation of western Austria. Fossils are rare and indicate a hostile, hypersaline depositional environment. The dolomites are finely crystalline, fairly stoichiometric, well ordered and non-ferroan. Closely spaced samples (94 in total) of individual dolomite units have been analysed for their carbon and oxygen isotopic composition. The data indicate surprisingly low δ¹⁸O values (-5.7 to -2.1%₀ PDB), whereas the δ¹³C values are comparable to the contemporary Triassic seawater (+0.2 to +2.6%₀ PDB). Sedimentological evidence, including (i) lack of any evidence for extensive dissolution, (ii) distinct oxygen and carbon isotope ratios of individual dolomite units, (iii) covariance of carbon and oxygen isotopes within some dolomite layers and (iv) inclusions of celestite in dolomite, indicates a nearly closed system after early diagenesis. Combining this information with water-rock interaction calculations suggests that the lightest oxygen isotope compositions are the result of freshwater influx into the basin during very early dolomite formation. A secondary factor may be dolomite recrystallization at elevated temperatures during burial.     

Carbon isotope geochemistry of the Precambrian Lomagundi carbonate province,Rhodesia

Carbon isotope measurements carried out on 67 dolomite samples from the Middle Precambrian Lomagundi Group (Rhodesia) have yielded a δ¹³C mean of +8.2 ± 2.6%. vs PDB. With the outcrop of these dolomites extending over a distance of almost 300 km, the Lomagundi dolomite faces is likely to represent the largest isotopically anomalous sedimentary carbonate province ever recorded. It is concluded that the anomalous carbonates formed in a closed basin whose δ¹³C level had been substantially increased as a result of a preferential removal (within sedimentary organics) of the light carbon isotope.     

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

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

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.     

C and O stable isotope variability in recent freshwater carbonates (River Krka, Croatia)

Three types of recent carbonate precipitates from the River Krka, Croatia, were analysed: (1) bulk tufa from four main cascades in a 34 km long section of the river flow through the Krka National Park; (2) a laminar stromatolite‐like incrustation formed in the tunnel of a hydroelectric power plant close to the lowest cascade; and (3) recent precipitates collected on artificial substrates during winter, spring and summer periods. Stable isotope compositions of carbon (δ¹³C) and oxygen (δ¹⁸O) in the carbonate and organic carbon (δ¹³C_org) were determined and compared with δ¹⁸O of water and δ¹³C of dissolved inorganic carbon (DIC). The source of DIC, which provides C for tufa precipitation, was determined from the slope of the line ([DIC]/[DIC₀]?1) vs. (δ¹³C‐DIC × ([DIC]/[DIC₀])) ( Sayles & Curry, 1988 ). The δ¹³C value of added DIC was ?13·6‰, corresponding to the dissolution of CO₂ with δ¹³C between ?19·5 and ?23·0‰ Vienna Pee Dee Belemnite (VPDB). The observed difference between the measured and calculated equilibrium temperature of precipitation of bulk tufa barriers indicates that the higher the water temperature, the larger the error in the estimated temperature of precipitation. This implies that the climatic signals may be valid only in tufas precipitated at lower and relatively stable temperatures. The laminar crust comprising a continuous record of the last 40 years of precipitation shows a consistent trend of increasing δ¹³C and decreasing δ¹⁸O. The lack of covariation between δ¹³C and δ¹⁸O indicates that precipitation of calcite was not kinetically controlled for either of the elements. δ¹³C and δ¹⁸O of precipitates collected on different artificial substrates show that surface characteristics both of substrates and colonizing biota play an important role in C and O isotope fractionation during carbonate precipitation.     

Dolomite formation in the dynamic deep biosphere: results from the Peru Margin

Early diagenetic dolomite beds were sampled during the Ocean Drilling Programme (ODP) Leg 201 at four reoccupied ODP Leg 112 sites on the Peru continental margin (Sites 1227/684, 1228/680, 1229/681 and 1230/685) and analysed for petrography, mineralogy, δ¹³C, δ¹⁸O and ⁸⁷Sr/⁸⁶Sr values. The results are compared with the chemistry, and δ¹³C and ⁸⁷Sr/⁸⁶Sr values of the associated porewater. Petrographic relationships indicate that dolomite forms as a primary precipitate in porous diatom ooze and siliciclastic sediment and is not replacing the small amounts of precursor carbonate. Dolomite precipitation often pre‐dates the formation of framboidal pyrite. Most dolomite layers show ⁸⁷Sr/⁸⁶Sr‐ratios similar to the composition of Quaternary seawater and do not indicate a contribution from the hypersaline brine, which is present at a greater burial depth. Also, the δ¹³C values of the dolomite are not in equilibrium with the δ¹³C values of the dissolved inorganic carbon in the associated modern porewater. Both petrography and ⁸⁷Sr/⁸⁶Sr ratios suggest a shallow depth of dolomite formation in the uppermost sediment (<30 m below the seafloor). A significant depletion in the dissolved Mg and Ca in the porewater constrains the present site of dolomite precipitation, which co‐occurs with a sharp increase in alkalinity and microbial cell concentration at the sulphate–methane interface. It has been hypothesized that microbial ‘hot‐spots’, such as the sulphate–methane interface, may act as focused sites of dolomite precipitation. Varying δ¹³C values from −15‰ to +15‰ for the dolomite are consistent with precipitation at a dynamic sulphate–methane interface, where δ¹³C of the dissolved inorganic carbon would likewise be variable. A dynamic deep biosphere with upward and downward migration of the sulphate–methane interface can be simulated using a simple numerical diffusion model for sulphate concentration in a sedimentary sequence with variable input of organic matter. Thus, the study of dolomite layers in ancient organic carbon‐rich sedimentary sequences can provide a useful window into the palaeo‐dynamics of the deep biosphere.     

Isotope Geochemistry of Groundwater from Fractured Dolomite Aquifers in Central Slovenia

The hydrogeochemistry and isotope geochemistry of groundwater from 85 wells in fractured dolomite aquifers of Central Slovenia were investigated. This groundwater represents waters strongly influenced by chemical weathering of dolomite with an average of δ¹³C_CARB value of +2.2 ‰. The major groundwater geochemical composition is HCO₃ ^? > Ca²⁺ > Mg²⁺. Several differences in hydrogeochemical properties among the classes of dolomites were observed when they were divided based on their age and sedimentological properties, with a clear distinction of pure dolomites exhibiting high Mg²⁺/Ca²⁺ ratios and low Na⁺, K⁺ and Si values. Trace element and nutrient concentrations (SO₄ ^2?, NO₃ ^?) were low, implying that karstic and fractured dolomite aquifers are of good quality to be used as tap water. Groundwater was generally slightly oversaturated with respect to calcite and dolomite, and dissolved CO₂ was up to 46 times supersaturated relative to the atmosphere. The isotopic composition of oxygen (δ¹⁸O_H2O), hydrogen (δD_H2O) and tritium ranged from ?10.3 to ?8.4 ‰, from ?68.5 to ?52.7 ‰ and from 3.5 TU to 10.5 TU, respectively. δ¹⁸O and δD values fell between the GMWL (Global Meteoric Water Line) and the MMWL (Mediterranean Meteoric Water Line) and indicate recharge from precipitation with little evaporation. The tritium activity in groundwater suggests that groundwater is generally younger than 50 years. δ¹³C_DIC values ranged from ?14.6 to ?9.3 ‰ and indicated groundwater with a contribution of degraded organic matter/dissolved inorganic carbon in the aquifer. The mass balances for groundwater interacting with carbonate rocks suggested that carbonate dissolution contributes from 43.7 to 65.4 % and degradation of organic matter from 34.6 to 56.3 %.     

海底天然气渗漏系统微生物作用及冷泉碳酸盐岩的特征

海底天然气渗漏系统是全球海洋环境中广泛分布的自然现象。部分渗漏天然气通过细菌作用转变为二氧化碳,同时海水硫酸盐被还原为硫化氢, 与孔隙水中的钙和铁结合而沉淀冷泉碳酸盐岩。冷泉碳酸盐岩的常见矿物有微晶方解石、文石、白云石和黄铁矿。冷泉碳酸盐岩常发育一些特殊的组构, 如黄铁矿环带结核、溶蚀面、平底晶洞、凝块和向下生长的叠层石组构等。碳酸盐岩特别负的δ13C值指示碳来源于生物成因的甲烷, 而18O富集可能与天然气水合物的分解有关。冷泉碳酸盐岩中黄铁矿的δ34S值低于海水的, 这指示硫来源于微生物还原的海水硫。冷泉碳酸盐岩中的生物标志化合物及其极负的δ13C值指示微生物的生命代谢活动。     

Constraining magnesium cycling in marine sediments using magnesium isotopes

Magnesium concentrations in deep-sea sediment pore-fluids typically decrease down core due to net precipitation of dolomite or clay minerals in the sediments or underlying crust. To better characterize and differentiate these processes, we have measured magnesium isotopes in pore-fluids and sediment samples from Ocean Drilling Program sites (1082, 1086, 1012, 984, 1219, and 925) that span a range of oceanographic settings. At all sites, magnesium concentrations decrease with depth. At sites where diagenetic reactions are dominated by the respiration of organic carbon, pore-fluid δ²⁶Mg values increase with depth by as much as 2‰. Because carbonates preferentially incorporate ²⁴Mg (low δ²⁶Mg), the increase in pore-fluid δ²⁶Mg values at these sites is consistent with the removal of magnesium in Mg-carbonate (dolomite). In contrast, at sites where the respiration of organic carbon is not important and/or weatherable minerals are abundant, pore-fluid δ²⁶Mg values decrease with depth by up to 2‰. The decline in pore-fluid δ²⁶Mg at these sites is consistent with a magnesium sink that is isotopically enriched relative to the pore-fluid. The identity of this enriched magnesium sink is likely clay minerals. Using a simple 1D diffusion-advection-reaction model of pore-fluid magnesium, we estimate rates of net magnesium uptake/removal and associated net magnesium isotope fractionation factors for sources and sinks at all sites. Independent estimates of magnesium isotope fractionation during dolomite precipitation from measured δ²⁶Mg values of dolomite samples from sites 1082 and 1012 are very similar to modeled net fractionation factors at these sites, suggesting that local exchange of magnesium between sediment and pore-fluid at these sites can be neglected. Our results indicate that the magnesium incorporated in dolomite is 2.0-2.7‰ depleted in δ²⁶Mg relative to the precipitating fluid. Assuming local exchange of magnesium is minor at the rest of the studied sites, our results suggest that magnesium incorporated into clay minerals is enriched in δ²⁶Mg by 0‰ to +1.25‰ relative to the precipitating fluid. This work demonstrates the utility of magnesium isotopes as a tracer for magnesium sources/sinks in low-temperature aqueous systems.     

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).     

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.