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).     

Pleistocene geochemical stratigraphy of the borehole 1317E (IODP Expedition 307) in Porcupine Seabight,SW of Ireland: applications to palaeoceanography and palaeoclimate of the coral mound development

Stable isotopes and element compositions of the fine‐grained matrix were measured for IODP Expedition 307 Hole U1317E drilled from the summit of Challenger Mound in Porcupine Seabight, northeast Atlantic, to explore the palaeoceanographic and palaeoclimatic background to development of the deep‐water coral mound. The 155 m long mound section was divided into two units by an unconformity at 23.6 mbsf: Unit M1 (2.6–1.7 Ma) and Unit M2 (1.0–0.5 Ma). Results from 519 specimens show a difference in δ¹³C value between Unit M1 (?0.6‰ to ?5.0‰) and Unit M2 (?1.0‰ to 1.0‰), but such a distinct difference was not seen in δ¹⁸O values (1.0‰–2.5‰), CaCO₃ content (40–60 wt%), Sr/Ca ratio (2.0–8.0 mmol mol^?1), and Mg/Ca ratio (10.0–20.0 mmol mol^?1) through the mound. Positive δ¹⁸O and negative δ¹³C shifts at the mound base are consistent with the oceanographic changes in the northeast Atlantic at the beginning of the Quaternary. The positive δ¹³C regression in Unit M2 suggests a linkage to the mid Pleistocene intensified glaciation in the Northern Hemisphere. Warm Mediterranean Upper Core Water of Mediterranean Outflow Water, Eastern North Atlantic Water and cold Labrador Sea Water of North Atlantic Deep Water are key oceanographic features that cause spikes and shifts in stable isotope and element composition. However, the stable isotope values of the sediment matrix could not primarily record the glacial–interglacial eustatic/temperature change, but indirectly indicate current regimes of the intermediate oceanic layer where the coral mound grew. Similarly, elemental ratios and CaCO₃ content may not represent the productivity and temperature of surface sea water, respectively, but superpose the fractions from both surface and bottom water. It is concluded that palaeoceanographic change coupled to the Pleistocene glacial/interglacial cycles is a key control on the geochemical stratigraphy of the matrix sediments of the carbonate mound developed in Porcupine Seabight. Copyright © 2011 John Wiley & Sons, Ltd.     

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

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

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.     

Geochemical evidence of microbial activity within ooids

Ooid formation remains elusive despite their importance as palaeoclimatic indicators and important contributors to global carbonate budget. Based on stable isotopes, nutrient and elemental analyses on solid components and ooidal leachates, this study supports the notion of microbial involvement in the development of ooids from Great Bahama Bank. Carbon and nitrogen isotopic analyses on organic fractions identified geochemical signatures of microbial activity. The δ¹³C values for organic carbon in the bulk (?11·9 to ?16·9‰); intercrystalline/intracrystalline (?11·9 to 16·7‰); and intracrystalline phases (?12·4 to ?17·7‰) were similar and, except for the more enriched values of ooids from Butterfly Beach, were within the range of photosynthesisers. The δ¹⁵N values for the bulk (+0·5 to ?0·2‰); intercrystalline/intracrystalline (?0·3‰ to ?0·7‰) and intracrystalline organic matter (?0·3 to ?1·7‰) showed a narrow range consistent with nitrogen fixation. While positive δ¹⁵N and δ¹⁸O values of the leached from the ooids provided evidence of denitrification, the carbonate associated sulphate δ³⁴S_CAS of the bulk sediments (+19·2 to +19·6‰) and δ³⁴S of the leachates (+16·6 to +18·3‰) provided weak indication of sulphate reduction, suggesting either that high concentrations of isotopically enriched S are overriding bio‐signatures of sulphate reduction or that microbes are preferentially using as an electron acceptor. In contrast, the elevated sulphate concentrations of the leachates suggest the occurrence of microbial sulphide oxidation within ooids. The high Mg/Ca of the leachates and scanning electron microscope analyses provide putative evidence of amorphous calcium carbonate and a formative role in CaCO₃ precipitation. Together, these findings indicate that a redox dependent microbial consortium may influence CaCO₃ precipitation in the form of ooid accretion, cementation and micritization. It is also inferred that ooid deposits are not suitable indicators of palaeoclimate because ooids are affected throughout their life by a complex chain of abiotic and biological processes which can lead to large geochemical offsets.     

Changes in carbon and oxygen isotope composition during limestone diagenesis

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

Origin of the Okrouhlá Radouň episyenite-hosted uranium deposit,Bohemian Massif,Czech Republic: fluid inclusion and stable isotope constraints

The Okrouhlá Radouň shear zone hosted uranium deposit is developed along the contact of Variscan granites and high-grade metasedimentary rocks of the Moldanubian Zone of the Bohemian Massif. The pre-ore pervasive alteration of wall rocks is characterized by chloritization of mafic minerals, followed by albitization of feldspars and dissolution of quartz giving rise to episyenites. The subsequent fluid circulation led to precipitation of disseminated uraninite and coffinite, and later on, post-ore quartz and carbonate mineralization containing base metal sulfides. The fluid inclusion and stable isotope data suggest low homogenization temperatures (～50–140 °C during pre-ore albitization and post-ore carbonatization, up to 230 °C during pre-ore chloritization), variable fluid salinities (0–25 wt.% NaCl eq.), low fluid δ¹⁸O values (?10 to +2 ‰ V-SMOW), low fluid δ¹³C values (?9 to ?15 ‰ V-PDB), and highly variable ionic composition of the aqueous fluids (especially Na/Ca, Br/Cl, I/Cl, SO₄/Cl, NO₃/Cl ratios). The available data suggest participation of three fluid endmembers of primarily surficial origin during alteration and mineralization at the deposit: (1) local meteoric water, (2) Na–Ca–Cl basinal brines or shield brines, (3) SO₄–NO₃–Cl–(H)CO₃ playa-like fluids. Pre-ore albitization was caused by circulation of alkaline, oxidized, and Na-rich playa fluids, whereas basinal/shield brines and meteoric water were more important during the post-ore stage of alteration.     

Protomylonite evolution potentially revealed by the 3D depiction and fractal analysis of chemical data from a feldspar

Tourmalinization associated with peraluminous granitic intrusions in metapelitic host-rocks has been widely recorded in the Iberian Peninsula, given the importance of tourmaline as a tracer of granite magma evolution and potential indicator of Sn-W mineralizations. In the Penamacor-Monsanto granite pluton (Central Eastern Portugal, Central Iberian Zone), tourmaline occurs: (1) as accessory phase in two-mica granitic rocks, muscovite-granites and aplites, (2) in quartz (±mica)-tourmaline rocks (tourmalinites) in several exocontact locations, and (3) as a rare detrital phase in contact zone hornfels and metapelitic host-rocks. Electron microprobe and stable isotope (δ¹⁸O, δD, δ¹¹B) data provide clear distinctions between tourmaline populations from these different settings: (a) schorl–oxyschorl tourmalines from granitic rocks have variable foititic component (^X□ = 17–57 %) and Mg/(Mg + Fe) ratios (0.19–0.50 in two-mica granitic rocks, and 0.05–0.19 in the more differentiated muscovite-granite and aplites); granitic tourmalines have constant δ¹⁸O values (12.1 ± 0.1 ‰), with wider-ranging δD (?78.2 ± 4.7 ‰) and δ¹¹B (?10.7 to ?9.0 ‰) values; (b) vein/breccia oxyschorl [Mg/(Mg + Fe) = 0.31–0.44] results from late, B- and Fe-enriched magma-derived fluids and is characterized by δ¹⁸O = 12.4 ‰, δD = ?29.5 ‰, and δ¹¹B = ?9.3 ‰, while replacement tourmalines have more dravitic compositions [Mg/(Mg + Fe) = 0.26–0.64], close to that of detrital tourmaline in the surrounding metapelitic rocks, and yield relatively constant δ¹⁸O values (13.1–13.3 ‰), though wider-ranging δD (?58.5 to ?36.5 ‰) and δ¹¹B (?10.2 to ?8.8 ‰) values; and (c) detrital tourmaline in contact rocks and regional host metasediments is mainly dravite [Mg/(Mg + Fe) = 0.35–0.78] and oxydravite [Mg/(Mg + Fe) = 0.51–0.58], respectively. Boron contents of the granitic rocks are low (<650 ppm) compared to the minimum B contents normally required for tourmaline saturation in granitic melts, implying loss of B and other volatiles to the surrounding host-rocks during the late-magmatic stages. This process was responsible for tourmalinization at the exocontact of the Penamacor-Monsanto pluton, either as direct tourmaline precipitation in cavities and fractures crossing the pluton margin (vein/breccia tourmalinites), or as replacement of mafic minerals (chlorite or biotite) in the host-rocks (replacement tourmalinites) along the exocontact of the granite. Thermometry based on ¹⁸O equilibrium fractionation between tourmaline and fluid indicates that a late, B-enriched magmatic aqueous fluid (av. δ¹⁸O ~12.1 ‰, at ~600 °C) precipitated the vein/breccia tourmaline (δ¹⁸O ~12.4 ‰) at ~500–550 °C, and later interacted with the cooler surrounding host-rocks to produce tourmaline at lower temperatures (400–450 °C), and an average δ¹⁸O ~13.2 ‰, closer to the values for the host-rock. Although B-metasomatism associated with some granitic plutons in the Iberian Peninsula seems to be relatively confined in space, extending integrated studies such as this to a larger number of granitic plutons may afford us a better understanding of Variscan magmatism and related mineralizations.     

A comprehensive approach to the study of methane-seep deposits from the Lincoln Creek Formation, western Washington State, USA

ABSTRACT A comprehensive approach using palaeontology, petrography, stable isotope geochemistry and biomarker analyses was applied to the study of seven small methane‐seep carbonate deposits. These deposits are in the Oligocene part of the Lincoln Creek Formation, exposed along the Canyon and Satsop Rivers in western Washington. Each deposit preserves invertebrate fossils, many representing typical seep biota. Authigenic carbonates with δ¹³C values as low as ?51‰ PDB reveal that the carbon is predominately methane derived. Carbonates contain the irregular isoprenoid hydrocarbons 2,6,11,15‐tetramethylhexadecane (crocetane) and 2,6,10,15,19‐pentamethylicosane (PMI), lipid biomarkers diagnostic for archaea. These lipids are strongly depleted in ¹³C (δ¹³C values as low as ?120‰ PDB), indicating that archaea were involved in the anaerobic oxidation of methane. Small filaments preserved in the carbonate may represent methanotrophic archaea. Archaeal methanogenesis induced the formation of a late diagenetic phase, brownish calcite, consisting of dumbbell‐shaped crystal aggregates that exhibit δ¹³C values as high as +7‰ PDB. Clotted microfabrics of primary origin point to microbial mediation of carbonate precipitation. Downward‐directed carbonate aggregation in the seeps produced inverted stromatactoid cavities. Large filaments, interpreted as green algae based on their size, shape, arrangement and biomarkers, imply that deposition occurred, in places, in water no deeper than 210 m.     

An 8-year record of gas geochemistry and isotopic composition of methane during baseline sampling at a groundwater observation well in Alberta (Canada)

Variability in baseline groundwater methane concentrations and isotopic compositions was assessed while comparing free and dissolved gas sampling approaches for a groundwater monitoring well in Alberta (Canada) over an 8-year period. Methane concentrations in dissolved gas samples (n?=?12) were on average 4,380?±?2,452 μg/L, yielding a coefficient of variation (CV) >50 %. Methane concentrations in free gas samples (n?=?12) were on average 228,756?±?62,498 ppm by volume, yielding a CV of 27 %. Quantification of combined sampling, sample handling and analytical uncertainties was assessed via triplicate sampling (CV of 19 % and 12 % for free gas and dissolved gas methane concentrations, respectively). Free and dissolved gas samples yielded comparable methane concentration patterns and there was evidence that sampling operations and pumping rates had a marked influence on the obtained methane concentrations in free gas. δ¹³C_CH4 and δ²H_CH4 values of methane were essentially constant (?78.6?±?1.3 and ?300?±?3?‰, respectively) throughout the observation period, suggesting that methane was derived from the same biogenic source irrespective of methane concentration variations. The isotopic composition of methane constitutes a robust and highly valuable baseline parameter and increasing δ¹³C_CH4 and δ²H_CH4 values during repeat sampling may indicate influx of thermogenic methane. Careful sampling and analytical procedures with identical and repeatable approaches are required in baseline-monitoring programs to generate methane concentration and isotope data for groundwater that can be reliably compared to repeat measurements once potential impact from oil and gas development, for example, may occur.     

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

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

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

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

Fluid Inclusions and Hydrogen,Oxygen, Sulfur Isotopes of Nuri Cu‐W‐Mo Deposit in the Southern Gangdese,Tibet

The Nuri Cu‐W‐Mo deposit is located in the southern subzone of the Cenozoic Gangdese Cu‐Mo metallogenic belt. The intrusive rocks exposed in the Nuri ore district consist of quartz diorite, granodiorite, monzogranite, granite porphyry, quartz diorite porphyrite and granodiorite porphyry, all of which intrude in the Cretaceous strata of the Bima Group. Owing to the intense metasomatism and hydrothermal alteration, carbonate rocks of the Bima Group form stratiform skarn and hornfels. The mineralization at the Nuri deposit is dominated by skarn, quartz vein and porphyry type. Ore minerals are chalcopyrite, pyrite, molybdenite, scheelite, bornite and tetrahedrite, etc. The oxidized orebodies contain malachite and covellite on the surface. The mineralization of the Nuri deposit is divided into skarn stage, retrograde stage, oxide stage, quartz‐polymetallic sulfide stage and quartz‐carbonate stage. Detailed petrographic observation on the fluid inclusions in garnet, scheelite and quartz from the different stages shows that there are four types of primary fluid inclusions: two‐phase aqueous inclusions, daughter mineral‐bearing multiphase inclusions, CO₂‐rich inclusions and single‐phase inclusions. The homogenization temperature of the fluid inclusions are 280°C–386°C (skarn stage), 200°C–340°C (oxide stage), 140°C–375°C (quartz‐polymetallic sulfide stage) and 160°C–280°C (quartz‐carbonate stage), showing a temperature decreasing trend from the skarn stage to the quartz‐carbonate stage. The salinity of the corresponding stages are 2.9%–49.7 wt% (NaCl) equiv., 2.1%–7.2 wt% (NaCl) equiv._, 2.6%–55.8 wt% (NaCl) equiv. and 1.2%–15.3 wt% (NaCl) equiv., respectively. The analyses of CO₂‐rich inclusions suggest that the ore‐forming pressures are 22.1 M Pa–50.4 M Pa, corresponding to the depth of 0.9 km–2.2 km. The Laser Raman spectrum of the inclusions shows the fluid compositions are dominated in H₂O, with some CO₂ and very little CH₄, N₂, etc. δD values of garnet are between ?114.4‰ and ?108.7‰ and δ¹⁸O_H2O between 5.9‰ and 6.7‰; δD of scheelite range from ?103.2‰ to ?101.29‰ and δ¹⁸O_H2O values between 2.17‰ and 4.09‰; δD of quartz between ?110.2‰ and ?92.5‰ and δ¹⁸O_H2O between ?3.5‰ and 4.3‰. The results indicate that the fluid came from a deep magmatic hydrothermal system, and the proportion of meteoric water increased during the migration of original fluid. The δ³⁴S values of sulfides, concentrated in a rage between ?0.32‰ to 2.5‰, show that the sulfur has a homogeneous source with characteristics of magmatic sulfur. The characters of fluid inclusions, combined with hydrogen‐oxygen and sulfur isotopes data, show that the ore‐forming fluids of the Nuri deposit formed by a relatively high temperature, high salinity fluid originated from magma, which mixed with low temperature, low salinity meteoric water during the evolution. The fluid flow through wall carbonate rocks resulted in the formation of layered skarn and generated CO₂ or other gases. During the reaction, the ore‐forming fluid boiled and produced fractures when the pressure exceeded the overburden pressure. Themeteoric water mixed with the ore‐forming fluid along the fractures. The boiling changed the pressure and temperature, oxygen fugacity, physical and chemical conditions of the whole mineralization system. The escape of CO₂ from the fluid by boiling resulted in scheelite precipitation. The fluid mixing and boiling reduced the solubility of metal sulfides and led the precipitation of chalcopyrite, molybdenite, pyrite and other sulfide.     

Mineralisation of amethyst-bearing geodes in Ametista do Sul (Brazil) from low-temperature sedimentary brines: evidence from monophase liquid inclusions and stable isotopes

Fluid inclusion studies in combination with hydrogen, oxygen and sulphur isotope data provide novel insights into the genesis of giant amethyst-bearing geodes in Early Cretaceous Paraná continental flood basalts at Amestita do Sul, Brazil. Monophase liquid inclusions in colourless quartz, amethyst, calcite, barite and gypsum were analysed by microthermometry after stimulating bubble nucleation using single femtosecond laser pulses. The salinity of the fluid inclusions was determined from ice-melting temperatures and a combination of prograde and retrograde homogenisation temperatures via the density maximum of the aqueous solutions. Four mineralisation stages are distinguished. In stage I, celadonite, chalcedony and pyrite formed under reducing conditions in a thermally stable environment. Low δ³⁴S_V-CDT values of pyrite (?25 to ?32?‰) suggest biogenic sulphate reduction by organotrophic bacteria. During the subsequent stages II (amethyst, goethite and anhydrite), III (early subhedral calcite) and IV (barite, late subhedral calcite and gypsum), the oxidation state of the fluid changed towards more oxidising conditions and microbial sulphate reduction ceased. Three distinct modes of fluid salinities around 5.3, 3.4 and 0.3 wt% NaCl-equivalent characterise the mineralisation stages II, III and IV, respectively. The salinity of the stage I fluid is unknown due to lack of fluid inclusions. Variation in homogenisation temperatures and in δ¹⁸O values of amethyst show evidence of repeated pulses of ascending hydrothermal fluids of up to 80–90 °C infiltrating a basaltic host rock of less than 45 °C. Colourless quartz and amethyst formed at temperatures between 40 and 80 °C, while the different calcite generations and late gypsum precipitated at temperatures below 45 °C. Calculated oxygen isotope composition of the amethyst-precipitating fluid in combination with δD values of amethyst-hosted fluid inclusions (?59 to ?51?‰) show a significant ¹⁸O-shift from the meteoric water line. This ¹⁸O-shift, high salinities of the fluid inclusions with chloride-sulphate composition, and high δ³⁴S values of anhydrite and barite (7.5 to 9.9?‰) suggest that sedimentary brines from deeper parts of the Guaraní aquifer system must have been responsible for the amethyst mineralisation.     

Dolomitization of Quaternary reef limestone, Aitutaki, Cook Islands

Six holes were drilled to depths of 30–69 m in the shallow lagoon of Aitutaki in the southern Cook Islands. One hole encountered pervasively dolomitized reef limestones at 36 m subbottom depth, which extended to the base of the drilled section at 69·3 m. This hole was drilled near the inner edge of the present barrier reef flat on the flank of a seismically defined subsurface ridge. Both the morphology and biofacies indicate that this ridge may represent an outer reef crest. Mineralogy, porosity and cementation change in concert downhole through three zones. Zone 1, 0–9 m, is composed of primary skeletal aragonite and calcite with minor void-filling aragonite and magnesian calcite cement of marine phreatic origin. Zone 2, 9–36 m, is composed of replacement calcite and calcite cement infilling intergranular, intragranular, mouldic and vuggy porosity. Stable isotopes (mean δ¹⁸O=—5·4‰ PDB for carbonate; δD =—50‰ SMOW for fluid inclusions) support the petrographic evidence indicating that sparry calcite cements formed in predominantly freshwater. Carbon isotope values of —4·0 to —11·0‰ for calcite indicate that organic matter and seawater were the sources of carbon. Zone 3, 36–69·3 m, is composed of replacement dolostone, consisting of protodolomite with, on average, 7 mol% excess CaCO₃ and broad and weak ordering X-ray reflections at 2·41 and 2·54 A. The fine-scale replacement of skeletal grains and freshwater void-filling cements by dolomite did not significantly reduce porosity. Stable isotopes (mean δ¹⁸O=+2·6‰₀ PDB for dolomite; maximum δD =—27‰ SMOW for fluid inclusions) and chemical composition indicate that the dolomite probably formed from seawater, although formation in the lower part of a mixed freshwater-seawater zone, with up to 40% freshwater contribution, cannot be completely ruled out. The carbon (δ¹³C=2·7‰) and magnesium were derived from seawater. Low-temperature hydrothermal iron hydroxides and associated transition metals occur in void space in several narrow stratigraphic intervals in the limestone section that was replaced by dolomite. The entire section of dolomite is also enriched in these transition metals. The metals dispersed throughout the dolostone section were introduced at the time of dolomitization by a different and later episode of hydrothermal circulation than the one(s) that produced the localized deposits near the base of the section. The primary reef framework is considered to have been deposited during several highstands of sea level. Following partial to local recrystallization of the limestone, a single episode of dolomitization occurred. Both tidal and thermal pumping drove large quantities of seawater through the porous rocks and perhaps maintained a wide mixing zone. However, the isotopic, geochemical and petrographic data do not clearly indicate the extent of seawater mixing.     

IODP 311航次底栖有孔虫碳稳定同位素对天然气水合物地质系统的指示

为了探索海洋天然气水合物背景下有孔虫特征的响应,对综合大洋钻探计划(IODP) 311航次岩芯沉积物中底栖有孔虫Uvigerina peregrina和Bulimina mexicana进行了初步研究。通过对冷泉站位U1328和毗邻的非冷泉站位U1327沉积物中底栖有孔虫Uvigerina peregrina和Bulimina mexicana的显微形貌特征和碳、氧稳定同位素测试等,证实有孔虫壳体未受到后期成岩作用的改造和自生碳酸盐岩的交代影响,有孔虫壳体的碳稳定同位素呈现明显的负偏。其中U1327站位中U.peregrina δ¹³C为-0.67‰～-2.75‰（PDB）,B.mexicana δ¹³C为-0.51‰～-1.52‰（PDB）;U1328站位中U.peregrina δ¹³C为 -0.72‰～-2.71‰（PDB）,B.mexicanaδ¹³C为 -0.58‰～-1.45‰（PDB）。底栖有孔虫壳体的碳稳定同位素负偏成因可能与水合物不稳定分解释放的甲烷厌氧氧化作用和食物源有关,因而可较好地指示海底天然气水合物系统地质背景。     

Factors influencing methane-derived authigenic carbonate formation at cold seep from southwestern Dongsha area in the northern South China Sea

This paper carried out mineral and geochemical studies on a profile through a diagenetic methane-derived authigenic carbonate sample that was collected from southwestern Dongsha area of the northern South China Sea. Five samples locating in the cross-sectional middle mainly consist of dolomite and quartz, and two samples close to the surface have a small amount of Mg-calcite. The δ¹³C values of the samples vary between ?30.59 and ?0.30 % VPDB, with δ¹⁸O values ranging from 3.07 to 3.59 % VPDB, δ^44/40Ca values ranging from 1.35 to 1.47 % SRM915a, indicating a contribution of methane to the carbon pool where the precipitation of authigenic carbonates occurred. Based on the isotope values alone, it can not be distinguished if the carbon source is thermogenic gas or a mixture of biogenic methane and marine dissolved inorganic carbon. The δ¹⁸O values are in general consistent with dolomite precipitation from a fluid similar to present seawater. The observed small variation might be related to the oxygen isotope composition of seep fluid. The relative small range in calcium isotope values suggests that relatively constant growth conditions and precipitation from seawater. The central part of the carbonate nodule formed under the strong influence of methane seepage, and the external part is less influenced by methane, either due to reduced methane flux to the surface or caused by erosional exhumation of the carbonate nodule from greater depth to the sediment surface.     

Ore genesis of Badi copper deposit,northwest Yunnan Province,China: evidence from geology,fluid inclusions,and sulfur,hydrogen and oxygen isotopes

The Badi copper deposit is located in Shangjiang town, Shangri-La County, Yunnan Province. Tectonically, it belongs to the Sanjiang Block. Vapor–liquid two-phase fluid inclusions, CO₂-bearing fluid inclusions, and daughter-bearing inclusions were identified in sulfide-rich quartz veins. Microthermometric and Raman spectroscopy studies revealed their types of ore-forming fluids: (1) low-temperature, low-salinity fluid; (2) medium-temperature, low salinity CO₂-bearing; and (3) high-temperature, Fe-rich, high sulfur fugacity. The δ¹⁸O values of chalcopyrite-bearing quartz ranged from 4.96‰ to 5.86‰, with an average of 5.40‰. The δD values of ore-forming fluid in equilibrium with the sulfide-bearing quartz were from ? 87‰ to ? 107‰, with an average of ? 97.86‰. These isotopic features indicate that the ore-forming fluid is a mixing fluid between magmatic fluid and meteoric water. The δ³⁴S values of chalcopyrite ranged from 13.3‰ to 15.5‰, with an average of 14.3‰. Sulfur isotope values suggest that the sulfur in the deposit most likely derived from seawater. Various fluid inclusions coexisted in the samples; similar homogenization temperature to different phases suggests that the Badi fluid inclusions might have been captured under a boiling system. Fluid boiling caused by fault activity could be the main reason for the mineral precipitation in the Badi deposit.     

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

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

Early diagenetic siderite as an indicator of depositional environment in the Triassic Rewan Group, southern Bowen Basin, eastern Australia

Early concretionary and non-concretionary siderites are common in subsurface Triassic sandstones and mudrocks of the Rewan Group, southern Bowen Basin. A detailed petrological and stable isotopic study was carried out on these siderites in order to provide information on the depositional environment of the host rocks. The siderites are extremely pure, containing 85–97 mol% FeCO₃, and are commonly enriched in manganese. δ¹³C (PDB) values are highly variable, ranging from - 18·4 to +2·9‰, whereas δ¹⁸O (PDB) values are very consistent, ranging from - 14·0 to - 10·2‰ (mean= - 11·9 ± 1·0‰). The elemental and oxygen isotopic composition of the siderites indicates that only meteoric porewaters were involved in siderite formation, implying that host rocks accumulated in totally non-marine environments. The carbon isotopic composition of the siderites is interpreted to reflect mixing of bicarbonate/carbon dioxide generated by methane oxidation and methanogenesis. Very low δ¹³C values demonstrate that, contrary to current views, highly ¹³C-depleted siderite can be produced at shallow burial depths in anoxic non-marine sediments.