Fibrous calcite from the Ordovician of Tennessee: preservation of marine oxygen isotopic composition and its implications

Three categories of fibrous calcite from early to middle Caradoc platform-marginal buildups in east Tennessee can be delineated using cathodoluminescent microscopy, minor element chemistry and stable C-O isotopic composition. Bright luminescent fibrous cement has elevated Mn (>1000 p.p.m.), negative δ¹³C and intermediate δ¹⁸O values relative to other types of fibrous calcite. This cement reflects fibrous calcite that interacted with reducing Mn-rich fluids. Dully luminescent fibrous cement has elevated Fe (>400 p.p.m.), positive δ¹³C and negative δ¹⁸O values relative to other fibrous cements. This cement was stabilized by burial fluids. Nonluminescent fibrous cement has low Mn and Fe (generally below 400 p.p.m.) and positive δ¹³C and δ¹⁸O values relative to other types of fibrous calcite. The latter cement is interpreted to be the best material for determining the isotopic composition of calcite precipitated in equilibrium with early to middle Caradoc seawater, which is δ¹³C=1% PDB and δ¹⁸O=?4 to ?5‰ PDB. Results from this study and Ashgillian brachiopods indicate that the average δ¹⁸O composition of the Ordovician ocean, during nonglacial periods, was probably never more negative than ?3‰ SMOW. Assuming an Ordovician seawater δ¹⁸O value of ?1‰ SMOW, Holston Formation fibrous cements would have precipitated at temperatures between 27 and 36 °C, which is near the upper temperature limit for metazoans. A seawater δ¹⁸O value of ?2‰ SMOW yields temperatures ranging from 23 to 31 °C, while a ?3‰ SMOW value yields temperatures of 18–26 °C.     

Origin and migration of palaeofluids in the Upper Visean of the Campine Basin, northern Belgium

Upper Visean limestones in the Campine Basin of northern Belgium are intensively fractured. The largest and most common fractures are cemented by non-ferroan, dull brown-orange luminescent blocky calcite. First melting temperatures of fluid inclusions in these calcites are around -57°C, suggesting that precipitation of the cements occurred from NaCl-CaCl₂-MgCl₂ fluids. The final melting temperatures (T_m^ice) are between -5 and -33°C. The broad range in the T_m^ice data can be explained by the mixing of high salinity fluids with meteoric waters, but other hypotheses may also be valid. Homogenization temperatures from blocky calcite cements in the shelf limestones are interpreted to have formed between 45 and 75°C. In carbonates which were deposited close to and at the shelf margin, precipitation temperatures were possibly in the range 70-85°C and 72-93°C, respectively. On the shelf, the calcites have a δ¹⁸O around -9.3‰ PDB and they are interpreted to have grown in a fluid with a δ¹⁸O between −3.5 and +1.0‰ SMOW. At the shelf margin, blocky calcites (δ¹⁸O∼ - 13.5‰ PDB) could have precipitated from a fluid with a δ¹⁸O betweenn -4.0 and -1.1‰ SMOW. The highest oxygen isotopic compositions are comparable to those of Late Carboniferous marine fluids (δ¹⁸O= - 1‰ SMOW). The lowest values are more positive than a previously reported composition for Carboniferous meteoric waters (δ¹⁸O= -7‰ SMOW). Precipitation is likely to have occurred in marine-derived fluids, which mixed with meteoric waters sourced from near the Brabant Massif. Fluids with a similar negative oxygen isotopic composition and high salinity are actually present in Palaeozoic formations. The higher temperature range in the limestones near the shelf margin is explained by the upward migration of fluids from the ‘basinal’ area along fractures and faults into the shelf.     

Isotopic geochemistry of burial-metamorphosed volcanogenic sediments,Great Valley sequence,northern California

Isotopic and mineralogic data from an 8500-m thick section of the Great Valley sequence, northern California, indicate that changes in the δ¹⁸O values of authigenic minerals resulted from the conversion of smectite to a 10 Å clay-mineral as temperature increased with burial in the Jurassic- Cretaceous outer-arc basin. The clay-mineral assemblage in mudstone is characterized by a proportional increase of the 10 Å clay-mineral with increasing stratigraphic depth, and by a depletion in the δ¹⁸O value of the mixed-layer smectite/10 Å clay-mineral with descending stratigraphic position from +21.9 to + 15.5%. SMOW. Modeling of the oxygen isotopic data from authigenic phases, based on equilibrium fractionation during clay-mineral diagenesis, indicates that δ¹⁸O values of calcite in mudstones and of calcite cements in sandstone precipitated along a temperature gradient of about 25°C/km during maximum burial to about 6–7 km. δD values of the mixed-layer smectite/10 Å clay-mineral range between ?69 to ?44%. SMOW. Using temperatures calculated from the oxygen isotopic data, the deuterium and oxygen isotopic data indicate that the smectite underwent late-stage dehydration and probably buffered the composition of formation waters from sea water values to isotopic compositions of δ¹⁸O ≈ +8%. SMOW and δD ≈ ?25%. SMOW. The δ¹³C values of calcite from mudstone and sandstone imply that crystallization of authigenic calcite was linked to organic diagenesis during which dissolved HCO^t-₃ was continuously enriched in ¹³C as temperature increased with burial. At the base of the sequence and immediately overlying the ophiolitic basement rocks, several hundred meters of strata were altered by more oxygen-depleted (δ¹⁸O ? +4 to +5%.) hydrothermal fluids emanating from the ophiolitic rocks, probably at maximum burial depth.     

Syntectonic hydrothermal calcite in a faulted carbonate platform margin (Albian of Jorrios, northern Spain)

ABSTRACT A calcite mass more than 1·5 km long and 20 m wide crops outs along the faulted margin of the Albian carbonate platform of Jorrios in northern Spain. The mass contains abundant dissolution cavities up to 7 m long and 1 m high, filled with cross‐stratified quartz sandstone and alternating sandstone–calcite laminae. Similar cavities are also present in a 50‐m‐wide zone of platform limestones adjacent to the calcite mass that are filled with limestone breccias and sandstone. The calcite mass has mean δ¹⁸O values of 19·6‰ (SMOW), whereas platform limestones have mean δ¹⁸O values of 24·4‰ (SMOW). Synsedimentary faulting of the carbonate margin and circulation of heated fault‐related waters resulted in replacement of a band of limestone by calcite. Soon after this replacement, dissolution by undersaturated fluids affected both the calcite mass and the adjacent limestones. Percolating marine quartz sand filled all dissolution cavities, sometimes alternating with precipitating calcite. The resulting cavities and fills, which recall products of meteoric diagenesis, are attributed to a hydrothermal origin based on their geometry, occurrence along the profile and synsedimentary tectonic relationships. The early faulting and diagenesis are related to local extensional tectonism in a large‐scale strike‐slip setting. Movements occurred during the early dispar/appenninica zone of the Late Albian.     

USGS46 Greenland Ice Core Water – A New Isotopic Reference Material for δ2H and δ18O Measurements of Water

Ice core from Greenland was melted, filtered, homogenised, loaded into glass ampoules, sealed, autoclaved to eliminate biological activity, and calibrated by dual‐inlet isotope‐ratio mass spectrometry. This isotopic reference material (RM), USGS46, is intended as one of two secondary isotopic reference waters for daily normalisation of stable hydrogen (δ²H) and stable oxygen (δ¹⁸O) isotopic analysis of water with a mass spectrometer or a laser absorption spectrometer. The measured δ²H and δ¹⁸O values of this reference water were ?235.8 ± 0.7‰ and ?29.80 ± 0.03‰, respectively, relative to VSMOW on scales normalised such that the δ²H and δ¹⁸O values of SLAP reference water are, respectively, ?428 and ?55.5‰. Each uncertainty is an estimated expanded uncertainty (U = 2u_c) about the reference value that provides an interval that has about a 95‐percent probability of encompassing the true value. This reference water is available in cases containing 144 glass ampoules that are filled with either 4 ml or 5 ml of water per ampoule.     

Oxygen,carbon and sulphur isotope studies in the Keban Pb–Zn deposits,eastern Turkey: An approach on the origin of hydrothermal fluids

Pb–Zn deposits are widespread and common in various parts of the Taurus Belt. Most of the deposits are of pyrometasomatic and hydrothermal origin. The Keban Pb–Zn deposits are located along the intrusive contact between the Paleozoic – Lower Triassic Keban Metamorphic Formation and the syenite porphyry of the Upper Cretaceous Keban igneous rocks. Various studies have already been carried out; using fluid inclusion studies on fluorite, calcite and quartz on the pyrite–chalcopyrite bearing Keban ore deposits. This study focuses on the interpretation of stable isotope compositions in connexion with fluid inclusion data. Sulphur isotope values (δ³⁴S) of pyrite are within the range of ?0.59 to +0.17‰_V-CDT (n = 10). Thus, the source of sulphur is considered to be magmatic, as evidenced by associated igneous rocks and δ³⁴S values around zero“0”. Oxygen isotope values δ¹⁸O of quartz vary between +10.5 and +19.9‰_(SMOW). However, δ¹⁸O and δ¹³C values of calcite related to re-crystallized limestone (Keban Metamorphic Formation) reach up to +27.3‰_(SMOW) and +1.6‰_(PDB), respectively. The δ³⁴S, δ¹³C and δ¹⁸O values demonstrate that skarn-type Pb–Zn deposits formed within syeno-monzonitic rocks and calc-schist contacts could have developed at low temperatures, by mixing metamorphic and meteoric waters in the final stages of magmatism.     

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.     

Speleothem record of the last 180 ka in Villars cave (SW France): Investigation of a large δ18O shift between MIS6 and MIS5

The Vil-car-1 flowstone core from Villars cave (SW France) provides one of the first European speleothem records extending back to 180 ka, based on U–Th TIMS and MC-ICP-MS measurements. The core offers a continuous record of Termination II and the Last Interglacial. The penultimate deglaciation is characterized by a prominent 5‰ depletion in calcite δ¹⁸O. Determining which specific environmental factors controlled such a large oxygen isotopic shift offers the opportunity to assess the impact of various factors influencing δ¹⁸O variations in speleothem calcite.Oxygen isotope analyses of fluid inclusions indicate that drip water δ¹⁸O remained within a very narrow range of ±1‰ from Late MIS6 to the MIS5 δ¹⁸O optimum. The possibility of such a stable behaviour is supported by simple calculations of various effects influencing seepage water δ¹⁸O.Although this could suggest that the isotopic shift in calcite is mainly driven by temperature increase, attempts to quantify the temperature shift from Late MIS6 to the MIS5 δ¹⁸O optimum by assuming an equilibrium relationship between calcite and fluid inclusion δ¹⁸O yield unreasonably high estimates of ～20 °C warming and Late MIS6 cave temperatures below 0 °C; this suggests that the flowstone calcite precipitated out of thermodynamic equilibrium at this site.Using a method proposed by Guo et al. (submitted for publication) combining clumped isotope measurements, fluid inclusion and modern calcite δ¹⁸O analyses, it is possible to quantitatively correct for isotopic disequilibrium and estimate absolute paleotemperatures. Although the precision of these absolute temperature reconstructions is limited by analytical uncertainties, the temperature rise between Late MIS6 and the MIS5 optimum can be robustly constrained between 13.2 ± 2.6 and 14.6 ± 2.6 °C (1σ), consistent with existing estimates from Western Europe pollen and sea-surface temperature records.     

Geochemical Characteristics and Sources of Ore-forming Fluids of the Mayuan Pb-Zn Deposit, Nanzheng, Shaanxi, China

The Mayuan stratabound Pb-Zn deposit in Nanzheng,Shaanxi Province,is located in the northern margin of the Yangtze Plate,in the southern margin of the Beiba Arch.The orebodies are stratiform and hosted in breciated dolostone of the Sinian Dengying Formation.The ore minerals are primarily sphalerite and galena,and the gangue minerals comprise of dolomite,quartz,barite,calcite and solid bitumen.Fluid inclusions from ore-stage quartz and calcite have homogenization tempreatures from 98 to 337℃ and salinities from 7.7 wt%to 22.2 wt%(NaCl equiv.).The vapor phase of the inclusions is mainly composed of CH_4 with minor CO_2 and H_2S.The δD_(fluid) values of fluid inclusions in quartz and calcite display a range from-68‰ to-113‰(SMOW),and the δ~(18)O_(fluid)values calculated from δ~(18)O_(quartz) and δ~(18)O_(calcite) values range from 4.5‰ to 16.7‰(SMOW).These data suggest that the ore-forming fluids may have been derived from evaporitic sea water that had reacted with organic matter.The δ~(13)C_(CH4) values of CH_4 in fluid inclusions range from-37.2‰ to-21.0‰(PDB),suggesting that the CH_4 in the ore-forming fluids was mainly derived from organic matter.This,together with the abundance of solid bitumen in the ores,suggest that organic matter played an important role in mineralization,and that the thermochemical sulfate reduction(TSR) was the main mechanism of sulfide precipitation.The Mayuan Pb-Zn deposit is a carbonate-hosted epigenetic deposit that may be classified as a Mississippi Valley type(MVT) deposit.     

Oxygen isotope composition of syngenetic inclusions in diamond from the Finsch Mine,RSA

Oxygen isotope data have been obtained for silicate inclusions in diamonds, and similar associated minerals in peridotitic and eclogitic xenoliths from the Finsch kimberlite by laser-fluorination. Oxygen isotope analyses of syngenetic inclusions weighing 20–400 μg have been obtained by laser heating in the presence of ClF₃. ¹⁸O/¹⁶O ratios are determined on oxygen converted to CO₂ over hot graphite and, for samples weighing less than 750 μg (producing <12 μmoles O₂) enhanced CO production in the graphite reactor causes a systematic shift in both δ¹³C and δ¹⁸O that varies as a function of sample weight. A “pressure effect” correction procedure, based on the magnitude of δ¹³C (CO₂) depletion relative to δ¹³C (graphite), is used to obtain corrected δ¹⁸O values for inclusions with an accuracy estimated to be ±0.3‰ for samples weighing 40 μg.Syngenetic inclusions in host diamonds with similar δ¹³C values (−8.4‰ to −2.7‰) have oxygen isotope compositions that vary significantly, with a clear distinction between inclusions of peridotitic (+4.6‰ to +5.6‰) and eclogitic paragenesis (+5.7‰ to +8.0‰). The mean δ¹⁸O composition of olivine inclusions is indistinguishable from that of typical peridotitic mantle (5.25 ± 0.22‰) whereas syngenetic purple garnet inclusions possess relatively low δ¹⁸O values (5.00 ± 0.33‰). Reversed oxygen isotope fractionation between olivine and garnet in both diamond inclusions and diamondiferous peridotite xenoliths suggests that garnet preserves subtle isotopic disequilibrium related to genesis of Cr-rich garnet and/or exchange with the diamond-forming fluid. Garnet in eclogite xenoliths in kimberlite show a range of δ¹⁸O values from +2.3‰ to +7.3‰ but garnets in diamondiferous eclogites and as inclusions in diamond all have values >4.7‰.     

Stable isotope evidence for the origin of diagenetic carbonate minerals from the Lower Jurassic Inmar Formation, southern Israel

The oxygen isotope compositions of diagenetic carbonate minerals from the Lower Jurassic Inmar Formation, southern Israel, have been used to identify porewater types during diagenesis. Changes in porewater composition can be related to major geological events within southern Israel. In particular, saline brines played an important role in late (Pliocene-Pleistocene) dolomitization of these rocks. Diagenetic carbonates included early siderite (δ¹⁸O_SMOW=+24.4 to +26.5‰δ¹³C_PDB=?1.1 to +0.8‰), late dolomite, ferroan dolomite and ankerite (δ¹⁸O_SMOW=+18.4 to +25.8‰; δ¹³C_PDB=?2.1 to +0.2‰), and calcite (δ¹⁸O_SMOW=+21.3 to +32.6‰; δ¹³C_PDB=?4.2 to + 3.2‰). The petrographic and isotopic results suggest that siderite formed early in the diagenetic history at shallow depths. The dolomitic phases formed at greater depths late in diagenesis. Crystallization of secondary calcite spans early to late diagenesis, consistent with its large range in isotopic values. A strong negative correlation exists between burial depth (temperature) and the oxygen isotopic compositions of the dolomitic cements. In addition, the δ¹⁸O values of the dolomitic phases in the northern Negev and Judea Mountains are in isotopic equilibrium with present formation waters. This behaviour suggests that formation of secondary dolomite post-dates the tectonic activity responsible for the present relief of southern Israel (Upper Miocene to Pliocene) and that the dolomite crystallized from present formation waters. Such is not the case in the Central Negev. In that locality, present formation waters have much lower salinities and δ¹⁸O values, indicating invasion of freshwater, and are out of isotopic equilibrium with secondary dolomite. Recharge of the Inmar Formation by meteoric water in the Central Negev occurred in the Pleistocene, and halted formation of dolomite.     

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.     

Investigation on the hydrodynamics of Ganga Alluvial Plain using environmental isotopes: a case study of the Gomati River Basin, northern India

An investigation using environmental isotopes (δ¹⁸O and δD) was conducted to gain insight into the hydrological processes of the Ganga Alluvial Plain, northern India. River-water, shallow-groundwater and lake-water samples from the Gomati River Basin were analyzed. During the winter season, the δ¹⁸O and δD compositions of the Gomati River water ranged from ?1.67 to ?7.62 ‰ and ?25.08 to ?61.50 ‰, respectively. Deuterium excess values in the river water (+0.3 to ?13 ‰) and the lake water (?20 ‰) indicate the significance of evaporation processes. Monthly variation of δ¹⁸O and δD values of the Gomati River water and the shallow groundwater follows a similar trend, with isotope-depleted peaks for δ¹⁸O and δD synchronized during the monsoon season. The isotopically depleted peak values of the river water (δ¹⁸O?=??8.30 ‰ and δD?=??57.10 ‰) can be used as a proxy record for the isotopic signature of the monsoon precipitation in the Ganga Alluvial Plain.     

Diagenesis and reservoir quality of the Aldebaran Sandstone, Denison Trough, east-central Queensland, Australia

The Lower Permian Aldebaran Sandstone is the principal hydrocarbon reservoir in the Denison Trough (Bowen Basin), east-central Queensland, Australia. It accumulated in a wide range of fluvio-deltaic and nearshore marine environments. Detailed petrological study of the unit by thin section, X-ray diffraction, scanning electron microscopy, electron microprobe and isotopic analysis reveals a complex diagenetic history which can be directly related to depositional environment, initial composition and burial-temperature history. Early diagenetic effects included the precipitation of pyrite, siderite and illite-smectite rims (δ¹⁸O (SMOW) =+8.9 to + 11.3‰). Deep burial effects included physico-chemical compaction and the formation of quartz overgrowths, siderite (δ¹³C(PDB) =?34.0 to + 11.5‰, δ¹⁸O =?0.7 to +22.7‰), illite/illite-smectite and ankerite (δ¹³C=?9.3 to ?4.9‰) δ¹⁸O=+ 7.6 to + 14.4‰). Involved fluids were in part ‘connate meteoric’ water derived from compaction of the underlying freshwater Reids Dome beds. Important post-maximum burial effects, controlled by deep meteoric influx from the surface, were ankerite and labile grain dissolution and formation of kaolinite (δ¹⁸O=+7.8 to +8.9‰, δD=?115 to ?99‰), calcite (δ¹³C=?9.5 to +0.9‰, δ¹⁸O=+9.0 to +20.0‰) and dawsonite (δ¹³C=?4.0 to +2.3‰, δ¹⁸O=+9.8 to +19.8‰), the formation of dawsonite reflecting eventual stagnation of the aquifer. Entrapment of contained hydrocarbons was a relatively recent event which may be continuing today. Reservoir quality varies from marginal to good in the west to poor in the east, with predictable trends being directly linked to depositional environment and diagenesis.     

Constraints on the application of carbon isotope thermometry in high- to ultrahigh-temperature metamorphic terranes

Nine marble horizons from the granulite facies terrane of southern India were examined in detail for stable carbon and oxygen isotopes in calcite and carbon isotopes in graphite. The marbles in Trivandrum Block show coupled lowering of δ¹³C and δ¹⁸O values in calcite and heterogeneous single crystal δ¹³C values (? 1 to ? 10‰) for graphite indicating varying carbon isotope fractionation between calcite and graphite, despite the granulite facies regional metamorphic conditions. The stable isotope patterns suggest alteration of δ¹³C and δ¹⁸O values in marbles by infiltration of low δ¹³C–δ¹⁸O‐bearing fluids, the extent of alteration being a direct function of the fluid‐rock ratio. The carbon isotope zonation preserved in graphite suggests that the graphite crystals precipitated/recrystallized in the presence of an externally derived CO₂‐rich fluid, and that the infiltration had occurred under high temperature and low f_O2 conditions during metamorphism. The onset of graphite precipitation resulted in a depletion of the carbon isotope values of the remaining fluid+calcite carbon reservoir, following a Rayleigh‐type distillation process within fluid‐rich pockets/pathways in marbles resulting in the observed zonation. The results suggest that calcite–graphite thermometry cannot be applied in marbles that are affected by external carbonic fluid infiltration. However, marble horizons in the Madurai Block, where the effect of fluid infiltration is not detected, record clear imprints of ultrahigh temperature metamorphism (800–1000 °C), with fractionations reaching <2‰. Zonation studies on graphite show a nominal rimward lowering δ¹³C on the order of 1 to 2‰. The zonation carries the imprint of fluid deficient/absent UHT metamorphism. Commonly, calculated core temperatures are > 1000 °C and would be consistent with UHT metamorphism.     

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.     

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.     

Genesis of the Weiquan Ag–Polymetallic Deposit in East Tianshan, China: Evidence from Zircon U–Pb Geochronology and C–H–O–S–Pb Isotope Systematics

The Weiquan Ag-polymetallic deposit is located on the southern margin of the Central Asian Orogenic Belt and in the western segment of the Aqishan-Yamansu arc belt in East Tianshan,northwestern China. Its orebodies, controlled by faults, occur in the lower Carboniferous volcanosedimentary rocks of the Yamansu Formation as irregular veins and lenses. Four stages of mineralization have been recognized on the basis of mineral assemblages, ore fabrics, and crosscutting relationships among the ore veins. Stage I is the skarn stage(garnet + pyroxene), Stage Ⅱ is the retrograde alteration stage(epidote + chlorite + magnetite ± hematite 士 actinolite ± quartz),Stage Ⅲ is the sulfide stage(Ag and Bi minerals + pyrite + chalcopyrite + galena + sphalerite + quartz ± calcite ± tetrahedrite),and Stage IV is the carbonate stage(quartz + calcite ± pyrite). Skarnization,silicification, carbonatization,epidotization,chloritization, sericitization, and actinolitization are the principal types of hydrothermal alteration. LAICP-MS U-Pb dating yielded ages of 326.5±4.5 and 298.5±1.5 Ma for zircons from the tuff and diorite porphyry, respectively. Given that the tuff is wall rock and that the orebodies are cut by a late diorite porphyry dike, the ages of the tuff and the diorite porphyry provide lower and upper time limits on the age of ore formation. The δ~(13)C values of the calcite samples range from-2.5‰ to 2.3‰, the δ~(18)O_(H2 O) and δD_(VSMOW) values of the sulfide stage(Stage Ⅲ) vary from 1.1‰ to 5.2‰ and-111.7‰ to-66.1‰, respectively,and the δ~(13)C, δ~(18)O_(H2 O) and δD_(V-SMOW) values of calcite in one Stage IV sample are 1.5‰,-0.3‰, and-115.6‰, respectively. Carbon, hydrogen, and oxygen isotopic compositions indicate that the ore-forming fluids evolved gradually from magmatic to meteoric sources. The δ~(34)S_(V-CDT) values of the sulfides have a large range from-6.9‰ to 1.4‰, with an average of-2.2‰, indicating a magmatic source, possibly with sedimentary contributions. The ~(206)Pb/~(204)Pb, ~(207)Pb/~(204)Pb, and ~(208)Pb/~(204)Pb ratios of the sulfides are 17.9848-18.2785,15.5188-15.6536, and 37.8125-38.4650, respectively, and one whole-rock sample at Weiquan yields~(206)Pb/~(204)Pb,~(207)Pb/~(204)Pb, and ~(208)Pb/~(204)Pb ratios of 18.2060, 15.5674, and 38.0511,respectively. Lead isotopic systems suggest that the ore-forming materials of the Weiquan deposit were derived from a mixed source involving mantle and crustal components. Based on geological features, zircon U-Pb dating, and C-H-OS-Pb isotopic data, it can be concluded that the Weiquan polymetallic deposit is a skarn type that formed in a tectonic setting spanning a period from subduction to post-collision. The ore materials were sourced from magmatic ore-forming fluids that mixed with components derived from host rocks during their ascent, and a gradual mixing with meteoric water took place in the later stages.     

Glendonites as a paleoenvironmental tool: implications for early Cretaceous high latitude climates in Australia

Glendonites, calcite pseudomorphs after the metastable mineral ikaite (CaCO₃ · 6H₂O), occur in the Late Aptian interval of the Bulldog Shale in the Eromanga Basin, Australia and in other Early Cretaceous basins at high paleolatitudes. Ikaite precipitation in the marine environment requires near-freezing temperatures (not higher than 4°C), high alkalinity, increased levels of orthophosphate, and high P_CO2. The rapid and complete transformation of ikaite to calcite at temperatures between 5 and 8°C provides an upper limit on the oxygen isotopic composition of the pore waters: −2.6 <δ_w <−3.4‰SMOW. If it is assumed that these pore waters are representative of the shallow Eromanga Basin, the calculated δ_w can be used to reassess belemnite fossil oxygen isotopic paleotemperatures—temperature recorded by fauna living in the basin at the time of ikaite precipitation. Data previously reported as 11 to 16°C (assuming δ_w = 0.0‰SMOW) yield paleotemperatures ranging from −1 to 5°C, squarely in the range of ikaite stability. The low δ_w indicates hyposaline conditions, most likely caused by mixing high latitude meteoric waters with seawater. The ¹⁸O depleted, low temperature waters suggest that the region was at least seasonally colder than previously accepted.     

Stable isotopic insights into paleoclimatic conditions and alluvial depositional processes in the Kaiparowits Formation (Campanian,south-central Utah,U.S.A.)

The Kaiparowits Formation contains an exceptionally rich history of tectonic, climatic, and biologic conditions within the Western Interior of North America during the Campanian. Here we reconstruct aspects of the southern Cordilleran foreland basin's paleohydrology using δ¹⁸O and δ¹³C values determined from unionoid bivalve shells and pedogenic carbonate nodules derived from a suite of lithofacies associations. Unionoid shells derived from fluvial deposits display average water δ¹⁸O estimates of −13.7‰ ± 2.1 (1σ) (VSMOW) and shell δ¹³C values of −4.0‰ ± 1.5 (VPDB), whereas pedogenic carbonate nodules display average values of −6.0‰ ± 0.5 and −8.7‰ ± 0.8, respectively. Unionoid shells derived from pond deposits fall in between the two other environments with average values of −9.5‰ ± 1.8 and −5.7‰ ± 2.1, in δ¹⁸O and δ¹³C values respectively. Water δ¹⁸O estimates are interpreted to represent high altitude runoff within river systems, low elevation precipitation within the basin onto floodplain soils, and varying degrees of mixing between these two components within floodplain ponds. δ¹³C values track the isotopic composition of dissolved inorganic carbon within river, soil, and pond waters with high values likely reflecting greater contribution from chemically weathered marine carbonates exposed in the hinterland and lower values reflecting greater contributions from the in situ degradation of plant matter. Up-section there is a shift to lower δ¹⁸O values and higher δ¹³C values in fluvially-derived unionoid shells that post-dates an incursion of the Western Interior Seaway, but coincides with a shift in sediment provenance, an increase in basin sedimentation rates, and a change to a more anastomosed-style channel morphology within the basin foredeep depocentre. By combining the isotopic patterns with previously published sedimentologic, climate model, and paleofloral records we find: 1) additional evidence for humid, wet, and potentially monsoonal conditions within the region, 2) support for a tectonic uplift event, potentially related to Laramide deformation, and 3) greater aggradation and overbank flooding within the alluvial system in response to the uplift event.