The speleothem record of climate variability in Southern Arabia

Uranium-series dated stalagmites from Oman indicate that pluvial conditions prevailed from 6.3 to 10.5, 78 to 82, 120 to 130, 180 to 200 and 300 to 330 kyr B.P.; all of these periods coincide with peak interglacials. Oxygen (δ¹⁸O) and hydrogen (δD) isotope ratios of speleothem calcite and fluid inclusions reveal the source of moisture and provide information on the amount of precipitation, respectively. δ¹⁸O and δD values of stalagmites deposited during peak interglacials vary between ?8 and ?4 ‰ (VPDB) and ?53 and ?20‰ (Vienna Standard Mean Ocean Water [VSMOW]) respectively, whereas modern stalagmites range from ?2.6 to ?1.1‰ in δ¹⁸O (VPDB) and ?7.6 and ?3.3‰ in δD (VSMOW), respectively. The growth and isotopic records indicate that during peak interglacial periods, the limit of the monsoon rainfall was shifted far north of its present location and each pluvial period was coinciding with an interglacial stage of the marine oxygen isotope record.     

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.     

A study of oxygen isotopic fractionation during bio-induced calcite precipitation in eutrophic Baldeggersee,Switzerland

In order to better understand environmental factors controlling oxygen isotope shifts in autochthonous lacustrine carbonate sequences, we undertook an extensive one-year study (March, 1995 to February, 1996) of water-column chemistry and daily sediment trap material from a small lake in Central Switzerland. Comparisons between calculated equilibrium isotope values, using the fractionation equation of Friedman and O’Neil, (1977) and measured oxygen isotope ratios of calcite in the sediment-traps reveal that oxygen isotopic values of autochthonous calcite (δ¹⁸O) are in isotopic equilibrium with ambient water during most of the spring and summer, when the majority of the calcite precipitates. In contrast, small amounts of calcite precipitated in early-spring and again in late-autumn are isotopically depleted in ¹⁸O relative to the calculated equilibrium values, by as much as 0.8‰. This seasonally occurring apparent isotopic nonequilibrium is associated with times of high phosphorous concentrations, elevated pH (∼8.6) and increased [CO₃²⁻] (∼50 μmol/l) in the surface waters. The resulting weighted average δ¹⁸O value for the studied period is −9.6‰, compared with a calculated equilibrium δ¹⁸O value of −9.4‰. These data convincingly demonstrate that δ¹⁸O of calcite are, for the most part, a very reliable proxy for temperature and δ¹⁸O of the water.     

Effects of speciation on equilibrium fractionations and rates of oxygen isotope exchange between (PO4)aq and H2O

The effects of phosphate speciation on both rates of isotopic exchange and oxygen isotope equilibrium fractionation factors between aqueous phosphate and water were examined over the temperature range 70 to 180°C. Exchange between phosphate and water is much faster at low pH than at high pH, an observation that is similar to what has been observed in the analogous sulfate-water system. Oxygen isotope fractionations between protonated species like H₃PO₄ and H₂PO₄⁻ that are dominant at relatively low pH and species like PO₄³⁻ and ion pairs like KHPO₄⁻ that are dominant at relatively high pH, range between 5 and 8‰ at the temperatures of the experiments. In aqueous phosphate systems at equilibrium, ¹⁸O/¹⁶O ratios increase with increasing degree of protonation of phosphate. This effect can be explained in part by the relative magnitudes of the dissociation constants of the protonated species. Under equilibrium conditions, carbonate in solution or in solid phases concentrates ¹⁸O relative to orthophosphate in solution or in solid phases at all temperatures, supporting the traditional view that biogenic phosphate is precipitated in near oxygen isotope equilibrium with body/ambient aqueous fluids with no attendant vital effects.     

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.     

Oxygen isotope signature of Pi regeneration from organic compounds by phosphomonoesterases and photooxidation

Phosphomonoesters are an important source of dissolved inorganic orthophosphate (PO₄ or P_i), the preferred form of P utilized by microbiota and aquatic plants in marine and freshwater ecosystems. Two enzymes involved in phosphomonoester metabolism and commonly detected in natural waters (alkaline phosphatase and 5′-nucleotidase) have been studied to determine the oxygen isotope signature of P_i-regeneration from phosphomonoesters by enzymatic degradation. Oxygen (O) isotope ratios of water and P_i released from phosphomonoesters during enzyme hydrolysis experiments demonstrate that released P_i incorporates one oxygen atom from water. The isotopic fractionation between this incorporated water O and ambient water O is −30 (±8)‰ for alkaline phosphatase and −10 (±1)‰ for 5′-nucleotidase, with very weak dependence on temperature. The result of these enzyme-specific isotopic fractionations at one of the four O sites in PO₄ is that the δ¹⁸O value of P_i regenerated by 5′-nucleotidase is 5‰ higher than P_i regenerated by alkaline phosphatase from the same phosphomonoester substrate. The δ¹⁸O value of regenerated P_i also reflects inheritance of 75% of O from the phosphomonoester substrate, thus making the δ¹⁸O of phosphomonoester-derived P_i a potential tracer of organophosphorous compound sources. Phosphomonoesterase-regenerated P_i has a distinct phosphate oxygen isotope signature that is different and distinguishable from that of biologically recycled and subsequently equilibrated P_i and P_i regenerated from photooxidation of organic matter. The δ¹⁸O value of regenerated P_i will correlate positively with the δ¹⁸O value of bulk water and the fractionation, α, between regenerated P_i and water, α_{regen Pi-water}, should converge toward equilibrium α_Pi-water values with increased biological cycling of P_i.     

The oxygen and carbon isotope composition of Carboniferous fossil components: sea-water effects

The aragonitic molluscs and lime-mud of the Pennsylvanian Buckhorn asphalt (Deese Group) of southern Oklahoma precipitated calcium carbonate in oxygen and carbon isotopic equilibrium with ambient sea-water. In addition, δ¹⁸O values indicate that the pelecypods precipitated their shells during the warmer months of the year. The coiled nautiloids probably precipitated their shells in the warm surface water and throughout the year. For the orthocone nautiloids, the δ¹⁸O values suggest that they precipitated their shells in deeper/cooler water. The low-Mg calcite brachiopods of the Mississippian Lake Valley Formation of New Mexico precipitated shells in oxygen and carbon isotopic equilibrium with ambient sea-water. The δ¹⁸O and δ¹³C values of the Buckhorn and Lake Valley faunas, in conjunction with other published results, suggest that Carboniferous sea-water was, on a average, depleted in δ¹⁸O by 1·5 ± 2‰, PDB, relative to Recent sea-water. However, the δ¹³C value of +2.6 ± 2‰, PDB, for average Carboniferous sea-water is similar to that of Recent ocean water. Early diagenetic alteration of metastable carbonates probably occurs in a meteoric-sea-water mixing zone. In this zone the oxygen and carbon isotopic compositions of these components are increased by about 2-4‰, PDB over their marine composition.     

Antarctic Ice‐Core Water (USGS49) – A New Isotopic Reference Material for δ2H and δ18O Measurements of Water

As a result of the scarcity of isotopic reference waters for daily use, a new secondary isotopic reference material for international distribution has been prepared from ice‐core water from the Amundsen–Scott South Pole Station. This isotopic reference material, designated as USGS49, was filtered, homogenised, loaded into glass ampoules, sealed with a torch, autoclaved to eliminate biological activity and measured by dual‐inlet isotope‐ratio mass spectrometry. The δ²H and δ¹⁸O values of USGS49 are ?394.7 ± 0.4 and ?50.55 ± 0.04 mUr (where mUr = 0.001 = ‰), respectively, relative to VSMOW, on scales normalised such that the δ²H and δ¹⁸O values of SLAP reference water are, respectively, ?428 and ?55.5 mUr. Each uncertainty is an estimated expanded uncertainty (U = 2u_c) about the reference value that provides an interval that has about a 95% probability of encompassing the true value. This isotopic reference material is intended as one of two isotopic reference waters for daily normalisation of stable hydrogen and oxygen isotopic analysis of water with an isotope‐ratio mass spectrometer or a laser absorption spectrometer. It is available by the case of 144 glass ampoules or as a set of sixteen glass ampoules containing 5 ml of water in each ampoule.     

Environmental setting, (micro)morphologies and stable C–O isotope composition of cold climate carbonate precipitates—a review and evaluation of their potential as paleoclimatic proxies

Given the growing interest in carbonate deposits from polar regions as paleoclimatic proxies, this review paper first provides a classification of the various types of cold-climate carbonate precipitates followed by a summary of the ¹³C and ¹⁸O composition of the carbonate deposits and parent water from which the carbonates precipitated. The cold-climate carbonate precipitates were classified into three broad categories: powders, crusts and speleothem. The carbonate powders include those that precipitated in relation to aufeis aggradation (cryogenic aufeis calcite) and in relation to the growth of various annual/perennial ice formations in freezing caves (cryptocrystalline calcite and calcite pearls). The carbonate crusts can be further subdivided based on their lithic environment; those that precipitated on the upper surface of bedrock/clasts (i.e. subglacially precipitated calcite and evaporative calcite crusts); those that are located on the underside of clasts (i.e. pedogenic carbonates); and those that precipitated in rock outcrop fissures (i.e. endostromatolites). The cold-climate carbonate precipitates have a highly variable isotopic composition with δ¹⁸O values ranging between −6.5‰ and 28‰ VSMOW and δ¹³C values in the −10–20‰ VPDB range. However, each type of carbonate precipitates has a specific δ¹³C and δ¹⁸O range, suggesting that their environmental setting and the mechanism by which they formed controls their ¹³C and ¹⁸O signature. It was found that carbonate deposits that precipitated under equilibrium physico-chemical conditions had a δ¹³C value that is in equilibrium with that of the parent water, while its δ¹⁸O composition was more variable, as it is in part controlled by the temperature of reaction and by the δ¹⁸O and calcite saturation state of the parent water. By contrast, the δ¹⁸O composition of biologically precipitated carbonate deposits (endostromatolites) reflect that of the parent water, while its δ¹³C composition was enriched over that of the parent water due to bacterial methanogenesis. In the case of kinetically precipitated carbonate deposits, the δ¹⁸O and δ¹³C values are out-of-equilibrium relative to that of the parent water due to the faster rate of reaction.     

Isotopic composition (δ<Superscript>13</Superscript>C and δ<Superscript>18</Superscript>O) and genesis of carbonates from the famennian manganiferous formation of Pai-Khoi

The results of isotope-geochemical studies of carbonates of different mineral types from manganese and host rocks of the Famennian manganiferous formation of Pai-Khoi are reported. Kutnahorite ores are characterized by δ¹³C values from–6.6 to 1.3‰ and δ¹⁸O from 20.0 to 27.4‰. Rhodonite–rhodochrosite rocks of the Silovayakha ore occurrence have δ¹³C from–5.2 to–2.9 and δ¹⁸O from 25.4 to 24.3‰. Mineralogically similar rocks of the Nadeiyakha ore occurrence show the lighter carbon and oxygen isotopic compositions: δ¹³C from–16.4 to–13.1 and δ¹⁸O from 24.8 to 22.5‰. Similar isotopic compositions were also obtained for rhodochrosite–kutnahorite rocks of this ore occurrence: δ¹³C from–13.0 to–10.4‰ and δ¹⁸O from 24.6 to 21.7‰. Siderorodochrosite ores differ in the lighter oxygen and carbon isotopic compositions: δ¹⁸O from 18.7 to 17.6‰ and δ¹³C from–10.2 to–9.3‰, respectively. In terms of the carbon and oxygen isotopic compositions, host rocks in general correspond to marine sedimentary carbonates. Geological-mineralogical and isotope data indicate that the formation of the manganese carbonates was related to the hydrothermal ore-bearing fluids with the light isotopic composition of oxygen and carbon dissolved in CO₂. The isotopic features indicate an authigenic formation of manganese carbonates under different isotopegeochemical conditions.     

Carbon and Oxygen Isotope Compositions of Calcite and Rhodochrosite from Geothermal Exploratory Drills TH‐4 and TH‐6 near the Toyoha Deposit,Hokkaido, Japan

We studied calcite and rhodochrosite from exploratory drill cores (TH‐4 and TH‐6) near the Toyoha deposit, southwestern Hokkaido, Japan, from the aspect of stable isotope geochemistry, together with measuring the homogenization temperatures of fluid inclusions. The alteration observed in the drill cores is classified into four zones: ore mineralized zone, mixed‐layer minerals zone, kaolin minerals zone, and propylitic zone. Calcite is widespread in all the zones except for the kaolin minerals zone. The occurrence of rhodochrosite is restricted in the ore mineralized zone associated with Fe, Mn‐rich chlorite and sulfides, the mineral assemblage of which is basically equivalent to that in the Toyoha veins. The measured δ¹⁸O_SMOW and δ¹³C_PDB values of calcite scatter in the relatively narrow ranges from ?2 to 5‰ and from ?9 to ?5‰, respectively; those of rhodochrosite from 3 to 9‰ and from ?9 to ?5‰, excluding some data with large deviations. The variation of the isotopic compositions with temperature and depth could be explained by a mixing process between a heated surface meteoric water (100°C δ¹⁸O =?12‰, δ¹³C =?10‰) and a deep high temperature water (300°C, δ¹⁸O =?5‰, δ¹³C =?4‰). Boiling was less effective in isotopic fractionation than that of mixing. The plots of δ¹⁸O and δ¹³C indicate that the carbonates precipitated from H₂CO₃‐dominated fluids under the conditions of pH = 6–7 and T = 200–300°C. The sequential precipitation from calcite to rhodochrosite in a vein brought about the disequilibrium isotopic fractionation between the two minerals. The hydrothermal fluids circulated during the precipitation of carbonates in TH‐4 and TH‐6 are similar in origin to the ore‐forming fluids pertaining to the formation of veins in the Toyoha deposit.     

Cretaceous–Neogene basin control on the formation of uranium deposits in South China: evidence from geology,mineralization ages,and H–O isotopes

ABSTRACT

The South China Uranium Province (SCUP) contains the largest number of discovered uranium deposits in China. This province includes seven uranium mineralization belts, at Wuyishan, Taoshan–Zhuguang, Chenzhou–Qinzhou, Gan–Hang, Xixia–Luzong, Mufushan–Hengshan, and Xuefengshan–Jiuwandashan. The uranium deposits can be classified according to their ore-hosting rocks into four general types: granite-, volcanic-, black-shale-, and sandstone-related. These uranium deposits crop out at the peripheries of Cretaceous–Neogene (K–N) redbed basins or are connected to the basins by NE–SW- to NNE–SSW-trending regional faults. Most of the volcanic-related uranium deposits were formed during the mid-Cretaceous (118 to 88 Ma); granite-related deposits have a wider range of ages from 124 to 11 Ma; the black-shale-related deposits have ages of 120 to 7 Ma; sandstone-related deposits yield ages of 111 to 22.5 Ma. As such, these four types of uranium deposits in South China have similar ages, irrespective of location, and are similar in age to K–N redbed basins in this region. δD_VSMOW(fluid) and δ¹⁸O_VSMOW(fluid) values of the volcanic-related uranium deposits generally range from – 105.9‰ to – 38.0‰ and – 11.1‰ to +5.3‰, respectively. The black-shale-related uranium deposits yield δD_VSMOW(fluid) and δ¹⁸O_VSMOW(fluid) values of – 74.5‰ to – 33.0‰ and – 4.4‰ to 9.3‰, respectively. However, the granite-related uranium deposits have a much wider range of δD_VSMOW(fluid) and δ¹⁸O_VSMOW(fluid) values from – 104.4‰ to – 23.1‰ and – 9.4‰ to +7.3‰, respectively. H–O isotopic compositions of the SCUP ore-forming fluids are similar to those of basinal fluids, again demonstrating the link between the uranium deposits and the basins. The spatial–temporal relationships and fluid isotopic similarities between the K–N basins and uranium mineralization indicate that the uranium deposits of the SCUP are genetically related to the K–N redbed basins, and are unconformity-related uranium deposits.     

Stable isotopic and elemental characteristics of recent tufa from a karstic Krka River (south‐east Slovenia): useful environmental proxies?

Tufa samples from 16 consecutive barrages along a 13 km section of the groundwater‐fed Krka River (Slovenia) were analysed for their petrographical, mineralogical, elemental and stable carbon (δ¹³C) and oxygen (δ¹⁸O) isotope composition, to establish their relation to current climatic and hydrological conditions. Waters constantly oversaturated with calcite and the steep morphology of the Krka riverbed stimulate rapid CO₂ degassing and subsequent tufa precipitation. The carbon isotope fractionation (Δ¹³C) between dissolved inorganic carbon and tufa in the Krka River evolves towards isotopic equilibrium being controlled by continuous CO₂ degassing and tufa precipitation rate downstream. The Δ¹³C increased from 1·9 to 2·5‰ (VPDB); however, since tufa precipitation rates remain similar downstream, the major controlling factor of carbon isotope exchange is most probably related to the continuous ¹²CO₂ degassing downstream leaving the carbon pool enriched in ¹³C. In the case of oxygen, the isotope fractionation (Δ¹⁸O) was found to be from 1·0 to 2·3‰ (VSMOW) smaller than reported in the literature. The observed discrepancies are due to different precipitation rates of calcite deposits because Krka tufas on cascades grow relatively faster compared to slowly precipitated calcite deposits in cave or stream pools. Due to non‐equilibrium oxygen isotope exchange between Krka tufa and water, the δ¹⁸O proxy showed from 1·2 to 8·2°C higher calculated water temperatures compared to measured water temperatures, demonstrating that δ¹⁸O proxy‐based temperature equations are not reliable for water temperature calculations of fast‐growing tufa on cascades. Because Mg is bound to the terrigenous dolomite fraction in the Krka tufa samples, the Mg/Ca was also found to be an unreliable temperature proxy yielding over up to 20°C higher calculated water temperatures.     

Characterisation and isotopic evolution of saline waters of the Outokumpu Deep Drill Hole,Finland – Implications for water origin and deep terrestrial biosphere

The isotopic composition of water and dissolved Sr as well as other geochemical parameters at the 2516 m deep Outokumpu Deep Drill Hole, Finland were determined. The drill hole is hosted by Palaeoproterozoic turbiditic metasediments, ophiolite-derived altered ultramafic rocks and pegmatitic granitoids. Sodium–Ca–Cl and Ca–Na–Cl-rich waters (total dissolved solids up to ca. 70 g L⁻¹) containing significant amounts of gas, mainly CH₄ (up to 32 mmol L⁻¹), N₂ (up to 10 mmol L⁻¹), H₂ (up to 3.1 mmol L⁻¹) and He (up to 1.1 mmol L⁻¹) discharge from fracture zones into the drill hole. This water is distinct from the shallow fresh groundwater of the area, and has an isotopic composition typical of shield brines that have been modified during long-term water–rock interaction. Based on water stable isotopes and geochemistry, the drill hole water profile can be divided into five water types, each discharging from separate fracture systems and affected by the surrounding rocks. The δ²H varies from −90‰ to −56‰ (VSMOW) and δ¹⁸O from −13.5‰ to −10.4‰ (VSMOW), plotting clearly above the Global and Local Meteoric Water Lines on a δ²H vs. δ¹⁸O diagram. The ⁸⁷Sr/⁸⁶Sr ratios range between 0.72423 and 0.73668. Simple two-component mixing between ²H and ¹⁸O rich end-member brine and meteoric water cannot explain the water stable isotopic composition and trends observed. Instead, hydration of silicates by ancient groundwaters recharged under different climatic conditions, warmer than at present, is the most likely mechanism to have caused the variation of the δ²H and δ¹⁸O values. Water types correlate with changes in microbial communities implying that different ecosystems occur at different depths. The different water types and microbial populations have remained isolated from each other and from the surface for long periods of time, probably tens of millions of years.     

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).     

The oxygen isotopic composition of phosphate as an effective tracer for phosphate sources in Hongfeng Lake

In order to characterize the oxygen isotopic composition of internal phosphate and explore the possibility of using these data to identify phosphate sources, we measured oxygen isotopic compositions of phosphate (δ¹⁸O_p) in sediment pore water in Hongfeng Lake, a typical deep-water lake in a mountainous area. These data, in combination with δ¹⁸O_p in surface water samples and water column samples, were successfully used to identify phosphate sources. The δ¹⁸O_p value of sediment pore water ranged from 15.2‰ to 15.8‰, with an average value of 15.5‰—the δ¹⁸O_p value of internal phosphate. The δ¹⁸O_p values decreased gradually through the water column from 19.4‰ in surface water to 16.4‰ in deeper water, implying that internal phosphate had more negative δ¹⁸O_p values than external phosphate. This finding was substantiated by horizontal variations in δ¹⁸O_P values, which decreased with increasing distance from inflowing rivers. All collected evidence suggests that external and internal phosphate have distinctly different isotopic signatures and that these signatures have not been considerably altered by biological mediation in Hongfeng Lake. Therefore, δ¹⁸O_P can be used to distinguish phosphate sources. A two-endmember mixing model showed that internal phosphate had an average contribution of 40%, highlighting the influence of internal phosphorus loading on aqueous phosphate and eutrophication. This study illustrates the need to reduce the internal phosphorus load from sediment and provides guidance for nutrient management and in-lake restoration treatment in Hongfeng Lake. The data presented here are limited, but serve to highlight the great potential of δ¹⁸O_p as an effective tracer for identifying phosphate sources. Systematic investigations of the oxygen isotopic compositions of external phosphate, internal phosphate, and phosphate through the water column, in combination with in-lake P biogeochemical cycle study, would be desirable in further research.     

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‰.     

Oxygen Isotopic Study on the Date‐Nagai Skarn‐Type Tungsten Deposit,Northeastern Japan

The skarn‐type tungsten deposit of the Date‐Nagai mine is genetically related to the granodiorite batholith of the Iidateyama body. Skarn is developed along the contact between pelitic hornfels and marble that remains as a small roof pendant body directly above the granodiorite batholith. Zonal arrangement of minerals is observed in skarn. The zonation consists of wollastonite, garnet, garnet‐epidote, and vesuvianite‐garnet zones, from marble to hornfels. Sheelite is included in garnet, garnet‐epidote, and vesuvianite‐garnet zones. The oxygen isotope values of skarn minerals were obtained as δ¹⁸O = 4.2–7.7‰ for garnet, 5.9–6.9‰ for vesuvianite, ?0.3–3.4‰ for scheelite, 6.0–10.9‰ for quartz, and 8.2‰ for muscovite. The temperature of skarn‐formation was calculated from oxygen isotopic values of scheelite‐quartz pairs to be 288°C. Calculated oxygen isotope values of fluid responsible for skarn minerals were 6.1–9.5‰ for garnet, 1.2–4.8‰ for scheelite, ?1.3‐3.6‰ for quartz, and 4.5‰ for muscovite. Garnet precipitated from the fluids of different δ¹⁸O values from scheelite, quartz, and muscovite. These δ¹⁸O values suggest that the origin of fluid responsible for garnet was magmatic water, while evidence for the presence of a meteoric component in the fluids responsible for middle to later stages minerals was confirmed.     

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.     

An approach to estimate Lower Jurassic seawater oxygen‐isotope composition using δ18O and Mg/Ca ratios of belemnite calcites (Early Pliensbachian,northern Spain)

Palaeotemperature estimates from the oxygen‐isotope compositions of belemnites have been hampered by not knowing ancient seawater isotope compositions well enough. We have tackled this problem using Mg/Ca as a proxy for temperature and here, we present a ~2 Ma record of paired Mg/Ca and δ¹⁸O measurements of Jurassic (Early Pliensbachian) belemnites from the Asturian basin as a palaeo‐proxy of seawater oxygen‐isotope composition. From the combined use of the two approaches, we suggest a δ¹⁸O_w composition of about ?0.1‰ for the Jamesoni–Ibex zones. This value may have been increased by about 0.6‰ during the Davoei Zone due to the effect of waters with a different δ¹⁸O_w composition. These findings illustrate the inaccuracy of using a globally homogeneous ice‐free value of δ¹⁸O_w = ?1‰ for δ¹⁸O_carb‐based palaeotemperature reconstructions. Our data suggest that previous palaeotemperatures calculated in the region from δ¹⁸O values of belemnites may have been underestimated as the seawater oxygen isotopic composition could have been higher.