First detection of glacial meltwater signature in tree‐ring δ18O: Reconstructing past major glacier runoff events at Lago Verde (Miage Glacier,Italy)

With the aim of evaluating the influence of glacial meltwater signature on tree‐ring stable isotopes, we analysed δ¹⁸O and δ¹³C in the tree rings of Larix decidua Mill. specimens growing in the area of an ice‐contact lake (Lago Verde, at Miage Glacier, European Alps). Additionally, we analysed δ¹⁸O in the glacial meltwater of the lake and of the glacier stream and compared it with the δ¹⁸O of precipitation predicted by a spatial model. We found that tree‐ring cellulose of trees fed by glacial meltwaters (LVW site) is significantly more depleted in δ¹⁸O than at a control site LVM (?0.91‰) fed only by precipitation, thus reflecting the measured higher depletion of glacial meltwaters with respect to local precipitation. δ¹³C values did not show significant differences in mean values between the two sites but an anomalous correlation with summer temperature was found at the LVW site, probably due to the different responses of trees stomatal conductance. Over the 30‐year period of analysis, four years at LVW (1992, 1995, 2003 and 2009) were markedly depleted in δ¹⁸O. These years are those when the highest summer temperatures were recorded in the area (the ones during which glacier ablation usually increases and more depleted meltwaters fill the lake), with the exception of 1995 during which high water levels occurred following the year with the second highest summer temperature (1994). Overall, our analysis demonstrates that tree‐ring δ¹⁸O, driven by the glacial meltwater signature in the lake, can be used for detecting past major glacier runoff events. The proposed approach could also be used for quantifying past glacier runoff and for defining past distribution areas of glacial meltwaters in glacier forefields, thus contributing to past environmental reconstructions and to hazard assessment.     

Ambiguity in the altitude effect of precipitation isotopes for estimating groundwater recharge elevation and paleoelevation reconstruction in the leeward side of a mountain

The altitude effect of isotopes in precipitation is not as significant on the leeward side of a mountain as it is on the windward side, which makes it difficult to use isotopes at leeward sites, especially if estimating elevation of groundwater recharge or reconstructing paleoelevations. Samples of precipitation were taken at three stations with different elevations—2,306–3,243 m above mean sea level (asl)—on the leeward side of the Meili Snow Mountains on the southeastern Tibetan Plateau from August 2017 to July 2018. The isotope vs. altitude gradients were calculated based on two adjacent stations at the daily, monthly, and annual scales. Most of the gradients are beyond the global ranges of –0.5 to –0.1‰ per 100 m for δ¹⁸O and –5 to –1‰ per 100 m for δ²H, and some of the gradients are even positive. Local processes of sub-cloud evaporation and mixing with recycled moisture are identified for the ambiguous altitude effect, while regional atmospheric circulation processes dominate the major patterns of stable isotope variation at the three stations. The groundwater recharge elevation is estimated to be in a very large range, 2,562–6,321 m asl, which could be caused by the differences in isotope vs. altitude gradient in the studied catchments. Considering the complex atmospheric processes affecting precipitation isotopes, sampling of event-based/monthly precipitation at more than two altitudes for at least one complete hydrological year is a minimum requirement to establish a reasonable isotope vs. altitude gradient.

     

Application of stable carbon isotopes for reconstructing salt‐marsh floral zones and relative sea level,New Jersey,USA

We investigated use of δ¹³C in bulk organic sediment to define the botanical origin of samples preserved in coastal sediment as a means to reconstruct relative sea level in New Jersey, USA. Modern transects at three sites demonstrated that low and high salt‐marsh floral zones dominated by C₄ species (Spartina alterniflora and Spartina patens) were associated with sediment δ¹³C values between ?18.9‰ and ?15.8‰ and occurred from mean tide level (MTL) to mean higher high water (MHHW). Brackish transitional settings vegetated by Phragmites australis with Iva fructescens and Typha sp. (C₃ species) and freshwater upland samples (C₃ species) were characterized by bulk sediment δ¹³C values of ?27.0‰ to ?22.0‰ and existed above MHHW. Parallel transects at one site suggested that intra‐site variability was not discernible. The utility of δ¹³C values for reconstructing relative sea level in New Jersey is limited by an inability to differentiate between brackish sediments related to sea level and freshwater upland samples. To facilitate this distinction in a 4.4 m core, we used a multi‐proxy approach (δ¹³C values with presence or absence of agglutinated foraminifera) to recognize indicative meanings for four sample types. Sediment with δ¹³C values greater than ?18.9‰ was derived from a vegetated salt‐marsh and formed between MTL and MHHW. Sediment with δ¹³C values less than ?22.0‰ and containing agglutinated foraminifera formed in a brackish transitional zone between MHHW and highest astronomical tide (HAT). This is the narrowest elevational range of the four sample types and most precise sea‐level indicator. Sediment with δ¹³C values less than ?22.0‰ and lacking foraminifera can only constrain the upper bound of former sea level. Samples with intermediate values (?22.0‰ to ?18.9‰) formed between MTL and HAT. Using these indicative meanings and radiocarbon dates, we suggest that a transition from brackish to salt‐marsh δ¹³C values recorded in the core took approximately 350 years (from 1800 to 1450 cal. a BP). Copyright © 2011 John Wiley & Sons, Ltd.     

Spatial distribution of mean winter air temperatures in Siberian permafrost at 20−18 ka BP using oxygen isotope data

Palaeotemperature reconstruction for the period of 20?18 ka BP in Siberia is here based on δ¹⁸O analysis and ¹⁴C dating of large syngenetic ice wedges. Dozens of yedoma exposures, from Yamal Peninsula to Chukotka, have been studied. Snow meltwater is considered to be the main source of ice‐wedge ice. The modern relationship between δ¹⁸O composition of ice‐wedge ice and winter temperature is used as a base for reconstruction. In modern ice wedges (elementary veins that have accumulated during the last 60–100 years) δ¹⁸O fluctuates between ?14 and ?20‰ in western Siberia and between ?23 and ?28‰ in northern Yakutia. The trend in δ¹⁸O distribution in ice wedges dated at 20?18 ka BP is similar to the modern one. For example, the δ¹⁸O values in Late Pleistocene wedges are more negative going from west to east by 8–10‰, i.e. from ?19 to ?25‰ in western Siberian ice wedges to ?30 to ?35‰ in northern Yakutia. However, values are as high as ?28 to ?33‰ in north Chukotka and the central areas of the Magadan Region and even as high as ?23 to ?29‰ in the east of Chukotka. The same difference between the oxygen isotope composition of ice wedges in the eastern and western regions of Siberian permafrost (about 8–10‰) is also preserved from 20?18 ka BP to the present: δ¹⁸O values obtained from large ice wedges from the Late Pleistocene vary from ?19 to ?25‰ in western Siberia to ?30 to ?35‰ in northern Yakutia. We conclude that, at 20?18 ka BP, mean January temperatures were about 8–12°C lower (in Chukotka up to 17–18°C) than at present.     

Changes to depositional palaeoenvironments within the Qikou depression (Bohaiwan Basin,China): carbon and oxygen isotopes in lacustrine carbonates of the Palaeogene Shahejie Formation

This paper reports the carbon and oxygen isotope compositions of lacustrine carbonate sediments from the Palaeogene Shahejie Formation, Qikou depression, Bohaiwan Basin, with the aim of determining the palaeoenvironmental conditions in the region. Results from Es₂, the second member of the Shahejie Formation, showed values of δ¹³C and δ¹⁸O from –1.2‰ to +2.4‰ (average +0.6‰) and from –6.8‰ to –4.7‰ (average –5.7‰), respectively, suggesting a relatively hot climate attending deposition. The slightly closed nature of the lake, which contains brackish water, resulted in higher carbonate δ¹³C and δ¹⁸O values than in a meteoric environment. The values of δ¹³C and δ¹⁸O preserved within the carbonates of the overlying lower Shahejie I (Es₁) varied between +1.3‰ and +4.9‰ (average +3.2‰) and from ?4.4‰ to ?1.8‰ (average ?3.1‰), respectively, indicating that the climate became colder at that time. Subsequently, a marine transgression caused the salinity of the lake water to increase. The values of δ¹³C and δ¹⁸O were controlled by salinity. The high δ¹³C values were also influenced by the rapid burial of the lake organisms and by algal photosynthesis. Values of δ¹³C and δ¹⁸O from carbonates in upper Es₁ ranged from ?8.0‰ to +11.0‰ (average +10.1‰) and from ?5.0‰ to ?1.5‰ (average ?3.4‰), respectively, indicating a slight increase in the temperature over time. In the closed and reducing environment, extremes in δ¹³C values resulted from biochemical fermentation. The positive δ¹³C excursion recorded in the carbonates of the Shahejie Formation in the Qikou depression indicates that the palaeoclimate underwent a significant transformation during the Eocene and the Oligocene.     

Hydrogen and oxygen isotopic compositions of meteoric waters in the eastern part of China

42 meteoric water samples were analyzed for their δ¹⁸O and δD values. It can be seen that both δ¹⁸O and δD values vary synchronously with latitude along our investigation-tour route from Guangxi (22.7 NL°) to Heilongjiang (48.8 NL°). Their relationship is presented as follows: δ¹⁸O(‰)=?0.24 NL° + 0.04 and δD(‰)=?1.84 NL° + 6.88. The relationship between δ¹⁸O, δD and altitude in the southeastern part of the Guizhou Plateau is: $$ - \delta ^{1{\rm B}} O(\% o) = 0.003H(m) + 5.24 and - \delta D(\% o) = 0.0134H(m) + 39.8.$$      

Oxygen isotope speedometry in granulite facies garnet recording fluid/melt–rock interaction (Sør Rondane Mountains,East Antarctica)

In situ analysis of a garnet porphyroblast from a granulite facies gneiss from Sør Rondane Mountains, East Antarctica, reveals discontinuous step‐wise zoning in phosphorus and large δ¹⁸O variations from the phosphorus‐rich core to the phosphorus‐poor rim. The gradually decreasing profile of oxygen isotope from the core (δ¹⁸O = ~15‰) to the rim (δ¹⁸O = ~11‰) suggests that the ¹⁸O/¹⁶O zoning was originally step‐wise, and modified by diffusion after the garnet rim formation at ~800°C and 0.8 GPa. Fitting of the ¹⁸O/¹⁶O data to the diffusion equation constrains a duration of the high‐T event (~800°C) to c. 0.5–40 Ma after the garnet rim formation. The low δ¹⁸O value of the garnet rim, together with the previously reported low δ¹⁸O values in metacarbonates, indicates regional infiltration, probably along a detachment fault, of low δ¹⁸O fluid/melt possibly derived from meta‐mafic to ultramafic rocks.     

The δ18O of UST Quartz in Two Porphyry Deposits,China

The unidirectional solidification textures (UST) quartz is generally thought to form from fluids exsolved from shallow intrusions and/or magma chambers, but such an idea is still poorly constrained from the evidence of stable isotopes. In this study, we report for the first time the δ¹⁸O of quartz that shows UST from the Qulong Cu–Mo and the Yechangping Mo porphyry deposits in China. The analysis results show that the UST quartz samples from the Qulong deposit have δ¹⁸O values ranging from +6.2 ‰ to +7.6 ‰, which are similar to that of quartz phenocrysts (+6.7 ‰ to +7.8 ‰). In contrast, the UST quartz samples from the Yechangping porphyry Mo deposit yield a high δ¹⁸O value (+10.0 ‰). The δ¹⁸O_water value of Yechangping UST quartz (+8.5 ‰) is also higher than that of Qulong (+4.6 ‰ to +5.8 ‰). Hydrothermal biotite from potassic alteration and sericite from early phyllic alteration at Qulong have similar δ¹⁸O values to UST quartz, suggesting the involvement of magmatic fluids during this stage of deposit evolution.     

The effect of species on lacustrine δ18Odiatom and its implications for palaeoenvironmental reconstructions

The oxygen isotope composition of diatom silica (δ¹⁸O_diatom) is increasingly being used to reconstruct climate from marine and lacustrine sedimentary archives. Although diatoms are assumed to precipitate their frustule in isotopic equilibrium with their surrounding water, it is unclear whether internal processes of a given species affect the fractionation of oxygen between the water and the diatom. We present δ¹⁸O_diatom data from two diatom size fractions (3–38 and >38 µm) characterized by different species in a sediment core from Heart Lake, Alaska. Differences in δ¹⁸O_diatom between the two size fractions varies from 0 to 1.2‰, with a mean offset of 0.01‰ (n = 20). Fourier transform infrared spectroscopy confirms our samples consist of pure biogenic silica (SiO₂) and δ¹⁸O_diatom trends are not driven by contamination. The maximum offset is outside the range of error, but the mean is within analytical error of the technique (± 1.06‰), demonstrating no discernible species‐dependent fractionation in δ¹⁸O_diatom. We conclude that lacustrine δ¹⁸O_diatom measurements offer a reliable and valuable method for reconstructing δ¹⁸O_water. Considering the presence of small offsets in our two records, we advise interpreting shifts in δ¹⁸O_diatom only where the magnitude of change is greater than the combined analytical error.     

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.     

Constraints from zircon U–Pb ages, O and Hf isotopic compositions on the origin of Neoproterozoic peraluminous granitoids from the Jiangnan Fold Belt, South China

Zircon textures and micro-chemical compositions precisely record the origin and petrogenesis of granitoids, which are crucial for evaluating crustal growth and reworking, thermal and geodynamic evolution. Zircons in peraluminous granitoids from the three largest 820 Ma complexes (Guibei, Yueyang and Jiuling) in the Jiangnan Fold Belt in South China are used to constrain their sources and petrogenetic processes. Zircons in the Guibei granitoids have complex internal structures. Nearly all magmatic and inherited zircons have similar εHf (?6.8 to +5.6) and δ¹⁸O values (8.8–11.6 ‰) and dominantly lie between εHf evolution vectors for a crust created between 1.7 and 2.1 Ga, suggesting that the Guibei granitoids were produced by partial melting of recycled heterogeneous supracrustal material. However, the Yueyang granitoids contain zircons with high εHf (?0.5 to +9.7) and relatively low δ¹⁸O values (5.9–8.4 ‰) and two-stage model ages of 1.1–1.8 Ga, and thus may have been formed by melting of mafic rocks from the lower crust. The Jiuling granitoids and their enclaves contain more complex zircons with more variable εHf (?7.2 to +9.7) and δ¹⁸O values (7.0–10.6 ‰), and lie along the mixing trend between the above-proposed infracrustal and supracrustal granitoids. Therefore, the Neoproterozoic peraluminous granitoids in the Jiangnan Fold Belt were produced by melting and mixing of continental crust. Compared with extremely low (≤4 ‰) and negative δ¹⁸O values of Neoproterozoic igneous zircons formed in its northern active continental margin, the high δ¹⁸O peraluminous granitoids in the southeastern Yangtze Block are considered to have been formed by melting of hydrothermally unaltered continental crust triggered by asthenosphere upwelling in the Nanhua back-arc basin.     

Evidence for high temperature and 18O‐enriched fluids in the Arab‐D of the Ghawar Field,Saudi Arabia

Using the clumped isotope method, the temperature of dolomite and calcite formation and the oxygen isotopic composition (δ¹⁸O_w) of the diagenetic fluids have been determined in a core taken from the Arab‐D of the Ghawar field, the largest oil reservoir in the world. These analyses show that while the dolomites and limestones throughout the major zones of the reservoir recrystallized at temperatures between ca 80°C and 100°C, the carbonates near the top of the reservoir formed at significantly lower temperatures (20 to 30°C). Although the δ¹⁸O values of the diagenetic fluids show large variations ranging from ca <0‰ to ca +8‰, the variations exhibit consistent downhole changes, with the highest values being associated with the portion of the reservoir with the highest permeability and porosity. Within the limestones, dolomites and dolomites associated with the zone of high permeability, there are statistically significant different trends between the δ¹⁸O_w values and recrystallization temperature. These relationships have different intercepts suggesting that fluids with varying δ¹⁸O_w values were involved in the formation of dolomite and limestone compared to the formation of dolomite associated with the zone of high permeability. These new data obtained using the clumped isotope technique show how dolomitization and recrystallization by deep‐seated brines with elevated δ¹⁸O_w values influence the δ¹⁸O values of carbonates, possibly leading to erroneous interpretations unless temperatures can be adequately constrained.     

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.     

Local distribution of oxygen isotopes and fluid exchange during genesis of the corundum-bearing rocks of Khitostrov Island

New data are presented on the distribution of oxygen isotopes and conditions of the local isotope equilibrium in high-Al rocks rocks of Khitostrov Island showing abnormally low δ¹⁸O values (below–25‰). The temperatures of isotope equilibrium are within 400–475°C. The minimum δ¹⁸O values have been registered in the in plagioclase, whereas the same phases in kyanite-bearing rocks lacking corundum demonstrate δ¹⁸O values usually 3–5‰ higher. The fluid δ¹⁸O value varies from–22 to–16‰ at 475 ± 15°C, from–18 to–23‰ at 425 ± 25°C, and from–17 to–22‰ at 380 ± 15°C. The results obtained do not require abnormal depletion of δ¹⁸O values owing to the infiltration of an external fluid under the Svecofennian transformations. The association of corundum-bearing rocks with the basic intrusions, the presence of zircon cores of older ages compared to these rocks, and the peculiarities of rock chemistry may be ascribed to the fact that lower crustal layers of ancient rocks depleted in δ¹⁸O before metamorphism were captured by basite melts.     

Physicochemical formation conditions of banded iron formations and high-grade iron ores in the region of the Kursk Magnetic Anomaly: Evidence from isotopic data

The oxygen and carbon isotopic compositions of minerals from banded iron formations (BIFs) and high-grade ore in the region of the Kursk Magnetic Anomaly (KMA) were determined in order to estimate the temperature of regional metamorphism and the nature of rock-and ore-forming solutions. Magnetite and hematite of primary sedimentary or diagenetic origin have δ¹⁸O within the range from +2 to 6‰. During metamorphism, primary iron oxides, silicates, and carbonates were involved in thermal dissociation and other reactions to form magnetite with δ¹⁸O = +6 to +11‰. As follows from a low δ¹⁸O_av = ?3.5‰ of mushketovite (magnetite pseudomorphs after hematite) in high-grade ore, this mineral was formed as a product of hematite reduction by organic matter. The comparison of δ¹⁸O of iron oxides, siderite, and quartz from BIFs formed at different stages of the evolution of the Kursk protogeosyncline revealed specific sedimentation (diagenesis) conditions and metamorphism of the BIFs belonging to the Kursk and Oskol groups. BIF of the Oskol Group is distinguished by a high δ¹⁸O of magnetite compared to other Proterozoic BIFs. Martite ore differs from host BIF by a low δ¹⁸O = ?0.2 to ?5.9‰. This implies that oxygen from infiltration water was incorporated into the magnetite lattice during the martite formation. Surface water penetrated to a significant depth through tectonic faults and fractures.     

Petrogenesis of low-δ<Superscript>18</Superscript>O quartz porphyry dykes,Koegel Fontein complex,South Africa

This paper investigates the origin of low-δ¹⁸O quartz porphyry dykes associated with the 144–133 Ma Koegel Fontein Igneous Complex, which was intruded during the initial phase of breakup of Africa and South America. The 25-km diameter Rietpoort Granite is the largest and youngest phase of activity, and is roofed by a 10-km diameter pendant of gneiss. Quartz porphyry (QP) dykes, up to 15 m in width, strike NW–SE across the complex. The QP dykes that intruded outside the granite have similar quartz phenocryst δ¹⁸O values (average 8.0‰, ± 0.7, n?=?33) to the granite (average 8.3?±?1.0, n?=?7). The QP dykes that intruded the roof pendant have quartz phenocrysts with more variable δ¹⁸O values (average 1.6‰, ± 2.1, n?=?55). In some cases quartz phenocrysts have δ¹⁸O values as low as ? 2.5‰. The variation in δ¹⁸O value within the quartz crystal population of individual dykes is small relative to the overall range, and core and rim material from individual quartz phenocrysts in three samples are identical within error. There is no evidence that quartz phenocryst δ¹⁸O values have been affected by fluid–rock interaction. Based on a ?_quartz?magma value of 0.6‰, magma δ¹⁸O values must have been as low as ? 3.1‰. Samples collected along the length of the two main QP dykes that traverse the roof pendant have quartz phenocryst δ¹⁸O values that range from +?1.1 to +?4.6‰, and ? 2.3 to +?5.6‰, respectively. These δ¹⁸O values correlate negatively (r = ? 0.96) with initial ⁸⁷Sr/⁸⁶Sr, which can be explained by the event that lowered δ¹⁸O values of the source being older than the dykes. We suggest that the QP dykes were fed by magma produced by partial melting of gneiss, which had been variably altered at high temperature by ¹⁸O-depleted meteoric water during global glaciation at ~?550 Ma. The early melts had variable δ¹⁸O value but as melt pockets interconnected during melting, the δ¹⁸O values approached that of average gneiss. Variable quartz phenocryst δ¹⁸O values in the same dyke can be explained by vertical emplacement, at variable rates of ascent along the dyke. The lateral variation in quartz, and hence magma δ¹⁸O value at a particular point along a single dyke would depend on the rate of ascent of magma at that point along the dyke, and the ‘age’ of the particular magma batch.     

High‐Precision,High‐Accuracy Oxygen Isotope Measurements of Zircon Reference Materials with the SHRIMP‐SI

Analytical protocols for SHRIMP‐SI oxygen isotope analysis (δ¹⁸O) of a suite of zircon reference materials (RMs) are presented. Data reduction involved a robust estimate of uncertainties associated with the individual spot as well as for groups where the spot data are combined. The repeatability of δ¹⁸O measurements is dependent on both the analytical conditions and the choice of the primary reference material. Under optimised conditions, repeatability was often better than 0.4‰ (2s) allowing sample uncertainties to be obtained to better than 0.2‰ (at 95% confidence limit). Single spot uncertainty combined the within‐spot precision with the scatter associated with repeated measurements of the primary zircon reference material during a measurement session. The uncertainty for individual spots measured under optimised conditions was between 0.3 and 0.4‰ (at 95% confidence). The analytical protocols described were used to assess a variety of zircon RMs that have been used for geochronology and for which laser fluorination oxygen isotope data are available (Temora 2, FC1, R33, QGNG and Ple?ovice), as well as zircons that have been used as RMs for trace element or other types of determination (Mud Tank, Monastery, 91500, AS57, AS3, KIM‐5, OG1, SL13, CZ3 and several other Sri Lankan zircons). Repeated analyses over nine sessions and seven different mounts show agreement within analytical uncertainty for Temora 2, FC1, R33, QGNG, Ple?ovice and 91500, when normalised to Mud Tank. For existing ion microprobe mounts with these materials, an appropriate δ¹⁸O can be determined. However, care should be taken when using zircons from the Duluth Complex (i.e., FC1, AS57 and AS3) as reference materials as our data indicated an excess scatter on δ¹⁸O values associated with low‐U zircon grains.     

Stable isotopic evidence for Middle Pleistocene environmental change from a loess‐paleosol sequence: Kärlich,Germany

Loess‐paleosol sequences are important terrestrial archives of palaeoenvironmental change. Such sequences are rich in pedogenic carbonate, the oxygen and carbon isotopic values of which can provide important palaeoenvironmental information. Although some studies have pioneered the use of O and C isotopes in loess‐paleosol sequences, they are not routinely used as palaeoclimate proxies. In this study we analysed the sedimentology, micromorphology, geochronology and isotopic geochemistry of a Middle Pleistocene loess‐paleosol section, located at Kärlich, Germany. The section studied correlates with the Elsterian glacial (MIS 12) and Holsteinian interglacial (MIS 11). Embedded tephra layers yielded ⁴⁰Ar/³⁹Ar ages of 466±3 ka, 447±1 ka and 361±3 ka. The sedimentology and micromorphology of the sequence record a shift from accretionary loess accumulation (MIS 12) to prolonged pedogenesis at a stable land surface (MIS 11). Soil carbonate δ¹⁸O values record an enrichment of ～3‰ during the accumulation of the loess, reaching peak values comparable with those found in the MIS 11 soil. The δ¹⁸O signal is interpreted as reflecting temperature, highlighting the potential of δ¹⁸O analysis of European loess soil carbonates as a means of reconstructing palaeotemperature history.     

Sub‐mantle δ18O Zircons in Malani rhyolites: Clues for a Rodinia Linkage between South China and NW India

The Malani Igneous Suite (MIS) in NW India represents one of the largest and well‐preserved Precambrian felsic igneous provinces, with minor mafic volcanics and dykes. The SIMS (Secondary Ion Mass Spectrometric) zircon U‐Pb geochronology yielded 776.8 ± 4.5 to 758.5 ± 6.9 Ma ages for rhyolites from Jodhpur region and Sindreth Basin while dacite sample from Punagarh Basin was dated to 760.5 ± 10 Ma. Zircons from rhyolitic and dacitic lavas have oxygen isotopic compositions that can be grouped into low δ¹⁸OV‐SMOW (4.12 to ‐1.11‰) and high (δ¹⁸O = 8.23‐5.12‰) categoroes, respectively. The low δ¹⁸O zircons have highly radiogenic Hf isotopic compositions (ε_Hf(t)= +13.0 to +3.6) suggesting high temperature bulk cannibalization of upper level juvenile crust as the essential process for magma generation. Older than 800 Ma xenocrystic zircons in dacite have high δ¹⁸O values whereas 795 Ma ones have mantle‐like Hf‐O isotopic compositions, reflecting a significant shift in tectono‐thermal regime in NW India during 800‐780 Ma. A synchronous transition in the South China Block and Madagascar suggests a spatially and temporally linked geodynamic system. Geochemical data in combination with the new isotopic results point towards an overall convergent plate margin setting undergoing localized lithospheric extension. The NW India and South China blocks together with Madagascar and the Seychelles lay either along the periphery of Rodinia or off the supercontinent with the age of convergent plate margin magmatism coinciding with breakup of the supercontinent.     

Tectonic environments of sapphire and ruby revealed by a global oxygen isotope compilation

Many sapphire and ruby occurrences are spatially linked with orogenic belts such as the Pan-African Orogen, the Himalayas, and regions of active or former subduction along the western margin of the Pacific Ocean. These gemstones have oxygen isotope compositions (δ¹⁸O) that span >45‰, reflecting the wide range of environments and conditions involved in corundum (Al₂O₃) formation. We compiled a global data base of sapphire and ruby δ¹⁸O, from which the following major groups of gemstones emerge: a dominant population of sapphires with δ¹⁸O centred around 5.5‰ (the mantle value) that is spatially related to regions of former subduction; a lesser population of sapphires and rubies with slightly higher δ¹⁸O that are associated with skarn and pegmatite; rubies with relatively low δ¹⁸O of 0‰–7‰ that occur in hydrothermally altered ultramafic metamorphic rocks in collision zones; and rubies with high δ¹⁸O of 14‰–25‰ that are found, almost exclusively, in Himalayan marble. The spatial distribution of the δ¹⁸O groups relative to plate boundaries provides insight into the two major periods of continental collision involved in sapphire and ruby formation: the Ediacaran collision of East and West Gondwana (the East African Orogeny) and the Cenozoic collision of India and Asia.