Secondary Ion Mass Spectrometry Bias on Isotope Ratios in Dolomite–Ankerite,Part II: δ13C Matrix Effects

This study is Part II of a series that documents the development of a suite of calibration reference materials for in situ SIMS analysis of stable isotope ratios in Ca‐Mg‐Fe carbonates. Part I explored the effects of Fe²⁺ substitution on SIMS δ¹⁸O bias measured from the dolomite–ankerite solid solution series [CaMg(CO₃)₂–CaFe(CO₃)₂], whereas this complementary work explores the compositional dependence of SIMS δ¹³C bias (calibrated range: Fe# = 0.004–0.789, where Fe# = molar Fe/(Mg+Fe)). Under routine operating conditions for carbonate δ¹³C analysis at WiscSIMS (CAMECA IMS 1280), the magnitude of instrumental bias increased exponentially by 2.5–5.5‰ (session‐specific) with increasing Fe‐content in the dolomite structure, but appeared insensitive to minor Mn substitution [< 2.6 mole % Mn/(Ca+Mg+Fe+Mn)]. The compositional dependence of bias (i.e., the matrix effect) was expressed using the Hill equation, yielding calibration residual values ≤ 0.3‰ relative to CRM NBS‐19 for eleven carbonate reference materials (6‐μm‐diameter spot size measurements). Based on the spot‐to‐spot repeatability of a drift monitor material that ‘bracketed’ each set of ten sample‐spot analyses, the analytical precision was ± 0.6–1.2‰ (2s, standard deviations). The analytical uncertainty for individual sample analyses was approximated by combining the precision and calibration residual values (propagated in quadrature), suggesting an uncertainty of ± 1.0–1.5‰ (2s).     

Secondary Ion Mass Spectrometry Bias on Isotope Ratios in Dolomite–Ankerite,Part I: δ18O Matrix Effects

We document the development of a suite of carbonate mineral reference materials for calibrating SIMS determinations of δ¹⁸O in samples with compositions along the dolomite–ankerite solid solution series [CaMg(CO₃)₂–CaFe(CO₃)₂]. Under routine operating conditions for the analysis of carbonates for δ¹⁸O with a CAMECA IMS 1280 instrument (at WiscSIMS, University of Wisconsin‐Madison), the magnitude of instrumental bias along the dolomite–ankerite series decreased exponentially by ~ 10‰ with increasing Fe content in the dolomite structure, but appeared insensitive to minor Mn substitution [< 2.6 mol% Mn/(Ca+Mg+Fe+Mn)]. The compositional dependence of bias (i.e., the sample matrix effect) was calibrated using the Hill equation, which relates bias to the Fe# of dolomite–ankerite [i.e., molar Fe/(Mg+Fe)] for thirteen reference materials (Fe# = 0.004–0.789); for calibrations employing either 10 or 3 μm diameter spot size measurements, this yielded residual values ≤ 0.3–0.4‰ relative to CRM NBS 19 for most reference materials in the suite. Analytical precision was ± 0.3‰ (2s, standard deviations) for 10‐μm spots and ± 0.7‰ (2s) for 3‐μm spots, based on the spot‐to‐spot repeatability of a drift monitor material that ‘bracketed’ each set of ten sample‐spot analyses. Analytical uncertainty for individual sample analyses was approximated by a combination of precision and calibration residual values (propagated in quadrature), suggesting an uncertainty of ± 0.5‰ (2s) for 10‐μm spots and ± 1‰ (2s) for 3‐μm spots.     

Development and Re‐Evaluation of Tourmaline Reference Materials for In Situ Measurement of Boron δ Values by Secondary Ion Mass Spectrometry

Six tourmaline samples were investigated as potential reference materials (RMs) for boron isotope measurement by secondary ion mass spectrometry (SIMS). The tourmaline samples are chemically homogeneous and cover a compositional range of tourmaline supergroup minerals (primarily Fe, Mg and Li end‐members). Additionally, they have homogeneous boron delta values with intermediate precision values during SIMS analyses of less than 0.6‰ (2s). These samples were compared with four established tourmaline RMs, that is, schorl IAEA‐B‐4 and three Harvard tourmalines (schorl HS#112566, dravite HS#108796 and elbaite HS#98144). They were re‐evaluated for their major element and boron delta values using the same measurement procedure as the new tourmaline samples investigated. A discrepancy of about 1.5‰ in δ¹¹B was found between the previously published reference values for established RMs and the values determined in this study. Significant instrumental mass fractionation (IMF) of up to 8‰ in δ¹¹B was observed for schorl–dravite–elbaite solid solutions during SIMS analysis. Using the new reference values determined in this study, the IMF of the ten tourmaline samples can be modelled by a linear combination of the chemical parameters FeO + MnO, SiO₂ and F. The new tourmaline RMs, together with the four established RMs, extend the boron isotope analysis of tourmaline towards the Mg‐ and Al‐rich compositional range. Consequently, the in situ boron isotope ratio of many natural tourmalines can now be determined with an uncertainty of less than 0.8‰ (2s).     

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 isotope geochemistry of magnesite from Holocene salt lake deposits,Taoudenni, Mali

Stable isotope data (δ¹⁸O, δ¹³C) were obtained for magnesite (MgCO₃) from Holocene salt lake deposits of the Taoudenni–Agorgott basin, Mali, in which it is the only carbonate mineral present. The deposits have a high glauberite content (Na₂Ca(SO₄)₂), representing a type of continental evaporite formation that is commonly magnesite‐bearing. Samples from seven different levels in a 5 m long sequence were analysed. δ¹⁸O_V‐PDB values are between +3.17 and +5.91‰, which is lower than might be expected for evaporitic environments, recording reduced ¹⁸O enrichment at high salinity. δ¹³C_V‐PDB values are between −1.32‰ and −4.79‰, showing an influence of carbon derived from the decomposition of organic matter rather than from exchange with atmospheric CO₂. Covariance between δ¹⁸O and δ¹³C is strong for the lower part of the sequence, recording coupled ¹⁸O and ¹³C enrichment as commonly observed for closed basins. Covariance is lacking for the upper part of the sequence, with only periodic massive magnesite deposition in a more shallow lake. Copyright © 2012 John Wiley & Sons, Ltd.     

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.     

NIST RM 8301 Boron Isotopes in Marine Carbonate (Simulated Coral and Foraminifera Solutions): Inter‐laboratory δ11B and Trace Element Ratio Value Assignment

The boron isotopic ratio of ¹¹B/¹⁰B (δ¹¹B_SRM951) and trace element composition of marine carbonates are key proxies for understanding carbon cycling (pH) and palaeoceanographic change. However, method validation and comparability of results between laboratories requires carbonate reference materials. Here, we report results of an inter‐laboratory comparison study to both assign δ¹¹B_SRM951 and trace element compositions to new synthetic marine carbonate reference materials (RMs), NIST RM 8301 (Coral) and NIST RM 8301 (Foram) and to assess the variance of data among laboratories. Non‐certified reference values and expanded 95% uncertainties for δ¹¹B_SRM951 in NIST RM 8301 (Coral) (+24.17‰ ± 0.18‰) and NIST RM 8301 (Foram) (+14.51‰ ± 0.17‰) solutions were assigned by consensus approach using inter‐laboratory data. Differences reported among laboratories were considerably smaller than some previous inter‐laboratory comparisons, yet discrepancies could still lead to large differences in calculated seawater pH. Similarly, variability in reported trace element information among laboratories (e.g., Mg/Ca ± 5% RSD) was often greater than within a single laboratory (e.g., Mg/Ca < 2%). Such differences potentially alter proxy‐reconstructed seawater temperature by more than 2 °C. These now well‐characterised solutions are useful reference materials to help the palaeoceanographic community build a comprehensive view of past ocean changes.     

Palaeoproterozoic magnesite: lithological and isotopic evidence for playa/sabkha environments

Magnesite forms a series of 1‐ to 15‐m‐thick beds within the ≈2·0 Ga (Palaeoproterozoic) Tulomozerskaya Formation, NW Fennoscandian Shield, Russia. Drillcore material together with natural exposures reveal that the 680‐m‐thick formation is composed of a stromatolite–dolomite–‘red bed’ sequence formed in a complex combination of shallow‐marine and non‐marine, evaporitic environments. Dolomite‐collapse breccia, stromatolitic and micritic dolostones and sparry allochemical dolostones are the principal rocks hosting the magnesite beds. All dolomite lithologies are marked by δ¹³C values from +7·1‰ to +11·6‰ (V‐PDB) and δ¹⁸O ranging from 17·4‰ to 26·3‰ (V‐SMOW). Magnesite occurs in different forms: finely laminated micritic; stromatolitic magnesite; and structureless micritic, crystalline and coarsely crystalline magnesite. All varieties exhibit anomalously high δ¹³C values ranging from +9·0‰ to +11·6‰ and δ¹⁸O values of 20·0–25·7‰. Laminated and structureless micritic magnesite forms as a secondary phase replacing dolomite during early diagenesis, and replaced dolomite before the major phase of burial. Crystalline and coarsely crystalline magnesite replacing micritic magnesite formed late in the diagenetic/metamorphic history. Magnesite apparently precipitated from sea water‐derived brine, diluted by meteoric fluids. Magnesitization was accomplished under evaporitic conditions (sabkha to playa lake environment) proposed to be similar to the Coorong or Lake Walyungup coastal playa magnesite. Magnesite and host dolostones formed in evaporative and partly restricted environments; consequently, extremely high δ¹³C values reflect a combined contribution from both global and local carbon reservoirs. A ¹³C‐rich global carbon reservoir (δ¹³C at around +5‰) is related to the perturbation of the carbon cycle at 2·0 Ga, whereas the local enhancement in ¹³C (up to +12‰) is associated with evaporative and restricted environments with high bioproductivity.     

The δ60/58Ni Values of Twenty‐Six Selected Geological Reference Materials

The high‐precision δ^60/58Ni values of twenty‐six geological reference materials, including igneous rocks, sedimentary rocks, stream sediments, soils and plants are reported. The δ^60/58Ni values of all samples were determined by double‐spike MC‐ICP‐MS (Nu Plasma III). Isotope standard solution (NIST SRM 986) and geological reference materials (BHVO‐2, BCR‐2, JP‐1, PCC‐1, etc.) were used to evaluate the measurement bias and intermediate precision over a period of six months. Our results show that the intermediate precision of Ni isotope determination was 0.05‰ (2s, n = 69) for spiked NIST SRM 986 and typically 0.06‰ for actual samples, and the δ^60/58Ni _{NIST SRM 986} values were in excellent agreement with previous studies. Eighteen high‐precision Ni isotope ratios of geological reference materials are first reported here, and their δ^60/58Ni values varied from ?0.27‰ to 0.52‰, with a mean of 0.13 ± 0.34‰ (2s, n = 18). Additionally, SGR‐1b (0.56 ± 0.04‰, 2s), GSS‐1 (?0.27 ± 0.06‰, 2s), GSS‐7 (?0.11 ± 0.01‰, 2s), GSD‐10 (0.46 ± 0.06‰, 2s) and GSB‐12 (0.52 ± 0.06‰, 2s) could potentially serve as candidate reference materials for Ni isotope fractionation and comparison of Ni isotopic compositions among different laboratories.     

New Reference Materials and Assessment of Matrix Effects for SIMS Measurements of Oxygen Isotopes in Garnet

Accurate ion microprobe analysis of oxygen isotope ratios in garnet requires appropriate reference materials to correct for instrumental mass fractionation that partly depends on the garnet chemistry (matrix effect). The matrix effect correlated with grossular, spessartine and andradite components was characterised for the Cameca IMS 1280HR at the SwissSIMS laboratory based on sixteen reference garnet samples. The correlations fit a second‐degree polynomial with maximum bias of ca. 4‰, 2‰ and 8‰, respectively. While the grossular composition range 0–25% is adequately covered by available reference materials, there is a paucity of them for intermediate compositions. We characterise three new garnet reference materials GRS2, GRS‐JH2 and CAP02 with a grossular content of 88.3 ± 1.2% (2s), 83.3 ± 0.8% and 32.5 ± 3.0%, respectively. Their micro scale homogeneity in oxygen isotope composition was evaluated by multiple SIMS sessions. The reference δ¹⁸O value was determined by CO₂ laser fluorination (δ¹⁸O_LF). GRS2 has δ¹⁸O_LF = 8.01 ± 0.10‰ (2s) and repeatability within each SIMS session of 0.30–0.60‰ (2s), GRS‐JH2 has δ¹⁸O_LF = 18.70 ± 0.08‰ and repeatability of 0.24–0.42‰ and CAP02 has δ¹⁸O_LF = 4.64 ± 0.16‰ and repeatability of 0.40–0.46‰.     

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.     

Stable isotopic signatures of the modern land snail Eremina desertorum from a low-latitude (hot) dry desert—A study from the Petrified Forest,New Cairo,Egypt

This study was conducted on recent desert samples—including (1) soils, (2) plants, (3) the shell, and (4) organic matter from modern specimens of the land snail Eremina desertorum—which were collected at several altitudes (316–360 m above sea level) from a site in the New Cairo Petrified Forest. The soils and shell_{E. desertorum} were analyzed for carbonate composition and isotopic composition (δ¹⁸O, δ¹³C). The plants and organic matter_{E. desertorum} were analyzed for organic carbon content and δ¹³C. The soil carbonate, consisting of calcite plus minor dolomite, has δ¹⁸O values from −3.19 to −1.78‰ and δ¹³C values −1.79 to −0.27‰; covariance between the two values accords with arid climatic conditions. The local plants include C3 and C4 types, with the latter being dominant. Each type has distinctive bulk organic carbon δ¹³C values: −26.51 to −25.36‰ for C3-type, and −13.74 to −12.43‰ for C4-type plants.The carbonate of the shell_{E. desertorum} is composed of aragonite plus minor calcite, with relatively homogenous isotopic compositions (δ¹⁸O_mean = −0.28 ± 0.22‰; δ¹³C_mean = −4.46 ± 0.58‰). Most of the δ¹⁸O values (based on a model for oxygen isotope fractionation in an aragonite-water system) are consistent with evaporated water signatures. The organic matter_{E. desertorum} varies only slightly in bulk organic carbon δ¹³C values (−21.78 ± 1.20‰) and these values suggest that the snail consumed more of C3-type than C4-type plants. The overall offset in δ¹³C values (−17.32‰) observed between shell_{E. desertorum} carbonate and organic matter_{E. desertorum} exceeds the value expected for vegetation input, and implies that 30% of carbon in the shell_{E. desertorum} carbonate comes from the consumption of limestone material.     

Quartz Reference Materials for Oxygen Isotope Analysis by SIMS

Two quartz samples of igneous origin, UNIL‐Q1 (Torres del Paine Intrusion, Chile) and BGI‐Q1 (Shandong province, China), were calibrated for their oxygen isotope composition for SIMS measurements. UNIL‐Q1 and BGI‐Q1 were evaluated for homogeneity using SIMS. Their reference δ¹⁸O values were determined by CO₂ laser fluorination. The average δ¹⁸O value found for UNIL‐Q1 is 9.8 ± 0.06‰ and that for BGI‐Q1 is 7.7 ± 0.11‰ (1s). The intermediate measurement precision of SIMS oxygen isotope measurements was 0.32–0.41‰ (2s; UNIL‐Q1) and 0.40–0.48‰ (2s; BGI‐Q1), respectively. While less homogeneous in its oxygen isotope composition, BGI‐Q1 is also suitable for SIMS trace element measurements.     

Early‐middle Holocene land snail shell stable isotope record from Grotta di Latronico 3 (southern Italy)

This paper compares stable isotope (δ¹⁸O and δ¹³C) records of early–middle Holocene land snail shells from the archaeological deposits of Grotta di Latronico 3 (LTR3; southern Italy) with modern shell isotopic data. No substantial interspecific variability was observed in shell δ¹⁸O (δ¹⁸Os) of modern specimens (Pomatias elegans, Cornu aspersum, Eobania vermiculata, Helix ligata and Marmorana fuscolabiata). In contrast, interspecific shell δ¹³C (δ¹³Cs) variability was significant, probably due to different feeding behaviour among species. The δ¹⁸Os values of living land snails suggest that species hibernate for a long period during colder months, so that the signal of ¹⁸O‐depleted winter rainfall in their δ¹⁸Os is lost. This suggests that δ¹⁸Os and δ¹³Cs values of Pomatias elegans from this archaeological succession provide valuable clues for seasonal (spring–autumn) climatic conditions during the early–middle Holocene. The δ¹⁸Os values of fossil specimens are significantly lower than in modern shells and in agreement with other palaeoclimatic records, suggesting a substantial increase of precipitation and/or persistent changes in air mass source trajectories over this region between ca. 8.8 cal ka BP and 6.2–6.7 ka ago. The δ¹³Cs trend suggests a transition from a slightly ¹³C‐enriched to a ¹³C‐depleted diet between early and middle Holocene compared to present conditions. We postulate that this δ¹³Cs trend might reflect changes in the C3 vegetation community, potentially combined with other environmental factors such as regional moisture increase and the progressive decrease of atmospheric CO₂ concentration. Copyright © 2010 John Wiley & Sons, Ltd.     

First Reliable Re–Os Ages of Pyrite and Stable Isotope Compositions of Fe(‐Cu) Deposits in the Hami Region,Eastern Tianshan Orogenic Belt,NW China

The Eastern Tianshan Orogenic Belt (ETOB) in NW China is composed of the Dananhu–Tousuquan arc belt, the Kanggurtag belt, the Aqishan–Yamansu belt and the Central Tianshan belt from north to south. These tectonic belts have formed through arc–continent or arc–arc collisions during the Paleozoic. A number of Fe(‐Cu) deposits in the Aqishan–Yamansu belt, including the Heifengshan, Shuangfengshan and Shaquanzi Fe(‐Cu) deposits, are associated with Carboniferous–Early Permian volcanic rocks and are composed of vein‐type magnetite ores. Metallic minerals are dominated by magnetite and pyrite, with minor chalcopyrite. Calcite, chlorite, and epidote are the dominant gangue minerals. Pyrite separates of ores from those three deposits have relatively high and variable Re contents ranging from 3.7 to 184 ppb. All pyrite separates have very low common Os, allowing us calculation of single mineral model ages for each sample. Pyrite separates from the Heifengshan Fe deposit have an ¹⁸⁷Re–¹⁸⁷Os isochron age of 310 ± 23 Ma (MSWD = 0.04) and a weighted mean model age of 302 ± 5 Ma (MSWD = 0.17). Those from the Shuangfengshan Fe deposit have an isochron age of 295 ± 7 Ma (MSWD = 0.28) and a weighted mean model age of 292 ± 5 Ma (MSWD = 0.33). The Shaquanzi Fe‐Cu deposit has pyrite with an isochron age of 295 ± 7 Ma (MSWD = 0.26) and a weighted mean model age of 295 ± 6 Ma (MSWD = 0.23). Pyrite separates from these Fe(‐Cu) deposits have δ³⁴S_CDT ranging from ?0.41‰ to 4.7‰ except for two outliers. Calcite from the Heifengshan Fe deposit and Shaquanzi Fe‐Cu deposit have similar C and O isotope compositions with δ¹³C_PDB and δ¹⁸O_SMOW ranging from ?5.5‰ to ?1.0‰ and from 10‰ to 12.7‰, respectively. These stable isotopic data suggest that S, C, and O are magmatic‐hydrothermal in origin. The association of low‐Ti magnetite and Fe/Cu‐sulfides resembles those of Iron–Oxide–Copper–Gold (IOCG) deposits elsewhere. Our reliable Re–Os ages of pyrite suggest that the Fe(‐Cu) deposits in the Aqishan–Yamansu belt formed at ～296 Ma, probably in a back‐arc extensional environment.     

Mineral compositions and fluid evolution of the Tonglushan skarn Cu–Fe deposit,SE Hubei,east-central China

The Tonglushan Cu–Fe deposit (1.12 Mt at 1.61% Cu, 5.68 Mt at 41% Fe) is located in the westernmost district of the Middle–Lower Yangtze River metallogenic belt. As a typical polymetal skarn metallogenic region, it consists of 13 skarn orebodies, mainly hosted in the contact zone between the Tonglushan quartz-diorite pluton (140 Ma) and Lower Triassic marine carbonate rocks of the Daye Formation. Four stages of mineralization and alterations can be identified: i.e. prograde skarn formation, retrograde hydrothermal alteration, quartz-sulphide followed by carbonate vein formation. Electron microprobe analysis (EMPA) indicates garnets vary from grossular (Ad_20.2–41.6Gr_49.7–74.1) to pure andradite (Ad_47.4–70.7Gr_23.9–45.9) in composition, and pyroxenes are represented by diopsides. Fluid inclusions identify three major types of fluids involved during formation of the deposit within the H₂O–NaCl system, i.e. liquid-rich inclusions (Type I), halite-bearing inclusions (Type II), and vapour-rich inclusions (Type III). Measurements of fluid inclusions reveal that the prograde skarn minerals formed at high temperatures (>550°C) in equilibrium with high-saline fluids (>66.57 wt.% NaCl equivalent). Oxygen and hydrogen stable isotopes of fluid inclusions from garnets and pyroxenes indicate that ore-formation fluids are mainly of magmatic-hydrothermal origin (δ¹⁸O = 6.68‰ to 9.67‰, δD = –67‰ to –92‰), whereas some meteoric water was incorporated into fluids of the retrograde alteration stage judging from compositions of epidote (δ¹⁸O = 2.26‰ to 3.74‰, δD= –31‰ to –73‰). Continuing depressurization and cooling to 405–567°C may have resulted in both a decrease in salinity (to 48.43–55.36 wt.% NaCl equivalent) and the deposition of abundant magnetite. During the quartz-sulphide stage, boiling produced sulphide assemblage precipitated from primary magmatic-hydrothermal fluids (δ¹⁸O = 4.98‰, δD = –66‰, δ³⁴S values of sulphides: 0.71–3.8‰) with an extensive range of salinities (4.96–50.75 wt.% NaCl equivalent), temperatures (240–350°C), and pressures (11.6–22.2 MPa). Carbonate veins formed at relatively low temperatures (174–284°C) from fluids of low salinity (1.57–4.03 wt.% NaCl equivalent), possibly reflecting the mixing of early magmatic fluids with abundant meteoric water. Boiling and fluid mixing played important roles for Cu precipitation in the Tonglushan deposit.     

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

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

Zinc Isotopic Compositions of NIST SRM 683 and Whole‐Rock Reference Materials

In this study the homogeneity of the zinc isotopic composition in the NIST SRM 683 reference material was examined by measuring the Zn isotopic signature in microdrilled sample powders from two metal nuggets. Zinc was purified using AG MP‐1M resin and then measured by MC‐ICP‐MS. Instrumental mass bias was corrected using the “sample‐standard bracketing” method and empirical external normalisation with Cu doping. After evaluating the potential effects of varying acid mass fractions and different matrices, high‐precision Zn isotope data were obtained with an intermediate measurement precision better than ± 0.05‰ (δ⁶⁶Zn, 2s) over a period of 5 months. The δ⁶⁶Zn_JMC‐Lyon mean values of eighty‐four and fourteen drilled powders from two nuggets were 0.11 ± 0.02‰ and 0.12 ± 0.02‰, respectively, indicating that NIST SRM 683 is a good isotopic reference material with homogeneous Zn isotopes. The Zn isotopic compositions of seventeen rock reference materials were also determined, and their δ⁶⁶Zn values were in agreement with most previously published data within 2s. The δ⁶⁶Zn values of most of the rock reference materials analysed were in the range 0.22–0.36‰, except for GSP‐2 (1.07 ± 0.06‰, n = 12), NOD‐A‐1 (0.96 ± 0.03‰, n = 6) and NOD‐P‐1 (0.78 ± 0.03‰, n = 6). These comprehensive data should serve as reference values for quality assurance and interlaboratory calibration exercises.