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).     

Matrix Corrections and Error Analysis in High‐Precision SIMS 18O/16O Measurements of Ca–Mg–Fe Garnet

We report technical and data treatment methods for making accurate, high‐precision measurements of ¹⁸O/¹⁶O in Ca–Mg–Fe garnet utilising the Cameca IMS 1280 multi‐collector ion microprobe. Matrix effects were similar to those shown by previous work, whereby Ca abundance is correlated with instrumental mass fractionation (IMF). After correction for this effect, there appeared to be no significant secondary effect associated with Mg/Fe²⁺ for routine operational conditions. In contrast, investigation of the IMF associated with Mn‐ or Cr‐rich garnet showed that these substitutions are significant and require a more complex calibration scheme. The Ca‐related calibration applied to low‐Cr, low‐Mn garnet was reproducible across different sample mounts and under a range of instrument settings and therefore should be applicable to similar instruments of this type. The repeatability of the measurements was often better than ± 0.2‰ (2s), a precision that is similar to the repeatability of bulk techniques. At this precision, the uncertainties due to spot‐to‐spot repeatability were at the same magnitude as those associated with matrix corrections (± 0.1–0.3‰) and the uncertainties in reference materials (± 0.1–0.2‰). Therefore, it is necessary to accurately estimate and propagate uncertainties associated with these parameters – in some cases, uncertainties in reference materials or matrix corrections dominate the uncertainty budget.     

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.     

Biotite Reference Materials for Secondary Ion Mass Spectrometry 18O/16O Measurements

Five new biotite reference materials were calibrated at the SwissSIMS laboratory (University of Lausanne) for oxygen isotope determination by secondary ion mass spectrometry (SIMS) and are available to the scientific community. The oxygen isotope composition of the biotites, UNIL_B1 to B5, was determined by laser‐heating fluorination to be 11.4 ± 0.11‰, 8.6 ± 0.15‰, 6.1 ± 0.04‰, 7.1 ± 0.05‰ and 7.6 ± 0.04‰, respectively. SIMS analyses on spots smaller than 20 μm gave a measurement repeatability of 0.3‰ (2 standard deviation, 2s). The matrix effect due to solid solution in natural biotite could be expressed as a linear function of X_Mg and X_F for biotite. No effect was found for different crystallographic orientations. SIMS analysis allows the oxygen isotope composition of biotite to be measured with a measurement uncertainty of 0.3–0.4‰ (2s) for biotites with similar major element compositions. A measurement uncertainty of 0.5‰ (2s) is realistic when F poor biotites (lower than 0.2% m/m oxides) within the compositional range of X_Mg of 0.3–0.9 were compared from different sessions. The linear correlation with F content offers a reasonable working curve for F‐rich biotites, but additional reference materials are needed to confirm the model.     

SIMS Bias on Isotope Ratios in Ca‐Mg‐Fe Carbonates (Part III): δ18O and δ13C Matrix Effects Along the Magnesite–Siderite Solid‐Solution Series

This study explores the effects of cation composition on mass bias (i.e., the matrix effect), which is a major component of instrumental mass fractionation (IMF) in the microanalyses of δ¹³C and δ¹⁸O by SIMS in carbonates of the magnesite–siderite solid‐solution series (MgCO₃–FeCO₃). A suite of twelve calibration reference materials (RMs) was developed and documented (calibrated range: Fe# = 0.002–0.997, where Fe# = molar Fe/[Mg + Fe]), along with empirical expressions for regressing calibration data (affording residuals < 0.5‰ relative to certified reference material NIST‐19). The calibration curves of both isotope systems are non‐linear and have, over a 2‐year period, fallen into one of two distinct but largely self‐consistent shape categories (data from ten measurement sessions), despite adherence to well‐established analytical protocols for carbonate δ¹³C and δ¹⁸O analyses at WiscSIMS (CAMECA IMS 1280). Mass bias was consistently most sensitive to changes in composition near the magnesite end‐member (Fe# 0–0.2), deviating by up to 4.5‰ (δ¹³C) and 14‰ (δ¹⁸O) with increasing Fe content. The cause of variability in calibration curve shapes is not well understood at present and demonstrates the importance of having available a sufficient number of well‐characterised RMs so that potential complexities of curvature can be adequately delineated and accounted for on a session‐by‐session basis.     

Combined Separation of Cu,Fe and Zn from Rock Matrices and Improved Analytical Protocols for Stable Isotope Determination

Isotope ratios of heavy elements vary on the 1/10000 level in high temperature materials, providing a fingerprint of the processes behind their origin. Ensuring that the measured isotope ratio is precise and accurate depends on employing an efficient chemical purification technique and optimised analytical protocols. Exploiting the disparate speciation of Cu, Fe and Zn in HCl and HNO₃, an anion exchange chromatography procedure using AG1‐×8 (200–400 mesh) and 0.4 × 7 cm Teflon columns was developed to separate them from each other and matrix elements in felsic rocks, basalts, peridotites and meteorites. It required only one pass through the resin to produce a quantitative and pure isolate, minimising preparation time, reagent consumption and total analytical blanks. A ThermoFinnigan Neptune Plus MC‐ICP‐MS with calibrator‐sample bracketing and an external element spike was used to correct for mass bias. Nickel was the external element in Cu and Fe measurements, while Cu corrected Zn isotopes. These corrections were made assuming that the mass bias for the spike and analyte element was identical, and it is shown that this did not introduce any artificial bias. Measurement reproducibilities were ± 0.03‰, ± 0.04‰ and ± 0.06‰ (2s) for δ⁵⁷Fe, δ⁶⁵Cu and δ⁶⁶Zn, respectively.     

Formation of lacustrine dolomite in the late Miocene marginal lakes of the East Mediterranean (Northern Israel)

The study focuses on the formation of lacustrine dolomite in late Miocene lakes, located at the East Mediterranean margins (Northern Israel). These lakes deposited the sediments of the Bira (Tortonian) and Gesher (Messinian) formations that comprise sequences of dolostone and limestone. Dolostones are bedded, consist of small‐sized (<7 μm), Ca‐rich (52 to 56 mol %) crystals with relatively low ordering degrees, and present evidence for replacement of CaCO₃ components. Limestones are comprised of a wackestone to mudstone matrix, freshwater macrofossils and intraclasts (mainly in the Bira Formation). Sodium concentrations and isotope compositions differ between limestones and dolostones: Na = ~100 to 150 ppm; ~1000 to 2000 ppm; δ¹⁸O = ?3·8 to ?1·6‰; ?2·0 to +4·3‰; δ¹³C = ?9·0 to ?3·4‰; ?7·8 to 0‰ (VPDB), respectively. These results indicate a climate‐related sedimentation during the Tortonian and early Messinian. Wet conditions and positive freshwater inflow into the carbonate lake led to calcite precipitation due to intense phytoplankton blooms (limestone formation). Dry conditions and enhanced evaporation led to precipitation of evaporitic CaCO₃ in a terminal lake, which caused an increased Mg/Ca ratio in the residual waters and penecontemporaneous dolomitization (dolostone formation). The alternating lithofacies pattern reveals eleven short‐term wet–dry climate‐cycles during the Tortonian and early Messinian. A shift in the environmental conditions under which dolomite formed is indicated by a temporal decrease in δ¹⁸O of dolostones and Na content of dolomite crystals. These variations point to decreasing evaporation degrees and/or an increased mixing with meteoric waters towards the late Messinian. A temporal decrease in δ¹³C of dolostones and limestones and appearance of microbial structures in close association with dolomite suggest that microbial activity had an important role in allowing dolomite formation during the Messinian. Microbial mediation was apparently the main process that enabled local growth of dolomite under wet conditions during the latest Messinian.     

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.     

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‰.     

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.     

Lithium Isotope Composition of Ultramafic Geological Reference Materials JP‐1 and DTS‐2

An organic solvent‐free two‐step column procedure is presented that provided robust, high yield and super clean separation of Li from silicate rock sample matrices. The measured δ⁷Li value for BHVO‐2 of +4.29 ± 0.23‰ (1s) is comparable with the reported values. The δ⁷Li values for GSJ JP‐1 (+3.14 ± 0.41‰, 1s) and USGS DTS‐2 (+4.91 ± 0.34‰, 1s) presented here provide new reference values for ultramafic rock reference materials.     

Zircon M127 – A Homogeneous Reference Material for SIMS U–Pb Geochronology Combined with Hafnium,Oxygen and,Potentially, Lithium Isotope Analysis

In this article, we document a detailed analytical characterisation of zircon M127, a homogeneous 12.7 carat gemstone from Ratnapura, Sri Lanka. Zircon M127 has TIMS‐determined mean U–Pb radiogenic isotopic ratios of 0.084743 ± 0.000027 for ²⁰⁶Pb/²³⁸U and 0.67676 ± 0.00023 for ²⁰⁷Pb/²³⁵U (weighted means, 2s uncertainties). Its ²⁰⁶Pb/²³⁸U age of 524.36 ± 0.16 Ma (95% confidence uncertainty) is concordant within the uncertainties of decay constants. The δ¹⁸O value (determined by laser fluorination) is 8.26 ± 0.06‰ VSMOW (2s), and the mean ¹⁷⁶Hf/¹⁷⁷Hf ratio (determined by solution ICP‐MS) is 0.282396 ± 0.000004 (2s). The SIMS‐determined δ⁷Li value is ?0.6 ± 0.9‰ (2s), with a mean mass fraction of 1.0 ± 0.1 μg g^?1 Li (2s). Zircon M127 contains ~ 923 μg g^?1 U. The moderate degree of radiation damage corresponds well with the time‐integrated self‐irradiation dose of 1.82 × 10¹⁸ alpha events per gram. This observation, and the (U–Th)/He age of 426 ± 7 Ma (2s), which is typical of unheated Sri Lankan zircon, enable us to exclude any thermal treatment. Zircon M127 is proposed as a reference material for the determination of zircon U–Pb ages by means of SIMS in combination with hafnium and stable isotope (oxygen and potentially also lithium) determination.     

High‐Precision Barium Isotope Measurements of Carbonates by MC‐ICP‐MS

This study presents a high‐precision method to measure barium (Ba) isotope compositions of international carbonate reference materials and natural carbonates. Barium was purified using chromatographic columns filled with cation exchange resin (AG50W‐X12, 200–400 mesh). Barium isotopes were measured by MC‐ICP‐MS, using a ¹³⁵Ba–¹³⁶Ba double‐spike to correct mass‐dependent fractionation during purification and instrumental measurement. The precision and accuracy were monitored by measuring Ba isotope compositions of the reference material JCp‐1 (coral) and a synthetic solution obtained by mixing NIST SRM 3104a with other matrix elements. The mean δ^137/134Ba values of JCp‐1 and the synthetic solution relative to NIST SRM 3104a were 0.21 ± 0.03‰ (2s, n = 16) and 0.02 ± 0.03‰ (2s, n = 6), respectively. Replicate measurements of NIST SRM 915b, COQ‐1, natural coral and stalagmite samples gave average δ^137/134Ba values of 0.10 ± 0.04‰ (2s, n = 18), 0.08 ± 0.04‰ (2s, n = 20), 0.27 ± 0.04‰ (2s, n = 16) and 0.04 ± 0.03‰ (2s, n = 20), respectively. Barium mass fractions and Ba isotopes of subsamples drilled from one stalagmite profile were also measured. Although Ba mass fractions varied significantly along the profile, Ba isotope signatures were homogeneous, indicating that Ba isotope compositions of stalagmites could be a potential tool (in addition to Ba mass fractions) to constrain the source of Ba in carbonate rocks and minerals.     

Syn-sedimentary hydrothermal dolomites in a lacustrine rift basin: Petrographic and geochemical evidence from the lower Cretaceous Erlian Basin,Northern China

Dolomites occur extensively in the lower Cretaceous along syn-sedimentary fault zones of the Baiyinchagan Sag, westernmost Erlian Basin, within a predominantly fluvial–lacustrine sedimentary sequence. Four types of dolomite are identified, associated with hydrothermal minerals such as natrolite, analcime and Fe-bearing magnesite. The finely-crystalline dolomites consist of anhedral to subhedral crystals (2 to 10 μm), evenly commixed with terrigenous sediments that occur either as matrix-supporting grains (Fd1) or as massive argillaceous dolostone (Fd2). Medium-crystalline (Md) dolomites are composed of subhedral to euhedral crystals aggregates (50 to 250 μm) and occur in syn-sedimentary deformation laminae/bands. Coarse-crystalline (Cd) dolomites consist of non-planar crystals (mean size >1 mm), and occur as fracture infills cross-cutting the other dolomite types. The Fd1, Md and Cd dolomites have similar values of δ¹⁸O (−20·5 to −11·0‰ Vienna PeeDee Belemnite) and δ¹³C (+1·4 to +4·5‰ Vienna PeeDee Belemnite), but Fd2 dolomites are isotopically distinct (δ¹⁸O −8·5 to −2·3‰ Vienna PeeDee Belemnite; δ¹³C +1·4 to +8·6‰ Vienna PeeDee Belemnite). Samples define three groups which differ in light rare-earth elements versus high rare-earth elements enrichment/depletion and significance of Tb, Yb and Dy anomalies. Medium-crystalline dolomites have signatures that indicate formation from brines at very high temperature, with salinities of 11·8 to 23·2 eq. wt. % NaCl and T_h values of 167 to 283°C. The calculated temperatures of Fd1 and Cd dolomites extend to slightly lower values (141 to 282°C), while Fd2 dolomites are distinctly cooler (81 to 124°C). These results suggest that the dolomites formed from hydrothermal fluid during and/or penecontemporaneous with sediment deposition. Faults and fractures bounding the basin were important conduits through which high-temperature Mg-rich fluids discharged, driven by an abnormally high heat flux associated with local volcanism. It is thought that differing amounts of cooling and degassing of these hydrothermal fluids, and of mixing with lake waters, facilitated the precipitation of dolomite and associated minerals, and resulted in the petrographic and geochemical differences between the dolomites.     

High‐Precision Iron Isotope Analysis of Geological Reference Materials by High‐Resolution MC‐ICP‐MS

We report high‐precision iron isotopic data for twenty‐two commercially available geological reference materials, including silicates, carbonatite, shale, carbonate and clay. Accuracy was checked by analyses of synthetic solutions with known Fe isotopic compositions but different matrices ranging from felsic to ultramafic igneous rocks, high Ca and low Fe limestone, to samples enriched in transition group elements (e.g., Cu, Co and Ni). Analyses over a 2‐year period of these synthetic samples and pure Fe solutions that were processed through the whole chemistry procedure yielded an average δ⁵⁶Fe value of ?0.001 ± 0.025‰ (2s, n = 74), identical to the expected true value of 0. This demonstrates a long‐term reproducibility and accuracy of < 0.03‰ for determination of ⁵⁶Fe/⁵⁴Fe ratios. Reproducibility and accuracy were further confirmed by replicate measurements of the twenty‐two RMs, which yielded results that perfectly match the mean values of published data within quoted uncertainties. New recommended values and associated uncertainties are presented for interlaboratory calibration in the future.     

In Situ Oxygen Isotope Determination in Serpentine Minerals by SIMS: Addressing Matrix Effects and Providing New Insights on Serpentinisation at Hole BA1B (Samail ophiolite,Oman)

The ability to constrain the petrogenesis of multiple serpentine generations recorded at the microscale is crucial for estimating the extent and conditions of modern versus fossil serpentinisation in ophiolites. To address matrix bias effects during oxygen isotope analysis by SIMS, we present the first investigation analysing antigorite in the compositional range Mg# = 77.5–99.5 mole %, using a CAMECA IMS‐1280 secondary ion mass spectrometer. Spot‐to‐spot homogeneity is ≤ 0.5‰ (2s) for the new antigorite reference materials. The relative bias between antigorite reference materials with different Mg/Fe ratios is described by a second‐order polynomial, and a maximum difference in bias of ~ 1.8‰ was measured for Mg# ~ 78 to 100. We observed a bias up to ~ 1.0‰ between lizardite and antigorite attributed to their different crystal structures. Orientation effects up to ~ 1‰ were observed in chrysotile. The new analytical protocol allowed the identification of oxygen isotope zoning up to ~ 7‰ in serpentine minerals from two serpentinites recovered from an area of active serpentinisation in the Samail ophiolite. Thus, in situ analysis is capable of resolving isotopic heterogeneity that may directly reflect changes in the physical and chemical conditions of multiple serpentinisation events in the Samail ophiolite.     

Precise Determination of Silicon Isotopes in Silicate Rock Reference Materials by MC‐ICP‐MS

A HF‐free sample preparation method was used to purify silicon in twelve geological RMs. Silicon isotope compositions were determined using a Neptune instrument multi‐collector‐ICP‐MS in high‐resolution mode, which allowed separation of the silicon isotope plateaus from their interferences. A 1 μg g^‐1 Mg spike was added to each sample and standard solution for online mass bias drift correction. δ³⁰Si and δ²⁹Si values are expressed in per mil (‰), relative to the NIST SRM 8546 (NBS‐28) international isotopic RM. The total variation of δ³⁰Si in the geological reference samples analysed in this study ranged from ‐0.13‰ to ‐0.29‰. Comparison with δ²⁹Si values shows that these isotopic fractionations were mass dependent. IRMM‐17 yielded a δ³⁰Si value of ‐1.41 ± 0.07‰ (2s, n = 12) in agreement with previous data. The long‐term reproducibility for natural samples obtained on BHVO‐2 yielded δ³⁰Si = ‐0.27 ± 0.08‰ (2s, n = 42) on a 12 month time scale. An in‐house Si reference sample was produced to check for the long‐term reproducibility of a mono‐elemental sample solution; this yielded a comparable uncertainty of ± 0.07‰ (2s, n = 24) over 5 months.     

Listvenite-related gold deposits of the South Urals (Russia): A review

The Urals is a complex fold belt, which underwent long geological evolution. The formation of most gold deposits in the Urals is related to the collision stage. In this paper, we review some relatively small listvenite-related gold deposits, which are confined to the large Main Uralian fault zone and some smaller faults within the Magnitogorsk zone. The Mechnikovskoe, Altyn-Tash, and Ganeevskoe deposits are studied in detail in this contribution. They comprise the ore clusters along with other numerous small gold deposits, and constituted the sources for the gold placers exploited in historical time. The gold is hosted by metasomatites (listvenites, beresites) and quartz veins with economic gold grades (up to 20 g/t Au). Listvenites are developed after serpentinites and composed of quartz, fuchsite, and carbonates (magnesite, dolomite) ± albite. Volcanic and volcanoclastic rocks are altered to beresites, consisting of sericite, carbonates (dolomite, ankerite), quartz and albite. Pyrite and chalcopyrite are major ore minerals associated with gold; pyrrhotite, Ni sulfides, galena, sphalerite, arsenopyrite and Au-Ag tellurides are subordinate and rare. Gold in these deposits is mostly high-fineness (>900‰). The lower fineness (∼800‰) is typical of gold in assemblage with polymetallic sulfides and tellurides. The ores have been formed from the NaCl–CO₂–H₂O ± CH₄ fluids of low (∼2 wt% NaCl-equiv.) to moderate (8–16 wt% NaCl-equiv.) salinity at temperatures of 210–330 °C. The oxygen isotopic composition of quartz (δ¹⁸O) varies from 14.7 to 15.4‰ (Mechnikovskoe deposit), 13.2 to 13.6‰ (Altyn-Tash deposit) and 12.0 to 12.7‰ (Ganeevskoe deposit). The oxygen isotopic composition of albite from altered rocks of the Ganeevskoe deposit is 10.1‰. The calculated δ¹⁸O_H2O values of the fluid in equilibrium with quartz are in a range of 5.7–6.3, 4.2–4.6 and 6.3–6.7‰ respectively, and most likely indicate a magmatic fluid source.     

Double carbonate breakdown reactions at high pressures: an experimental study in the system CaO–MgO–FeO–MnO–CO2

The pressure–temperature conditions of the reactions of the double carbonates CaM(CO₃)₂, where M = Mg (dolomite), Fe (ankerite) and Mn (kutnohorite), to MCO₃ plus CaCO₃ (aragonite) have been investigated at 5–8 GPa, 600–1,100°C, using multi-anvil apparatus. The reaction dolomite = magnesite + aragonite is in good agreement with the results of Sato and Katsura (Earth Planet Sci 184:529–534, 2001), but in poor agreement with the results of Luth (Contrib Mineral Petrol 141:222–232, 2001). The dolomite is partially disordered at 620°C, and fully disordered at 1,100°C. All ankerite and kutnohorite samples, including the synthetic starting materials, are disordered. The P–T slopes of the three reactions increase in the order M = Mg, Fe, Mn. The shallower slope for the reaction involving magnesite is due partly to its having a higher compressibility than expected from unit-cell volume considerations. At low pressures there is a preference for partitioning into the double carbonate of Mg > Fe > Mn. At high pressures the partitioning preference is reversed. Using the measured reaction positions, the P–T conditions at which dolomite solid solutions will break down on increasing P and T in subduction zones can be estimated.     

Accurate and Precise Silicon Isotope Analysis of Sulfur‐ and Iron‐Rich Samples by MC‐ICP‐MS

Silicon isotope determination of sulfur‐rich samples by MC‐ICP‐MS can be challenging because cation‐exchange chromatography used for Si purification does not efficiently remove anionic sulfur species. Results for pure Si standard solutions with addition of sulfate showed shifts of up to +1.04 ± 0.10‰ (2s) in δ³⁰Si. Doping of both standard solutions and samples with S to a fixed S/Si ratio can eliminate the relative change in instrumental mass fractionation due to variable S/Si in samples and also boosts the relative sensitivity of Si by up to 66%. Moreover, Fe hydroxide precipitation during sample processing adsorbs Si resulting in isotopic fractionations. Tests using Fe‐rich samples showed that this could be a major factor for observed shifts in δ³⁰Si. Acidification of the sample and standard solutions to a pH < 1 aggressively dissolved any Fe hydroxide precipitates, even in relatively Fe‐rich samples such as chondrite meteorites. The pH values of the sample solutions were subsequently adjusted to a range of 2–3 by adding ultra‐pure NaOH solutions. The combination of sulfur doping and the pH adjustment protocol ensured a full recovery of Si and proved to be an efficient and reliable method for Si isotope determination of S‐ and Fe‐rich materials.