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.     

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.     

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).     

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.     

Off‐Mount Calibration and One New Potential Pyrrhotite Reference Material for Sulfur Isotope Measurement by Secondary Ion Mass Spectrometry

Sulfur isotope measurements in three sulfide (two pyrite and one pyrrhotite) samples on two epoxy mounts showed that the mount‐to‐mount variation of raw δ³⁴S values was negligible when secondary ion mass spectrometry (SIMS) analytical settings remained stable. In consequence, an off‐mount calibration procedure for SIMS sulfur isotope analysis was applied in this study. YP136 is a pyrrhotite sample collected from northern Finland. Examination of thin sections with a polarising microscope, backscattered electron image analyses and wavelength dispersive spectrometry mapping showed that the sample grains display no internal growth or other zoning. A total of 318 sulfur isotope (spot) measurements conducted on more than 100 randomly selected grains yielded highly consistent sulfur isotope ratios. The repeatability of all the analytical results of ³⁴S/³²S was 0.3‰ (2s, n = 318), which is the same as that of the well‐characterised pyrite reference materials PPP‐1 and UWPy‐1. Its δ³⁴S value determined by gas mass spectrometry was 1.5 ± 0.1‰ (2s, n = 11), which agrees with the SIMS data (1.5 ± 0.3‰, 2s) calibrated by pyrrhotite reference material Po‐10. Therefore, YP136 pyrrhotite is considered a candidate reference material for in situ sulfur isotope determination.     

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.     

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.     

A Potential New Chalcopyrite Reference Material for Secondary Ion Mass Spectrometry Sulfur Isotope Ratio Analysis

Chalcopyrite is an important sulfide mineral in many types of ore deposits, but matrix‐matched chalcopyrite reference materials for microanalysis are lacking. A new natural chalcopyrite‐bearing specimen (HTS4‐6) was analysed in this study to investigate its potential as a reference material for microbeam sulfur isotope ratio measurement. Detailed textural examination and major element determination showed that the HTS4‐6 chalcopyrite grains have no growth rim or zoning. A total of 607 sulfur isotope ratio spot measurements with secondary ion mass spectrometry (SIMS) conducted on the cruciform sections, and over 120 randomly selected grains yielded highly consistent sulfur isotope ratio. The intermediate measurement precision for four measurement sessions of the ³⁴S/³²S measurement results was better than 0.39‰ (2s). Randomly selected chalcopyrite grains of HTS4‐6 were further analysed by LA‐MC‐ICP‐MS, which gave a mean δ³⁴S value of +0.58 ± 0.38‰ (2s, n = 95). The maximum variance (expressed as intermediate precision from SIMS and LA‐MC‐ICP‐MS measurements) is not worse than 0.39‰ (the SIMS value), indicating that HTS4‐6 chalcopyrite is a potential reference material for in situ microbeam sulfur isotope measurements. The mean δ³⁴S value determined by gas source isotope ratio mass spectrometry (GS‐IRMS) is +0.63 ± 0.16‰ (2s, n = 23), consistent with that derived by LA‐MC‐ICP‐MS, and can represent the recommended value for this potential reference material.     

SA01 – A Proposed Zircon Reference Material for Microbeam U‐Pb Age and Hf‐O Isotopic Determination

A new natural zircon reference material SA01 is introduced for U‐Pb geochronology as well as O and Hf isotope geochemistry by microbeam techniques. The zircon megacryst is homogeneous with respect to U‐Pb, O and Hf isotopes based on a large number of measurements by laser ablation‐inductively coupled plasma‐mass spectrometry (LA‐ICP‐MS) and secondary ion mass spectrometry (SIMS). Chemical abrasion isotope dilution thermal ionisation mass spectrometry (CA‐ID‐TIMS) U‐Pb isotopic analyses produced a mean ²⁰⁶Pb/²³⁸U age of 535.08 ± 0.32 Ma (2s, n = 10). Results of SIMS and LA‐ICP‐MS analyses on individual shards are consistent with the TIMS ages within uncertainty. The δ¹⁸O value determined by laser fluorination is 6.16 ± 0.26‰ (2s, n = 14), and the mean ¹⁷⁶Hf/¹⁷⁷Hf ratio determined by solution MC‐ICP‐MS is 0.282293 ± 0.000007 (2s, n = 30), which are in good agreement with the statistical mean of microbeam analyses. The megacryst is characterised by significant localised variations in Th/U ratio (0.328–4.269) and Li isotopic ratio (?5.5 to +7.9‰); the latter makes it unsuitable as a lithium isotope reference material.     

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

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

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.     

Genesis of metapelitic migmatites in the Adirondack Mountains, New York

Oxygen isotope ratios and rare earth element (REE) concentrations provide independent tests of competing models of injection v. anatexis for the origin of migmatites from amphibolite and granulite facies metasedimentary rocks of the Adirondack Mountains, New York. Values of δ¹⁸O and REE profiles were measured by ion microprobe in garnet–zircon pairs from 10 sample localities. Prior U–Pb SIMS dating of zircon grains indicates that inherited cores (1.7–1.2 Ga) are surrounded by overgrowths crystallized during the Grenville orogenic cycle (～1.2–1.0 Ga). Cathodoluminescence imaging records three populations of zircon: (i) featureless rounded ‘whole grains’ (interpreted as metamorphic or anatectic), and rhythmically zoned (igneous) cores truncated by rims that are either (ii) discordant rhythmically zoned (igneous) or (iii) unzoned (metamorphic or anatectic). These textural interpretations are supported by geochronology and oxygen isotope analysis. In both the amphibolite facies NW Adirondacks and the granulite facies SE Adirondacks, δ¹⁸O_(Zrc) values in overgrowths and whole zircon are highly variable for metamorphic zircon (6.1–13.4‰; n = 95, 10 μm spot). In contrast, garnet is typically unzoned and δ¹⁸O_(Grt) values are constant at each locality, differing only between leucosomes and corresponding melanosomes. None of the analysed metamorphic zircon–garnet pairs attained oxygen isotope equilibrium, indicating that zircon rims and garnet are not coeval. Furthermore, REE profiles from zircon rims indicate zircon growth in all regions was prior to significant garnet growth. Thus, petrological estimates from garnet equilibria (e.g. P–T) cannot be associated uncritically with ages determined from zircon. The unusually high δ¹⁸O values (>10‰) in zircon overgrowths from leucocratic layers are distinctly different from associated metaigneous rocks (δ¹⁸O_(Zrc) < 10‰) indicating that these leucosomes are not injected magmas derived from known igneous rocks. Surrounding melanosomes have similarly high δ¹⁸O_(Zrc) values, suggesting that leucosomes are related to surrounding melanosomes, and that these migmatites formed by anatexis of high δ¹⁸O metasedimentary rocks.     

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).     

Tourmaline Reference Materials for the In Situ Analysis of Oxygen and Lithium Isotope Ratio Compositions

Three tourmaline reference materials sourced from the Harvard Mineralogical and Geological Museum (schorl 112566, dravite 108796 and elbaite 98144), which are already widely used for the calibration of in situ boron isotope measurements, are characterised here for their oxygen and lithium isotope compositions. Homogeneity tests by secondary ion mass spectrometry (SIMS) showed that at sub‐nanogram test portion masses, their ¹⁸O/¹⁶O and ⁷Li/⁶Li isotope ratios are constant within ± 0.27‰ and ± 2.2‰ (1s), respectively. The lithium mass fractions of the three materials vary over three orders of magnitude. SIMS homogeneity tests showed variations in ⁷Li/²⁸Si between 8% and 14% (1s), which provides a measure of the heterogeneity of the Li contents in these three materials. Here, we provide recommended values for δ¹⁸O, Δ’¹⁷O and δ⁷Li for the three Harvard tourmaline reference materials based on results from bulk mineral analyses from multiple, independent laboratories using laser‐ and stepwise fluorination gas mass spectrometry (for O), and solution multi‐collector inductively coupled plasma‐mass spectroscopy (for Li). These bulk data also allow us to assess the degree of inter‐laboratory bias that might be present in such data sets. This work also re‐evaluates the major element chemical composition of the materials by electron probe microanalysis and investigates these presence of a chemical matrix effect on SIMS instrumental mass fractionation with regard to δ¹⁸O determinations, which was found to be < 1.6‰ between these three materials. The final table presented here provides a summary of the isotope ratio values that we have determined for these three materials. Depending on their starting mass, either 128 or 512 splits have been produced of each material, assuring their availability for many years into the future.     

Mineral and stable isotope compositions,phase equilibria and 40Ar–39Ar geochronology from the iron skarn deposit in Sangan,northeastern Iran

The Sangan iron skarn deposit is located on the eastern edge of the Sabzevar-Doruneh Magmatic Belt, northeastern Iran. Mineralization occurs at the contact between Eocene igneous rocks and Cretaceous carbonates. The silicate-dominant prograde skarn stage consists of garnet and clinopyroxene, whereas the retrograde stage is dominated by magnetite associated with minor hematite, phlogopite, pyrite, and chalcopyrite. Phase equilibria and mineral chemistry studies reveal that the skarn formed within a temperature range of ∼375° to 580 °C and that the mineralizing fluid evolved from a hot, low oxygen fugacity, alkaline fluid during the silicate-dominant stage to a fluid of relatively lower temperature and higher oxygen fugacity at the magnetite-dominant stage. The δ¹⁸O values of magnetite and garnet vary from +3.1 to +7.5‰ and +7.7 to +11.6‰, respectively. The calculated δ¹⁸O_H2O values of fluid in equilibrium with magnetite and garnet range from +9.8 to +11.1‰ and +10.1 to +14.8‰, respectively. These elevated δ¹⁸O_H2O values suggest interaction of magmatic water with ¹⁸O-enriched carbonates. The high δ³⁴S values (+10.6 to +17.0‰) of pyrite separates from the Sangan iron ore indicate that evaporites had an important role in the evolution of the hydrothermal fluid. Phlogopite separates from the massive ores yield ⁴⁰Ar/³⁹Ar plateau ages of 41.97 ± 0.2 and 42.47 ± 0.2 Ma, indicating that the skarn formation and associated iron mineralization was related to the oldest episode of magmatism in Sangan at ∼42 Ma. Eocene time marked a peak of magmatic activity and associated skarn in the post-collisional setting in northeastern Iran, whereas Oligo-Miocene magmatic activity and associated skarn in the Urumieh-Dokhtar Magmatic Belt are related to subduction. In addition, skarn mineralization in northeastern and eastern Iran is iron type, but skarn mineralization in the Urumieh-Dokhtar magmatic belt is copper – iron and copper type.     

Garnet re‐equilibration by coupled dissolution–reprecipitation: evidence from textural,major element and oxygen isotope zoning of ‘cloudy’ garnet

The analysis of texture, major element and oxygen isotope compositions of cloudy garnet crystals from a metapelite sampled on Ikaria Island (Greece) is used to assess the model of growth and re‐equilibration of these garnet crystals and to reconstruct the pressure–temperature–fluid history of the sample. Garnet crystals show complex textural and chemical zoning. Garnet cores (100–200 μm) are devoid of fluid inclusions. They are characterized by growth zoning demonstrated by a bell‐shaped profile of spessartine component (7–3 mol.%), an increase in grossular from 14 to 22 mol.% and δ¹⁸O values between 9.5 ± 0.3‰ and 10.4 ± 0.2‰. Garnet inner rims (90–130 μm) are fluid inclusion‐rich and show a decreasing grossular component from 22 to 5 mol.%. The trend of the spessartine component observed in the inner rim allows two domains to be distinguished. In contrast to domain I, where the spessartine content shows the same trend as in the core, the spessartine content of domain II increases outwards from 2 to 14 mol.%. The δ¹⁸O values decrease towards the margins of the crystals to a lowest value of 7.4 ± 0.2‰. The outer rims (<10 μm) are devoid of fluid inclusions and have the same chemical composition as the outermost part of domain II of the inner rim. Garnet crystals underwent a four‐stage history. Stage 1: garnet growth during the prograde path in a closed system for oxygen. Garnet cores are remnants of this growth stage. Stage 2: garnet re‐equilibration by coupled dissolution–reprecipitation at the temperature peak (630 < T < 650 °C). This causes the creation of porosity as the coupled dissolution–reprecipitation process allows chemical (Ca) and isotopic (O) exchange between garnet inner rims and the matrix. The formation of the outer rim is related to the closure of porosity. Stage 3: garnet mode decreases during the early retrograde path, but garnet is still a stable phase. The resulting garnet composition is characterized by an increasing Mn content in the inner rim’s domain II caused by intracrystalline diffusion. Stage 4: dissolution of garnet during the late retrograde path as garnet is not a stable phase anymore. This last stage forms corroded garnet. This study shows that coupled dissolution–reprecipitation is a possible re‐equilibration process for garnet in metamorphic rocks and that intra‐mineral porosity is an efficient pathway for chemical and isotopic exchange between garnet and the matrix, even for otherwise slow diffusing elements.     

Ban-1 Zircon: A New Natural Zircon Reference Material for LA-MC-ICP-MS Zr and Hf Isotopic Determinations

New zircon reference materials for in situ zircon radiogenic Hf isotope and stable Zr isotopic determinations made by laser ablation multi-collector inductively coupled plasma-mass spectrometry (LA-MC-ICP-MS) are required due to high data productivity and consequently high reference material consumption rate. This study examines a new natural zircon for Zr isotope ratios by double spike thermal ionisation mass spectrometry (TIMS), and for Hf isotopes by bulk solution nebuliser (SN)-MC-ICP-MS with both Zr and Hf determined by LA-MC-ICP-MS. A total of five zirconium isotope measurements from drilled zircons, determined by TIMS, yield a mean δ^94/90Zr_IPGP-Zr value of -0.09 ± 0.06‰ (2s). Five and eight hafnium isotope measurements for powders from the drilled zircons and Ban-1-4 by SN-MC-ICP-MS, yield mean ¹⁷⁶Hf/¹⁷⁷Hf ratios of 0.282985 ± 0.000011 (2s) and 0.282982 ± 0.000007 (2s), respectively. The mean δ^94/90Zr_IPGP-Zr value and ¹⁷⁶Hf/¹⁷⁷Hf ratio determined by LA-MC-ICP-MS analyses are -0.06 ± 0.09‰ (2s, n = 504) and 0.282985 ± 0.000035 (2s, n = 327), respectively. The isotopic homogeneities suggest that the Ban-1 zircon is a suitable reference material for microbeam Zr and Hf isotopic measurements.     

Inter‐laboratory Characterisation of Apatite Reference Materials for Chlorine Isotope Analysis

Here we report on a set of six apatite reference materials (chlorapatites MGMH#133648, TUBAF#38 and fluorapatites MGMH#128441A, TUBAF#37, 40, 50) which we have characterised for their chlorine isotope ratios; these RMs span a range of Cl mass fractions within the apatite Ca₁₀(PO₄)₆(F,Cl,OH)₂ solid solution series. Numerous apatite specimens, obtained from mineralogical collections, were initially screened for ³⁷Cl/³⁵Cl homogeneity using SIMS followed by δ³⁷Cl characterisation by gas source mass spectrometry using both dual‐inlet and continuous‐flow modes. We also report major and key trace element compositions as determined by EPMA. The repeatability of our SIMS results was better than ± 0.10‰ (1s) for the five samples with > 0.5 % m/m Cl and ± 0.19‰ (1s) for the low Cl abundance material (0.27% m/m). We also observed a small, but significant crystal orientation effect of 0.38‰ between the mean ³⁷Cl/³⁵Cl ratios measured on three oriented apatite fragments. Furthermore, the results of GS‐IRMS analyses show small but systematic offset of δ³⁷Cl_SMOC values between the three laboratories. Nonetheless, all studied samples have comparable chlorine isotope compositions, with mean 10³δ³⁷Cl_SMOC values between +0.09 and +0.42 and in all cases with 1s ≤ ± 0.25.     

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.