Preparation and Certification of Re-Os Dating Reference Materials: Molybdenites HLP and JDC

Two Re-Os dating reference material molybdenites were prepared. Molybdenite JDC and molybdenite HLP are from a carbonate vein-type molybdenum-(lead)-uranium deposit in the Jinduicheng-Huanglongpu area of Shaanxi province, China. The samples proved to be homogeneous, based on the coefficient of variation of analytical results and an analysis of variance test. The sampling weight was 0.1 g for JDC and 0.025 g for HLP. An isotope dilution method was used for the determination of Re and Os. Sample decomposition and pre-concentration of Re and Os prior to measurement were accomplished using a variety of methods: acid digestion, alkali fusion, ion exchange and solvent extraction. Negative thermal ionisation mass spectrometry and inductively coupled plasma-mass spectrometry were used for the determination of Re and ¹⁸⁷Os concentration and isotope ratios. The certified values include the contents of Re and Os and the model ages. For HLP, the Re content was 283.8 ± 6.2 μg g⁻¹, ¹⁸⁷Os was 659 ± 14 ng g⁻¹ and the Re-Os model age was 221.4 ± 5.6 Ma. For JDC, the Re content was 17.39 ± 0.32 μg g⁻¹, ¹⁸⁷Os was 25.46 ± 0.60 ng g⁻¹ and the Re-Os model age was 139.6 ± 3.8 Ma. Uncertainties for both certified reference materials are stated at the 95% level of confidence. Three laboratories (from three countries: PR. China, USA, Sweden) joined in the certification programme. These certified reference materials are primarily useful for Re-Os dating of molybdenite, sulfides, black shale, etc.     

High Pressure Asher Digestion and an Isotope Dilution-ICP-MS Method for the Determination of Platinum-Group Element Concentrations in Chromitite Reference Materials CHR-Bkg, GAN Pt-1 and HHH

New concentration data for Ru, Rh, Pd, Re, Os, Ir and Pt are presented for three chromitite reference materials. A simple and very effective procedure was applied for the measurements. Samples were spiked with enriched isotopes and digested in a HNO₃/HCl (5+2) acid mixture at 300 °C and 125 bar (1.25 × 10⁷ Pa) pressure in a high pressure asher (HPA-S, Anton Paar). The programme settings were changed as a function of mass (0.5, 1, 2 and 4 g) and time (5 and 15 hours). Complete chromitite dissolutions for three digestions at each setting were monitored using XRD analyses of the amorphous residue after digestion. The osmium concentration was determined by sparging the OsO₄ that was formed during digestion into a quadrupole ICP-MS. After drying and re-dissolution of the remaining residue, the other PGEs were separated on-line from their matrix in a simple cation-exchange column that was coupled to the ICP-MS. The concentrations were determined through isotope dilution and external calibration (Rh). By using the on-line separation, we were able to control interference effects (isobaric and molecular), which resulted in highly reproducible data. Replicate measurements of the reference material CHR-Bkg (SARM CRPG-CNRS) with sample masses ranging from 0.5 to 4 g showed very small standard deviations compared to the results from the initial collaborative trials and published data (e.g., 3.2% RSD vs. 32% RSD for Ru). Results for platinum showed the largest scatter, which is currently attributed to the small size of the test portion. In addition to CHR-Bkg, the first results for two chromitite reference materials "platinumore" GAN Pt-1 and "chromiumore" HHH issued by the Central Geological Laboratory of Mongolia are presented.     

Determination of rhenium and osmium by ICP-MS for galena and sphalerite

Digestion with aqua regia in a Carius tube and separation of Re with anion exchange resin is commonly employed for Re–Os dating of molybdenite and pyrite. However, the recovery of Re is extremely low when this routine anion exchange method is applied to galena, causing difficulty in Re–Os dating of galena. In this study, we investigated the mechanism of Re loss during sample preparation and tested a revised procedure for Re–Os dating of galena and sphalerite.     

Re-Os Dating of Sulfides from the Volcanogenic Massive Sulfide Deposit at Gacun, Southwestern China

Abstract. The Re-Os isotopic compositions of sulfide ores were analyzed for the Gacun, a volcanogenic massive sulfide deposit in southwestern China, to constrain the timing of mineralization. Sulfide ores from the deposit have a wide range of Re and Os concentrations, varying from 80.2 to 1543.2 ppb and from 0.307 to 8.83 ppb, respectively, and yielded a limited field of high ¹⁸⁷Re/¹⁸⁸Os and high ¹⁸⁷Os/188Os ratios, ranging from 1452 to 3309 and from 5.77 to 13.24, respectively. All sulfide samples yielded an isochron with an age of 217±28 Ma and an initial ¹⁸⁷Os/¹⁸⁸Os ratio of around 0.52±0.73. The Re-Os isochron age agrees with ages previously constrained by the other isotopic dating of the host rocks and fossil strata for the deposit. The rhythmic variation in ¹⁸⁷Os/¹⁸⁸Os and ¹⁸⁷Re/¹⁸⁸Os ratios within massive sulfide zone records a complicated process for ore-forming fluids episodically vented into the brine pool on the Mesozoic seafloor.     

Refinement of the Micro‐Distillation Technique for Isotopic Analysis of Geological Samples with pg‐Level Osmium Contents

In recent years, the ¹⁸⁷Re–¹⁸⁷Os isotope system has been increasingly used to study samples containing very small quantities of Os. For such samples, optimisation of measurement procedures is essential to minimise the loss of Os before mass spectrometric measurements. Micro‐distillation is a necessary purification step that is applied after the main Os chemical separation procedure, prior to Os isotope ratio measurements by negative‐thermal ionisation mass spectrometry (N‐TIMS). However, unlike the other separation steps, this procedure has not yet been optimised for small samples. In this study, we present a refined micro‐distillation method that achieved higher yields and allowed high‐precision R(¹⁸⁷Os/¹⁸⁸Os) expressed as ¹⁸⁷Os/¹⁸⁸Os measurements for small‐sized geological samples that contain only a few pg Os. The Os recovery in the micro‐distillation step was tested by changing the operating conditions including heating time and temperature, and amounts of oxidant and reductant. Recoveries were measured by the isotope dilution ICP‐MS method after the addition of ¹⁹⁰Os‐enriched spike solution. We found that the most critical factor controlling the chemical yield of Os during micro‐distillation is the extent of dilution of the reductant (HBr) by H₂O evaporated from the oxidant. A refined micro‐distillation method, in which the amount of oxidant solution is reduced from the conventional method, achieved an improved chemical yield of Os (~ 90%). This refined method was applied to the measurement of ¹⁸⁷Os/¹⁸⁸Os by N‐TIMS of varying test portions of the geological reference material BIR‐1a. The resulting ¹⁸⁷Os/¹⁸⁸Os ratios of BIR‐1a matched the literature data, with propagated uncertainties of 0.2, 1.1 and 11% digested sample quantities containing 150, 10 and 1 pg of Os, respectively.     

Variations in seawater osmium isotope composition since the last glacial maximum: A case study from the Japan Sea

Concentrations of Re and Os, and the isotopic composition of Os have been measured in the Japan Sea sediments to assess the response of the Japan Sea to glacial–interglacial climate change and associated weathering fluxes. The osmium concentrations in the sediment samples analyzed vary from 59 to 371 pg/g, and ¹⁸⁷Os/¹⁸⁸Os from 0.935 to 1.042. Only ¹⁸⁷Os/¹⁸⁸Os of sediment samples from dark laminations deposited under suboxic to anoxic conditions and having elevated concentrations of Re and Os, and with ≥ 80% hydrogenous Os are explained in terms of seawater composition. Lower ¹⁸⁷Os/¹⁸⁸Os were observed for sediments deposited during the last glacial maximum (LGM) when planktonic foraminifera from the Japan Sea recorded lighter oxygen isotopic composition. Decrease in dissolved Os fluxes from continents and/or change in the composition of the dissolved load to the Japan Sea are suggested as the driving mechanisms for the observed lower LGM ¹⁸⁷Os/¹⁸⁸Os. The results of this study, coupled with lower ¹⁸⁷Os/¹⁸⁸Os during the last glacial observed at other sites from ocean basins with different lithology and contrasting sediment accumulation rates, suggest that this trend is characteristic of the global oceans.

Data from this study show that the Japan Sea recorded higher ¹⁸⁷Os/¹⁸⁸Os during the current interglacial coinciding with excursions of oxygen isotopic compositions of planktonic foraminifera to heavier values. This is explained in terms of preferential release of ¹⁸⁷Os during deglacial weathering and/or higher continental Os flux driven by warm and wet climate. This study demonstrates that Os isotopic composition of reducing margin sediments has immense potential to track variations in the seawater composition. In addition, ¹⁸⁷Os/¹⁸⁸Os of reducing sediments may be used to draw inferences about local paleoceanographic processes in semi-enclosed basins such as the Japan Sea.     

Effective Correction of Mass Bias for Rhenium Measurements by MC-ICP-MS

The geochemistry of Re-Os and the recent use of Re as a non-traditional stable isotope both need accurate and precise quantification of ¹⁸⁷Re/¹⁸⁵Re ratios. This paper reports rhenium isotopic data obtained from the analysis of a standard solution and geological samples by MC-ICP-MS. We show that measured isotopic ratios are modified by matrix effects that cannot be accounted for by the standard solution bracketing technique. The bias resulting from measurements on a spiked (¹⁸⁵Re-enriched) sample is shown to alter the apparent Re concentration by several percent. When spiking samples and calibrators with tungsten, simultaneous measurement of tungsten and rhenium isotopes compensates for the matrix-induced modification of mass bias. Rhenium and tungsten are shown to have different fractionation factors. This may be due to the fact that the two elements fractionate in a different but systematic way, or that the reference isotopic ratios used for elemental Re and W are incoherent with one another. The consistency of fractionation through time can be used to obtain an empirical relationship between W and Re measured ratios from a standard solution to obtain a sample's fractionation-corrected ¹⁸⁷Re/¹⁸⁵Re spiked ratio on samples containing pg g⁻¹ levels of Re, even if some matrix capable of affecting mass bias remains in the final solution.     

Quantitative Separation of Molybdenum and Rhenium from Geological Materials for Isotopic Determination by MC-ICP-MS

We have developed a new chemical procedure for the quantitative separation of molybdenum (Mo) and rhenium (Re) from a wide variety of geological samples. A single pass anion exchange separation provided complete recovery of pure Mo and Re in a form that was ideal for subsequent isotope and abundance determination by multi-collector inductively coupled plasma-mass spectroscopy (MC-ICP-MS). An enriched ¹⁰⁰Mo-⁹⁷Mo solution, mixed with the sample before digestion, enabled natural mass-dependant isotopic fractionation of Mo to be determined with an external reproducibility of < 0.12‰ (δ⁹⁸Mo/⁹⁵Mo, 2 s ). Determination of the concentration of Mo and Re in the same sample was achieved by isotope dilution, with instrumental mass-fractionation of Re being corrected by the simultaneous measurement of the ¹⁹¹Ir/¹⁹³Ir ratio. We have applied the new procedure to a variety of samples, including seawater, basalt and organic-rich mudrock. The procedure is ideally suited to palaeoredox studies requiring the precise determination of the Mo isotope composition and the Re/Mo ratio from the same sample.     

利用同一化学流程分析地质样品中的铂族元素含量和铼-锇同位素组成

报道了利用一次溶样和同一化学流程分离富集地质样品中铂族元素(Pt、Pd、Os、Ir和Ru)和Re的方法.该化学流程包括以下几个步骤:(1) Carius管溶样法分解岩石样品中富集铂族元素的矿物;(2)四氯化碳萃取法分离出Os;(3)微蒸馏法进一步纯化Os;(4)阳离子交换树脂法将铂族元素(Pt、Pd、Ir和Ru)以及R...     

A double spike for osmium analysis of highly radiogenic samples

Geologic samples containing highly radiogenic Os (molybdenites and low-level, highly radiogenic (LLHR) samples) have no internal means by which to correct for mass fractionation during isotopic measurement by mass spectrometry. We describe a double spike for use with highly radiogenic samples, created by combining isotopically enriched ¹⁸⁸Os and ¹⁹⁰Os. Spiking molybdenite and other highly radiogenic minerals with this tracer allows for a fractionation correction, as well as a more reliable determination of common Os relative to analysis using single spikes.

The precise isotopic composition of the double spike is determined by a calibration against natural Os, in which two separate measurements are necessary: one each for the pure double spike and the spike–standard mixture. An estimate of the true composition of the spike is obtained by least squares approximation, and the errors are obtained by Monte Carlo methods. Sample analyses are then much more straightforward than the calibration because isotopic compositions of all components are known a priori.

Results obtained with a mixed Re-double Os spike demonstrate an improved reproducibility over individual ¹⁸⁵Re and ¹⁹⁰Os spikes. For an Archean in-house molybdenite standard we now observe a reproducibility of 0.08%. The ability to make a fractionation correction is essential for Os measurements made by ion counting. With the double Os spike, young samples and those with low Re contents (i.e., LLHR) can now be accurately analyzed. The ¹⁸⁸Os–¹⁹⁰Os double spike also allows a determination of the common Os contents of highly radiogenic samples. Common Os is poorly determined for ancient samples with high concentrations of ¹⁸⁷Os, which fortunately are not sensitive to estimates of common Os. Common Os can be reasonably well determined for younger samples and those with low Re contents. We report a common Os concentration of 0.4±0.1 ppb for an 11 Ma molybdenite. Consideration of common Os content is important for age determination of young samples and LLHR samples, and is not possible by other published means of Os analysis.     

High Precision Hf-W Isotopic Measurements in Meteoritic Material Using Negative Thermal Ionisation Mass Spectrometry (NTIMS)

This paper presents a two-stage anion-exchange procedure for tungsten extraction, an improved mass spectrometric procedure for tungsten analysis and a simplified chemical separation and TIMS procedure for the determination of Hf concentrations. The chemical separation of tungsten is based on its complexing properties with HF and H₂O₂. The blank level for a sample size of 300 mg is about 80 pg for tungsten. The procedure is designed for the high sensitivity of negative thermal ionisation mass spectrometry (NTIMS) provided by the use of Mg oxide as an emitter on Ir filaments. Tungsten can be readily measured with a high precision in various meteoritical material and especially in small W-poor silicate fractions. Samples containing as little as a few ng g^-1 tungsten can be analysed reliably with this method.     

A Method for Rapid Determination of Re and Os Isotope Compositions Using ID‐MC‐ICP‐MS Combined with the Sparging Method

A simple, rapid method for the determination of Re and Os concentrations and isotope compositions using isotope dilution multi‐collector inductively coupled plasma‐mass spectrometry (ID‐MC‐ICP‐MS) combined with Carius tube digestion and sparging introduction of Os was developed. For Os measurement, four channeltron ion counters to detect different Os isotopes were used simultaneously, which led to a drastic reduction in the measurement time. Rhenium isotopes were measured by means of eight Faraday cups with solution nebulisation and an ultrasonic membrane desolvator. The representative ¹⁸⁸Os count rate of an Os standard solution containing 50 pg of total Os was approximately 110000–120000 cps at the onset of measurement; the Re intensity of our in‐house 10 pg g^?1 standard solution reached 1820 V/μg g^?1 with a sample uptake rate of 95–99 μl min^?1. These values indicate that the sensitivity of the method was sufficient even for samples with low Re and Os concentrations, such as chert. As the temporal variations of the amplification efficiency of the ion counters differed from one another, we adopted a sample‐calibrator bracketing method to correct the measured Re and Os isotope ratios. The Re and Os concentrations via the isotope dilution method and the ¹⁸⁷Os/¹⁸⁸Os ratios of two sedimentary rock reference materials (JMS‐2 and JCh‐1) on the basis of the isotope ratios determined by the MC‐ICP‐MS and by negative thermal ionisation mass spectrometry (N‐TIMS) were comparable within their ranges. Based on Os isotope measurement of the IAG reference material [Durham Romil Os (DROsS)], the average difference from the recommended value and precision of Os isotope measurements by the sparging method in combination with multi‐ion‐counters were 0.72% and 0.76% [1RSD (%), n = 29], respectively. The precisions in the ¹⁸⁷Os/¹⁸⁸Os ratios [1RSD (%)] of JMS‐2, JCh‐1 and DROsS were 0.35–0.71, 1.56–3.31 and 0.99–1.28%, respectively, which depended on their Os ion intensities. No systematic difference was observed between the Re and Os geochemical compositions of JCh‐1 and JMS‐2 obtained by means of digestion with inverse aqua regia and CrO₃‐H₂SO₄ solutions, suggesting that either acid solution can be used for the sparging method of sedimentary rock samples. As CrO₃‐H₂SO₄ solution is believed to liberate predominantly the hydrogenous Re and Os fraction from organic‐rich sediment, the sparging method combined with CrO₃‐H₂SO₄ digestion and multi‐ion‐counters in the mass spectrometry is expected to be a powerful tool for reconstructing the secular change in marine Os isotope compositions with high sample throughput.     

Re–Os geochronology of organic rich sediments: an evaluation of organic matter analysis methods

Rhenium and osmium in organic-rich sedimentary rocks are dominantly hydrogenous, but any nonhydrogenous component will influence the accuracy and precision of the Re–Os date obtained. To minimize the influence of any nonhydrogenous Re and Os, we evaluate analysis of isolated organic matter from the whole rock, together with whole rock analysis using a CrO₃–H₂SO₄ digestion medium instead of inverse aqua regia, for a black shale unit of the Exshaw Formation, Canada. This unit previously returned a whole rock Re–Os date of 358±10 Ma (Model 3) [Geochim. Cosmochim. Acta (2002)] using inverse aqua regia dissolution. Organic matter isolated from the whole rock matrix using the HF–BF₃ technique [Org. Geochem. 20 (1993) 249] yields scattered data and a Re–Os date of 449±220 Ma (Model 3, MSWD=616). The organic matter analyses show similar ¹⁸⁷Os/¹⁸⁸Os values, but significantly lower ¹⁸⁷Re/¹⁸⁸Os values in comparison to the whole rock analyses. We show that the Re–Os systematics of organic matter are altered during chemical isolation, and as such we suggest that the HF–BF₃ method should not be used for Re–Os analysis of organic matter. Whole rock Re–Os analysis using a CrO₃–H₂SO₄ digestion medium yields significantly better regression analysis compared with the inverse aqua regia method, and the Re–Os data identify two distinct initial ¹⁸⁷Os/¹⁸⁸Os values for the sample set. Separate regressions of these data yield precise dates [366.1±9.6, MSWD=2.2 and 363.4±5.6 Ma, MSWD=1.6 (Model 3)], which are indistinguishable from the age constraints for this formation (363.4±0.4 Ma, U–Pb monazite). Comparison of the Re–Os dates obtained from aqua regia and CrO₃–H₂SO₄ methods suggests that the former may contain nonhydrogenous Re and Os, whereas the CrO₃–H₂SO₄ method dominantly liberates hydrogenous Re–Os from organic matter, allowing for better stratigraphic age determinations and evaluation of the Os isotope composition of seawater.     

Platinum-Group Element and Rhenium Concentrations in Low Abundance Reference Materials

One or two gram aliquots of twelve reference materials with low platinum-group element (PGE) abundances (Ir concentrations ranging from 30 to 510 pg g^-1) were analysed by isotope dilution ICP-MS using an on-line chromatographic matrix separation after acid digestion in a high pressure asher (HPA-S) to determine the concentrations of Ru, Pd, Re, Ir and Pt. Osmium concentrations were determined via ID-ICP-MS but as volatile OsO₄, whereas Rh concentrations were calculated by comparing the peak areas of the chromatographic peak with that of a standard solution. Validation of the method was performed and the concepts of traceability and measurement uncertainty were applied to assure comparability. The reference materials BCR-2, BHVO-1, BHVO-2, BIR-1, DNC-1, EN026 10D-3, MAG-1, RGM-1, SCo-1, SDO-1, TDB-1 and W-2 were investigated to test for their usefulness for certification. The use of TDB-1 is highly recommended because it is homogeneous at the two gram level and many values based on several different analytical procedures have been published. It is recommended that our efforts should focus on the certification of this reference material to reduce the uncertainties of its currently certified values (Pd and Pt only) and to assign certified values to the other PGE and Re. It is necessary to have at least one well-characterised RM for validation of methods applied to the analysis of PGE and Re in low abundance samples, although the matrix of TDB-1 might not completely match those of many samples.     

Evaluation of Simultaneous Analyte Leaching/Vapour Phase Introduction for Direct Osmium Isotope Ratio Measurements in Solid Samples by Double-Focusing Sector Field ICP-MS

The analytical performance of a method for Os isotope ratio measurement by double‐focusing, sector field ICP‐MS (ICP‐SFMS) was evaluated. The method is based on several optimised, concurrent processes: Os extraction from samples in hot concentrated nitric acid; separation of Os from the digest solution by the formation of volatile osmium tetroxide accelerated by continuous hydrogen peroxide addition; transport of analyte vapour by an oxygen flow into the ICP; and isotopic determination by ICP‐SFMS. Due to the very efficient utilisation of analyte (approaching 0.5‰), Os isotope ratio measurement could be performed at low pg levels. Combined with an ability to process sample sizes up to 2 g (up to 50 g if the organic matrix of biological or botanical samples is eliminated by ashing), materials with Os concentrations in the low, or even sub pg g^?1 range could be determined by this method. Given that two complete digestion/distillation systems were available for interchangeable use, throughputs of up to fifteen samples per 8 hour shift could be achieved. The method precision, evaluated as the long‐term reproducibility of ¹⁸⁷ Os/¹⁸⁸Os ratio measurements in a commercial Os reference sample containing 0.5 ng Os, was 0.16% relative standard deviation (RSD, 1s). The method has been applied to perform replicate ¹⁸⁷ Os/¹⁸⁸ Os ratio measurements on a suite of fifty reference materials of various origins and matrix compositions, with Os concentrations varying from < 0.1 pg g^?1 to > 100 ng g^?1, yielding an average precision of 3% RSD. Though none of the materials tested are certified for Os content or Os isotope composition, comparison of the obtained data with published Os isotope information for similar sample types revealed close agreement between the two. The method can also be used for the simultaneous, semi‐quantitative determination of Os concentrations.     

Analysis of Re, Au, Pd, Pt and Rh in NIST Glass Certified Reference Materials and Natural Basalt Glasses by Laser Ablation ICP-MS

A new technique for the in situ analysis of Re, Au, Pd, Pt and Rh in natural basalt glass by laser ablation (LA)-ICP-MS is described. The method involves external calibration against NIST SRM 612/613 or 614/615 glass certified reference materials, internal standardisation using Ca, and ablation with a 200 μm wide beam spot and a pulsed laser repetition rate of 50 Hz. Under these conditions, sensitivities for Re, Au, Pd, Pt and Rh analyte ions are ˜ 5000 to 100,000 cps/μg g^-1. This is sufficient to make measurements precise to ˜ 10% at the 2-10 μg g^-1 level, which is well within the range of concentrations expected in many basalts. For LA-ICP-MS calibration and a demonstration of the accuracy of the technique, concentrations of Re, Au, Pd, Pt and Rh in the NIST SRM 610/611 (˜ 1 to 50 μg g^-1), 612/613 (˜ 1 to 7 μg g^-1), 614/615 (˜ 0.2 to 2 μg g^-1) and 616/617 (˜ 0.004 to 2 μg g^-1) glasses were determined by solution-nebulisation (SN)-ICP-MS. Using the 612/613 or 614/615 glasses as calibration standards, LA-ICP-MS measurements of these elements in the other NIST glasses fell within ˜ 15% of those determined by SN-ICP-MS. Replicate LA-ICP-MS analyses of the 612/613 and 614/615 glasses indicate that, apart from certain anomalous domains, the glasses are homogeneous for Re, Au, Pd, Pt and Rh to better than 3.5%. Two LA-ICP-MS analyses of natural, island-arc basalt glasses exhibit large fractionations of Re, Au and Pd relative to Pt and Rh, compared to the relative abundances in the primitive mantle.     

云南丽江苦橄岩Re-Os同位素地球化学初步研究

报导了云南丽江地区大具和仕满剖面12个苦橄岩和6个玄武岩的Re，Os含量和Os同位素组成。苦橄岩和玄武岩具有明显不同的Re-Os体系的特征。苦橄岩具有高的Os元素丰度［(1.5~3)×10-9］和低的Re元素丰度（<0.05×10-9）；共生的玄武岩具有低的Os元素丰度（<0.5×10-9）和相对高的Re元素丰度（<0.8×10-9）；苦橄岩具有低放射成因的 187Os/188Os 比值（0.123 3~0.126 6），而玄武岩具有高放射成因的187Os/188Os比值（0.133 8~0.157 7）。苦橄岩的Re-Os同位素特征与越南西北部二叠—三叠纪科马提岩具有低放射成因Os同位素特征相似，而玄武岩的Re-Os同位素特征与峨眉山大火成岩省（LIP）其他地区玄武岩的高放射成因的Os同位素特征相似。苦橄岩的Re-Os同位素特征表明，形成峨眉山LIP的地幔柱可能来自对流上地幔而不是深部的核-幔界面。换言之，峨眉山LIP的形成受控于岩石圈地幔过程而不是地幔柱过程。     

Comparison of reductive accumulation of Re and Os in seawater-sediment systems

In order to understand the fractionation of Re and Os in marine environments, their removal from artificial seawater to Tokyo Bay sediments is studied using a multitracer technique. The chemical processes of the removal of Re and Os are also estimated based on their speciation analyses by X-ray absorption fine structure (XAFS) spectroscopy. The partitioning experiments, which use the multitracer technique, provide information on Re and Os regarding (i) their distributions between artificial seawater-sediment systems, (ii) their complexation with humic acid, and (iii) their carriers in sediments. In addition, XAFS spectroscopy provides direct information on the chemical states of Re and Os in the sediments.In an artificial seawater-sediment system containing a multitracer, Re is removed from the artificial seawater only under a reducing environment. The speciation of Re by X-ray absorption near-edge structure (XANES) suggests that the majority of Re remains as in the artificial seawater even under highly reducing conditions, during laboratory time scale (about 2 weeks). Moreover, XANES simulation shows that some Re exists at a lower oxidation state, such as ReO₂, in the reducing sediment. These results can be explained by the slow kinetics of the reaction which is similar to those suggested by previous geochemical studies.In contrast, Os is readily removed from the artificial seawater into sediments under various redox conditions. Even under oxic conditions, a large fraction of Os is removed from the artificial seawater to sediments without organic matter. Based on the Os XANES study, it is confirmed that the oxidation states of Os incorporated in the reducing sediment and oxic sediment are trivalent and tetravalent, respectively. Sequential extraction suggests that the main carrier of Os in the organic-rich sediment is either ferromanganese oxides or organic matter, and that the Os in these two fractions may correspond to hydrolyzed insoluble Os species and Os species interacting with organic matter, at lower valence, respectively. The results of distribution study of Os in the absence and presence of humic acid (HA) also imply that Os assumes more than one chemical species, and a small fraction of Os may interact with HA in the experimental system. Meanwhile, extended X-ray absorption fine structure (EXAFS) confirms that the first neighboring atom of Os in the reducing sediment is oxygen. If Os(VIII) is the main dissolved species in seawater, as is expected thermodynamically, reductive removal may control the enrichment of Os in the sediment. Osmium, which is removed as Os(IV), is reduced further to Os(III) by a diagenetic process and may be complexed with organic matter in the reducing sediment.The results of the removal behaviors of Re and Os obtained in the current study show that Re can be removed from the artificial seawater only under highly reducing conditions within 2 weeks, but Os removal from the artificial seawater can be found under various redox conditions. Thus, a high ¹⁸⁷Re/¹⁸⁸Os ratio can occur only in reducing sediments, such as black shales. The high¹⁸⁷Re/¹⁸⁸Os ratio, in turn, makes black shales suitable for Re-Os dating. In contrast, authigenic sediments (and minerals) under oxic environments can enrich Os, but since Re is not distributed to the sediments under oxic conditions, this will cause a much lower ¹⁸⁷Re/¹⁸⁸Os ratio than that of seawater. The Os isotope system of these materials can be used as a paleo-marine environmental tracer since the ¹⁸⁷Os/¹⁸⁸Os ratio cannot grow significantly due to its extremely low ¹⁸⁷Re/¹⁸⁸Os ratio.     

一种简单的辉钼矿Re-Os同位素年龄测定中Re化学分离方法：“钽试剂”萃取法

介绍了一种简单的辉钼矿Re-Os同位素定年中Re的化学分离方法,采用“钽试剂”（N-苯甲酰基苯基羟胺）的氯仿溶液萃取辉钼矿中的主要基体和干扰元素,如Mo、Fe和W,达到Re与这些主要基体元素分离的目的。在此基础上,建立了Carius管溶样-四氯化碳萃取分离Os-“钽试剂”萃取分离Re以及同位素稀释电感耦合等离子体质谱法测定的分析流程。利用该分析流程,对辉钼矿标准物质JDC进行Re-Os同位素年龄测定研究,测得其Re、Os的平均含量及年龄分别为（17．6±0．2）μg／g、（25．9±0．3）ng／g和（140．1±2．4）Ma,该结果在误差范围内与标准参考值一致。与目前常用的辉钼矿Re-Os同位素定年方法相比,该方法具有操作简便、快速、高效以及成本低的优势,非常适合作为辉钼矿Re-Os同位素定年的化学分离常规方法。     

Determination of High Field Strength Elements, Rb, Sr, Mo, Sb, Cs, Tl and Bi at ng g−1 Levels in Geological Reference Materials by Magnetic Sector ICP-MS after HF/HClO4 High Pressure Digestion

Six low abundance rock reference materials (basalt BIR-1, dunite DTS-1, dolerite DNC-1, peridotite PCC-1, serpentine UB-N and basalt TAFAHI) have been analysed for high field strength elements (Zr, Nb, Hf, Ta, Th and U), Rb, Sr, Mo, Sb, Cs, Tl and Bi at ng g⁻¹ levels (in rock) by magnetic sector inductively coupled plasma-mass spectrometry after HF/HClO₄ high pressure decomposition. The adopted method uses only indium as an internal standard. Detection limits were found to be in the range of 0.08 to 16.2 pg ml⁻¹ in solution (equivalent to 0.08 to 16.2 ng g⁻¹ in rock). Our data for high field strength elements, Rb, Sr, Mo, Sb, Cs, Tl and Bi for the six selected low abundance geological reference materials show general agreement with previously published data. Our Ta values in DTS-1 and PCC-1 (1.3 and 0.5 ng g⁻¹) are lower than in previously published studies, providing smooth primitive mantle distribution patterns. Lower values were also found for Tl in BIR-1, DTS-1 and PCC-1 (2, 0.4 and 0.8 ng g⁻¹). Compared with quadrupole ICP-MS studies, the proposed magnetic sector ICP-MS method can generally provide better detection limits, so that the measurement of high field strength elements, Rb, Sr, Mo, Sb, Cs, Tl and Bi at ng g⁻¹ levels can be achieved without pre-concentration, ion exchange separation or other specialised techniques.