186锇和188锇双同位素稀释法在辉钼矿铼—锇测年中的应用

以经过负离子热表面电离质谱仪准确标定的＾１８６Ｏｓ和＾１８８Ｏｓ双同位素作为稀释剂,利用＾１８６Ｏｓ和＾１８８Ｏｓ计算＾１８７Ｏｓ的含量,能有效地减少用等离子体质谱仪测定＾１８７Ｏｓ时由于仪器本身的不稳定性及质量歧视效应所产生的误差,使测量准确度比用单同位素作为稀释剂有明显提高。方法应用于辉钼矿Ｒｅ－Ｏｓ年龄标准参考物及样品的测定,结果与参考值一致,５份试样测定的ＲＳＤ〈３％。     

金川铜镍硫化物样品中锇同位素比值的高精度分析

采用两种独立的190Os稀释剂、4个不同的化学流程,用等离子体质谱仪、TRITON热表面电离质谱仪和MAT-262固体质谱仪3种质谱仪器,在4个实验室分别对采自金川铜镍硫化物样品的187Os/188Os同位素比值进行分析,样品分析数量达到56个。4个实验室获得的结果分别为0.3356±0.0018(n=12,2s)、0.3363±0.0008(n=6,2s)、0.3363±0.0010(n=18,2s)和0.3353±0.0034(n=20,2s)。采用ISOPLOT软件对所得56个数据进行加权平均计算,得到187Os/188Os同位素比值为0.33602±0.00022(置信度95%)。两台TRITON热表面电离质谱仪测量的结果几乎完全一致,且精度高于MAT-262固体质谱仪和等离子体质谱仪。比较了碱熔和Carius管两种溶样方法,结果表明,对于所研究的样品,用Carius管溶矿方式可以将含锇矿物完全溶解。     

铜镍硫化物铼-锇标准物质定值的溯源性讨论及总不确定度评估

对按国家一级标准物质技术规范研制的铜镍硫化物Re-Os标准物质定值的溯源性及其总不确定度进行讨论与评估。铜镍硫化物标准物质样品采用Carius管溶解,高精度的TRITON同位素质谱仪、MAT-262热电离质谱仪、四极杆等离子体质谱仪、多接收器等离子体质谱仪和高分辨四极杆等离子体质谱仪测量Re、Os含量和Os同位素比值,其中Re-Os含量可以溯源至基准物质,而187Os/188Os同位素比值可以溯源至国际纯粹与应用化学联合会(IUPAC)。在定值数据误差计算时,采用国际通用的ISOPLOT软件利用加权的方法对数据进行处理;在合成总不确定度时,考虑了物质的均匀性和稳定性,同时考虑了稀释剂标定和同位素丰度以及称量误差等影响测定因素的不确定度。标准值的不确定度由三部分组成:第一部分是通过所有参与定值数据,采用ISOPLOT软件,利用加权的方法对数据进行计算处理得到的不确定度;第二部分是物质的均匀性和稳定性的不确定度;第三部分是影响测定其他因素的不确定度。     

电感耦合等离子体质谱法测量铼和锇同位素比值的质量分馏校正

用Re标准溶液测定出X Series-7电感耦合等离子体质谱(ICP-MS)检测器的死时间为43ns。由于Re和Ir的对数分馏系数线性相关,可以用Ir对Re进行在线分馏校正。利用配制的Re同位素比值标准溶液检验该方法,大多数校正值对标准值的相对偏差在±0.1%以下。ICP-MS测量时,Os的分馏系数与中位质量数成正比,采用由迭代方法得到的样品和稀释剂混合物的同位素比值(192Os/188Os)mix作为标准化值对其他Os同位素比值进行分馏校正。用已知Os同位素比值的标准溶液对该方法进行检验,结果表明,经校正后,大多数校正值与标准值的相对偏差在±0.3%以下。上述Re-Os同位素分馏校正方法将改善用ICP-MS进行Re-Os定年时的精密度和准确度。     

微量地质样品铼锇含量及其同位素组成的高精度测定方法

报道了采用新型IsoProbe—T热电离质谱计测定Os含量及其同位素组成和Neptune多接收器等离子体质谱仪（MC—ICPMS）测定Re含量的分析方法。样品化学处理采用Carius管溶样、小型蒸馏法分离和微蒸馏法纯化提取Os以及阴离子树脂交换分离Re的方法。采用IsoProbe—T质谱计测定Os同位素组成具有灵敏度高和精度高的特点。对溶液标样，采用多法拉第接收器系统测定Os总量低至0．2ng的样品时，平均^192Os^16O3-离子流强度可达100mV以上并可维持约20min，其^187Os／^188Os同位素比值的测定精度可优于0．1％（1RSD）。采用所建立的化学分离流程和高精度质谱测量方法，测定了铂族元素橄榄岩标样WPR-1中Re、Os含量和Os同位素组成，测定结果与文献报道值在误差范围内吻合。     

石灰岩铼-锇同位素分析方法研究及应用初探

针对石灰岩样品Re-Os同位素分析,在选样和溶样方法上进行了改进,在Carius管封闭前加入HCl与石灰岩反应释放出大量CO2,然后加入氧化剂和稀释剂封闭Carius管溶解样品,大大增加了样品取样量。利用改进的方法对采自青海玉树地区二叠世九十道班组底部的灰黑色微细晶灰岩的Re-Os同位素体系进行了分析测定,得到了精确的沉积年龄(283.1±7.1)Ma(MSWD=0.61,Model1,n=7)。187Os/188Os同位素初始值为0.56±0.12,与二叠纪时海水的187Os/188Os值相一致,反映了石灰岩沉积时海水的187Os/188Os比值。所得石灰岩年龄与其中的生物化石年龄相吻合,并且与区域上岩浆岩锆石年龄相互印证,表明Re-Os同位素体系在该石灰岩中的封闭性较好。通过石灰岩中有机碳含量以及其中Re、Os含量关系研究,得出了Re、Os在灰岩中主要赋存于有机质中的结论。从原理上解释了Re-Os同位素体系在灰岩中的应用具有十分广泛的前景。     

铼-锇同位素的等离子体质谱法测定及其在辉钼矿测年中的应用

研究了用ICPMS法测定地质样品Re-Os同位素的条件。通过选用Meinhard同心雾化器进样对Os(Ⅷ)水溶液进行测定,可使Os的测定灵敏度提高50倍。讨论了质量歧视效应校正中的有关问题。采用氧化剂清洗,克服了Os在进样系统中的严重记忆效应。用同位素稀释法测定了辉钼矿中Re和~(187)Os的含量,计算了成矿年龄。     

一种高纯度锇盐中锇含量的重量法测定

<正>Re-Os体系是一种重要的放射性同位素体系,187Re通过β衰变成187Os,因此可以利用Re-Os体系定年,它是目前厘定金属矿床成矿时代的最直接手段。Re和Os都是高亲铁性元素,集中分布在地核内,地幔及地壳丰度极低,对于常见地质样品,要想获得准确的Re、Os含量必须使用同位素稀释法进行测定。同位素稀释法是一种高精度的化学分析方法,向样品中加入已知质量和同位素组成的稀释剂,待样品溶解、同位素交换平衡后,测定样品+稀释剂的同位素组成变化,以此计算样品中待测     

铼—锇定年法中碱熔分解样品方法的改进

为改进铼锇测年的准确度 ,试验了 4种熔样和稀释剂加入方式 ,最后选择了锆埚熔样和加入混合稀释剂溶液的方法。先用NaOH溶液中和混合稀释剂溶液 ,在碱性稀释剂溶液烤干后 ,再分层加入NaOH、样品、NaOH、Na2 O2 进行高温熔融。采用同位素稀释 -等离子体质谱 (ID-ICP -MS)对所研制的Re -Os年龄参考样辉钼矿JDC的年龄进行了 4次测定 ,测定值为1 39.1 0± 0 .2 6Ma ,相对标准偏差为 0 .2 %。采用 φ =5 %的NH3·H2 O和浓H2 O2 交替清洗测量系统 ,可更有效地消除ICP -MS测量中Os的记忆效应。浓HNO3浸煮和加热烘烤可较有效地除去Teflon器皿中残留的Os。     

铼-锇同位素地球化学进展

Re和Os是强亲铁元素。Re同位素有：^185Re(37．07％)和^187Re(62．93％)。Os有7个同位素：^184Os(0．018％)、^186Os(1．59％)、^187Os(1．64％)、^188Os(13．20％)、^189Os(16．10％)、^180Os(26．40％)和^192Os(41．0％)。^186Os和^187Os为放射性衰变产物。^186Os由^190Pt通过α衰变而成,^187Os由^187Re通过β衰变而成。     

锇—锇测年方法研究

采用负离子热电离质谱和等离子体质谱（ＩＣＰ－ＭＳ）技术建立了＾１８７Ｏｓ－＾１８６Ｏｓ和＾１８７Ｏｓ－＾１８８Ｏｓ测年方法。方法基于利用核反应＾１８５Ｒｅ（ｎ,γ）＾Ｒｅ和＾１８７Ｒｅ（ｎ,γ）＾Ｒｅ所产生的＾１８６Ｒｅ和＾１８８Ｒｅ分别经过β衰变生成稳定同位素＾１８６Ｏｓ和＾１８８Ｏｓ。＾１８６Ｏｓ和＾１８８Ｏｓ的生成量由照射参数和样品中Ｒｅ含量决定。只要测定Ｏｓ同位素比值就可计算出Ｒｅ含量和Ｏ     

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.     

The remarkable Re–Os chronometer in molybdenite: how and why it works

The Re–Os (rhenium–osmium) chronometer applied to molybdenite (MoS₂) is now demonstrated to be remarkably robust, surviving intense deformation and high‐grade thermal metamorphism. Successful dating of molybdenite is dependent on proper preparation of the mineral separate and analysis of a critical quantity of molybdenite, unique to each sample, such that recognized spatial decoupling of ¹⁸⁷Re parent and ¹⁸⁷Os daughter within individual molybdenite crystals is overcome. Highly precise, accurate and reproducible age results are derived through isotope dilution and negative thermal ion mass spectrometry (ID‐NTIMS). Spatial decoupling of parent–daughter precludes use of the laser ablation ICP‐MS microanalytical technique for Re–Os dating of molybdenite. The use of a reference or control sample is necessary to establish laboratory credibility and for interlaboratory comparisons. The Rb–Sr, K–Ar and ⁴⁰Ar/³⁹Ar chronometers are susceptible to chemical and thermal disturbance, particularly in terranes that have experienced subsequent episodes of hydrothermal/magmatic activity, and therefore should not be used as a basis for establishing accuracy in Re–Os dating of molybdenite, as has been done in the past. Re–Os ages for molybdenite are almost always in agreement with observed geological relationships and, when available, with zircon and titanite U–Pb ages. For terranes experiencing multiple episodes of metamorphism and deformation, molybdenite is not complicated by overgrowths as is common for some minerals used in U–Pb dating (e.g. zircon, monazite, xenotime), nor are Re and Os mobilized beyond the margins of individual crystals during solid‐state recrystallization. Moreover, inheritance of older molybdenite cores, incorporation of common Os, and radiogenic Os loss are exceedingly rare, whereas inheritance, common Pb and Pb loss are common complications in U–Pb dating techniques. Therefore, molybdenite ages may serve as point‐in‐time markers for age comparisons.     

含有普通锇的辉钼矿Re-Os同位素定年研究

通过大量数据统计,表明较高比例的辉钼矿中存在普通锇。普通锇可能以类质同像形式存在于辉钼矿样品中,理论上辉钼矿中可能含有较高含量普通锇。辉钼矿样品含有较高含量普通锇可能对Re-Os定年结果产生很大影响,从原理上并结合实例证实了普通锇含量对辉钼矿Re-Os年龄影响程度。对于一般辉钼矿样品来讲,如果187Os总量(放射成因187Os与非放射成因187Os之和)与普通锇比值小于20,需要考虑普通锇对Re-Os模式年龄的影响,并提出了对于含有普通锇辉钼矿模式年龄的计算方法。先做出187Os/188Os-187Re/188Os等时线,求得初始187Os/188Os值,再根据初始187Os/188Os值和单个样品的普Os含量求得非放射成因的普Os中187Os的量。最后根据Re含量以及放射成因187Os含量得到模式年龄。     

Platinum-osmium isotope evolution of the Earth’s mantle: Constraints from chondrites and Os-rich alloys

Separation of a metal-rich core strongly depleted the silicate portion of the Earth in highly siderophile elements (HSE), including Pt, Re, and Os. To address the issues of how early differentiation, partial melting, and enrichment processes may have affected the relative abundances of the HSE in the upper mantle, ¹⁸⁷Os/¹⁸⁸Os and ¹⁸⁶Os/¹⁸⁸Os data for chondrites are compared with data for Os-rich alloys from upper mantle peridotites. Given that ¹⁸⁷Os and ¹⁸⁶Os are decay products of ¹⁸⁷Re and ¹⁹⁰Pt, respectively, these ratios can be used to constrain the long-term Re/Os and Pt/Os of mantle reservoirs in comparison to chondrites. Because of isotopic homogeneity, H-group ordinary and other equilibrated chondrites may be most suitable for defining the initial ¹⁸⁶Os/¹⁸⁸Os of the solar system. The ¹⁸⁶Os/¹⁸⁸Os ratios for five H-group ordinary chondrites range only from 0.1198384 to 0.1198408, with an average of 0.1198398 ± 0.0000016 (2σ). Using the measured Pt/Os and ¹⁸⁶Os/¹⁸⁸Os for each chondrite, the calculated initial ¹⁸⁶Os/¹⁸⁸Os at 4.567 Ga is 0.1198269 ± 0.0000014 (2σ). This is the current best estimate for the initial ¹⁸⁶Os/¹⁸⁸Os of the bulk solar system. The mantle evolution of ¹⁸⁶Os/¹⁸⁸Os can be defined via examination of mantle-derived materials with well-constrained ages and low Pt/Os. Two types of mantle-derived materials that can be used for this task are komatiites and Os-rich alloys. The alloys are particularly valuable in that they have little or no Re or Pt, thus, when formed, evolution of both ¹⁸⁷Os/¹⁸⁸Os and ¹⁸⁶Os/¹⁸⁸Os ceases. Previously published results for an Archean komatiite and new results for Os-rich alloys indicate that the terrestrial mantle evolved with Pt-Os isotopic systematics that were indistinguishable from the H-group ordinary and some enstatite chondrites. This corresponds to a Pt/Os of 2.0 ± 0.2 for the primitive upper mantle evolution curve. This similarity is consistent with previous arguments, based on the ¹⁸⁷Os/¹⁸⁸Os systematics and HSE abundances in the mantle, for a late veneer of materials with chondritic bulk compositions controlling the HSE budget of the upper mantle. It is very unlikely that high pressure metal-silicate segregation leading to core formation can account for the elemental and isotopic compositions of HSE in the upper mantle.     

Geochronology of the Xihuashan Tungsten Deposit in Southeastern China: Constraints from Re–Os and U–Pb Dating

Xihuashan tungsten deposit is one of the earliest explored tungsten deposits in southeastern China. It is a vein type deposit genetically associated with the Xihuashan granite pluton. Here we report new dating and zircon geochemistry results. Re–Os isotopic dating for molybdenite intergrowth with wolframite in the oldest generation of the Xihuashan pluton yielded an isochron age of 157.0 ± 2.5 Ma (2σ). Zircon U–Pb laser ablation inductively coupled plasma mass spectrometry (LA‐ICP‐MS) dating shows that the pluton crystallized at 155.7 ± 2.2 Ma (2σ). This age is similar to the molybdenite Re–Os age for the ore deposit within error. This, together with published data, suggests that the major W(Mo)‐Sn mineralization occurred between 160–150 Ma in southeastern China. These deposits constitute a major part of the magmatic‐metallogenic belt of eastern Nanlin. The lower Re content in molybdenite of the Xihuashan tungsten deposit shows crustal origin for the ore‐forming material. The limited direct contributions from the subducting slab for the tungsten mineralization in the Nanling region suggest a change of the style of the paleo‐Pacific plate beneath southeastern China.     

An atomic level study of rhenium and radiogenic osmium in molybdenite

Local atomic structures of Re and radiogenic Os in molybdenite from the Onganja mine, Namibia, were examined using X-ray absorption fine structure (XAFS). Rhenium L_III-edge X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) show that the oxidation state of Re, the interatomic distances between Re and the neighboring atoms, and the coordination number of Re to S are very similar to those of Mo in molybdenite. The results confirm that Re is present as Re(IV) in the Mo site in molybdenite.Measurement of L_III-edge XANES and EXAFS of a minor concentration (8.55 ppm) of radiogenic Os was accomplished in fluorescence mode by removing the interfering X-rays from Re and other elements using a crystal analyzer system. The data indicate that the oxidation state of radiogenic Os is Os(III) and Os(IV) and clearly different from Os(II) in natural sulfide minerals, such as OsS₂ (erlichmanite). XANES data also suggest that radiogenic Os does not form a secondary Os phase, such as OsS₂ or Os metal, in molybdenite.EXAFS of radiogenic Os was successfully simulated assuming that Os is present in the Mo site in molybdenite. The data are consistent with the XANES data; Os does not form Os phases in molybdenite. The EXAFS simulation showed that the interatomic distance between Os and S is 2.27 Å, which is 0.12 Å smaller than the distances of Re-S and Mo-S (2.39 Å) in molybdenite. Similar valences and ionic sizes of Re and Mo in molybdenite support the fact that large amounts of Re can be incorporated into the Mo site as has been observed in previous studies, whereas the different properties of Os compared to Mo and Re suggested here support much lower abundance of common Os in molybdenite. This makes molybdenite an ideal mineral for the Re-Os geochronometer as shown in many studies. However, the shorter distance between radiogenic Os and S compared to those of Re-S and Mo-S in molybdenite suggests that the radiogenic Os has a smaller ionic size than Re(IV) and Mo(IV). Furthermore, Os may be partly present as Os(III). Smaller and lower charge Os can diffuse faster than larger and higher charge Re in molybdenite at a given set of conditions. Hence, our study provides an atomic-level explanation for the high mobility of Os compared to Re, which has been suggested by earlier workers using laser ablation ICP-MS.     

Os-Os systematics of Hawaiian picrites revisited: New insights into Os isotopic variations in ocean island basalts

Eighteen picrites (MgO > 13 wt.%) and three related basalts from six Hawaiian volcanoes were analyzed for ¹⁸⁷Os/¹⁸⁸Os and ¹⁸⁶Os/¹⁸⁸Os. Variations in these ratios reflect long-term Re/Os and Pt/Os differences in the mantle source regions of these volcanoes. ¹⁸⁷Os/¹⁸⁸Os ratios vary from ∼0.129 to 0.136, consistent with the range defined by previous studies of Hawaiian picrites and basalts. Samples with lower ¹⁸⁷Os/¹⁸⁸Os are mainly from Kea trend volcanoes (Mauna Kea and Kilauea), and the more radiogenic samples are mainly from Loa trend volcanoes (Mauna Loa, Hualalai, Koolau and Loihi). As previously suggested, differences in ¹⁸⁷Os/¹⁸⁸Os between volcanic centers are most consistent with the presence of variable proportions of recycled materials and/or pyroxenitic components in the Hawaiian source.¹⁸⁶Os/¹⁸⁸Os ratios vary from 0.1198332 ± 26 to 0.1198480 ± 20, with some samples having ratios that are significantly higher than current estimates for the ambient upper mantle. Although the range of ¹⁸⁶Os/¹⁸⁸Os for the Hawaiian suite is consistent with that reported by previous studies, the new data reveal significant heterogeneities among picrites from individual volcanoes. The linear correlation between ¹⁸⁷Os/¹⁸⁸Os and ¹⁸⁶Os/¹⁸⁸Os reported by a previous study is no longer apparent with the larger dataset. The postulated recycled materials and pyroxenites responsible for the dominant variations in ¹⁸⁷Os/¹⁸⁸Os are likely not responsible for the variations in ¹⁸⁶Os/¹⁸⁸Os. Such materials are typically characterized by both insufficiently high Os concentrations and Pt/Os to account for the ¹⁸⁶Os/¹⁸⁸Os heterogeneities. The lack of correspondence between ¹⁸⁶Os/¹⁸⁸Os variations and the Kea and Loa trends supports this conclusion.The primary cause of ¹⁸⁶Os/¹⁸⁸Os variations are evaluated within the framework of two mixing scenarios: (1) metasomatic transport of Pt and/or ¹⁸⁶Os-rich Os into some portions of the Hawaiian source, and (2) interaction between an isotopically complex plume source with a common, Os- and ¹⁸⁶Os-enriched reservoir (COs). Both scenarios require large scale, selective transport of Pt, Re and/or Os. Current estimates of HSE concentrations in the mantle source of these rocks, however, provide little evidence for either process, so the dominant cause of the ¹⁸⁶Os/¹⁸⁸Os variations remains uncertain.     

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.     

Sources of unique rhenium enrichment in fumaroles and sulphides at Kudryavy volcano

Rhenium (Re) is one of the least abundant elements in Earth, averaging 0.28 ppb in the primitive mantle. The unique occurrence of rheniite ReS₂ (74.5 wt% of Re) in Kudryavy volcano precipitates raises questions about recycling of Re-rich reservoirs within the Kurile-Kamchatka volcanic Island arc setting. The sources of this unique Re enrichment have been inferred from studies of Re-Os isotope systematic and trace elements in volcanic gases, sulphide precipitates and host volcanic rocks. The fumarolic gas condensates are enriched in hydrophile trace elements relative to fluid-immobile elements and exhibit high Ba/Nb (133-204), Rb/Y (16-406) and Th/Zr (0.01-0.25) ratios. They are characterised by high Re (7-210 ppb) and Os abundances (0.4-0.9 ppb), with ¹⁸⁷Os/¹⁸⁸Os ratios in a range 0.122-0.152. This Os isotopic compositional range is similar to that of the peridotite xenoliths from the metasomatised mantle wedge above the subducted Pacific plate, the radiogenic isotopic signature of which is probably due to radiogenic addition from a slab-derived fluid.Re- and Os-rich sulphide and oxide minerals precipitate from volcanic gases within fumarolic fields. Molybdenite (MoS₂), powellite (CaMoO₄) and cannizzarite (Pb₄Bi₆S₁₃) contain 1.5-1.7 wt%, 10 ppm, and 65-252 ppb of Re, respectively. Both molybdenite and rheniite contain normal Os concentrations, with total Os abundances in a range from 0.6 to 3.1 ppm for molybdenite, and 2.3-24.3 ppb for the rheniite samples. Repeated analyses of osmium isotope ratios for two rheniite samples form a best-fit line with an initial ¹⁸⁷Os/¹⁸⁸Os ratio of 0.32 ± 0.15 and an age of 79 ± 11 yr, which is the youngest age ever measured in natural samples. The high Re contents in molybdenite and rheniite led to high radiogenic ¹⁸⁷Os values, even in the limited period of time, with ¹⁸⁷Os/¹⁸⁸Os ratios up to 3.3 for molybdenite and up to 4.4 for rheniite.The Os isotopic compositions of andesite-basaltic rocks from the Kudryavy volcano (¹⁸⁷Os/¹⁸⁸Os up to 0.326) are more radiogenic than those of residual peridotites and fumarolic gas condensates that are mainly constituted from magmatic vapor. Such radiogenic values can be attributed either to the addition of a radiogenic Os-rich subduction component to the depleted mantle, or to the assimilation of older dacitic caldera walls (¹⁸⁷Os/¹⁸⁸Os = 0.6) during arc magma ascent and emplacement. The latter hypothesis is supported by the correlation between ¹⁸⁷Os/¹⁸⁸Os ratio and indicators of fractionation such as MgO or Ni, and by low contents of potentially hydrophile trace elements such as Ba, Rb and Th relative to fluid-immobile elements such as Nb, Zr and Y. The high Re flux in the Kudryavy volcano (estimated at ∼46 kg/yr) can be explained by remobilisation of Re by Cl-rich water from an underplated mantle wedge and subducted organic-rich sediments of the Pacific plate.