The Design of Re‐usable Carius Tubes for the Determination of Rhenium,Osmium and Platinum‐Group Elements in Geological Samples

The traditional Carius tube technique is cumbersome and requires skilful work to seal the Carius tube, which can be used only once. We describe a modification to the technique that does not require the use of a high‐temperature welding torch to melt the Carius tube to seal it. The newly designed Carius tube consists of a main body with a 3 mm‐thick glass wall, a neck and head with walls 4 mm in thickness, and an efficient screw‐thread stopper. These new features allowed the tube to be used repeatedly. We demonstrate relatively low procedural blanks derived for Re and Os, and platinum‐group elements (PGEs), using the redesigned tube. A temperature of 220 °C could be reached for about 5 ml of HNO₃ for a 47 ml tube and for 32 ml of inverse aqua regia for a 200 ml tube. This digestion technique can be used for routine analysis of Re and PGEs in geological samples.     

Determination of Platinum‐Group Elements in OPY‐1: Comparison of Results using Different Digestion Techniques

A new proficiency testing sample, OPY‐1 (ultramafic rock), the basis of the twentieth international proficiency test of analytical geochemistry laboratories (GeoPT 20), was recently prepared by the International Association of Geoanalysts (IAG). This paper reports analytical data for Os, Ir, Ru, Rh, Pt and Pd with different digestion techniques, including an improved Carius tube, Carius tube combined with HF dissolution and alkaline fusion. About 4–15% of the PGEs are in the silicate phase, which cannot be leached by aqua regia even when digested at 300 °C with the Carius tube technique. Both the Carius tube technique combined with HF dissolution and alkaline fusion can obtain reliable data. The results demonstrated that OPY‐1 is sufficiently homogeneous at a 2 g test portion level to be suitable as a reference material for method validation. The procedure for sealing the Carius tube was simplified and the recommended digestion procedures are provided.     

Reassessment of Hydrofluoric Acid Desilicification in the Carius Tube Digestion Technique for Re–Os Isotopic Determination in Geological Samples

In this study, Re and Os isotopes were systematically determined in six geological reference materials (RMs; covering a wide range of lithologies) using the Carius tube (CT) digestion technique with and without hydrofluoric acid desilicification. Our results show that the HF desilicification increased the Re extraction efficiency (by 9–15%) evidenced from basaltic and andesitic rocks (e.g., BHVO‐2, TDB‐1 and AGV‐2). This implies that a small proportion of Re resides in silicate phases. For mafic–ultramafic rocks (e.g., BCR‐2, WGB‐1 and WPR‐1), Re extraction efficiencies obtained by the CT digestion with and without HF desilicification were similar. This may indicate that Re in these rocks may dominantly reside in some phases (e.g., magnetite and sulfides) that could be completely dissolved in aqua regia solutions without the aid of HF desilicification. Our results also show that the HF desilicification increased Os extraction efficiency (by 13–99%) in some RMs (e.g., BHVO‐2, WGB‐1 and AGV‐2). This observation suggests that a portion of Os‐rich trace phases may occur as inclusions in the silicate phases that act as isolators at ~ 200 mesh sizes. This study demonstrates that the HF desilicification step prior to CT digestion is important for complete extraction of Re and Os in geological samples.     

A Method to Suppress Isobaric and Polyatomic Interferences for Measurements of Highly Siderophile Elements in Desilicified Geological Samples

Sample decomposition using inverse aqua regia at elevated temperatures and pressures (e.g., Carius tube or high‐pressure asher) is the most common method used to extract highly siderophile elements (HSEs: Ru, Rh, Pd, Re, Os, Ir, Pt and Au) from geological samples. Recently, it has been recognised that additional HF desilicification is necessary to better recover HSEs, potentially contained within silicate or oxide minerals in mafic samples, which cannot be dissolved solely by inverse aqua regia. However, the abundance of interfering elements tends to increase in the eluent when conventional ion‐exchange purification procedures are applied to desilicified samples. In this study, we developed an improved purification method to determine HSEs in desilicified samples. This method enables the reduction of the ratios of isobaric and polyatomic interferences, relative to the measured intensities of HSE isotope masses, to less than a few hundred parts per million. Furthermore, the total procedural blanks are either comparable to or lower than conventional methods. Thus, this method allows accurate and precise HSE measurements in mafic and ultramafic geological samples, without the need for interference corrections. Moreover, the problem of increased interfering elements, such as Zr for Pd and Cr for Ru, is circumvented for the desilicified samples.     

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.     

内蒙古柯单山蛇绿岩地幔橄榄岩铂族元素(PGEs)的分布特征及分异机制探讨

采用Carius管结合MC-ICPMS法分析了内蒙古柯单山蛇绿岩地幔橄榄岩中Ir、Ru、 Pt 和Pd 的含量,与典型的地幔橄榄岩进行对比研究,发现柯单山地幔橄榄岩中Ir和Ru明显亏损,Pt和Pd强烈富集,具有极高的Pd/Ir值,PGEs地幔标准化配分模式具有较陡的正斜率,明显不同于通常观测到的代表部分熔融残留相中铂族元素配分模式(负斜率或平坦型)。柯单山地幔橄榄岩的Ir和Ru与MgO呈正相关关系,表明Ir和Ru的亏损可能与部分熔融过程中硫化物的消耗程度有关,而与PGEs在硫化物/硅酸盐间的能斯特分配系数没有直接关系; Pt、Pd的富集表明本区的地幔橄榄岩不仅仅是经历过部分熔融的残余,而与来自深海的橄榄岩和大陆岩石圈地幔(SCLM)中的方辉橄榄岩相似,因此推测,本区地幔橄榄岩在部分熔融后又经历了富Pd的熔/流体交代,而熔/流体的来源可能是在岩浆分异演化过程中"熔离"出来的硫化物。     

镁铁-超镁铁岩铼-锇同位素体系分析方法

通过试验建立了镁铁-超镁铁岩Re-Os同位素体系分析方法，包括Re-Os的化学分离纯化流程，Re同位素比值的电感耦合等离子体质谱测量方法和Os同位素比值的负离子热电离质谱测量方法。化学流程包括Carius管溶样，小型蒸馏分离Os，微蒸馏纯化Os，阴离子交换法分离、纯化Re。用该流程测定了汉诺坝幔源橄榄岩、辉石岩捕虏体和大别山饶拔寨超镁铁岩样品的Re、Os含量和Os同位素比值。     

High‐precision Determination of Gold Mass Fractions in Geological Reference Materials by Internal Standardisation

Determination of gold abundances in natural rock is critical for applications, but very challenging. Here, we report a method for determining gold with a very low mass fraction (> 0.01 ng g^?1) in rocks. The method involves Carius tube digestion with reverse aqua regia, chromatographic separation to remove most of the sample matrix and measurement by high‐sensitivity ICP‐MS. The mono‐isotopic element gold was quantified by external calibration using an internal standardisation of gold to platinum that was precisely determined by isotope dilution. The method is robust and the obtained results are indistinguishable (< 5–10%, 2s) from those independently obtained by a standard addition technique on the same solution. The results from reference materials TDB‐1 and GPt‐2 are consistent with the certified values and those determined by HF‐aqua regia digestion, confirming the validity of the method. TDB‐1 (n = 20), GPt‐2 (n = 6), BHVO‐2 (n = 9) and other mafic RMs are homogenous for gold (10–20%, 2s) at the 2 g test portion level; however, sample heterogeneity affects some RMs. Gold and platinum‐group elements also display different extents of sample heterogeneity for different RMs. Given the homogeneity observed for TDB‐1, GPt‐2 and BHOV‐2, they are recommended as well‐suited RMs for inter‐laboratory comparison studies of gold.     

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...     

铼—锇同位素分析中试样化学预处理方法进展

评述了用于Re-Os同位素体系分析的化学前处理技术的发展。简要介绍了卡洛斯管熔样法、Os的CCl4提取、溴提取和微蒸馏方法。卡洛斯管封闭熔样方法，有效地防止了Os的挥发损失和保证了Os同位素平衡，是一种很有发展前景的熔样方法。蒸馏法仍是分离和纯化Os的有效方法，溶剂（CCl4)提取和溴提取法在许多实验室里应用，而微蒸馏则是Os的二次纯化的主要方法。Re的化学分离和纯化仍是离子交换和萃取法。引用主要文献29篇。     

用三氧化铬-硫酸溶剂对黑色页岩铼-锇定年方法初探

讨论了铼-锇同位素稀释法测定黑色页岩年龄的溶样方式,比较了王水和不同温度下CrO3-H2SO4的Carius管溶样技术,通过改进流程将铼空白控制在10pg之内,并结合高灵敏度的电感耦合等离子体质谱分析手段,初步研究建立了一种用CrO3-H2SO4溶剂准确测定黑色页岩年龄的方法。     

Ruthenium in komatiitic chromite

The distinction between Ru in solid solution and Ru-bearing inclusions is essential for the predictive modeling of platinum-group element (PGE) geochemistry in applications such as the lithogeochemical exploration for magmatic sulfide deposits in komatiites. This study investigates the role of chromite in the fractionation of Ru in ultramafic melts by analyzing chromite grains from sulfide-undersaturated komatiites and a komatiitic basalt from the Yilgarn Craton in Western Australia. In situ analysis using laser ablation ICP-MS yields uniform Ru concentrations in chromites both within-grain and on a sample scale, with concentrations between 220 and 540 ppb. All other platinum-group elements are below the detection limit of the laser ablation ICP-MS analysis. Carius tube digestion isotope dilution ICP-MS analysis of chromite concentrates confirms the accuracy of the in-situ method. Time resolved laser ablation ICP-MS analyses have identified the presence of sub-micron Ir-bearing inclusions in some chromite grains from the komatiitic basalt. However, Ru-bearing inclusions have not been recognized in the analyzed chromites and this combined with the in situ data suggests that Ru exists in solid solution in the crystal lattice of chromite. These results show that chromite can control the fractionation and concentration of Ru in ultramafic systems.     

Secondary Ca–Al silicates in plutonic rocks: implications for their cooling history

Secondary Ca-Al silicates are used to constrain the P-T-x conditions of the very early post-magmatic stage of the intermediate to basic Hercynian plutonic complexes of Charroux-Civray (NW Massif Central, France) and Fichtelgebirge (NE Bavaria, Germany). The secondary Ca-Al silicates hydrogarnet, prehnite, pumpellyite, epidote and laumontite form lenses within unaltered or only slightly chloritized biotite. Hydrogarnet as the first occurring Ca-Al silicate phase crystallizes at temperatures above 340 °C. The common paragenesis prehnite + pumpellyite post-dates hydrogarnet and indicates rather narrow ranges of temperature (200-280 °C) and pressure (2-3 kbar). Laumontite is formed at the end of Ca-Al silicate crystallization (180-260 °C, 1-3 kbar), mostly in small fractures in association with prehnite and adularia. The observed crystallization sequence of the Ca-Al silicates and their stabilities define a retrograde alteration path for the plutonic rocks. The Ca-Al silicate assemblage results from an early pervasive alteration of the plutonic rocks by low X_CO2 fluids during post-magmatic cooling. Subsolidus cooling starts at about 4 kbar at solidus temperatures as indicated by magmatic epidote stability, hornblende barometry and fluid inclusion data, and continues under slightly decreasing pressure (uplift) down to 2-3 kbar at 200-280 °C (prehnite-pumpellyite paragenesis). This shows that Ca-Al silicate assemblages may be a unique tool to constrain the P-T conditions of the subsolidus cooling of intermediate to basic plutonic bodies.     

铼-锇同位素分析样品预处理研究进展

文章评述并归纳了近年来地质样品中Re-Os同位素分析的化学前处理方法研究进展。总结了锍镍火试金法、碱熔法、Carius管溶样法以及HPA-S高温高压釜溶样法等常用的Re-Os同位素样品消解方法。归纳了离子交换、溶剂萃取富集Re以及蒸馏、萃取等分离富集Os的方法。由于地质样品的复杂性,Re、Os含量的不均一性及测试方法的多样性,要求在具体分析过程中不同的样品使用不同的消解方法和分离富集方法。当前国内应用较成熟的Re、Os分离方法是Carius管逆王水分解样品,原位蒸馏或CCl4萃取方法分离Os,阴离子交换法或丙酮萃取分离Re。     

Physicochemical conditions of crystallization of dunites of the Nizhnii Tagil Pt-bearing massif (Middle Urals)

Studies of primary multiphase silicate inclusions in accessory Cr-spinels from the fine-grained dunites of the Nizhnii Tagil Pt-bearing massif reveal their similarity to melt inclusions trapped by chromite during its growth. The analyzed Cr-spinels with multiphase silicate inclusions differ in composition from ore chromites of the same massif and from chromites (with melt inclusions) from ultramafic oceanic complexes but are similar to Cr-spinels in dunites from Pt-bearing alkaline ultramafic massifs (Konder and Inagli). According to petro- and geochemical data on heated multiphase silicate inclusions, the studied Cr-spinels crystallized with the participation of subalkalic picrobasaltic melts similar to the magmas of the Konder Pt-bearing massif and having almost the same chemical composition as tylaites. The differences between the compositions of olivines formed within the multiphase silicate inclusions and of the rock-forming minerals show that the studied Cr-spinels formed from an intercumulus liquid melt in the olivine crystal interstices during the cumulate crystallization of most of the Nizhnii Tagil massif dunites in the intrusive chamber. Numerical modeling based on the compositions of heated multiphase silicate inclusions in accessory Cr-spinels demonstrates that olivines and Cr-spinels from the studied dunites crystallized at 1430 to 1310 °C and then olivine formation continued to 1280 °C during the evolution of melts.     

The Il’mensky-Vishnevogorsky miaskite-carbonatite complex,the Urals,Russia: Origin,ore resource potential,and sources

The origin and sources of the Il’mensky-Vishnevogorsky miaskite-carbonatite complex, one of the world’s largest alkaline complexes, with unique rare-metal and colored-stone mineralization and Nb, Zr, and REE deposits, are discussed in this paper. Geochemical and isotopic studies, including of Nd, Sr, C, and O isotopes, as well as estimation of PT formation conditions, of miaskites and carbonatites from various deposits of the Il’mensky-Vishnevogorsky Complex have been carried out. The Vishnevogorsky, Potaninsky, and Buldym Nb-REE deposits and the Il’mensky, Baidashevo, and Uvil’dy occurrences related to carbonatites were investigated. Their geological setting, composition, and ore resource potential are characterized. The genetic models and typical features of the Il’mensky-Vishnevogorsky Complex are considered. The rocks of the Il’mensky-Vishnevogorsky Complex were formed at T = 1000?230°C and P = 2–5 kbar. Carbonated miaskite melt was divided into immiscible silicate and carbonate liquids at T = 1000°C and P = 5 kbar. Miaskite crystallized at T = 850?700°C and P = 3.5–2.5 kbar. The formation temperature of carbonatite I of the Vishnevogorsky pluton was close to the temperature of miaskite crystallization (700–900°C). The crystallization temperature of carbonate-silicate rock and carbonatite I in the Central alkaline tract was 650–600°C. The formation temperature of carbonatite II varied from 590 to 490°C. Dolomite-calcite carbonatite III and dolomite carbonatite IV of the Buldym massif were formed at T = 575?410°C and T = 315?230°C, respectively. The geochemical features of carbonatites belonging to the Il’mensky-Vishnevogorsky Complex differ from those of carbonatites related to alkaline ultramafic rocks and are close to those of carbonatites related to nepheline syenite or carbonatites localized in linear fracture zones. A high Sr content in early carbonatites along with relatively low Ba, Nb, Ta, Ti, Zr, and Hf contents and a certain enrichment in HREE (a low La/Yb ratio) in comparison with carbonatites of the alkaline ultramafic association are typical. The geochemistry of carbonatites of the Il’mensky-Vishnevogorsky Complex corresponds to the trend of geochemical evolution of carbonatitic melts and their fluid derivatives. The Sr, Nd, C, and O isotopic compositions indicate a mantle magmatic source of the Il’mensky-Vishnevogorsky Complex and participation of moderately depleted mantle (DM) and enriched mantle EM1 in magma generation. Carbonatite and miaskite of the Vishnevogorsky pluton are related to the DM magma source, and carbonatite of the Buldym massif, to the EM1 source, probably, involved in the plume ascent.     

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。     

Carius管直接蒸馏快速分离锇方法的改进

蒸馏法是Re-Os同位素测量体系从基质中分离Os的一种快捷方法,但装置繁琐,清洗工作量大,已成为限制其应用的瓶颈。文章对Carius管传统蒸馏装置进行了改进,利用橡胶滴头代替硅胶管和玻璃堵头自制Carius管直接蒸馏接口装置,简化了气体进出口管路,使用电蒸笼代替电热套,对蒸馏时间、样品溶液稀释倍数和吸收液体积等蒸馏条件进行了优化。改进后的装置升温速度、稳定性和简便性得到提高,简化了实验器皿,有利于降低空白,实现在较小操作空间内大批量样品的同时处理。Carius管直接蒸馏实验结果表明,Os的回收率可达86.7%～95.2%。在长时间(2 h)蒸馏条件下,Os回收率比传统蒸馏瓶法高约41%。针对不同样品类型和测试仪器,可选择相应的蒸馏条件,有效压缩了样品处理时间,提高了测量计数。对Re-Os定年标准物质GBW 04436(JDC)测定5次的模式年龄为(139.5±1.9)Ma～(142.0±2.1)Ma,标准物质GBW 04435(HLP)测定2次的模式年龄为(220±3.3)Ma～(223.0±3.2)Ma,分别与标准值(139.6±3.8)Ma和(221.4±5.6)Ma在不确定度范围内一致。改进后的Carius管直接蒸馏装置已应用于日常样品处理。     

Rock weathering by indigenous heterotrophic bacteria of Bacillus spp. at different temperature: a laboratory experiment

The bio-weathering of basalt, granite and gneiss was experimentally investigated in this study. These rock-forming minerals weathered more rapidly via the ubiquitous psychrotrophic heterotrophic bacteria. With indigenous bacteria of Bacillus spp. from sediments of Lake Baikal, we traced the degradation process of silicate minerals to understand the weathering processes occurring at the change temperature in the subsurface environment with organic input. The bacteria mediated dissolution of minerals was monitored with solution and solid chemistry, X-ray analyses as well as microscopic techniques. We determined the impact of the bacteria on the mineral surface and leaching of K, Ca, Mg, Si, Fe, and Al from silicate minerals. In the samples the release of major structural elements of silicates was used as an overall indicator of silicate mineral degradation at 4°C and 18°C from five medium exchanges over 255?days of rock bioleaching. The increase of temperature importantly affected the efficiency of Fe extraction from granite and basalt as well as Si extraction from granite and gneiss. In comparison with elemental extraction order at 4°C, Ca was substituted first by Fe or Si. It is evident that temperature influences rock microbial weathering and results in a change of elements extraction.     

黄铁矿 Re-Os 同位素定年化学前处理若干条件初探

对黄铁矿 Re-Os 同位素定年化学前处理过程中的溶样温度、溶样酸介质及溶样时间进行了条件实验.温度实验结果表明,溶样温度对 Re 的测定结果影响不大,而对 Os 的测定结果影响较明显.溶样温度在120~220℃之间时,无论是 HNO3还是逆王水溶样, Re 含量在误差范围内都是一致的,但在120℃、150℃时, Os 的含量偏离真实值,可能是样品和稀释剂中的 Os 同位素并未完全达到平衡,在180℃、200℃和220℃时, Os 的含量基本一致且接近真实值.溶样酸介质实验表明, HNO3和逆王水溶样对 Re 的测定影响不大,而对 Os 的测定影响较明显.无论是用 HNO3还是逆王水溶样,在不同温度下所得到的 Re 含量是一致的,而在120℃、150℃时,逆王水溶样较 HNO3溶样所得到的 Os 含量更加接近真实值,180℃、200℃和220℃时,两种酸介质溶样得到的 Os 含量基本一致且接近真实值.用逆王水在200℃时溶样,时间为5 h、8 h、12 h、18 h所得到的 Re、187Os 含量基本一致,说明较高温度下在较短的时间内便能达到较好的溶样效果.Fe3+浓度对Re 的阴离子交换效率实验表明, Re 的回收率随着 Fe3+浓度的不断升高而逐渐下降.当黄铁矿取样量为3 g时,上柱体积控制在40 mL 左右可获得较高的 Re 回收率