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1.
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.  相似文献   

2.
Atom probe microscopy (APM) is a relatively new in situ tool for measuring isotope fractions from nanoscale volumes (< 0.01 μm3). We calculate the theoretical detectable difference of an isotope ratio measurement result from APM using counting statistics of a hypothetical data set to be ± 4δ or 0.4% (2s). However, challenges associated with APM measurements (e.g., peak ranging, hydride formation and isobaric interferences), result in larger uncertainties if not properly accounted for. We evaluate these factors for Re‐Os isotope ratio measurements by comparing APM and negative thermal ionisation mass spectrometry (N‐TIMS) measurement results of pure Os, pure Re, and two synthetic Re‐Os‐bearing alloys from Schwander et al. (2015, Meteoritics and Planetary Science, 50, 893) [the original metal alloy (HSE) and alloys produced by heating HSE within silicate liquid (SYN)]. From this, we propose a current best practice for APM Re‐Os isotope ratio measurements. Using this refined approach, mean APM and N‐TIMS 187Os/189Os measurement results agree within 0.05% and 2s (pure Os), 0.6–2% and 2s (SYN) and 5–10% (HSE). The good agreement of N‐TIMS and APM 187Os/189Os measurements confirms that APM can extract robust isotope ratios. Therefore, this approach permits nanoscale isotope measurements of Os‐bearing alloys using the Re‐Os geochronometer that could not be measured by conventional measurement principles.  相似文献   

3.
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.  相似文献   

4.
To evaluate the homogeneity of geological reference material BIR‐1a (basalt; United States Geological Survey, USGS) for Re‐Os isotopic studies at the 0.2–1.0 g test portion size level, sixty‐three precise measurement results of Re and Os mass fractions and isotope amount ratios were obtained over an 18‐month period. These data reveal that the reference material has higher Re (0.691 ± 0.022 ng g?1, 2s, n = 63) and lower Os mass fractions (0.343 ± 0.089 ng g?1, 2s, n = 63) than UB‐N (serpentinite, CRPG) and is homogeneous in 187Os/188Os isotope amount ratio (0.13371 ± 0.00092, 2s, n = 63) at the 0.2–1.0 g test portion size level. The results are essentially consistent with previous views indicating that BIR‐1a gives precise measurement results for Re‐Os isotope amount ratio measurements at the 1 g test portion size level (Ishikawa et al., Chemical Geology, 2014, 384, 27–46; Meisel and Horan, Reviews in Mineralogy and Geochemistry, 2016, 81, 89–106). Based on these new Re‐Os data and previous studies, we propose BIR‐1a as a useful reference material that can be used in method validation and quality control and interlaboratory comparisons for studies dealing with mafic geological samples at test portion sizes of > 0.4 g.  相似文献   

5.
This study presents two matrix‐matched reference materials developed for petroleum Re‐Os measurements. We present the Re and Os mass fractions and 187Re/188Os and 187Os/188Os values (ratio of the number of atoms of the isotopes) for repeatedly measured aliquots (ca. 120–150 mg test portions) of the NIST Research Material 8505 (RM 8505) crude oil, and its asphaltene and maltene fractions, and ~ 90 g of homogeneous asphaltene powder isolated from this oil. Measurements were performed using the Carius tube‐isotope dilution negative‐thermal ionisation mass spectrometry methodology. The RM 8505 crude oil contains 1.98 ± 0.07 ng g?1 Re and 25.0 ± 1.1 pg g?1 Os, with Re‐Os isotope amount ratios of 452 ± 6 for 187Re/188Os and 1.51 ± 0.01 for 187Os/188Os (n = 20, 95% conf.). The homogeneous asphaltene sample contains 16.52 ± 0.10 ng g?1 Re and 166.0 ± 0.9 pg g?1 total Os, and possesses isotope amount ratios of 574 ± 3 for 187Re/188Os and 1.64 ± 0.01 for 187Os/188Os (n = 24, 95% conf.). The intermediate precision of these data makes the RM 8505 whole oil and the (~ 90 g) homogenised asphaltene appropriate petroleum matrix‐matched reference materials for Re‐Os measurements. The asphaltene fraction of the oil is the main carrier of Re and Os of the RM 8505 whole oil, and caution is suggested in using asphaltene and maltene fractions of a single oil for Re‐Os geochronology.  相似文献   

6.
Properly combining highly siderophile element (HSE: Re, Pd, Pt, Ru, Ir, Os) abundance data, obtained by isotope dilution, with corresponding 187Os/188Os and 186Os/188Os measurements of rocks requires efficient digestion of finely‐ground powders and complete spike‐sample equilibration. Yet, because of the nature of commonly used methods for separating Os from a rock matrix, hydrofluoric acid (HF) is typically not used in such digestions. Consequently, some silicates are not completely dissolved, and HSE residing within these silicates may not be fully accessed. Consistent with this, some recent studies of basaltic reference materials (RMs) have concluded that an HF‐desilicification procedure is required to fully access the HSE (Ishikawa et al. (2014) Chemical Geology, 384, 27–46; Li et al. (2015) Geostandards and Geoanalytical Research, 39, 17–30). Highly siderophile element abundance and Os isotope studies of intraplate basalts typically target samples with a range of MgO contents (< 8 to > 18% m/m, or as mass fractions, < 8 to > 18 g per 100 g), in contrast to the lower MgO mass fractions (< 10 g per 100 g) of basalt and diabase RMs (i.e., BIR‐1, BHVO‐2, TDB‐1). To investigate the effect of HF‐desilicification on intraplate basalts, experiments were performed on finely ground Azores basalts (8.1–17 g per 100 g MgO) using a ‘standard acid digestion’ (2:1 mixture of concentrated HNO3 and HCl), and a standard acid digestion, followed by HF‐desilicification. No systematic trends in HSE abundances were observed between data obtained by standard acid digestion and HF‐desilicification. Desilicification procedures using HF do not improve liberation of the HSE from Azores basalts, or some RMs (e.g., WPR‐1). We conclude that HF‐desilicification procedures are useful for obtaining total HSE contents of some young lavas, but this type of procedure is not recommended for studies where Re‐Pt‐Os chronological information is desired. The collateral effect of a standard acid digestion to liberate Os, followed by HF‐desilicification to obtain Re and Pt abundances in samples, is that the measured Re/Os and Pt/Os may not correspond with measured 187Os/188Os or 186Os/188Os.  相似文献   

7.
Geological reference materials (RMs) with variable compositions and NIST SRM 612 were analysed by isotope dilution mass spectrometry for bulk rock concentrations of chalcogen elements (sulfur, selenium and tellurium), rhenium and platinum‐group elements (PGEs: Ru, Pd, Os, Ir and Pt), including the isotope amount ratios of 187Os/188Os. All concentrations were obtained from the same aliquot after HCl‐HNO3 digestion in a high pressure asher at 320 °C. Concentrations were determined after chemical separation by negative TIMS, ICP‐MS and hydride generation ICP‐MS (Se, Te). As in previous studies, concentrations of the PGEs in most RMs were found to be highly variable, which may be ascribed to sample heterogeneity at the < 1 g level. In contrast, S, Se and Te displayed good precision (RSD < 5%) in most RMs, suggesting that part of the PGE budget is controlled by different phases, compared with the chalcogen budget. The method may minimise losses of volatile chalcogens during the closed‐system digestion and indicates the different extent of heterogeneity of chalcogens, Re and PGEs in the same sample aliquot. OKUM, SCo‐1, MRG‐1, DR‐N and MAG‐1 are useful RMs for the chalcogens. NIST SRM 612 displays homogenous distribution of S, Se, Te, Pt and Pd in 30 mg aliquots, in contrast with micro‐scale heterogeneity of Se, Pd and Pt.  相似文献   

8.
pg-ng级Os同位素热表面电离质谱高精度分析测试技术   总被引：5，自引：4，他引：1  
随着Os同位素在地质学领域定年与示踪的广泛应用,对分析测试精度和检出限提出了更高的要求。本文利用热表面电离质谱负离子模式(NTIMS)对Os O-3进行测定,通过试剂纯化、器皿清洗等前处理步骤的优化保证了超低的化学流程空白和获得灵敏而稳定的仪器测量信号,建立了高精度pg-ng级Os同位素分析测试方法。采用逐级剥谱法扣除氧同位素干扰,采用内标迭代法按照指数规律对仪器的质量歧视效应进行校正,全流程Os空白为0.41 pg,1 pg的190Os计数约85000 cps,质量分馏系数在0.1%以内。pg级Os采用离子计数器动态跳峰扫描模式进行测量,187Os/188Os值测量精度小于在0.2%以内;ng级Os采用法拉第杯静态接收模式采集信号,187Os/188Os值测量精度在0.005%以内。经国际上Os同位素标准溶液N2、JMC以及国家一级Re-Os同位素标准物质JCBY的验证,分析精度达到了国际同类实验室先进水平。本方法具有低空白、高灵敏度、高精度的特点,可为地质学研究提供高精度Os同位素数据。  相似文献   

9.
N(187Os)/N(188Os) ratios of six geological reference materials were measured using static Faraday cups (FCs) with 1013 Ω amplifiers by N‐TIMS. Our results show that the repeatability precision was 2–3‰ (2 RSD, n = 3), when taking ~ 1 g of BHVO‐2 with 76 pg g?1 of Os mass fraction and ~ 2 g of BCR‐2 with 21 pg g?1 of Os mass fraction for each sample, whether measured by FCs or by secondary electron multiplier. The repeatability precision measured by FCs was 1–0.2‰ (2 RSD, n = 3) when taking ~ 1 g of BIR‐2 with 350 pg g?1 of Os mass fraction, ~ 1 g of WGB‐1 with 493 pg g?1 of Os mass fraction or ~ 0.5 g of WPR‐1 with 13.3 ng g?1 of Os mass fraction for each sample, which is much better than those measured by secondary electron multiplier. Instead, when taking ~ 2 g of AGV‐2 with 4 pg g?1 Os mass fraction, the repeatability precision measured by secondary electron multiplier is 3–4‰ (RSD, n = 3), which is better than those measured by FCs. Of the six reference materials analysed, WPR‐1 and BIR‐1a are the most homogeneous with regard to Os isotopic composition (2 RSD of 0.08% and 0.23%, respectively) when test portion masses are 0.5–1 g.  相似文献   

10.
In this study, the USGS black shale reference material SBC‐1 was investigated as a matrix‐matched reference material for both intra‐laboratory calibration and inter‐laboratory comparison of high‐precision Re‐Os dating for organic‐rich sedimentary rocks. This reference material was analysed for Re‐Os isotopic composition by three digestion protocols – inverse aqua regia, CrO3‐H2SO4 and H2O2‐HNO3. The results for SBC‐1 obtained by inverse aqua regia digestion yielded similar Re mass fractions but slightly (~ 5%) higher Os mass fractions and lower 187Os/188Os values than the CrO3‐H2SO4 and H2O2‐HNO3 digestions. The data set of inverse aqua regia digestion exhibited strong correlations in plots of 187Os/188Os vs. 1/192Os and 187Os/188Os vs. 187Re/188Os, which may signify the incorporation of detrital Re and Os into organic matter in the Re‐Os system. Similar correlations were also observed for the CrO3‐H2SO4 digestion data set, but not for that of H2O2‐HNO3. The data indicate that there is an amount of non‐hydrogenous Os in SBC‐1 and that CrO3‐H2SO4 and H2O2‐HNO3 digestions would minimise liberation of the non‐hydrogenous Os component. We propose that SBC‐1 may be a more suitable reference material to monitor the influence of detrital Re and Os on Re‐Os isochron age data, especially for samples with less organic matter and more siliceous detritus.  相似文献   

11.
The marine osmium isotope record   总被引：3，自引：0，他引：3  
Over the past decade the marine osmium isotope record has been developed into a new tracer in palaeoceanographic research. Several analytical developments, particularly in the past few years, have significantly increased our ability to study the behaviour of osmium in the surficial environment. The 187Os/188Os and osmium concentration of seawater, river water, rain, and hydrothermal vent fluids have been measured directly. Recently, the behaviour of osmium in estuaries–critical for estimating the marine residence time of osmium–has been studied. Our knowledge of the surficial osmium cycle has thus significantly improved. In addition, reconstructions of past variations in the marine 187Os/188Os recently have been extended back into the Mesozoic. This review attempts to summarize our current understanding of the marine osmium system–present and past. The 187Os/188Os of seawater during the Cenozoic to first order mimics the marine 87Sr/86Sr record. It is therefore tempting to interpret both records as reflecting increased input of radiogenic osmium and strontium resulting from enhanced continental weathering regulated by climatic/tectonic processes. However, the marine osmium isotope system differs fundamentally from the marine strontium isotope system. This review emphasizes three important differences. First, large impacts are capable of resetting the 187Os/188Os to unradiogenic values without significantly affecting the marine strontium system. Second, organic‐rich sediments are characterized by high 187Re/188Os; resulting 187Os/188Os ingrowth‐trajectories are similar to the average slope of the Cenozoic 187Os/188Os seawater record. Trends towards more radiogenic 187Os/188Os seawater therefore can be caused by weathering of organic‐rich sediments at a constant rate. Third, the marine residence time of osmium is sufficiently short to capture short‐periodic (glacial‐interglacial) fluctuations that are inaccessible to the buffered marine strontium isotope system. This offers the opportunity to discriminate between high‐frequency (climatic) and low‐frequency (tectonic) forcing.  相似文献   

12.
石灰岩铼-锇同位素分析方法研究及应用初探   总被引：2，自引：2，他引：0  
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。  相似文献   

13.
A two‐step Th isolation protocol, involving micro‐columns of TRU‐Spec extraction chromatography material and AG1 resin, was evaluated. The MC‐ICP‐MS procedure included 232Th tailing characterisation and correction, and calibrator bracketing using an in‐house standard solution (ThS1) to correct for instrumental mass bias and Faraday cup to secondary electron multiplier relative gain. Repeated analyses of reference solutions (UCSC Th ‘A’, WUN, OU Th ‘U’, IRMM‐36) were consistent with published data. Six reference materials (A‐THO, BCR‐2, AGV‐2, BHVO‐2, BE‐N and BIR‐1) were processed. The average 230Th/232Th values obtained for these samples are in excellent agreement with published data. In addition, we report the first 230Th/232Th values for BE‐N and BIR‐1. The intermediate precisions for rock samples ranged from ± 0.24 to ± 0.49% (2 RSD) and were similar to those achieved for synthetic solutions, thereby supporting the overall validity of the chemical separation, data acquisition and reduction procedures. Counting statistics on the 230Th isotope was the most significant source of uncertainty. The intermediate precision of the mean 230Th/232Th for the Th‐depleted BIR‐1 (5.64 × 10?6 ± 0.27%, 2 RSD) is in the range of the analyses of other reference materials analysed in this study.  相似文献   

14.
We report an improved procedure for the determination of the platinum‐group elements (PGE) and Re, and Os isotopes from a single sample aliquot by isotope dilution (ID) using inductively coupled plasma‐mass spectrometry (ICP‐MS) and negative thermal ionisation mass spectrometry (N‐TIMS), respectively. A two‐stage column method was used to purify PGE‐Re from their sample matrix and interfering elements (e.g., Mo, Zr and Hf) after Os had been separated by CCl4 solvent extraction. The first column separation step used cation exchange resin (AG50W‐X8) to concentrate PGE‐Re and some potential interfering elements (e.g., Mo, Zr and Hf). In the second step, N‐benzoyl‐N‐phenylhydroxylamine (BPHA) extraction resin was used to separate PGE‐Re from the remaining interfering elements, which all remained strongly absorbed to the resin. The method was used to determine the PGE and rhenium, and Os isotope ratios in a range of geochemical reference materials (TDB‐1, WGB‐1, BHVO‐2 and UB‐N). The obtained results agree well with those previously published. This new method enables PGE‐Re abundances and Os isotopic ratios to be determined on the same sample digestion, and circumvents the problems created by sample heterogeneity when comparing PGE and Re‐Os isotope data.  相似文献   

15.
湖南鲁塘石墨矿Re-Os同位素研究   总被引：5，自引：1，他引：4  
石墨具有较高的Re、Os含量,可望成为理想的Re-Os同位素测年对象,但迄今国内外研究较少,尤其在煤层经变质作用形成石墨过程中,其中Re-Os同位素体系的变化还有待研究。湖南鲁塘石墨矿是我国典型的隐晶质石墨矿床之一,矿体产于二叠系龙潭组煤系地层中。本文采用Carius管逆王水溶解样品,直接蒸馏、微蒸馏分离纯化Os,丙酮萃取法分离富集Re,热表面电离质谱法对鲁塘矿区石墨样品以及外围原煤进行了Re-Os同位素分析。结果表明:鲁塘石墨的Re含量为0.901~9.794 ng/g,Os含量为7.3~189.5 pg/g,Re-Os同位素等时线年龄为155.6±3.6 Ma,该年龄与鲁塘石墨矿东侧骑田岭岩体第二阶段中粒黑云母花岗岩锆石U-Pb年龄153~157 Ma一致,表明了龙潭组煤层受到骑田岭岩体"烘烤"作用,发生热接触变质作用,使得靠近骑田岭岩体原煤变质为石墨,形成石墨矿床。通过对比石墨、原煤和骑田岭岩体Re、Os含量及比值,发现石墨中的Re、Os主要来源于原煤,并根据石墨Re-Os等时线初始(187Os/188Os)i值(0.686±0.032),推测骑田岭岩体在侵入煤系地层过程中,有少量具有较低187Os/188Os值的Os被碳质吸附。  相似文献   

16.
Whale carcasses (whale falls) deposited on the deep seafloor are associated with a distinctive biotic community. A fossil whale bone recovered from São Paulo Ridge, South Atlantic Ocean, during cruise YK13–04 Leg 1 of R/V Yokosuka was covered by a ferromanganese (Fe–Mn) crust approximately 9 mm thick. Here, we report an age constraint for this fossil bone on the basis of Os isotopic stratigraphy (187Os/188Os ratio) of the Fe–Mn crust. Major‐ and trace‐element compositions of the crust are similar to those of Fe–Mn crusts of predominantly hydrogenous origin. Rare earth element concentrations in samples of the crust, normalized with respect to Post‐Archean average Australian Shale, exhibit flat patterns with positive Ce and negative Y anomalies. These results indicate that the Fe–Mn crust consists predominantly of hydrogenous components and that it preserves the Os isotope composition of seawater at the time of its deposition. 187Os/188Os ratios of three Fe–Mn crust samples increased from 0.904 to 1.068 in ascending stratigraphic order. The value of 1.068 from the surface slice (0–3 mm depth in the crust) was identical to that of present‐day seawater within error (~1.06). The value of 0.904 from the basal slice (6–9 mm) equaled seawater values from ca. 4–5 Ma. Because it is unknown how long the bone lay on the seafloor before the Fe–Mn crust was deposited, the Os stratigraphic age of ca. 5 Ma is a minimum age of the fossil. This is the first application, to our knowledge, of marine Os isotope stratigraphy for determining the age of a fossil whale bone. Such data may offer valuable insights into the evolution of the whale‐fall biotic community.  相似文献   

17.
A method was developed for the determination of platinum‐group elements (PGE) in geological samples by isotope dilution‐inductively coupled plasma‐mass spectrometry combined with sulfide fire assay preconcentration. Samples were fused and PGE analytes were concentrated in sulfide buttons. The buttons were dissolved using HCl leaving PGE analytes in insoluble residues, which were digested in HNO3 and simultaneously processed for the distillation of Os. The remaining solutions were further prepared for the purification of Ru, Rh, Pd, Ir and Pt using a tandem assembly of cation and Ln resin columns. The eluents were directly analysed by membrane desolvation‐ICP‐MS. Ruthenium, Pd, Os, Ir and Pt were determined by isotope dilution, whereas Rh was determined by conventional reference material calibration combined with 193Ir as the internal standard element. The method was validated using a series of PGE reference materials, and the measurement data were consistent with the recommended and the literature values. The measurement precision was better than 10% RSD. The procedural blanks were 0.121 ng for Ru, 0.204 for Rh, 0.960 ng for Pd, 0.111 ng for Os, 0.045 ng for Ir and 0.661 ng for Pt, and the limits of detection (3s) were 0.011 ng g?1 for Ru, 0.008 ng g?1 for Rh, 0.045 ng g?1 for Pd, 0.009 ng g?1 for Os, 0.006 ng g?1 for Ir and 0.016 ng g?1 for Pt when a test portion mass of 10 g was used. This indicates that the proposed method can be used for the determination of trace amounts of PGE in geological samples.  相似文献   

18.
Paired analyses of Os isotope composition and concentration of bulk sediment and leachable Os in a metalliferous pelagic clay sequence from the North Pacific, ODP Site 886C, are used to reconstruct the marine Os isotope record and the particulate meteoritic Os flux between 65.5 and 78 Ma. Measured 187Os/188Os of bulk sediments ranges from approximately 0.64 to 0.32 and those of leach analyses are very similar to bulk analyses. Hydrogenous Os dominates the sedimentary Os inventory throughout most of the studied interval. As a result the measured 187Os/188Os of leachable Os approximates that of contemporaneous seawater. The ODP 886C record shows rising 187Os/188Os in the deepest portion of the core, with a local maximum of 0.66 close to 74 Ma. The 67-72 Ma portion of the record is characterized by nearly constant 187Os/188Os ratios close to 0.6. The structure of the marine Os isotope record from ODP 886C differs markedly from the seawater 87Sr/86Sr curve, which rises monotonically throughout the time interval studied here. Calculated particulate meteoritic Os fluxes are between 0.5 and 2 pg cm−2 kyr−1 throughout most of the studied interval. Two discrete intervals of the core (one of which is within Cretaceous Tertiary, boundary KTB interval) are characterized by higher fluxes of meteoritic Os. Excluding these two intervals, the average background flux of particulate meteoritic Os is roughly half of that estimated from analyses of Cenozoic marine sediments. These are the first Os isotope data to provide evidence of resolvable temporal variations in the background flux of particulate meteoritic material to the Earth.  相似文献   

19.
Spinel lherzolite xenoliths from Mont Briançon, French Massif Central, retain evidence for multiple episodes of melt depletion and melt/fluid infiltration (metasomatism). Evidence for primary melt depletion is still preserved in the co-variation of bulk-rock major elements (MgO 38.7-46.1 wt.%; CaO 0.9-3.6 wt.%), and many samples yield unradiogenic bulk-rock Os isotope ratios (187Os/188Os = 0.11541-0.12626). However, many individual xenoliths contain interstitial glasses and melt inclusions that are not in equilibrium with the major primary minerals. Incompatible trace element mass balance calculations demonstrate that metasomatic components comprise a significant proportion of the bulk-rock budget for these elements in some rocks, ranging to as much as 25% of Nd and 40% of Sr Critically, for Re-Os geochronology, melt/fluid infiltration is accompanied by the mobilisation of sulfide. Consequently, bulk-rock isotope measurements, whether using lithophile (e.g. Rb-Sr, Sm-Nd) or siderophile (Re-Os) based isotope systems, may only yield a perturbed and/or homogenised average of these multiple events.Osmium mass balance calculations demonstrate that bulk-rock Os in peridotite is dominated by contributions from two populations of sulfide grain: (i) interstitial, metasomatic sulfide with low [Os] and radiogenic 187Os/188Os, and (ii) primary sulfides with high [Os] and unradiogenic 187Os/188Os, which have been preserved within host silicate grains and shielded from interaction with transient melts and fluid. The latter can account for >97% of bulk-rock Os and preserve geochronological information of the melt from which they originally precipitated as an immiscible liquid. The Re-depletion model ages of individual primary sulfide grains preserve evidence for melt depletion beneath the Massif Central from at least 1.8 Gyr ago despite the more recent metasomatic event(s).  相似文献   

20.
Osmium isotope composition (187Os/188Os) and concentrations of Os, Ir and Pt are reported for an early Pleistocene section from the ODP Site 849 in the eastern equatorial Pacific. Using the data obtained in this study, the contributions from detrital and extraterrestrial particulate matter to Os concentration and 187Os/188Os of sediment are estimated. Our calculations show that detrital contributions to sedimentary Os are too small (<2%) to significantly shift measured bulk sediment 187Os/188Os away from seawater values. A moderate but significant negative correlation between 187Os/188Os and 3He/188Os indicate that the average particulate extraterrestrial Os flux to this site is 1.21 ± 0.47 pg cm−2 kyr−1, which constitutes ?3% of total Os burial flux. The estimates of detrital and extraterrestrial Os are used to calculate the seawater 187Os/188Os in the early Pleistocene. The most notable features of this early Pleistocene 187Os/188Os record are: (1) glacial-interglacial 187Os/188Os differences are insignificant within errors of estimates, (2) glacial 187Os/188Os values are higher compared to those reported for the late Pleistocene glacials. Comparison of 187Os/188Os values at Site 849 to the late Pleistocene records suggests that average seawater 187Os/188Os change has been modest (∼5%) since the early Pleistocene. Assuming that 187Os/188Os difference between the glacial periods of the late and the early Pleistocene results solely from temperature dependence of weathering rates, it has been calculated that average surface temperature during the late Pleistocene glacials was 0.8 ± 0.2 °C lower than glacials in the early Pleistocene. This inference is consistent with temperature estimates based on a recent study of pCO2 reconstruction in the Pleistocene. This observation based on limited studies of marine 187Os/188Os records seems to suggest that temperature played an important role in influencing chemical weathering during the Pleistocene glacials. However, more studies are needed to confirm if this temperature-weathering feedback was operational throughout the Pleistocene. A significant down core Ir-3He co-variation coupled with similar burial fluxes of Ir at Site 849 and at LL44 GPC-3 in the north Pacific point to the utility of Ir concentration as a point paleoflux tracer. However, a twofold difference in Ir burial fluxes between the eastern and the western equatorial Pacific suggests that calibration in space and time is required to use Ir concentration as a robust indicator of paleoflux through time. Significant co-variation of concentrations of Os and total alkenone during the glacials coupled with lighter δ13C of benthic foraminifera indicates that productivity and carbon burial played a dominant control on scavenging of Os at Site 849. In a broader context, this data set encourages future investigation of response of PGE behavior to paleoceanographic processes.  相似文献   

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