Re–Os systematics of diamond-bearing eclogites from the Newlands kimberlite

A suite of 14 diamond-bearing and 3 diamond-free eclogite xenoliths from the Newlands kimberlite, South Africa, have been studied using the Re–Os isotopic system to provide constraints on the age and possible protoliths of eclogites and diamonds. Re concentrations in diamond-bearing eclogites are variable (0.03–1.34 ppb), while Os concentrations show a much more limited range (0.26–0.59 ppb). The three diamond-free eclogites have Re and Os concentrations that are at the extremes of the range of their diamond-bearing counterparts. ¹⁸⁷Os/¹⁸⁸Os ranges from 0.1579 to 1.4877, while ¹⁸⁷Re/¹⁸⁸Os varies from 0.54 to 26.2 in the diamond-bearing eclogites. The highly radiogenic Os in the diamond-bearing eclogites (γ_Os=23–1056) is consistent with their high ¹⁸⁷Re/¹⁸⁸Os and requires long-term isolation from the convecting mantle. Re–Os model ages for 9 out of 14 diamond-bearing samples lie between 3.08 and 4.54 Ga, in agreement with FTIR spectra of Newlands diamonds that show nitrogen aggregation states consistent with diamond formation in the Archean. Re–Os isochron systematics for the Newlands samples do not define a precise isochron relationship, but lines drawn between subsets of the data provide ages ranging from 2.9 to 4.1 Ga, all of which are suggestive of formation in the Archean. The Re–Os systematics combined with mineral chemistry and stable isotopic composition of the diamond-bearing eclogites are consistent with a protolith that has interacted with surficial environments. Therefore, the favored model for the origin of the Newlands diamond-bearing eclogites is via subduction. The most likely precursors for the Kaapvaal eclogites include komatiitic ocean ridge products or primitive portions of oceanic plateaus or ocean islands.     

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.     

Advances in Re-Os Isotopic Dating in Geochronology of Hydrocarbon Accumulation

Rhenium-Osmium (Re-Os) isotopic dating applied to the geochronology of hydrocarbon accumulation has been the forefront of international research in the last 10 years and has achieved significant achievements. However, our current researches are lacking in Re-Os isotopic chronology on the geochronology of hydrocarbon accumulation. The successful application of the Re-Os geochronology has enabled the determination of accurate and precise depositional ages for Organic-Rich Sedimentary rocks (ORS), the establishment of timing constraints of oil generation or migration, and the fingerprinting of the source of oil. On the basis of literatures study both at home and abroad, this article mainly dealt with the principle of Re-Os isotopic dating and analyzed the accumulation processes of Re and Os in a seawater-sediment system. Meanwhile, the test samples, sample preparation and analytical methodology of Re-Os isotopic dating were summarized. The results revealed that the initial ¹⁸⁷Os/¹⁸⁸Os ratio could constrain the age of oil generation or migration, and effectively evaluated the relationship between source rock and oil. The radiogenic ¹⁸⁷Os/¹⁸⁸Os ratio showed a positively correlated relationship with source rock age. This article proposed that hydrocarbon mature, biodegradation and water washing had minimal or no effect on data scatter about Re-Os isochron. However, the effects of postdepositional mobility of Re and Os, variations in the initial ¹⁸⁷Os/¹⁸⁸Os ratio, and thermochemical sulfate reduction could result in data scatter. The reproducibility and accuracy of Re-Os age was also closely related to the sample particle size and sample amount. Compared with other isotopic dating, the biggest advantage of Re-Os isotopic dating is to study geological body related to accumulation process, and to obtain direct evidence of hydrocarbon accumulation period. From what was discussed above, the article discussed the existing problems and put forward the future hot research and development direction of Re-Os isotope system, so as to promote the deep development of relative theory and technology of Re-Os isotopic dating.     

Crustal contamination of mafic magmas: evidence from a petrological, geochemical and Sr–Nd–Os–O isotopic study of the Proterozoic Isortoq dike swarm, South Greenland

The mid-Proterozoic Isortoq dike swarm in the Gardar Province, South Greenland, comprises a variety of alkaline rocks ranging from gabbroic to syenitic in composition. Major magmatic mineral phases are olivine, clinopyroxene, Fe–Ti oxides, amphibole, plagioclase and alkali feldspar. Quartz occurs in some samples as a late magmatic phase. Liquidus temperatures of olivine-bearing samples range between 1120 and 1145 °C and solidus temperatures are 850–930 °C. Calculated silica activities are highly variable between 0.53 and unity. Oxygen fugacities vary from −3 to +1 log units relative to the fayalite–magnetite–quartz buffer.

The rocks have MgO contents <6 wt.% with Mg# between 53 and 17. Primitive mantle-normalized trace element patterns show a relative enrichment of LIL elements with Ba peaks and Nb troughs. Clinopyroxenes show a general enrichment in REE relative to chondritic values with variable slightly positive to prominent negative Eu anomalies. Two of the dikes were dated with Sm–Nd three-point isochrons at 1190±44 and 1187±87 Ma, respectively. Initial ⁸⁷Sr/⁸⁶Sr ratios of mafic mineral separates range from 0.70289 to 0.70432 and initial _Nd values vary from +0.3 to −10.7. Whole-rock initial ¹⁸⁷Os/¹⁸⁸Os ratios are highly variable including very radiogenic values of up to 7.967. δ¹⁸O_v-smow values of separated clinopyroxene and amphibole range from +5.2‰ to +6.2‰ and fall within the range of typical mantle-derived rocks, although mixing with a lower crustal component is permitted by the data. Using energy-constrained assimilation-fractional crystallization (EC-AFC) modeling equations, the Sr–Nd isotope data of the more radiogenic samples can successfully be modeled by addition of up to 10% lower crustal granulite-facies Archean gneisses as contaminants. The Os isotopic data also suggest the involvement of old radiogenic crust. In accordance with seismic data, we conclude that a wedge of Archean crust extends from West Greenland further to the south below the present erosion level.     

辉钼矿Re-Os同位素定年方法的改进与应用

公认的Re-Os同位素定年代表物辉钼矿,目前已在金属硫化物矿床年代学研究领域获得了广泛的应用。本研究采用浓HNO₃分解辉钼矿样品,大大地简化了Re和Os的化学制备过程,并根据辉钼矿中正常Os含量水平相对放射成因¹⁸⁷Os可以忽略的特点,以正常Os标准为稀释剂,实现了仪器测量过程中Os同位素质量分馏的在线校正,改善了分析数据的质量。该方法经辉钼矿国家标准物质进行验证,获得了满意的Re、Os含量及Re-Os年龄数据,并且在南岭地区与连阳复式岩体相关的姓坪夕卡岩型钼矿床成矿年龄研究中获得了成功应用。在实际应用中,为了获得有意义的能反映真实地质事件的年龄数据,辉钼矿样品不仅要有足够的取样量,而且还要保证粒度细、混合均匀。     

Origin of layered continental mantle (Karelian craton, Finland): Geochemical and Re–Os isotope constraints

Studies of mantle xenolith and xenocryst studies have indicated that the subcontinental lithospheric mantle (SCLM) at the Karelian Craton margin (Fennoscandian Shield) is stratified into at least three distinct layers cited A, B, and C. The origin and age of this layering has, however, remained unconstrained. In order to address this question, we have determined Re–Os isotope composition and a comprehensive set of major and trace elements, from xenoliths representing all these three layers. These are the first Re–Os data from the SCLM of the vast East European Craton.

Xenoliths derived from the middle layer B (at  110–180 km depth), which is the main source of harzburgitic garnets and peridotitic diamonds in these kimberlites, are characterised by unradiogenic Os isotopic composition. ¹⁸⁷Os/¹⁸⁸Os shows a good correlation with indices of partial melting implying an age of  3.3. Ga for melt extraction. This age corresponds with the oldest formation ages of the overlying crust, suggesting that layer B represents the unmodified SCLM stabilised during the Paleoarchean. Underlying layer C (at 180–250 km depths) is the main source of Ti-rich pyropes of megacrystic composition but is lacking harzburgitic pyropes. The osmium isotopic composition of layer C xenoliths is more radiogenic compared to layer B, yielding only Proterozoic T_RD ages. Layer C is interpreted to represent a melt metasomatised equivalent to layer B. This metasomatism most likely occurred at ca. 2.0 Ga when the present craton margin formed following continental break-up. Shallow layer A (at  60–110 km depth) has knife-sharp lower contact against layer B indicative of shear zone and episodic construction of SCLM. Layer A peridotites have “ultradepleted” arc mantle-type compositions, and have been metasomatised by radiogenic ¹⁸⁷Os/¹⁸⁸Os, presumably from slab-derived fluids. Since layer A is absent in the core of the craton, its origin can be related to Proterozoic processes at the craton margin. We interpret it to represent the lithosphere of a Proterozoic arc complex (subduction wedge mantle) that became underthrusted beneath the craton margin crust during continental collision  1.9 Ga ago.     

PGE and Os-isotopic variations in lavas from Kohala Volcano, Hawaii: Constraints on PGE behavior and melt/crust interaction

We have examined Re, Platinum-Group Element (PGE) and Os-isotope variations in suites of variably fractionated lavas from Kohala Volcano, Hawaii, in order to evaluate the effects of melt/crust interaction on the mantle isotopic signature of these lavas. This study reveals that the behavior of Os and other PGEs changes during magma differentiation. The concentrations of all PGEs strongly decrease with increasing fractionation for melts with MgO < 8 wt.%. Fractionation trends indicate significantly higher bulk partition coefficients for PGEs in lavas with less than 8 wt.% MgO (D_PGE = 35–60) when compared to values for more primitive lavas with MgO > 8 wt.% (D_PGE ≤ 6). This sudden change in PGE behavior most likely reflects the onset of sulfur saturation and sulfide fractionation in Hawaiian magmas at about 8 wt.% MgO.

The Os-rich primitive lavas (≥ 8 wt.% MgO, > 0.1 ppb Os) display a narrow range of ¹⁸⁷Os/¹⁸⁸Os values (0.130–0.133), which are similar to values in high-MgO lavas from Mauna Kea and Haleakala Volcanoes and likely represent the mantle signature of Kohala lavas. However, Os-isotopic ratios become more radiogenic with decreasing MgO and Os content in evolved lavas, ranging from 0.130 to 0.196 in the shield-stage Pololu basalts and from 0.131 to 0.223 in the post-shield Hawi lavas. This reflects assimilation of local oceanic crust material during fractional crystallization of the magma at shallow level (AFC processes). AFC modeling suggests that assimilation of up to 10% upper oceanic crust could produce the most radiogenic Os-isotope ratios recorded in the Pololu lavas. This amount of upper crust assimilation has a negligible effect on the Sr and Nd-isotopic compositions of Kohala lavas. Thus, these isotopic compositions likely represent the composition of the mantle source of Kohala lavas.     

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.     

特提斯洋对流上地幔Os同位素组成估算的新方法及初步运用

对流上地幔Os同位素组成的准确估算是运用Re-Os同位素体系探讨地幔演化的基础。前人研究主要是以地幔橄榄岩为研究对象,由于地幔橄榄岩Os同位素存在明显的不均一性,因而直接影响估算值的准确性。对流上地幔中包含的不同亏损程度的难熔组分在部分熔融过程中难以熔融,对形成的熔体相的Os同位素组成贡献很少或者没有。因此,与对流上地幔具有相同的Os同位素组成初始值的早期分离结晶岩石(如堆晶岩),结合堆晶岩中锆石的准确定年,可以用来估算对流上地幔Os同位素组成。本文根据这一方法测试了那曲地区弧后盆地堆晶岩的Os同位素组成和锆石U-Pb年龄,推测那曲地区新特提斯洋对流上地幔Os同位素组成为碳质球粒陨石型的。根据这一模型,对比了罗布莎和东巧铬铁矿岩、含矿围岩以及不含矿围岩的Os同位素特征,揭示出矿石及围岩均具有古老大陆岩石圈地幔信息,而不含矿围岩(泽当岩体)的Os同位素组成为碳质球粒陨石型的,无古老大陆岩石圈地幔信息。     

A Re–Os isotope and PGE study of kimberlite-derived peridotite xenoliths from Somerset Island and a comparison to the Slave and Kaapvaal cratons

The concentrations of platinum-group elements (PGE; Os, Ir, Ru, Pd and Pt) and Re, and the Os isotopic compositions were determined for 33 lithospheric mantle peridotite xenoliths from the Somerset Island kimberlite field. The Os isotopic compositions are exclusively less radiogenic than estimates of bulk-earth (¹⁸⁷Os/¹⁸⁸Os as low as 0.1084) and require a long-term evolution in a low Re–Os environment. Re depletion model ages (T_RD) indicate that the cratonic lithosphere of Somerset Island stabilised by at least 2.8 Ga, i.e. in the Neoarchean and survived into the Mesozoic to be sampled by Cretaceous kimberlite magmatism. An Archean origin also is supported by thermobarometry (Archean lithospheric keels are characterised by >150 km thick lithosphere), modal mineralogy and mineral chemistry observations. The oldest ages recorded in the lithospheric mantle beneath Somerset Island are younger than the Mesoarchean (>3 Ga) ages recorded in the Slave craton lithospheric mantle to the southwest [Irvine, G.J., et al., 1999. Age of the lithospheric mantle beneath and around the Slave craton: a Rhenium–Osmium isotopic study of peridotite xenoliths from the Jericho and Somerset Island kimberlites. Ninth Annual V.M. Goldschmidt Conf., LPI Cont., 971: 134–135; Irvine, G.J., et al., 2001. The age of two cratons: a PGE and Os-Isotopic study of peridotite xenoliths from the Jericho kimberlite (Slave craton) and the Somerset Island kimberlite field (Churchill Province). The Slave–Kaapvaal Workshop, Merrickville, Ontario, Canada]. Younger, Paleoproterozoic, T_RD model ages for Somerset Island samples are generally interpreted as the result of open system behaviour during metasomatic and/or magmatic processes, with possibly the addition of new lithospheric material during tectono-thermal events related to the Taltson–Thelon orogen. PGE patterns highly depleted in Pt and Pd generally correspond to older Archean T_RD model ages indicating closed system behaviour since the time of initial melt extraction. Younger Proterozoic T_RD model ages generally correspond to more complex PGE patterns, indicating open system behaviour with possible sulfide or melt addition. There is no correlation between the age of the lithosphere and depth, at Somerset Island.     

Os, Nd, and Sr isotopic and chemical compositions of ultramafic xenoliths from Kurose, SW Japan: Implications for contribution of slab-derived material to wedge mantle

We examined seven ultramafic xenoliths from 1~3 Ma alkali olivine basalt reefs near the Eurasian continent and one sample of the host alkali basalt to identify the mantle wedge material and to constrain the origin and evolution of mantle beneath SW Japan. Six xenoliths are from Kurose and one xenolith is from Takashima, northern part of the Kyushu islands, SW Japan. The Sr and Nd isotopic ratios vary from 0.70416 to 0.70773 and from 0.51228 to 0.51283, respectively. The Kurose and Takashima xenoliths have higher Sr isotopic ratios and lower Nd isotopic ratios than those of the peridotite xenoliths from the other arc settings such as Simcoe and NE Japan.

The Kurose xenoliths have less radiogenic Os isotopic ratios (¹⁸⁷Os/¹⁸⁸Os = 0.123–0.129) than the primitive upper mantle (PUM) estimate and limited variation compared to the other arc xenoliths. Their Os isotope compositions are rather similar to the ultramafic xenoliths from NE and east China. In addition, the samples of the Kurose and Takashima xenoliths plot along a mixing line between ultramafic xenoliths from SE and NE China and a slab component in Sr–Nd–Os isotopic space. Our results suggest that fragments of continental lithospheric mantle from the China craton may exist beneath Kurose and Takashima after the Sea of Japan expansion when the Japanese islands were rifted away from the Eurasian continent during Miocene. Later magmatism due to subduction of the Philippine Sea Plate beneath the SW Japan arc around 15 Ma ago may have introduced fluids or melts derived from slab component, interpreted to be oceanic sediments rather than altered oceanic crust, that possibly modified the original composition of the lithospheric mantle sampled by the peridotite xenoliths from Kurose and Takashima.     

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.     

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.     

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.     

Accurate Isotopic and Concentration Analyses of Small Amounts of Pb Using Isotope Dilution Coupled with the Double Spike Technique

A new method has been developed for the simultaneous determination of Pb abundance and Pb isotopic composition with high precision and accuracy for small test portion masses by thermal ionisation mass spectrometry. In this method, a ²⁰⁵pb-²⁰⁴pb double spike is added to samples prior to the chemical separation of Pb, and the isotopic composition of the spike-sample mixture is determined rigorously by the double spike technique using a ²⁰⁷Pb-²⁰⁴Pb spike. The isotopic composition and concentration of Pb in the sample are then obtained by utilising the principle of isotope dilution. Using this technique, replicate determinations of Pb from NIST SRM 981 and GSJ JP-1 (peridotite; 0.07 μg g⁻¹ Pb) were performed. The measured concentration and isotopic data were identical, within uncertainty, to published data or to data that were determined independently in this study. The application of this method to U-Pb dating and the determination of the "initial" Pb isotopic composition was also tested. Lead isotopic compositions and the concentrations of Pb, Th and U were determined for a single batch of samples, through the addition of ²⁰⁵pb-²⁰⁴pb, ²³⁰Th and ²³⁵U spikes to samples prior to chemical separation. Also in these experiments, we confirmed that this routine gives accurate data for Pb, Th and U concentrations and Pb isotopic compositions.     

西藏日喀则蛇绿岩镁铁质岩石Re-Os同位素特征及意义

通过对日喀则蛇绿岩的镁铁质岩石进行岩石学和地球化学研究,探讨其岩石成因及源区性质,同时根据Re-Os同位素的地球化学约束来探索雅鲁藏布蛇绿岩的形成机制。研究表明,日喀则蛇绿岩镁铁质岩石微量元素的标准化配分型式与洋中脊玄武岩类似,又具有岛弧玄武岩的地球化学特征。结合微量元素和同位素特征,均表明岩石的形成与俯冲作用有关。日喀则蛇绿岩产出于远离大陆地壳的SSZ环境,其形成过程未受到陆壳的混染;同时,Re-Os同位素体系受蚀变作用的影响也不明显。日喀则蛇绿岩镁铁质岩石的Re、Os含量低,¹⁸⁷Os/¹⁸⁸Os同位素比值较高,主要是源区性质和俯冲作用影响的结果。特提斯洋早期发生的多次俯冲作用造成地幔源区不均一。新特提斯洋壳俯冲过程中,上述不均一地幔发生部分熔融产生的镁铁质岩浆上升,经过遭受了早期熔体/岩石作用的纯橄岩通道,发生强烈的Re-Os同位素分馏,使熔体与地幔残余Os同位素组成表现出明显的解耦现象,进而形成现今的日喀则蛇绿岩。     

Isotopic constraints on time scales and mechanisms of slab material transport in the mantle wedge: evidence from the Simcoe mantle xenoliths, Washington, USA

Spinel harzburgite and websterite mantle xenoliths from Simcoe volcano in southern Washington represent fragments of mantle lithosphere from the back-arc side of the Cascade arc front. Previous studies have shown that metasomatism by either silica-rich fluids or hydrous melts crystallized phlogopite, imparted high oxygen fugacities (0.3 to 1.4 log units above QFM), and more radiogenic Os isotopic compositions on these peridotites. These features are consistent with part or all of the metasomatic agent being derived from the Juan de Fuca slab. New Re–Os, Sm–Nd, Sr, and U–Th–Pb isotopic data shed further light on the origin and composition of the metasomatic agent. The clinopyroxenes from the xenoliths have correlated Pb isotopic compositions (²⁰⁶Pb/²⁰⁴Pb=18.63–19.55, ²⁰⁷Pb/²⁰⁴Pb=15.56–15.63, ²⁰⁸Pb/²⁰⁴Pb=38.22–38.87). The most radiogenic Pb isotopic compositions extend beyond the most radiogenic Pb isotopic compositions for the Cascade arc lavas and display a shallower trend. Mixtures between Juan de Fuca basalts and pelagic or terrigenous sediments would result in Pb isotopic compositions that are not radiogenic enough in ²⁰⁷Pb/²⁰⁴Pb and ²⁰⁸Pb/²⁰⁴Pb at the high ²⁰⁶Pb/²⁰⁴Pb end of this array. Therefore, models for rapid transfer of components from the slab to the mantle lithosphere are not viable in this case. Instead, a multi-stage model is preferred. In the first stage, the slab component is transferred via fluid or melt into, and reacts with the hanging wall mantle. This results in a residual slab depleted in Pb relative to U and Th, and consequent high U/Pb and Th/Pb. Additional dehydration or melting of the slab imparts this chemical signature to the peridotite in the hanging wall. In the second stage, the hybridized hanging wall peridotite evolves for tens of million years until corner flow drags it down to deeper levels in the mantle wedge where melting occurs in response to higher temperatures. In the third stage, this melt migrates upward where it metasomatizes the mantle lithosphere represented by the Simcoe xenoliths. Trace element compositions of the clinopyroxenes, and the presence of high alkali glasses in the xenoliths, are consistent with the metasomatic agent derived from the hybridized hanging wall being alkali-rich, and possibly similar to potassic-rich lavas found in arc and back-arc settings. These data therefore demonstrate the importance of the hybridized hanging wall mantle above slabs as a source for melts which can be metasomatic agents in the upper mantle, and as a site for storage of material derived from the slab for periods of at least tens of million years.     

一种新的 K-Ar定年方法：峰值比较法

K-Ar法定年技术经历了体积法和稀释法等不断趋于成熟，但对于年轻火山岩进行定年时，由于同位素质量分馏的影响，上述方法都具有不可克服的缺陷。随着质谱仪稳定度和精度的提高，直接建立氩同位素含量与峰强度之间的定量关系，从而不再使用稀释剂（ 38 Ar）成为可能，这就是 K-Ar定年的新方法：峰值比较法（或无稀释剂法）。该方法可以消除质量分馏作用带来的误差，对年轻火山岩定年具有重要意义。近代火山物质都含有初始氩，且有不同程度的质量分馏，其同位素比值落在质量分馏线上，这表明质量分馏作用影响 K-Ar定年的准确性，尤其是非常年轻的样品。通过精确测定样品的 38 Ar／ 36 Ar比值，可以准确扣除样品中的初始 40 Ar，从而得到放射成因 40 Ar含量。这种测量方法可以用于较老岩石、矿物样品的年龄测定，其结果与 K-Ar稀释法以及 40 Ar－ 39 Ar法相一致；更重要的是可以用于年轻样品的年龄测定，可以测 2～5ka的岩矿样品，对富钾矿物的测量误差小于 1ka；对老于 0．1Ma的样品，相对误差不大于 1．5％。介绍了峰值比较法的基本原理和测试过程，同时还讨论它的使用条件和定年范围。     

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.     

The role of mantle-hybridization and crustal contamination in the petrogenesis of lithospheric mantle-derived alkaline rocks: constraints from Os and Hf isotopes

The Rhön area as part of the Central European Volcanic Province (CEVP) hosts an unusual suite of Tertiary 24-Ma old hornblende-bearing alkaline basalts that provide insights into melting and fractionation processes within the lithospheric mantle. These chemically primitive to slightly evolved and isotopically (Sr, Nd, Pb) depleted basalts have slightly lower Hf isotopic compositions than respective other CEVP basalts and Os isotope compositions more radiogenic than commonly observed for continental intraplate alkaline basalts. These highly radiogenic initial ¹⁸⁷Os/¹⁸⁸Os ratios (0.268–0.892) together with their respective Sr–Nd–Pb isotopic compositions are unlikely to result from crustal contamination alone, although a lack of Os data for lower crustal rocks from the area and limited data for CEVP basalts or mantle xenoliths preclude a detailed evaluation. Similarly, melting of the same metasomatized subcontinental lithospheric mantle as inferred for other CEVP basalts alone is also unlikely, based on only moderately radiogenic Os isotope compositions obtained for upper mantle xenoliths from elsewhere in the province. Another explanation for the combined Nd, Sr and Os isotope data is that the lavas gained their highly radiogenic Os isotope composition through a mantle “hybridization”, metasomatism process. This model involves a mafic lithospheric component, such as an intrusion of a sublithospheric primary alkaline melt or a melt derived from subducted oceanic material, sometime in the past into the lithospheric mantle where it metasomatized the ambient mantle. Later at 24 Ma, thermal perturbations during rifting forced the isotopically evolved parts of the mantle together with the peridotitic ambient mantle to melt. This yielded a package of melts with highly correlated Re/Os ratios and radiogenic Os isotope compositions. Subsequent movement through the crust may have further altered the Os isotope composition although this effect is probably minor for the majority of the samples based on radiogenic Nd and unradiogenic Sr isotope composition of the lavas. If the radiogenic Os isotope composition can be explained by a mantle-hybridization and metasomatism model, the isotopic compositions of the hornblende basalts can be satisfied by ca. 5–25% addition of the mafic lithospheric component to an asthenospheric alkaline magma. Although a lack of isotope data for all required endmembers make this model somewhat speculative, the results show that the Re–Os isotope system in continental basalts is able to distinguish between crustal contamination and derivation of continental alkaline lavas from isotopically evolved peridotitic lithosphere that was contaminated by mafic material in the past and later remelted during rifting. The Hf isotopic compositions are slightly less radiogenic than in other alkaline basalts from the province and indicate the derivation of the lavas from low Lu–Hf parts of the lithospheric mantle. The new Os and Hf isotope data constrain a new light of the nature of such metasomatizing agents, at least for these particular rocks, which represent within the particular volcanic complex the first product of the volcanism.