Determination of Ge, As, Se and Te in Silicate Samples Using Isotope Dilution-Internal Standardisation Octopole Reaction Cell ICP-QMS by Normal Sample Nebulisation

A method for the determination of Ge, As, Se and Te in silicate samples using isotope dilution-internal standardisation (ID-IS) octopole reaction cell (ORC) ICP-QMS by normal sample nebulisation was developed. The method does not involve either hydride generation or ion exchange. Germanium, Se and Te were determined by isotope dilution (ID), and As was determined by ID-IS. A silicate sample with an added Ge-Se-Te spike was digested with an HF-HNO₃-HBr mixture, dried, re-dissolved with HF and the supernatant liquid was directly aspirated into an ORC-ICP-QMS instrument with He or H₂ gas. No matrix effects were observed down to a dilution factor (DF) of ∼ 70 for Ge, Se and Te and DF of ∼ 1000 for As, which resulted in 3s detection limits in silicates of 2, 1, 0.1 and 4 ng g⁻¹, respectively. Advantages of the method are the simple sample introduction as well as a capability of determining S, Ti, Zr, Nb, Mo, Sn, Sb, Hf and Ta by ID-IS-ICP-QMS/SFMS from the same solution. Furthermore, the total sample solution consumption was only 0.253 ml with DF = 2000. Therefore, only a 0.13 mg test portion was required. To demonstrate the applicability of this technique, Ge, As, Se and Te in eight silicate reference materials were determined, as well as S, Ti, Zr, Nb, Mo, Sn, Sb, Hf and Ta in four carbonaceous chondrites.     

Determination of Molybdenum, Antimony and Tungsten at sub μg g−1 Levels in Geological Materials by ID-FI-ICP-MS

We have developed a rapid and accurate method for the determination of Mo, Sb and W in geological samples using isotope dilution inductively coupled plasma-mass spectrometry with a flow injection system (ID-FI-ICP-MS). The chemical procedure requires HF digestion of the sample with a Mo-Sb-W mixed spike, subsequent evaporation and dissolution of Mo, Sb and W from Mg and Ca fluorides with HF. Recovery yields of Mo, Sb and W in the extraction were > 94% for samples of peridotite, basalt and andesite composition, with the exception of W in samples of peridotite composition for which recovery was 81%. No matrix effects were observed in the determination of the isotope ratios of Mo, Sb and W in solutions prepared from peridotite, basalt and andesite samples down to a dilution factor of 100. Detection limits of Mo, Sb and W in silicate materials were at the several ng g⁻¹ level. Analysis of the silicate reference materials PCC-1, DTS-1, BCR-1, BHVO-1, AGV-1 from the US Geological Survey and JP-1, JB-1, -2, -3, JA-1, -2, and -3 from the Geological Survey of Japan as well as the Smithsonian reference Allende powder yielded reliable Mo, Sb and W concentrations. The repeatability in the analysis of basalts and andesites was < 9%. This technique requires only 0.2 ml sample solution, and is therefore suitable for analyzing small and/or precious samples such as meteorites, mantle peridotites and their mineral separates.     

Coprecipitation of Ti,Mo, Sn and Sb with fluorides and application to determination of B,Ti, Zr,Nb, Mo,Sn, Sb,Hf and Ta by ICP-MS

We examined the coprecipitation behavior of Ti, Mo, Sn and Sb in Ca–Al–Mg fluorides under two different fluoride forming conditions: at < 70 °C in an ultrasonic bath (denoted as the ultrasonic method) and at 245 °C using a Teflon bomb (denoted as the bomb method). In the ultrasonic method, small amounts of Ti, Mo and Sn coprecipitation were observed with 100% Ca and 100% Mg fluorides. No coprecipitation of Ti, Mo, Sn and Sb in Ca–Al–Mg fluorides occurred when the sample was decomposed by the bomb method except for 100% Ca fluoride. Based on our coprecipitation observations, we have developed a simultaneous determination method for B, Ti, Zr, Nb, Mo, Sn, Sb, Hf and Ta by Q-pole type ICP-MS (ICP-QMS) and sector field type ICP-MS (ICP-SFMS). 9–50 mg of samples with Zr–Mo–Sn–Sb–Hf spikes were decomposed by HF using the bomb method and the ultrasonic method with B spike. The sample was then evaporated and re-dissolved into 0.5 mol l^− 1 HF, followed by the removal of fluorides by centrifuging. B, Zr, Mo, Sn, Sb and Hf were measured by ID method. Nb and Ta were measured by the ID-internal standardization method, based on Nb/Mo and Ta/Mo ratios using ICP-QMS, for which pseudo-FI was developed and applied. When 100% recovery yields of Zr and Hf are expected, Nb/Zr and Ta/Hf ratios may also be used. Ti was determined by the ID-internal standardization method, based on the Ti/Nb ratio from ICP-SFMS. Only 0.053 ml sample solution was required for measurement of all 9 elements. Dilution factors of ≤ 340 were aspirated without matrix effects. To demonstrate the applicability of our method, 4 carbonaceous chondrites (Ivuna, Orgueil, Cold Bokkeveld and Allende) as well as GSJ and USGS silicate reference materials of basalts, andesites and peridotites were analyzed. Our analytical results are consistent with previous studies, and the mean reproducibility of each element is 1.0–4.6% for basalts and andesites, and 6.7–11% for peridotites except for TiO₂.     

Constraints from eclogite and MARID xenoliths on origins of mantle Zr/Hf–Nb/Ta variability

New trace-element data of rutile in kimberlite-borne ~1.85 Ga eclogite and pyroxenite xenoliths from the central Slave craton, as well as ~110 Ma MARID xenoliths from the Kaapvaal craton, provide constraints on the origins of lithospheric and sublithospheric mantle variability in high field strength element ratios. Rutiles in eclogites and pyroxenites have Zr/Hf ranging from 20 to 62 and Nb/Ta ranging from 10 to 40. Rutiles in MARID xenoliths have Zr/Hf from 24 to 33 and Nb/Ta from 10 to 41. Calculated whole-rock Zr/Hf is suprachondritic for eclogites with suggested gabbroic protoliths and subchondritic for boninite-like eclogites; the latter is consistent with cpx-controlled depletion in the protolith source. Within each eclogite type, positive correlations of Zr/Hf with La/Lu and negative correlations with Lu/Hf likely reflect fractionation of cpx and/or plagioclase during crystallisation of the protoliths. Zr/Hf–Nb/Ta relationships of some MARID-type rocks, which are products of lithospheric mantle metasomatism, and eclogite xenoliths plot on a silicate differentiation trend, whereas other samples have higher Nb/Ta at a given Zr/Hf. Fractionation of a few percent rutile from an HFSE-rich mafic melt can generate a trend towards strongly increased Nb/Ta at minimally changed Zr/Hf in the residual melt. Superposition of rutile fractionation on the effects of silicate differentiation, which fractionates Zr/Hf more strongly than Nb/Ta, can explain the Zr/Hf–Nb/Ta relationships of most eclogites from the central Slave craton as well as those of MARID rocks, metasomatised peridotites and group II kimberlites. By contrast, Zr/Hf–Nb/Ta relationships suggest that Group I kimberlites are mixtures between depleted peridotite and carbonatite. Thus, high Nb/Ta is a signature of lithospheric processes and may not be important in deeply subducted eclogites that bypass extended residence in the lithosphere. Conversely, considerable primary Zr/Hf variability was inherited by the eclogites, which is indicative of the compositional diversity of ancient subducted oceanic crust, which is expected to have generated substantial heterogeneity in sublithospheric basalt sources.     

Isotope Dilution Determinations of Lu,Hf, Zr,Ta and W,and Hf Isotope Compositions of NIST SRM 610 and 612 Glass Wafers

Isotope dilution determinations of Lu, Hf, Zr, Ta and W are reported for nine test portions (five for W) of NIST SRM 610 and 612 glass wafers. Additionally, all test portions were analysed for their Hf isotope compositions. In general, high field strength elemental (HFSE) distributions in NIST SRM 610 and 612 were reproducible to ～± 1%, except for Zr (± 5%) in NIST SRM 612, and absolute reported concentrations agreed with previously published values, but with higher precision. The slightly worse reproducibility of Zr in NIST SRM 612 compared to other HFSE is interpreted to result from analytical scatter, rather than sample inhomogeneity. The analyses demonstrated elemental homogeneity for both glass wafers for samples of 1–2 mg with respect to the precision of the method, i.e., ± 1% or better. Average Hf isotope compositions for both glass wafers agreed within uncertainty and the weighted average of all determinations yielded a mean ¹⁷⁶Hf/¹⁷⁷Hf ratio of 0.282111 ± 0.000009 (95% confidence level). However, although mean values for NIST SRM 610 and 612 agreed within analytical limits, NIST SRM 610 test portions showed a tendency of systematically elevated isotope composition of ～ 0.5 _?Hf units when compared to NIST SRM 612, which may indicate a slightly more radiogenic Hf isotope composition of NIST SRM 610. The results of this study suggest that NIST SRM 610 and 612 are valuable calibrators for HFSE in situ analyses within the given uncertainties.     

Mechanisms of Archean crust formation inferred from high-precision HFSE systematics in TTGs

It has been proposed that Archean tonalitic-trondhjemitic-granodioritic magmas (TTGs) formed by melting of mafic crust at high pressures. The residual mineralogy of the TTGs (either (garnet)-amphibolite or rutile-bearing eclogite) is believed to control the trace element budget of TTGs. In particular, ratios of high-field-strength elements (HFSE) can help to discriminate between the different residual lithologies. In order to place constraints on the source mineralogy of TTGs, we performed high-precision HFSE measurements by isotope dilution (Nb, Ta, Zr, Hf) together with Lu-Hf and Sm-Nd measurements on representative, ca. 3.85-2.8 Ga TTGs and related rock types from southern West Greenland, W-India and from the Superior Province. These measurements are complemented by major and trace element data for the TTGs. Texturally homogeneous early Archean (3.85-3.60 Ga old) and Mesoarchean (ca. 3.1-2.8 Ga old) TTGs have both low Ni (<11 ppm) and Cr contents (<20 ppm), indicating that there was little or no interaction with mantle peridotite during ascent. Ratios of Nb/Ta in juvenile Eoarchean TTGs range from ca. 7 to ca. 24, and in juvenile Mesoarchean TTGs from ca. 14 to ca. 27. Even higher Nb/Ta (14-42) were obtained for migmatitic TTGs and intra-crustal differentiates, most likely mirroring further fractionation of Nb from Ta as a consequence of partial melting, fluid infiltration and migmatisation. In the juvenile TTGs, positive correlations between Nb/Ta and Gd/Yb, La/Yb, Sr/Y, Zr/Sm and Zr/Nb are observed. These compositional arrays are best explained by melting of typical Isua tholeiites in both, the rutile-bearing eclogite stability field (>15 kbar, high Nb/Ta) and the garnet-amphibolite stability field (10-15 kbar, low Nb/Ta). With respect to the low end of Nb/Ta found for TTGs, there is currently some uncertainty between the available experimental datasets for amphibole. Independent of these uncertainties, the TTG compositions found here still require the presence of both endmember residues. A successful geological model for the TTGs therefore has to account for the co-occurrence of both low- and high-Nb/Ta TTGs within the same geologic terrane. An additional feature observed in the Eoarchean samples from Greenland is a systematic co-variation between Nb/Ta and initial εHf(t), which is best explained by a model where TTG-melting occured at progressively increasing pressures in a pile of tectonically thickened mafic crust. The elevated Nb/Ta in migmatitic TTGs and intra-crustal differentiates can shed further light on the role of intra-crustal differentiation processes in the global Nb/Ta cycle. Lower crustal melting processes at granulite facies conditions may generate high-Nb/Ta domains in the middle crust, whereas mid-crustal melting at amphibolite facies conditions may account for the low Nb/Ta generally observed in upper crustal rocks.     

HFSE systematics of rutile-bearing eclogites: New insights into subduction zone processes and implications for the earth’s HFSE budget

The depleted mantle and the continental crust are generally thought to balance the budget of refractory and lithophile elements of the Bulk Silicate Earth (BSE), resulting in complementary trace element patterns. However, the two high field strength elements (HFSE) niobium and tantalum appear to contradict this mass balance. All reservoirs of the silicate Earth exhibit subchondritic Nb/Ta ratios, possibly as a result of Nb depletion.In this study a series of nineteen orogenic MORB-type eclogites from different localities was analyzed to determine their HFSE concentrations and to contribute to the question of whether subducted oceanic crust could form a hidden reservoir to account for the mass imbalance of Nb/Ta between BSE and the chondritic reservoir. Concentrations of HFSE were analyzed with isotope dilution (ID) techniques. Additionally, LA-ICPMS analyses of clinopyroxene, garnet and rutile have been performed. Rutile is by far the major host for Nb and Ta in all analyzed eclogites. However, many rutiles revealed zoning in Nb/Ta ratios, with cores being higher than rims. Accordingly, in situ analyses of rutiles have to be evaluated carefully and rutile cores do not necessarily reflect a bulk rock Nb and Ta composition, although over 90% of these elements reside in rutile.The HFSE concentration data in bulk rocks show that the orogenic eclogites have subchondritic Nb/Ta ratios and near chondritic Zr/Hf ratios. The investigated eclogites show neither enrichment of Nb compared to similarly incompatible elements (e.g. La), nor fractionation of Nb/Ta ratios relative to MOR-basalts, the likely precursor of these rocks. This indicates that during the conversion of the oceanic crust to eclogites in most cases, (1) HFSE and REE have similar mobility on average, possibly because both element groups remain in the down going slab, and (2) no significant fractionation of Nb/Ta occurs in subducted oceanic crust. With an average Nb/Ta ratio of 14.2 ± 1.4 (2s.e.), the investigated eclogites cannot balance the differences between BSE and chondrite. Additionally, as their average Nb/Ta is indistinguishable from the Nb/Ta of MORB, they are also an unlikely candidate to balance the potentially small differences in Nb/Ta between the continental crust and the mantle.     

丹宁棉分离富集—发射光谱法同时测定地质样品中微量铌钽锆铪

采用丹宁棉对地质样品溶液中的铌、钽、锆、铪进行分离富集，将写信后的丹宁棉在600℃灼烧30min，灰分用发射光谱法同时测定四元素。检出限与通常的发射光谱法相比降低约2个数量级，经国家级标准物质检验，结果与标准值相符，精密度试验，各元素的RSD（n＝20）为2.6％－7.9％。     

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

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

The Direct Determination of Rare Earth Elements in Basaltic and Related Rocks using ICP-MS: Testing the Efficiency of Microwave Oven Sample Decomposition Procedures

Tests are described showing the results obtained for the determination of REE and the trace elements Rb, Y, Zr, Nb, Cs, Ba, Hf, Ta, Pb, Th and U with ICP-MS methodology for nine basaltic reference materials, and thirteen basalts and amphibolites from the mafic-ultramafic Niquelândia Complex, central Brazil. Sample decomposition for the reference materials was performed by microwave oven digestion (HF and HNO₃, 100 mg of sample), and that for the Niquelândia samples also by Parr bomb treatment (5 days at 200°C, 40 mg of sample). Results for the reference materials were similar to published values, thus showing that the microwave technique can be used with confidence for basaltic rocks. No fluoride precipitates were observed in the microwave-digested solutions. Total recovery of elements, including Zr and Hf, was obtained for the Niquelândia samples, with the exception of an amphibolite. For this latter sample, the Parr method achieved a total digestion, but not so the microwave decomposition; losses, however, were observed only for Zr and Hf, indicating difficulty in dissolving Zr-bearing minerals by microwave acid attack.     

大兴安岭南段林西地区中生代酸性岩类岩浆的混染作用

大兴安岭南段林西地区广泛出露以海相玄武安山岩、安山岩为主的晚古生代火山．沉积岩。中生代火山-侵入杂岩也广泛分布其中。花岗岩体的边部普遍二长花岗岩化和花岗闪长岩化(甚至出现闪长岩)，并含有丰富的以玄武质-安山质为主的岩石包体。侵入体-围岩接触带附近为围岩被岩浆侵蚀的港湾状交代反应过渡带。英安岩-粗面英安岩也含有相同的岩石包体，并且与流纹岩密切共生。岩石包体周缘的寄主岩常见淬冷边，聚集针状磷灰石，表明它被捕获时已是冷却的岩石，而非热的玄武岩浆团；它们的Nb／Ta、Zr／Hf比值、弱交代者的化学成分与晚古生代火山-沉积岩一致，Rb-Sr同位素比值散布在晚古生代火山-沉积岩等时线附近，其含量、未交代程度、尖棱状程度、刚性程度在侵入体中从内部到边部增多(强)，且较新鲜者结构构造与围岩相同，表明它们来自晚古生代火山-沉积岩组成的围岩；其含量与岩体边部的位置及二长花岗岩、花岗闪长岩、(粗面)英安岩的成分变化有关，表明包体成分已加入到这些岩石当中。这些岩石的环带状斜长石有两种内核：一种较富钙；另一种较贫钙。两种内核的斜长石外环成分趋同，强交代岩石包体成分和富含岩石包体的酸性岩成分趋同。两者皆记录了两种来源的物质成分同化的过程。同一岩体边部(或火山岩中)酸度较低的岩石化学成分、高场强元素在Harker图解和Nb／Ta(和Zr／Hf)-SiO2及Nb／Ta-Zr／Hf图解中具有中生代花岗或流纹岩浆与晚古生代火山-沉积岩物质混合的特征。这些事实证明林西地区中生代酸性岩浆被较基性的晚古生代火山物质混染，并生成酸度较低的混染岩浆。较基性的火山物质是在低绿片岩相变质的基础上，经钠化交代反应被酸性岩浆同化的。     

High-precision high field strength element partitioning between garnet, amphibole and alkaline melt from Kakanui, New Zealand

The high field strength elements (HFSE: Zr, Hf, Nb, Ta, and W) are an important group of chemical tracers that are increasingly used to investigate magmatic differentiation processes. Successful modeling of these processes requires the availability of accurate mineral-melt partition coefficients (D). To date, these have largely been determined by ion microprobe or laser ablation-ICP-MS analyses of the run products of high-pressure, high-temperature experiments. Since HFSE are (highly) incompatible, relatively immobile, high-charge, and difficult to ionize, these experiments and their analysis are challenging. Here we explore whether high-precision analyses of natural mineral-melt systems can provide additional constraints on HFSE partitioning.The HFSE concentrations in natural garnet and amphibole and their alkaline host melt from Kakanui, New Zealand are determined with high precision isotope dilution on a multi-collector-ICP-MS. Major and trace element compositions combined with Lu-Hf isotopic systematics and detailed petrographic sample analysis are used to assess mineral-melt equilibrium and to provide context for the HFSE D measurements. The whole-rock nephelinite, ∼1 mm sized amphiboles in the nephelinite, and garnet megacrysts have similar initial Hf isotope ratios with a mean initial ¹⁷⁶Hf/¹⁷⁷Hf_{(34 Ma)} = 0.282900 ± 0.000026 (2σ). In contrast, the amphibole megacrysts are isotopically distinct (¹⁷⁶Hf/¹⁷⁷Hf_{(34 Ma)} = 0.282830 ± 0.000011). Rare earth element D values for garnet megacryst-nephelinite melt and ∼1 mm amphibole-nephelinite melt plotted as a function of ionic radii show classic near-parabolic trends that are in excellent agreement with crystal lattice-strain models. These observations are consistent with equilibrium between the whole-rock nephelinite, the ∼1 mm amphibole grains within the nephelinite and the garnet megacrysts.High-precision isotope dilution results for Zr and Hf in garnet (D_Zr = 0.220 ± 0.007 and D_Hf = 0.216 ± 0.005 [2σ]), and for all HFSE in amphibole are consistent with previous experimental findings. However, our measurements for Nb and Ta in garnet (D_Nb = 0.0007 ± 0.0001 and D_Ta = 0.0011 ± 0.0006 [2σ]) show that conventional methods may overestimate Nb and Ta concentrations, thereby overestimating both Nb and Ta absolute D values for garnet by up to 3 orders of magnitude and underestimating D_Nb/D_Ta by greater than a factor of 100. As a consequence, the role of residual garnet in imposing Nb/Ta fractionation may be less important than previously thought. Moreover, garnet D_Hf/D_W = 17 and D_Nb/D_Zr = 0.003 imply fractionation of Hf from W and Nb from Zr upon garnet crystallization, which may have influenced short-lived ¹⁸²Hf-¹⁸²W and ⁹²Nb-⁹²Zr isotopic systems in Hadean time.     

阿尔泰造山带南缘中泥盆世苦橄岩及其大地构造和岩石学意义

阿尔泰造山带南缘中泥盆世苦橄岩位于北塔山组地层的下部, 其上依次为玄武岩和安山岩.3种岩性共同的特点是贫钛、富铁, 具Nb和Ta的负异常以及高场强元素的丰度与MORB相当, 具有典型的岛弧火山岩系的特点, 是准噶尔洋板块向南西俯冲的结果.苦橄岩和玄武岩的Zr/Nb和Sm/Nd比值与MORB相当, 表明其源区为亏损的MORB源.然而玄武岩的Ti/V和Zr/Sm比值均高于苦橄岩, 而且玄武岩的稀土元素配分曲线呈平缓型, 而苦橄岩则显示出低的稀土总量以及弱富集轻稀土型, 指示了玄武岩是被从俯冲的洋壳释放的流体交代的含角闪石的尖晶石橄榄岩的地幔源区低程度部分熔融形成的, 苦橄岩则是在高温条件下被流体交代过的石榴石橄榄岩高程度熔融的产物.安山岩则可能是榴辉岩部分熔融形成的.      

青藏高原北羌塘盆地治多地区松赛弄一带火山岩的特征及构造意义

测区松赛弄晚三叠世-带火山岩为-套酸性-中性-基性火山岩组合,由玄武岩、安山岩、英安岩、流纹岩及少量火山碎屑岩等组成.火山岩中SiO2含量为48.89%～88.15%,平均67.44%,TiO2为0.22%～1.85%,平均0.63%,MgO含量0.23%～7.81%,与岛弧钙碱性火山岩相似;高场强元素Nb、Ta、Zr、Hf、Ti等亏损,大离子亲石元素Rb、Sr、Ba等相对富集,(La/Sm)n为1.79～5.19,LREE/HREE值多数在4.08～6.63,属轻稀土元素富集型,δEu多数在0.47～0.99.铕呈负异常;La/Nb多数大于2.00,Nb/Zr>0.04;Th/Ta>4.41,Th×Ta/Hf2>0.042,具有陆缘火山弧的特性.上述特征表明,羌塘盆地治多地区松赛弄一带晚三叠世火山岩产于大陆碰撞与陆缘弧并存的环境.     

Voltammetric Determination of High Field‐Strength Elements (Ti,Zr, Hf,Nb, Ta) in Geological Matrices

A voltammetric method for the determination of the high field‐strength elements Ti, Zr, Hf, Nb and Ta by adsorptive stripping of their tartrate complexes is presented. The applicability of the method to geological and metallurgical samples is illustrated by the analysis of certified reference materials (USGS BCR‐2 basalt, BCS‐CRM 388 zircon and Euronorm CRM 579‐1 ferroniobium). Suitable sample preparation techniques, involving fusion with LiBO₂ and acidic and basic fluxes, followed by preliminary separation by anion chromatography are described. The method is rapid, affordable and environmentally friendly as it does not require problematic compounds such as hydrofluoric acid or toxic solvents and represents an alternative to more commonly used methods (AAS, ICP‐OES, ICP‐MS).     

滇东南马关巨晶单斜辉石原位Sr同位素特征及其含水性

对滇东南马关火山爆砾岩筒以及玄武岩中的单斜辉石巨晶进行了主量元素、微量元素、原位Sr同位素以及含水性研究,结果显示,单斜辉石巨晶均为铝质普通辉石,Mg#与Al、Fe、Ti呈负相关,与Ca呈正相关;稀土元素总量不高,HREE及LREE亏损,而MREE相对富集,大离子亲石元素均出现明显亏损,高场强元素Nb、Zr出现亏损而Hf略富集,Nb、Ta与Zr、Hf分馏明显,Rb、Ba的变化范围较大。原位Sr同位素87Sr/86Sr值为0. 703 92～0. 705 06,巨晶单斜辉石来源于上地幔,形成于同一母岩浆,与寄主玄武岩同源,为源岩浆在高压下的结晶产物。运用显微红外-傅里叶变换红外光谱仪(Micro-FTIR)分析测试了单斜辉石巨晶的水含量,结果显示OH吸收峰位于3 700～2 800cm-1,含水量赋值范围为318×10-6～693×10-6,水含量稍富于女山及汉诺坝地区的单斜辉石巨晶,也高于马关地区幔源橄榄岩包体中的单斜辉石结构水含量,暗示该区上地幔岩石圈具高含水性,这同时证实了俯冲洋壳在研究区的活动。新近纪到达地幔过渡带的西太平洋洋壳俯冲发生转向东撤,此时新特提斯洋洋壳正在NE向俯冲,是马关地区深部地幔富水的主因,到达软流圈(或地幔过渡带)的新特提斯洋俯冲洋壳导致该区地幔熔融,岩浆随之而生。     

河北承德盆地114 Ma大北沟组玄武岩地球化学及其对华北克拉通岩石圈地幔减薄作用的制约

华北克拉通罕见年龄界于120～100Ma的火山岩。承德盆地大北沟组火山岩下部主要由柱状节理橄榄玄武岩组成,中上部主要由安山岩组成。对紧邻玄武岩的上覆安山岩的火山锆石U-PbLA-ICPMS定年结果表明,形成年龄为(113.6±0.87)Ma,代表了该套火山岩的喷发年龄,表明它们形成于早白垩世晚期。对3件玄武岩样品的分析结果表明,它们亏损高场强元素(Nb、Ta、Zr、Hf),初始87Sr/86Sr同位素比值为0.7059,εNd(114Ma)为-11.04,具有富集型岩石圈地幔的特征。但该套玄武岩的主量和微量元素特征则介于华北克拉通中生代年龄>120Ma具古老富集型地幔特征的玄武岩和年龄<100Ma具亏损软流圈性质的玄武岩之间,表明113.6Ma时华北克拉通岩石圈地幔在元素组成方面已具有由富集地幔向亏损型软流圈地幔转变的特征。大北沟组玄武岩的地球化学特征表明,114Ma时华北克拉通岩石圈地幔已减薄。     

Determination of Chromium, Nickel, Copper and Zinc in Milligram Samples of Geological Materials Using Isotope Dilution High Resolution Inductively Coupled Plasma-Mass Spectrometry

A simple and accurate method for the determination of Cr, Ni, Cu and Zn at μg g^?1 levels in milligram‐sized bulk silicate materials is reported using isotope dilution high‐resolution inductively coupled plasma‐mass spectrometry (HR‐ICP‐MS) with a flow injection system. Silicate samples with Cr, Ni, Cu and Zn spikes were digested with HF‐HBr and Br₂, and subsequently decomposed at 518 K in a Teflon bomb. In this procedure, all sulfides and chromite, major hosts of these elements, were completely decomposed, thus allowing for isotope equilibration between the sample and spike. Magnesium and Al fluorides formed after the digestion of the sample were removed by centrifugation, and the supernatant was directly aspirated into a HR‐ICP‐MS at a mass resolution of 7500, where interfering oxide ions, ArO⁺, CaO⁺, TiO⁺, CrO⁺ and VO⁺, were separated from Cr⁺, Ni⁺, Cu⁺ and Zn⁺. No matrix effects were observed down to a dilution factor of 50. Detection limits for these elements in silicate samples were < 0.04 μg g^?1. The effectiveness of the technique was demonstrated by the analysis of 13 to 40 mg test portions of USGS and GSJ silicate reference materials with a major element composition ranging from andesite to peridotite, in addition to 8‐23 mg of the Smithsonian reference Allende. Both the reproducibility and the deviation from the reference value for most reference materials of various rock types were < 9%, and thus confirm that the method gives accurate analytical results for small sample sizes over a wide range of Cr, Ni, Cu and Zn contents. This method is, therefore, suitable for analysing small and/or precious bulk samples, such as meteorites, mantle peridotites and mineral separates, and for the characterisation of silicate and sulfide minerals for use as calibration samples in secondary ion mass spectrometry or laser ablation ICP‐MS.     

电感耦合等离子体质谱法测定岩石样品中的锆铌铪钽两种预处理方法的比较

研究了微波消解酸溶和过氧化钠碱熔两种测定岩石样品中锆、铌、铪、钽前处理方法,利用电感耦合等离子体质谱法进行测定。对所选用不同种类的岩石国家标准物质样品进行了条件实验,结果表明:采用过氧化钠碱熔法处理岩石样品后,锆、铌、铪、钽的测量值准确度高,且相对标准偏差(RSD,n=10)小于6%,该方法更适用于岩石样品中锆、铌、铪、钽的测定。     

Analysis of Standard Reference Materials for Zr,Nb, Hf and Ta by ICP-MS after Lithium Metaborate Fusion and Cupferron Separation*

Results are presented of the determination of Zr, Nb, Hf and Ta in 74 standard reference materials by inductively coupled plasma mass spectrometry (ICP-MS). Samples are decomposed by fusion with lithium metaborate and the analytes are separated prior to analysis by precipitation of their cupferrates. Calibration is made using synthetic solutions and internal standardization with Ru (for Zr and Nb) and Re (for Hf and Ta). Accuracy is assessed by comparison with recommended values and precision is evaluated by replicate analyses of five SRMs.