等离子体质谱法测定玄武岩中微量元素三种样品预处理方法的比较

在测定玄武岩的微量元素时,为了保证得到的微量元素结果反映源区特征,需经预处理去除玄武岩的孔洞中充填的碳酸盐等物质。选取雷州半岛新生代玄武岩三个样品,每一个样品用三种预处理方法进行预处理,等离子体质谱法测定其中的微量元素。分析结果表明,用稀硝酸浸泡样品,会导致玄武岩中大多数微量元素严重丢失,得到的数据失真;而用稀盐酸浸泡去除碳酸盐的方法基本不改变玄武岩中微量元素的含量。     

内蒙古正蓝旗羊蹄子山-磨石山钛矿区硅质岩地球化学特征及沉积环境意义

文章通过详细的野外地质调查和系统的岩石化学、稀土元素、微量元素及硅、氧同位素等研究,探讨了羊蹄子山-磨石山钛矿区无矿白色硅质岩和富钛硅质岩的成因及形成地质构造环境。研究结果表明,呈厚层状产出的无矿白色硅质岩具较高的SiO2、Al2O3含量及Al/(Al Fe Mn)、Al2O3/(Al2O3 Fe2O3)比值,稀土元素总量很低,其北美页岩标准化配分模式为向右倾的曲线,无明显铈异常和铕异常,表明其形成于受陆源影响的大陆边缘构造环境;赋矿岩系中薄层状富钛硅质岩的TiO2、Fe2O3、Cu、V含量较高,但Al/(Al Fe Mn)、Al2O3/(Al2O3 Fe2O3)比值较低,稀土元素总量较高,北美页岩标准化曲线为明显左倾型-平坦型,具弱的负铈异常,表明其形成于洋脊及附近环境。两种硅质岩的δ30Si值为变化较小的负值,与热水沉积和某些生物成因硅质岩的硅同位素组成相似,两者的δ18O值范围和平均值均相似。两类硅质岩的成因及形成构造环境不同,富钛硅质岩的地球化学特征表明,该矿床的形成与本区元古宙海底火山热液喷流作用有关。     

内蒙古敖包吐萤石矿床的Sr、Nd、Pb同位素地球化学特征

敖包吐萤石矿床是内蒙古北部苏莫查干地区单一萤石矿集区中的一个代表性矿床,产于早二叠世大石寨组火山-沉积岩与早白垩世敖包吐花岗岩的接触带上。文章通过分析该矿床岩、矿石的微量元素和稀土元素,揭示出萤石的成矿作用可分为2个阶段,即交代作用和充填作用。交代作用过程中大石寨组的结晶灰岩可能为萤石的形成提供了部分Ca来源,萤石矿石的稀土元素配分模式与海水基本类似,具有Ce负异常;成矿作用后期主要表现为充填作用,形成颗粒粗大的萤石,表现为重稀土元素富集的特征,并随着萤石的沉淀析出,稀土元素总量逐渐下降,反映出成矿流体经历了较长期的演化过程。各地层单元、花岗岩体和萤石矿石的Sr、Nd、Pb同位素研究表明,萤石的放射性同位素组成具有壳、幔源混合的特点,成矿物质来源具有多源性。早白垩世敖包吐花岗岩可能是萤石中F的主要来源,而大石寨组的结晶灰岩则可能提供了Ca。另外,Pb、Nd同位素的极大不均一性,有可能是成矿流体在运移过程中对艾力格庙群放射性组分的选择性吸收的结果。萤石成矿作用与钾玄岩的时空关系暗示了萤石的成矿过程可能是中国东部岩石圈减薄和下地壳的置换地质事件的结果。在构造转型的过程中,燕山中期富碱的酸性花岗岩浆的活动分异出富含F的成矿流体,与幔源流体混合,沿区域重新活化的深大断裂和大石寨组的层间破碎带上升,交代其间的灰岩透镜体,从而形成敖包吐中型萤石矿床。     

藏南白垩系黑-红层沉积岩有机质组成分布特征

对藏南江孜县床得剖面白垩系黑层和红层沉积岩进行的有机地球化学研究表明,黑层有机碳含量高于红层5～10倍,红层和黑层饱和烃主峰碳数分别为nC25和nC23;黑层和红层沉积有机质的母质来源都以水生植物和菌藻类等低等生物为主,陆源有机质的输入非常有限;但饱和烃的分布和主峰碳数的差异可能反映了有机母源物质在种群方面的差异,而这种差异可能主要是水体温度存在差异造成的,即红层发育时期水体温度可能高于黑层沉积时期.而在高温度条件下,水生生物和陆生植物的生长发育受到限制,造成原始有机质产率和有机质沉积保存量低可能是红层沉积岩形成的主要原因.     

Sulfur isotope measurement of sulfate and sulfide by high-resolution MC-ICP-MS

We have developed a technique for the accurate and precise determination of ³⁴S/³²S isotope ratios (δ³⁴S) in sulfur-bearing minerals using solution and laser ablation multiple-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). We have examined and determined rigorous corrections for analytical difficulties such as instrumental mass bias, unresolved isobaric interferences, blanks, and laser ablation- and matrix-induced isotopic fractionation. Use of high resolution sector-field mass spectrometry removes major isobaric interferences from O₂⁺. Standard-sample bracketing is used to correct for the instrumental mass bias of unknown samples. Background on sulfur masses arising from memory effects and residual oxygen-tailing are typically minor (< 0.2‰, within analytical error), and are mathematically removed by on-peak zero subtraction and by bracketing of samples with standards determined at the same signal intensity (within 20%). Matrix effects are significant (up to 0.7‰) for matrix compositions relevant to many natural sulfur-bearing minerals. For solution analysis, sulfur isotope compositions are best determined using purified (matrix-clean) sulfur standards and sample solutions using the chemical purification protocol we present. For in situ analysis, where the complex matrix cannot be removed prior to analysis, appropriately matrix-matching standards and samples removes matrix artifacts and yields sulfur isotope ratios consistent with conventional techniques using matrix-clean analytes. Our method enables solid samples to be calibrated against aqueous standards; a consideration that is important when certified, isotopically-homogeneous and appropriately matrix-matched solid standards do not exist. Further, bulk and in situ analyses can be performed interchangeably in a single analytical session because the instrumental setup is identical for both. We validated the robustness of our analytical method through multiple isotope analyses of a range of reference materials and have compared these with isotope ratios determined using independent techniques. Long-term reproducibility of S isotope compositions is typically 0.20‰ and 0.45‰ (2σ) for solution and laser analysis, respectively. Our method affords the opportunity to make accurate and relatively precise S isotope measurement for a wide range of sulfur-bearing materials, and is particularly appropriate for geologic samples with complex matrix and for which high-resolution in situ analysis is critical.     

The relationship between hydrodynamic properties and weathering of soils derived from volcanic rocks,Galapagos Islands (Ecuador)

The aim of this interdisciplinary study is to examine a component of the hydrological cycle in Galapagos by characterizing soil properties. Nine soil profiles were sampled on two islands. Their physical and hydrodynamic properties were analyzed, along with their mineralogical composition. Two groups of soils were identified, with major differences between them. The first group consists of soils located in the highlands (>350 m a.s.l.), characterized by low hydraulic conductivity (<10⁻⁵ m s⁻¹) and low porosity (<25%). These soils are thick (several meters) and homogeneous without coarse components. Their clay fraction is considerable and dominated by gibbsite. The second group includes soils located in the low parts of the islands (<300 m a.s.l.). These soils are characterized by high hydraulic conductivity (>10⁻³ m s⁻¹) and high porosity (>35%). The structure of these soils is heterogeneous and includes coarse materials. The physical properties of the soils are in good agreement with the variations of the rainfall according to the elevation, which appears as the main factor controlling the soil development. The clayey alteration products constrain soils physical and hydrodynamic properties by reducing the porosity and consequently the permeability and also by increasing water retention.     

Timing of UHP metamorphism in the Hong’an area,western Dabie Mountains,China: evidence from zircon U–Pb age,trace element and Hf isotope composition

The Hong’an area (western Dabie Mountains) is the westernmost terrane in the Qinling-Dabie-Sulu orogen that preserves UHP eclogites. The ages of the UHP metamorphism have not been well constrained, and thus hinder our understanding of the tectonic evolution of this area. LA-ICPMS U–Pb age, trace element and Hf isotope compositions of zircons of a granitic gneiss and an eclogite from the Xinxian UHP unit in the Hong’an area were analyzed to constrain the age of the UHP metamorphism. Most zircons are unzoned or show sector zoning. They have low trace element concentrations, without significant negative Eu anomalies. These metamorphic zircons can be further subdivided into two groups according to their U–Pb ages, and trace element and Lu–Hf isotope compositions. One group with an average age of 239 ± 2 Ma show relatively high and variable HREE contents (527 ≥ Lu_N ≥ 14) and ¹⁷⁶Lu/¹⁷⁷Hf ratios (0.00008–0.000931), indicating their growth prior to a great deal of garnet growth in the late stage of continental subduction. The other group yields an average age of 227 ± 2 Ma, and shows consistent low HREE contents and ¹⁷⁶Lu/¹⁷⁷Hf ratios, suggesting their growth with concurrent garnet crystallization and/or recrystallization. These two groups of age are taken as recording the time of prograde HP to UHP and retrograde UHP–HP stages, respectively. A few cores have high Th/U ratios, high trace element contents, and a clear negative Eu anomaly. These features support a magmatic origin of these zircon cores. The upper intercept ages of 771 ± 86 and 752 ± 70 Ma for the granitic gneiss and eclogite, respectively, indicate that their protoliths probably formed as a bimodal suite in rifting zones in the northern margin of the Yangtze Block. Young Hf model ages (T _DM1) of magmatic cores indicate juvenile (mantle-derived) materials were involved in their protolith formation. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

An experimental study of the grain-scale processes of peridotite melting: implications for major and trace element distribution during equilibrium and disequilibrium melting

The grain-scale processes of peridotite melting were examined at 1,340°C and 1.5 GPa using reaction couples formed by juxtaposing pre-synthesized clinopyroxenite against pre-synthesized orthopyroxenite or harzburgite in graphite and platinum-lined molybdenum capsules. Reaction between the clinopyroxene and orthopyroxene-rich aggregates produces a melt-enriched, orthopyroxene-free, olivine + clinopyroxene reactive boundary layer. Major and trace element abundance in clinopyroxene vary systematically across the reactive boundary layer with compositional trends similar to the published clinopyroxene core-to-rim compositional variations in the bulk lherzolite partial melting studies conducted at similar P–T conditions. The growth of the reactive boundary layer takes place at the expense of the orthopyroxenite or harzburgite and is consistent with grain-scale processes that involve dissolution, precipitation, reprecipitation, and diffusive exchange between the interstitial melt and surrounding crystals. An important consequence of dissolution–reprecipitation during crystal-melt interaction is the dramatic decrease in diffusive reequilibration time between coexisting minerals and melt. This effect is especially important for high charged, slow diffusing cations during peridotite melting and melt-rock reaction. Apparent clinopyroxene-melt partition coefficients for REE, Sr, Y, Ti, and Zr, measured from reprecipitated clinopyroxene and coexisting melt in the reactive boundary layer, approach their equilibrium values reported in the literature. Disequilibrium melting models based on volume diffusion in solid limited mechanism are likely to significantly underestimate the rates at which major and trace elements in residual minerals reequilibrate with their surrounding melt. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Magma Ascent and Crustal Accretion at Ultraslow-Spreading Ridges: Constraints from Plagioclase Ultraphyric Basalts from the Arctic Mid-Ocean Ridge

Plagioclase ultraphyric basalts (PUBs) with up to 54% plagioclasephenocrysts were dredged in the rift valley and adjacent flanksof the ultraslow-spreading Mohns and Knipovich ridges. The PUBsshow large variations in crystal morphologies and zoning. Thelarge variations suggest that single basalt samples containa mixture of plagioclase crystals that aggregated at differentlevels in the magma conduits. Resorbed crystals and repeatedreverse zones suggest that the magma reservoirs were replenishedand heated several times. Thin concentric zones with melt inclusions,and sharp reductions in the anorthite content of 3–7%,are common between the reverse zones. These zones, and skeletalcrystals with distinctly lower anorthite contents than massivecrystals, are interpreted to be the result of rapid crystalliztionduring strong undercooling. The changes between short periodsof cooling and longer periods with reheating are explained bymultiple advances of crystal-rich magma into cool regions followedby longer periods of gradual magma inflow and temperature increase.The porphyritic basalts are characterizd by more depleted andmore fractionated compositions than the aphyric basalts, withlower (La/Sm)_N, K₂O and Mg-numbers. This relationship, and theobservation that PUBs are sampled only close to segment centresalong these ridges, suggests that the PUBs formed by higherdegrees of melting and evolved in more long-lived magma reservoirs.We propose that the zoning patterns of plagioclase crystalsand crystal morphologies of these PUBs reflect the developmentand flow of magma through a stacked sill complex-like conduitsystem, whereas the aphyric equivalents represent later flowof magma through the conduit. The formation of voluminous higher-degreemelts may trigger the development of the magma conduits andexplain the generally depleted compositions of PUB magmas. KEY WORDS: basalt; mineral chemistry; MORB; magma mixing; magma chamber; major element