Decoupling of stalagmite-derived Asian summer monsoon records from North Atlantic temperature change during marine oxygen isotope stage 5d

The Asian monsoon is an important component of the global climate system. Seasonal variations in wind, rainfall, and temperature associated with the Asian monsoon systems affect a vast expanse of tropical and subtropical Asia. Speleothem-derived summer monsoon variation in East Asia was previously found to be closely associated with millennial-scale change in temperature in the North Atlantic region between 75 and 10 ka. New evidence recovered from East Asia, however, suggests that the teleconnection between summer monsoon in East Asia and temperature change in the North Atlantic region may have significantly reduced during 120 to ~ 110 ka, a period directly after the full last interglaciation and corresponding roughly to marine oxygen isotope stage 5d. This reduction may be due to the low ice volume in the North Hemisphere at that time, which makes the millennial-scale change in temperature in the North Atlantic region less effective in influencing the Asian summer monsoon. This is important for investigating the mechanisms controlling the Asian summer monsoon and the paleoclimatic teleconnection between East Asia and the North Atlantic region, and for predicting monsoon-associated precipitation in East Asia under a global-warming trend.     

The geochemistry of gem opals as evidence of their origin

Seventy-seven gem opals from ten countries were analyzed by inductively coupled plasma-mass spectrometry (ICP-MS) through a dilution process, in order to establish the nature of the impurities. The results are correlated to the mode of formation and physical properties and are instrumental in establishing the geographical origin of a gem opal. The geochemistry of an opal is shown to be dependant mostly on the host rock, at least for examples from Mexico and Brazil, even if modified by weathering processes. In order of decreasing concentration, the main impurities present are Al, Ca, Fe, K, Na, and Mg (more than 500 ppm). Other noticeable elements in lesser amounts are Ba, followed by Zr, Sr, Rb, U, and Pb. For the first time, geochemistry helps to discriminate some varieties of opals. The Ba content, as well as the chondrite-normalized REE pattern, are the keys to separating sedimentary opals (Ba > 110 ppm, Eu and Ce anomalies) from volcanic opals (Ba < 110 ppm, no Eu or Ce anomaly). The Ca content, and to a lesser extent that of Mg, Al, K and Nb, helps to distinguish gem opals from different volcanic environments. The limited range of concentrations for all elements in precious (play-of-color) compared to common opals, indicates that this variety must have very specific, or more restricted, conditions of formation. We tentatively interpreted the presence of impurities in terms of crystallochemistry, even if opal is a poorly crystallized or amorphous material. The main replacement is the substitution of Si⁴⁺ by Al³⁺ and Fe³⁺. The induced charge imbalance is compensated chiefly by Ca²⁺, Mg²⁺, Mn²⁺, Ba²⁺, K⁺, and Na⁺. In terms of origin of color, greater concentrations of iron induce darker colors (from yellow to “chocolate brown”). This element inhibits luminescence for concentrations above 1000 ppm, whereas already a low content in U (≤ 1 ppm) induces a green luminescence.     

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.     

He–Ar and Nd–Sr isotopic compositions of late Pleistocene felsic plutonic back arc basin rocks from Ulleungdo volcanic island, South Korea: Implications for the genesis of young plutonic rocks in a back arc basin

We report analyses of noble gases and Nd–Sr isotopes in mineral separates and whole rocks of late Pleistocene (< 0.2 Ma) monzonites from Ulleungdo, South Korea, a volcanic island within the back arc basin of the Japan island arc. A Rb–Sr mineral isochron age for the monzonites is 0.12 ± 0.01 Ma. K–Ar biotite ages from the same samples gave relatively concordant ages of 0.19 ± 0.01and 0.22 ± 0.01 Ma. ⁴⁰Ar/³⁹Ar yields a similar age of 0.29 ± 0.09 Ma. Geochemical characteristics of the felsic plutonic rocks, which are silica oversaturated alkali felsic rocks (av., 12.5 wt% in K₂O + Na₂O), are similar to those of 30 alkali volcanics from Ulleungdo in terms of concentrations of major, trace and REE elements. The initial Nd–Sr isotopic ratios of the monzonites (⁸⁷Sr/⁸⁶Sr = 0.70454–0.71264, ¹⁴³Nd/¹⁴⁴Nd = 0.512528–0.512577) are comparable with those of the alkali volcanics (⁸⁷Sr/⁸⁶Sr = 0.70466–0.70892, ¹⁴³Nd/¹⁴⁴Nd = 0.512521–0.512615) erupted in Stage 3 of Ulleungdo volcanism (0.24–0.47 Ma). The high initial ⁸⁷Sr/⁸⁶Sr values of the monzonites imply that seawater and crustally contaminated pre-existing trachytes may have been melted or assimilated during differentiation of the alkali basaltic magma.A mantle helium component (³He/⁴He ratio of up to 6.5 RA) associated with excess argon was found in the monzonites. Feldspar and biotite have preferentially lost helium during slow cooling at depth and/or during their transportation to the surface in a hot host magma. The source magma noble gas isotopic features are well preserved in fluid inclusions in hornblende, and indicate that the magma may be directly derived from subcontinental lithospheric mantle metasomatized by an ancient subduction process, or may have formed as a mixture of MORB-like mantle and crustal components. The radiometric ages, geochemical and Nd–Sr isotopic signatures of the Ulleungdo monzonites as well as the presence of mantle-derived helium and argon, suggests that these felsic plutonic rocks evolved from alkali basaltic magma that formed by partial melting of subcontinental lithospheric mantle beneath the back arc basin located along the active continental margin of the southeastern part of the Eurasian plate.     

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.     

Recharge source and hydrogeochemical evolution of shallow groundwater in a complex alluvial fan system,southwest of North China Plain

Many cities around the world are developed at alluvial fans. With economic and industrial development and increase in population, quality and quantity of groundwater are often damaged by over-exploitation in these areas. In order to realistically assess these groundwater resources and their sustainability, it is vital to understand the recharge sources and hydrogeochemical evolution of groundwater in alluvial fans. In March 2006, groundwater and surface water were sampled for major element analysis and stable isotope (oxygen-18 and deuterium) compositions in Xinxiang, which is located at a complex alluvial fan system composed of a mountainous area, Taihang Mt. alluvial fan and Yellow River alluvial fan. In the Taihang mountainous area, the groundwater was recharged by precipitation and was characterized by Ca–HCO₃ type water with depleted δ¹⁸O and δD (mean value of −8.8‰ δ¹⁸O). Along the flow path from the mountainous area to Taihang Mt. alluvial fan, the groundwater became geochemically complex (Ca–Na–Mg–HCO₃–Cl–SO₄ type), and heavier δ¹⁸O and δD were observed (around −8‰ δ¹⁸O). Before the surface water with mean δ¹⁸O of −8.7‰ recharged to groundwater, it underwent isotopic enrichment in Taihang Mt. alluvial fan. Chemical mixture and ion exchange are expected to be responsible for the chemical evolution of groundwater in Yellow River alluvial fan. Transferred water from the Yellow River is the main source of the groundwater in the Yellow River alluvial fan in the south of the study area, and stable isotopic compositions of the groundwater (mean value of −8.8‰ δ¹⁸O) were similar to those of transferred water (−8.9‰), increasing from the southern boundary of the study area to the distal end of the fan. The groundwater underwent chemical evolution from Ca–HCO₃, Na–HCO₃, to Na–SO₄. A conceptual model, integrating stiff diagrams, is used to describe the spatial variation of recharge sources, chemical evolution, and groundwater flow paths in the complex alluvial fan aquifer system.     

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.     

Chemical and boron-isotope variations in tourmalines from an S-type granite and its source rocks: the Erongo granite and tourmalinites in the Damara Belt,Namibia

Tourmaline is widespread in metapelites and pegmatites from the Neoproterozoic Damara Belt, which form the basement and potential source rocks of the Cretaceous Erongo granite. This study traces the B-isotope variations in tourmalines from the basement, from the Erongo granite and from its hydrothermal stage. Tourmalines from the basement are alkali-deficient schorl-dravites, with B-isotope ratios typical for continental crust (δ¹¹B average −8.4‰ ± 1.4, n = 11; one sample at −13‰, n = 2). Virtually all tourmaline in the Erongo granite occurs in distinctive tourmaline-quartz orbicules. This “main-stage” tourmaline is alkali-deficient schorl (20–30% X-site vacancy, Fe/(Fe + Mg) 0.8–1), with uniform B-isotope compositions (δ¹¹B −8.7‰ ± 1.5, n = 49) that are indistinguishable from the basement average, suggesting that boron was derived from anatexis of the local basement rocks with no significant shift in isotopic composition. Secondary, hydrothermal tourmaline in the granite has a bimodal B-isotope distribution with one peak at about −9‰, like the main-stage tourmaline, and a second at −2‰. We propose that the tourmaline-rich orbicules formed late in the crystallization history from an immiscible Na–B–Fe-rich hydrous melt. The massive precipitation of orbicular tourmaline nearly exhausted the melt in boron and the shift of δ¹¹B to −2‰ in secondary tourmaline can be explained by Rayleigh fractionation after about 90% B-depletion in the residual fluid. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.