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 absolute paleotemperature record from 10 to 6 Ka inferred from fluid inclusion D/H ratios of a stalagmite from Vancouver Island, British Columbia, Canada

By using continuous helium flow during the crushing of calcite speleothem samples, we are able to recover liberated inclusion waters without isotopic fractionation. A paleotemperature record for the Jacklah Jill Cave locality, Vancouver Island, BC, was obtained from a 30-cm tall stalagmite that grew 10.3-6.3 Ka ago, using δ¹⁸O values of the crushed calcite and of the inclusion water as inferred from its δD. It is found that the locality experienced mean annual temperature variations up to 11 °C over a 4-Ka period in the early Holocene. At the beginning of the period, local temperature quickly increased from a minimum of ∼1 °C to around 10 °C, but this early climate optimum, about 3 °C warmer than today, only lasted for ∼1200 years. About 8.6 Ka ago, temperature had declined to ∼7 °C, approximately the same as the modern cave temperature. Since then, the study area has experienced only minor temperature fluctuations, but there was a brief fall to ∼4 °C at around 7 Ka ago, which might be caused by a short lived expansion of local alpine glaciers. The long-term T-dependence of δD was 1.47‰/°C, identical to the value in modern precipitation.     

Silicon isotope fractionation in bamboo and its significance to the biogeochemical cycle of silicon

A systematic investigation on silica contents and silicon isotope compositions of bamboos was undertaken. Seven bamboo plants and related soils were collected from seven locations in China. The roots, stem, branch and leaves for each plant were sampled and their silica contents and silicon isotope compositions were determined. The silica contents and silicon isotope compositions of bulk and water-soluble fraction of soils were also measured. The silica contents of studied bamboo organs vary from 0.30% to 9.95%. Within bamboo plant the silica contents show an increasing trend from stem, through branch, to leaves. In bamboo roots the silica is exclusively in the endodermis cells, but in stem, branch and leaves, the silica is accumulated mainly in epidermal cells. The silicon isotope compositions of bamboos exhibit significant variation, from −2.3‰ to 1.8‰, and large and systematic silicon isotope fractionation was observed within each bamboo. The δ³⁰Si values decrease from roots to stem, but then increase from stem, through branch, to leaves. The ranges of δ³⁰Si values within each bamboo vary from 1.0‰ to 3.3‰. Considering the total range of silicon isotope composition in terrestrial samples is only 7‰, the observed silicon isotope variation in single bamboo is significant and remarkable. This kind of silicon isotope variation might be caused by isotope fractionation in a Rayleigh process when SiO₂ precipitated in stem, branches and leaves gradually from plant fluid. In this process the Si isotope fractionation factor between dissolved Si and precipitated Si in bamboo (α_pre-sol) is estimated to be 0.9981. However, other factors should be considered to explain the decrease of δ³⁰Si value from roots to stem, including larger ratio of dissolved H₄SiO₄ to precipitated SiO₂ in roots than in stem. There is a positive correlation between the δ³⁰Si values of water-soluble fractions in soils and those of bulk bamboos, indicating that the dissolved silicon in pore water and phytoliths in soil is the direct sources of silicon taken up by bamboo roots. A biochemical silicon isotope fractionation exists in process of silicon uptake by bamboo roots. Its silicon isotope fractionation factor (α_bam-wa) is estimated to be 0.9988. Considering the distribution patterns of SiO₂ contents and δ³⁰Si values among different bamboo organs, evapotranspiration may be the driving force for an upward flow of a silicon-bearing fluid and silica precipitation. Passive silicon uptake and transportation may be important for bamboo, although the role of active uptake of silicic acid by roots may not be neglected. The samples with relatively high δ³⁰Si values all grew in soils showing high content of organic materials. In contrast, the samples with relatively low δ³⁰Si values all grew in soil showing low content of organic materials. The silicon isotope composition of bamboo may reflect the local soil type and growth conditions. Our study suggests that bamboos may play an important role in global silicon cycle.     

Experimental investigation on thermochemical sulfate reduction by H2S initiation

Hydrogen sulfide (H₂S) is known to catalyze thermochemical sulfate reduction (TSR) by hydrocarbons (HC), but the reaction mechanism remains unclear. To understand the mechanism of this catalytic reaction, a series of isothermal gold-tube hydrous pyrolysis experiments were conducted at 330 °C for 24 h under a constant confining pressure of 24.1 MPa. The reactants used were saturated HC (sulfur-free) and CaSO₄ in the presence of variable H₂S partial pressures at three different pH conditions. The experimental results showed that the in-situ pH of the aqueous solution (herein, in-situ pH refers to the calculated pH of aqueous solution under the experimental conditions) can significantly affect the rate of the TSR reaction. A substantial increase in the TSR reaction rate was recorded with a decrease in the in-situ pH value of the aqueous solution involved. A positive correlation between the rate of TSR and the initial partial pressure of H₂S occurred under acidic conditions (at pH ∼3-3.5). However, sulfate reduction at pH ∼5.0 was undetectable even at high initial H₂S concentrations. To investigate whether the reaction of H₂S_(aq) and occurs at pH ∼3, an additional series of isothermal hydrous pyrolysis experiments was conducted with CaSO₄ and variable H₂S partial pressures in the absence of HC at the same experimental temperature and pressure conditions. CaSO₄ reduction was not measurable in the absence of paraffin even with high H₂S pressure and acidic conditions. These experimental observations indicate that the formation of organosulfur intermediates from H₂S reacting with hydrocarbons may play a significant role in sulfate reduction under our experimental conditions rather than the formation of elemental sulfur from H₂S reacting with sulfate as has been suggested previously (Toland W. G. (1960) Oxidation of organic compounds with aqueous sulphate. J. Am. Chem. Soc.82, 1911-1916).Quantification of labile organosulfur compounds (LSC), such as thiols and sulfides, was performed on the products of the reaction of H₂S and HC from a series of gold-tube non-isothermal hydrous pyrolysis experiments conducted at about pH 3 from 300 to 370 °C and a 0.1-°C/h heating rate. Incorporation of sulfur into HC resulted in an appreciable amount of thiol and sulfide formation. The rate of LSC formation positively correlated with the initial H₂S pressure. Thus, we propose that the LSC produced from H₂S reaction with HC are most likely the reactive intermediates for H₂S initiation of sulfate reduction. We further propose a three-step reaction scheme of sulfate reduction by HC under reservoir conditions, and discuss the geological implications of our experimental findings with regard to the effect of formation water and oil chemistry, in particular LSC content.     

The age of the Nantuo Formation and Nantuo glaciation in South China

A U–Pb sensitive high‐resolution ion microprobe (SHRIMP) age of 654.5 ± 3.8 Ma from an ash bed immediately below the Nantuo Formation in South China provides the lowest age constraint for the Nantuo glaciation, which has been correlated with the global ‘Marinoan’ glaciation. A U–Pb SHRIMP age of 636.3 ± 4.9 Ma from a fallout tuff within the basal layer of the Nantuo Formation, along with the existing age of 635.2 ± 0.6 Ma from its overlying Doushantuo cap carbonate, suggests that the traditionally defined Nantuo Formation may have been deposited in a short time period at the end of the Nantuo glaciation. In combination with available ages globally, the data support a relatively short duration and rapid termination of ‘Marinoan’ glaciations.     

墨西哥湾GC238区冷泉碳酸盐岩的微结构与石化微生物特征

采于墨西哥湾GC238海底天然气渗漏区浅表层的冷泉碳酸盐岩呈结核状产出,由方解石微晶和胶结物及少量的黄铁矿构成。胶结物由直径为0.1～0.5 m的方解石化的球体、卵形体、棒状体组成,充填于方解石晶体之间。冷泉碳酸盐岩结核下表面发育有由方解石化的球体、卵形体、棒状体组成的薄层,其中的一些球状集合体（约5 m）断面显示发育有核和外壳的层圈结构。黄铁矿呈草莓状,也具有相似的层圈结构。这种层状结构与活体古细菌被硫酸盐还原细菌包裹的层圈结构相似。样品中所保存的球体、卵形体、棒状体及其所组成的层圈结构可能是石化的甲烷氧化古细菌和硫酸盐还原细菌。     

青藏高原西部赛利普中新世火山岩源区:地球化学及Sr-Nd同位素制约

青藏高原拉萨地块西部赛利普地区新生代火山岩依据主量元素可划分为超钾质、钾质和钙碱性系列,主要的岩石类型为粗面安山岩、粗面岩,一个超钾质岩石的40Ar-39Ar年龄为17.58Ma,指示出火山活动为中新世.超钾质、钾质和钙碱性火山岩都显示出富集LREE及LILE(Th、U)、亏损HFSE(Nb、Ta、Ti)的特征.超钾质火山岩具有较高的K2O(6.31%～8.55%)、MgO(6.75%～8.96%)、Cr(270.7×10-6～460.4×10-6)、Ni(142.3×10-6～233.9×10-6)含量,较高的(87Sr/86Sr)i(0.71883～0.72732)和较低的εNd(-14.78～-15.37),指示可能起源于一个前期亏损并经后期俯冲作用改造的富钾的方辉橄榄岩富集地幔源区.钾质火山岩具有比超钾质火山岩低的K2O、MgO、Cr、Ni含量以及高的Ba、Sr含量,初始87Sr/86Sr为0.71553～0.71628,初始143Nd/144Nd为0.51197～0.51198,在空间上与超钾质火山岩共生,可能是前者母岩浆的演化产物.钙碱性火山岩具有较高的Sr(881.7×10-6～1309.2×10-6)、Sr/Y比值(50～108)和较低的Y(12.05×10-6～18.02×10-6),明显亏损重稀土Yb(0.93×10-6～1.30×10-6),类似于典型的埃达克质岩成分特征但相对高钾,并具有相对低的(87Sr/86Sr);(0.70928～0.71374)以及高的εNd(-7.90～-10.91),指示起源于富钾增厚下地壳物质的部分熔融.区域上拉萨地块超钾质岩、钾质岩与N-S向地堑系在空间上共存、时间上相吻合,由此本文认为拉萨地块中新世钾质.超钾质岩和南北向地堑系的形成可能与中新世早期北向俯冲的印度大陆岩石圈断离有关.     

青藏高原东南木里地区二叠纪苦橄岩的Os-Sr-Nd同位素地球化学研究

本文报道了在青藏高原东南木里地区发现的二叠纪苦橄岩和与其共生玄武岩的主微量元素地球化学特征以及Os-Sr-Nd同位素组成。苦橄岩和与其共生玄武岩受地壳混染作用影响较小。根据苦橄岩的Ti/Y比值和初始的Os同位素组成,将木里苦橄岩分为两类:高Ti/Y型苦橄岩和低Ti/Y型苦橄岩,其中高Ti/Y型苦橄岩具有高的γ_(Os)= 5.3～ 10.7和ε_(Nd)= 5.9～ 6.4,与全球典型洋岛玄武岩的Os和Nd同位素组成接近,代表了地幔柱源区的同位素特征;而低Ti/Y型苦橄岩具有低的γ_(Os)=-4.1～ 1.2和ε_(Nd)= 3.2～ 5.0,可能表明受到了SCLM(大陆岩石圈地幔)源区物质的混染。与其共生的玄武岩具有低的γ_(Os)=-3.5～-1.6和ε_(Nd)=-0.6～ 0.7,表明其来自于不同于低Ti/Y型苦橄岩也有异于高Ti/Y型苦橄岩的地幔源区,但是也可能受到了SCLM物质的混染。基于Nd-Os同位素的地幔柱与SCLM的二端元混合模型显示:低Ti/Y型苦橄岩可能是SCLM物质组分与地幔柱起源的苦橄质原始岩浆混合形成的;与苦橄岩共生的玄武岩可能是由地幔柱来源的玄武质岩浆与SCLM小比例熔融的熔体混合形成的。     

冈底斯新近纪钾质火山作用:消减沉积物折返的地球化学与Sr-Nd-Pb同位素证据

在冈底斯岩浆岩带的羊八井地区,林子宗火山岩系上部出现小规模的粗面质火山岩.岩石学与地球化学研究表明粗面岩与时空密切相关的大体积安山质-英安质-流纹质火山岩属于不同的火山岩系:碱性钾质系列与钙碱性系列.详细的地球化学研究证明林子宗晚期小体积钾质岩具有独立的岩浆源区,而非早期钙碱性系统低压岩浆过程演化的产物.粗面质熔岩SiO2含量为62.91%～64.63%,具有高K2O(7.52%～8.05%)、Al2O3(16.64%-17.35%)、低TiO2(0.59%～0.68%)与MsO(0.15%～0.77%).钾质熔岩富集LILE与LREE,亏损HFSE,具有高Rb/Sr(1.1～2.3)、Th/La(0.59～0.80)、Th/U(6.3～10.9)和低Ce/Pb(4.1～6.2)与Ba/Th(4.3～14.5)比值,其同位素组成变化范围分别是87Sr/86Sr(I)=0.7068～0.7075、143Nd/144Nd(I)=0.51241～0.51252、206Pb/204Pb=18.87～18.95、207Pb/204Pb=15.63～15.70和208Pb/204Pb=39.24～39.68.粗面岩的地球化学与同位素特征表明冈底斯新近纪钾质火山岩来源于角闪岩相的消减沉积物熔融.因此,羊八井新近纪钾质火山熔岩提供了印度-亚洲大陆碰撞早期消减沉积物折返的证据.     

延边东部五道沟岩群的单颗粒锆石SHRIMP U-Pb 年代学及其地质意义

通过对延边地区东部五道沟岩群黑云阳起石片岩的单颗粒锆石SHRIMP U-Pb年龄测定.获得21个单点年龄,其中包括7组谐和年龄和1组不谐和年龄.谐和年龄分别为1347.8 Ma、844.8 Ma、340.2～313.7 Ma(平均值为323±23 Ma,N=4,MSWD=0.23,置信度=0.88)、292.9～288.3 Ma(平均值=291±25 Ma,N=3,MSWD=0.031.置信度=0.86)、279.2～266.2 Ma(平均值为279±28 Ma,N=4,MSWD=0.031,置信度=0.86)、127.4～124.2 Ma(206Pb/208U年龄平均值为126.5±3.7 Ma,N=5,MSWD=0.12;置信度=O.97)、116.1～106.3 Ma(平均值为115±39 Ma,N=2,MSWD=1.2置信度=0.27),不谐和年龄的下交点年龄为(451±120)Ma、上交点年龄为(1811±400)Ma(MSWD=7.2);这一结果表明:阳起石片岩的原岩主要是来自中元古代、新元古代和早古生代的碎屑物,指示五道沟群的沉积成岩作用发生在石炭世(323±23 Ma),变质作用发生在晚二叠世(291±25 Ma),之后在279.2～266.2 Ma、126.5～106.3 Ma先后受两次岩浆用和蚀变作用的改造.