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.     

Evolution of subcontinental lithospheric mantle beneath eastern China: Re–Os isotopic evidence from mantle xenoliths in Paleozoic kimberlites and Mesozoic basalts

The ages of subcontinental lithospheric mantle beneath the North China and South China cratons are less well-constrained than the overlying crust. We report Re–Os isotope systematics of mantle xenoliths entrained in Paleozoic kimberlites and Mesozoic basalts from eastern China. Peridotite xenoliths from the Fuxian and Mengyin Paleozoic diamondiferous kimberlites in the North China Craton give Archean Re depletion ages of 2.6–3.2 Ga and melt depletion ages of 2.9–3.4 Ga. No obvious differences in Re and Os abundances, Os isotopic ratios and model ages are observed between spinel-facies and garnet-facies peridotites from both kimberlite localities. The Re–Os isotopic data, together with the PGE concentrations, demonstrate that beneath the Archean continental crust of the eastern North China Craton, Archean lithospheric mantle of spinel- to diamond-facies existed without apparent compositional stratification during the Paleozoic. The Mesozoic and Cenozoic basalt-borne peridotite and pyroxenite xenoliths, on the other hand, show geochemical features indicating metasomatic enrichment, along with a large range of the Re–Os isotopic model ages from Proterozoic to Phanerozoic. These features indicate that lithospheric transformation or refertilization through melt-peridotite interaction could be the primary mechanism for compositional changes during the Phanerozoic, rather than delamination or thermal-mechanical erosion, despite the potential of these latter processes to play an important role for the loss of garnet-facies mantle. A fresh garnet lherzolite xenolith from the Yangtze Block has a Re depletion age of ∼1.04 Ga, much younger than overlying Archean crustal rocks but the same Re depletion ages as spinel lherzolite xenoliths from adjacent Mesozoic basalts, indicating Neoproterozoic resetting of the Re–Os system in the South China Craton.     

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.     

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.     

Simple models for dynamic melting in an upwelling heterogeneous mantle column: Analytical solutions

Several lines of evidence suggest that the melt generation and segregation regions of the mantle are heterogeneous, consisting of chemically and lithologically distinct domains of variable size and dimension. Partial melting of such heterogeneous mantle source regions gives rise to a diverse range of basaltic magmas. In order to better assess the role of source heterogeneity during mantle melting, we have undertaken a theoretical study of trace element distribution and fractionation during concurrent melting and melt migration in an upwelling, chemically heterogeneous, two-porosity double lithology melting column. Analytical solutions for the abundance of a trace element in the matrix and channel were obtained under the assumptions that the porosity, melt and solid velocities, and solid-melt partition coefficients are constant and uniform. For simplicity, we neglected diffusion and dispersion in the melt. Chemical source heterogeneities of arbitrary size and shape were integrated into the simple melting models by allowing trace element abundance in the source region to vary as a function of time and space. Concurrent melting and melt migration in an upwelling heterogeneous mantle may be approximated as a quasi-steady state problem in which time-dependent concentration patterns produced by melting of heterogeneous source regions are superimposed on a reference steady-state concentration distribution established by melting of the ambient or background mantle. Chromatographic fractionation is especially important for the matrix melt and solid when chemical heterogeneities are involved during melting and melt migration in the mantle, giving rise to significant phase-shift between two incompatible trace elements in the matrix melt and scattered correlations among incompatible trace elements in residual peridotites. Mixing is the chief mass transfer process in the dunite channel where the chromatographic effect is negligible for most of the incompatible trace elements. The lack of chromatographic fractionation among incompatible trace elements and isotopic ratios in MORB suggests either most MORB are channel melts or mixing in magma conduit and chamber is very efficient such that the phase-shift is averaged out during magma transport and storage processes. Advection brings melt produced by smaller-degree of melting in the deeper part of the melting column to the overlying melting region, increasing the incompatible trace element abundance in the matrix and the channel. This advection-induced self-enrichment is especially important when heterogeneous sources are involved and may account for some of the enriched incompatible trace element patterns observed in residual peridotite that were previously interpreted to be a result of mantle metasomatism. Systematic studies of high-resolution spatially correlated mantle samples may help to constrain the melting history and the size and nature of chemical heterogeneities in the mantle.     

Considerations for conducting incubations to study the mechanisms of As release in reducing groundwater aquifers

Microbial Fe reduction is widely believed to be the primary mechanism of As release from aquifer sands in Bangladesh, but alternative explanations have been proposed. Long-term incubation studies using natural aquifer material are one way to address such divergent views. This study addresses two issues related to this approach: (1) the need for suitable abiotic controls and (2) the spatial variability of the composition of aquifer sands. Four sterilization techniques were examined using orange-colored Pleistocene sediment from Bangladesh and artificial groundwater over 8 months. Acetate (10 mM) was added to sacrificial vials before sterilization using either (1) 25 kGy of gamma irradiation, (2) three 1-h autoclave cycles, (3) a single addition of an antibiotic mixture at 1× or (4) 10× the typical dose, and (5) a 10 mM addition of azide. The effectiveness of sterilization was evaluated using two indicators of microbial Fe reduction, changes in diffuse spectral reflectance and leachable Fe(II)/Fe ratios, as well as changes in P-extractable As concentrations in the solid phase. A low dose of antibiotics was ineffective after 70 days, whereas autoclaving significantly altered groundwater composition. Gamma irradiation, a high dose of antibiotics, and azide were effective for the duration of the experiment.     

西藏马攸木金矿床金银互化物的赋存状态

马攸木金矿床是西藏近年发现的首例规模较大、矿石品位富、金成色高的岩金矿床.作者通过对马攸木金矿床矿石组构、矿石共生组合及矿物特征研究发现,金银互化物主要有自然金、含银自然金、银金矿、自然银.载金矿物为黝铜矿、针铁矿、脆硫锑铅矿及石英;金银互化物的赋存形式主要为包裹体金、裂隙金及粒间金.金银互化物的形成、富集与热液成矿作用及表生风化作用关系密切.     

库车坳陷东部山前带古近系不同体系域内扇三角洲沉积砂体的对比研究

通过对塔里木盆地库车坳陷南天山山前带克孜勒努尔沟与依奇克里克野外露头沉积相的精细研究,结合山前带大量地震剖面分析与迪那201井、东秋5井等多口钻井测井相和岩心精细描述,将古近系库姆格列木群划分为2个层序。层序2低位域以冲积扇沉积为主,自湖侵体系域始,研究区广泛发育退积与进积型扇三角洲沉积。库姆格列木群层序2湖侵体系域内扇三角洲平原砂体以正韵律沉积为主,砂砾岩占地层厚度的(68.4～87)%;扇三角洲前缘砂体正、反韵律均有分布,砂砾岩占地层的百分比有所降低,为(55.2～77)%。高位体系域内主要发育以反韵律砂体为主的扇三角洲前缘沉积。古近系苏维依组只发育一个层序,其低位体系域的砂体为扇三角洲平原与前缘的分流河道砂体,湖侵体系域内扇三角洲前缘砂体正、反韵律均发育,高位体系域内主要发育扇三角洲前缘沉积,以反韵律砂体为主,正韵律砂体相对较少。对比苏维依组不同体系域内砂体储集性,湖侵域内砂体优于高位域内砂体。扇三角洲沉积体中有利储集砂体首选为湖侵体系域内的扇三角洲前缘水下分流河道和河口坝砂体,次之为低位域扇三角洲前缘(平原)分流河道砂体,最后是高位域内的河口坝及席状砂沉积砂体。特别要指出:低位体系域或者湖侵体系域底部发育的扇三角洲前缘(平原)分流河道砂体(底砂砾岩)被快速湖侵的较厚的暗色泥岩所覆盖,可形成较好储集场所。