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.     

晚三叠世松潘甘孜和川西前陆盆地的物源对比：构造演化和古地理变迁的线索

为了研究龙门山褶皱冲断带两侧的松潘甘孜和川西前陆盆地在大地构造和沉积学方面存在的联系,笔者等分别在松潘甘孜东缘马尔康—理县地区和川西前陆盆地都江堰地区进行了采样和碎屑锆石的LAICPMS UPb定年工作。269颗锆石的定年结果显示,中—晚三叠世拉丁期—诺利期松潘甘孜复理石盆地东缘沉积地层中的碎屑锆石年龄主要集中在250~280 Ma、1800~1900 Ma和2400~2500 Ma、200~245 Ma、400~450 Ma,对应的物源主要为东昆仑岛弧、华北陆块基底、义敦岛弧以及北秦岭。与之相比,川西前陆盆地诺利期—瑞替期的须家河组地层中的碎屑锆石年龄大致主要集中在1800~1900 Ma和2400~2500 Ma、720~850 Ma、950~1200 Ma、400~450 Ma。该统计结果总体上继承了松潘甘孜数据体的特征,揭示出须家河组物源来自西部——松潘甘孜褶皱带的再旋回沉积和龙门山前陆冲断带。     

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。     

新疆库车新生代前陆褶皱冲断带的变形特征、时代和机制

库车前陆褶皱冲断带自北向南可分为基底冲断带、箱状背斜带、梳状背斜带和挠曲褶皱带,东西方向上可分为西段、中段和东段。本文分段叙述了各变形带的变形特征,指出东段箱状背斜带不发育,秋里塔格山脉(构造带)东延未进入东段,因而总体看自西向东变形强度减弱,地形上趋于夷平。该冲断带的形成经历了两次重大的冲断活动,分别发生在中新世和早(-中)更新世;相应地,该带可分为南、北两个"盆""山"亚系统,两者在地层记录、变形期次和变形机制上尚有若干差异。库车前陆褶皱冲断带的发育,除了受南天山的冲断和向南扩展引起的近南北向挤压应力场控制外,还受到基底断裂在新生代的活化和膏盐层底辟的制约,前者以近北西向的构造变换带及其共轭发育的近北东向断层最为重要,后者既控制了秋里塔格山脉的形成(主要受垂直的挤压应力场作用),也在库车前陆褶皱冲断带东西方向的变形分段中起了重要作用。文章还讨论了变形与地貌发育的关系和在油气勘探中的指导意义。     

东营凹陷北部沙河街组四段深部储层多重成岩环境及演化模式

主要通过薄片鉴定、扫描电镜观察、包裹体分析、粘土矿物分析、镜质体反射率测试和岩心物性分析等手段,结合构造发育史和有机质热演化史等研究成果,以揭示东营凹陷北带古近系深部碎屑岩储层成岩环境及演化模式为目的展开研究工作。结果表明:东营凹陷北带古近系深部碎屑岩储层存在酸性、碱性和酸性碱性交替等多重成岩环境。酸性成岩环境以碳酸盐矿物溶解、长石溶解蚀变为高岭石并伴生石英次生加大等为标志,碱性成岩环境以石英质颗粒及其次生加大边溶解、长石次生加大和晚期碳酸盐矿物沉淀为标志。研究区古近系深部碎屑岩储层成岩环境由浅至深大致经历了碱性—酸性—酸性碱性交替(局部碱性较强)—碱性—弱碱性的演化过程,并建立了沙河街组四段的成岩演化和储层改造模式。     

库车坳陷大北地区下白垩统巴什基奇克组储层成因地质分挝

塔里木盆地库车坳陷大北地区白垩系巴什基奇克组储层以细一中粒岩屑砂岩为主夹少量长石岩屑砂岩,杂基为铁泥质和泥质(2%～10%).胶结物以方解石(3%～15%)为主.粘土矿物以伊利石、绿泥石和伊/蒙混层为主,不含高岭石,伊/蒙混层中的蒙皂石含量一般为(15～20)%;主要孔隙组合为残余原生粒问孔-溶蚀孔-微孔隙,占储集空间总量的(50～90)%,其次为构造缝-溶蚀孔,主要的孔隙类型为溶蚀孔和裂缝,总体属于低孔低渗-特低孔特低渗储层.综合分析认为:阶段性的前陆构造逆冲推覆作用对沉积旋回性、水体盐度变化及物源区距离变化的控制至关重要;构造活跃期扇三角洲前缘环境中形成的差分选中-粗砂岩、近源快速堆积造成的高岩屑含量、干旱成湖导致的高碳酸盐胶结和早成岩期相对深埋-后期持续快速深埋压实作用,是特低孔特低渗储层的主要成因;而较优质储层足构造平缓期辫状河三角洲前缘环境中形成的分选好的中-细砂岩、早期表生溶蚀及弱碳酸盐胶结作用、早期构造破裂的复合作用及其叠加效应的结果.