锆石Ce 氧逸度计和早期地球的氧化还原状态

氧逸度可以用于定量描述一个体系的氧化还原状态,是地球科学非常重要的一个热力学指标。早期地球的氧逸度及其变化趋势的重建,对大气圈、水圈、生物圈乃至整个地球的起源和演化具有重要的科学意义,也是地球科学长期探索的重要目标。锆石提供了地球上已发现的最古老天然样品,几乎是目前研究早期(冥古宙)地球的唯一可靠对象。近年来的研究发现,锆石中Ce的含量对其母岩浆体系的氧逸度很敏感,并由此发展出了锆石的Ce氧逸度计。这一技术对认识早期地球的氧化还原状态十分关键。文章对锆石Ce氧逸度计进行了简单介绍,进而对早期地壳和地幔的氧化还原状态进行了综合评述。在此基础上,对早期地球几个重要圈层(大气圈、大陆地壳和上地幔)氧逸度的演化及相互间的耦合关系进行了讨论。     

深部地球中水的分布和循环

深部地球中的主要物相(橄榄石、辉石、石榴石等及其高压相变产物)是理想化学式中不含H的“名义上无水矿物”,以缺陷形式存在于它们结构中的OH/H2O(统称为结构水)的发现是近二十年来地球科学领域最重要的进展之一。从天然样品的观察和高温高压实验结果来看,深部地球矿物中普遍含有结构水,其总量可能远远超过了水圈。水在深部地球不同层圈中的分布可能具有时间上和空间上的不均一性。在板块俯冲过程中,即使温压条件超过了含水矿物的稳定范围,名义上的无水矿物(如石榴石、辉石等)也可以携带大量的水(质量分数至少数百10-6)进入深部地球,构成了壳幔之间水循环的重要途径。     

高温高压和控制氧逸度条件下透辉石电导率的各向异性实验研究

在1.0～4.0GPa 和1073～1373K 及控制氧分压条件下,借助于 YJ-3000t 紧装式六面顶固体高压设备和1260阻抗/增益-相位分析仪,就位测定了沿着不同晶轴方向的透辉石的电导率。氧逸度控制是由 Ni+NiO 固体缓冲剂完成的。实验结果表明:(1)在选择的频率范围,无论从复阻抗的模与频率还是从相角与频率关系上,部可以看出复阻抗对频率具有很强的依赖性;(2)随着温度升高,阻抗降低,电导率增大,Logo 与1/T 之间符合 Arrenhius 线性关系式;(3)随着压力升高,[001]方向的透辉石电导率降低,活化焓和指前因子亦随之减小,并首次获得了透辉石中主要载流子的活化能和活化体积分别为1.80±0.04eV 和0.035±0.015cm~3/mol;(4)在2.0GPa 下按照[001]、[100]、[010]的顺序,样品的电导率和指前因子降低,活化焓依次升高,高压下的透辉石电学性质存在各向异性;(5)小极化子导电机制可为透辉石在高温高压下的导电行为提供合理的解释。     

地球深部物质的某些物性测量方法研究

文中介绍了地球深部物质实验室近 2 0年来开展高温高压下地球深部物质物性实验研究过程中 ,在测量方法方面的进步和应用情况。这些测量方法包括了高温、高压下弹性的超声测量方法、高温高压下电性的测量方法、高压差热分析法和高压下热学Gr櫣ｎｅｉｓｅｎ参数的测量方法诟呶赂哐瓜卵沂涂笪锏牡猿饬恐?,我们由超声脉冲透射方法改进为超声脉冲透射反射法 ,克服了样品室中压力和温度梯度对样品的影响。在高温高压下岩石和矿物的电学性质测量中 ,我们由直流法发展为阻抗谱法 ,不仅克服了样品极化对测量结果的影响 ,还可以获得离子在溶液中的多种物理化学参数 ,以及监测含水矿物在高温高压下的脱水动力学特征。在固体传压介质中建立的高压热学Gr櫣ｎｅｉｓｅｎ参数的测量方法 ,由于升压速率比较小且叶蜡石在高压下的热导系数增大 ,其测量结果需要进行校正 ,其测量方法有待进一步改进。     

地球深部与表层的相互作用

板块理论和全球变化是20世纪地球科学中的2大突破性进展.进入21世纪,地球系统科学进入将这两方面结合起来,探索地球深部和表层系统的相互作用,即"固体地球动力学与行星循环(planetary cycle)"的新阶段.根据最近国际综合大洋钻探计划关于2013年后学术新方向的讨论,从俯冲带加工厂、大洋中脊与巨型火成岩省3个方面进行介绍,提出我国打破传统的学科界限、迎接新方向的建议.     

俯冲带的碳循环及其对地球深部动力学过程的启示

俯冲带的碳循环不仅在维持地球表层和地球深部之间的碳平衡方面起着关键的作用,而且还和许多重要的地球深部动力学过程密切相关。热动力学数值模拟和高温高压实验的研究结果表明,俯冲大洋板片中的大多数碳酸盐能够在弧前和弧下深度幸存下来,从而进入更深的地幔中。在地幔过渡带,因为板片滞留所带来的热松弛效应将使幸存下来的碳酸盐以熔体的形式释放出去,其独特的物理化学性质使这些熔体构成了一种有效的交代组分。考虑到地幔过渡带的氧逸度特别低,那些进入未经交代地幔中的碳酸盐熔体将变得不稳定而被还原成其他形式。不过在随后地幔对流上升的过程中,这些被还原的表壳碳又会因为氧逸度在某些临界深度发生突变而氧化熔融,这也许可以解释地幔不同深度所存在的某些高导低速体和地震波各向异性等现象。作为洋壳俯冲的后续过程,陆壳的深俯冲作用也可以将表壳碳带至地幔深处,例如超高压大理岩和碳酸盐化榴辉岩的广泛产出就是最好的证明。超高压变质岩中金刚石的产出表明其构成了表壳碳在地幔深处的一种重要赋存形式,研究显示其形成过程和富碳熔体、流体的活动密切相关。虽然前人针对俯冲带的碳循环已经取得了若干研究进展,然而仍有大量的科学问题亟待解决。最后就一些关键性的问题进行了列举说明,并对未来的研究方向进行了展望。     

广西大厂锡多金属矿田深部碳酸盐岩的碳、氧同位素特征及其对于深部找矿的意义

以广西大厂超大型锡多金属矿田深部钻探ZK39-1钻孔获得的新鲜岩心为研究对象,详细分析了钻遇中下泥盆统灰岩样品的碳、氧同位素组成及矿化元素含量。结果表明,各类样品的δ18OV-SMOW为12.07‰~24.31‰,钻孔深度1000 m以下岩心样品的δ18OV-SMOW明显偏低;δ13CV-PDB为-4.6‰~1.7‰,1000 m以下样品的δ13CV-PDB逐步降低。岩心碳、氧同位素组成负异常的部位同时也出现了矿化元素显著的正异常,由此推测1000 m深度以下存在热液流体活动。研究表明,钻孔岩心碳酸盐岩样品的碳、氧同位素组成的变化规律可以提供蚀变作用及相关流体的重要信息,可作为一种重要的找矿标志,从而为深部找矿勘查提供科学依据。     

滇西北休瓦促钨钼矿区复式岩体地质及其成矿特征——来自年代学、氧逸度和地球化学的约束

休瓦促钨钼矿床位于义敦岛弧南段的香格里拉北部,目前已达中-大型。该区发育由两期岩体(晚三叠世的黑云母花岗岩和晚白垩世的斑状二长花岗岩)叠加而成的复式岩体,而该矿区钨钼矿形成于82~86Ma。然而,两期岩体间关系,以及晚三叠世岩体对矿床的形成有怎样的贡献,目前未有报道。笔者通过对两期岩体形成时间及其地球化学特征的研究,从成岩年代学、岩浆氧逸度等方面探究上述问题,并揭示两期岩体的成矿特征,为找矿实践提供一定的参考依据。研究表明,黑云母花岗岩结晶年龄为211.7±2.6Ma,SiO_2偏高(69.48%~73.73%),属高钾的钾玄质系列,偏铝质,富集轻稀土元素和大离子亲石元素而亏损重稀土元素以及高场强元素Nb、Sr、Ti等,有微弱的负Eu异常,岩浆氧逸度相对较高(fO_2=-19.4~-9.1,平均-13.7);斑状二长花岗岩结晶年龄为76.8±3.8Ma,且有一颗锆石核部的年龄值为219±2.6Ma,该岩体与前者有相似的地球化学特征,SiO_2高(67.35%~75.65%),属偏铝质的钾玄质系列,ΣREE较高,高于黑云母花岗岩,铕负异常明显大于前者,岩浆氧逸度相对较低(fO_2=-30.4~-18.2,平均-23.4)。据此,结合休瓦促矿区断层发育情况,提出矿区内两期岩体以近南北向F_4为界呈断层接触关系,北西向走滑断层(F_1-F_3)为控矿构造。本文认为,晚期斑状二长花岗岩对早期黑云母花岗岩具有一定的继承性关系,黑云母花岗岩来源于晚三叠世甘孜-理塘洋向西俯冲环境下地壳的部分熔融,岩浆富水、氧逸度高,利于形成Cu-Au矿床,且在找矿实践中得到部分验证;斑状二长花岗岩来源于加厚下地壳的部分熔融,岩浆贫水、氧逸度低于黑云母花岗岩,与W-Mo矿床相关。即,晚白垩世岩浆热液沿矿区断裂-裂隙系统运移,继承和发展早期岩浆活动,形成脉状细晶岩和W-Mo矿床。     

不同温度、压强、氧逸度条件下斜方辉石含水性的实验研究

斜方辉石的含水性显著影响着上地幔的物理化学性质。前人对于斜方辉石的水溶解度的制约因素研究并不充分,特别是氧逸度的影响很少被单独考虑。为了厘清斜方辉石的水溶解度的制约因素,我们借助高温高压设备(MAVO LPC250型活塞圆筒压机)在1.0～3.0 GPa, 800～1100℃和两种典型的氧逸度条件控制下开展了系统性地实验研究,即Ni+Ni O (NNO),Fe+FeO (IW)。通过傅里叶变换红外光谱测量(FTIR),斜方辉石的天然和实验样品显示出7组典型的OH-吸收峰。含水量结果表明,在上地幔浅部条件下,斜方辉石的水溶解度均随温度或压强升高而增大,而随氧逸度值升高而减小,仅氧逸度变化其它条件不变时,还原条件比相对氧化条件高达50%,这与橄榄石等其它名义上无水矿物的氧逸度效应存在不一致。通过估算,橄榄石和斜方辉石间水的分配系数在不同氧逸度条件下可以相差55%。因此,与名义上无水矿物中结构水相关的实验研究,未有效控制氧逸度的结果需要被重新考虑。     

不同温度、压强、氧逸度条件下斜方辉石含水性的实验研究

斜方辉石的含水性显著影响着上地幔的物理化学性质。前人对于斜方辉石的水溶解度的制约因素研究并不充分,特别是氧逸度的影响很少被单独考虑。为了厘清斜方辉石的水溶解度的制约因素,我们借助高温高压设备(MAVO LPC250型活塞圆筒压机)在1.0～3.0 GPa, 800～1100℃和两种典型的氧逸度条件控制下开展了系统性地实验研究,即Ni+Ni O (NNO),Fe+FeO (IW)。通过傅里叶变换红外光谱测量(FTIR),斜方辉石的天然和实验样品显示出7组典型的OH-吸收峰。含水量结果表明,在上地幔浅部条件下,斜方辉石的水溶解度均随温度或压强升高而增大,而随氧逸度值升高而减小,仅氧逸度变化其它条件不变时,还原条件比相对氧化条件高达50%,这与橄榄石等其它名义上无水矿物的氧逸度效应存在不一致。通过估算,橄榄石和斜方辉石间水的分配系数在不同氧逸度条件下可以相差55%。因此,与名义上无水矿物中结构水相关的实验研究,未有效控制氧逸度的结果需要被重新考虑。     

Properties of iron alloys under the Earth's core conditions

The Earth's core is constituted of iron and nickel alloyed with lighter elements. In view of their affinity with the metallic phase, their relative high abundance in the solar system and their moderate volatility, a list of potential light elements have been established, including sulfur, silicon and oxygen. We will review the effects of these elements on different aspects of Fe–X high pressure phase diagrams under Earth's core conditions, such as melting temperature depression, solid–liquid partitioning during crystallization, and crystalline structure of the solid phases. Once extrapolated to the inner–outer core boundary, these petrological properties can be used to constrain the Earth's core properties.     

Hydration of mantle olivine under variable water and oxygen fugacity conditions

The incorporation of H into olivine is influenced by a significant number of thermodynamic variables (pressure, temperature, oxygen fugacity, etc.). Given the strong influence that H has on the solidus temperature and rheological behavior of mantle peridotite, it is necessary to determine its solubility in olivine over the range of conditions found in the upper mantle. This study presents results from hydration experiments carried out to determine the effects of pressure, temperature, and the fugacities of H₂O and O₂ on H solubility in San Carlos olivine at upper mantle conditions. Experiments were carried out at 1–2 GPa and 1,200 °C using a piston-cylinder device. The fugacity of O₂ was controlled at the Fe⁰–FeO, FeO–Fe₃O₄, or Ni⁰–NiO buffer. Variable duration experiments indicate that equilibration is achieved within 6 h. Hydrogen contents of the experimental products were measured by secondary ion mass spectrometry, and relative changes to the point defect populations were investigated using Fourier transform infrared spectroscopy. Results from our experiments demonstrate that H solubility in San Carlos olivine is sensitive to pressure, the activity of SiO₂, and the fugacities of H₂O and O₂. Of these variables, the fugacity of H₂O has the strongest influence. The solubility of H in olivine increases with increasing SiO₂ activity, indicating incorporation into vacancies on octahedral lattice sites. The forsterite content of the olivine has no discernible effect on H solubility between 88.17 and 91.41, and there is no correlation between the concentrations of Ti and H. Further, in all but one of our experimentally hydrated olivines, the concentration of Ti is too low for H to be incorporated dominantly as a Ti-clinohumite-like defect. Our experimentally hydrated olivines are characterized by strong infrared absorption peaks at wavenumbers of 3,330, 3,356, 3,525, and 3,572 cm^?1. The heights of peaks at 3,330 and 3,356 cm^?1 correlate positively with O₂ fugacity, while those at 3,525 and 3,572 cm^?1 correlate with H₂O fugacity.     

上天、入地、下海:极端条件下矿物学研究

上天、入地、下海,进行极端条件下的矿物学研究,研究微矿物,发现新矿物。主要利用金刚石压机,结合使用国内外同步辐射X-光源、中子源,以及其他多种物理的、化学的、光学的测试手段(如岩石矿物化学分析,光薄片测定,电子探针,离子探针,扫描电镜,透射电镜,红外、紫外、拉曼光谱,激光加热等),对来自天外的陨石、陨石坑样品、地球深处地幔源矿物以及海底甲烷水合物进行了一些研究。模拟不同温度和压力下各种不同成分的矿物材料的晶体结构、物理和化学性质。文章着重研究从地球内核到地壳海底的各种不同组分在不同温度、压力极端环境下形成的各种各样的典型矿物:从金属固体内核和金属液体外核中的ε-Fe到核幔边界(CMB)地球D″层的后钙钛矿(Post-Perovskite)结构(ppv)镁铁硅酸盐(Mg,Fe)SiO₃,从下地幔中的铁磁性钙钛矿(Perovskite)结构(pv)镁铁硅酸盐布里奇曼石(Bridgmanite)(Mg,Fe)SiO₃、镁铁氧化物(Fe,Mg)O和后尖晶石(Post-Spinel)结构的含Fe³⁺毛河光矿(Maohokite)(HP-Mg$Fe^{3+}_{2}O_{4}$)到过渡带、上地幔和地壳中的镁铁硅酸盐、硅氧化物、铬铁氧化物和金刚石及其内含物以及甲烷水合物(CH₄·H₂O)等。进行高温高压极端条件下的矿物学研究,为探索地球结构性质、形成动力和发展历史提供了新的窗口。     

地球内部极端条件下流体和物质相互作用:透过金刚石窗口探测地球深部流体

报道关于地球内部极端条件下的流体实验研究的最新进展。使用金刚石压砧结合各种谱学方法及同步辐射光源技术,在高温超高压条件下原位直接测量物质的结构和性质,已经获得分子-原子尺度信息新的实验数据。本项工作使用金刚石压砧对高压(10GPa)和高温高压(800℃,3GPa)条件下的NaCl-H2O进行红外谱原位直测,研究了高压和高温高压下水分子结构,发现水分子的O—H振动特征峰频率随温度向高波数变化,而且,在临界态区域时水分子间的氢键网格被破坏。实验说明:地球内部流体性质由深到浅不断变化,如水的密度、介电常数等物理参数随温度压力而改变,在临界态出现突变。这些变化可以用高压高温的物质的各种谱学特征来表征。水的性质与它的分子结构、分子振动有关。在跨越临界区时水的性质异常涨落是由水分子结构异常变化、分子振动形式变化和氢键网格破坏所导致的。从分子尺度认识地球内部流体在极端条件下的性质和高压原位实验观测有助于我们进一步了解地球深部物质的性质及其相互作用,有助于认识深部过程。     

A method for studying iron silicate liquids under reducing conditions with negligible iron loss

In studies of iron silicate liquids under reducing conditions at 1 atm pressure, iron losses from the melt can be minimized by suspending the liquid as a drop from a short segment of fine Pt wire. For a basaltic composition at 1275°C and oxygen fugacities appropriate to terrestrial magmas, iron losses from the melt are less than 0.5 wt.% of the amount present for run times less than about 20 hr.     

Structural stability of coprecipitated natural organic matter and ferric iron under reducing conditions

The objective was to assess the interaction of Fe coprecipitated with dissolved organic matter (DOM) and its effect on Fe (hydr)oxide crystallinity and DOM retention under abiotic reducing conditions. A Fe-based coagulant was reacted with DOM from an agricultural drain and the resulting precipitate (floc) was exposed to S(-II) and Fe(II). Solution concentrations of Fe(II/III) and DOM were monitored, floc crystallinity was determined using X-ray diffraction, and the composition and distribution of functional groups were assessed using scanning transmission X-ray microscopy (STXM) and near edge X-ray absorption fine structure (NEXAFS) spectroscopy. Results indicate coprecipitation of Fe(III) with DOM forms a non-crystalline floc that withstands crystallization regardless of change in pH, Fe:DOM ratio and type of reductant added. There was no evidence that exposure to reducing conditions led to release of DOM from the floc, indicating that coprecipitation with complex natural DOM in aquatic environments may stabilize Fe (hydr)oxides against crystallization upon reaction with reduced species and lead to long term sequestration of the DOM. STXM analysis identified spatially distinct regions with remarkable functional group purity, contrary to the model of DOM as a relatively uniform complex polymer lacking identifiable organic compounds. Polysaccharide-like OM was strongly and directly correlated with the presence of Fe but showed different Fe binding strength depending on the presence of carboxylic acid functional groups, whereas amide and aromatic functional groups were inversely correlated with Fe content.     

不良地质环境中基坑边坡加固技术分析及其应用

结合现有边坡加固理论和加固经验,对一紧临道路和8层老楼房且下部有厚度达14 m淤泥软弱土层的基坑边坡进行了复合加固设计。通过对边坡稳定性计算、分析,加固后的边坡满足最小安全系数的要求。按照本设计进行施工后,基坑边坡的变形和周围建筑物的沉降均在安全允许的范围之内,保证了地下室结构部分的顺利施工。所提供的加固技术对同类深基坑支护工程具有重要的参考价值。     

The mechanism of cation and oxygen isotope exchange in alkali feldspars under hydrothermal conditions

The mechanism of re-equilibration of albite in a hydrothermal fluid has been investigated experimentally using natural albite crystals in an aqueous KCl solution enriched in ¹⁸O at 600°C and 2 kbars pressure. The reaction is pseudomorphic and produces a rim of K-feldspar with a sharp interface on a nanoscale which moves into the parent albite with increasing reaction time. Transmission electron microscopy (TEM) diffraction contrast and X-ray powder diffraction (XRD) show that the K-feldspar has a very high defect concentration and a disordered Al, Si distribution, compared to the parent albite. Raman spectroscopy shows a frequency shift of the Si-O-Si bending vibration from ~476 cm⁻¹ in K-feldspar formed in normal ¹⁶O aqueous solution to ~457 cm⁻¹ in the K-feldspar formed in ¹⁸O-enriched solution, reflecting a mass-related frequency shift due to a high enrichment of ¹⁸O in the K-feldspar silicate framework. Raman mapping of the spatial distribution of the frequency shift, and hence ¹⁸O content, compared with major element distribution maps, show a 1:1 correspondence between the reaction rim formed by the replacement of albite by K-feldspar, and the oxygen isotope re-equilibration. The textural and chemical characteristics as well as the kinetics of the replacement of albite by K-feldspar are consistent with an interface-coupled dissolution-reprecipitation mechanism.     

Experimentally-controlled carbon and oxygen isotope exchange between bioapatites and water under inorganic and microbially-mediated conditions

Modern bone and enamel powders have reacted at 301 K with ¹³C- and ¹⁸O-labelled waters under inorganic and microbial conditions. The aim of the study is to investigate the resistance of stable isotope compositions of bioapatite carbonate (δ¹³C, δ¹⁸Oc) and phosphate (δ¹⁸Op) to isotopic alteration during early diagenesis. Rapid and significant carbon and oxygen isotope changes were observed in the carbonate and phosphate fractions of bone apatite before any detectable change occurred in the crystallinity or organic matter content. These observations indicate that chemical alterations of bone apatite are likely to start within days of death. Enamel crystallites are much more resistant than bone crystallites, but are not exempt of alteration. Non removable carbon and oxygen isotope enrichments were measured in the carbonate phase of bone (50-90%) and enamel (40%) after the acetic acid treatment. This result indicates that a significant part of ¹³C and ¹⁸O-labelled coming from the aqueous fluid has been durably incorporated into the apatite structure, probably through isotopic exchange or secondary carbonate apatite precipitation. As a result, acetic acid pre-treatments that are currently used to remove exogenous material by selective dissolution, are not adequate to restore pristine δ¹³C and δ¹⁸Oc values of fossil apatites. Under inorganic conditions, kinetics of oxygen isotope exchange are 10 times faster in carbonate than in phosphate. On the opposite, during biologically-mediated reactions, the kinetics of oxygen isotope exchange between phosphate and water is, at least, from 2 to 15 times faster than between carbonate and water. Enamel is a more suitable material than bone for paleoenvironmental or paleoclimatical reconstructions, but interpretations of δ¹⁸Op or δ¹³C values must be restricted to specimens for which no or very limited trace of microbial activity can be detected.     

Competition between enzymatic and abiotic reduction of uranium(VI) under iron reducing conditions

Reduction of U(VI) under iron reducing conditions was studied in a model system containing the dissimilatory metal-reducing bacterium Shewanella putrefaciens and colloidal hematite. We focused on the competition between direct enzymatic uranium reduction and abiotic reduction of U(VI) by Fe(II), catalyzed by the hematite surface, at relatively low U(VI) concentrations (< 0.5 μM) compared to the concentrations of ferric iron (> 10 mM). Under these conditions surface catalyzed reduction by Fe(II), which was produced by dissimilatory iron reduction, was the dominant pathway for uranium reduction. Reduction kinetics of U(VI) were identical to those in abiotic controls to which soluble Fe(II) was added. Strong adsorption of U(VI) at the hematite surface apparently favored the abiotic pathway by reducing the availability of U(VI) to the bacteria. In control experiments, lacking either hematite or bacteria, the addition of 45 mM dissolved bicarbonate markedly slowed down U(VI) reduction. The inhibition of enzymatic U(VI) reduction and abiotic, surface catalyzed U(VI) reduction by the bicarbonate amendments is consistent with the formation of aqueous uranyl-carbonate complexes. Surprisingly, however, more U(VI) was reduced when dissolved bicarbonate was added to experimental systems containing both bacteria and hematite. The enhanced U(VI) reduction was attributed to the formation of magnetite, which was observed in experiments. Biogenic magnetite produced as a result of dissimilatory iron reduction may be an important agent of uranium immobilization in natural environments.