顽火辉石中Li同位素扩散与分馏

顽火辉石作为斜方辉石晶系的重要Mg端元矿物,是地球上地幔主要组成矿物之一。Li同位素作为重要的地幔地球化学示踪剂,在主要地幔矿物中(如橄榄石,辉石等)的扩散分馏相关性质的研究显得尤为重要。我们通过经典力学的方法,计算模拟了原子尺度下Li同位素在顽火辉石晶格以2种不同的迁移机制(填隙机制和取代空位机制)迁移的活化能和其在不同晶格位上不同温度条件下的分馏作用程度。计算结果表明,Li同位素易以填隙位机制在顽火辉石中迁移。重同位素~7Li会更多的进入晶格填隙位中,而6Li相对更多进入Mg位。温度是影响这种分馏作用的1个关键因素,相应的结果可用来解释地幔Li同位素组成特征及冷却条件下的同位素分馏等科学问题。     

简述贵州施秉下翁哨含铬镁铝榴石和镁铬尖晶石重砂异常之谜

贵州施秉下翁哨地区含铬镁铝榴石和镁铬尖晶石自然重砂,高度浓集于下翁哨盆地北岸对门坡一带新近系翁哨组含砾黏土岩和盆地南侧2 km处斜坡带"不明成因"砂砾石堆积物中,构成罕见高含量重砂异常,文中通过钾镁煌斑岩、金伯利岩和一般基性-超基性岩及榴辉岩等石榴子石含量特征的对比分析,尚难解释异常来源问题,甚至利用章人骏(1985)关于沅水流域金刚石及其伴生矿物分布的"古冰碛物次生源"观点,亦难解其来源和矿物组合问题,故此权称为谜,特撰文简述抛砖引玉以期共勉,尤籍此为贵州金刚石原生矿的找矿突破寻找指导。     

辽宁金伯利岩中镁铝榴石与金刚石的关系

辽宁金伯利岩中镁铝榴石的含量与金刚石的含量成正比。富含矿的岩体中镁铝榴石颜色有紫色、红色和橙色等种类,其中以紫色的为主,金刚石的含量越多紫色类型所占比例就越大。 镁铝榴石中Cr_2O_3和CaO的含量随其颜色的加深而升高;Al_2O_3、MgO、TiO_2的含量变化则相反。富矿岩体中富铬(>5％)镁铝榴石的含量高于中等含矿和贫含矿的岩体。 文中还列出了山东和贵州金刚石矿中镁铝榴石的资料以资对比。     

贵州施秉下翁哨地区镁铝榴石和铬尖晶石自然重砂罕见特高异常查证

综合利用以往资料发现,贵州施秉下翁哨地区存在特高浓度镁铝榴石、铬尖晶石等自然重砂异常,且长期未能解释其来源及金刚石找矿指示问题。由于资料形成于"文革"时期,有人怀疑其可靠性,通过针对性的野外调查和采样分析,佐证了该异常的客观存在和以往资料的可靠性。镁铝榴石和铬尖晶石自然重砂含量水平实属罕见,异常区分布于高出现代河床200m的斜坡上部,残积于古河道砂砾石冲积层(?)中,矿物学分析未见重砂矿物明显的搬运磨蚀痕迹,电子探针分析分属于G9镁铝榴石和S5铬尖晶石,应主要来源于石榴和尖晶二辉橄榄岩,系载体母岩——钾镁煌斑岩就近风化残积的结果。     

贵州施秉下翁哨地区镁铝榴石及铬尖晶石重砂异常地球化学指示源岩

以往资料显示,贵州施秉下翁哨地区镁铝榴石和铬尖晶石自然重砂,高度浓集于下翁哨盆地北岸对门坡一带新近系翁哨组含砾粘土岩和盆地南侧2km处斜坡带"不明成因"砂砾石堆积物中,构成罕见的高含量重砂异常,在贵州众多金刚石找矿信息中尤为瞩目,其来源及其金刚石找矿指示意义长期成谜。通过对盆地南侧2km处斜坡带"不明成因"砂砾石堆积物采样分析查证,原样中镁铝榴石为2.7粒/L,铬尖晶石大于5.0粒/L,异常客观存在;电子探针研究表明,镁铝榴石和铬尖晶石分属G9镁铝榴石和S5贫钛高铝富镁铬铁矿,其来源与金伯利岩关系不大。     

斜方顽火辉石-正铁辉石固溶体中Fe2+,Mg2+有序-无序扩散机制的研究

从对固溶体中离子的扩散机制研究中发现：保温温度为773K－1023K时，斜方顽火辉石－正铁辉石固溶液中Fe^2 ，Mg^2 发生有序－无序扩散；扩散机制有两种类型：等价于spinadal分解机制或等价于“成核－生长”机制；并对扩散条件进行了探讨。     

锂同位素在伟晶岩矿床成因研究中的应用

稀有金属矿产对现代工业和科技的发展极其重要,伟晶岩矿床作为稀有金属的主要来源,其成因与成矿作用有待深入研究,普遍争论的成因模式包括:花岗岩结晶分异、地壳部分熔融以及岩浆液态不混溶。研究表明地壳深熔过程中锂同位素不发生有意义的分馏,因此在解决花岗岩和伟晶岩的岩浆源区性质方面提供了强有力的证据。文章主要从花岗伟晶岩的成因、锂同位素分馏机制以及锂同位素在伟晶岩矿床中的应用三个方面系统综述了国内外近年来取得的一些研究进展。国内外学者以锂同位素分馏机制详细论述了花岗伟晶岩的Li同位素组成,认为伟晶岩矿床的成因主要为花岗岩结晶分异或地壳部分熔融。但是锂同位素应用于伟晶岩矿床成因方面的研究还不够成熟,需要开展更多的工作。     

XAFS characterization of the structural site of Yb in synthetic pyrope and grossular garnets

The incorporation and site preference of minor amounts (about 1 wt%) of Yb³⁺ in synthetic pyrope (Mg₃Al₂Si₃O₁₂) and grossular (Ca₃Al₂Si₃O₁₂) garnet were studied by X-ray Absorption Fine-Structure (XAFS) Spectroscopy. The measurements, performed in the temperature range 77–343 K at both Yb L_I- and L_III-edges, demonstrate that Yb³⁺ enters the garnet structure and is located in the dodecahedral site in both samples. The coordination environment of Yb³⁺ in the two samples was compared to that of the X-site cation in end-member synthetic pyrope and grossular and in Yb₃Al₅O₁₂ as determined by single-crystal X-ray diffraction. The local geometry around Yb³⁺ is different from that of Mg and Ca in the bulk of the garnet, and also from that of Yb³⁺ in Yb₃Al₅O₁₂. Τhe XAFS results indicate that, (1) structural relaxation occurs around Yb³⁺ in the garnet structure; (2) the host garnet matrix exerts a major structural control on the incorporation of Yb³⁺, and (3) minor amounts of Yb³⁺ in garnet are located in structural sites and not in ill-defined defects. Received: 15 January 1998/ Revised, accepted: 21 July 1998     

硼同位素分馏的实验理论认识和矿床地球化学研究进展

硼是一种中等挥发性元素,具有¹¹B和¹⁰B两个稳定同位素。两个同位素间高达10%的相对质量差使其在地质过程中引起高达-70‰至+75‰的硼同位素变化。硼在自然界主要与氧键合形成三配位(BO₃)和四配位(BO₄)结构,因而¹¹B和¹⁰B间同位素分馏主要受控于三配体(BO₃)和四面体(BO₄)间配分。本文综述了低温和高温地质过程的硼同位素分馏的理论和实验研究进展。在溶液中B(OH)₃和${B(OH)^{-}_{4}}$间硼同位素分馏受pH和热力学p-T条件控制,实验和理论表征获得常温常压条件下的B(OH)₃和$B(OH)^{-}_{4}$间同位素分馏系数(α_3-4)变化范围为1.019 4至1.033 3。低温条件下矿物(如碳酸盐、黏土矿物(蒙脱石和伊利石)、针铁矿、水锰矿、硼酸盐)与溶液间硼同位素分馏行为除了受p-T-pH影响外,矿物表面吸附引起的分馏效应十分显著。在中高温过程(蒙脱石伊利石化、富硼电气石和白云母矿物与热液流体,以及硅酸盐熔体与流体)中硼同位素分馏行为受到硼配位构型、化学成分以及物理化学条件的控制。随着硼同位素分馏机理研究的深入以及越来越完善的地质储库硼同位素端员特征表征,硼同位素地球化学指标可以灵敏示踪成矿物质来源、探究成矿作用与成因模式和重建成矿过程物理化学条件。目前矿床硼同位素地球化学研究的难点在于实现不同赋存相(如流体、矿物和熔体)中硼配位键合结构和硼同位素组成的精细化表征。     

蒸发皿中水面蒸发氢氧同位素分馏的实验研究

气象要素与蒸发密切相关,通过室内外不同气象条件下的器皿水蒸发实验,获得了水面蒸发氢氧稳定同位素分馏因子与气象要素的关系。实验结果表明,随着蒸发的进行,剩余水体中逐渐富集重同位素;自由水体蒸发同位素分馏在垂线上有分层现象,表层水体同位素值比垂线平均的同位素值略富集;不同温度条件下的室内蒸发实验中,温度越高,液-气间分馏系数越小,相应于同一剩余水体体积比,剩余水体稳定同位素值则越低。室外器皿水自由蒸发实验中得出的蒸发线方程斜率较大地偏离了当地降水线,表明实验期间水体蒸发分馏作用较明显。该研究为进一步揭示水体蒸发分馏规律提供了可靠的实验依据。     

Oxygen isotopic fractionation during inorganic calcite precipitation ― Effects of temperature, precipitation rate and pH

Stable oxygen isotopic fractionation during inorganic calcite precipitation was experimentally studied by spontaneous precipitation at various pH (8.3 < pH < 10.5), precipitation rates (1.8 < log R < 4.4 μmol m^− 2 h^− 1) and temperatures (5, 25, and 40 °C) using the CO₂ diffusion technique.The results show that the apparent stable oxygen isotopic fractionation factor between calcite and water (α_{calcite–water}) is affected by temperature, the pH of the solution, and the precipitation rate of calcite. Isotopic equilibrium is not maintained during spontaneous precipitation from the solution. Under isotopic non-equilibrium conditions, at a constant temperature and precipitation rate, apparent 1000lnα_{calcite–water} decreases with increasing pH of the solution. If the temperature and pH are held constant, apparent 1000lnα_{calcite–water} values decrease with elevated precipitation rates of calcite. At pH = 8.3, oxygen isotopic fractionation between inorganically precipitated calcite and water as a function of the precipitation rate (R) can be described by the expressions

at 5, 25, and 40 °C, respectively.The impact of precipitation rate on 1000lnα_{calcite–water} value in our experiments clearly indicates a kinetic effect on oxygen isotopic fractionation during calcite precipitation from aqueous solution, even if calcite precipitated slowly from aqueous solution at the given temperature range. Our results support Coplen's work [Coplen T. B. (2007) Calibration of the calcite–water oxygen isotope geothermometer at Devils Hole, Nevada, a natural laboratory. Geochim. Cosmochim. Acta 71, 3948–3957], which indicates that the equilibrium oxygen isotopic fractionation factor might be greater than the commonly accepted value.     

安徽铜陵狮子山矿田铜、金共生与分离的热力学研究

狮子山矿田是安徽铜陵矿集区内最具代表性的大型铜金多金属矿田.矿田内铜、金矿床或矿体既各自独立产出,义相互共生或伴生,铜矿化和金矿化在时间上和空间上存在既共生又分离的现象.本文选择矿田内代表性铜矿床和金矿床开展系统的流体包裹体地球化学研究,并进行成矿流体中铜、金溶解度的热力学理论计算和1分析,探索铜、金共生与分离的机制和...     

蒸发过程中水体稳定同位素富集与空气湿度的关系

通过同位素分馏模型的物理意义分析及实验模拟分析,探讨空气湿度对蒸发过程水体稳定同位素富集过程的影响机理,研究认为：①空气相对湿度决定了扩散系数和自由空气同位素组成对分馏系数的影响比例,空气相对湿度越小,分馏系数受扩散分馏系数影响越大,分馏系数受自由空气水汽同位素组成影响则越小,反之亦然;②空气相对湿度与蒸发残余水体氢氧稳定同位素富集程度具有负相关性,即空气湿度越大越不利于残余水体重同位素富集;③模拟残余水体同位素丰度对空气相对湿度的敏感性呈负指数关系。在无外界气态水介入的蒸发实验中,残余系数为0.194条件下,当相对湿度小于80%时,H、O稳定同位素模拟结果对湿度的敏感性均小于0.0002,即相对湿度变化对模拟残余水体同位素丰度影响很小;当湿度大于80%时,湿度变化对模拟结果的影响呈指数关系急剧增加,湿度大于80%的蒸发实验需要准确观测相对湿度值。     

An Experimental Study of Oxygen Isotope Fractionation in the Quartz—Wolframite—Water System

Oxygen isotope fractionation was experimentally studied in the quartz-wolframite-water system from 200 to 420 °C. The starting wolframite was synthesized in aqueous solutions of Na₂WO₄ · 2H₂O + FeCl₂ · 4H₂O or MnCl₂ · 4H₂O. The starting solutions range in salinity from 0 to 10 equivalent wt.% NaCl. Experiments were conducted in a gold-lined stainless steel autoclave, with filling degrees of about 50%. The results showed no significant difference in equilibrium isotope fractionation between water and wolframite, ferberite and huebnerite at the same temperature (310 °C ). The equilibrium oxygen isotope fractionation factors of wolframite and water tend to be equal with increasing temperature above 370 °C, but to increase significantly with decreasing temperature below 370 °C: 1000 ln α_wf-H₂o= 1.03×10⁶T−2-4.91 (370 °C ±200 °C ) 1000 ln α_wf-H₂o = 0.21×10⁶T −2-2.91 (420 °C -370 °C ±) This projects was financially supported by the National Natural Science Foundation of China.     

Stable chlorine isotopes in arid non-marine basins: Instances and possible fractionation mechanisms

Stable chlorine isotopes are useful geochemical tracers in processes involving the formation and evolution of evaporitic halite. Halite and dissolved chloride in groundwater that has interacted with halite in arid non-marine basins has a δ³⁷Cl range of 0 ± 3‰, far greater than the range for marine evaporites. Basins characterized by high positive (+1 to +3‰), near-0‰, and negative (−0.3 to −2.6‰) are documented. Halite in weathered crusts of sedimentary rocks has δ³⁷Cl values as high as +5.6‰. Salt-excluding halophyte plants excrete salt with a δ³⁷Cl range of −2.1 to −0.8‰. Differentiated rock chloride sources exist, e.g. in granitoid micas, but cannot provide sufficient chloride to account for the observed data. Single-pass application of known fractionating mechanisms, equilibrium salt-crystal interaction and disequilibrium diffusive transport, cannot account for the large ranges of δ³⁷Cl. Cumulative fractionation as a result of multiple wetting-drying cycles in vadose playas that produce halite crusts can produce observed positive δ³⁷Cl values in hundreds to thousands of cycles. Diffusive isotope fractionation as a result of multiple wetting-drying cycles operating at a spatial scale of 1–10 cm can produce high δ³⁷Cl values in residual halite. Chloride in rainwater is subject to complex fractionation, but develops negative δ³⁷Cl values in certain situations; such may explain halite deposits with bulk negative δ³⁷Cl values. Future field studies will benefit from a better understanding of hydrology and rainwater chemistry, and systematic collection of data for both Cl and Br.