地球深部水的新形式:分子氢

<正>地球上水的起源以及地幔中水的存储,是长期以来的前沿领域和热门方向。学术界广为流行的学说是:早期地球生长过程中,水来自其他星体中氧化形式的H_2O或OH(+1价的氢);地幔主要由各种硅酸盐矿物组成,以OH等点缺陷形式赋存在矿物结构中的氢(结构水)构成了深部地球最重要的水储库。在长达四十多亿年的漫长地质演化过程中,这些水在地球内外不同层圈中不断发生交换和循环,影响整个地球的动力学过程乃至     

大别山超高压硬玉石英岩中的水:来自红外光谱的证据

为了探讨大别山“名义上无水矿物”(NAMs)中结构水的分布特征, 研究相关的流体活动、矿物变形以及板块俯冲和折返动力学过程提供重要的微观信息.对大别山双河和碧溪岭地区超高压硬玉石英岩中的石英、硬玉、石榴石和金红石进行了傅立叶变换红外光谱(FTIR)分析, 研究结果显示这些矿物都含有以OH-或者H₂O形式存在的氢, 硬玉中结构水平均含量在1000×10-6左右; 石榴石结构水含量在(900~1600)×10-6之间, 各样品颗粒结构水的分布不均匀; 副矿物金红石结构水含量在2000×10-6以上, 而石英结构中基本不含或仅含微量水(< 4×10-6).双河和碧溪岭地区的硬玉石英岩全岩含水量分别为(490~600)×10-6和545×10-6, 不同地区同一种NAMs中结构水含量基本相同.表明在高压-超高压变质岩的形成过程中, 地壳或原岩中的水可以通过这些超高压变质岩中的NAMs携带到地球深部.      

水铁矿的结构、组成及环境地球化学行为

水铁矿广泛分布于水、土壤、沉积物和生物体中,它具有大比表面积和高表面活性,控制和影响着环境中某些污染物质和营养元素的形态、迁移和转化。此外,它也是环境中其他晶质铁(氢)氧化物形成的前驱体。然而,人们对水铁矿在环境中的作用和重要性的认识还存在不足,主要表现在：(1)水铁矿通常被混淆为无定形铁氢氧化物或水合铁氧化物,环境中的水铁矿因难以分离和进行定量分析而使其含量常被低估;(2)水铁矿结晶弱,结构表征困难,对其在环境中的分布、组成、结构及性质的认识较欠缺。水铁矿以弱晶质的纳米颗粒形式存在,其XRD(X射线衍射)线少且宽、强度弱。根据衍射线的条数可将水铁矿分为结晶较弱的2 线水铁矿(2LFh)和结晶较好的6 线水铁矿(6LFh)。目前,普遍接受的水铁矿化学式为Fe5HO8·4H2O,但大量实验表明H2O不是水铁矿结构的必要成分,且容易被吸附的外来物质取代。有人提出水铁矿是一种二元结构,中心为八面体配位Fe,表面以四面体配位Fe为主,这有待论证。最近,通过PDF(配对分布函数)研究水铁矿的结构表明,理想水铁矿结构包含20%四面体配位Fe和80%八面体配位Fe,化学式为Fe10O14(OH)2。然而, 不少学者对这一新的水铁矿结构模型提出了质疑。对近年来水铁矿的分布、组成、结构和环境行为方面的研究和存在的问题进行了综述和讨论,并且对水铁矿的未来研究方向进行了展望。     

天然金刚石结构中氢的赋存状态

利用振动光谱（IR、RAMAM）研究金刚石结构中的含氢物相，发现金刚石结构中存在晶格氢和间隙氢两种。其中HF的存在为首次提出。同时不同的含氢物相在金刚石结构中的赋存状态不尽相同。     

大别山超高压榴辉岩中结构水的赋存状态及其地质意义

对大别山石马和英山超高压榴辉岩中的“名义上无水矿物”(NAM s)石榴石和绿辉石的Fourier变换红外光谱(FT IR)观察表明,它们都含有以OH-或者H2O形式存在的氢,而且发现NAM s从不同地区到同一样品不同颗粒、再到同一颗粒的不同部位的水含量并不均匀。研究结果表明:石马和英山地区绿辉石中结构水的含量范围分别为90×10-6~1 670×1-0 6,110×10-6~710×10-6;石榴石中结构水的含量分别为510×10-6~830×1-0 6,0~180×1-0 6。同时结合地球物理化学等因素对NAM s中结构水在促进榴辉岩变形方面的效应及其与流体包裹体之间的关系进行了初步探讨。     

怎样应用硫同位素组成判断金属矿床硫源

一稳定同位素对确定矿床物质的来源、进而判断矿床成因问题,有其独特的功效.譬如碳同位素组成能说明碳的来源;锶的同位素组成能反映锶的来源;氢-氧的同位素研究能帮助区别成矿溶液中的水是岩浆水、雨水、地下水或大洋水;等等.同样,不同来源的硫,其同位素组成也各有特色,可以借助它判断硫的来源.鉴于硫是许多金属矿床的重要组成元素,有些金属元素的矿石矿物就是含硫化合物,所以硫同位素矿床地质研究在稳定同位素地质领域中占有突出的位置.自然界中我们遇到的硫大体上可以分为:1.陨石、月岩及其它天体物质中的硫.2.来自上地幔、未发生明显的同位素分馏效应的原生硫.     

新疆彩霞山铅锌矿床硫、碳、氢、氧同位素地球化学

文章通过对彩霞山铅锌矿床硫、碳、氢、氧同位素的研究,探讨了矿床成矿流体来源及演化,揭示了成矿作用过程中的某些重要信息.初步认为矿石中的硫主要来自同化了海水硫酸盐的岩浆硫,同时有少量生物还原硫参与;碳、氧同位素组成指示碳来源于壳幔混合.成矿流体以建造水为主,早期有岩浆水参与.     

地震波数据揭示Casadia俯冲带“干”的Juan De Fuca板片

<正>俯冲板片中的水(包括孔隙水和含水矿物中的结构水)对地球圈层之间的水循环、岛弧岩浆作用和地震活动等都有至关重要的影响。但是至今尚未综合研究过一个单一板片中水的含量、储存方式(孔隙水和结构水的相对比例)和分布(在沉积物、俯冲板片上地壳、下地壳和地幔中的分配)。基于有效介质理论,美国伍兹霍尔海洋研究所的Canales博士及其研究小组用地震波层析成像技术得到的纵波速率估算了Casadia俯冲带中Juan De Fuca板片的水含量,首次得到了这     

橄榄石中氢的实际溶解度及其对地幔中水储存的意义

水在地球上地幔的地球动力学过程中起着重要的作用，例如，氢（正如水）能影响部分熔融产生的岩浆的数量和组成，而微量氢（～０．００１ｗｔ％的水）可使上地幔的主要矿物—橄榄石弱化。氢离子的适移可能是造成软流圈异常高的电导率的主要原因，氢在地幔过程中的重要性必然取决于无水橄榄石中所储存的氢或水的数量以及氢在橄榄石晶格中所处的位置。本文报道了橄榄石单晶的水热实验结果，该实验表明，在１５７３Ｋ和５０－３００ＭＰ     

氢、氧同位素在矿床研究中的应用

<正>氢、氧是自然界中最主要的元素之一,分布很广。在水圈中,基本上由氢和氧两个元素组成。在岩石圈中,氧占整个体积的90%左右。目前对各种水以及各类岩石的氢、氧同位素组成进行了大量的研究,积累了丰富的资料,并在实际应用方面取得了显著的成效。     

大陆俯冲带流体活动:超高压变质岩矿物水含量和稳定同位素制约

对超高压变质岩中含水矿物和名义上无水矿物的地球化学研究,极大地深化了我们对大陆碰撞带地壳俯冲和折返过程中流体体制的认识。就流体体制和化学地球动力学来说,有关研究在大别-苏鲁造山带进行的最为详细,因此已经成为研究大陆俯冲带变质的典型地区。本文以大别-苏鲁造山带为对象,从矿物水含量的角度,结合稳定同位素论述了大陆俯冲带流体活动。超高压变质岩中名义上无水矿物含有大量的水,以结构羟基和分子水形式存在。名义上无水矿物中结构羟基和分子水出溶与含水矿物分解共同构成了折返过程中退变质流体的主要来源。名义上无水矿物所释放的水以富集轻的氢氧同位素为特征,而含水矿物分解则提供了富集D的流体来源。折返过程中,名义上无水矿物降压脱水存在亏损D的分子水的优先丢失和不同形式水之间的相互转化。不同岩性的水含量差异导致了它们在折返过程中不同的流体活动行为。大陆板块俯冲和折返过程中,在不同矿物、不同岩性以及板片不同部位之间存在水的再分配;板片的一部分作为富水流体的源,而另一部分可能作为汇。     

Water incorporation in synthetic and natural MgAl2O4 spinel

The solubility and incorporation mechanisms of water in synthetic and natural MgAl₂O₄ spinel have been investigated in a series of high-pressure/temperature annealing experiments. In contrast to most other nominally anhydrous minerals, natural spinel appears to be completely anhydrous. On the other hand, non-stoichiometric Al-rich synthetic (defect) spinel can accommodate several hundred ppm water in the form of structurally-incorporated hydrogen. Infrared (IR) spectra of hydrated defect spinel contain one main O-H stretching band at 3343-3352 cm⁻¹ and a doublet consisting of two distinct O-H bands at 3505-3517 cm⁻¹ and 3557-3566 cm⁻¹. IR spectra and structural refinements based on single-crystal X-ray data are consistent with hydrogen incorporation in defect spinel onto both octahedral and tetrahedral O-O edges. Fine structure of O-H bands in IR spectra can be explained by partial coupling of interstitial hydrogen with cation vacancies, or by the effects of Mg-Al disorder on the tetrahedral site. The concentration of cation vacancies in defect spinel is a major control on hydrogen affinity. The commercial availability of large single crystals of defect spinel coupled with high water solubility and similarities in water incorporation mechanisms between hydrous defect spinel and hydrous ringwoodite (Mg₂SiO₄) suggests that synthetic defect spinel may be a useful low-pressure analogue material for investigating the causes and consequences of water incorporation in the lower part of Earth’s mantle transition zone.     

Hydrogen and oxygen isotope evidence for fluid–rock interactions in the stages of pre- and post-UHP metamorphism in the Dabie Mountains

Hydrogen and oxygen isotope studies were carried out on high and ultrahigh pressure metamorphic rocks in the eastern Dabie Mountains, China. The δ¹⁸O values of eclogites cover a wide range of −4.2 to +8.8‰, but the δD values of micas from the eclogites fall within a narrow range of −87 to −71‰. Both equilibrium and disequilibrium oxygen isotope fractionations were observed between quartz and the other minerals, with reversed fractionations between omphacite and garnet in some eclogite samples. The δ¹⁸O values of −4 to −1‰ for some of the eclogites represent the oxygen isotope compositions of their protoliths which underwent meteoric water–rock interaction before the high to ultrahigh pressure metamorphism. Heterogeneous δ¹⁸O values for the eclogite protoliths implies not only the varying degrees of the water–rock interaction before the metamorphism at different localities, but also the channelized flow of fluids during progressive metamorphism due to rapid plate subduction. Retrograde metamorphism caused oxygen and hydrogen isotope disequilibria between some of the minerals, but the fluid for retrograde reactions was internally buffered in the stable isotope compositions and could be derived from structural hydroxyls dissolved in nominally anhydrous minerals.     

Origin of retrograde fluid in ultrahigh-pressure metamorphic rocks: Constraints from mineral hydrogen isotope and water content changes in eclogite-gneiss transitions in the Sulu orogen

By taking advantage of having depth profiles between contrasting lithologies from core samples of the Chinese Continental Scientific Drilling (CCSD) project, a combined study was carried out to examine changes in mineral H isotope, total water and hydroxyl contents in garnet and omphacite across the contacts between ultrahigh-pressure (UHP) eclogite and gneiss in the Sulu orogen, east-central China. The samples of interest were from two continuous core segments from the CCSD main hole at depths of 734.21-737.16 and 929.67-932.86 m, respectively. The results show δD values of −116‰ to  − 64‰ for garnet and −104‰ to −82‰ for omphacite, consistent with incorporation of meteoric water into protoliths of UHP metamorphic rocks by high-T alteration. Both equilibrium and disequilibrium H isotope fractionations were observed between garnet and omphacite, suggesting fluid-assisted H isotope exchange at local scales during amphibolite-facies retrogression. While bulk water analysis gave total H₂O concentrations of 522-1584 ppm for garnet and 1170-20745 ppm for omphacite, structural hydroxyl analysis yielded H₂O contents of 80-413 ppm for garnet and 228-412 ppm for omphacite. It appears that significant amounts of molecular H₂O are present in the minerals, pointing to enhanced capacity of water storage in the UHP eclogite minerals. Hydrogen isotope variations in the transition between eclogite and gneiss show correlations with variations in their water contents. Petrographically, the degree of retrograde metamorphism generally increases with decreasing distance from the eclogite-gneiss boundary. Thus, retrograde metamorphism results in mineral reactions and H isotope variation. Because hydroxyl solubility in nominally anhydrous minerals decreases with dropping pressure, significant amounts of water are expected to be released from the minerals during decompression exhumation. Decompression exsolution of structural hydroxyl from 1 m³ volume of eclogite composed of only garnet and omphacite results in release of a quantitative estimate of 3.07-3.44 kg water that can form 140-156 kg amphibole during exhumation. Therefore, it is concluded that fluid for retrogression of the eclogites away from the eclogite-gneiss boundary was derived from the decompression exsolution of structural hydroxyl and molecular H₂O in nominally anhydrous minerals. For the eclogites adjacent to gneiss, in contrast, the retrograde metamorphism was principally caused by aqueous fluid from the gneiss which is relatively rich in water. Consequently, both the origin and availability of metamorphic fluid during exhumation of deeply subducted continental crust are deciphered by this combined study focusing on the transitions and the retrograde processes between the felsic and mafic UHP rocks.     

浙江高岭土矿床中氢氧同位素的研究

浙江省是我国高岭土矿的产地之一,矿床主要集中于浙南火山岩地区。浙南地区广泛分布中生代的中酸性火山碎屑岩、熔岩及浅成侵入岩,构造断裂发育,气候温暖湿润,具有风化或热液作用形成高岭土矿床的有利地质条件。     

高压—超高压变质流体的一种重要载体：名义上的无水矿物

本文运用显微傅立叶变换红外光谱技术对３个大别山榴辉岩中的石榴子石和绿辉石进行了观察,发现它们都含有结构水,以ＯＨ＾－的形式赋存。结果表明,这些名义上的无水矿物可能是陆壳俯冲过程中将水携带进地球深部的重要载体;这些矿物中的结构水是孪质流体的组成部分之一;即使在超高压阶段,变质系统也并不是“干”的。     

超高压变质作用过程中的流体——来自苏鲁超高压变质岩岩石学、氧同位素和流体包裹体研究的限定

苏鲁造山带超高压变质岩岩石学、氧同位素、流体包裹体和名义上无水矿物的研究表明，流体-岩石相互作用在大陆地壳的俯冲与折返过程中起到多重的重要作用，并形成了复杂的流体演化过程：（1）大陆表壳岩通过与高纬度大气降水的交换作用被广泛水化，并获得了异常低的氧同位素成分；（2）在水化陆壳物质的俯冲过程中发生了一系列的进变质脱水反应，所释放的流体主要结合进了高压、超高压含水矿物和名义上无水超高压矿物；（3）在超高压变质过程中，以水为主的变质流体通过选择性的吸收使其盐度逐渐升高，并在峰期出现高密度、高盐度的H2O或CO2-H2O流体。有机质的分解反应在局部形成了以CO2、N2、CH4或它们的混合物为主要成分的变质流体；（4）名义上无水超高压矿物的结构水出溶是早期退变质流体的主要来源，并在局部富集形成了高压变质脉体；（5）透入性的中、低盐度水流体活动使超高压变质岩通过一系列的水化反应转变成角闪岩相变质岩；（6）沿韧性剪切带和脆性破碎带的强烈水流体活动为绿片岩相退变质作用和低压石英脉的形成提供了变质流体；（7）可变盐度的H2O或CO2-H2O流体是整个超高压变质岩形成与折返过程中的主要流体，但局部的流体．岩石相互作用形成了非极性的变质流体。     

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。     

Studies of OH in nominally anhydrous minerals

Hydrous components in nominally anhydrous minerals have been the object of increasing study for the past three decades. OH ions and, less commonly, H₂O molecules are found in many anhydrous minerals at concentrations ranging from ppms to tenth's of a percent by weight. Infrared spectroscopy remains the preferred method to characterize these components because of its sensitivity to chemical species, crystallographic orientation and analytical concentration. Improved calibration of the infrared measurements provides a quantitative understanding of the importance of the global hydrogen reservoir contained in the “anhydrous” phases. New and revised values for the amount of H₂O in anhydrous minerals are summarized.