蛇纹石化和俯冲带蛇纹岩变质脱水过程中流体活动性元素的行为

蛇纹石是大洋岩石圈和俯冲带内水和流体活动性元素最重要的载体之一。研究蛇纹石化和蛇纹岩变质脱水过程中流体活动性元素的行为是认识俯冲带元素地球化学循环的关键。蛇纹岩是指主要由蛇纹石类矿物构成的岩石,包括利蛇纹石、纤蛇纹石和叶蛇纹石。蛇纹石化过程中会造成流体活动性元素(B、Li、As、Sb、Pb、Cs、U、Sr和Ba等)的显著富集,并且由于原岩性质、流体成分和氧逸度等条件的不同,大洋岩石圈蛇纹岩和弧前蛇纹岩的特征也略有不同。例如,弧前蛇纹岩具有相对高的As、Sb、B和相对低的U,这反映了俯冲沉积物来源流体的贡献。在俯冲带蛇纹岩的变质脱水过程中,利蛇纹石向叶蛇纹石的转变伴随着矿物内超过50%F和Cl的释放,以及一些流体活动性元素(如B和Li)的迁出;此外,蛇纹石分解形成的变质橄榄石中的流体包裹体指示,蛇纹石脱水分解所产生的流体具有高于原始地幔几个数量级的Cl、Cs、Pb、As、Sb、Ba、Rb、B、Sr、Li和U含量。由于利蛇纹石中的Fe~(3+)含量较叶蛇纹石高,这种矿物相转变过程中也伴随着俯冲通道内的一系列氧化还原过程,从而影响流体性质和新形成的叶蛇纹石的成分。蛇纹岩与岛弧岩浆在流体活动性元素富集规律上的相似性说明蛇纹岩在俯冲带元素循环中扮演着重要的角色。此外,蛇纹石矿物相转变过程中F、Cl、B等元素的释放,可能对于斑岩型金矿、蛇绿岩中的金矿和某些蛇纹岩作为赋矿围岩的硼矿的形成起到重要的作用。     

俯冲带蛇纹岩变质脱水过程中的Mg、Fe同位素分馏行为:进展与展望

蛇纹岩在俯冲带地球化学循环中发挥着重要作用.蛇纹岩是俯冲带中极富Mg和Fe的矿物,其变质脱水释放的流体含有显著量的Mg和Fe,对俯冲带中Mg、Fe元素的循环及其同位素的分馏行为起着重要作用.蛇纹岩脱水过程中的Mg、Fe同位素分馏特征与不同温度、压力条件下蛇纹岩体系的矿物组合、释放流体的氧化还原状态、流体中Mg、Fe的价态和种型等密切相关.本文在总结俯冲带蛇纹岩的产出特征、稳定性和主要脱水反应的基础上,系统评述了俯冲带蛇纹岩在变质脱水过程中Mg、Fe同位素分馏行为的研究现状和存在的关键科学问题,并对未来的研究方向进行了展望.     

内蒙古贺根山蛇纹岩化流体来源的H-O-B同位素地球化学制约

对内蒙古贺根山蛇绿岩带内3个采样点的蛇纹岩样品开展了主量、微量元素和H-O-B同位素分析,以揭示其构造属性、蛇纹石化温度和流体来源。贺根山蛇纹岩具有低Al_2O_3含量(0.2%~1.3%)、高Mg~#(89~92)特征,为难熔地幔残余。蛇纹岩的U型稀土元素配分模式、相对富集LILE和亏损HFSE的微量元素地球化学特点,反映其原岩为化学成分高度亏损的俯冲带型(SSZ)超基性岩。样品的dD值相对均一(dD=-120‰~-133‰);理论计算显示,这些蛇纹岩的H同位素组成可能是蛇绿岩剥露地表后与区域大气降水发生再平衡作用的结果。贺根山蛇纹岩的d~(18)O变化在4.3‰~9.8‰之间,反映不同地点蛇纹石化的温度存在差别:其中贺根山东样品具有相对较高的d~(18)O值(d~(18)O=7.7‰~9.8‰),蛇纹石化温度为90~130℃,同时部分样品中出现碳酸盐矿物,表明蛇纹石化作用发生在近海底环境;小坝梁样品具有最低的d~(18)O值(d~(18)O=4.3‰~5.0‰),其蛇纹石化温度在205~235℃之间;贺根山南样品的d~(18)O值变化范围较大(d~(18)O=6.0‰~9.7‰),其蛇纹石化温度在90~170℃之间。3个采样点蛇纹岩的d~(11)B值也显示出一定的变化(d~(11)B=9.1‰~14.7‰),指示蛇纹石化流体来源于脱水的蚀变洋壳和海底沉积物;理论模拟和计算结果显示,这些板片流体的d~(11)B值变化在15‰~25‰之间。     

苏鲁造山带中胡家林超镁铁质岩岩石地球化学特征

苏鲁造山带中胡家林超镁铁质岩地块主要由两部分组成:南部滑石山以蛇纹岩和蛇纹石化橄榄岩为主,夹薄层状石榴橄辉岩-(石榴)单斜辉石岩;北部胡家林主要由(石榴)单斜辉石岩组成,夹厚层状蛇纹岩。蛇纹岩-蛇纹石化橄榄岩低Al2O3、低Ca O和高Mg O,REE含量低,但LREE稍富集。石榴橄辉岩和(石榴)单斜辉石岩低Mg O和Ca O,高REE含量高,其稀土配分曲线均表现出单斜辉石单矿物的配分特征。这些超镁铁岩块中不同岩石的微量元素均具有Pb的正异常,弱的Nb、Ta的负异常,显示地壳流体交代信息。Nd、Sr、Pb同位素特征显示存在亏损地幔与地壳之间的混合作用。亲石元素含量最低的蛇纹石化石榴橄辉岩的Sr、Nd、Pb同位素组成受交代流体控制明显,而石榴橄辉岩和(石榴)单斜辉石岩不明显。胡家林和滑石山超镁铁岩中所含的交代地壳成分不同,胡家林样品受到含水熔体和富水流体的双重交代,滑石山样品主要受富水流体的交代。     

西藏谷露—亚东裂谷南部温泉稀土元素特征及其控制因素

西藏构造运动强烈,南部地区发育了多条近南北向拉张性裂谷,其中谷露—亚东裂谷活动性最为强烈。该裂谷从南到北分布了多个温泉群,康布、康马、查当、孟则等温泉集中在南部。本文通过对谷露—亚东裂谷南部温泉的稀土元素（rare earth element,简称REE）地球化学特征的研究,探讨控制温泉稀土元素特征的主要因素。南部温泉pH值在6.14~9.01之间,属于弱酸性—碱性温泉。稀土元素总质量浓度\[ρ（ΣREE）\]变化范围在1.41~46.18 ng/L之间,与全球其它弱酸性—碱性温泉相比,处于低值水平。大部分样品表现出LREE（light rare earth element,轻稀土）和HREE（heavy rare earth element,重稀土）相对亏损,MREE（middle rare earth element,中稀土）富集和Ce负异常的配分模式。pH值影响Fe/Mn（氢）氧化物胶体的存在方式。温泉的稀土元素主要以REECO+3和REE(CO3)-2形式存在,并影响温泉稀土元素的分异。亚东地区大部分温泉的稀土配分模式受富铁沉积物的影响,MREE优先释放到水溶液中。康马温泉的稀土元素分布特征受到水岩反应的影响,包括富铁沉积物的溶解和当地基性岩浆岩的反应。Ce负异常是由于氧化环境下,Ce3+形成CeO2沉淀导致的。研究表明pH值、Fe/Mn（氢）氧化物胶体、络合反应以及水岩反应是控制谷露—亚东裂谷南部温泉水REE分布的主要因素。     

西藏谷露—亚东裂谷南部温泉稀土元素特征及其控制因素

西藏构造运动强烈,南部地区发育了多条近南北向拉张性裂谷,其中谷露—亚东裂谷活动性最为强烈。该裂谷从南到北分布了多个温泉群,康布、康马、查当、孟则等温泉集中在南部。本文通过对谷露—亚东裂谷南部温泉的稀土元素（rare earth element,简称REE）地球化学特征的研究,探讨控制温泉稀土元素特征的主要因素。南部温泉pH值在6.14~9.01之间,属于弱酸性—碱性温泉。稀土元素总质量浓度\[ρ（ΣREE）\]变化范围在1.41~46.18 ng/L之间,与全球其它弱酸性—碱性温泉相比,处于低值水平。大部分样品表现出LREE（light rare earth element,轻稀土）和HREE（heavy rare earth element,重稀土）相对亏损,MREE（middle rare earth element,中稀土）富集和Ce负异常的配分模式。pH值影响Fe/Mn（氢）氧化物胶体的存在方式。温泉的稀土元素主要以REECO+3和REE(CO3)-2形式存在,并影响温泉稀土元素的分异。亚东地区大部分温泉的稀土配分模式受富铁沉积物的影响,MREE优先释放到水溶液中。康马温泉的稀土元素分布特征受到水岩反应的影响,包括富铁沉积物的溶解和当地基性岩浆岩的反应。Ce负异常是由于氧化环境下,Ce3+形成CeO2沉淀导致的。研究表明pH值、Fe/Mn（氢）氧化物胶体、络合反应以及水岩反应是控制谷露—亚东裂谷南部温泉水REE分布的主要因素。     

板块俯冲过程中的Mg-Li-Fe-Cr同位素分馏

金属稳定同位素体系是示踪板块俯冲对壳幔物质再循环影响的全新工具,因此其在俯冲带的地球化学行为备受关注.Mg同位素在俯冲过程中不发生显著分馏,但大陆玄武岩具有低于洋中脊玄武岩的Mg同位素,这可能是碳酸岩的俯冲再循环导致的.与角闪岩继承原岩的Li同位素组成不同,榴辉岩具有轻于原岩的Li同位素组成,可归因于俯冲折返过程中的动力学扩散、脱水反应或低Li同位素的流体交代.作为变价元素,Fe和Cr的同位素在榴辉岩的形成过程中均不发生显著分馏,但是蛇纹岩的Fe同位素和Cr同位素与氧逸度指标具有相关性,指示氧化还原条件变化时脱水过程或流体交代会导致同位素分馏.      

苏鲁超高压变质带仰口蛇纹岩的成因——矿物化学、地球化学和年代学证据

通过矿物化学、全岩主微量元素和铂族元素研究,结合锆石年代学判断苏鲁造山带仰口蛇纹岩的原岩成因和演化历史。蛇纹岩中尖晶石经历了多阶段变质;全岩主量元素具有超基性堆晶岩的性质,代表玄武质组分含量的Ca O+Al_2O_3变化于2.0%~5.83%之间;部分不相容微量元素富集;铂族元素中Ir的含量低(0.64×10~(-9)~1.43×10~(-9)),Pd/Ir值高(1.05~3.42)。蛇纹岩中的锆石一部分为新形成的变质成因锆石(年龄平均为230±3Ma),与高压-超高压变质的年代吻合;另一部分可能是在三叠纪变质阶段古老锆石重结晶形成的。由此认为,仰口蛇纹岩的原岩可能为超基性堆晶岩,三叠纪时随着俯冲的扬子板块发生变质,在发生蛇纹石化作用之前经历了熔体/流体的改造。     

青海茫崖超镁铁质岩蛇纹石化作用的氢氧同位素研究

对青海茫崖石棉矿床中的蛇纹岩和纤蛇纹石石棉进行了氢氧同位素分析,蛇纹岩的δ~(18)O为+5.9—+7.5‰,δD为—115——133‰,纤蛇纹石石棉的δ~(18)O为+7.4—+8.9‰,δD为—115——136‰。共生蛇纹石-磁铁矿同位素温度表明各种蛇纹岩的形成温度为210—320℃,纤蛇纹石石棉为120—170℃。超镁铁质岩的蛇纹石化作用是多阶段的,蛇纹石化作用的水可能以具有一定盐度、CO_2分压较高的深循环大气变质水为主。蛇纹石作用发生在大陆环境中,纤蛇纹石石棉是在蛇纹石化最后阶段于近地表环境中形成的。     

蚀变洋壳和俯冲带变质流体的Fe-Mg同位素组成

贫碳酸盐的蚀变洋壳具有与新鲜洋中脊玄武岩一致的Mg同位素组成,说明低温和高温洋壳蚀变不会导致Mg同位素分馏.大别山港河和花凉亭的早期变质脉比榴辉岩具有偏高的δ56Fe-δ26Mg值,而且早期到晚期变质脉的δ56Fe-δ26Mg值逐渐降低.这些结果说明,在流体-岩石反应和流体演化过程中,Fe-Mg同位素发生了显著的分馏,且矿物溶解-再沉淀是同位素分馏的控制因素.相比洋中脊玄武岩,蚀变洋壳和变质脉具有相似或偏高的δ56Fe-δ26Mg值,说明蚀变洋壳脱水产生的流体富集重Fe-Mg同位素,不能解释弧岩浆岩的轻Fe/重Mg同位素组成.因此,弧岩浆岩异常的Fe-Mg同位素组成是熔体提取和富集54Fe-26Mg的蛇纹岩流体交代地幔楔两个过程共同作用的结果.      

锂同位素与大陆风化

气候变化与大气二氧化碳浓度息息相关.大陆岩石圈风化是影响大气二氧化碳浓度的重要过程.通过还原陆壳古风化信息,我们可以有效地了解地球气候条件的演化历史.传统方法上,前人曾使用锶同位素示踪大陆风化,但其解释尚有不足.例如,海水锶同位素比值会受到海洋热液的影响,而河流锶同位素比值则易受风化岩石类型的影响.此外,只有硅酸盐风化被认为在长时间尺度控制着大气碳汇,但锶的碳酸盐风化却与硅酸盐风化很难分辨.因此,我们需要一种更理想的同位素体系作为示踪大陆风化历史的介质.锂,作为微量元素,主要集中在岩石圈的硅酸盐矿物中,在碳酸盐岩含量较少.所以,硅酸盐风化可以使用锂同位素予以记录.同时,锂同位素受生物分馏效应影响较小,可以在海相碳酸盐岩中保存良好.这些优势为海相碳酸盐岩的锂同位素信号示踪大陆风化历史提供了有力支撑,但我们仍需对风化、迁移和结晶等过程的锂同位素地球化学行为有清晰的认识.为此,本文回顾不同储库的锂同位素组成以及各物相间锂元素配分和同位素分馏特征,总结了近年来锂同位素在重建大陆风化历史方面的进展,并详述了有待解决的关键问题.     

Hydrothermal uranium deposits and sulfur isotopes

Research on sulfur isotopes in hydrothermal uranium deposits with acid alterations shed much light on the genetic aspects of hydrothermal uranium deposits. Based on the studies of uranium deposits of different genesis, it is concluded that σ³⁴S of Sulfides in hydrothermal uranium deposits derived from residual magma is within the range of +2‰ ?2.6‰, approximately the same as meteorite sulfur. δ³⁴S of Sulfides in polygenetic hydrothermal uranium deposits is slightly lighter than meteorite sulfur and varies over a restricted range (6.7‰), averaging ?10.15‰. Two intervals can be recognized with respect to sulfur isotopic compositions in palingenetic hydrothermal uranium deposits. δ³⁴S of sulfides formed in diagenesis, autometamorphism and hypothermal stages is similar to meteorite sulfur. On the other hand, at the stage starting from the alteration of uranium mineralization to the formation o uranium deposits and postmineralization the average δ³⁴S is -7.89‰, with a wider range of δ³⁴S variation (13.7‰), which can be attributed to the enrichment of δ³⁴S in palingenetic hydrothermal solutions.     

Ar isotopes and Earth-atmosphere evolution models

Earth-atmosphere evolution models are mathematically simulated and the resulting present isotopic ratio (⁴⁰Ar/³⁶Ar) in the mantle is given for each.Differential outgassing experiments on several recent submarine glasses were made to estimate an isotopic ratio (⁴⁰Ar/³⁶Ar) in the present mantle. Estimations of (⁴⁰Ar/³⁶Ar) in the mantle by various methods are also critically reviewed. From the experimental results and these considerations a minimum value of 2000 for (⁴⁰Ar/³⁶Ar) ratio in the present mantle is inferred. By assuming that $\text{(}{}^{40}\text{Ar/}{}^{36}\text{Ar)}{}_{\mathrm{M}}$ is larger than 2000 and that the potassium content in the present mantle is larger than 50 ppm, we can limit considerably a choice among various Earth-atmosphere evolution models, i.e. (1) a continuous degassing process can not explain rare gas evolution in the atmosphere, (2) early sudden degassing is more likely and (3) such sudden degassing must have occurred earlier than 4.35 b.y.     

Stable isotopes in mineralogy

Stable isotope fractionations between minerals are functions of the fundamental vibrational frequencies of the minerals and therefore bear on several topics of mineralogical interest. Isotopic compositions of the elements H, C, O, Si, and S can now be determined routinely in almost any mineral. A summary has been made of both published and new results of laboratory investigations, analyses of natural materials, and theoretical considerations which bear on the importance of temperature, pressure, chemical composition and crystal structure to the isotopic properties of minerals. It is shown that stable isotope studies can sometimes provide evidence for elucidating details of crystal structure and can be a powerful tool for use in tracing the reaction paths of mineralogical reactions.     

Carbon isotopes, time boundaries and evolution

The carbon isotope composition of carbonate rocks in time-boundary zones is interpreted as a reflection of the variations in the total biomass at mass extinction events. Better stratigraphic control and identification of hiatuses can be gained by stable isotope stratigraphic methods than with any other type of stratigraphy. It is suggested that the use of carbon isotopes can help in solving some of the problems confronting palaeontologists and lead to a better understanding of the evolutionary significance of these events.     

Geochemistry and cosmochemistry of potassium stable isotopes

Stable potassium isotopes are one of the emerging non-traditional isotope systems enabled in recent years by the advance of Multi-Collector Inductively-Coupled-Plasma Mass-Spectrometry (MC-ICP-MS). In this review, we first summarize the geochemical and cosmochemical properties of K, its major reservoirs, and the analytical methods of K isotopes. Following this, we review recent literature on K isotope applications in the fields of geochemistry and cosmochemistry. Geochemically, K is a highly incompatible lithophile element, and a highly soluble, biophile element. The isotopic fractionation of K is relatively small during magmatic processes such as partial melting and fractional crystallization, whereas during low-temperature and biological processes fractionation is considerably larger. This resolvable fractionation has made K isotopes promising tracers for a variety of Earth and environmental processes, including chemical weathering, low-temperature alteration of igneous rocks, reverse weathering, and the recycling of sediments into the mantle during subduction. Sorption and interactions of aqueous K with different clay minerals during cation exchange and clay formation are likely to be of fundamental significance in generating much of the K isotope variability seen in samples from the Earth surface and samples carrying recycled surface materials from the deep Earth. The magnitude of this fractionation is process- and mineral-dependent. Comprehensive quantification of pertinent K isotope fractionation factors is currently lacking and urgently needed. Significant fractionation during biological activities, such as plant uptake, demonstrates the potential utility of K isotopes in the study of the nutrient cycle and its relation to the climate and various ecosystems, enabling new and largely unexplored avenues for future research.Of significant importance to the cosmochemistry community, K is a moderately volatile element with large variations in K/U ratio observed among chondrites and planetary materials. As this indicates different degrees of volatile depletion, it has become a fundamental chemical signature of both chondritic and planetary bodies. This volatile depletion has been attributed to various processes such as solar nebula condensation, mixing of volatile-rich and -poor reservoirs, planetary accretional volatilization via impacts, and/or magma ocean degassing. While K isotopes have the potential to distinguish these different processes, the current results are still highly debated. A good correlation between the K isotope compositions of four differentiated bodies (Earth, Mars, Moon, and Vesta) and their masses suggests a ubiquitous volatile depletion mechanism during the formation of the terrestrial planets. It is still unknown whether any of the K isotopic variation among chondrites and differentiated bodies can be attributed to inherited signatures of mass-independent isotopic anomalies.     

Ion-exchange fractionation of copper and zinc isotopes

Whether transition element isotopes can be fractionated at equilibrium in nature is still uncertain. Standard solutions of Cu and Zn were eluted on an anion-exchange resin, and the isotopic compositions of Cu (with respect to Zn) of the eluted fractions were measured by multiple-collector inductively coupled plasma mass spectrometry. It was found that for pure Cu solutions, the elution curves are consistent with a ⁶³Cu/⁶⁵Cu mass fractionation coefficient of 0.46‰ in 7 mol/L HCl and 0.67‰ in 3 mol/L HCl between the resin and the solution. Batch fractionation experiments confirm that equilibrium fractionation of Cu between resin and 7 mol/L HCl is ∼0.4‰ and therefore indicates that there is no need to invoke kinetic fractionation during the elution. Zn isotope fractionation is an order of magnitude smaller, with a ⁶⁶Zn/⁶⁸Zn fractionation factor of 0.02‰ in 12 mol/L HCl. Cu isotope fractionation results determined from a chalcopyrite solution in 7 mol/L HCl give a fractionation factor of 0.58‰, which indicates that Fe may interfere with Cu fractionation.Comparison of Cu and Zn results suggests that the extent of Cu isotopic fractionation may signal the presence of so far unidentified polynuclear complexes in solution. In contrast, we see no compelling reason to ascribe isotope fractionation to the coexistence of different oxidation states. We further suggest that published evidence for iron isotopic fractionation in nature and in laboratory experiments may indicate the distortion of low-spin Fe tetrahedral complexes.The isotope geochemistry of transition elements may shed new light on their coordination chemistry. Their isotopic fractionation in the natural environment may be interpreted using models of thermodynamic fractionation.     

华北蓟县中元古界剖面中燧石条带的形成机制——硼硅同位素证据

天津蓟县中新元古界海相沉积碳酸盐岩建造中分布大量燧石条带,特别是雾迷山组燧石条带与白云岩互层密集产出,沉积韵律非常明显,记录了其形成时海洋的化学和生物等信息,但关于其成因和形成机制还存在不同的认识。我们对蓟县中元古界剖面中碳酸盐岩的硼同位素和燧石条带的硅氧同位素进行了系统研究。燧石条带的 δ 30 Si NBS 28 值为0. 6‰~3. 3‰,平均2. 2‰,较热水化学沉积硅质岩的 δ 30 Si NBS 28 值显著偏高,与浅海生物沉积硅质岩的硅同位素组成相近。燧石条带的 δ 18 O V SMOW 值为21. 7‰~27. 8‰,平均25. 5‰,较热液成因硅质岩的值明显偏高,而与常温海相硅质岩的 δ 18 O值相似。蓟县剖面白云岩和灰岩等碳酸盐岩的 δ 11 B SRM 951 值为0‰~11. 0‰之间,平均4. 8‰,较现代海相碳酸盐的值明显偏低。高于庄组至雾迷山组燧石条带白云岩的 δ 11 B值普遍高于白云岩和灰岩的值,在3. 3‰~12. 9‰之间,平均8. 4‰。在酸性条件下富集重硼同位素的B(OH) 3掺入碳酸盐的比例增加,可导致其 δ 11 B值升高。这表明燧石条带白云岩可能形成于局部酸性水环境。结合碳酸盐和SiO 2溶解/沉淀与pH之间相互关系,提出蓟县剖面中的燧石条带是一种具有时代特征的同沉积的生物化学沉积硅质岩。中元古代海水中SiO 2浓度高,基本呈饱和状态,Mg/Ca比值高,生物活动已成为影响海洋环境的重要因素。在生物活动繁盛期大量有机质沉积于海底,导致海水-沉积物界面附近pH值大幅下降(pH＜7. 8),白云石等碳酸盐溶解度升高,难以沉淀;与此相反,SiO 2溶解度降低,达到过饱和,大量沉淀形成燧石条带/透镜体。生物活动羸弱期,海底pH值升高恢复到正常水平,SiO 2溶解度升高,碳酸盐溶解度降低,形成白云岩等碳酸盐沉淀。生物活动的周期性变化,则形成白云岩与燧石互层的条带状韵律层。燧石条带白云岩的硼同位素组成反映的是局部流体的 δ 11 B和pH值,不适合用来反演海水的硼同位素组成。