云南春都斑岩铜矿床岩体氧逸度特征

<正>岩浆氧逸度是岩浆结晶分异时氧化还原状态的一个重要表征参数,研究表明岩浆的氧逸度对多种金属的成矿起明显的制约作用,尤其体现在铜、金等亲硫元素矿床的形成过程中。岩浆氧逸度有多种测试方法,常通过所含矿物变价元素的价态来确定,但受后期风化作用和热液作用的影响较大。Ballard et al.(2002)最早提出利用锆石中Ce4+/Ce3+比值来计算岩浆结晶分异时的相对氧逸度。锆石是中酸性岩浆中广泛存在的副矿物,具有良好的抗风化和抗热液蚀变能力,其中变价元素Ce对氧化还原环境敏     

活塞圆筒和多面砧高压装置中常用的氧逸度控制和原位监测方法

氧逸度是定量表示一个体系氧化还原能力的指标，反映了体系中氧气的分压或者逃逸能力。在地球科学中，它反映了岩石和矿物中变价元素的氧化还原状态，指示了不同岩石矿物氧化性/还原性的相对强弱。相同岩石矿物不同氧逸度可以导致其物理化学性质发生大的改变，因此在实验地球科学中准确控制并监测高温高压实验条件下的氧逸度具有非常重要的意义。本文从实验技术角度出发，首先介绍了活塞圆筒和多面砧高压装置中利用双胶囊技术在不含水和含水体系中控制氧逸度的方法、原理、装置和注意事项；接着描述了用过渡金属合金固溶体和惰性金属合金作为氧传感器原位测量氧逸度的原理、注意事项和地质应用，然后展示了氧离子固体电解质法控制和监测氧逸度的原理、装置和局限，提出了可能的改进方法。目前由于技术限制，氧逸度在高压实验中的控制和监测方法还不成熟，导致其对矿物和岩石物理化学性质的影响极可能被低估甚至错估。因此积极研究发展并推动高压下氧逸度的控制和监测技术非常重要且必要。     

Fe-Cu-Zn-Mo同位素示踪氧化还原过程

非传统稳定同位素（Fe-Cu-Zn-Mo）理论与数据相结合提高了科研工作者对地质体系氧化还原过程的理解。本文对这一相对较新的领域进行了综述,包括与氧化还原过程相关的同位素分馏理论和实验约束、时空尺度下的氧逸度以及同位素示踪氧化还原过程。稳定同位素理论预测,Fe-Cu-Zn-Mo同位素应该对氧化还原状态的变化能够做出响应。结果表明,Fe同位素作为岩浆过程、表生过程、俯冲带流体性质"氧逸度计"应用前景广阔;Cu同位素在岩浆、热液、陆地系统可以很好地示踪氧化还原过程;Zn同位素由于络合过程分馏已经被用在许多不同环境中作为含硫/碳流体迁移的敏感示踪剂;Mo同位素作为古氧逸度计可有效重建古海洋-大气氧化还原状态。     

西藏多龙矿集区波龙、多不杂斑岩铜金矿床岩体锆石Ce4+/Ce3+比值及氧逸度特征

波龙、多不杂斑岩铜金矿床是青藏高原中部发现的两个大型斑岩铜金矿床。对波龙、多不杂斑岩铜金矿床含矿花岗闪长斑岩和不含矿花岗闪长斑岩的锆石Ce~(4+)/Ce~(3+)比值以及氧逸度等特征进行研究,并且通过计算得到了3个含矿花岗闪长斑岩的锆石Ce~(4+)/Ce~(3+)比值分别为536.03,492.18,454.02;1个不含矿的花岗闪长斑岩的锆石Ce~(4+)/Ce~(3+)比值为0.67。说明波龙、多不杂斑岩矿床中与成矿相关的岩体具有相对更高的氧化状态。对比西藏冈底斯成矿带中的斑岩矿床、云南中甸岛弧成矿带中的烂泥塘斑岩铜矿床、金沙江-红河成矿带中的马厂箐、铜厂铜钼矿以及玉龙成矿带铜钼矿床岩体的锆石Ce~(4+)/Ce~(3+)比值,发现含矿岩体锆石Ce~(4+)/Ce~(3+)比值一般250。结合波龙、多不杂矿床的锆石Ce~(4+)/Ce~(3+)的计算结果发现Ce~(4+)/Ce~(3+)基本300,因此将锆石Ce~(4+)/Ce~(3+)300作为波龙、多不杂矿床斑岩成矿的一个地球化学标志。此外,通过(Ce/Ce~*)_D锆石氧逸度计和(X_(Ce~(4+))~(melt)/X_(Ce~(3+))~(melt))锆石氧逸度计计算得到的波龙、多不杂矿床含矿花岗闪长斑岩体的氧逸度(log(f_(O_2)))分别位于MH(磁铁矿-赤铁矿)缓冲带和FMQ(铁橄榄石-磁铁矿-石英)缓冲带之上,平均值为ΔMH+3.24和ΔFMQ+1.78,前人研究发现多不杂含矿石英斑岩的氧化状态较高,平均ΔNNO+2.4,含矿斑岩体的形成具有较高的氧逸度条件,说明高氧逸度更有利于多龙矿集区斑岩型铜矿成矿。     

金属稳定同位素示踪地球增氧事件

早期贫氧地球如何演化至现今富氧地球是理解地球宜居性形成与演化的关键,但重建地质历史时期地球大气与海洋氧含量仍是地球科学领域的重大挑战.金属稳定同位素的高精度测试分析为示踪地球大气与海洋氧化历史提供了新的研究手段.以Mo、U、Tl、Cr四种氧化还原敏感金属稳定同位素体系为例,详细介绍了氧化还原敏感金属稳定同位素地球化学行为及分馏机理.在此基础上,系统回顾了金属稳定同位素在研究产氧光合作用的起源、大氧化事件（Great Oxidation Event,GOE）、中元古代大气和海洋氧化还原状态、新元古代氧化事件（NOE）等重大科学问题中的研究进展.金属稳定同位素在重建地球表层圈层氧化过程具有广阔的应用前景,对认识地球宜居性的演化历史以及探索其未来发展趋势具有深远意义.      

中酸性侵入岩的氧逸度计算

氧逸度是岩石物理化学的1个重要参数,对岩浆演化、岩石成因和岩浆热液成矿具有明显的控制作用。含有变价元素的矿物常被用来计算成岩与成矿过程中的氧逸度,但是不同方法之间的对比研究较少,各种方法的适用性还不明晰。作者对晋东北黑狗背花岗岩体的氧逸度进行了较为系统的研究,通过黑云母、角闪石、磁铁矿-钛铁矿矿物对和锆石的Ce异常的氧逸度计算,发现不同方法的估算结果存在较大的差异,甚至会得出完全相左的结论。其中,基于Fe~(3+)/Fe~(2+)比值的黑云母和磁铁矿-钛铁矿氧逸度计计算结果吻合度较高,可适用于中酸性侵入岩的氧逸度研究,而基于Fe/(Fe+Mg)比值的氧逸度计算方法可能受到母岩浆化学成分的影响,不适合应用于低镁侵入岩的氧逸度估算。     

地幔氧逸度的研究进展

通过对目前国际上诸多有关地幔氧逸度的研究结果的系统分析和总结 ,提出了地幔中自由氧对地幔物质的性质、状态及运动过程产生影响的基本作用方式 ;介绍了目前地幔氧逸度研究的主要研究手段 ,包括本征氧逸度的实验室测量、模拟氧逸度的实验室测量、地幔氧逸度计及理论计算等及其优缺点 ;定性探讨了地幔氧逸度的时空分布规律 ,获得了地幔随时间的推移变得愈来愈氧化 ,随深度的增加变得愈来愈还原 ,以及在横向上不同大地构造部位的地幔区域具有不同的氧逸度等诸多结论。结合目前人们对地幔物质组成、性质、状态、运动过程及地球的起源与演化历史等的认识 ,初步提出了地幔不同圈层氧逸度的约束机制。最后 ,针对目前地幔氧逸度的研究现状 ,为今后提出了一些参考性的研究方向。     

早期大气圈的氧化状态

如果生命是在早期地球表面环境中起源于有机化合物,大气圈的氧化状态则是一个重要的因素。因为高还原性的大气圈比弱还原性的大气圈更有利于前生物合成作用。然而,关于早期大气圈的最流行的模式都认为大气圈是N_2、CO_2、H_2O和微量H_2、CO组成的弱还原性混合物。这里,笔者检验了两种作用:(1)后来微星体的爆炸;(2)地幔氧化还原状态的改变。月球陨石坑告诉我们,月球,当然也有地球,在3.8Ga之前,被碰撞爆炸     

小秦岭金矿区花岗岩磷灰石-锆石对岩浆氧逸度的约束

小秦岭金矿区华山和文峪花岗岩体形成年龄与金成矿年龄相近,已知金矿多集中在文峪岩体周围,比较两岩体岩浆氧逸度的异同有利于判断其对金成矿影响的异同。本文利用两岩体磷灰石中锰离子价态和锆石钛含量,对岩浆的氧逸度进行了约束。计算表明,华山岩体成岩氧逸度lgf(O2)在-9.3^-5.1之间,而文峪岩体成岩氧逸度在-8.5^-6.1之间,均属大于HM缓冲线的高氧逸度环境。Au在还原状态易呈自然金而沉淀,氧化状态时易以Au+或Au3+迁移。故华山和文峪岩体的岩浆都不能对金形成地球化学障而使之分散。     

三江北衙金多金属矿床容矿岩体相对氧化状态特征

氧逸度反应了岩浆的温度、压力和物质组成等信息,目前通过计算锆石Ce(Ⅳ)/Ce(Ⅲ)比值来指示岩浆氧逸度特征是一个行之有效的方法。本文计算分析了北衙金多金属矿床中容矿岩体的锆石Ce(Ⅳ)/Ce(Ⅲ)比值。北衙超大型金矿床位于金沙江-哀牢山钾质岩浆岩带中段,发育与钾质侵入岩密切相关的金多金属成矿系统,本次研究了矿区中一个成矿前容矿岩体不同部位的锆石Ce(Ⅳ)/Ce(Ⅲ)比值特征,结果显示其总体趋势是岩体外带Ce(Ⅳ)/Ce(Ⅲ)平均值高于岩体内带,即位于岩体外带的斑岩相对氧化性较强,且单颗粒锆石Ce(Ⅳ)/Ce(Ⅲ)比值变化较大,可能受到岩体空间位置分布的影响。对比分析钾质岩浆岩带上其它典型矿床的岩体锆石Ce(Ⅳ)/Ce(Ⅲ)比值特点,显示出不同矿床之间该比值差异较大;Ce(Ⅳ)/Ce(Ⅲ)比值高并不一定指示是成矿岩体,应开展单一锆石颗粒单点Ce(Ⅳ)/Ce(Ⅲ)比值分布特征统计。     

地幔氧逸度与俯冲带深部碳循环

地幔氧逸度通过改变含碳相的存在形式和迁移方式来影响深部碳循环。本文结合最新的地幔氧逸度实验模拟和岩石学研究成果,探讨了地幔氧逸度时空分布对深部碳循环的影响。文章重点结合地幔减压熔融形成洋壳、新生洋壳蚀变、洋壳俯冲变质、深俯冲洋壳熔融以及俯冲洋壳物质(流体和固体)通过岩浆(岛弧和地幔柱)作用循环出地表等重要地质过程,探讨了伴随洋壳俯冲作用的深部碳循环过程。由于地幔氧逸度的时空变化,俯冲带含碳相表现出不同的存在形式和迁移能力。通过对西南天山俯冲带碳循环的岩石学和实验研究,我们认为应当进一步深入研究俯冲带氧化还原状态及其对俯冲带深部碳循环的影响。     

大气圈氧气含量水平上升的时间进程:一个与地球动力学过程紧密相关的地球生物学过程

两种气体,氮气和氧气,以压倒优势的状态主导着地球的大气圈。氮气是原生的,而且其存在和丰度不是生物过程所驱动的;相反,氧气是生物通过水的氧化作用而连续产生的,这个氧化作用得到了太阳光的能量驱动。氧气,一种对动物生命进化最为关键的气体,是如何变成大气圈中丰度第2的气体?问题并非以前所设想的那么简单;为了了解大气圈氧化的时间进程,我们不但要知道氧气是什么时候而且是如何第1次出现的,而且还要知道氧气是如何在大气圈中保持一个高浓度的。可以肯定的2个事实是:地球最早期的大气圈是缺乏氧气的,而今天的大气圈则为21%的氧气所组成。需要特别强调的是,大多数古代大气圈氧气水平的地质标志,只是意味着存在与缺乏,而且发生在以下2个时间点的大多数事件是高度不肯定的;但是,一系列地质证据已经表明,大气圈氧气含量水平上升的时间进程发生在2个时间点上:(1)一个从缺氧的到含氧的大气圈的转变,大致发生在2.0~2.5,Ga期间,这个转变就是著名的巨型氧化作用事件(GOE);(2)发生在前寒武纪-寒武纪过渡时期的大约540~850,Ma的第2次巨型氧化作用事件(GOE-Ⅱ),被进一步命名为新元古代氧化作用事件(NOE)。GOE与NOE,就得出了地球大气圈氧气含量水平上升三段式的盛行图像。随着研究的深入,得到了以下重要认识:如果说大气圈氧气含量的总体增加,从太古宙微不足道的水平增加到今天21%,是由于氧气生产作用增强的结果而代表了一个复杂的地球生物学过程的话,那么,这个过程则发生在随着侵蚀作用与沉积作用相对于火山活动而变得更加重要的状况下,更进一步讲,叠加在这个总体趋势下的则是一系列的阶梯式的氧气含量水平上升,这与超大陆聚合作用之后异常高的沉积作用周期是相联系的,从而进一步说明了大气圈氧气含量水平上升是与地球动力学过程紧密相关的地球生物学过程的作用结果。大气圈氧气含量水平一系列的阶梯式的上升,被总结为7个事件而与超大陆汇聚事件得到了良好的对比,从而提供了一个更加清晰的图像;也就是说,在超大陆汇聚作用之后,得到增强的沉积作用促进了大部分有机碳和黄铁矿的埋藏,因而阻碍了它们与自由氧的反应,结果就是大气圈氧气含量水平的实质性上升。新颖的观点和重要的认识,为深入理解地球大气圈氧气含量水平上升这一个重要的地球生物学过程,提供了重要的思考途径和研究线索;追索这些研究进展,将有助于揭开地球大气圈演变历史的神秘面纱并寻找出更多的科学研究生长点。     

Evolution of the early Earth: Constraints from Nd---Nd isotopic systematics

Combined ¹⁴⁷Sm---¹⁴³Nd and the now extinct [τ(1/2)₁₄₆=103×10⁶ yr] ¹⁴⁶Sm---¹⁴²Nd isotopic systematics are reported for early Archean gneisses from Greenland (Amîtsoq and Akilia associations), and Canada (Acasta gneiss). Using both field relationships and high resolution U---Pb SHRIMP ion-probe ages, it has been possible to identify the most ancient rocks in these terrains for isotopic analyses. Preliminary ¹⁴²Nd analyses of a still limited number of samples have failed to identify terrestrial ¹⁴²Nd anomalies. Effects, if present, are limited to < 10 ppm and we have thus been unable to confirm the +33±4 ppm ε₁₄₂ value claimed by Harper and Jacobsen (1992a, b) for a single sample. From the lack of ¹⁴⁶Sm---¹⁴²Nd effects we infer that large-scale fractionation events that may have occurred in the first 200 Ma of Earth history did not leave a significant nor widespread imprint on the early Archean mantle or crust. If a terrestrial magma ocean, with associated LREE fractionation, formed as a result of planetary accretion, then it had a lifetime of at most 250 m.y. before being remixed into the Earth's mantle.

The samples analysed in this study have a range of ε₁₄₃ values including highly positive values of up to +4.2. This requires that the earliest known Archean crust was differentiated from a reservoir that was strongly depleted in the LREE as compared with chondritic compositions. In the early Archean it is proposed that the depletions in LREE are a consequence of extraction of a limited fraction of the Earth's continental crust ( < 10%) from the upper 200 km of the mantle. A three reservoir model, consisting of the continental crust, depleted mantle and a more primitive mantle reservoir can be extended to account for both the present-day, as well as the evolving Nd isotopic composition of the Earth's crust and mantle. In contrast to previous models, the rate of growth of the continental crust is used as an input parameter to constrain the concomitant growth and evolution of the depleted mantle reservoir. Recycling of large volumes of bulk continental crust into the mantle is not considered to be an important process, nor is the existence of an additional major enriched component in the early Archean mantle.     

湘南道县辉长岩包体的锆石LA-ICP-MS定年、Hf同位组成及其地质意义

道县虎子岩碱性玄武岩筒产出较多的辉长岩包体。用于锆石定年的辉长岩样品的岩石化学特征显示：其K₂O、Fe₂O₃、TiO₂高于其他同类样品,稀土元素、微量元素总量也相对较高,样品的K^*值（2K_N/（Ta_N+La_N））为7.60>1,显示岩浆具有亲岛弧性质,反映源区地幔受到较强的交代作用;Nb^*值（2 Nb_N/（K_N+La_N））为0.11<1,反映基性岩浆侵入时受到了地壳混染;辉长岩中的锆石具有清晰的韵律环带,Th/U值=0.91~4.35,具有岩浆锆石的特征;锆石²⁰⁶Pb/²³⁸U加权平均年龄为（201.50±0.53）Ma,代表了辉长岩的结晶年龄;ε_Hf （t）值为-0.88~4.45,投点落入球粒陨石附近,暗示强烈的壳幔交换作用;Hf模式年龄平均为751 Ma,反映早期地壳对岩石源区的贡献。Hf同位素组成特征反映辉长质岩浆是在印支晚期局部拉张背景下,岩石圈上地幔上隆减压熔融的产物。     

Insights into the Hadean Earth from experimental studies of zircon

Geologists investigate the evolution of the atmosphere, crust, and mantle through time by direct study of the rock record. However, the Hadean eon (>3.85 Ga) has been traditionally viewed as inaccessible due to the absence of preserved rocks. The discovery of >4.0 Ga detrital zircons from Western Australia in the 1980s — coupled with the development of new micro-analytical capabilities — made possible new avenues of early Earth research. The prevailing view that emerged is that the early Earth may have contained a stable hydrosphere, water-saturated or (near watersaturated) granitic magmas, and volcanic emanations dominated by neutral gas species (e.g., CO₂, H₂O, and SO₂). The Hadean Earth may have been capable of supporting life ～200 Ma after accretion and perhaps earlier. Many of these models are formulated — or have been subsequently supported — by laboratory experiments of zircon. Important petrological variables such as temperature, pressure, oxygen fugacity, and component activities (e.g., SiO₂/TiO₂-activities) can be controlled. These experiments are fundamental for extrapolation to ‘deep time’ because they provide a means to understand primary chemistry preserved in ancient zircons. This review paper specifically focuses on zircon experimental studies (oxygen isotope fractionations, Ti-thermometry, and redox sensitive element incorporation into zircon), which have influenced our view of the very early Earth.     

月球的化学演化

月球是一个发生了化学分异的星球,它由月壳、月幔±一个小的金属月核组成。大量观察事实显示月球曾经有过岩浆洋,岩浆洋的结晶分异主导了月球的化学演化。目前主流观点认为,月球是在太阳系演化的早期,至少45亿年前,一个火星大小的星球,与即将完成原始吸积的地球胚胎发生偏心撞击,造成地球的熔融,形成岩浆洋,飞溅出来的物质迅速吸积形成绕地球运动的月球,并且在月球上形成了全球规模的岩浆洋,进而发生了结晶分异。,由于月球上没有海洋和板块俯冲,岩浆洋分异是其化学演化的主要途径。月球岩浆洋的80％～85％在大撞击后的100Ma内已经固化,这可能是由于月球体积小、表面没有大气包裹所致。月球极贫水,因此在岩浆结晶过程中斜长石首先结晶。斜长石由于密度小于玄武质岩浆而漂浮在岩浆洋的表层,橄榄石等密度大的矿物则堆积在岩浆洋的底部。随着结晶分异的进行,残余岩浆不断富集不相容元素,包括K、U等放射性元素;与此同时,密度较大的钛铁矿开始结晶,造成高钛堆晶岩密度大于其下的橄榄石堆晶岩的不稳定结构,进而发生月幔翻转,引发一系列岩浆活动,进而形成月球上特有的镁质系列、碱质系列等岩石。由于月球氧逸度较低,Eu主要以＋2价形式存在,因此斜长石高度富集Eu,相应地除高地斜长岩外,其他岩石均表现为Eu高度亏损的特点。与此同时,Re在低氧逸度下表现为强亲铁元素的特点,Re／Os在月球岩浆过程中不发生分异。月球的体积远小于地球,因而其演化时间远远短于地球,很多原始的分异被完整地保留下来。因此月球的化学演化是类地行星早期演化过程的“化石”,尽管与现代的地球存在较大差异,但是对于认识地球早期演化具有借鉴意义。     

鄂东南地区程潮大型矽卡岩型铁矿区岩体成因探讨

湖北程潮铁矿是鄂东南矿集区内最大的矽卡岩型铁矿床。为了系统研究矿区内不同侵入体的成因,对程潮矿区内不同时代的侵入体进行了矿物学、地球化学和Sr-Nd-Pb同位素研究。矿区内花岗岩、石英二长斑岩、闪长岩中的黑云母成分特征暗示它们均为壳幔物质混合成因的镁质黑云母;与成矿相关的花岗岩、石英二长斑岩中原生黑云母矿物学成分显示出原始岩浆具有高氧逸度的特征,高氧逸度为磁铁矿的形成提供了有利条件。岩石地球化学特征研究表明,不同类型的岩石都具有富钾和准铝质的特征,富集Rb、Ba、K等大离子亲石元素和轻稀土元素,亏损Nb、Ta、Ti等高场强元素。矿区岩石的(⁸⁷Sr/⁸⁶Sr)_i值为0.705 0~0.709 1,ε_Nd(t)值为-14.16~-6.95,²⁰⁶Pb/²⁰⁴Pb值为17.636~18.919,²⁰⁷Pb/²⁰⁴Pb值为15.451~15.613,²⁰⁸Pb/²⁰⁴Pb值为37.833~39.556。矿物学、地球化学、Sr-Nd-Pb同位素特征暗示矿区岩体为富集地幔发生部分熔融并同化混染了不同比例下地壳物质的产物,早期闪长岩（（140±1） Ma）比晚期花岗岩和石英二长斑岩（（128±1） Ma）的源区有更多的地幔成分,花岗岩和石英二长斑岩与闪长岩具有相近的锆石饱和温度（平均值分别为783、788、765℃）。     

Mantle redox evolution and the oxidation state of the Archean atmosphere

Current models predict that the early atmosphere consisted mostly of CO2, N2, and H2O, along with traces of H2 and CO. Such models are based on the assumption that the redox state of the upper mantle has not changed, so that volcanic gas composition has remained approximately constant with time. We argue here that this assumption is probably incorrect: the upper mantle was originally more reduced than today, although not as reduced as the metal arrest level, and has become progressively more oxidized as a consequence of the release of reduced volcanic gases and the subduction of hydrated, oxidized seafloor. Data on the redox state of sulfide and chromite inclusions in diamonds imply that the process of mantle oxidation was slow, so that reduced conditions could have prevailed for as much as half of the earth's history. To be sure, other oxybarometers of ancient rocks give different results, so the question of when the mantle redox state has changed remains unresolved. Mantle redox evolution is intimately linked to the oxidation state of the primitive atmosphere: A reduced Archean atmosphere would have had a high hydrogen escape rate and should correspond to a changing mantle redox state; an oxidized Archean atmosphere should be associated with a constant mantle redox state. The converses of these statements are also true. Finally, our theory of mantle redox evolution may explain why the Archean atmosphere remained oxygen-deficient until approximately 2.0 billion years ago (Ga) despite a probable early origin for photosynthesis.     

The redox state of subduction zones: insights from arc-peridotites

Spinel peridotites from a variety of island arcs have been utilised to calculate the redox state of the mantle wedge above subduction zones. Oxygen fugacities (f_O2 values) calculated from the ferric iron content of spinels, measured by Electron Microprobe (EMP) using secondary standards [Wood, B.J., Virgo, D., 1989. Upper mantle oxidation state: ferric iron contents of lherzolite spinels by ⁵⁷Fe Mössbauer spectroscopy and resultant oxygen fugacities. Geochim. Cosmochim. Acta, 53, 1277–1291.], yield values which range from 0.3 to 2.0 above the fayalite–magnetite–quartz (FMQ) buffer. These data provide further evidence that the mantle wedge is ubiquitously oxidised relative to oceanic and ancient cratonic mantle. There is no correlation between f_O2 values and the presence of hydrous phases and, in fact, the most oxidised samples contain no hydrous phases. Within individual suites there is no correlation between f_O2 and degree of depletion as indicated by spinel Cr#, except for a suite of reacted forearc-peridotites. However, when the data is viewed as a whole there is broad a positive correlation between f_O2 and spinel Cr# suggesting that partial melting processes may influence the redox state of the mantle wedge. We suggest that the ultimate source of the oxygen which oxidises the mantle wedge is from the subducted slab. It is not clear whether this oxidising agent is a solute-rich hydrous fluid or a water-bearing silicate melt. However, our data does indicate that silicate melts are effective oxidisers of the depleted shallow upper mantle. Simple mass balance calculations based on the ferric iron content of primitive subduction zone magmas indicates that the source region must contain 0.6–1.0 wt.% Fe₂O₃. This amount of Fe₂O₃ in a fertile spinel peridotite yields an oxygen fugacity of 0.5–1.7 log units above FMQ in the IAB source. If water is the sole oxidising agent in the mantle wedge then 0.030–0.075 wt.% H₂O is required which is considerably less than the 0.25% H₂O envisaged by Stolper and Newman [Stolper, E.M., Newman, S., 1994. The role of water in the petrogenesis of Mariana trough magmas. Earth Planet. Sci. Lett., 121, 293–325.], suggesting water is not necessarily an efficient oxidising agent. Alternatively, ferric iron may be added to the mantle wedge by addition of a ferric iron-rich sediment melt or more likely as a solute-rich hydrous fluid. This model would produce spinel, orthopyroxene or amphibole in the wedge with only a slight increase in f_O2 of the source region. Although it is unclear which model is correct the maximum f_O2 of the fertile mantle wedge is unlikely to be above FMQ+2 and therefore some decompression melting in the mantle wedge is required to explain the higher f_O2 values of primitive arc lavas than arc-peridotites.     

CO2 transfer between the upper mantle and the atmosphere: temporary storage in the lower continental crust

The CO₂ atmospheric content has shown large variations over geological times. High contents (up to one order of magnitude more than present-day values) ultimately correspond to discrete episodes of mantle degassing, either juvenile, or subduction-related (carbon recycling). A number of arguments (e.g. the continuous volume increase of carbonate-bearing sediments with time) suggest that, throughout the Earth's history, juvenile CO₂ has formed a major contribution to the global carbon budget of the Earth.
The absence of a direct relationship between major volcanic episodes and the average CO₂ atmospheric content suggests that volcanoes might not be the only way by which mantle CO₂ is transported to the surface. It is proposed that large quantities of juvenile CO₂ could temporarily be stored in the lower continental crust during major episodes of granulite formation. These are primarily caused by magmatic underplating and they result in a vertical accretion of the crust by accumulation of CO₂-bearing, mantle-derived magmas. Most of the CO₂ migrates through the crust during post-metamorphic evolution and isostatic restoration of the normal continental thickness. However, large quantities of CO₂ can still be present in some areas, notably as high-density fluids enclosed in minerals.