俯冲带脱碳和固碳作用过程

俯冲带作为联系地表和地球深部系统的纽带,不仅是将地表碳带入地球深部的主要通道,也是地表物质和地球深部物质发生交换的重要场所。俯冲作用可以将地表碳以有机碳或无机碳酸盐矿物等形式带入地球深部,再通过火山作用或去气作用返回到地表系统。俯冲带深部碳循环控制着地表碳通量变化,对于研究全球气候变化和地球宜居环境具有重要意义。本文结合前人的相关研究成果,综合探讨了俯冲带的脱碳机制及固碳作用过程。俯冲带脱碳机制主要有变质反应脱碳、流体溶解脱碳和熔融作用脱碳。从俯冲板块释放的含碳流体不一定都会迁移返回地表,有一部分含碳流体在迁移演化过程中会和围岩发生反应,形成不易迁移的其他含碳相(碳酸盐、石墨或金刚石)而重新固存在俯冲板块以及上覆地幔楔中(固碳作用),进而影响碳在不同储库中的含量变化,在计算俯冲带释放碳通量时需要考虑这一过程的影响。     

俯冲带深部碳循环:问题与探讨

碳循环可以分为地球表层短周期的地表碳循环和地球内部长周期的深部碳循环。地球的碳90%以上是赋存在固体地球内部,因此深部碳循环研究对于探讨地表碳循环过程具有重要意义。本文较深入地探讨了俯冲带深部碳循环研究的现状和问题。目前俯冲带深部碳循环研究关键的科学问题包括:(1)俯冲带变质过程中含碳物质相的转变,(2)俯冲带脱碳机制,(3)俯冲带深部碳循环和地幔交代作用。俯冲带变质过程中含碳物质相的转变是深部碳循环研究的最基本问题,将是深部碳进一步研究的重点。俯冲带脱碳机制主要包括纯变质反应脱碳、流体溶解脱碳(流体渗透作用)、熔融作用脱碳和氧化还原反应脱碳4个方面,这是目前深部碳循环研究的前沿领域。俯冲带深部碳循环研究对于探讨地幔不均一性以及地幔交代过程都具有重要研究意义。     

俯冲板片的脱碳机制及通量估算:问题与进展SCIEI北大核心CSCD

地球98%以上的碳赋存在地球深部地幔和地核中。地球深部储库(地幔和地核)中的碳以各类岩浆作用释放到地表,而地球表层系统(大气圈、水圈、生物圈)中的碳又可以伴随板块俯冲作用进入地球深部地幔。然而俯冲过程中不同的脱碳机制会将俯冲板片中部分乃至全部碳带出板片,而后经由岛弧岩浆作用、流体扩散作用等途径返回地表。因此,板片俯冲过程中的脱碳机制及其通量深刻地影响了地质时间尺度中地表系统的二氧化碳浓度,进而改变地球的宜居性。本文总结了目前主流观点认可的五种俯冲板片脱碳机制:变质反应脱碳、流体溶解脱碳、熔融脱碳、底辟脱碳和氧化还原脱碳。另一方面,目前对于俯冲板片各种脱碳机制对应的脱碳效率还有很大的争议,因此本文进一步梳理了板片俯冲过程中不同脱碳机制相关的通量估算的研究进展与存在的问题,建议将来综合多种方法对比研究俯冲带碳循环问题,以期在俯冲带深部碳循环过程和通量方面取得突破性进展。     

地幔岩中流体包裹体研究

地幔岩石中的流体包裹体代表地幔流体的样品。地幔流体包裹体可以存在从地幔来的金刚石,地幔捕虏体和岩浆碳酸岩中。研究这些岩石和矿物中的流体包裹体可以得出其所代表的地幔流体的温度、压力、成分和同位素。我们目前见到的这三类地幔岩石的包裹体主要可在橄榄石、辉石、金刚石、方解石和磷灰石中见到。这些包裹体可以粗略地分为CO2包襄体和硅酸盐熔融体包裹体。又可细分为四类包裹体：（1）富碳酸盐的硅酸盐熔融包裹体。这种包裹体在金刚石、地幔岩捕虏体和岩浆碳酸盐岩中见到,它又可分为结晶质熔融包裹体和玻璃包裹体。（2）CO2包裹体。这种包裹体大多见于地幔捕虏体中,在金刚石和岩浆碳酸岩中也可见到。（3）含硫化物的包裹体。这种包裹体见于地幔捕虏体中,与纯CO2包裹体和含CO2的熔融包裹体共存。（4）高密度的流体包裹体。这种包裹体见于金刚石中,是一种高盐度、高密度的含K、Cl和H2O的流体包裹体,又可分为高卤水包裹体和含卤水的富硅的碳酸盐岩浆包裹体。从对金刚石、地幔捕虏体和岩浆碳酸盐岩中流体包裹体的研究表明,地幔流体存在不均匀性和不混溶性。     

昌乐玄武岩内刚玉巨晶（蓝宝石）中发现富碳酸盐和硫酸盐熔融包裹体及其意义

山东昌乐新生代玄武岩内的刚玉巨晶(蓝宝石)中含有多种类型熔融包裹体,其成分对了解华北深部地幔交代过程中的流/熔体性质和刚玉母岩浆特点具有重要意义.详细的岩相学和激光拉曼分析鉴定出一类富碳酸盐和硫酸盐成分的原生熔融包裹体以及一类含硫酸盐和氯化物等成分的次生熔融包裹体,二者同时还含有CO2和H2O.碳酸盐和硫酸盐成分在世界范围玄武岩内刚玉巨晶中是首次发现,结合已有的包裹体稀有气体同位素和测温资料,反映两种成分可能来源于交代地幔的碳酸岩熔体,预示着华北深部地幔不仅经历了硅酸盐成分的交代还经历了富碳酸盐和硫酸盐成分(碳酸岩)的交代,同时也显示刚玉母岩浆成分复杂,至少有富这两类成分物质的参与,刚玉很可能是硅酸盐岩浆/岩石和幔源碳酸岩岩浆相互作用的产物,后被玄武岩喷发携带至地表.     

蚀变洋壳玄武岩俯冲过程中含碳矿物相变质演化及脱碳作用的研究

俯冲作用是连接地表系统和地球深部系统的最为关键的地质过程,其对研究地球深部碳循环具有重要的意义。俯冲洋壳岩石圈中的碳主要存储在沉积物、蚀变洋壳玄武岩以及蛇纹岩中。俯冲变质作用过程含碳岩石的变质演化控制着其中含碳矿物相的转变及碳迁移过程。本文选取了蚀变洋壳玄武岩进行相平衡模拟,来研究其含碳矿物相的变质演化过程。计算结果表明,变质玄武岩体系中的碳酸盐矿物之间的转变反应除了受压力控制之外,还受到温度和体系中铁含量的影响。随着压力的升高蚀变玄武岩中碳酸盐矿物会发生方解石/文石-白云石-菱镁矿的转变,但在高压/超高压条件下,温度的升高可以使菱镁矿转变成白云石。碳酸盐矿物中的铁含量受到体系中铁含量的影响,白云石和菱镁矿中的铁含量随着体系中铁含量的增加而增加。在水不饱和条件下,洋壳不管是沿着低温还是高温地热梯度线俯冲到岛弧深度,蚀变玄武岩体系几乎都不发生脱碳作用。然而在水饱和条件下,当洋壳沿着高温以及哥斯达黎加地热梯度线俯冲到岛弧深度时,蚀变玄武岩体系中的碳几乎可以全部脱出去。蚀变玄武岩体系中水含量的增加可以促进体系的脱碳作用。     

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。     

俯冲带碳酸盐化对深部碳循环的启示:以中国西南天山碳酸盐化云母片岩为例

俯冲带可将地球表层碳输送至深部地幔,同时也记录着俯冲板片来源碳质流体的迁移沉淀机制,对地球深部碳循环具有重大影响。近年来,俯冲带脱碳机制的研究表明流体溶解脱碳作用是冷的大洋俯冲板片释放COH流体的重要方式,而上覆板块(尤其地幔楔)则被认为是缓冲这些COH流体的重要场所,甚至是俯冲带CO_2的唯一"归宿"。事实上,俯冲带岩石本身的固碳能力却受到了忽视,而对俯冲带岩石捕获和固存CO_2(carbon capture and storage,CCS)能力的评估对全球碳通量的估算尤为重要。本文以中国西南天山高压-超高压变质带中碳酸盐化云母片岩为例,探讨俯冲带岩石的碳酸盐化对深部碳循环的影响。西南天山长阿吾子一带的碳酸盐化云母片岩记录了俯冲板片起源的碳质流体对俯冲带云母片岩的交代作用,地球化学特征表明蛇纹岩释放的富水流体溶解俯冲洋壳中的碳酸盐可能是产生COH流体的重要机制。基于碳质流体对多硅白云母(Si(a.p.f.u.)=3.58～3.73)的交代及相对高压的碳酸盐矿物(主要为白云石和菱镁矿)与金红石的共生,结合区域上碳酸盐化云母片岩与高压碳酸盐化蛇纹岩(HP-ophidolomite)的伴生,我们认为云母片岩的碳酸盐化作用可能发生在俯冲板片峰期稍后的高压折返阶段。俯冲带云母片岩的固碳作用表明除了上覆板块,俯冲带岩石本身对于碳质流体也具有很好的吸收能力。初步估算表明俯冲带云母片岩的碳酸盐化每年可固存至少2.46～6.68Mt/yr,约占俯冲板片每年进碳量的4%～17%。     

大陆俯冲带地壳深熔作用的记录:来自超高压变质岩中多相晶体包裹体的研究北大核心CSCD

大陆碰撞过程中会发生广泛的部分熔融现象,形成深熔熔体。深入认识深熔熔体的组成和演化是大陆俯冲带化学地球动力学的主要研究内容。在熔融过程中产生的熔体会被超高压岩石中的转熔矿物所捕获,最终以多相晶体包裹体(multiphase crystal inclusion,简称MCI)的形式保存下来。多相晶体包裹体通常具有典型的负晶形和爆裂纹,主要以硅酸盐和碳酸盐矿物为主含有少量的硫酸盐矿物。矿物学、岩石学和地球化学原位微区分析的研究结果表明,多相晶体包裹体是由岩石部分熔融产生的初始硅酸盐或/和碳酸盐初始熔体熔体结晶而成。在降压折返过程中,高压岩石中的含水矿物,如多硅白云母、钠云母和帘石等脱水引发部分熔融产生硅酸盐熔体,而碳酸盐熔体则由碳酸盐矿物部分熔融产生。富Na矿物如钠云母脱水熔融产生的包裹体具有相对较高的Na含量,而部分富K的包裹体主要由富K矿物如多硅白云母脱水熔融所产生。近年来随着微区原位技术的飞速发展,从矿物的形态结构到矿物地球化学组成的测定技术有了飞速发展,通过对超高压岩石中包裹的多相晶体的详细研究,可限定大陆碰撞造山过程中部分熔融的组成、时限和形成机制,对大陆深俯冲的构造热演化和折返机制有重要制约。     

高压-超高压变质岩石中不同成因的石榴石

石榴石是高压-超高压变质岩石中最重要的变质矿物之一,是研究俯冲带深部变质和熔融过程的理想研究对象.通过对俯冲带内不同条件下形成的石榴石进行详细研究,确定了岩浆成因、变质成因和转熔成因石榴石.岩浆石榴石是岩浆熔体在冷却过程中结晶形成,成分主要为锰铝榴石-铁铝榴石,通常含有石英、长石、磷灰石等晶体包裹体.变质石榴石是在亚固相条件下通过变质反应形成,包裹体为参与变质反应的矿物组合;进变质生长的石榴石通常显示核部到边部锰铝榴石降低的特征.转熔石榴石是在超固相条件下通过转熔反应形成,通常含有晶体包裹体,其中既有从转熔熔体结晶的矿物包裹体,也有转熔反应残留的矿物包裹体.对超高压变质岩石中转熔石榴石的识别,可以为深俯冲陆壳岩石的部分熔融提供重要的岩石学证据,是大陆俯冲带部分熔融研究的重要进展之一.      

俯冲隧道内不同深度的壳幔相互作用:地幔楔超镁铁质岩的镁同位素记录

在不同的俯冲深度,俯冲板片会释放出不同来源和组成的熔/流体进入俯冲隧道中,并进而影响上覆地幔楔及衍生岛弧岩浆的地球化学组成.然而,如何识别俯冲隧道中不同深度熔/流体组分的来源一直是俯冲带研究中的难点.对不同深度来源的地幔楔超基性岩进行了Mg同位素研究,发现了Mg同位素具有示踪俯冲板块熔/流体来源的能力.首先,研究了美国加州Franciscan杂岩中一套经历了多期次流体交代作用的浅部来源（< ~60 km）的变质超基性岩.这些部分蛇纹石化的地幔楔超基性岩在蛇纹石脱水形成滑石的过程中会释放轻Mg同位素进入流体,而重Mg同位素更多地残留在滑石相中;随后进一步受俯冲板块来源流体的交代形成具有高CaO和轻Mg同位素组成的透闪石化变橄榄岩,暗示流体中含有源自俯冲板片的、富集轻Mg同位素的碳酸盐,说明在弧前~60 km深度,部分含Mg碳酸盐（方解石）可以在俯冲隧道中发生溶解并迁移交代上覆地幔楔橄榄岩.对深部地幔楔来源（~160 km）的大别造山带毛屋地区超镁铁质岩体岩相学和元素地球化学研究结果证实了其交代成因.结合多相包裹体、元素地球化学以及前人估计的温-压条件,推测交代介质更接近超临界流体.锆石U-Pb年代学研究揭示,交代作用主要发生在古生代洋壳俯冲阶段（454±58 Ma）,超高压变质作用则发生在三叠纪陆壳俯冲阶段（232.8±7.9 Ma）.古生代锆石中大量的碳酸盐矿物包裹体和重O同位素特征说明古生代洋壳俯冲交代过程中有沉积碳酸盐组分加入.全岩和单矿物的Mg同位素组成均显著低于地幔值以及大别新元古代榴辉岩,说明交代的碳酸盐组分来源应为循环的沉积富Mg碳酸盐,暗示了在俯冲带深部富Mg沉积碳酸盐在超临界流体中会发生溶解迁移.由于沉积碳酸盐具有独特的、显著富集轻Mg同位素组成的特征,这种交代作用会造成地幔楔局部具有异常的Mg同位素组成,从而解释目前观察到的岛弧火山岩的Mg同位素特征.因此,Mg同位素是示踪俯冲碳酸盐与上覆地幔楔相互作用的有效工具.      

Dolomite-bearing orogenic garnet peridotites witness fluid-mediated carbon recycling in a mantle wedge (Ulten Zone,Eastern Alps,Italy)

We document the presence of dolomite ± apatite in orogenic peridotites from the Ulten Zone (UZ, Italian Alps), the remnants of a Variscan mantle wedge tectonically coupled with eclogitized continental crust. These dolomite peridotites are associated with dominant carbonate-free amphibole peridotites, which formed in response to infiltration of aqueous subduction fluids lost by the associated crustal rocks during high-pressure (HP) metamorphism and retrogression. Dolomite-free and dolomite-bearing peridotites share the same metamorphic evolution, from garnet- (HP) to spinel-facies (low-pressure, LP) conditions. Dolomite and the texturally coexisting phases display equilibrium redistribution of rare earth elements and of incompatible trace elements during HP and LP metamorphism; clinopyroxene and amphiboles from carbonate-free and carbonate-bearing peridotites have quite similar compositions. These features indicate that the UZ mantle rocks equilibrated with the same metasomatic agents: aqueous CO₂-bearing fluids enriched in incompatible elements released by the crust. The P–T crystallization conditions of the dolomite peridotites (outside the field of carbonatite melt + amphibole peridotite coexistence), a lack of textures indicating quench of carbonic melts, a lack of increase in modal clinopyroxene by reaction with such melts and the observed amphibole increase at the expense of clinopyroxene, all suggest that dolomite formation was assisted by aqueous CO₂-bearing fluids. A comparison of the trace element compositions of carbonates and amphiboles from the UZ peridotites and from peridotites metasomatized by carbonatite and/or carbon-bearing silicate melts does not help to unambiguously discriminate between the different agents (fluids or melts). The few observed differences (lower trace element contents in the fluid-related dolomite) may ultimately depend on the solute content of the metasomatic agent (CO₂-bearing fluid versus carbonatite melt). This study provides strong evidence that C–O–H subduction fluids can produce ‘carbonatite-like’ assemblages in mantle rocks, thus being effective C carriers from the slab to the mantle wedge at relatively low P–T. If transported beyond the carbonate and amphibole solidus by further subduction, dolomite-bearing garnet + amphibole peridotites like the ones from Ulten can become sources of carbonatite and/or C-bearing silicate melts in the mantle wedge. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users. In memory of Lauro Morten 1941–2006.     

Redox evolution of western Tianshan subduction zone and its effect on deep carbon cycle

Knowing the phase relations of carbon-bearing phases at high-pressure(HP) and high-temperature(HT) condition is essential for understanding the deep carbon cycle in the subduction zones.In particular,the phase relation of carbon-bearing phases is also strongly influenced by redox condition of subduction zones,which is poorly explored.Here we summarized the phase relations of carbon-bearing phases(calcite,aragonite,dolomite,magnesite,graphite,hydrocarbon) in HP metamorphic rocks(marble,metapelite,eclogite) from the Western Tianshan subduction zone and high-pressure experiments.During prograde progress of subduction,carbonates in altered oceanic crust change from Ca-carbonate(calcite) to Ca,Mg-carbonate(dolomite),then finally to Mgcarbonate(magnesite) via Mg-Ca cation exchange reaction between silicate and carbonate,while calcite in sedimentary calcareous ooze on oceanic crust directly transfers to high-pressure aragonite in marble or amorphous CaCO3 in subduction zones.Redox evolution also plays a significant effect on the carbon speciation in the Western Tianshan subduction zone.The prograde oxygen fugacity of the Western Tianshan subduction zone was constrained by mineral assemblage of garnet-omphacite from FMQ-1.9 to FMQ-2.5 at its metamorphic peak(maximum P-T) conditions.In comparison with redox conditions of other subduction zones,Western Tianshan has the lowest oxygen fugacity.Graphite and light hydrocarbon inclusions were ubiqutously identified in Western Tianshan HP metamorphic rocks and speculated to be formed from reduction of Fe-carbonate at low redox condition,which is also confirmed by high-pressure experimental simulation.Based on petrological observation and high-pressure simulation,a polarized redox model of reducing slab but oxidizing mantle wedge in subduction zone is proposed,and its effect on deep carbon cycle in subduction zones is further discussed.     

大陆俯冲带壳幔相互作用

由板块俯冲引发的深部物质循环过程是地球内部的一级运行机制,主宰了地球从内到外的演化进程,是地球科学研究的重要前沿.俯冲带化学地球动力学研究不仅需要确定俯冲带地壳物质再循环的机制和形式,而且需要确定俯冲带动力来源和热体制及其随时间的变化.为了识别不同类型壳源熔/流体对地幔楔的交代作用、寻求板片-地幔界面反应的岩石学和地球化学证据、理解汇聚板块边缘地壳俯冲和拆沉对地幔不均一性的贡献,我们必须将俯冲带变质作用、交代作用和岩浆作用作为一个地球科学系统来考虑.板块俯冲带变质过程中发生一系列物理化学变化,这些变化不但是导致板块进一步俯冲的主要驱动力,同时也控制着释放的熔/流体组成和俯冲到地球深部的物质组成,对俯冲带化学地球动力学过程产生重要影响.地幔楔作为俯冲系统中连接俯冲盘和仰冲盘的关键构造单元,在地球层圈之间物质循环和能量交换等方面起着重要作用.造山带地幔楔橄榄岩直接记录了俯冲带多种性质的熔/流体交代作用,以及复杂的壳幔物质循环过程.俯冲带岩浆岩是大洋/大陆板块俯冲物质再循环的表现形式,这些岩石样品记录了俯冲带从深部地幔到浅部地壳的过程,也为认识地球深部物质循环提供了理想的天然样品.尽管国际上在俯冲带岩石学和地球化学领域针对地球深部过程的研究方面取得了多项重要进展,但由于研究工作缺乏密切的协同配合,包括俯冲带熔/流体的物理化学性质、俯冲带壳幔相互作用的机制和过程、俯冲带幔源岩浆活动的物质来源和启动机制以及深部地幔过程对地表环境的影响等许多关键科学问题尚未得到根本解决.将来的研究需要聚焦俯冲带物质循环这一核心科学问题,进一步查明俯冲带变质作用、交代作用、岩浆作用等过程的各自特征和相互联系,包括挥发性组分在地球深部的迁移过程及其资源和环境效应,着力考察研究相对薄弱的古俯冲带,阐明板块俯冲与地球深部物质循环之间的耦合机制.      

The importance of talc and chlorite “hybrid” rocks for volatile recycling through subduction zones; evidence from the high-pressure subduction mélange of New Caledonia

The transfer of fluid and trace elements from the slab to the mantle wedge cannot be adequately explained by simple models of slab devolatilization. The eclogite-facies mélange belt of northern New Caledonia represents previously subducted oceanic crust and contains a significant proportion of talc and chlorite schists associated with serpentinite. These rocks host large quantities of H₂O and CO₂ and may transport volatiles to deep levels in subduction zones. The bulk-rock and stable isotope compositions of talc and chlorite schist and serpentinite indicate that the serpentinite was formed by seawater alteration of oceanic lithosphere prior to subduction, whereas the talc and chlorite schists were formed by fluid-induced metasomatism of a mélange of mafic, ultramafic and metasedimentary rocks during subduction. In subduction zones, dehydration of talc and chlorite schists should occur at sub-arc depths and at significantly higher temperatures (∼ 800°C) than other lithologies (400–650°C). Fluids released under these conditions could carry high trace-element contents and may trigger partial melting of adjacent pelitic and mafic rocks, and hence may be vital for transferring volatile and trace elements to the source regions of arc magmas. In contrast, these hybrid rocks are unlikely to undergo significant decarbonation during subduction and so may be important for recycling carbon into the deep mantle. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Subduction metamorphism of serpentinite‐hosted carbonates beyond antigorite‐serpentinite dehydration (Nevado‐Filábride Complex,Spain)

At sub‐arc depths, the release of carbon from subducting slab lithologies is mostly controlled by fluid released by devolatilization reactions such as dehydration of antigorite (Atg‐) serpentinite to prograde peridotite. Here we investigate carbonate–silicate rocks hosted in Atg‐serpentinite and prograde chlorite (Chl‐) harzburgite in the Milagrosa and Almirez ultramafic massifs of the palaeo‐subducted Nevado‐Filábride Complex (NFC, Betic Cordillera, S. Spain). These massifs provide a unique opportunity to study the stability of carbonate during subduction metamorphism at P–T conditions before and after the dehydration of Atg‐serpentinite in a warm subduction setting. In the Milagrosa massif, carbonate–silicate rocks occur as lenses of Ti‐clinohumite–diopside–calcite marbles, diopside–dolomite marbles and antigorite–diopside–dolomite rocks hosted in clinopyroxene‐bearing Atg‐serpentinite. In Almirez, carbonate–silicate rocks are hosted in Chl‐harzburgite and show a high‐grade assemblage composed of olivine, Ti‐clinohumite, diopside, chlorite, dolomite, calcite, Cr‐bearing magnetite, pentlandite and rare aragonite inclusions. These NFC carbonate–silicate rocks have variable CaO and CO₂ contents at nearly constant Mg/Si ratio and high Ni and Cr contents, indicating that their protoliths were variable mixtures of serpentine and Ca‐carbonate (i.e., ophicarbonates). Thermodynamic modelling shows that the carbonate–silicate rocks attained peak metamorphic conditions similar to those of their host serpentinite (Milagrosa massif; 550–600°C and 1.0–1.4 GPa) and Chl‐harzburgite (Almirez massif; 1.7–1.9 GPa and 680°C). Microstructures, mineral chemistry and phase relations indicate that the hybrid carbonate–silicate bulk rock compositions formed before prograde metamorphism, likely during seawater hydrothermal alteration, and subsequently underwent subduction metamorphism. In the CaO–MgO–SiO₂ ternary, these processes resulted in a compositional variability of NFC serpentinite‐hosted carbonate–silicate rocks along the serpentine‐calcite mixing trend, similar to that observed in serpentinite‐hosted carbonate‐rocks in other palaeo‐subducted metamorphic terranes. Thermodynamic modelling using classical models of binary H₂O–CO₂ fluids shows that the compositional variability along this binary determines the temperature of the main devolatilization reactions, the fluid composition and the mineral assemblages of reaction products during prograde subduction metamorphism. Thermodynamic modelling considering electrolytic fluids reveals that H₂O and molecular CO₂ are the main fluid species and charged carbon‐bearing species occur only in minor amounts in equilibrium with carbonate–silicate rocks in warm subduction settings. Consequently, accounting for electrolytic fluids at these conditions slightly increases the solubility of carbon in the fluids compared with predictions by classical binary H₂O–CO₂ fluids, but does not affect the topology of phase relations in serpentinite‐hosted carbonate‐rocks. Phase relations, mineral composition and assemblages of Milagrosa and Almirez (meta)‐serpentinite‐hosted carbonate–silicate rocks are consistent with local equilibrium between an infiltrating fluid and the bulk rock composition and indicate a limited role of infiltration‐driven decarbonation. Our study shows natural evidence for the preservation of carbonates in serpentinite‐hosted carbonate–silicate rocks beyond the Atg‐serpentinite breakdown at sub‐arc depths, demonstrating that carbon can be recycled into the deep mantle.     

Phase-Equilibrium Controls on SiO2 Metasomatism by Aqueous Fluid in Subduction Zones: Reaction at Constant Pressure and Temperature

The mineral-fluid equilibria that govern silica redistribution by aqueous fluids in subduction zones were evaluated at constant pressure and temperature in the model system MgO-SiO₂-H₂O (MSH). At <20 kbar and <1000° C, model H₂O-SiO₂ fluids liberated via devolatilization in subducting crust will be buffered at or near quartz saturation along any specified subduction P-T path, whereas fluids in equilibrium with model metaperidotites, ranging from dunite to orthopyroxenite protoliths, have silica concentrations significantly below quartz saturation. Isothermalisobaric flow of fluid from the slab to the mantle wedge therefore drives metasomatic reactions that increase the bulk silica content of metaperidotites and decrease the silica content of the fluid. The potential for silica metasomatism increases with depth for all subduction paths and model bulk compositions. At a given depth, the capacity for silica metasomatism increases with temperature and with abundance of forsterite relative to enstatite. Water-rock ratios required to produce metasomatic mineral assemblages decrease with increasing pressure and temperature. Mineral assemblages diagnostic of silica metasomatism at shallow subduction levels require water-rock ratios of >100 moles fluid/cm³ rock; but at depth, flow of only several moles fluid/cm³ rock is sufficient to produce assemblages characteristic of silica metasomatism. Decreasing temperature with time in most subduction zones suggests that the potential for silica metasomatism is greatest at early stages of convergence. Subducted ultramafic rocks showing evidence of high-temperature silica metasomatism therefore may provide windows into early subduction processes. In general, temporal changes in subduction parameters favoring increasing temperatures will enhance the potential for silica metasomatism, whereas those leading to lower temperatures should be expected to decrease the capacity for silica transfer with time.     

Melting phase relation of nominally anhydrous,carbonated pelitic-eclogite at 2.5–3.0 GPa and deep cycling of sedimentary carbon

We have experimentally investigated melting phase relation of a nominally anhydrous, carbonated pelitic eclogite (HPLC1) at 2.5 and 3.0 GPa at 900–1,350°C in order to constrain the cycling of sedimentary carbon in subduction zones. The starting composition HPLC1 (with 5 wt% bulk CO₂) is a model composition, on a water-free basis, and is aimed to represent a mixture of 10 wt% pelagic carbonate unit and 90 wt% hemipelagic mud unit that enter the Central American trench. Sub-solidus assemblage comprises clinopyroxene + garnet + K-feldspar + quartz/coesite + rutile + calcio-ankerite/ankerite_ss. Solidus temperature is at 900–950°C at 2.5 GPa and at 900–1,000°C at 3.0 GPa, and the near-solidus melt is K-rich granitic. Crystalline carbonates persist only 50–100°C above the solidus and at temperatures above carbonate breakdown, carbon exists in the form of dissolved CO₂ in silica-rich melts and as a vapor phase. The rhyodacitic to dacitic partial melt evolves from a K-rich composition at near-solidus condition to K-poor, and Na- and Ca-rich composition with increasing temperature. The low breakdown temperatures of crystalline carbonate in our study compared to those of recent studies on carbonated basaltic eclogite and peridotite owes to Fe-enrichment of carbonates in pelitic lithologies. However, the conditions of carbonate release in our study still remain higher than the modern depth-temperature trajectories of slab-mantle interface at sub-arc depths, suggesting that the release of sedimentary carbonates is unlikely in modern subduction zones. One possible scenario of carbonate release in modern subduction zones is the detachment and advection of sedimentary piles to hotter mantle wedge and consequent dissolution of carbonate in rhyodacitic partial melt. In the Paleo-NeoProterozoic Earth, on the other hand, the hotter slab-surface temperatures at subduction zones likely caused efficient liberation of carbon from subducting sedimentary carbonates. Deeply subducted carbonated sediments, similar to HPLC1, upon encountering a hotter mantle geotherm in the oceanic province can release carbon-bearing melts with high K₂O, K₂O/TiO₂, and high silica, and can contribute to EM2-type ocean island basalts. Generation of EM2-type mantle end-member may also occur through metasomatism of mantle wedge by carbonated metapelite plume-derived partial melts.     

The problem of CO2 recycling in subduction zones

In connection with the imbalance between the carbon dioxide absorbed in the carbonate minerals in subduction zones and that emitted during island arc volcanism, the problem of redistribution the rest of the CO₂ from the plate to the mantle arises. Experimental modeling of the interaction between model analogs of the oceanic crust and the mantle wedge was performed for two systems: glaucophane schist-olivine and glaucophane schist-silicate marble-olivine under high pressure and varying temperature conditions that correspond to the oceanic crust-mantle transition zone in the subduction zone beneath the Cascade Mountains. The experiments carried out showed that there is a possibility that intensive CO₂ degassing occurs from the plate in the forearc area, which is controlled by carbonate dissolution in an aqueous fluid. As a result of this process, carbonates can redeposit in the form of magnesite in the overlying mantle rocks according to the vertical temperature gradient. It is assumed that part of the carbon dioxide bonded in mantle rocks can be transported by viscous flow from the forearc area to the deep mantle horizons within the field of the thermodynamic stability of magnesite. In addition, the experiments we carried out showed that between marble and olivine in the ultrahigh pressure a metasomatic column consisting of four zones develops: Fe-Mg-Ca carbonate|dolomite|diopside|magnesite.     

Distinctive petrological, geochemical, and geodynamic features of subduction-related magmatism

Geological-petrological and geochemical data on subduction-related magmatism (including the volumes and compositions of the corresponding magmatic series) are compared to the results of experiments and numerical simulation. The subduction zone is subdivided into five depth sectors and volcanic zones I, II, and III: 1 is the accretionary wedge that controls the geodynamic stability of subduction; 2 is the sector of dehydration and fluid filtration; 3 is the zone of eclogitization and initial partial melting in the slab above which boninite volcanic zone I is formed during early stages; 4 is the main zone of melting of the sedimentary-basite layer and the development of volcanic zone II with the predominance of andesites; and 5 is the zone of higher degree melting, above which volcanic zone III (basaltic andesite and alkali basalt) is formed. The criterion of volcanism intensity, which was obtained within the scope of the melting model, is proportional to the subduction velocity and the thickness of the melting zone, and the distance between the groups of volcanics along the subduction zone is 75–100 km, at a thickness of the melting zone of 15–20 km. The calculated isotherm of 600°C, which controls the stability of serpentine and chlorite, is not identified at depth above 150 km, and this is confirmed by the composition and P-T conditions of the high-pressure rocks (containing diamond and coesite), which were brought from depths of 150–200 km in subduction zones. Seismic sections constructed with regard for the amplitude characteristics of seismic waves show two melting zones (“wet” melting at a depth of 100–200 km and “dry” melting at a depth of 150–200 km) and a complicated thermal structure of the suprasthenospheric wedge, which can include slant magma conduits. The mineralogical and geochemical features of arc magmatic series are formed at a decisive role of an H₂O-CO₂ fluid and an elevated oxidation potential. The predominant buffer minerals are as follows: garnet in the slab melting zone; magnetite, Ca-pyroxene, and amphibole in intermediate magmatic chambers; and amphibole, protoenstatite-bronzite (in place of olivine), and Cr-spinel (in place of magnetite) for boninite series generated in a “hot” asthenospheric wedge at interaction with fluids or water-rich melts. Actively disputable problems are the interactions scale of melts and fluids generated in a subduction zone with a “hot” mantle wedge, the possibility of transporting water-rich minerals deep into the mantle (to depths greater than 150 km), and the evolution of the scale at which young continental crust is generated by subduction melts.