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。     

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。     

俯冲带变质过程中的含碳流体

俯冲带含碳岩石通过俯冲过程的变质反应生成了含碳水流体、富硅酸盐的超临界流体和含碳熔体。不同类型流体的形成与岩石成分和岩石经历的温压条件相关。岩石中碳酸盐矿物脱碳反应的温压条件取决于岩石起初的流体成分:有水存在时,反应发生在低温条件下。在高压条件下,碳酸盐矿物在水或含盐水流体的溶解是生成含碳流体重要的机制,其导致的碳迁移作用可能超过脱碳变质反应的作用。高温条件下,含碳岩石的部分熔融可以生成含碳的熔体,这在热俯冲环境和俯冲带岩石底辟到上覆地幔的情况下是碳迁移重要载体。富硅酸盐的超临界流体可能是在第二临界端点上形成的超临界流体,目前在超高压岩石中观察到的非花岗质成分的多相固体包裹体被认为是这种流体结晶的产物,然而对其理解尚存在很多问题,需要进一步的实验研究。地表含碳岩石在俯冲带被带到深部,俯冲带地温特征的不同导致了不同类型含碳流体的形成,这些流体运移至上覆地幔引起岩石部分熔融产生含碳的岛弧岩浆,岩浆喷出到地表释放了其中的碳,这构成了俯冲带-岛弧系统的碳循环。     

柴达木北缘超高压变质带中的岛弧火山岩

青藏高原北部柴北缘发育一套与超高压变质带并行的早古生代岛弧火山岩带,岛弧火山岩以玄武岩类为主,包括一些中酸性岩类,岩石以普遍遭受绿片岩相蚀变为特征,区别于该地区普遍遭受角闪岩相区域变质的元古代的基性火山岩。该早古生代的岛孤火山岩显示三组地球化学特征:①VTG-Ⅰ,岛弧拉斑玄武岩(IAT);②VTG-Ⅱ,高Al次钙碱性-碱性过渡型玄武岩;③VTG-Ⅲ,较N-MORB更亏损的拉斑玄武岩(异常MORB)。研究认为前两组火山岩是成熟岛弧两个发育阶段的特征性产物:洋壳俯冲到陆壳的初用,由俯冲洋壳和地幔楔的部分熔融形成岛弧拉斑玄武岩(IAT),随着俯冲板块的速度加快和岛弧周围地壳的加厚,则形成钙碱性玄武岩(CA)、高Al玄武岩。第三组火山岩形成于弧间盆地,由亏损的地幔楔高度部分熔融形成比N-MORB亏损的的火山岩(异常MORB)。岛弧火山岩的锆石LA-ICP-MS法U-Pb年龄为514.2±8.5 Ma,说明柴北缘在早古生代发生过洋壳向陆壳的俯冲作用。鉴于该地区代表陆-陆俯冲作用的柴北缘超高压变质岩石也是形成于早古生代(494Ma),认为陆-陆俯冲作用发生在洋-陆俯冲作用之后,二者时间和空间相伴随。     

碳酸盐化榴辉岩的岩石学研究进展

碳循环进入地幔中主要是通过大洋板块俯冲作用完成的,再通过火山去气作用释放出来,以维持大气中CO2的平衡。洋壳主要由玄武岩组成,一般经热液改造后的洋壳含有一定数量的碳酸盐(质量分数大约为3％),而这些以脉或角砾形式存在的碳酸盐是碳沉淀的一个巨大储库。这些碳酸盐化的玄武岩在俯冲带背景下经历高压变质作用,相应地形成了碳酸盐化榴辉岩。碳酸盐化榴辉岩的部分熔融形成的熔体和气体对于弧岩浆的生成、CO2去气都有非常重要的作用,从而对整个碳循环研究具有重要的意义。文中较全面地总结了近年来,在不同的超高压变质地区发现的碳酸盐化榴辉岩的岩石学和野外产状特征,对比经热液改造的玄武岩 碳酸盐体系的高温高压岩石学研究取得的进展,明确了在俯冲带变质过程中碳酸盐与榴辉岩质硅酸盐体系是如何发生变化的,并对于NCFMASH+CO2体系的热力学相平衡计算的研究进展展开了讨论,对于探讨碳的深部循环过程具有重要意义。     

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%。     

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.      

金属硫化物对俯冲洋壳高压变质作用的制约

<正>硫化物作为主要的金属元素赋存形式,是世界上主要矿产资源的开采矿物,因此在地质学研究中具有重要的经济学意义。大洋中脊玄武岩在形成过程中可含有少量的硫,另外,洋底热液蚀变过程中,硫会被带入到表层洋壳中形成金属硫化物(Alt et al.,1989)。俯冲带是全球最大的物质循环系统,洋壳可携带这些金属硫化物进入俯冲带并遭受高压—超高压变质作用。因此,在全球多个高压洋壳变质带中,金属硫化物都作为一个常见的副矿物产出于榴辉岩及相关岩石中,如在西Alps(Barnicoat and Fry,1986;     

洋壳深俯冲过程中碳酸盐的稳定性与金刚石成因初探

<正>深部碳循环是全球碳循环体系的重要组成部分,它是指伴随洋壳俯冲作用,大量含碳矿物被带入地球深部,经历一系列地质作用后,再通过岩浆和火山作用将碳带回地表的过程。地震学、地质学和地球化学等研究表明,洋壳能够俯冲到地幔过渡带底部、甚至核幔边界;最近,Walter等人(2011)对产自巴西Juina金伯利矿床的"超深"金刚石进行了研究,发现该金刚石含有源自地表的轻碳同位素,而且其包裹体中含有洋壳玄武岩组分。这一发现有力地证实了碳循环可以深入下地幔1400 km[1]。     

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。     

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.     

Effects of Spin Transition and Cation Substitution on the Optical Properties and Iron Partitioning in Carbonate Minerals

The high-pressure behavior of deep carbonate dictates the state and dynamics of oxidized carbon in the Earth’s mantle, playing a vital role in the global carbon cycle and potentially influencing long-term climate change. Optical absorption and Raman spectroscopic measurements were carried out on two natural carbonate samples in diamond-anvil cells up to 60 GPa. Mg-substitution in high-spin siderite FeCO₃ increases the crystal field absorption band position by approximately 1000 cm     

Fate of carbonates within oceanic plates subducted to the lower mantle, and a possible mechanism of diamond formation

We report on high-pressure and high-temperature experiments involving carbonates and silicates at 30–80 GPa and 1,600–3,200 K, corresponding to depths within the Earth of approximately 800–2,200 km. The experiments are intended to represent the decomposition process of carbonates contained within oceanic plates subducted into the lower mantle. In basaltic composition, CaCO₃ (calcite and aragonite), the major carbonate phase in marine sediments, is altered into MgCO₃ (magnesite) via reactions with Mg-bearing silicates under conditions that are 200–300°C colder than the mantle geotherm. With increasing temperature and pressure, the magnesite decomposes into an assemblage of CO₂ + perovskite via reactions with SiO₂. Magnesite is not the only host phase for subducted carbon—solid CO₂ also carries carbon in the lower mantle. Furthermore, CO₂ itself breaks down to diamond and oxygen under geotherm conditions over 70 GPa, which might imply a possible mechanism for diamond formation in the lower mantle.     

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.     

Hydrothermal carbonates in altered wall rocks at the Uwamuki Kuroko deposits, Japan

Magnesite, siderite and dolomite are characteristic alteration minerals occurring in Miocene hanging wall rocks of dacitic composition which host the Kuroko orebodies. These carbonates generally occur in a more stratigraphically upper horizon than chlorite alteration zone surrounding the orebodies. The Mg/(Mg+Fe) ratios of the carbonates decrease from the central alteration zone to marginal zone. The Mg/(Mg+Fe) ratios of carbonates and chlorite positively correlate. The δ¹⁸O and δ¹³C values of magnesite, siderite and dolomite positively correlate with each other and lie between the igneous and marine carbonate values. The petrographic, isotopic and fluid inclusion characteristics and thermochemical modelling calculations indicate that magnesite and dolomite formed in the central zone close to the orebodies due to the interaction of hydrothermal solutions with the biogenic marine carbonates. Calcite formed further from the orebodies from hydrothermal fluids which did not contain a biogenic marine carbon component. The compositional and textural relationships indicate that superimposed alterations (chlorite alteration and carbonate alteration) occurred in hanging wall rocks. The mode of occurrences and the Mg/(Mg+Fe) ratios of magnesite and dolomite occurring in hanging wallrocks are useful in the exploration for concealed volcanogenic massive sulfide-sulfate deposits. Received: 9 September 1997 / Accepted: 23 September 1997     

Slab decarbonation and CO2 recycling in the Southwestern Colombian volcanic arc

The contribution of subducted carbonate sediments to the genesis of the Southwestern Colombian arc magmas was investigated using a comprehensive petrography and geochemical analysis, including determination of major and trace element contents and Sr, Nd, Hf and Pb isotope compositions. These data have been used to constrain the depth of decarbonation in the subducted slab, indicating that the decarbonation process continues into the sub-arc region, and ultimately becomes negligible in the rear arc. We propose on the basis of multi-isotope approach and mass balance calculations, that the most important mechanism to induce the slab decarbonation is the infiltration of chemically reactive aqueous fluids from the altered oceanic crust, which decreasingly metasomatize the mantle wedge, triggering the formation of isotopically different primary magmas from the volcanic front (VF) with relatively high ¹⁷⁶Hf/¹⁷⁷Hf, high ⁸⁷Sr/⁸⁶Sr, negative values of εNd and lower Pb isotopes compared to the rear arc (RA).The presence of more aqueous fluids at the volcanic front may increase the degree of decarbonation into carbonate-bearing lithologies. Moreover, with increasing pressure and temperature in the subduction system, the decrease in dehydration of the slab, leads to cessation of fluid-induced decarbonation reactions at the rear arc. This development allows the remaining carbonate materials to be recycled into the deep mantle.     

Carbonate Minerals in the Warrawoona Group, Pilbara Craton: Implications for Continental Crust, Life, and Global Carbon Cycle in the Early Archean

Abstract: The occurrences of the Early Archean carbonate minerals are compiled and their precipitation processes are investigated for the Warrawoona Group, Pilbara Craton. Sedimentary carbonate rocks such as limestone and dolostone are very rare, and only a small amount of sedimentary carbonate minerals are sometimes contained in the hydrothermal bedded chert, implying that a sink of CO₂ was minor in the Early Archean sediments. Moreover, it is very likely that the activity of cyanobacteria forming stromatolites was considerably low in the Early Archean. Microfossils and carbonaceous matter in the hydrothermal cherts are probably derived from a non-photosynthetic microorganisms related to the seafloor hydrothermal activity. Their preservation in sediments may play a very minor role in carbon sink of the Earth's surface.
On the other hand, carbonatized volcanic rocks subjected to seafloor hydrothermal alteration occur ubiquitously in the Early Archean greenstone belts such as the Warrawoona Group, suggesting that the hydrothermally altered oceanic crust had large amounts of CO₂ as carbonate minerals. Global carbon cycle in the Early Archean is considered to have been controlled by the intense seafloor hydrothermal alteration. Large amounts of CO₂ were sunk into the oceanic crust by the alteration. The carbonatized oceanic crust was partly accreted to the continents and/or island–arcs, and partly subducted into the mantle without decomposition. Significant amounts of carbonate minerals in the carbonatized oceanic crust were very likely to store in the accretionary prisms and mantle, consequently giving rise to a decrease of atmospheric and oceanic CO₂.     

X射线粉晶衍射仪在大理岩鉴定与分类中的应用

大理岩主要有方解石大理岩、白云石大理岩和菱镁矿大理岩三种。以往大理岩是依据偏光显微镜下观察岩石结构构造及矿物成分进行分类定名,由于方解石、白云石、菱镁矿都属于三方晶系,具有闪突起、高级白干涉色、一轴晶负光性和菱形解理等相同晶体光学特征,偏光显微镜下区分十分困难。为了准确鉴定大理岩中碳酸盐矿物种类及其相对含量,本文利用岩石薄片偏光显微镜和X射线粉晶衍射技术对32件大理岩岩石样品进行分析测试。岩石薄片鉴定结果表明:大理岩造岩矿物主要有方解石、白云石、菱镁矿、石英、斜长石、白云母、黑云母、绿泥石、黏土和金属矿物。根据岩石结构构造及矿物组分特征,可把32件大理岩样品划分为方解石大理岩、长英质方解石大理岩、石英绿泥白云石大理岩、白云石大理岩、云英质白云石大理岩和菱镁矿大理岩等15个类型。X射线粉晶衍射分析表明:大理岩造岩矿物主要有方解石、白云石、菱镁矿、石英、斜长石、钾长石、云母、绿泥石、滑石和蒙脱石。综合分析认为:岩石薄片偏光显微镜鉴定技术很难区分方解石、白云石和菱镁矿等碳酸盐矿物,以及细小的石英、钾长石和斜长石、滑石和白云母等鳞片状硅酸盐矿物;X射线粉晶衍射分析技术不仅能准确检测出大理岩中方解石、白云石和菱镁矿等碳酸盐矿物种类及相对含量(方解石、白云石和菱镁矿的X射线衍射主峰有明显差异,d值分别为0.303 nm、0.288 nm和0.274 nm),而且能够有效鉴别岩石中粉砂级斜长石、钾长石与石英(三种矿物的X射线衍射主峰d值分别为0.319 nm、0.324 nm、0.334 nm);且能区分蒙脱石、绿泥石、云母和滑石等层状硅酸盐矿物(四种硅酸盐矿物的X射线衍射主峰d值分别为1.400 nm、0.705 nm、0.989 nm、0.938 nm)。综合岩石薄片偏光显微镜鉴定和X射线粉晶衍射分析结果,最终确定32件大理岩样品划分为22个岩石类型。研究认为:仅根据岩石薄片偏光显微镜鉴定或X射线粉晶衍射技术其中一种方法不能准确鉴定大理岩岩石,应将大理岩岩石野外观察、岩石薄片鉴定和X射线粉晶衍射技术结合起来,才能准确确定大理岩岩石类型。