A chlorine isotope study of DSDP/ODP serpentinized ultramafic rocks: Insights into the serpentinization process

Eight DSDP/ODP cores were analyzed for major ion concentrations and δ³⁷Cl values of water-soluble chloride (δ³⁷Cl_WSC) and structurally bound chloride (δ³⁷Cl_SBC) in serpentinized ultramafic rocks. This diverse set of cores spans a wide range in age, temperature of serpentinization, tectonic setting, and geographic location of drilled serpentinized oceanic crust. Three of the cores were sampled at closely spaced intervals to investigate downhole variation in Cl concentration and chlorine isotope composition.The average total Cl content of all 86 samples is 0.26 ± 0.16 wt.% (0.19 ± 0.10 wt.% as water-soluble Cl (X_WSC) and 0.09 ± 0.09 wt.% as structurally bound Cl (X_SBC)). Structurally bound Cl concentration nearly doubles with depth in all cores; there is no consistent trend in water-soluble Cl content among the cores. Chlorine isotope fractionation between the structurally bound Cl⁻ site and the water-soluble Cl⁻ site varies from − 1.08‰ to + 1.16‰, averaging to + 0.21‰. Samples with negative fractionations may be related to reequilibration of the water-soluble chloride with seawater post-serpentinite formation. Six of the cores have positive bulk δ³⁷Cl values (+ 0.05‰ to + 0.36‰); the other two cores (173-1068A (Leg-Hole) and 84-570) have negative bulk δ³⁷Cl values (− 1.26‰ and − 0.54‰). The cores with negative δ³⁷Cl values also have variable Cl⁻ / SO₄² ratios, in contrast to all other cores. The isotopically positive cores (153-920D and 147-895E) show no isotopic variation with depth; the isotopically negative core (173-1068A) decreases by ∼1‰ with depth for both the water-soluble and structurally bound Cl fractions.Non-zero bulk δ³⁷Cl values indicate Cl in serpentinites was incorporated during original hydration and is not an artifact of seawater infiltration during drilling. Cores with positive δ³⁷Cl values are most likely explained by open system fractionation during hydrothermal alteration, with preferential incorporation of ³⁷Cl from seawater into the serpentinite and loss of residual light Cl back to the ocean. Fluid / rock ratios were probably low as evidenced by the presence of water-soluble salts. The two isotopically negative cores are characterized by a thick overlying sedimentary package that was in place prior to serpentinization. We believe the low δ³⁷Cl values of these cores are a result of hydration of ultramafic rock by infiltrating aqueous pore fluids from the overlying sediments. The resulting serpentinites inherit the characteristic negative δ³⁷Cl values of the pore waters. Chlorine stable isotopes can be used to identify the source of the serpentinizing fluid and ultimately discern chemical and tectonic processes involved in serpentinization.     

Formation and alteration of plagiogranites in an ultramafic-hosted detachment fault at the Mid-Atlantic Ridge (ODP Leg 209)

We examined small-scale shear zones in drillcore samples of abyssal peridotites from the Mid-Atlantic Ridge. These shear zones are associated with veins consisting of chlorite + actinolite/tremolite assemblages, with accessory phases zircon and apatite, and they are interpreted as altered plagiogranite melt impregnations, which originate from hydrous partial melting of gabbroic intrusion in an oceanic detachment fault. Ti-in-zircon thermometry yields temperatures around 820°C for the crystallization of the evolved melt. Reaction path modeling indicates that the alteration assemblage includes serpentine of the adjacent altered peridotites. Based on the model results, we propose that formation of chlorite occurred at higher temperatures than serpentinization, thus leading to strain localization around former plagiogranites during alteration. The detachment fault represents a major pathway for fluids through the oceanic crust, as evidenced by extremely low δ¹⁸O of altered plagiogranite veins (+3.0–4.2‰) and adjacent serpentinites (+ 2.6–3.7‰). The uniform oxygen isotope data indicate that fluid flow in the detachment fault system affected veins and adjacent host serpentinites likewise. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

藏北昂吾地区超基性岩的蛇纹石化和磁铁矿化过程及影响因素

班公湖-怒江缝合带广泛分布超基性岩及蛇纹石化超基性岩,已有研究表明它们与区域成矿关系密切,其蛇纹石化过程使一些元素活化并具有一定的成矿潜力。位于班-怒带中段的昂吾地区蛇纹石化超基性岩主要矿物成分有橄榄石、单斜辉石、铬铁矿、利蛇纹石、磁铁矿和绿泥石等,原岩恢复表明该超基性岩为单辉橄榄岩。镜下鉴定、背散射电子图像、能谱成分分析和电子探针分析结果显示单辉橄榄岩的蛇纹石化及蚀变过程可分为三个阶段:(Ⅰ)以形成相对富铁蛇纹石(Mg#=75～88)为主,基本无磁铁矿析出;(Ⅱ)形成相对富镁的蛇纹石(Mg# 90),析出磁铁矿;(Ⅲ)蛇纹石进一步蚀变成绿泥石。热力学模拟及多组分矿物相平衡图表明,在蛇纹石化过程中,昂吾地区超基性岩中的辉石脱硅致使反应体系SiO_2活度升高,限制了磁铁矿的生成。同时也发现,在利蛇纹石稳定存在的温度区间内(100～300℃),本研究的蛇纹石化体系温度倾向高值区,不利于磁铁矿的析出。进而探讨了原岩成分、反应体系SiO_2活度及温度等因素对蛇纹石化过程中磁铁矿析出的影响。本研究有助于理解班-怒带内超基性岩的蛇纹石化过程及磁铁矿化机制。     

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。     

橄榄岩蛇纹石化过程中氢气和烷烃的形成

蛇纹石化过程中形成氢气、烷烃和有机酸,为海底热液区生命活动提供物质和能量来源,可能对地球和其他行星早期生命起源和演化有重要影响。目前关于蛇纹石化过程中氢气和烷烃形成的研究大多以橄榄石为初始物,且温度和压力较低(≤300℃,500bar)。本研究通过一系列的水热实验,研究300~500℃、1~3kbar时橄榄石、斜方辉石、单斜辉石、橄榄岩、玄武岩以及玄武岩与橄榄岩混合物发生蛇纹石化反应后氢气和烷烃的生成。300℃、3kbar时,橄榄石蛇纹石化后产生的氢气远大于辉石蚀变后产生氢气的量。随着温度的增加,400~500℃、3kbar时,橄榄石蚀变程度极低,产生氢气的量低于斜方辉石。单斜辉石实验后没有发生蚀变,不产生氢气和烷烃。400~500℃、3kbar时,橄榄岩蛇纹石化后产生的氢气和烷烃远高于橄榄石、斜方辉石和单斜辉石。玄武岩蛇纹石化后生成氢气和甲烷的量低于橄榄岩,但与玄武岩和橄榄岩混合物相当。这是因为玄武岩的单斜辉石蚀变后形成富铁的透辉石(~8.1%FeO),透辉石的Fe以Fe2+为主,这降低了Fe3+和氢气的量。以上表明,橄榄岩的蛇纹石化不同于橄榄石和斜方辉石。不仅是海底热液蚀变产生氢气和甲烷,洋壳俯冲过程中地幔楔橄榄岩蛇纹石化也会生成氢气和甲烷,但由于洋壳玄武岩的加入,氢气和甲烷的量会远小于橄榄岩蚀变时的量。     

Structural architecture of the ocean–continent boundary at an oblique transform margin through deep-imaging seismic interpretation and gravity modelling: Equatorial Guinea, West Africa

Along the Rio Muni transform margin, the transition from continental to oceanic crust occurs across a region of approximately 75-km width. The crust in this transition region, termed proto-oceanic crust (POC), is neither purely oceanic nor continental in composition and structure. Improved seismic reflection images from the PROBE deep-imaging dataset, combined with gravity modelling, have shed new light on the structural architecture of the margin and the composition of the POC. On these newly migrated seismic reflection sections, four fracture zones associated with large steps in the Moho are identified, splitting the POC into three segments. Models in which these segments are composed of oceanic or stretched continental crust do not provide satisfactory predictions of the gravity anomaly. A model of serpentinized peridotite for two segments of POC, with the third segment composed of oceanic crust in between, does satisfy the observed gravity anomaly. Three alternative geological scenarios are proposed to explain the segmentation and composition of the POC: (a) serpentinized upper mantle becoming unroofed and emplaced at basement surface level along detachment surfaces confined to discrete segments by the fracture zones, (b) oblique-slip on transform faults that allow the circulation of water into the mantle and emplacement of serpentinized upper mantle material; or (c) intense faulting of anomalous oceanic crust as a result of magma depletion allowing hydrothermal circulation and the emplacement of serpentinized peridotites.     

异剥钙榴岩及其岩石成因意义

异剥钙榴岩作为一种特殊的交代变质岩,绝大多数与超镁铁岩的蛇纹石化有关,是超镁铁岩蛇纹石化过程中所产生的富钙流体对与其伴生的相关岩石进行钙交代的结果。蛇纹石化的超镁铁岩或为蛇绿岩的端员组分,或为太古代绿岩带、阿拉斯加型和阿尔卑斯型等其它成因类型的超镁铁岩。它们多为纯橄榄岩、方辉橄榄岩和辉石岩等。异剥钙榴岩的形成主要取决于超镁铁岩的蛇纹石化作用和钙交代程度,而与超镁铁岩的成因类型、构造属性和时代归属没有多大的关系。那种将异剥钙榴岩片面地看成蛇绿岩的组成部分或者作为鉴别蛇绿岩辅助标志的观点需要改正。     

Titan's methane cycle

Methane is key to sustaining Titan's thick nitrogen atmosphere. However, methane is destroyed and converted to heavier hydrocarbons irreversibly on a relatively short timescale of approximately 10-100 million years. Without the warming provided by CH₄-generated hydrocarbon hazes in the stratosphere and the pressure induced opacity in the infrared, particularly by CH₄-N₂ and H₂-N₂ collisions in the troposphere, the atmosphere could be gradually reduced to as low as tens of millibar pressure. An understanding of the source-sink cycle of methane is thus crucial to the evolutionary history of Titan and its atmosphere. In this paper we propose that a complex photochemical-meteorological-hydrogeochemical cycle of methane operates on Titan. We further suggest that although photochemistry leads to the loss of methane from the atmosphere, conversion to a global ocean of ethane is unlikely. The behavior of methane in the troposphere and the surface, as measured by the Cassini-Huygens gas chromatograph mass spectrometer, together with evidence of cryovolcanism reported by the Cassini visual and infrared mapping spectrometer, represents a “methalogical” cycle on Titan, somewhat akin to the hydrological cycle on Earth. In the absence of net loss to the interior, it would represent a closed cycle. However, a source is still needed to replenish the methane lost to photolysis. A hydrogeochemical source deep in the interior of Titan holds promise. It is well known that in serpentinization, hydration of ultramafic silicates in terrestrial oceans produces H_2(aq), whose reaction with carbon grains or carbon dioxide in the crustal pores produces methane gas. Appropriate geological, thermal, and pressure conditions could have existed in and below Titan's purported water-ammonia ocean for “low-temperature” serpentinization to occur in Titan's accretionary heating phase. On the other hand, impacts could trigger the process at high temperatures. In either instance, storage of methane as a stable clathrate-hydrate in Titan's interior for later release to the atmosphere is quite plausible. There is also some likelihood that the production of methane on Titan by serpentinization is a gradual and continuous on-going process.     

Reactions between olivine and CO2-rich seawater at 300 °C: Implications for H2 generation and CO2 sequestration on the early Earth

To understand the influence of fluid CO₂ on ultramafic rock-hosted seafloor hydrothermal systems on the early Earth, we monitored the reaction between San Carlos olivine and a CO₂-rich NaCl fluid at 300 °C and 500 bars. During the experiments, the total carbonic acid concentration (ΣCO₂) in the fluid decreased from approximately 65 to 9 mmol/kg. Carbonate minerals, magnesite, and subordinate amount of dolomite were formed via the water-rock interaction. The H₂ concentration in the fluid reached approximately 39 mmol/kg within 2736 h, which is relatively lower than the concentration generated by the reaction between olivine and a CO₂-free NaCl solution at the same temperature. As seen in previous hydrothermal experiments using komatiite, ferrous iron incorporation into Mg-bearing carbonate minerals likely limited iron oxidation in the fluids and the resulting H₂ generation during the olivine alteration. Considering carbonate mineralogy over the temperature range of natural hydrothermal fields, H₂ generation is likely suppressed at temperatures below approximately 300 °C due to the formation of the Mg-bearing carbonates. Nevertheless, H₂ concentration in fluid at 300 °C could be still high due to the temperature dependency of magnetite stability in ultramafic systems. Moreover, the Mg-bearing carbonates may play a key role in the ocean-atmosphere system on the early Earth. Recent studies suggest that the subduction of carbonated ultramafic rocks may transport surface CO₂ species into the deep mantle. This process may have reduced the huge initial amount of CO₂ on the surface of the early Earth. Our approximate calculations demonstrate that the subduction of the Mg-bearing carbonates formed in komatiite likely played a crucial role as one of the CO₂ carriers from the surface to the deep mantle, even in hot subduction zones.     

The production of iron oxide during peridotite serpentinization: Influence of pyroxene

Serpentinization produces molecular hydrogen(H2)that can support communities of microorganisms in hydrothermal fields;H2 results from the oxidation of ferrous iron in olivine and pyroxene into ferric iron,and consequently iron oxide(magnetite or hematite)forms.However,the mechanisms that control H2 and iron oxide formation are poorly constrained.In this study,we performed serpentinization experiments at 311℃ and 3.0 kbar on olivine(with 5% pyroxene),orthopyroxene,and peridotite.The results show that serpentine and iron oxide formed when olivine and orthopyroxene individually reacted with a saline starting solution.Olivine-derived serpentine had a significantly lower FeO content(6.57±1.30 wt.%)than primary olivine(9.86 wt.%),whereas orthopyroxene-derived serpentine had a comparable FeO content(6.26±0.58 wt.%)to that of primary orthopyroxene(6.24 wt.%).In experiments on peridotite,olivine was replaced by serpentine and iron oxide.However,pyroxene transformed solely to serpentine.After 20 days,olivine-derived serpentine had a FeO content of 8.18±1.56 wt.%,which was significantly higher than that of serpentine produced in olivine-only experiments.By contrast,serpentine after orthopyroxene had a slightly higher FeO content(6.53±1.01 wt.%)than primary orthopyroxene.Clinopyroxene-derived serpentine contained a significantly higher FeO content than its parent mineral.After 120 days,the FeO content of olivine-derived serpentine decreased significantly(5.71±0.35 wt.%),whereas the FeO content of orthopyroxene-derived serpentine increased(6.85±0.63 wt.%)over the same period.This suggests that iron oxide preferentially formed after olivine serpentinization.Pyroxene in peridotite gained some Fe from olivine during the serpentinization process,which may have led to a decrease in iron oxide production.The correlation between FeO content and SiO_2 or AI_2 O_3 content in olivine-and orthopyroxene-derived serpentine indicates that aluminum and silica greatly control the production of iron oxide.Based on our results and data from natural serpentinites reported by other workers,we propose that aluminum may be more influential at the early stages of peridotite serpentinization when the production of iron oxide is very low,whereas silica may have a greater control on iron oxide production during the late stages instead.