铁橄榄石高温高压流变性的实验研究

通过高温高压实验研究了铁橄榄石集合体的流变性.首先,利用高精度的Paterson气体介质变形装置对铁橄榄石集合体Fe2SiO4进行了高温三轴压缩蠕变试验.变形试验条件为:温度1273～1423K,围压300MPa,差应力10～250MPa,应变率10-7～10-4s-1,试件的最大变形量不超过20%.利用三维非线性拟合方法对蠕变试验数据进行分析,得到铁橄榄石集合体的微观变形机制为扩散域和位错域,扩散域的应力指数为1左右.位错蠕变域中,干燥铁橄榄石集合体的应力指数为5.4.活化能为781kJ/mol;含水铁橄榄石集合体的应力指数为3.4,活化能为516kJ/mol.实验结果表明,含水时铁橄榄石的流变强度比干燥时小一个数量级.将实验结果与铁橄榄石单晶的强度进行对比,发现铁橄榄石集合体的流变强度比铁橄榄石单晶的强度高.从而得到了铁橄榄石集合体高温高压流变性(强度)的初步试验结果.     

橄榄石水溶性与含铁量相关性的实验研究

本文首次报导了含铁量不同的橄榄石单晶在不同温压条件下水溶性的试验研究结果。橄榄石单晶试件在300MPa静水压和1000℃至1300℃的温度条件下进行热压，每隔50℃进行一组试验，氧逸度被控制在Ni/NiO水平上。对热压后试件的抛光无包裹体区域做了显微红外光谱分析，红外光束平行于试件的[010]方向，最小直径为15－25μm。分析结果表明，在实验温压范围内，橄榄石中的水含量随铁含量的增加而增加。对于同样铁含量的橄榄石，则随湿度的增加，橄榄石的水含量也增加。最后，本文就实验结果对地幔动力学过程的启示进行了简单的讨论。     

压力对橄榄石流变性的影响

本文给出细粒橄榄石集合体在位错蠕变域中压力效应的实验结果。对干燥、人工合成的橄榄石集合体进行了三轴压缩实验,试验在一台高分辨率的气体介质试验机上进行。典型的常载荷蠕变试验温度为1473K或1523K,围压为400MPa、200MPa、400MPa、200MPa。当差压力和温度给定时,试件在400MPa围压下,变形速度较200MPa围压下要慢。实验得出的细粒橄榄石集合体在位错蠕变域中的活化体积值为(23±3)×10~(-6)m~3/mol。最后,对实验结果在地幔动力学中的应用进行了讨论。     

8块新发现的西北非球粒陨石的矿物岩石学特征

为了解不同种类小行星母体的起源与演化信息,选取8块近期在西北非地区发现的未经过详细研究的球粒陨石,利用扫描电子显微镜观察其显微结构,利用能谱仪及电子探针测试样品的成分。结果显示,NWA 7613与NWA 8340为CV3_(oxA)型陨石,另外5块普通球粒陨石的热变质程度变化更为广泛且球粒中橄榄石铁含量更高。NWA 7613(LL3)球粒中橄榄石CaO含量稍高(0.08%~0.24%),高于平衡型普通球粒陨石(小于0.05%)。NWA 6468(R4)与普通球粒陨石具有相似的岩相结构,但不发育铁镍金属,且橄榄石铁含量(Fa_(35.9~42.1))及镍含量(平均含0.23%)更高,是强氧化环境下的产物。NWA 7251(Limpact melt)具有特殊的火成结构,是大规模灾难性撞击事件产物,橄榄石铁指数(Fa_(21.4~26.7))与L型球粒陨石的橄榄石成分一致,但CaO含量(0.16%~0.31%)高于平衡型普通球粒陨石。     

富铁橄榄石的高温变形实验研究

利用高精度Paterson气体介质变形装置对(Mg0.5,Fe0.5)2SiO4和(Mg0.7,Fe0.3)2SiO4橄榄石集合体进行了高温三轴压缩变形试验。首先用人工合成了纯铁橄榄石Fe2SiO4,然后用合成的纯铁橄榄石与天然圣卡罗橄榄石按一定比例混合烧结合成了含铁量分别为50％和30％的富铁橄榄石集合体Fo50和Fo70。三轴压缩蠕变变形试验在温度1223-1473 K和围压 300 MPa的条件下进行,差应力为10-300 MPa,应变率为10-7-10-4s-1,每个试件的最大变形量为20％．利用三维非线性方法对蠕变数据进行拟合,得出的流动律中,Fo50应力指数为4．1,活化能为499kJ／mol;Fo70应力指数为4．3,活化能为510kJ／ mol。将实验结果与Fo90圣卡罗橄榄石集合体的强度进行对比,发现含铁量的增加使橄榄石的强度明显下降,Fo50橄榄石集合体比Fo70的粘性低一个量级,Fo70比Fo90的粘性低一个量级。从而得到了含铁量对橄榄石的粘性(强度)影响的初步试验结果。     

含水对富铁橄榄石流变性的影响

橄榄石是下地壳上地幔最丰富的造岩矿物,橄榄石集合体的高温高压流变性对地幔动力学过程有着很大的影响。以往对橄榄石单晶和集合体进行过的流变性实验研究,涉及了温度、压力、氧逸度、含铁量以及含水等因素的影响,本文研究了含水对富铁橄榄石集合体流变性能的影响,首先,利用高精度 Paterson 气体介质变形装置对含水富铁橄榄石集合体(Mg_(0.9),Fe_(0.1))_2SiO_4、(Mg_(0.7),Fe_(0.3))_2SiO_4和(Mg_(0.5),Fe_(0.5))_2SiO_4进行了高温三轴压缩蠕变试验,变形试验条件为:温度1323～1473K,围压300MPa,差应力10～300MPa,应变率10~(-7)～10~(-4)s~(-1),每个试件的最大变形量为20%。利用三维非线性拟合方法对蠕变试验数据进行分析,结果表明,含水富铁橄榄石集合体的微观变形机制为扩散域和位错域,对三种铁含量,扩散域的应力指数为1。位错蠕变域中,Fo_(50)应力指教为3.8,活化能为444kJ/mol;Fo_(70)应力指数为3.7,活化能为479kJ/mol,Fo_(90)应力指数为3.6,活化能为514kJ/mol。将实验结果与不含水富铁橄榄石集合体的强度进行对比,发现含水使富铁橄榄石的强度明显下降,舍铁量相同时,含水橄榄石集合体的流变强度比干燥时小至少一个数量级。从而得到了含水对含铁量不同的橄榄石集合体粘性(强度)影响的初步试验结果。     

橄榄石集合体扭转大变形实验研究

对(Mg0.5,Fe0.5)2SiO4和(Mg0.7、Fe0.3)2SiO4橄榄石集合体进行了高温高压扭转大变形实验研究.试验在高精度和高分辨率Paterson气体介质变形试验机上进行,试验温度为1473K,围压为300MPa,应变率为10-4～10-5S-1,剪切应力为82～124MPa,剪切应变为～400%,将变形后试件沿轴向切开进行了显微结构分析,确定了不同纵截面上橄榄石的颗粒尺寸.由蠕变数据拟合出的流动律中,应力指数为与三轴压缩实验给出的应力指数吻合.利用EBSD方法分别对变形前后试件中橄榄石的晶格最优取向(LPO)进行了测定.在富铁橄榄石样品中观测到的最优晶格取向表明滑动属于(okl)[100]滑动系统.这个结果与Bystficky等人在Fo90种观测到的最优晶格取向特征是一致的.     

大变形橄榄石动态重结晶的实验观测研究

本文利用高温高压大变形扭转实验,对富铁橄榄石大变形情况下的动态重结晶和颗粒尺度变化的特点进行了实验观测分析.富铁橄榄石集合体由纯铁橄榄石Fa100和圣卡罗橄榄石Fa10混合物经人工合成得到,试件的几何形状为圆柱体,直径9.6mm,高度4.86mm.实验在常角速率条件下进行,温度为1473K,围压为300MPa,剪应力为72 ～ 99MPa,剪应变率为1.35×10-4～3.11×10-4s-1,累积剪应变为3.98.对变形后样品的微结构进行了光学和扫描电镜的观测分析,得到橄榄石颗粒随应变增加而产生动态重结晶的具体物理图像,由EBSD观测结果给出了晶格取向随外加应变增加而产生的变化过程,利用两种统计方法得到了颗粒尺寸随应变增加而变化的过程,探讨了橄榄石动态重结晶的微观机制.与已有三轴压缩、简单剪切以及圣卡罗橄榄石的扭转变形结果进行了对比分析,同时对实验结果在地球物理方面的应用进行了讨论.     

长江中下游典型火山盆地的水岩相互作用和金属矿床蚀变分带

长江中下游火山岩盆地中金属矿床和蚀变分带的的地球化学研究表明,它们具有内带深色蚀变带和外带浅色蚀变带,形成于600℃到100℃范围。两类蚀变带分界温度大致是300℃。大金属矿床蚀变分带剖面显示出热液系统存在有明显的温度梯度。通过与背景岩石(玄武岩石)对比研究表明,自下而上的不同蚀变岩石中主要元素含量显著变化,交代作用中的代出和代入元素在空间上是演化的。25~400℃和23MPa下矿物(钠长石、阳起石、透辉石、钙铁辉石)-H2O、岩石(玄武岩)-H2O反应的化学动力学实验表明,金属元素释放速率是温度的函数。在恒压升温过程中,从20℃到400℃,硅酸盐矿物、玄武岩中Si溶解速率不断上升;在300~350℃时,Si、Al溶解速率到最大数值。随后,温度再上升导致溶解速率下降。在300℃时,大部分矿物中Ca、Mg、Fe、Na溶解速率较高,溶液里的Ca/Si、Mg/Si、Fe/Si、Na/Si等都高于矿物中对应元素的计量比。矿物反应后的表面存在富集硅的淋失层,或有富硅铝矿物(粘土矿物)出现。在300℃时,Si溶解快于其他金属元素,溶液中金属元素与硅摩尔浓度比(Ca/Si、Mg/Si、Fe/Si、Na/Si)等都低于矿物中的计量比。矿物反应后的表面缺少硅的淋失层,或者有贫硅矿物和铁氧化物出现。作者还进行23~35MPa、20~550℃玄武岩与水反应实验。上述高温高压下矿物在水溶液中的溶解反应动力学实验和流体-玄武岩相互作用实验,对于理解金属矿床及蚀变分带形成机制提供新的依据。     

Cl-/SO42-铁盐对含可溶性胞外多聚物Acidithiobacillus ferrooxidans溶液中铁矿物形成的影响

铁细菌胞外多聚物作用下聚集的铁可通过氧化或者沉淀作用使铁稳定或沉积,从而形成铁矿物。本文基于铁细菌胞外多聚物(extracellular polymeric substances,EPS)对铁矿物形成的调控作用,介绍了Cl-/SO_4~(2-)的Fe(Ⅲ)或Fe(Ⅱ)盐作用下,含可溶性EPS的氧化亚铁硫杆菌(Acidithiobacillus ferrooxidans)溶液中铁矿物的形成,观察了溶液pH值变化及形成铁矿物的矿相与结构,并采用XRD、FTIR和FESEM对其进行表征。结果发现反应溶液中OH-离子可与Fe3+形成微米级"针垫"聚集球状或纳米级小球形施威特曼石和微米级"菱形"块状黄钾铁矾铁矿物沉淀。反应溶液中的可溶性EPS可调控和促进铁矿物的形成,但对Fe2+的氧化未产生影响;外源Fe盐可促进施威特曼石向黄钾铁矾转化。随着Cl-/SO_4~(2-)摩尔比例的增加(即Cl-含量的不断增加),两矿相间的转化明显受到抑制,且铁矿物颗粒之间的集聚作用明显减弱;反之,SO_4~(2-)含量升高时,有利于铁矿物间的转化和聚集球状颗粒形貌结构的形成。     

Reactions of iron with calcium carbonate at 6 GPa and 1273–1873 K: implications for carbonate reduction in the deep mantle

Experimental data on Fe-CaCO₃ interaction at 6 GPa and 1273–1873 K are presented. The system models the hypothetical redox interaction in subducting slabs at the contact with the reduced mantle and a putative process at the core-mantle boundary. The reaction is accompanied by carbonatite melt formation. It also produces Fe3C and calcium wustite, which form solid or liquid phases depending on experimental conditions. In iron-containing systems at 6 GPa, calcium carbonate melts in the range 1473–1573 K, which is consistent with aragonite disappearance from complex carbonate systems. The composition of calcium carbonate liquid is not influenced by metallic Fe. It corresponds to nearly pure CaCO₃. Along the mantle adiabat or at slightly higher temperatures, nearly pure CaCO₃ coexists with metallic iron or calcium wustite. This hypothesis explains the coexistence of metallic iron and carbonate inclusions in lithospheric and superdeep diamonds.     

An experimental investigation into the metastable formation of phosphoran olivine and pyroxene

The formation of phosphoran olivine by crystallization from a melt was investigated experimentally using a one atmosphere furnace, using San Carlos olivine [(Mg,Fe)₂SiO₄] mixed with either iron phosphide (FeP) or magnesium pyrophosphate (Mg₂P₂O₇). Both dynamic crystallization and isothermal experiments produced phosphoran olivine as zoned single crystals and as overgrowths surrounding normal, phosphorus-free olivine grains. The crystallization pathways that form phosphoran olivine were traced and confirm that it is a metastable phase that can crystallize from a phosphorus-rich melt over timescales of hours to days. Removal of the P and equilibration of the olivine however requires weeks to months in the presence of silicate melt. Phosphoran olivine with up to 27 wt% P₂O₅ was generated and up to 69% of the Si tetrahedral sites were replaced by P. The substitution of Si by P into olivine was confirmed as 4^VIM⁺² + 2^IVSi⁺⁴ ↔ 3^VIM⁺² + 2^IVP⁺⁵ + ^VI[]. Phosphoran olivine compositions that vary from (Mg,Fe)₂SiO₄ to (Mg,Fe)_1.65[]_0.35Si_0.3P_0.7O₄ have been produced in these experiments.Phosphoran pyroxene was also generated in a few experiments and forms when phosphoran olivine reacts with either tridymite or melt. It has compositions compatible with protopyroxene, orthopyroxene, pigeonite and sub-calcic augite, and can contain up to 31.5 wt% P₂O₅. Like phosphoran olivine, it is also a metastable phase. Phosphorus replaces Si in pyroxene by the following substitution methods: 8^IVSi⁺⁴ ↔ 3^IVSi⁺⁴ + 4^IVP⁺⁵ + ^IV[] with Al entering the structure by the exchange 2^IVSi⁺⁴ ↔ ^IVAl⁺³ + ^IVP⁺⁵. Phosphoran pyroxene compositions vary from (Mg,Fe)₈Si₈O₂₄ to (Mg,Fe)₈Si₃P₄[]O₂₄.     

Alkali differentiation in LL-chondrites

The LL-group chondrites Krähenberg (Krbg) and Bhola are heterogeneous agglomerates containing a variety of lithic fragments and chondrules as well as crystal fragments. The $\text{Fe}\text{Fe}$ + Mg content of most olivine grains is uniform (Fa₂₈), although a few with distinctly lower Fe contents were found (Fa₁₉). Both meteorites contain large, cm-sized, fragments with high enrichments of K (~12×), Rb (~45×) and Cs (~70×) relative to LL-chondrites, while the REE concentrations are normal (except for a negative Eu anomaly); Na and Sr are depleted (~0.5×) and the $\text{Na}\text{K}$ weight ratio is 0.33 compared to 11 in the host. However, there is no difference in the sum of Na + K atoms. Also, the major elements, Si, Al, Mg, Ca and Fe, are nearly the same in fragments as in the host material. The K-rich igneous lithic fragments have a microporphyritic texture of euhedral to skeletal olivines in a partly devitrified glass with ~4% K₂O. The main pans of both Krbg and Bhola contain mesostasis glasses in porphyritic chondrules and lithic fragments with varying K content (0.1–8.6% K₂O) and $\text{Na}\text{K}$ ratios (0.2–100). Crystalline plagioclase is depleted in K with an average $\text{Na}\text{K}$ ratio of 22, i.e. higher than that for ordinary chondritic plagioclase, 8.4. Olivines in the large, K-rich fragments and in the host meteorites have the same iron content (Fa₂₈), indicating that both formed under the same oxygen fugacity and probably on the same parent body.Conceivable mechanisms for the formation of the K-rich rocks from normal LL-chondrite parent material are: 1, magmatic differentiation: 2. Na-K exchange via a vapor phase; 3. silicate liquid immiscibility; 4. volatilization and condensation in impact events. Process 2 appears most feasible for forming a rock enriched only in K and heavier alkalies and depleted in Na without noticeably changing other elements including the REE.     

Solubility of water in the α, β and γ phases of (Mg,Fe)2SiO4

 The solubility of hydroxyl in the α, β and γ phases of (Mg,Fe)₂SiO₄ was investigated by hydrothermally annealing single crystals of San Carlos olivine. Experiments were performed at a temperature of 1000° or 1100 °C under a confining pressure of 2.5 to 19.5 GPa in a multianvil apparatus with the oxygen fugacity buffered by the Ni:NiO solid-state reaction. Hydroxyl solubilities were determined from infrared spectra obtained of polished thin sections in crack-free regions ≤100 μm in diameter. In the α-stability field, hydroxyl solubility increases systematically with increasing confining pressure, reaching a value of ∼20,000 H/10⁶Si (1200 wt ppm H₂O) at the α-β phase boundary near 13 GPa and 1100 °C. In the β field, the hydroxyl content is ∼400,000 H/10⁶Si (24,000 wt ppm H₂O) at 14–15 GPa and 1100 °C. In the γ field, the solubility is ∼450,000 H/10⁶Si (27,000 wt ppm H₂O) at 19.5 GPa and 1100 °C. The observed dependence of hydroxyl solubility with increasing confining pressure in the α phase reflects an increase in water fugacity with increasing pressure moderated by a molar volume term associated with the incorporation of hydroxyl ions into the olivine structure. Combined with published results on the dependence of hydroxyl solubility on water fugacity, the present results for the α phase can be summarized by the relation C _OH = A(T)f nH₂Oexp(−PΔV/RT), where A(T) = 1.1 H/10⁶Si/MPa at 1100 °C, n = 1, and ΔV = 10.6×10^–6 m³/mol. These data demonstrate that the entire present-day water content of the upper mantle could be incorporated in the mineral olivine alone; therefore, a free hydrous fluid phase cannot be stable in those regions of the upper mantle with a normal concentration of hydrogen. Free hydrous fluids are restricted to special tectonic environments, such as the mantle wedge above a subduction zone. Received: 10 February 1995 / Accepted: 23 October 1995     

Titanium solubility in olivine in the system TiO<Subscript>2</Subscript>–MgO–SiO<Subscript>2</Subscript>: no evidence for an ultra-deep origin of Ti-bearing olivine

The finding of ilmenite rods in olivine from orogenic peridotites has sparked a discussion about the processes of incorporation and exsolution of titanium in olivine. We have experimentally investigated the solubility of Ti in olivine as a function of composition, temperature and pressure in the synthetic TiO₂–MgO–SiO₂ system. Experiments at atmospheric pressure in the temperature range 1,200–1,500°C showed that the highest concentration of TiO₂ is obtained when olivine coexists with spinel (Mg₂TiO₄). The amount of TiO₂ in olivine in the assemblages olivine + spinel + periclase and olivine + spinel + ilmenite at 1,500°C was 1.25 wt.%. Changes in the coexisting phases and decreasing temperature result in a significant reduction of the Ti solubility. Olivine coexisting with pseudobrookite (MgTi₂O₅) and a Ti–Si-rich melt at 1,500°C displays a fourfold lower TiO₂ content than when buffered with spinel. A similar decrease in solubility is obtained by a decrease in temperature to 1,200°C. There is a negative correlation between Ti and Si and no correlation between Ti and Mg in Ti-bearing olivine. Together with the established phase relations this suggests that there is a direct substitution of Ti for Si at these temperatures, such that the substituting component has the stoichiometry Mg₂TiO₄. The unit cell volume of olivine increases systematically with increasing TiO₂ content demonstrating that the measured TiO₂ contents in olivine are not caused by micro-inclusions but by incorporation of Ti in the olivine structure. Least squares fitting of 20 olivine unit cell volumes against the Ti content yield the relation: V (ų)=290.12(1) + 23.67(85) N_Ti. The partial molar volume of end-member Mg₂TiO₄ olivine (N_Ti=1) is thus 47.24±0.13 cm³. The change of the Ti solubilty in olivine coexistent with rutile and orthopyroxene with pressure was investigated by piston cylinder experiments at 1,400°C from 15 to 55 kbar. There is no increase in TiO₂ contents with pressure and in all the experiments olivine contains ~0.2 wt.% TiO₂. Moreover, a thermodynamic analysis indicates that Ti contents of olivine coexisting with rutile and orthopyroxene should decrease rather than increase with increasing pressure. These data indicate that the ilmenite exsolution observed in some natural olivine does not signify an ultra-deep origin of peridotite massifs.     

The role of olivine in the crystallization of the prehistoric Makaopuhi tholeiitic lava lake,Hawaii

On eruption, the tholeiitic basalt lava of the prehistoric Makaopuhi lake contained nearly seven percent euhedral olivine phenocrysts of approximately Fa₁₄ composition. In the center of the 225 foot vertical section of the lake, the lava became more than 90 percent solid at 1000° C after about 30 years. At the surface the lava was quenched to air temperature, whereas, at the bottom, quenching to 800° C was followed by a 40 year period before the temperature reached 700° C. The olivine phenocrysts settled at an average rate of about 4 × 10^–6 cm Sec^–1 to form a zone that contains 21 percent olivine 75 feet above the base. Sinking of olivines continued until some time after the beginning of the crystallization of augite and plagioclase. Thin rims of iron-rich olivine (up to Fa₅₅) surrounding the phenocrysts, and a second generation of fine-grained olivines (Fa₂₀ Fa₄₈) restricted to the uppermost 20 feet indicate local extensions of the period of crystallization of olivine. During crystallization of the groundmass and later subsolidus cooling in the range 1000° C to at least as low as 800° C, the olivine phenocrysts were converted to Fa_30–40 by interdiffusion of Fe, Mg, Ni, and Mn. Homogenization of Mg-rich cores and Fe-rich margins and equilibration of olivine composition with the groundmass phases was progressively less well achieved toward the top of the lake. Reaction rims around the olivines are composed primarily of Ca-rich pyroxene. Pigeonite crystallized alongside augite except in the uppermost 5 feet where there is abundant ground mass olivine. Poikilitic hypersthene grew at the expense of pre-existing ferromagnesian minerals in the cumulate zone.Publication authorized by the Director, U.S. Geological Survey.     

Structure and formation of the San Cristobal meteorite,other IB irons and group IIICD

San Cristobal is an unusual group IB ataxite with 25 per cent Ni, composed of taenite grains 2–3 cm in diameter and silicate-troilite-graphite nodules concentrated on the grain boundaries. Silicate compositions are typical of group IAB: olivine Fa_3.3, orthopyroxene Fs_6.9 and feldspar Ab₈₈. Plagioclase shows peristerite unmixing, previously unrecorded in meteorites, and occasional K-rich feldspar grains have an unusual antiperthite exsolution. Brianite Na₂CaMg(PO₄)₂ and haxonite (Fe, Ni)₂₃C₆ are common in nodules and matrix, respectively, while cohenite is rare. Part of the matrix contains a pearlitic kamacite precipitate instead of the usual oriented platelets.San Cristobal has extreme concentrations of many elements; e.g. the highest published Ag, Cu, In and Sb contents and the lowest Mo and Pt in irons. These data and the mineralogy show that San Cristobal has many characteristics of both groups IB and IIID, but that it fits group IB trends better. Ratios of refractory element abundances to those in Cl chondrites (both normalized to Ni) decrease through IB from l in IA to 0.03 in San Cristobal, but the other siderophilic elements have a small range of abundance ratios, 0.5–2, throughout IAB. We suggest that IB grains either formed in a part of the solar nebula where refractories had been previously removed, or else failed to equilibrate with a refractory-rich, high-temperature condensate. After condensation of the volatiles, Fe was partially removed, perhaps by oxidation. Group IIICD seems to have experienced similar fractionations. Unlike other iron meteorite groups, neither IAB nor IIICD appears to have been fully molten.     

Heating duration of igneous rim formation on a chondrule in the Northwest Africa 3118 CV3oxA carbonaceous chondrite inferred from micro-scale migration of the oxygen isotopes

Due to their common occurrence in various types of chondrites, igneous rims formed on pre-existing chondrules throughout chondrule-forming regions of the solar nebula. Although the peak temperatures are thought to reach similar values to those achieved during chondrule formation events, the heating duration in chondrule rim formation has not been well defined. We determined the two-dimensional chemical and oxygen isotopic distributions in an igneous rim of a chondrule within the Northwest Africa 3118 CV3_oxA chondrite with sub-micrometer resolution using secondary ion mass spectrometry and scanning electron microscopy. The igneous rim experienced aqueous alteration on the CV parent body. The aqueous alteration resulted in precipitation of the secondary FeO-rich olivine (Fa_40–49) and slightly disturbed the Fe-Mg distribution in the MgO-rich olivine phenocrysts (Fa_11–22) at about a 1 μm scale. However, no oxygen isotopic disturbances were observed at a scale greater than 100 nm. The MgO-rich olivine, a primary phase of igneous rim formation, has δ¹⁷O = −6 ± 3‰ and δ¹⁸O = −1 ± 4‰, and some grains contain extreme ¹⁶O-rich areas (δ¹⁷O, δ¹⁸O = ∼−30‰) nearly 10 μm across. We detected oxygen isotopic migration of approximately 1 μm at the boundaries of the extreme ¹⁶O-rich areas. Using oxygen self-diffusivity in olivine, the heating time of the igneous rim formation could have continued from several hours to several days at near liquidus temperatures (∼2000 K) in the solar nebula suggesting that the rim formed by a similar flash heating event that formed the chondrules.     

Petrological and Geochemical Constraints on the Protoliths of Serpentine‐Magnetite Ores in the Zhaoanzhuang Iron Deposit,Southern North China Craton

The uncommon Mg-rich and Ti-poor Zhaoanzhuang serpentine-magnetite ores within Taihua Group of the North China Craton(NCC) remain unclear whether the protolith was sourced from ultramafic rocks or chemical sedimentary sequences. Here we present integrated petrographic and geochemical studies to characterize the protoliths and to gain insights on the ore-forming processes. Iron ores mainly contain low-Ti magnetite(TiO_2 ~0.1 wt%) and serpentine(Mg#=92.42–96.55), as well as residual olivine(Fo=89–90), orthopyroxene(En=89–90) and hornblende. Magnetite in the iron ores shows lower Al, Sc, Ti, Cr, Zn relative to that from ultramafic Fe-Ti-V iron ores, but similar to that from metamorphic chemical sedimentary iron deposit. In addition, interstitial minerals of dolomite, calcite, apatite and anhydrite are intergrown with magnetite and serpentine, revealing they were metamorphic, but not magmatic or late hydrothermal minerals. Wall rocks principally contain magnesian silicates of olivine(Fo=83–87), orthopyroxene(En=82–86), humite(Mg#=82–84) and hornblende [XMg=0.87–0.96]. Dolomite, apatite and anhydrite together with minor magnetite, thorianite(Th-rich oxide) and monazite(LREE-rich phosphate) are often seen as relicts or inclusions within magnesian silicates in the wall rocks, revealing that they were primary or earlier metamorphic minerals than magnesian silicates. And olivine exists as subhedral interstitial texture between hornblende, which shows later formation of olivine than hornblende and does not conform with sequence of magmatic crystallization. All these mineralogical features thus bias towards their metamorphic, rather than magmatic origin. The dominant chemical components of the iron ores are SiO_2(4.77–25.23 wt%), Fe_2O_3 T(32.9–80.39 wt%) and MgO(5.72–27.17 wt%) and uniformly, those of the wall rocks are also SiO_2(16.34–48.72 wt%), Mg O(16.71–33.97 wt%) and Fe_2O_3 T(6.98–30.92 wt%). The striking high Fe-Mg-Si contents reveal that protolith of the Zhaoanzhuang iron deposit was more likely to be chemical sedimentary rocks. The distinct high-Mg feature and presence of abundant anhydrite possibly indicate it primarily precipitated in a confined seawater basin under an evaporitic environment. Besides, higher contents of Al, Ti, P, Th, U, Pb, REE relative to other Precambrian iron-rich chemical precipitates(BIF) suggest some clastic terrestrial materials were probably input. As a result, we think the Zhaoanzhuang iron deposit had experienced the initial Fe-Mg-Si marine precipitation, followed by further Mg enrichment through marine evaporated process, subsequent high-grade metamorphism and late-stage hydrothermal fluid modification.