An EFTEM/HRTEM high-resolution study of the near surface of labradorite feldspar altered at acid pH: evidence for interfacial dissolution-reprecipitation

Using an approach combining high-resolution and energy-filtered transmission electron microscopy (HRTEM and EFTEM), we have studied with Å to nm-spatial resolution the interfacial region that delimits the near-surface altered zone and non-altered labradorite feldspar after dissolution under acid pH conditions. The interface is characterized by extremely sharp and spatially coincident changes in structure and chemistry. The 500-nm-thick altered zone is depleted in interstitial cations (Ca, Na, K) and Al, a framework element, whereas it is enriched in H, O, and Si. Modeling H⁺-alkali interdiffusion within a 500-nm-thick altered zone shows that volume interdiffusion cannot reproduce the sharp chemical interfaces measured by EFTEM. Based on these new data, we propose that the near-surface altered zone is a result of interfacial dissolution-reprecipitation, and not of preferential leaching of cations and interdiffusion with H⁺. This implies an intrinsic dissolution process that is stoichiometric, where the breaking of bonds and release of interstitial cations and framework elements (Al, Si, and O) to solution occur contemporaneously at equal relative rates from the original fluid–mineral interface.     

Chemical and textural equilibration of garnet during amphibolite facies metamorphism: The influence of coupled dissolution–reprecipitation

Metamorphic equilibration requires chemical communication between minerals and may be inhibited through sluggish volume diffusion and or slow rates of dissolution in a fluid phase. Relatively slow diffusion and the perceived robust nature of chemical growth zoning may preclude garnet porphyroblasts from readily participating in low‐temperature amphibolite facies metamorphic reactions. Garnet is widely assumed to be a reactant in staurolite‐isograd reactions, and the evidence for this has been assessed in the Late Proterozoic Dalradian pelitic schists of the Scottish Highlands. The 3D imaging of garnet porphyroblasts in staurolite‐bearing schists reveals a good crystal shape and little evidence of marginal dissolution; however, there is also lack of evidence for the involvement of either chlorite or chloritoid in the reaction. Staurolite forms directly adjacent to the garnet, and its nucleation is strongly associated with deformation of the muscovite‐rich fabrics around the porphyroblasts. “Cloudy” fluid inclusion‐rich garnet forms in both marginal and internal parts of the garnet porphyroblast and is linked both to the production of staurolite and to the introduction of abundant quartz inclusions within the garnet. Such cloudy garnet typically has a Mg‐rich, Mn‐poor composition and is interpreted to have formed during a coupled dissolution–reprecipitation process, triggered by a local influx of fluid. All garnet in the muscovite‐bearing schists present in this area is potentially reactive, irrespective of the garnet composition, but very few of the schists contain staurolite. The staurolite‐producing reaction appears to be substantially overstepped during the relatively high‐pressure Barrovian regional metamorphism reflecting the limited permeability of the schists in peak metamorphic conditions. Fluid influx and hence reaction progress appear to be strongly controlled by subtle differences in deformation history. The remaining garnet fails to achieve chemical equilibrium during the reaction creating distinctive patchy compositional zoning. Such zoning in metamorphic garnet created during coupled dissolution–reprecipitation reactions may be difficult to recognize in higher grade pelites due to subsequent diffusive re‐equilibration. Fundamental assumptions about metamorphic processes are questioned by the lack of chemical equilibrium during this reaction and the restricted permeability of the regional metamorphic pelitic schists. In addition, the partial loss of prograde chemical and textural information from the garnet porphyroblasts cautions against their routine use as a reliable monitor of metamorphic history. However, the partial re‐equilibration of the porphyroblasts during coupled dissolution–reprecipitation opens possibilities of mapping reaction progress in garnet as a means of assessing fluid access during peak metamorphic conditions.     

Garnet re‐equilibration by coupled dissolution–reprecipitation: evidence from textural,major element and oxygen isotope zoning of ‘cloudy’ garnet

The analysis of texture, major element and oxygen isotope compositions of cloudy garnet crystals from a metapelite sampled on Ikaria Island (Greece) is used to assess the model of growth and re‐equilibration of these garnet crystals and to reconstruct the pressure–temperature–fluid history of the sample. Garnet crystals show complex textural and chemical zoning. Garnet cores (100–200 μm) are devoid of fluid inclusions. They are characterized by growth zoning demonstrated by a bell‐shaped profile of spessartine component (7–3 mol.%), an increase in grossular from 14 to 22 mol.% and δ¹⁸O values between 9.5 ± 0.3‰ and 10.4 ± 0.2‰. Garnet inner rims (90–130 μm) are fluid inclusion‐rich and show a decreasing grossular component from 22 to 5 mol.%. The trend of the spessartine component observed in the inner rim allows two domains to be distinguished. In contrast to domain I, where the spessartine content shows the same trend as in the core, the spessartine content of domain II increases outwards from 2 to 14 mol.%. The δ¹⁸O values decrease towards the margins of the crystals to a lowest value of 7.4 ± 0.2‰. The outer rims (<10 μm) are devoid of fluid inclusions and have the same chemical composition as the outermost part of domain II of the inner rim. Garnet crystals underwent a four‐stage history. Stage 1: garnet growth during the prograde path in a closed system for oxygen. Garnet cores are remnants of this growth stage. Stage 2: garnet re‐equilibration by coupled dissolution–reprecipitation at the temperature peak (630 < T < 650 °C). This causes the creation of porosity as the coupled dissolution–reprecipitation process allows chemical (Ca) and isotopic (O) exchange between garnet inner rims and the matrix. The formation of the outer rim is related to the closure of porosity. Stage 3: garnet mode decreases during the early retrograde path, but garnet is still a stable phase. The resulting garnet composition is characterized by an increasing Mn content in the inner rim’s domain II caused by intracrystalline diffusion. Stage 4: dissolution of garnet during the late retrograde path as garnet is not a stable phase anymore. This last stage forms corroded garnet. This study shows that coupled dissolution–reprecipitation is a possible re‐equilibration process for garnet in metamorphic rocks and that intra‐mineral porosity is an efficient pathway for chemical and isotopic exchange between garnet and the matrix, even for otherwise slow diffusing elements.     

辽宁鞍本地区沉积变质型富铁矿的成因：Fe、Si、O、S同位素证据

辽宁鞍本地区是我国最重要的鞍山式沉积变质型(BIF)铁矿矿集区,弓长岭铁矿是我国唯一的由鞍山式贫铁矿经后期热液改造形成的大型磁铁富矿.本文在前人工作基础上,对比研究了鞍本地区贫铁矿、富铁矿和蚀变围岩的铁、硅、氧、硫同位素组成特征和空间变化规律,结合磁铁富矿的地质特征,对成矿流体的性质、来源、成矿作用和富矿成矿机制提出了新的认识.指出鞍本地区富铁矿的成矿作用与辽东地区古元古代造山运动结束后(1.85 Ga)地壳抬升引发的非造山岩浆侵入和热液活动有关,成矿溶液由大气降水演化形成,而非变质热液或混合岩化热液;成矿溶液淋滤了辽河群蒸发盐地层中富13C碳酸盐、富34S石膏、CH4等成矿物质,成矿溶液具偏酸性弱还原特征;铁质活化再富集是鞍本地区富铁矿形成的重要机制,成矿溶液与贫铁矿及围岩反应使铁质以Fe2+形式活化迁移.温度降低、氧逸度升高或与大气降水混合是溶液中Fe2+氧化形成磁铁矿沉淀的主要原因;在Fe2+被氧化形成磁铁矿的同时,成矿溶液中的CH4被氧化形成石墨,与磁铁矿一起沉淀下来,形成含石墨磁铁富矿;溶液中SO42-被还原形成富34S黄铁矿.     

Mechanism of the olivine–ringwoodite transformation in the presence of aqueous fluid

The mechanism of the high pressure transformation of olivine in the presence of aqueous fluid was investigated by high pressure experiments conducted nominally at the wadsleyite + ringwoodite stability field at 14.5 GPa and 700 and 800°C. The microstructures of recovered samples were observed using an analytical transmission electron microscope (ATEM) for which foils were prepared using a focused ion beam technique. Glass films approximately 1 μm in width always occupied the interface between olivine and hydrous ringwoodite. ATEM measurements showed that the chemical compositions of the glass films had approximately the same Mg/Fe ratio as that of olivine, but a higher Si content. Micro-structural and -chemical observations suggest that these glass films formed as quenched glass from the aqueous fluid dissolving olivine and that hydrous ringwoodite was crystallized from the fluid. This indicates that the transformation of olivine to hydrous ringwoodite was prompted by the dissolution–reprecipitation process. The dissolution–reprecipitation process is considered an important mineral replacement mechanism in the Earth’s crust by which one mineral is replaced by a more stable phase or phases. However, this process has not previously been reported for deep mantle conditions.     

一种降低重铀酸铵产品水份的方法——反复沉淀法

在研究降低重铀酸铵产品水份的工艺过程中,通过小试、中试确立了反复沉淀法工艺,并成功应用于生产中,使重铀酸铵产品中水份含量大幅度降低并达到国家标准,同时又降低了生产成本。     

鄂东程潮铁矿床磁铁矿的微量元素组成及其矿床成因意义

程潮铁矿床是长江中下游成矿带最大的矽卡岩型铁矿床,位于鄂东南矿集区北缘,矿体主要产于鄂城杂岩体与下三叠统大冶组碳酸盐岩的接触带。本文报道程潮铁矿床不同产状磁铁矿的LA-ICPMS(激光剥蚀等离子体质谱)微量元素分析结果,以讨论磁铁矿的微量元素组成和变化规律及其与成矿环境的关系,为深入认识程潮铁矿床的矿床成因及成矿演化提供重要制约。研究结果显示,程潮铁矿床与成矿有关岩体(花岗岩)中的岩浆磁铁矿(副矿物)与内矽卡岩和外矽卡岩中的热液磁铁矿在显微结构和微量元素组成上具有显著差异。花岗岩中的磁铁矿不发育环带,也没有遭受后期热液的交代。内矽卡岩以发育具有振荡环带的富Si磁铁矿为特征,而外矽卡岩中的磁铁矿则以无明显环带的富Mg磁铁矿为主。内矽卡岩和外矽卡岩中的原生磁铁矿都遭受了广泛的热液交代作用而形成次生磁铁矿,即具有明显的磁铁矿溶解-再沉淀作用。与矽卡岩矿石中的热液磁铁矿相比,岩体中的副矿物磁铁矿具有高得多的V、Ti、Ni、Cr、Co及Ga等亲铁元素(相容元素)和较低的Si、Al、Mg、Sr及Ba等亲石元素(不相容元素)。这种岩浆副矿物磁铁矿和矿石矿物磁铁矿微量元素组成的系统差异表明,程潮铁矿床属于典型的矽卡岩型矿床,而非矿浆型铁矿。另一方面,内矽卡岩和外矽卡岩矿石中的原生磁铁矿也具有明显不同的微量元素组成:前者具有较高的V、Ti、Ni、Cr、Ga、Sr和Ba等,而后者具有较高的Sn、Zn、U和Sn/Ga、Zn/V及Co/Ni比值,表明外矽卡岩中的磁铁矿受地层围岩成分的影响较大,而内矽卡岩中的磁铁矿则更多地受岩浆流体组分的控制。对原生磁铁矿和次生磁铁矿微量元素的系统分析结果表明,在磁铁矿的溶解-再沉淀过程中,内矽卡岩中的次生磁铁矿相对原生磁铁矿具有显著不同的微量元素组成,前者的Si、Al、Mg、Ti、Sr及Ga等元素含量大大降低,而Zn、V、Mn、Pb、Th及U等元素含量则升高,Co、Ni、Sn及Ba等元素基本不变。外矽卡岩中的原生磁铁矿被交代形成次生磁铁矿时,Mg、Mn、Al、Zn及Co等元素发生丢失,Pb、U、Nb及Sr等元素发生富集,而Sn和Ga的含量基本不变。根据不同产状、不同结构和不同成因磁铁矿的微量元素分析可以得出以下认识:(1)程潮铁矿床属于典型的热液成因,矿区不存在矿浆型铁矿;(2)磁铁矿的溶解-再沉淀作用使大部分微量元素发生明显亏损,少部分元素发生富集,表明流体交代对磁铁矿的微量元素组成具有显著影响;(3)对磁铁矿微量元素组成的研究可为磁铁矿及矽卡岩型铁矿床的矿床成因和成矿演化提供重要信息;对磁铁矿的原位微量元素分析必须建立在详细的显微结构研究基础上,对发生过溶解-再沉淀作用的磁铁矿,需要分别对原生和次生磁铁矿区域进行高精度、高分辨率的微量元素分析,只有这样才能对磁铁矿及含磁铁矿矿床的成因进行正确的分析和认识。     

The partial equilibration of garnet porphyroblasts in pelitic schists and its control on prograde metamorphism,Glen Roy,Scotland

Garnet porphyroblasts in sillimanite‐bearing pelitic schists contain complex textural and compositional zoning, with considerable variation both within and between adjacent samples. The sillimanite‐bearing schists locally occur in regional Barrovian garnet zone assemblages and are indicative of a persistent lack of equilibrium during prograde metamorphism. Garnet in these Dalradian rocks from the Scottish Highlands preserves evidence of a range of metamorphic responses including initial growth and patchy coupled dissolution–reprecipitation followed by partial dissolution. Individual porphyroblasts each have a unique and variable response to prograde metamorphism and garnet with mainly flat compositional profiles co‐exists with those containing largely unmodified characteristic bell‐shaped Mn profiles. This highlights the need for caution in applying traditional interpretations of effective volume diffusion eliminating compositional variation. Cloudy garnet with abundant fluid inclusions is produced during incomplete modification of the initial porphyroblasts and these porous garnet are then particularly prone to partial replacement in sillimanite‐producing reactions. The modification of garnet via a dissolution–reprecipitation process releases Ca into the effective whole‐rock composition, displacing the pressure–temperature positions of subsequent isograd reactions. This represents the first report of internal metasomatism controlling reaction pathways. The behaviour of garnet highlights the importance of kinetic factors, especially deformation and fluids, in controlling reaction progress and how the resulting variability influences subsequent prograde history. The lack of a consistent metamorphic response, within and between adjacent schists, suggests that on both local and regional scales these rocks have largely not equilibrated at peak metamorphic conditions.     

Fluid‐induced breakdown of monazite in medium‐grade metasedimentary rocks of the Pontremoli basement (Northern Apennines,Italy)

The last (decompression) stages of the metamorphic evolution can modify monazite microstructure and composition, making it difficult to link monazite dates with pressure and temperature conditions. Monazite and its breakdown products under fluid‐present conditions were studied in micaschist recovered from the cuttings of the Pontremoli1 well, Tuscany. Coronitic microstructures around monazite consist of concentric zones of apatite + Th‐silicate, allanite and epidote. The chemistry and microstructure of the monazite grains, which preserve a wide range of chemical dates ranging from Upper Carboniferous to Tertiary times, suggest that this mineral underwent a fluid‐mediated coupled dissolution–reprecipitation and crystallization processes. Consideration of the chemical zoning (major and selected trace elements) in garnet, its inclusion mineralogy (including xenotime), monazite breakdown products and phase diagram modelling allow the reaction history among accessory minerals to be linked with the reconstructed P–T evolution. The partial dissolution and replacement by rare earth element‐accessory minerals (apatite–allanite–epidote) occurred during a fluid‐present decompression at 510 ± 35 °C. These conditions represent the last stage of a metamorphic history consisting of a thermal metamorphic peak at 575 °C and 7 kbar, followed by the peak pressure stage occurring at 520 °C and 8 kbar. An anticlockwise P–T path or two clockwise P–T loops can fit the above P–T constraints. The former path may be related to a context of late Variscan strike‐slip‐dominated exhumation with minor Tertiary (Alpine‐related) reworking and fluid infiltration, while the latter requires an Oligocene–Miocene fluid‐present tectono‐metamorphic overprint on the Variscan paragenesis.