Controls on metamorphic equilibration: the importance of intergranular solubilities mediated by fluid composition

A dramatic demonstration of the role of intergranular solubility in promoting chemical equilibration during metamorphism is found in the unusual zoning of garnet in pelitic schist exposed at Harpswell Neck, Maine, USA. Many garnet crystals have irregular, patchy distributions of Mn, Cr, Fe and Mg in their inclusion‐rich interiors, transitioning to smooth, concentric zoning in their inclusion‐poor outer rims; in contrast, zoning of Ca and Y is comparatively smooth and concentric throughout. We re‐assess the disputed origin of these zoning features by examining garnet growth in the context of the thermal and structural history of the rocks, and by evaluating the record of fluid–rock interaction revealed in outcrop‐scale veining and fluid‐inclusion assemblages. The transition in the character of garnet zoning correlates with the onset of a synkinematic, simple‐shear‐dominated phase of garnet growth and with a shift in the composition of the intergranular fluid from CO₂‐rich to H₂O‐rich. Compositional variations in garnet are therefore best explained by a two‐stage growth history in which intergranular diffusive fluxes reflect differences in the concentration of dissolved species in these two contrasting fluids. Interiors of garnet crystals grew in the presence of a CO₂‐rich fluid, in which limited solubility for Mn and Cr (and perhaps Fe and Mg) produced patchy disequilibrium overprint zoning, while appreciable solubility for Ca and Y permitted their rock‐wide equilibration. Rims grew in the presence of an H₂O‐rich fluid, in which high intergranular concentrations for all elements except Cr enabled diffusion over length scales sufficient for rock‐wide equilibration. This striking example of partial chemical equilibrium during reaction and porphyroblast growth implies that thermal effects may commonly be subsidiary in importance to solubilities in the intergranular medium as determinants of length scales for metamorphic equilibration.     

Reaction softening by dissolution–precipitation creep in a retrograde greenschist facies ductile shear zone,New Hampshire,USA

We describe strain localization by a mixed process of reaction and microstructural softening in a lower greenschist facies ductile fault zone that transposes and replaces middle to upper amphibolite facies fabrics and mineral assemblages in the host schist of the Littleton Formation near Claremont, New Hampshire. Here, Na‐poor muscovite and chlorite progressively replace first staurolite, then garnet, and finally biotite porphyroblasts as the core of the fault zone is approached. Across the transect, higher grade fabric‐forming Na‐rich muscovite is also progressively replaced by fabric‐forming Na‐poor muscovite. The mineralogy of the new phyllonitic fault‐rock produced is dominated by Na‐poor muscovite and chlorite together with late albite porphyroblasts. The replacement of the amphibolite facies porphyroblasts by muscovite and chlorite is pseudomorphic in some samples and shows that the chemical metastability of the porphyroblasts is sufficient to drive replacement. In contrast, element mapping shows that fabric‐forming Na‐rich muscovite is selectively replaced at high‐strain microstructural sites, indicating that strain energy played an important role in activating the dissolution of the compositionally metastable muscovite. The replacement of strong, high‐grade porphyroblasts by weaker Na‐poor muscovite and chlorite constitutes reaction softening. The crystallization of parallel and contiguous mica in the retrograde foliation at the expense of the earlier and locally crenulated Na‐rich muscovite‐defined foliation destroys not only the metastable high‐grade mineralogy, but also its stronger geometry. This process constitutes both reaction and microstructural softening. The deformation mechanism here was thus one of dissolution–precipitation creep, activated at considerably lower stresses than might be predicted in quartzofeldspathic rocks at the same lower greenschist facies conditions.     

从平衡-封闭-静态转向非平衡-开放-动力学研究-热液矿床成因的若干新概念概述

热液金属矿床成因研究过程中,观测与实验始终是密切结合的。上世纪70年代,平衡热力学的实验数据的快速积累,使人们用热力学理论计算可以预测和反演矿石和岩石的成因。但是,没有矿物-水溶液的反应速率数据,又没有与流体力学的结合,搞清楚矿石成因是困难的。七、八十年代,开始研究矿物与水溶液的反应动力学实验。科学家们开始瞄准了从平衡-封闭-静态转向非平衡-开放-动力学研究的这个大方向。1992年我们建立地球化学动力学开放研究实验室。研究高温高压矿物与水反应速率,发现固液的开放体系的自组织现象。实验发现温度影响矿物的各个元素反应速率改变,发现在跨越水临界态时矿物与水反应速率涨落、在近临界的气-液两相不混溶区一些金属进入气相、超临界流体的氧化作用及特别的溶剂性能影响矿物溶解性质。实验证实:临界态区流体与矿石成因有关。水岩相互作用的反应动力学实验温度从低温到550度,揭示矿石的金属来源、迁移、金属与蚀变分带机制。一大批大于300度的矿物与水反应动力学实验在国际界是少有报道的。九十年代,超高压的科学发展,与同步辐射光源的技术进步的结合,使固体地球科学又迈向了地球深内部。我们发展了高温高压流体性质的原位直测(测量850℃水溶液)红外谱,发现深部流体的新性质:气液两相流体的新结构,在临界温度区(300~400℃),水分子氢键网络的破坏受压力影响不大(23MPa~3GPa),同时,出现水的高电导率。研发新仪器为开放-流动-非平衡的反应动力学实验与极端条件下物质性质的直接观测结合,在科学前沿领域开辟了创新道路。     

Reactivity of micas and cap-rock in wet supercritical CO2 with SO2 and O2 at CO2 storage conditions

Seal or cap-rock integrity is a safety issue during geological carbon dioxide capture and storage (CCS). Industrial impurities such as SO₂, O₂, and NOx, may be present in CO₂ streams from coal combustion sources. SO₂ and O₂ have been shown recently to influence rock reactivity when dissolved in formation water. Buoyant water-saturated supercritical CO₂ fluid may also come into contact with the base of cap-rock after CO₂ injection. Supercritical fluid-rock reactions have the potential to result in corrosion of reactive minerals in rock, with impurity gases additionally present there is the potential for enhanced reactivity but also favourable mineral precipitation.The first observation of mineral dissolution and precipitation on phyllosilicates and CO₂ storage cap-rock (siliciclastic reservoir) core during water-saturated supercritical CO₂ reactions with industrial impurities SO₂ and O₂ at simulated reservoir conditions is presented. Phyllosilicates (biotite, phlogopite and muscovite) were reacted in contact with a water-saturated supercritical CO₂ containing SO₂, or SO₂ and O₂, and were also immersed in the gas-saturated bulk water. Secondary precipitated sulfate minerals were formed on mineral surfaces concentrated at sheet edges. SO₂ dissolution and oxidation resulted in solution pH decreasing to 0.74 through sulfuric acid formation. Phyllosilicate dissolution released elements to solution with ∼50% Fe mobilized. Geochemical modelling was in good agreement with experimental water chemistry. New minerals nontronite (smectite), hematite, jarosite and goethite were saturated in models. A cap-rock core siltstone sample from the Surat Basin, Australia, was also reacted in water-saturated supercritical CO₂ containing SO₂ or in pure supercritical CO₂. In the presence of SO₂, siderite and ankerite were corroded, and Fe-chlorite altered by the leaching of mainly Fe and Al. Corrosion of micas in the cap-rock was however not observed as the pH was buffered by carbonate dissolution. Ca-sulfate, and Fe-bearing precipitates were observed post SO₂-CO₂ reaction, mainly centered on surface cracks and an illite rich illite-smectite precipitate quantified. Water saturated impure supercritical CO₂ was observed to have reactivity to rock-forming biotite, muscovite and phlogopite mineral separates. In the cap-rock core however carbonates and chlorite were the main reacting minerals showing the importance of assessing actual whole core.     

兴蒙造山带—华北克拉通地球化学走廊带沉积物主成分的含量与空间分布研究

选取兴蒙造山带—华北克拉通地球化学走廊带上沉积物的SiO_2、Al_2O_3、CaO、MgO、Na_2O、K_2O、TFe_2O_3、FeO、TiO_2、MnO、P_2O_5、CO_2、H_2O~+、pH十四个指标,研究其在不同二级构造单元、地理景观、土壤类型、降雨量等级下的含量与空间分布特征,并讨论该地球化学走廊带上化学蚀变指数。结果表明:在兴蒙造山带—华北克拉通地球化学走廊带上,作为沉积物主体的SiO_2、Al_2O_3两者含量为明显负相关而空间分布表现出此消彼长的特征;CaO、MgO、CO_2高含量分布区则与碳酸盐岩地层或含碳酸盐矿物的土壤有关,而MgO的高含量还与走廊带上镁铁质基性-超基性岩有一定关系,表明了这三个指标的高含量受特定岩性或矿物的影响较大;Na_2O、K_2O含量除了受继承的基岩影响外,还受到后期的风化作用和气候及自身地球化学性质等复杂因素综合影响,对Na_2O来说尤为如此;TFe_2O_3、MnO、TiO_2、P_2O_5相对于在地质背景复杂地段,经过冲积平原的沉积物混匀后,含量差异更小;相对干冷的内蒙古半干旱草原的气候条件有利于FeO存在,使得其相对燕山地区含量差异较TFe_2O_3要小,在章丘以南相对温暖湿润地区更易被氧化而导致其含量整体较低;北方干冷气候条件下,沉积物H_2O~+含量普遍较低,局部高含量位于碳酸盐岩地层或第四系分布区;走廊带上的pH值反映了沉积物偏碱性的特征,而在章丘以南的地区随着降雨量的增加,相对温暖湿润的气候条件,沉积物pH值表现为中性-偏弱酸性;兴蒙造山带—华北克拉通地球化学走廊带沉积物的CIA值反映出在寒冷、干燥气候条件下低等的化学风化程度,兴蒙造山带沉积物平均风化程度相对华北克拉通沉积物的平均风化程度差异变化相对要小,显示兴蒙造山带的降雨量与温度等风化影响因素变化较小。作为反映元素的地球化学亲和性的量化指标,离子电位可以更好地帮助理解沉积物元素的含量和空间分布差异。     

新疆博格达山北麓白杨河剖面页岩地球化学特征及其地质意义

通过博格达山北麓白杨河剖面芦草沟组页岩的地球化学特征的综合研究,讨论了芦草沟组页岩的元素富集特征和沉积环境以及源区物源特征和构造背景。结果表明:1研究区页岩P元素极为富集,这受控于页岩中凝灰质火山灰夹层的广泛发育;2对比于世界页岩微量元素分布,白杨河页岩相对富集Li、B、Pr、Tb、Dy、Ho、Er、Tm和Lu元素,其他元素相对亏损;3白杨河剖面页岩地化参数揭示芦草沟组自下而上气候由温湿向干热转变,进而引起水体由淡水向咸水的转变和还原程度的进一步加强;4物源区遭受低级-中等风化程度,物源类型主要为长英质火成岩,其次为铁镁质火成岩;5物源区大地构造背景以大陆岛弧-活动大陆边缘构造背景为主。     

LA-ICP-MS测定锡石U-Pb同位素年龄时两种普通铅扣除方法的原理及适用性比较

根据近年来激光烧蚀电感耦合等离子体质谱仪锡石微区原位U-Pb同位素定年的实验结果,结合相关资料,对实验过程中普通铅扣除的2种主要方法,即谐和图法和等时线法的原理、效果、优点和局限性进行了深入的比较。研究成果表明,2种主要方法各有不同的优点及局限性。在实际工作中,要想获得比较准确的测试结果,需要根据具体矿物样品的年龄范围、总的U和Pb含量、普通铅相对含量、测年精度要求等因素,灵活地选择普通铅扣除的方法。     

云南磷铝石谱学特征研究

使用电子探针、X射线粉晶衍射仪、傅里叶变换红外光谱仪、激光拉曼光谱仪、紫外可见分光光度计等仪器,对最近在云南发现的一种达到宝石级别的磷铝石进行了化学成分、矿物组成、红外吸收光谱、拉曼光谱、紫外可见吸收光谱等方面的研究。化学成分分析结果表明,该磷铝石的主要化学成分为P和Al,并含有少量的Fe和V;X射线粉晶衍射结果显示,该磷铝石的矿物成分主要为磷铝石,杂质较少;红外光谱与拉曼光谱分析均检出磷酸根基团的特征峰,红外光谱分析还显示有结晶水与结构水的存在;紫外可见吸收光谱在300和420 nm附近的吸收归属于Fe3+,630 nm附近较宽缓的吸收带由Fe3+和V3+共同产生。并将磷铝石与绿松石进行了谱学方面的对比分析,以便更好地区分两者。     

缅甸与莫桑比克红宝石的元素含量及紫外可见光谱学特征对比研究

采用镜下观察、激光剥蚀电感耦合等离子体质谱、紫外-可见吸收光谱等观察测试方法,对缅甸和莫桑比克红宝石的常规宝石学、包裹体、化学元素含量及紫外光谱特征进行了系统的对比研究。结果表明,缅甸红宝石在紫外荧光灯下呈现较强的红色荧光,内部含有互为60°夹角定向排列的短针状金红石、"糖浆状"构造等特征包裹体,具有低Fe、高V、高Ga的微量元素特征,紫外区吸收截止边小于320 nm,且694 nm处的荧光较强。莫桑比克红宝石在紫外荧光灯下荧光较弱,内部可见双晶面、无序排列的金红石和角闪石晶体等特征包裹体,具有高Fe、低V、低Ga的微量元素特征,紫外区吸收截止边在350 nm附近。上述性质可用作区分缅甸和莫桑比克红宝石的标志性识别特征。     

Defining the Potential of Nanoscale Re‐Os Isotope Systematics Using Atom Probe Microscopy

Atom probe microscopy (APM) is a relatively new in situ tool for measuring isotope fractions from nanoscale volumes (< 0.01 μm³). We calculate the theoretical detectable difference of an isotope ratio measurement result from APM using counting statistics of a hypothetical data set to be ± 4δ or 0.4% (2s). However, challenges associated with APM measurements (e.g., peak ranging, hydride formation and isobaric interferences), result in larger uncertainties if not properly accounted for. We evaluate these factors for Re‐Os isotope ratio measurements by comparing APM and negative thermal ionisation mass spectrometry (N‐TIMS) measurement results of pure Os, pure Re, and two synthetic Re‐Os‐bearing alloys from Schwander et al. (2015, Meteoritics and Planetary Science, 50, 893) [the original metal alloy (HSE) and alloys produced by heating HSE within silicate liquid (SYN)]. From this, we propose a current best practice for APM Re‐Os isotope ratio measurements. Using this refined approach, mean APM and N‐TIMS ¹⁸⁷Os/¹⁸⁹Os measurement results agree within 0.05% and 2s (pure Os), 0.6–2% and 2s (SYN) and 5–10% (HSE). The good agreement of N‐TIMS and APM ¹⁸⁷Os/¹⁸⁹Os measurements confirms that APM can extract robust isotope ratios. Therefore, this approach permits nanoscale isotope measurements of Os‐bearing alloys using the Re‐Os geochronometer that could not be measured by conventional measurement principles.