有效全岩成分的计算方法及其在变质相平衡模拟中的应用

变质相平衡模拟是变质岩领域近几十年最重要的进展之一，它已经成为确定变质作用P-T-t轨迹和探索变质演化过程的有力工具。变质岩的矿物组合不但与其形成的温度（T）和压力（P）条件有关，而且受控于岩石的全岩成分（X）。但是变质岩通常是不均匀的并且往往保留两期以上的矿物组合，因此计算不同成分域或不同变质演化期次的有效全岩成分是模拟P-T视剖面图的核心问题之一。在中-低温变质岩中，石榴石变斑晶的生长会不断地将其核部成分"冻结"而不参与后续变质反应，这导致根据实测全岩成分计算的P-T视剖面图无法有效地模拟石榴石幔部或边部生长阶段的变质演化过程。"瑞利分馏法"和"球体积法"利用电子探针实测的石榴石成分环带可以模拟计算石榴石各个生长阶段所对应的有效全岩成分，本文推荐使用这两个方法来处理石榴石变斑晶的分馏效应问题。相比较而言，石榴石在高温变质岩中通常无法保留生长阶段的成分环带特征，这是因为石榴石成分在高温条件下会发生扩散再平衡，并同时与多数基质矿物达到热力学平衡，这时一般不需要考虑石榴石的分馏效应。但是高温变质岩通常会发生部分熔融并伴随熔体的迁移，进而改变岩石的有效全岩成分。因此，通过P-T视剖面图模拟熔体迁移前后的变质演化过程需要使用"相平衡法"计算迁移的熔体成分以及熔体迁移前后岩石的有效全岩成分。此外，后成合晶与反应边是变质岩中最常见的退变质反应结构，但是后成合晶或反应边中的矿物之间并未达到热力学平衡。这种情况需要结合岩相学观察和矿物成分，利用最小二乘法确定后成合晶或反应边中发生的平衡反应方程式，进而获取变质反应发生时的有效全岩成分并通过计算P-T视剖面图来估算退变质的温压条件。除此之外，岩石体系中三价铁（Fe₂O₃）和H₂O含量的估算一直以来都是相平衡模拟研究中的难点，本文推荐使用P/T-X（Fe³⁺/Fe^tot，MH₂O）视剖面图来确定这两个组分的含量，这是因为P/T-X图可以估算各个变质演化阶段或特定矿物组合的Fe₂O₃或H₂O含量。     

南极月球陨石MIL05035矿物学、岩石学及演化历史

月球陨石MIL05035岩石类型上属于普通辉石低钛玄武岩,粗粒辉长结构,无角砾化。主要矿物为辉石(60.2%)、斜长石(27.3%)和橄榄石(6.05%),次要矿物为石英(4.36%)、钛铁矿(1.25%)和陨硫铁(0.84%),含极少量富Ti、Fe尖晶石和磷灰石,广泛发育由钙铁辉石+铁橄榄石+石英组成的后成合晶三相集合体。辉石颗粒具有明显的化学成分不均匀性和出溶片晶,核部相对贫铁钙富镁(Fs30.2-60.8Wo14.2-35.0),边部富铁钙贫镁(Fs47.5-64.9Wo22.8-44.3)。熔长石化斜长石具有微弱的成分环带,边部相对富碱金属元素(Ab9.3-12.3,Or0.31-1.03),核部则相反(Ab7.6-10.6,Or0.12-0.36),含有未熔长石化的残留斜长石。橄榄石具有粗晶橄榄石(Fa95.5-96.6)和后成合晶中细粒橄榄石(Fa88.9-93.5)两种产状。石英具有脉状、团块状和蠕虫状等产状:脉状石英大部分转变为二氧化硅玻璃,核部石英具有较宽的拉曼谱特征峰(448~502cm-1),证明其经历了冲击变质与退变质作用;团块状石英分布于粗粒橄榄石颗粒间或橄榄石与斜长石和辉石接触边界上,与斜长石构成充填结构;蠕虫状石英分布于细粒后成合晶中。粗粒辉石边部铁辉石和后成合晶中辉石成分的继承性、结构上的延续性、光学特征上的冲击暗化现象、与冲击熔脉结构上的相关性和后成合晶中发育与粗粒辉石方向几乎一致的解理等方面的证据,认为后成合晶可能由于铁辉石在冲击压力释放与温度降低后的退变质作用下分解形成。根据岩石矿物结构观察、成分分析和MELTS模拟表明该陨石母岩的岩浆演化过程可能为:母岩浆在温度降低后首先产生极少量钛铁尖晶石、其次是普通辉石和钙长石先后结晶;随着温度下降,贫钙铁普通辉石、铁钙铁辉石和铁普通辉石等在普通辉石边部大量结晶,钙长石边部分异结晶少量培长石或拉长石;随着温度继续下降,早期结晶的普通辉石析出易变辉石等出溶片晶,橄榄石在辉石和斜长石边部结晶;其后,钛铁矿和陨硫铁析出,石英沿橄榄石和钙长石等先结晶矿物裂隙充填。出露月表后强烈的冲击变质作用使斜长石几乎全部转变为熔长石、石英大部分转变为二氧化硅玻璃,并具有一系列面状变形,冲击熔脉发育,冲击变质程度至少为S5。本研究为月球的岩浆演化和冲击变质过程提供了重要证据。     

Microstructures of olivine-plagioclase corona in meta-ultramafic rocks from Sefuri Mountains, NW Kyushu, Japan

Two types of reaction rims occur between olivine and plagioclase in ultramafic rocks from the Sefuri Mountains, NW Kyushu, Japan, which were metamorphosed under granulite-facies conditions. One occurs as a thin film of orthopyroxene along the boundary between olivine and plagioclase (orthopyroxene zone). The other is composed of two zones: symplectite of calcic amphibole and spinel on the plagioclase-side (symplectite zone) and calcic amphibole with sporadic orthopyroxene on the olivine-side (tremolite zone). In the tremolite zone, calcic amphibole shows a systematic decrease in Al content and increase in Mg/(Fe +Mg) with decreasing distance from olivine. Local equilibria maintained during the diffusion-controlled corona-forming reaction enable us to apply equilibrium thermodynamics to calcic amphibole and adjacent orthopyroxene. An integrated formulation of the Gibbs method for an Fe–Mg exchange reaction constrains the equilibrium temperature recorded in the tremolite zone to be 600–710 °C. It is significantly lower than the temperature of the granulite-facies metamorphism (800–900 °C) estimated using conventional geothermobarometry. Except for H₂O, the association of calcic amphibole and spinel in the symplectite zone is chemically equivalent to the association of olivine, plagioclase and orthopyroxene that was stable before the corona formation. This suggests that the following orthopyroxene-consuming reaction describes the paragenetic change taking place between 800–900 °C and 600–710 °C, olivine + plagioclase + orthopyroxene + aqueous fluid = calcic amphibole + spinel. In contrast, the overall reaction inferred from microstructures produces orthopyroxene as well as calcic amphibole and spinel at the expense of olivine and plagioclase. This reaction requires removal mainly of MgO that is also responsible for destabilizing the local association of olivine and plagioclase. These features suggest that the presence of orthopyroxene as a product in the corona is not always indicative of an orthopyroxene-producing reaction being responsible for the change of paragenetic relation. Microstructural features should be carefully applied to infer the reaction describing paragenetic change by which we argue the P–T path of the rocks.     

Symplectite in spinel lherzolite xenoliths from the Little Hungarian Plain, Western Hungary: A key for understanding the complex history of the upper mantle of the Pannonian Basin

Two spinel lherzolite xenoliths from Hungary that contain pyroxene–spinel symplectites have been studied using EPMA, Laser ablation ICP-MS and universal stage. Based on their geochemical and structural characteristics, the xenoliths represent two different domains of the shallow subcontinental lithospheric mantle beneath the Pannonian Basin. The occurrence of symplectites is attributed to the former presence and subsequent breakdown of garnets due to significant pressure decrease related to lithospheric thinning. This implies that both mantle domains were once part of the garnet lherzolitic upper mantle and had a similar history during the major extension that formed the Pannonian Basin.

Garnet breakdown resulted in distinct geochemical characteristics in the adjacent clinopyroxene crystals in both xenoliths. This is manifested by enrichment in HREE, Y, Zr and Hf towards the clinopyroxene porphyroclast rims and also in the neoblasts with respect to porphyroclast core compositions. This geochemical feature, together with the development and preservation of the texturally very sensitive symplectites, enables us to determine the relative timing of mantle processes. Our results indicate that garnets had been metastable in the spinel lherzolite environment and their breakdown to pyroxene and spinel is one of the latest processes that took place within the upper mantle before the xenoliths were brought to the surface.     

Omphacite breakdown reactions and relation to eclogite exhumation rates

Clinopyroxene + plagioclase (±Hbl ± Qtz) symplectites after omphacite are widely cited as evidence for prior eclogite-facies or high-pressure (HP) metamorphism. Precursor omphacite compositions of retrograde eclogites, used for reconstructing retrograde P–T paths, are commonly estimated by reintegrating symplectite phases with the assumption that the symplectite-forming reactions were isochemical. Comparisons of broadbeam symplectite compositions to adjacent unreacted pyroxene from various symplectites after clinopyroxene from the Appalachian Blue Ridge (ABR) and Western Gneiss Region (WGR) suggest that the symplectite forming reactions are largely isochemical. Endmember calculations based on reintegrated symplectite compositions from the ABR and WGR suggest that a minor Ca-Eskola (CaEs) component (X_CaEs = 0.04–0.15) was present in precursor HP clinopyroxene. WGR symplectites consist of fine-grained (∼1 μm-scale), vermicular intergrowths of Pl + Cpx II ± Hbl that occur at grain boundaries or internally. ABR symplectites contain coarser (∼10 μm-scale) planar lamellae and rods of Pl + Cpx II + Qtz + Hbl within clinopyroxene cores. The contrasting textures correlate with decompression and cooling rate, and degree of overstepping of the retrograde reaction (lamellar: slow, erosionally controlled exhumation with slow/low overstepping; fine-grained, grainboundary symplectite: rapid, tectonic exhumation with rapid/high overstepping). Variations in X_CaEs, X_jd, and X_CaTs of precursor HP omphacite are related to the symplectic mineral assemblages that result from decompression. Quartz-normative symplectities indicate quartz-producing retrograde reactions (e.g., breakdown of precursor CaEs); quartz-free symplectities (e.g., diopside + plagioclase after omphacite) indicate quartz-consuming reactions (jd, CaTs breakdown) outpaced quartz-producing reactions. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.