Temperature,pressure and composition: Structurally analogous variables

Changes in temperature, pressure and composition cause changes in the ratios of polyhedral sizes in oxygen-based minerals. Polyhedra with large, high-coordination, low-valence cations expand and compress more than polyhedra with small, low-coordination, high-valence cations. Changes in cation composition alter the ratios of polyhedral sizes by changing mean cation radii. Thus temperature, pressure and composition are structurally analogous variables. Since temperature, pressure and composition change structures in similar ways, it is possible to construct isostructural surfaces in P-T-X space. For structures in which stability is limited to specific ranges of polyhedral size ratios (e.g. octahedral-tetrahedral layers in mica), certain P-T-X isostructural surfaces may coincide with phase boundaries. If geometrical constraints on mineral stability are known, then phase equilibria may be predicted. Examples of stability limit calculations are given for several major oxygen-based mineral groups.     

Equilibriums between Cu,Fe, and Zn sulfides and oxides in chloride solution: A thermodynamic study

The results of thermodynamic modeling of equilibriums between Cu, Fe, and Zn sulfides and oxides pertaining to the Cu-Fe-Zn-S-O₂ system in water and aqueous chloride solution are presented. The system comprises solid phases of constant composition: pyrite, pyrrhotite, hematite, magnetite, wüstite, γ-iron, chalcocite, covellite, cuprite, native copper, chalcopyrite, and bornite, as well as more than 100 ions, complexes, and molecules in an aqueous solution. The GIBBS program with the UNITHERM thermodynamic dataset used in calculations allows numerical analysis of phase assemblages in a dry system and in equilibrium with an aqueous solution. How the temperature, pressure, and the composition of the solution in the system opened for oxygen and sulfur affects the composition of phase assemblages was considered in temperature and pressure ranges of 50–350 C and 100–1000 bar, respectively. Decrease in temperature leads to a shift in stability fields of the studied phases toward the region of elevated oxygen and sulfur partial pressures. Variation of temperature is an important factor affecting precipitation of ore minerals, primarily, Cu- and Zn-bearing. The calculation results are presented in tables and diagrams. Each point in the $ (\log m_{S_{tot} } - \log f_{O_2 } ) $ (\log m_{S_{tot} } - \log f_{O_2 } ) diagram is characterized by a single possible assemblage of phases equilibrated with a solution of the given composition within the considered temperature and pressure range. Since the composition of the mineral assemblage is controlled by physicochemical conditions at the moment of mineral formation, comparison of the calculation results with mineral assemblages at ore deposits makes it possible to estimate the parameters of ore deposition at the early stage of investigation, including oxygen and sulfur activity and, occasionally, the composition and salinity of the solution. These parameters control the formation of such assemblages.     

The mineral chemistry of hydrothermally altered and metamorphosed wall-rocks at the Stollberg Fe-Pb-Zn-Mn(-Ag) deposit,Bergslagen, Sweden

The c. 1.9 Ga old Stollberg sulphide and Mnrich skarn iron ores and sulphide ores in Bergslagen, south-central Sweden are hosted by hydrothermally altered and metamorphosed felsic volcanic and volcaniclastic rocks. The ores are underlain by comformable alteration zones characterized by albite-gedrite-quartz and biotite-muscovite-plagioclase-K-feldspar-quartz +/– garnet assemblages. The present mineralogies are interpreted as medium-grade metamorphic equivalents to the original alteration mineral assemblages. PT-conditions during prograde regional metamorphism are semiquantatively determined to be 510 to 560 °C at approximately 3 kbar. With increasing modal content of gedrite and biotite in the alteration zones, the Mg/Fe ratios and X_Mg's in octahedral positions of these minerals also increase. In the gedrite-bearing strata, whole-rock Mg/Fe ratios remain constant, whereas in the biotite-rich unit the wholerock Mg/Fe trend is parallel to that of the biotites.The trends in the metamorphic mineral composition are interpreted to be a product of original changes in fluid composition during the evolution of a sub-seafloor hydrothermal system. During the initial stage of alteration, Fe-Mn-rich fluids altered the rocks, and during a later stage, the fluids became more Mg-rich, possibly due to entrainment of fresh seawater, and the alteration zones became relatively more Mg-rich. Sulphide precipitation was contemperaneous with Mg metasomatism, suggesting base metal precipitation was a function of the mixing of cool seawater with hydrothermal fluid. It is proposed that early hydrothermal alteration was associated with the deposition of areally extensive Fe-oxide formation, and that Mg metasomatism defines a second stage of hydrothermal activity during which sulphide mineralization overprinted the earlier formed Fe-oxide deposit.     

Migration of platinum,palladium, and gold in the water systems of platinum deposits

In order to explore the behavior of platinum group elements in the ecosystems of mineral deposits, the migration characteristics of platinum and palladium were determined in the pH range typical of surface waters. Model sorption experiments on the precipitation of platinum and palladium on iron oxyhydroxide in the presence of major natural inorganic and organic ligands showed that platinum interacts most actively with an iron oxyhydroxide (ferrihydrite) precipitate within the whole pH range, both in the absence and presence of natural organic substances, whereas palladium is preferentially bound to dissolved, suspended, and sedimentary humic substances. The thermodynamic calculation of coexisting platinum and palladium species is qualitatively consistent with experimental data on the character of accumulation and migration of these elements. The obtained data suggest that the migration of platinum and palladium into highly colored waters in the zones of platinum group element deposits results in their extensive deposition on natural geochemical barriers.     

On thermobarometry

Thermobarometry, the estimation of the pressure–temperature ( P – T ) conditions of metamorphism, can be undertaken by using pseudosection calculations as well as by conventional methods. Conventional thermobarometry uses only the equilibrium thermodynamics of balanced reactions between end-members of minerals, combined with the observed compositions of minerals. In contrast, pseudosections involve a forward calculation of mineral equilibria for a given rock composition. When related to observed rock data such as mineral assemblages, mineral proportions and mineral compositions, pseudosections have the power to provide valuable additional thermobarometric information. This is because the rock composition provides added constraints on P – T , unavailable in conventional thermobarometry, such as when minerals in the mineral assemblage are no longer stable, or when additional minerals join the mineral assemblage. Considering both conventional and pseudosection thermobarometry, a minimum requirement is that they use the same thermodynamic data and activity–composition models for the minerals involved. A new thermocalc facility is introduced that allows pseudosection datafile coding to be used for conventional thermobarometry. Guidelines are given and pitfalls discussed relating to pseudosection modelling and conventional thermobarometry. We argue that, commonly, pseudosection modelling provides the most powerful thermobarometric tools.     

The effect of trapped liquid crystallization on cumulus mineral compositions in layered intrusions

A series of calculations have been carried out to evaluate the effect on cumulus mineral compositions of solidification of trapped intercumulus liquid in orthocumulates. The calculation assumes local equilibrium between phases, and that the system remains chemically closed during crystallization of the trapped liquid. The latter assumption is held to be valid on a scale of tens to hundreds of centimeters. It is not necessary to know the composition of the trapped liquid, as the calculation only requires an estimate of FeO content and trapping temperature.The change in composition of a mineral from that of the initially precipitated cumulus crystals to the final composition after complete solidification is termed the trapped liquid shift. Its magnitude depends on the modal proportions of cumulus phases and the initial porosity, and is only weakly dependent on initial phase compositions. Trapped liquid shifts are significant when compared with mineral composition changes occurring during fractional crystallization. Crystallization of 30% trapped liquid gives rise to shifts of up to 10 mol. percent in Mg number of olivine or pyroxene. The size of the shift becomes greater when the initial cumulus assemblage has a lower total FeO+MgO content, and vice versa.As a result of the relationship between trapped liquid shift and cumulus mode, mineral composition variations and trends may be generated in sequences of cumulates which originally had constant compositions of cumulus minerals. For example, in a cyclic unit grading from a pyroxenitic base to an anorthositic top, crystallization of a uniform proportion of trapped liquid will result in an apparent iron enrichment trend from bottom to top of the cycle, as has been observed in the Upper Critical Zone of the Bushveld Complex.     

A Linear Programming Approach to Determine the Normative Composition of Sedimentary Rocks

The analysis of modal and normative composition of sedimentary rocks is widely used for studying their sources and tectonic settings. The normative calculation of the mineral composition of rocks in this study is formulated as a linear programming problem and is solved by means of the simplex method. This enables both simultaneous and successive subtraction of a set of basic minerals from a rock sample represented by its chemical composition {SiO₂...LOI}. Such an approach provides a more exact calculation of the contribution of basic minerals in the rock. This mathematical approach is used to study two representative sets of sandstones and fine-grained rocks from a Meso- to Neoproterozoic marginal basin of southeastern Siberia (Uchur–Maya region, Yakutia) and a Pennsylvanian-Lower Permian uplifted continental block in Colorado, USA. The calculated normative mineral compositions of the Siberian sandstones are consistent with the observed modal compositions. These sandstones vary from K- Feldspar rich arkoses at the base of the sequence (the Uchur Group, lower Riphean) to quartz arenites or lithic sandstones and wacke in transgressive successions of the middle-upper Riphean. Arkoses and quartz arenites are dominant in Meso- to Neoproterozoic Siberia. These samples represent craton interior uplifted basement and quartzose, recycled orogen provenance of a stable craton in Rodinia. There are higher but consistent discrepancies between the calculated and observed compositions for the Pennsylvanian to Lower-Permian arkoses and quartz arenites (Sangre de Cristo, Belden, and Maroon Formations). The differences between the predicted and observed mineralogy may be due to uncertainties in the modes in the matrix and cement of the sandstones. This normative program should supplement modal calculations and provide better genetic constructions, especially in case of matrix-rich sandstones.     

Compositions, Proportions, and Equilibrium Temperature of Coexisting Two-feldspar in Crystalline Rocks

Compositions, proportions, and equilibrium temperature of coexisting two-feldspar in crystalline rocks are of great importance to classification in petrography and interpretation of petrogenesis. Crystalline rocks are usually composed of 4-6 minerals (phases), depending on their independent chemical components and the equilibrium temperature of crystallizations. In general, number of mineral phases can be determined by the “Phase Rule”. According to the mass balance principle, bulk composition of coexisting two-feldspar could be evaluated from the bulk chemistry of a rock, provided that the compositions of the coexisting mafic mineral phases containing calcium, sodium, and potassium oxides are determined, e.g., by microprobe analysis. The compositions, proportions, and temperature of two-feldspar in equilibrium can thus be simultaneously resolved numerically from bulk composition of the rock, by incorporating the activity/composition relations of the ternary feldspars with the mass balance constraints. Upon the numerical approximation method presented in this paper, better-quality, internally consistent data on feldspar group could usually be obtained, which would be expected more realistic and accurate in consideration of thermodynamic equilibria in the system of crystalline rocks, as well as bulk chemistry of a rock and the composing minerals.     

Mineralogy and equilibrium P-T estimates for peridotite assemblages from the V. Grib kimberlite pipe (Arkhangelsk Kimberlite Province)

This study presents mineralogical and thermobarometric data for equilibrium peridotite assemblages from the V. Grib kimberlite pipe of the Arkhangelsk diamond province. We provided the first constraints on the composition, structure, thermal state, and lower boundary of the lithospheric mantle beneath the V. Grib kimberlite pipe. It was found that phlogopite-free and phlogopite-bearing peridotite xenoliths can be distinguished by their mineral chemistry. The occurrence of phlogopite in peridotites may represent evidence for modal metasomatism responsible for variation in the mineral composition of phlogopite-pyrope and pyrope peridotites. On the basis of P-T estimates, we conclude that modal metasomatism may have affected the entire thickness of the lithospheric mantle beneath the V. Grib kimberlite pipe. Comparison of our results with the available data from the literature shows strong vertical and lateral mantle heterogeneity beneath kimberlite pipes of the Lomonosov deposit and the V. Grib pipe.     

Perfect fractionation in multicomponent, multiphase systems

Perfect fractionation models help infer the conditions under which molten rock material travels from the planet’s interior to the Earth’s surface where it cools and crystallizes. Quantitative models of melt crystallization, perfect fractionation paths through P–T-composition space, return calculated values of predicted quantities that can be compared to glass, rock, and mineral compositions measured in lava flows. Perfect fractionation models are based on thermodynamics and material balance constraints. Linear combinations of chemical potentials define equilibrium positions. The composition of the melt follows a path directly away from the composition of the phases at saturation, a material balance criterion. The number of adjustable parameters in a perfect fraction model is limited to two by Duhem’s theorem. Perfect fractionation models with one or two phases at saturation require only one mole fraction and one adjustable parameter be specified to calculate the fractionation path. The temperature and compositions of the saturating phases are determined by the equilibrium equations for one- or two-phase saturation in a melt of known compositions. With three or more phases at saturation, the composition of the melt has to be adjusted in the general case. Fractionation paths can also be inferred from a sequence of thermodynamic states calculated by minimizing a thermodynamic potential. The minimization procedure produces a fraction path that is conceptually different from the perfect fractionation path. Perfect fractionation models can be constructed to conserve a particular thermodynamic potential or variable such as enthalpy or density.     

视剖面图温压计研究进展评述

视剖面图温压计是目前定量估算变质温度和压力的主要方法之一。其理论基础为热力学平衡原理与质量守恒定律。利用内恰的热力学数据库和相应的成分-活度模型对特定成分体系进行视剖面图计算,可以正演模拟给定温度和压力条件下的矿物组合、矿物丰度及其成分,与实测岩石对比,可以准确获取岩石的形成温度和压力。在应用视剖面图温压计时,应选择受全岩成分影响小、且受退变质作用影响微弱的矿物成分;对于有成分变化的体系,应结合多种方法恢复有效全岩成分。文中通过视剖面图对KFMASH(K2O-Fe O-Mg O-Al2O3-Si O2-H2O)体系下不同矿物组合内多硅白云母硅含量及其等值线斜率的研究,认为多硅白云母硅含量及其等值线斜率主要由不同矿物组合内多硅白云母参与的契尔马克替换及纯转换端元反应中的主导反应决定,进一步深化了对变质过程中控制矿物成分变化的内部缓冲反应机制的理解,从而也可为选择和应用矿物温压计提供指导。因此,视剖面图方法是目前研究变质岩石形成条件及变质作用精细过程的最佳方法之一。     

Rock Maker: an MS Excel? spreadsheet for the calculation of rock compositions from proportional whole rock analyses, mineral compositions, and modal abundance

Rock Maker is a simple software tool that computes bulk rock compositions resulting from mixing or unmixing of rocks or minerals. The calculations describe the chemical expression of processes such as magma mixing, fractional crystallization, assimilation, residual melt extraction, or formation of solid solutions. Rock Maker can also be used for the elimination of thermodynamically inactive or unwanted chemical components from the whole rock composition, such as cores of porphyroblasts that are considered not to be in equilibrium with the matrix. The calculation of the resulting rock composition is essentially based on modal proportions and compositions of different components in rocks, which may include specific portions of the rock or individual mineral phases. Compositional data, obtained using XRF, ICPMS, EDS, or EPMA, may include major and trace element concentrations. Depending upon the nature of the problem to be solved, the concentrations of oxidic and elemental components can be added to, or subtracted from, each other, producing the calculated normalized whole rock composition after completion of the investigated process (mixing, unmixing, depletion, enrichment, etc.). Furthermore, the software allows the calculation of whole rock compositions from ideal mineral compositions, for which modal proportions can be chosen from pre-defined mineral compositions. The data set includes the most common rock forming minerals and allows the addition of further phases. This section can be used to calculate the approximate whole rock compositions from petrographic modal analysis. This part of Rock Maker is specifically suitable as a teaching tool that illustrates the interrelationship between mineral compositions, modes, and the corresponding whole rock compositions.     

Mixing between granitic and dioritic crystal mushes, Guernsey, Channel Islands, UK

The contact zone between the Cobo Granite and Bordeaux Diorite Complex of Guernsey (Channel Islands, UK) displays numerous features which result from the interaction of these two penecontemporaneously emplaced intermediate to felsic magmas. Initial interaction resulted in the formation of chilled mafic enclaves in granite magma. As thermal equilibrium was approached, some physical mixing took place to produce a heterogeneous “Marginal Facies”. Continued interaction resulted in incorporation of previously mixed magma into intruding magma. The early mixed material is locally preserved as enclaves, but more commonly underwent disaggregation promoted by its incompletely crystallised nature, the mineral components becoming distributed as xenocrysts and often as microenclaves, or glomeroxenocrysts, into surrounding magma. Further modification within the contact zone was brought about by the infiltration of melt through the interconnected pore space of the magma mushes on the scale of centimetres to hundreds of metres. These processes produced geochemical profiles which do not exhibit perfect mixing trends. The petrographic and geochemical features described not only demonstrate the efficacy of mixing between partially crystallised magma mushes of broadly similar composition, but also provide criteria by which such interaction may be recognised elsewhere. Many features, in particular mineral scale disequilibria and small scale modal heterogeneity, bear striking similarities to those which occur widely in granite plutons where obvious evidence for magma mixing is absent. As such, it is possible that many granite bodies preserve a subtle record of hitherto overlooked mixing events.     

The K-Ar system, lithomineralogical, and geostructural characteristics of the Jurassic terrigenous complex in the Northeastern Caucasus

The paper discusses changes in both mineral composition and structural-textural characteristics of the Jurassic terrigenous complex along the Avar Koisu River (Dagestan) profile that intersects rocks with significantly various types of deformation. The profile extends from the monoclinal zone to the intense deformation and cleavage development zone. The alterations are manifested in the change of clay mineral assemblages, polytype modifications of micaceous minerals and their crystallinity index, rock density, reflectance of vitrinite, and other properties. Growth of the degree of secondary alterations (primarily, cleavage intensity) is accompanied by an appreciable decrease in K-Ar age of rocks and simultaneous increase of their stratigraphic age.     

PT Paths from modal proportions: application to the Koralm Complex,Eastern Alps

Thermodynamic pseudosections portray those parts of a petrogenetic grid that are relevant to a given bulk composition and the reactions appearing on them can therefore be used directly to infer the PT path that the rock followed. However, for many ‘normal’ bulk compositions the use of pseudosections is hampered by the fact that they display only few large fields of high thermodynamic variance in the PT range of interest. Here it is discussed how modal information on reaction progress within these fields can be used to determine PT path information for thermodynamically high variant metamorphic assemblages. We use this information on reaction progress to contour pseudosections for modal proportions of minerals using the software package THERMOCALC. The approach is applied to di- tri- and quadrivariant assemblages from the Koralm complex in the eastern Alps. A PT path for these rocks is derived from modal considerations and compared with interpretations of mineral composition contours on the same pseudosection and with conventional thermobarometry. It is shown that at least part of the complex must have cooled initially near isobarically from prevalent peak conditions around 700°C and 14 kbar before the rocks commenced a Barroviantype decompression path.     

辽河群变质序列再讨论

辽河群的原岩以泥质和泥砂质岩石为主,其经历了绿片岩相至角闪岩相变质作用,产生了丰富的变质矿物（矿物组合）.不同变质级别的矿物组合,是各自在变质作用峰期生成的,它们是空间上的并列关系,绝非时间上的先后关系,不能依此划分变质阶段和幕次,更不能用它们来做P-T-t轨迹.同一矿物组合内,通过滑动反应和综合反应,矿物之间达到一定温压条件下的平衡共生关系,各种矿物变质程度是相同的,形成时间是同时的或交错的.有的研究者认为,变质矿物形成序列为Chl→Bt→Gt→Stau→And（Ky）→Sill（Cord）,这种观点是值得商榷的.     

引领世纪的地球系统科学研究现状

随着人类社会谋求可持续发展意愿的加强,突出系统科学的服务和规范已成为我国公益性地质工作的战略要求,并且成为引领新世纪地球科学的发展方向。建立在地球探针等技术基础之上的系统科学,必将促进多学科交叉融合,从地球系统整体行为研究寻求解决办法。由此提出了地球系统和地球系统科学的概念。通过自由性、统计性、组合性的研究,研究自然界中的秩序与和谐,通过体系的完全性、参数性、层次性的研究,揭示不同空间的物质组成,解释不同结构的物性参数,通过地质学、地球物理、地球化学信息的研究,探索开发矿物原料、资源估算、水文生态、污染治理、矿山监测。     

三种类型烃-烃不混溶包裹体组合的特征和热力学条件的计算

在自然界广泛分布着烃-烃不混溶体系中捕获的流体包裹体,由于这些包裹体具有复杂的组成和相态,因此不混溶包裹体组合的判别和热力学参数的计算常常难以进行。根据烃-烃不混溶体系中两个端员组分流体包裹体室温下的相态特征和在温度-压力平面图上等容线交点显示的位置,划分成三种类型流体包裹体组合,本介绍了三种类型流体包裹体组合特征,叙述了不混溶烃-烃包裹体组合的测定和判别方法,并且阐述均一化包裹体相态方程和气-液平衡常数原理和方法与此同时列举了自然界简单的三种类型不混溶烃-烃包裹体组合的测定、判别和计算的几个实例,利用相态方程和气-液平衡常数,不但精确地计算出包裹体均一压力,并且精确地计算出流体密度和体积等热力学参数。最后,利用均一成气相和液相的两种包裹体在 p-T 平面图上等容线交点同样计算出流体包裹体组合的捕获温度和压力。     

Rcrust: a tool for calculating path‐dependent open system processes and application to melt loss

Earth's continental crust is stabilized by crustal differentiation that is driven by partial melting and melt loss: Magmas segregate from their residuum and migrate into the upper crust, leaving the deep crust refractory. Thus, compositional change is an integral part of the metamorphic evolution of anatectic granulites. Current thermodynamic modelling techniques have limited abilities to handle changing bulk composition. New software is developed (Rcrust) that via a path‐dependent iteration approach enables pressure, temperature and bulk composition to act as simultaneous variables. Path‐dependence allows phase additions or extractions that will alter the effective bulk composition of the system. This new methodology leads to a host of additional investigative tools. Singular paths within pressure–temperature–bulk composition (P–T–X) space give details of changing phase proportions and compositions during the anatectic process, while compilations of paths create path‐dependent P–T mode diagrams. A case study is used to investigate the effects of melt loss in an open system for a pelite starting bulk composition. The study is expanded upon by considering multiple P–T paths and considering the effects of a lower melt threshold. It is found that, for the pelite starting composition under investigation, open systems produce less melt than closed systems, and that melt loss prior to decompression drastically reduces the ability of the system to form melt upon decompression.