Theory of metasomatic zonation with parallel reactions

A mathematical model of infiltrational and diffusional metasomatism, based on equations of the balance of substance and kinetics of the accompanying reactions between the solutes and the rocks, shows that a system of mineralogically different metasomatic zones develops during filtration and diffusion of hydrothermal solutions; in the infiltrational metasomatism, if the reactions are rapid, the interzonal boundaries are strikingly definite, but no such definite boundaries can be developed in the diffusional metasomatism. V.P. Sokoloff.     

Computational models of metasomatic processes

It is possible to calculate quantitative models of chemical transfer by metasomatic processes if rock density values are available with chemical analyses. A unique solution for the magnitude and sign of chemical transfer can be obtained only if the volume change or absolute variation in any chemical constituent can be established. However, even if evidence for volume change and chemical behavior is ambiguous, constraints can be placed on the chemical and physical characteristics of the chemical transfer process by making calculations based on reasonable assumptions.     

The theory of metasomatic zoning

The main features of the theory of metasomatic zoning, developed by the author, are here exposed. The basic differential equations of metasomatic zoning, of the infiltration as well as of the diffusion type, are deduced for the conditions of local equilibrium, the kinetic phenomena being neglected. The sharpness of the fronts of replacement and other regularities of metasomatic columns are established and the differences between infiltration and diffusion columns are shown. The mathematical model of the outstripping wave of acidic components in the flow of postmagmatic solutions is discussed, in relation with the acidic filtration effect, i.e., with the higher filtration rate of acidic components as compared with basic ones. The passage of this acidity wave causes the acid leaching of metals out of rocks and their subsequent concentrated redeposition in veins. One may therefore speak of a lateral and vertical hydrothermal acid-base differentiation.

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Zusammenfassung Die wesentlichsten Ergebnisse der vom Autor entwickelten Theorien über metasomatische Zonenbildungen werden dargelegt. Die grundlegenden Gleichungen der metasomatischen Infiltrations- und Diffusionszonalität werden unter der Annahme entwickelt, daß lokales Gleichgewicht geherrscht hat unter Vernachlässigung der kinetischen Beziehungen. Die Bildung scharfer Verdrängungsfronten und anderer Regelmäßigkeiten im Aufbau der metasomatischen Kolonnen und Unterscheidungsmerkmale zwischen Infiltrationsund Diffusionskolonnen werden festgehalten. Das mathematische Modell der Überholenden Aziditätswelle im Migrationsstrom der postmagmatischen Lösungen wird betrachtet. Diese Welle ist mit dem azidischen Filtrationseffekt verbunden, d.h., mit der schnelleren Filtration der azidischen Komponenten im Vergleich zu den basischen. Der Durchlauf der Aziditätswelle im Strom der postmagmatischen Lösungen ruft die azidische Auslaugung der Metalle aus Gesteinen hervor, mit darauffolgender angereicherter Ablagerung der Metalle in Gängen. Dadurch wird eine laterale und vertikale hydrothermale azid-basische Differentiation hervorgerufen.

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A report prepared for a lecture tour in France in 1967.     

Corundum-bearing metasomatic rocks in the Central Pamirs

The Muzkol metamorphic complex in the Central Pamirs contains widespread occurrences of corundum mineralization, sometimes with gem-quality corundum. These occurrences are spatially related to zones of metasomatic alterations in calcite and dolomite marbles and crystalline schists. The calcite marbles contain corundum together with muscovite, scapolite, and biotite; the dolomite marbles contain corundum in association with biotite; and the schists bear this mineral coexisting with biotite and chlorite. All these rocks additionally contain tourmaline, apatite, rutile, and pyrite. The biotite is typically highly aluminous (up to 1.9 f.u. Al), and the scapolite is rich in the marialite end member (60–75 mol %). The crystallization parameters of corundum were estimated using mineral assemblages at T = 600–650°C, P = 4–6 kbar, X _{CO 2} = 0.2–0.5 at elevated alkalinity of the fluid. The Sr concentration in the calcite and dolomite marbles is low (345–460 and 62–110 ppm, respectively), as is typical of recrystallized sedimentary carbonates. The variations in the ⁸⁷Sr/⁸⁶Sr ratio in the calcite and dolomite marbles (0.70852–0.70999 and 0.70902–0.71021, respectively) were controlled by the introduction of radiogenic ⁸⁷Sr during the metasomatic transformations of the rocks. The isotopic-geochemical characteristics obtained for the rocks and the results of numerical simulations of the fluid-rock interactions indicate that the corundum-bearing metasomatic rocks developed after originally sedimentary Phanerozoic carbonate rocks, with the desilication of the terrigenous material contained in them. This process was a manifestation of regional alkaline metasomatism during the closing stages of Alpine metamorphism. In the course of transformations in the carbonate reservoir, the juvenile fluid flow became undersaturated with respect to silica, which was a necessary prerequisite for the formation of corundum.     

Experimental study of silica diffusion during metasomatic reactions in the presence of water at 550°C and 1000 bars

Metasomatic reactions between quartz and incompatible oxides or hydroxides were experimentally studied at 550°C and 1000 bars water pressure. Two porous pellets of the initial reagents pressed one against the other were used. Reaction rims in the millimeter range develop at the initial boundary in the oxide pellet. All the experiments show that an important transfer of silica occurs by diffusion in the stationary intergranular solution.The chemical transfer of silica through the intergranular fluid is quantitatively determined by studying the kinetics of growth of the forsterite rim in the system quartz-brucite. The kinetics limiting stage being silica transfer, the experiments allow the determination of the diffusion coefficient of silica through the solution. At 550°C and 1000 bars, a value of 2.4 × 10^?1cm² s¹ is found.This high value shows the importance of chemical diffusion in the intergranular fluid of rocks during metamorphic processes.     

玉：产状及交代作用成因

真正的玉是指二种可以作为雕刻工艺品和宝石饰品的极其坚韧的单矿物岩石.其中软玉是指具叶片状的微晶习性的透闪石-阳起石岩,硬玉(华人称之为翡翠)指的是具微晶-粗晶结构的单矿物硬玉岩.软玉更普遍一些,在加拿大的British Columbia、中国的昆仑山(新疆和田玉)、俄罗斯的东Sayan山、南澳洲的Cowell和新西兰南部岛中产有重要的矿床.软玉矿体形成于岩浆流体交代白云岩或蛇绿岩流体交代硅质岩的接触带.形成条件为经白云岩质而成的高绿片岩-角闪岩相(<550°C)至中-低压(＜2kbar?)下蛇绿岩内的中-低温(400°C ～100°C).硬玉岩较软玉稀少,重要矿床产于缅甸北部、危地马拉的Motagua 山谷、俄罗斯的极地乌拉尔山和Borus山、哈萨克斯坦的Itmurundy等,仅产于沿深大断裂带内的与俯冲有关的蛇纹岩体中.硬玉岩中具韵律环带的硬玉显示了含水流体的结晶作用,并且毫无疑问呈脉状产于主岩蛇纹岩中.硬玉指示高压力,但是共生矿物中无石英,硬玉岩可在低温(200～400°C)、压力大于5～6kbar的条件下形成.形成硬玉需要去气作用,主要表现为在俯冲板片至蓝闪石片岩相-榴辉岩相过渡带的沉积物去水作用及在地幔楔通过断裂的蛇纹岩底辟的流体管涌.因此,绝大多数玉石矿床记录了蛇纹岩化橄榄岩内或其周围的有流体作用参与的、在汇聚板块边缘的事件.     

Corundum formation by metasomatic reactions in Archean metapelite,SW Greenland:Exploration vectors for ruby deposits within high-grade greenstone belts

Corundum (ruby-sapphire) is known to have formed in situ within Archean metamorphic rocks at several localities in the North Atlantic Craton of Greenland. Here we present two case studies for such occurrences: (1) Maniitsoq region (Kangerdluarssuk), where kyanite paragneiss hosts ruby corundum, and (2) Nuuk region (Storø), where sillimanite gneiss hosts ruby corundum. At both occurrences, ultramafic rocks (amphibole-peridotite) are in direct contact with the ruby-bearing zones, which have been transformed to mica schist by metasomatic reactions. The bulk-rock geochemistry of the ruby-bearing rocks is consistent with significant depletion of SiO₂ in combination with addition of Al₂O₃, MgO, K₂O, Th and Sr relative to an assumed aluminous precursor metapelite. Phase equilibria modelling supports ruby genesis from the breakdown of sillimanite and kyanite at elevated temperatures due to the removal of SiO₂. The juxtaposition of relatively silica- and aluminum-rich metasedimentary rocks with low silica ultramafic rocks established a chemical potential gradient that leached/mobilized SiO₂ allowing corundum to stabilize in the former rocks. Furthermore, addition of Al₂O₃ via a metasomatic reaction is required, because Al/Ti is fractionated between the aluminous precursor metapelites and the resulting corundum-bearing mica schist. We propose that Al was mobilized either by complexation with hydroxide at alkaline conditions, or that Al was transported as K-Al-Si-O polymers at deep crustal levels. The three main exploration vectors for corundum within Archean greenstone belts are: (1) amphibolite- to granulite-facies metamorphic conditions, (2) the juxtaposition of ultramafic rocks and aluminous metapelite, and (3) mica-rich reactions zones at their interface.     

Chemistry of metasomatic conversions in Uralian dunite-pyroxenite-gabbro formation

Moskaleva's data show that the olivinization of pyroxenites, their feldspathization, and conversion of porphyrites into gabbro are due to loss of silicon, a process called basification of the rocks. The sequence of rock formation was conditioned by the chemical properties of the elements (chiefly magnesium and aluminum), which also determine its potential migration capacity.--IGR Staff     

Thermodynamic conditions of migration as factor in metasomatic zonation

The temperature of mineralogenesis and hence metasomatic zonations in rock is determined by rates of transfers of heat from hydrothermal solution to rock. These rates, in turn, depend on the rates of migration of the solution, the solution-rock reactions, concentrations, shifting equilibria, etc., as proved by thermodynamic analysis of the solution-rock system. Under the circumstances, the- normal geothermal gradient is found to be negligible. -- V.P. Sokoloff.     

Geochemistry of metasomatic zircons from the Terskii greenstone belt

Local isotopic and geochemical studies of the zircons from metasomatites of the Terskii greenstone belt allowed us to determine two stages of metamorphism (2680 and 2025 My) and two stages of metasomatosis (2600 and 1800 My). Almost all the zircons were either metasomatic or affected to some degree by metasomatic processes caused by the enrichment of zircons in light rare earth elements, Th, U, Sr, and Ba, and flattening of the Ce anomaly.

     

The metasomatic development of zoned ultrabasic bodies in Unst,Shetland

Read (1934b) described the mineralogy and regional setting of spectacularly zoned ultrabasic bodies occurring in Unst, Shetland. Chemical and phase compositional data are presented here for a selection of samples taken from each of the several monomineralic zones.The phase sequence and elemental distribution are discussed in some detail since both are complicated. It is shown that virtually all distributional features may be explained on the basis of a diffusion model: transport most probably having occurred via aqueous solutions in pore space.The present configurations represent frozen reaction intermediates. Controls upon the nature and extent of reaction are analysed. Certain features may be explained on the basis of local equilibrium thermodynamics. These arguments, however, are inadequate. Fairly simple kinetic considerations lead to a much more satisfactory analysis.Some of the problems associated with concepts of element mobility are discussed briefly.     

Beryllium mineralization in metasomatic processes within a zone of crushing

In the test area, at the junction of a platform with a folded terrain, berylliferous metasomatic bodies are associated with contacts between rocks of a highly diverse composition which may be taken as evidence of some kind of localization of the metasomatizing solutions in zones of the inter-formational stratification produced at the time when the intrusion itself is being formed. Ruptures, faults, overthrusts in the zone of crumpling, often along contacts between different rocks, are definitive in the structural control of the mineralization. — IGR Staff.     

A study of natural and experimental metasomatic assemblages in an ultramafic-quartzofeldspathic metasomatic system from the haast schist,South Island,New Zealand

The mineralogy of a metasomatic sequence formed between ultramafic and quartzofeldspathic protoliths from the Southern Alps of New Zealand consists of a forsterite-antigorite core surrounded concentrically by zones of antigorite-magnesite, magnesite-talc, talc, tremolite, chlorite and muscovite with discontinuous pods of albite associated with the muscovite zone. On the basis of trace element data the original ultramafite-schist contact is positioned between the present tremolite and chlorite zones.An experimental study of a metasomatic system was undertaken in an attempt to clarify diffusion relationships during the metasomatic event. To simulate the natural event, ultramafic and quartzofeldspathic natural starting materials were tightly packed in a gold tube with a graphite layer between to allow later identification of the original lithological interface. Run conditions were 450° C at 2 kb for 40 days. Phase dissolution and formation were analysed petrographically and component migration was examined with the electron-microprobe. The following hierarchical scheme of component migration, phase dissolution and phase formation is delineated: CO₂ migrates from the schist into the ultramafite forming first the antigorite-magnesite zone and then the magnesite-talc zone at higher values of CO₂. These zones are then partially overprinted by the formation of talc due to SiO₂ metasomatism. The SiO₂ is supplied from the schist by the dissolution of quartz and albite in the region adjacent to the ultramafite. The tremolite zone forms at the expense of the metasomatic talc zone upon the introduction of CaO from the schist into the ultramafite. Concurrent with tremolite formation, MgO migrates from the ultramafite into the schist to form the chlorite metasomatic zone. The growth of the chlorite zone causes dissolution of the pre-metasomatic micas and displaces K₂O from the chlorite zone further into the schist. Displaced K₂O and Na₂O are responsible for the formation of the muscovite zone and the albitite pods.     

Ree minerals of alkaline metasomatic rocks in the Main Sayan Fault

The composition of accessory REE minerals (allanite, chevkinite, fergusonite, and REE carbonates) in alkaline metasomatic rocks of the Main Sayan Fault (quartz-albite-microcline-riebeckite-aegirine, quartzalbite-microcline-magnetite, and clinopyroxene-albite) was studied using back-scattered scanning electron microscopy. Chevkinite occurs only in quartz-albite-microline metasomatic rock. The paragenesis of allanite and titanite is stable in clinopyroxene-albite metasomatic rocks. Allanite and fergusonite are typical of all zones of the metasomatic column. Chevkinite and allanite are often altered due to interaction with hydrothermal fluid and lose some amount of LREE. Secondary bastnaesite, synchysite, and ancylite are formed after allanite, while secondary monazite is developed after chevkinite. Presumably, the low-temperature alteration of allanite and chevkinite under effect of F^?, CO ₃ ^2? , and P ₄ ^3? -bearing fluids had not any significant manifestation in the total REE content in metasomatic rocks.     

Transbaikal Mesozoic granites: Mode of crystallization and subsequent metasomatic transformations

Crystallization conditions and early post-magmatic rock alteration have been studied for three orebearing granite massifs using the method of stochastic modeling. These Mesozoic granites were crystallized from a relatively dry melt, whose barren (ore-free) parts were crystallized from a volatile-enriched magma under sealed conditions. Surface zones of weak rock alteration over subsurface mineralization reflect the subsurface structural patterns controlling the mineralization.     

Water contents of Roberts Victor xenolithic eclogites: primary and metasomatic controls

A suite of eclogites from the Roberts Victor kimberlite has been extensively characterized in terms of petrology and geochemical compositions (Gréau et al. in Geochim Cosmochim Acta 75(22):6927–6954, 2011; Huang et al. in Lithos 142–143:161–181, 2012a). In the present study, the water contents of eclogitic garnet and omphacite were analyzed by Fourier transform infrared spectrometry. Garnet does not contain measureable OH in any sample. The water content of omphacite in the studied eclogites ranges from 211 to 1,496 ppm. Mantle metasomatism has modified the water content of some of the eclogites, while others retain water contents characteristic of their original environment. The OH contents of the metasomatized eclogites may be mainly controlled by the H₂O fugacity and mineral compositions. The OH contents of the non-metasomatized samples are interpreted to be more sensitive to their mantle equilibration temperature, pressure, and the local fugacities of H₂O and O₂. The calculated water content of the metasomatic medium is similar to that of carbonatitic–kimberlitic melts/fluids. Eclogites contain more water than peridotites recorded in the literature (341 ± 161 vs 122 ± 54 ppm) and represent an important water reservoir in the lithospheric mantle wherever they occur. This is an important parameter to be considered in the interpretation of mantle processes and geophysical data such as seismic wave speeds and electrical conductivity, and in geodynamic modeling.