Theory of metamorphic segregation and related processes

Metamorphic segregation is defined here as the formation and growth of bands or domains of different bulk compositions within an originally unbanded rock. It can result from an instability arising in some deforming rocks when diffusion transfer is significant. The nature of this instability is demonstrated separately for a differentiation associated with a crenulation (Type C) and for one without crenulation (Type L). However, the continuous gradation between the two types observed in nature is also expected from the models.A requirement for both types is that one chemical component of the rock, typically silica, diffuse more rapidly than others, e.g. phyllosilicate components, in response to stress-induced pressure gradients. In addition, Type L requires that, at least at an early stage, portions of the rock rich in this mobile component, e.g. rich in quartz, be more competent than those portions which are poor in quartz. By a process akin to the development of pressure shadows, silica diffuses toward domains which are already the richest in quartz. Alternatively, if the rock is chemically open to loss of silica, this silica preferentially originates from dissolution of quartz in the more mica-rich domains. In either case the compositional contrast between domains is increased and metamorphic segregation results. Type C differentiation is best explained if we accept the suggestion made by many petrographers that layer silicates catalyse the pressure-induced transfer of silica. This suggestion can in fact account for other features of metamorphic segregation bands.Metamorphic segregation should also proceed during the development of quartz segregations, quartz rods, slaty cleavage and mylonite banding. The stress distribution argued for Type L bands may also occur in many banded migmatites. In migmatites. however, the assemblage crystallizing in the leucosome may be derived from a circulating hydrothermal fluid as well as from diffusion transfer.     

地幔流体与铀成矿作用:以下庄矿田仙石铀矿床为例

仙石大型铀矿床位于粤北贵东复式岩体东部，矿区内NWW和NNE向基性岩脉十分发育。矿床位于NNE向硅化带和NWW向基性岩脉(辉绿岩)交接部位，矿体严格赋存于基性岩脉内部或其边缘。金属矿物以沥青铀矿和黄铁矿为主，脉石矿物以方解石和(微晶)石英为主，蚀变作用发育，主要类型包括碱交代、硅化和赤铁矿化。沥青铀矿U-Pb年龄测定结果表明，矿床中存在81Ma(主要)和125Ma(次要)两期铀矿化。H、O同位素研究表明，矿前期和成矿期成矿流体的δ^1aOH2O=1.4‰～65％，δDH2O=-65‰-34‰，反映成矿流体主要由地幔流体组成。矿脉中方解石的δ13C=-8．5‰～-3．1‰，反映矿化剂∑CO2来自地幔。上述特征表明，地幔流体在仙石铀矿床的形成中具有十分重要的意义。     

Ultrahigh-pressure metamorphic rocks from the Chinese Continental Scientific Drilling Project: II Oxygen isotope and fluid inclusion distributions through vertical sections

In order to reconstruct the formation and exhumation mechanisms of UHP metamorphic terrains, the Chinese Continental Scientific Drilling Program (CCSD) has been carried out in Donghai of the Dabie-Sulu ultrahigh-pressure (UHP) metamorphic belt, East China. Eclogite, gneiss, amphibolite (retrograded from eclogite), ultramafic rocks, and minor schist and quartzite have been drilled. Aiming to reveal the fluid behaviour in a vertical sequence of an UHP slab, we investigated fluid inclusion and oxygen isotope characteristics of selected drillcores from the main hole and the pilot-holes PP2 and ZK 703 of the CCSD. More than 540 laser-ablation oxygen isotope analyses on garnet, omphacite, quartz, kyanite, amphibole, phengite, rutile, epidote, amphibole, plagioclase, and biotite from various rocks in the depth range of 0–3,000 m (mainly eclogite and gneiss) show that the investigated rocks can be divided into two groups: ¹⁸O-depleted rocks (as low as δ¹⁸O = −7.4‰ for garnet) indicate interaction with cold climate meteoric waters, whereas ¹⁸O-normal rocks (with bulk δ¹⁸O > +5.6‰) have preserved the O-isotopic compositions of their protoliths. Meteoric water/rock interaction has reached depths of at least 2,700 m. Oxygen isotope equilibrium has generally been achieved. Isotopic compositions of mineral phases are homogeneous on a mm to cm scale regardless of lithology, but heterogeneous on the scale of a few metres. Oxygen isotope distributions in the vertical sections favour an “in situ” origin of the UHP metamorphic rocks. The very negative δ¹⁸O eclogites usually have higher hydroxyl-mineral contents than the normal δ¹⁸O rocks, indicating higher water content during UHP metamorphism. Fluid inclusion data suggest that rocks with depleted ¹⁸O compositions have had different fluid histories compared to those with normal δ¹⁸O values. Rocks with depleted ¹⁸O mainly have primary medium-to-high salinity inclusions in omphacite, kyanite and quartz, and abundant secondary low-salinity or pure water inclusions in quartz, indicating a high-salinity-brine-dominated fluid system during peak UHP metamorphism; no carbonic inclusions have been identified in these rocks. By contrast, primary very high-density CO₂ inclusions are commonly found in the rocks with normal δ¹⁸O values. These observations suggest that fluid and oxygen isotope composition of minerals are related and reflect variable degrees of alterations of the Dabie-Sulu UHP metamorphic rocks.     

Origins of yttrium and rare earth element distributions in metamorphic garnet

Highly variable distributions of yttrium and rare earth elements (Y+REEs) are documented in pelitic garnet from the Picuris Mountains, New Mexico, and from Passo del Sole, Switzerland, and in mafic garnet from the Franciscan Complex, California. The wide variety of these Y+REE zoning patterns, and those described previously in other occurrences, imply diverse origins linked to differing degrees of mobility of these elements through the intergranular medium during garnet growth. In the Picuris Mountains, large, early‐nucleating crystals have radial profiles of Y+REE dominated by central peaks and annular maxima, in patterns that vary systematically with atomic number. Superimposed on these features are narrow spikes in HREEs and MREEs, located progressively rimward with decreasing atomic number. In contrast, profiles in small, late‐nucleating crystals contain only broad central maxima for all Y+REEs. In garnet from Passo del Sole, Y+REE zoning varies radically from sample to sample: in some rocks, crystals of all sizes display only central peaks for all Y+REEs; in others, profiles exhibit irregular fluctuations in Y+REE contents that match up with small‐scale patchy zoning in Y and Ca X‐ray maps. In the Franciscan Complex, Y+REE in garnet cores fluctuate unsystematically, but mantles and rims display concentric oscillatory zoning for both major elements and Y+REEs. Our interpretation of the complexity of Y+REE distributions in metamorphic garnet centres on the concept that these distributions vary primarily in response to the length scales over which these elements can equilibrate during garnet growth. Very short length scales of equilibration, due to low intergranular mobility, produce overprint zoning characterized by small‐scale irregularities. Higher but still restricted mobility yields diffusion‐controlled uptake, characterized by patterns of central peaks and annular maxima that vary with atomic number and are strongly influenced by T–t paths during garnet growth. Still greater mobility permits progressively greater, potentially rock‐wide, equilibration with major‐ and accessory‐phase assemblages, leading to mineralogical controls: an unchanging mineral assemblage during garnet growth produces bell‐shaped profiles resembling those produced by Rayleigh fractionation, whereas changes in major‐ and/or accessory‐phase assemblages produce profiles with distinct annuli and sharp discontinuities in concentration. The very high mobility associated with influxes of Y+REE‐bearing fluids can cause these element distributions to be dominated by factors external to the rock, yielding profiles characterized by abrupt shifts or oscillations that are not correlated to changes in mineral assemblages.     

Trace-element distributions in silicates during prograde metamorphic reactions: implications for monazite formation

To assess the petrogenetic relationship between monazite and major silicates during prograde metamorphism, REE were measured across coexisting zoned silicates in garnet through kyanite‐grade pelitic schists from the Great Smoky Mountains, western Blue Ridge terrane, southern Appalachians, to establish REE concentrations and distributions before and after the monazite‐in isograd, and to identify the role major silicates play in the formation of monazite. Results indicate significant scavenging of light rare‐earth elements (LREE) from silicates during the monazite‐in isograd reaction; however, the absolute concentration of LREE hosted in the silicates was insufficient to produce monazite in the quantity observed in these schists. Monazite must have formed mainly from either the dissolution of allanite or some other source of concentrated LREE (possibly adsorbed onto grain boundaries), even though direct evidence for allanite is lacking in a majority of the samples. Laser‐ablation ICP‐MS analyses and theoretical thermodynamic calculations show that monazite may have formed as a result of contributions from both allanite and major silicates. Allanite breakdown initially formed monazite, and monazite production drew LREE liberated from allanite, major silicates and possibly from crystal boundaries. In many rocks the reaction was further promoted by the staurolite‐in reaction, allowing for rapid, isogradic monazite growth.     

Mineral and fluid inclusions in zircon of UHP metamorphic rocks from the CCSD-main drill hole: A record of metamorphism and fluid activity

The Chinese Continental Scientific Drilling (CCSD) main drill hole (0–3000 m) in Donghai, southern Sulu orogen, consists of eclogite, paragneiss, orthogneiss, schist and garnet peridotite. Detailed investigations of Raman, cathodoluminescence, and microprobe analyses show that zircons from most eclogites, gneisses and schists have oscillatory zoned magmatic cores with low-pressure mineral inclusions of Qtz, Pl, Kf and Ap, and a metamorphic rim with relatively uniform luminescence and eclogite-facies mineral inclusions of Grt, Omp, Phn, Coe and Rt. The chemical compositions of the UHP metamorphic mineral inclusions in zircon are similar to those from the matrix of the host rocks. Similar UHP metamorphic P–T conditions of about 770 °C and 32 kbar were estimated from coexisting minerals in zircon and in the matrix. These observations suggest that all investigated lithologies experienced a joint in situ UHP metamorphism during continental deep subduction. In rare cases, magmatic cores of zircon contain coesite and omphacite inclusions and show patchy and irregular luminescence, implying that the cores have been largely altered possibly by fluid–mineral interaction during UHP metamorphism.

Abundant H₂O–CO₂, H₂O- or CO₂-dominated fluid inclusions with low to medium salinities occur isolated or clustered in the magmatic cores of some zircons, coexisting with low-P mineral inclusions. These fluid inclusions should have been trapped during magmatic crystallization and thus as primary. Only few H₂O- and/or CO₂-dominated fluid inclusions were found to occur together with UHP mineral inclusions in zircons of metamorphic origin, indicating that UHP metamorphism occurred under relatively dry conditions. The diversity in fluid inclusion populations in UHP rocks from different depths suggests a closed fluid system, without large-scale fluid migration during subduction and exhumation.     

Chemical and isotopic effects of retrogression in metamorphic fluid inclusions

Fluid inclusions may provide compositional and isotopic information about fluids from which the host mineral precipitated as long as the host mineral does not react with the fluid. Our transmission electron microscope (TEM) investigation of grain boundaries and of fluid inclusions in zoisite and quartz of high-pressure metamorphic rocks from Dabie Shan (eastern China) demonstrates daughter minerals, such as margarite, muscovite, calcite, and anhydrite. Their precipitation changes (1) the composition of the fluid by selective and mineral-specific removal of CO₂ (carbonates), H₂O (sheet silicates, hydration of the walls), or S (gypsum, anhydrite, sulfides), (2) the concentrations and proportions of ions dissolved in the fluid, and (3) the isotopic composition of the fluid because of isotopic fractionation between mineral precipitate and fluid and between unmixed fluids. Fluid leakage from overpressurized fluid inclusions with daughter minerals changes the overall chemical and isotopic composition of the inclusion irreversibly, even when the daughter crystals later redissolve. Such fluid loss yields a wide range of compositionally and isotopically different fluids from a single starting fluid. Depending on the relation between mineral reactions in and fluid loss from the inclusion, the fluid remaining in the inclusion and the fluid lost from the inclusion may appear entirely unrelated.     

The timing and direction of metamorphic fluid flow in Vermont

A suite of metabasite dykes, emplaced within the Albee Formation, east-central Vermont, preserves evidence of interaction with a CO₂-bearing hydrous fluid during Acadian metamorphism. Coupled advective and diffusive cross-layer fluxes of CO₂ are recorded by forwards progress of the hydration-carbonation reaction: 3 amphibole + 2 epidote + 8 H₂O + 10 CO₂ = 3 chlorite + 10 calcite + 21 quartz Advection, diffusion and mineral reaction rates are modelled from reaction progress data through application of an analytical solution to the 1-D mass conservation equation for linear reaction kinetics (Lichtner 1988; Lasaga and Rye 1993; Skelton et al. in press). Dimensionless Peclet (Pe) and Damköhler (N_D) numbers which describe the ratios of advection to diffusion and reaction rate to advection are thus resolved, from which time-integrated fluid fluxes are calculated. Small Pe (<10), large N_D (>10) and small time-integrated fluid fluxes (<5 m³/m²) are obtained, predicting that cross-layer fluxes of CO₂ are largely diffusive. It follows that, within the Albee schists, fluid flow must have been layer parallel. Where fluid flow is layer parallel, it is both interesting and informative to consider the geometry of fluid flow at a fold hinge. For layer-parallel fluid flow to be maintained, the flow direction must reverse which is difficult to justify with regards to the driving force. It is perhaps more reasonable that fluid should “escape” through the fold hinge (cf. Skelton et al. 1995), either via close-spaced microveins (cf. Cole and Graham 1994) or macro-scale axial-planar quartz veins (Ferry 1992, 1994). At present, the Albee schists are ～ vertical and strike ～ N–S. This reflects: (1) E–W recumbent folding of strata (early Acadian “nappe-stage” deformation; D₁); (2) N–S arching of strata (late Acadian “dome-stage” deformation; D₂). In the Strafford Quadrangle, east-central Vermont, curious “Coarse Garnet Schists” occur in the axial regions of D₁ fold closures. On the basis of this spatial association, crystal morphologies, reaction textures and chemical zoning profiles, it is postulated that the Coarse Garnet Schists developed in response to structurally focused fluid escape. That fluid flow was syn-D₁ is implicit to this argument. As such, layer-parallel fluid flow must have been ～ horizontal. Although this conclusion is in close agreement with that of Ferry (1994), up-temperature fluid flow is not implicated.     

Sapphirine-bearing granulites and related high-temperature metamorphic rocks from the Higo metamorphic terrane, west-central Kyushu, Japan

The Higo metamorphic unit in west-central Kyushu island, southwest Japan is an imbricated crustal section in which a sequence of units with increasing metamorphic grade from high (northern part) to low (southern part) structural levels is exposed. The basal part of the metamorphic sequence representing an original depth of 23–24  km consists mainly of garnet–cordierite–biotite gneiss, garnet–orthopyroxene gneiss, orthopyroxene-bearing amphibolite and orthopyroxene-bearing S-type tonalite. These metamorphic rocks underwent high amphibolite-facies up to granulite facies metamorphism with peak P – T  conditions of 720  MPa, 870  °C. In addition sapphirine-bearing granulites and related high-temperature metamorphic rocks also occur as tectonic blocks in a metamorphosed peridotite intrusion. The sapphirine-bearing granulites and their related high-temperature metamorphic rocks can be subdivided into five types of mineral assemblages reflecting their bulk chemical compositions as follows: (1) sapphirine–corundum–spinel–cordierite (2) corundum–spinel–cordierite (3) garnet–corundum–spinel–cordierite (4) garnet–spinel–gedrite–corundum, and (5) orthopyroxene–spinel–gedrite. These metamorphic rocks are characterized by unusually high Al₂O₃ and low SiO₂ contents, which could represent a restitic nature remaining after partial melting of pelitic granulite under the ultra high-temperature contact metamorphism at the peak metamorphic event of the Higo metamorphic unit. The metamorphic conditions are estimated to be about 800  MPa and above 950  °C which took place at about 250  Ma as a result of the thermal effect of the regional gabbroic rock intrusions.     

High arsenic and boron concentrations in groundwaters related to mining activity in the Bigadiç borate deposits (Western Turkey)

This study documents the environmental impacts of borate mines in Bigadiç district, which are the largest colemanite and ulexite deposits in the world. Borate-bearing formations have affected the concentrations of some contaminants in groundwater. Groundwater quality is directly related to the borate zones in the mines as a result of water–rock interaction processes. Calcium is the dominant cation and waters are Ca–SO₄ and HCO₃ type in the mine (Tülü borate mine) from which colemanite is produced. However in the Simav and Acep Borate Mines, ulexite and colemanite minerals are produced and waters from these open pit mines are Na–HCO₃–SO₄ types. High SO₄ concentrations (reaching 519 mg/L) might be explained by the existence of anhydrite, gypsum and celestite minerals in the borate zone. Groundwater from tuff and borate strata showed relatively low pH values (7–8) compared to surface and mine waters (>8). EC values ranged from 270 to 2850 μS/cm. Boron and As were the two important contaminants determined in the groundwaters around the Bigadiç borate mines. Arsenic is the major pollutant and it ranged from 33 to 911 μg/L in the groundwater samples. The concentrations of B in the study area ranged from 0.05 to 391 mg/L. The highest B concentrations were detected at the mine areas. The extension of the borate zones in the aquifer systems is the essential factor in the enrichment of B and As, and some major and trace elements in groundwaters are directly related to the leaching of the host rock which are mainly composed of tuffs and limestones. According to drinking water standards, all of the samples exceed the tolerance limit for As. Copper, Mn, Zn and Li values are enriched but do not exceed the drinking water standards. Sulfate, Al and Fe concentrations are above the drinking water standard for the groundwater samples.     

Permeability generation and resetting of tracers during metamorphic fluid flow: implications for advection-dispersion models

Advection-dispersion fluid flow models implicitly assume that the infiltrating fluid flows through an already fluid-saturated medium. However, whether rocks contain a fluid depends on their reaction history, and whether any initial fluid escapes. The behaviour of different rocks may be illustrated using hypothetical marble compositions. Marbles with diverse chemistries (e.g. calcite + dolomite + quartz) are relatively reactive, and will generally produce a fluid during heating. By contrast, marbles with more restricted chemistries (e.g. calcite + quartz or calcite-only) may not. If the rock is not fluid bearing when fluid infiltration commences, mineralogical reactions may produce a reaction-enhanced permeability in calcite + dolomite + quartz or calcite + quartz, but not in calcite-only marbles. The permeability production controls the pattern of mineralogical, isotopic, and geochemical resetting during fluid flow. Tracers retarded behind the mineralogical fronts will probably be reset as predicted by the advection-dispersion models; however, tracers that are expected to be reset ahead of the mineralogical fronts cannot progress beyond the permeability generating reaction. In the case of very unreactive lithologies (e.g. pure calcite marbles, cherts, and quartzites), the first reaction to affect the rocks may be a metasomatic one ahead of which there is little pervasive resetting of any tracer. Centimetre-scale layering may lead to the formation of self-perpetuating fluid channels in rocks that are not fluid saturated due to the juxtaposition of reactants. Such layered rocks may show patterns of mineralogical resetting that are not predicted by advection-dispersion models. Patterns of mineralogical and isotopic resetting in marbles from a number of terrains, for example: Chillagoe, Marulan South, Reynolds Range (Australia); Adirondack Mountains, Old Woman Mountains, Notch Peak (USA); and Stephen Cross Quarry (Canada) vary as predicted by these models. Received: 3 February 1997 / Accepted: 26 June 1997     

The geochemical cycle of boron: Constraints from boron isotope partitioning experiments between mica and fluid

The fractionation of boron isotopes between synthetic boromuscovite and fluid was experimentally determined at 3.0 GPa/500 °C and 3.0 GPa/700 °C. For near-neutral fluids Δ¹¹B_(mica-fluid) = δ¹¹B_(mica) − δ¹¹B_(fluid) is − 10.9 ± 1.3‰ at 500 °C, and − 6.5 ± 0.4‰ at 700 °C. This supports earlier assumptions that the main fractionation effect is due to the change from trigonal coordination of boron in neutral fluids to tetrahedrally coordinated boron in micas, clays and melts. The T-dependence of this effect is approximated by the equation Δ¹¹B_{(mica,clay,melt–neutral fluid)} = − 10.69 · (1000/T [K]) + 3.88; R² = 0.992, valid from 25 °C for fluid–clay up to about 1000 °C for fluid–silicate melt. Experiments at 0.4 GPa that used strongly basic fluids produced significantly lower fractionations with Δ¹¹B_{(mica–fluid)} of − 7.4 ± 1.0‰ at 400 °C, and − 4.8 ± 1.0‰ at 500 °C, showing the reduced fractionation effect when large amounts of boron in basic fluids are tetrahedrally coordinated. Field studies have shown that boron concentrations and ¹¹B/¹⁰B-ratios in volcanic arcs systematically decrease across the arc with increasing distance from the trench, thus reflecting the thermal structure of the subducting slab. Our experiments show that the boron isotopic signature in volcanic arcs probably results from continuous dehydration of micas along a distinct P–T range. Continuous slab dehydration and boron transport via fluid into the mantle wedge is responsible for the boron isotopic signature in volcanic arcs.     

Poorly crystalline carbonaceous matter in high grade metasediments: implications for graphitisation and metamorphic fluid compositions

Poorly crystalline carbonaceous matter was observed in chlorite to sillimanite grade metasediments from the Trois Seigneurs Massif, in contrast to other studies of carbon crystallinity which observed well crystallised graphite under upper greenschist facies conditions. Using transmission electron microscopy four types of carbon particle were identified; globular carbon, composite flakes, homogeneous flakes and crystalline graphite. Globular carbon and composite flakes are poorly crystalline microporous carbon. Homogeneous flakes decompose in the electron beam and are probably composed of heavy volatile hydrocarbons. Graphite is confined to samples from retrograde shear zones and often occurs with globular carbon. The lack of graphitisation in metasediments is probably a consequence of the microporous structure of the carbonaceous matter combined with low f _{O 2}. The preservation of carbonaceous matter in the Trois Seigneurs metasediments is not compatible with the metasediments having been externally buffered by a high X _H2_O fluid syn-metamorphism. An alternative hypothesis of internal buffering is preferred to explain the carbonaceous matter in the Trois Seigneurs metasediments.     

砂岩型铀矿的“双阶段双模式”成矿作用

长期以来,盆地中砂岩型铀矿的成矿与找矿仅关注表生低温氧化作用形成的铀矿化,忽视了复杂地质演化过程中多阶段、多模式的成矿作用.中国北方东部盆地自晚中生代以来经历了伸展-挤压-伸展的多阶段演化过程,铀成矿作用必将对这种多阶段构造演化密切响应.本研究通过中国北方东部巴音戈壁盆地塔木素矿床、二连盆地哈达图矿床、松辽盆地南部钱家店—白兴吐矿床等大型、巨型砂岩型铀矿床的精细解剖,分析矿床中矿体的变化特征和含矿目的层流体-岩石相互作用的标记,探索矿床形成的构造、沉积、铀源、还原剂等成矿控制因素,尤其是(古)太平洋板块在不同阶段、以不同的方式俯冲给研究区盆地带来的深刻影响.以区域构造演化为主线,确定早白垩世至晚白垩世早期,盆地在古太平洋板块高角度俯冲下发生伸展裂陷和拗陷作用,厘定砂岩型铀矿含矿目的层巴音戈壁组(K1b)辫状三角洲、赛汉组(K1bs)辫状河、姚家组(K2y)辫状河及曲流河等沉积环境.晚白垩世晚期,由于古太平洋板块的俯冲由高角度转变为低角度,盆地首次出现由伸展裂陷转变为挤压抬升的正反转演化,表生含铀含氧流体与砂岩相互作用,形成以赤铁矿、褐铁矿化等氧化作用为标志的早期氧化带型"卷状"铀矿化.始新世以来,太平洋板块的俯冲再次由低角度转变为高角度,盆地构造由挤压抬升转变为伸展张裂的负反转演化,导致正断层与基性岩浆活动,并伴随热流体与含矿目的层砂岩相互作用,出现大量的Fe、Mg碳酸盐、热液硫化物、绿泥石、绢云母等蚀变组合,铀矿体形态由原来的"卷状"变成了"透镜状"、"囊状"、"板状",并伴有高温钛铀矿的出现,形成晚期热液叠加铀矿化.两个成矿时期和两种不同方式的成矿作用被本文凝练为"双阶段双模式"铀成矿.结果表明,针对在中国北方东部提出的"双阶段双模式"铀成矿作用模型,下一步找矿上既要关注早期的氧化带型铀矿化,更要注重晚期的热流体叠加改造型铀矿化.     

Synthetic fluid inclusions - VII. Re-equilibration of fluid inclusions in quartz during laboratory-simulated metamorphic burial and uplift

ABSTRACT P-T conditions inferred from fluid inclusions in metamorphic rocks often disagree with the values predicted from mineral equilibria calculations. These observations suggest that inclusions formed during early stages of regional metamorphism continue to re-equilibrate during burial and subsequent uplift in response to differential pressure. P-T conditions accompanying burial and uplift were experimentally simulated by initially forming pure H₂O inclusions in quartz at elevated temperatures and pressures, and then re-equilibrating the inclusions in the presence of a 20 wt% NaCl solution such that final confining pressures ranged from 5 kbar above to 4 kbar below the initial internal pressure of the inclusions at the temperature of re-equilibration. In all samples re-equilibrated at confining pressures below the internal pressure, some inclusions were formed that had compositions of 20 wt% NaCl and densities in accord with the final P-T conditions. Additionally, some inclusions were observed to contain fluids of intermediate salinities (between 0 and 20 wt% NaCl). Densities of these inclusions were also consistent with formation at the re-equilibration P-T conditions. The remainder of the fluid inclusions observed in these samples contained pure H₂O and their homogenization temperatures corresponded to densities intermediate between the initial and final P-T conditions. In short-term experiments (7 days) where the initial internal overpressure exceeded 1 kbar, no inclusions were found that contained the original density and none were found to have totally re-equilibrated. Instead, most H₂O inclusions re-equilibrated until their internal pressures were between ∼750 and 1500 bars above the confining pressure, regardless of the initial pressure differential. In a long-term experiment (52 days), inclusions re-equilibrated at a lower confining pressure than the initial internal pressure displayed homogenization temperatures corresponding to a range in final internal pressures between 0 kbar (i.e. total re-equilibration) and 1.2 kbar above the confining pressure. In experiments where the confining pressure during re-equilibration exceeded the initial internal pressure, densities of pure H₂O inclusions increased to values intermediate between the initial and final P-T conditions. Additionally, these inclusions were generally surrounded by a three-dimensional halo of smaller inclusions, also of intermediate density, resulting in a texture similar to that previously ascribed to decrepitation from internal overpressure. In extreme cases where confining pressures were 4–5 kbar above the initial pressure, the parent inclusion almost completely closed leaving only the three-dimensional array of small (5 μm) inclusions, the outline of which may be several times the volume of the original inclusion. Groups of such inclusions closely resemble textures commonly observed in medium- to high-grade metamorphic rocks. Inclusions containing 10 and 42 wt% NaCl solutions trapped at 600 °c and 3 kbar were re-equilibrated at 600 °c and 1 kbar for 5 days in dry argon to evaluate the importance of H₂O diffusion as a mechanism of lowering the inclusion bulk density. Salinities of re-equilibrated inclusions obtained from freezing point depressions and halite dissolution temperatures indicate that original compositions were preserved. Density changes similar to those previously described were noted in these experiments, in inclusions showing no visible microfractures. Therefore, density variations observed in inclusions in this study, re-equilibrated under rapid deformation conditions, are considered to result from a change in the inclusion volume, without significant loss of contents by diffusion or leakage.     

Rhodope and Vardar: the metamorphic and the olistostromic paired belts related to the Cretaceous subduction under Europe

Abstract

The Rhodope massif of Bulgaria and Greece is a complex of Mesozoic synmetamorphic nappes stacked in an Alpine active margin environment. A new analysis of the Triassic to Eocene history of the Vardar suture zone m Greece discloses its Cretaceous setting as a subduction trench. We present a geological traverse that takes into account these new observatons and runs from the Hellenides to the Balkans, i.e. from he African to the Eurasian sides of the Tethys ocean, respectively. The present review first defines the revisited limits of the Rhodope metamorphic complex. In particular, the lower part of the Serbo- Macedonian massif is an extension of the Rhodope units west of the Struma river. Its upper part is separated as the Frolosh greenschist unit, which underlies tectonic slivers of Carpathc-Balkanic type. Several greenschist units which locally yield Mesozoic fossils, follow the outer limits of the Rhodope. Their former attribution to a stratigraphic cover of the Rhodope has been proven false. They are divided into roof greenschists, which partly represent an extension of the Strandza Jurassic black shales basin, and western greenschists, which mostly derive from the Vardar Cretaceous olistostromic assemblage. The Rhodope complex of synmetamorphic nappes includes Continental Units and Mixed Units. The Continental Units comprise quartzo-feld-spathic gneisses in addition to thick marble layers. The Mixed Units comprise meta-ophiolites as large bodies or small knockers. They are imbricated, forming an open dome whose lower, Continental Unit constitutes the Drama window. The uppermost Mixed Unit is overlain by remnants of the European plate. The present-day structure results from combined large-scale thrust and exhumation tectonics. Regional inversions of synmetamorphic sense-of-shear indicate that intermediate parts of the wedge moved upward and forward with respect to both the lower and upper plates. A kinematic model is based on buoyancy-driven decoupling at depth between subducted continental crust and the subducting lithosphere. Continuing convergence allows coeval underthrusting of continental crust at the footwall, decoupling at depth, and upward-forward expulsion of a low-density metamorphic wedge above. The continental crust input and its upward return may have lasted for at least the whole of the Early Cretaceous, as indicated by isotopic ages and the deformation history of the upper plate. A Late Eocene marine transgression divides the ensuing structural and thermal evolution into a follow-up uplift stage and a renewed uplift stage. Revision of the limits of the Vardar belt in Greece first resulted in separating the Paikon mountain as a tectonic window below the Vardar nappes. It belongs to the western, Hellenic foreland into which a system of thrust developed downward between 60 and 40 Ma. The eastern limit is a dextral strike-slip fault zone that developed greenschist facies foliations locally dated at 50–40 Ma. Revision of the lithological components discloses the preponderance of Cretaceous volcano-detritic and olistostromic sequences that include metamorphite blocks of Rhodope origin. Rock units that belong to the Vardar proper (ophiolites, Triassic and Jurassic radiolarites, remnants of an eastern Triassic passive margin) attest for a purely oceanic basin. The Guevgueli arc documents the Jurassic change of the eastern Triassic passive margin into an active one. This arc magmatic activity ended in the Late Jurassic and plate convergence was transferred farther northeast to the subduction boundary along which the Rhodope metamorphic complex formed. We interpret the Rhodope and the Vardar as paired elements of a Cretaceous accretionary wedge. They document the tectonic process that exhumed metamorphic material from under the upper plate, and the tectonic-sedimentary process that fed the trench on the lower plate. The history of the Rhodope-Vardar pair is placed in the light of the history of the Tethys ocean between Africa and Europe. The Cretaceous subduction then appears as the forerunner of the present Hellenic subduction, accounting for several shifts at the expense of the lower plate. The Late Eocene shift, at the closure of the Pindos basin, is coeval with the initiation of new uplift and magmatism in the Rhodope, which probably document the final release of the low-density, continental root of the Rhodope from subduction drag.     

Convergent boundaries and related igneous and metamorphic complexes in caledonides of Central Asia

Fragments of the crystalline complexes where Vendian metamorphism of moderate and elevated pressure predated Early Paleozoic metamorphism have been established in the accretionary-collisional domain of the eastern segment of the Central Asian Foldbelt (Early Caledonian superterrane of Central Asia). The geodynamic setting of the Vendian (??560?C570 Ma) South Hangay metamorphic belt located in the junction zone of the Baydrag Block and the Late Riphean (??665 Ma) ophiolite complex of the Bayanhongor Zone is considered. The origination of this belt was related to the formation of the convergent boundary in the framework of the Zabhan microcontinent about 570 Ma ago. At the same time, an island-arc complex was formed in the paleo-oceanic domain. Metamorphism of elevated pressure indicates that Vendian structures with sufficiently thick continental crust were formed in the framework of the continental blocks. Vendian metamorphism is also established in the Tuva-Mongolia Massif and the Kan Block of the Eastern Sayan. These data show that the Late Baikalian stage predated the evolution of the Early Caledonian superterrane of Central Asia. The development of its accretionary-collisional structure was accompanied by Late Cambrian-Early Ordovician low-pressure regional metamorphism. Granulite-facies conditions were reached only at the deep levels of the accretionary-collisional edifice. The outcrops of crystalline complexes in the southern framework of the Caledonian paleocontinent are regarded as fragments of the Early Paleozoic Central Mongolian metamorphic belt.     

Rhodope and Vardar: the metamorphic and the olistostromic paired belts related to the Cretaceous subduction under Europe

In the Gondwanian Moesia Plate and Balkanid terranes, accreted to the Palaeo-Europe during the Palaeozoic, the Late Permian—Early Triassic unconformity and the Triassic system are known only from deep boreholes. In the Chiren, Veslets and Golyamo Peshtene regions (Northern Bulgaria), an Early Triassic igneous activity results from eleven drills.

Trachytes, outpoured from sub aerial to shallow sea submarine vents, and later basalt breccias emplaced in shallow water conditions, represent the bimodal volcanic products.

The transitional anorogenic features of the volcanism are consistent with the extensional regime evidenced by the progressively subsiding depositional environment. The extensional Triassic event corresponds to development of branches of a composite rift system, propagating from the Karakaya basin to separate the Moesia with Balkanids p.p. and the Istanbul block to the North, from the Serbian— Macedonian—Thracian microplate with Balkanid p.p. to the south.     

Oxidation potential and the composition of metamorphic fluid as a solution to the inverse problem of convex programming

Using the Selektor-C software program package, oxidation potential and the composition of metamorphogenic fluid were determined for mineral assemblages from nine samples of granulite-grade metamorphic rocks by solving the inverse problems of convex programming. The calculated and real mineral assemblages are in good agreement with respect to the composition and association of minerals, which is compelling evidence for the attainment of chemical equilibrium (minimum of Gibbs free energy) under given P-T conditions. Based on the dual solution of the inverse problem, a new approach was proposed for the estimation of the oxidation potential of fluid and mineral assemblages, which can be used to determine oxygen potential for almost any mineral association, independent of the presence of magnetite, ilmenite, or graphite. It was found that magnetite-free mineral associations are characterized by highly reducing conditions corresponding to oxygen potentials close to the CCO buffer. The external metamorphic fluid that was present during granulite-facies metamorphism was probably formed in the graphite stability field. The results of calculations for the model aqueous electrolyte solution-mineral assemblage suggest high SiO₂ solubility in the metamorphogenic fluid. Therefore, the process of granulite metamorphism may be a potent geochemical factor of the redistribution and transportation of silica from lower to upper crustal levels.