Geochemistry and geochronology of A-type Barabazar granite: Implications on the geodynamics of South Purulia Shear Zone,Singhbhum craton,Eastern India

The Barabazar granite, exposed at the northern margin of Singhbhum craton, Eastern India, occurs along the South Purulia Shear Zone (SPSZ) and is emplaced into the Palaeoproterozoic metapelites and felsic volcanics of Singhbhum Group. Geochemical, petrographical and geochronological studies on the Barabazar granite addressed in the work have wide implications on understanding the geodynamics of SPSZ during Palaeoproterozoic to Mesoproterozoic. Geochemically, Barabazar granite displays limited range of major oxides, alkali enrichment and highly fractionated features (SiO₂ > 75%; Eu/Eu* = 0.16–0.33; enrichment of K, Rb, Th, U and Nb; depletion of Ba, Sr, P and Ti). It is predominantly peraluminous (molar Al₂O₃/CaO+Na₂O+K₂O (A/CNK) =1.14–144) and contains abundant alkali feldspar, perthite, and minor plagioclase, biotite and accessory minerals. Geochemical and petrological data indicates that it is A-type granite, which formed in ‘Within plate granite’ tectonic set up. The Barabazar granite was emplaced at ca. 1771 Ma (Pb-Pb) in rift related environs and evolved by partial melting of stabilized lower/middle crust (initial ⁸⁷Sr/⁸⁶Sr = 0.7302 ± 0.0066 and μ₁ = 8.5 ± 0.5). Subsequently, the shear zone (SPSZ) developed during the closure of the riftogenic basin and was reactivated during the Grenvillian orogeny (Ca. 900–1300 Ma), resulting in rehomogenisation of the strontium isotopes and thereby yielding younger whole-rock Rb-Sr isotope age of c. 971 Ma for the Barabazar granite. Probably during this tectonic event, the Singhbhum craton (Southern India Shield) would have finally juxtaposed with Northern Indian Shield along Central Indian Tectonic Zone (CITZ) during the global Grenvillian orogeny.     

Heat capacity and phase equilibria of hollandite polymorph of KAlSi3O8

The low-temperature heat capacity (C _p ) of KAlSi₃O₈ with a hollandite structure was measured over the range of 5–303 K with a physical properties measurement system. The standard entropy of KAlSi₃O₈ hollandite is 166.2±0.2 J mol⁻¹ K⁻¹, including an 18.7 J mol⁻¹ K⁻¹ contribution from the configurational entropy due to disorder of Al and Si in the octahedral sites. The entropy of K₂Si₄O₉ with a wadeite structure (Si-wadeite) was also estimated to facilitate calculation of phase equilibria in the system K₂O–Al₂O₃–SiO₂. The calculated phase equilibria obtained using Perple_x are in general agreement with experimental studies. Calculated phase relations in the system K₂O–Al₂O₃–SiO₂ confirm a substantial stability field for kyanite–stishovite/coesite–Si-wadeite intervening between KAlSi₃O₈ hollandite and sanidine. The upper stability of kyanite is bounded by the reaction kyanite (Al₂SiO₅) = corundum (Al₂O₃) + stishovite (SiO₂), which is located at 13–14 GPa for 1,100–1,400 K. The entropy and enthalpy of formation for K-cymrite (KAlSi₃O₈·H₂O) were modified to better fit global best-fit compilations of thermodynamic data and experimental studies. Thermodynamic calculations were undertaken on the reaction of K-cymrite to KAlSi₃O₈ hollandite + H₂O, which is located at 8.3–10.0 GPa for the temperature range 800–1,600 K, well inside the stability field of stishovite. The reaction of muscovite to KAlSi₃O₈ hollandite + corundum + H₂O is placed at 10.0–10.6 GPa for the temperature range 900–1,500 K, in reasonable agreement with some but not all experiments on this reaction.     

The petrochemistry characteristics and petrogenesis of peraluminous granite in Tibet

There are 61 major peraluminous granitic bodies in Tibet (TPGs) along the south of the Bangong Co-Gêrzê-Amdo-Nujiang suture, whose lithology includes tourmaline granite, muscovite granite and two-mica granite. The TPGs have SiO₂ = 65.7%−79.52%, K₂O + Na₂O = 2.20%−12.51%, K₂O/Na₂O = 0.49−1.04 and A/CNK = 1.04−1.38. Al₂O₃ gradually decreases and the other oxides disperse with the increase in SiO₂. The rock series is mainly calc-alk series with high potassium. It has typical characteristics of strongly peraluminous granite. Based on the aluminum saturation index and QAP plots, the peraluminous granite plot is mostly within the continental collision granite (CCG) field, indicating that the peraluminous granites in Tibet formed in a continental collisional setting. Ab-Or-Q-H₂O phase diagram indicates the pressure of 0.5 × 10⁸−2 × 10⁸ Pa in TPGs, from which it can be deduced that the forming temperature was under 700°C. The TPGs mainly occurred at the collision stage between two continental crust plates, and the original magma is rooted in the remelting from the upper crust. It is the S-type granite in petrogenesis. The South Gandise belt and the Lhagoi Kangri belt have similar characteristics, suggesting that the two belts have the same magma source and the same tectonic setting. Translated from Acta Geologica Sinica, 2006, 80(9): 1329–1341 [译自: 地质学报]     

Origin of high-Si dacite from rhyolitic melt: evidence from melt inclusions in mingled lavas of the 1.6 Ga Gawler Range Volcanics, South Australia

Summary ?Part of the Mesoproterozoic (1.6 Ga) Gawler Range Volcanics in South Australia is composed of mingled feldspar- quartz- phyric dacite, rhyodacite and rhyolite lavas. Field relationships suggest that dacite erupted first, locally grading into rhyodacite, followed by mingled dacite and rhyolite or rhyodacite and rhyolite, and finally in some areas rhyolite, and imply that the three lithofacies co-existed in a compositionally stratified magma chamber. Data on the bulk rock, groundmass and melt inclusion compositions suggest that post-eruption alteration has had very little effect on the original rock compositions. Melt inclusions in quartz from rhyolite and rhyodacite-dacite, respectively, belong to two compositional populations. Inclusions in the rhyolitic quartz have less evolved compositions with lower SiO₂ (72–76.4 wt %) and higher Al₂O₃ (13.2–15.6 wt%) and Na₂O (2.5–4.2 wt%) abundances. In contrast, melt inclusions in quartz from the rhyodacite-dacite are more “evolved” (i.e., 75.5–78.3 wt% SiO₂, 11.2–12.7 wt% Al₂O₃ and 1.7–2.2 wt% Na₂O). The two melt populations define a single compositional trend towards groundmass compositions, which are essentially similar in all three lithofaci es (77.8–80.5 wt% SiO₂, 9.9–11.1  wt% Al₂O₃ and 2.2–2.4 wt% Na₂O). This trend is consistent with the derivation of the groundmass melt from a single precursor melt of rhyolitic composition by means of crystallisation of dominant plagioclase, K-feldspar and minor quartz. Plagioclase-enriched dacite-rhyodacite magma comprises a mixture of the residual melt and plagioclase phenocryst s that accumulated in the upper part of the magma chamber and erupted first. Similar residual melt containing quartz and K-feldspar phenocrysts was present deeper in the magma chamber and erupted later to form quartz-, K-feldspar-phyric rhyolite.

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Zusammenfassung ?Die Bildung von Si-reichem Dacit aus rhyolitischer Schmelze: Evidenz aus Schmelzeinschlüssen in Laven der 1.6 Ga Gawler Range Volcanics, Südaustralien Ein Teil der mesoproterozoischen (1.6 Ga) Gawler Range Volcanics in Südaustralien setzt sich aus “mingled” Feldspat- Quarz-phyrischen dacitischen, rhyodacitischen und rhyolithischen Laven zusammen. Gel?ndebefunde legen nahe, da? die Dacite, die lokal in Rhyodacite übergehen, zuerst eruptierten, gefolgt vom “mingled” Dacit und Rhyolith oder Rhyodacit und Rhyolith. Schlie?lich bildeten sich in einigen Gebieten Rhyolithe. Diese Beobachtungen lassen die Schlu?folgerung zu, da? die drei Lithofazies in einer geschichteten Magmenkammer koexistierten. Die Daten der Gesamtgesteins-, Grundmasse- und Schmelzeinschlu?- Zusammensetzungen zeigen, da? Alterationsvorg?nge nach der Eruption einen sehr minimalen Effekt auf die ursprüngliche Gesteinszusammensetzung hatten. Die Schmelzeinschl üsse in den Rhyolithen und Rhyodaciten geh?ren zwei unterschiedlich en Populationen an. Die Schmelzeinschlüsse in Quarz der Rhyolithe sind weniger deutlich “entwickelt” mit niedrigeren SiO₂ (72–76.4 Gew.%) und h?heren Al₂O₃ (13.2–15.6 Gew.%) und Na₂O-(2.5–4. 2 Gew.%) Gehalten. Im Unterschied dazu sind die Einschlüss e in Quarz aus Rhyodacit-Dacit st?rker “entwickelt” (i.e., 75.5–78.3 Gew.% SiO₂, 11.2–12.7 G ew.% Al₂O₃ und 1.7–2.2 Gew.% Na₂O). Die beiden Populationen von Schmelzeinschlüssen definieren einen einzigen Entwicklungstrend hin zur Zusammensetzung der Grundmasse, die in allen drei Lithofazies ?hnlich ist (77.8–80.5 Gew.% SiO₂, 9.9–11.1 Gew.% Al₂O₃ und 2.2–2.4 Gew.% Na₂O). Dieser Trend ist mit der Herkunft der Grundmasse-bildenden Schmelze aus einer einzigen Ausgangsschmelze rhyolithischer Zusammensetzung infolge der Kristallisation von haupts?chlich Plagioklas, Alkalifeldspat und untergeordnet Quarz konsistent. Dacit-Rhyodacitmagmen, die an Plagioklas angereichert sind, stellen eine Mischung der Residualschmelze mit Plagioklas- Ph?nokristallen, die sich in den oberen Teilen der Magmenkammer akkumuli ert haben, dar; sie eruptierten zuerst. ?hnliche residuale Schmelzen mit Quarz und Akalifeldspat-Ph?nokristallen waren auf die tieferen Teilen der Magmenkammer beschr?nkt; sie eruptierten sp?ter und bildeten die Quarz- und Akalifeldspat-phyrischen Rhyolithe.

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Received April 1, 1999;/revised version accepted July 27, 1999     

Hydrothermal synthesis of pumpellyite–okhotskite series minerals

Summary ?Hydrothermal experiments to synthesize pumpellyite group minerals of the pumpellyite–okhotskite series and to investigate their stability have been carried out at 200, 300 and 400 MPa P _fluid and 250–500 °C by using cold-seal pressure vessels and solid buffers of MnO₂–Mn₂O₃, Cu₂O–CuO and Cu₂O–Cu buffer assemblages. Okhotskite and pumpellyite rich in the okhotskite component crystallized from an oxide mixture starting material of Ca₄MgMn³⁺ ₃Al₂Si₆O_24.5-oxide+excess H₂O at P _fluid of 200, 300 and 400 MPa and temperatures of 300 and 400 °C. However, a single phase of okhotskite was not produced, and associated piemontite, hausmannite, wollastonite, clinopyroxene, corundum, braunite–neltnerite solid solution and alleghanyite also formed. Mn-pumpellyite of the okhotskite–pumpellyite join occurs as aggregates of needle crystals, rounded grains or flaky crystals. Chemical compositions are variable and range from pumpellyite-(Mn²⁺) to okhotskite: 31–36 SiO₂, 13–21 Al₂O₃, 12–25 total Mn₂O₃, 0.6–4 MgO and 20–24 wt.% CaO. Reconnaissance experiments using a starting material of synthetic Ca₂Mn³⁺Al₂Si₃O₁₂(OH)-piemontite at 300 MPa and temperatures of 250, 300, 400 and 500 °C indicate that Mn-rich pumpellyite can crystallize from piemontite at lower temperatures than the stability field of piemontite. The Mn-rich pumpellyite was accompanied by garnet, wollastonite and alleghanyite. The chemical compositions of the Mn-pumpellyites are 32–36 SiO₂, 18–27 Al₂O₃, 8–18 total Mn₂O₃ and 20–23 wt.% CaO. This study shows that the stability fields of piemontite, piemontite+Mn-pumpellyite, and Mn-pumpellyite range in this order with decreasing temperature under high fO₂ conditions. The maximum stability temperature of Mn-rich pumpellyite lies between 400 and 500 °C at 200–400 MPa in high fO₂ conditions. Received March 3, 2000; revised version accepted December 28, 2001     

内蒙古嘎仙镍钴矿区岩浆作用与成矿

内蒙古嘎仙矿床为大兴安岭北段与岩浆作用有关的大型低品位镍钴硫化物矿床,成矿作用主要与花岗质岩浆作用有关。文章主要对矿区内矿体下盘的花岗岩类(花岗斑岩、长石斑岩、伟晶状花岗岩、黑云母花岗岩)进行了锆石LA-ICP-MS U-Pb定年,获得花岗斑岩的谐和线年龄(125.3±1.1)Ma～(127.5±4.5)Ma,长石斑岩的谐和线年龄为(128.1±2.2)Ma,伟晶状花岗岩的谐和线年龄为(127.9±2.3)Ma,黑云母花岗岩的谐和线年龄为(127.9±1.4)Ma,说明这些花岗岩类主要形成于中生代早白垩世。通过对矿化超镁铁岩、科马提岩、镁铁岩(辉绿岩、玄武岩)、长英质岩(闪长岩、长石斑岩、斜长花岗岩、花岗斑岩、伟晶状花岗岩、黑云母花岗岩)及围岩(大理岩)的主量、微量元素地球化学测试分析,结果表明,与吉峰科马提岩成分相比较,矿化超镁铁岩具有较高的w(SiO_2)(40.53%～54.96%)、w(TiO_2)(0.24%～0.86%)、w(Al_2O_3)(3.58%～10.47%)、w(FeO)(5.30%～8.80%)、w(CaO)(7.35%～13.66%)、w(Na_2O)(0.01%～0.76%)、w(K_2O)(0.02%～0.66%)和w(P_2O_5)(0.06%～0.61%);镁铁岩(包括辉绿辉长岩、玄武岩)铝含量较高,w(Al_2O_3)=16.34%～17.74%;长英质岩类也富铝质(Al_2O_3/(CaO+Na_2O+K_2O)=1.34～1.63),多数岩石属于钙碱性系列。闪长岩与镁铁岩相比,具有较高的硅、铝、钾、钠,较低的铁、镁和钙,微量元素具有大离子亲石元素富集,高场强元素相对亏损的右倾模式;稀土元素具有轻稀土元素富集,重稀土元素相对亏损特征,超镁铁岩类成分点位于N-MORB与OIB范围之间,而镁铁岩和长英质岩类成分点位于E-MORB和OIB之间。镁铁岩落入火山弧玄武岩范围,长英质岩落入火山弧花岗岩+同碰撞花岗岩范围,同属于造山后花岗岩的范围,因此镁铁质岩的形成应属于俯冲-碰撞环境,而长英质岩的形成应属于造山后伸展环境。根据各岩类所含成矿元素和亲流体元素分析,认为含矿热液来自矿区西部的深部,并且构建了嘎仙矿床的成矿模型,即超镁铁岩先期侵位,后期经历了区域的变质变形,最后发生燕山期大规模花岗质岩浆活动及成矿流体的蚀变矿化。     

Geochemistry and petrogenesis of radioactive Palaeoproterozoic granitoids of Kinwat crystalline inlier,Nanded and Yeotmal districts,Maharashtra

Kinwat crystalline inlier exposes Palaeoproterozoic granitoids belonging to the northern extensions of younger phase of Peninsular gneissic complex (PGC) within Deccan Trap country in Eastern Dharwar Craton (EDC) and bounded in south by a major NW-SE trending lineament (Kaddam fault). Geochemically, the Kinwat granitoids are similar to high-K, calc-alkaline to shoshonite magnesian granitoids and subdivided into two major groups, i.e. felsic group (pink and grey granites) and intermediate to felsic group (hybrid granitoids). The felsic group (∼67–74% SiO₂) shares many features with Neoarchaean to Palaeoproterozoic high potassic granites of PGC such as higher LILE and LREE content and marked depletion in Eu, P and HFSE, especially Nb, Ti, relative to LILE and LREE. The hybrid granitoids (∼58–67% SiO₂) have comparatively higher Ca, Mg and Na contents and slightly lower REE content than the granitoids of felsic group. Both, felsic and hybrid granitoids are metaluminous to weakly peraluminous and belong to highly fractionated I-type suite as evidenced by negative correlation of SiO₂ with MgO, FeO^t, CaO, Na₂O, Al₂O₃, whereas K₂O, Rb and Ba show sympathetic relationship with SiO₂. Moderate to strong fractionated REE patterns (Ce/Yb_N: ∼54–387) and strong negative Eu anomalies (Eu/Eu*: 0.13–0.41) are quite apparent in these granitoids. The geochemical characteristics together with mineralogical features such as presence of biotite±hornblende as the dominant ferromagnesian mineral phases point towards intracrustal magma source, i.e. derivation of magma by partial melting of probably tonalitic igneous protolith at moderate crustal levels for felsic granites, whereas hybrid granitoids appear to be products of juvenile mantle-crust interaction, in an active continental margin setting.     

The Ca-Eskola component in eclogitic clinopyroxene as a function of pressure, temperature and bulk composition: an experimental study to 15 GPa with possible implications for the formation of oriented SiO2-inclusions in omphacite

Experiments have been conducted in the P-T range 2.5–15 GPa and 850–1,500°C using bulk compositions in the systems SiO₂–TiO₂–Al₂O₃–Fe₂O₃–FeO–MnO–MgO–CaO–Na₂O–K₂O–P₂O₅ and SiO₂–TiO₂–Al₂O₃–MgO–CaO–Na₂O to investigate the Ca-Eskola (CaEs Ca_0.5□_0.5AlSi₂O₆) content of clinopyroxene in eclogitic assemblages containing garnet + clinopyroxene + SiO₂ ± TiO₂ ± kyanite as a function of P, T, and bulk composition. The results show that CaEs_ss in clinopyroxene increases with increasing T and is strongly bulk composition dependent whereby high CaEs-contents are favoured by bulk compositions with high normative anorthite and low diopside contents. In this study, a maximum of 18 mol% CaEs_ss was found at 6 GPa and 1,350°C in a kyanite-eclogite assemblage garnet + clinopyroxene + kyanite + rutile + coesite. By comparison, no significant increase in CaEs_ss with increasing P could be observed. If the formation of oriented SiO₂-rods frequently observed in eclogititc clinopyroxenes is due to the retrogressive breakdown of a CaEs-component then these textures are a cooling rather than a decompression phenomenon and are most likely to be found in kyanite-bearing eclogites cooled from temperatures ≥750°C. The presence of clinopyroxene with approx. 4 mol% CaEs_ss in an experiment conducted at 2.5 GPa/850°C confirms earlier suggestions based on field data that vacancy-rich clinopyroxenes are not necessarily restricted to ultrahigh pressure metamorphic conditions. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Al zoning in orthopyroxene in a sapphirine quartzite: evidence for >1120 °C UHT metamorphism in the Napier Complex, Antarctica, and implications for the entropy of sapphirine

A unique sapphirine + orthopyroxene + quartz granulite from Mt. Riiser-Larsen in the Tula Mountains of Enderby Land, East Antarctica, preserves two generations of coarse and texturally equilibrated orthopyroxene and sapphirine coexisting with quartz. Initial subhedral orthopyroxene porphyroblasts retain core compositions enriched in Al₂O₃ (12.2 ± 0.5 wt%) compared with their rims and finer orthopyroxene (9.6 ± 0.5 wt% Al₂O₃) that forms granoblastic textures with sapphirine. Sapphirine and quartz also form symplectites on and along cleavage planes within orthopyroxene. These compositional and textural features are consistent with the reaction [2MgAl₂SiO₆=Mg₂Al₄ SiO₁₀ + SiO₂] leading to the formation of sapphirine + quartz at the expense of aluminous orthopyroxene. Calculations in the MAS and FMAS systems and theoretical considerations involving the phases enstatite, sapphirine, sillimanite, quartz and cordierite indicate that the reaction above progresses from left to right with decreasing temperature in the orthopyroxene + sapphirine + quartz field, at pressures of ca. 8–10 kbar. The temperature difference required to account for the ca. 2.5–3 wt% decrease in Al₂O₃ in orthopyroxene is at least 60–80 °C, and implies peak temperatures for the initial assemblage of at least 1120 °C if the second granoblastic assemblage equilibrated at 1040 °C, the P–T conditions required by the sapphirine + quartz association and other P–T-sensitive assemblage indicators in the Napier Complex. It is not possible to distinguish whether the two assemblages are simply related by cooling and re-equilibration or reflect a polyphase evolution involving the superposition of a second UHT event on an earlier, even higher temperature, UHT metamorphism. Preliminary thermodynamic modelling of the reaction above incorporating the observed range in orthopyroxene Al₂O₃ zoning indicates that present estimates for the entropy of high-temperature sapphirine are potentially too high by 15–18% compared with sapphirine entropy estimates that are consistent with MAS system experiments. The Mt. Riiser-Larsen sapphirine–quartz rocks preserve the first definitive record of regional metamorphic temperatures in excess of 1120 °C in the Napier Complex, or indeed any UHT granulite terrain worldwide. Similarly high peak temperatures may be retrieved from detailed studies of sapphirine–quartz granulites from other regions, further expanding the thermal realm of crustal metamorphism, but progress will critically depend on the experimental acquisition of new entropy data for sapphirine. Received: 3 September 1998 / Accepted: 8 November 1999     

Origin of a Mesozoic granite with A-type characteristics from the North China craton: highly fractionated from I-type magmas?

We report geochronological, geochemical and isotopic data for the Mesozoic Shangshuiquan granite from the northern margin of the North China craton. The granite is highly fractionated, with SiO₂ > 74%. Occurrence of annitic biotite, high contents of alkalis (K₂O + Na₂O), Rb, Y, Nb and heavy rare earth elements, high FeO_t/MgO, low contents of CaO, Al₂O₃, Ba, and Sr, and large negative Eu anomalies, makes it indistinguishable from typical A-type granites. A mantle-derived origin for the rocks of the granite is not favored because their high initial ⁸⁷Sr/⁸⁶Sr (≥0.706) and low ε_Nd (t) (<−15) are completely different from either those of the lithospheric or asthenospheric mantle. In fact, their Sr–Nd isotopes fall within the range of Sr–Nd isotopic compositions of the Archean granulite terrains and are comparable to those of Mesozoic crustal-derived I-type granitoids in the region. Therefore, the Shangshuiquan granite is considered to be dominantly derived from partial melting of the ancient lower crust. Its parental magmas prove to be similar to I-type magmas and to have undergone extensive fractionation during its ascent. This is supported by the fact that some of the nearby Hannuoba feldspar-rich granulite xenoliths can be indeed regarded as the early cumulates in terms of their mineralogy, chemistry, Sr–Nd isotopes and zircon U–Pb ages and Hf isotopes. It is furthermore argued that some of highly fractionated granites worldwide, especially those with A-type characteristics and lacking close relationship with unfractionated rocks, may in fact be fractionated I-type granites. This suggestion can explain their close temporal and spatial associations as well as similar Sr–Nd isotopes with I-type granites. Our study also sheds new light on the petrogenesis of deep crustal xenoliths.     

High-pressure phases in the Al2SiO5 system and the problem of aluminous phase in the Earth's lower mantle: ab initio calculations

 One of the main uncertainties in mineralogical models of the Earth's lower mantle is the nature of the aluminous mineral: it is not clear whether Al forms its own minerals or is mainly contained in (Mg,Fe)SiO₃-perovskite. This question is very important, since it is known that if Al were mainly hosted by perovskite, it would radically change Fe/Mg-partitioning and phase equilibria between mantle minerals, and also alter many physical and chemical properties of perovskite, which is currently believed to comprise ca. 70% of the volume of the lower mantle. This, in turn, would require us to reconsider many of our geochemical and geophysical models for the lower mantle. This work considers the possibility of a V₃O₅-type structured modification of Al₂SiO₅ to be the main host of Al in the lower mantle, as proposed by previous workers. We report ab initio calculations, based on density functional theory within the generalised gradient approximation (GGA) with plane wave basis set and nonlocal pseudopotentials. We consider polymorphs of Al₂SiO₅ (kyanite, andalusite, sillimanite, and hypothetical V₃O₅-like and pseudobrookite-like phases), SiO₂ (stishovite, quartz) and Al₂O₃ (corundum). Computational conditions (e.g., plane-wave energy cutoff, Brillouin zone sampling) were carefully chosen in order to reproduce small energy changes associated with phase transitions between the Al₂SiO₅ polymorphs. Good agreement of crystal structures, bulk moduli, atomisation energies and the phase diagram of Al₂SiO₅ with experimental data was found. Strong disagreement between the calculated lattice parameters and density of V₃O₅-like phase of Al₂SiO₅ and experimental values, assigned to it by previous workers, suggests that a V₃O₅-structured phase of Al₂SiO₅ was never observed experimentally. In addition, we found that the most stable high-pressure assembly in Al₂SiO₅ system is corundum+stishovite, and the value of the transition pressure at T = O K (113 kbar) is in excellent agreement with experimental estimates (95–150 kbar). We explain the instability of octahedrally coordinated silicates of Al to decomposition on the basis of Pauling's second rule. Received: 18 May 1999 / Accepted: 5 November 1999     

Dissolved silica in the Garonne River waters: changes in the weathering dynamics

 The major ion chemistry of the Garonne River is indicative of seasonal variations in the weathering dynamics of the drainage basin. Using the geochemical model MEGA for calculation of the contribution of atmospheric CO₂ to the total bicarbonate fluxes exported by the Garonne River allows estimations of the concentrations of the major dissolved elements that originate from silicate- and carbonate-rock weathering. The molecular ratio SiO₂/Al₂O₃ was calculated for the 1989–1992 period to identify the main type of weathering in the Garonne River, and montmorillonite was shown to be the major mineral occurring in the weathering products. The seasonal variations of the SiO₂/Al₂O₃ ratio also showed that removal of silica was accelerated during humid periods. Revision received: 14 May 1999 · Accepted: 12 January 2000     

The effect of Cr on the solubility of Al in orthopyroxene: experiments and thermodynamic modelling

The partitioning of chromium and aluminium between coexisting orthopyroxene and spinel in equilibrium with forsterite in the system MgO–Al₂O₃–SiO₂–Cr₂O₃ (MAS–Cr) has been experimentally determined as a function of temperature, pressure and Cr/(Cr + Al) ratio. Experiments were conducted at temperatures between 1300 and 1500 °C and at pressures from 5 to 54 kbar. Previous experimental results on the (Al, Cr)₂O₃ and Mg(Al, Cr)₂O₄ solid solutions have been combined with the present results plus relevant data from the CMAS system to derive a thermodynamic model for Al–Cr-bearing orthopyroxenes, spinels and corundum–eskolaite solid solutions. The orthopyroxene solid solution can be modelled within the accuracy of all experimental constraints as a ternary solid solution involving the components Mg₂Si₂O₆ ( E), MgAl₂SiO₆ (M) and MgCr₂SiO₆ (C), in which the activities are related to composition through the equations: The mole fractions are defined as where n _Al and n _Cr are the number of Al and Cr cations per orthopyroxene formula unit of six oxygens. These expressions reduce to one-site mixing for Mg₂Si₂O₆–MgAl₂SiO₆ orthopyroxenes in the Cr-free system, but are equivalent to two-site mixing for the exchange of Al and Cr between orthopyroxene and spinel, as required by the experimental data. We find W ^opx _EM =W ^opx _EC  = 20 kJ mol⁻¹ and W ^opx _MC =0. Received: 9 August 1999 / Accepted: 18 February 2000     

古特提斯洋俯冲碰撞在南羌塘的岩浆岩证据:西藏荣玛乡冈塘错花岗岩

西藏荣玛乡冈塘错花岗岩岩体分布于南羌塘地块中,由中粗粒巨斑状黑云母二长花岗岩和中细粒含电气石二云母二长花岗岩组成。中粗粒花岗岩的锆石测年结果为214.4±4.0Ma,中细粒花岗岩锆石测年结果为222.2±6.6Ma,均为晚三叠世。中粗粒花岗岩A/CNK为1.00~1.09,刚玉标准分子的百分含量均大于1%(1.84~3.04%),Al2O3的含量均大于14%,属于含白云母过铝质花岗岩。中细粒花岗岩的A/CNK1.1,刚玉标准分子的百分含量均大于1%(2.40~3.42%),Al2O3的含量均大于14%,属于强过铝质S型花岗岩。虽主量元素特征相近,但两类花岗岩的微量元素特征差异较大。根据锆石饱和温度计得出中粗粒花岗岩为高温类型的花岗岩,中细粒花岗岩为低温类型的花岗岩。结合区域地质背景推断中细粒花岗岩形成可能与三叠纪俯冲碰撞作用有关,而中粗粒花岗岩为碰撞后拆沉岩浆底侵的结果。冈塘错岩体中两种成因类型不同的花岗岩的形成时代对古特提斯洋的演化以及缝合带增生杂岩的形成具有时代约束意义。     

Petrology and geochemistry of late archaean granitoids in the northern part of Eastern Dharwar Craton,Southern India: Implications for transitional geodynamic setting

The results of field, petrographic and geochemical work of the granitoids of Hutti-Gurgunta area in the northern part of Eastern Dharwar Craton (EDC) is presented in this paper. This crustal section comprises polyphase banded to foliated TTG gneisses, middle amphibolite facies Gurgunta schist belt and upper greenschist facies Hutti schist belt and abundant granite plutons. The focus of the present study is mainly on basement TTG gneisses and a granite pluton (∼ 240 sq km areal extent), to discuss crustal accretion processes including changing petrogenetic mechanism and geodynamic setting. The TTGs contain quartz, plagioclase, lesser K-feldspar and hornblende with minor biotite while the granite contain quartz, plagioclase, K-feldspar and hornblende. Late stage alteration (chloritisation, sericitisation and epidotisation) is wide spread in the entire area. A huge synplutonic mafic body which is dioritic to meladioritic in composition injects the granite and displays all stages of progressive mixing and hybridization. The studied TTGs and granite show distinct major and trace element patterns. The TTGs are characterized by higher SiO₂, high Al₂O₃, and Na₂O, low TiO₂, Mg#, CaO, K₂O and LILE, and HFS elements compared to granite. TTGs define strong trondhjemite trend whilst granite shows calc-alkaline trend. However, both TTGs and granite show characteristics of Phanerozoic high-silica adakites. The granite also shows characteristics of transitional TTGs in its high LILE, and progressive increase in K₂O with differentiation. Both TTGs and granite define linear to sub-linear trends on variation diagrams. The TTGs show moderate total REE contents with fractionated REE patterns (La/Yb_N =17.73–61.73) and slight positive or without any significant Eu anomaly implying little amount of amphibole or plagioclase in residual liquid. On the other hand, the granite displays poor to moderate fractionation of REE patterns (La/Yb_N = 9.06–67.21) without any significant Eu anomaly. The TTGs have been interpreted to be produced by low-K basaltic slab melting at shallow depth, whereas the granite pluton has been formed by slab melting at depth and these melts interacted with peridotite mantle wedge. Such changing petrogenetic mechanisms and geodynamic conditions explain increase in the contents of MgO, CaO, Ni and Cr from 2700 Ma to 2500 Ma granitoids in the EDC.     

Cenozoic volcanic rocks in the Belog Co area, Qiangtang, northern Tibet, China： Petrochemical evidence for partial melting of the mantle-crust transition zone

Neogene volcanic rocks in the Belog Co area, Qiangtang, northern Tibet, are represented by a typical intermediate-basic and intermediate alkaline rock association, with latite-trachyte as the main rock type. The results of chemical analysis are: SiO2=52%–62%, Al2O3>15%, Na2O/K2O>1 and MgO<3.30%. In addition, the volcanic rocks are LREE-enriched with LREE/HREE=10–13, (La/Yb)N=15–19, and show a weak negative Eu anomaly with δEu=0.71–0.89. The close relationship between Mg# and SiO2 and the co-variation of the magmatophile elements and ultra-magmatophile elements such as La/Sm-La and Cr-Tb indicate that this association of volcanic rocks is the product of comagmatic fractional crystallization. The rock association type and lower Sm/Yb values (Sm/Yb=3.23–3.97) imply that this association of volcanic rocks should have originated from partial melting of spinel lherzolite in the lithospheric mantle. On the other hand, the weak negative Eu anomaly and relative depletion in Nb, Ta and Ti reflect the features of terrigenous magma. So the Neogene Belog Co alkaline volcanic rocks should be the result of partial melting of the special crust-mantle transition zone on the Qinghai-Tibet Plateau.     

Dissociation of CAS phase in the uppermost lower mantle

The high-pressure stability limit of calcium aluminosilicate (CAS) phase has been examined in its end-member CaAl₄Si₂O₁₁ composition at 18–39 GPa and 1,670–2,300 K in a laser-heated diamond-anvil cell (LHDAC). The in-situ synchrotron X-ray diffraction measurements revealed that the CAS phase decomposes into three-phase assemblage of cubic Al-bearing CaSiO₃ perovskite, Al₂O₃ corundum, and SiO₂ stishovite above 30 GPa and 2,000 K with a positive pressure–temperature slope. Present results have important implications for the subsolidus mineral assemblage of subducted sediment and the melting phase relation of basalt in the lower mantle.     

Titanium in phengite: a geobarometer for high temperature eclogites

Phengite chemistry has been investigated in experiments on a natural SiO₂–TiO₂-saturated greywacke and a natural SiO₂–TiO₂–Al₂SiO₅-saturated pelite, at 1.5–8.0 GPa and 800–1,050°C. High Ti-contents (0.3–3.7 wt %), Ti-enrichment with temperature, and a strong inverse correlation of Ti-content with pressure are the important features of both experimental series. The changes in composition with pressure result from the Tschermak substitution (Si + R²⁺ = Al^IV + Al^VI) coupled with the substitution: Al^VI + Si = Ti + Al^IV. The latter exchange is best described using the end-member Ti-phengite (KMgTi[Si₃Al]O₁₀(OH)₂, TiP). In the rutile-quartz/coesite saturated experiments, the aluminoceladonite component increases with pressure while the muscovite, paragonite and Ti-phengite components decrease. A thermodynamic model combining data obtained in this and previous experimental studies are derived to use the equilibrium MgCel + Rt = TiP + Cs/Qz as a thermobarometer in felsic and basic rocks. Phengite, rutile and quartz/coesite are common phases in HT-(U)HP metamorphic rocks, and are often preserved from regression by entrapment in zircon or garnet, thus providing an opportunity to determine the T–P conditions of crystallization of these rocks. Two applications on natural examples (Sulu belt and Kokchetav massif) are presented and discussed. This study demonstrates that Ti is a significant constituent of phengites that could have significant effects on phase relationships and melting rates with decreasing P or increasing T in the continental crust.     

Evolution of the trachydacite and pantellerite magmas of the bimodal volcanic association of Dzarta-Khuduk, Central Mongolia: Investigation of inclusions in minerals

Using various methods of melt inclusion investigation, including electron and ion microprobe techniques, we estimated the composition, evolution, and formation conditions of melts producing the trachydacites and pantellerites of the Late Paleozoic bimodal volcanic association of Dzarta-Khuduk, Central Mongolia. Primary crystalline and melt inclusions were detected in anorthoclase from trachydacites and quartz from pantellerites and pantelleritic tuffs. Among the crystalline inclusions, we identified hedenbergite, fluorapatite, and pyrrhotite in the trachydacites and F-arfvedsonite, fluorite, ilmenite, and the rare REE diorthosilicate chevkinite in the pantellerites. Melt inclusions in anorthoclase from the trachydacites are composed of glass, a gas phase, and daughter minerals (F-arfvedsonite, fluorite, villiaumite, and anorthoclase rim on the inclusion wall). Melt inclusions in quartz from the pantellerites are composed of glass, a gas phase, and a fine-grained salt aggregate consisting of Li, Na, and Ca fluorides (griceite, villiaumite, and fluorite). Melt inclusions in quartz crystalloclasts from the pantelleritic tuffs are composed of homogeneous silicate glasses. The phenocrysts of the trachydacites and pantellerites crystallized at temperatures of 1060–1000°C. During thermometric experiments with quartz-hosted melt inclusions from the pantellerites, the formation of immiscible silicate and salt (fluoride) melts was observed at a temperature of 800°C. Homogeneous melt inclusions in anorthoclase from the trachydacites have both trachydacite and rhyolite compositions (wt %): 68–70 SiO₂, 12–13 Al₂O₃, 0.34–0.74 TiO₂, 5–7 FeO, 0.4–0.9 CaO, and 9–12 Na₂O + K₂O. The agpaitic index ranges from 0.92 to 1.24. The glasses of homogenized melt inclusions in quartz from the pantellerites and pantelleritic tuffs have rhyolitic compositions. Compared with the homogeneous glasses trapped in anorthoclase of the trachydacites, quartz-hosted inclusions from the pantellerites show higher SiO₂ (72–78 wt %) and lower Al₂O₃ contents (7.8–10.0 wt %). They also contain 0.14–0.26 wt % TiO₂, 2.5–4.9 wt % FeO, 9–11 wt % Na₂O + K₂O, and 0.9–0.15 wt % CaO and show an agpaitic index of 1.2–2.05. Homogeneous melt inclusions in quartz from the pantelleritic tuffs contain 69–72 wt % SiO₂. The contents of other major components, including TiO₂, Al₂O₃, FeO, and CaO, are close to those in the homogeneous glasses of quartzhosted melt inclusions in the pantellerites. The contents of Na₂O + K₂O are 4–10 wt %, and the agpaitic index is 1.0–1.6. The glasses of melt inclusions from each rock group show distinctive volatile compositions. The H₂O content is up to 0.08 wt % in anorthoclase of the trachydacites, 0.4–1.4 wt % in quartz of the pantellerites, and up to 5 wt % in quartz of the pantelleritic tuffs. The content of F in the glasses of melt inclusions in the phenocrysts of the trachydacites is no higher than 0.67 wt %, and up to 1.4–2.8 wt % in quartz from the pantellerites. The Cl content is up to 0.2 wt % in the glasses of melt inclusions in the minerals of the trachydacites and up to 0.5 wt % in the glasses of quartz-hosted melt inclusions from the pantellerites. The investigation of trace elements in the homogenized glasses of melt inclusions in minerals showed that the trachydacites and pantellerites were formed from strongly evolved rare-metal alkaline silicate melts with high contents of Li, Zr, Rb, Y, Hf, Th, U, and REE. The analysis of the composition of homogeneous melt inclusions in the minerals of the above rocks allowed us to distinguish magmatic processes resulting in the enrichment of these rocks in trace and rare earth elements. The most important processes are the crystallization differentiation and immiscible separation of silicate and fluoride salt melts. It was also shown that all the melts studied evolved in spatially separated magma chambers. This caused the differences in the character of melt evolution between the trachydacites and pantellerites. During the final stages of differentiation, when the magmatic system was saturated with respect to ore elements, Na-Ca fluoride melts were separated and extracted considerable amounts of Li.     

Influence of SiO2 and Al2O3 on the activity coefficients of alkalis in melts: An experimental study

The simultaneous saturation of silicate melts with variable Al₂O₃ and SiO₂ contents in sodium, potassium, and rubidium was investigated at a total pressure of 1 atm and temperatures of 1300–1470°C using the crucible supported loop technique. It was shown that an increase in both SiO₂ and Al₂O₃ contents in the melt results in a significant decrease in the activity coefficients of the alkalis, and the effect of Al₂O₃ is especially pronounced in silicic compositions. The extrapolation of the experimental data allowed us to estimate the influence of SiO₂ and Al₂O₃ contents in the melt on the behavior of Li and Cs. Using a numerical experiment, it was shown how the inert and perfectly mobile behavior of alkalis in magmatic processes can be discriminated. A methodic investigation was performed on the loss of Na, K, and Rb from silicic glasses during microprobe analysis depending on beam diameter.