A Cl stable isotope fractionation factor between amphibole and fluid has been determined at 700 °C and 0.2 GPa. Rates of isotope exchange between pargasite and water at 600-800 °C were slow; therefore synthesis of amphibole in the presence of a fluid was necessary to facilitate the incorporation of Cl into amphibole. Hastingsite was synthesized from an oxide mixture and reacted with a NaCl-bearing supercritical fluid for periods of 3 to 14 days, approximately at the wüstite-magnetite buffer. Based on these synthesis-reaction experiments, the fractionation between hastingsite and a NaCl-bearing solution (~20000 ppm Cl) at 700 °C is 103lnαamphibole-fluid = 0.19‰ ± 0.23‰. These data display near zero fractionation at 700 °C, but suggest that amphibole is slightly enriched in 37Cl relative to the fluid, in agreement with empirical and theoretical results. / text

A continuum of rhyolite compositions has been observed throughout the Taupo Volcanic Zone (TVZ) over the past 550 kyr. reflecting changes in the ƒH2O, ƒO₂, and P-T conditions in a lower crustal 'hot-zone' (10-30 km) where these evolved melts are generated by crystal fractionation of successively intruded basaltic magmas. The rhyolite compositional continuum is bound by two distinct end-member types: R1 is characterized by hydrous minerals (hornblende ± biotite), low FeO*/MgO (calc-alkaline series), low MREE, Y, and Zr, and high Sr; and R2 is characterized by anhydrous minerals (orthopyroxene ± clinopyroxene), high FeO*/MgO (tholeiitic series), high MREE, Y, and Zr, and low Sr. Slab-derived aqueous fluid components (Ba, Cl) correlate well with oxygen fugacity, and other well defined characteristics of silicic magmas in the Taupo Volcanic Zone (TVZ) between a cold-wet-oxidizing magma type (R1: amphibole ± biotite; high Sr, low Zr and FeO*/MgO, depleted MREE) and a hot-dry-reducing magma type (R2: orthopyroxene ± clinopyroxene; low Sr, high Zr, and FeO*/MgO, less depleted MREE). Oxygen fugacity was obtained from analysis of Fe-Ti oxides and ranges between -0.039 to +2.054 log units (ΔQFM; where QFM = quartz + fayalite + magnetite buffer) and is positively correlated with the bulk-rock Ba/La ratio, indicating that slab-derived fluid is the oxidizing agent in the rhyolites. Chlorine contents in hornblende also correlate with the bulk-rock Ba/La ratio. Hence, high fluid-flux typically correlates with the R1 and low fluid-flux with R2 rhyolite magma types. A geochemical evolution and distribution can be tracked in time and space throughout the central region of the TVZ from 550 ka to present and has revealed two distinct magmatic cycles that vary in length. The first cycle included widespread R1 type magmatism across the central TVZ beginning ca. 550 ka and was directly associated with previously unreported dome-building and ignimbrite-forming volcanism, and led to a voluminous (>3000 km³) ignimbrite 'flare-up' between ca. 340 and 240 ka. These magmas also display the highest K₂O and Pb isotopic compositions compared to those erupted more recently, and is consistent with a peak in slab-derived sediment input. The second cycle began roughly 180 ka, erupting ca. 800 km³ of magma, and continues to the present. The duration, rate, and composition of melt production within these cycles appears to be governed by the flux of fluid/sediment released from the subducting slab, while the distribution of melts may be governed more by extension along the central rift axis. The Matahina Ignimbrite (~160 km³ rhyolite magma; 330 ka) was deposited during a caldera-forming eruption from the Okataina Volcanic Centre, TVZ. The outflow sheet is distributed primarily from the northeast to southeast and consists of a basal plinian fall member and three ash-flow members. Pumice clasts are separated into three groups defined by differences in bulk geochemistry and mineral contents: high CaO, MgO, Fe₂O₃T, TiO₂, and low Al₂O₃, +hornblende (A2), low CaO, MgO, Fe2O3T, TiO2, ±hornblende (A1), and a subset to A1, which has high-K, +biotite (B). Two types of crystal-rich mafic clasts were also deposited during the final stages of the eruption. The distinct A and B rhyolite magma types are petrogenetically related to corresponding type A and B andesitic magma by up to 50% crystal fractionation under varying ƒO₂-ƒH₂O conditions. Further variations in the low- to high-silica rhyolites can be accounted for by up to 25% crystal fractionation, again under distinct ƒO₂-ƒH₂O conditions. Reconstruction of the P-T-ƒO₂-ƒ’H₂O conditions of the andesite to rhyolite magmas are consistent with the existence of a compositional and thermal gradient prior to the eruption. Magma mingling/mixing between the basalt to andesite and main compositionally zoned rhyolitic magma occurred during caldera-collapse, modifying the least-evolved rhyolite at the bottom of the reservoir and effectively destroying the pre-eruptive gradients. A detailed examination of the diverse range of calcic-amphibole compositions from the ca. 330 ka Matahina eruption (ca. 160 km³ rhyolitic magma) of the Okataina Volcanic Complex, Taupo Volcanic Zone, including crystal-rich basalt to dacite pumice from post-collapse deposits, reveals several pre- and syn-eruption magmatic processes. (1) Amphibole phenocrysts in the basaltic-andesite and andesite crystallized at the highest pressures and temperatures (P: up to 0.6±0.06 GPa and T: up to 950°C), equivalent to mid-crustal depths (13-22 km). Inter- and intra-crystalline compositions range from Ti-magnesiohornblende → Ti-tschermakite → tschermakite → magnesiohornblende and some display gradual decreases in T from core to rim, both consistent with magma differentiation by cooling at depth. (2) The largest amphibole crystals from the basaltic-andesite to andesite display several core to rim increases in T (up to 70°C), indicating new hotter magma periodically fluxed the crystal mush. (3) The dominant population of amphibole (magnesiohornblende) from the rhyolite is small and bladed and crystallized at low P-T conditions (P: 0.3 GPa, T: 765°C), equivalent to the eruptive P-T conditions. Amphibole (tschermakite-magnesiohornblende) from the dacitic and low-silica rhyolitic pumice form two distinct populations, which nucleated at two different T (High: 820°C and Low: 750°C). These compositional variations, governed primarily by differences in T conditions during crystal growth, record the mixing of two distinct amphibole populations that approached a thermal equilibrium at the eruptive T. Therefore, the diversity in amphibole compositions can be reconciled as an exchange of crystals+liquid between the basaltic-andesite to dacite from the mid-crust and rhyolite from the upper-crust, which quenched against one another, modifying the dacite to low-silica rhyolite compositions as the eruption progressed.

This research studies 6 eclogites from Qinglongshan Donghai in the Sulu ultrahigh-pressure (UHP) province, eastern China. Petrographic microscope, Ramam spectrometer, scanning electron microscope (SEM) and transmission electron microscope (TEM) are utilized to identify mineral compositions, microstructures and mineral precipitates. Optical observations show the eclogites with the following mineral assemblage: garnet + omphacite + amphibole + epidote + rutile ¡Ó quartz ¡Ó phengite ¡Ó kyanite ¡Ó coesite pseudomorph ¡Ó apatite ¡Ó talc. Oriented mineral precipitates are found within omphacite and within apatites. The parallel precipitates in omphacite are quartz rods confirmed by electron probe microanalysis (EPMA) and TEM diffraction patterns. The direction of the long axes of the quartz rods seem to have relation with the cleavage and with the parting of omphacite. The direction of the long axis of quartz is not necessarily the c axis direction of quartz. Pargasite is intergrown with quartz and the amounts of both minerals seem to have a positive relation. Pargasite contain element K which is not found in omphacite and there is no obvious crystallographic relation between quartz, pargasite, and omphacite. There is amphibole exsolved from the omphacite and the crystallographic axes of tht exsolved amphibole parallel to those of omphacite. The a and c parameters for the two phases are equal while the b parameter of the amphibole is almost twice that of omphacite. A two-stage growth mechanism for quartz and amphibole intergrown within omphacite is proposed: (1) very fine quartz rods exsolved (or aided with infilling fluids) from a supersilicic clinopyroxene during decompression, creating grain boundaries between quartz rods and host, (2) growth of amphibole and quartz along the grain boundaries with fluid participation and an expense of omphacite during retrograde metamorphism. There are two different precipitates within apatites in different eclogites. One of the precipitates is calcium sulfate (anhydrite or gypsum) and the other is ferrous sulfide (pyrrhotite?). There was no report about calcium sulfate within apatite in UHP rocks before. The formation of sulfide (reduced) or sulfate (oxidized) is controlled by the fugacity of oxygen. According to the previous reports and the discoveries of this research, there are many different kinds of precipitates containing silicate incompatible elements in apatites. It can¡¦t be ruled out that the precipitates exsolved from apapites but apatites are more likely to act as sinks of silicate incompatible elements and different minerals precipitated within apatites under different redox conditions rather than exsolution processes.

A continuum of rhyolite compositions has been observed throughout the Taupo Volcanic Zone (TVZ) over the past 550 kyr. reflecting changes in the ƒH2O, ƒO₂, and P-T conditions in a lower crustal 'hot-zone' (10-30 km) where these evolved melts are generated by crystal fractionation of successively intruded basaltic magmas. The rhyolite compositional continuum is bound by two distinct end-member types: R1 is characterized by hydrous minerals (hornblende ± biotite), low FeO*/MgO (calc-alkaline series), low MREE, Y, and Zr, and high Sr; and R2 is characterized by anhydrous minerals (orthopyroxene ± clinopyroxene), high FeO*/MgO (tholeiitic series), high MREE, Y, and Zr, and low Sr. Slab-derived aqueous fluid components (Ba, Cl) correlate well with oxygen fugacity, and other well defined characteristics of silicic magmas in the Taupo Volcanic Zone (TVZ) between a cold-wet-oxidizing magma type (R1: amphibole ± biotite; high Sr, low Zr and FeO*/MgO, depleted MREE) and a hot-dry-reducing magma type (R2: orthopyroxene ± clinopyroxene; low Sr, high Zr, and FeO*/MgO, less depleted MREE). Oxygen fugacity was obtained from analysis of Fe-Ti oxides and ranges between -0.039 to +2.054 log units (ΔQFM; where QFM = quartz + fayalite + magnetite buffer) and is positively correlated with the bulk-rock Ba/La ratio, indicating that slab-derived fluid is the oxidizing agent in the rhyolites. Chlorine contents in hornblende also correlate with the bulk-rock Ba/La ratio. Hence, high fluid-flux typically correlates with the R1 and low fluid-flux with R2 rhyolite magma types. A geochemical evolution and distribution can be tracked in time and space throughout the central region of the TVZ from 550 ka to present and has revealed two distinct magmatic cycles that vary in length. The first cycle included widespread R1 type magmatism across the central TVZ beginning ca. 550 ka and was directly associated with previously unreported dome-building and ignimbrite-forming volcanism, and led to a voluminous (>3000 km³) ignimbrite 'flare-up' between ca. 340 and 240 ka. These magmas also display the highest K₂O and Pb isotopic compositions compared to those erupted more recently, and is consistent with a peak in slab-derived sediment input. The second cycle began roughly 180 ka, erupting ca. 800 km³ of magma, and continues to the present. The duration, rate, and composition of melt production within these cycles appears to be governed by the flux of fluid/sediment released from the subducting slab, while the distribution of melts may be governed more by extension along the central rift axis. The Matahina Ignimbrite (~160 km³ rhyolite magma; 330 ka) was deposited during a caldera-forming eruption from the Okataina Volcanic Centre, TVZ. The outflow sheet is distributed primarily from the northeast to southeast and consists of a basal plinian fall member and three ash-flow members. Pumice clasts are separated into three groups defined by differences in bulk geochemistry and mineral contents: high CaO, MgO, Fe₂O₃T, TiO₂, and low Al₂O₃, +hornblende (A2), low CaO, MgO, Fe2O3T, TiO2, ±hornblende (A1), and a subset to A1, which has high-K, +biotite (B). Two types of crystal-rich mafic clasts were also deposited during the final stages of the eruption. The distinct A and B rhyolite magma types are petrogenetically related to corresponding type A and B andesitic magma by up to 50% crystal fractionation under varying ƒO₂-ƒH₂O conditions. Further variations in the low- to high-silica rhyolites can be accounted for by up to 25% crystal fractionation, again under distinct ƒO₂-ƒH₂O conditions. Reconstruction of the P-T-ƒO₂-ƒ’H₂O conditions of the andesite to rhyolite magmas are consistent with the existence of a compositional and thermal gradient prior to the eruption. Magma mingling/mixing between the basalt to andesite and main compositionally zoned rhyolitic magma occurred during caldera-collapse, modifying the least-evolved rhyolite at the bottom of the reservoir and effectively destroying the pre-eruptive gradients. A detailed examination of the diverse range of calcic-amphibole compositions from the ca. 330 ka Matahina eruption (ca. 160 km³ rhyolitic magma) of the Okataina Volcanic Complex, Taupo Volcanic Zone, including crystal-rich basalt to dacite pumice from post-collapse deposits, reveals several pre- and syn-eruption magmatic processes. (1) Amphibole phenocrysts in the basaltic-andesite and andesite crystallized at the highest pressures and temperatures (P: up to 0.6±0.06 GPa and T: up to 950°C), equivalent to mid-crustal depths (13-22 km). Inter- and intra-crystalline compositions range from Ti-magnesiohornblende → Ti-tschermakite → tschermakite → magnesiohornblende and some display gradual decreases in T from core to rim, both consistent with magma differentiation by cooling at depth. (2) The largest amphibole crystals from the basaltic-andesite to andesite display several core to rim increases in T (up to 70°C), indicating new hotter magma periodically fluxed the crystal mush. (3) The dominant population of amphibole (magnesiohornblende) from the rhyolite is small and bladed and crystallized at low P-T conditions (P: 0.3 GPa, T: 765°C), equivalent to the eruptive P-T conditions. Amphibole (tschermakite-magnesiohornblende) from the dacitic and low-silica rhyolitic pumice form two distinct populations, which nucleated at two different T (High: 820°C and Low: 750°C). These compositional variations, governed primarily by differences in T conditions during crystal growth, record the mixing of two distinct amphibole populations that approached a thermal equilibrium at the eruptive T. Therefore, the diversity in amphibole compositions can be reconciled as an exchange of crystals+liquid between the basaltic-andesite to dacite from the mid-crust and rhyolite from the upper-crust, which quenched against one another, modifying the dacite to low-silica rhyolite compositions as the eruption progressed.

No description available.

No description available.

<p>This study was planned as a combination of detailed field mapping, thin section petrography, whole rock geochemistry and amphibole chemistry of the rocks of the Port Coldwell intrusion. It was hoped that the results of the detailed field mapping would give a clearer picture of the stratigraphy and structure of the intrusion. It was hoped to define the mineralogy and textures of the various phases of the Port Coldwell intrusion enabling a postulation of possible physical conditions under which crystallization occurred. Through whole rock chemical analysis it was hoped to correlate the petrochemistry with the stratigraphy, and so to provide a chemical explanation of the differentiation process. Furthermore, it was hoped to classify the gabbros and through differentiation trends provided by the plots of the analyses, to determine whether the gabbro could be a feasible parent of the other phases of the intrusionThe amphibole found in each phase of the intrusion was to be determined in order to discover elemental trends and to provide corroborating evidence of a differentiation sequence suggested by other sources. </P> / Thesis / Master of Science (MSc)

En tant que laboratoire naturel, les énormes quantités de granites mésozoïques du sud de la Chine fournissent une occasion unique de comprendre la formation et l'évolution de la croûte mésozoïque et de guider les efforts d'exploration minière dans cette région. Quelles sont les conditions de mise en place de ces granites mésozoïques en Chine du Sud ? Quelle est la relation entre les conditions de mise en place et la minéralisation associée à ces granites mésozoïques?Nous avons établi expérimentalement les relations de phase du granite Jurassique de Qitianling en Chine du Sud. Trois échantillons représentatifs de granites métalumineux contenant des amphiboles ont été choisis pour définir les conditions de cristallisation de ce pluton. Des expériences de cristallisation ont été réalisées à 100-700 MPa, mais principalement à 200 MPa ou 300 MPa, à une fO₂ de ~ NNO-1,3 (1,3 log sous le tampon Ni-NiO) ou ~ NNO + 2,4, à 660 ° C à 900 ° C, et à des teneurs variables en eau (~ 3-8% en poids). Le champ de stabilité des amphiboles et les données de barométrie montrent tous deux que la pression de mise en place du magma se situait autour de 300-350 MPa. Les rapports Fe / Mg amphiboles et biotites suggèrent en outre que la fO₂ magmatique se situait autour de NNO-1 ± 0,5 près du solidus, alors que les oxydes de Fe-Ti enregistrent une augmentation de fO₂ jusqu’à NNO + 1 en conditions sub-solidus. La cristallisation de l'amphibole est limitée aux conditions proches de la saturation en H₂O, nécessitant au moins 5,5% en poids de H₂O dissout à 200 MPa, ou 6 à 8% en poids à> 300 MPa. La présence d'amphibole dans des magmas siliceux métalumineux riches en K₂O indique donc des teneurs en eau significativement supérieures à la valeur canonique de 4% en poids. Les compositions de liquides expérimentaux obtenus à 200-300 MPa reproduisent la tendance géochimique définie par le pluton, ce qui suggère qu'une différenciation dans le réservoir de la croûte supérieure a pu se produire. L'ensemble de ces résultats indique que la fugacité relativement faible en oxygène, la température élevée du magma lors de sa mise en place et sa richesse en eau constituent un environnement favorable à la concentration d'éléments minéralisés au stade magmatique précoce. / As a natural laboratory, the huge amounts of Mesozoic granite distributing in South China provided a unique opportunity to unravel the Mesozoic crust formation and evolution in southern China as well as for guiding mining exploration efforts in this area. What are the emplacement conditions of those Mesozoic granite in South China? What are the relationship between the emplacement conditions and the mineralization among those Mesozoic granites?We have experimentally established the phase relationships for the tin-bearing Jurassic Qitianling granite in South China. Three representative amphibole-bearing, metaluminous granitic samples were chosen for constraining crystallization conditions of the Qitianling pluton. Crystallization experiments were performed at 100-700 MPa, albeit mainly at 200 MPa or 300 MPa, at an fO₂ of ~NNO-1.3 (1.3 log unit below the Ni-NiO buffer) or ~NNO+2.4, at 660°C to 900°C, and at variable melt water contents (~3-8 wt%). Amphibole stability field and barometry both show that the pressure of magma emplacement was around 300-350 MPa. Amphibole and biotite Fe/Mg ratios further suggest that magmatic fO₂ was around NNO-1±0.5 near solidus, while Fe-Ti oxides record an fO2 increase up to NNO+1 below solidus. Amphibole crystallization is restricted to near H₂O-saturation conditions, requiring at least 5.5 wt% H₂Omelt at 200 MPa, or 6-8 wt % at ≥ 300 MPa. Amphibole occurrence in K₂O-rich metaluminous silicic magmas thus indicates water contents significantly higher than the canonical value of 4 wt%. The experimental liquid line of descent obtained at 200-300 MPa mimic the geochemical trend expressed by the pluton suggesting that fractionation in the upper crustal reservoir could happen. We deduced that the relatively low oxygen fugacity, high liquidus temperature and melt water rich condition may be an enabling environment for concentrating the ore elements in the early magmatic stage

Carbonatites are igneous rocks comprising more than 50 modal percent of carbonate minerals and characterized by highly variable modal compositions. The majority of carbonatites are confined to intra-continental rifts, whereas occurrences associated with plate margins and orogenic settings are less common. Petrogenesis of carbonatites has been a matter of intense debate for several decades. The possible genetic models include crystallisation from a primary carbonatite magma, liquid immiscibility and crystal fractionation from carbonate-rich silicate magma. In contrast to the voluminous bulk-rock trace-element data and major-element analyses of minerals from carbonatites available in the literature, there has been no systematic study concerned with the trace-element signatures of the most common constituents of these rocks. This work is the first comprehensive study of the interrelations between the trace-element chemistry of the most common constituents of carbonatites, the geochemistry of these rocks, and their tectonic setting. The rock samples examined represent 21 different localities worldwide. The extent of major- and trace-element substitutions in amphibole, clinopyroxene, trioctahedral micas, dolomite, magnetite and perovskite is investigated in detail. The silicate minerals from carbonatites exhibit much larger compositional diversity than previously recognized. They can incorporate significant amounts of such petrogenetically important elements as Sr, REE, Zr, Nb and Ta. The majority of studied clino-amphibole- and clinopyroxene-group minerals exhibit previously unrecognized a bimodal distribution patterns of REE, which can be explained in terms of crystal chemistry of these phases. The trace-element signature of phlogopite from carbonatites, particularly Nb, Mn, Ni and Cr, is distinctly different from that of phlogopite from kimberlites, and can be used as a reliable petrogenetic indicator. Compositional variations in dolomite reflect magmatic and subsolidus processes in carbonatites. Magnetite from carbonatites follows a well-defined magmatic and previously unrecognized reaction trend. Contrary to prior studies, this mineral is only a minor host of HFSE in carbonatitic rocks. The U-Pb age data, trace-element and Sr-isotopic composition of perovskite from the Afrikanda carbonatite and clinopyroxenite suggest that the two rocks are not related by crystal fractionation. This study underlines the importance of a systematic approach in petrogenetic studies based on trace-element distribution.

Carbonatites are igneous rocks comprising more than 50 modal percent of carbonate minerals and characterized by highly variable modal compositions. The majority of carbonatites are confined to intra-continental rifts, whereas occurrences associated with plate margins and orogenic settings are less common. Petrogenesis of carbonatites has been a matter of intense debate for several decades. The possible genetic models include crystallisation from a primary carbonatite magma, liquid immiscibility and crystal fractionation from carbonate-rich silicate magma. In contrast to the voluminous bulk-rock trace-element data and major-element analyses of minerals from carbonatites available in the literature, there has been no systematic study concerned with the trace-element signatures of the most common constituents of these rocks. This work is the first comprehensive study of the interrelations between the trace-element chemistry of the most common constituents of carbonatites, the geochemistry of these rocks, and their tectonic setting. The rock samples examined represent 21 different localities worldwide. The extent of major- and trace-element substitutions in amphibole, clinopyroxene, trioctahedral micas, dolomite, magnetite and perovskite is investigated in detail. The silicate minerals from carbonatites exhibit much larger compositional diversity than previously recognized. They can incorporate significant amounts of such petrogenetically important elements as Sr, REE, Zr, Nb and Ta. The majority of studied clino-amphibole- and clinopyroxene-group minerals exhibit previously unrecognized a bimodal distribution patterns of REE, which can be explained in terms of crystal chemistry of these phases. The trace-element signature of phlogopite from carbonatites, particularly Nb, Mn, Ni and Cr, is distinctly different from that of phlogopite from kimberlites, and can be used as a reliable petrogenetic indicator. Compositional variations in dolomite reflect magmatic and subsolidus processes in carbonatites. Magnetite from carbonatites follows a well-defined magmatic and previously unrecognized reaction trend. Contrary to prior studies, this mineral is only a minor host of HFSE in carbonatitic rocks. The U-Pb age data, trace-element and Sr-isotopic composition of perovskite from the Afrikanda carbonatite and clinopyroxenite suggest that the two rocks are not related by crystal fractionation. This study underlines the importance of a systematic approach in petrogenetic studies based on trace-element distribution.