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Showing papers in "Contributions to Mineralogy and Petrology in 1997"


Journal ArticleDOI
TL;DR: In this paper, a new method to separate and determine isotopic compositions of both Hf and Lu from various types of geological materials using MC-ICP-MS is presented.
Abstract: Potential applications of the Lu-Hf isotope system have long been impeded by the analytical difficulties of obtaining data on a wide variety of geological materials. Many of these limitations will now be eliminated because Hf isotopes can be readily measured with high precision and accuracy on small and/or Hf-poor samples using the newly developed magnetic sector-multiple collector ICP-MS, also known as MC-ICP-MS or the `Plasma 54'. We present here a new method to separate and determine isotopic compositions of both Hf and Lu from various types of geological materials using MC-ICP-MS. The chemical separation of Hf and Lu has been designed to take advantage of the characteristics of this unique instrument. The separation of Hf can be achieved with a straightforward two-step ion-exchange column chemistry, which has a high efficiency (better than 85% recovery) and low blanks (typical total blanks less than 150 pg for the largest samples of 1 g bulk rock). The isolation of Lu is achieved with a single-stage ion-exchange column procedure with near 100% yields and blanks below 20 pg. Hf isotopic compositions can be routinely measured on 50 ng Hf with an internal precision better than 20 ppm in less than 15 min and with an external precision better than 40 ppm. Our value for the 176Hf/177Hf ratio of the JMC 475 Hf standard currently is 0.282163 ± 9 (2s). The Lu isotopic ratio is measured rapidly and precisely without isolating Lu from the bulk of Yb, and a mass fractionation correction increases the accuracy of the results compared with TIMS data. Our current reproducibility of the Lu/Hf ratio is ≈1%. Selected Lu-Hf isotope analyses of some modern and ancient geological samples validate the technique we have described here and illustrate the new opportunities for Lu-Hf isotope geochemistry that have opened up with the advent of magnetic-sector ICP mass spectrometry.

713 citations


Journal ArticleDOI
TL;DR: In this paper, a quantitative model to describe the partitioning of rare earth elements (REE) and Y between clinopyroxene and anhydrous silicate melt as a function of pressure (P), temperature (T), and bulk composition (X) is presented.
Abstract: We present a quantitative model to describe the partitioning of rare earth elements (REE) and Y between clinopyroxene and anhydrous silicate melt as a function of pressure (P), temperature (T) and bulk composition (X). The model is based on the Brice (1975) equation, which relates the partition coefficient of element i (Di) to that of element o (Do) where the latter has the same ionic radius ro as the crystallographic site of interest, in this case the clinopyroxene M2 site: $$$$

515 citations


Journal ArticleDOI
TL;DR: Bulk compositions and mineral analyses for forty-one, large, garnet and spinel-facies peridotite xenoliths from the Udachnaya kimberlite in the central Siberian platform have many similarities to those of well-studied peridodites from the Kaapvaal craton in southern Africa.
Abstract: Bulk compositions and mineral analyses for forty-one, large, garnet- and spinel-facies peridotite xenoliths from the Udachnaya kimberlite in the central Siberian platform have many similarities to those of well-studied peridotites from the Kaapvaal craton in southern Africa. Coarse Mg-rich lherzolites and harzburgites with equilibration temperatures below 1000 °C are abundant and are believed to form the principal rock type in the Siberian lithosphere. The low-temperature Udachnaya peridotites have an average mg number [Mg/(Mg+Fe)] of 92.6 with a wide dispersion in modal enstatite, ranging to over 40 wt%. High-temperature peridotites are relatively richer in Fe and Ti and are commonly deformed, with porphyroclastic or mosaic-porphyroclastic textures, some of the latter having fluidized enstatite. The Udachnaya peridotites have experienced late-stage metasomatism before, during and after eruption. Garnets and pyroxenes in many of the high-temperature rocks are zoned, probably by reaction with melt prior to eruption. Virtually all the peridotites contain secondary diopside, inhomogeneous on a micron scale, that mantles primary orthopyroxene. It is believed to have crystallized along with lesser amounts of intergranular calcite and monticellite during eruption. Bulk analyses for total Fe in many specimens are higher than whole-rock Fe calculated from the electron probe analyses and the modes. The magnitude of the difference between the two measurements of total Fe correlates with loss-on-ignition, suggesting that Fe has been introduced during serpentinization following eruption. These late metasomatic processes have thus affected some major as well minor and trace element compositions. The similarities in bulk composition of peridotites from Udachnaya and the Kaapvaal are evidence of a common origin. Low-temperature cratonic peridotites differ from oceanic peridotites in having higher mg numbers (>92) and in having relatively high but wide-ranging modal enstatite (Mg/Si = 1.06–1.49 weight fraction). The Udachnaya low-temperature peridotites have an inverse correlation between FeO (calculated from the probe analyses and modes) and SiO2. This correlation is also present in the Kaapvaal data but is complicated by a greater range in fertility that produces a positive variation of Fe with Si. A negative trend for Fe/Si can be seen within a portion of the Kaapvaal data, that for low-Ca harzburgites, in which the variation in fertility is restricted. The negative trends for Fe/Si can be interpreted as a consequence of either segregation of olivine and orthopyroxene by metamorphic differentiation or partial sorting during cumulate formation.

380 citations


Journal ArticleDOI
TL;DR: In this article, the chemical composition of the phases present in the experimental charges as determined by electron microprobe was reported, including biotite, plagioclase, orthopyroxene, garnet, cordierite, hercynite, staurolite, gedrite, oxide, and glass, over the range 100-1000"MPa, 780-1025"°C.
Abstract: A series of experiments on the fluid-absent melting of a quartz-rich aluminous metagreywacke has been carried out. In this paper, we report the chemical composition of the phases present in the experimental charges as determined by electron microprobe. This analytical work includes biotite, plagioclase, orthopyroxene, garnet, cordierite, hercynite, staurolite, gedrite, oxide, and glass, over the range 100–1000 MPa, 780–1025 °C. Biotites are Na- and Mg-rich, with Ti contents increasing with temperature. The compositions of plagioclase range from An17 to An35, with a significant orthoclase component, and are always different from the starting minerals. At high temperature, plagioclase crystals correspond to ternary feldspars with Or contents in the range 11–20 mol%. Garnets are almandine pyrope grossular spessartine solid solutions, with a regular and significant increase of the grossular content with pressure. All glasses are silicic (SiO2 = 67.6–74.4 wt%), peraluminous, and leucocratic (FeO + MgO = 0.9–2.9 wt%), with a bulk composition close to that of peraluminous leucogranites, even for degrees of melting as high as 60 vol.%. With increasing pressure, SiO2 contents decrease while K2O increases. At any pressure, the melt compositions are more potassic than the water-saturated granitic minima. The H2O contents estimated by mass balance are in the range 2.5–5.6 wt%. These values are higher than those predicted by thermodynamic models. Modal compositions were estimated by mass balance calculations and by image processing of the SEM photographs. The positions of the 20 to 70% isotects (curves of equal proportion of melt) have been located in the pressure-temperature space between 100 MPa and 1000 MPa. With increasing pressure, the isotects shift toward lower temperature between 100 and 200 MPa, then bend back toward higher temperature. The melting interval increases with pressure; the difference in temperature between the 20% and the 70% isotects is 40 °C at 100 MPa, and 150 °C at 800 MPa. The position of the isotects is interpreted in terms of both the solubility of water in the melt and the nature of the reactions involved in the melting process. A comparison with other partial melting experiments suggests that pelites are the most fertile source rocks above 800 MPa. The difference in fertility between pelites and greywackes decreases with decreasing pressure. A review of the glass compositions obtained in experimental studies demonstrates that partial melting of fertile rock types in the crust (greywackes, pelites, or orthogneisses) produces only peraluminous leucogranites. More mafic granitic compositions such as the various types of calk-alkaline rocks, or mafic S-type rocks, have never been obtained during partial melting experiments. Thus, only peraluminous leucogranites may correspond to liquids directly formed by partial melting of metasediments. Other types of granites involve other components or processes, such as restite unmixing from the source region, and/or interaction with mafic mantle-derived materials.

377 citations


Journal ArticleDOI
TL;DR: In this paper, the authors conducted fluid-absent partial melting experiments, at 0.5 and 1.0 GPa in the temperature range 750 to 1000 °C, to investigate the influence of bulk rock Mg? [100Mg/(Mg+Fe)] and the effects of additional TiO2 on the granulite-grade anatectic evolution of relatively magnesian metapelites and metagreywackes.
Abstract: We conducted fluid-absent partial melting experiments, at 0.5 and 1.0 GPa in the temperature range 750 to 1000 °C, to investigate the influence of bulk rock Mg ? [100Mg/(Mg+Fe)] and the effects of additional TiO2 on the granulite-grade anatectic evolution of relatively magnesian metapelites and metagreywackes. In these experiments, melting began between 780 and 830 °C by the incongruent breakdown of biotite to produce quartz-saturated, granulite-facies residual mineral assemblages in equilibrium with H2O-undersaturated granitic melt. The glass (quenched melt) compositions produced in this study vary little. Generally, the glasses have compositions similar to those of many natural strongly peraluminous leucogranites. The solidus temperatures in both rock types increase with increasing Mg ?, but are unaffected by the presence or absence of a TiO2 component. At 0.5 GPa the metapelites melted at temperatures up to 50 °C lower than the equivalent metagreywackes, but at 1 GPa there was no discernible difference. This study suggests that the fluid-absent solidus has a steep positive dP/dT slope in metapelites and steep negative dP/dT slope in metagreywackes. The pattern of melt production with increasing temperature is strongly controlled by the upper limit of biotite stability. In TiO2-free compositions this was found to increase by 15 to 20 °C in the metapelites and by 30 to 40 °C in the metagreywackes, as a function of increasing Mg ? from 49 to 81. The presence of a TiO2 component increases the upper limit of biotite stability by ∼50 °C in the metapelites and by ∼80 °C in the metagreywackes, over that observed in the equivalent TiO2-free compositions. In consequence, in the TiO2-free samples large pulses of melt (up to 35 wt%) are produced over narrow temperature ranges (as little as 15 °C in these experiments) between 830 and 875 °C. In the TiO2-bearing samples the major pulse of melt production occurs more gradually between 830 and >900 °C.

349 citations


Journal ArticleDOI
TL;DR: In this paper, the authors measured the diffusion coefficient of three tetravalent rare earth cations (U, Th and Hf) in synthetic zircon and found that they are essentially immobile under most geologic conditions, permitting the preservation of fine-scale chemical zoning and isotopic signatures of inherited cores.
Abstract: Diffusion rates for the three tetravalent cations U, Th and Hf have been measured in synthetic zircon. Diffusant sources included oxide powders and ground pre-synthesized silicates. Rutherford backscattering spectrometry (RBS) was used to measure depth profiles. Over the temperature range 1400–1650 °C, the following Arrhenius relations were obtained (diffusion coefficients in m2sec−1): log D Th = (1.936 ± 0.9820) + (− 792 ± 34 kJ mol−1 /2.303 RT) log D U = (0.212 ± 2.440) + (− 726 ± 83 kJ mol−1 /2.303 RT) log D Hf = (3.206 ± 1.592) + (− 812 ± 54 kJ mol−1 /2.303 RT) The data show a systematic increase in diffusivity with decreasing ionic radius (i.e., faster diffusion rates for Hf than for U or Th), a trend also observed in our earlier study of rare earth diffusion in zircon. Diffusive fractionation may be a factor in the Lu-Hf system given the much slower diffusion rates of tetravalent cations when compared with the trivalent rare earths. The very slow diffusion rates measured for these tetravalent cations suggest that they are essentially immobile under most geologic conditions, permitting the preservation of fine-scale chemical zoning and isotopic signatures of inherited cores.

306 citations


Journal ArticleDOI
TL;DR: Partial fusion experiments with basic granulites (S6, S37) believed to represent the lower crust beneath the Eifel region (Germany) were performed at pressures from 5 to 15 kbar as mentioned in this paper.
Abstract: Partial fusion experiments with basic granulites (S6, S37) believed to represent the lower crust beneath the Eifel region (Germany) were performed at pressures from 5 to 15 kbar. Water-undersaturated experiments were carried out in the presence of 1 wt% H2O plus 2.44 or 0.81 wt% CO2 equivalent to mole fractions of H2O/(H2O + CO2) of 0.5 and 0.75, respectively, of the volatile components added. At temperatures from 850 to 1100 °C the weight proportions of melt range from 7 to 30 %. Melt compositions change from trondhjemitic over tonalitic to dioritic with increasing degree of partial melting. Crystalline residua are plagioclase/pyroxene dominated at 5 kbar to garnet/pyroxene dominated at 15␣kbar. Dehydration melting was studied in granulite S35 similar in composition to S6. The magmatic precursors of the granulite xenoliths used in this study had geochemical characteristics of cumulate gabbro (metagabbro S37) and evolved melts (metabasalts S6, S35), respectively. Melts from granulite S37 match the major element compositions of natural trondhjemites and tonalites. At 5 kbar, their Al2O3 is relatively low, similar to tonalites from ophiolites. At 15 kbar, Al2O3 in the melts is high due to the near absence of plagioclase in the crystalline residua. The Al2O3 concentrations in 15 kbar melts from S6 (˜20 wt%) are higher than in natural tonalites. Depth constraints on the formation of tonalitic magmas in the continental crust are provided by REE (rare earth element) patterns of the synthetic melts calculated from the known REE abundances in metagabbro S37 and metabasalt S6 assuming batch melting and using partition coefficients from the literature. The REE patterns of tonalites from active continental margins and Archean trondhjemite-tonalite-granodiorite␣associations low in REE with LaN (chondrite normalised) from 10 to 30 and YbN from 1 to 2 are reproduced at pressures of 10 and 12.5 kbar from metagabbro S37 which displays a slightly L(light)REE enriched pattern with LaN = 8 and YbN = 3. Natural tonalites with LaN from 30 to 100 require a source richer in REE than granulite S37. At 15 kbar, H(heavy)REEN in melts from granulite S37 are depressed below the level observed in natural tonalites due to the high proportion of garnet (>30 wt%) in the residue. Melts from metabasalt S6 (enriched in REE with LaN = 38 and YbN = 16) do not match the REE characteristics of natural tonalites under any conditions.

297 citations


Journal ArticleDOI
TL;DR: In this paper, the behavior of niobium and tantalum in magmatic processes has been investigated by conducting MnNb2O6 and MnTa2O 6 solubility experiments in nominally dry to water-saturated peralkaline (aluminium saturation index, A.I.S. 0.64) to peraluminous (A.IS. 1.22) granitic melts at 800 to 1035 C and 800 to 5000 bars.
Abstract: The behaviour of niobium and tantalum in magmatic processes has been investigated by conducting MnNb2O6 and MnTa2O6 solubility experiments in nominally dry to water-saturated peralkaline (aluminium saturation index, A.S.I. 0.64) to peraluminous (A.S.I. 1.22) granitic melts at 800 to 1035 °C and 800 to 5000 bars. The attainment of equilibrium is demonstrated by the concurrence of the solubility products from dissolution, crystallization, Mn-doped and Nb- or Ta-doped experiments at the same pressure and temperature. The solubility products of MnNb2O6 (Ksp Nb) and MnTa2O6 (Ksp Ta) at 800 °C and 2 kbar both increase dramatically with alkali contents in water-saturated peralkaline melts. They range from 1.2 × 10−4 and 2.6 × 10−4 mol2/kg2, respectively, in subaluminous melt (A.S.I. 1.02) to 202 × 10−4 and 255 × 10−4 mol2/kg2, respectively, in peralkaline melt (A.S.I. 0.64). This increase from the subaluminous composition can be explained by five non-bridging oxygens being required for each excess atom of Nb5+ or Ta5+ that is dissolved into the melt. The Ksp Nb and Ksp Ta also increase weakly with Al content in peraluminous melts, ranging up to 1.7 × 10−4 and 4.6 × 10−4 mol2/kg2, respectively, in the A.S.I. 1.22 composition. Columbite-tantalite solubilities in subaluminous and peraluminous melts (A.S.I. 1.02 and 1.22) are strongly temperature dependent, increasing by a factor of 10 to 20 from 800 to 1035 °C. By contrast columbite-tantalite solubility in the peralkaline composition (A.S.I. 0.64) is only weakly temperature dependent, increasing by a factor of less than 3 over the same temperature range. Similarly, Ksp Nb and Ksp Ta increase by more than two orders of magnitude with the first 3 wt% H2O added to the A.S.I. 1.02 and 1.22 compositions, whereas there is no detectable change in solubility for the A.S.I. 0.64 composition over the same range of water contents. Solubilities are only slightly dependent on pressure over the range 800 to 5000 bars. The data for water-saturated sub- and peraluminous granites have been extrapolated to 600 °C, conditions at which pegmatites and highly evolved granites may crystallize. Using a melt concentration of 0.05 wt% MnO, 70 to 100 ppm Nb or 500 to 1400 ppm Ta are required for manganocolumbite and manganotantalite saturation, respectively. The solubility data are also used to model the fractionation of Nb and Ta between rutile and silicate melts. Predicted rutile/melt partition coefficients increase by about two orders of magnitude from peralkaline to peraluminous granitic compositions. It is demonstrated that the γNb2O5/γTa2O5 activity coefficient ratio in the melt phase depends on melt composition. This ratio is estimated to decrease by a factor of 4 to 5 from andesitic to peraluminous granitic melt compositions. Accordingly, all the relevant accessory phases in subaluminous to peraluminous granites are predicted to incorporate Nb preferentially over Ta. This explains the enrichment of Ta over Nb observed in highly fractionated granitic rocks, and in the continental crust in general.

294 citations


Journal ArticleDOI
TL;DR: In this paper, a revised model for the volume and thermal expansivity of K2O-NaO-CaO-MgO-Al2O3-SiO2 liq- uids, which can be applied at crustal magmatic tem- peratures, was derived from new low temperature (701-1092 K) density measurements on sixteen super- cooled liquids, for which high temperature (1421- 1896 K) liquid density data are available.
Abstract: A revised model for the volume and thermal expansivity of K2O-Na2O-CaO-MgO-Al2O3-SiO2 liq- uids, which can be applied at crustal magmatic tem- peratures, has been derived from new low temperature (701-1092 K) density measurements on sixteen super- cooled liquids, for which high temperature (1421- 1896 K) liquid density data are available. These data were combined with similar measurements previously performed by the present author on eight sodium al- uminosilicate samples, for which high temperature den- sity measurements are also available. Compositions (in mol%) range from 37 to 75% SiO2, 0 to 27% Al2O3 ,0t o 38% MgO, 0 to 43% CaO, 0 to 33% Na2O and 0 to 29% K2O. The strategy employed for the low tempera- ture density measurements is based on the assumption that the volume of a glass is equal to that of the liquid at the limiting fictive temperature, T 0 f . The volume of the glass and liquid at T 0 f was obtained from the glass den- sity at 298 K and the glass thermal expansion coeAcient from 298 K to T 0 f . The low temperature volume data were combined with the existing high temperature measurements to derive a constant thermal expansivity of each liquid over a wide temperature interval (767- 1127 degrees) with a fitted 1r error of 0.5 to 5.7%. Calibration of a linear model equation leads to fitted values of Vi 1r (cc/mol) at 1373 K for SiO2 O26:86 0:03U ,A l 2 O 3O37:42 0:09U, MgOO10:71 0:08U, CaO O15:41 0:06U ,N a 2 O O26:57 0:06U ,K 2 O O42:45 0:09U, and fitted values of d Vi=dT (10 )3 cc/mol-K) for MgO O3:27 0:17U, CaO O3:74 0:12U ,N a 2 O O 7 :68 0:10U and K2OO12:08 0:20U. The results indi- cate that neither SiO2 nor Al2O3 contribute to the thermal expansivity of the liquids, and that dV=dT liq is independent of temperature between 701 and 1896 K over a wide range of composition. Between 59 and 78% of the thermal expansivity of the experimental liquids is derived from configurational (vs vibrational) contribu- tions. Measured volumes and thermal expansivities can be recovered with this model with a standard deviation of 0.25% and 5.7%, respectively.

221 citations


Journal ArticleDOI
TL;DR: In this article, it was shown that during cooling of pelitic rocks from amphibolite facies conditions, typical aluminous peak parageneses of garnet-muscovite-kyanite ± biotite may react to form either staurolite, chlorite, or muscovitic (or different combinations thereof) depending on grain size.
Abstract: Diffusive processes are a strong function of temperature. Thus, during cooling of rocks, mineral grains may develop zoning profiles as successively larger parts of the grain “close” to the diffusive exchange with the rock. One of the consequences of this process is that, during cooling, successively larger parts of zoned minerals (depending on grain size) are effectively removed from the reacting part of the rock volume. Thus, the effective bulk composition of metamorphic rocks changes during cooling and the rate of its change will be a function of grain size. Because the sequence of metamorphic reactions seen by a given rock is a strong function of its bulk composition, this process may have the consequence that two rocks of identical overall bulk composition, but of different grain size, may experience a different sequence of reactions. Qualitatively identical peak paragenesis may therefore react to form qualitatively different retrograde reaction textures. The model is applied to examples in the pelitic system. There, garnet is usually the slowest diffusing phase developing zoning profiles during cooling and the effective removal of garnet from the reacting rock volume will cause changes of the effective bulk composition. It is shown that, during cooling of pelitic rocks from amphibolite facies conditions, typical aluminous peak parageneses of garnet-muscovite-kyanite ± biotite may react to form either staurolite, chlorite or muscovite (or different combinations thereof), depending on grain size. During cooling from the granulite facies, aluminous peak parageneses of garnet-cordierite-sillimanite may form biotite, either on the expense of cordierite or garnet, also depending on grain size. The two examples are illustrated with a series of reaction textures reported for amphibolite and granulite terrains in the literature.

216 citations


Journal ArticleDOI
TL;DR: In this paper, phase relations and phase compositions of UHP metamorphism were investigated in subducted continental crusts, and phase relations showed that the most important UHP paragenesis consists of coesite, kyanite, phengite, clinopyroxene, and garnet.
Abstract: Synthesis piston cylinder experiments were carried out in the range 2.0–4.5 GPa and 680–1,050 °C to investigate phase relations in subducted continental crust. A model composition (KCMASH) has been used because all major ultrahigh-pressure (UHP) minerals of the whole range of rock types typical for continental crust can be reproduced within this system. The combination of experimental results with phase petrologic constraints permits construction of a UHP petrogenetic grid. The phase relations demonstrate that the most important UHP paragenesis consists of coesite, kyanite, phengite, clinopyroxene, and garnet in subducted continental crust. Below 700 °C talc is stable instead of garnet. As most of these minerals are also stable at much lower pressure and temperature conditions it is thus not easy to recognize UHP metamorphism in subducted crust. A general feature, however, is the absence of feldspars at H2O-saturated conditions. Plagioclase is never stable at UHP conditions, but K-feldspar can occur in H2O-undersaturated rocks. Mineral compositions in the experiments are fully buffered by coexisting phases. The Si content of phengite and biotite increase with increasing pressure. At 4.0 GPa, 780 °C, biotite contains 3.28 Si per formula unit, which is most probably caused by solid solution of biotite with talc. Above 800 °C, the CaAl2SiO6 component in clinopyroxene buffered with kyanite, coesite and a Mg-phase increases with increasing temperature, providing a tool to distinguish between 'cold' and 'hot' eclogites. Up to 10% Ca-eskolaite (Ca0.5[]0.5AlSi2O6) in clinopyroxene has been found at the highest temperature and pressure investigated (>900 °C, 4.5 GPa). Garnet buffered with coesite, kyanite and clinopyroxene displays an increase of grossular component with increasing pressure for a given temperature. Although the investigated system represents a simplification with respect to natural rocks, it helps to constrain general features of subducted continental crust. The observed phase relations and phase compositions demonstrate that at pressures >3.0 GPa and temperatures >800 °C continental crust can retain significant amounts of H2O (>1 wt%), whereas K-free mafic or ultramafic rocks are dry at these conditions. UHP parageneses are only preserved if the whole exhumation path is situated within the stability field of phengite, i.e. if there is cooling during exhumation or if the whole exhumation occurred at T <700 °C. In contrast, break down of phengite and concomitant partial melting in terranes that show isothermal decompression may lead to a complete recrystallization of the subducted crust during exhumation. The density of UHP rocks can be estimated on the basis of the established phase relations. Pelitic rocks are likely to have a density close to mantle rocks (3.3 g/cm3) because of significant amounts of dense garnet and kyanite whereas granitic rocks are less dense (3.0 g/cm3). Hence, subducted average continental crust is most probably buoyant with respect to mantle rocks and tends to get exhumed as soon as it is detached from the down-going slab. Electronic supplementary material to this paper can be obtained by using the Springer LINK server located at http://dx.doi.org/10.1007/s00410-001-0336-3.

Journal ArticleDOI
TL;DR: In this article, the role of fractional crystallization in the origin of the rhyolite of Glass Mountain was investigated and the presence and composition of amphibole in magmatic inclusions preserve evidence for crystallization of the andesite at pressures of at least 200 MPa (6 km depth) under near H2O-saturated conditions.
Abstract: Glass Mountain consists of a 1 km3, compositionally zoned rhyolite to dacite glass flow containing magmatic inclusions and xenoliths of underlying shallow crust. Mixing of magmas produced by fractional crystallization of andesite and crustal melting generated the rhyolite of Glass Mountain. Melting experiments were carried out on basaltic andesite and andesite magmatic inclusions at 100, 150 and 200 MPa, H2O-saturated with oxygen fugacity controlled at the nickel-nickel oxide buffer to provide evidence of the role of fractional crystallization in the origin of the rhyolite of Glass Mountain. Isotopic evidence indicates that the crustal component assimilated at Glass Mountain constitutes at least 55 to 60% of the mass of erupted rhyolite. A large volume of mafic andesite (2 to 2.5 km3) periodically replenished the magma reservoir(s) beneath Glass Mountain, underwent extensive fractional crystallization and provided the heat necessary to melt the crust. The crystalline residues of fractionation as well as residual liquids expelled from the cumulate residues are preserved as magmatic inclusions and indicate that this fractionation process occurred at two distinct depths. The presence and composition of amphibole in magmatic inclusions preserve evidence for crystallization of the andesite at pressures of at least 200 MPa (6 km depth) under near H2O-saturated conditions. Mineralogical evidence preserved in olivine-plagioclase and olivine-plagioclase-high-Ca clinopyroxene-bearing magmatic inclusions indicates that crystallization under near H2O-saturated conditions also occurred at pressures of 100 MPa (3 km depth) or less. Petrologic, isotopic and geochemical evidence indicate that the andesite underwent fractional crystallization to form the differentiated melts but had no chemical interaction with the melted crustal component. Heat released by the fractionation process was responsible for heating and melting the crust.

Journal ArticleDOI
TL;DR: In this article, a low-grade bimodal association of metabasalts and metarhyolites is exposed, together with intrusive trondhjemite bodies.
Abstract: In the Brevenne Series (NE Massif Central), a low-grade bimodal association of metabasalts and metarhyolites is exposed, together with intrusive trondhjemite bodies. Zircon U-Pb dating constrains their magmatic emplacement at 366 ± 5 Ma and 358 ± 1 Ma, respectively. The metabasalts are characterized by a distinct enrichment in incompatible elements (e.g. Th and LREE) and positive ɛNdi (from +5 to +8). Combined isotope and trace element systematics rule out crustal contamination of mafic melts as a suitable cause of the LILE (large ion lithophile element)-enrichment. Rather, a mixing process between a component similar to mid ocean ridge basalts and an enriched end-member with ɛNdi > +5 is suggested. An enriched-mantle source of ocean island basalt affinity is precluded by the relative depletion of high field strength elements, especially Nb which shows negative anomalies in chondrite-normalized patterns. On the contrary, a subduction-related origin for the LILE enrichment would be more consistent. It may be inferred that arc-like melts [enriched in Th and LREE (light rare earth elements) and depleted in Nb, with ɛNdi > +5] were produced through partial melting of a depleted-mantle source, to which a small amount of crustally derived component had been added. The metarhyolites are enriched in LILE, and have a close genetic relationship with the metabasalts, as evidenced by their high ɛNdi (from +4.7 to +6.8). Although the chemical evidence remains ambiguous, it is suggested that fractional crystallization, accompanied by subordinate assimilation, is the petrogenetic process most consistent with the data. The trondhjemites are isotopically distinct from the metarhyolites. Their ɛNdi values (from −1.0 to +2.2) reflect an important contribution of continental crust to their genesis, and disprove their inferred cogenetism with the felsic volcanics. A review of modern environments in which such bimodal suites are exposed, shows that settings involving incipient rifting of a volcanic arc fringing a continental margin, or built upon young, thin continental crust might provide suitable analogues. Geodynamic reconstructions are complicated by subsequent tectonic events which disrupted the initial patterns, and by Mesozoic-Cenozoic sedimentary cover. However, this subduction-related magmatism enlarges the growing body of evidence for southward subduction processes until the Late Devonian during the evolution of the northern flank of the European Variscides. As a general implication, it is suggested that the combined use of the Sm-Nd system with incompatible elements relatively resistant during alteration and low-grade metamorphism (REE, Th, Zr, Nb) may provide diagnostic criteria for recognizing the tectonic setting of bimodal metaigneous suites in ancient orogenic belts.

Journal ArticleDOI
TL;DR: In this paper, the authors investigated the solubility and incorporation mechanism of water in natural, almost pure pyrope from Dora Maira, Western Alps, showing that the infrared spectrum of the natural, untreated sample (58 ppm water) shows several exceptionally sharp bands in the OH-stretching region, including a single band at 3601.9 cm−1 and a band system with main components at 3640.5, 3650.8 and 3660.6
Abstract: The solubility and incorporation mechanism of water in natural, almost pure pyrope from Dora Maira, Western Alps was investigated. The infrared spectrum of the natural, untreated sample (58 ppm water) shows several exceptionally sharp bands in the OH-stretching region, including a single band at 3601.9 cm−1 and a band system with main components at 3640.5, 3650.8 and 3660.6 cm−1. High-temperature and high-pressure infrared spectra suggest that the two absorption features arise from almost free OH groups in sites with different compressibility and thermal expansivity, with the site causing the 3601.9 cm−1 band being much stiffer. Pyrope samples were annealed in a piston-cylinder or multi-anvil apparatus for several days in the presence of excess water, excess SiO2 and excess Al2SiO5 to determine the equilibrium solubility of water in pyrope to 100 kbar. Total solubility increases with pressure, however, this is exclusively due to the high-frequency band system, while the intensity of the low-frequency band decreases with pressure. At 1000 °C and the oxygen fugacity of the Ni-NiO buffer, the bulk solubility can be described by the equation c OH =Af H2O 0.5exp(−PΔV/RT) with A = 0.679 ppm/bar0.5 and ΔV = 5.71 cm3/mol. This equation implies the incorporation of water in the crystal as isolated OH groups. With increasing temperature, solubility appears to decrease with ΔH = − 14 kJ/mol. At Fe-FeO buffer conditions, solubility is 30 to 50% lower than with the Ni-NiO buffer, suggesting that the incorporation of OH is not coupled to the reduction of Fe3+. Possibly, the 3601.9 cm−1 band is associated with the tetrahedral OH B defect and the high-frequency system with the dodecahedral OH Li defect. Based on the experimentally established solubility model, it is estimated that garnet in a hot subducted slab will transport 170 ppm of water into the mantle beyond the breakdown limit of amphibole. In a cold slab, 470 ppm of water can be incorporated into garnet at the breakdown limit of phengite. These numbers imply that a significant fraction of the total water in the hydrosphere has been recycled into the mantle since the Proterozoic.

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TL;DR: In this paper, the U-Pb isotopic system in monazite can be influenced by a variety of processes that partially obscure the early growth history, and they suggest that the secondary domains formed at least 26 million years after the crystal formed.
Abstract: Monazite is accepted widely as an important U-Pb geochronometer in metamorphic terranes because it potentially preserves prograde crystallization ages. However, recent studies have shown that the U-Pb isotopic system in monazite can be influenced by a variety of processes that partially obscure the early growth history. In this paper, we attempt to interpret complex monazite and xenotime U-Pb data from three Paleoproterozoic granite dikes exposed in the Grand Canyon. Single-crystal monazite analyses from an unfoliated granite dike spread out along concordia from the crystallization age of the dike (defined by U-Pb zircon data to be 1685 ± 1 Ma) to 1659 ± 2 Ma, a span of 26 million years. Back-scattered electron (BSE) imaging reveals that magmatic domains within most crystals from this sample are truncated by secondary domains associated with prominent embayments at the grain margin. Fragments of a single crystal yield contrasting, concordant dates and fragments from the edges and tips of crystals yield the youngest dates. Based on these observations we suggest that the secondary domains formed at least 26 million years after the crystal formed. Monazite and xenotime dates from the second sample, a sheared dike that cross-cuts the previous dike, spread out along concordia over 16 million years and range up to 2.4% normally discordant. Again, BSE imaging reveals secondary domains that truncate both magmatic zoning and xenocrystic cores. Fragments sliced from specific domains of a previously imaged monazite crystal demonstrate that the secondary domain is 13 million years younger than the core domain. Textures revealed in BSE images suggest that the secondary domains formed by fluid-mineral interaction. Normal discordance appears to result from both radiation damage accumulated at temperatures below 300 °C and water-mineral interaction. Monazite data from the third sample exhibit dispersion in both the 207Pb/206Pb dates (1677–1690 Ma) and discordance (+ 1.6% to − 3.1%). Reverse discordance in these monazites cannot be explained by incomplete dissolution or excess (thorogenic) 206Pb. Sliced fragments from several crystals reveal dramatic intragrain U-Pb disequilibrium that does not correlate with either Th or U concentration or position within the crystal. We suggest that reverse discordance resulted from mechanisms that involve exchange or fractionation of elemental U or elemental Pb, and that neither the U-Pb dates nor the 207Pb/206Pb dates are reliable indicators of the rock's crystallization age. Given the large number of processes proposed in the recent literature to explain monazite U-Pb systematics from rocks of all ages, our results can be viewed as another cautionary note for single-crystal and multi-crystal monazite geochronometry. However, we suggest that because individual crystals can preserve a temporal record of primary and secondary monazite growth, micro-sampling of individual monazite crystals may provide precise absolute ages on a variety of processes that operate during the prograde, peak and/or retrograde history of metamorphic terranes.

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TL;DR: In this paper, a chlorite geothermometer was used to predict the chemical composition of the chlorite from basaltic and dacitic samples in the Barberton greenstone belt.
Abstract: IIb trioctahedral chlorite in the Barberton greenstone belt (BGB) metavolcanic rocks was formed during pervasive greenschist metamorphism. The chem‐ical composition of the chlorite is highly variable, with the Fe/(Fe+Mg) ratio ranging from 0.12 to 0.8 among 53 samples. The chemical variation of the chlorite results from the chemical diversity of the host rock, especially the MgO content of the rock, but major details of the variation pattern of the chlorite are due to the crystal structure of the chlorite. All major cation abundances in the chlorite are strongly correlated with each other. Sil‐icon increases with Mg and decreases with Fe, while AlIV and AlVI decrease with Mg and increase with Fe2+. A complex exchange vector explains over 90% of the chlorite compositional variation: Mg4SiFe2+−3AlVI−1 AlIV−1, which has 3 parts Fe-Mg substitution coupled with one part tschermakite substitution. This ratio is required to maintain the charge and site balances and the dimensional fit between the tetrahedral and octahedral sheets. The subtle change in Al substitution in chlorite implies that AlVI is preferentially ordered in the M(4) site, and about 84% of the AlVI present is in the M(4) sites when they are nearly filled with AlVI. Based on 47 analyzed chlorite-bearing rock samples, chlorite (Chl) composition is strongly correlated with the MgO content of the host rock. Calculated correlation coefficients are +0.91 for SiO2Chl-MgORock, −0.87 for Al2O3Chl-MgORock, +0.89 for MgOChl-MgORock, and −0.85 for FeOChl-MgORock. Only weak correlations have been found between chlorite oxides and other oxides of rock (between same oxides in chlorite and rock: SiO2−0.67, Al2O3 + 0.59, FeO −0.41). However, MgOChl is saturated at about 36 wt% in rocks that have MgO above 22 wt%.The MgOChl is about 5 wt% when the host rock approaches 0 wt% of MgO. This implies that Mg substituting into the chlorite is approximately limited to 1.5–9.2 Mg atoms per formula unit and 1.0–3.2 AlIV. Chlorite geothermometers can not be applied to all BGB samples. However, the empirical chlorite geothermometer based on AlIV of chlorite may be applicable to chlorites formed under metamorphic conditions because it can predict the chemical composition of the chlorite from basaltic and dacitic samples in this study. An estimated temperature of about 320°C for the greenschist metamorphism of the greenstone belt through this geothermometer is consistent with that obtained by other geothermometers.

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TL;DR: In the Tso Morari area (Ladakh, Himalaya) as discussed by the authors, whole-rock analyses and petrologic observations show that the metasediments correspond to Fe-rich metapelites, Mg-rich meta-metapels, intermediate metapels and metagreywackes of the Indian continental margin.
Abstract: Metasediments in the Tso Morari area (Ladakh, Himalaya) provide new insights into the Higher Himalayan metamorphism in the northwestern part of the Himalayan belt. Whole-rock analyses and petrologic observations show that the metasediments correspond to Fe-rich metapelites, Mg-rich metapelites, intermediate metapelites and metagreywackes of the Indian continental margin. Jadeite + chloritoid + paragonite + garnet in the Fe-rich metapelites indicate pressures of 20 ±2 kbar at temperatures of 550 ±50 °C according to major element partitioning thermobarometry, stability fields of minerals and Thermocalc P-T estimates. These results are consistent with P-T estimates on other metasediments and with the occurrence of eclogites. Subsequent retrogression at the eclogite-blueschist facies transition (from 18 to 13 kbar and 540 ±50 °C) was followed by an increase in temperature to 630 ±30 °C at amphibolite facies conditions. The metamorphic evolution is related to subduction of the Indian continental margin beneath the southern Asian margin at the onset of the Indian-Eurasian collision.

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Abstract: The diffusivity of water has been investigated for a haplogranitic melt of anhydrous composition Qz28Ab38Or34 (in wt %) at temperatures of 800–1200°C and at pressures of 0.5–5.0 kbar using the diffusion couple technique. Water contents of the starting glass pairs varied between 0 and 9 wt %. Concentration-distance profiles for the different water species (molecular water and hydroxyl groups) were determined by near-infrared microspectroscopy. Because the water speciation of the melt is not quenchable (Nowak 1995; Nowak and Behrens 1995; Shen and Keppler 1995), the diffusivities of the individual species can not be evaluated directly from these profiles. Therefore, apparent chemical diffusion coefficients of water (D water) were determined from the total water profiles using a modified Boltzmann-Matano analysis. The diffusivity of water increases linearly with water content <3 wt % but exponentially at higher water contents. The activation energy decreases from 64 ± 10 kJ/mole for 0.5 wt % water to 46 ± 5 kJ/mole for 4 wt % water but remains constant at higher water contents. A small but systematic decrease of D water with pressure indicates an average activation volume of about 9 cm3/mole. The diffusivity (in cm2/s) can be calculated for given water content (in wt %), T (in K) and P (in kbar) by in the ranges 1073 K ≤ T ≤ 1473 K; 0.5 kbar ≤ P≤ 5␣kbar; 0.5 wt % ≤ C water ≤ 6 wt %. The absence of alkali concentration gradients in the glasses after the experiments shows that interdiffusion of alkali and H+ or H3O+ gives no contribution to the transport of water in aluminosilicate melts. The H/D interdiffusion coefficients obtained at 800°C and 5 kbar using glass pieces with almost the same molar content of either water or deuterium oxide are almost identical to the chemical diffusivities of water. This indicates that protons are transported by the neutral component H2O under these conditions.

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TL;DR: In this article, the molar volumes of 19 hydrous albitic liquids (1.9 to 6.1 wt% H2Ototal) were determined at one bar and 505-765 K. These volume data were derived from density measurements on hydrous glasses at 298 K, followed by measurements of the thermal expansion of each glass from 298 K to its respective glass transition temperature.
Abstract: The molar volumes of 19 hydrous albitic liquids (1.9 to 6.1 wt% H2Ototal) were determined at one bar and 505–765 K. These volume data were derived from density measurements on hydrous glasses at 298 K, followed by measurements of the thermal expansion of each glass from 298 K to its respective glass transition temperature. The technique exploits the fact that the volume of a glass is equal to that of the corresponding liquid at the limiting fictive temperature (Tf′), and that Tf′ can be approximated as the temperature near the onset of the rapid increase in thermal expansion that occurs in the glass transition interval. The volume data of this study were combined with available volume data for anhydrous, Na2O-Al2O3-SiO2 liquids to derive the partial molar volume (±1) of the H2O component \(\) in an albitic melt at ∼565 K and one bar. To extend the determination of \(\) to higher temperatures and pressures, the molar volumes of the hydrous albitic liquids determined in this study were combined with those measured by previous authors at 1023–1223 K and 480–840 MPa, leading to the following fitted values (±1) at 1673 K and one bar: \(\) (±0.46)×10−3 cm−3/mol-K, and dV¯H2Ototal/dP=−3.82 (±0.36)×10−4 cm3/mol-bar. The measured molar volumes of this study and those of previous authors can be recovered with a standard deviation of 0.5%, which is within the respective experimental errors. There is a significant difference between the values for \(\) derived in this study as a function of temperature and pressure and those obtained from an existing polynomial, primarily caused by the previous absence of accurate density measurements on anhydrous silicate liquids. The coefficients of thermal expansion (=4.72×10−4/K) and isothermal compressibility (T=1.66×10−5/bar) for the H2O component at 1273 K and 100 MPa, indicate that H2Ototal is the single most expansive and compressible component in silicate liquids. For example, at 1473 K and 70 MPa (conditions of a mid-ocean ridge crustal magma chamber), the presence of just 0.4 wt% H2O will decrease the density of a basaltic liquid by more than one percent. An equivalent decrease in melt density could be achieved by increasing the temperature by 175 degrees or the decreasing pressure by 230 MPa. Therefore, even minor quantities of dissolved water will have a marked effect on the dynamic properties of silicate liquids in the crustal environment.

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TL;DR: In this paper, phase equilibrium experiments were conducted to determine the effect of pressure and temperature on the silicate-carbonate liquid miscibility gap in bulk compositions appropriate for magmas in the upper mantle.
Abstract: In order to define the conditions for the formation of immiscible carbonatite magmas in the lithosphere and in the crust, we have conducted phase equilibrium experiments to determine the effect of pressure and temperature on the silicate-carbonate liquid miscibility gap in bulk compositions appropriate for magmas in the upper mantle. A primitive (magnesian) nephelinite (NEPH) was used as a starting material, mixed with carbonates. Experiments were made with mixtures in the joins NEPH-dolomite-Na2CO3 (NEPH-Dol-NC) at 1.0 to 2.5 GPa, and NEPH-calcite (NEPH-CC) at 1.0 GPa. The miscibility gap was intersected by the join NEPH-Dol-NC (liquids with olivine), but not by NEPH-CC. Together with previous results for the Mg-free system (Na2O-CaO-Al2O3-SiO2-CO2), it was established that the size of the miscibility gap for magnesian compositions increases with decreasing pressures from depths of ˜100 km to ˜ 35 km; it increases further as compositions are changed by decreasing Mg/Ca. The maximum CaCO3 in liquids associated with the miscibility gap is 50 wt % for Mg-bearing liquids, and 80 wt % for Mg-free liquids. There is no experimental evidence for nearly pure-CaCO3 immiscible liquids, but abundant evidence for the precipitation of rounded calcite crystals from carbonate-rich liquids. The join NEPH-CC locates a piercing point on the liquidus field boundary for coprecipitation of olivine and calcite at NEPH50CC50 (wt %), part of the silicate-carbonate liquidus field boundary which defines the locus of liquids formed from carbonate-peridotites. The miscibility gap results are compared with magmas formed during partial fusion of CO2-bearing mantle peridotites, and during fractional crystallization of mantle-derived magmas. None of the probable magma paths in mantle processes intersects the miscibility gap. CO2-bearing mantle-derived alkalic magmas such as nephelinites and melilitites may fractionate during uprise through the mantle and crystallization within the crust. The compositions of these evolved nephelinites and phonolites approach the silicate side of the miscibility gap, confirming the probable generation of immiscible, alkalic carbonate-rich liquids at crustal pressures.

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TL;DR: In this article, the equilibrium among tourmaline, biotite, cordierite, and melt (± spinel, aluminosilicate, or corundum) occurs with ∼2 wt% B2O3 in strongly peraluminous melt with an aluminosity, measured by the parameter ASI, of > 1.2.
Abstract: Experiments at 750 °C, 200 MPa(H2O), a(H2O)=1, and fO2∼Ni-NiO established that the equilibrium among tourmaline, biotite, cordierite, and melt (± spinel, aluminosilicate, or corundum) occurs with ∼2 wt% B2O3 in strongly peraluminous melt with an aluminosity, measured by the parameter ASI, of >1.2. The experiments demonstrate the relationship of tourmaline stability to the activity product of the tourmaline components boron and aluminum, which are inversely related to one another. Tourmaline is unstable in metaluminous to mildly peraluminous melts (ASI 2 wt% B2O3 in their bulk magmas.

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TL;DR: In this paper, H2O activities in supercritical fluids in the system KCl-H2O-(MgO) were measured at pressures of 1, 2, 4, 7, 10 and 15 kbar by numerous reversals of vapor compositions in equilibrium with brucite and periclase.
Abstract: H2O activities in supercritical fluids in the system KCl-H2O-(MgO) were measured at pressures of 1, 2, 4, 7, 10 and 15 kbar by numerous reversals of vapor compositions in equilibrium with brucite and periclase. Measurements spanned the range 550–900 °C. A change of state of solute KCl occurs as pressures increase above 2 kbar, by which H2O activity becomes very low and, at pressures of 4 kbar and above, nearly coincident with the square of the mole fraction (xH2O). The effect undoubtedly results primarily from ionic dissociation as H2O density (ρH2O) approaches 1 gm/cm3, and is more pronounced than in the NaCl-H2O system at the same P-T-X conditions. Six values of solute KCl activity were yielded by terminal points of the isobaric brucite-periclase T-xH2O curves where sylvite saturation occurs. The H2O mole fraction of the isobaric invariant assemblage brucite-periclase-sylvite-fluid is near 0.52 at all pressures, and the corresponding temperatures span only 100 °C between 1 and 15 kbar. This remarkable convergence of the isobaric equilibrium curves reflects the great influence of pressure on lowering of both KCl and H2O activities. The H2O and KCl activities can be expressed by the formulas: aH2O = γH2O[xH2O+(1 + (1 + α)xKCl)], and aKCL = γKCl[(1 + α)xKCl/(xH2O +(1 + α)xKCl)](1 + α), where α is a degree of dissociation parameter which increases from zero at the lowest pressures to near one at high pressures and the γ's are activity coefficients based on an empirical regular solution parameter W: ln γi = (1 − xi)2W. Least squares fitting of our H2O and KCl activity data evaluates the parameters: α = exp(4.166 −2.709/ρH2O) − 212.1P/T, and W = (−589.6 − 23.10P) /T, with ρH2O in gm/cm3, P in kbar and T in K. The standard deviation from the measured activities is only ± 0.014. The equations define isobaric liquidus curves, which are in perfect agreement with previous DTA liquidus measurements at 0.5–2 kbar, but which depart progressively from their extrapolation to higher pressures because of the pressure-induced dissociation effect. The great similarity of the NaCl-H2O and KCl-H2O systems suggests that H2O activities in the ternary NaCl-KCl-H2O system can be described with reasonable accuracy by assuming proportionality between the binary systems. This assumption was verified by a few reconnaissance measurements at 10 kbar of the brucite-periclase equilibrium with a Na/(Na + K) ratio of 0.5 and of the saturation temperature for Na/(Na + K) of 0.35 and 0.50. At that pressure the brucite-periclase curves reach a lowest xH2O of 0.45 and a temperature of 587 °C before salt saturation occurs, values considerably lower than in either binary. This double-salt eutectic effect may have a significant application to natural polyionic hypersaline solutions in the deep crust and upper mantle in that higher solute concentrations and very low H2O activities may be realized in complex solutions before salt saturation occurs. Concentrated salt solutions seem, from this standpoint, and also because of high mechanical mobility and alkali-exchanging potential, feasible as metasomatic fluids for a variety of deep-crust and upper mantle processes.

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TL;DR: In this paper, the peridotite xenoliths from the Atsagin-Dush volcanic centre, SE Mongolia range from fertile lherzolites to clinopyroxene(cpx)-bearing harzburgites.
Abstract: Spinel peridotite xenoliths from the Atsagin-Dush volcanic centre, SE Mongolia range from fertile lherzolites to clinopyroxene(cpx)-bearing harzburgites. The cpx-poor peridotites typically contain interstitial fine-grained material and silicate glass and abundant fluid inclusions in minerals, some have large vesicular melt pockets that apparently formed after primary clinopyroxene and spinel. No volatile-bearing minerals (amphibole, phlogopite, apatite, carbonate) have been found in any of the xenoliths. Fifteen peridotite xenoliths have been analysed for major and trace elements; whole-rock Sr isotope compositions and O isotope composition of all minerals were determined for 13 xenoliths. Trace element composition and Sr-Nd isotope compositions were also determined in 11 clinopyroxene and melt pocket separates. Regular variations of major and moderately incompatible trace elements (e.g. heavy-rare-earth elements) in the peridotite series are consistent with its formation as a result of variable degrees of melt extraction from a fertile lherzolite protolith. The Nd isotope compositions of LREE (light-rare-earth elements)-depleted clinopyroxenes indicate an old (≥ 1 billion years) depletion event. Clinopyroxene-rich lherzolites are commonly depleted in LREE and other incompatible trace elements whereas cpx-poor peridotites show metasomatic enrichment that can be related to the abundance of fine-grained interstitial material, glass and fluid inclusions in minerals. The absence of hydrous minerals, ubiquitous CO2-rich microinclusions in the enriched samples and negative anomalies of Nb, Hf, Zr, and Ti in primitive mantle-normalized trace element patterns of whole rocks and clinopyroxenes indicate that carbonate melts may have been responsible for the metasomatic enrichment. Low Cu and S contents and high δ34S values in whole-rock peridotites could be explained by interaction with oxidized fluids that may have been derived from subducted oceanic crust. The Sr-Nd isotope compositions of LREE-depleted clinopyroxenes plot either in the MORB (mid-ocean-ridge basalt) field or to the right of the mantle array, the latter may be due to enrichment in radiogenic Sr. The LREE-enriched clinopyroxenes and melt pockets plot in the ocean island-basalt field and have Sr-Nd isotope signatures consistent with derivation from a mixture of the DMM (depleted MORB mantle) and EM (enriched mantle) II sources.

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TL;DR: In this paper, the authors investigated the effect of variable Mg′ on the partitioning of fluorine and chlorine between biotite (Bt) and melt and found that Bt is the sole liquidus phase.
Abstract: Experiments from 640 to 680 °C, 200 MPa H2O at␣fO2 ≈ NNO, employing a natural␣F-rich␣vitrophyric rhyolite from Spor Mountain, Utah, assessed the effect of variable Mg′ [100Mg/(Mg + Mn + Fe)] on the partitioning of fluorine and chlorine between biotite (Bt) and melt. Over this temperature interval, Bt ( ± fluorite, ± quartz) is the sole liquidus phase. Partition coefficients for fluorine between biotite and glass (DFBt/melt) show a strong dependence on the Mg′ of Bt.␣DFBt/melt varies from ˜ 1.5 to 7.2 over the range of Mg′ from 21 to 76. A strong linear correlation between␣DFBt/melt␣and Mg′ has a slope of 9.4 and extrapolates through the origin (i.e., DFBt/melt ≈ 0 at Mg′ = 0, an annite-siderophyllite solid solution in these experiments). DClBt/melt values ( ˜ 1 to 6) in the same experiments vary inversely with Mg′. The Al-content of biotite does not vary with the aluminum saturation index (ASI = molar Al2O3/Σ alkali and alkaline earth oxides) of melt, but two exchange mechanisms involving Al appear to operate in these micas: (1) Alvi + Aliv ? Siiv + Mgiv, and Mgiv + 2Aliv? 2Siiv + □iv. The effects of other components such as Li or other intensive parameters including fO2 have yet to be evaluated␣systematically. At comparable Mg′ of Bt, however, the Spor Mountain rhyolite yields higher DFBt/melt values than an Li-rich, strongly peraluminous melt previously investigated. The results indicate that the Mg′ of Bt exerts the principal control on halogen partitioning, with ASI and T as second-order variables. The experimental partition coefficients compare well with other experimental results but not with most volcanic rocks. Magmatic Bt from most rhyolites records higher DFBt/melt due to reequilibration with degassed (H2O-depleted) magma and perhaps with F2O−1 exchange that may accompany oxidation ([Fe3+O] [Fe2+OH]−1). This behavior is evident in magmatic biotite from a zoned peraluminous rhyolite complex near Morococala, Bolivia: Bt is sharply zoned with F-rich rims, but Bt(core)-melt inclusion pairs fall on our experimental curve for DFBt/melt. These experimental data can be used in part to assess the preservation of magmatic volatile contents in plutonic or volcanic silicic rocks. For plutonic rocks, the actual F-content of melt, not a relative activity ratio involving HF species, can be reasonably estimated if the mica has not undergone subsolidus reequilibration. This information is potentially useful for some shallow-level Ca-poor magmas that are thought to be rich in F (e.g., A- and S-type granites) but do not conserve F well as rocks.

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TL;DR: In this article, trace element concentrations in the four principal peridotitic silicate phases (garnet, olivine, orthopyroxene, clinopyroxenes) included in diamonds from Akwatia (Birim Field, Ghana) were determined using SIMS, and the separation between lherzolitic and harzburgitic inclusion parageneses was made using compositional fields for garnets in a CaO versus Cr2O3 diagram.
Abstract: Trace element concentrations in the four principal peridotitic silicate phases (garnet, olivine, orthopyroxene, clinopyroxene) included in diamonds from Akwatia (Birim Field, Ghana) were determined using SIMS. Incompatible trace elements are hosted in garnet and clinopyroxene except for Sr which is equally distributed between orthopyroxene and garnet in harzburgitic paragenesis diamonds. The separation between lherzolitic and harzburgitic inclusion parageneses, which is commonly made using compositional fields for garnets in a CaO versus Cr2O3 diagram, is also apparent from the Ti and Sr contents in both olivine and garnet. Titanium is much higher in the lherzolitic and Sr in the harzburgitic inclusions. Chondrite normalised REE patterns of lherzolitic garnets are enriched (10–20 times chondrite) in HREE (LaN/YbN = 0.02–0.06) while harzburgitic garnets have sinusoidal REEN patterns, with the highest concentrations for Ce and Nd (2–8 times chondritic) and a minimum at Ho (0.2–0.7 times chondritic). Clinopyroxene inclusions show negative slopes with La enrichment 10–100 times chondritic and low Lu (0.1–1 times chondritic). Both a lherzolitic and a harzburgitic garnet with very high knorringite contents (14 and 21 wt% Cr2O3 respectively) could be readily distinguished from other garnets of their parageneses by much higher levels of LREE enrichment. The REE patterns for calculated melt compositions from lherzolitic garnet inclusions fall into the compositional field for kimberlitic-lamproitic and carbonatitic melts. Much more strongly fractionated REE patterns calculated from harzburgitic garnets, and low concentrations in Ti, Y, Zr, and Hf, differ significantly from known alkaline and carbonatitic melts and require a different agent. Equilibration temperatures for harzburgitic inclusions are generally below the C-H-O solidus of their paragenesis, those of lherzolitic inclusions are above. Crystallisation of harzburgitic diamonds from CO2-bearing melts or fluids may thus be excluded. Diamond inclusion chemistry and mineralogy also is inconsistent with known examples of metasomatism by H2O-rich melts. We therefore favour diamond precipitation by oxidation of CH4-rich fluids with highly fractionated trace element patterns which are possibly due to “chromatographic” fractionation processes.

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TL;DR: In this article, the authors combine geochemical data and field evidence from the Poxoreu Igneous Province, western Brazil to show how more intense lithospheric extension above the western margin of the postulated impact zone permitted greater upwelling and melting of the Trindade plume than further east.
Abstract: High mantle potential temperatures and local extension, associated with the Late-Cretaceous impact of the Trindade mantle plume, produced substantial widespread and voluminous magmatism around the northern half of the Parana sedimentary basin. Our previous studies have shown that, above the central and eastern portions of the postulated impact zone where lithosphere extension is minimal, heat conducted by the plume caused large-scale melting of the more fusible parts of the subcontinental lithospheric mantle beneath the margin of the Sao Francisco craton and the surrounding Brasilia mobile belt. Here we combine geochemical data and field evidence from the Poxoreu Igneous Province, western Brazil to show how more intense lithospheric extension above the western margin of the postulated impact zone permitted greater upwelling and melting of the Trindade plume than further east. Laser 40Ar/39Ar age determinations indicate that rift-related basaltic magmas of the Poxoreu Igneous Province were emplaced at ˜ 84 Ma. Our detailed geochemical study of the mafic magmas shows that the parental melts underwent polybaric crystal fractionation within the crust prior to final emplacement. Furthermore, some magmas (quartz-normative) appear to have assimilated upper crust whereas others (nepheline- and hypersthene-normative) appear to have been unaffected by open-system crustal magma chamber processes. Incompatible trace element ratios (e.g. chondrite-normalised La/Nb = 1) and isotopic ratios (87Sr/86Sr = 0.704 and 143Nd/144Nd = 0.51274) of the Hy-normative basalts resemble those of oceanic islands (OIB). We therefore propose that these “OIB-like” magmas were predominantly derived from convecting-mantle-source melts (i.e. Trindade mantle plume). Inverse modelling of rare-earth element (REE) abundances suggests that the initial melts were predominantly generated within the depth range of ˜80–100 km, in mantle with a potential temperature of ˜1500 °C.

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TL;DR: In this paper, a general model for the solubility of a volatile component in a liquid is adopted, which requires the definition of a mixing equation for the excess Gibbs free energy of the liquid phase and an appropriate reference state for the dissolved volatile.
Abstract: The modeling of the solubility of water and carbon dioxide in silicate liquids (flash problem) is performed by assuming mechanical, thermal, and chemical equilibrium between the liquid magma and the gas phase. The liquid phase is treated as a mixture of ten silicate components + H2O or CO2, and the gas phase as a pure H2O or CO2. A general model for the solubility of a volatile component in a liquid is adopted. This requires the definition of a mixing equation for the excess Gibbs free energy of the liquid phase and an appropriate reference state for the dissolved volatile. To constrain the model parameters and identify the most appropriate form of the solubility equations for each dissolved volatile, a large number of experimental solubility determinations (640 for H2O and 263 for CO2) have been used. These determinations cover a large region of the P-T-composition space of interest. The resultant water and carbon dioxide solubility models differ in that the water model is regular and isometric, and the carbon dioxide model is regular and non-isometric. This difference is consistent with the different speciation modalities of the two volatiles in the silicate liquids, producing a composition-independent partial molar volume of dissolved water and a composition-dependent partial molar volume of dissolved carbon dioxide. The H2O solubility model may be applied to natural magmas of virtually any composition in the P-T range 0.1 MPa–1 GPa and > 1000 K, whereas the CO2 solubility model may be applied to several GPa pressures. The general consistency of the water solubility data and their relatively large number as compared to the calibrated model parameters (11) contrast with the large inconsistencies of the carbon dioxide solubility determinations and their low number with respect to the CO2 model parameters (22). As a result, most of the solubility data in the database are reproduced within 10% of approximation in the case of water, and 30% in the case of carbon dioxide. When compared with the experimental data, the H2O and CO2 solubility models correctly predict many features of the saturation surface in the P-T-composition space, including the change from retrograde to prograde H2O solubility in albitic liquids with increasing pressure, the so-called alkali effect, the increasing CO2 solubility with increasing degree of silica undersaturation, the Henrian behavior of CO2 in most silicate liquids up to about 30–50 MPa, and the proportionality between the fugacity in the gas phase, or the saturation activity in the liquid phase, and the square of the mole fraction of the dissolved volatile found in some unrelated silicate liquid compositions.

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TL;DR: In this paper, single zircon and titanite U-Pb SHRIMP data presented for tonalite-trondhjemite-granodiorite (TTG) suite gneisses and an ultramafic rock from the northern and central regions of the Lewisian Complex of northwest Scotland, show that protolith ages of the northern region (2800-2840 Ma) are significantly younger than those in the central region (2960-3030 Ma).
Abstract: Single zircon and titanite U-Pb SHRIMP data presented for tonalite-trondhjemite-granodiorite (TTG) suite gneisses and an ultramafic rock from the northern and central regions of the Lewisian Complex of northwest Scotland, show that protolith ages of tonalitic gneisses in the northern region (2800–2840 Ma) are significantly younger than those in the central region (2960–3030 Ma). Further evidence of a major (2490–2480 Ma) metamorphic event in the central region is documented by a metamorphic zircon associated with a granulite facies ultramafic body. A dioritic gneiss from the northern region has also been dated at c. 2680 Ma. The northern region therefore does not comprise reworked central region rocks and consequently the old models for the evolution of the Lewisian which were based upon this concept need replacing. It is instead proposed that two distinct crustal blocks, now the northern and central regions, were tectonically juxtaposed along a boundary corresponding to the Laxford Front. Juxtaposition would appear to have occurred in Proterozoic times, as it must have postdated the 2490–2480 Ma (?Inverian) metamorphism recorded only in the central region, and the emplacement of granite sheets restricted to the northern side of the boundary. The first recorded event common to both regions is resetting of titanite ages associated with c. 1750 Ma Laxfordian amphibolite facies metamorphism. Zircon inheritance in rocks of both regions is scarce. Within one zircon from the northern region a c. 3550 Ma core was found. This represents the oldest known material from the region.

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TL;DR: In this paper, the first detailed data collection for the West African Craton was provided, where diamond and syngenetic mineral inclusions from placer deposits (Akwatia mine) along the Birim River, Ghana were studied.
Abstract: Diamonds and their syngenetic mineral inclusions from placer deposits (Akwatia mine) along the Birim River, Ghana were studied, thus providing the first detailed data collection for the West African Craton. Inclusion contents indicate an almost exclusively peridotitic diamond suite, with the vast majority being part of the harzburgitic paragenesis. Chemically the Akwatian diamond inclusions differ from those in our 1100 sample world-wide data base mainly by shifts towards lower Mg/Fe ratios for harzburgitic olivines and orthopyroxenes, extremely high Ni contents in both harzburgitic and lherzolitic olivines, and a higher mean Cr content in chromites. The inconsistency between the low Mg/Fe ratios and the highly refractory compatible trace element signature seems best to be explained by re-fertilisation of a previously depleted source, similar to the metasomatic re-enrichment of deformed, Fe-Ti-rich and hot peridotites discussed by Harte (1983). Geothermometry shows Akwatian inclusions to be 140–190 °C hotter than the peridotitic average (1050 °C) given by Harris (1992). Since garnet-opx equilibria (1100 °C/50 kbar to 1370 °C/67 kbar) indicate a typical shield geotherm (40–42 mW/m2), these elevated temperatures imply an origin of the Akwatian diamonds unusually deep for a peridotitic suite. This is consistent with the presence of extraordinary amounts of silicate spinel component in chromite inclusions, indicative of crystallisation under higher pressures than recorded for most peridotitic suites. In addition, one garnet showed the highest knorringite component (66.4 mol%) so far observed in an inclusion in diamond. The same garnet also contained a minor enstatite solid-solution component, which indicates crystallisation at pressures just below 80 kbar. Akwatian diamond inclusions, therefore, represent the most complete cross-section through peridotitic subcontinental lithospheric upper mantle so far observed, down to a maximum depth between 200–240 km.

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TL;DR: In this paper, it was shown that the Ardgour gneiss is essentially an in situ anatectic granite formed during deformation and regional high-grade metamorphism from Moine metasediments.
Abstract: The age and Precambrian history of the Moine Supergroup within the Caledonide belt of north-west Scotland have long been contentious issues. The Ardgour granite gneiss is essentially an in situ anatectic granite formed during deformation and regional high-grade metamorphism from Moine metasediments. High-precision TIMS and SHRIMP U-Pb zircon dating shows that the age of the anatectic Ardgour granite gneiss and its enclosed segregation pegmatites is 873 ± 7 Ma. This demonstrates the reality of a Neoproterozoic episode of high-grade metamorphism in the Glenfinnan Group Moine and, contrary to previous evidence, the absence of Grenvillian-aged metamorphism. This conclusion places constraints on Neoproterozoic palaeogeographic reconstructions of the North Atlantic region, indicating that the Moine rocks cannot be used as a link between the Grenvillian belt of North America and the Sveconorwegian orogen in Scandinavia. SHRIMP ages of between c. 1100 and 1900 Ma were obtained from detrital, inherited zircons and reflect the provenance of the Glenfinnan Group Moine sediments which must, therefore, have been deposited between c. 1100 and 870 Ma. Potential sources are found as relatively minor, tectonically bounded basement inliers within the British Caledonides, although more widespread source areas occur outside Britain in both Laurentia and Baltica. The most important feature of the provenance is the absence of detrital Archaean grains. This suggests that the Archaean Lewisian gneiss complex, which forms the basement component of the western foreland to the Caledonides in Britain, was not a major contributor to the Glenfinnan Group basin.