Showing papers in "Contributions to Mineralogy and Petrology in 2013"

Partial melting of lower crust at 10–15 kbar: constraints on adakite and TTG formation

Abstract: The pressure–temperature (P–T) conditions for producing adakite/tonalite–trondhjemite–granodiorite (TTG) magmas from lower crust compositions are still open to debate. We have carried out partial melting experiments of mafic lower crust in the piston-cylinder apparatus at 10–15 kbar and 800–1,050 °C to investigate the major and trace elements of melts and residual minerals and further constrain the P–T range appropriate for adakite/TTG formation. The experimental residues include the following: amphibolite (plagioclase + amphibole ± garnet) at 10–15 kbar and 800 °C, garnet granulite (plagioclase + amphibole + garnet + clinopyroxene + orthopyroxene) at 12.5 kbar and 900 °C, two-pyroxene granulite (plagioclase + clinopyroxene + orthopyroxene ± amphibole) at 10 kbar and 900 °C and 10–12.5 kbar and 1,000 °C, garnet pyroxenite (garnet + clinopyroxene ± amphibole) at 13.5–15 kbar and 900–1,000 °C, and pyroxenite (clinopyroxene + orthopyroxene) at 15 kbar and 1,050 °C. The partial melts change from granodiorite to tonalite with increasing melt proportions. Sr enrichment occurs in partial melts in equilibrium with 20 wt%, respectively. Major elements and trace element patterns of partial melts produced by 10–40 wt% melting of lower crust composition at 10–12.5 kbar and 800–900 °C and 15 kbar and 800 °C closely resemble adakite/TTG rocks. TiO2 contents of the 1,000–1,050 °C melts are higher than that of pristine adakite/TTG. In comparison with natural adakite/TTG, partial melts produced at 10–12.5 kbar and 1,000 °C and 15 kbar and 1,050 °C have elevated HREE, whereas partial melts at 13.5–15 kbar and 900–1,000 °C in equilibrium with >20 wt% garnet have depressed Yb and elevated La/Yb and Gd/Yb. It is suggested that the most appropriate P–T conditions for producing adakite/TTG from mafic lower crust are 800–950 °C and 10–12.5 kbar (corresponding to a depth of 30–40 km), whereas a depth of >45–50 km is unfavorable. Consequently, an overthickened crust and eclogite residue are not necessarily required for producing adakite/TTG from lower crust. The lower crust delamination model, which has been embraced for intra-continental adakite/TTG formation, should be reappraised.

Timescales of crustal melting in the Higher Himalayan Crystallines (Sikkim, Eastern Himalaya) inferred from trace element-constrained monazite and zircon chronology

Abstract: The petrology and timing of crustal melting has been investigated in the migmatites of the Higher Hima- layan Crystalline (HHC) exposed in Sikkim, India. The metapelites underwent pervasive partial melting through hydrous as well as dehydration melting reactions involving muscovite and biotite to produce a main assemblage of quartz, K-feldspar, plagioclase, biotite, garnet ± sillima- nite. Peak metamorphic conditions were 8-9 kbar and *800 C. Monazite and zircon crystals in several migmatites collected along a N-S transect show multiple growth domains. The domains were analyzed by micro- beam techniques for age (SHRIMP) and trace element composition (LA-ICP-MS) to relate ages to conditions of formation. Monazite preserves the best record of meta- morphism with domains that have different zoning pattern, composition and age. Zircon was generally less reactive than monazite, with metamorphic growth zones preserved in only a few samples. The growth of accessory minerals in the presence of melt was episodic in the interval between 31 and 17 Ma, but widespread and diachronous across samples. Systematic variations in the chemical composition of the dated mineral zones (HREE content and negative Eu anomaly) are related to the variation in garnet and K-feldspar abundances, respectively, and thus to meta- morphic reactions and P-T stages. In turn, this allows prograde versus decompressional and retrograde melt production to be timed. A hierarchy of timescales charac- terizes melting which occurred over a period of *15 Ma (31-17 Ma): a given block within this region traversed the field of melting in 5-7 Ma, whereas individual melting reactions lasted for time durations below, or approaching, the resolution of microbeam dating techniques (*0.6 Ma). An older *36 Ma high-grade event is recorded in an al- locthonous relict related to mafic lenses. We identify two sections of the HHC in Sikkim that traversed similar P-T conditions at different times, separated by a tectonic dis- continuity. The higher structural levels reached melting and peak conditions later (*26-23 Ma) than the lower structural levels (*31-27 Ma). Diachronicity across the HHC cannot be reconciled with channel flow models in their simplest form, as it requires two similar high-grade sections to move independently during collision.

The robustness of the Zr-in-rutile and Ti-in-zircon thermometers during high-temperature metamorphism (Ivrea-Verbano Zone, northern Italy)

Abstract: This study investigates the behaviour of the Zr-in-rutile and Ti-in-zircon thermometers in granulite facies metapelites from the Ivrea-Verbano Zone lower crustal section. U–Pb ages of zircon constrain the timing of regional amphibolite–granulite facies metamorphism to 316 ± 3 Ma and record zircon recrystallisation and resetting of U–Pb ages at 276 ± 4 Ma and 258 ± 3 Ma. Zr-in-rutile thermometry records peak contact metamorphic temperatures related to intrusion of mafic magmatic rocks and gives peak temperatures between 900–930 °C and 1,000–1,020 °C that are consistent with the geological settings of the samples. Ti-in-zircon temperatures of 700–800 °C and 810–870 °C record growth or re-equilibration of zircon after cooling from peak temperatures. Ti-in-quartz thermometry for one sample records both peak and retrograde temperatures. Some rutiles in all samples record resetting of Zr-in-rutile temperatures at ~750–800 °C. Electron microprobe profiles across individual rutiles demonstrate that Zr expulsion occurred by recrystallisation rather than by diffusive exchange. Exsolution of small needles of baddelyite or zircon from rutile is an important method of Zr redistribution, but results in no net Zr loss from the grain. The demonstration that Zr-in-rutile thermometry can robustly record peak temperatures that are not recorded by any other thermometer emphasises the relevance of this technique to investigating the evolution of high-grade metamorphic terranes, such as those that characterise the lower crust.

Volatile loss from melt inclusions in pyroclasts of differing sizes

Abstract: We have investigated the loss of H2O from olivine-hosted melt inclusions (MIs) by designing an experiment using tephra samples that cooled at different rates owing to their different sizes: ash, lapilli, and bomb samples that were deposited on the same day (10/17/74) of the sub-Plinian eruption of Volcan de Fuego in Guatemala. Ion microprobe, laser ablation-ICPMS, and electron probe analyses show that MIs from ash and lapilli record the highest H2O contents, up to 4.4 wt%. On the other hand, MIs from bombs indicate up to 30 % lower H2O contents (loss of ~1 wt% H2O) and 10 % post-entrapment crystallization of olivine. This evidence is consistent with the longer cooling time available for a bomb-sized clast, up to 10 min for a 3–4-cm radius bomb, assuming conductive cooling and the fastest H diffusivities measured in olivine (D~10−9 to 10−10 m2/s). On the other hand, several lines of evidence point to some water loss prior to eruption, during magma ascent and degassing in the conduit. Thus, results point to both slower post-eruptive cooling and slower magma ascent affecting MIs from bombs, leading to H2O loss over the timescale of minutes to hours. The important implication of this study is that a significant portion of the published data on H2O concentrations in olivine-hosted MIs may reflect unrecognized H2O loss via diffusion. This work highlights the importance of reporting clast and MI sizes in order to assess diffusive effects and the potential benefit of using water loss as a chronometer of magma ascent.

Crystallization of oxidized, moderately hydrous arc basalt at mid- to lower-crustal pressures: implications for andesite genesis

Abstract: This study focuses on the production of convergent margin calc-alkaline andesites by crystallization–differentiation of basaltic magmas in the lower to middle crust. Previous experimental studies show that dry, reduced, subalkaline basalts differentiate to tholeiitic (high Fe/Mg) daughter liquids, but the influences of H2O and oxidation on differentiation are less well established. Accordingly, we performed crystallization experiments at controlled oxidized fO2 (Re–ReO2 ≈ ΔNi–NiO + 2) on a relatively magnesian basalt (8.7 wt% MgO) typical of mafic magmas erupted in the Cascades near Mount Rainier, Washington. The basalt was synthesized with 2 wt% H2O and run at 900, 700, and 400 MPa and 1,200 to 950 °C. A broadly clinopyroxenitic crystallization interval dominates near the liquidus at 900 and 700 MPa, consisting of augite + olivine + orthopyroxene + Cr-spinel (in decreasing abundance). With decreasing temperature, plagioclase crystallizes, Fe–Ti-oxide replaces spinel, olivine dissolves, and finally amphibole appears, producing gabbroic and then amphibole gabbroic crystallization stages. Enhanced plagioclase stability at lower pressure narrows the clinopyroxenitic interval and brings the gabbroic interval toward the liquidus. Liquids at 900 MPa track along Miyashiro’s (Am J Sci 274(4):321–355, 1974) tholeiitic versus calc-alkaline boundary, whereas those at 700 and 400 MPa become calc-alkaline at silica contents ≥56 wt%. This difference is chiefly due to higher temperature appearance of magnetite (versus spinel) at lower pressures. Although the evolved liquids are similar in many respects to common calc-alkaline andesites, the 900 and 700 MPa liquids differ in having low CaO concentrations due to early and abundant crystallization of augite, with the result that those liquids become peraluminous (ASI: molar Al/(Na + K + 2Ca) > 1) at ≥61 wt% SiO2, similar to liquids reported in other studies of the high-pressure crystallization of hydrous basalts (Muntener and Ulmer in Geophys Res Lett 33(21):L21308, 2006). The lower-pressure liquids (400 MPa) have this same trait, but to a lesser extent due to more abundant near-liquidus plagioclase crystallization. A compilation of >6,500 analyses of igneous rocks from the Cascades and the Sierra Nevada batholith, representative of convergent margin (arc) magmas, shows that ASI increases continuously and linearly with SiO2 from basalts to rhyolites or granites and that arc magmas are not commonly peraluminous until SiO2 exceeds 69 wt%. These relations are consistent with plagioclase accompanying mafic silicates over nearly all the range of crystallization (or remelting). The scarcity of natural peraluminous andesites shows that progressive crystallization–differentiation of primitive basalts in the deep crust, producing early clinopyroxenitic cumulates and evolved liquids, does not dominate the creation of intermediate arc magmas or of the continental crust. Instead, mid- to upper-crustal differentiation and/or open-system processes are critical to the production of intermediate arc magmas. Primary among the open-system processes may be extraction of highly evolved (granitic, rhyolitic) liquids at advanced degrees of basalt solidification (or incipient partial melting of predecessor gabbroic intrusions) and mixing of such liquids into replenishing basalts. Furthermore, if the andesitic-composition continents derived from basaltic sources, the arc ASI–SiO2 relation shows that the mafic component returned to the mantle was gabbroic in composition, not pyroxenitic.

A new chlorite geothermometer for diagenetic to low-grade metamorphic conditions

Abstract: The evolution of chlorite composition with temperature (and pressure) serves as basis to a number of chlorite chemical thermometers, for which the oxidation state of iron has been recognised as a recurrent issue, especially at low temperature (T). A new chlorite geothermometer that does not require prior Fe3+ knowledge is formulated, calibrated on 161 analyses with well-constrained T data covering a wide range of geological contexts and tested here for low-T chlorites (T < 350 °C and pressures below 4 kbar). The new solid-solution model used involves six end-member components (the Mg and Fe end-members of ‘Al-free chlorite S’, sudoite and amesite) and so accounts for all low-T chlorite compositions; ideal mixing on site is assumed, with an ordered cationic distribution in tetrahedral and octahedral sites. Applied to chlorite analyses from three distinct low-T environments for which independent T data are available (Gulf Coast, Texas; Saint Martin, Lesser Antilles; Toyoha, Hokkaido), the new pure-Fe2+ thermometer performs at least as well as the recent models, which require an estimate of Fe3+ content. This relief from the ferric iron issue, combined with the simple formulation of the semi-empirical approach, makes the present thermometer a very practical tool, well suited for, for example, the handling of large analytical datasets—provided it is used in the calibration range (T < 350 °C, P < 4 kbar).

From mush to eruption in centuries: assembly of the super-sized Oruanui magma body

Abstract: The magmatic systems that give rise to voluminous crystal-poor rhyolite magma bodies can be considered to operate on two contrasting timescales: Those governed by longer-term processes by which a magma acquires its chemical and isotopic characteristics (e.g., fractional crystallisation and assimilation), and those operating at shorter timescales during the physical accumulation of the melt-dominant magma body that finally erupts. We explore the compositional and textural relationships between amphibole and orthopyroxene crystals from the 25.4 ka, 530 km3 (magma) Oruanui eruption products (Taupo volcano, New Zealand) to investigate how processes related to the physical assembly of the pre-eruptive magma body are represented in the crystal record. Over 90 % of orthopyroxenes from the volumetrically dominant high-SiO2 (>74 wt%) rhyolite pumices record textural evidence for a significant disequilibrium event (partial dissolution ± resorption of cores and interiors) prior to the growth of 40–500 μm thick rim zones. This dissolution/regrowth history of orthopyroxene is recorded in the chemistry of co-crystallising amphiboles as a prominent inflection in the concentrations of Mn and Zn, two elements notably enriched in orthopyroxene relative to amphibole. Textural and chemical features, linked with in situ thermobarometric estimates, indicate that a major decompression event preceded the formation of the melt-dominant body. The decompression event is inferred to represent the extraction of large volumes of melt plus crystals from the Oruanui crystal mush/source zone at pressures of 140–300 MPa (~6–12 km depth). Orthopyroxene underwent partial dissolution during ascent before reestablishing in the melt-dominant magma body at pressures of 90–140 MPa (~3.5–6 km). We model Fe–Mg diffusion across the core-rim boundaries along the crystallographic a or b-axes to constrain the timing of this decompression event, which marked establishment of the melt-dominant magma body. Maximum modelled ages indicate that this event did not begin until ~1,600 years before eruption, consistent with constraints from zircon model-age spectra. Once extraction began, it underwent runaway acceleration with a peak extraction age of ~230 years, followed by an apparent period of stasis of ~60 years prior to eruption. The rapidity of the extraction and accumulation processes implies the involvement of a dynamic driving force which, in the rifted continental arc setting of the Taupo Volcanic Zone, seems likely to be represented by magma-assisted extensional tectonic processes.

Petrological cannibalism: the chemical and textural consequences of incremental magma body growth

Abstract: The textures of minerals in volcanic and plutonic rocks testify to a complexity of processes in their formation that is at odds with simple geochemical models of igneous differentiation. Zoning in plagioclase feldspar is a case in point. Very slow diffusion of the major components in plagioclase means that textural evidence for complex magmatic evolution is preserved, almost without modification. Consequently, plagioclase affords considerable insight into the processes by which magmas accumulate in the crust prior to their eventual eruption or solidification. Here, we use the example of the 1980–1986 eruptions of Mount St. Helens to explore the causes of textural complexity in plagioclase and associated trapped melt inclusions. Textures of individual crystals are consistent with multiple heating and cooling events; changes in total pressure (P) or volatile pressure ( $$P_{{{\text{H}}_{ 2} {\text{O}}}}$$ ) are less easy to assess from textures alone. We show that by allying textural and chemical analyses of plagioclase and melt inclusions, including volatiles (H2O, CO2) and slow-diffusing trace elements (Sr, Ba), to published experimental studies of Mount St. Helens magmas, it is possible to disambiguate the roles of pressure and temperature to reconstruct magmatic evolutionary pathways through temperature–pressure–melt fraction (T– $$P_{{{\text{H}}_{ 2} {\text{O}}}}$$ –F) space. Our modeled crystals indicate that (1) crystallization starts at $$P_{{{\text{H}}_{ 2} {\text{O}}}}$$ > 300 MPa, consistent with prior estimates from melt inclusion volatile contents, (2) crystal cores grow at $$P_{{{\text{H}}_{ 2} {\text{O}}}}$$ = 200–280 MPa at F = 0.65–0.7, (3) crystals are transferred to $$P_{{{\text{H}}_{ 2} {\text{O}}}}$$ = 100–130 MPa (often accompanied by 10–20 °C of heating), where they grow albitic rims of varying thicknesses, and (4) the last stage of crystallization occurs after minor heating at $$P_{{{\text{H}}_{ 2} {\text{O}}}}$$ ~ 100 MPa to produce characteristic rim compositions of An50. We hypothesize that modeled $$P_{{{\text{H}}_{ 2} {\text{O}}}}$$ decreases in excess of ~50 MPa most likely represent upward transport through the magmatic system. Small variations in modeled $$P_{{{\text{H}}_{ 2} {\text{O}}}}$$ , in contrast, can be effected by fluxing the reservoir with CO2-rich vapors that are either released from deeper in the system or transported with the recharge magma. Temperature fluctuations of 20–40 °C, on the other hand, are an inevitable consequence of incremental, or pulsed, assembly of crustal magma bodies wherein each pulse interacts with ancestral, stored magmas. We venture that this “petrological cannibalism” accounts for much of the plagioclase zoning and textural complexity seen not only at Mount St. Helens but also at arc magmas generally. More broadly we suggest that the magma reservoir below Mount St. Helens is dominated by crystal mush and fed by frequent inputs of hotter, but compositionally similar, magma, coupled with episodes of magma ascent from one storage region to another. This view both accords with other independent constraints on the subvolcanic system at Mount St. Helens and supports an emerging view of many active magmatic systems as dominantly super-solidus, rather than subliquidus, bodies.

Clinopyroxene–liquid thermometers and barometers specific to alkaline differentiated magmas

Abstract: We present new thermometers and barometers based on clinopyroxene–liquid equilibria specific to alkaline differentiated magmas. The new models were calibrated through the regression analyses of experimental datasets obtained by merging phase equilibria experiments from the literature with new experiments performed by using trachytic and phonolitic starting compositions. The regression strategy was twofold: (1) we have tested previous thermometric and barometric equations and recalibrated these models using the new datasets; (2) we have calibrated a new thermometer and a new barometer including only regression parameters that closely describe the compositional variability of the datasets. The new models yield more precise estimates than previous thermometers and barometers when used to predict temperatures and pressures of alkaline differentiated magmas. We have tested the reliability of the new equations by using clinopyroxene–liquid pairs from trachytes and phonolites erupted during major explosive eruptions at the Phlegrean Fields and Mt. Vesuvius (central Italy). The test yielded crystallization conditions comparable to those determined by means of melt and fluid inclusion analyses and phase equilibria studies; this validates the use of the proposed models for precise estimates of crystallization temperatures and pressures in differentiated alkaline magmas. Because these magmas feed some of the most voluminous, explosive, and threatening volcanic eruptions in the world, a better understanding of the environmental conditions of their reservoirs is mandatory and this is now possible with the new models provided here.

Post-collisional, K-rich mafic magmatism in south Tibet: constraints on Indian slab-to-wedge transport processes and plateau uplift

Abstract: Post-collisional (23–8 Ma), potassium-rich (including ultrapotassic and potassic) mafic magmatic rocks occur within the north–south-trending Xuruco lake–Dangre Yongcuo lake (XDY) rift in the Lhasa terrane of the southern Tibetan Plateau, forming an approximately 130-km-long semi-continuous magmatic belt. They include both extrusive and intrusive facies. Major and trace element and Sr–Nd–Pb isotopic data are presented for all of the known exposures within the XDY rift. The potassium-rich, mafic igneous rocks are characterized by high MgO (5.9–10.8 wt.%), K2O (4.81–10.68 wt.%), Ba (1,782–5,618 ppm) and Th (81.3–327.4 ppm) contents, and relatively high SiO2 (52.76–58.32 wt.%) and Al2O3 (11.10–13.67 wt.%). Initial Sr isotopic compositions are extremely radiogenic (0.712600–0.736157), combined with low (206Pb/204Pb) i (18.28–18.96) and (143Nd/144Nd) i (0.511781–0.512046). Chondrite-normalized rare earth element patterns display relatively weak negative Eu anomalies. Primitive mantle-normalized incompatible trace element patterns exhibit strong enrichments in large ion lithophile elements relative to high-field-strength elements and display strongly negative Ta–Nb–Ti anomalies. The combined major and trace element and Sr–Nd–Pb isotopic characteristics of the K-rich igneous rocks suggest that the primitive magmas were produced by 1–10 % partial melting of an asthenospheric mantle source enriched by both fluids and partial melts derived from Indian passive continental margin sediments subducted into the shallow mantle as a consequence of the northward underthrusting of the Indian continental lithosphere beneath Tibet since the India–Asia collision at ~55 Ma. The best-fit model results indicate that a melt with trace element characteristics similar to those of the K-rich rocks could be generated by 8–10 % partial melting of a metasomatized mantle source in the south and 1–2 % melting in the north of the XDY rift. Trace element and Sr–Nd–Pb isotopic modeling indicate that the proportion of fluid derived from the subducted sediments, for which we use as a proxy the Higher Himalayan Crystalline Sequence (HHCS), in the mantle source region increases from north (rear-arc) to south (front-arc), ranging from 0 to 5 %, respectively. Correspondingly, the proportion of the melt derived from the subducted HHCS in the source increases from north (2 %) to south (15 %). The increasing proportion of the fluid and melt component in the mantle source from north to south, together with a southward decreasing trend in the age of the K-rich magmatism within the XDY rift, is inferred to reflect rollback of the subducted Indian lithospheric mantle slab during the period 25–8 Ma. Slab rollback may be linked to a decreasing convergence rate between India and Asia. As a consequence of slab rollback at 25 Ma beneath the Lhasa terrane, its geodynamic setting was transformed from a convergent (55–25 Ma) to an extensional (25–8 Ma) regime. The occurrence of K-rich magmatism during the period 25–8 Ma is a consequence of the decompression melting of an enriched mantle source, which may signal the onset of extension in the southern Tibetan Plateau and provide a petrological record of the extension process.

A method for estimating the activity of titania in magmatic liquids from the compositions of coexisting rhombohedral and cubic iron–titanium oxides

Abstract: A method is described for estimating the activity of titania (TiO2) in a magmatic liquid from the compositions of coexisting cubic oxide (spinel) and rhombohedral oxide (ilmenite). These estimates are derived from the thermodynamic models of Ghiorso and Evans (Am J Sci 308:957–1039, 2008; see also Sack and Ghiorso in Contrib Mineral Petrol 106:474–505, 1991a; Am Mineral 76:827-847, 1991b) and may be computed self consistently along with temperature and oxygen fugacity for an assumed pressure. The method is applied to a collection of 729 naturally occurring oxide pairs from rhyolites and dacites. For this suite of oxides, values of titania activity relative to rutile saturation range from 0.3 to 0.9. Genetically related groups of oxide pairs display activity–temperature trends with negative slopes at higher activities (0.6–0.9) or positive slopes at lower activities (0.3–0.7). Thermodynamic analysis supports the assumption of two-oxide, liquid equilibrium for the former group, but suggests that such an interpretation for oxide sequences with positive activity–temperature trends may be problematic. Application of the estimation method to oxide pairs from the Shiveluch Volcano and the Bishop Tuff reveals that the former are consistent with having equilibrated with known matrix glass compositions, whereas the latter pairs are inconsistent with equilibration with pre-eruptive liquids trapped in quartz inclusions.

On some fundamentals of igneous petrology

Abstract: The age-old process of crystal fractionation leading to the diversity of the igneous rocks and Earth itself is an exceedingly well-understood chemical process in magmatism and physical chemistry. But the broader physical aspects of this and related processes have proven elusive on many fronts, especially in its relation to the spatial variations in rock composition, texture, and macroscopic features like layering. Magmatic systems, be they volcanic, dikes, sills, or plutons, are generally analyzed with a problem at hand and an end result in mind. The processes invoked to solve these problems, which are most often purely chemical, are often unique to each problem with few if any general principles emerging that are central to understanding the wider perspective of magmatic processes and problems. An attempt is made at the outset to provide a list of inviolate Magmatic First Principles that are relevant to analyzing most magmatic problems. These involve: initial conditions; critical crystallinity; solidification fronts; transport and emplacement fluxes; phenocrysts, xenocrysts, primocrysts; crystal size; layering and crystal sorting; thermal convection; magmatic processes are physical. Along with these principles, two reference magmatic systems are suggested where the initial conditions and outcome are unequivocal: the Sudbury impact melt sheet and the Hawaiian lava lakes. Sudbury formed in ~5 min by superheated magma crystallized to a near uniform sequence, while the tiny lava lakes, formed of crystal-laden slurries, form a highly differentiated layered sequence. The major difference is in the initial conditions of formation, especially the nature of the input materials. The challenge is to construct and analyze magmatic systems (i.e., magma chambers, sills, dikes, and lavas) using these reference end members and the suggested principles. The Hawaiian 500,000 year volcanic record exhibits what can be expected as input materials, namely a highly varied output of magma of an overall composition reflecting the abundance of entrained olivine primocrysts. The provenance of these crystals is varied, and within any single sample, the population may be highly heterogeneous in composition from crystal to crystal, yet the overall pattern of chemical fractionation is exceedingly regular and well defined. If similar inputs go to form large intrusions, these systems will undoubtedly be dominated by crystal-rich slurries, which provide a vast set of physical processes promoting exotic layering and, at the same time, given the effects of annealing and continued crystal growth, a final chemical record adhering to all the time-honored effects of crystal fractionation. The long assumed initial condition of instantaneously emplaced crystal-free magmas cannot reasonably produce the observed rock records.

Fe–Mg interdiffusion rates in clinopyroxene: experimental data and implications for Fe–Mg exchange geothermometers

Abstract: Chemical interdiffusion of Fe-Mg along the c-axis [001] in natural diopside crystals (XDi = 0.93) was experimentally studied at ambient pressure, at temperatures ranging from 800 to 1,200 °C and oxygen fugacities from 10-11 to 10-17 bar. Diffusion couples were prepared by ablating an olivine (XFo = 0.3) target to deposit a thin film (20-100 nm) onto a polished surface of a natural, oriented diopside crystal using the pulsed laser deposition technique. After diffusion anneals, compositional depth profiles at the near surface region (~400 nm) were measured using Rutherford backscattering spectroscopy. In the experimental temperature and compositional range, no strong dependence of DFe-Mg on composition of clinopyroxene (Fe/Mg ratio between Di93-Di65) or oxygen fugacity could be detected within the resolution of the study. The lack of fO2-dependence may be related to the relatively high Al content of the crystals used in this study. Diffusion coefficients, DFe-Mg, can be described by a single Arrhenius relation with (Formula presented). DFe-Mg in clinopyroxene appears to be faster than diffusion involving Ca-species (e.g., DCa-Mg) while it is slower than DFe-Mg in other common mafic minerals (spinel, olivine, garnet, and orthopyroxene). As a consequence, diffusion in clinopyroxene may be the rate-limiting process for the freezing of many geothermometers, and compositional zoning in clinopyroxene may preserve records of a higher (compared to that preserved in other coexisting mafic minerals) temperature segment of the thermal history of a rock. In the absence of pervasive recrystallization, clinopyroxene grains will retain compositions from peak temperatures at their cores in most geological and planetary settings where peak temperatures did not exceed ~1,100 °C (e.g., resetting may be expected in slowly cooled mantle rocks, many plutonic mafic rocks, or ultra-high temperature metamorphic rocks). © 2013 Springer-Verlag Berlin Heidelberg.

40Ar–39Ar dating, whole-rock and Sr–Nd–Pb isotope geochemistry of post-collisional Eocene volcanic rocks in the southern part of the Eastern Pontides (NE Turkey): implications for magma evolution in extension-induced origin

Abstract: The Eocene volcano-sedimentary units in the southern part of the Eastern Pontides (NE Turkey) are confined within a narrow zone of east–west trending, semi-isolated basins in Bayburt, Gumushane, Siran and Alucra areas. The volcanic rocks in these areas are mainly basalt and andesite through dacite, with a dominant calc-alkaline to rare tholeiitic tendency. 40Ar–39Ar dating of these volcanic rocks places them between 37.7 ± 0.2 and 44.5 ± 0.2 Ma (Middle Eocene). Differences in the major and trace element variations can be explained by the fractionation of clinopyroxene ± magnetite in basaltic rocks and that of hornblende + plagioclase ± magnetite ± apatite in andesitic rocks. Primitive mantle-normalized multi-element variations exhibit enrichment of large-ion lithophile elements and to a lesser extent, of light rare earth elements, as well as depletion of high field strength elements, thus revealing that volcanic rocks evolved from a parental magma derived from an enriched mantle source. Chondrite-normalized rare earth element patterns of the aforementioned volcanic rocks resemble each other and are spoon-shaped with low-to-medium enrichment (LaN/LuN = 2–14), indicating similar spinel lherzolitic mantle source(s). Sr, Nd and Pb isotopic systematics imply that the volcanic rocks are derived from a subduction-modified subcontinental lithospheric mantle. Furthermore, post-collisional thickened continental crust, lithospheric delamination and a subduction-imposed thermal structure are very important in generating Tertiary magma(s). The predominantly calc-alkaline nature of Eocene volcanic rocks is associated with increasing geodynamic regime-extension, whereas tholeiitic volcanism results from local variations in the stress regime of the ongoing extension and the thermal structure, as well as the thickness of the crust and the mantle-crust source regions. Based on volcanic variety and distribution, as well as on petrological data, Tertiary magmatic activity in Eastern Pontides is closely related to post-collisional thinning of the young lithosphere, which, in turn, is caused by extension and lithospheric delamination after collisional events between the Tauride–Anatolide Platform and the Eurasian Plate.

Constraints from zircon U–Pb ages, O and Hf isotopic compositions on the origin of Neoproterozoic peraluminous granitoids from the Jiangnan Fold Belt, South China

Abstract: Zircon textures and micro-chemical compositions precisely record the origin and petrogenesis of granitoids, which are crucial for evaluating crustal growth and reworking, thermal and geodynamic evolution. Zircons in peraluminous granitoids from the three largest 820 Ma complexes (Guibei, Yueyang and Jiuling) in the Jiangnan Fold Belt in South China are used to constrain their sources and petrogenetic processes. Zircons in the Guibei granitoids have complex internal structures. Nearly all magmatic and inherited zircons have similar eHf (−6.8 to +5.6) and δ18O values (8.8–11.6 ‰) and dominantly lie between eHf evolution vectors for a crust created between 1.7 and 2.1 Ga, suggesting that the Guibei granitoids were produced by partial melting of recycled heterogeneous supracrustal material. However, the Yueyang granitoids contain zircons with high eHf (−0.5 to +9.7) and relatively low δ18O values (5.9–8.4 ‰) and two-stage model ages of 1.1–1.8 Ga, and thus may have been formed by melting of mafic rocks from the lower crust. The Jiuling granitoids and their enclaves contain more complex zircons with more variable eHf (−7.2 to +9.7) and δ18O values (7.0–10.6 ‰), and lie along the mixing trend between the above-proposed infracrustal and supracrustal granitoids. Therefore, the Neoproterozoic peraluminous granitoids in the Jiangnan Fold Belt were produced by melting and mixing of continental crust. Compared with extremely low (≤4 ‰) and negative δ18O values of Neoproterozoic igneous zircons formed in its northern active continental margin, the high δ18O peraluminous granitoids in the southeastern Yangtze Block are considered to have been formed by melting of hydrothermally unaltered continental crust triggered by asthenosphere upwelling in the Nanhua back-arc basin.

The partitioning of trace elements between clinopyroxene and trachybasaltic melt during rapid cooling and crystal growth

Abstract: We present the variation in trace element partition coefficients measured at the interface between rapidly cooled clinopyroxene crystals and co-existing melts. Results indicate that, as the cooling rate is increased, clinopyroxene crystals are progressively depleted in Si, Ca and Mg counterbalanced by enrichments in Al (mainly tetrahedral Aliv), Na and Ti. Partition coefficients (Ds) for rare earth elements (REE), high field strength elements (HFSE) and transition elements (TE) increase with increasing cooling rate, in response to clinopyroxene compositional variations. The entry of REE into the M2 site is facilitated by a coupled substitution where either Na substitutes for Ca on the M2 site or Aliv substitutes for Si in the tetrahedral site. The latter substitution reflects an increased ease of locally balancing the excess charge at M2 as the number of surrounding Aliv atoms increases. Due to the lower concentration of Ca in rapidly cooled clinopyroxenes, divalent large ion lithophile elements (LILE) on M2 decrease at the expense of monovalent cations. Conversely, higher concentrations of HFSE and TE on the M1 site are facilitated as the average charge on this site increases with the replacement of divalent-charged cations by Alvi. Although crystallization kinetics modify clinopyroxene composition, deviations from equilibrium partitioning are insufficient to change the tendency of a trace element to be compatible or incompatible. Consequently, there are regular relationships between ionic radius, valence of the trace element and D. At both equilibrium and cooling rate conditions, Ds for isovalent cations define parabola-like curves when plotted against ionic radius, consistent with the lattice strain model, demonstrating that the partitioning of trace elements is driven by charge balance mechanisms; cation substitution reactions can be treated in terms of the energetics of the various charge-imbalanced configurations.

The origin of coarse garnet peridotites in cratonic lithosphere: new data on xenoliths from the Udachnaya kimberlite, central Siberia

Abstract: We report new textural and chemical data for 10 garnet peridotite xenoliths from the Udachnaya kimberlite and examine them together with recent data on another 21 xenoliths from the 80–220 km depth range. The samples are very fresh (LOI near zero), modally homogeneous and large (>100 g). Some coarse-grained peridotites show incipient stages of deformation with <10 % neoblasts at grain boundaries of coarse olivine. Such microstructures can only be recognized in very fresh rocks, because fine-grained interstitial olivine is strongly affected by alteration, and may have been overlooked in previous studies of altered peridotite xenoliths in the Siberian and other cratons. Some of the garnet peridotites are similar in composition to low-opx Udachnaya spinel harzburgites (previously interpreted as pristine melt extraction residues), but the majority show post-melting enrichments in Fe and Ti. The least metasomatized coarse peridotites were formed by 30–38 % of polybaric fractional melting between 7 and 4 GPa and ≤1–3 GPa. Our data together with experimental results suggest that garnet in these rocks, as well as in some other cratonic peridotites elsewhere, may be a residual mineral, which has survived partial melting together with olivine and opx. Many coarse and all deformed garnet peridotites from Udachnaya underwent modal metasomatism through interaction of the melting residues with Fe-, Al-, Si-, Ti-, REE-rich melts, which precipitated cpx, less commonly additional garnet. The xenoliths define a complex geotherm probably affected by thermal perturbations shortly before the intrusion of the host kimberlite magmas. The deformation in the lower lithosphere may be linked to metasomatism.

Monazite and xenotime U–Th–Pb geochronology by ion microprobe: dating highly fractionated granites at Xihuashan tungsten mine, SE China

Abstract: Zircon, monazite, and xenotime have proven to be valuable chronometers for various geological processes due to their commonly high-U–Th and low common Pb contents. However, zircons that have crystallized in highly fractionated granites often have such high-U contents that radiation damage can lead to scattered U–Pb ages when measured with secondary ion mass spectrometry (SIMS). In this study, monazite and xenotime were separated from a number of highly fractionated granites at the Xihuashan tungsten mine, Southeast China, for alternative dating methods by SIMS. For monazite analysis, obvious excess 204Pb signal (mainly from interference of 232Th144Nd16O2 ++) was observed in high-Th (>2 wt%) monazite, which hinders 204Pb-based common Pb corrections. A 207Pb-based common Pb correction method was used instead. By employing power law relationships between Pb+/U+ versus UO2 +/U+, Pb+/Th+ versus ThO2 +/Th+ and suitable exponentials, monazites with ThO2 contents in the range of ~3–19 % do not exhibit this matrix effect. Independent SIMS U–Pb ages and Th–Pb ages of three phases of Xihuashan granite samples were consistent with each other and yielded dates of 158.7 ± 0.7, 158.0 ± 0.7, and 156.9 ± 0.7 Ma, respectively. Xenotime does show marked matrix effects due to variations of U, Th, and Y [or total rare earth element (REE), referred as ΣREE hereafter] contents. Suitable correction factors require end-member standards with extremely high or low U, Th, and Y (or ΣREE) contents. No excess 204Pb was observed, indicating that the 204Pb-based common Pb correction method is feasible. Independent 207Pb/206Pb ages can be obtained, although multi-collector mode is necessary to improve precision. The main difficulties with dating xenotime are when high-Th (U) mineral inclusions are ablated. We can identify when this occurs, however, by comparing the measured UO2 +/U+ and ThO2 +/Th+ with those in xenotime standards. Three xenotime samples from the first phase of Xihuashan granite yielded a weighted mean 207Pb/206Pb date of 159.5 ± 4.4 Ma (MSWD = 1.0) and a 206Pb/238U date of 159.4 ± 0.9 Ma (MSWD = 1.6), which are consistent with monazite U–Pb and Th–Pb ages from the same granites. This study demonstrates that monazite and xenotime are better SIMS chronometers for highly fractionated granites than zircon, which can yield doubtful ages due to high-U contents.

Quantification of the ferric/ferrous iron ratio in silicates by scanning transmission X-ray microscopy at the Fe L2,3 edges

Abstract: Estimation of Fe3+/ΣFe ratios in materials at the submicrometre scale has been a long-standing challenge in the Earth and environmental sciences because of the usefulness of this ratio in estimating redox conditions as well as for geothermometry. To date, few quantitative methods with submicrometric resolution have been developed for this purpose, and most of them have used electron energy-loss spectroscopy carried out in the ultra-high vacuum environment of a transmission electron microscope (TEM). Scanning transmission X-ray microscopy (STXM) is a relatively new technique complementary to TEM and is increasingly being used in the Earth sciences. Here, we detail an analytical procedure to quantify the Fe3+/ΣFe ratio in silicates using Fe L2,3-edge X-ray absorption near edge structure (XANES) spectra obtained by STXM, and we discuss its advantages and limitations. Two different methods for retrieving Fe3+/ΣFe ratios from XANES spectra are calibrated using reference samples with known Fe3+ content by independent approaches. The first method uses the intensity ratio of the two major peaks at the L3-edge. This method allows mapping of Fe3+/ΣFe ratios at a spatial scale better than 50 nm by the acquisition of 5 images only. The second method employs a 2-eV-wide integration window centred on the L2 maximum for Fe3+, which is compared to the total integral intensity of the Fe L2-edge. These two approaches are applied to metapelites from the Glarus massif (Switzerland), containing micrometre-sized chlorite and illite grains and prepared as ultrathin foils by focused ion beam milling. Nanometre-scale mapping of iron redox in these samples is presented and shows evidence of compositional zonation. The existence of such zonation has crucial implications for geothermometry and illustrates the importance of being able to measure Fe3+/ΣFe ratios at the submicrometre scale in geological samples.

The Bishop Tuff giant magma body: an alternative to the Standard Model

Abstract: The Bishop Tuff, one of the most extensively studied high-silica rhyolite bodies in the world, is usually considered as the archetypical example of a deposit formed from a magma body characterized by thermal and compositional vertical stratification—what we call the Standard Model for the Bishop magma body. We present here new geothermometry and geobarometry results derived using a large database of previously published quartz-hosted glass inclusion compositions. Assuming equilibrium between melt and an assemblage composed of quartz, ±plagioclase, ±sanidine, +zircon, ±fluid, we use Zr contents in glass inclusions to derive quartz crystallization temperatures, and we use (1) silica contents in glass, (2) projection of glass compositions onto the haplogranitic (quartz-albite-orthoclase) ternary, and (3) phase equilibria calculations using rhyolite-MELTS, to constrain crystallization pressures. We find crystallization temperatures of ~740–750 °C for all inclusions from both early- and late-erupted pumice. Crystallization pressures for both early- and late-erupted inclusions are also very similar to each other, with averages of ~175–200 MPa. We find no evidence of late-erupted inclusions having been entrapped at higher temperatures or pressures than early-erupted inclusions, as would be expected by the Standard Model. We argue that the thermal gradient inferred from Fe–Ti oxides—the backbone of the Standard Model—does not reflect equilibrium pre-eruptive conditions; we also note that H2O–CO2 systematics of glass inclusions yields overlapping pressure ranges for early- and late-erupted inclusions, similar to the results presented here; and we show that glass inclusion and phenocryst compositions show bimodal distributions, suggestive of compositional separation between early- and late-erupted populations. These findings are inconsistent with the Standard Model. The similarity in crystallization conditions and the compositional separation between early- and late-erupted magmas suggest that two laterally juxtaposed independent magma reservoirs existed in the same region at the same time and co-erupted to form the Long Valley Caldera and the Bishop Tuff. This hypothesis would explain the lack of mixing between early- and late-erupted crystal populations in pumice clasts; it could also explain the inferred eruption pattern—which resulted in early-erupted magmas being deposited only to the south of the caldera—if the early-erupted magma body resided to the south and the late-erupted magma body was located to the north. Our alternative model is consistent with the patchy distribution of thermal anomalies and the inference of co-eruption of distinct magma types in active volcanic areas such as the central Taupo Volcanic Zone.

Garnet and spinel in fertile and depleted mantle: insights from thermodynamic modelling

Abstract: We performed thermodynamic calculations based on model and natural peridotitic compositions at pressure and temperature conditions relevant to the Earth's upper mantle, using well-established free energy minimi- zation techniques. The model is consistent with the avail- able experimental data in Cr-bearing peridotitic systems and can therefore be used to predict phase relations and mineral compositions in a wide range of realistic mantle compositions. The generated phase diagrams for six dif- ferent bulk compositions, representative of fertile, depleted and ultra-depleted peridotitic mantle, shown that the gar- net ? spinel stability field is always broad at low temper- atures and progressively narrows with increasing temperatures. In lithospheric sections with hot geotherms (ca. 60 mW/m 2 ), garnet coexists with spinel across an interval of 10-15 km, at ca. 50-70 km depths. In colder, cratonic, lithospheric sections (e.g. along a 40 mW/m 2 geotherm), the width of the garnet-spinel transition strongly depends on bulk composition: In fertile mantle, spinel can coexist with garnet to about 120 km depth, while in an ultra-depleted harzburgitic mantle, it can be stable to over 180 km depth. The formation of chromian spinel inclusions in diamonds is restricted to pressures between 4.0 and 6.0 GPa. The modes of spinel decrease rapidly to less than 1 vol % when it coexists with garnet; hence, spinel grains can be easily overlooked during the petrographical character- ization of small mantle xenoliths. The very Cr-rich nature of many spinels from xenoliths and diamonds from cratonic settings may be simply a consequence of their low modes in high-pressure assemblages; thus, their composition does not necessarily imply an extremely refractory composition of the source rock. The model also shows that large Ca and Cr variations in lherzolitic garnets in equilibrium with spinel can be explained by variations of pressure and temperature along a continental geotherm and do not necessarily imply variations of bulk composition. The slope of the Cr# (i.e. Cr/(Cr ? Al)mol) isopleths in garnet in equilibrium with spinel changes significantly at high temperatures, posing serious limitations to the applicability of empirical geo- barometric methods calibrated on cratonic mantle xenoliths in hotter, off-craton, lithospheric mantle sections.

Sedimentary recycling in arc magmas: geochemical and U–Pb–Hf–O constraints on the Mesoproterozoic Suldal Arc, SW Norway

Abstract: The Hardangervidda-Rogaland Block within southwest Norway is host to ~1.52 to 1.48 Ga continental building and variable reworking during the ~1.1 to 0.9 Ga Sveconorwegian orogeny. Due to the lack of geochronological and geochemical data, the timing and tectonic setting of early Mesoproterozoic magmatism has long been ambiguous. This paper presents zircon U–Pb–Hf–O isotope data combined with whole-rock geochemistry to address the age and petrogenesis of basement units within the Suldal region, located in the centre of the Hardangervidda-Rogaland Block. The basement comprises variably deformed grey gneisses and granitoids that petrologically and geochemically resemble mature volcanic arc lithologies. U–Pb ages confirm that magmatism occurred from ~1,521 to 1,485 Ma, and conspicuously lack any xenocrystic inheritance of distinctly older crust. Hafnium isotope data range from eHf(initial) +1 to +11, suggesting a rather juvenile magmatic source, but with possible involvement of late Palaeoproterozoic crust. Oxygen isotope data range from mantle-like (δ18O ~5 ‰) to elevated (~10 ‰) suggesting involvement of low-temperature altered material (e.g., supracrustal rocks) in the magma source. The Hf–O isotope array is compatible with mixing between mantle-derived material with young low-temperature altered material (oceanic crust/sediments) and older low-temperature altered material (continent-derived sediments). This, combined with a lack of xenoliths and xenocrysts, exposed older crust, AFC trends and S-type geochemistry, all point to mixing within a deep-crustal magma-generation zone. A proposed model comprises accretion of altered oceanic crust and the overlying sediments to a pre-existing continental margin, underthrusting to the magma-generation zone and remobilisation during arc magmatism. The geodynamic setting for this arc magmatism is comparable with that seen in the Phanerozoic (e.g., the Sierra Nevada and Coast Range batholiths), with compositions in the Suldal Sector reaching those of average upper continental crust. As within these younger examples, factors that drive magmatism towards the composition of the average continental crust include the addition of sedimentary material to magma source regions, and delamination of cumulate material. Underthrusting of sedimentary materials and their subsequent involvement in arc magmatism is perhaps a more widespread mechanism involved in continental growth than is currently recognised. Finally, the Suldal Arc magmatism represents a significant juvenile crustal addition to SW Fennoscandia.

Geochronology and geochemistry of Cenozoic basalts from eastern Guangdong, SE China: constraints on the lithosphere evolution beneath the northern margin of the South China Sea

Abstract: The 40Ar–39Ar dating reveals three episodes of basaltic volcanism in eastern Guangdong of SE China since the late Eocene (i.e., 35.5, ~20 and 6.6 Ma). The Miocene alkali olivine basalts (~20 and 6.6 Ma) have OIB-like trace element characteristics, which is coupled with low (87Sr/86Sr)i, high eNd(t), and high eHf(t). In contrast, the late Eocene basalts (35.5 Ma) have overall characteristics of “Island Arc” basalts with strong negative Ta–Nb–Ti anomalies in the primitive mantle-normalized multi-element diagram with high (87Sr/86Sr)i, negative eNd(t), and relatively low eHf(t). All basalts have unexpectedly high 207Pb/204Pb and 208Pb/204Pb, delineating a DUPAL signature in the sources. The late Eocene Arc-like basalts may reflect contributions of relict ancient metasomatized mantle lithosphere that melted as the result of extension-induced asthenospheric upwelling and heating, whereas the Miocene OIB-like basalts may represent partial melting of the asthenospheric mantle beneath the thickened lithosphere. We propose that the Cenozoic basaltic volcanism in eastern Guangdong records an overall lithospheric thickening process beneath SE China, that is, a continental rift system from its maximum extension in the late Eocene to its waning in the Miocene. This interpretation is consistent with the evolution of the South China Sea, whose origin is most consistent with the development of a passive continental margin. The seafloor spreading of the South China Sea during ~ 32–16 Ma may not result from the effect of the “Hainan” mantle plume, but rather played a positive role in allowing the mantle plume to express on the surface.

Disturbance versus preservation of U–Th–Pb ages in monazite during fluid–rock interaction: textural, chemical and isotopic in situ study in microgranites (Velay Dome, France)

Abstract: Monazite is extensively used to date crustal processes and is usually considered to be resistant to diffusive Pb loss. Nevertheless, fluid-assisted recrystallisation is known to be capable of resetting the monazite chronometer. This study focuses on chemical and isotopic disturbances in monazite grains from two microgranite intrusions in the French Central Massif (Charron and Montasset). Petrologic data and oxygen isotopes suggest that both intrusions have interacted with alkali-bearing hydrothermal-magmatic fluids. In the Charron intrusion, regardless of their textural location, monazite grains are sub-euhedral and cover a large domain of compositions. U–Pb chronometers yield a lower intercept age of 297 ± 4 Ma. An inherited component at 320 Ma is responsible for the scattering of the U–Th–Pb ages. The Montasset intrusion was later affected by an additional F-rich crustal fluid with crystallisation of Ca-REE-fluorocarbonates, fluorite, calcite and chloritisation. Pristine monazite is chemically homogeneous and displays 208Pb/232Th and 206Pb/238U concordant ages at 307 ± 2 Ma. By contrast, groundmass monazite shows dissolution-recrystallisation features associated with apatite and thorite precipitation (Th-silicate) and strong chemical reequilibration. 208Pb/232Th ages are disturbed and range between 270 and 690 Ma showing that the Th/Pb ratio is highly fractionated during the interaction with fluids. Apparent U–Pb ages are older due to common Pb incorporation yielding a lower intercept age at 312 ± 10 Ma, the age of the pristine monazite. These results show that F-rich fluids are responsible for Th mobility and incorporation of excess Pb, which thus strongly disturbed the U–Th–Pb chronometers in the monazite.

Generation of CO2-rich melts during basalt magma ascent and degassing

Abstract: To test mechanisms of basaltic ma gma degassing, continuous decompressions of volatile-bearing (2.7-3.8 wt% H2O, 600-1300 ppm CO2) Stromboli melts were performed from 250-200 to 50-25 MPa at 1180-1140°C. Ascent rates were varied from 0.25 to ~ 1.5 m/s. Glasses after decompression show a wide range of textures, from totally bubble-free to bubble-rich, the latter with bubble number densities from 104 to 106/cm3, similar to Stromboli pumices. Vesicularities range from 0 to ~ 20 vol%. Final melt H2O concentrations are homogeneous and always close to solubilities. In contrast, the rate of vesiculation controls the final melt CO2 concentration. High vesicularity charges have glass CO2 concentrations that follow theoretical equilibrium degassing paths whereas glasses from low vesicularity charges show marked deviations from equilibrium, with CO2 concentrations up to one order of magnitude higher than solubilities. FTIR profiles and maps reveal glass CO2 concentration gradients near the gas-melt interface. Our results stress the importance of bubble nucleation and growth, and of volatile diffusivities, for basaltic melt degassing. Two characteristic distances, the gas interface distance (distance either between bubbles or to gas-melt interfaces) and the volatile diffusion distance control the degassing process. Melts containing numerous and large bubbles have gas interface distances shorter than volatile diffusion distances, and degassing proceeds by equilibrium partitioning of CO2 and H2O between melt and gas bubbles. For melts where either bubble nucleation is inhibited or bubble growth is limited, gas interface distances are longer than volatile diffusion distances. Degassing proceeds by diffusive volatile transfer at the gas-melt interface and is kinetically limited by the diffusivities of volatiles in the melt. Our experiments show that CO2-oversaturated melts can be generated as a result of magma decompression. They provide a new explanation for the occurrence of CO2-rich natural basaltic glasses and open new perspectives for understanding explosive basaltic volcanism.

The pre-eruptive magma plumbing system of the 2007–2008 dome-forming eruption of Kelut volcano, East Java, Indonesia

Abstract: Kelut volcano, East Java, is an active volcanic complex hosting a summit crater lake that has been the source of some of Indonesia’s most destructive lahars. In November 2007, an effusive eruption lasting approximately 7 months led to the formation of a 260-m-high and 400-m-wide lava dome that displaced most of the crater lake. The 2007–2008 Kelut dome comprises crystal-rich basaltic andesite with a texturally complex crystal cargo of strongly zoned and in part resorbed plagioclase (An47–94), orthopyroxene (En64–72, Fs24–32, Wo2–4), clinopyroxene (En40–48, Fs14–19, Wo34–46), Ti-magnetite (Usp16–34) and trace amounts of apatite, as well as ubiquitous glomerocrysts of varying magmatic mineral assemblages. In addition, the notable occurrence of magmatic and crustal xenoliths (meta-basalts, amphibole-bearing cumulates, and skarn-type calc-silicates and meta-volcaniclastic rocks) is a distinct feature of the dome. New petrographical, whole rock major and trace element data, mineral chemistry as well as oxygen isotope data for both whole rocks and minerals indicate a complex regime of magma-mixing, decompression-driven resorption, degassing and crystallisation and crustal assimilation within the Kelut plumbing system prior to extrusion of the dome. Detailed investigation of plagioclase textures alongside crystal size distribution analyses provide evidence for magma mixing as a major pre-eruptive process that blends multiple crystal cargoes together. Distinct magma storage zones are postulated, with a deeper zone at lower crustal levels or near the crust-mantle boundary (>15 km depth), a second zone at mid-crustal levels (~10 km depth) and several magma storage zones distributed throughout the uppermost crust (<10 km depth). Plagioclase-melt and amphibole hygrometry indicate magmatic H2O contents ranging from ~8.1 to 8.6 wt.% in the lower crustal system to ~1.5 to 3.3 wt.% in the mid to upper crust. Pyroxene and plagioclase δ18O values range from 5.4 to 6.7 ‰, and 6.5 to 7.6 ‰, respectively. A single whole rock analysis of the 2007–2008 dome lava gave a δ18O value of 7.6 ‰, whereas meta-basaltic and calc-silicate xenoliths are characterised by δ18O values of 6.2 and 10.3 ‰, respectively. Magmatic δ18O values calculated from individual pyroxene and plagioclase analyses range from 5.7 to 7.0 ‰, and 6.2 to 7.4 ‰, respectively. This range in O-isotopic compositions is explained by crystallisation of pyroxenes in the lower to mid-crust, where crustal contamination is either absent or masked by assimilation of material having similar δ18O values to the ascending melts. This population is mixed with isotopically distinct plagioclase and pyroxenes that crystallised from a more contaminated magma in the upper crustal system. Binary bulk mixing models suggest that shallow-level, recycled volcaniclastic sedimentary rocks together with calc-silicates and/or limestones are the most likely contaminants of the 2007–2008 Kelut magma, with the volcaniclastic sediments being dominant.

On the iron isotope heterogeneity of lithospheric mantle xenoliths: implications for mantle metasomatism, the origin of basalts and the iron isotope composition of the Earth

Abstract: With the aim to better understand the cause of the iron isotope heterogeneity of mantle-derived bulk peridotites, we compared the petrological, geochemical and iron isotope composition of four xenolith suites from different geodynamic settings; sub-arc mantle (Patagonia); subcontinental lithospheric mantle (Cameroon), oceanic mantle (Kerguelen) and cratonic mantle (South Africa). Although correlations were not easy to obtain and remain scattered because these rocks record successive geological events, those found between δ57Fe, Mg#, some major and trace element contents of rocks and minerals highlight the processes responsible for the Fe isotope heterogeneity. While partial melting processes only account for moderate Fe isotope variations in the mantle ( 0.9 ‰). The kinetic nature of rapid metasomatic exchanges between low viscosity melts/fluids and their wall-rocks peridotite in the mantle is the likely explanation for this large range. There are a variety of responses of Fe isotope signatures depending on the nature of the metasomatic processes, allowing for a more detailed study of metasomatism in the mantle with Fe isotopes. The current database on the iron isotope composition of peridotite xenoliths and mafic eruptive rocks highlights that most basalts have their main source deeper than the lithospheric mantle. Finally, it is concluded that due to a complex geological history, Fe isotope compositions of mantle xenoliths are too scattered to define a mean isotopic composition with enough accuracy to assess whether the bulk silicate Earth has a mean δ57Fe that is chondritic, or if it is ~0.1 ‰ above chondrites as initially proposed.

Evidence for distinct stages of magma history recorded by the compositions of accessory apatite and zircon

Abstract: Accessory minerals contain a robust and accessible record of magma evolution. However, they may reflect relatively late-stage conditions in the history of the host magmas. In the normally zoned Criffell granitic pluton (Scotland), whole-rock (WR) compositions reflect open system assimilation and fractional crystallisation at depths of >11 km, whereas amphibole barometry and the absence of inherited zircon suggest that the observed mineral assemblages crystallised following emplacement of magmas with little or no crystal cargo at depths of 4–6 km. The crystallisation history is documented by large trace-element variations amongst apatite crystals from within individual samples: decreasing LREE and Th concentrations in apatite crystals from metaluminous samples reflect broadly synchronous crystallisation of allanite, whereas lower LREE and Th, and more negative Nd anomalies in apatites from peraluminous samples reflect the effects of monazite crystallisation. WR evolution is likely to have occurred within a deep crustal hot zone where H2O-rich (~6 wt%), low-viscosity magmas segregated and ascended adiabatically in a super-liquidus state, leading to resorption of most entrained crystals. Stalling, emplacement and crystallisation resulted from intersection with the H2O-saturated liquidus at ~4 km. H2O contents are as important as temperature in the development of super-liquidus magmas during ascent, blurring distinctions between apparently ‘hot’ and ‘cold’ granites. The trace-element contents of most accessory minerals are controlled by competitive crystallisation of other accessory minerals in small melt batches, consistent with the incremental assembly of large granitic plutons.

Crystallization kinetics of alkali feldspars in cooling and decompression-induced crystallization experiments in trachytic melt

Abstract: Cooling and decompression experiments have been carried out on trachytic melts in order to investigate crystallization kinetics of alkali feldspar, the effect of the degree of undercooling (ΔT = T liquidus − T experimental) and time on nucleation and crystal growth process. This experimental work gives us new data about crystallization kinetics of trachytic melts, and it that will be useful to better understand the natural system of Campi Flegrei volcanoes. Experiments have been conducted using cold seal pressure vessel apparatus, at pressure between 30 and 200 MPa, temperature between 750 and 855 °C, time between 7,200 and 57,600 s and redox condition close to the NNO +0.8 buffer. These conditions are ideal to reproducing pre- and syn-eruptive conditions of the Campi Flegrei volcanoes, where the “conditions” pertain to the complete range of pressures, temperatures and time at which the experiments were performed. Alkali feldspar is the main phase present in this trachyte, and its abundance can strongly vary with small changes in pressure, temperature and water content in the melt, implying appreciable variations in the textures and in the crystallization kinetics. The obtained results show that crystallization kinetics are strictly related to ΔT, time, final pressure, superheating (−ΔT) and water content in the melt. ΔT is the driving force of the crystallization, and it has a strong influence on nucleation and growth processes. In fact, the growth process dominates crystallization at small ΔT, whereas the nucleation dominates crystallization at large ΔT. Time also is an important variable during crystallization process, because long experiment durations involve more nucleation events of alkali feldspar than short experiment durations. This is an important aspect to understand magma evolution in the magma chamber and in the conduit, which in turn has strong effects on magma rheology.

Small volume andesite magmas and melt–mush interactions at Ruapehu, New Zealand: evidence from melt inclusions

Abstract: Historical eruptions from Mt. Ruapehu (New Zealand) have been small (<0.001 km3 of juvenile magma) and have often occurred without significant warning. Developing better modelling tools requires an improved understanding of the magma storage and transport system beneath the volcano. Towards that end, we have analysed the volatile content and major element chemistry of groundmass glass and phenocryst-hosted melt inclusions in erupted samples from 1945 to 1996. We find that during this time period, magma has been stored at depths of ~2–9 km, consistent with inferences from geophysical data. Our data also show that Ruapehu magmas are relatively H2O-poor (<2 wt%) and CO2-rich (≤1,000 ppm) compared to typical arc andesites. Surprisingly, we find that melt inclusions are often more evolved than their transporting melt (as inferred from groundmass glass compositions). Furthermore, even eruptions that are separated by less than 2 years exhibit distinct major element chemistry, which suggests that each eruption involved magma with a unique ascent history. From these data, we infer that individual melt batches rise through, and interact with, crystal mush zones formed by antecedent magmas. From this perspective, we envision the magmatic system at Ruapehu as frequently recharged by small magma inputs that, in turn, cool and crystallise to varying degrees. Melts that are able to erupt through this network of crystal mush entrain (to a greater or lesser extent) exotic crystals. In the extreme case (such as the 1996 eruption), the resulting scoria contain melt inclusion-bearing crystals that are exotic to the transporting magma. Finally, we suggest that complex interactions between recharge and antecedent magmas are probably common, but that the small volumes and short time scales of recharge at Ruapehu provide a unique window into these processes.