Igneous layering through oscillatory nucleation and crystal settling in well-mixed magmas

Oscillatory or competitive nucleation about a binary (or perhaps pseudo binary) eutectic and ensuing crystal growth and settling is a commonly suggested means of producing layering in magmatic systems. A quantitative model is presented of this, outwardly, relatively simple process of crystal nucleation, growth, and settling in an otherwise initially crystal-free magma. Avrami-style kinetics of crystallization in an always wellmixed body, buried in conductive wall rock, are coupled to a Stokes-like formulation of crystal settling in magma whose viscosity depends on temperature and crystallinity. Two dimensionless numbers (Se, the settling number and Av, the Avrami or kinetic number) govern all the results. Av and Se measure the relative importance of crystallization time and settling time, respectively, relative to the overall cooling time. For any value of Av, which increases strongly with the maximum nucleation and growth rates and cooling time, layering is possible only over a range or window of values of Se. Both above and below this window a single layer (crystalline below, vitric above) forms, and within this window the number of layers increases systematically with increasing Av and Se. Grain size within any single layer generally coarsens upward. Because the characteristic settling and cooling times both depend on body thickness, the lower limit of the settling window is also dependent on sheet thickness. Within the confines of this model and for nucleation and growth rates set by those observed in natural systems, layering is unlikely in sheet-like magmas thinner than about 100 m. When the body is not always well-mixed and crystallization is within inward-propagating solidification fronts, it is expected that this minimum body thickness will increase.     

Development of crystallographic preferred orientations by nucleation and growth of new grains in experimentally deformed quartz single crystals

Deformation experiments have been carried out to investigate the effect of dynamic recrystallisation on crystallographic preferred orientation (CPO) development. Cylindrical samples of natural single crystals of quartz were axially deformed together with 1 vol.% of added water and 20 mg of Mn₂O₃ powder in a Griggs solid medium deformation apparatus in different crystallographic orientations with compression direction: (i) parallel to <c>, (ii) at 45° to <c> and 45° to <a> and (iii) parallel to <a>. The experiments were performed at a temperature of 800 °C, a confining pressure of 1.2 GPa, a strain rate of  10^− 6 s^− 1, to bulk finite strains of  14–36%. The deformed samples were analysed in detail using optical microscopy, electron backscatter diffraction (EBSD) and transmission electron microscopy (TEM). Two different microstructural domains were distinguished in the deformed samples: (i) domains with undulatory extinction and deformation lamellae, and (ii) domains with new recrystallised grains. Within the domains of undulatory extinction, crystal-plastic deformation caused gradual rotations of the crystal lattice up to  30° away from the host orientation. New recrystallised grains show a strong CPO with c-axis maxima at  45° to the compression direction. This is the case in all experiments, irrespective of the initial crystallographic orientation. The results show that c-axes are not continuously rotated towards the new maxima. The new grains thus developed through a mechanism different from subgrain rotation recrystallisation. New grains have a subeuhedral shape and numerous microcavities, voids, fluid channels and fluid inclusions at their grain boundaries. No host control is recorded in misorientation axes across their large angle grain boundaries. New grains might have been created by nucleation from solution in the μm-scale voids and microfractures. The CPO most likely developed due to preferred growth of the freshly precipitated grains with orientations suitable for intracrystalline deformation at the imposed experimental conditions.     

An experimental study of Ostwald ripening of olivine and plagioclase in silicate melts: implications for the growth and size of crystals in magmas

We carried out an experimental study to characterize the kinetics of Ostwald ripening in the forsterite-basalt system and in the plagioclase (An₆₅)-andesite system. Eight experiments were done in each system to monitor the evolution of mean grain size and crystal size distribution (CSD) with time t; the experiments were performed in a 1-atmosphere quench furnace, at 1,250°C for plagioclase and 1,300°C for olivine. Very contrasted coarsening kinetics were observed in the two series. In the plagioclase series, the mean grain size increased as log(t), from ≈3 μm to only 8.7 μm in 336 h. The kinetic law in log(t) means that Ostwald ripening was rate-limited by surface nucleation at plagioclase-liquid interfaces. In the olivine series, the mean grain size increased as t ^1/3, from ≈3 μm to 23.2 μm in 496 h. A kinetic law in t ^1/3 is expected when Ostwald ripening is rate-limited either by diffusion in the liquid or by grain growth/dissolution controlled by a screw dislocation mechanism. The shape of olivine CSDs, in particular their positive skewness, indicates that grain coarsening in the olivine experiments was controlled by a screw dislocation mechanism, not by diffusion. As the degrees of undercooling ΔT (or supersaturation) involved in Ostwald ripening are essentially <1°C, the mechanisms of crystal growth identified in our experiments are expected to be those prevailing during the slow crystallisation of large magma chambers. We extrapolated our experimental data to geological time scales to estimate the effect of Ostwald ripening on the size of crystals in magmas. In the case of plagioclase, Ostwald ripening is only efficient for mean grain sizes of a few microns to 20 μm, even for a time scale of 10⁵ years. It can, however, result in a significant decrease of the number of small crystals per unit volume, and contribute to the development of convex upwards CSDs. For olivine, the mean grain size increases from 2–3 μm to ≈70 μm in 1 year and 700 μm in 10³ years; a mean grain size of 3 mm is reached in 10⁵ years. Accordingly, the rate of grain size-dependent processes, such as compaction of olivine-rich cumulates or melt extraction from partially molten peridotites, may significantly be enhanced by textural coarsening.     

Dependence of clinopyroxene composition on cooling rate in basaltic magmas: Implications for thermobarometry

The compositional variation of clinopyroxene and the partitioning of major elements between clinopyroxene and melt are estimated as a function of the cooling rate. Clinopyroxenes were crystallized under variable cooling regimes (15, 9.4, 3, 2.1, and 0.5 °C/min from 1250 down to 1000 °C) and at isothermal conditions of 1000 °C from a basaltic composition at a pressure of 500 MPa under anhydrous and hydrous (H₂O = 1.3 wt.%) conditions. The clinopyroxene chemistry shows that, as the cooling rate increases, crystals are progressively depleted in Ca, Mg, Fe²⁺ and Si and enriched in Na, Fe³⁺, Al (mainly Al^IV), and Ti. Di and Hd versus CaTs and CaFeTs form a continuous binary solid solution characterized by higher amounts of tschermakitic components with increasing cooling rate. Two parameters (DH = Di + Hd and TE = CaTs + CaFeTs + En) are calculated to describe the effect of cooling rate on the clinopyroxene composition. The variation of DH/TE with increasing cooling rate evidences the kinetic process induced by rapid cooling in basic rocks under hydrous and anhydrous conditions.Dynamic crystallization conditions affect the partitioning of major elements between clinopyroxene and melt; with increasing cooling rate, the value of crystal–melt partition coefficient departs from that obtained at the isothermal condition. However, in spite of these variations, the values of ^cpx–meltKd_Fe–Mg remain almost constant. Therefore, the Fe²–Mg exchange between clinopyroxene and melt is not suitable to prove the (dis)equilibrium conditions in basaltic cooling magmas, giving rise to possible mismatches in the application of thermobarometers. The results of our study are consistent with that observed at the margin of dikes or in the exterior portions of lavas, where the cooling rate is maximized and disequilibrium compositions of clinopyroxene have been found.     

Diffusive fractionation of volatiles and their isotopes during bubble growth in magmas

Bubbles grow in decompressing magmas by simple expansion and by diffusive supply of volatiles to the bubble/melt interface. The latter phenomenon is of significant geochemical interest because diffusion can fractionate elements and isotopes (or isotopologues) of dissolved components. This raises the possibility that the character of volatile components in bubbles may not reflect that of volatiles dissolved in the host melt over the lifetime of a bubble—even in the absence of equilibrium vapor/melt isotopic fractionation. Recent experiments have confirmed the existence of an isotope mass effect on diffusion of the volatile element Cl in silicate melt [Fortin et al. (Isotopic fractionation of chlorine during chemical diffusion in a dacitic melt and its implications for isotope behavior during bubble growth (abstract), 2016 Fall AGU Meeting, 2016)], so there is a clear need to understand the efficacy of diffusive fractionation during bubble growth. In this study, numerical models of diffusion and mass redistribution during bubble growth were implemented for both “passive” volatiles—those whose concentrations are generally well below saturation levels—and “active” volatiles such as CO₂ and H₂O, whose elevated concentrations and limited solubilities are the cause of bubble nucleation and growth. Both diffusive and convective bubble-growth scenarios were explored. The magnitude of the isotope mass effect on passive volatiles partitioned into bubbles growing at a constant rate R in a static system depends upon R/D _L, K _d and D _H/D _L (K _d = bubble/melt partition coefficient; D _H/D _L = diffusivity ratio of the heavy and light isotopes). During convective bubble growth, the presence of a discrete (physical) melt boundary layer against the growing bubble (of width x _BL) simplifies outcomes because it leads to the quick onset of steady-state fractionation during growth, the magnitude of which depends mainly upon R?x _BL/D _L and D _H/D _L (bubble/melt fractionation is maximized at R?x _BL/D _L ≈0.1). Constant R is unrealistic for most real systems, so other scenarios were explored by including the solubility and EOS of an “active” volatile (e.g., CO₂) in the numerical simulations. For plausible decompression paths, R increases exponentially with time—leading, potentially, to larger isotopic fractionation of species partitioned into the growing bubble. For volatile species whose isotope mass effects on diffusion have been measured (Cl, Li), predicted isotope fractionation in the exsolved vapor can be as large as ?4‰ for Cl and ?25‰ for Li.     

Variations in rates of nucleation and growth of biotite porphyroblasts

Differences in rates of nucleation and diffusion‐limited growth for biotite porphyroblasts in adjacent centimetre‐scale layers of a garnet‐biotite schist from the Picuris Mountains of New Mexico are revealed by variations in crystal size and abundance between two layers with strong compositional similarity. Relationships between fabrics recorded by inclusion patterns in biotite and garnet porphyroblasts are interpreted to reflect garnet growth following biotite growth, without substantial alteration of the biotite sizes. Sizes and locations of biotite crystals, obtained via high‐resolution X‐ray computed tomography, document that of the two adjacent layers, one has a larger mean crystal volume (9.5 × 10^?4v. 2.4 × 10^?4 cm³), fewer biotite crystals per unit volume (232 v. 576 crystals cm^?3), and a higher volume fraction of biotite (23%v. 14%). The two layers have similar mineral assemblages and mineral chemistry. Both layers show evidence for diffusional control of nucleation and growth. Pseudosection analysis suggests that the large‐biotite layer began to crystallize biotite at a temperature ～67 °C greater than the small‐biotite layer. Diffusion rates differed between layers, because of their different temperature ranges of crystallization, but this effect can be quantified. The bulk compositional difference between the layers, manifested in different modal amounts of biotite, has an effect on the biotite sizes that is also quantifiable and insufficient to account for the difference in biotite size. After these other possible causes of variation in crystal sizes have been eliminated, variability in nucleation and diffusion rates remain as the dominant factors responsible for the difference in porphyroblastic textures. Numerical simulations suggest that relative to the small‐biotite layer, the large‐biotite layer experienced elevated diffusion rates because of the higher crystallization temperature, as well as increased nucleation rates in order to achieve the observed size and number density of crystals. The simulations can replicate the observed textures only by invoking unreasonably large values for the thermal dependence of nucleation rates (activation energies), strongly suggesting that the observed textural differences arise from variations between layers in the abundance and energetics of potential nucleation sites.     

Toward a quantitative model of metamorphic nucleation and growth

The formation of metamorphic garnet during isobaric heating is simulated on the basis of the classical nucleation and reaction rate theories and Gibbs free energy dissipation in a multi-component model system. The relative influences are studied of interfacial energy, chemical mobility at the surface of garnet clusters, heating rate and pressure on interface-controlled garnet nucleation and growth kinetics. It is found that the interfacial energy controls the departure from equilibrium required to nucleate garnet if attachment and detachment processes at the surface of garnet limit the overall crystallization rate. The interfacial energy for nucleation of garnet in a metapelite of the aureole of the Nelson Batholith, BC, is estimated to range between 0.03 and 0.3?J/m² at a pressure of ca. 3,500?bar. This corresponds to a thermal overstep of the garnet-forming reaction of ca. 30°C. The influence of the heating rate on thermal overstepping is negligible. A significant feedback is predicted between chemical fractionation associated with garnet formation and the kinetics of nucleation and crystal growth of garnet giving rise to its lognormal??shaped crystal size distribution.     

Composition,nucleation, and growth of iron oxide concretions

Iron oxide concretions are formed from post depositional, paleogroundwater chemical interaction with iron minerals in porous sedimentary rocks. The concretions record a history of iron mobilization and precipitation caused by changes in pH, oxidation conditions, and activity of bacteria. Transport limited growth rates may be used to estimate the duration of fluid flow events. The Jurassic Navajo Sandstone, an important hydrocarbon reservoir and aquifer on the Colorado Plateau, USA, is an ideal stratum to study concretions because it is widely distributed, well exposed and is the host for a variety of iron oxide concretions.Many of the concretions are nearly spherical and some consist of a rind of goethite that nearly completely fills the sandstone porosity and surrounds a central sandstone core. The interior and exterior host-rock sandstones are similar in detrital minerals, but kaolinite and interstratified illite–smectite are less abundant in the interior. Lepidocrocite is present as sand-grain rims in the exterior sandstone, but not present in the interior of the concretions.Widespread sandstone bleaching resulted from dissolution of early diagenetic hematite grain coatings by chemically reducing water that gained access to the sandstone through fault conduits. The iron was transported in solution and precipitated as iron oxide concretions by oxidation and increasing pH. Iron diffusion and advection growth time models place limits on minimum duration of the diagenetic, fluid flow events that formed the concretions. Concretion rinds 2 mm thick and 25 mm in radius would take place in 2000 years from transport by diffusion and advection and in 3600 years if transport was by diffusion only. Solid concretions 10 mm in radius would grow in 3800 years by diffusion or 2800 years with diffusion and advection.Goethite (α-FeO (OH)) and lepidocrocite (γ-FeO (OH)) nucleated on K-feldspar grains, on illite coatings on sand grains, and on pore-filling illite, but not on clean quartz grains. Model results show that regions of detrital K-feldspar in the sandstone that consume H⁺ more rapidly than diffusion to the reaction site determine concretion size, and spacing is related to diffusion and advection rates of supply of reactants Fe²⁺, O₂, and H⁺.     

Simulation of the nucleation and growth of binary solid solutions in aqueous solutions

We present a model which, for the first time, accounts for nucleation, growth and/or resorption of particles of variable composition in aqueous solutions (AS). Devised for describing the precipitation of binary solid solutions, it yields the time evolution of all ion activities in the AS, together with the particle population characteristics: number, size and composition profile of particles as a function of time and of their time of nucleation. We apply this numerical approach to the prototypical case of (Ba,Sr)CO₃ solid solution precipitation. We demonstrate the great sensitivity of the composition profiles and particle sizes to the initial conditions under which the AS is prepared, and thus illustrate the possibility of engineering the particle characteristics into a chosen state. Finally, by comparing the precipitation of two solid solutions (Ba,Sr)CO₃ and (Ba,Sr)SO₄, we evidence the sensitivity of the particle composition profiles to the ratio of the end-member solubility products, which leads to the formation of core-shell particles in the case of (Ba,Sr)SO₄.     

Kinetics of gypsum nucleation and crystal growth from Dead Sea brine

The Dead Sea brine is supersaturated with respect to gypsum (Ω = 1.42). Laboratory experiments and evaluation of historical data show that gypsum nucleation and crystal growth kinetics from Dead Sea brine are both slower in comparison with solutions at a similar degree of supersaturation. The slow kinetics of gypsum precipitation in the Dead Sea brine is mainly attributed to the low solubility of gypsum which is due to the high Ca²⁺/SO₄²⁻ molar ratio (115), high salinity (∼280 g/kg) and to Na⁺ inhibition.Experiments with various clay minerals (montmorillonite, kaolinite) indicate that these minerals do not serve as crystallization seeds. In contrast, calcite and aragonite which contain traces of gypsum impurities do prompt precipitation of gypsum but at a considerable slower rate than with pure gypsum. This implies that transportation inflow of clay minerals, calcite and local crystallization of minerals in the Dead Sea does not prompt significant heterogeneous precipitation of gypsum. Based on historical analyses of the Dead Sea, it is shown that over the last decades, as inflows to the lake decreased and its salinity increased, gypsum continuously precipitated from the brine. The increasing salinity and Ca²⁺/SO₄²⁻ ratio, which results from the precipitation of gypsum, lead to even slower kinetics of nucleation and crystal growth, which resulted in an increasing degree of supersaturation with respect to gypsum. Therefore, we predict that as the salinity of the Dead Sea brine continues to increase (accompanied by Dead Sea water level decline), although gypsum will continuously precipitate, the degree of supersaturation will increase furthermore due to progressively slower kinetics.     

Crystal nucleation and growth produced by continuous decompression of Pinatubo magma

High-temperature decompression experiments demonstrate that crystal textures preserve a record of the style and rate of magmatic ascent. To reinforce this link, we performed a suite of isothermal decompression experiments using starting material from the climactic 1991 Pinatubo eruption. We decompressed experiments from 220 MPa to final, quench pressures of 75 or 30 MPa using continuous decompression rates of 100, 30, 10, 3, 1, and 0.3 MPa h^?1. Amphibole, clinopyroxene, and plagioclase crystallized during the experiments, with plagioclase microlites dominating the assemblage. Total microlite number densities range from 10^7.6±0.4 up to 10^8.2±0.2 cm^?3, with plagioclase accounting for up to 65% of the total number. Plagioclase microlite area increased systematically from 19?±?8 to 937?±?487 µm² with increasing experiment duration. Our textures provide time-integrated records of crystal kinetics. Average nucleation and areal growth rates of plagioclase are highest in the fastest decompressions (~?10^7.5 cm^?3 h^?1 and 10.1?±?4.1 µm² h^?1, respectively) and more than an order of magnitude lower in the slowest experiments (~?10^5.5 cm^?3 h^?1 and 0.8?±?0.2 µm² h^?1, respectively). Both nucleation and growth rates are highest at high degrees of disequilibrium. We find that peak supersaturation-dependent instantaneous rates are generally more than an order of magnitude faster than average rates. We use those instantaneous nucleation and growth rates to introduce an iterative model to evaluate the effects of different decompression rates, decompression paths (continuous, single-step or multistep), and the presence of phenocrysts on final crystallinity and microlite size distribution.     

Stepwise accumulation and ascent of magmas

One of the currently popular theories on magma ascent is that it mainly occurs by propagating hydrofractures (dykes) and that magma viscosity is the primary rate‐controlling factor. This theory is based on mathematical models for single hydrofractures under idealised conditions. We simulated magma ascent with air ascending through gelatine and observed that the air ascended in batches, following paths made by their predecessors. Multiple batches accumulate at obstacles along the path. Although magma viscosity may control ascent rate during movement, obstacles ultimately control the size and average ascent velocity of ascending batches. We propose that step‐wise movement of magma batches is the mechanism of primary accumulation and ascent from the partially molten source rock of a magma to its first emplacement site and therefore the main ascent mechanism for granitic magmas. ‘Classical’ dyking is the mechanism for secondary ascent from a magma chamber.     

Olivine xenocrysts in picritic magmas

Experimental partial melting of plagioclase lherzolite at 0.7 MPa confining pressure has produced euhedral olivine crystals by corrosion and overgrowth during cooling. The particular conditions of this experiment allow observation of both processes recorded in the crystal shape: corrosion boundaries are rounded, or straight when parallel to [001] intersection of {110} planes; (010) and {110} facets are developed by fast overgrowth during quenching. These observations support the contention that phenocrysts in basaltic or picritic magmas are, in part, xenocrysts. The possible mantle origin of olivine crystals in two natural occurrences of ultramafic magmas; the picritic pillow lavas of the Troodos, and a wehrlitic intrusion of the oman ophiolite, is investigated. In both cases discriminant characteristics are deduced from detailed microstructural study. The mantle origin of olivine megacrysts in the investigated picrites raises the question about the existence of picritic magmas in the mantle.     

Fluorite stability in silicic magmas

Recent experimental evidence is used to assess the conditions under which fluorite forms an early crystallising phase in silicic magmas. Fluorite solubility primarily depends on the (Na + K)/Al balance in the coexisting silicic melt, reaching a minimum in metaluminous melts. It can display reaction relationships with topaz and titanite, depending on changes in melt composition during crystallisation. An empirical model of fluorite stability in Ca-poor peralkaline rhyolite melts is derived and applied to selected rocks:

Numerical simulation of diffusion‐controlled nucleation and growth of porphyroblasts

This article presents the conceptual basis for a new numerical model of diffusion‐controlled nucleation and growth of porphyroblasts, describes its implementation, and illustrates the range of crystallization behaviours encompassed by it. The model differs from previous efforts principally in its ability to track explicitly the evolution in time and space of the chemical affinity for reaction in the intergranular medium, which provides a more accurate characterization of nucleation suppression in the vicinity of pre‐existing crystals and of growth suppression due to competition for nutrients among neighbouring crystals. Critical new features of these numerical simulations include: maintenance of local equilibrium for fluid in contact with reactants or products; persistence of reactants until they are eliminated by dissolution due to reaction progress and local diffusive flux; nucleation rates that vary as the local reaction affinity evolves; complex initial distributions of reactants if desired; and the flexibility to encompass any porphyroblast‐forming reaction for which changes in free energy as a function of time and temperature are specified. Model results reveal that radial growth rates remain proportional to the square‐root of time in diffusion systems buffered by persistent reactants; they document the interchangeable effects of diffusivity, porosity, and solubility on material fluxes and thus growth rates; and they illustrate the offsetting textural effects of rates of diffusion, nucleation, and heating. The initial distribution of reactants is found to exert a first‐order effect on crystal size distributions, confirming their limited utility for diagnosing crystallization mechanisms. These numerical simulations yield novel and rigorous confirmation of the textural effects of nucleation‐site saturation and variation in interconnected porosity, and reproduce with high fidelity much of the textural and chemical information gathered from natural specimens.     

Formation and ascent of granitic magmas

New results obtained by the investigation of liquidus and solidus phase relationships in the haplogranite system Qz-Ab-Or are used to discuss the evolution of magmas during their ascent in the crust. It is assumed that the magmas are formed at 720°C, 820°C, 920°C and at a depth corresponding to a pressure of 8 kbar. The starting composition of the magma is taken as 50% melt plus 50% quartz and feldspars. In case of a closed system (no heat exchange and no transfer of elements) the melt fraction of magmas, the water activity and the viscosity increase with decreasing pressure. The temperature slightly decreases. At 700°C the viscosity is approximatively 2 orders of magnitude lower than at 900°C. This is related to the higher amount of water in the (H₂O-undersaturated) melt at low T. It is also shown that dehydration melting is only realistic at high T (900°C). At lower temperatures water has to be added from outside to obtain an intrusive magma with approximatively 50% melt.

---

Zusammenfassung Neue Ergebnisse, erzielt durch Untersuchungen von Liquidus und Solidus Phasenbeziehungen des Granitsystems Qz-Ab-Or, werden benutzt, um die Entwicklung eines granitoiden Magmas während seines Aufstiegs zu diskutieren. Es wird vorausgesetzt, daß die Magmen bei Temperaturen von 720°C, 820°C und 920°C gebildet werden, sowie in einer Tiefe die einem Druck von 8 kbar entspricht. Die anfängliche Zusammensetzung des Magmas wird mit einem Verhältnis von 50% Schmelze sowie 50% Quarz und Feldspäten angenommen. Im Falle eines geschlossenen Systems (kein Austausch von Wärme und Elementen) steigt die Teilschmelzbildung von Magmen, die Aktivität des Wassers und die Viskosität bei abnehmenden Druck; hierbei sinkt die Temperatur leicht. Bei 700°C ist die Viskosität um ca. 2 Größenordnungen geringer als bei 900°C. Dies wird bedingt durch den höheren Gehalt an Wasser in der (H₂O-untersättigten) Schmelze bei tieferen Temperaturen. Es wird außerdem gezeigt, daß Magmenbildung durch Dehydratation nur bei hohen Temperaturen realistisch ist (900°C). Bei tieferen Temperaturen muß Wasser von außen zugeführt werden um ein intrusives Magma zu erhalten, das ungefähr 50% Schmelze besitzt.

---

Résumé L'évolution des magmas granitiques au cours de leur ascension dans la croûte est discutée à la lumière de données nouvelles relatives aux relations entre phases liquides et solides dans le système Q-Ab-Or. On suppose que les magmas se forment à des températures de 720°C, 820°C, 920°C et à une profondeur correspondant à une pression de 8 Kb. On admet pour leur composition initiale un mélange de 50% de liquide et 50% de quartz + feldspaths. Dans le cas d'un système fermé (pas d'échange de chaleur ni de matière), la fraction liquide du magma, l'activité de l'eau et la viscosité augmentent quand la pression diminue; en même temps, la température décroît légèrement. A 700°C, la viscosité est d'environ 2 ordres de grandeur plus basse qu'à 900°C. Cette propriété est en relation avec la teneur en eau plus élevée dans le liquide (sous-saturé en eau) à basse température. On peut également montrer qu'une fusion déshydratante n'est vraisemblable qu'à haute température (900°C). Aux températures plus basses, de l'eau doit être apportée de l'extérieur pour l'obtention d'un magma à 50% de liquide.

---

. , 720°, 820°, 920°, 8 . , 50% 50% . , , , , . . 700° 2 , 900°. ( ) . , 900°. , 50% , - .

     

Magnetite scavenging and the buoyancy of bubbles in magmas. Part 2: Energetics of crystal-bubble attachment in magmas

The fate of pre-eruptive bubbles depends largely on their buoyancy, which can be strongly modified by the presence of crystals attached to the bubble–melt interface. We define the attachment energy and attachment force as those resulting from the attachment of a crystal to a bubble. The attachment energy is such that (1) attachment of crystals to bubbles is always favored energetically, and (2) oxide minerals attach to bubbles much more strongly than silicates, because the attachment energy is a strong function of the wetting angle. Attaching crystals to bubbles can cause bubble–crystal pairs to become neutrally buoyant. There is a critical bubble radius below which the attachment force will be strong enough to keep the pair together; we show that crystals as large as 1 mm in diameter can form neutrally buoyant pairs. For early erupted Bishop magma, if all magnetite forms neutrally buoyant pairs with gas bubbles, ca. 0.1–0.2 vol% gas can be stored in the magma; 2–3 vol% of gas can be accounted for if all minerals form neutrally buoyant aggregates. These values are an order of magnitude lower than what is inferred from melt inclusions. Hence, both magnetite-free and magnetite-rich bubbles might have existed, but only a very small fraction of them could have been neutrally buoyant. Importantly, an intrinsic association between magnetite crystals and bubbles is expected. However, most magnetite crystals in the early erupted Bishop are free of bubbles; the puzzling conclusion is that nucleation away from crystals is favored over heterogeneous nucleation on crystal substrates. Electronic Supplementary Material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Evidence for the nucleation and epitaxial growth of Zn phyllosilicate on montmorillonite

Zinc uptake in suspensions (?3.7 g L⁻¹) of MX80 montmorillonite was investigated at pH 4.0 and 7.3, a total Zn concentration ([Zn]_total) of 500 μM, and dissolved Si concentrations ([Si]_aq) of ∼70 and ∼500 μM in 0.5 M NaCl, by kinetics experiments and polarized extended X-ray absorption fine structure (P-EXAFS) spectroscopy. Differential thermogravimetric analysis verified the cis-vacant character of the montmorillonite. No Zn uptake occurred at pH 4.0, confirming that cation exchange was hampered by the high ionic strength of the suspension. At pH 7.3 and low [Si]_aq (∼70 μM), Zn uptake occurred rapidly during the first hour of reaction, and then leveled off to 50 μmol/g montmorillonite at 168 h. The uptake rate is consistent with Zn sorption on pH-dependent edge sites. At pH 7.3 and high [Si]_aq (∼500 μM), the initial sorption rate was similar, but Zn sorption continued, reaching 130 μmol/g at 168 h, and was paralleled by Si uptake with a Si/Zn uptake ratio of 1.51(10), suggesting formation of a Zn (hydrous) silicate. P-EXAFS data indicated that the first oxygen coordination shell of sorbed Zn is split into two subshells at 1.97(2) and 2.08(3)-2.12(2) Å for all EXAFS samples. These two distances are assigned to a mixture of tetrahedral (^IVZn) and octahedral (^VIZn) Zn complexes. The proportion of ^IVZn was lower in the high [Si]_aq samples and decreased with reaction time. Al low [Si]_aq and 216 h of reaction, nearest cationic shells of 0.6(4) Al in the film plane and 0.5(4) Si out of the film plane were detected at 3.00(2) and 3.21(2) Å, respectively, and were interpreted as the formation of ^IVZn and ^VIZn mononuclear complexes at the edges of montmorillonite platelets, in structural continuity to the (Al, Mg) octahedral sheets. At high [Si]_aq, in-plane Zn and Al and out-of-plane Si neighbors were detected at 4 h, indicating the formation of Zn phyllosilicate nuclei at the layer edges. At 313 h, Zn-Al pairs were no longer detected, and Zn atoms were surrounded on average by 3.4(5) in-plane Zn at 3.10(1) Å and 1.7(9) out-of-plane Si at 3.30(2) Å, supporting the precipitation of a Zn phyllosilicate. Thus, dioctahedral Al phyllosilicate may act as a nucleating surface for the heterogeneous formation of trioctahedral Zn phyllosilicate at [Si]_aq relevant to natural systems.     

Plagioclase nucleation and growth kinetics in a hydrous basaltic melt by decompression experiments

Isothermal single-step decompression experiments (at temperature of 1075 °C and pressure between 5 and 50 MPa) were used to study the crystallization kinetics of plagioclase in hydrous high-K basaltic melts as a function of pressure, effective undercooling (ΔT _eff) and time. Single-step decompression causes water exsolution and a consequent increase in the plagioclase liquidus, thus imposing an effective undercooling (?T _eff), accompanied by increased melt viscosity. Here, we show that the decompression process acts directly on viscosity and thermodynamic energy barriers (such as interfacial-free energy), controlling the nucleation process and favoring the formation of homogeneous nuclei also at high pressure (low effective undercoolings). In fact, this study shows that similar crystal number densities (N _a) can be obtained both at low and high pressure (between 5 and 50 MPa), whereas crystal growth processes are favored at low pressures (5–10 MPa). The main evidence of this study is that the crystallization of plagioclase in decompressed high-K basalts is more rapid than that in rhyolitic melts on similar timescales. The onset of the crystallization process during experiments was characterized by an initial nucleation event within the first hour of the experiment, which produced the largest amount of plagioclase. This nucleation event, at short experimental duration, can produce a dramatic change in crystal number density (N _a) and crystal fraction (?), triggering a significant textural evolution in only 1 h. In natural systems, this may affect the magma rheology and eruptive dynamics on very short time scales.