The interfacial energy penalty to crystal growth close to equilibrium

Understanding the origin of rock microstructure is critical for refining models of the geodynamics of the Earth. We use the geometry of compositional growth zoning of a population of garnet porphyroblasts in a mica schist to gain quantitative insight into (1) the relative growth rates of individual crystals, (2) the departure from equilibrium during their growth, and (3) the mobility of the porphyroblast-matrix interface. The driving force for garnet growth in the studied sample was exceedingly small and is comparable in magnitude to the interfacial energy associated with the garnet-matrix interface. This resulted in size-dependent garnet growth at macroscopic length scales, with a decrease in radial growth rates for smaller crystals caused by the penalty effect of the interfacial energy. The difference in growth rate between the largest and the smallest crystal is ~45%, and the interface mobility for garnet growth from ~535 °C, 480 MPa to 565 °C, 560 MPa in the phyllosilicate-dominated rock matrix ranged between ~10–19 and 10–20 m4 J–1 s–1. This is the first estimation of interface mobility in natural rock samples. In addition to the complex structural and chemical reorganization associated with the formation of dodecahedral coordination polyhedra in garnet, the presence of abundant graphite may have exerted drag on the garnet-matrix interface, further decreasing its mobility.

Documenting isobaric cooling in the lower crust using cordierite breakdown textures (Mont Mary nappe, Western Alps)

<p>Intracrystalline diffusion is an efficient mechanism in high-grade rocks. Therefore, growth zoning in garnet is erased and the evidence for prograde path is lost. However, information recorded by the textures may store significant clues for deciphering part of the P-T path. An example is provided here from the migmatitic paragneisses from the Mont Mary nappe (Western Alps).</p><p>The latter is made of a pre-Alpine basement consisting of an upper and a lower unit. The upper unit is made of paragneisses, marbles and amphibolites similar to those of the Valpelline Unit and of the Ivrea Zone. The lower unit displays granitic orthogneisses, paraschists (with muscovite, biotite, garnet with local occurrences of staurolite, kyanite and andalusite) (Dal Piaz et al. 2015). In this unit, we discovered a hectometre-sized volume with no Alpine overprint, preserving migmatitic paragneisses, the topic of this study.</p><p>The paragneisses display quartzo-feldspathic leucocratic layers interpreted as crystallized melts. The leucosomes are separated by biotite- and sillimanite-rich layers, with conspicuous garnet porphyroblasts. In addition, fresh cordierite crystals are found in these layers. Sillimanite included in garnet rims has the same orientation than the one in the matrix. There, the foliation is defined by the shape fabric of biotite and sillimanite, wrapping both garnet and cordierite crystals.</p><p>Such textures may be used to propose a P-T path. A sequence of prograde reactions, including dehydration-melting of muscovite, then biotite, result in the production of a large amount of sillimanite. Garnet growth was continuing during incongruent melting. However, intracrystalline diffusion has erased the prograde chemical zoning, as well as the distribution and shape of mineral inclusions. The late replacement of garnet and cordierite by biotite and sillimanite indicates near-isobaric cooling, also recorded by chemical zoning along garnet rims.</p><p>Chemical data on coexisting minerals will be used to provide quantitative constraints on the P-T path. In addition, preliminary geochronological data suggest that detrital zircons grains were significantly reset during the HT metamorphism, which could have taken place c. 270 Ma ago. To conclude, the studied paragneisses offer another example of Permian near-isobaric cooling in the middle crust of the Adriatic plate.</p><p>Dal Piaz G.V., Bistacchi A., Gianotti F., Monopoli B., Passeri L., Schiavo A. & collaboratori (2015) – Note illustrative della carta Geologica d’Italia alla scala 1:50.000. Foglio 070, Monte Cervino. ISPRA, Servizio Geologico d’Italia, 070, 1-431.</p>

Growth, replacement and element diffusion in metamorphic garnet revealed by trace element mapping

<p>Garnet is one of the most robust and ubiquitous minerals that record element zoning during crustal metamorphism. In addition to major element distribution, zoning in trace elements can provide a wealth of information to document the changing conditions of garnet growth and modification. Trace element distribution in garnet grains was mapped in 2D in thin section with laser ablation inductively coupled plasma time of flight mass spectrometry (LA-ICP-TOFMS) and conventional LA-ICP-MS to achieve a lateral resolution of 15-5 µm and limits of detection for the heavy rare earth elements (REE) down to 0.2 µg/g (Rubatto et al. 2020).</p><p>In granulite-facies garnet, major elements show diffusional resetting, whereas trace elements still largely document the growth history. Enrichment of trace elements in the garnet mantle is attributed to the consumption of biotite (V, Cr) and the dissolution of zircon (Zr) and monazite (Y+REE) in the coexisting melt. Lu is notably enriched in the garnet mantle with implications for geochronology. The gradual zoning of Y+HREE between mantle and core is reconcilable with diffusion over ~200 µm in 10 My at temperatures of 750–800°C</p><p>In amphibolite facies garnet, Y+REE trace element zoning closely matches the growth zoning in Ca with no notable diffusive modification. Y+REE zoning is dominated by Rayleigh fractionation in the core and in the outer zones it shows annuli that mark the sporadic breakdown of accessory phases.</p><p>Garnet in eclogite facies samples that underwent fluid-rock interaction show growth zoning in major and trace elements, with local oscillations and sectors. In certain samples, the overall distribution of REE can be reconciled with diffusion-limited uptake. Where garnet displays fluid-related veinlets, visible in major elements, that cross-cut the primary growth zoning, the regular Y+REE and Cr growth zoning is not affected by the veinlets. This indicates that the veinlets did not form by a crack-seal mechanism but are rather related to a selective replacement process.</p><p> </p><p><strong>References </strong></p><p>Rubatto D, Burger M, Lanari P, Hattendorf B, Schwarz G, Neff C, Keresztes Schmidt P, Hermann J, Vho A, Günther D (2020) Identification of growth mechanisms in metamorphic garnet by high-resolution trace element mapping with LA-ICP-TOFMS. Contrib Mineral Petrol 175:61 doi.org/10.1007/s00410-020-01700-5</p>

Ti3+ in corundum traces crystal growth in a highly reduced magma

Aggregates of corundum crystals with skeletal to hopper morphology occur in pyroclastic rocks erupted from Cretaceous basaltic volcanoes on Mt Carmel, N. Israel. The rapid growth of the crystals trapped volumes of the parental Al2O3-supersaturated melt; phenocrysts of tistarite (Ti2O3) in the trapped melts indicate crystallization at oxygen fugacities 6–7 log units below the Iron-Wüstite buffer (fO2 = ΔIW − 6 to − 7), induced by fluxes of mantle-derived CH4-H2 fluids. Cathodoluminescence images reveal growth zoning within the individual crystals of the aggregates, related to the substitution of Ti3+ in the corundum structure. Ti contents are < 0.3 wt% initially, then increase first linearly, then exponentially, toward adjacent melt pockets to reach values > 2 wt%. Numerical modelling indicates that the first skeletal crystals grew in an open system, from a moving magma. The subsequent linear increase in Ti reflects growth in a partially closed system, with decreasing porosity; the exponential increase in Ti close to melt pockets reflects closed-system growth, leading to dramatic increases in incompatible-element concentrations in the residual melts. We suggest that the corundum aggregates grew in melt/fluid conduits; diffusion modelling implies timescales of days to years before crystallization was terminated by explosive eruption. These processes probably operate in explosive volcanic systems in several tectonic settings.

Distribution of Trace Elements Controlled by Sector and Growth Zonings in Zircon from Feldspathic Pegmatites (Ilmen Mountains, the Southern Urals)

The present study contains the detailed ion microprobe data on trace and rare earth elements distribution in the large zircon crystal about 10 × 6 mm in size with distinct growth and sector zonings from Ilmen Mountains feldspathic pegmatite. The zircon crystal morphology is a combination of a prism {110} and a dipyramid {111}. It is found out that the growth sector of the prism {110} generally contains higher concentrations of Th, U, REE, Y, and Nb and exhibits a more gently sloping HREE distribution pattern and a steeper LREE distribution pattern, in contrast to zircon from the growth sector of the dipyramid {111} development. Such a sector zoning pattern was formed at a late stage in crystal growth, when the prism {110} began to prevail over the dipyramid {111}. The zircon studied displays the growth zoning formed of alternating bands in back-scattered electron (BSE) image: wide dark and thin light bands. The last ones contain elevated Th, U, REE, Y, Nb, and Ti concentrations, Th/U ratio and Ce/Ce*. This growth zoning is most probably due to simultaneous crystallization of other minerals that concentrate trace elements, e.g., apatite and monazite, and the lack of equilibrium between zircon and fluid (melt).

Slow ascent of unusually hot intermediate magmas triggering Strombolian to sub-Plinian eruptions

To assess whether magma ascent rates control the style of volcanic eruption, we have studied the petrography, geochemistry and size distribution of microlites of plagioclase and pyroxene from historical eruptions from Tongariro, Ruapehu and Ngauruhoe volcanoes located in the southern Taupo Volcanic Zone, New Zealand. The studied deposits represent glassy andesitic and dacitic tephra shards from the Mangamate, Mangatawai, Tufa Trig and the Ngauruhoe tephra formations, ranging in age from 11,000 years BP to 1996 AD. Covering a range in eruption styles and sizes from Strombolian to Plinian, these samples provide an excellent opportunity to explore fundamental volcanic processes such as pre-eruptive magma ascent processes. Our quantitative petrographic analysis shows that larger microlites (&gt; 30 µm) display complex growth zoning, and only the smallest crystals (&lt; 30 µm) have formed during magma ascent in the conduit. Using a combination of orthopyroxene geothermometry, plagioclase hygrometry, and MELTS modelling, we show that these microlites nucleated at maximum pressures of 550 MPa (c. 16.5 km) from hot andesitic magmas (1010-1130 ˚C) with low H2O content (0-1.5 wt%). Size distributions of a total of &gt; 60,000 microlites, involving 22 tephras and 99 glass shards, yield concave-up curves, and the slopes of the pyroxene microlite size distributions, in combination with well-constrained orthopyroxene crystal growth rates from one studied tephra, indicate microlite population growth times of ∼3 ± 1 days, irrespective of eruption style. These data imply that microlites form in response to cooling of melts ascending at velocities of &lt; 5 cm s-1 prior to H2O exsolution, which only occurs at &lt; 33 MPa. Maximum magma ascent rates in the upper conduit, calculated using the exsolution of water during final decompression, range between 3 to 12 m s-1, i.e. at least an order of magnitude lower than the hypersonic vent velocities typical of Vulcanian or sub-Plinian eruptions (up to 400 m s-1). This implies that magma ascent from depths of an average of 4 km occurs in dykes, and that vent velocities at the surface are controlled by a reduction of conduit cross-section towards the surface (e.g. dyke transiting to cylindrical conduit).

Determining the speed of intracontinental subduction – preliminary results of zoned garnet geochronology in micaschists from the Schneeberg Complex, Eastern Alps.

&lt;p&gt;In collisional orogens continental crust is subducted to (ultra-)high-pressure (HP/UHP) conditions as constrained by petrologic, tectonic and geophysical observations. These (U)HP rocks are exhumed by an extremely fast process (few Ma) as numerous rocks still preserve their high-pressure metamorphic assemblages, which would not be the case if they had time to re-equilibrate at lower pressure conditions. Despite a wealth of studies on the subduction and exhumation of UHP rocks, the duration of prograde metamorphism during subduction is still not well constrained.&lt;/p&gt;&lt;p&gt;We plan to do Lu-Hf and Sm-Nd geochronology on metamorphic rock samples to date the duration of garnet growth, which represents a major part of prograde metamorphism from the greenschist-facies on. Micaschist samples from the Schneeberg and Radenthein Units in the Eoalpine high-pressure belt (Eastern Alps) will be used for dating as they contain cm- to dm-sized garnets, which experienced only one subduction-exhumation cycle with P-T conditions reaching 600 &amp;#176;C and up to 1 GPa. With dating different parts of big garnet grains we test (1) if it is possible to resolve the duration of garnet growth within single crystals, (2) if both systems, Lu-Hf and Sm-Nd, are needed for better age-constraints, and (3) whether both systems date the same events in the PT-path or give differing information. Additionally we will perform U-Pb geochronology on titanite in order to obtain the age of the first stages of exhumation and on rutile inclusions as well as matrix rutiles to confirm the Eoalpine prograde age with this additional method. Therefore, we will be able to compare the duration of subduction and the timing of initial exhumation in a single sample. We then will constrain the PT-path of the samples that will be dated by pseudosection modeling combined with Zr-in-rutile geothermometer, quartz-in-garnet geobarometer, and carbonaceous material geothermometer. In addition EPMA, &amp;#181;-XRF, LA-ICPMS, and &amp;#181;CT will be used to control if garnets preserved major and trace elemental growth zoning and to provide spatial 3D information on inclusion patterns. With dating different parts of single garnet crystals separately with Lu-Hf and Sm-Nd geochronology, we will add tight time constraints to the PT-path and constrain the duration of garnet growth.&lt;/p&gt;&lt;p&gt;With this contribution we formulate the working hypothesis that prograde subduction together with&amp;#160; exhumation is a fast process. The basis for testing the idea of fast prograde metamorphism is that many geochronological studies propose a prograde duration of &lt; 10 Ma and studies using geospeedometry sometimes propose an even shorter duration, which is the impetus for this investigation.&lt;/p&gt;

Coupled Substitutions of Minor and Trace Elements in Co-Existing Sphalerite and Wurtzite

The nature of couple substitutions of minor and trace element chemistry of expitaxial intergrowths of wurtzite and sphalerite are reported. EPMA and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) analyses display significant differences in the bulk chemistries of the two epitaxial intergrowth samples studied. The sample from the Animas-Chocaya Mine complex of Bolivia is Fe-rich with mean Fe levels of 4.8 wt% for wurztite-2H and 2.3 wt% for the sphalerite component, while the sample from Merelani Hills, Tanzania, is Mn-rich with mean Mn levels in wurztite-4H of 9.1 wt% and for the sphalerite component 7.9 wt% In both samples studied the wurtzite polytype is dominant over sphalerite. LA-ICP-MS line scans across the boundaries between the wurtzite and sphalerite domains within the two samples show significant variation in the trace element chemistries both between and within the two coexisting polytypes. In the Merelani Hills sample the Cu+ + Ga3+ = 2Zn2+ substitution holds across both the wurztite and sphalerite zones, but its levels range from around 1200 ppm of each of Cu and Ga to above 2000 ppm in the sphalerite region. The 2Ag+ + Sn4+ = 3Zn2+ coupled substitution does not occur in the material. In the Animas sample, the Cu+ + Ga3+ = 2Zn2+ substitution does not occur, but the 2(Ag,Cu)+ + Sn4+ = 3Zn2+ substitution holds across the sample despite the obvious growth zoning, although there is considerable variation in the Ag/Cu ratio, with Ag dominant over Cu at the base of the sample and Cu dominant at the top. The levels of 2(Ag,Cu)+ + Sn4+ = 3Zn2+ vary greatly across the sample from around 200 ppm to 8000 ppm Sn, but the higher values occur in the sphalerite bands.