Biominerals typically form within localized volumes, affording organisms great control over the mineralization process. The influence of such confinement on crystallization is studied here by precipitating CaCO3 within the confines of an annular wedge, formed around the contact point of two crossed half‐cylinders. The cylinders are functionalized with self‐assembled monolayers of mercaptohexadecanoic acid on gold. This configuration enables a systematic study of the effects of confinement since the surface separation increases continuously from zero at the contact point to macroscopic (mm) separations. While oriented rhombohedral calcite crystals form at large (>10 µm) separations, particles with irregular morphologies and partial crystallinity are observed as the surface separation approaches the dimensions of the unconfined crystals (5–10 µm). Further increase in the confinement has a significant effect on the crystallization process with flattened amorphous CaCO3 (ACC) particles being formed at micrometer separations. These ACC particles show remarkable stability when maintained within the wedge but rapidly crystallize on separation of the cylinders. A comparison of bulk and surface free‐energy terms shows that ACC cannot be thermodynamically stable at these large separations, and the stability is attributed to kinetic factors. This study therefore shows that the environment in which minerals form can have a significant effect on their stability and demonstrates that ACC can be stabilized with respect to the crystalline polymorphs of CaCO3 by confinement alone. That ACC was stabilized at such large (micrometer) separations is striking, and demonstrates the versatility of this strategy, and its potential value in biological systems.

Silicic volcanic rocks are associated with most, if not all, continental ×ood basalt provinces and volcanic rifted margins, where they can form substantial parts of the eruptive stratigraphy and have eruptive volumes > 10 4 km 3 . Poor preservation of silicic volcanic rocks following kilometer-scale uplift and denudation of the volcanic rifted margins, however, can result in only deeper level structural features being exposed (i.e., dike swarms, major intrusions, and deeply subsided intracaldera µlls; e.g., North Atlantic igneous province). The role of silicic magmatism in the evolution of a large igneous province and rifted margin may therefore be largely overlooked.There are silicic-dominated igneous provinces that have extrusive volumes comparable to those of maµc large igneous provinces (> 10 6 km 3 ), but that have low proportions of basalt expressed at the surface. Some silicic large igneous provinces are associated with intraplate magmatism and continental breakup (e.g., Jurassic Chon Aike province of South America, Early Cretaceous eastern Australian margin), whereas others are tectonically and geochemically associated with backarc environments (e.g., Sierra Madre Occidental). Silicic volcanic rocks formed in these two environments are similar in terms of total eruptive volumes, dominant lithologies, and rhyolite geochemistry, but show fundamental differences in tectonic setting and basalt geochemistry.Large-volume ignimbrites are the dominant silicic volcanic rock type of continental ×ood basalt and silicic large igneous provinces. Individual silicic eruptive units can have thicknesses, areal extents, and volumes that are comparable to, or exceed, 97 *

No abstract

In this work, we studied the heterogeneous nucleation and growth of CaCO(3) within regular arrays of picoliter droplets created on patterned self-assembled monolayers (SAMs). The SAMs provide well-defined substrates that offer control over CaCO(3) nucleation, and we used these impurity-free droplet arrays to study crystal growth in spatially and chemically controlled, finite-reservoir environments. The results demonstrate a number of remarkable features of precipitation within these confined volumes. CaCO(3) crystallization proceeds significantly more slowly in the droplets than in the bulk, allowing the mechanism of crystallization, which progresses via amorphous calcium carbonate, to be easily observed. In addition, the precipitation reaction terminates at an earlier stage than in the bulk solution, revealing intermediate growth forms. Confinement can therefore be used as a straightforward method for studying the mechanisms of crystallization on a substrate without the requirement for specialized analytical techniques. The results are also of significance to biomineralization processes, where crystallization typically occurs in confinement and in association with organic matrices, and it is envisaged that the method is applicable to many crystallizing systems.

Contrary to general belief, not all large igneous provinces (LIPs) are characterised by rocks of basaltic composition. Silicicdominated LIPs, such as the Whitsunday Volcanic Province of NE Australia, are being increasingly recognised in the rock record. These silicic LIPs are consistent in being: (1) volumetrically dominated by ignimbrite; (2) active over prolonged periods (40-50 m.y.), based on available age data; and (3) spatially and temporally associated with plate break-up. This silicicdominated LIP, related to the break-up of eastern continental Gondwana, is also significant for being the source of Ͼ 1:4 × 10 6 km 3 of coeval volcanogenic sediment preserved in adjacent sedimentary basins of eastern Australia. The Whitsunday Volcanic Province is volumetrically dominated by medium-to high-grade, dacitic to rhyolitic lithic ignimbrites. Individual ignimbrite units are commonly between 10 and 100 m thick, and the ignimbrite-dominated sequences exceed 1 km in thickness. Coarse lithic lag breccias containing clasts up to 6 m diameter are associated with the ignimbrites in proximal sections. Pyroclastic surge and fallout deposits, subordinate basaltic to rhyolitic lavas, phreatomagmatic deposits, and locally significant thicknesses of coarse-grained volcanogenic conglomerate and sandstone are interbedded with the ignimbrites. The volcanic sequences are intruded by gabbro/dolerite to rhyolite dykes (up to 50 m in width), sills and comagmatic granite. Dyke orientations are primarily from NW to NNE.The volcanic sequences are characterised by the interstratification of proximal/near-vent lithofacies such as rhyolite domes and lavas, and basaltic agglomerate, with medial to distal facies of ignimbrite. The burial of these near-vent lithofacies by ignimbrites, coupled with the paucity of mass wastage products such as debris-flow deposits indicates a low-relief depositional environment. Furthermore, the volcanic succession records a temporal change in: (1) eruptive styles; (2) the nature of source vents; and (3) erupted compositions. An early explosive dacitic pyroclastic phase was succeeded by a later mixed pyroclasticeffusive phase producing an essentially bimodal suite of lavas and rhyolitic ignimbrite. volcanic lithofacies, the volcanic sequences are interpreted to record the evolution of a multiple vent, low-relief volcanic region, dominated by several large caldera centres. ᭧