Michael R. Ackerson

Structure and Properties of Silica Glass Densified in Cold Compression and Hot Compression.

Silica glass has been shown in numerous studies to possess significant capacity for permanent densification under pressure at different temperatures to form high density amorphous (HDA) silica. However, it is unknown to what extent the processes leading to irreversible densification of silica glass in cold-compression at room temperature and in hot-compression (e.g., near glass transition temperature) are common in nature. In this work, a hot-compression technique was used to quench silica glass from high temperature (1100 °C) and high pressure (up to 8 GPa) conditions, which leads to density increase of ~25% and Young’s modulus increase of ~71% relative to that of pristine silica glass at ambient conditions. Our experiments and molecular dynamics (MD) simulations provide solid evidences that the intermediate-range order of the hot-compressed HDA silica is distinct from that of the counterpart cold-compressed at room temperature. This explains the much higher thermal and mechanical stability of the former than the latter upon heating and compression as revealed in our in-situ Brillouin light scattering (BLS) experiments. Our studies demonstrate the limitation of the resulting density as a structural indicator of polyamorphism, and point out the importance of temperature during compression in order to fundamentally understand HDA silica.

Trace elements in quartz shed light on sediment provenance

Quartz is one of the most common minerals on the surface of the earth, and is a primary rock-forming mineral across the rock cycle. These two factors make quartz an obvious target for sediment provenance studies. Observations from experimental and natural samples demonstrate that the trace element content of quartz often reflects the conditions of quartz formation. When quartz is weathered from its primary crystallization setting (i.e., quartz from a granitoid) it can retain many chemical signatures of formation throughout the sedimentation processes. These geochemical signatures can be used to understand the primary source of individual quartz grains within a sediment. Here we present a case study from the Bega River catchment to demonstrate that quartz grains in sediments at the mouth of the Bega River are sourced from granitoids within the drainage basin. Data presented here also indicate that a portion of the beach sediment is also derived from either (i) sedimentary rocks within the basin or; (ii) mixing with sediments at the mouth of the river. The Bega River catchment was selected for this study because it is both small and has a well-constrained bedrock lithology, making it an ideal location to test the utility of this provenance technique. However, quartz trace element provenance has broad applications to modern and ancient sediments and can be used in lieu of, or in conjunction with, other provenance techniques to elucidate sediment transport through time.

Experimental investigation into the substitution mechanisms and solubility of Ti in garnet

Abstract Garnet is a common and important mineral in metamorphic systems, but the mechanisms by which it incorporates Ti—one of the major elements in the crust—are not well constrained. This study draws upon garnets synthesized at a range of temperatures and pressures to understand Ti solubility and the substitution mechanisms that govern its incorporation into garnet at eclogite and granulite facies conditions. Garnets from these synthesis experiments can incorporate up to several wt% TiO2. Comparison of Ti content with deficits in Al and Si in garnet indicates that Ti is incorporated by at least two substitution mechanisms (VITi4+ + VIM2+ ↔ 2VIAl3+, and VITi4+ + IVAl3+ ↔ VIAl3+ + IVSi4+). Increasing Ti solubility is correlated with increasing Ca and Fe/Mg ratios in garnet, clinopyroxene and melt. The complexity of the substitution mechanisms involved in Ti solubility in garnet makes practical Ti-in- garnet thermobarometry infeasible at present. However, a model fit to Ti partitioning between garnet and melt can be used to predict melt compositions in high-grade metamorphic systems. Additionally, the solubility and substitution mechanisms described here can help explain the presence of crystallographically aligned rutile needles in high-grade metamorphic systems.

Low-temperature crystallization of granites and the implications for crustal magmatism

The structure and composition of granites provide clues to the nature of silicic volcanism, the formation of continents, and the rheological and thermal properties of the Earths upper crust as far back as the Hadean eon during the nascent stages of the planet’s formation1–4. The temperature of granite crystallization underpins our thinking about many of these phenomena, but evidence is emerging that this temperature may not be well constrained. The prevailing paradigm holds that granitic mineral assemblages crystallize entirely at or above about 650–700 degrees Celsius5–7. The granitoids of the Tuolumne Intrusive Suite in California tell a different story. Here we show that quartz crystals in Tuolumne samples record crystallization temperatures of 474–561 degrees Celsius. Titanium-in-quartz thermobarometry and diffusion modelling of titanium concentrations in quartz indicate that a sizeable proportion of the mineral assemblage of granitic rocks (for example, more than 80 per cent of the quartz) crystallizes about 100–200 degrees Celsius below the accepted solidus. This has widespread implications. Traditional models of magma formation require high-temperature magma bodies, but new data8,9 suggest that volcanic rocks spend most of their existence at low temperatures; because granites are the intrusive complements of volcanic rocks, our downward revision of granite crystallization temperatures supports the observations of cold magma storage. It also affects the link between volcanoes, ore deposits and granites: ore bodies are fed by the release of fluids from granites below them in the crustal column; thus, if granitic fluids are hundreds of degrees cooler than previously thought, this has implications for research on porphyry ore deposits. Geophysical interpretations of the thermal structure of the crust and the temperature of active magmatic systems will also be affected.Thermobarometry and diffusion modelling in quartz crystals show that some granites may crystallize at much lower temperatures than we had thought, possibly explaining observations of cold magma storage.

Thermally induced amorphous to amorphous transition in hot-compressed silica glass

In situ Raman and Brillouin light scattering techniques were used to study thermally induced high-density amorphous (HDA) to low-density amorphous (LDA) transition in silica glass densified in hot compression (up to 8 GPa at 1100 °C). Hot-compressed silica samples are shown to retain structural and mechanical stability through 600 °C or greater, with reduced sensitivity in elastic response to temperature as compared with pristine silica glass. Given sufficient thermal energy to overcome the energy barrier, the compacted structure of the HDA silica reverts back to the LDA state. The onset temperature for the HDA to LDA transition depends on the degree of densification during hot compression, commencing at lower temperatures for samples with higher density, but all finishing within a temperature range of 250-300 °C. Our studies show that the HDA to LDA transition at high temperatures in hot-compressed samples is different from the gradual changes starting from room temperature in cold-compressed silica glass, indicating greater structural homogeneity achieved by hot compression. Furthermore, the structure and properties of hot-compressed silica glass change continuously during the thermally induced HDA to LDA transition, in contrast to the abrupt and first-order-like polyamorphic transitions in amorphous ice. Different HDA to LDA transition mechanisms in amorphous silica and amorphous ice are explained by their different energy landscapes.

XAFS spectroscopic study of Ti coordination in garnet

Abstract Titanium can be incorporated either tetrahedrally (IVTi) or octahedrally (VITi) in most silicate minerals. Ti K-edge X-ray absorption fine structure (XAFS) spectroscopy enables observation of Ti coordination in minerals and melts. In this study, XAFS is used to determine the coordination of Ti in synthetic and natural garnets. Garnets grown synthetically at eclogite- and granulite-facies conditions can contain several wt% TiO2, most of which is incorporated as VITi. This observation aligns with major element trends in these garnets. In natural garnets grown at lower temperatures and pressures, on the other hand, Ti is observed to occupy both the octahedral and tetrahedral sites in garnet—in some cases Ti is almost entirely fourfold coordinated. Combined with previous research (see Ackerson et al. 2017, this issue) on substitution mechanisms for VITi, the results of this study demonstrate that Ti is incorporated on two crystallographic sites in garnet by at least three primary substitution mechanisms. In both natural and synthetic garnets, there is a discernible increase in VITi content in garnet with increasing temperature and pressure, suggesting a significant role for these two parameters in determining Ti solubility. However, a continuous increase in VITi with increasing grossular content also suggests that the Ca content of the garnet plays a critical role.