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 Earth's 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.

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.

Massive methane fluxing from magma-sediment interaction in the end-Triassic Central Atlantic Magmatic Province.

Exceptional magmatic events coincided with the largest mass extinctions throughout Earth's history. Extensive degassing from organic-rich sediments intruded by magmas is a possible driver of the catastrophic environmental changes, which triggered the biotic crises. One of Earth's largest magmatic events is represented by the Central Atlantic Magmatic Province, which was synchronous with the end-Triassic mass extinction. Here, we show direct evidence for the presence in basaltic magmas of methane, generated or remobilized from the host sedimentary sequence during the emplacement of this Large Igneous Province. Abundant methane-rich fluid inclusions were entrapped within quartz at the end of magmatic crystallization in voluminous (about 1.0 × 106 km3) intrusions in Brazilian Amazonia, indicating a massive (about 7.2 × 103 Gt) fluxing of methane. These micrometre-sized imperfections in quartz crystals attest an extensive release of methane from magma-sediment interaction, which likely contributed to the global climate changes responsible for the end-Triassic mass extinction.

29Si solid state NMR and Ti K-edge XAFS pre-edge spectroscopy reveal complex behavior of Ti in silicate melts.

An understanding of the mechanisms of Ti is incorporation into silicate glasses and melts is critical for the field of petrology. Trace-element thermobarometry, high-field-strength element partitioning, and the physical properties of magmas are all be influenced by Ti incorporation into glasses and changes therein in response to changes in composition and temperature. In this study, we combine 29Si solid state NMR and Ti K-edge XAFS spectroscopy to investigate how Ti is incorporated into quenched Na-silicate glasses, and the influence of Ti on the structure of silicate species in these glasses. 29Si NMR shows that in both Ti-bearing Na2O•4SiO2 (NS4) and Na2O•8SiO2 (NS8) glasses, increasing the amount of Ti in the melt results in a shift of Si Q4 peak in the 29Si NMR spectra reflecting Ti nearest neighbors for Si in Q4 speciation. The Ti XAFS results from NS8 glass indicate that Ti is primarily incorporated in [5]-fold coordination. At higher Ti content, there is a shift of the XAFS pre-edge feature suggesting mixing of [4]-fold Ti into the spectra. Combined, the 29Si NMR and XAFS pre-edge data are consistent with Ti incorporation as isolated [5]Ti atoms and the formation of [5]Ti clusters at relatively low Ti concentrations, with no evidence for Ti-Na interactions as suggested by previous studies. As the Ti content increases, the Ti atoms begin to occupy 4-fold coordinated sites interacting primarily with Si in Q4 speciation (no significant Na-[4] Ti bonding). The internal consistency of these two techniques provides a uniquely complete snapshot of the complexity of Ti incorporation in silicate melts and underlies the importance of understanding Ti incorporation mechanisms in natural magmatic systems.

Possible Biosphere-Lithosphere Interactions Preserved in Igneous Zircon and Implications for Hadean Earth.

Granitoids are silicic rocks that make up the majority of the continental crust, but different models arise for the origins of these rocks. One classification scheme defines different granitoid types on the basis of materials involved in the melting/crystallization process. In this end-member case, granitoids may be derived from melting of a preexisting igneous rock, while other granitoids, by contrast, are formed or influenced by melting of buried sedimentary material. In the latter case, assimilated sedimentary material altered by chemical processes occurring at the near surface of Earth-including biological activity-could influence magma chemical properties. Here, we apply a redox-sensitive calibration based on the incorporation of Ce into zircon crystals found in these two rock types, termed sedimentary-type (S-type) and igneous-type (I-type) granitoids. The ∼400 Ma Lachlan Fold Belt rocks of southeastern Australia were chosen for investigation here; these rocks have been a key target used to describe and explore granitoid genesis for close to 50 years. We observe that zircons found in S-type granitoids formed under more reducing conditions than those formed from I-type granitoids from the same terrain. This observation, while reflecting 9 granitoids and 289 analyses of zircons from a region where over 400 different plutons have been identified, is consistent with the incorporation of (reduced) organic matter in the former and highlights one possible manner in which life may modify the composition of igneous minerals. The chemical properties of rocks or igneous minerals may extend the search for ancient biological activity to the earliest period of known igneous activity, which dates back to ∼4.4 billion years ago. If organic matter was incorporated into Hadean sediments that were buried and melted, then these biological remnants could imprint a chemical signature within the subsequent melt and the resulting crystal assemblage, including zircon.

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.