Manipulation by external pressure of the optical response of 2D Metal Halide Perovskites (MHPs) is a fascinating route to tune their properties and promote the emergence of novel features. We investigate here DA(2)PbI(4) and DA(2)GeI(4) (DA = decylammonium) perovskites in the pressure range up to similar to 12 GPa by X-ray powder diffraction, absorption, and photoluminescence spectroscopy. Although the two systems share a similar structural evolution with pressure, the optical properties are rather different and influenced by Pb or Ge. DA(2)PbI(4) shows a progressive red shift from 2.28 eV (P = 0 GPa) to 1.64 eV at 11.5 GPa, with a narrow PL emission, whereas DA(2)GeI(4), changes from a non-PL system at ambient pressure to a clear broadband emitter centered around 730 nmwith an intensity maximum at about 3.7GPa. These results unveil the role of the central atom on the nature of emission under pressure in 2D MHPs containing a long alkyl chain.

The strongest evidence to support the classical plume hypothesis comes from seismic imaging of the mantle beneath hot spots. However, imaging results are often ambiguous and it is questionable whether narrow plume tails can be detected by present-day seismological techniques. Here we carry out synthetic tomography experiments based on spectral element method simulations of seismic waves with period T > 10s propagating through geodynamically derived plume structures. We vary the source-receiver geometry in order to explore the conditions under which lower mantle plume tails may be detected seismically. We determine that wide-aperture (4,000-6,000km) networks with dense station coverage (<100-200km station spacing) are necessary to image narrow (<500km wide) thermal plume tails. We find that if uncertainties on traveltime measurements exceed delay times imparted by plume tails (typically <1s), the plume tails are concealed in seismic images. Vertically propagating SKS waves enhance plume tail recovery but lack vertical resolution in regions that are not independently constrained by direct S paths. We demonstrate how vertical smearing of an upper mantle low-velocity anomaly can appear as a plume originating in the deep mantle. Our results are useful for interpreting previous plume imaging experiments and guide the design of future experiments.

Metamorphic dehydration reactions in a subducting slab release fluids that trigger arc volcanism and are thought to be responsible for intermediate-depth seismicity. The fluid flow from the source is controlled by buoyancy and compaction pressure which is modified by viscous and elastic effects. In this paper, we investigate how fluid migrates in viscoelastic slab by using 2-D and 3-D numerical models based on a theory of two-phase flow. When bulk viscosity is sufficiently low, viscosity plays a dominant role and fluid goes up almost vertically soon after its release producing porosity waves. When a higher bulk viscosity is assumed, a large amount of fluid is trapped in a high porosity region produced by the fluid source and migrates along the source except for a case where the ratio of permeability (K) to fluid viscosity () is relatively low. We also find that porosity increases in the deeper part of the fluid source in cases with intermediate and low values of K/. In 3-D, fluid focusing occurs where the slab bends away from the trench causing a local increase in porosity and compaction pressure. These findings may help us explain several types of observations in subduction zones including slow earthquakes at the plate interface, low seismic wave velocities in the oceanic crust, double seismic zones in the slab, and shallow subduction angle at the bend of the slab.

The scattering of PKP waves in the lower mantle produces isolated signals before the PKIKP phase. We explore whether these so-called PKIKP precursors can be related to wave scattering off mid ocean ridge basalt (MORB) fragments that have been advected in the deep mantle throughout geologic time. We construct seismic models of small-scale (>20 km) heterogeneity in the lower mantle informed by mantle mixing simulations from Brandenburg et al. (2008) and generate PKIKP precursors using 3D, axisymmetric waveform simulations up to 0.75 Hz. We consider two end-member geodynamic models with fundamentally different distributions of MORB in the lower mantle. Our results suggest that the accumulation of MORB at the base of the mantle is a viable hypothesis for the origin of PKP scattering. We find that the strength of the PKIKP precursor amplitudes is consistent with P wave speed heterogeneity of 0.1-0.2%, as reported previously. The radial distribution of MORE has a profound effect on the strength of PKIKP precursors. Simulation of PLUMP precursors for models with an increasing MORB concentration in the lower-most 500 km of the mantle appears to reproduce most accurately the strength of PKIKP precursors in Global Seismic Network waveforms. These models assume that MORB has an excess density of at least 7%. Additional simulations of more complex geodynamic models will better constrain the geodynamic conditions to explain the significant variability of PKP scattering strength. (C) 2017 Elsevier B.V. All rights reserved.

The oceanic crust that enters a subduction zone is generally recycled to great depth. In rare and punctuated episodes, however, blueschists and eclogites derived from subducted oceanic crust are exhumed. Compilations of the maximum pressure-temperature conditions in exhumed rocks indicate significantly warmer conditions than those predicted by thermal models. This could be due to preferential exhumation of rocks from hotter conditions that promote greater fluid productivity, mobility, and buoyancy. Alternatively, the models might underestimate the forearc temperatures by neglecting certain heat sources. We compare two sets of global subduction zone thermal models to the rock record. We find that the addition of reasonable amounts of shear heating leads to less than 50 degrees C heating of the oceanic crust compared to models that exclude this heat source. Models for young oceanic lithosphere tend to agree well with the rock record. We test the hypothesis that certain heat sources may be missing in the models by constructing a global set of models that have high arbitrary heat sources in the forearc. Models that satisfy the rock record in this manner, however, fail to satisfy independent geophysical and geochemical observations. These combined tests show that the average exhumed mafic rock record is systematically warmer than the average thermal structure of mature modern subduction zones. We infer that typical blueschists and eclogites were exhumed preferentially under relatively warm conditions that occurred due to the subduction of young oceanic lithosphere or during the warmer initial stages of subduction.

The formation and segregation of oceanic and continental crust from the mantle, and its return to the mantle via subduction and/or delamination, leads to the development of distinct geochemical reservoirs in the terrestrial mantle. Fundamental questions remain regarding the location, nature, and residence time of these reservoirs, as well as the respective roles of oceanic and continental crust in the development of the mantle's geochemical endmembers. The Lu-Hf and Sm-Nd isotope systems behave similarly in magmatic systems and together form the terrestrial mantle Hf-Nd isotopic array. Here we combine a geodynamic model of mantle convection with isotope and trace element (TE) geochemistry to investigate the evolution of the Hf-Nd mantle array. This study examines the sensitivity to: TE partition coefficients used in the formation of oceanic crust; density contrasts between subducting oceanic crust and the mantle; and the formation and recycling of continental crust. We show that the fractionation between the parent (Lu and Sm) and daughter (Hf and Nd) species needs to be higher than is indicated by partition coefficients determined from the present-day melting environment. This is consistent with the suggestion of deeper mantle melting earlier in Earth history and an increased role for residual garnet. Subduction and accumulation of dense oceanic crust produces a large mass of incompatible TE enriched material in the deep mantle. This deep mantle enrichment appears to play a more significant role than the extraction and recycling of continental crust in developing the Hf and Nd isotope and TE compositions of the mid-ocean ridge mantle source. The corollary of this result is that the formation of the continental crust plays a secondary role, contrary to the currently accepted paradigm. Nevertheless, the inclusion of continental crust formation and recycling produces a broader model mantle array, which better reproduces the spread in the natural data set. This model also produces the Hf and Nd isotope and TE compositions of the upper mantle and continental crust, as well as deep mantle compositions similar to those of plume-fed ocean island basalts. Our model is consistent with continental growth models based on the Lu-Hf isotopic composition of zircon, which suggest that 50-70% of the present-day mass of the continental crust is produced prior to 3 Ga, and that the recycling of continental crust becomes more prevalent after this time. (C) 2019 Elsevier B.V. All rights reserved.

Sand-shale melanges from the Kodiak accretionary complex and Shimanto belt of Japan record deformation during underthrusting along a paleosubduction interface in the range 150 to 350 degrees C. We use observations from these melanges to construct a simple kinetic model that estimates the maximum time required to seal a single fracture as a measure of the rate of fault zone healing. Crack sealing involves diffusive redistribution of Si from mudstones with scaly fabric to undersaturated fluid-filled cracks in sandstone blocks. Two driving forces are considered for the chemical potential gradient that drives crack sealing: (1) a transient drop in fluid pressure P-f, and (2) a difference in mean stress between scaly slip surfaces in mudstones and cracks in stronger sandstone blocks. Sealing times are more sensitive to mean stress than P-f, with up to four orders of magnitude faster sealing. Sealing durations are dependent on crack spacing, silica diffusion kinetics, and magnitude of the strength contrast between block and matrix, each of which is loosely constrained for conditions relevant to the seismogenic zone. We apply the model to three active subduction zones and find that sealing rates are fastest along Cascadia and several orders of magnitude slower for a given depth along Nicaragua and Tohoku slab-top geotherms. The model provides (1) a framework for geochemical processes that influence subduction mechanics via crack sealing and shear fabric development and (2) demonstration that kinetically driven mass redistribution during the interseismic period is a plausible mechanism for creating asperities along smooth, sediment-dominated convergent margins.

This study investigates the variability of spatio-temporal microseismicity clustering and the occurrence of mutual triggering of events along the subduction interface in south-eastern Aegean as indication for fluid flow along and above the plate interface. We quantify spatial, temporal and spatio-temporal microseismicity clustering from the outer to the inner forearc and at intermediate depths. Waveform similarity indicates a decreasing of spatially clustered events from the outer and central towards the inner forearc and at intermediate depths. Highly similar events (cross-correlation >0.9), used as proxy for spatial clustering, decrease from the outer (30.2%) and central forearc (34.9%), towards the inner forearc (205%) and at intermediate depth (6.9%). Such highly similar events show increasing median inter-event times from the outer and central towards the inner forearc and at intermediate depth: 0.35, 0.34, 16.45, and 70 days, respectively. The Epidemic-Type-Aftershock-Sequences (ETAS) model, employed to investigate microseismicity temporal clustering, indicates an increase of the percentage of independent events from the outer (32%) and central (46%) forearc, to the inner forearc (93%) and at intermediate depth (93%). Hence, ETAS results suggest that mutual triggering of events is significant in the outer and central forearc, and it is almost absent in the inner forearc and at intermediate depths. Autocorrelation analysis, investigating spatio-temporal clustering, shows the tendency of earthquakes to occur close in space and time in the outer and central forearc, while in the inner forearc, and especially at intermediate depth, earthquakes are more homogeneously and randomly distributed. Combining the results from spatial, temporal and spatiotemporal analysis, we suggest that the different spatio-temporal patterns hint at systematic variations in the presence of migrating fluids on active faults close to failure. Triggering of seismicity is significant in the outer and central forearc, indicating fluid flow from the subduction interface, and it is diminishing towards the inner forearc. At intermediate depths, the nearly complete absence of mutual triggering of earthquakes indicates that there is little evidence for migration of fluids on active faults close to failure. Because intermediate depth seismicity in the Hellenic subduction zone occurs at P-T conditions where dehydration reactions are expected, fluids released by dehydration reactions within the slab are very likely migrating directly into the overlying mantle without triggering earthquakes. (C) 2019 Elsevier B.V. All rights reserved.

Mantle tomography reveals the existence of two large low-shear-velocity provinces (LLSVPs) at the base of the mantle. We examine here the hypothesis that they are piles of oceanic crust that have steadily accumulated and warmed over billions of years. We use existing global geodynamic models in which dense oceanic crust forms at divergent plate boundaries and subducts at convergent ones. The model suite covers the predicted density range for oceanic crust over lower mantle conditions. To meaningfully compare our geodynamic models to tomographic structures, we convert them into models of seismic wavespeed and explicitly account for the limited resolving power of tomography. Our results demonstrate that long-term recycling of dense oceanic crust naturally leads to the formation of thermochemical piles with seismic characteristics similar to the LLSVPs. The extent to which oceanic crust contributes to the LLSVPs depends upon its density in the lower mantle for which accurate data is lacking. We find that the LLSVPs are not composed solely of oceanic crust. Rather, they are basalt rich at their base (bottom 100-200 km) and grade into peridotite toward their sides and top with the strength of their seismic signature arising from the dominant role of temperature. We conclude that recycling of oceanic crust, if sufficiently dense, has a strong influence on the thermal and chemical evolution of Earth's mantle.

Molnar and England (1990, ) introduced equations using a semianalytical approach that approximate the thermal structure of the forearc regions in subduction zones. A detailed new comparison with high-resolution finite element models shows that the original equations provide robust predictions and can be improved by a few modifications that follow from the theoretical derivation. The updated approximate equations are shown to be quite accurate for a straight-dipping slab that is warmed by heat flowing from its base and by shear heating at its top. The approximation of radiogenic heating in the crust of the overriding plate is less accurate but the overall effect of this heating mode is small. It is shown that the previous and updated approximate equations become increasingly inaccurate with decreasing thermal parameter and increasing variability of slab dip. It is also shown that the approximate equations cannot be extrapolated accurately past the brittle-ductile transition. Conclusions in a recent paper (Kohn et al., 2018, ) that modest amount of shear heating can explain the thermal conditions of past subduction from the exhumed metamorphic rock record are invalid due to a number of compounding errors in the application of the Molnar and England (1990, ) equations past the brittle-ductile transition. The use of the improved approximate equations is highly recommended provided their limitations are taken into account. For subduction zones with variable dip and/or low thermal parameter finite element modeling is recommended.