A switch from horizontal compression to vertical extension in the Vrancea slab explained by the volume reduction of serpentine dehydration

The Vrancea slab, Romania, is a subducted remnant of the Tethyan lithosphere characterized by a significant intermediate-depth seismicity (60–170 km). A recent study showed a correlation between this seismicity and major dehydration reactions, involving serpentine minerals up to 130 km depth, and high-pressure hydrated talc deeper. Here we investigate the potential link between the triggering mechanisms and the retrieved focal mechanisms of 940 earthquakes, which allows interpreting the depth distribution of the stress field. We observe a switch from horizontal compression to vertical extension between 100 and 130 km depth, where the Clapeyron slope of serpentine dehydration is negative. The negative volume change within dehydrating serpentinized faults, expected mostly sub-horizontal in the verticalized slab, could well explain the vertical extension recorded by the intermediate-depth seismicity. This apparent slab pull is accompanied with a rotation of the main compressive stress, which could favour slab detachments in active subduction zones

Petrophysical properties across scales and compositions

The scales at which observations from geophysical imaging are made are orders of magnitude larger than those made in field-based studies of fossil subduction and collision zones. Even more so, the determination of petrophysical properties of rocks is typically based on millimeter to centimeter-scale samples, and the so-obtained information is then used to inform large-scale geophysical imaging studies. Information on how such properties can be up-scaled to geophysically relevant scales is rare, underlining the need to combine petrophysical properties with structural data, obtained from relevant field analogues. We provide results from three field analogues; (1) Tenda massif, Corsica, (2) Monte Mucrone, Sesia Zone, western Alps, and (3) Holsnøy, Lindås nappe, Scandinavian Caledonides. The bulk rock compositions cover a gradient from felsic (1-2) to mafic (3), as would be expected in the upper and lower continental crust, respectively. Petrophysical properties (P and S wave velocities and their ratios and anisotropies) were determined by direct measurement (ultrasonic pulse transmission technique) and calculated (based on texture data from neutron diffraction measurements). The data set is then used for numerical modeling (finite element method) of meter to kilometer-scale structural associations as mapped in the field (3). The obtained results show that high-pressure metamorphism of mafic rocks results in significant increase in both P and S wave velocities, that in principle would generate a sufficient impedance contrast to be imaged by seismic methods. While structures observed in the field are typically below the scale of geophysical imaging techniques, our considerations of bulk petrophysical properties indicate that significant anisotropy may still be detectable on the kilometer scale. On the other hand, the increase of P and S wave velocities of felsic rocks during high pressure metamorphism is much smaller, however, as such compositions have a higher potential to form rocks with high mica contents, they display a large variability in seismic anisotropy, hinting at the potential to link relatively low seismic velocities, combined with high anisotropy to fluid intake during metamorphism

Large-scale synthesis of mixed valence K3_3[Fe2_2S4_4] with high dielectric and ferrimagnetic characteristics

High yields of phase-pure K(3)[Fe(2)S(4)] are obtained using a fast, straight-forward, and efficient synthetic technique starting from the binary precursors K(2)S and FeS, and elemental sulphur. The compound indicates soft ferrimagnetic characteristics with magnetization of 15.23 A m(2) kg(−1) at 300 K due to the mixed valence of Fe(II)/Fe(III). Sintering at different temperatures allows the manipulation of the microstructure as well as the ratio of grains to grain boundaries. This results in a variation of dielectric and impedance properties. Samples sintered at 923 K demonstrate a dielectric constant (κ) of around 1750 at 1 kHz, which lies within the range of well-known high-κ dielectric materials, and an ionic conductivity of 4 × 10(−2) mS cm(−1) at room temperature. The compound has an optical band gap of around 2.0 eV, in agreement with tailored quantum chemical calculations. These results highlight its potential as a material comprising non-toxic and abundant elements for electronic and magnetic applications

Large Exchange Bias, High Dielectric Constant, and Outstanding Ionic Conductivity in a Single‐Phase Spin Glass

The multigram synthesis of K2[Fe3S4] starting from K2S and FeS is presented, and its electronic and magnetic properties are investigated. The title compound obtains a defect variant of the K[Fe2Se2] structure type. Dielectric and impedance measurements indicate a dielectric constant of 1120 at 1 kHz and an outstanding ionic conductivity of 24.37 mS cm–1 at 295 K, which is in the range of the highest reported value for potential solid‐state electrolytes for potassium‐ion batteries. The Seebeck coefficient of the n‐type conductor amounts to −60 µV K−1 at 973 K. The mismatch of the measured electrical resistivity and the predicted metal‐like band structure by periodic quantum chemical calculations indicates Mott insulating behavior. Magnetometry demonstrates temperature‐dependent, large exchange bias fields of 35 mT, as a consequence of the coexistence of spin glass and antiferromagnetic orderings due to the iron vacancies in the lattice. In addition, the decreasing training effects of 34% in the exchange bias are identified at temperatures lower than 20 K. These results demonstrate the critical role of iron vacancies in tuning the electronic and magnetic properties and a multifunctional material from abundant and accessible elements

Formation of Olivine Veins by Reactive Fluid Flow in a Dehydrating Serpentinite

Many exposed high-pressure meta-serpentinites comprise a channelized network of olivine-rich veins that formed during dehydration at depth and allowed the fluid to escape from the dehydrating rock. While previous studies have shown that chemical heterogeneities in rocks can control the formation of olivine-enriched vein-like interconnected porosity networks on the sub-millimeter scale, it is still unclear how these networks evolve toward larger scales and develop nearly pure olivine veins. To explore this, we study the effect of reactive fluid flow on a dehydrating serpentinite. We use thermodynamic equilibrium calculations to investigate the effect of variations in the bulk silica content in serpentinites on the dehydration reaction of antigorite + brucite = olivine + fluid and the silica content of this fluid phase. Further, we develop a numerical model that combines the effects of intrinsic chemical heterogeneities with reactive transport with dissolved silica as metasomatic agent. Our model shows how reactive transport can lead to vein widening and olivine enrichment within a vein in an antigorite-rich matrix, such as observed in the veins of the Erro Tobbio meta-serpentinites. This is a critical step in the evolution toward larger-scale vein systems and in the evolution of dynamic porosity, as this step helps account for the chemical feedback between the dehydrating rock and the liberated fluid

Reactive fluid flow guided by grain-scale equilibrium reactions during eclogitization of dry crustal rocks

Fluid flow in crystalline rocks in the absence of fractures or ductile shear zones dominantly occurs by grain boundary diffusion, as it is faster than volume diffusion. It is, however, unclear how reactive fluid flow is guided through such pathways. We present a microstructural, mineral chemical, and thermodynamic analysis of a static fluid-driven reaction from dry granulite to ‘wet’ eclogite. Fluid infiltration resulted in re-equilibration at eclogite-facies conditions, indicating that the granulitic protolith was out of equilibrium, but unable to adjust to changing P–T conditions. The transformation occurred in three steps: (1) initial hydration along plagioclase grain boundaries, (2) complete breakdown of plagioclase and hydration along phase boundaries between plagioclase and garnet/clinopyroxene, and (3) re-equilibration of the rock to an eclogite-facies mineral assemblage. Thermodynamic modelling of local compositions reveals that this reaction sequence is proportional to the local decrease of the Gibbs free energy calculated for ‘dry’ and ‘wet’ cases. These energy differences result in increased net reaction rates and the reactions that result in the largest decrease of the Gibbs free energy occur first. In addition, these reactions result in a local volume decrease leading to porosity formation; i.e., pathways for new fluid to enter the reaction site thus controlling net fluid flow. Element transport to and from the reaction sites only occurs if it is energetically beneficial, and enough transport agent is available. Reactive fluid flow during static re-equilibration of nominally impermeable rocks is thus guided by differences in the energy budget of the local equilibrium domains

Reactive fluid flow guided by grain-scale equilibrium reactions during eclogitization of dry crustal rocks

Fluid flow in crystalline rocks in the absence of fractures or ductile shear zones dominantly occurs by grain boundary diffusion, as it is faster than volume diffusion. It is, however, unclear how reactive fluid flow is guided through such pathways. We present a microstructural, mineral chemical, and thermodynamic analysis of a static fluid-driven reaction from dry granulite to ‘wet’ eclogite. Fluid infiltration resulted in re-equilibration at eclogite-facies conditions, indicating that the granulitic protolith was out of equilibrium, but unable to adjust to changing P–T conditions. The transformation occurred in three steps: (1) initial hydration along plagioclase grain boundaries, (2) complete breakdown of plagioclase and hydration along phase boundaries between plagioclase and garnet/clinopyroxene, and (3) re-equilibration of the rock to an eclogite-facies mineral assemblage. Thermodynamic modelling of local compositions reveals that this reaction sequence is proportional to the local decrease of the Gibbs free energy calculated for ‘dry’ and ‘wet’ cases. These energy differences result in increased net reaction rates and the reactions that result in the largest decrease of the Gibbs free energy occur first. In addition, these reactions result in a local volume decrease leading to porosity formation; i.e., pathways for new fluid to enter the reaction site thus controlling net fluid flow. Element transport to and from the reaction sites only occurs if it is energetically beneficial, and enough transport agent is available. Reactive fluid flow during static re-equilibration of nominally impermeable rocks is thus guided by differences in the energy budget of the local equilibrium domains

Effect of grain-scale pressure variations on garnet growth: A numerical approach

ISSN:0263-4929ISSN:1525-131

Next generation reactive transport models

ISSN:1864-565