Search

We performed an in situ dehydroxylation kinetics study of brucite under water-saturated conditions in the pressure and temperature ranges of 593–633 K and 668–1655 MPa using a hydrothermal diamond anvil cell. The kinetic analysis of the isothermal–isobaric data using an Avrami-type model involving nucleation and growth processes yields values for the dehydroxylation rate and reaction order compatible with a reaction mechanism limited by the monodimensional diffusion of water molecules from structural OH groups. Our results show a negative pressure dependence on the reaction rate k and a positive temperature dependence on the k. The dehydroxylation of brucite yields an activation volume ∆V value of 5.03 cm3/mol. Following the Arrhenius relationship, the apparent activation energy E a of the process is calculated to be 146 kJ/mol within the experimental P–T ranges. It is determined that the fluid production rates varying from 4.4 × 10−7 to 10.7 × 10−7 $${\text{m}}_{\text{fluid}}^{3} \;{\text{m}}_{\text{rock}}^{ - 3} \;{\text{s}}^{ - 1}$$ are a few orders of magnitude greater than the strain rate of the mantle serpentinites, which may be fast enough to result in the brittle fracture of rocks. Moreover, the rate of fluid production will be enhanced when brucite occurs in the non-/low H2O environments of the subduction zone.

Electrical conductivity of talc was measured at 0.5 GPa and ~473 to ~1,300 K by using impedance spectroscopy both before and after dehydration. Before dehydration, the electrical conductivity of talc increased with temperature and is ~10−4 S/m at 1,078 K. After dehydration, most of the talc changed to a mixture of enstatite and quartz and the total water content is reduced by a factor 6 or more. Despite this large reduction in the total water content, the electrical conductivity increased. The activation enthalpy of electrical conductivity (~125 kJ/mol) is too large for the conduction by free water but is consistent with conduction by small polaron. Our results show that a majority of hydrogen atoms in talc do not enhance electrical conductivity, implying the low mobility of the hydrogen atoms in talc. The observed small increase in conductivity after dehydration may be attributed to the increase in oxygen fugacity that enhances conductivity due to small polaron.

The electrical conductivity of upper-mantle rocks—dunite, pyroxenite, and lherzolite—was measured at ∼2–3 GPa and ∼1,273–1,573 K using impedance spectra within a frequency range of 0.1–106 Hz. The oxygen fugacity was controlled by a Mo–MoO2 solid buffer. The results indicate that the electrical conductivity of lherzolite and pyroxenite are approximately half and one order of magnitude higher than that of dunite, respectively. A preliminary model involving water and iron content effects on the electrical conductivity was derived and is summarized by the relation: $$ \sigma = 10^{{5.2\,\pm\,0.4}} \,C^{{0.67\,\pm\,0.07}}_{W} \,\exp{\left( { - \frac{{(183\,\pm\,9){\text{kJ}}/{\text{mol}}}} {{RT}}} \right)}\,\exp {\left( {X\,\frac{{(79\, \pm\,3){\text{kJ}}/{\text{mol}}}} {{RT}}} \right)}.$$ The results also indicate that pyroxenes dominate the bulk conductivity of upper mantle in hydrous conditions and suggest the maximum water content in oceanic upper mantle is as high as ∼0.09 wt%.