Numerical models of ionic diffusion in one and three dimensions: application to dehydration of mantle olivine

The hydrogen content of nominally anhydrous minerals is of great interest, because it can influence many physical and mechanical properties of mantle rocks. Moreover, the hydrogen diffusion profiles can be used to constrain timescales related to magma eruptions. Here, we report models of ionic diffusion for trace elements in anisotropic crystals and apply them to hydrogen diffusing out of mantle-derived olivine. We first compare and discuss the characteristics of 1D and 3D models and show that only 3D anisotropic diffusion models can lead to diffusion profiles exhibiting non-equilibrium plateau at the center of the solid along the slowest axis, as measured in natural samples. In a second part, we discuss the differences between hydration and dehydration of olivine for diffusion that is linked to two different atomic sites involved in hydrogen mobility. Finally, we apply our 3D anisotropic model to previous results on mantle-derived olivine from Pali-aike to better characterize diffusion coefficients and their anisotropy that could be relevant for dehydration of olivine. Our results show that dehydration has to be strongly anisotropic, with a fast [100] axis and a significantly slower [001] axis.     

Effects of volcanic eruptions on the CO2 content of the atmosphere and the oceans: the 1996 eruption and flood within the Vatnajökull Glacier, Iceland

The October 1996 eruption within the Vatnajökull Glacier, Iceland, provides a unique opportunity to study the net effect of volcanic eruptions on atmospheric and oceanic CO₂. Volatile elements dissolved in the meltwater that enclosed the eruption site were eventually discharged into the ocean in a dramatic flood 35 days after the beginning of the eruption, enabling measurement of 50 dissolved element fluxes. The minimum concentration of exsolved CO₂ in the 1×10¹² kg of erupted magma was 516 mg/kg, S was 98 mg/kg, Cl was 14 mg/kg, and F was 2 mg/kg. The pH of the meltwater at the eruption site ranged from about 3 to 8. Volatile and dissolved element release to the meltwater in less than 35 days amounted to more than one million tonnes, equal to 0.1% of the mass of erupted magma. The total dissolved solid concentration in the floodwater was close to 500 mg/kg, pH ranged from 6.88 to 7.95, and suspended solid concentration ranged from 1% to 10%. According to H, O, C and S isotopes, most of the water was meteoric whereas the C and S were of magmatic origin. Both C and S went through isotopic fractionation due to precipitation at the eruption site, creating “short cuts” in their global cycles. The dissolved fluxes of C, Ca, Na, Si, S and Mg were greatest ranging from 1.4×10¹⁰ to 1.4×10⁹ mol. The dissolved C flux equaled 0.6 million tonnes of CO₂. The heavy metals Ni, Mn, Cu, Pb and Zn were relatively mobile during condensation and water–rock interactions at the eruption site. About half of the measured total carbon flood flux from the 1996 Vatnajökull eruption will be added to the long-term CO₂ budget of the oceans and the atmosphere. The other half will eventually precipitate with the Ca and Mg released. Thus, for eruptions on the ocean floor, one can expect a net long-term C release to the ocean of less than half that of the exsolved gas. This is a considerably higher net C release than suggested for the oceanic crust by Staudigel et al. [Geochim. Cosmochim. Acta, 53 (1989) 3091]. In fact, they suggested a net loss of C. Therefore, magma degassed at the ocean floor contributes more C to the oceans and the atmosphere than magma degassed deep in the oceanic crust. The results of this study show that subglacial eruptions affecting the surface layer of the ocean where either Mn, Fe, Si or Cu are rate-determining for the growth of oceanic biomass have a potential for a transient net CO₂ removal from the ocean and the atmosphere. For eruptions at high latitudes, timing is crucial for the effect of oceanic biota. Eruptions occurring in the wintertime when light is rate-determining for the growth of biota have much less potential for bringing about a transient net negative CO₂ flux from the ocean atmosphere reservoir.     

Sorption of lanthanides on smectite and kaolinite

Experiments were carried out to investigate the sorption of the complete lanthanide series (Ln or rare earth elements, REE) on a kaolinite and an a Na-montmorillonite at 22°C over a wide range of pH (3-9). Experiments were conducted at two ionic strengths, 0.025 and 0.5 M, using two different background electrolytes (NaNO₃ or NaClO₄) under atmospheric conditions or N₂ flow (glove box). The REE sorption does not depend on the background electrolyte or the presence of dissolved CO₂, but is controlled by the nature of the clay minerals, the pH and the ionic strength. At 0.5 M, both clay minerals exhibit the same pH dependence for the Ln sorption edge, with a large increase in the sorption coefficient (K_D) above pH 5.5. At 0.025 M, the measured K_D is influenced by the Cation Exchange Capacity (CEC) of the minerals. Two different behaviours are observed for smectite: between pH 3 and 6, the K_D is weakly pH-dependent, while above pH 6, there is a slight decrease in log K_D. This can be explained by a particular arrangement of the particles. For kaolinite, the sorption coefficient exhibits a linear increase with increasing pH over the studied pH range. A fractionation is observed that due to the selective sorption between the HREEs and the LREEs at high ionic strength, the heavy REE is being more sorbed than the light REE. These results can be interpreted in terms of the surface chemistry of clay minerals, where two types of surface charge are able to coexist: the permanent structural charge and the variable pH-dependent charge. The fractionation due to sorption observed at high ionic strength can be interpreted either because of a competition with sodium or because of the formation of inner-sphere complexes. Both processes could favour the sorption of HREEs according to the lanthanide contraction.