| Research Abstract |
In order to obtain the information on the aqueous speciation of metals under supercritical hydrothermal solutions, the effect of NaCl on the ion exchange equilibria between minerals and aqueous chloride solution under the coexistence of two phase minerals almost immiscible to each other. In the present study, experiments on the aqueous speciation for Mg^<2+>, Sr^<2->, Fe^<2+>, Mn^<2+>, Co^<2+> and Ni^<2+> were carried out using the CaWO_4-MeWO_4, system and for Zn^<2+> using the CaTiO_3MeTiO_3 system. The experimental conditions are mainly 600ﾟC and 1kb.
As for Mg^<2+> and Sr^<2+>, the Ca/(Ca+Me)ratios of the aqueous chloride solution coexisting with the two solid phases are constant in spite of the increase of NaCl. This indicates that under supercritical hydrothermal solutions, Mg^<2+> and Sr^<2-> dissolve as neutral species, but not as higher-order chloro complexes. On the other hand, for Fe^<2+>, Mn^<2+>, Co^<2+>, Ni^<2+>, and Zn^<2+> the Ca/(Ca+Me) ratios decreased significantly with the increases of NaCl. This can be attributed to the formation of the higher-order chloro complexes of the metals. On the assumption that the metals exist as tri-chloro complexes under the experimental conditions, the formation constants of the tri-chloro complexes are in the order of Mn^<2+>>Co^<2+>>Fe^<2+>>Ni^<2+>. Based on the ligand field theory, it is supposed that the metals form tetrahedral chloro complexes with low-spin state under supercritical hydrothermal solutions.
As for Zn^<2+>, the experiments were performed at 500 to 700ﾟC,1kb and 600ﾟC,0.5kb. As a result, it is clarified that the formation constant of the tri-chloro complex incerases with the increase of temperature but decreases with the increase of pressure. This suggests that transition metals can be leached effectively from magmas under higher tempearature and lower pressures.
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