Melt-Fluid and Fluid-Fluid Immiscibility in a Na_(2)SO_(4)-SiO_(2)-H_(2)O System and Implications for the Formation of Rare Earth Deposits

Liquid-liquid immiscibility has crucial influences on geological processes,such as magma degassing and formation of ore deposits.Sulfate,as an important component,associates with many kinds of deposits.Two types of immiscibility,including(i)fluid-melt immiscibility between an aqueous solution and a sulfate melt,and(ii)fluid-fluid immiscibility between two aqueous fluids with different sulfate concentrations,have been identified for sulfate-water systems.In this study,we investigated the immiscibility behaviors of a sulfate-and quartz-saturated Na_(2)SO_(4)-SiO_(2)-H_(2)O system at elevated temperature,to explore the phase relationships involving both types of immiscibility.The fluid-melt immiscibility appeared first when the Na_(2)SO_(4)-SiO_(2)-H_(2)O sample was heated to~270℃,and then fluid-fluid immiscibility emerged while the sample was further heated to~450℃.At this stage,the coexistence of one water-saturated sulfate melt and two aqueous fluids with distinct sulfate concentrations was observed.The three immiscible phases remain stable over a wide pressure-temperature range,and the appearance temperature of the fluid-fluid immiscibility increases with the increased pressure.Considering that sulfate components occur extensively in carbonatite-related deposits,the fluid-fluid immiscibility can result in significant sulfate fractionation and provides implications for understanding the formation of carbonatite-related rare earth deposits.

Sensitive Method for Enantioseparation of Rivastigmine with Highly Sulfated Cyclodextrin as Chiral Selector by Capillary Electrophoresis

A sensitive method for enantioseparation of a basic drug rivastigmine and determination of its optical impurity by capillary electrophoresis with highly sulfated β-cyclodextrin （HS-β-CD） as the chiral selector is described. In general, enantioseparation of basic chiral compounds is carried out in acidic condition （pH 2.5） to prevent analytes from adsorption on the capillary wall. However, in the case of rivastigmine, the detection sensitivity was too limited to determine the optical impurity of S-rivastigmine lower than 1% when buffer pH was 2.5. It was found that the detection sensitivity was improved 1.6 times just by raising the buffer pH value from 2.5 to 5.8. The poor column efficiency due to the adsorption of the analytes on the capillary wall was resolved by using dynamical coating of the capillary wall with the linear polyacrylamide solution. The experimental parameters such as the concentration of HS-β-CD, buffer pH and buffer ionic strength were optimized, respectively. The method was validated in terms of repeatability, linearity, limit of detection （LOD） and limit of quantitation （LOQ）. Using the present method, the optical purity of nonracemic rivastigmine with the enantiomeric excess （ee） value of 99.14% was determined.