Wen-Gang Liu,Shuang Wei,Jian Zhang,Cong Ao,Fu-Tian Liu,Bin Cai,Hong-Ying Zhou,Ji-Long Yang,Chao-Feng Li
A cation-exchange resin is commonly used to separate Sr from geological and environmental samples. AG50 resin is the most traditional cation-exchange resin and has the advantages of good reusability and low cost. Although AG50 resin can meet the demands of most conventional geological samples, eliminating 87Rb isobaric interference from samples with high Rb/Sr ratios (>30) is difficult during one-step separation. Separating Sr twice using AG50 resin is the general approach to Rb removal. The two-step separation method is time consuming and leads to a low Sr yield. This study aimed to improve the sample throughput and overcome the problem of 87Rb isobaric interference from imperfect separation. A new separation method involving hydrofluoric acid (HF acid) coprecipitation combined with a cation-exchange resin (i.e. AG50 resin) for samples with high Rb/Sr ratios was developed. HF acid was used as a coprecipitator to remove most Rb (>90%) and recover Sr before performing AG50 column chemistry. The reliability of this method was examined using the rhyolite standard JR-2, a typical sample with a high Rb/Sr ratio (Rb/Sr = 37.36). Results in the JR-2 case showed that approximately 92% of Rb and most of the matrix elements (K, Ti, Fe, Al, Mn and Na) could be removed effectively. Moreover, Sr recovery exceeded 91% during HF acid coprecipitation. After the removal of Rb by HF acid coprecipitation, the Sr fraction with high purity was easily obtained through one-step separation using the AG50 resin column. However, we found that the removal rates of Rb and some matrix elements (such as Al and Na) were strongly affected by the composition of Al–Ca–Mg in samples. Our separation method is more suitable for samples with high Rb/Sr ratios and low Ca and Mg contents. A series of silicate rock reference materials were selected to evaluate the applicability of our method, and the Sr isotopic results were consistent with previously reported values. Overall, this rapid, simple and low-cost method shows great potential for the separation of Sr from geological samples with high Rb/Sr ratios, such as alkaline feldspar granite, alkaline granite and alkaline rhyolite.
Alum is an important intermediate for the extraction and purification of Cs or Rb chemicals, due to its excellent separation ability for Cs, Rb and K. Although the solubility sequence K-alum > Rb-alum > Cs-alum has been well known, the separation factors among Cs, Rb and K during the formation of alum have not been determined. The formation of solid solution of alum controls the Cs or Rb content and Cs/Rb/K ratio in the sequentially precipitated Cs, Rb and K alums. In this study, the thermodynamic equilibrium separation factors were determined from the solid solution-aqueous solution equilibrium data of the two mixed alum systems: (i) RbAl(SO 4 ) 2 , CsAl(SO 4 ) 2 , and H 2 O, and (ii) KAl(SO 4 ) 2 , RbAl(SO 4 ) 2 and H 2 O. The separation factor β Cs/Rb varied from 48 to 2 with the increase of the Rb/Cs ratio in system (i), and β Rb/K varied from 22 to 0.2 with the increase of the K/Rb ratio in system (ii). This suggests that the purification of Cs or Rb using alums is more efficient from raw materials containing high Cs/Rb or Rb/K ratio than that from low Cs/Rb or Rb/K ratio. In kinetic studies, the apparent separation factors β Cs/Rb and β Rb/K were highly affected by the recrystallization process of cooling or non-cooling and the initial composition of raw alum, showing asymmetric kinetic intensification. The separation factors β Cs/Rb or β Rb/K obtained in the “dissolution by heating and crystallization by cooling (DHCC)” process for the raw alum with high initial Cs/Rb or Rb/K molar ratio is several times larger than the equilibrium value expected from thermodynamics. Finally, CsAl(SO 4 ) 2 and RbAl(SO 4 ) 2 with a metal-based purity of 99.97 % and 99.94 %, respectively, were obtained by using the DHCC process 3–4 times.