Silicate and metal species with both positive and negative ions in solutions were examined by electrospray ionization mass spectrometry (ESI-MS). Comparing with detected species in chloride solutions of group-2 elements and transition metals (MCl
2), and silicate solutions with MCl
2, the reaction mechanism of the silicate and metal complexes through the ESI-MS was elucidated, and the information on their stability was obtained. In the positive ion, it was shown that in both MCl
2 solutions and silicate solutions with MCl
2 that bivalent transition metals (Mn, Fe, Co, Ni, Cu, Zn) were more easily hydrolyzed than group-2 elements (Mg, Ca, Sr, Ba). It was also confirmed that Ca
2+ made the most stable complex with silicate ion among Mg
2+, Ca
2+, Sr
2+ and Ba
2+. Concerning the negative ion, Ca
2+ and Na
+ were found to make stable complexes with silicate. Furthermore, the stability of M
2+ with silicate were examined by controlling the ionization conditions, such as the CDL temperature or the ESI probe voltage, for both positive and negative ions. The results showed that, the silicate complexes with Ca
2+ and Na
+ were identified by negative ions. These negative complexes are concluded to exist as they were as original species in the solutions. From these results, the stability between silicate and M
2+ depends on their ionic size. Thus, Ca
2+ and Na
+ with silicate possess high stability.
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