The solid solution in the system NaMgAl(SO4)3-KMgAl(SO4)3

We synthesized six samples in the compositional field NaMgAl(SO 4 ) 3 -KMgAl(SO 4 ) 3 in 20 mol% increments from pure Na to pure K compounds. We investigated them by Powder X-Ray Diffraction, 23 Na, and 27 Al Nuclear Magnetic Resonance spectroscopy. The results confirm NaMgAl(SO 4 ) 3 as a unique phase identical to a new mineral found in fumaroles of Eldfell and Hekla volcanoes in Iceland. It tolerates less than 10 mol% K substitution for Na. There exists a compositional gap to around Na 0.65 K 0.35 MgAl(SO 4 ) 3 from where a solid solution extends to KMgAl(SO 4 ) 3 . The mineral koryakite [NaKMg 2 Al 2 (SO 4 ) 6 ] is a member of the latter solid solution series. The crystal structures of all (Na,K)MgAl(SO 4 ) 3 phases are akin to NASICON (NA Super Ionic CONductor). NaMgAl(SO 4 ) 3 has R-3c symmetry and a disordered distribution of Mg and Al among the octahedral sites with only one unique site for the alkali atom. The members of the solid solution have R-3 symmetry with ordered Mg-Al distribution and two unique alkali sites with different preference for Na and K. In the crystal structure, the coordination of Na or K are trigonal antiprismatic and these share bases with two octahedral Mg/Al coordinations. These polyhedra are arranged in rows parallel to [001] interconnected by SO 4 tetrahedral groups. The alkali atoms from a row lie on approximately the same (001) layers as the octahedrally coordinated atoms from the three neighboring rows. On the same level, parallel to (001), there are gaps in the other three neighboring rows where channels containing Na + or K + ions are formed.