THE CRYSTAL CHEMISTRY OF THE SCAPOLITE-GROUP MINERALS. I. CRYSTAL STRUCTURE AND LONG-RANGE ORDER

Abstract

Scapolite-group minerals are a group of rock-forming framework aluminosilicates common in a wide variety of igneous and metamorphic rocks. They have the general formula M 4 [ T 12 O 24 ] A , where M represents Na, K, Ca, Sr, Ba and Fe 2+ , T stands for Si, Al, (Fe 3+ ), and A represents Cl, (CO 3 ), (SO 4 ). They constitute a non-binary solid-solution series involving the end members marialite (Na 4 [Al 3 Si 9 O 24 ] Cl, Ma ) and meionite (Ca 4 [Al 6 Si 6 O 24 ] CO 3 , Me ). The crystal structures of eighteen scapolite-group minerals from Me 4.9 to Me 92.8 [ Me = 100 ∑ M 2+ /∑( M 2+ + M + )] have been refined with Mo K α X-radiation. The crystals, a 12.045–12.208, c 7.564–7.586 A, V 1099.7–1130.1 A 3 , I 4/ m or P 4 2 / n , Z = 2, were analyzed with an electron microprobe subsequently to collection of the X-ray intensity data. There are subtle differences between the behavior of the distinct T tetrahedra in the I 4/ m and P 4 2 / n structures. For Si and Al, determinative curves for the assignment of site populations from T –O> distances were developed for each T site in each structure type, and T -site populations were assigned from these curves. In I 4/ m marialite, there is no Al at the T (1) site. In P 4 2 / n scapolite, Al is strongly ordered at T (2), and Si is strongly ordered at T (3), but this order is never complete. The A -site cation (Na, Ca, K) is [8]-coordinated in end-member marialite and is (on average) [8.5]-coordinated in end-member meionite. Each ( M ϕ n ) polyhedron shares two edges with adjacent ( M ϕ n ) polyhedra, forming a three-dimensional framework that interpenetrates the [ T 12 O 24 ] silicate framework. In (CO 3 )-bearing structures, the model proposed by previous workers, four (CO 3 ) groups arranged about the 4 axis ( I 4/ m ) or 4 axis ( P 4 2 / m ), is consistent across the series from marialite to meionite. Any (SO 4 ) present is disordered by rotation of 90° about the central 4-fold axis; in I 4/ m structures, each arrangement is 50% occupied, whereas in P 4 2 / n structures, the occupancies of the two arrangements are not required to be equal.