Demagistrisite, the Missing Link in a Polysomatic Series from Lawsonite to Orientite

Demagistrisite, ideally BaCa2Mn3+4(Si3O10)(Si2O7)(OH)4·3H2O, is a new mineral found at the Cerchiara mine (eastern Liguria, La Spezia province, Italy). The ore consists of rhythmic interlaying of braunite-bearing metasediments (5–15 cm thick) and hematite-rich cherts. Demagistrisite occurs in association with cerchiaraite-(Mn), namansilite, noelbensonite, orientite, richterite, ruizite, and saponite in matrix consisting of braunite, calcite, cryptomelane, orthoclase, and quartz. Demagistrisite crystals occur as tightly intergrown blades or as millimeter-sized prisms and needles with square cross-section, typically with irregular terminations, and rarely terminated by a low-angle pyramid. The mineral is orange brown to red brown, streak is beige, and luster is vitreous, translucent to transparent. Fracture is irregular. In thin section, it is orange brown. The mineral is optically biaxial (–) with α 1.805(5), β 1.825(5), γ 1.8305(5) (white light); 2Vmeas 58(5)°, 2Vcalc 54.7°; optical orientation X = c, Y = b, Z = a. Dispersion is very strong, r > v. Pleochroism is strong with X orange yellow, Y red brown, Z red brown; X << Z < Y. It is unreactive in concentrated HCl at room temperature. Thirteen chemical analyses by WDS-EMPA gave the following empirical formula (based on 24 O apfu): (Ba0.69Ca1.25Mn2+0.70Sr0.21Na0.12Mg0.02)Σ2.99(Mn3+3.97Al0.03)Σ4(Si3O10)(Si2O7)(OH)3.87·3.13H2O. The mineral is orthorhombic, space group Amm2, with unit-cell parameters a 16.312(8), b 6.176(4), c 9.075(6) Å, V 914.2(10) Å3, and Z = 2. The seven strongest X-ray powder diffraction lines are [d Å (I%; hkl)]: 16.21 (49; 100), 4.86 (44; 111), 4.34 (56; 102,211), 2.871 (54; 220), 2.731 (100; 511,013), 2.671 (74; 320,113,502), and 2.426 (51; 222,313,611). The crystal structure (R1 = 0.0572 for 1485 reflections with I > 2σI) is based on straight edge-sharing chains of Mn3+-centered octahedra extending along [010], which are bridged by disilicate (Si2O7) and trisilicate (Si3O10) groups, yielding a framework. Cavities within this framework contain two large cation sites. The structure of demagistrisite can be considered transitional between the structures of orientite and noelbensonite. Demagistrisite is named in honor of Leandro de Magistris (1906–1990).