Abstract
The crystal structure and crystal chemistry of meyerhofferite, ideally CaB 3 O 3 (OH) 5 ·H 2 O, was investigated by a multi-methodological approach based on titrimetric determination of boron, gravimetric determination of calcium, determination of fluorine by ion selective electrode, determination of water content by heating, other minor elements by inductively coupled plasma atomic emission spectroscopy, along with single-crystal synchrotron X-ray and neutron diffraction. The concentration of more than 50 chemical elements was measured. The combination of these techniques proves that the composition of meyerhofferite approaches the ideal one (i.e., (Ca 1.012 Mg 0.003 ) (B 2.984 Si 0.001 )O 3 (OH) 5 ·1.018H 2 O), with only a modest fraction of Mg (with MgO ≈ 0.03 wt%) replacing Ca, and with Si the only potential substituent of tetrahedral B (with SiO 2 ≈ 0.02 wt%). The content of REE and other minor elements is, overall, not significant, including that of fluorine as a potential OH − substituent (i.e., < 0.01 wt%). These findings have some relevant geochemical and technical implications, here discussed. The X-ray and neutron structure model obtained in this study prove that the building units of the structure of meyerhofferite consist of: two BO 2 (OH) 2 tetrahedra and one BO 2 (OH) triangle, linked by corner-sharing to form [B 3 O 3 (OH) 5 ] 2− rings, and distorted Ca-polyhedra (with CN = 8, CaO 3 (OH) 4 (OH 2 )), linked by edge-sharing to form infinite chains along [001]. The B 3 O 3 (OH) 5 rings are connected to the Ca-polyhedra chains by corner- and edge-sharing, on two sides of the chains. These heteropolyhedral chains, made by Ca-polyhedra and B 3 O 3 (OH) 5 rings, are mutually connected through hydrogen bonding only, giving rise to the tri-dimensional edifice of meyerhofferite. The neutron structure refinement showed no evidence of static or dynamic disorder pertaining to the H sites; their libration regime was found to be significantly anisotropic. At least seven of the nine oxygen sites of the structure are involved in H-bonding, as donors or as acceptors . The role played by the H-bonding scheme on the physical properties of meyerhofferite is discussed.