Geochemistry - The Crystal Chemistry of Some Sedimentary Apatites

The commercially exploited sedimentary apatites exhibit a number of variable lattice substitutions which affect their chemical composition. Carbonate is a major diluent of phosphorus values in sedimentary apatites. Substantial amounts of water as hydroxyl, hydronium, and tetrahedral hydroxyl ions substitute for fluorine and oxygen, calcium, and phosphate, respectively. Calcium is also replaced by several other divalent and monovalent cations. The structural formula demonstrates the substitutions in the lattice of the sedimentary apatites studied in view of the crystal-chemical relationships which have been postulated for the isomorphous apatite series. The lattice constant a. varies from 9.29 to 9.40 A for the apatites studied. Quantitative relationships between this constant and lattice substitution are complicated by the interaction of multiple substitutions whose influence is non-additive. The mineral apatite, the principal raw material source of phosphorus for agricultural and industrial applications, offers a wide area for investigation. Considerable research effort has been expended in the study of apatite crystal-chemistry by medical, biological, and earth scientists. Few of these studies deal directly with the sedimentary apatites from the major occurrences which are widely exploited for commercial uses. It is the purpose here to present chemical analyses of several sedimentary apatites and discuss their chemical composition in relation to the structural and crystalchemical principles which have been postulated for the apatite isomorphous series. THE STRUCTURE OF FLUORAPATITE The atomic structure of fluorapatite was described, independently, by Ngray-Szabd and Mehmel in 1930 and has been accepted as presented, with only minor changes,4 since that time. The hexaogonal unit cell with dimensions of a = 9.37 0.01 A and c = 6.88 0.01 A contains two molecules of the composition "There are six (PO4) groups in the cell, four calcium ions on the trigonal axes, surrounded prismati-cally by six oxygen ions and six calcium ions surrounded by an irregular polyhedron of a fluorine and five oxygens. Fluorines are at the comers of the reflexion planes, touching three calcium ions each".l7