No abstract

The Kovdor baddeleyite-apatite-magnetite deposit in the Kovdor phoscorite-carbonatite pipe is situated in the western part of the zoned alkali-ultrabasic Kovdor intrusion (NW part of the Fennoscandinavian shield; Murmansk Region, Russia). We describe major intrusive and metasomatic rocks of the pipe and its surroundings using a new classification of phoscorite-carbonatite series rocks, consistent with the IUGS recommendation. The gradual zonation of the pipe corresponds to the sequence of mineral crystallization (forsterite-hydroxylapatite-magnetite-calcite). Crystal morphology, grain size, characteristic inclusions, and composition of the rock-forming and accessory minerals display the same spatial zonation pattern, as do the three minerals of economic interest, i.e. magnetite, hydroxylapatite, and baddeleyite. The content of Sr, rare earth elements (REEs), and Ba in hydroxylapatite tends to increase gradually at the expense of Si, Fe, and Mg from early apatite-forsterite phoscorite (margins of the pipe) through carbonate-free, magnetite-rich phoscorite to carbonate-rich phoscorite and phoscorite-related carbonatite (inner part). Magnetite displays a trend of increasing V and Ca and decreasing Ti, Mn, Si, Cr, Sc, and Zn from the margins to the central part of the pipe; its grain size initially increases from the wall rocks to the inner part and then decreases towards the central part; characteristic inclusions in magnetite are geikielite within the marginal zone of the phoscoritecarbonatite pipe, spinel within the intermediate zone, and ilmenite within the inner zone. The zoning pattern seems to have formed due to both cooling and rapid degassing (pressure drop) of a fluid-rich magmatic column and subsequent pneumatolytic and hydrothermal processes.

Two quintinite polytypes, 3R and 2T, which are new for the Kovdor alkaline-ultrabasic complex, have been structurally characterized. The crystal structure of quintinite-2T was solved by direct methods and refined to R1 = 0.048 on the basis of 330 unique reflections. The structure is trigonal, P$\bar 3$c1, a = 5.2720(6), c = 15.113(3) Å and V = 363.76(8) Å3. The crystal structure consists of [Mg2Al(OH)6]+ brucite-type layers with an ordered distribution of Mg2+ and Al3+ cations according to the $\sqrt 3 $ × $\sqrt 3 $ superstructure with the layers stacked according to a hexagonal type. The complete layer stacking sequence can be described as …=Ab1C = Cb1A=…. The crystal structure of quintinite-3R was solved by direct methods and refined to R1 = 0.022 on the basis of 140 unique reflections. It is trigonal, R$\bar 3$m, a = 3.063(1), c = 22.674(9) Å and V = 184.2(1) Å3. The crystal structure is based upon double hydroxide layers [M2+,3+(OH)2] with disordered distribution of Mg, Al and Fe and with the layers stacked according to a rhombohedral type. The stacking sequence of layers can be expressed as …=АB = BC = CA=… The study of morphologically different quintinite generations grown on one another detected the following natural sequence of polytype formation: 2H → 2T → 1M that can be attributed to a decrease of temperature during crystallization. According to the information-based approach to structural complexity, this sequence corresponds to the increasing structural information per atom (IG): 1.522 → 1.706 → 2.440 bits, respectively. As the IG value contributes negatively to the configurational entropy of crystalline solids, the evolution of polytypic modifications during crystallization corresponds to the decreasing configurational entropy. This is in agreement with the general principle that decreasing temperature corresponds to the appearance of more complex structures.

No abstract

No abstract

We have developed an approach for automatic 3D geological mapping based on conversion of chemical composition of rocks to mineral composition by logical computation. It allows to calculate mineral composition based on bulk rock chemistry, interpolate the mineral composition in the same way as chemical composition, and, finally, build a 3D geological model. The approach was developed for the Kovdor phoscorite-carbonatite complex containing the Kovdor baddeleyite-apatite-magnetite deposit. We used 4 bulk rock chemistry analyses – Femagn, P2O5, CO2 and SiO2. We used four techniques for prediction of rock types – calculation of normative mineral compositions (norms), multiple regression, artificial neural network and developed by logical evaluation. The two latter became the best. As a result, we distinguished 14 types of phoscorites (forsterite-apatite-magnetite-carbonate rock), carbonatite and host rocks. The results show good convergence with our petrographical studies of the deposit, and recent manually built maps. The proposed approach can be used as a tool of a deposit genesis reconstruction and preliminary geometallurgical modelling.

No abstract

Hydronium (oxonium) cation H3O+ plays an important role in mineralogy and mineral structures. However, it is rather difficult to detect it using conventional methods of crystal structure analysis. In particular, hydronium‐bearing eudialyte‐group minerals (EGMs) are well known. In this paper, we provide data on a low‐temperature X‐ray structure analysis and vibrationl spectroscopy study of previously described “potassium‐oxonium eudialyte” from the Khibiny alkaline massif (Kola Peninsula, Russia) as well as new data on vibrational spectra and hydrogen bonding of a series of sodium‐deficient hydrated EGMs including new samples and minerals whose crystal structures were investigated earlier. Based on single‐crystal X‐ray structural analysis and Raman spectroscopy, it is shown that natural sodium‐deficient hydrated zirconosilicates related to eudialyte contain different hydrated proton complexes with extremely strong hydrogen bonds. The data obtained have been compared with recent high‐level quantum electronic and vibrational calculations. Some hydrated proton complexes in hydrated eudialyte‐related minerals have Zundel‐ and Eigen‐type configurations with the O˙˙˙O distances of ~2.40 and ~2.55 Å, respectively.