Wiesław Heflik

“Silicified” pyrochlore from nepheline syenite (mariupolite) of the Mariupol Massif, SE Ukraine: A new insight into the role of silicon in the pyrochlore structure

Abstract Pyrochlore-supergroup minerals containing relatively high Si concentration are quite common in various geochemical parageneses, e.g., carbonatites, alkaline syenites, pegmatites. However, the role of Si and the mechanism of its incorporation into the structure of these minerals, although widely discussed, have not been explained definitively. Our paper reports the results of comprehensive SEM, EPMA, XRD, TEM, and MAS-NMR studies performed for the first time on a natural pyrochlore, which is the late-magmatic to early hydrothermal accessory component of the nepheline syenite in the alkaline Mariupol massif in Ukraine. It represents partly metamict, patchy-zoned, A-cation depleted, REE-, U-, and Th-bearing fluornatropyrochlore, locally exceptionally rich in SiO2 (up to 13.01 wt%) that underwent both primary and secondary alterations, leading to kenopyrochlore or hydropyrochlore species. The primary alteration was induced by high-temperature, Ca2+- and Si4+-rich, and F- moderate fluids, which affected only some domains of the pyrochlore crystals and resulted in filling the A site vacancies mainly by Ca2+, but also Mn2+, Sr2+, and K+. The secondary alteration, induced by the exposure of the host rock to ground water driving fluid-mediated coupled dissolution-reprecipitation process, affected the whole pyrochlore crystals (both Si-enriched and Si-free domains) and caused, among others, the leaching of some A- and Y-site components. TEM investigations indicate that the selected-area electron diffraction patterns taken from Si-poor areas show strong and sharp diffraction spots related to well-crystalline pyrochlore, whereas the Si-rich areas show weaker spots with a diffuse diffraction halo that are typical of metamict material. Due to the fact that no intergrowth with other Si-bearing phases was observed in the TEM images even at very high magnification, it might be concluded that Si4+ can occupy severely a-decay damaged and chemically altered portions of this structure. The absence of Si in the sixfold-coordinated B site has been corroborated both by compositional relationships, and by the lack of any [6]Si4+ signal around -200 ppm in the MAS-NMR spectrum. A broad signal in the spectrum appearing at around -84 ppm, points to an amorphous species with tetrahedrally coordinated Si, close to Q(2) species defined as Si atom with two bridging O atoms, i.e., [Si(OSi)2(-)2], in the form of finite-length chain-like structures, located in the damaged A and B sites of the primary structure.

Cancrinite from nepheline syenite (mariupolite) of the Oktiabrski massif, SE Ukraine, and its growth history.

Secondary cancrinite, (Na5.88K<0.01)∑5.88(Ca0.62 Fe0.01Mn0.01Zn<0.01 Mg<0.01)∑0.64[Si6.44Al 5.56O24](CO3)0.67(OH)0.26(F<0.01,Cl<0.01)·2.04H2O), was found as accessory component of mariupolite (albite-aegirine nepheline syenite) from the Oktiabrski massif in the Donbass (SE Ukraine). It probably crystallized from a subsolidus reaction involving nepheline (and sodalite?) and calcite dissolved in the aqueous-carbonic fluid at the maximum temperature of 930 °C, decreasing to hydrothermal conditions. It is depleted in sodium, calcium and carbon, what results in the occurrence of vacant positions at both cationic and anionic sites. Ca-deficient cancrinite crystallized from the same hydrothermal Si-undersaturated fluids enriched in the ions such as Na(+), Ca(2+), Cl(-), F(-), HCO3(-), which formed calcite, sodalite, natrolite and fluorite. It has dark-red CL colours with patchy zoning, what indicates the variable/diverse fluid composition during its formation. In the CL spectrum of cancrinite only one broad emission band at 410 nm is observed, which can be attributed to O* center (the recombination of a free electron with an O(-) hole center). The formation of secondary CO3-rich species, i.e. cancrinite and calcite in mariupolite suggests that redox conditions in the Oktiabrski massif were oxidizing at the postmagmatic stage.

The transformation of nepheline and albite into sodalite in pegmatitic mariupolite of the Oktiabrski Massif (SE Ukraine)

Sodalite, Na8Al6Si6Cl2, from a pegmatitic variety of mariupolite in the Oktiabrski Massif (SE Ukraine) was studied using electron microprobe, electron microscopy, spectroscopic cathodoluminescence and Raman techniques to determine its growth history during the evolution of the host rock. Three generations of the mineral were distinguished: (1) the oldest forms patches with a pink-violet cathodoluminescence colour, (2) a younger one, with a dark blue colour, forms the matrix of the crystals, and (3) the youngest generation forms veins with light blue cathodoluminescence in the older sodalite generations; all are undoubtedly secondary phases formed during the post-magmatic evolution of the host rock. The close spatial association of the sodalite with coexisting albite, nepheline, natrolite and K-feldspar, forming inclusions in each other, and the embayed contacts of sodalite with nepheline and albite, and the patchy appearance of sodalite under CL, together suggest that the two older sodalite varieties formed from the conversion of nepheline and albite under the action of Na-, Cl- and Al-bearing, but Si undersaturated basic fluids released during cooling of the host. The excess of SiO2 (aq.) released as a result of albite metasomatism could be accommodated by natrolite occurring as tiny inclusions within the sodalite crystals. The youngest, veinlet, generation was probably formed via a fluid-mediated dissolution-recrystallization process, perhaps simultaneously with the coexisting veins of natrolite.