Transmission electron microscopy (TEM) and analytical electron microscopy (AEM) methods were used to study the crystal chemistry of phyllosilicates occurring in green grains of Miocene sediments from the Congo continental shelf. Using diagrams based on wt. % K and the (Fe + Mg)/Al ratio, minerals were distinguished from mixed-layer phases. The most abundant detrital mineral is Fe-kaolinite. The morphology and composition identify this mineral as a component of ferralitic soils. This Fe-rich kaolinite has undergone a complex process of partial dissolution and recrystallization and further enrichment in Fe and, to a lesser extent, in Mg in the marine environment. The detrital mica observed with TEM retains the original morphology and chemistry of muscovite. Alteration processes resulted in the crystallization of 1:1 trioctahedral Fe2+ and Mg-rich minerals and interstratified phases with 1:1 and 2:1 layers in varying proportions observed with the aid of high-resolution transmission electron microscopy (HRTEM) imaging. Included among the newly formed 7-Å phases are those apparently containing excess Si. The smectites are apparently neoform, and chemical analyses showed that these marine K-smectites belong to the beidellite-nontronite series and have tetrahedral substitutions similar to muscovite. Their compositions are closer to beidellite than to nontronite, although the latter was observed in association with goethite. The TEM observations and crystallochemical data show that mineral alteration ceased after forming mixed-layer minerals, and alteration did not reach the glauconitization stage. Apparently, the Miocene assemblages experienced rapidly changing environmental conditions and high sedimentation rates that continue today.

The aim of this work was to investigate whether neoformed Ni-phyllosilicates can be observed and identified using transmission electron microscopy (TEM) in combination with energy dispersive spectroscopy (EDS). The investigations focused on Ni-phyllosilicates formed from Ni-doped montmorillonite. The reaction conditions (pH 8, [Ni]initial = 660 and 3300 µM, 0.2 M Ca(NO3)2) employed were similar to those used in previous polarized extended X-ray absorption fine structure (P-EXAFS) investigations of neoformed Ni-phyllosilicates in a Ni-montmorillonite system.

The TEM investigations of Ni-doped montmorillonite revealed the presence of small, thin particles consisting of coherent stacks that yielded only three to five lattice fringes with spacings consistent with smectites. These small particles were neoformed phyllosilicates, based on the fact that the small particles were only observed in Ni-doped samples and their Ni content, as determined from EDS analysis, was high (up to 10 wt.% NiO). Furthermore, the particles did not possess the characteristic properties of montmorillonite particles, such as a 2:1 Si to Al ratio; instead these particles were rich in Si (up to 75 wt.% SiO2). Unlike montmorillonite, these particles did not contain any Fe. The particles were also significantly more resistant to electron beam damage than montmorillonite particles, and EXAFS measurements confirmed the presence of neoformed Ni-phyllosilicates.

The TEM study further indicates the presence of a variety of additional minerals (e.g. cristobalite, halloysite) and an X-ray amorphous Si-rich phase. A Ni signal could only be detected in the latter phase at high Ni loadings (403 µmol/g), suggesting that Ni uptake at low metal loadings (<90 µmol/g) is mainly controlled by the neoformation of phyllosilicates.