Mechanochemical treatment of kaolinite

Kaolinite surfaces were modified by mechanochemical treatment for periods of time up to 10 h. X-ray diffraction shows a steady decrease in intensity of the d(001) spacing with mechanochemical treatment, resulting in the delamination of the kaolinite and a subsequent decrease in crystallite size with grinding time. Thermogravimetric analyses show the dehydroxylation patterns of kaolinite are significantly modified. Changes in the molecular structure of the kaolinite surface hydroxyls were followed by infrared spectroscopy. Hydroxyls were lost after 10 h of grinding as evidenced by a decrease in intensity of the OH stretching vibrations at 3695 and 3619 cm−1 and the deformation modes at 937 and 915 cm−1. Concomitantly an increase in the hydroxyl stretching vibrations of water is found. The water-bending mode was observed at 1650 cm−1, indicating that water is coordinating to the modified kaolinite surface. Changes in the surface structure of the OSiO units were reflected in the SiO stretching and OSiO bending vibrations. The decrease in intensity of the 1056 and 1034 cm−1 bands attributed to kaolinite SiO stretching vibrations were concomitantly matched by the increase in intensity of additional bands at 1113 and 520 cm−1 ascribed to the new mechanically synthesized kaolinite surface. Mechanochemical treatment of the kaolinite results in a new surface structure.

An infrared spectroscopic study of the some Autunite minerals

A series of selected autunites with phosphate as the anion have been studied using infrared spectroscopy. Each autunite mineral has its own characteristic spectrum. The spectra for different autunites with the same composition are different. It is proposed that this difference is due to the structure of water and hydrated cations in the interlayer region between the uranyl phosphate sheets. This structure is different for different autunites. The position of the water hydroxyl stretching bands is related to the strength of the hydrogen bonds as determined by hydrogen bond distance. The highly ordered structure of water is also observed in the water HOH bending modes where a high wavenumber bands are observed. The phosphate and uranyl stretching vibrations overlap and are obtained by curve resolution.

Tuning the valence of the cerium center in (Na)phthalocyaninato and porphyrinato cerium double-deckers by changing the nature of the tetrapyrrole ligands

A series of 7 cerium double-decker complexes with various tetrapyrrole ligands including porphyrinates, phthalocyaninates, and 2,3-naphthalocyaninates have been prepared by previously described methodologies and characterized with elemental analysis and a range of spectroscopic methods. The molecular structures of two heteroleptic \[(na)phthalocyaninato](porphyrinato) complexes have also been determined by X-ray diffraction analysis which exhibit a slightly distorted square antiprismatic geometry with two domed ligands. Having a range of tetrapyrrole ligands with very different electronic properties, these compounds have been systematically investigated for the effects of ligands on the valence of the cerium center. On the basis of the spectroscopic (UV−vis, near-IR, IR, and Raman), electrochemical, and structural data of these compounds and compared with those of the other rare earth(III) counterparts reported earlier, it has been found that the cerium center adopts an intermediate valence in these complexes. It assumes a virtually trivalent state in cerium bis(tetra-tert-butylnaphthalocyaninate) as a result of the two electron rich naphthalocyaninato ligands, which facilitate the delocalization of electron from the ligands to the metal center. For the rest of the cerium double-deckers, the cerium center is predominantly tetravalent. The valences (3.59−3.68) have been quantified according to their LIII-edge X-ray absorption near-edge structure (XANES) profiles.

Brucite Microbialites in Living Coral Skeletons: Indicators of Extreme Microenvironments in Shallow-Marine Settings

Brucite [Mg(OH)2] microbialites occur in vacated interseptal spaces of living scleractinian coral colonies (Acropora, Pocillopora, Porites) from subtidal and intertidal settings in the Great Barrier Reef, Australia, and subtidal Montastraea from the Florida Keys, United States. Brucite encrusts microbial filaments of endobionts (i.e., fungi, green algae, cyanobacteria) growing under organic biofilms; the brucite distribution is patchy both within interseptal spaces and within coralla. Although brucite is undersaturated in seawater, its precipitation was apparently induced in the corals by lowered pCO2 and increased pH within microenvironments protected by microbial biofilms. The occurrence of brucite in shallow-marine settings highlights the importance of microenvironments in the formation and early diagenesis of marine carbonates. Significantly, the brucite precipitates discovered in microenvironments in these corals show that early diagenetic products do not necessarily reflect ambient seawater chemistry. Errors in environmental interpretation may arise where unidentified precipitates occur in microenvironments in skeletal carbonates that are subsequently utilized as geochemical seawater proxies.