Mineralogical and isotopic properties of inorganic nanocrystalline magnetites

Inorganic magnetite nanocrystals were synthesized in an aqueous medium at 25°C, atmospheric pressure, ionic strength of 0.1 M, oxygen fugacity close to 0, and under controlled chemical affinity, which was maintained constant during an experiment and varied between different experiments. The total concentration of iron in the initial solutions, with Fe(III)/Fe(II) ratios of 2, was varied in order to measure the role of this parameter on the reaction rate, particle morphology, and oxygen isotopic composition. The reaction rates were followed by a pHstat apparatus. The nature and morphology of particles were studied by transmission electron microscopy and electron energy loss spectroscopy. Fractionation factors of oxygen isotopes were determined by mass spectrometry after oxygen extraction from the solid on BrF₅ lines. At low total iron concentrations, goethite and poorly crystalline iron oxides were observed coexisting with magnetite. At higher concentrations, euhedral single crystals of pure magnetite with an average characteristic size of 10 nm were formed, based on a first-order rate law with respect to total iron concentration. These results confirm that, under high supersaturation conditions, low-temperature inorganic processes can lead to the formation of well-crystallized nanometric magnetite crystals with narrow size distribution. The observed oxygen isotope fractionation factor between magnetite crystals and water was of 0-1‰, similar to the fractionation factor associated with bacterially produced magnetite. We suggest that the solution chemistry used in this study for inorganic precipitation is relevant to better understanding of magnetite precipitation in bacterial magnetosomes, which might thus be characterized by high saturation states and pH.