Local environment and valence state of iron in microinclusions in fibrous diamonds: X-ray Absorption and Mössbauer data

Abstract

Iron valence state and local environment in a set of fibrous diamonds from Brazilian and Zairean placers were investigated using X-ray Absorption and Mössbauer spectroscopies. It is shown that the diamonds could be divided into two main groups, differing in the type of dominant Fe-bearing inclusions. In the first group Fe is mostly trivalent and is present in octahedral coordination; diamonds from the second group contain a mixture of Fe^2+^ and Fe^3+^, most likely with Fe^2+^ in dodecahedral coordination. A few other diamonds contain iron in a more reduced state: the presence of metallic Fe and Fe~3~O~4~ is inferred from XAS measurements. Spatially resolved XANES and Mössbauer measurements on polished diamond plates show that in some cases the Fe valence state may change considerably between the core and rim, whereas in other cases Fe speciation and valence remain constant. It is shown that Fe valence does not correlate with water and/or carbonate content or ratio, suggesting that iron is a minor element in the growth medium of fibrous diamonds and plays a passive role. This study suggests that, when present, evolution of the C isotopic composition with diamond growth is largely due to changes in chemistry of the growth medium and not due to variations of fO~2~.