Mössbauer and chemical investigations of mudrocks

Abstract The oxidation state and mineralogical distribution of Fe in two different shale sequences have been studied by Mössbauer spectroscopy and chemical methods. Kimmeridge Clay Formation sediments proved to be richer in total Fe than Gulf Coast shales. In such sediments, Fe may be present in clay minerals (Fe(II) in chlorite, Fe(III) in illite and illite/smectite), pyrite, and ferroan carbonates (siderite, dolomite and ankerite). Pyrite accounts for a much greater proportion of the total Fe in the Kimmeridge Clay samples in which it is difficult to reconcile chemical data with Mössbauer data. There is major doublet overlap of Fe(III) in silicates with Fe(II) in pyrite and spectra cannot be satisfactorily deconvoluted. This would appear to be a fundamental limitation for simple applications. In the pyrite-poor Gulf Coast material, however, chemical and spectroscopic evaluations of overall valence state are much more consistent. Confidence in both determinative techniques is generated, and useful information documenting progressive reduction and redistribution of Fe with burial is obtained.