Diagenetic smectite-to-illite transition in clay-rich sediments: A reappraisal of X-ray diffraction results using the multi-specimen method

Smectite illitization is a common mineralogical reaction occurring during the burial diagenesis of clay-rich sediments and shales, and has thus attracted sustained interest over the last fifty years. Prior studies have concluded that smectite illitization proceeds through a steady set of homogeneous reactions involving intermediate mixed layers of varying compositions. In these intermediate structures, illite and smectite or, more generally, expandable layers (I and Exp layers, respectively) coexist among the same crystallites giving rise to non-periodic structures (I-Exp) characterized by specific diffraction effects. Consistent with this model, reaction progress was characterized by the simultaneous increase in the illite content in I-Exp and in their stacking order leading to the following mineralogical sequence: smectite → randomly interstratified I-Exp with high smectite contents (\> 50% Exp layers) → ordered I-Exp with high illite contents (\> 50% I layers) → illite. Although reaction mechanisms have been extensively debated, this structural characterization has not been challenged, possibly due to a methodological bias. In the present study, X-ray diffraction patterns typical of the diagenetic illitization of smectite are interpreted using modern approaches involving profile fitting (multi-specimen method). Novel insights into the structure of intermediate reaction products are thus obtained. In particular, original clay parageneses are described that include the systematic presence of illite, kaolinite, chlorite and a mixed layer containing kaolinite and expandable layers (K-Exp). In contrast to previous descriptions, the early stages of smectite illitization are characterized by the coexistence of discrete smectite and of a randomly interstratified I-Exp with a high content of illite layers (\>50% I layers). Both the smectite and the I-Exp are authigenic and form under shallow burial, that is at low temperature conditions. With increasing burial depth, the relative proportion of I-Exp increases, essentially at the expense of discrete smectite, and the composition of I-Exp becomes slightly more illitic. In the second stage of smectite illitization, two illite-containing mixed layers are observed. They result from two parallel reaction mechanisms affecting the randomly interstratified I-Exp present in the shallow section of the series. The first reaction implies the dissolution of this randomly interstratified I-Exp and leads to the crystallization of an ordered I-Exp without significant illitization, possibly because of the low K-availability. The second reaction affecting the randomly interstratified I-Exp implies the growth of trioctahedral (Mg, Al) hydroxide sheets in Exp interlayers, thus developing di-trioctahedral chlorite layers (Ch layers) in the initial I-Exp to form an I-Exp-Ch. A layer-by-layer mechanism is hypothesized for this reaction. In this scheme, Mg cations released by the dissolution-recrystallization reaction of I-Exp likely represent the source of Mg for the formation of brucite-like sheets in expandable interlayers, and thus of the I-Exp-Ch. The reported structural characterization of smectite illitization intermediate products contradicts the conventional wisdom of a homogeneous reaction through a series of pure mixed layers of variable composition. In contrast, the coexistence of different phases implies a heterogeneous reaction via a sequence of intermediate phases and requires reassessing the reaction mechanisms proposed in the literature. The compositional range (relative proportion of the different layer types) of these phases is limited and smectite illitization proceeds essentially as relative proportions of the different phases vary. In addition, reaction kinetics and stability of the different intermediate products also need to be reconsidered.