First-principles study of illite-smectite and implications for clay mineral systems

Illite-smectite interstratified clay minerals are ubiquitous in sedimentary basins and they have been linked to the maturation, migration and trapping of hydrocarbons(1), rock cementation(2), evolution of porewater chemistry during diagenesis(3) and the development of pore pressure(4). But, despite the importance of these clays, their structures are controversial. Two competing models exist, each with profoundly different consequences for the understanding of diagenetic processes: model A views such interstratified clays as a stacking of layers identical to endmember illite and smectite layers, implying discrete and independently formed units (fundamental particles)(5), whereas model B views the clays as composed of crystallites with a unique structure that maintains coherency over much greater distances, in line with local charge balance about interlayers(6). Here we use first-principles density-functional theory to explore the energetics and structures of these two models for an illite-smectite interstratified clay mineral with a ratio of 1:1 and a Reichweite parameter of 1. We find that the total energy of model B is 2.3 kJ atom(-1) mol(-1) lower than that of model A, and that this energy difference can be traced to structural distortions in model A due to local charge imbalance. The greater stability of model B requires re-evaluation of the evolution of the smectite-to-illite sequence of clay minerals, including the nature of coexisting species, stability relations, growth mechanisms and the model of fundamental particles.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/62760/1/nature01155.pd

Chemical signature of two Permian volcanic ash deposits within a bentonite bed from Melo, Uruguay

A Permian bentonite deposit at Melo, Uruguay is composed of a calcite-cemented sandstone containing clay pseudomorphs of glass shards (0-0.50 m) overlying a pink massive clay deposit (0.50-2.10m). The massive bed is composed of two layers containing quartz and smectite or pure smectite respectively. The smectite is remarkably homogeneous throughout the profile: it is a complex mixed layer composed of three layer types whose expandability with ethylene glycol (2EG 1EG or 0EG sheets in the interlayer zone which correspond to low-, medium- and high-charge layers respectively) varies with the cation saturating the interlayer zone. The smectite homogeneity through the profile is the signature of an early alteration process in a lagoonal water which was over saturated with respect to calcite. Compaction during burial has made the bentonite bed a K-depleted closed system in which diagenetic illitization was inhibited. Variations in major, REE and minor element abundances throughout the massive clay deposit suggest that it originated from two successive ash falls. The incompatible element abundances are consistent with that of a volcanic glass fractionated from a rhyolite magma formed in a subduction/collision geological context.<br>Um depósito Permiano de bentonita em Melo, Uruguai,é composto por um arenito com cimento calcítico contendo pseudomorfos de argila sobre detritos vítreos(0-0.50 m) superpostos a um deposito maciço de argila rosado (0.50-2.10 m). A camada maciça é composta por dois níveis contendo quartzo e esmectita ou esmectita pura, respectivamente. A homogeneidade de esmectita ao longo do perfil é notável: trata-se de um interestratificado composto de três tipos de camadas, cuja expansibilidade com etileno-glicol (folhas 2EG, 1EG ou 0EG na zona interfoliar correspondentes a camadas com baixa, média e alta carga, respectivamente) variam com o tipo de cátion que satura a zona interfoliar. A homogeneidade da esmectita ao longo do perfil é a assinatura de um processo de alteração precoce em uma água lagunar supersaturada em calcita. A compactação durante o soterramento tornou a camada de bentonita um sistema fechado empobrecido em K no qual a ilitização diagenética foi inibida. Variações nas abundâncias de elementos maiores, menores e ETR no depósito maciço de argila sugere que este foi originado a partir de duas quedas sucessivas de cinza. A abundância de elementos incompatíveis é consistente com a de um vidro vulcânico fracionado a partir de um magma riolitico formado em um ambiente geológico de subducção/colisão