Lawrence Berkeley National Laboratory

The ability to predict the permeability of fine-grained soils, sediments, and sedimentary rocks is a fundamental challenge in the geosciences with potentially transformative implications in subsurface hydrology. In particular, fine-grained sedimentary rocks (shale, mudstone) constitute about two-thirds of the sedimentary rock mass and play important roles in three energy technologies: petroleum geology, geologic carbon sequestration, and radioactive waste management. The problem is a challenging one that requires understanding the properties of complex natural porous media on several length scales. One inherent length scale, referred to hereafter as the mesoscale, is associated with the assemblages of large grains of quartz, feldspar, and carbonates over distances of tens of micrometers. Its importance is highlighted by the existence of a threshold in the core scale mechanical properties and regional scale energy uses of shale formations at a clay content X_clay ≈ 1/3, as predicted by an ideal packing model where a fine-grained clay matrix fills the gaps between the larger grains. A second important length scale, referred to hereafter as the nanoscale, is associated with the aggregation and swelling of clay particles (in particular, smectite clay minerals) over distances of tens of nanometers. Mesoscale phenomena that influence permeability are primarily mechanical and include, for example, the ability of contacts between large grains to prevent the compaction of the clay matrix. Nanoscale phenomena that influence permeability tend to be chemomechanical in nature, because they involve strong impacts of aqueous chemistry on clay swelling. The second length scale remains much less well characterized than the first, because of the inherent challenges associated with the study of strongly coupled nanoscale phenomena. Advanced models of the nanoscale properties of fine-grained media rely predominantly on the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory, a mean field theory of colloidal interactions that accurately predicts clay swelling in a narrow range of conditions (low salinity, low compaction, Na⁺ counterion). An important feature of clay swelling that is not predicted by these models is the coexistence, in most conditions of aqueous chemistry and dry bulk density, of two types of pores between parallel smectite particles: mesopores with a pore width of >3 nm that are controlled by long-range interactions (the osmotic swelling regime) and nanopores with a pore width <1 nm that are controlled by short-range interactions (the crystalline swelling regime). Nanogeochemical characterization and simulation techniques, including coarse-grained and all-atom molecular dynamics simulations, hold significant promise for the development of advanced constitutive relations that predict this coexistence and its dependence on aqueous chemistry.