The mobility of radiocesium in the environment is largely mediated by cation exchange in micaceous clays, in particular Illite-a non-swelling clay mineral that naturally contains interlayer K⁺ and has high affinity for Cs⁺. Although exchange of interlayer K⁺ for Cs⁺ is nearly thermodynamically nonselective, recent experiments show that direct, anhydrous Cs⁺-K⁺ exchange is kinetically viable and leads to the formation of phase-separated interlayers through a mechanism that remains unclear. Here, using classical atomistic simulations and density functional theory calculations, we identify a molecular-scale positive feedback mechanism in which exchange of the larger Cs⁺ for the smaller K⁺ significantly lowers the migration barrier of neighboring K⁺, allowing exchange to propagate rapidly once initiated at the clay edge. Barrier lowering upon slight increase in layer spacing (∼0.7 Å) during Cs⁺ exchange is an example of "chemical-mechanical coupling" that likely explains the observed sharp exchange fronts leading to interstratification. Interestingly, we find that these features are thermodynamically favored even in the absence of a heterogeneous layer charge distribution.

The charged surfaces of micaceous minerals, especially illite, regulate the mobility of the major radioisotopes of Cs (¹³⁴Cs, ¹³⁵Cs, ¹³⁷Cs) in the geosphere. Despite the long history of Cs adsorption studies, the nature of the illite surface sites remains incompletely understood. To address this problem, we present atomistic simulations of Cs competition with Na for three candidate illite adsorption sites - edge, basal plane, and interlayer. Our simulation results are broadly consistent with affinities and selectivities that have been inferred from surface complexation models. Cation exchange on the basal planes is thermodynamically ideal, but exchange on edge surfaces and within interlayers shows complex, thermodynamically non-ideal behavior. The basal planes are weakly Cs-selective, while edges and interlayers have much higher affinity for Cs. The dynamics of NaCs exchange are rapid for both cations on the basal planes, but considerably slower for Cs localized on edge surfaces. In addition to new insights into Cs adsorption and exchange with Na on illite, we report the development of a methodology capable of simulating fully-flexible clay mineral nanoparticles with stable edge surfaces using a well-tested interatomic potential model.