Boron and lithium were analyzed in three nanometer-sized (<20, 20-50 and 50-100 nm) separates of two Santonian (85.8-83.5 Ma) bentonite samples collected closely in the Campos Basin along the southeastern Atlantic coast (Brazil). The B and Li data give various trends that suggest varied crystallization conditions for separates that consist of overwhelming smectite with less than 9% illitic layers. The δ11B of the few illitic tetrahedral sites from one of the samples remains quite constant, while its contents are strictly correlated with those of K, which suggests that illitization proceeded by interaction with pore fluids of the host sediments that supplied the K. In the second sample, the δ11B of the illite layers from the two coarser fractions is indicative of an early volcanic origin, while the smaller size fraction also interacted with sedimentary fluids. Favored by octahedral substitutions of the smectite layers, the δ7Li is more strictly regulated by a volcanic link. In turn, the information of the B and Li isotopic compositions and contents from studied mixed-layers suggests a various origin for the few illite layers of the smectite-rich I-S that contain more B than the smectite layers that host more Li. The difference appears to be sample-site and crystal-size dependent, fueled by pore fluids of the hosting turbidites.

K-Ar isotopic dating has been applied to alkali-rich nanometer-sized illite separates of bentonites since the late 1990s. In the present study, K-Ar and Rb-Sr isotopic analyses were based on mineralogical determinations and morphological observations of similarly nm-sized separates (<0.02, 0.02–0.05, and 0.05–0.1 μm) depleted in alkalis and recovered from Santonian (85.8–83.5 Ma) bentonites of the Campos Basin located offshore the southeastern Atlantic coast (Rio de Janeiro State, Brazil). On the basis of XRD analyses and geochemical/mineralogical simulations, the size fractions consist essentially of the smectite-rich end-member of the smectite-to-illite trend with no more than 9% authigenic illite layers. High K-Ar values from 42.6 ± 3.2 to 70.2 ± 2.1 Ma confirm the occurrence of detrital illite in one sample at least, the age data being meaningless. A second group of K-Ar values ranges from 15.5 ± 10.7 to 41.3 ± 10.8 Ma, while the smallest (<0.02 and 0.02–0.05 μm) fractions with <0.42% K2O lack detectable radiogenic 40Ar and yield analytically 0 Ma ages. Two samples including that with the detrital illite were leached with dilute acid and the Rb-Sr method was applied to the untreated, leachate, and residual fractions of the different separates. The combined isotopic data suggest that illitization started at ~44 ± 4 Ma when the bentonites were subjected to a temperature of ~60°C. The leachable Sr yielded 87Sr/86Sr ratios of 0.7106–0.7108, which is greater than those of seawater either during deposition or recently, and of the initial ashes. They do not correspond to the chemical signature of pore fluids, but more likely to removals from fragile edges of the illite-smectite layers probably impacted by the rough initial chemical treatment applied to empty the smectite interlayers. Illitization was either a side effect of a major contemporaneous smectitization or an independent process that occurred later, in the progressively buried bentonite beds. Of variable duration, it was probably dependent on burial-induced temperature increase in the bentonites, which monitored the fixation of K in the smectite layering with or without a changing fluid chemistry. On the basis of the combined K-Ar and Rb-Sr isotopic data, illitization lasted either until ~15 Ma or even 0 Ma for some of the finest size fractions.

Nanometre-sized illite-type crystals extracted from mixed-layer illite-smectite of cored bentonite beds from the East Slovak Basin were studied to investigate timing, duration and physical/chemical conditions of their nucleation and growth. The study includes application of the results to an evaluation of the regional extent of illitization. Close to salt-bearing formations, the nanometric particles underwent a more intense illitization, of identical duration, but with changing oxygen and hydrogen isotope characteristics of the parental brines.

A comparison of the stratigraphic ages of the bentonite beds with the K-Ar ages of the authigenic crystals shows that illitization started during the Middle-Miocene Serravalian (Lower Sarmatian) subsidence that lasted from 17 to 11.5 Ma. Duration of illitization was bracketed between 14.5 and 9.0 Ma, with further episodes until recently at 0 Ma, depending on the geographic location of the host beds. The calculated subsidence rate varies from less than 300 m/Ma to more than 500 m/Ma and the thermal gradient ranges from ~60°C/km to less than 50°C/km. The K-Ar ages of the nanometric illite point to either short-duration illitization when the onset was soon after sedimentation, or long-duration when the onset was significantly later after sedimentation. The illite δ18O varies little with increasing crystal size, whereas the δD changes significantly. In most samples the crystallization temperature determined by different criteria did not change significantly during crystal growth, but the oxygen and hydrogen isotopic compositions of the interacting fluids varied depending on sample location, immediate environment, timing and duration of illitization.

The stable isotope composition of illite in bentonite beds with reduced fluid-rock ratios gives insight into the fluid-temperature regime of sedimentary basins through identifying local processes rather than wide-scale ones. Illitization is episodic with variable duration along different crystallization pathways, and to various extents in low-porosity, low-permeability bentonite beds. Depending on local conditions, illitization may vary even within apparently homogeneous beds. This contrasts with the situation for porous aquifers having large-scale fluid connectivity.