Mixed-layer illite-smectite samples from the Ordovician and Silurian K-bentonites of the Baltic Basin and the Baltic Shield (Norway, Sweden, Denmark, Poland and Estonia) were dated by K-Ar on several grain fractions and were studied by X-ray diffraction (XRD), both on oriented and random preparations, in order to reveal the conditions of smectite illitization in the area. Authigenic K-feldspar was also dated. The geographic pattern of the degree of illitization (% smectite in illite-smectite measured by XRD) is consistent with other indicators of palaeotemperatures (acritarchs, conodont alteration index, vitrinite reflectance, apatite fission track ages). It reveals the highest maximum palaeotemperatures (up to at least 200ºC) along the Norwegian and the German-Polish branches of the Caledonides and the lowest palaeotemperatures (120ºC) in the central part of the studied area. The distribution of K-Ar ages is not well correlated with this pattern, revealing a zone of older ages (Lower Devonian-Lower Carboniferous) between Denmark and Estonia, and areas of younger ages (Upper Devonian to Carboniferous/Permian boundary) to the north and south of this zone. The zone of older ages is interpreted as the result of illitization induced by a thermal event in front of the Caledonian orogenic belt (migration of hot metamorphic fluids?). The areas of younger ages are considered as representing deep burial illitization under a thick Silurian-Carboniferous sedimentary cover, perhaps augmented by a tectonic load. The K-Ar dates invalidate the hypothesis of a long-lasting low-temperature illitization as the mechanism of formation of the Estonian Palaeozoic illite-smectite. The ammonium content of illite-smectite from the Baltic K-bentonites reflects the proximity of organic-rich source rocks that underwent thermal alteration at the time of illite crystallization.

The Upper SilurianÀLower Devonian section of the Dniester gorge in Podolia and samples from boreholes located S and N of this area were studied in order to reconstruct the thermal history of Lower Paleozoic sedimentary rocks in the Dniester segment of the Peri-Tornquist margin of the East European Craton which is the most eastern part of a major shale-gas target in Europe. X-ray diffraction data for illite-smectite from shales and carbonates indicate very advanced diagenesis and maximum paleotemperatures of~200ºC, higher than interpreted from the 'conodont alteration index' (CAI) data. Diagenesis of the Devonian section is slightly less advanced than that of the underlying Silurian section, indicating that it is a regional feature and the result of burial. The regional distribution of the diagenetic grade based on illite matches well with the pattern established from the CAI data. K-Ar dating of illitesmectite from Silurian bentonites and shales gave a consistent set of dates ranging from 390 to 312 Ma. To explain such advanced levels of diagenesis and such K-Ar dates, the extension of the Carboniferous foreland basin (which today is only preserved to the NW of L'viv) toward the SE on the craton margin has to be assumed. The diagenetic zonation pattern of the Carboniferous coals supports this hypothesis. The Carboniferous cover may have been either sedimentary or partially tectonic (Variscan intracratonic duplexes) in origin and the thickness, necessary for the observed level of diagenesis, may have been reduced by an elevated heat flow along the major tectonic zone at the edge of the craton (TESZ). The presence of such cover is confirmed by completely reset Cretaceous apatite fission track (AFT) ages of the Silurian bentonites. The AFT dates also imply a Tertiary heating event in the area.The 10 Å clay mineral present in the dolomitic part of the profile (Silurian), both in bentonites and in other rocks, is aluminoceladonite or intermediate between illite and aluminoceladonite, while in the Devonian shale section only illite was documented. Chlorite is also common in the studied rocks and is at least partially authigenic. It is non-expandable in the samples from boreholes, while often expandable to variable extents in the samples from outcrops, which also contain goethite. Such variation in chlorite is attributed to contemporary weathering.

The K-Ar dating of glauconite has been used as an important stratigraphic tool for many decades. The application of this technique is limited to pure glauconites, free of detrital contamination by K-bearing phases, often not easy to detect. This study extends the application of isotope dating to the contaminated glauconites and offers a precise technique for detecting the detrital contamination of glauconites.The most common K-bearing detrital contaminants have smaller (K-feldspars, Al-rich dioctahedral micas) or greater (trioctahedral micas) dissolution rates than glauconite in extremely low pH solutions. The differences in the dissolution rates can be applied to evaluate the purity of the glauconite and its crystallization age.The interlaboratory GLO glauconite standard and grain-size fractions separated from glauconitic sandstones of the Paleogene (sample GL) and Jurassic (sample GW8) ages were treated with acid (3M HCl, at 99±2°C) for different reaction times (0.5–7 h) and measured for their apparent isotopic ages.Microporous amorphous silica with large specific surface area is the solid product of the reaction and its content increases with reaction time. The K-Ar dates (apparent ages) of the solid residues increase significantly with reaction time: from 44.6 to 107 Ma for the GL sample and from 125.7 to 394.7 Ma for GW8. The increase is negligible in the case of the GLO standard. The Rb-Sr data of the GL sample were modeled using initial 87Sr/Sr ratios of 0.707–0.709, which resulted in a 29.9–35.8 Ma date for the untreated portions of GL, and ∼42.6 Ma after 7 h of treatment.The increase of isotopic K-Ar date with increasing time of dissolution is interpreted to be a result of increasing concentration of detrital, acid-resistant, K-bearing minerals, observed also with the electron microscope and X-ray diffraction. Probabilistic modeling based on single (K-Ar) or double (K-Ar and Rb-Sr) isotopic systems evaluated the isotopic ages of the detrital and authigenic minerals, and their K2O and Rb concentrations. The crystallization ages computed using these two methods are: 24.0, 26.5, and 32.3 Ma for the GL material, and 117.3–121.8 Ma for the GW8 series.The proposed method based on partial dissolution is a potential tool for evaluating the reliability of glauconite dating.