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.

K-Ar measurements were used in this study of upland Savannah River Site soils to distinguish between sorbed K and the K remaining in remnants of primary minerals. Study of sorbed K contributes to understanding further the interaction of alkali metals (Cs in particular) with the soils. Primary mineral K and the associated radiogenic Ar were studied to characterize soil mica with respect to its provenance and its relationship to hydroxy-interlayered vermiculite. K-Ar age values of Na-saturated clay fractions from five samples of these soils range in age from 270 to 370 Ma. After a moderate acid treatment (6% HNO3 v/v, ~1 mol dm-3, 3 h, 80°C) of the clay fractions, K-Ar age values (270-325 Ma) were little changed on the whole, but they were more closely grouped near 300 Ma. Earlier work had shown that most of the K in these soils is found in material resistant to moderate acid extraction. The K-Ar age values show that this acid-resistant material is much older than any pedogenic minerals could be, even much older than the sedimentary parent rocks from which the soils were derived. These observations support earlier inferences by others that the K in these well leached soils is largely in remnants of primary muscovite from the parent sediments. Age values near 300 Ma suggest that the muscovite is largely from proximal Piedmont terranes of the Appalachian orogen, where the K-Ar relationship in most micas was set by Alleghanian tectonic processes late in the Paleozoic Era. The structural location of the K within mica, shown by the retention of the associated radiogenic Ar, is in contrast to the sorption-dominated behavior of the Cs and most of the Rb in these soils during pedogenesis. Stronger acid treatment (~6 mol dm-3 HNO3, 3 h, 100°C) extracted substantial fractions of both the K and the radiogenic Ar from bulk-soil portions, indicating destruction of some of the primary mica. K-Ar age values for the sand-rich bulk soils were not useful for this study because the sand contains excess radiogenic Ar, probably in sand-sized vein quartz.

The radiogenic isotope systematics of clay minerals are complex because of the intimate mixture of minerals from different origins such as detrital and authigenic sources. An important aspect of dating clays is the primary sample preparation and disintegration method. In the present study, a sample of weakly deformed Opalinus claystone from the Mont Terri underground site (Switzerland) was investigated after disintegration by three different methods. The Opalinus Clay was sedimented in the late Toarcian and early Aalenian and reached maximum temperatures of ~85°C during burial in the Cretaceous. The present study reports data from a comprehensive investigation comparing the effects of disintegration by: (1) disc milling; (2) repeated freezing and thawing; and (3) high-voltage discharges. K-Ar age values of the finest clay (<0.1 µm) released by the different disintegration methods are indistinguishable, indicating that the high-voltage liberation method does not influence grains as small as 100 nm. The K-Ar age values of particle-size separates decreased with decreasing particle size. The age values of the 2–6 µm separates correspond to the Carboniferous Period, which reflects the dominance of Paleozoic detritus in that size range. The age values of the smallest separates (<0.1 µm), on average 213 ± 4 Ma, exceed the numerical age of the formation (~177−172 Ma), which show predominance of detrital grains over authigenic grains even in the finest illite. In summary, isotope geochronology data suggest that the high-voltage method can be applied reliably for disintegrating claystones.

In order to elucidate the process of mineralization of clay minerals in fault gouge and its spatial-temporal relationship with fault-zone evolution and hydrothermal alteration, X-ray diffraction (XRD) analysis and K-Ar dating were performed on clay samples from the Kojaku Granite of central Japan, including fault gouge along an active fault. The area studied is suitable for understanding thermal constraints on clay mineralization because the wall rock is homogeneous and its thermal history well defined. The results from XRD indicated that the clay minerals in the gouge samples are dioctahedral smectite, kaolinite, and 1Md illite, whereas clay fillings in fractures and joints in the intact granite (clay vein) include 2M1 illite in addition to dioctahedral smectite and 1Md illite. The evolution of clay mineralization is reconstructed as follows: (1) high-temperature hydrothermal alteration of feldspar and biotite produced 2M1 illite in clay veins; and (2) alteration accompanied by shearing at a lower temperature resulted in the formation of 1Md illite in the gouges. This scenario is consistent with the cooling history of the granite constrained by fission-track, U-Pb, and K-Ar dating methods. K-Ar dating of the clay samples separated into multiple particle-size fractions indicated that the low-temperature alteration leading to the production of 1Md illite was dated to ~40 Ma. Based on the cooling history of the granite, the 1Md illite formed at temperatures of 60–120°C. This temperature range was at the lower limit of the range reported in previous studies for faults. The spatial and geometrical relation of the faults studied and their K-Ar ages infer evolution which can be described as extensive development of small-scale faults at ~40 Ma followed by coalescence of the small-scale faults to form a larger, recently reactivated, active fault. The K-Ar ages have not been reset by the recent near-surface fault activity.

In a study of wall-rock alteration in the 1.4 km long Würmtal adit at the Käfersteige hydrothermal vein deposit (northern Black Forest, Germany) illite was found to be the only clay mineral within the Bunter sandstone and intercalated claystone. Illite occurs mainly as a detrital mineral in the claystone, whereas it is hydrothermally neoformed in the sandstone, either in the pores or as an alteration product of K-feldspar. The extensive occurrence of authigenic illite along the entire 1.4 km long profile confirms that the fluids migrated far into the sandstone.

The authigenic illite formed during a first pulse of high-temperature fluids (Th of ~220°C) with a low salinity (~1 wt.% NaCleq). These fluids also dissolved Sr and Rb from detrital illite of the claystones at the vein. A later hydrothermal pulse with a lower temperature (~70–150°C) and higher salinity (21–28 wt.% NaCleq) silicified the sandstone adjacent to the vein and caused partial substitution of OH- by F- in the structure of the detrital and neoformed illite along the profile.

Within analytical error, the K-Ar dates for the neoformed illite of the <2 µm fraction are the same along the profile (~150 Ma). During this hydrothermal process, the age of the detrital illite within the claystone was reset from 310 to 190 Ma. The illite-rich <0.2 µm fractions yield ages of ~142 Ma (sandstone) indicating a Jurassic origin. The uniform age data for illite in the sandstone and in the claystone are probably due to extensive migration of hot fluids through the wall rocks.

The hydrothermal fluids are attributed to recycled meteoric water and brines that ascended from the basement into the cover rocks during the opening of the North Atlantic and/or the nearby Tethys area.

Micrometric and nanometric illite-rich size fractions of claystones, bentonites and shales were exchanged with alkylammonium cations that have the specificity of stoichiometrically replacing K in trioctahedral mica interlayers. The purpose of the study was a separate evaluation of the K-Ar ages of potentially dioctahedral residual particles not affected by alkylammonium leaching and of potentially trioctahedral illites that were exchanged by the organic molecules.

The K-Ar ages of micrometric size fractions from an Estonian Blue Clay sample collected next to another studied previously show that, even if identical in their mineralogical characteristics, the fractions contain variable amounts of trioctahedral particles that are of different origins. The alkylammonium treatment modifies slightly, within analytical uncertainty, the K-Ar ages of the <0.1 and 0.1–0.4 mm size fractions from, respectively, 464±13 and 530±14 Ma before organic exchange to 480 ± 11 and 546±12 Ma after. The K-Ar ages of alkylammonium exchanged nanometric size fractions from the rim and centre of a thick Upper Cretaceous bentonite bed in Montana suggest that trioctahedral illite-rich particles mineralogically and chemically homogeneous and about 30 Ma old precipitated next to older dioctahedral particles of ∼60–65 Ma. The untreated mixtures consist of two generations of authigenic illite having apparently different di/trioctahedral layerings. The same type of authigenic di/trioctahedral illite layering could be demonstrated for nanometric illite particles of a bentonite bed from the East Slovak Basin, one size fraction appearing to even consist of a pure trioctahedral illite as the alkylammonium exchange emptied completely the illite interlayers. The nearby shale level consisted of detrital illite particles that were found to be of different ages, di/trioctahedral layerings and therefore varied origin.

K-Ar ages of alkylammonium exchanged micrometric to nanometric illite and illite-smectite mixed layers, either increasing or decreasing, appear to outline variable di/trioctahedral layering assemblages or independent particle mixtures resulting from a more complex smectite illitization process than the conventionally assumed homogeneous reaction. It could record changing chemical compositions of the interacting pore fluid during crystallization, even when illitization progressed slowly. Similar ages before and after alkylammonium exchange suggest a constant chemical composition and therefore an homogeneous dioctahedral crystal structure. Alternatively, a changing chemical composition of the fluids during illitization is potentially recorded by variable K-Ar ages of the alkylammonium-leached illite resulting from differentiated ion exchanges.

K-Ar isotopic dating of very low-grade metamorphism affecting Triassic-Jurassic rocks in the Coastal Range of central Chile was carried out on whole rocks and their <2 mm size fractions. In the study area, a regional-burial low-grade metamorphism at anchizone conditions (T ≤190°C) and low-pressure conditions (P ≥1.3 kbar) has been described. The highest observed temperatures are related to a contact metamorphism produced by nearby Jurassic intrusions, with a P-T estimate at the immediate contact zone of ~650–690°C and 4 kbar.

The whole-rock K-Ar age of 174±5 Ma is interpreted as belonging to the contact metamorphism due to the intrusion of Jurassic plutons (165±5 Ma to 175±5 Ma). A time-interval of ~20 Ma between the diagenesis (206 Ma) and the anchizonal very low-grade metamorphism (181–184 Ma) is obtained, and a rate of subsidence of ~120 m/Ma is proposed for these Triassic-Jurassic basins. A thermal influence on the burial, very low-grade, regional metamorphism is invoked.

The thermal history of the Buntsandstein (Lower Triassic) sedimentary rocks that crop out in the Vosges Mountains, or are deeply buried in the Rhine Graben, was evaluated on the basis of a combined mineralogical, morphological, oxygen isotope and K-Ar-dating study of illite separates from five locations over a limited 120 km2 area. The results indicate a complex pre-rift evolution characterized by the following features: (1) in the northern Vosges, no record of diagenetic illite formation could be detected; (2) in the nearby Saverne rifting fracture-field, tectonic activity favoured the formation of faults in the crystalline basement ~210 Ma ago. This induced fluid migrations into the porous sandstone cover with illite precipitation occurring either repetitively over a period of ~25 Ma or as two separate events, the latter at ~185 Ma, affecting rocks to the east in the deeper part of the post-Eocene Upper Rhine Graben system; this latter stage of tectonic activity and fluid migration continued until 160 Ma, unless overprinted by another tectonic pulse at that time; (3) afterwards, the main tectonic activity moved to the Soultz-sous-Forêts area where two episodes could be identified at ~95 and 70 Ma by dating mineral crystallization; the latter illite age was also detected in more deeply buried Buntsandstein lithologies of the rift basin, west of Strasbourg, reflecting diverse crystallization under different physical and/or chemical conditions; (4) further illitization which at present is poorly constrained may have restarted ~55 My ago in the same deep part of the rift graben.

The youngest detected illitization age is clearly older than the main Miocene rifting episode of the Rhine Graben, suggesting that no illite crystallization occurred in the Buntsandstein sandstones during this tectonic event. This is explained by the fact that these rocks, as well as most of the underlying crystalline basement, were already sealed by fluid migration and mineralization during late Mesozoic rifting, and were therefore almost impermeable to the circulation of Tertiary fluids. The overall evolution of the region between the Vosges Mountains and the central Rhine Graben appears to be more complex than that of equivalent rock lithologies elsewhere in Western Europe. Several episodes identified here have been detected in other regions, but no single location exists which was affected by all events.

K-Ar ages of Eocene glauconite pellets from the Isle of Wight are related to quantified amounts of older glauconite pellets and to occurrences of detrital mica/illite particles that might have been added to synsedimentary pellets during reworking processes. Addition of older glauconite did not significantly bias the K-Ar dates, as the results most often provide the expected stratigraphic reference ages or even significantly lower ages. Alternatively, K-Ar dates significantly greater than those suggested by the stratigraphy appear to result from non-glauconized detrital mica in the pellets which is not always removable, even by high-gradient magnetic separation.

Unexpected ‘old’ K-Ar glauconite ages do not result from misapplication of the method, but from inability to systematically identify and remove the `contaminant' particles from glauconite splits. Analysis of highly evolved glauconite separates is definitely appropriate for reliable isotopic age determinations, but it might not be enough for the final selection, as long-lasting diagenesis might have taken over the synsedimentary process. Much if not all depends on the separation and characterization of the separates, but also on the completion of the glauconitization process which effects cannot always be anticipated.

The composition and particle morphology of diagenetic mixed-layer illite-smectite (I-S) in the shallow buried Ordovician Kinnekulle K-bentonite were studied to understand the process of illitization in the Baltic Basin. The same K-bentonite bed from 12 different locations in the Basin was sampled and analysed by means of X-ray diffraction (XRD), atomic-force microscopy (AFM) and K-Ar dating. Illite-smectite in the samples was identified as a highly illitic R1 type illite-smectite vermiculite (high-charge smectite) mixed-layer mineral with 63–78% illitic layers. Illite-smectite was characterized by log-normally distributed thin particles with an area-weighted mean thickness varying from 1.9 to 3.6 nm and 2.1 to 3.8 nm by XRD-PVP and AFM analysis, respectively. The K-Ar diagenetic ages of the mixed-layer minerals suggest an illitization age of 370 to 420 Ma that agrees with the latest phase of the Caledonian orogeny. Illitization of the Kinnekulle bentonite was probably driven by the intrusion of K-rich fluids.

Diagenesis in the Podhale and Orava Paleogene flysch basins and in the underlying Mesozoic structural units was studied by XRD measurement of the percent smectite in the mixedlayer illite-smectite from shales and K-Ar dating of the illite-smectite from bentonites, supported by XRD quantitative mineral analysis, grain density, and porosity measurements of the bulk shales. The diagenetic mineral reactions identified in the flysch shales include illitization of smectite (>60 to <5%S), dissolution of K-feldspar and kaolinite, crystallization of quartz, albite and chlorite. An unusually large amount of basin history information was obtained by combining the illite-smectite data from wells and from the present erosional surface of the basin.

The rocks underwent burial diagenesis at a stable geothermal gradient similar to the present-day value of 21±2°C/km. The maximum burial temperatures were reached very quickly (high sedimentation rate) close to the basin inversion time, at ∼17 Ma in the western part and 18 Ma in the eastern part.

The basin floor, which included the present-day Tatra Mts., was inclined towards the East. The thickness of the sedimentary filling of the basin ranged from 3.5–4.5 km in the western Tatra (removed entirely), to 5–6 km in the western Podhale (<3–4 km removed), to 6.5–7.5 km in the eastern Podhale (>4–5 km removed), and even more in the eastern Tatra and Spisská Magura close to the Ružbachy Fault. These data imply a major subsidence followed by uplift of the Podhale plus Tatra block along the Ružbachy Fault and the deposition of a thick sequence of Lower Miocene sediments over the entire area (latter removed by erosion).

The Mesozoic rocks of all the structural units underlying the flysch basin underwent advanced diagenesis (maximum palaeotemperatures of 160–270°C) during an Upper Cretaceous tectonic burial event at ∼80–90 Ma. The tectonic overload was removed before the Eocene transgression (49–42 Ma).

Variegated palaeosols, which formed from weathering of clays, silts and brackish to freshwater limestones, are present in the Late Eocene–Early Oligocene Solent Group of the Hampshire Basin, southern UK. The composition and origin of the clay in three segments of the lower part of the Solent Group have been investigated by X-ray diffraction, microprobe analysis, inductively coupled plasma-mas spectrometry, K/Ar dating, high resolution scanning electron microscopy, analytical transmission electron microscopy and wet chemistry. The detrital clay mineral suite is dominated by illite and smectite with minor kaolinite and chlorite. Seasonal wetting and drying in gley soils has resulted in replacement of smectite by Fe-rich, or illite-rich illitesmectite. Illite has also formed with gypsum and calcite in ephemeral hypersaline alkaline lakes that periodically dried out. This illite may have precipitated directly from solution. X-ray diffraction data and probe analyses indicate that the neoformed illite is Fe-rich. The K and Fe for the illitization are thought to be derived from weathered glauconite reworked from the underlying Bracklesham Group and Barton Beds.

The relationship between the K-Ar dates of mixed natural clays and the ratios of detrital and diagenetic components follows in most cases a linear trend, which agrees with the theory when the K2O contents of the end-members are similar. However, significant deviations from a linear trend may occur and take the form of poorly-defined concave curves. The absence of a linear trend is less likely to be due to the imprecise determination of the ratio between the two end-members than to heterogeneities of the natural samples which may arise from complex K-Ar evolutions of the detrital and diagenetic end-members. The straight-line approach is of limited use in the definition of diagenetic ages in shales by extrapolating linear trends to diagenetic end-members.

K-Ar dating of mixed-layer illite-smectite from clay fractions extracted from pyroclastic horizons was used to address the controversy about the age and mechanism of the thermal alteration of Carboniferous rocks from the Upper Silesia Coal Basin (USCB). The clay fractions were also investigated by X-ray diffraction in order to select for dating samples possibly rich in illitesmectite, and to evaluate the K-Ar dates for possible contamination by K-bearing pre-diagenetic minerals, of pyroclastic or epiclastic origin.

The K-Ar dates document intense Variscian tectonic burial illitization produced by thrusting (~290 Ma) in the SW of the basin, and the lack of intense burial illitization in the NE, which is consistent with sedimentological models of the basin. The burial illitization in its final phase (<30%S in illite-smectite) involved incorporation of measurable amounts of ammonium cation in the illite structure (substitution for K).

Advanced illitization in the NE of the basin is much younger than its tectonic inversion (uplift and erosion started in Permian), and the corresponding K-Ar dates have to be interpreted as the result of a Mesozoic thermal event, which produced widespread pervasive illitization at shallow depth. This event was dated at 175 Ma, but it may have started earlier and could have lasted longer. This conclusion is consistent with widespread evidence of a major Mesozoic thermal event all over Central Europe, produced by rifting and lithospheric thinning during the opening of the Tethys and Atlantic oceans.

This study demonstrates that smectite illitization histories may be very complex, and that the nature of the illitization mechanism results in mixed K-Ar dates encompassing pro-longed or multiple illitization histories. Dating of several grain-size fractions may help to unravel such histories.

When a calibration using data from Neogene sedimentary basins is applied, vitrinite reflectance and %S in I-S indicate similar palaeotemperatures of tectonic burial diagenesis in the USCB, but they produce very different estimates of the temperature of the thermal event.

Clays are the most complicated objects in quantitative mineral analysis of sedimentary rocks. Complex quantitative analysis of clays comprises four major steps: measuring bulk quantities, quantifying the mixed layering, determining the three-dimensional organization, and measuring the particle size. Computerization has resulted in major progress in all four areas during the last decade. X-ray diffraction remains the major tool of the quantitative studies of clays, supported by Fourier Transform Infrared Spectroscopy (bulk quantities), chemical analysis (bulk quantities) and electron microscopy (particle size). This contribution reviews recent developments in the techniques used for quantifying clays and their properties, and looks at the use of these quantification techniques in K-Ar dating of geological processes.

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.

Rb-Sr ages of Swanson Formation on Edward VII Peninsula, West Antarctica, indicate a late Ordovician age, 421–432 Ma for regional metamorphism. K-Ar ages of 113–440 Ma, reflect a second thermal metamorphism during emplacement of widespread Cretaceous granites. Rb-Sr ages of five monzogranite/syenogranitic plutons of Byrd Coast Granite are in the range 95–105 Ma (initial 87Sr/86Sr ratios 0.710–0.715) and represent stages of crystallization of anorogenic granite (A subtype). These correlate with Byrd Coast Granite (100–110 Ma) farther east in Marie Byrd Land, and with Cretaceous granitoids on the Campbell Plateau and in southern New Zealand. K-Ar mica/hornblende and fission-track apatite/zircon ages indicate that regional cooling began c. 90–100 M.y. ago immediately after granite emplacement. Uplift continued throughout the peninsula during the period 55–100 Ma (late Cretaceous-early Tertiary), associated with regional uplift in the rift-drift stages of Gondwana break-up at the South-west Pacific spreading centre. Apatite fission track ages show that during late Cretaceous-early Tertiary time the peninsula behaved as two blocks. The Alexandra Mountains were exhumed 20 m.y. before the Rockefeller Mountains and are possibly separated by a fault active initially in the mid-Cretaceous or earlier, and later reactivated in the late Cretaceous-early Tertiary. An averaged uplift rate (50–100 Ma) of 0.025 mm yr−1 is characteristic of the inferred intraplate tectonic setting.