Phyllosilicates are hypothesized to be primarily of pedogenic origin in shallowly buried paleosols (≤3 km depth), regardless of the age of the paleosol. To test this hypothesis, this work evaluates the possible presence of detrital and diagenetic phyllosilicates in middle and upper Pennsylvanian paleosols, collected from three drill cores along a north–south transect in the Illinois Basin. The abundances of 2M1 muscovite, quartz, and K-feldspar are greater in a morphologically immature Protosol from the southernmost core; 1Md illite and interstratified illite-smectite with R1 and R0 stacking orders are more abundant in the more mature Vertisols of the central and northern cores. K-Ar age values of multiple clay-size fractions from each paleosol averaged ~260 Ma in the northern core, 270 Ma in the central core, and 295 Ma in the southern core. While considering the complex tectonic and thermal history of the Illinois Basin, detrital minerals are more abundant in immature paleosols that experienced relatively greater maximum burial depths and thus greater sediment supply whereas illitization in more mature paleosols was probably initiated primarily during protracted burial diagenesis. As the present study found evidence for diagenetic and detrital minerals in clay-size fractions of shallowly buried, deep-time paleosols, caution is advised when using paleosol minerals for ancient climate and environment reconstructions.

The thermal effects, as well as the survivability and origins of microorganisms in Cretaceous rocks, are evaluated from the timing and extent of the smectite to illite transformation in Cretaceous bentonites collected from cores outside the thermal aureole of the Pliocene Cerro Negro volcanic neck. Overall, randomly ordered mixed-layered illite-smectite (I-S) is the predominant clay mineral in these bentonites, and the K-Ar ages of I-S range from 36 to 48 Ma (21 analyses, two additional analyses were outside this range). Increased temperature from burial is thought to be the primary factor forming I-S in these bentonites. Kinetic model calculations of the smectite to illite transformation are also consistent with I-S formed by burial without any appreciable thermal effects due to the emplacement of Cerro Negro. In a core angled toward Cerro Negro, the percentages of illite layers in I-S from the bentonite closest to Cerro Negro are slightly higher (32-37%) than in most other bentonites in this study. The K-Ar ages of the closest I-S are slightly younger as a group (38-43 Ma; Average = 41 Ma; N = 4) than those of I-S further from Cerro Negro in the same core (41-48 Ma; Average = 44 Ma; N = 6). A small amount of illite in this I-S may have formed by heat from the emplacement of Cerro Negro, but most illite formed from burial. Vitrinite reflectance, however, appears to record the effects of heating from Cerro Negro better than I-S. Tentatively, the temperature of this heat pulse, based on vitrinite data alone, ranged from 100 to 125°C and this is most evident in the CNAR core. The upper temperature, 125°C, approximates the sterilization temperatures for most microorganisms, and these temperatures probably reduced a significant portion of the microbial population. Thermophiles may have survived the increased temperatures from the combined effects of burial and the intrusion of Cerro Negro.

Two clay fractions of a Cambrian claystone from Estonia, consisting essentially of illite and 20% expandable illite-smectite, (I-S) were treated with C12 and C18 alkylammonium cations for K-exchange. Both the untreated and treated samples were dated by the K-Ar method. The treated clays lost several percent of their original K2O, with greater losses for longer-chain cations and for longer reaction time, in accordance with previously published studies. The dates of the treated clay fractions were 20–30 Ma lower than those of the untreated clays. The decrease in the dates suggests preferential opening of older, detrital clays. The K-Ar dates of the illite layers susceptible to K extraction by the various treatments were calculated by subtracting K2O and radiogenic 40Ar values of the consecutive step products, and they were plotted against the total % K2O removed, used as an indicator of the reaction progress. Extrapolation of the plot revealed a detrital (1550 Ma) and a diagenetic (380 Ma) age for the 2 illitic minerals present in the investigated shale sample. The inferred Devonian age of diagenesis of the Estonian clay corresponds to the period of massive dolomitization in the area. Both alteration processes can be related to a Devonian incursion of hot or alkaline fluids, which helps to explain the occurrence of 20% expandable I-S in claystones that have never been buried more than 1000 m.

Extrapolated K-Ar ages and K2O contents of the illitic minerals, estimated from the X-ray diffraction (XRD) data, were used to model the experimental data. A good agreement was reached when dilution effects (chlorite and expanded illite) were taken into account.

The hypothesis that chemical remanent magnetization (CRM) in argillaceous rocks may be due to release of Fe during smectite illitization has been tested by study of spatial and temporal relationships of CRM acquisition, smectite illitization, and organic-matter maturation to deformation in the Montana Disturbed Belt. New K-Ar ages and stacking order and percentages of illite layers in illite-smectite (I-S) are consistent with conclusions from previous studies that smectite illitization of bentonites in Subbelts I and II of the Disturbed Belt was produced by thrust-sheet burial resulting from the Laramide Orogeny. Internally concordant, early Paleogene, K-Ar age values (55–57 Ma) were obtained from clay subfractions of thick bentonites which were significantly different in terms of their ages (i.e. Jurassic Ellis Formation and late Cretaceous Marias River Shale), further supporting a model of smectite illitization as a result of the Laramide Orogeny. Internally concordant K-Ar ages were found also for clay sub-fractions from a thick bentonite at Pishkun Canal (54 Ma) and from an undeformed bentonite near Vaughn on the Sweetgrass Arch (48 Ma). In Subbelts I and II, a greater degree of smectite illitization corresponds to increased thermal maturation, increased natural remanent magnetization intensity, and increased deformation (dip of beds). A dissolution-precipitation model over a short duration is proposed for the formation of illite layers in Subbelts I and II. A characteristic remanent magnetization was developed before or just after folding began in the early Paleogene. More smectite-rich I-S, low thermal maturity, and the absence of a CRM were noted in one outcrop of an undeformed rock on the Sweetgrass Arch. Strontium isotope data allow for the possibility that internal or externally derived fluids may have influenced illitization, but the K-Ar age values suggest that illitization was probably in response to conductive heating after the overthrusting had occurred. The differences in K-Ar dates among the bentonites studied herein may be due to differences in the timing of peak temperature related to differences in distance below the overthrust slab, in rates of burial and exhumation, and in initial temperature.

Burial-induced and hydrothermal-related illitization in bentonites and in sandstones can be modeled on the basis of isotopic studies of fundamental particles separated from mixed-layer illitesmectite. The model envisages different reaction rates and durations relative to the varied impacts of temperature, considering that the water:rock ratio also has an influence. The different pathways for illitization are suggested on the basis of the K-Ar, Rb-Sr and δ18O compositions of previously studied materials.

New information is provided on why fundamental particles separated from mixed-layer illite-smectite in shales yield K-Ar age data that are systematically greater than the ages of the fundamental particles from associated bentonites and/or sandstones, and greater than the reported stratigraphic ages. The study of pure authigenic, recent to present-day smectite from Pacific sediments shows that (1) those collected from active hydrothermal vents have 40Ar/36Ar ratios identical to that of the atmosphere, and (2) those of mud sediments have 40Ar/36Ar ratios above the atmospheric value, indicating addition of 40Ar not generated in situ by radioactive decay. A preliminary but detailed analysis of the noble-gas (Ar, Xe, Kr) contents of authigenic smectite-rich size fractions from Pacific deep-sea red clays suggests trapping of these gases by smectite. Therefore, the results point to the fact that fundamental particles can incorporate excess 40Ar into their structure when nucleating in restricted to closed systems, such as shales. This excess 40Ar, which represents radiogenic 40Ar released from nearby altered silicates, might be temporarily adsorbed at the surface of the rock pore spaces and is therefore available for incorporation in nucleating and growing particles.

Illite age analysis (IAA) is a classical method for extracting diagenetic and detrital ages from mixed ages measured by K-Ar. This approach is based on measuring the masses of diagenetic and detrital illitic components in a few different grain-size fractions of one rock sample and measuring the mixed ages of these fractions. The 1Md illitic polytype is usually considered to be diagenetic, while 2M1 is considered detrital. A plot of the function: exp(λt)−1 (where t is time and λ is the decay constant) vs. weight percent of the detrital fraction is constructed. On the basis of linear extrapolation to end-member fractions, the diagenetic and the detrital age is obtained. This approach does not take into account various K contents in different polytypes (%Kdetrital and %Kdiagenetic). In order to do that, the detrital mass fraction (wt.%detrital) should be recalculated into the percentage of detrital K (%Id(K)):

Analytical constraint of the K content of different polytypes is very difficult, so a new approach to this problem has been developed. In the present study, the plot of 40Ar*/40K vs. %Id(K) for a precisely determined ratio of 40Kdetrital/40Kdiagenetic was observed to be linear. On the basis of this observation, a computer program, MODELAGE, was written in the Java programming language using as input a few measured detrital illite mass fractions along with the mixed K-Ar ages of the relevant grain fractions. It then calculates the end-member ages and the 40Kdetrital/40Kdiagenetic ratio using genetic algorithms.

The errors in diagenetic and detrital illite mass-fraction determination mean that the 40Kdetrital/40Kdiagenetic ratio and the end-member ages can be evaluated only with some uncertainty. The best results are obtained if the measured mass fractions represent a relatively broad range. Constraining one of the unknowns (particularly the 40Kdetrital/40Kdiagenetic ratio) improves the results significantly.

Evaluation of data obtained from the literature using the proposed approach leads to the conclusion that the 40Kdetrital/40Kdiagenetic ratio is often >1.00, and some of 1Md illite polytype materials may be of detrital origin. If this is not the case, if a broad range of mass fractions is covered, and if the differences between end-member ages are relatively small, IAA analysis still gives appropriate results, even if the true 40Kdetrital/40Kdiagenetic ratio is different from 1.00.

The Upper Silurian–Lower 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 illite-smectite 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 clay fractions of Jurassic marls in the Great Estuarine Group in southern Isle of Skye are composed of mixed-layered illite-smectite (I-S) with large percentages (>85%) of illite layers, kaolinite, and generally smaller amounts of chlorite. These marls have not been buried to the depths normally required to convert smectite to illite-rich I-S, so it is possible that the conversion was in response to heat and hydrothermal fluids from nearby early Tertiary igneous activity ∼55 Ma ago. The large percentages of illite layers in I-S, the Środoń intensity ratios, and the Kübler index values appear to be consistent with the formation of diagenetic I-S as a result of relatively brief heating caused by igneous activity. The Jurassic rocks in southern Skye contain a secondary chemical remanent magnetization (CRM) that resides in magnetite and formed at approximately the same time as the Tertiary igneous rocks on Skye. K-Ar age values for I-S based on illite age analysis have been determined to test the hypothesis that the CRM was acquired coincidently with the smectite-to-illite conversion. However, linear extrapolation of K-Ar age vs. percentage of 2M1 polytype (detrital illite) from one marl (EL-6) yields an estimate for the age of diagenetic illite of 106 Ma, which is close to the measured age of the finest subfraction (108 Ma). These estimated and measured age values, however, could be substantially greater than the true age of the diagenetic illite in I-S because of the presence of detrital 1Md illite that was recycled from early Paleozoic shales and whose abundance relative to the diagenetic I-S may have been enhanced because the diagenetic fluid had a low K/Na ratio, limiting the amount of diagenetic illite formed. Nevertheless, most of the illite in the Elgol marls (80% or more in the finest fractions) must be diagenetic and probably formed in response to the early Tertiary magmatism.

Residual clays that developed on Permian and Carboniferous glass-rich silicic volcanic rocks (pitchstones, ignimbrites) at the Seilitz and Kemmlitz kaolin deposits, Saxony, Eastern Germany, contain locally abundant lath-shaped illite-rich illite-smectite mixed-layer minerals (I-S). Analyses by XRD and TEM-AES reveal a large illite percentage (>∼90%) and R3 ordering in I-S from Seilitz (>∼90%) and smaller illite percentage (∼70%) and R1 ordering in I-S from Kemmlitz. The clays never suffered a deep burial and there is no geological, petrographic or fluid inclusion evidence for aeolian input or hydrothermal origin of I-S at either deposit. The I-S formed exclusively at the expense of volcanic glass and not from K-feldspar. Residual quartz phenocrysts in the clays still preserve primary glassy silicate melt inclusions and lack secondary aqueous fluid inclusion trails. The dD and δ18O values of kaolinite and I-S are suggestive of low formation temperatures (<40ºC). Rb-Sr and K-Ar dating of I-S-bearing clay separates yield Lower Cretaceous ages at Seilitz and indicates the presence of excess or inherited 40Ar in illite-rich I-S. In contrast, Triassic to Jurassic Rb-Sr ages are obtained for I-S from the Kemmlitz kaolin deposit.

Ammonium illite and ammonium illite-smectite mixed layers, together with potassium illite, smectite and minute amounts of kaolinite were identified in hydrothermally altered andesite rocks from the Harghita Bãi area of the Eastern Carpathians, Romania. K-Ar dating and oxygen isotope tracing, as well as rare-earth elemental analyses were made to provide new information on the timing and crystal-chemical processes characterizing the crystallization and further evolution of these illite-type mineral phases.

The combined results suggest the occurrence of hydrothermal activity in two distinct episodes with nucleation of two generations of illite-type particles of different chemistry and morphology. About 9.5 Ma ago, potassium illite crystallized in alteration halos of the porphyry Cu system, probably at a temperature of ~270ºC from fluids having a δ18O of ~2.9% (V-SMOW). Associated smectite seems to have precipitated slightly later in external alteration halos at a similar temperature, but from fluids depleted in alkalis and with a different δ18O. Alternately, ammonium-rich illite-smectite mixed layers formed very recently, less than ~1 million years ago at a temperature of ~90ºC from fluids of probable meteoric origin that altered the previously crystallized potassium illite, resulting in the crystallization of a new generation of ammonium illite-smectite mixed layers. Evidence of this dissolution-precipitation process is provided by a significant increase in the δ18O of the mixed-layer structures and by a significant change in their REE contents and distribution patterns. Occurrence of potassium in the ammonium-rich mixed layers probably relates to the progressive alteration of the first-generation potassium illite and a discrete concomitant take up of released K by the new NH4-rich interlayers of the ammonium mixed layered sequence.

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.

Illite age analysis (Pevear, 1992) and similar mixing methods demonstrate nearlinear behaviour when corrected for smectite content in illite-smectite and substitutions for K+ in illite layers. Srodon (1999) found that highly curved mixing lines result from theoretical calculations and challenged the validity of IAA. However, our theoretical calculations indicate near-linear mixing lines result when corrected for the amount of smectite and known K+ substitutions (Na+ or NH4+). We conclude that perfect linearity is unattainable because IAA attempts to unmix a system linearly, but the system is based on an exponential function (K-Ar equation). In practice, we believe IAA can successfully determine the age range of illite diagenesis, even though perfect linearity is not attainable because: (1) significant deviations from linearity occur only if >500 Ma separate the diagenetic and detrital ages; (2) IAA analytical uncertainties result in diagenetic and detrital ages that span a range of ages.

Clay and glauconite fractions separated from sedimentary rocks in Israel were analysed for their mineralogical composition by X-ray diffraction and dated by the K-Ar method. The main goal was to evaluate early diagenetic processes which might have affected the K-Ar system. One series of samples was taken from two contemporaneous mid-Albian to mid-Turonian (~105–91 Ma) shallow marine successions in which early diagenetic K-feldspar was found to be widespread. Another series was of samples of large spatial distribution associated with a mid- Turonian emergence event. None of the outcrops had been subjected to high temperatures due to deep burial or other thermal events. The abundant clay minerals in the first series are randomly ordered illite-smectite (I-S) phases of various discrete and mixed compositions. Illite, kaolinite, ordered I-S and palygorskite are sometimes present. The variability in clay assemblages and I-S composition within short vertical distances and the proximity to the provenance implies mostly a detrital origin for the clay minerals. The K-Ar ages of clay fractions in the first series are no older than 30% of the stratigraphie ages, much younger than the known detritus provenance ages. A few have known stratigraphie ages and one is younger by 10%. The K-Ar ages of associated glauconite fractions are younger by 5–13% than the stratigraphie ages. The ages of the clay fractions of the second series, which are on average more illitic, are mostly younger and no older than 22% more than the stratigraphie age. The age distribution and the clay mineralogy in the two series suggests that illitization of detrital I-S phases may start right after deposition under specific conditions, namely, contact of the sediments with K-rich brines, produced by evaporation in restricted marine environments. The process may continue from a few to many millions of years after burial, as long as K-enriched solutions are available. However, in most cases the near-surface temperatures did not enable a completion of the K-Ar reset process. It seems that low-temperature illitization is better explained as being dependent on solution composition and not on wetting-drying cycles.

Mudstones and claystones from the southern marginal area of the European Upper Triassic, midcontinental Keuper basin (Silesia, southern Poland) were investigated using XRD, organic and inorganic geochemistry, SEM, K-Ar of illite-smectite, AFT, and stable isotopes of O and C in carbonates in order to unravel the consequent phases of the geological history of these rocks, known for abundant fossils of land vertebrates, and in particular to evaluate the diagenetic overprint on the mineral composition. The detected and quantified mineral assemblage consists of quartz, calcite, dolomite, Ca-dolomite, illite, mixed-layer illite-smectite, and kaolinite as major components, plus feldspars, hematite, pyrite, chlorite, anatase, siderite, goethite as minor components. Palygorskite, gypsum, jarosite and apatite were identified in places.

The K-Ar dates document a post-sedimentary thermal event, 164 Ma or younger, which resulted in partial illitization of smectite and kaolinite. The maximum palaeotemperatures were estimated from illite-smectite as ∼125°C. Apatite fission track data support this conclusion, indicating a 200–160 Ma age range of the maximum temperatures close to 120°C, followed by a prolonged period of elevated temperatures. These conclusions agree well with the available data on the Mesozoic thermal event, which yielded Pb-Zn deposits in the area. Organic maturity indicators suggest the maximum palaeotemperatures <110°C.

Palygorskite was identified as authigenic by crystal morphology (TEM), and calcite by its accumulation in soil layers and by its isotopic composition evolving with time, in accordance with the sedimentary and/or climatic changes. Dolomite isotopic composition indicates more saline (concentrated) waters. Palygorskite signals a rapid local change of sedimentary conditions, correlated with algal blooms. This assemblage of authigenic minerals indicates an arid climate and the location at the transition from a distal alluvial fan to mudflat.

Fe-rich smectite, kaolinite, and hematite were products of chemical weathering on the surrounding lands and are therefore mostly detrital components of the investigated rocks. Kaolinite crystal morphology and ordering indicates a short transport distance. Hematite also crystallized in situ, in the soil horizons. A large variation in kaolinite/2:1 minerals ratio reflects hydraulic sorting, except of the Rhaetian, where it probably signals a climatic change, i.e. a shift in the weathering pattern towards kaolinite, correlated with the disappearance of hematite. Quartz, 2M1 illite, and minor feldspars and Mg-chlorite were interpreted as detrital minerals. The documented sedimentation pattern indicates that in more central parts of the Keuper playa system, where an intense authigenesis of the trioctahedral clays (chlorite, swelling chlorite, corrensite, sepiolite) took place, illite and smectite were the dominant detrital clay minerals.

Cr/Nb and Cr/Ti ratios were found as the best chemostratigraphic tools, allowing for the correlation of all investigated profiles. A stable decrease of these ratios up the investigated sedimentary sequence is interpreted as reflecting changes in the provenance pattern from more basic to more acidic rocks.

In an attempt to establish a chronology for volcanic neck emplacement and so elucidate petrogenesis, isotopic studies have been carried out on various cumulate inclusions, blocks and megacrysts which occur chiefly in association with tuffs infilling several Scottish vents. K-Ar ages of 13 samples of low-pressure cumulate minerals (biotite, hornblende and pyroxene) from necks in East Fife indicate crystallisation at shallow depth at 314 Ma. U-Pb analyses of zircons are concordant at 318 Ma suggesting they are also members of this suite and their formation is penecontemporaneous with the Namurian volcanic activity which is welldocumented stratigraphically. By 295 Ma crystallisation of anorthoclase megacrysts had been completed, perhaps from the fractionated residuum. An eruption from considerable depth (within the stability field of garnet precipitation) then broke through to the surface bearing high-pressure megacrysts. This penetrated and disrupted the early cumulates carrying them to the surface and producing the diverse vent assemblages. K-Ar dating of basanites suggest that the Duncansby Ness neck in Caithness was emplaced around 270 Ma in the early Permian. For two Fife necks the balance of evidence favours an age of 290 Ma (Stephanian) for this final explosive activity associated with vent formation.