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Identifying Detrital and Diagenetic Minerals in Paleosols of the Illinois Basin
- Julia A. McIntosh, W. Crawford Elliott, J. Marion Wampler, Neil J. Tabor
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- Journal:
- Clays and Clay Minerals / Volume 71 / Issue 6 / December 2023
- Published online by Cambridge University Press:
- 02 April 2024, pp. 722-744
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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 Kinetics of the Smectite to Illite Transformation in Cretaceous Bentonites, Cerro Negro, New Mexico
- W. Crawford Elliott, Andrea M. Edenfield, J. Marion Wampler, Gerald Matisoff, Philip E. Long
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- Journal:
- Clays and Clay Minerals / Volume 47 / Issue 3 / June 1999
- Published online by Cambridge University Press:
- 28 February 2024, pp. 286-296
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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.
Origin of the Mg-Smectite at the Cretaceous/Tertiary (K/T) Boundary at Stevns Klint, Denmark
- W. Crawford Elliott
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- Clays and Clay Minerals / Volume 41 / Issue 4 / August 1993
- Published online by Cambridge University Press:
- 28 February 2024, pp. 442-452
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The clay mineralogy and major element geochemistry of four distinct layers within the Cretaceous/Tertiary (K/T) boundary marl (i.e., II, IIIa, IIIb, and IV) at Stevns Klint, Denmark, including “impact layer” (layer IIIa), were examined, and there was not a marked change in the clay mineralogy throughout this K/T boundary marl. A magnesium smectite (i.e., Mg-smectite) was the predominant clay mineral at the K/T boundary not only at Stevns Klint and at Nye Kløv; it was also found to be the predominant clay mineral in the K/T boundary at Karlstrup Quarry. In addition, Mg-smectite was found in a smectitic marl 32 meters below the K/T boundary at the Limhamn Quarry (near Malmö, Sweden), and it did not have anomalous concentrations of iridium or other siderophile trace elements. Given its occurrence in a Maastrichtian marl, it is therefore argued that the Mg-smectite is not derived from meteorite impact.
The rare earth element (REE) signatures of the Mg-smectites ranged from being comparable to the North American Shale Standard (NASC) to being one-half an order of magnitude depleted relative to NASC. One Mg-smectite collected from layer IIIb, immediately above the “impact/red layer,” was depleted in REE by one order of magnitude relative to NASC, and these levels of REE are comparable to those of smectite and illite/smectite (I/S) formed authigenically in bentonites and K-bentonites, respectively. Thus, the REE data suggest this Mg-smectite in all likelihood was formed authigenically from a glassy precursor. The presence of the low levels of REE of the Mg-smectite in the layer IIIb has no particular significance other than to suggest that this Mg-smectite separate was the least contaminated with illite or apatite having higher REE levels. With better separation, the other Mg-smectites would be expected to have comparably low levels of REE. Given the presence of the Mg-smectite throughout the K/T boundary and in Maastrichtian and Danian marls, the Mg-smectite is thought to be of volcanic origin. However, is not certain whether the Mg-smectite formed from volcanic glass deposited at the K/T boundary or whether it was formed from volcanic glass as young as late Cretaceous.
Evaluation of Kinetic Models for the Smectite to Illite Transformation
- W. Crawford Elliott, Gerald Matisoff
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- Clays and Clay Minerals / Volume 44 / Issue 1 / February 1996
- Published online by Cambridge University Press:
- 28 February 2024, pp. 77-87
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Three different models have been reported previously to describe the kinetics of the transformation of smectite to illite (Pytte 1982; Velde and Vasseur 1992; Huang et al. 1993). In order to evaluate the general utility of these models to calculate the timing and extent of this transformation, each model was applied to four different geologic settings (Denver Basin, Gulf Coast, the Salton Sea Geothermal System, and Paris Basin) in which the ages, geothermal gradients and potassium ion activities vary markedly. The model results are compared to the measured percentages of illite in illite/smectite (I/S) and the K/Ar ages of I/S (if available) to test the utility of a given model to a particular basin.
Although individual models can be applied to study this transformation within a specific setting, none of these models was successful in simulating the transformation for all four basins. The Salton Sea was simulated best using the model by Huang et al. (1993), which incorporated an increased geothermal gradient during the last 20,000 years. These results indicate that a large fraction of illite formed due to this increased geothermal gradient, and underscores that temperature is a dominant kinetic factor in forming illite. The Denver Basin was simulated well by the models of Velde and Vasseur (1992) and Pytte (1982). The Gulf Coast was simulated very well by the model of Huang et al. (1993) using a term that terminates the transformation at 75% illite. For the Paris Basin, the results are mixed. The models can be refined by comparing the calculated and measured ages of illite such as the K/Ar ages of I/S to understand the thermal history of a particular basin. The calculated ages of illitization derived from these refined models can be used to indicate the time at which source rocks became thermally mature to form oil and gas.
The Timing of Diagenesis and Thermal Maturation of the Cretaceous Marias River Shale, Disturbed Belt, Montana
- Stephen G. Osborn, Louise Totten Duffield, W. Crawford Elliott, J. M. Wampler, R. Douglas Elmore, Michael H. Engel
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- Journal:
- Clays and Clay Minerals / Volume 62 / Issue 2 / April 2014
- Published online by Cambridge University Press:
- 01 January 2024, pp. 112-125
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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.
A New Look at the Occurrences of the Rare-Earth Elements in the Georgia Kaolins
- W. Crawford Elliott, Daniel J. Gardner, Prakash Malla, Ed Riley
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- Journal:
- Clays and Clay Minerals / Volume 66 / Issue 3 / June 2018
- Published online by Cambridge University Press:
- 01 January 2024, pp. 245-260
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The high-density siliciclastic minerals (e.g. zircon) in the coarse fractions (>44 mm, informally known as grit) of the mined Georgia kaolins are potential and significant sources of the rare-earth elements (REE). The abundances and provenance of the REE signature have not been studied extensively for the Georgia kaolins. The objective of the present study was, therefore, to define the contribution of these heavy minerals (e.g. zircon) to the REE inventory of the coarse fractions of Georgia kaolins. Heavy-mineral subfractions separated from the coarse fractions contained 1647 mg/kg REE from the Jeffersonville Member of the Lower Tertiary Huber Formation and 5012 mg/kg REE from the Buffalo Creek Kaolin Member of the Upper Cretaceous Galliard Formation, respectively. These heavy-mineral subfractions were enriched 10–100 times in the heavy rare-earth elements (HREE, Gd—Lu,), Hf, and Zr relative to the concentrations of these elements in Upper Continental Crust. The heavy-mineral subfractions comprised 5% of the coarse fractions (grit) of these two kaolin-producing formations. The heavy-mineral subfractions consisted of zircon, anatase, rutile, kaolinite, and minor amounts of muscovite, trace ilmenite, and staurolite. The large concentrations of REE were obtained by separating the dense heavy minerals from the coarse fraction (grit) obtained during the typical production of kaolin-group minerals (kaolinite) from kaolin ore. The amount of zircon (estimated from the 6–11 wt.% Zr) and the absence of monazite did not explain the high concentrations of REE in the heavy-mineral subfractions. The large amounts of REE could have resulted from the sorption of REE released during weathering reactions, or from the presence of small amounts (0.025 wt.%) each of monazite and xenotime in addition to the presence of zircon. This heavymineral subfraction represented a novel domestic resource of extractable REE, especially the HREE, of a grade as high as 0.50 wt.% total REE.
Interactions of Radioactive and Stable Cesium with Hydroxy-Interlayered Vermiculite Grains in Soils of the Savannah River Site, South Carolina, USA
- Momoko Goto, Robert Rosson, W. Crawford Elliott, J. M. Wampler, Steven Serkiz, Bernd Kahn
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- Clays and Clay Minerals / Volume 62 / Issue 3 / June 2014
- Published online by Cambridge University Press:
- 01 January 2024, pp. 161-173
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Sorption and fixation of Cs by the upland soils of the US Department of Energy’s Savannah River Site (SRS) have been attributed to micaceous grains consisting mostly of hydroxy-interlayered vermiculite (HIV). Results of experiments to characterize SRS soil samples, to examine aspects of their radiocesium sorption, and to determine how much of their natural Cs is accessible for chemical extraction and isotope dilution are presented in support of mechanistic hypotheses to explain Cs sorption and fixation in HIV grains. The HIV is responsible for most of the soil cation exchange capacity, and concentrations of naturally occurring Cs, Rb, and K in soil samples are closely related to the concentration of HIV. Experiments with 137Cs to examine (1) sorption kinetics, (2) blocking of exchange sites with silver thiourea, and (3) susceptibility of sorbed 137Cs to chemical extraction, support the idea that added Cs is sorbed at different kinds of cation exchange sites in HIV grains. Sites highly selective for Cs but relatively few in number are inferred to exist in interlayer wedge zones within such grains. Little of the naturally occurring Cs in the soil samples was extractable by chemical agents that would remove Cs from ordinary cation-exchange sites and from within non-silicate soil components. Furthermore, most of the natural Cs was inaccessible for isotope dilution under slightly acidic conditions approximating the natural soil environment. These observations support the idea that most of the Cs in these soils has become effectively fixed in the narrower parts of interlayer wedge zones. Control of Cs uptake and fixation by highly Csselective interlayer wedge sites would account for the large distribution coefficients found for 137Cs at the low aqueous Cs concentrations typical of environmental systems and also for the relatively large concentrations of stable Cs in the SRS soils.
Mineralogy, Geochemistry, and Genesis of Bentonites in Miocene Volcanic-Sedimentary Units of the Ankara-Çankiri Basin, Central Anatolia, Turkey
- Selahattin Kadir, Tacit Külah, Nergis Önalgil, Hülya Erkoyun, W. Crawford Elliott
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- Clays and Clay Minerals / Volume 65 / Issue 2 / April 2017
- Published online by Cambridge University Press:
- 01 January 2024, pp. 64-91
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Widespread alteration in the Miocene lacustrine volcanic/sedimentary rocks of the Ankara-Çankiri basin of central Anatolia has resulted in the formation of sizeable (economic) quantities of bentonite deposits. No detailed characterization of the geological, mineralogical, and geochemical properties or the depositional environments of these primary and secondary bentonite deposits has been carried out to date. The present study was undertaken to close this knowledge gap. Two possible hypothetical processes were examined to explain the genesis of the bentonites: 1) The bentonites were formed by the devitrification of volcanic glass in a lacustrine setting; and 2) The bentonites were formed by the chemical weathering of previously deposited volcaniclastic sediments and ophiolitic materials. The characteristics of the bentonites were examined using X-ray diffractometry, scanning and transmission electron microscopy, energy dispersive spectroscopy, and chemical analyses of major and trace elements. The Ankara-Çankırı bentonites are found gradationally interbedded with parent Miocene volcanic and volcaniclastic rocks. These bentonites were deposited in a shallow lacustrine setting based on observed desiccation cracks, locally enclosed coal seams, plant rootlets, gypsum lenses, yellow sulfate-like fracture infillings, and ferric iron oxide stains. Smectite resulted from the chemical weathering of feldspar and possibly also the weathering of biotite and hornblende. This smectite was precipitated in situ on partially dissolved glass and feldspar. The average major-element composition of the smectite-rich clay fractions yielded the following montmorillonitic smectite structural formula: (Na0.33Ca0.31K0.18) (Al2.35Fe0.80Mg0.78)(Si7.79Al0.21)O20(OH)4.
The interlayer cation occupancy in the smectite-rich clay fractions was based on the use of Na+/(Na++Ca2+) ratios and showed a composition between a Ca-smectite and a Na-smectite. The relative increases in several groups of elements according to the LREE/(MREE+HREE) ratio, Al2O3, the sum of Ni+Co+Cr, the sum of Fe2O3+MgO+TiO2, the positive correlation between Rb+Ba and Na2O+K2O, Sr and Rb, Rb/Sr and Zr, Zr/Sm and SiO2, the negative Eu anomaly, and the field and petrographic observations further showed that the Si, Al, Fe, and Mg required to form smectite were mainly supplied from the decomposition of feldspars, amphiboles, and volcanic glass from volcanic materials and were partially supplied from the chemical weathering of ophiolitic basement units. The bentonite deposits examined in this study are mainly primary bentonites derived from volcanics and local secondary bentonites from previously deposited volcaniclastic sediments and ophiolitic materials.
K-Ar Age Constraints on the Origin Of Micaceous Minerals in Savannah River Site Soils, South Carolina, USA
- Thomas E. Naumann, W. Crawford Elliott, J. M. Wampler
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- Clays and Clay Minerals / Volume 60 / Issue 5 / October 2012
- Published online by Cambridge University Press:
- 01 January 2024, pp. 496-506
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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.
Rare-Earth Minerals in Kaolin Ore, Mine Tailings, and Sands – Central Georgia, Upper Coastal Plain
- Anthony Boxleiter, W. Crawford Elliott
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- Clays and Clay Minerals / Volume 71 / Issue 3 / June 2023
- Published online by Cambridge University Press:
- 01 January 2024, pp. 274-308
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The total concentrations of rare-earth elements (REE) in the mined kaolin (0.02–0.06 wt.%), kaolin mine tailings (0.03–1.9 wt.%), and the kaolin-associated Marion Member sand lithology (0.03–4.6 wt.%) opened questions regarding the modes of occurrence of the REE and the role(s) of chemical weathering and secondary processes to explain the presence of REE in these materials. The REE were hosted primarily by phosphate minerals (monazite, xenotime) based on mineralogic analyses (scanning electron microscopy, X-ray diffraction). Enrichments in the light rare-earth elements (LREE: La–Gd) and the high correlation coefficient values were noted between P and the total REE concentrations (r2 = 0.99) for the sands and the mine tailings. Lower correlation coefficient values were noted between total REE concentrations and Zr (r2 = 0.31). The coarse fractions of the mined kaolins were enriched in the heavy rare-earth elements (HREE: Y, Tb–Lu) relative to the kaolin-associated sand lithologies. The REE inventory cannot be explained solely by mineral inheritance within the mined kaolins. Lower correlation coefficient values between P and total REE, positive Eu/Eu* anomalies, and the presence of xenotime overgrowths on zircon showed the importance of the role of chemical weathering of the detrital minerals during post-depositional processes (such as diagenesis) leading to redistributed and fractionated REE within the mined kaolin. The possibility of adsorption of the REE to kaolin mineral surfaces in the fine fraction of the mined kaolins remains open and permits further study to characterize fully the multi-modal fractionation of REE possible in the Georgia kaolin deposits.
Comparison of K-Ar Ages of Diagenetic Illite-Smectite to the Age of a Chemical Remanent Magnetization (CRM): An Example from the Isle of Skye, Scotland
- W. Crawford Elliott, Ankan Basu, J. Marion Wampler, R. Douglas Elmore, Georg H. Grathoff
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- Clays and Clay Minerals / Volume 54 / Issue 3 / June 2006
- Published online by Cambridge University Press:
- 01 January 2024, pp. 314-323
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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.