bluuebunny/crossref_metadata_2025_split huggingface dataset:
Magnetic Ordering At 4.2 And 1.3 K in Nontronites of Different Iron Contents: A 57Fe Mössbauer Spectroscopic Study
Authors: Cardile C. M. , Johnston J. H. , Dickson D. P. E. 
Published: September 2006

AbstractThe 57Fe Mössbauer spectra of six nontronite samples were measured at appropriate temperatures of 4.2 and 1.3 K. Three of the nontronites gave a complex magnetic hyperfine spectrum showing magnetic ordering at 4.2 K, and the other three required a lower temperature of 1.3 K to produce similar magnetic ordering. The spectra were computer-fitted with three closely overlapping sextets which are considered to arise from: (1) Fe3+ that is ordered magnetically in the cis-octahedral sites with a greater number of neighboring tetrahedral Fe3+ ions (51 T); (2) the cis-octahedral site with the greater number of neighboring Si4+ ions (46 T); and (4) the tetrahedral sites (41 T). In an untreated sample a further sextet corresponding to interlayer Fe3+ (36 T) was identified. The magnetic ordering was complicated and not directly related to the iron content of these sites. It probably depended also on the overall composition and structural order of the particular nontronite. The ordering appears to have been essentially two-dimensional, consistent with the layer structure of this material.
Dehydration of K-Exchanged Montmorillonite at Elevated Temperatures and Pressures
Authors: Koster van Groos A. F. , Guggenheim Stephen 
Published: September 2006

AbstractThe dehydration temperature of K-montmorillonite, obtained by ion exchange of a Na-mont-morillonite, was determined at pressures to 2 kbar, using high-pressure differential thermal analysis. Dehydration reactions were found at about 50° and 100°C above the liquid-vapor curve of water. At pressures above the critical point of water the dehydration temperatures increased only slightly. The temperature of the first dehydration reaction is 10°C higher than for Na-montmorillonite, indicating a slightly greater stability of the hydration shell around the potassium interlayer cation. The second dehydration reaction occurs at a slightly lower temperature. The data were used to determine the enthalpy of the dehydration ΔH(dh) and the bonding enthalpy of the interlayer water ΔH(iw) at 1 atm. The first dehydration reaction of the K-exchanged montmorillonite has a ΔH(dh) = 46.16 ± 0.06 kJ/mole and a ΔH(iw) = 7.8 ± 0.5 kJ/mole, whereas for the second reaction, ΔH(dh) = 56.7 ± 2 kJ/mole and ΔH(iw) = 19.8 ± 2 kJ/mole. These values compare with a ΔH(dh) = 46.8 ± 0.3 kJ/mole and a ΔH(iw) = 7.8 ± 0.5 kJ/mole for the first dehydration reaction of the Na-montmorillonite and a ΔH(dh) = 62.9 ± 2 kJ/mole and ΔH(iw) = 27.1 ± 2 kJ/mole for the second dehydration.
Reactions of the Conjugated Dienes Butadiene and Isoprene Alone and with Methanol Over Ion-Exchanged Montmorillonites
Authors: Adams J. M. , Clapp T. V. 
Published: September 2006

AbstractThe reactions of simple conjugated dienes over divalent and trivalent transition metal-exchanged montmorillonites yield, in the absence of nucleophiles, a variety of products. Some of these products are a result of Diels-Alder cycloaddition reactions, whereas others are indicative of carbocation intermediates, i.e., other dimers, oligomers, and isomerization products of these intermediates. The reactions in sealed cells between 20° and 150°C show trends in the yields of the various product groups. Dimers of butadiene and isoprene formed by cycloaddition (i.e., 4-vinylcyclohexene and the monoterpene p-menthadiene (limonene)) were formed at low temperatures (20–50°C). As the temperature was raised, the total yield of dimers increased and higher oligomers were formed along with isomerization products of the dimers and oligomers. The products of cycloaddition, however, did not increase markedly. The type of solvent used for the reaction was found to influence the reactivity, e.g., the use of 1,4-dioxan rather than chloroform led to a reduction in total conversion and also to a markedly higher degree of selectivity. In the presence of a suitable nucleophile (methanol), both dienes gave the 1,4-addition product predominantly, which suggests that an allylic carbocation intermediate was involved. The use of an interlayer-supported nickel complex, [HNi(P(OEt)3)4]+, produced the only large scale polymerization observed in this work.
Mössbauer Spectroscopic Study of the Iron Mineralogy of Post-Glacial Marine Clays
Authors: Torrance J. Kenneth , Hedges Sheila W. , Bowen Lawrence H. 
Published: September 2006

AbstractThree post-glacial marine clays from eastern Canada and one marine clay from Japan have been studied by Mössbauer spectroscopy to ascertain their iron mineralogy. Small amounts of hematite (in two samples) and magnetite (in one sample) were found in the Canadian clays, and hematite was detected in the Japanese clay. The major spectral components were ferrous and ferric doublets, consistent with X-ray powder diffraction results that show chlorite, mica, and amphibole in the Canadian samples and smectite in the Japanese sample. Citrate-dithionite extraction removed hematite and most of the magnetite from these samples. Acid-base extraction also removed chlorite and some mica from the Canadian samples. Samples treated by these extractions had appreciably lower geotechnical yield stresses at given water contents.
Expandable Phyllosilicate Reactions with Lithium on Heating
Authors: Lim C. H. , Jackson M. L. 
Published: September 2006

AbstractA method using Li saturation and heating to 250°C to differentiate montmorillonite from beidellite and nontronite has been developed. The test utilizes three washings with 3 M LiCl and two washings with 0.01 M LiCl in 90% methanol to prevent dispersion. An 'infinitely thick’ sample (6–8 mg/cm2) on a glass slide is used to avoid the effects of the reaction of a thin clay film with sodium of the slide when it is heated at 250°C. Solvation with glycerol rather than ethylene glycol is used, because all of the Li smectites studied expanded to some extent in ethylene glycol after the heating. The smectites included several montmorillonites, a nontronite, and saponites. The presence of interstratified montmorillonite and beidellite layers was clearly shown by the test for several smectite samples, including the so-called beidellites from Beidell, Colorado, and Chen-yuan, Taiwan, and several soil clays. The test thereby provides more mineralogical information than the often-used arbitrary dividing point between montmorillonite and beidellite at 50% tetrahedral charge. Heating the Li-saturated clays at 250°C caused substitution of 35 to 125 meq/100 g of nonexchangeable Li. These amounts exceeded the changes in cation-exchange capacity plus Li by 4 to 21 meq/100 g, except for the end-member beidellite from the Black Jack mine, Idaho. Fusion with LiNO3 at 300°C could not be used to differentiate between smectites instead of washing with LiCl solution and heating to 250°C, because fused montmorillonite subsequently expanded to 18 Å with glycerol. Large increases in nonexchangeable Li were caused by the fusion of smectites, a vermiculite, and two partially expanded micas.
The Lorentz-Polarization Factor and Preferred Orientation in Oriented Clay Aggregates
Authors: Reynolds R. C. 
Published: September 2006

AbstractA closed-form equation was derived that describes the powder-ring distribution factor as a function of 2θ, soller slit collimation, and σ*, which is defined as the standard deviation of an axially symmetrical Gaussian orientation function. Methods were developed for measuring σ* in the reflection mode by means of a θ/2θ diffractometer. Six experimental arrangements for a sedimentary chlorite showed widely different intensity ratios of the 001/005 reflections and gave a standard deviation of ±5.8% when corrected by the theory. The absolute integrated intensities of the 003 reflection from eleven illite samples provided an eight-fold maximum range which, when corrected, yielded a standard deviation of ±7.7%.The intensity distributions within each of two X-ray powder diffraction patterns obtained from instruments with different soller-slit configurations could not be directly compared at low diffraction angles unless corrections, based on σ*, were introduced to allow for the differences in axial divergence.
Ordered Interstratification of Dehydrated and Hydrated Na-Smectite
Authors: Moore D. M. , Hower John 
Published: September 2006

AbstractThe 001 spacing of Na-smectite was found to vary from 9.6 Å at 0% relative humidity (RH) to 12.4 Å at 60-65% RH. The 9.6-Å spacing corresponds to dehydrated Na-smectite, and the 12.4-Å corresponds to Na-smectite with one water layer. A regular series of intermediate values resulted from ordered interstratification of the 9.6- and 12.4-Å units. Ordered interstratification was confirmed by the presence of a 001 spacing of 9.6 + 12.4 Å = 22 Å. This peak appeared under experimental conditions at about 35% RH. It appeared for calculated simulations of ordered stacking of 50/50 mixtures (±10%) of 9.6- and 12.4-Å units. The 004 peak of this 22-Å spacing interacted with the 002 of the 9.6-Å spacing of ordered mixtures of more than 50% 9.6-Å units and with the 002 of the 12.4-Å spacing of ordered mixtures of more than 50% 12.4-Å units. The result of this interaction was a complex peak, the position of which was a function of the ratio of 9.6- and 12.4-Å units. This complex peak was noted for experimental and for calculated conditions. Calculated tracings assuming ordered stacking matched the experimental tracings closely, whereas those assuming random stacking did not.Ordering was apparently due to the interaction of the positive charge of the interlayer cation repelling the positive charge of the hydrogens of the hydroxyl ions, one above and one below, closest to the interlayer space. The collapse of a single interlayer space (dehydration) brought the interlayer cation closer to the hydrogens of the hydroxyls causing the hydroxyls to rotate such that the hydrogens shifted toward the adjacent interlayer spaces. Collapse of these two interlayer spaces was therefore more difficult. This same mechanism helps explain ordering in illite/smectite. The difference is that hydration/dehydration is quick and reversible, whereas the change from smectite to illite is slow and irreversible.
Relationship Between Illite/Smectite Diagenesis and Hydrocarbon Generation in Lower Cretaceous Mowry and Skull Creek Shales of The Northern Rocky Mountain Area
Authors: Burtner Roger L. , Warner Maurice A. 
Published: September 2006

AbstractThe percentage of expandable layers in illite/smectite (I/S) mixed-layer clay decreases with increasing temperature and depth in a section through marine Cretaceous shales in the Champlin 1 Hartley Federal well in the Powder River basin, Wyoming. This systematic change in I/S expandability is evidence that low-expandable I/S in Cretaceous shales of the northern Rocky Mountain area reflects, at least in part, thermal alteration during burial diagenesis. In eastern Montana and western North Dakota where I/S in the Lower Cretaceous Mowry and Skull Creek source rocks is diagenetically unaltered, only trace amounts of hydrocarbons have been found in the Lower Cretaceous and other Cretaceous sandstones. Elsewhere in the northern Rocky Mountain-Great Plains region, hydrocarbons in the Lower Cretaceous Muddy Sandstone and its equivalents occur within or immediately adjacent to areas in which I/S clay in the Mowry and Skull Creek shales has been diagenetically altered during burial. Altered I/S and thermally mature organic matter, as defined by Rock-Eval pyrolysis values, coexist in these source rocks. Both may be used as maturation indicators in the search for Cretaceous-source hydrocarbons in the northern Rocky Mountain area.
Composition of Some Smectites and Diagenetic Illitic Clays and Implications for their Origin
Authors: Nadeau P. H. , Bain D. C. 
Published: September 2006

AbstractChemical analysis by X-ray fluorescence (XRF) and calculated structural formulae of clay-size fractions of smectites from Cretaceous bentonites and illitic clays from Cretaceous, Devonian, and Ordovician bentonites and Jurassic and Permian sandstones indicate the nature and extent of various types of ionic substitution. The determination of tetrahedral (Al, Si) and octahedral (Al, Mg, Fe) composition shows the variable chemistry of these materials. Structural formulae of the illitic clays show that they have tetrahedral charges between 0.4 and 0.8 per half unit cell, and can be divided into phengitic types having octahedral charges of 0.2-0.4 and muscovitic types having octahedral charges <0.2. Evaluation of the formulae in the light of X-ray powder diffraction (XRD) and transmission electron microscopy (TEM) data shows that the occupancy of non-exchangeable interlayer sites (predominantly K) varies from 47% to 90% of that of ideal muscovite. In some minerals as much as 20% of these sites is occupied by ammonium ions (determined independently). The amount of surface silicate charge balanced by non-exchangeable cations versus that balanced by exchangeable cations has been examined in conjunction with TEM data and suggests that in most samples the charges are about equal. The octahedral composition of smectites in Cretaceous bentonites precludes their having served as transformation precursors for most of the Cretaceous illitic bentonites. The results suggest that these illitic clays originated by neoformation.
K/Ar Systematics of Bentonite and Shale in a Contact Metamorphic Zone, Cerrillos, New Mexico
Authors: Aronson James L. , Lee Mingchou 
Published: September 2006

AbstractTo test the ability of illitic clay minerals to retain argon, K/Ar ages were measured on grain-size separates from the Cretaceous Mancos Shale and associated bentonites that have been transformed into K-bentonite near the contact with a large Tertiary igneous stock. The ages of size separates of illite/ smectite from the K-bentonite nearest the contact were internally concordant and matched the hornblende K/Ar age of the stock. In contrast, K/Ar data from clay size fractions from shales adjacent to each K-bentonite were internally discordant with measured ages that were much greater than the age of the intrusion. Thus, significant radiogenic argon was retained by fine-grained detrital illite, even in shale samples very near the igneous contact. These results are convincing evidence that illitic clay minerals are excellent K/Ar clocks under conditions prevailing in sedimentary and diagenetic environments.
Vanadium Chlorite from a Sandstone-Hosted Vanadium-Uranium Deposit, Henry Basin, Utah
Authors: Whitney Gene , Northrop H. Roy 
Published: September 2006

AbstractAn unusual vanadium chlorite precipitated during the formation of a vanadium-uranium ore deposit in the Henry Basin, southeastern Utah. The ore deposit formed by reduction and precipitation of U and V in the presence of organic matter at the interface between a stagnant brine and overlying, circulating meteoric water. Some samples of the vanadium chlorite (heated before analysis) contain ≥ 10% V2O5. In fresh samples, most of the vanadium is in the trivalent oxidation state. X-ray powder diffraction data suggest that Fe and V are concentrated preferentially in the interlayer hydroxide sheets of the chlorite. A d(060) value of 1.52 Å indicates that the chlorite probably has a dioctahedral structure which is distended by the presence of octahedral Fe and V. The vanadium ore zone is flanked by peripheral zones containing perfectly ordered chlorite/smectite. This chlorite/smectite contains much less V than the pure chlorite. This chlorite may have formed by the progressive precipitation of vanadium-rich interlayer hydroxide sheets in the mixed-layer chlorite/smectite in the most reducing portion of the ore zone. The pure chlorite is a IIb polytype, which, for nonvanadiferous analogs, is ordinarily found in high-temperature environments; however, no evidence exists to show that these rocks have ever been exposed to elevated temperatures. In fact, the presence of unreacted smectite in a potassium-rich setting and the low vitrinite reflectance of coalified plant debris indicate a low-temperature history for these sediments.
The Nature of Vermiculite in Adirondack Soils and Till
Authors: April Richard H. , Hluchy Michele M. , Newton Robert M. 
Published: September 2006

AbstractThe clay and bulk mineralogy of soil and till from 26 Adirondack watersheds was studied. The materials consist typically of quartz, K-feldspar, plagioclase, mica, vermiculite, and kaolinite. Talc, smectite, halloysite, and hornblende are present in some samples. The clay fraction of the soils is composed predominantly of vermiculite, likely derived from the transformation of a mica precursor, and kaolinite. The soil vermiculite commonly contains hydroxy-Al interlayers which are especially prevalent in the B-horizon samples. Despite significant variation in the type of bedrock and the composition of heavy mineral assemblages in these watersheds, the clay mineralogy is remarkably uniform. This finding supports earlier suggestions that the occurrence of vermiculite in soils is more dependent on climate than on the nature of the parent material.
Supergene Vermiculitization of A Magnesian Chlorite: Iron and Magnesium Removal Processes
Authors: Proust Dominique , Eymery Jean-Paul , Beaufort Daniel 
Published: September 2006

AbstractAn X-ray powder diffraction study of a vermiculitized chlorite in an amphibole schist near Limoges, France, shows the following weathering sequence: chlorite → ordered interstratified chlorite/vermiculite → vermiculite. Mössbauer spectroscopy indicates that vermiculitization proceeded by the release of ferrous iron from the 2:1 mica layer of the chlorite. The ferric iron content of the vermiculite product is almost the same as that of the initial chlorite. Infrared spectroscopy and chemical microprobe analyses show that Mg was preferentially extracted from the hydroxide sheet of the chlorite, whereas the Si and Al contents progressively increased to the point of the formation of a pure dioctahedral aluminous vermiculite. The Si, Al, and Mg removal processes support currently accepted vermiculitization mechanisms, but the behavior of Fe is slightly different. In this weathering sequence, vermiculitization does not appear to have taken place by the oxidation of Fe2+, but rather, by the simultaneous leaching of Fe2+ and Mg.
X-Ray Photoelectron Spectroscopic Study of the Effect of Heating on Montmorillonite Containing Sodium and Potassium Cations
Authors: Seyama Haruhiko , Soma Mitsuyuki 
Published: September 2006

AbstractThe effect of heating on montmorillonites containing exchangeable Na and K has been studied by X-ray photoelectron spectroscopy (XPS). The surface composition of the unheated montmorillonite was consistent with the bulk composition, but after the sample recrystallized at 1100°C, the surface abundance of Na increased, whereas that of K decreased. Because Na and K were not present in the high-temperature crystalline products, this behavior suggests that a noncrystalline material separated from the crystalline products. The Na 1s binding energy and KL23L23 Auger kinetic energy of montmorillonite were comparable with those of Na in typically ionic compound, such as NaCl. These electron energies became smaller and larger, respectively, on heating and approached those of feldspar (albite). The K 2p3/2 binding energy of montmorillonite increased slightly on heating. The K 2p3/2 binding energy of heated sample of montmorillonite was also comparable with that of feldspar (orthoclase). These results suggest that Na and K were incorporated into feldspar-like noncrystalline materials.
Current Problems with the Nomenclature of Phyllosilicates
Authors: Zvyagin B. B. 
Published: September 2006

AbstractThe nomenclature of phyllosilicates is discussed in relation to structural variations of layers and interlayers. Some discrepancies in the nomenclature which arose due to historical reasons and different viewpoints may be reconciled if the choice of the construction units (layers or their parts) is related to definite sets of structures for which these units are common. Features of idealized models approximating real structures should be considered for classification and derivation of nomenclature sets, whereas priority is given to structural variations before lattice and symmetry characteristics. Layer polymorphs, pseudo-polytypes, polytypes (both simple and complex), and OD structures are distinguished. Particular results obtained for micas as a model example of phyllosilicates in relation to modular structures in general are considered in an Appendix.
Quantitative X-Ray Diffraction Analysis of Clay-Bearing Rocks From Random Preparations
Authors: Środoń Jan , Drits Victor A. , McCarty Douglas K. , Hsieh Jean C. C. , Eberl Dennis D. 
Published: September 2006

AbstractAn internal standard X-ray diffraction (XRD) analysis technique permits reproducible and accurate calculation of the mineral contents of rocks, including the major clay mineral families: Fe-rich chlorites + berthierine, Mg-rich chlorites, Fe-rich dioctahedral 2:1 clays and micas, Al-rich dioctahedral 2:1 clays and micas, and kaolinites. A single XRD pattern from an air-dried random specimen is used. Clays are quantified from their 060 reflections which are well resolved and insensitive to structural defects. Zincite is used as the internal standard instead of corundum, because its reflections are more conveniently located and stronger, allowing for a smaller amount of spike (10%). The grinding technique used produces powders free of grains coarser than 20 µm and suitable for obtaining random and rigid specimens.Errors in accuracy are low, <2 wt. % deviation from actual values for individual minerals, as tested on artificial shale mixtures. No normalization is applied and thus, for natural rocks, the analysis is tested by the departure of the sum of the measured components from 100%. Our approach compares favorably with other quantitative analysis techniques, including a Rietveld-based technique.
Microtextures and the Origin of Muscovite-Kaolinite Intergrowths in Sandstones of the Utrillas Formation, Basque Cantabrian Basin, Spain
Authors: Arostegui Javier , Irabien María Jesús , Nieto Fernando , Sangüesa Javier , Zuluaga María Cruz 
Published: September 2006

AbstractMuscovite-kaolinite intergrowths found in Albian sandstones of the Basque Cantabrian basin (northern Spain) were studied by optical, scanning and electron microscopy and electron microprobe analysis. Kaolinitization begins at grain edges, forming the characteristic fanned-out textures, and propagates toward the interior along the cleavages of muscovite. Kaolinite and muscovite occur as thick packets, being free of interlayering. Phase boundaries between both minerals show bidimensional crystallographic continuity, and no intermediate phases have been identified. The data obtained suggest that muscovite only supplied a template suitable for the epitactic crystallization of kaolinite, while Al was available in sufficient amounts due to the dissolution of detrital K-feldspar. Very small packets of magnetite or maghemite showing a coherent orientation with the kaolinite crystals have been recognized, and could be responsible for the small Fe contents usually detected in electron microprobe analyses of kaolinite.Textural relationships between authigenic kaolinite and deformation microstructures in the intergrowths, combined with previous information about burial conditions, show that alteration proceeded during a late stage of the diagenetic history, related to the uplift of the studied materials as a result of the Alpine orogeny.