bluuebunny/crossref_metadata_2025_split huggingface dataset:
Reduction of Nitrate By Fe2+ in Clay Minerals
Authors: Ernstsen Vibeke 
Published: August 2006

AbstractIn the 12 km2 catchment area of Syv creek, Denmark, moderate to high concentrations of nitrate (NO3−) occurred in the upper part of the oxidized zone (oxic-I), but dropped within the lower suboxic part (oxic-II), to below the detection limit in the unoxidized zone. Structural Fe2+ in the clay minerals made up 10 to 12% of the Fe in the oxidized zone and increased to approximately 50% in the unoxidized zone. Concurrent with changes in the distribution of structural Fe2+ the clay mineral constituents changed. Vermiculite was typically found in the oxidized zone whereas chlorite was found in the unoxidized zone only. A conversion of illite and chlorite into vermiculite seems to take place. A significant correlation between NO3− and the amount of reduced Fe2+ in the suboxic (oxic-II) zone, indicates that primary structural Fe2+ in the clay minerals is the reductant in a NO3− reduction process.
The Dehydroxylation of the Kaolinite Clay Minerals using Infrared Emission Spectroscopy
Authors: Frost Ray L. , Vassallo Anthony M. 
Published: August 2006

AbstractThe dehydroxylation of a series of the kaolinite clay minerals, kaolinite, halloysite and dickite, has been investigated by Fourier transform in situ infrared emission spectroscopy over a temperature range of 100 to 800°C at both 50 and 5° intervals. Excellent correspondence was obtained between the high temperature emission spectra and FTIR absorption spectra of the quenched clay mineral phases. The major advantage of the technique lies in the ability to obtain vibrational spectroscopic information in situ at the elevated temperature. Dehydroxylation at a number of temperatures was determined by the loss of intensity of hydroxyl bands as indicated by intensity changes of the 3550 cm−1 to 3750 cm−1 emission spectra. As with all clay minerals, kaolinite clay mineral dehydroxylation is structure dependent. No clay phase changes occur until after dehydroxylation takes place. The kaolinite clay mineral loses the inner sheet and inner hydroxyl groups simultaneously, whereas dickite and halloysites are shown to lose the outer hydroxyls, as evidenced by the intensity loss of the ~3684 cm−1 peak, before the inner hydroxyl groups as determined by the intensity loss of the 3620 cm−1 peak. Evidence for a high temperature stable hydroxyl band at 3730 cm−1 for dickite and halloysite was obtained. This band is attributed to the formation of a silanol group formed during the dehydroxylation process. It is proposed that the dehydroxylation process for kaolinite takes place homogenously and involves 2 mechanisms. The dehydroxylation of dickite and halloysite takes place in steps, with the first hydroxyl loss taking place homogenously and the second inhomogenously.
The Natural Occurrence of Eta-Alumina (η-Al2O3) in Bauxite
Authors: Tilley David B. , Eggleton Richard A. 
Published: August 2006

AbstractApproximately 20 wt.% of the bauxite from Andoom in northern Queensland, Australia is composed of material that cannot be accounted for by identifiable well-crystallized phases. This poorly-diffracting material (PDM), found within the core of bauxitic pisoliths, has similar characteristics to that of eta-alumina (η-Al2O3); a cubic form of alumina. A differential XRD pattern of the PDM displayed a series of broad diffraction maxima attributed to eta-alumina with a mean crystal size of 9 nm. Unit cell refinement, on the basis of a cubic cell, gave a lattice parameter of a = 7.98 Å for Andoom eta-alumina. TEM and selected-area electron diffraction revealed the PDM to be composed of minute (10 nm wide), randomly oriented crystals of eta-alumina in close association with Al-hematite. Chemical analysis using a nanoprobe showed Andoom eta-alumina to be almost pure alumina with <2 M% Fe, <1 M% Si and <1 M% Ti. The closely associated Al-hematite may contain as much as 22 M% Al, however a value closer to the theoretical limit of 17 M% is more likely. A broad absorption band at 3450 cm−1 and 1630 cm−1 in the infra-red spectrum of the PDM indicates the presence of a substantial quantity of H2O, strongly adsorbed onto the surface of the crystals. This is presumably due to η-Al2O3's large surface area of approximately 2200 m2/g. The natural occurrence of η-Al2O3 in bauxite may be the result of low H2O activities within the micro-environment of pores at the time of crystallization. The epigenetic replacement of kaolinite with η-Al2O3 and Al-hematite is put forward as an explanation for the formation of bauxitic pisoliths at Andoom.
Particle Shape versus Coherent Scattering Domain of Illite/Smectite: Evidence from HRTEM of Dolná Ves Clays
Authors: Šucha Vladimír , Środoń Jan , Elsass Francoise , McHardy William J. 
Published: August 2006

AbstractFundamental particle thickness measurements of Dolná Ves hydrothermal illite/smectite (I/S) samples confirmed earlier findings regarding the content of fixed cations in illite interlayers (ca. 0.9/O10(OH)2). The distributions of fundamental particles and mixed-layer crystals of a given sample are internally consistent. In samples dominated by bilayer fundamental particles, mixed-layer crystals most often contain even numbers of layers. The expandabilities measured by XRD are much higher than so-called minimum expandabilities obtained from HRTEM measurements. This discrepancy is explained by assuming that the coherent scattering domains of Dolná Ves clays do not correspond to natural mixedlayer crystals but are thicker, probably due to parallel association of crystals on the oriented XRD slide. This tendency to produce intercrystal contacts is probably related to the unusually large ab dimensions of crystals of Dolná Ves clays.
Comparison of Techniques for Determining the Fractal Dimensions of Clay Minerals
Authors: Malekani Kalumbu , Rice James A. , Lin Jar-Shyong 
Published: August 2006

AbstractSmall-angle X-ray scattering (SAXS), adsorption and nuclear magnetic resonance (NMR) techniques were used to determine the fractal dimensions (D) of 3 natural reference clays: 1) a kaolinite (KGa-2); 2) a hectorite (SHCa-1), and 3) a Ca-montmorillonite (STx-1). The surfaces of these clays were found to be fractal with D values close to 2.0. This is consistent with the common description of clay mineral surfaces as smooth and planar. Some surface irregularities were observed for hectorite and Ca-montmorillonite as a result of impurities in the materials. The SAXS method generated comparable D values for KGa-2 and STx-1. These results are supported by scanning electron microscopy (SEM). The SAXS and adsorption methods were found to probe the surface irregularities of the clays while the nuclear magnetic resonance (NMR) technique seems to reflect the mass distribution of certain sites in the material. Since the surface nature of clays is responsible for their reactivity in natural systems, SAXS and adsorption techniques would be the methods of choice for their fractal characterization. Due to its wider applicable characterization size-range, the SAXS method appears to be better suited for the determination of the fractal dimensions of clay minerals.
Estimation of the Zeolite Contents of Tuffaceous Samples from the Bigadiç Clinoptilolite Deposit, Western Turkey
Authors: Sirkecioğlu Ahmet , Erdem-Şenatalar Ayşe 
Published: August 2006

AbstractVariation of the NH4+-exchange and CO2-adsorption capacities with zeolite content was investigated in detail to assess the potential use of these capacities for the estimation of the zeolite contents of the samples taken from the Bigadiç clinoptilolite deposit in western Anatolia, as an alternative to the widely used semi-quantitative X-ray diffraction (XRD) technique. Samples with known clinoptilolite contents taken from 2 different zones with fine- and coarse-grained tuffs of the Bigadiç deposit were used for this purpose. Na-enriched forms of the samples were prepared by repeated ion-exchange with NaCl solutions, and NH4+-forms by repeated Na exchange followed by NH4+ exchange with NH4Cl solutions, which in turn were calcined to obtain the H-forms. NH4+-exchange capacities by Kjeldahl analyses of the NH4+-forms and CO2 adsorption isotherms in the 0 to 100 kPa range of Na- and H-forms of the samples were determined. Dubinin-Astakhov model parameters were calculated from the isotherm data.A strong relationship exists between the experimental CO2-adsorption capacities at 100 kPa of the Na-forms and the zeolite contents of the samples. Although the Dubinin-Astakhov model represented the isotherm data quite well, the relationships between the amounts of adsorbate at saturation pressure, calculated from the model, and the zeolite contents of the samples were weaker. The strength of the relationship between NH4+ exchange capacities and zeolite contents was seen to vary with the zone of origin. There is a very strong relationship between the adsorption and ion-exchange capacities of the samples in their Na-forms taken from the fine-grained zone, indicating that either ion-exchange or adsorption capacity measurements can be used to estimate the zeolite contents of the samples taken from this zone, whereas, significant diffusion hindrance was observed against ion-exchange of hydrated cations from aqueous solutions for some samples from the coarse-grained zone. Inspection of the data pointed to systematic errors in the zeolite contents determined by a semi-quantitative XRD technique. When both zones are considered together, CO2-adsorption capacities at 100 kPa of the samples in their Na-forms can be used as a reliable measure of the zeolite content, which in turn is an important index to predict the performance of natural samples in various applications.
Illite Polytype Quantification Using Wildfire© Calculated X-Ray Diffraction Patterns
Authors: Grathoff Georg H. , Moore D. M. 
Published: August 2006

AbstractIllite polytype quantification allows the differentiation of diagenetic and detrital illite components. In Paleozoic shales from the Illinois Basin, we observe 3 polytypes: 1Md, 1M and 2M1. 1Md and 1M are of diagenetic origin and 2M1 is of detrital origin. In this paper, we compare experimental X-ray diffraction (XRD) traces with traces calculated using WILDFIRE© and quantify mixtures of all 3 polytypes, adjusting the effects of preferred orientation and overlapping peaks. The broad intensity (“illite hump”) around the illite 003, which is very common in illite from shales, is caused by the presence of 1Md illite and mixing of illite polytypes and is not an artifact of sample preparation or other impurities in the sample. Illite polytype quantification provides a tool to extrapolate the K/Ar age and chemistry of the detrital and diagenetic end-members by analysis of different size fractions containing different proportions of diagenetic and detrital illite polytypes.
Hydrothermal Crystallization of Ammonium-Saponite at 200 °C and Autogenous Water Pressure
Authors: Vogels Roland J. M. J. , Breukelaar Johan , Kloprogge J. Theo , Jansen J. Ben H. , Geus John W. 
Published: August 2006

AbstractThe effects of reaction time (2 to 72 h) and NH4+/A13+ molar ratio (1.6, 2.4 and 3.2) on the hydrothermal synthesis of ammonium-saponites are investigated. The gels are obtained by mixing powders, resulting in a stoichiometric composition, Mg3Si34Al0.6O10(OH)2, with aqueous ammonium solutions, with and without F, to result in initial NH4+/Al3+ molar ratios of 1.6, 2.4 and 3.2. The solid bulk products are characterized by X-raydiffraction (XRD), X-ray fluorescence (XRF) and scanning electron microscopy (SEM) combined with energy-dispersive X-ray (EDX) analysis. The cation exchange capacity (CEC) is determined with an ammonia selective electrode and the pH of the water from the first washing is measured. Ammonium-saponite is formed rapidly within 16 h. A higher NH4+/A13+ molar ratio and the presence of F facilitate the crystallization of saponite. Small metastable amounts of bayerite, Al(OH)3, are present at low NH4+/A13+ molar ratios; after short reaction times, they disappear. During the first 4 h, the pH decreases rapidly, then drops slowly to a constant level of approximately 4.6 after 60 h. With increasing reaction time, saponite crystallites grow in the ab directions of the individual sheets with almost no stacking to thicker flakes. The NH4+ CEC of the solid products increases strongly within the first 24 h. A maximum of 53.3 meq/100 g is observed. The saponite yield increases from approximately 25% after 2 h to almost 100% after 72 h.
Weathering of Chlorite to a Low-Charge Expandable Mineral in a Spodosol on the Apennine Mountains, Italy
Authors: Carnicelli Stefano , Mirabella Aldo , Cecchini Guia , Sanesi Guido 
Published: August 2006

AbstractThe clay fraction of a Spodosol and its parent rock in the Apennine mountains of central Italy were studied by powder X-raydiffraction (XRD) and infrared (IR) spectroscopy, to evaluate the possibility of transformation of chlorite into low-charge expandable minerals. Results indicated that the main phyllosilicate in the rock was a slightly weathered trioctahedral chlorite, rich in both Mg and Fe, together with dioctahedral mica and minor amounts of kaolinite. In the BC horizon, chlorite has undergone partial transformation into 2 vermiculitic components, in 1 of which the interlayer could be removed by hot Na-citrate treatment; the presence of a regular interstratified mineral (high-charge corrensite) was also observed. Further changes in the structure of chlorite were detected in the Bsl horizon, becoming more evident towards the soil surface. The first stage of weathering of chlorite involved Fe oxidation and partial expulsion of Mg from the hydroxide sheet, followed by deposition of Al in the interlayer space. Iron is also removed from the interlayer sheet, possibly remaining, in the oxidized state, in the 2:1 octahedral sheet, and so contributing to the lowering of layer charge and transformation to a dioctahedral structure. When approaching the surface, Al removal from the interlayers is enhanced by complexing agents, and further charge reduction leads to the formation of 2:1 minerals with a smectite nature. Illite, because of its low content in the soil clay fraction, contributes marginally to this weathering sequence, forming the high charged expandable component observed in the Bhs horizon. At the soil surface, arandomly interstratified vermiculite/illite was detected, which probably originated from K fixation by the higher-charged expandable minerals. This study of weathering in a natural soil strongly supports the hypothesis, previously ascertained by laboratory experiments, that chlorite can transform into a low-charge expandable mineral.
Smectite Illitization in Pliocene-Age Gulf of Mexico Mudrocks
Authors: Rask J. H. , Bryndzia L. T. , Braunsdorf N. R. , Murray T. E. 
Published: August 2006

AbstractUtilizing high-resolution transmission electron microscopy (TEM), energy-dispersive spectroscopy (EDS) and X-raydiffraction (XRD) techniques, we have studied the transition from shallower smectite-rich mudrocks to deeper illite-rich mudrocks in Pliocene-age turbidite sediments from the northern Gulf of Mexico (GOM). Our objective in this work was to better understand how the smectite-illite transition may affect the onset of geopressuring in GOM sediments. The samples studied were sidewall cores from an offshore Louisiana well. In previous studies of GOM sediments, the smectite-to-illite reaction has mainly been documented in considerably older, Miocene-age sediments.The results of this study elucidate the reaction mechanisms entailed in the transformation of clays in this sediment from smectitic to illitic. We found that illite formed at the expense of smectite in 2 ways: 1) growth of preexisting discrete illite flakes, and 2) creation of new illite layers within mixed-layer illite-smectite. Also, illitization apparently proceeded via a dissolution/precipitation, Al-conserving reaction rather than a solid-state, layer-conserving reaction. Smectite illitization is commonly believed to require input of K from feldspar dissolution. Our XRD results found little correlation between decreases in K-feldsparand increases of illite. However, in 1 instance TEM/EDS analyses indicated the presence of high-charge smectite, which suggests that insufficient K was available for illitization. TEM images also show small packets of authigenic chlorite in illite-rich mudrock. This chlorite may act as a sink for Fe liberated upon smectite illitization.
Illite Crystallinity and Fluid Inclusion Analysis Across a Paleozoic Disconformity in Central Korea
Authors: Lee Yong Il , Ko Hee Kyeong 
Published: August 2006

AbstractIllite crystallinity and fluid inclusion techniques are used to understand the thermal histories of rocks on either side of the disconformity between the Lower and Upper Paleozoic strata in South Korea. Illite crystallinity studies show that the metamorphic grade of the upper strata of the Lower Paleozoic Joseon Supergroup, platform carbonates with subordinate siliciclastics, belongs to the epizone and that of the lowermost strata of the Upper Paleozoic Pyeongan Supergroup, paralic to nonmarine clastics, belongs to the anchizone. The maximum mode of homogenization temperature for fluid inclusion of the uppermost strata of the Joseon Supergroup is 260 to 270 °C and that of the lowermost strata of the Pyeongan Supergroup is 240 to 250 °C. These data reveal a difference in thermal histories of strata below and above the unconformity, suggesting that, in contrast to the previous supposition of a period of non-deposition, at least a 1-km thick section of sediment was removed by erosion during development of the unconformity. Burial and heat flux from a proposed hot spot are suggested as the dominant factors causing differences in a metamorphic grade for the Joseon Supergroup before the deposition of the Upper Paleozoic strata.
Wettability Contrasts in Kaolinite and Illite Clays: Characterization by Infrared and X-Ray Absorption Spectroscopies
Authors: Bantignies Jean-Louis , Cartier dit Moulin Christophe , Dexpert Hervé 
Published: August 2006

AbstractA reservoir rock is a porous geological formation in contact with 2 liquids, brine and oil. An improved knowledge of rock wettability is of primary importance to estimate the amount of crude oil in underground resources. The petroleum industries have observed that wettability contrasts in sedimentary reservoir rocks are largely correlated to the presence of clays, illite and/or kaolinite in the rocks’ intergranular space.More precisely, the grain surfaces of illite show a preference for brine. Kaolinite preferentially adsorbs oil, which imparts its hydrophobic characteristics to the mineral surface. Using X-ray absorption spectroscopy (XAS) and Fourier transform infrared (FTIR) spectroscopy, we studied the adsorption process of asphaltenes in the presence of water at the microscopic level. We demonstrate experimentally that the wettability contrasts observed in kaolinite and illite are related to structural differences between these 2 clays, and we show the role of the grain surface hydroxyls. With clay materials, the purity of the samples is the most important limitation of the quantitative use of extended X-ray absorption fine structure (EXAFS).
Thermal Characterization of Poly(Styrene Sulfonate)/Layered Double Hydroxide Nanocomposites
Authors: Oriakhi Christopher O. , Farr Isaac V. , Lerner Michael M. 
Published: August 2006

AbstractPhase and morphological changes during thermolysis of Mg4Al2(OH)12CO3·nH2O and Zn6Al2(OH)16CO3·nH2O layered double hydroxides (LDH) and their nanocomposites with poly(styrene sulfonate) (PSS) are studied by X-ray powder diffraction (XRD), scanning and transmission electron micrography (SEM and TEM) and thermal analyses. Mg4Al2(OH)12CO3·nH2O and Mg2Al(OH)6[CH2CH(C6H4SO3)]·3H2O show comparable thermal stabilities: the layered structure is lost above 300 °C with the nucleation of the MgO phase at approximately 400 °C and the MgAl2O4 phase at approximately 800 °C Zn3Al(OH)8[CH2CH(C6H4SO3)]·nH2O undergoes complete oxidative pyrolysis of the polyanion by 500 °C. Crystalline oxide products are obtained at a temperature approximately 300 °C lower than that of thermolysis of Zn6Al2(OH)16CO3·nH2O. The SEM and TEM images show that the thermolysis of LDH carbonates produces dense aggregates containing microcrystalline particles, whereas Mg2Al(OH)6[CH2CH(C6H4SO3)]·3H2O forms a macroporous solid.
Equilibrium Modeling of Clinoptilolite-Analcime Equilibria at Yucca Mountain, Nevada, USA
Authors: Chipera Steve J. , Bish David L. 
Published: August 2006

AbstractYucca Mountain, Nevada, is being investigated to determine its suitability to host a potential high-level radioactive waste respository. An important reason for its choice as a potential repository site was the presence of thick zeolite-rich horizons in the altered volcanic tufts that compose the mountain. Clinoptilolite is the most abundant zeolite at Yucca Mountain and may be important in radionuclide retardation and in determining hydrologic properties. Therefore, it is necessary to understand the geochemical conditions affecting its long-term stability. For example, it has been suggested that long-term, repository-induced heating of the rocks at Yucca Mountain may lead to the transformation of clinoptilolite to analcime, thereby significantly affecting the hydrologic properties and retardation capabilities of the rock.Thermodynamic modeling of clinoptilolite-analcime equilibria was conducted with the program Ge0-Calc PTA-SYSTEM using estimated thermodynamic data for measured chemical compositions of clinoptilolite and analcime at Yucca Mountain. Log[aK+)2/aCa2+] versus log[aNa+)2/aCa2+] diagrams were calculated to model the conditions under which clinoptilolite may transform to analcime. Temperature, relative cation abundances and silica activity are all important factors in determining clinoptilolite-analcime equilibria. Increased Na+ concentrations in either clinoptilolite or the fluid phase, increased clinoptilolite K+ concentration, increased temperature and decreased aqueous silica activity all stabilize analcime relative to clinoptilolite, assuming present-day Yucca Mountain water compositions. However, increased Ca2+ concentrations in either clinoptilolite or the fluid phase, increased aqueous K+ concentration and increased Al:Si ratios in clinoptilolite (heulandite) all stabilize clinoptilolite with respect to analcime.Assuming well J-13 water as the analog chemistry for Yucca Mountain water, clinoptilolite should remain stable with respect to analcime if temperatures in the clinoptilolite-bearing horizons do not significantly exceed 100 °C. Even if temperatures rise significantly (for example, to 150 °C not all clinoptilolite should alter to analcime. Perhaps more importantly, thermodynamic modeling suggests that some Yucca Mountain clinoptilolites, particularly those rich in Ca and Al, will remain stable at elevated temperatures, even with an aqueous silica activity at quartz saturation.