Volume 47 - June 1999
Research Article
Direct Imaging of Zirconia Pillars in Montmorillonite by Analytical Electron Microscopy
- P. A. Crozier, M. Pan, C. Bateman, J. J. Alcaraz, J. S. Holmgren
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- 28 February 2024, pp. 683-687
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Analytical electron microscopy was used to confirm the location of pillars of zirconia in pillared montmorillonite. Data show that the pillared clay is of “high” quality, with surface areas ranging from 200 to 250 m2/g and (001) spacings in the 17–18 Å range. The zirconia-rich pillars were observed using bright-field imaging, annular dark-field imaging, and energy-filtered imaging. The composition of the pillars was confirmed by performing nano-analysis using energy-dispersive X-ray spectroscopy and electron energy-loss spectroscopy. The pillars apparently have an irregular shape <50 Å in size. The shape and relatively large size of the pillars suggest that zirconia dispersion is not ideally distributed in this sample. This study is apparently the first report of electron microscopy observation of pillaring material in clays.
Application of an Internal Standard Technique by Transmission X-Ray Diffraction to Assess Layer Charge of a Montmorillonite by Using the Alkylammonium Method
- M. Janek, L’. Smrčok
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- 28 February 2024, pp. 113-118
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Transmission X-ray diffraction (XRD) of C6–16 alkylammonium ion-exchanged montmorillonite SAz-1 with Ag-behenate as an internal standard provided accurate estimates of d(001) values of the alkylammonium ion-exchanged montmorillonite. Inspection of d(001) values were made to assess the possible formation of gauche conformers (alternate arrangements of the molecules) in the interlayer and to determine the critical carbon chain length, nC. Using conventional constraints for nC(I′) and nC(II) equal to 1.36 and 1.77 nm, respectively, provided ambiguous nC(I′) and nC(II) values. The dependence of full-width at half-maximum values on nC allowed better estimates of nC(I′) and nC(II) because “integral” and “non-integral” peak characteristics relating to interstratification could be included in the assessment.
The effect of inaccurate estimates of nC(I′) and nC(II) values on calculated interlayer cation exchange capacity (Ci) using two conventional concepts of calculation were compared. It was found that a procedure based on the summation of fractions of the layer charge gave relative errors of Ci <2%, even where the number of carbon atoms corresponding to both nC(I′) and nC(II) differed by ± 1 nC from the correct values. This method of calculation of Ci is recommended when reliable values of Ci are needed.
Clay Mineralogy and Occurrence of Ferrian Smectites Between Serpentinite Saprolites and Basalts in Biga Peninsula, Northwest Turkey
- Ö. Işik Ece, Fazli Çoban, Nurfer Güngör, Fikret Suner
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- 28 February 2024, pp. 241-251
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The clay mineralogy of an oxisol-saprolite overlying serpentinite and underlying basalt was studied with different techniques to evaluate the clay mineral transformation that occurred and to understand the origin of Fe3+-rich smectite. The saprolite zone of the oxisol, up to 30 m thick, contains smectites of the montmorillonite-beidellite and montmorillonite-nontronite series, as well as illite, chlorite, talc, and goethite or amorphous oxyhydrates. Illite is mainly concentrated in the upper 50 cm thick zone underlying the basalt layer and chlorite-content increases toward altered serpentinite at the base. Minor amounts of nontronite formed mostly toward westward exposures where the hot contact layer between serpentinite and basalt is only 20 cm thick. Greene-Kelly Li-tests revealed that all samples contain montmorillonite, but one sample shows the presence of a minor amount of beidellite.
Parent rocks are a mixture of mainly mica schist (the source of beidellite), and minor serpentinite in different percentages and laterally distributed. These rocks were intensely weathered under humid climatic conditions. Silica was concentrated as amorphous transparent (pure silica) cobbles and milky quartz pebbles, and originated from geothermal solutions rising through the Ovaclk thrust fault. The Mg partly formed chlorite. Ferrian smectites in serpentinites were derived obviously from the Mg-rich minerals but Mg is lost much more rapidly than Si during the formation of the clay deposit. The structural formula of the most Fe-rich smectite samples from the study area is (Si6.60−7.10Al1.40−0.90)(Al2.54−1.22Mg0.32−0.92Fe3+1.18−1.68−Ti0.06−0.04)(Ca0.16−0.10Na0.02K0.02−0.12)O20(OH)4. This composition is within the range recorded for the ferrian montmorillonite-beidellite series, with very little vermiculite forming the oxisol-vertisol horizon.
Destinezite (“Diadochite”), Fe2(PO4)(SO4)(OH)·6H2O: Its Crystal Structure and Role as a Soil Mineral at Alum Cave Bluff, Tennessee
- Donald R. Peacor, Roland C. Rouse, T. Dennis Coskren, Eric J. Essene
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- 28 February 2024, pp. 1-11
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A new occurrence of destinezite (diadochite), ideally Fe2(PO4)(SO4)(OH)·6H2O, is described from Alum Cave Bluff, Great Smoky Mountains National Park, Tennessee, where it occurs in soil and in a weathered Precambrian phyllite in unusually large crystals associated with other hydrated sulfates such as pickeringite-apjohnite. Destinezite is triclinic, P1̄, with a = 9.570(1), b = 9.716(1), c = 7.313(1) Å, α = 98.74(1)°, β = 107.90(1)°, γ = 63.86(1)° and Z = 2. Its crystal structure consists of infinite chains of Fe(O,OH,H2O)6 octahedra, sulfate tetrahedra and phosphate tetrahedra linked by a unique system of vertex sharing. The chains are weakly bonded into slabs by hydrogen bonding between OH and H2O of the Fe(III) octahedra and oxygen ions of the sulfate tetrahedra. Slabs of tetrahedral/octahedral chains alternate with sheets of H2O molecules. The structure thus somewhat resembles hydrated clay minerals, with H2O molecules that act as hydrogen bond donors and acceptors to oxygen atoms of adjacent slabs. Destinezite and diadochite occur at numerous localities worldwide and have been assumed to be identical, but this identity has never been proven. It is proposed that the name “destinezite” be applied to visibly crystalline, triclinic Fe2(PO4)(SO4)(OH)·6H2O and “diadochite” to massive to earthy, poorly ordered, X-ray amorphous materials that approximate destinezite in composition. Diadochite/destinezite may be an unrecognized component of soils where weathering of pyrite and apatite has occurred and pH is low. It may thus be a significant sink for phosphorus and sulfur in such soils.
Review Article
Synthesis of Smectite Clay Minerals: A Critical Review
- J. Theo Kloprogge, Sridhar Komarneni, James E. Amonette
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- 28 February 2024, pp. 529-554
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Smectites are one of the most important groups of phyllosilicates found in soils and sediments, and certainly one of the most difficult to study. New information about the formation mechanisms, impact of structural features on surface properties, and long-term stability of smectites can best be gained from the systematic study of single-phase specimens. In most instances, these specimens can only be obtained through synthesis under controlled conditions. Syntheses of smectites have been attempted (1) at ambient pressure and low-temperature (<100°C), (2) under moderate hydrothermal conditions (100–1000°C, pressures to several kbars), (3) under extreme hydrothermal conditions (>1000°C or pressures >10 kbars), and (4) in the presence of fluoride. Of these approaches, syntheses performed under moderate hydrothermal conditions are the most numerous and the most successful in terms of smectite yield and phase-purity. Using hydrothermal techniques, high phase-purity can be obtained for beidellites and several transition-metal smectites. However, synthesis of montmorillonite in high purity remains difficult. Starting materials for hydrothermal syntheses include gels, glasses, and other aluminosilicate minerals. The presence of Mg2+ seems to be essential for the formation of smectites, even for phases such as montmorillonite which contain low amounts of Mg. Highly crystalline smectites can be obtained when extreme temperatures or pressures are used, but other crystalline impurities are always present. Although the correlation between synthesis stability fields and thermodynamic stability fields is good in many instances, metastable phases are often formed. Few studies, however, include the additional experiments (approach from under-and over-saturation, reversal experiments) needed to ascertain the conditions for formation of thermody-namically stable phases. Thorough characterization of synthetic products by modern instrumental and molecular-scale techniques is also needed to better understand the processes leading to smectite formation.
Research Article
Smectites in Iron-Rich Calcareous Soil and Black Soils of Taiwan
- Chuang-Wen Pai, Ming-Kuang Wang, Wei-Min Wang, Kun-Huang Houng
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- 28 February 2024, pp. 389-398
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The iron-rich calcareous soil (Typic Rhodustalf) from the Penghu island group represents a volcanic area. The black soils (Typic Haplustert, Vertic Endoaquoll, Typic Hapludolls) are typical of eastern Taiwan. Four A horizons and a pedon from the iron-rich calcareous soil and four pedons from the black soils were studied to analyze soil properties and clay compositions. The objective was to compare the properties of smectites developed from different parent materials. The materials were studied by using conventional X-ray diffraction (XRD) of K- and Mg-saturated clays and involved the alkylam-monium (C = 12) method and the Greene-Kelly test. The mean-layer charge of smectites (0.48–0.52 cmol(c)/O10(OH)2) in the iron-rich calcareous soil was found to be higher than the black soils (0.43–0.48 cmol(c)/O10(OH)2). A smectite of higher charge developed from the basalts. This smectite is enriched in Fe and Mg, and lacks Si, thereby forming beidellite and/or nontronite. In contrast, under high precipitation, elevated temperature, base saturation (e.g., Na, K, Ca, Mg), and about equal wet and dry cycles per year in the black soil environments, smectites developed from the complicated geologic site of eastern Taiwan. These smectites transformed to smectite-kaolinite mixed-layer clay and thus, resulted in lower-charge smectites. The K fixation capacity of the iron-rich calcareous soil was higher than the black soils.
“Retrograde Diagenesis” of Clay Minerals in the Precambrian Freda Sandstone, Wisconsin
- Gengmei Zhao, Donald R. Peacor, S. Douglas Mcdowell
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- 28 February 2024, pp. 119-130
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Siltstones from the Precambrian Freda Formation in Wisconsin have been studied by scanning, scanning-transmission and analytical electron microscopy (SEM, STEM and AEM), and X-ray diffraction (XRD). XRD data for drill core samples show a change from smectite-rich Illite-Smectite (I-S) in shallow samples to illite in deeper samples, implying a transition during burial diagenesis.
Transmission electron microscopy (TEM) observations of shallow samples reveal the presence of three clearly distinguishable kinds of dioctahedral clay minerals: (1) detrital grains of micrometer-sized, mature muscovite; (2) small packets in the matrix consisting of dominant (Reichweite) R1 I-S or (3) small packets of illite. The illite and I-S stacks occur separately and have similar textures, with packet thicknesses averaging ∼400 Å, within the range of anchizonal illite. Illite and detrital muscovite commonly display strain features typical of the effects of tectonic stress. Void space within I-S or illite packets is inferred to be a strain feature, and to have served as pathways for fluids. Detrital muscovite shows abundant alteration features including (001) boundaries which are continuous with parallel packets of I-S; individual layers commonly show along-layer transitions of muscovite to smectite or I-S. Trioctahedral clays consist primarily of detrital chlorite which commonly shows direct alteration to R1 I-S and smectite, as with detrital muscovite.
Deep samples contain only unaltered, coarse detrital muscovite, and thin packets of illite forming stacks and comprising most of the matrix. The texture of the illite appears to be identical to that of shallow samples, with characteristics such as packet size typical of anchizonal illite. Trioctahedral clays consist almost entirely of detrital grains of chlorite and corrensite. They occur as separate grains with rather constant composition, without signs of alteration.
The data imply that all of the studied rocks have been subjected to a uniform anchizonal grade of metamorphism in which detrital grains were largely unchanged but matrix clays were transformed to packets of illite. The unusually abrupt transition with depth from highly expandable I-S to illite is inferred to actually be the result of subsequent alteration of authigenic illite and detrital chlorite and muscovite to R1 I-S and smectite in shallow rocks. This late overprinting of the anchimetamorphic clay mineral assemblage is inferred to have been locally caused by fluids with temperatures less than those of peak metamorphism. This process, called “retrograde diagenesis”, gave rise to a sequence of dioctahedral I-S and illite which mimics classic prograde sequences. Interpretations of such sequences as being prograde, especially in cases of ancient rocks, should be interpreted with caution when high-resolution images of textures are not available.
Mg-Smectite Authigenesis in a Marine Evaporative Environment, Salina Ometepec, Baja California
- Victoria C. Hover, Lynn M. Walter, Donald R. Peacor, Anna M. Martini
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- 28 February 2024, pp. 252-268
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Formation of authigenic trioctahedral Mg-rich smectite is common in evaporative lake sediments, but was not described previously in modern marine evaporative environments. This study documents formation of authigenic K-rich, Mg-smectite during very early diagenesis in the dominantly siliciclastic Salina Ometepec (Baja California), a large supratidal evaporative sabkha complex near the mouth of the Colorado River. Here, sediment pore waters are exceptionally Mg2+-rich relative to other marine evaporative environments due to suppressed sulfate reduction which limits production of carbonate alkalinity and, hence, carbonate (particularly dolomite) precipitation. Sediment cores were obtained along a five km transect seaward across the hypersaline mud flat to evaluate how these atypical geochemical conditions would affect the clay mineral compositions.
Scanning transmission electron microscopy (STEM) observations show that the smectite from the marine Inlet, near the sediment source, consists of grains of irregular shape that give selected area diffraction (SAED) patterns reflecting dominant turbostratic stacking. Analytical electron microscopy (AEM) analyses indicate that K+ is the dominant interlayer cation; the mean composition is approximately K0.7(Al3.3Fe(III)0.3Mg0.5)(Al0.5Si7.5)O20(OH)4. Such smectite is implied to be detrital in part because it is similar to smectite known to be deposited by the Colorado River.
Smectite from the hypersaline mud flat occurs as aggregates of small subhedral pseudohexagonal plate or lath-shaped crystals ≤250 nm in diameter, with thicknesses varying between three and ten layers. The SAED patterns reflect substantial turbostratic stacking, but with a greater frequency of interlayer coherency as compared with detrital smectite. Crystals from greater sediment depths are larger and more nearly euhedral. This smectite is dominantly trioctahedral, with mean composition approximately K0.7(Al0.7Fe(III)0.5Mg4.45)(Al1.2Si6.8)O20(OH)4 (saponitic). This smectite is inferred to be dominantly authigenic in origin.
The X-ray diffraction (XRD) and STEM/AEM data collectively imply that detrital aluminous dioctahedral smectite reacts to form authigenic Mg-rich trioctahedral smectite, driven in part by the high Mg2+/ Ca2+ ratio of pore waters. Such early-formed Mg-rich smectite may be the precursor for the trioctahedral mixed-layer smectite, corrensite, and chlorite assemblages found in ancient marine evaporative sequences. These results also add to the accumulating evidence that interlayer K+ in marine smectite is fixed during the earliest stages of marine diagenesis near the sediment water interface.
A New Approach to Compositional Limits for Sepiolite and Palygorskite
- Emilio Galan, Ma Isabel Carretero
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- 28 February 2024, pp. 399-409
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Most bulk chemical analyses of sepiolite and palygorskite available in the literature are erroneous because samples analyzed are admixtures of minerals that are difficult to separate or identify by other techniques. Some chemical analyses performed on selected individual particles by energy dispersive X-ray analysis (EDX) are also influenced by the same problem. Chemical analyses are summarized for sepiolite and palygorskite reported in the literature (bulk and EDX analyses). The analyses are evaluated by comparison to three sepiolite and three palygorskite pure samples analyzed by EDX techniques. Results indicate that sepiolite is a true trioctahedral mineral, very pure (near end-member) with negligible structural substitution and with eight octahedral positions filled with magnesium, close to the theoretical formula Mg8Si12O30(OH)4(OH2)4(H2O)8. Palygorskite is intermediate between di- and trioctahedral phyllosilicates. The octahedral sheet contains mainly Mg, Al, and Fe with a R2/R3 ratio close to 1, and with four of the five structural positions occupied. The theoretical formula is close to (Mg2R23+?1)(Si8-xAlx)O20(OH)3(OH2)4·R2+x/2(H2O)4, where x = 0–0.5. Sepiolite and palygorskite are thus more compositionally limited than previously reported.
Cation-Exchange Capacity (CEC) of Zeolitic Volcaniclastic Materials: Applicability of the Ammonium Acetate Saturation (AMAS) Method
- Konstantinos P. Kitsopoulos
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- 28 February 2024, pp. 688-696
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The ammonium acetate saturation (AMAS) method was used to study the cation-exchange capacity (CEC) of zeolitic volcaniclastic materials from Santorini and Polyegos Islands, Greece. The AMAS method was tested with respect to the time required to saturate the samples of zeolites with ammonium (NH4+) ions, the efficient liberation of NH4+ ions, and the suitability of two widely used techniques to measure ammonia (NH3) (Kjeldahl ammonia distillation technique and the ammonia electrode technique). By using the inductively coupled plasma-mass spectrometry (ICP-MS) technique and measuring the number of cations exchanged during ammonium acetate (NH4OAc) saturation, it was found that the saturation period for zeolitic materials must be increased to 12-day cycles to ensure effective saturation. Following NH4OAc saturation, the AMAS method produces NH4+ solutions, after the NH4+-saturated samples of zeolites are washed with 10% NaCl. The amount of the NH4+ ions in solution (i.e., exchangeable cations) is a measure of the CEC. The NH4+ ions can not be directly measured and must be converted to NH3. The Kjeldahl ammonia distillation technique and the ammonia electrode technique for measuring NH3 give identical CEC results. However, the ammonia electrode technique, when used directly with the NH4+ samples of zeolite without 10% NaCl treatment, generally gives higher CEC values. The amount of NH4+ treated (converted to NH3), when the NH4+-saturated zeolitized samples were used directly, was higher than the amount of the NH4+ treated when the NH4+ solutions were obtained after washing the NH4+-saturated zeolitized samples with 10% NaCl. Therefore, washing with 10% NaCl does not facilitate the release of all NH4+ initially within the zeolite structure. A modified AMAS technique is proposed for measuring the CEC of zeolitic material.
Determination of Illite-Smectite Structures using Multispecimen X-Ray Diffraction Profile Fitting
- Boris A. Sakharov, Holger Lindgreen, Alfred Salyn, Victor A. Drits
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- 28 February 2024, pp. 555-566
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A procedure for structural investigations by X-ray diffraction of mixed-layer structures incorporating swelling layers has been developed. For each sample, specimens saturated with different cations (Na, Mg, and Ca), are analyzed both as air-dried and as glycolated. One structural model fitting all the observed patterns then provides the structure of the sample. Samples tested include: Mite-smectite (I-S) minerals from Kazachstan (a rectorite), Dolna Ves in Slovakia, Kinnekulle in Sweden, the North Sea, and Scania in Sweden. The fitting of the patterns of the Kazachstan rectorite demonstrated that the instrumental parameters applied in the modeling were correct. For the I-S minerals from Slovakia and Kinnekulle the observed patterns were fitted with one two-component I-S model. However, the Ca-saturated and air-dried specimen of the Kinnekulle bentonites had two types of swelling interlayers. For the Slovakian I-S with Reichweite = 2, an alternative two-phase I-S plus I–V (V = vermiculite) model fitted the experimental X-ray diffraction patterns equally well. The I-S mineral from Scania is in fact a three-component I-T-S (T = tobelite) and the North Sea sample is a four-component I-S-V-V, one type of the swelling layers having swelling characteristics intermediately between smectite and vermiculite. In addition to layer types and distribution, interlayer compositions, such as the amount of interlayer glycol and water and of fixed and exchangeable cations, were determined.
Mineralogical Interference on Kaolinite Crystallinity Index Measurements
- Patricia Aparicio, Emilio Galán
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- 28 February 2024, pp. 12-27
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This study examines the influence of minerals and amorphous phases associated with kaolin and kaolinitic rocks on kaolinite crystallinity indices (KCI) derived from X-ray diffraction (XRD) data in order to select the best index for systematic studies of commercial kaolins or geological sequences. For this purpose, 8 kaolins of differing structural order were chosen and used to prepare mixtures containing different weight fractions of quartz, feldspar, illite, smectite, chlorite, halloysite and iron hydroxide and silica gels. An additional 17 samples of kaolin were also studied to test the results and evaluate the restrictions. KCIs used included Hinckley (HI), Range and Weiss (QF), Liètard (R2), Stoch (IK), Hughes and Brown (H&B) and Amigó et al. (full width at half maximum, FWHM), and the “expert system” of Plançon and Zacharie.
Based on more than 15,000 KCI determinations, the HI and QF are influenced by quartz, feldspar, iron hydroxide gels, illite, smectite and halloysite. IK can be used in the presence of quartz, feldspar and iron hydroxide and silica gels. Also, R2 is the only KCI that could be measured in the presence of halloysite; FWHM indices should not be used in the presence of chlorite and/or halloysite; and H&B should only be used with pure kaolinite samples. The “expert system” of Plançon and Zacharie is strongly affected by the presence of other mineral phases, particularly with more than 25% of well-ordered kaolinite. Their system is less sensitive to other mineral phases when only disordered kaolinite is present, and it should not be used with kaolinite of medium order-disorder because the well-ordered phase is present in an inappreciable proportion (<10%). KCI is only measurable in kaolinitic rocks if kaolinite is >20 wt% and the precision increases with an increase in the quantity of kaolinite. In all cases, the reliability will depend on the other minerals present. When a KCI can be measured accurately, the others can be obtained by using the empirical relationships reported in this paper.
Impact of Different Asbestos Species and Other Mineral Particles on Pulmonary Pathogenesis
- C. J. van Oss, J. O. Naim, P. M. Costanzo, R. F. Giese, Jr., W. Wu, A. F. Sorling
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- 28 February 2024, pp. 697-707
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Factors that are potentially important in the pulmonary pathogenesis of asbestos and other mineral particles are: 1) morphology, 2) Fe-content, 3) solubility under intraphagosomal conditions, 4) value and sign of the surface potential of the particle, 5) hydrophobicity or hydrophilicity, 6) capacity to activate phagocytic leukocytes, and 7) duration of exposure to the particles. The order of importance of these factors in causing severe or fatal pulmonary pathogenicity is estimated to be: 1 > 3 > 7 > 6 ≫ 5 > 4 > 2. The order of pathogenicity of the minerals is estimated as: amphibole asbestos: crocidolite, tremolite, amosite > erionite > serpentine asbestos: chrysotile > talc > silica > simple metal oxides. Particle length, duration of exposure to the particles, and pre-treatment of the particles may however enhance the pathogenic potential of any of the lower-ranked particles.
Removal of Nickel and Cobalt from Aqueous Solutions by Na-Activated Bentonite
- Stella Triantafyllou, Eirini Christodoulou, Paraskevi Neou-Syngouna
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- 28 February 2024, pp. 567-572
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The ability of Na-activated bentonite to remove Ni2+ and Co2+ from aqueous solutions at room temperature (22 ± 1°C) was studied under various experimental conditions. The parameters studied were solid-to-liquid ratios and initial cation concentrations. Experiments involved the behavior of bentonite vs. Ni and Co separately and where Ni and Co were present in solution at different concentrations and ratios. Bentonite retained substantial amounts of both metals readily, but it showed a higher affinity for Ni. Over-exchange appears when initial metal concentration exceeds the concentration corresponding to the cation exchange capacity (CEC) of bentonite. The presence of both metals in solution may be either synergistic or antagonistic sorption, depending on the initial ion concentrations.
A Synthetic Na-Rich Mica: Synthesis and Characterization by 27Al and 29Si Magic Angle Spinning Nuclear Magnetic Resonance Spectroscopy
- Sridhar Komarneni, Rajyalakshmi Pidugu, W. Hoffbauer, Hartmut Schneider
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- 28 February 2024, pp. 410-416
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A swelling mica, Na2Mg3(Al2Si2)O10F2·xH2O, (hereafter “Na-4 mica”) was synthesized from metakaolinite + MgO and Mg aluminosilicate gels at different temperatures and durations using NaF flux. The various samples were characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), and 27A1 and 29Si magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy. The results showed that phase-pure Na-4 mica was obtained from metakaolinite which serves as a cost-effective aluminosilicate source. 27Al MAS NMR spectra showed that all or nearly all Al is in tetrahedral coordination whereas 29Si MAS NMR spectra showed that the nearest neighbor environment of Si is mainly Si(3Al), as expected based on the Si:Al ratio.
Properties of Water in Calcium- and Hexadecyltrimethylammonium-Exchanged Bentonite
- Michael A. Anderson, Frans R. Trouw, Cheok N. Tam
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- 28 February 2024, pp. 28-35
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Dynamical and thermodynamic properties of water at room temperature in Ca- and hexade-cyltrimethylammonium- (HDTMA) exchanged bentonite were determined for 4 different water contents (~0.03–0.55 g water g-1 clay). Incoherent quasi-elastic neutron scattering (QENS) was used to measure the translational and rotational mobility of water in the clays, while chilled mirror dewpoint psychrometry measured water activity of the samples, differential scanning calorimetry (DSC) provided information about the temperature of dehydration and X-ray diffraction (XRD) quantified layer spacings for the clays. The neutron scattering data were fit to a jump diffusion model that yielded mean jump lengths, jump diffusion residence times and rotational relaxation times for water in the clays. Mean jump lengths were quite similar for the 2 different cation saturations at equivalent water contents, and decreased with increasing water content. The fitted jump lengths ranged from 0.27–0.5 nm and were 2–4 times larger than that found for bulk water (0.13 nm). Jump diffusion residence times were 3–30 times longer than that for bulk water (1.2 ps) and also decreased with increasing water content. The residence times were somewhat shorter for HDTMA-clay as compared with Ca-clay at equivalent water contents. Rotational motion was less strongly influenced than translational motion by the presence of the clay surface. The energy state of water in the 2 cation saturations were quite different; dehydration temperatures for the HDTMA-clay were approximately 30 °C lower than the Ca-clay at equal water contents, while water activities, as P/P0, were up to 0.6 units higher. A linear relationship was found between water activity and the translational diffusion coefficient, although at the highest water content, the diffusion coefficient of water for the HDTMA-clay was approximately 30% higher than that measured for bulk water.
Effect of Permo-Carboniferous Climate on Illite-Smectite, Haushi Group, Sultanate of Oman
- Bernhard H. Hartmann, Katalin Juhász Bodnár, Karl Ramseyer, Albert Matter
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- 28 February 2024, pp. 131-143
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The Late Westphalian to Artinskian Haushi Group in the Sultanate of Oman consists of the glaciogenic Al Khlata Formation and the Gharif Formation which contains marginal marine, coastal plain, and fluvial sediments. The sequence was deposited during a global-warming event following the Permo-Carboniferous glaciation of Gondwana. Because of a varied subsidence history, these sediments range from the surface in the SE to almost 5000 m in the NW of the basin.
Mixed-layer illite-smectite (I-S) is an important constituent of the <2 µm size fraction of sandstone and shale samples in both formations at all depths. Different starting compositions lead to three distinct trends of illite layers in I-S versus temperature for different sedimentary environments and paleoclimatic conditions. The starting compositions of I-S at the surface range from an ordered I-S in the Al Khlata Formation to smectite-rich in the Upper+Middle Gharif members.
Physical, chemical and environmental factors were investigated as causes for the different starting compositions of I-S. Both formations share an identical burial history, paragenesis, thermal evolution, and source of detrital material. They differ only in environmental conditions during sedimentation. Thus, the variation in starting composition of I-S appears to be best explained by distinct weathering conditions during sedimentation of the three units. In particular, the expected low intensity of chemical weathering during glaciogenic conditions is marked by the presence of higher amounts of unstable volcanic and sedimentary rock fragments in the Al Khlata Formation.
Clay Diagenesis in the Sandstone Reservoir of the Ellon Field (Alwyn, North Sea)
- Lhoussain Hassouta, Martine D. Buatier, Jean-Luc Potdevin, Nicole Liewig
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- Published online by Cambridge University Press:
- 28 February 2024, pp. 269-285
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The nature, composition, and relative abundance of clay minerals in the sandstones of the Brent Group reservoir were studied between 3200–3300 m in a well of the Ellon Field (Alwyn area, North Sea). The sandstones have a heterogeneous calcite cement which occurred during early-diagenesis. Clay diagenesis of the cemented and uncemented sandstones was investigated using optical microscopy, scanning electron microscopy (SEM), X-ray diffraction analyses (XRD), and infrared spectroscopy (IR). The influence of cementation on clay neoformation is demonstrated in this study. Detrital illite and authigenic kaolinite are present in both the calcite-cemented and uncemented sandstones suggesting that kaolinite precipitated before calcite cementation. In the uncemented sandstones, blocky dickite replaces vermiform kaolinite with increasing depth. At 3205 m, authigenic illite begins to replace kaolinite and shows progressive morphological changes (fibrous to lath-shape transition). At 3260 m, all sandstones are not cemented by calcite. Illite is the only clay mineral and shows a platelet morphology.
In the cemented samples, vermiform kaolinite is preserved at all depths, suggesting that dickite transformation was inhibited by the presence of the calcite cement. This observation suggests that calcite cement would prevent fluid circulation and dissolution-precipitation reactions.
Colloid Chemical Control of Kaolinite Properties Related to Ceramic Processing
- Lyudmyla A. Pavlova, Michael J. Wilson
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- Published online by Cambridge University Press:
- 28 February 2024, pp. 36-43
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Experimental data on structure formation in highly concentrated aqueous dispersions of kaolinite were analyzed using rheological models. The physicochemical properties of the clay mineral surface were studied during heating at a range of temperatures, and correlation of acid-base properties with physicomechanical characteristics of the spatial structures formed during heating was obtained. It was shown that interparticle interactions and plastic yield mechanisms under load are dependent upon interfacial phenomena. A method for estimating optimal structural parameters was developed for semidry dispersions, enabling regulation of physicochemical and mechanical properties of ceramic mixtures during processing.
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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- 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.