bluuebunny/crossref_metadata_2025 huggingface dataset:
EFFECT OF Bi SURFACTANT IN THE HETEROEPITAXIAL GROWTH OF Co ON Cu SURFACES
Authors: KAMIKO MASAO , CHIHAYA HIROAKI , SUGIMOTO WATARU , YAMAMOTO RYOICHI , OH SANGMUN , XU JUNHUA , KOJIMA ISAO
Published: November 2006

We have investigated the effect of Bi on the heteroepitaxial growth of Co on Cu by reflection high-energy electron diffraction (RHEED) measurements. It was found that Bi enhanced the layer-by-layer growth of Co on the Cu (111) surfaces at 100°C. The dependence of the growth on Bi layer thickness suggested that there existed a suitable amount of Bi surfactant layer that enhanced smoother layered growth. On the contrary, for the case of Co growth on Cu (100), Bi depressed the layer-by-layer growth of Co on Cu (100). The surface segregation effect of Bi was also studied by Auger electron spectroscopy (AES).
Exercise-induced brachial artery vasodilation: role of free radicals
Authors: Richardson Russell S. , Donato Anthony J. , Uberoi Abhimanyu , Wray D. Walter , Lawrenson Lesley , Nishiyama Steven , Bailey Damian M.
Published: November 2006

Originally thought of as simply damaging or toxic “accidents” of in vivo chemistry, free radicals are becoming increasingly recognized as redox signaling molecules implicit in cellular homeostasis. Indeed, at the vascular level, it is plausible that oxidative stress plays a regulatory role in normal vascular function. Using electron paramagnetic resonance (EPR) spectroscopy, we sought to document the ability of an oral antioxidant cocktail (vitamins C, E, and α-lipoic acid) to reduce circulating free radicals, and we employed Doppler ultrasound to examine the consequence of an antioxidant-mediated reduction in oxidative stress on exercise-induced vasodilation. A total of 25 young (18–31 yr) healthy male subjects partook in these studies. EPR spectroscopy revealed a reduction in circulating free radicals following antioxidant administration at rest (∼98%) and as a consequence of exercise (∼85%). Plasma total antioxidant capacity and vitamin C both increased following the ingestion of the antioxidant cocktail, whereas vitamin E levels were not influenced by the ingestion of the antioxidants. Brachial artery vasodilation during submaximal forearm handgrip exercise was greater with the placebo (7.4 ± 1.8%) than with the antioxidant cocktail (2.3 ± 0.7%). These data document the efficacy of an oral antioxidant cocktail in reducing free radicals and suggest that, in a healthy state, the aggressive disruption of the delicate balance between pro- and antioxidant forces can negatively impact vascular function. These findings implicate an exercise-induced reliance upon pro-oxidant-stimulated vasodilation, thereby revealing an important and positive vascular role for free radicals.
Acid aspiration-induced lung inflammation and injury are exacerbated in NADPH oxidase-deficient mice
Authors: Segal Brahm H. , Davidson Bruce A. , Hutson Alan D. , Russo Thomas A. , Holm Bruce A. , Mullan Barbara , Habitzruther Michael , Holland Steven M. , Knight Paul R.
Published: November 2006

Increased reactive oxidant intermediates (ROIs) from primed leukocytes have been implicated in the pathogenesis of acid aspiration lung injury. To evaluate the specific role of the phagocyte NADPH oxidase-derived ROIs in acid lung injury, the p47phox−/−knockout mouse model of chronic granulomatous disease was used. p47phox−/−mice developed a significantly greater alveolar neutrophilic leukocytosis compared with wild-type mice at all time points after acid injury, with the difference between genotypes being most marked at 48 h. In contrast, the p47phox−/−mice had a decreased number of macrophages in bronchoalveolar lavage (BAL) compared with wild-type at 48 h after acid or saline aspiration. Albumin concentration in BAL reflecting capillary leak was also greater in p47phox−/−compared with wild-type mice. BAL concentrations of proinflammatory cytokines and chemokines were greater in p47phox−/−compared with wild-type mice. These findings suggest that NADPH oxidase, directly or indirectly, plays a role in attenuating the acute neutrophilic response after acid lung injury. We speculate that this downmodulating effect may be mediated by promoting the transition from production of cytokines and chemokines involved in neutrophilic infiltration to a less injurious, chronic inflammatory response.
Morphometry of the extremely thin pulmonary blood-gas barrier in the chicken lung
Authors: Watson Rebecca R. , Fu Zhenxing , West John B.
Published: November 2006

The gas exchanging region in the avian lung, although proportionally smaller than that of the mammalian lung, efficiently manages respiration to meet the high energetic requirements of flapping flight. Gas exchange in the bird lung is enhanced, in part, by an extremely thin blood-gas barrier (BGB). We measured the arithmetic mean thickness of the different components (endothelium, interstitium, and epithelium) of the BGB in the domestic chicken lung and compared the results with three mammals. Morphometric analysis showed that the total BGB of the chicken lung was significantly thinner than that of the rabbit, dog, and horse (54, 66, and 70% thinner, respectively) and that all layers of the BGB were significantly thinner in the chicken compared with the mammals. The interstitial layer was strikingly thin in the chicken lung (∼86% thinner than the dog and horse, and 75% thinner than rabbit) which is a paradox because the strength of the BGB is believed to come from the interstitium. In addition, the thickness of the interstitium was remarkably uniform, unlike the mammalian interstitium. The uniformity of the interstitial layer in the chicken is attributable to a lack of the supportive type I collagen cable that is found in mammalian alveolar lungs. We propose that the surrounding air capillaries provide additional structural support for the pulmonary capillaries in the bird lung, thus allowing the barrier to be both very thin and extremely uniform. The net result is to improve gas exchanging efficiency.
In vitro and In vivo Activity of SKI-606, a Novel Src-Abl Inhibitor, against Imatinib-Resistant Bcr-Abl+ Neoplastic Cells
Authors: Puttini Miriam , Coluccia Addolorata Maria Luce , Boschelli Frank , Cleris Loredana , Marchesi Edoardo , Donella-Deana Arianna , Ahmed Shaheen , Redaelli Sara , Piazza Rocco , Magistroni Vera , Andreoni Federica , Scapozza Leonardo , Formelli Franca , Gambacorti-Passerini Carlo
Published: November 2006

Resistance to imatinib represents an important scientific and clinical issue in chronic myelogenous leukemia. In the present study, the effects of the novel inhibitor SKI-606 on various models of resistance to imatinib were studied. SKI-606 proved to be an active inhibitor of Bcr-Abl in several chronic myelogenous leukemia cell lines and transfectants, with IC50 values in the low nanomolar range, 1 to 2 logs lower than those obtained with imatinib. Cells expressing activated forms of KIT or platelet-derived growth factor receptor (PDGFR), two additional targets of imatinib, were unaffected by SKI-606, whereas activity was found against PIM2. SKI-606 retained activity in cells where resistance to imatinib was caused by BCR-ABL gene amplification and in three of four Bcr-Abl point mutants tested. In vivo experiments confirmed SKI-606 activity in models where resistance was not caused by mutations as well as in cells carrying the Y253F, E255K, and D276G mutations. Modeling considerations attribute the superior activity of SKI-606 to its ability to bind a conformation of Bcr-Abl different from imatinib. (Cancer Res 2006; 66(23): 11314-22)
Macrophages Regulate the Angiogenic Switch in a Mouse Model of Breast Cancer
Authors: Lin Elaine Y. , Li Jiu-Feng , Gnatovskiy Leoid , Deng Yan , Zhu Liyin , Grzesik Dustin A. , Qian Hong , Xue Xiao-nan , Pollard Jeffrey W.
Published: November 2006

The development of a tumor vasculature or access to the host vasculature is a crucial step for the survival and metastasis of malignant tumors. Although therapeutic strategies attempting to inhibit this step during tumor development are being developed, the biological regulation of this process is still largely unknown. Using a transgenic mouse susceptible to mammary cancer, PyMT mice, we have characterized the development of the vasculature in mammary tumors during their progression to malignancy. We show that the onset of the angiogenic switch, identified as the formation of a high-density vessel network, is closely associated with the transition to malignancy. More importantly, both the angiogenic switch and the progression to malignancy are regulated by infiltrated macrophages in the primary mammary tumors. Inhibition of the macrophage infiltration into the tumor delayed the angiogenic switch and malignant transition whereas genetic restoration of the macrophage population specifically in these tumors rescued the vessel phenotype. Furthermore, premature induction of macrophage infiltration into premalignant lesions promoted an early onset of the angiogenic switch independent of tumor progression. Taken together, this study shows that tumor-associated macrophages play a key role in promoting tumor angiogenesis, an essential step in the tumor progression to malignancy. (Cancer Res 2006; 66(23): 11238-46)
Marked Genomic Differences Characterize Primary and Secondary Glioblastoma Subtypes and Identify Two Distinct Molecular and Clinical Secondary Glioblastoma Entities
Authors: Maher Elizabeth A. , Brennan Cameron , Wen Patrick Y. , Durso Laura , Ligon Keith L. , Richardson Aaron , Khatry Deepak , Feng Bin , Sinha Raktim , Louis David N. , Quackenbush John , Black Peter McL. , Chin Lynda , DePinho Ronald A.
Published: November 2006

Glioblastoma is classified into two subtypes on the basis of clinical history: “primary glioblastoma” arising de novo without detectable antecedent disease and “secondary glioblastoma” evolving from a low-grade astrocytoma. Despite their distinctive clinical courses, they arrive at an indistinguishable clinical and pathologic end point highlighted by widespread invasion and resistance to therapy and, as such, are managed clinically as if they are one disease entity. Because the life history of a cancer cell is often reflected in the pattern of genomic alterations, we sought to determine whether primary and secondary glioblastomas evolve through similar or different molecular pathogenetic routes. Clinically annotated primary and secondary glioblastoma samples were subjected to high-resolution copy number analysis using oligonucleotide-based array comparative genomic hybridization. Unsupervised classification using genomic nonnegative matrix factorization methods identified three distinct genomic subclasses. Whereas one corresponded to clinically defined primary glioblastomas, the remaining two stratified secondary glioblastoma into two genetically distinct cohorts. Thus, this global genomic analysis showed wide-scale differences between primary and secondary glioblastomas that were previously unappreciated, and has shown for the first time that secondary glioblastoma is heterogeneous in its molecular pathogenesis. Consistent with these findings, analysis of regional recurrent copy number alterations revealed many more events unique to these subclasses than shared. The pathobiological significance of these shared and subtype-specific copy number alterations is reinforced by their frequent occurrence, resident genes with clear links to cancer, recurrence in diverse cancer types, and apparent association with clinical outcome. We conclude that glioblastoma is composed of at least three distinct molecular subtypes, including novel subgroups of secondary glioblastoma, which may benefit from different therapeutic strategies. (Cancer Res 2006; 66(23): 11502-13)
Primary Tumor Levels of Tissue Inhibitor of Metalloproteinases-1 Are Predictive of Resistance to Chemotherapy in Patients with Metastatic Breast Cancer
Authors: Schrohl Anne-Sofie , Meijer-van Gelder Marion E. , Holten-Andersen Mads N. , Christensen Ib Jarle , Look Maxime P. , Mouridsen Henning T. , Brünner Nils , Foekens John A.
Published: November 2006

Purpose: Only about 50% of metastatic breast cancer patients benefit from cytotoxic chemotherapy. Today, no validated markers exist for prediction of chemotherapy sensitivity/resistance in this patient group. Tissue inhibitor of metalloproteinases-1 (TIMP-1) has been shown to protect against apoptosis, and the purpose of the present study was to test the hypothesis that tumors expressing high levels of TIMP-1 are protected against apoptosis-inducing agents and thus less sensitive to apoptosis-inducing chemotherapeutic drugs.

Experimental Design: We investigated the association between primary tumor expression levels of TIMP-1 protein and objective response to first-line chemotherapy in 173 patients with metastatic breast cancer.

Results: When analyzed as a continuous log-transformed variable, increasing TIMP-1 levels were significantly associated with lack of response to cyclophosphamide/methotrexate/5-fluorouracil and anthracycline-based chemotherapy (P = 0.01; odds ratio, 2.0; 95% confidence interval, 1.1-3.3). In a multivariate model, including lymph node status, steroid hormone receptor status, menopausal status, dominant metastases site, type of chemotherapy, and disease-free interval, TIMP-1 was significantly associated with resistance to treatment (P = 0.03; odds ratio, 1.7; 95% confidence interval, 1.1-3.3).

Conclusions: In the present exploratory study, we showed that elevated tumor tissue TIMP-1 levels were significantly associated with a poor response to chemotherapy. By using TIMP-1, we identified a group of patients with metastatic breast cancer, which hardly respond to the most frequently used chemotherapy regimes (i.e., cyclophosphamide/methotrexate/5-fluorouracil and anthracyclines).
Attitudinal and Relational Factors Predicting the Use of Solar Water Disinfection: A Field Study in Nicaragua
Authors: Altherr Anne-Marie , Mosler Hans-Joachim , Tobias Robert , Butera Fabrizio
Published: November 2006

Solar water disinfection (SODIS) is an uncomplicated and cheap technology providing individuals with safe drinking water by exposing water-filled plastic bottles to sunlight for 6 hours to kill waterborne pathogens. Two communities were visited, and 81 families (40 SODIS users and 41 nonusers) were interviewed. The relationship between several factors and the intention to use SODIS in the future and actual use were tested. The results showed that intention to use and actual use are mainly related to an overall positive attitude, intention to use is related to the use of SODIS by neighbors, and actual use is related to knowledge about SODIS; SODIS users reported a significantly lower incidence in diarrhea than SODIS nonusers. These results suggest that promotion activities should aim at creating a positive attitude, for example, by choosing a promoter that is able to inspire confidence in the new technology.
Effects of factors on physical attributes of self-piercing riveted joints
Authors: Xu Y.
Published: November 2006

Self-piercing riveting (SPR) as an attractive sheet joining method has been more and more used in various applications. Physical attributes of self-piercing riveted joints are used in industry empirically to assess the qualities of SPR joints. The physical attributes are part of the criteria used to determine whether or not an SPR joint is acceptable. Physical attributes of an SPR joint include bottom thickness, undercut and spread. The relationships between the factors and the physical attributes of SPR joints were discovered in the present paper. Design of experiments (DOE) method was used in the present study. The effects of the different factors upon the physical attributes were investigated. Physical attributes of an SPR joint include bottom thickness, undercut and spread. Analysis of variance (ANOVA), effects analysis and effects plots were employed in this research.
Microjoining with a scanning electron microscope
Authors: Knorovsky G. A. , Nowak-Neely B. M. , Holm E. A.
Published: November 2006

In the present work the authors describe the adaptation of a standard SEM into a flexible microjoining tool. The system incorporates exceptional control of energy input and its location, environmental cleanliness, part manipulation and especially, part imaging. Beam energetics, modelling of thermal flow in a simple geometry, significant effects of surface energy on molten pools and beam size characterisation are treated. Examples of small to micro fusion welds and molten zones produced in a variety of materials (Ni, tool steel, Tophet C, Si) and sizes are given. Future directions are also suggested.
Selection of parameters for μE-beam welding
Authors: Knorovsky G. A. , MacCallum D. O. , Meyers M. T.
Published: November 2006

Electron beam welding is a well known process used where high precision, high reliability welds are needed, often in exotic materials. Recently, it has been proposed to apply the electron beam produced in a standard scanning electron microscope (SEM), with reversible modifications to increase beam current, for microscale welding. In addition to providing the clean environment associated with the column vacuum, the SEM in imaging mode provides exceptional capabilities in visualising extremely small parts. Furthermore, the standard stage and beam motion controls offer the possibility of flexible programming of beam path with relatively minor software additions. In order to better evaluate the requirements for and effects of μE-beam welding (μEBW) on typical microtechnologically important materials, a clear understanding of the characteristics of the SEM's beam and its interaction with possible target materials is needed. The penetration ability of electrons depends strongly upon their accelerating voltage and the target they are being directed at. Hence, in some circumstances the beam may interact as a surface heat source, while in others it may act as a volume heat source, with important consequences on weld schedule development for the parts and geometry being welded. In this work, the authors explore some of the factors involved and propose simple models for the electron beam heat source which depend on the parameters being used.
Numerical study on stress induced cambering distortion and its mitigation in welded titanium alloy sheet
Authors: Soul F. A. , Zhang Y.-H.
Published: November 2006

Arc welding process is widely used for fabricated thin structures in aerospace, shipyard, etc. Welding deformation is undesirable owing to the decrease in buckling strength and injures the beautiful appearance of structures. In addition, it causes errors during the assembly which result in more rework and productivity restriction. Welding deformation is complicated in real structure and is difficult to control. In the present study, numerical simulation by applying finite element has been performed using ANSYS to predict residual stress and cambering distortion in welded titanium alloy sheet. Furthermore, attempt was made to eliminate this distortion by applying dynamic spot cooling source technique behind the welding torch. The computed result revealed that the cambering could be eliminated under proper control of the parameters of this technique, such as the distance between the two sources. Transient residual stress through the thickness exhibit different behaviour and magnitude from that in conventional welding, and its cost is minimised by such technique. Explanation of this minimising mechanism was discussed.
Microstructure and corrosion behaviour of alloy 690–SUS 304L butt joints formed by electron beam welding
Authors: Lee H. T. , Lin Y. D.
Published: November 2006

This study investigates the microstructure and corrosion behaviour of alloy 690–SUS 304L stainless steel dissimilar weldments formed by electron beam welding (EBW). Slow strain rate tensile tests (SSRTs) are performed in air and in a 0·01M Na2S2O3 + 1 wt-%NaCl corrosive environment. The microstructure, mechanical properties and corrosion behaviour of the weldments are analysed. Experimental results of this study reveal that the precipitation of chromium carbide is suppressed owing to the effect of rapid solidification of EBW in fusion zone (FZ). In addition, there is no chromium depletion found at the grain boundary at all. The interdendritic region of the FZ contains fine precipitates, which are a mixture of Ti rich phases with a rectangular shape and Cr rich phases with an oval shape. Fewer interdendritic phases are formed in the root than in the cap owing to the higher cooling rate in the root region of the weldment. Fracture tests indicate that all the specimens ruptured in the FZ by SSRTs preformed either in air and or in a corrosive environment. The tensile strength and total tensile elongation of the specimen deformed in the 0·01M Na2S2O3 + 1 wt-%NaCl corrosive environment are lower than those of the specimen deformed in air. Fractographic investigations revealed that the fracture mode, in good accordance with mechanical behaviour and performance, transits from a ductile dimple rupture in the specimens tested in air to a mixed rupture of dimples and corrosion formation on fractured surface which obviously assisted the cracking in the specimens tested in the corrosive environment.
Experimental defect analysis and force prediction simulation of high weld pitch friction stir welding
Authors: Crawford R. , Cook G. E. , Strauss A. M. , Hartman D. A. , Stremler M. A.
Published: November 2006

Experimental data for AA 6061-T6 friction stir welded at rotational and travel speeds ranging from 1000 to 5000 rev min−1 and from 290 to 1600 mm min−1 (11–63 ipm) are presented. The present paper examines the forces and torques during friction stir welding (FSW) with respect to mechanistic defect development owing to process parameter variation. Two types of defects are observed: wormholes and weld deformation in the form of significant excess flash material. A 3D numerical model, implemented using the computational fluids dynamics package Fluent, is used to simulate and investigate the parametric relationship of the forces and torques during FSW. In order to establish a mechanistic quantification of the FSW process, two mechanical models, the Couette and the viscoplastic fluid flow models, were simulated and compared with experimental data for AA 6061-T6.
Laser brazing of alloy 600 with precious filler metals
Authors: Saida K. , Song W. , Nishimoto K.
Published: November 2006

The diode laser brazing of Ni base heat resistant alloy with precious filler metals has been conducted using the tandem beam for preheating and brazing. A couple of 1 mm thick plates of alloy 600 (Inconel 600) were butt brazed using Au–18Ni, Ag–10Pd and Ag–21Cu–25Pd filler metals of 0·5 mm diameter with a brazing flux. Sound butt joints which were free from brazing defects such as porosity and lack of penetration could be obtained at brazing clearances of 0·1–1·5 mm. The tensile strength of the braze joint produced using Ag–Pd filler metal increased with decreasing brazing clearance and reached ∼70% of the base metal strength at a brazing clearance of 0·1 mm while those obtained by using Au–Ni and Ag–Cu–Pd filler metals were comparable with the base metal strength at any clearances between 0·1 and 1·5 mm. The laser brazing technique could be successfully applied to the brazing of Ni base superalloy to attain a joint with high performance and reliability.
Monitoring of plasma arc cutting process by cutting sound
Authors: Kusumoto K. , Chen Q. G. , Xue W.
Published: November 2006

Plasma arc cutting sound containing useful information about the cutting process has close relation with cut quality. The present paper investigates quality diagnosis method of plasma arc cutting by the cutting sound. In the present study the cut quality is divided into three types based on bottom kerf width and dross attached state. There are attached dross state (type 1), free dross state (type 2) and uncut through state (type 3). It is shown that a peak about 20 Hz appears obviously at cut quality type 2 and as cut quality becomes the type 3 the value of ∼40 kHz decreases remarkably. And influence of the emitted area of molten metal from plasma arc cutting on the cutting sound also has been revealed. At last corresponding relationship between the cutting sound and the cut quality has been discussed as cutting condition such as arc current and torch standoff height varied suddenly during the cutting process. Experimental results also suggest the possibility to make an acoustic based monitoring system for plasma arc cutting process by the cutting sound.
Ultrasonic fast identification of automotive body spot weld defect based on echo characteristics qualitative analysis
Authors: Zhao X. , Zhang Y. S. , Chen G. L.
Published: November 2006

Spot welds are used extensively by automobile manufacturers as an efficient method for joining sheet steel. The quality of them can be tested non-destructively by using ultrasound. But when spot weld defect happens, the current ultrasonic inspection methods of weld quality are difficult to achieve an ideal result especially for the stick weld defect which is one of the most important types of spot weld defects in the automotive body. At first, this paper detailedly analyses the echo characteristics of ultrasonic curves which can reflect different spot welding joint defects. After echo characteristics qualitative analysis of different spot weld defects, a peak value marking algorithm is developed to identify the joint defects especially the stick weld defect rapidly and efficiently through selecting and confirming many optimal characteristic parameters. Finally, a lot of experiments are performed to verify the proposed methods. The results indicate that this fast identification method is credible and the identification rate can reach 95% in total test samples.
Mathematical modelling of rotational arc sensor in GMAW and its applications to seam tracking and endpoint detection
Authors: Shi Y. H. , Yoo W. S. , Na S. J.
Published: November 2006

High speed rotational arc sensing is an important method to detect the torch deviation during automatic seam tracking of arc welding. In the present paper, a mathematic model of high speed rotational arc sensing is analysed. Simulations have been implemented in two conditions, namely considering or without considering weld bead profile. The simulation results are consistent with the experimental results. The current waveforms at the beginning of the welding are different from those at middle of the welding because of the formation of the weld bead profile. The signal patterns for seam tracking and endpoint detection are proposed. A phase shift between the rotation and the current variation is also discovered in the experiments. The mathematical model can be helpful for the interpretation and improvement of arc sensing systems.
Evidence by transmission electron microscopy of weathering microsystems in soils developed from crystalline rocks
Authors: Romero R. , Robert M. , Elsass F. , Garcia C.
Published: November 2006

High-resolution electron microscopy and microanalytical studies were performed on clay and bulk soil samples developed on various igneous and metamorphic rocks from Galicia in the Coruna province in NW Spain. Two mineralogical microsystems can be distinguished showing different stages of weathering. For feldspars, exsolution and mass transformation lead to the delineation of parallel domains, and to formation of gel or paracrystalline minerals. For micas, alteration starts with a physical breakdown, i.e. exfoliation and crystal microdivision; individualization of monolayers is followed by gel formation. A solid phase diffusion phenomenon can explain the formation of 1 : 1 phyllosilicates inside 2 : 1 phyllosilicates or within the continuum of the original crystals. Evidence of such weathering stages in crystalline rocks can be related to the occurrence of specific climatic conditions between temperate and tropical areas.
X-ray diffraction measurement of the quartz content of clay and silt fractions in soils
Authors: Hardy M.
Published: November 2006

An XRD method for measurement of quartz content using ZnO as the internal standard was tested on different particle sizes between 0 and 20µm. Calibration curves showed a good correlation coefficient for particle-size fractions up to 20µm; the slope increased for the fractions from 0·7 to 5µm and was relatively constant for coarser particle sizes. Fine quartz fractions were etched with hydrofluoric acid to remove the surface layer damaged during dry grinding. The use of such etched quartz increased the slopes of the calibration curves for small particle-size fractions and approximated the natural fine quartz fraction much better than the original dry-ground material. The mean of six measurements gave good accuracy provided that the slope of the calibration curve was adjusted for the particular particle-size fraction. This method was used on 0–2µm, 0–0·2µm and 0·2–2µm fractions of French silty soils and the results are in agreement with the data from chemical analysis and with the mineralogical interpretation.
Characterization of FeOOH polymorphs and ferrihydrite using low-temperature, applied-field, Mössbauer spectroscopy
Authors: Pollard R. J. , Cardile C. M. , Lewis D. G. , Brown L. J.
Published: November 2006

Mössbauer spectroscopy obtained with the sample at low temperatures and subject to large magnetic fields is discussed in terms of its use in analysing the naturally occurring polymorphs of FeOOH and the common growth precursor, ferrihydrite. Experiments on well-characterized synthetic samples provided benchmark results. A relatively simple means of quantitative analysis was used, in which sextets of Voigtian-shaped lines were summed and least-squares fitted. The results are discussed in terms of the magnetic structures of each compound.
A comparison of methods for the extraction of smectites from calcareous rocks by acid dissolution techniques
Authors: Cook R. J.
Published: November 2006

Four methods of extracting clays from calcite-rich samples were compared: (i) sodium acetate buffer solution; (ii) lithium acetate buffer solution; (iii) hydrochloric acid; (iv) liquid cation-exchange acid. The methods were tested on mixtures consisting of 80% calcite, 10% quartz and 10% hectorite. Potassium had previously been exchanged on to the interlayer sites of the clay. XRD traces of the extracted clays appeared identical with those of the original clays except for a sharpening of the 001 reflection. The bulk chemistry of the clay was unchanged except by the HCl extraction, which appeared to cause a stripping of the octahedral cations. With all of the methods the exchangeable cation content was altered; the sodium acetate method, for example, retained only 17% of the original exchangeable K+, the other methods all retaining <10%.
Exchange selectivity of lanthanide ions in montmorillonite
Authors: Maza-Rodriguez J. , Olivera-Pastor P. , Bruque S. , Jimenez-Lopez A.
Published: November 2006

The exchange of Ca2+ and Na+ by tanthanide ions (Ln3+ = Pr3+, Gd3+, Er3+) in montmorillonite was investigated at two different ionic strengths (0·01 and 0·1 mol/kg). Preferential sorption of Ln3+ was observed and variable selectivity coefficients were found depending upon the lanthanide concentration in the solid, and ionic strength. The highest exchange extent of Ln3+ always occurred for the system Na+/Ln3+, but the exchange selectivities of Ln3+ were generally higher in the exchange system Ca2+/Ln3+. Although the relative affinity of montmorillonite for the three lanthanide ions was similar, distinctive behaviour between Pr3+ and the heavier lanthanides, Gd3+ and Er3+, was noted. The study of Ln3+ adsorption in trace amounts showed specific adsorption of lanthanides at high concentrations of Na+ in the external solution and that the exchange stoichiometries in the interlayer regions were 3 : 1 at equilibrium pH = 4.
Clay adsorbed dyes: methylene blue on Laponite
Authors: Schoonheydt R. A. , Heughebaert L.
Published: November 2006

The adsorption of methylene blue (MB) from aqueous solution on Laponite (a synthetic 2:1 layer-silicate) exchanged with Na+, Cs+ and tetraethylammonium ions has been studied. At low loadings the monomer form predominates, but as the loading increases dimers and trimers (or higher aggregates) are formed, the latter being the most important species when the loading is equal to, or larger than, the Na+-CEC. The distribution of the molecules over the surface is time-dependent due to changes in the aggregation of the clay particles. On Cs+-Laponite, and to a lesser extent on Na+-Laponite, a small amount of MB is protonated by cation-coordinated water molecules. In similar work where adsorption was from ethanolic solution, MB is adsorbed as monomers and dimers only at small loadings and precipitates on the surface of the clay aggregates at high loadings. These precipitates can be broken up by sonication.
Stereoselectivity of montmorillonite in the adsorption and deamination of some amino acids
Authors: Siffert B. , Naidja A.
Published: November 2006

Optical isomers deamination of L- and D-glutamic and aspartic amino acids and of their DL racemic mixtures has been achieved in the presence of Na-montmorillonite at pH = 6 and room temperature. The adsorption curves showed that the enantiomer adsorbed depends on the type of amino acid. Nevertheless, deamination reaction kinetics brought about a stereoselectivity of the clay mineral for the L-isomer and implicitly showed an unquestionable “structural chirality character” of the clay mineral.
Synthesis of zeolites from thermally activated kaolinite. Some observations on nucleation and growth
Authors: Murat M. , Amokrane A. , Bastide J. P. , Montanaro L.
Published: November 2006

Depending on the preparation temperature and the origin of the raw mineral, the products obtained by thermal activation of kaolinite lead, by hydrothermal treatment with sodium hydroxide at 102°C, either to zeolite 4A, or to cubic zeolite P, or to a mixture of cubic and tetragonal zeolite P. The change in the type of zeolite obtained was explained on the basis of a radical change of the zeolite nucleation process due to either the presence of soluble potassium or high silica content resulting from dehydration of muscovite (an impurity in the raw-kaolinite), or from “segregation” associated with the first step of the metakaolinite to mullite transformation. These phenomena occur at a lower calcination temperature with poorly-crystallized kaolinite, and iron in such a sample promotes a sensitive decrease in the formation rate of zeolite crystals. Such results could be used to characterize the crystallinity of kaolinites.
Chemistry of illite-smectite inferred from TEM measurements of fundamental particles
Authors: Środoń J. , Elsass F. , McHardy W. J. , Morgan D. J.
Published: November 2006

Mixed-layer illite-smectites (I-S) have a stable charge on the illite interlayer equal to 0·89/O10(OH)2, as shown by electron microscope measurements of mean fundamental particle thickness, using both Pt-shadowing and high-resolution techniques. This has been verified by independent measurements of total surface area and CEC. Typically, the smectite interlayer charge is close to 0·4/O10(OH)2 but clays evolving in K-deficient environments may exhibit higher values. In the course of illitization, the silicate layer composition becomes more restricted than the smectite composition, AlIV and AlVI increasing while Fe and Mg decrease. These substitutions lead to the composition of non-expandable illite differing distinctly from that of muscovite and phengite, close to FIX0·89Al1·85Fe0·05Mg0·10Si3·20Al0·80. HRTEM data show that XRD systematically underestimates %S layers in I-S due to the small size of coherent scattering domains. An experimental curve is proposed for correcting XRD data. The above results were obtained for I-S formed from volcanic materials in different diagenetic and hydrothermal environments. The illite interlayer charge value close to 0·9 reconciles well the available data on I-S produced by wetting and drying of K-smectites.
Identification of vermiculite by transmission electron microscopy and X-ray diffraction
Authors: Vali H. , Hesse R.
Published: November 2006

The expandability of K-depleted biotite and natural vermiculite was studied using transmission electron microscopy (TEM) and X-ray diffraction (XRD). K-depletion in layer-silicates was achieved by treating ultrathin sections with 0·1 m CaCl2 and BaCl2 solutions. The natural sample of biotite, which by XRD revealed no expandability on ethylene glycol or glycerol solvation, displayed 10–15% expanded layers when viewed by TEM after alkylammonium intercalation. The proportion of expanded layers increased after CaCl2 treatment. XRD of vermiculite samples revealed two sets of expandable interlayers after alkylammonium treatment, corresponding to two types of particles with different layer structures observed by TEM. Identification of vermiculite by TEM based on basal spacings is reliable with alkylammonium treatment. Intercalation of alkylammonium ions into the interlayers of vermiculite improved the degree of stacking order of the 2:1 layers.
The Influence of analytical error upon the interpretation of chemical variations in clay minerals
Authors: Warren E. A. , Ransom B.
Published: November 2006

Understanding the chemical variability of clay minerals depends on the analytical reliability of the techniques used. Uncertainties in clay mineral compositions were computed for common sources of analytical error such as those that arise from contaminant phases present in clay size-fractions in concentrations below the detection limit of routine XRD screening techniques, and the analytical limits of precision for TEM/AEM analysis. When plotted on standard diagrams used to represent clay mineral compositions, the calculated error envelopes were found to be of significant size, such that analyses of pure illites and pure smectites straddled the field for mixed-layered illite-smectites. In addition, on some diagrams random analytical errors resulted in linear trends identical to those caused by mixtures of two or more clay minerals. It follows that variations in the compositions of clay minerals reported in the literaure do not always necessarily represent the actual chemical variation of the minerals. As a result, current interpretations of clay compositional variations may not be as definitive as hoped.
Dating thermal anomalies in sedimentary basins: the diagenetic history of clay minerals in the Triassic sandstones of the Paris Basin, France
Authors: Mossmann J. R. , Clauer N. , Liewig N.
Published: November 2006

Rhaetian (Upper Triassic) sandy horizons were sampled from the Paris Basin from SW to NE, crosscutting the Rhaetian at different depths from outcrop in the NE to 2700 m in the centre of the basin. The smallest day sub-fractions (<0·2 μm) from the deepest samples consist mainly of illite and chlorite having a K-Ar age of 〜190 Ma. Both minerals probably formed under specific hydrothermal conditions at high temperature, but at a burial depth of only 500 m. This thermal event could represent an echo of the "crustal" breakdown of the Northwestern European craton during the opening of the North Atlantic Ocean. Two other generations of illite-smectite mixed-layers formed in the same Rhaetian horizons at somewhat lower temperatures about 150 and 80 Ma ago. The three generations of clay minerals could be characterized and dated because of combined mineralogical, crystallographical and morphological data supporting the dating attempts.
Ferripyrophyllite and related Fe3+-rich 2:1 clays in Recent deposits of Atlantis II Deep, Red Sea
Authors: Badaut D. , Decarreau A. , Besson G.
Published: November 2006

Iron-rich dioctahedral 2:1 clays were sampled in metalliferous sediments from Atlantis II Deep (Red Sea), and studied by XRD, TEM, FTIR and Mössbauer spectroscopy. One sample with the structural formula (Si3·94Fe3+0·06)(Fe3+1·90Mg0·10)K0·1(Mg, Ca)0·03 is closer to the theoretical end-member ferripyrophyllite Si4Fe3+2O10(OH)2 than any other Fe-rich clay previously described. Other samples appear as mixed-layered clays: ferripyrophyllite-hydroferripyrophyllite or hydroferripyrophyllite-celadonite.
Sudoite in some Visean (Lower Carboniferous) K-bentonites from Belgium
Authors: Anceau A.
Published: November 2006

Sudoite occurs as a cryptocrystalline clay in some Visean K-bentonites from Belgium. Usually associated with illite-smectite mixed-layers, this chlorite has been found locally as a monomineralic clay component of a K-bentonite bed. The mineral has a composition close to (Al3Mg2)(Si3Al)O10(OH)8. The cell parameters have been calculated from the diffractogram using the space group C2/m (a = 5·228, b = 9·056, c = 14·326 Å, β = 97°00′, d(060) = 1·509 Å). The polytype corresponds to a IIb structure. Some hypotheses are proposed for the origin of this chlorite. The coexistence of sudoite and pyrite could explain why the chlorite present in Visean K-bentonites is not a Fe-rich species typical of diagenetic conditions, but a Fe-poor one.
Chemical and mineralogical characteristics of Pleistocene caliche deposits from the Central Ebro Basin, NE Spain
Authors: Sancho C. , Melendez A. , Signes M. , Bastida J.
Published: November 2006

Chemical and mineralogical analyses of fossil caliche profiles developed on top of Lower Pleistocene alluvial formations in the East-central sector of the Ebro basin indicate that they have high content of carbonate (average 84%) and high Ca/Mg ratios (average 136). The clay mineral assemblages vary slightly depending on the host material, and, therefore, on the alluvial formation in the source area. Inherited detrital minerals (illite, kaolinite and chlorite), transformed components (from chlorite to mixed-layers of chlorite-vermiculite, and from smectite to palygorskite) and a neoformed phase (palygorskite) have been observed. The contents of carbonate and magnesian clay minerals (smectite and palygorskite) increase from the bottom to the top of the profiles, in relation to hardpan laminated caliche facies. The amount of palygorskite is controlled by the concentration of Mg2+ which in turn depends on the absolute content of Mg2+ in the host material and on its relative concentration by processes of evaporation linked to decreasing permeability in the profile during the biogenic-pedogenetic carbonate accumulation stages. These processes form part of the development of caliche profiles in a semi-arid environment.
Adsorption Behaviour of Cesium on Marl
Authors: Cornell R. M.
Published: November 2006

Adsorption of Cs on two samples of marl with different calcite, quartz and clay contents and surface areas of ∼10 m2/g was followed using the batch sorption technique. The experiments were carried out in an atmosphere of N2/1% CO2 using a synthetic groundwater of pH 7·3 and an ionic strength of 0·1 m. The initial Cs concentration ranged from 10−8 to 10−4m. Sorption of Cs was non-linear, fast and reversible. At equilibrium Cs concentrations <10−8m, an isotope exchange mechanism appeared to operate, whereas at higher concentrations, sorption involved ion exchange. The distribution coefficients ranged from 23–995 ml/g. They varied markedly with rock/water ratio; this variation could be explained in terms of the non-linear isotherm displayed by Cs. Although the two samples of marl differed in composition, uptake of Cs on both samples was very similar because the content of the principal sorbing component (illite) was the same in both samples.
Local environment of lanthanum ions in montmorillonite upon heating
Authors: Trillo J. M. , Alba M. D. , Castro M. A. , Muñoz A. , Poyato J. , Tobías M. M.
Published: November 2006

Structural differences which occur on heating La-montmorillonite have been studied and compared with those for montmorillonite saturated with Na(I) and Li(I). Rehydration experiments show that La-montmorillonite swells after preheating up to 500°C. However, FT-IR spectra suggest partial migration of the La(III) cations from the interlamellar region to the structural sheets and(or) deprotonation of hydrated La(III) cations, followed by migration of the resulting protons to vacant octahedral sites. Additional measurements of X-ray absorption spectra (EXAFS, XANES) and heating to 700°C suggest that interlamellar hydrated La(III) partially deprotonates producing polyoxocations.
Chemical and structural properties of clay minerals modified by inorganic and organic material
Authors: Bandosz T. J. , Jagiełło J. , Amankwah K. A. G. , Schwarz J. A.
Published: November 2006

Modification of clay minerals by exchange, intercalation, calcination and imbibition of organics followed by their polymerization and carbonization was studied. The surface properties of the clays were investigated by inverse gas chromatography at infinite dilution employing alkanes and alkenes as probes; the structural properties were measured directly by X-ray diffraction and inferred from the results of high pressure hydrogen adsorption. Calcination of pillared smectites prior to polymerization and carbonization of organic material in the interlayer space leads to a microporous “activated carbon” that demonstrates unique properties as an adsorbent for hydrogen, significantly different from clays that have not been calcined.
Organometallic cation-exchanged phyllosilicates: exchange with cations derived from (CH3)2SnCl2
Authors: Breen C. , Fleming J. P. E. , Molloy K. C.
Published: November 2006

Complexes formed between 0·034 m dimethyltin dichloride solutions and Na-montmorillonite at pH 2·4 and 4·0 have been characterized using 119Sn Mössbauer spectroscopy, X-ray diffraction, infrared spectroscopy, thermogravimetric analysis and water sorption isotherms. The dominant exchange cation at pH 2·4 is Me2Sn2+ characterized by an isomer shift, δ, and quadrupole splitting, Δ values of 1·25 and 3·80 mm s−1, respectively. The major exchange cation at pH 4·0 is the dimer, [Me2SnOH]22+, (δ = 1·38, Δ = 3·34 mm s−1) although the monomer, Me2Sn(OH)+, (δ = 0·95, Δ = 3·29 mm s−1) is also present. These complexes have basal spacings of 15·0 and 16·0 Å, respectively, which are stable up to 200°C. Mössbauer spectroscopy has shown that these ions are converted to SnO2 via Me2SnO upon thermal degradation. The temperature at which these oxides appear coincides with the collapse of the basal spacing. Both complexes display BET Type IV isotherms for the adsorption of water, following thermal pretreatment at 150°C, but the complex prepared at pH 4·0 has a lower sorption capacity. Both complexes, contrary to the normal behaviour of layer-silicates, have a definite pore volume and no further uptake occurs when this is filled.
Chlorite interstratified with a 7 Å mineral: an example from offshore Norway and possible implications for the interpretation of the composition of diagenetic chlorites
Authors: Hillier S. , Velde B.
Published: November 2006

X-ray diffraction (XRD) patterns of a pore-lining diagenetic chlorite (14 Å) from a reservoir sandstone, offshore Norway, show broad odd-order and sharp even-order basal reflections indicating that it contains 7 Å layers. Using NEWMOD, simulated XRD patterns with 15% 7 Å serpentine layers and a maximum crystallite thickness of 30 layers match the natural mineral well. Microprobe analyses of the 7 Å-14 Å mineral indicate that it is Fe-rich and aluminous suggesting that it is interstratified berthierine-chamosite. Apparent octahedral vacancies, however, suggest a significant dioctahedral component, and an alternative interpretation is interstratified kaolinite-chlorite. Indeed, chemical analyses of the mineral suggest a mixture of chlorite with 15% kaolinite, precisely the proportion of 7 Å layers indicated by XRD. Two other examples from the literature, previously identified as diagenetic chlorite, are probably also 7 Å-14 Å interstratified minerals, and the proportion of 7 Å layers indicated by XRD is also correlated with their structural formulae, if the 7 Å layers are, in fact, kaolinitic. This type of interstratification could explain why Fe-rich diagenetic chlorites appear to be compositionally distinct from metamorphic chlorites. The structure and chemistry of the Norwegian chlorite tend to support the idea that pore-lining chlorites form early in the diagenetic history, inhibiting the precipitation of later diagenetic minerals, and hence preserving abnormally high porosity at greater depths.