Volume 56 - Issue 4 - August 2008
Article
Influence of Mn(III) availability on the phase transformation from layered buserite to tunnel-structured todorokite
- Haojie Cui, Xiangwen Liu, Wenfeng Tan, Xionghan Feng, Fan Liu, Huada Daniel Ruan
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- Published online by Cambridge University Press:
- 01 January 2024, pp. 397-403
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Todorokite is a common Mn oxide mineral in terrestrial and ocean-floor environments, and it is commonly synthesized from layered Na-buserite. Pyrophosphate, which is known to form strong complexes with Mn(III) at a pH range of 1–8, was added to a suspension of Na-buserite in order to sequester the available Mn(III) in Na-buserite. No Mn(III)-pyrophosphate complex was formed in solution at pH 10, and the treated Na-buserites were converted completely to todorokite. Significant transformation reductions were observed when Na-buserite was treated with pyrophosphate solution at pH 7. The presence of Mn(III) within the MnO6 octahedral sheets of Na-buserite is critical for the transformation from layered buserite to tunnel-structured todorokite at atmospheric pressure. At lower pH, two effects are combined to reduce the amount of Mn(III) in the layers: (1) the complexing power of pyrophosphate is increased; and (2) the transformation from Na-buserite to H-birnessite, which is concomitant with the migration of Mn(III) from layers to the interlayer, and the partial disproportionation of Mn(III). The results showed that Mn(III) played a key role in the transformation of layered Na-buserite to tunnel-structured todorokite at atmospheric pressure.
Preferred orientation of mineral grains in sample mounts for quantitative XRD measurements: How random are powder samples?
- Reinhard Kleeberg, Thomas Monecke, Stephen Hillier
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- Published online by Cambridge University Press:
- 01 January 2024, pp. 404-415
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The degree of preferred orientation of mineral grains in powder X-ray diffraction (XRD) samples prepared by standard techniques has been evaluated by means of a correction model implemented in the Rietveld program, BGMN. It is demonstrated that neither front- nor side-loading of mineral powders obtained by wet grinding in a McCrone micronizing mill yield powder mounts with randomly oriented particles. Despite fine grinding, the primary sizes and shapes of mineral grains contained in multi-phase samples influence the degree of preferred orientation in XRD powder mounts. Two minerals, both of platy habit, were found to show different degrees of preferred orientation in front- and side-loaded samples. In contrast to these methods of sample preparation, the spray-drying technique yielded perfect randomness of the particles. The experiments on artificial mineral mixtures demonstrate that the model applied can effectively correct for preferred orientation allowing reliable Rietveld quantitative phase analysis of moderately textured samples prepared by standard techniques.
Role of Microbial Fe(III) Reduction and Solution Chemistry in Aggregation and Settling of Suspended Particles in the Mississippi River Delta Plain, Louisiana, USA
- Deb P. Jaisi, Shanshan Ji, Hailiang Dong, Ruth E. Blake, Dennis D. Eberl, Jinwook Kim
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- Published online by Cambridge University Press:
- 01 January 2024, pp. 416-428
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River-dominated delta areas are primary sites of active biogeochemical cycling, with productivity enhanced by terrestrial inputs of nutrients. Particle aggregation in these areas primarily controls the deposition of suspended particles, yet factors that control particle aggregation and resulting sedimentation in these environments are poorly understood. This study was designed to investigate the role of microbial Fe(III) reduction and solution chemistry in aggregation of suspended particles in the Mississippi Delta. Three representative sites along the salinity gradient were selected and sediments were collected from the sediment-water interface. Based on quantitative mineralogical analyses 88–89 wt.% of all minerals in the sediments are clays, mainly smectite and illite. Consumption of \$\end{document} and the formation of H2S and pyrite during microbial Fe(III) reduction of the non-sterile sediments by Shewanella putrefaciens CN32 in artificial pore water (APW) media suggest simultaneous sulfate and Fe(III) reduction activity. The pHPZNPC of the sediments was ⩽3.5 and their zeta potentials at the sediment-water interface pH (6.9–7.3) varied from −35 to −45 mV, suggesting that both edges and faces of clay particles have negative surface charge. Therefore, high concentrations of cations in pore water are expected to be a predominant factor in particle aggregation consistent with the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. Experiments on aggregation of different types of sediments in the same APW composition revealed that the sediment with low zeta potential had a high rate of aggregation. Similarly, addition of external Fe(II) (i.e. not derived from sediments) was normally found to enhance particle aggregation and deposition in all sediments, probably resulting from a decrease in surface potential of particles due to specific Fe(II) sorption. Scanning and transmission electron microscopy (SEM, TEM) images showed predominant face-to-face clay aggregation in native sediments and composite mixtures of biopolymer, bacteria, and clay minerals in the bioreduced sediments. However, a clear need remains for additional information on the conditions, if any, that favor the development of anoxia in deep- and bottom-water bodies supporting Fe(III) reduction and resulting in particle aggregation and sedimentation.
Kaolinite formation from palygorskite and sepiolite in rhizosphere soils
- H. Khademi, J. M. Arocena
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- Published online by Cambridge University Press:
- 01 January 2024, pp. 429-436
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Palygorskite and sepiolite are fibrous clays that occur mostly in agricultural soils of arid regions. Although many investigations have examined the environmental conditions for the formation and stability of these clays, information on the transformation of these clays in the root zone (or rhizosphere) of agricultural crops is limited. In this study, changes in palygorskite and sepiolite within the rhizosphere of selected agricultural crops were determined and the ability of plants to extract Mg from these minerals compared. Alfalfa, barley, and canola were cultivated in pots under controlled conditions in a growth chamber using growth media that consisted of a mixture of Ottawa sand and clay-sized Florida palygorskite (PFl-1) or Spanish sepiolite (SepSp-1). After 100 days of cultivation, the biomass of plant roots and shoots were determined and Mg uptake measured by inductively coupled plasma analysis of the plant biomass after microwave oven digestion. The clay fraction in each pot was separated from the sand and analyzed using X-ray diffraction (XRD) and examined using transmission electron microscopy (TEM). The XRD reflection at 0.718 nm clearly indicated kaolinite in the rhizosphere after growth of the three crops. Furthermore, hexagonal kaolinite particles were observed, using TEM, and the amount of Mg extracted by the three crops was significantly greater for sepiolite than for palygorskite. Palygorskite and sepiolite kaolinization in the rhizosphere was apparently due: (1) to high acidity in the rhizosphere caused by root activity and organic matter decomposition; and (2) to fibrous clay destabilization caused by Mg uptake by plants. This study shows that kaolinite in agricultural soils of arid and semi-arid regions might be partly due to neoformation after fibrous clay dissolution and not entirely inherited from parent materials, as has been suggested in earlier literature.
Chemical and mineralogical characteristics of French green clays used for healing
- Lynda B. Williams, Shelley E. Haydel, Rossman F. Giese, Jr., Dennis D. Eberl
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- Published online by Cambridge University Press:
- 01 January 2024, pp. 437-452
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The worldwide emergence of infectious diseases, together with the increasing incidence of antibiotic-resistant bacteria, elevate the need to properly detect, prevent, and effectively treat these infections. The overuse and misuse of common antibiotics in recent decades stimulates the need to identify new inhibitory agents. Therefore, natural products like clays, that display antibacterial properties, are of particular interest.
The absorptive properties of clay minerals are well documented for healing skin and gastrointestinal ailments. However, the antibacterial properties of clays have received less scientific attention. French green clays have recently been shown to heal Buruli ulcer, a necrotic or ‘flesh-eating’ infection caused by Mycobacterium ulcerans. Assessing the antibacterial properties of these clays could provide an inexpensive treatment for Buruli ulcer and other skin infections.
Antimicrobial testing of the two clays on a broad-spectrum of bacterial pathogens showed that one clay promotes bacterial growth (possibly provoking a response from the natural immune system), while another kills bacteria or significantly inhibits bacterial growth. This paper compares the mineralogy and chemical composition of the two French green clays used in the treatment of Buruli ulcer.
Mineralogically, the two clays are dominated by 1Md illite and Fe-smectite. Comparing the chemistry of the clay minerals and exchangeable ions, we conclude that the chemistry of the clay, and the surface properties that affect pH and oxidation state, control the chemistry of the water used to moisten the clay poultices and contribute the critical antibacterial agent(s) that ultimately debilitate the bacteria.
The trapping of B from water by exfoliated and functionalized vermiculite
- Mohamed Kehal, Laurence Reinert, David Maurin, Jean-Louis Bantignies, Fumihiko Ohashi, Ammar Mennour, Laurent Duclaux
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- Published online by Cambridge University Press:
- 01 January 2024, pp. 453-460
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Micron-grade natural vermiculite was modified by several physical and chemical treatments in order to increase the adsorption capacity of this material for B. A thermal exfoliation (T = 600°C) of pristine material, a chemical exfoliation through reaction with hydrogen peroxide (H2O2 35%), or grafting of a specific B complexant (i.e. N-methyl-D-glucamine: NMDG) led to an increase in the uptake of B at low initial concentrations of the aqueous solutions ([B] ≈ 5 mg L−1). The more efficient material is the NMDG-grafted clay, for which the adsorption uptake is four times greater than that of raw vermiculite, and reaches 0.04 mmol g−1. For all modified materials, the effect of the pH on B adsorption and the adsorption kinetics were studied and compared to raw vermiculite. Adsorption isotherms were also plotted and fitted well with the Freundlich equation.
XRD, FTIR, and thermal analysis of bauxite ore-processing waste (red mud) exchanged with heavy metals
- Paola Castaldi, Margherita Silvetti, Laura Santona, Stefano Enzo, Pietro Melis
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- Published online by Cambridge University Press:
- 01 January 2024, pp. 461-469
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The present work shows the results of X-ray diffraction (XRD), Fourier transform infrared (FTIR), and thermal analysis of untreated (RMnt) and acid-treated red mud (RMa), a bauxite ore-processing waste, exchanged with Pb2+, Cd2+, and Zn2+ cations. These studies were performed in order to investigate the changes in the sorbent structure caused by the exchange with metals of different ionic radii.
The XRD pattern of RMnt, analyzed according to the Rietveld method, showed a mixture of eight different phases. However, just three phases made up 78 wt.% of the RMnt: cancrinite (33 wt.%), hematite (29 wt.%), and sodalite (16 wt.%). X-ray diffraction patterns of RMnt exchanged with Pb2+ and Cd2+ cations revealed two additional phases, namely hydrocerussite [Pb3(CO3)2(OH)2 (10 wt.%))] and octavite [CdCO3 (8 wt.%)].
These two phases probably originated from the carbonate precipitation processes which were due to the decarbonation of cancrinite. Hydrocerussite and octavite were not found in the case of acid-treated red mud samples.
In the FTIR spectra, the introduction of cations caused a distinct shift to higher wavenumbers in the peak at ∼1100 cm−1, which is attributed to the asymmetric stretch of Si-O-Al. This effect may be associated with the Pb2+, Cd2+, and Zn2+ adsorbed by the red muds which caused a deformation of the initial structure.
Thermal analysis data of the red mud samples were obtained by thermogravimetric/differential thermogravimetric analysis, and these methods were employed to evaluate the desorption behavior of water and to clarify the thermal stability of the chemical phases of the different red mud samples. The loss of metal-bound water in the red mud samples was found to depend on the size of non-framework cations and water loss consistently followed the order: Zn2+>Cd2+>Pb2+.
Low-temperature FTIR study of kaolin-group minerals
- Cliff T. Johnston, Jessica Elzea Kogel, David L. Bish, Toshihiro Kogure, Haydn H. Murray
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- Published online by Cambridge University Press:
- 01 January 2024, pp. 470-485
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Low-temperature FTIR spectroscopy was used to characterize the v(OH) region of kaolin-group minerals including well ordered to poorly ordered kaolins from Georgia, Brazil, and England, along with samples of discrete dickite and nacrite. Low-temperature FTIR spectra were useful in resolving dickite- and nacrite-like features present in the spectra of kaolins when cooled to <30 K. These features were not resolved at room temperature and only partially resolved at liquid N2 temperature (77 K). The room-temperature and low-temperature positions of the ν(OH) bands of kaolinite, dickite, and nacrite were linearly correlated with the interatomic OH⋯O distances and this relationship served as the basis for polytype/disorder identification. Dickite or dickite-like disorder was found in high Hinckley-Index kaolinite from Keokuk, Iowa, and from Cornwall, England. Dickite- and nacrite-like features were observed in both high- and low-Hinckley-index kaolinite and the amounts of these stacking sequences generally increased with decreasing Hinckley Index.