THE FATE OF SMECTITE IN KOH SOLUTIONS

International audienceThe aim of the present study was to investigate the detailed evolution of the SAz-1 smectite in 1 M KOH at 80°C at a solid/liquid ratio of 1/80. AFM observations indicated no change in crystal size or shape. XRD measurements at 40% relative humidity revealed changes in expandability of the smectite. The 001 reflection profile of smectite was modelled using the trial-and-error approach of Sakharov et al., 1999b. The results indicate that with increasing run time the number of non expandable layers with zero or one water layer increases and that the coherent scattering domain size of the smectite decreases. Infrared spectroscopy of the reacted smectite suggests that there is no change from the initial clay products. The dehydroxylation temperature showed a slight decrease from 619° to 605°C. STA measurements demonstrated that the cis-vacant character of the octahedral sheet remained nearly unchanged throughout the experiment. Determination of the average layer charge showed a continuous increase from 0.32 to 0.42 eq/Si (Si/Al)4O10 whereas the layer charge distribution indicated the appearance of high charged smectite layers with a charge of ~ 0.6 eq/Si (Si/Al)4O10 and the disappearance of the low charged layers. XPS and SEM measurements indicate an increase of the aluminium in the smectite samples. Isotope data support the theory of a internal diffusion mechanism by gradual changes in δ 18O values. From these data it appears that KOH solutions provoke a mineralogical change in the 2:1 layer of the smectite minerals which increases the layer charge by increasing the Al content. This mineralogical change does not involve dissolution/crystallization processes and then must show solid state transformation of the clays at 80°C

Formation of Zn–Ca phyllomanganate nanoparticles in grass roots

International audienceIt is now well established that a number of terrestrial and aquatic microorganisms have the capacity to oxidize and precipitate Mn as phyllomanganate. However, this biomineralization has never been shown to occur in plant tissues, nor has the structure of a natural Mn(IV) biooxide been characterized in detail. We show that the graminaceous plant Festuca rubra (red fescue) produces a Zn-rich phyllomanganate with constant Zn:Mn and Ca:Mn atomic ratios (0.46 and 0.38, respectively) when grown on a contaminated sediment. This new phase is so far the Zn-richest manganate known to form in nature (chalcophanite has a Zn:Mn ratio of 0.33) and has no synthetic equivalent. Visual examination of root fragments under a microscope shows black precipitates about ten to several tens of microns in size, and their imaging with backscattered and secondary electrons demonstrates that they are located in the root epidermis. In situ measurements by Mn and Zn K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy and X-ray diffraction (XRD) with a micro-focused beam can be quantitatively described by a single-phase model consisting of Mn(IV) octahedral layers with 22% vacant sites capped with tetrahedral and octahedral Zn in proportions of 3:1. The layer charge deficit is also partly balanced by interlayer Mn and Ca. Diffracting crystallites have a domain radius of 33 Å in the ab plane and contain only 1.2 layers (not, vert, similar8.6 Å) on average. Since this biogenic Mn oxide consists mostly of isolated layers, basal 00l reflections are essentially absent despite its lamellar structure. Individual Mn layers are probably held together in the Mn–Zn precipitates by stabilizing organic molecules. Zinc biomineralization by plants likely is a defense mechanism against toxicity induced by excess concentrations of this metal in the rhizosphere

The Journal of the Friends' Historical Society vol. 5 No. 3

1. Notices. 2. Notes and Queries. 3. Documents from the Paris National Archives relating to Stephen Grellet II. 4. Presentations of Quakers in Episcopal Visitations, 1662-1679. 5. Extracts from the Minute Book of the Women's Quarterly Meeting of Nottingham and Mansfield II. 6. Pennsylvenian Motions. 7. The Quaker Allusions in "The Diary of Samuel Pepys" III. 8. Obituary. 9. An Eighteenth Century Friends - Thomas Pole, M.D. 10. A Glimpse of Ancient Friends in Dorset III. 11. Friends in Current Literature. 12. Some Addenda to First Publishers of Truth in Staffordshire. 13. Officers for the Year 1908-9. 14. Balance Sheet for 1907