X-ray absorption study of 3d transition-metals and Mg in glasses and analogue crystalline materia... more X-ray absorption study of 3d transition-metals and Mg in glasses and analogue crystalline materials in AFe 3 + Si 2 O 6 and A 2 X 2 + Si 5 O 12 , where A = K, Rb, or Cs and X = Mg, Mn, Fe, Co, Ni, Cu, or Zn Crystalline and glassy phases in the 'leucite' systems (K,Rb,Cs)Fe 3+ Si 2 O 6 and (K,Rb,Cs) 2 –(Mg,Mn,Fe,Co,Ni,Cu,Zn) 2+ Si 5 O 12 have been studied using K-edge X-ray Absorption Spectroscopy (XAS) for 3d transition elements and Mg. Crystalline samples of known structure are used as model compounds for deducing the local structures of the equivalent glasses. 'Ideal' tetrahedral framework X 2+ –O distances are: Mn 2+ –O 2.02, Fe 2+ –O 1.98; Co 2+ –O 1.96, Ni 2+ –O 1.95, Cu 2+ –O 1.92, Zn 2+ –O 1.93 and Mg 2+ –O 1.93 Å. The quenched glasses have Extended X-ray Absorption Fine Structure (EXAFS) first-shell distances and coordination numbers consistent with Mg and 3d elements occurring in tetrahedral coordination in most cases. The X-ray Absorption Near Edge Structure (XANES) spectra of the glasses are basically the same as those for the crystalline samples showing that they have similar medium range order, consistent with most of the Mg and 3d elements acting as network formers along with the associated alkalis as X 2 Y 2+ O 2 complexes. Anhydrous glasses in the system CaO–MgO–Al 2 O 3 –SiO 2 together with a basalt glass from Hawaii show examples of Mg in octahedral-(2.07 Å, basalt), tetrahedral-(1.97 Å, siliceous glass) and 5-coordinated (2.01–2.04 Å) sites. Although most Earth scientists assume that Mg and Fe 2+ act as network modifiers in natural magmas, ultra-potassic, peralkaline compositions ((Na + K)/(Al + Fe 3+) N 1) could have had some Fe 2+ and Mg complexes with alkalis in the melt network as K 2 (Mg,Fe 2+)O 2 and the implications of this to melt density and viscosity are considered.
This work elucidates spatio-temporal aspects of the biogeochemical transformation of copper mobil... more This work elucidates spatio-temporal aspects of the biogeochemical transformation of copper mobilized from malachite (Cu2 (CO3 )(OH)2 ) and bioaccumulated within Aspergillus niger colonies when grown on different inorganic nitrogen sources. It was shown that the use of either ammonium or nitrate determined how copper was distributed within the colony and its microenvironment and the copper oxidation state and succession of copper coordinating ligands within the biomass. Nitrate-grown colonies yielded ∼1.7× more biomass, bioaccumulated ∼7× less copper, excreted ∼1.9× more oxalate and produced ∼1.75× less water-soluble copper in the medium in contrast to ammonium-grown colonies. Microfocus X-ray absorption spectroscopy revealed that as the mycelium matured, bioaccumulated copper was transformed from less stable and more toxic Cu(I) into less toxic Cu(II) which was coordinated predominantly by phosphate/malate ligands. With time, a shift to oxalate coordination of bioaccumulated copper...
The chemical composition oft he natural arsenate-apatite mineral johnbaumite [nominally Ca10(AsO4... more The chemical composition oft he natural arsenate-apatite mineral johnbaumite [nominally Ca10(AsO4)6(OH)2] and its alteration product hedyphane [Ca4Pb6(AsO4)6Cl2] have been determined by electron microprobe analysis and the structures ofjohnbaumite and synthetic Sr-, Ba- and Pbarsenate apatites have been studied by As K-edge X-ray absorption spectroscopy and synchrotron X-ray powder diffraction. All samples belong to the holosymmetric apatite space group P63/m with As5+ substituted for P5+ in the tetrahedral structural site. Johnbaumite contains small amounts ofF and Pb (~0.9 and ~4.4 wt.% respectively) and hedyphane has the ideal composition (formula given above); the compositions of these coexisting phases define the two limbs ofa solvus occurring between Ca- and Pb-arsenate apatite end members. The unit-cell parameters and cation–oxygen bond lengths for the arsenate apatites studied are discussed alongside published data for end-member Ca-, Sr-, Ba- and Pbphosphate apatite analogu...
X-ray absorption study of 3d transition-metals and Mg in glasses and analogue crystalline materia... more X-ray absorption study of 3d transition-metals and Mg in glasses and analogue crystalline materials in AFe 3 + Si 2 O 6 and A 2 X 2 + Si 5 O 12 , where A = K, Rb, or Cs and X = Mg, Mn, Fe, Co, Ni, Cu, or Zn Crystalline and glassy phases in the 'leucite' systems (K,Rb,Cs)Fe 3+ Si 2 O 6 and (K,Rb,Cs) 2 –(Mg,Mn,Fe,Co,Ni,Cu,Zn) 2+ Si 5 O 12 have been studied using K-edge X-ray Absorption Spectroscopy (XAS) for 3d transition elements and Mg. Crystalline samples of known structure are used as model compounds for deducing the local structures of the equivalent glasses. 'Ideal' tetrahedral framework X 2+ –O distances are: Mn 2+ –O 2.02, Fe 2+ –O 1.98; Co 2+ –O 1.96, Ni 2+ –O 1.95, Cu 2+ –O 1.92, Zn 2+ –O 1.93 and Mg 2+ –O 1.93 Å. The quenched glasses have Extended X-ray Absorption Fine Structure (EXAFS) first-shell distances and coordination numbers consistent with Mg and 3d elements occurring in tetrahedral coordination in most cases. The X-ray Absorption Near Edge Structure (XANES) spectra of the glasses are basically the same as those for the crystalline samples showing that they have similar medium range order, consistent with most of the Mg and 3d elements acting as network formers along with the associated alkalis as X 2 Y 2+ O 2 complexes. Anhydrous glasses in the system CaO–MgO–Al 2 O 3 –SiO 2 together with a basalt glass from Hawaii show examples of Mg in octahedral-(2.07 Å, basalt), tetrahedral-(1.97 Å, siliceous glass) and 5-coordinated (2.01–2.04 Å) sites. Although most Earth scientists assume that Mg and Fe 2+ act as network modifiers in natural magmas, ultra-potassic, peralkaline compositions ((Na + K)/(Al + Fe 3+) N 1) could have had some Fe 2+ and Mg complexes with alkalis in the melt network as K 2 (Mg,Fe 2+)O 2 and the implications of this to melt density and viscosity are considered.
This work elucidates spatio-temporal aspects of the biogeochemical transformation of copper mobil... more This work elucidates spatio-temporal aspects of the biogeochemical transformation of copper mobilized from malachite (Cu2 (CO3 )(OH)2 ) and bioaccumulated within Aspergillus niger colonies when grown on different inorganic nitrogen sources. It was shown that the use of either ammonium or nitrate determined how copper was distributed within the colony and its microenvironment and the copper oxidation state and succession of copper coordinating ligands within the biomass. Nitrate-grown colonies yielded ∼1.7× more biomass, bioaccumulated ∼7× less copper, excreted ∼1.9× more oxalate and produced ∼1.75× less water-soluble copper in the medium in contrast to ammonium-grown colonies. Microfocus X-ray absorption spectroscopy revealed that as the mycelium matured, bioaccumulated copper was transformed from less stable and more toxic Cu(I) into less toxic Cu(II) which was coordinated predominantly by phosphate/malate ligands. With time, a shift to oxalate coordination of bioaccumulated copper...
The chemical composition oft he natural arsenate-apatite mineral johnbaumite [nominally Ca10(AsO4... more The chemical composition oft he natural arsenate-apatite mineral johnbaumite [nominally Ca10(AsO4)6(OH)2] and its alteration product hedyphane [Ca4Pb6(AsO4)6Cl2] have been determined by electron microprobe analysis and the structures ofjohnbaumite and synthetic Sr-, Ba- and Pbarsenate apatites have been studied by As K-edge X-ray absorption spectroscopy and synchrotron X-ray powder diffraction. All samples belong to the holosymmetric apatite space group P63/m with As5+ substituted for P5+ in the tetrahedral structural site. Johnbaumite contains small amounts ofF and Pb (~0.9 and ~4.4 wt.% respectively) and hedyphane has the ideal composition (formula given above); the compositions of these coexisting phases define the two limbs ofa solvus occurring between Ca- and Pb-arsenate apatite end members. The unit-cell parameters and cation–oxygen bond lengths for the arsenate apatites studied are discussed alongside published data for end-member Ca-, Sr-, Ba- and Pbphosphate apatite analogu...
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2016 by John Charnock
Papers by John Charnock