scholarly journals Germanium Crystal Chemistry in Cu-Bearing Sulfides from Micro-XRF Mapping and Micro-XANES Spectroscopy

Minerals ◽  
2019 ◽  
Vol 9 (4) ◽  
pp. 227 ◽  
Author(s):  
Rémi Belissont ◽  
Manuel Munoz ◽  
Marie-Christine Boiron ◽  
Béatrice Luais ◽  
Olivier Mathon

Germanium is considered a critical element, with a demand that has sharply increased due to booming high-technology industries. To understand Ge incorporation mechanisms in natural systems, we investigate Ge speciation in Cu-bearing sulfide minerals using synchrotron X-ray fluorescence (XRF) chemical mapping and Ge K-edge µ-X-ray absorption near-edge structures (µ-XANES) spectroscopy. The samples investigated include (i) a homogeneous chalcopyrite from the Kipushi polymetallic deposit (Central African copperbelt, D.R. Congo) and (ii) a zoned Ge-rich chalcopyrite from the Barrigão Cu deposit (Iberian pyrite belt, Portugal). First, our spectroscopic analysis supports the occurrence of tetrahedrally-coordinated Ge4+ in chalcopyrite, independently from origins or zoning patterns observed for these minerals. Then, based on statistical analyses of XRF chemical maps, we demonstrate that tetravalent germanium most likely incorporates chalcopyrite through the Fe crystallographic site via coupled substitutions with the following form: (2x + 3y)Fe3+ ⟷ (x + 2y)(Ge,Sn)4+ + x(Zn,Pb)2+ + y(Cu,Ag)+, although the presence of lattice vacancies cannot be completely excluded.

AMBIO ◽  
2017 ◽  
Vol 47 (S1) ◽  
pp. 62-72 ◽  
Author(s):  
Christian Vogel ◽  
Camille Rivard ◽  
Verena Wilken ◽  
Andreas Muskolus ◽  
Christian Adam

2018 ◽  
Vol 25 (6) ◽  
pp. 1736-1744 ◽  
Author(s):  
Jörg Prietzel ◽  
Wantana Klysubun

Phosphorus (P) K-edge X-ray absorption near-edge structure (XANES) spectra of orthophosphate (oPO4) bound to soil FeIII minerals (e.g. ferrihydrite, goethite) show a pre-edge signal at 2148–2152 eV. It is unknown whether organic P bound to FeIII oxyhydroxides also show this feature. Otherwise, Fe-bound soil P may be underestimated by P K-edge XANES spectroscopy, because a large portion of Fe oxyhydroxide-bound P in soils is organic P. K-edge XANES spectra were obtained for different organic P compounds present in soils [inositol hexaphosphate (IHP), glucose-6-phosphate (G6P), adenosine triphosphate (ATP)] after sorption to ferrihydrite or goethite and compared with spectra of oPO4 adsorbed to these minerals. P sorption to ferrihydrite increased in the sequence IHP ≪ G6P < oPO4 < ATP. P sorption to goethite increased in the sequence G6P < oPO4 ≪ ATP = IHP. Pre-edge signals in P K-edge XANES spectra of organic P adsorbed to Fe oxyhydroxides were markedly smaller compared with those of oPO4 adsorbed to these minerals and absent for FeIII oxyhydroxide-bound ATP as well as goethite-bound IHP. Linear combination fitting (LCF) performed on spectra of IHP, G6P or ATP adsorbed to ferrihydrite or goethite, using only spectra of FeIII oxyhydroxide-bound oPO4 as reference compounds for Fe-bound P, erroneously assigned >93% (ferrihydrite) or >41% (goethite) of Fe-bound P to non-Fe-bound P species. Inclusion of FeIII oxyhydroxide-bound IHP as reference compounds markedly increased the recovery of oxyhydroxide-bound organic P. Thus, Fe-bound soil P has probably often been underestimated by LCF in soil XANES studies where IHP adsorbed to ferrihydrite and to goethite were not included as reference compounds.


2005 ◽  
Vol 58 (6) ◽  
pp. 423 ◽  
Author(s):  
Adam P. Hitchcock ◽  
Harald D. H. Stöver ◽  
Lisa M. Croll ◽  
Ronald F. Childs

Recently, synchrotron-based soft X-ray spectromicroscopy techniques have been applied to studies of polymer microstructure at the ~50 nm spatial scale. Functional group based chemical speciation and quantitative mapping is provided by near edge X-ray absorption fine structure spectral (NEXAFS) contrast. The techniques, sample data, and analysis methods of scanning transmission X-ray microscopy (STXM) and X-ray photoemission electron microscopy (X-PEEM) are outlined. The capabilities of STXM are illustrated by results from recent studies of (a) controlled release microcapsules and microspheres, (b) microcapsules being developed for gene therapy applications, (c) conducting polymer films studied in the presence of electrolyte and under potential control, and (d) studies of protein interactions with patterned polymer surfaces. In the latter area, the capabilities of STXM and X-PEEM are compared directly.


2004 ◽  
Vol 84 (2) ◽  
pp. 171-175 ◽  
Author(s):  
C. R. Christensen ◽  
J. N. Cutler ◽  
D. A. Christensen

Synchrotron-based X-ray absorption near edge structure (XANES) spectroscopy is a relatively new technique within the life sciences. XANES has been utilized to identify the location, oxidation state and spatial distribution of heavy metal elements in plants , neurons, blood and DNA, but has not been widely used in the animal sciences. Selenium content in animal feeds is monitored, as both selenium deficiencies and toxicities are associated with physiological disorders. Selenium is available as an animal feed in both inorganic and organic states. The bioavailability of selenium species has been tested in numerous animal trials; however, a simple, non-destructive test for selenium speciation is not available. The objective of this study was to determine whether XANES spectroscopy could be used to determine the selenium oxidation state found in various commercial animal feed products. A comparison of absorption spectra indicated that the animal mineral supplements contained an organoselenium or selenite. The processed animal feeds had a spectral profile similar to that of elemental selenium. Further experiments are necessary to determine the implication of selenium speciation on animal physiology. Key words: Selenium speciation, mineral supplements, ruminants, non-ruminants, synchrotron, XANES, X-ray


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