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7014274 
Journal Article 
A multi-method characterization of natural terrestrial birnessites 
Ling, FT; Post, JE; Heaney, PJ; Santelli, CM; Ilton, ES; Burgos, WD; Rose, AW; , 
2020 
Yes 
American Mineralogist
ISSN: 0003-004X 
MINERALOGICAL SOC AMER 
CHANTILLY 
105 
6 
833-847 
WOS:000540324900005 
With a focus on a large set of natural birnessites collected from terrestrial, freshwater systems, we applied and compared the capabilities of X-ray diffraction (XRD), extended X-ray absorption fine structure (EXAFS), Fourier-transform infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS) to characterize crystal structure and chemistry. Using XRD, we successfully identified 3 of the 11 natural birnessite samples as hexagonal rancieite-like phases, but the remaining samples yielded less interpretable "3-line" diffraction patterns with broad, asymmetrical peaks at d-spacings of similar to 7.2, similar to 2.4, and similar to 1.4 angstrom. EXAFS analysis suggested that many of these samples had characteristics of both triclinic and hexagonal birnessite. However, application of EXAFS to the rancieite-like phases yielded unreasonably high concentrations of triclinic birnessite as an intergrowth, calling into question the use of synthetic hexagonal H-birnessite as an appropriate standard in the linear combination fitting of EXAFS data for natural birnessites. FTIR spectroscopy of the "3-line" birnessite samples successfully distinguished triclinic and hexagonal constituents, and analyses of peak positions suggested that natural birnessites occur as a full spectrum of triclinic and hexagonal intergrowths. XPS analysis of these samples revealed that higher Mn3+ concentrations relative to Mn2+ and Mn4+ are correlated to increased proportions of triclinic birnessite. 
Manganese oxide; birnessite; FTIR; EXAFS; XPS; XRD