Journal
AMERICAN MINERALOGIST
Volume 105, Issue 6, Pages 833-847Publisher
MINERALOGICAL SOC AMER
DOI: 10.2138/am-2020-7303
Keywords
Manganese oxide; birnessite; FTIR; EXAFS; XPS; XRD
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Funding
- NSF [EAR-1147728, EAR1552211]
- Committee on Institutional Cooperation (CIC)
- Smithsonian Institution Fellowship
- DOE Office of Science by Argonne National Laboratory [DE-AC02-06CH11357]
- PNNL managed Geosciences Research Program of the U.S. Department of Energy (DOE), Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences Biosciences
- U.S. DOE's Office of Biological and Environmental Research
- Pacific Northwest National Laboratory (PNNL)
- DOE by Battelle Memorial Institute [DE-AC06-76RLO-1830]
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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.
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