Journal
CHEMICAL GEOLOGY
Volume 606, Issue -, Pages -Publisher
ELSEVIER
DOI: 10.1016/j.chemgeo.2022.120995
Keywords
Hematite; Goethite; 2-line Ferrihydrite; Iron Oxides; Time-resolved X-ray diffraction
Categories
Funding
- National Science Foundation [EAR-1552211, EAR-1925903]
- Pennsylvania State University Biogeochemistry dual-title Ph.D. program
- Pennsylvania State University Geosciences Department
- NSF [EAR-1634415]
- DOE GeoSciences [DE-FG02-94ER14466]
- DOE [DE-AC02-06CH11357]
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Iron (oxyhydr)oxides, such as goethite and hematite, are important indicators of pH, Eh, temperature, microbial activity, and climate conditions in the Critical Zone. This study examined the transformation of two-line ferrihydrite to goethite and hematite under various temperature and pH conditions. The results showed that both goethite and hematite nucleated simultaneously from ferrihydrite and their relative abundances changed with temperature, pH, and water activity. These findings have implications for using hematite-goethite ratios as paleoclimate proxies in low pH buffering systems.
Iron (oxyhydr)oxides are sensitive indicators of pH, Eh, temperature, microbial activity, and climate conditions in the Critical Zone. The most ubiquitous and environmentally significant iron oxides in most soils are two-line ferrihydrite, goethite, and hematite. Here we present a comprehensive study of the transformation of two-line ferrihydrite to hematite and goethite over a wide range of temperature (25-170 degrees C) and initial pH (2-13) conditions through ex situ batch and in situ synchrotron X-ray diffraction (XRD) experiments. Within the high time resolution of our experiments, goethite and hematite nucleated nearly simultaneously from ferrihydrite in nearly equal concentrations by mass. Hematite increased in abundance relative to goethite until a steady-state ratio was achieved, and both phases ceased growth on the depletion of ferrihydrite. Higher temperatures and lower water activities favored hematite formation at all pH values studied. In both our batch and our time-resolved, angle-dispersive synchrotron X-ray diffraction experiments, hematite was favored relative to goethite at an initial pH of 3 to 5. In contrast, goethite preferentially formed in neutral (initial pH 7-8) and highly alkaline conditions (initial pH >= 11). Surprisingly, mildly alkaline conditions (initial pH 9-11) induced the precipitation of a highly Fe-deficient (Fe-occ = similar to 0.80-0.90) variety of hematite known as hydrohematite in greater concentrations than goethite. Our results are useful for the application of hematite-goethite ratios as paleoclimate proxies for soil and sediment systems with low pH buffering capacities.
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