Origin of Magnetism in Hydrothermally Aged 2-Line Ferrihydrite Suspensions

As an iron oxyhydroxide, nanosized ferrihydrite (Fh) is important in Earth science, biology, and industrial applications. However, its basic structure and origin of its magnetism have long been debated. We integrate synchrotron-based techniques to explore the chemical structures of 2-line ferrihydrite and to determine the origin of its magnetism during hydrothermal aging in air. Our results demonstrate that both the magnetism and X-ray magnetic circular dichroism (XMCD) signal of 2-line ferrihydrite are enhanced with aging time, and that XMCD spectral patterns resemble that of maghemite (γ-Fe₂O₃) rather than magnetite (Fe₃O₄). Fe L-edge and K-edge X-ray absorption spectroscopy (XAS) further indicate formation of both maghemite and hematite (α-Fe₂O₃) with increasing concentrations with longer hydrothermal aging time. Thus, magnetic enhancement with longer hydrothermal aging time is attributed to increasing maghemite concentration instead of a magnetically ordered ferrihydrite as previously reported. Moreover, L-edge and K-edge XAS spectra with different probing depths yield different ratios of these Fe oxides, which suggest the formation of a core (ferrihydrite-rich)-shell (with a mixture of both allotropes; α-Fe₂O₃ and γ-Fe₂O₃) structure during hydrothermal aging. Our results provide insights into the chemical evolution of 2-line ferrihydrite that reveal unambiguously the origin of its magnetism.