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A detailed understanding of ultrathin film surface properties is crucial forthe proper interpretation of spectroscopic, catalytic and spin-transport data.We present x-ray magnetic circular dichroism (XMCD) and x-ray resonant magneticreflectivity (XRMR) measurements on ultrathin $\mathrm{Fe_3O_4}$ films toobtain magnetic depth profiles for the three resonant energies corresponding tothe different cation species $\mathrm{Fe^{2+}_{oct}}$, $\mathrm{Fe^{3+}_{tet}}$and $\mathrm{Fe^{3+}_{oct}}$ located on octahedral and tetrahedral sites of theinverse spinel structure of $\mathrm{Fe_3O_4}$. By analyzing the XMCD spectrumof $\mathrm{Fe_3O_4}$ using multiplet calculations, the resonance energy ofeach cation species can be isolated. Performing XRMR on these three resonantenergies yields magnetic depth profiles that correspond each to one specificcation species. The depth profiles of both kinds of $\mathrm{Fe^{3+}}$ cationsreveal a $\mathrm{3.9 \pm 1~\r{A}}$-thick surface layer of enhancedmagnetization, which is likely due to an excess of these ions at the expense ofthe $\mathrm{Fe^{2+}_{oct}}$ species in the surface region. The magneticallyenhanced $\mathrm{Fe^{3+}_{tet}}$ layer is additionally shifted about$\mathrm{3\pm 1.5~\r{A}}$ farther from the surface than the$\mathrm{Fe^{3+}_{oct}}$ layer.

Cation- and lattice-site-selective magnetic depth profiles of ultrathin $\mathrm{Fe_3O_4}$(001) films