The crystal chemistry of Cr (0.73%), Mn (0.88%), Co (0.166%), Ni (0.898%), Cu (0.263%), and Zn (0.026%) in natural goethite (αFeOOH) from an earthy saprolite formation in West-Africa was investigated by fluorescence-yield extended X-ray absorption fine structure (EXAFS) spectroscopy. Synthetic goethites and phyllomanganates were used as model compounds for structural determinations. The measurement of EXAFS spectra at energies higher than the Fe K-edge (Co, Ni, Cu, and Zn) is notoriously difficult because the fluorescence signal from trace elements is typically two orders of magnitude less intense than the Fe fluorescence from the matrix. This difficulty was circumvented by measuring total intensity (signal + background) with high precision on the ID26 undulator EXAFS spectrometer of the European Synchrotron Radiation Facility (ESRF) with a fast, highly linear, and low-noise diode detector. Cr, Cu, and Zn have the same local structure in natural and synthetic goethites. With the exception of the Cu polyhedron, which is distorted by the Jahn-Teller effect, Me-O and Me-Fe distances are similar to Fe-O and Fe-Fe distances in goethite. No significant steric effect was observed around Cu and Zn in spite of the ∼14% increase in ionic radii compared to Fe 3+. The compliance of the Fe site to these substitutional impurities probably is accomplished by displacement of nearest O and Fe shells (relaxation effect) and modification of interpolyhedral angles (compliance effect) owing to the corner-sharing topology of the goethite structure. X-ray absorption near-edge structure analysis reveals an average valence of ∼3.7 to 3.8 for Mn, and EXAFS indicates that manganese is present as a phyllomanganate impurity having a hexagonal layer symmetry like asbolane, lithiophorite, and hexagonal birnessite. Cobalt is trivalent and located in the phyllomanganate layer, and also possibly in the interlayer, substituting for Mn. Selective uptake of cobalt by the Mn oxide impurity results from the oxidation of soluble Co 2+ to insoluble Co 3+ by Mn 3+/Mn 4+, this mineral-surface redox reaction accounting for the well-known geochemical affinity of Co for Mn at the earth's surface. No more than ∼20% of the amounts of Mn and Co in natural goethite substitute for Fe in the structure, if present at all. About 75% of total Ni is substituted for Fe in natural goethite and ∼25% is associated with the phyllomanganate impurity as a Ni(OH) 2-MnO 2 mixed-layer phase (Ni-asbolane). The Ni site in synthetic goethite is strongly relaxed with a contraction of the goethite structure in the plane of edge-sharing double chains ( bc plane), and an expansion in the direction of corner linkages (approximately the ab plane). This anisotropic relaxation of the Ni site locally reduces the distortion of the goethite structure, and could be due to a clustering of Ni atoms.