We provide a step towards classifying Riemannian four-manifolds in which the curvature tensor has zero divergence, or – equivalently – the Ricci tensor Ric satisfies the Codazzi equation. Every known compact manifold of this type belongs to one of five otherwise-familiar classes of examples. The main result consists in showing that, if such a manifold (not necessarily compact or even complete) lies outside of the five classes – a non-vacuous assumption – then, at all points of a dense open subset, Ric has four distinct eigenvalues, while suitable local coordinates simultaneously diagonalize Ric, the metric and, in a natural sense, also the curvature tensor. Furthermore, in a local orthonormal frame formed by Ricci eigenvectors, the connection form (or, curvature tensor) has just twelve (or, respectively, six) possibly-nonzero components, which together satisfy a specific system, not depending on the point, of homogeneous polynomial equations. A part of the classification problem is thus reduced to a question in real algebraic geometry.

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