The ability to probe the three-dimensional atomic structure of materials is an essential tool for material design and failure analysis. Atom-probe tomography has proven very powerful to analyze the detailed structure and chemistry of metallic alloys and semiconductor structures while ceramic materials have remained outside its standard purview. In the current work, we demonstrate that bulk alumina can be quantitatively analyzed and microstructural features observed. The analysis of grain boundary carbon segregation – barely achievable by electron microscopy – opens the possibility of understanding the mechanistic effects of dopants on mechanical properties, fracture and wear properties of bulk oxides.