Biotite and its alteration products (primarily chlorite) from igneous rocks around the Ray and Esperanza (Esperanza-Sierrita) porphyry copper deposits, Arizona, were analyzed for copper by electron microprobe. The copper occurs in amounts >90 p/m (limit of detection) in most of the chlorites analyzed, is concentrated at the optical and chemical boundary of chlorite and biotite, and is not associated with sulfur. Most unaltered igneous and hydrothermal biotites analyzed contain