X-ray photoelectron spectroscopy was used to characterize the chemical species of lead in bryophyte and pebble samples obtained in a stream passing through a lead mine in England. The 4f7/2 photoelectron binding energy of lead in the three bryophytes agreed fairly well with each other, but differed from the binding energies for the mineral phases, where lead exists as sulfide, and possibly also sulfate and Pb2+ion bound to silicate.