Polonium has no biological role and any sample used to kill the former KGB spy must have come from either a research laboratory or nuclear facility. It is found in uranium ores but at miniscule levels 0.00000001%. So small that the Curie's were awarded the Nobel prize for their superhuman effort to extract it. Could a terrorist smuggle Polonium into this country or is there a human leak at a UK Defence Establishment? Gramme quantities of polonium-210 are synthesized from bismuth in nuclear reactors. Carrying quantities of polonium is difficult because of the high temperature from radioactive decay [500oC] and the emission of deadly alpha particles. These radioactive particles are most dangerous when ingested. They pick up electrons from cells in the body and escape as helium gas. Polonium-210 has a relatively short half life [138 days] so the 'evidence' diminishes constantly with time. Also Polonium is fairly volatile and will evaporate if not kept in a sealed container. Polonium is one of the deadliest known substances and is believed to be a trillion more times toxic than HCN weight for weight.

Info: from the excellent book Nature's Building Blocks by J. Emsley
BBC News