Polonium the Curies while they were investigating the cause of pitchblende radioactivity. Pitchblende, after removal of the radioactive elements uranium and thorium, was more radioactive than the uranium and thorium combined. This spurred the Curies to search for additional radioactive elements. They first separated out polonium from pitchblende in July 1898, and five months later, also isolated radium. German scientist Willy Marckwald successfully isolated 3 milligrams of polonium in 1902, though at the time he believed it was a new element, which he dubbed "radio-tellurium", and it was not until 1905 that it was demonstrated to be the same as polonium.
Chemical element so long (at least 100 million times longer than the estimated age of the universe) that their radioactive decay has yet to be detected by experiment. Elements with atomic numbers 83 through 94 are unstable to the point that their radioactive decay can be detected. Three of these elements, bismuth (element 83), thorium (element 90), and uranium (element 92) have one or more isotopes with half-lives long enough to survive as remnants of the explosive stellar nucleosynthesis that produced the heavy elements before the formation of our solar system. For example, at over 1.9 years, over a billion times longer