By accident.
Helium was discovered in the late 1800s when scientists pointed spectrometers at the sun during an eclipse and saw a line they’d never seen before. Later in the 1800s it was successfully separated from clevetite, an ore containing uranium. One of the products of uranium decay is helium.
We don’t know when natural gas was discovered precisely, but the French encountered Native Americans setting it on fire in the 1600s.
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