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Natural gas consists mostly of methane, which is a compound (CH4), but there are usually a small amount of other gases mixed in (such as butane and propane, and may have water vapor and other gases) when it is piped out of the ground.
These other gases are removed, so then it's just methane gas (a compound).
Before it is piped to your house, trace amounts of an odorant are added, so that you can smell the gas if there is a leak (methane does not have an odor), so that would make it a mixture.
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