We know because we’ve smelled it.
Apollo needed to open the door to let the people in and out.
Neil and Buzz went for a wander, took some photos, raised a flag, then got back in the spacecraft and took their helmets off. The smell came with.
I believe though, that they found the ozone smell of space earlier during orbital tests.
There are two ways that people claim to have smelled space. I’ll address both.
First, is astronauts claiming to “smell space” on their clothes after going on a space walk.
What are they smelling? Well during re-pressurization, the chemical reaction of oxidation occurs; atoms of oxygen in space attach to the astronaut’s suit and float in during the de-pressurized time when the airlock is open and combine to form real breathable oxygen.
That process is similar to combustion without the flame and smoke. It also smells similar, which would explain why astronauts report the smell as being like burning material.
The second scenario is when scientists say something like “this nebula smells like strawberries”.
What they are doing is examining what chemicals and gases are in the nebula (this can be done with scanners and telescopes). We know what these chemicals smell like because we have them on Earth. So if you bottled up a piece of that nebula and then brought it to earth and smelled it, it would smell like strawberries to you.
The same way you can smell cigarettes on someone even if they’re in a building that no one has ever smoked in. It got on their space suits and when they came inside the smell came with them on their suits. And I imagine being a smell that humans have never encountered before it was probably pretty noticeable.
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