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They measure it from bubbles of gas trapped in Antarctic ice.

Primarily by the scientific examination of Ice Core Samples taken thousands of feet Deep from thousands of Sites around Earth.

It is an interesting process really. When ice freezes, it has very tiny atmospheric gas bubbles trapped in the ice. There is a place in the Antarctic, known as Lake Vostok, that we are able to take and drill down very deep and get very clean samples of what the air was like. These samples will tell us what the atmosphere was like at a given time, by how far down the sample was taken from. From these cores, we are able to get actual gas bubbles of atmosphere from up to 650,000 years ago.

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Q: How do scientists know the atmospheric levels of carbon dioxide that exist on earth hundreds or thousands of years ago?
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