Well volcanoes produce quite a bit of greenhouse gases. However, supervolcanoes are said to be the biggest naturally devastating event. This is eventually what will literally blow up Yellowstone National Park and beyond. It is such a large disruption that the problem is beyond that of mere greenhouse gas emissions, as supervolcanoes move up to 240 cubic miles of matter. Also, asteroid, comet, and meteor/ite collisions probably rank pretty high in the list having likely killed the dinosaurs and having almost innumerable side-effects.
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