Because the sky is blue (on Earth).
Transparent materials, like air and water, aren’t perfect; they absorb and/or bend different wavelengths of light by different amounts. So if we can detect light that’s gone through the atmosphere of an exoplanet, we can compare that to light from the planets star to see how it’s been changed. If it bends/absorbs light in specific ways, we can tell that a specific gas is present.
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