Caves are formed mainly by a chemical reaction involving limestone dissolution. Materials from plants and soil on the earth’s surface decays and releases Carbon Dioxide, which mixes with the limestone and creates carbonic acid.
The carbonic acid seeps its way into the ground, mixes with the limestone naturally there and dissolves it. This starts an erosion process, forming cracks in the ground. Water fills the cracks, and the force of the water causes the cracks to get bigger and become holes. Sooner or later, the holes become caves.
The carbonic acid discussed in the other answer is not out there as pure carbonic acid… it’s in the water, naturally (both in rain and groundwater), and this slightly acid water is what dissolves the limestone. Water’s mechanical activity has a small role in cave development, and larger later on when the openings are large and collapse can happen, but it is dissolution that does most of the work throughout a cave’s development.
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