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Most small pebbles are the remains of older larger pebbles, and even larger rocks many millions of years old. They became smaller and smaller through natural erosion processes (such as wind and water.)

These processes affect all parts of the pebble equally (the pebble, whether it is on land or in the water, is constantly being tumbled around.) This constant erosion on all sides ends up making it smooth and round, much in the same way that rubbing sand paper across wood makes that side of it smooth. The erosion sort of "cleans up" any jagged irregularities of the pebble.

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