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As a rock forms, any magnetic elements tend to align with the Earth's magnetic field. This can happen in a number of ways, from tiny grains physically rotating as they sink to form a sedimentary rock, to crystals tending to grow in a certain direction as a volcanic rock cools.
Either way, the Earth's magnetic field switches direction occasionally (roughly every 300,000 years). So you can look at the orientation of the magnetic grains in a rock and correlate that to the record of the Earth's magnetic field. This lets you figure out how old it is.
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