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Air pressure is greater near the surface because air has mass, which means that the mass of the Earth causes the force of gravity to pull the air towards the surface. This causes the air molecules to compress, which increases air pressure. At the same time, the air molecules want to depressurize, because they are a gas, causing them to physically push on each other. This causes the air pressure closest to the surface to be highest, because the depth of the air above those closest to the surface is greatest. As altitude increases, air pressure decreases for the same reason - there is less mass pushing from above.

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