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The most appropriate tool for assessing air velocity in a spray booth is an anemometer. An anemometer is specifically designed to measure the speed of air flow. In environments like spray booths, where managing air velocity is crucial for both worker safety and product quality, an anemometer provides accurate and real-time air velocity readings to ensure that the ventilation system is functioning properly.

A velometer, while sometimes referenced in similar contexts, is generally less common and may not provide the precise measurements required for assessing air velocity in industrial applications like a spray booth. Therefore, the use of an anemometer is favored for its reliability and ease of use in these specific settings.

The barometer measures atmospheric pressure, and a hydrometer is used for measuring the specific gravity of liquids, making them unsuitable for assessing air velocity. Hence, the anemometer is the clear choice for this application.