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When there is a hazardous materials emergency, what should you do?

A Do both of the above.

If there is an emergency involving the hazardous materials you're transporting, follow all instructions that your employer gave you. Keep bystanders away, preferably upwind, while warning them of the danger. Try to keep open flames away and don't let anyone smoke near the hazardous materials. Take a copy of your shipping papers with you to provide to first responders who arrive at the scene.