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Adjust rack to middle position and preheat oven to 425 degrees. Wash and dry produce.
Cut broccoli florets into bite-size pieces if necessary. Dice potatoes into ½-inch pieces. Thinly slice chives.
Peel garlic. Place whole clove in the center of a small piece of foil; drizzle with olive oil and season with salt and pepper. Cinch into a packet.