Arrange broccoli on a foil-lined baking sheet; coat with cooking spray. Bake at 450° for 12 minutes or until crisp-tender and lightly browned, stirring once. Heat broiler to high, leaving pan in oven; broil 2 minutes or until lightly charred.
Melt butter in a small skillet over medium heat; cook 3 minutes or until browned. Remove from heat. Stir in rind and juice. Combine broccoli and butter mixture in a large bowl. Sprinkle with salt and pepper; toss to coat.
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