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In a 4-quart Dutch oven, cook bell peppers, celery, onion and garlic in hot oil over medium heat for 5 minutes, stirring occasionally. Stir in black pepper and cayenne pepper.
Add water, barley and ham. Bring to a boil; reduce heat. Simmer, covered, for 15 minutes or until barley is tender. Stir in tomatoes and okra. Cook, uncovered, for 5 minutes more, stirring occasionally. Divide mixture among six shallow serving bowls. If desired, sprinkle with parsley.