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Preheat the oven to 425 F.
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Bring the water to a boil in a medium saucepan and add the salt, bay leaf, and barley. Simmer, partially covered, until the barley is tender, about 35 minutes. Remove from heat and keep covered until you're ready to mix up the salad.
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Toss the vegetables, onion, olive oil, thyme, a few pinches of salt and a few grinds of black pepper and spread on a sheet pan.
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Roast for about 25 minutes, stirring once or twice, until tender.
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Toss the barley and vegetables together in a large bowl with the balsamic, walnuts, and orange zest. Taste and adjust the seasonings.
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Serve warm or at room temperature, garnished with a few sprigs of fresh thyme