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Whether the fermentation happens at the milk stage, or whether the buttermilk is left to ferment after it's churned, the important part is that the aging process produces lactic acid. This is what gives the buttermilk its distinctive, tangy taste, and also what allows it to react so ferociously with alkali ingredients, causing breads and sponges to rise. Supermarket varieties don't naturally-ferment the buttermilk. They introduce a culture and artificially-ferment it, which still creates high acidity levels and a tangy taste. Nothing on the nostril-stinging ripeness or traditional farm-made buttermilk, but effective nonetheless.
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