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Green peppercorns are the exact same berry that black peppercorns are made from, but instead of sun-drying which turns the outer hull of the berry black, green peppercorns are either freeze-dried or packed in a brine to preserve the soft green color and the delicate flavor.
When pepper berries are sundried the outer hull oxidizes setting off an enzymatic reaction that turns the outer skin black and initiates other chemical reactions that develop the aromas and pungency unique to black pepper. If the berries are boiled briefly, the enzyme responsible for turning the outer skin black is disrupted, and they can be sundried without turning black. Green peppercorns are also freeze-dried, pickled, an occasionally frozen as alternative preservation methods. Frozen green pepper is starting to appear on the market, but is expensive and has very limited distribution.
Green peppercorns have less aroma and pungency than black pepper because much of the flavor of black pepper is developed through enzymatic activity that takes place during sun drying. Green pepper is wonderful with lighter flavored foods and can always be combined with black pepper if a bit more of that lingering peppery bite is desired.
See the Black Pepper entry to read more about the flavor components, trade, and Piper nigrum plant that pepper comes from.
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