The chemical that produces the purple color is the same as the one that makes red cabbage purple-red. It will react in the same way, if it is cooked with an acid or base- turning pinkish for acids and bluish in a base- an alkaline like soda. It will leach some blue coloring into water that is closer to a neutral pH. However, if you steam it in just a bit of water, it will retain most of the color. Well- if you don't cook it to death, that is. Orange cauliflower is due to betacarotin, like in carrots- and behaves the same way in cooking as carrots do. Purple bell peppers are the same as the red cabbage and purple cauliflower. However, the chemical also decomposes in heat- and as peppers are usually sauteed with high heat- it's more likely to happen. Same with the purple "green" beans you see. The less you cook them, the more color they will retain. The cauliflower will lose some color as well, but has more pigment to start with than the bell pepper, so it can retain it more easily. I generally try to not cook purple veggies like this much more than to tender crisp, so they stay more vibrant. Well, except for red cabbage- which I do like braised like the Germans do.
They have them at our local farmer's market at the moment. I've also seen them at various area natural or organic food stores- like Whole Foods or Trader Joes, and a few of the Co-op stores. If you check the frozen veg sections, they may have a mix of various colors of cauliflower. I found one, surprisingly enough, in a Walmart SuperCenter frozen section. I haven't noticed that it tastes any differently, but it is very pretty in dishes, salads, and pickles.
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