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The majority of urinary calculi cases in goats aren't so much a problem of 'deposits' of minerals as a situation where the urine is too base and becomes saturated with ammonia, phosphorus, and magnesium.. These three combine into struvite crystals, and it can happen quickly under those circumstances.
Alfalfa hay contains a lot of calcium, and calcium helps the body bring phosphorus into the bloodstream instead of it basically passing directly on to the urine. That's why proper goat feed contains twice the calcium that it has phosphorus; to try and make sure that phosphorus has the best possible chance of being taken up in the blood. That said, alfalfa hay is good for bucks and wethers.
Not only is it a good source of calcium, but also a higher protein hay than grass, which -- if you're supplementing with grain according to condition -- means you can probably get by feeding less grain.
Every now and then I will give them a cup of Purina Goat Feed as a treat if it looks like it's going to get cold at night.
Feeding extra grain when it's cold isn't terribly helpful. I think the whole idea of feeding grain or higher protein hay on cold nights comes from the old saying about one feed being 'hotter' than another, based on protein content. Sometimes, though, it's taken to literally mean that it provides heat.
The problem is...it's almost the exact opposite when it comes to grain. The rumen plays a huge roll in keeping the goat warm on a cold night, as the process of breaking down the fibers of the forage consumed generates a lot of actual, physical heat. Grain, on the other hand -- especially pelleted grain, which I recommend for goats -- breaks down pretty doggone easily in the rumen. Since it's more easily broken down, it doesn't generate as much heat.
My recommendation is to feed your coursest, stemmiest hay on a cold night. I don't really care what the protein content is...whether it's really stemmy timothy or first cut stemmy alfalfa...or stemmy, weedy hay...makes no difference to me. My primary concern (and something I love) is hearing 'crunch, crunch, crunch' at the hay feeder when it's mind-numbingly cold out. When I hear the crunching, I know my goats will be warm that night.
I'll also say that if giving extra grain causes the goats to walk away from the hayfeeder more quickly than they would have otherwise...that can actually work against them as kind of a double whammy on a cold night.