Yes, any time releasing forms of calicium would be great to add in late winter or early spring so they get a chance to start breaking down by the time the plants need them. I'm not so sure egg shells would be of any use to orchids since the mix is so open (it even takes them forever to break down in my composter), but the leaves are dying now and any slow release amendment would be of zero use to them since they are already showing massive damage from deficiency. They need immediately available calcium in larger than normal doses to stop the damage, and from what I've read, calcium nitrate is the only water soluble form of calcium that plants can readily take up.
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