The simple explanation? Calcium is a +2 ion, so it has two arms reaching out, able to grab some negative charge. It can pull things together like a parent reining in toddler twins headed in different directions. Sodium can't do this. It is only a +1 ion, so if it grabs onto something, it just goes along for the ride wherever the negative charge was headed.
Clay particles that are so light that it takes them a very long time to settle out. But once a few particles get agglomerated together, courtesy of the calcium ions, they are big enough to settle.
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