The first time your Zotero library syncs, Firefox may appear to hang, especially if you have a large library. Be patient. If the Zotero sync icon continues to spin and you're convinced there is a problem, see Sync Queuing.
By default, Zotero will merge your local Zotero library with your library on zotero.org—any changes you make in one place will be applied to the other and on all other synced computers.
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