If you go through the motions of creating a new Catalog Item under a given Catalog Type, it should point you to the default XML file where those specific Catalog Items are stored. That's not to say that every Item under one Type *has* to exist in the same physical XML file. You may actually want to store custom Catalog Items in a separate XML file so that when upgrading to the next version your changes are not overwritten by any changes to these default location(s).
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