Each item has an Attachments tab in the right column. Some attachments are automatically added (e.g., PDF of journal article, Snapshot image of the webpage). You can also manually attach your own files (e.g., Word document with notes, image file). To add an attachment to an item that is already in your Library, right click the item and select the Add Attachment command. This will open a drop down with options for adding a file.
Source: U of T Zotero Library Guide.