In as I am lacking technological experience to properly address the problem of, "the significance of pins tacked onto shortcut icons on Firefox opening page"; I will confront the situation with a simple picture. ⇘ I suppose I will never know: Two days ago this inquiry was attempted. However all was curtailed upon the realization several minutes passed during the process of uploading the image. Be it known, today, twenty minutes have passed in attempt to upload 238KB png file. Apparently security is prohibiting this. In any event, perchance some of this does get through... HELP
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The pin shows that the top site is pinned to the new tab page, whereas non pinned sites will change based on your browsing history.
This article has more info on how to modify your Shortcuts section on the built-in Firefox Home / new tab page: