Probably Preston putting them in there since he gave u the original flare gun
Very likely, as I think it's only in the Sanctuary workstation (or perhaps whichever settlement Preston is at --- I left him there). If you set up a Salvage station in a settlement, and assign a settler to it, you'll get a wide assortment of random crap, but mostly (only?) junk for scrapping. If you have surplus food and water, those go into the local workstation, too, along with profits from stores you set up. Not sure if non-flare ammo ever gets added....