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Iron Arrows are the earliest arrows encountered in The Elder Scrolls V: Skyrim. If you follow Hadvar at the start, you find your first set of iron arrows on a Stormcloak Soldier. If you side with Ralof, you get your first set from an Imperial Archer.
In The Elder Scrolls V: Hearthfire, placing iron arrows in the Dragonborn's house's cupboard may render them unable to be retrieved, causing them to be stuck in the cupboard. This does not seem to happen with other arrow types.