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You can only obtain it near the end of the game. During the initial part of the Landsmeet mission chain, you will be asked to rescue Queen Anora from Arl Howe's estate. During this mission, you will meet and rescue Riordan, a Grey Warden from Orlais.

Back at Arl Eamon's estate, you can speak to Riordan who will thank you for the rescue and mention the location of a Grey Warden cache in Denerim. You may have already been there earlier, it is the warehouse location that contains a blocked off area behind a bookcase. When you visit it again, you will be able to move the bookcase and access the cache, which contains useful items including Duncan's Shield, a gift item that turns into a usable shield when gifted to Alistair.

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