actually a question in the name
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Although the comments on wowhead display earliest patch 2.3.3 , the gear was actually introduced with the release of sunwell (patch 2.4). The reason is the public test realm and data mining.
http://wowwiki.wikia.com/wiki/Patch_2.4.0
"Players will now be able to purchase level 70 Superior quality PvP items from reputation vendors."