Java Edition:Obsidian (Item)
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Obsidian has existed in the game since c0.28 but was not normally obtainable until Infdev 20100618 when mining the block dropped itself. Before, it dropped cobblestone.
Obtaining
Classic Creative Inventory
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Indev Item Chests
From Indev 20100124-2119 to Indev 20100128 new worlds would generate with the Indev House, and inside the house were debug chests. Between Indev 20100124 and Indev 20100125 the chests held items in stacks of 99, while in Indev 20100128 the chests held items in stacks of 100. Obsidian was one of the such items that generated inside the debug chests.
Mining
From Infdev 20100618 to 1.21.6 Release Candidate 1 (present), obsidian can be obtained by mining the block with an appropriate tool.