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Occurrence and production

Iodine is the least abundant of the stable halogens, comprising only 0.46 parts per million of Earth's crustal rocks (compare: fluorine: 544 ppm, chlorine: 126 ppm, bromine: 2.5 ppm) making it the 60th most abundant element. Iodide minerals are rare, and most deposits that are concentrated enough for economical extraction are iodate minerals instead. Examples include lautarite, Ca(IO), and dietzeite, 7Ca(IO) ·8CaCrO. These are the minerals that occur as trace impurities in the caliche, found in Chile, whose main product is sodium nitrate. In total, they can contain at least 0.02% and at most 1% iodine by mass. Sodium iodate is extracted from the caliche and reduced to iodide by sodium bisulfite. This solution is then reacted with freshly extracted iodate, resulting in comproportionation to iodine, which may be filtered off.

The caliche was the main source of iodine in the 19th century and continues to be important today, replacing kelp (which is no longer an economically viable source), but in the late 20th century brines emerged as a comparable source. The Japanese Minami Kantō gas field east of Tokyo and the American Anadarko Basin gas field in northwest Oklahoma are the two largest such sources. The brine is hotter than 60 °C from the depth of the source. The brine is first purified and acidified using sulfuric acid, then the iodide present is oxidised to iodine with chlorine. An iodine solution is produced, but is dilute and must be concentrated. Air is blown into the solution to evaporate the iodine, which is passed into an absorbing tower, where sulfur dioxide reduces the iodine. The hydrogen iodide (HI) is reacted with chlorine to precipitate the iodine. After filtering and purification the iodine is packed.

These sources ensure that Chile and Japan are the largest producers of iodine today. Alternatively, the brine may be treated with silver nitrate to precipitate out iodine as silver iodide, which is then decomposed by reaction with iron to form metallic silver and a solution of iron(II) iodide. The iodine is then liberated by displacement with chlorine.