Mackinawite has been identified in mafic and ultramafic rocks of the Bushveld igneous complex and Insizwa and also in the carbonatite and pegmatoid of Loolekop, Phalaborwa complex in South Africa. The mineral occurs predominantly as somewhat irregular to oriented intergrowths in pentlandite in all these occurrences and less commonly as regular oriented lamellae in chalcopyrite and rarely in cubanite. The textural evidence suggests that mackinawite may represent an exsolution product of pentlandite, chalcopyrite and cubanite.

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