You can remove a marriage by:
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Clicking on one of the people
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Click "Change or delete"
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Click "Set to no current partner"
At this point, there is still probably a line between them, and that's not what you want. Depending on the kind of mistake, you could simply delete the no longer partner person from the tree entirely, but that's probably not what you want. So if both people should remain on the tree, then you probably want to do this.
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Click on one of the people
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Click "Change or delete"
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Click "Change partners"
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Click "Remove ex-partner <name of ex partner>"
That should remove the line between them. If it doesn't, you might have to repeat those steps from the other "partner".