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Assignment is performed by Left Clicking on a colonist, then Right Clicking on the subject of the action, and then Left Clicking on an action from the context menu that should have appeared.
If there is no result from Right Clicking the subject, select it and use one of the icons that appears to designate an action. If the selected colonist cannot perform the action, open the Work menu to enable the work type or to find another colonist. Clicking a colonist's name in the Work menu conveniently selects the colonist and centers the map to them.