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However you can use the Character Editor mode and just remove the relationship.
https://steamcommunity.com/sharedfiles/filedetails/?id=1874644848&searchtext=character+edit
They probably need a very high opinion of each other, as like 20-30 ended with them getting a mood debuff - but for some reason they still romanced and married later without me doing anything. I only tied it manually, because it was the only viable option for a romance, and they mainly worked together, so their opinion would automatically raise.
In the end there´s no difference in being married or in being in a romance for gameplay - if You choose the free love precept. Of course if You choose another one - they need to be married to share the same bed, else You can´t even assign them.
At one point or another you can romance that colonist with someone else. The other person will get a heavy blow, but given that you say that person is off map and not in your colony/rooster it should be fine. I found out the hard way that this is posible when your not carefull, as your pops do stuff themself sometimes without your consent (wich is still sad AF... want more micro on them)
Open Debug Actions Menu>>>Add/Remove pawn relation>>>(pick married pawn)>>>Remove>>>(pick Spouse option)
Now, my game is heavily moded, but I think that's vanilla feature
Relationships of any kind between a pawn you control and a pawn you don't control, will influence raids, events, quests, etc. to include those lost pawns. If it's your wife, she will raid you, have rescue quests tied to her, and you can potentially recruit her. Far as I know, pawns tied to yours with relationships are never Unwavering.
If you want to do it quickly, use the Character Editor mod, you can edit any pawn at any time to tweak almost everything about them, including relationships. I don't know how to do it without this mod though.
With the Biotech DLC, there is a romance button in their social tab so you might be able to force a relationship between two pawns despite the fact that one is married. Otherwise I don't think that there is really anything that you can do.