I want to second all those who counselled the OP to clarify the marriage situation by going to the priest, especially by those who consistently and prudently urge people with questions to do that. No one here or elsewhere should be speculating about a concrete situation, even though attempting to assist someone in good faith.
In this case, there were major unasked questions that would have been asked in the first thirty seconds of discussion by any knowledgeable priest or canon lawyer. (For example, since we didn’t look into the poster’s baptismal status, we don’t know if we should even be talking about a nullity investigation or the application of a pauline privilege. Another example, since we don’t know the dates of the husband’s marriages, we don’t know whether the old code or the new code would apply to possible marriages outside the Church.)
Another point only mentioned in passing is sufficiently technical that it normally takes a consultation among several canon lawyers when it comes up in a particular case.
Finally, one statement about the civil marriage of non Catholics was just flat out wrong.
I’m not mentioning any of that to be offensive, elitist or arrogant, or to pass myself off as superior to anyone. I really know people have the best of intentions and are generally knowledgeable. Most CAF posters understand how canon law is a servant or a tool for the salvation of souls. Some people are pretty expert in canon law.
But this thread does point out the limits of giving technical advice on a very specific and personal situation.
There are many questions that would have to be asked to clarify any* particular* situation. They would have to be asked by the people who are not only qualified to practice Church law but who are in the position to actually do something about it. The parish priest or someone he designates to do this needs to be the point of entry.
It’s one thing to talk in general about different types of processes, or to give encouragement to those with problems. It’s wonderful to see how the faith of posters spills over with encouragement, the promise of prayerful support, and understanding.
It’s another thing to give specific technical counsel — even with the best of intention. The risk is giving incorrect information, making the problem worse, and harming the person who is asking for help. None of us want to do that.