Her original marriage wasn’t in the Catholic church nor blessed by it… her ex didn’t care at the time…
Probably your wife can get an annulment for defect of form. I was in a similar situation, but I was the Catholic party. I did have to apply for an annulment but since the following were all true, it was a “defect of form” and my ex-husband didn’t have to be contacted (which was good as I had no idea how to contact him):
– I was baptised Catholic
– I never officially declared myself an atheist or officially joined another church (just
going to another church for years doesn’t count

)
– I was married in a non-Catholic church, with no Catholic priest present and no permission from the local bishop
I had already been divorced for a few years when I came back to the Church, so I had to confess “going through a form of marriage” etc., during my confession when returning to the Church, and then once I applied it took about a month for the annulment.
Also this means that your wife’s ex-husband could have applied for and received an annulment for defect of form without your wife being contacted. I believe that the ex-spouse is supposed to be contacted (well, informed, really) if contact information for the ex-spouse is available, but I’d think it’s possible that the ex-husband might not have provided any contact information. It might not even be with any malicious intent, as for example, I would not expect that my ex-husband (who was baptised a Presbyterian but who was a self-declared atheist) would have any interest whatsoever in the annulment, also since he had already married someone else at the time.
The annulment would have gone thru the local tribunal where the ex got married this time, not the one where they were originally married?
You can apply for an annulment in any of three dioceses: the one where you were married, the one where the husband currently (at the time of the annulment application) lives, or the one where the wife currently lives. You might want to check the records of any other relevant dioceses. I don’t know anything about the recordkeeping and distribution of this information, though.
–Jen