I have absolutely no idea, but if you've got a suspected mother for one or both children, I would focus on her ancestry. If you can trace her family a few generations back, you may well start to hit matches on her side. If you have a known descendant from her side of the family, you can compare whether or not they match to both of your target siblings. If one of your pair starts making many connections and the other doesn't match any of them, you may get your answer there. The flaw is a man who married/had children with two women from the same family, but I'd think that was comparatively uncommon.