I think Fe, Ni dissolved faster/easier than Cr, resulting in Cr-rich metal. And this is one of reasons electropolishing could enhance corrosion resistance.
@Ed: when you mentioned 85-90%, did you mean the metals deposited on the cathode? Fe ions concentration in electrolyte will start from 0 to some percentage, that seems not be comparable to the source metal. Also, I think 316 is about 65%Fe. There are tens of 316 versions, Fe content varies, but all of them seem unlikely go as high as 75%.