It depends on the doping type of atoms

small doping atoms have probability of interstitial form while atoms having a size near to or larger than the hosted atoms (ions) will take place as a substitutional position

EDS uses X ray from core electrons. Those electrons energy doesn't change much when the chemical environment of the atom changes (as neighbor atoms), this makes it a bit hard for you to determine information about how the atom is binded to others... you should try XPS or EELS for this information.

If we are dealing with "doping" of a semiconductor, I suspect that neither EDS nor XPS or EELS could help, just because of sensitivity of such spectroscopies (for example, XPS may reveal atomic percentages not below about 0.5% or the like, while doping levels are usually much lower than that threshold).