C,H,N,S analysis can give the composition of N and S doing but if there is other type of dopin present then what could be used for elemental composition analysis accept XPS, ICP-MS and EDX?
Atomic absorption spectroscopy (AAS), atomic emission spectroscopy (AES), atomic fluorescence spectroscopy (AFS), ion microprobe (IM), laser-induced breakdown spectroscopy (LIBS), X-ray fluorescence (XRF), and even other more exotic methods exist. But their use critically depends on the elements you want to quantify (not all are suitable for some elements), and on the detection limit that you want to reach (as their accuracy and sensitivity are also different). ICP-MS, that you want to avoid, is certainly one of the most accurate and universal method !
Generally speaking, all contents above 1 wt.% are high enough for all the suggested techniques. The results become different because inaccurate in the range of fractions of %, ppm or less. As your doping level is quite high, all techniques should work.
If the hetero-atom is expected to decompose under temprature into gas phase products, you can also use TGA-MS - use O2 or Air as flowing gas, carbon will go and the volatile heteroatoms will also give you signals on the MS.
If you don't have TGA handy, you can use only MS hooked to tube-furnance.
If you can dissolve the hetero-atoms, and they expected to form Ions, it is also possible to use Ion chromatograph, and if you don't have Ion chromatograph, if the Ion chromatograph is not available, and if the "heteroatoms" are in fact ions once dissolved in electrolyte you can also identify them electrochemically by their redox potential.
Time of Flight techniques can also be an option if available ( TOF SIMS or TOFMS)