ICP-MS Is only going to tell you total Iron, not oxidation state.
AA is not good for anything less then 1ppm due to the boltzman distribution (do not let any equipment manufacture tell you otherwise, it is shady statistics to get less then that).
As Borek said, ppb is to low for classical titration.
The easiest way to determine the ratio of Fe3+ to Fe2+ would probably be voltammetry. And by combining that with total iron from ICP-MS, you know what you need.