I would be interested to know if you have any thoughts on how this limitation could be addressed, since usually the S/B ratio affects the Hydrogen concentration positively.
I understand your question as that you're wondering why the H2 concentration is low at very high S/B ratios. You're not taking about H2 yield, are you.
I'm not an expert for gasification, but I think, you find the answer when considering the steam reforming reaction.
CH4 + H2O = CO + 3H2
Biomass is not exactly CH4, but it reacts in a similar fashion. C is oxidized by water which releases H2. High S/B ratio means, you have only few C. As soon as all C is oxidized, you cannot get more H2, regardless of how much more steam, i. e. water you add.
However, I expect that the H2 yield is better at high S/B ratios.