Using the most advanced model of the hadron resonance gas we reveal, at chemical freeze-out, remarkable irregularities such as an abrupt change of the effective number of degrees of freedom and plateaus in the collision-energy dependence of the entropy per baryon, total pion number per baryon, and thermal pion number per baryon at laboratory energies 6.9-11.6 AGeV. On the basis of the generalized shock adiabat model we show that these plateaus give evidence for the thermodynamic anomalous properties of the mixed phase at its boundary to the quark-gluon plasma (QGP). A new signal for QGP formation is suggested and justified.