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Melt dynamics and glass Topological phases of especially dry and homogenized binary AsxS100−x melts/glasses are examined in Modulated-DSC, Raman scattering, and volumetric experiments. In the S-rich glasses (12% < x < 23%), direct evidence for the elusive 537 cm−1 stretch vibrational mode of the Quasi-Tetrahedral (QT), S = As(S1/2)3, local structure is observed in FT-Raman scattering once melts are homogenized and glasses cycled through Tg+10°C for an extended period. The enthalpy of relaxation at Tg, ΔHnr(x), fragility index, m(x), Molar volumes, Vm(x) each display three distinct regimes of variation. Specifically, m(x) displays a Gaussian like global minimum (fragility window), and ΔHnr(x) displays an abrupt square-well like variation (reversibility window), while Vm(x) displays a Gaussian-like local minimum (Volumetric window) in the isostatically rigid phase (22.5% < x < 28.5%). At low x (< 20%) in the Flexible phase, glasses are segregated with a S8-rich nanophase that decouples from the As-S glassy backbone. At medium x (22.5% < x < 28.5%) glassy backbones form an isostatically rigid phase displaying a vanishing ΔHnr(x) term, and compacted structures with corresponding melts being superstrong (m < 20). At high x (28.5% < x < 40%) in the Stressed-Rigid phase, glasses possess an increasing ΔHnr(x) term, and melts become increasingly fragile, with m(x) >20 as x increases. Taken together, these results underscore that superstrong melts yield isostatically rigid glasses, while fragile ones form either Flexible or Stressed-rigid glasses upon cooling. The onset of the rigidity transition near <r> = 2.22, instead of the usual value of <r> = 2.40, is identified with presence of QT local structures in addition to Pyramidal As(S1/2)3 local structures in the glassy backbone, and with a small but finite fraction of polymeric Sn chains being decoupled from the backbone.