Two air entrainment mechanisms driven by vortex instability are reported in the unstable relaxation of a horizontal shear layer below a free surface. This flow is experimentally investigated by means of planar laser-induced fluorescence (PLIF) and particle image velocimetry (PIV) coupled with surface profilometry. PLIF identifies counter-rotating vortex pairs (CRVP) emanating from the surface following the growth of high steepness two-dimensional millimetre-size waves for Reynolds and Weber numbers based on the momentum thickness of 177 to 222 and 7.59 to 13.9, respectively. High spatio-temporal resolution PIV reveals the role of surface-generated vorticity and flow separation in the highly curved trough of the waves on the injection of a CRVP. Air bubbles are entrapped in the wake of these CRVPs at Reynolds number above 190. PIV data and spanwise PLIF images show two initiation mechanisms: primary vortex instability modulating the spanwise location where the flow separates, resulting in the pinch off of an air ligament, and secondary vortex instability turning a CRVP into$\unicode[STIX]{x1D6FA}$-shaped loops pulling the surface down. Instability wavelengths agree with linear stability analysis, and models for these new air entrainment mechanisms are proposed.
