  We experimentally demonstrate the emergence of a purely azimuthally polarized
vectorial vortex beam with a phase singularity upon Brewster reflection of
focused circularly polarized light from a dielectric substrate. The effect
originates from the polarizing properties of the Fresnel reflection
coefficients described in Brewster's law. An astonishing consequence of this
effect is that the reflected field's Cartesian components acquire local phase
singularities at Brewster's angle. Our observations are crucial for
polarization microscopy and open new avenues for the generation of exotic
states of light based on spin-to-orbit coupling, without the need for
sophisticated optical elements.
