We provide a conclusive demonstration of vibrational pumping under Surface Enhanced Raman Scattering (SERS) conditions by performing anti-Stokes/Stokes ratio measurements over a large spatial area and low power density, down to 10 K with dried silver colloids, the dye rhodamine 6G, and 676 nm laser excitation. The method we propose allows for the measurement of the cross sections for different modes and also provides the determination of the asymmetry between the anti-Stokes and Stokes SERS cross sections for each mode.