SERS evolution recorded over a drop-coated coffee-ring pattern of citrate-capped gold colloids was investigated as a function of time under low-specific laser power. Spectral changes caused by plasmon-induced reaction could not be detected, but a long-term transient original spectral profile showing additional lines was observed. We performed deep qualitative and quantitative SERS intensity variation analysis based on the complementary use of extreme deviation and cross-correlation statistics, which provided further insights on the behavior of citrate-capping layers of gold nanoparticles upon laser illumination. More precisely, the cross-correlation analysis made possible to follow the so-called individual events denoting particular resonance structures, in which groups of modes were assigned to an evolution of citrate coordination on gold surface driven by photo-activation. As a consequence, the detection limit was increased and new lines were related to the presence of a very low amount of dicarboxy-acetone (DCA), which was already present in the system.