Fluctuations in energy distribution during additive manufacturing (AM) can result in spatial and temporal thermal transients. These transients can lead to complexities, most significantly when alloys with multi phases are subjected to AM. Here we unveil such complexities in a duplex stainless steel, where we report an unanticipated formation of a Ni-Mn-Si rich phase at grain boundaries and a local fluctuation in Cr and Fe concentrations in regions close to grain boundaries, providing Cr-rich precursors for Cr2N formation after laser powder bed fusion (LPBF). The formation of these phases is believed to be due to severe thermal gyrations and thermal stresses associated with LPBF resulting in a high-volume fraction of ferrite supersaturated with N and Ni, and a high density of dislocations accelerating diffusion and phase transformations.