The results of the investigations of the interaction between the different impurities in intentionally contaminated block-cast multi-crystalline silicon by means of synchrotron-based microprobe techniques XBIC (X-ray beam induced current), μ-XRF (X-ray fluorescence microscopy) and μ-XAS (X-ray absorption microspectroscopy) recently implemented at beamlines ID-21 and ID-22 of ESRF, Grenoble, are presented. It was found that Si3N4/SiC particles frequently observed in the upper part of multi-crystalline Si blocks represent effective sinks for Fe and Cu impurities. The amount of precipitated iron was the same order magnitude both at nitride and carbide particles. The amount of Cu precipitated at the SiC inclusions was significantly larger than that at Si3N4 rods. Chemical state of the copper precipitates was identified as copper-rich silicide Cu3Si. The anneal at 950 °C that is known to enhance oxygen precipitation in silicon was found to accompany with the enhanced formation of nanoscale iron disilicide precipitates both inside the grains and at grain boundaries.