Characterization of chemical heterogeneities such as microsegregation resulting from solidification of metallic alloys is most often performed by EDS or WDS microanalysis with spot measurements located at corners of a regular grid. Rather than attempting a theoretical treatment of the statistics of such analyses, the quality of the procedure has been investigated by implementing "measurement" grids on numerical images that mimic solidification structures. Microstructures either with no geometrical constraints (uniform distribution of the solid nuclei) or with limited constraints that give some periodicity have been investigated. Systematic analysis of the effect of the location and size of the "measurement" grid enlightens the procedures which should be followed to minimize bias.