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The feasibility of RIKEN high-resolution PIXE system for direct chemical state analysis of 3d transition elements was examined. Kβ spectra of Cr and Fe from several compounds were measured in air at atmospheric pressure using a crystal spectrometer consisting of a position-sensitive proportional counter and a curved crystal in v. Hamos geometry. Fine structures which reflect the chemical states of Cr and Fe were well recognized with the measuring time of tens minutes.