Photon-counting computed tomography (PCCT) could potentially offer significant improvements in image quality over conventional CT. This study leverages PCCT technology to achieve simultaneous multi-contrast imaging of barium (Z=56) and iodine (Z=53), addressing the limitations of conventional CT in differentiating materials with similar atomic numbers. Using a bench-top PCCT system with a cadmium zinc telluride (CZT) detector, experiments were conducted with various phantom setups and 1-5\% contrast agent concentrations and in a biological sample. Energy thresholds were adjusted to the K-edge absorption energies of barium (37.4 keV) and iodine (33.2 keV) to capture multi-energy CT images. K-edge decomposition was performed with K-edge subtraction and principal component analysis (PCA) techniques, demonstrating clear differentiation and accurate quantification of contrast agents in phantom combinations and the biological sample. The PCCT system successfully differentiated and quantified barium and iodine, with high correlations ($R^2 \approx 1$) between true and reconstructed concentrations. PCA outperformed K-edge subtraction by providing a superior capability to differentiate barium and iodine, particularly when calcium was present in the scanned object. These findings highlight the potential of PCCT for reliable, detailed imaging in clinical and research applications, particularly for contrast agents with close atomic numbers.
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