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To combat the risk of nuclear smuggling, radiography systems are deployed at ports to scan cargo containers for concealed illicit materials. Dual energy radiography systems enable a rough elemental analysis of cargo containers due to the Z -dependence of photon attenuation, allowing for improved material detection. This work studies the capabilities for atomic number discrimination using dual energy MeV systems by considering dual energy { 6 , 4 } MeV , { 10 , 6 } MeV , and { 10 , 4 } MeV bremsstrahlung beams. Results of this analysis show that two different pure materials can sometimes produce identical transparency measurements, leading to a fundamental ambiguity when differentiating between materials of different atomic numbers. Previous literature has observed this property, but the extent of the limitation is poorly understood and the cause of the degeneracy is generally inadequately explained. This non-uniqueness property stems from competition between photoelectric absorption and pair production and is present even in systems with perfect resolution and zero statistical noise. These findings are validated through Monte Carlo transparency simulations. Results of this study show that currently deployed commercial radiographic systems are fundamentally incapable of distinguishing between high- Z nuclear materials and miscellaneous mid- Z cargo contents. • Dual energy cargo scanners are incapable of uniquely characterizing high-Z materials. • This stems from competition between photoelectric absorption and pair production. • Even systems with perfect statistical resolution cannot resolve this degeneracy. • Results are validated through Monte Carlo simulations. [ABSTRACT FROM AUTHOR]