Intrinsic impurity behaviour and transport properties in neutral beam heated L- and H-mode PBX tokamak plasmas were studied with a variety of impurity diagnostics. Central impurity accumulation was most often observed in H-mode discharges; sometimes it resulted in a thermal collapse due to high central metallic radiation (∼1.5 W • cm−3). The impurity accumulation was evident from peaked Zeff and radiated power profiles and was further substantiated by specific vacuum ultraviolet and X-ray spectroscopy measurements. It is shown that impurity accumulation was neither unique nor inevitable in H-mode discharges and it could be suppressed by sufficient gas puffing. Central impurity accumulation was also seen in L-mode plasmas even with co-injected neutral beams. This usually occurred at high beam power and relatively low density. While there was no significant difference in the degree of accumulation between L-mode and H-mode discharges, the Zeff profile itself was more peaked in the H-mode because the electron density profiles are flatter in H-mode plasmas than in L-mode plasmas. The degree of accumulation increased as Zeff(0) itself increased, which suggests that neoclassical convection and diffusion driven by both impurity-impurity and impurity-plasma ion collisions contribute to the central plasma particle transport.