This work extends the research of the basic regularities of segregation processes in the grain boundaries (GB) of VVER-1000 reactor pressure vessel (RPV) steels. The paper considers the influence of irradiation with different fast neutron fluxes on the structure, yield strength and ductile-to-brittle transition temperature (TK) changes as well as on changes of the share of brittle intergranular fracture and development of segregation processes in the VVER-1000 RPV weld metal (WM). The obtained experimental results allow to separate the contribution of the hardening and non-hardening mechanisms to mechanical properties degradation of material irradiated at the operating temperature. It is shown that the difference in TK shift in WM irradiated to the same fluence with different fast neutron fluxes is mainly due to the difference in the GB accumulation kinetics of impurities and only to a small extent due to the material hardening. Phosphorus bulk diffusion coefficients were evaluated for the temperature exposure, accelerated irradiation and irradiation within surveillance specimens (SS) using a kinetic model of phosphorus GB accumulation in low-alloyed low-carbon steels under the influence of operational factors. The correlation between the GB segregation level of phosphorus and nickel, and the TK shift - in WM SS was obtained experimentally and indicates the non-hardening mechanism contribution to the total radiation embrittlement of VVER-1000 RPV steels throughout its extended lifetime.