Influence of humic acid on neptunium(V) sorption and diffusion in Opalinus Clay

Summary

The influence of ¹⁴C-labeled M42 humic acid (HA) on the interaction between neptunium(V) and natural clay rock (Opalinus Clay (OPA), Switzerland) has been investigated in batch sorption and diffusion experiments under ambient air conditions. The effect of 10 mg/L HA on the diffusion of 8 μM Np(V) in OPA has been investigated in synthetic OPA pore water (pH 7.6, I = 0.4M) for the first time. Batch sorption experiments as a function of solid-to-liquid ratio (4-20 g/L) were performed under same experimental conditions to compare distribution coefficients obtained from both diffusion and sorption experiments. These experiments showed only a slight influence of HA on Np(V) uptake by OPA in both cases and provided comparable distribution coefficients (presence of HA: K_d = 22-32 L/kg, absence of HA: K_d = 30-46 L/kg). As it is known that the interactions of humic substances with actinides depend on various experimental parameters, the effect of HA on Np(V) sorption on 15 g/L OPA was also investigated as a function of pH (6-10) and initial Np concentration (8 μM and 7 pM). A saturated calcite solution was used as a background electrolyte in this case to prevent any dissolution of calcite contained in OPA at low pH. The results showed that the presence of M42 HA increases Np(V) sorption at pH < 7 while lower sorption was obtained above pH 8. Higher sorption at acidic pH can be attributed to strong sorption of HA which increases the number of sorption sites, while sorption decreases at higher pH probably due to formation of soluble ternary neptunium humate carbonate species.