Metal ion complexation by soft nanoparticles: the effect of Ca2+ on electrostatic and chemical contributions to the Eigen-type reaction rate

Environmental context The speciation of trace metals in the environment is often dominated by complexation with natural organic matter such as humic acid. Humic acid is a negatively charged soft nanoparticle and its electrostatic properties play an important role in its reactivity with metal ions. The presence of major cations, such as Ca2+, can decrease the effective negative charge in the humic acid particle body and thus modify the chemodynamics of its interactions with trace metal ions. Abstract The effect of Ca2+ on the chemodynamics of PbII complexation by humic acid (HA) is interpreted in terms of theory for permeable charged nanoparticles. The effect of the electrostatic field of a negatively charged nanoparticle on its rate of association with metal cations is governed by the interplay of (i) conductive enhancement of the diffusion of cations from the medium to the particle and (ii) ionic Boltzmann equilibration with the bulk solution leading to accumulation of cations in the particle body. Calcium ions accumulate electrostatically within the HA body and thus lower the magnitude of the negative potential in the particle. For the case where trace metal complexation takes place in a medium in which the particulate electrostatic field is set by pre-equilibration in the electrolyte, the lability of Pb-HA complexes is found to be significantly increased in Ca2+-containing electrolyte, consistent with the predicted change in particle potential. Furthermore, the rate-limiting step changes from diffusive supply to the particle body in a 1–1 electrolyte, to inner-sphere complexation in a 2–1 electrolyte. The results provide insights into the electrostatic and covalent contributions to the thermodynamics and kinetics of trace metal binding by soft nanoparticles.