Kinetic and thermodynamic determinants of trace metal partitioning at biointerphases: the role of intracellular speciation dynamics.

There is a large body of work evidencing the necessity to evaluate chemical speciation dynamics of trace metals in solution for an accurate definition of their bioavailability to microorganisms. In contrast, the integration of intracellular metal speciation dynamics in biouptake formalisms is still in its early stages. Accordingly, we elaborate here a rationale for the interplay between chemodynamics of intracellular metal complexes and dynamics of processes governing metal biouptake under non-complexing outer medium conditions. These processes include the conductive diffusion of metal ions to the charged soft biointerphase, metal internalisation, excretion of intracellular free metal species and metal depletion from bulk solution. The theory is formulated from Nernst-Planck equations corrected for electrostatic and reaction kinetic terms applied at the biosurface and in the intracellular volume. Computational illustrations demonstrate how biointerfacial metal distribution dynamics inherently reflects the chemodynamic properties of intracellular complexes. In the practical limits of high and weak metal affinity to biosurface internalisation sites, the metal concentration profile is explicitly solved under conditions of strong intracellular complexing agents. Exact analytical expression is further developed for metal partitioning at equilibrium. This provides a way to evaluate the metal biopartition coefficient from refined analysis of bulk metal depletion measured at various cell concentrations. Depending on here-defined dimensionless parameters involving rates of metal internalisation-excretion and complex formation, the formalism defines the nature of the different kinetic regimes governing bulk metal depletion and biouptake. In particular, the conditions leading to an internalisation flux limited by diffusion as a result of demanding intracellular metal complexation are identified.