Distribution of protons and Cd between bacterial surfaces and dissolved humic substances determined through chemical equilibrium modeling

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Bacteria and dissolved humic substances are capable of binding significant concentrations of metals in natural environments. Recent advances in understanding bacteria-metal and humic-metal complexation have provided a framework for directly comparing the binding capacities of these components. In this study, we use chemical equilibrium modeling to construct an internally consistent set of thermodynamic equilibrium constants for proton and Cd binding onto dissolved humic substances, using a variety of published data sets. Our modeling approach allows for the direct comparison of humic substance binding constants and site densities to those previously published for proton and Cd binding onto natural consortia of bacteria. We then combine these constants into a unified model that accounts for the competition between bacterial surfaces and humic and fulvic acids in order to determine the relative importance of each component on the total Cd budget. The combined model is used to examine the relative contributions of bacteria and dissolved humic substances to Cd complexation in natural settings. Calculations are performed for three representative systems: (1) one with a maximum realistic concentration of bacteria and a minimum realistic concentration of humic substance, (2) one with a maximum realistic concentration of humic substance and a minimum concentration of bacteria, and (3) one with an intermediate concentration of both components. Our modeling results indicate that dissolved humic substances have 2 orders of magnitude more available binding sites than bacterial surfaces (per gram). Humic substances also have a greater affinity than bacterial surfaces for binding Cd over circumneutral pH ranges. The combined model results demonstrate that, depending upon their relative concentrations, both Cd-humic and Cd-bacteria complexes are capable of dominating Cd-speciation in specific natural environments. This modeling approach is useful in that it can easily be extended to include other metals and binding ligands; however, thermodynamic data must be gathered on additional components to facilitate the modeling of more realistic systems.