Unravelling Metal Speciation in the Microenvironment Surrounding Phytoplankton Cells to Improve Predictions of Metal Bioavailability

[Image: see text] A lack of knowledge on metal speciation in the microenvironment surrounding phytoplankton cells (i.e., the phycosphere) represents an impediment to accurately predicting metal bioavailability. Phycosphere pH and O(2) concentrations from a diversity of algae species were compiled. For marine algae in the light, the average increases were 0.32 pH units and 0.17 mM O(2) in the phycosphere, whereas in the dark the average decreases were 0.10 pH units and 0.03 mM O(2), in comparison to bulk seawater. In freshwater algae, the phycosphere pH increased by 1.28 units, whereas O(2) increased by 0.38 mM in the light. Equilibrium modeling showed that the pH alteration influenced the chemical species distribution (i.e., free ion, inorganic complexes, and organic complexes) of Al, Cd, Co, Cu, Fe, Hg, Mn, Ni, Pb, Sc, Sm, and Zn in the phycosphere, and the O(2) fluctuation increased oxidation rates of Cu(I), Fe(II) and Mn(II) from 2 to 938-fold. The pH/O(2)-induced changes in phycosphere metal chemistry were larger for freshwater algae than for marine species. Reanalyses of algal metal uptake data in the literature showed that uptake of the trivalent metals (Sc, Sm and Fe), in addition to divalent metals, can be better predicted after considering the phycosphere chemistry.