Macroscopic measurements show that Pb(II) uptake on iron(hydr)oxides can be altered significantly by dissolved carbonate (enhanced up to 18% at pH 5 and decreased above pH similar to 6.5 in analyses at 1 atm CO2). This study elucidates the molecular-scale processes giving rise to these macroscopic effects by characterizing the structures of Pb(II) sorption complexes formed an goethite (alpha-FeOOH) in the presence of carbonate using in situ Pb L-III-EXAFS and ATR-FTIR spectroscopies. Bond valence and structural constraints are applied to develop mineral surface site-specific models for Pb sorption. Under all conditions studied (pH 5-7, Gamma(Pb) = 0.4-4 mu mol/m(2), and P-CO2 = 0-1 atm), Pb(II) forms predominantly inner-sphere edge-sharing (bidentate and/or tridentate) complexes with Fe(O,OH)(6) octahedra (RPb-Fe similar to 3.3 Angstrom). Corner-sharing complexes (RPb-Fe similar to 3.9 Angstrom) are observed only in low pH (5) samples (P-CO2 0-1 atm). Consistent with this pH sensitivity, site-specific analyses suggest that the relative abundance of corner-sharing sites reflects changes in the proton affinity of triply coordinated sites on the goethite (110) surface as suggested previously. FTIR results suggest the existence of ternary surface complexes in which carbonate groups bond to Pb as monodentate ligands. EXAFS data indicate that these ternary complexes are bound to the surface through Pb, forming metal-bridged (Type A) complexes. Findings are summarized as structural models and corresponding mineral surface site-specific chemical reactions.