Macroscopic Pb(II) uptake experiments and Pb L3-edge extended X-ray absorption fine structure (EXAFS) spectroscopy were combined to examine the mechanisms of Pb(II) sequestration by a biogenic manganese oxide and its synthetic analogues, all of which are layer-type manganese oxides (phyllomanganates). Relatively fast Pb(II) sorption was observed, as well as extremely high sorption capacities, suggesting Pb incorporation into the structure of the oxides. EXAFS analysis revealed similar uptake mechanisms regardless of the specific nature of the phyllomanganate, electrolyte background, total Pb(II) loading, or equilibration time. One Pb-O and two Pb-Mn shells at distances of 2.30, 3.53, and 3.74 A, respectively, were found, as well as a linear relationship between Brunauer-Emmett-Teller (BET; i.e., external) specific surface area and maximum Pb(II) sorption that also encompassed data from previous work. Both observations support the existence of two bonding mechanisms in Pb(II) sorption: a triple-corner-sharing complex in the interlayers above/ below cationic sheet vacancies (N theoretical = 6), and a double-corner-sharing complex on particle edges at exposed singly coordinated -O(H) bonds (N theoretical = 2). General prevalence of external over internal sorption is predicted, but the two simultaneous sorption mechanisms can account for the widely noted high affinity of manganese oxides for Pb(ll) in natural environments.