Physiochemical controls on the crystal-chemistry of Ni in birnessite: Genetic implications for ferromanganese precipitates

Sorption of Ni to birnessite is a fundamental control on the concentration of Ni in natural waters and associated sediments. Recent XAS work suggests the crystal-chemistry of Ni in birnessite is dependent on both structural and physiochemical factors. This work investigates the physiochemical controls on Ni crystal-chemistry in hexagonal birnessite with EXAFS of time series and pH series Ni-birnessite sorption experiments. At circumneutral pH Ni surface adsorbed above/below Mn octahedral vacancy sites in the phyllomanganate layers is progressively structurally incorporated into the vacancy sites with time (30% Ni incorporation after 408 h contact time). Ni structural incorporation into hexagonal birnessite occurs via rearrangement of surface adsorbed Ni with time rather than direct Ni incorporation from solution. At low pH (pH 4) Ni surface adsorbed at the vacancies is structurally incorporated into the vacancies upon increasing solution pH to circumneutral (∼20% Ni incorporation after 24 h contact time at circumneutral pH); newly incorporated Ni is stable with increasing contact time at pH circumneutral. However, upon decreasing solution pH from circumneutral back to pH 4, EXAFS shows a significant decrease in the proportion of Ni structurally incorporated; preliminary results indicate structural incorporation of Ni in hexagonal birnessite is reversible with decreasing pH. Time series results at circumneutral pH help explain the significant enrichment of Ni in marine ferromanganese precipitates; work here is combined with previous studies to provide a model correct at the molecular-level for Ni uptake by marine vernadite-rich ferromanganese precipitates. With Ni migrating from surface adsorbed to structurally incorporated, results suggest formation of a solid solution between an end-member vernadite and an end-member Ni-vernadite phase, with surface adsorption acting as a mechanism of transition from one composition to the other. pH series results call into question the viability of Ni crystal-chemistry in natural vernadite as a paleo-proxy for paleo-pH conditions in freshwater systems and challenge the traditional view that structurally incorporated trace-metals are stable within the Eh-pH field of the host mineral phase. Natural birnessite may not be as permanent a sink for Ni as first suggested by Ni crystal-chemistry.