Jianshuiite in oceanic manganese nodules at the Paleocene-Eocene boundary

Synchrotron powder X-ray diffraction and scanning electron microscopy examinations of man-ganese oxide concretions/nodules (∼0.3-1.0 mm diameter) from ODP Site 1262 on Walvis Ridge in the Southeastern Atlantic Ocean revealed that they consist primarily of the layered Mn oxide phase jianshuiite [(Mg,Mn,Ca)Mn₃⁴+O7 3H₂O]. The nodules are from an interval with severe carbonate dis-solution that represents the Paleocene/Eocene (P/E) thermal maximum (∼5 5.8 Ma). Most nodules from the middle of the carbonate dissolution interval contain internal open space, and consist almost entirely of euhedral plate-like jianshuiite crystals, 2-4 μm in diameter and ∼0.1-0.5 μm thick. Backscattered electron images and energy-dispersive X-ray analyses revealed stacks of interleaved Al-rich and Al-poor jianshuiite crystals in some nodules. The crystals in other nodules contain predominantly Mg (with trace K and Al) in addition to Mn and O, making them near "end-member" jianshuiite. Rietveld refinements in space group R3 confirmed the isostructural relationship between jianshuiite and chalcophanite, with Mg occupying the interlayer position above and below the vacant sites in the Mn/O octahedral sheet, and coordinated to 3 octahedral layer O atoms (1.94 Å) and 3 interlayer water O atoms (2.13 Å). Final refined occupancy factors suggest that small quantities of Ni and possibly Mn²⁺ are located on the Mg site. The transient appearance of the Mg-rich birnessite-like phase jianshuiite, probably abiotically produced, must indicate an exceptional transient change in the chemistry of the pore fluids within deep ocean sediments directly following the P/E boundary, possibly as a result of decreasing oxygen levels and pH, followed by a return to pre-event conditions.