Crystal chemistry of clay-Mn oxide associations in soils, fractures, and matrix of the Bandelier Tuff, Pajarito Mesa, New Mexico

The upper 25 m of Bandelier Tuff at Pajarito Mesa, New Mexico, include soils, shallow fractures, deeper fractures, and tuff matrices in which clays provide a record of transport and alteration. The principal pathways within this system are fractures that penetrate the tuff. Large fractures that host deep root penetration provide a setting in which clay deposits accumulate through particulate or colloidal migration from the soil zone. Clays throughout the system are predominantly expandable interstratified illite/smectites (I/S), but clays of the tuff matrix at depth are distinctly Fe-rich and are not mixed with clays transported from the surface into fractures. Chemical alteration superimposed on clay particles transported into fractures results in clays with lower Al : Si ratios, higher Na, and higher lanthanide content with increasingly negative Eu anomalies with depth. These changes are accompanied by invasion and precipitation of Mn oxides, principally birnessite, within clay bodies. Investigation of the Mn oxides by synchrotron X-ray fluorescence (SXRF) shows that Mn is associated with Ba, Ce, Ni, and Pb. In addition, synchrotron X-ray absorption near-edge structure (XANES) spectra show that Ce in Mn oxides occurs as Ce 3 and Ce 4 , with average Ce oxidation state of 3.75. The Mn oxides intergrown with clays actively participate in removal of Ce from solution, accompanied by oxidation of Ce 3 to Ce 4 . Other lanthanides are accumulated by the clays but are not concentrated along with Ce in the Mn oxides. Extraction of Ce from solution by Mn oxides is more effective than lanthanide accumulation in clay, a process that is variable and likely influenced by defects, extent of recrystallization, and particle sizes. This dichotomy in lanthanide interaction results in locally constant Ce content but either negative or positive Ce anomalies in the clay-Mn oxide system as a consequence of variability in the abundance of the other lanthanides. Nevertheless, the net lanthanide pattern for the sum of all clay-Mn oxide samples in either shallow or deep fractures has no Ce anomaly, indicating that other lanthanides segregated from Ce are not transported beyond the range of either the shallow or deep fracture systems. Evidence from Eu anomalies indicates that lanthanides accumulated in the fracture clays are acquired from the local tuff. The clay-Mn oxide assemblage is more effective than clay alone in accumulating of a wide variety of heavy metals. Copyright © 2002 Elsevier Science Ltd