Redox-controlled differential weathering of andesitic pumice: Possible catalytic effects of ferrous/ferric iron on rapid halloysite accumulation in a Holocene tephra layer

Differential weathering process of Holocene andesitic tephra in Atsuma, Hokkaido, northern Japan, were investigated with a specific focus on the flame-like occurrence of halloysite bands and their formation mechanism. The parent material was coarse-grained pumice (Ta-d2) deposited 9 ka to form a highly permeable metre-thick layer atop fine-grained impervious periglacial loam, which is covered by humic soil-tephra sequences. The shallower part of the Ta-d2 layer was weathered to a reddish or yellowish brown colour, which is characterized by intensive leaching of Si and Al, with abundant precipitation of iron (hydr)oxide and amorphous secondary minerals in an oxidizing environment. A reductive grey colour was observed only at the Ta-d2 bottom below the halloysite band, where pumice grains survived significant elemental leaching and contained ferrous iron in the solid phase with abundant dissolved Fe in the liquid phase. Between these oxidized and preserved zones, an irregularly shaped, fine-grained, white iron-rich halloysite layer with a decimetre-scale thickness developed. In this clay band, the molar ratio of Si to (Al + Fe) was nearly 1:1, with a small amount of remnant Ca. M & ouml;ssbauer analysis revealed that Fe2+ was initially incorporated into the aluminosilicate sheet via Al3+ substitution and transformed into Fe3+ within the structure. The halloysite band was formed at depths in the tephra layer corresponding to the redox front. The abundance of Si and Al in pore water in any zone of the tephra layer meets the stability requirements of halloysite, indicating that the redox condition controls the rapid local accumulation of halloysite through the isomorphous substitution followed by valence change of iron. We propose a new hypothesis stating that iron catalyses halloysite nucleation via a stepwise function, including layer charging to absorb hydrated cations and subsequent charge loss resulting in cation desorption and passive intercalation of water molecules within the 1:1 layer.