Mineralogical characteristics of Mn coatings from different weathering environments in China: clues on their formation

Abstract

Identification of Mn oxides in natural Mn coatings is very difficult due to their poor crystallinity, fine grains, complex chemistry and tiny amounts. In this work, we investigated three types of Mn coatings including rock varnish, dendrite and soil Fe-Mn cutan from different weathering environments in China. Optical microscope, scanning electron microscope, energy dispersive X-ray spectroscopy and micro-Raman spectrometer were employed to achieve non-destructive, sensitive, in-situ and micro analysis on their mineral assemblages, micromorphological features and elemental distribution characteristics. The observed results suggest that rock varnish and soil cutan comprise birnessite, while dendrite is mainly composed of hollandite. Rock varnish with a layered structure has a clear boundary with its substrate, and microlaminations which arise from the fluctuations in Mn content (6.42–17.07 wt%) within the sample profile are obvious on closer inspection. Branch-like dendrite is rich in Mn (32.53–42.96 wt%) but poor in Si and Al, which shows a pilotaxitic texture with its substrate. Soil Fe-Mn cutan can be further divided into an outer black Mn-rich (8.26–13.58 wt%) belt and an inner yellowish-brown Fe-rich (2.06–4.85 wt%) belt, and a clear border can be identified between these two belts. Mn in the substrate of rock varnish and soil cutan is below detection limit while it can be detected in the substrate of dendrite (1.43–7.83 wt%). Our in-situ analysis provides more precise results than traditional powder test. These mineralogical characteristics indicate that dendrite is most likely endogenic, while rock varnish and soil cutan are external accretion formed under different weathering environments.