Characteristics of desert varnish from nanometer to micrometer scale: A photo-oxidation model on its formation

Rock varnish is a widespread Mn-rich rock coating commonly developed in arid environments, but the mechanism for its formation is still under debate. In this study, rock varnish and adjacent soil dust collected from Gobi Desert were analyzed for exploring the possible abiotic oxidation mechanism of Mn oxides. The occurrence of rock varnish shows a direct and close relationship with strong irradiation of sunlight, giving the first evidence of photochemical genesis. Abundant caves and tunnels with average diameter of ~1–5 μm are observed on varnish surface regions, which facilitate the penetration of sunlight and water. Metal (oxyhydr)oxides, including birnessite, hematite, goethite, rutile and anatase, account for the major components of rock varnish, which are all solar light-responsive semiconducting minerals. The trace elements enrichment patterns revealed by LA-ICP-MS provide the indication of an aqueous origin. The positive Ce anomalies in varnish in contrast to the rock substrate, as well as the positive correlation between Ce and Mn suggest a strong oxidizing environment in the genesis of rock varnish. Therefore, the photo-generated holes and reactive oxygen species (ROSs) on metal oxides in varnish can promote Mn(II) oxidation, which are further demonstrated from thermodynamic and kinetic considerations. ROSs including 1O2 and OH with strong oxidizing capability are detected by EPR in varnish suspension, providing the direct evidence for Mn(II) oxidation. Laboratory experimental simulations show the photocatalysis of metal oxides in rock varnish greatly promote Mn(II) oxidation by 2.10–7.97 times in comparison with homogenous solution oxidation. All these lines of evidence suggest that light-induced abiotic process may play important roles in the formation of rock varnish together with other abiotic and biotic pathways, which can even provide implications for the evolution of Mn oxides on surface of terrestrial planets.