Photodegradation is considered as a universal contributing factor to litter decomposition and carbon (C) cycling within the Earth’s biomes. Identifying how solar radiation modifies the molecular structure of litter is essential to understand the mechanism controlling its decomposition and reaction to shifts in climatic conditions and land-use. In this study, we performed a spectral-attenuation experiment following litter decomposition in an understory and gap of a temperate deciduous forest. We found that short-wavelength visible light, especially blue light, was the main factor driving variation in litter molecular structure of Fagus crenata Blume, Quercus crispula Blume, Acer carpinifolium Siebold & Zuccarini and Betula platyphylla Sukaczev, explaining respectively 56.5%, 19.4%, 66.3%, and 16.7% of variation in its chemical composition. However, the variation also depended on canopy openness: Only in the forest gap was lignin aromatic C negatively associated with C-oxygen (C–O) bonding in polysaccharides receiving treatments containing blue light of the full spectrum of solar radiation. Regardless of species, the decomposition index of litter that explained changes in mass and lignin loss was driven by the relative content of C–O stretching in polysaccharides and lignin aromatic C. The results suggest that the availability of readily degradable polysaccharides produced by the reduction in lignin aromatic C most plausibly explains the rate of litter photodegradation. Photo-products of photodegradation might augment the C pool destabilized by the input of readily degradable organic compounds (i.e., polysaccharides).
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