Effect of light on birnessite catalysis of the Maillard reaction and its implication in humification

The Maillard reaction between carbohydrates and nitrogenous compounds originally investigated in 1912 has subsequently been proposed as a possible pathway for the formation of humic substances in natural environments. However, the role of mineral catalysis of the Maillard reaction is little understood and the promoting effect of light on such catalysis is not known. Birnessite (δ-MnO₂), which is commonly present in soil environments, was investigated for its activity in promoting the Maillard reaction between glucose and glycine at a light intensity of 168 μE s^-1 m^-2 or in the dark. The presence of substantial quantities of Mn(II) was detected in both the supernatant and solid phase of the glucose-glycine-birnessite systems. The spectroscopic evidence indicates that birnessite, in the presence of light, is a very effective catalyst in abiotic browning of solutions of glucose and glycine. Furthermore, birnessite significantly promoted the reaction even in the absence of light. Therefore, the abiotic heterogeneous catalytic role of soil minerals such as birnessite in polycondensation of simple sugars and amino acids merits close attention in the formation of humic substances in natural environments.