Tanning process promotes abiotic humification: separation and characterization of humic acid-like polymers complex

Humic-like substances are essential components of soluble organic matter in tannery wastewater. However, the tannery process can promote the abiotic humification in wastewater. Therefore, it is of great significance to clarify the pathway and degree of abiotic humification and the properties of the as-derived humic acid-like (HAL) complex polymers in the tannery process in order to control the refractory organic compounds. In the present study, considering the catechol-Maillard system and commercial humic acid (HA) as control, the polyphenol-Maillard humification in the tannery process was simulated under the catalysis of MnO2. Moreover, physicochemical and spectroscopic techniques were used to characterize the separated fractions of HAL further. As a result, it was found that the catechol-Maillard system with small molecule organic matter as precursor had higher humification degree. Furthermore, the ultraviolet-visible (UV-Vis), Fourier transform infrared (FTIR), and excitation-emission matrix (EEM) fluorescence spectrum of humic acid-like 0 (HAL0) derived from it was different from those of humic acid-like 1 and 2 (HAL1 and HAL2) of polyphenol-Maillard system, indicating the differences of polymer structure between them. In the polyphenol-Maillard system, tannin was the skeleton of polymerization or polycondensation reaction, and the high content of N and the H/C value of HAL2 indicated that in adding to amino acids, proteins promoted the humification, forming industry-specific HAL polymers with a high degree of aliphatic nature. Therefore, it can be concluded that controlling the raw materials in the tannery process (especially tannins), in order to reduce the occurrence of abiotic humification may be the key to improve the efficiency of wastewater treatment.