School of Environmental Science and Engineering, Shaanxi University of Science and Technology, Xi'an, 710021, China.
School of Science, Xi'an University of Architecture and Technology, Xi'an, 710055, China.
Environ Sci Pollut Res Int. 2020 Nov;27(33):41437-41445. doi: 10.1007/s11356-020-10111-9. Epub 2020 Jul 18.
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 MnO. 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.
类腐殖质物质是制革废水中可溶性有机物的重要组成部分。然而,制革过程会促进废水中的非生物腐殖化。因此,阐明制革过程中非生物腐殖化的途径和程度以及所衍生的类腐殖酸(HAL)复杂聚合物的性质,对于控制难降解有机化合物具有重要意义。在本研究中,考虑儿茶酚-美拉德体系和商品腐殖酸(HA)作为对照,在 MnO 的催化下模拟制革过程中多酚-美拉德的腐殖化。此外,还采用物理化学和光谱技术对分离得到的 HAL 进一步进行了表征。结果表明,以小分子有机物为前体的儿茶酚-美拉德体系具有较高的腐殖化程度。此外,其紫外-可见(UV-Vis)、傅里叶变换红外(FTIR)和激发-发射矩阵(EEM)荧光光谱与多酚-美拉德体系中衍生的类腐殖质 0(HAL0)的不同,表明它们的聚合物结构存在差异。在多酚-美拉德体系中,单宁是聚合或缩聚反应的骨架,而 HAL2 中高含量的 N 和 H/C 值表明,在添加氨基酸后,蛋白质促进了腐殖化,形成了具有高度脂肪性质的工业专用 HAL 聚合物。因此,可以得出结论,控制制革过程中的原材料(特别是单宁),以减少非生物腐殖化的发生可能是提高废水处理效率的关键。