Citation:
WANG Shuai, XU Jun-Ping, CHEN Hou-Fu, YIN Xin-Hua, WANG Nan. Structural Characteristics of Humic-like Acid from Microbial Transformation of Lignin Participated by Metal (hydro) Oxides[J]. Chinese Journal of Analytical Chemistry,
;2019, 47(11): 1809-1815.
doi:
10.19756/j.issn.0253-3820.191206
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Lignin can provide fundamental materials for the formation of humus (HS). The process of HS formation can benefit from the microorganisms and their microbial residues. To reveal the contribution of metal (hydro) oxides in promoting the conversion of lignin to HS, a method of liquid flask culture was adopted with lignin as C source. During the process, the fluid medium added with goethite, bayerite and δ-MnO2 respectively was inoculated with the mixed inoculant composed of nine strains. During the culture of 110 d, the mineral-microbial residue was dynamically collected, from which the humic-like acid (HLA) was extracted and analyzed by scanning electron microscope (SEM) and 13C cross-polarization magic-angle-spinning nuclear magnetic resonance spectrum (CPMAS 13C-NMR). The results showed different micro-structures of HLA molecules were formed from the transformation of lignin because of the additions of goethite, bayerite and δ-MnO2. From the perspective of microscopic appearance, the shapes were, respectively:flaky structures in different sizes, irregular spheres with wrinkled edges, and black fungus with uneven surface and irregular wrinkles, among which the HLA particles formed by δ-MnO2 had a tendency to aggregate together. Compared with lignin, the qualities of HLA formed by the participations of three metal (hydro) oxides were improved, and their aliphaticity and hydrophobicity degrees were also enhanced. Compared with humic acid (HA) recommended by the International Humic Substances Society (IHSS), goethite was more likely to promote the hydrophobicity degree of HLA, enhance the protection mechanism to lignin, and stabilize the degree of aliphaticity, while δ-MnO2 had more advantages in improving the quality and hydrophilicity of HLA. Peak positions and their attributions of HLA formed by three metal (hydro) oxides had huge similarity to HA from a soil with straw returning. However, there were some residual components from lignin remained in the HLA molecules. Part of the aromatic C structure in HLA molecules might be replaced by O, N, and the content of carboxylic acid was lower than that of HA recommended by IHSS. Under the participation of δ-MnO2, quinone groups were observed in the HLA molecules, which was a necessary precursor for HS formation. It indicated that δ-MnO2 was superior to goethite and bayerite in promoting lignin humification and could provide precursors for HS formation.
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