Spectral characteristics coupled with self-organizing maps analysis on different molecular size-fractionated...

Biochar-derived water-soluble organic carbon (BWSOC) plays important roles in the environmental effect of biochar. The environmental behavior and fate of BWSOC are closely related to its size distribution and chemical components. However, the molecular size-dependent BWSOC components and properties remain little known. To evaluate molecular size-dependent BWSOC characteristics, BWSOC samples were prepared by pyrolyzing biomasses in air-limitation and N₂-flow atmospheres at 300-600 °C and fractionated through a series of membranes with different pore sizes including 0.7 μm, 0.45 μm, 100 kDa, 10 kDa, 3 kDa, and 1 kDa. In all BWSOCs, <1 kDa and 0.45-0.7 μm fractions had the maximum abundance (mean: 40.6 %) and the minimum abundance (mean: 4.4 %), respectively. The spectral characteristics of BWSOC including polarity index, spectral slope, and humification index varied significantly with molecular size. The fluorescence excitation-emission matrix parallel factor (EEM-PARAFAC) analysis indicated that BWSOC was mainly composed of three organic components (humic-like, fulvic-like, and aromatic protein/polyphenol-like substances). Humic-like and fulvic-like substances mainly existed in <1 kDa fraction, while aromatic protein/polyphenol-like substances mainly existed in medium-size fractions (3 kDa-0.45 μm). The different locations of <1 kDa, 1 kDa-0.45 μm, and 0.45-0.7 μm fractions in EEM and PARAFAC self-organizing maps indicated self-organizing maps could effectively distinguish 0.45-0.7 μm, 1 kDa-0.45 μm, and < 1 kDa fractions via the variations of fluorescence intensity and organic components. Additionally, the distribution ratio of different molecular size fractions as well as the abundances of organic components in different molecular size fractions were strongly controlled by pyrolysis atmospheres (air-limitation and N₂-flow). This study systematically clarified the organic components and properties of different molecular size fractions in BWSOC, and the results are helpful to understand the possible environmental behavior and fate of BWSOC.