This study elucidated the compositional and structural variations of size fractions of microbially-induced dissolved organic matter (DOM) caused by short-term temperature changes (5 to 35 °C), taking riverine DOM as an example. A simple and efficient method combining fractionation-[parallel factor analysis and two-dimensional Fourier-transform infrared correlation spectroscopy (PARAFAC-2D FTIR COS)]-correlation was introduced to link fluorescent DOM components and their structures in terms of surface functional groups. Results indicated that the higher temperature stimulated the decomposition of aromatics (sizes decreased from 10 kDa-0.22 μm to <10 kDa) and the transformation of proteins to humics (with sizes <0.22 μm); while both the higher and lower temperatures inhibited the utilization of larger-sized DOM (>0.22 μm, especially the non-fluorescence part) and synthesis of larger-sized microbial-derived proteins and humics (>0.22 μm), which may result in more smaller-sized (<10 kDa) and refractory aromatics transported from rivers to oceans in the warming future. However, the structure-determined DOM behaviors could be less affected by temperature since the fluorescent proteins and humics revealed similar functional group compositions, such as carboxyl, hydroxyl, carbonyl/aldehyde, carboxylic anhydride, and carboxamide groups. These findings have strong implications for DOM biogeochemistry in future temperature-shock scenarios. The proposed method will support in-depth analyses of structure-regulated processes from a mechanistic perspective.
Keywords: Composition-structure correlation; Dissolved organic matter; Microbial metabolism; PARAFAC-2D FTIR COS; Size fraction; Temperature.
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