Molecular weight-dependent spectral and metal binding properties of sediment dissolved organic matter from different origins

Abstract

The metal binding potential of dissolved organic matter (DOM) is highly related with its inherent properties such as molecular weight (MW). Here sediment DOMs with different origins, i.e., algae- and macrophyte-dominated sediment DOM (named as ASDOM and MSDOM, respectively), were size-fractionated into low MW (LMW-, <1 kDa) and high MW (HMW-, 1 kDa~0.45 μm) fractions, with the spectral and metal binding properties in different MW fractions exploring via total organic carbon, absorption spectroscopy, fluorescence parallel factor (PARAFAC) analysis, and Cu(II) titration techniques. The MSDOM contained more organic carbon, lower specific UV absorbance, lower fluorescence index, higher humification index, and lower biological index compared to the ASDOM. As for the MW-fractionated samples, the humic- and fulvic-like fluorophores were mainly distributed in the LMW-DOM, while the protein-like ones were located richly in the HMW-DOM. Thus, obvious MW- and origin-dependent heterogeneities in abundance and spectral properties were observed for sediment DOMs. One humic-like, one fulvic-like, and two protein-like fluorescent components were identified by PARAFAC analysis, with different components exhibiting different variable patterns in response to Cu(II) addition. Irrespective of sample sources, humic- and fulvic-like components had higher condition stability constants (logKM > 4.96) than protein-like components (logKM < 4.86). As for the MW-fractionated samples, the HMW-DOM, especially the HMW humic-/fulvic-like components, exhibited higher metal binding potential than the bulk and LMW counterparts. This study highlighted the importance of HMW-DOM in manipulating the behavior, fate, and bioavailability of heavy metals in lake sediments.