Comparison of copper binding properties of DOM derived from fresh and pyrolyzed biomaterials: Insights from multi-spectroscopic investigation

Abstract

The binding of dissolved organic matter (DOM) with metals affects the latter's biogeochemical processing in the environment. This study used multi-spectroscopic analyses to compare the heterogeneities of the Cu(II) binding properties of DOM derived from fresh and pyrolyzed biomaterials. The results showed that the DOM derived from fresh macrophyte (MDOM) and their corresponding biochar (BDOM) consisted mostly of protein-like and humic-like substances, respectively. The stability constant (log K_M) of protein-like matter in the MDOM was 5.27, and the values of humic-like components in the BDOM were 4.32-5.15. Compared with the MDOM, the BDOM exhibited lower affinities and active binding sites for Cu(II). In addition, the BDOM contents decreased after pyrolysis. Therefore, the pyrolysis of fresh biomaterials into biochar is a promising method for reducing the potential migration risk posed by Cu(II) due to the MDOM being a positive carrier for Cu(II) contamination. Polysaccharide was the only functional group that participated in the binding of Cu(II) in both MDOM and BDOM. Aliphatic groups and amides associated with protein-like matter were responsible for the Cu(II) binding to MDOM, whereas phenolic and aromatic groups mainly participated in the complexation of BDOM-Cu(II). The CO group of amide I in the MDOM, and polysaccharide in the BDOM, showed the fastest response to Cu(II). This study was helpful for elucidating the effects of fresh and pyrolyzed biomaterials (biochars) on the environmental behavior of Cu(II) at the molecular level.

Keywords: Biochar; Cu(II) binding; Dissolved organic matter; Fresh biomaterials; Multi-spectroscopic analyses.