Effect of hydrothermal temperature on the optical properties of hydrochar-derived dissolved organic matter and their interactions with copper (II)

Abstract

Hydrothermal carbonization (HTC) has been regarded as a promising technique for turning wet biomass into hydrochar due to its low energy consumption, low exhaust gas emissions, etc. In addition, hydrochar is an important source of dissolved organic matter (DOM), which plays a crucial part in the migration and destiny of pollutants in the environmental medium. However, there are limited studies that focus on the factors that influence the formation of DOM in hydrochar, such as hydrothermal temperature. Therefore, the current study comprehensively characterized the optical properties of DOM within hydrochar derived from sawdust (HDOM) under different hydrothermal temperatures (150–300 °C) by Ultraviolet–visible (UV–Vis) and fluorescence spectroscopy, as well as its complexation characteristic with Cu(II). The findings revealed that the organic carbon content of HDOM reached a peak of 37.3 mg L⁻¹ when the temperature rose to 240 °C and then decreased as the temperature increased. UV–Vis spectroscopy analysis showed that the absorption capacity of HDOM at 275 nm increases with temperature and reaches a maximum value at 240 °C, indicating that high temperature promotes the formation of monocyclic aromatic compounds. High temperature enhances the aromaticity, hydrophobicity, and humification degree of HDOM, thus improving its stability and aromaticity. The E3/E4 ratios are all greater than 3.5, confirming that the main component of HDOM is fulvic acid, which corresponds to 3D-EEM and Pearson's correlation coefficient analysis. The humification index (HIX) of HDOM increased with the rise in hydrothermal temperature (150–240 °C), as observed by the three-dimensional excitation-emission matrix spectroscopy (3D-EEMs). After reaching its peak at 240 °C, the HIX value gradually dropped in line with the trend of the DOC change. Moreover, the bioavailability (BIX) value of DOM was all high and greater than 1, indicating all the HDOM are readily bioavailable. Two microbial humic substances (C1 and C4), a humic-like substance (C2), and a protein-like substance (C3) were discovered in DOM by integrating 3D-EEMs with parallel factor analysis (PARAFAC). Their fluorescence intensity decreases as the Cu(II) concentration increases, indicating the formation of complexes with Cu(II). As the temperature rises, the binding ability of DOM and Cu(II) changes significantly, reaching the optimum at 300 °C. Meanwhile, the substance C2 has the strongest binding ability with Cu(II). This research emphasizes the significance of spectroscopy analysis in determining the evolution of hydrochar-derived DOM, the potential for heavy metal binding and migration, and its characteristics and features.

Highlights

1.	The effect of temperature on the spectral properties of hydrochar-derived DOM was studied.
2.	The aromaticity and humification degree of HDOM were enhanced by the increase in hydrothermal temperature, which enhanced the stability of hydrochar.
3.	Fulvic acid and protein-like material were the dominant component, and the humic-like component (C2) had the highest binding capacity with Cu(II).

Keywords

Hydrochar / Hydrothermal temperature / Dissolved organic matter / EEM-PARAFAC / Metal complex

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Funding

Outstanding Youth Research Project in Anhui Provincial Scientific Research Plan Project(2022AH020089); Anhui Province University Top Talent Funding Project(gxbjZD2021069); Commissioned R&D Project(BOFA202007)