Study on the complexation of heavy metals onto biogas slurry DOM using two-dimensional correlation spectroscopy combined with the log-transformed synchronous fluorescence spectroscopy.

Abstract

The fluorescent components of dissolved organic matter (DOM) in biogas slurry can react with heavy metals (HMs) and affect the migration, transformation, toxicity, and bioavailability of HMs in soil. Fluorescence quenching titration combined with two-dimensional correlation spectroscopy (2D-COS) can reveal the binding mechanism between HMs and different fluorescent components of biogas slurry DOM. The logarithmic-transformed (log-transformed) 2D-COS can be used to decrease the difference in the fluorescence intensity between low-intensity and high-intensity fluorophores that provides a better insight into the binding mechanism between biogas slurry DOM and HMs. Synchronous maps suggest that protein-like substances are more susceptive to the variation of the concentration of metal ions than fulvic-like substances. Asynchronous maps show that the preferential bonding of Cu(II) and Cr(III) to humic-like substances can be found in the biogas slurry DOM, as well as Fe(III) and Pb(II) to protein-like materials. DOM-Cu(II) may lead to an increasing risk of the migration of Cu(II) from soil to water environment due to the low log K values in the range from 2.93 to 3.46. Protein-like substances can also increase the environmental risk of HMs when these low-stable complexes occur migration and transformation. The potential environmental risk of protein-like with HMs follows the order: Pb(II) > Cu(II) > Cr(III). Here we demonstrate that the log-transformed 2D-COS can also identify fluorescence components at longer wavelength with relatively low content and reveals their preferential binding sequence and the number of binding sites. The study on the complexation between biogas slurry DOM and HMs provides a scientific basis for the environmental chemical behavior of HMs after the application of biogas slurry in agricultural soils.