Comparative study on the relative significance of low-/high-condensation aromatic moieties in biochar to organic contaminant sorption

Abstract

Aromatic moieties of biochar are considered as key components for immobilizing hydrophobic organic contaminants in the environment. However, the relative importance of different aromatic moieties such as low-/high-condensation components in sorption has not been comprehensively investigated. In this study, biochar was produced from flue-cured tobacco straw (TB) and pine wood sawdust (WB) at various pyrolysis temperatures (200–600 °C). Aromatic moieties were characterized via elemental analysis, Fourier transform infrared spectroscopy, Raman spectroscopy, and benzene polycarboxylic acid molecular markers (BPCAs). The significance of different aromatic moieties in the sorption of phenanthrene (PHE) and bisphenol A (BPA) was assessed based on the individual BPCA patterns. The results indicated that aromaticity and aromatic moiety contents increased with increasing pyrolysis temperature. Biochar at 200 °C produced lower mellitic acid (B6CA) contents (18.7–27.9%) than the others. When the pyrolysis temperature was increased to 600 °C, the B6CA contents representing high-condensation aromatic moieties accounted for 55.4–60.9% of all the aromatic moieties. The unitary linear regressions between the individual BPCA distribution patterns and the n values and log Kd suggested that the high-condensation aromatic moieties played a more significant role than the low-condensation aromatic moieties (represented by B3CA–B5CA) in facilitating sorption nonlinearity (for PHE and BPA) and sorption capacity (for PHE). The elevated sorption of PHE can be attributed to the increased specific surface area and hydrophobicity of the newly formed aromatic moieties. Hydrogen bonds and π–π electron–donor–acceptor were the main mechanisms of BPA sorption. Because the WB biochar contained more aromatic moieties and more O-containing groups on the surface of the TB biochar, the WB exhibited a higher sorption for PHE; however, slightly elevated sorption was observed on the TB for BPA. This research may provide a new perspective in understanding the behavior of biochar aromatic moieties in sorption of organic contaminants.