Competitive adsorption of polycyclic aromatic hydrocarbons on phosphorus tailing-modified sludge biochar provides mechanistic insights.

Biochar has been widely used to solve the wastewater pollution of polycyclic aromatic hydrocarbons (PAHs). However, the competition of PAHs with different benzene ring numbers (e.g., phenanthrene [Phe], pyrene [Pyr], and benzo[a]pyrene [BaP]) for adsorption sites on biochar has received little attention. In this study, biochar was produced by co-pyrolysis of sludge and phosphorus tailing at different temperatures (300, 500, or 800 °C) to adsorb PAHs. The results show that phosphorus tailing increased the adsorption of PAH by increasing the biochar's BET surface area (SBET), micropore volume, hydrophobicity (at low temperatures) and aromaticity (at high temperatures). The maximum adsorption capacities were 29.90 µmol/g for Phe, 25.58 µmol/g for Pyr and 20.45 µmol/g for BaP, respectively. Importantly, the types and functions of groups involved in the adsorption of various PAHs were discussed. Adsorption of Phe and Pyr on the biochar mainly involved C=O and C-O-C functional groups, and there was a certain degree of competition between these PAHs for those sites. In contrast, BaP mainly adsorbed at C-OH and C=C moieties, without competing with Phe or Pyr at C-OH sites. The competitive edge of BaP was also stronger than that of Phe and Pyr on C=C functional groups. The adsorption mechanisms involving pore filling, hydrophobic interactions, and π-π interactions governed the adsorption of the evaluated PAHs. Overall, the adsorption of PAHs on biochar followed a heterogeneous chemical adsorption process.