Effect of fulvic acid coating on biochar surface structure and sorption properties towards 4-chlorophenol

Fulvic acid (FA) in soil ubiquitously affected the long-term benefits of biochars as soil amendments. The sorption of ionizable organic pollutants on biochars was complicated by FA because of the presence of ionic groups. To investigate the effect of FA coating on the interaction between biochars and 4-chlorophenol (4-CP), sorption isotherms at pH 4.0 and 12.0 and pH-sorption edge curves were generated. The biochars derived from platane wood were pyrolyzed at 300°C, 500°C and 700°C, resulting in low-, medium- and high-temperature biochars, respectively. The FA coating increased the surface area of the low-temperature biochar but decreased those of the medium- and high-temperature biochars. After coating biochars with FA, the aromaticity and the surface charge of the biochars decreased, but the content of oxygen-containing functional groups, especially carboxyl groups, on the biochar surfaces increased. The results from the sorption isotherm and pH-sorption edge curves showed that FA coating inhibited the sorption under alkaline conditions but did not change the sorption under acidic conditions, which indicated that coating by FA not only occupied the sorption sites but also strengthened the hydrogen bonding between 4-CP and biochars. As determined by characterization of biochars before and after coating, the number of carboxyl groups on the biochar surface increased after coating, which participated in hydrogen bonding with the hydroxyl groups of non-dissociated 4-CP. This research indicated that FA in the soil influenced the interaction between biochar with 4-CP, and the influences varied mainly due to the formation of hydrogen bonds at different pH values. This study could help us better understand the environmental behavior of biochar after aging, and provided a reference for sustainable utilization of biochar.