Insight into effects of citric acid on adsorption of phthalic acid esters (PAEs) in mangrove sediments

The adsorption of phthalate esters (PAEs) in mangrove sediment greatly influences their availability to aquatic organisms, however, the adsorption processes of PAEs in mangrove sediment, as well as the effects of root exudates, are poorly understood. In this study, dimethyl phthalate (DMP), diethyl phthalate (DEP) and dibutyl phthalate (DBP) was used as model PAEs to determine the effects and mechanism of citric acid on the adsorption kinetics and isotherms of PAEs in the mangrove sediments. The adsorption kinetics followed pseudo-second order model, describing the characteristics of heterogeneous chemisorption of PAEs in mangrove sediments. The adsorption isotherms of DMP and DEP followed Freundlich model, implying the characteristics of surface multilayer heterogeneous adsorption; while the Henry model better described the adsorption isotherms of DBP, suggesting that hydrophobic partition accounted for DBP adsorption in the mangrove sediments. Inter-chemical variability was observed in adsorption capacity (q(e)) with the sequence of DBP > DEP > DMP. Surface polarity index ((C-O + COOH + C=0)%) of particulate organic matter (POM) regulated the adsorption capacity of DMP and DEP in mangrove sediments, while different POM content among mangrove sediments explained the difference in the sorption strength for DBP. The presence of citric acid enhanced the q(e) of the three PAEs by 6.4-12.6%. These findings are of great significance to reveal that the root exudates play a crucial role in the PAEs adsorption in mangrove sediments, and provide valuable information for availability of PAEs in mangrove ecosystem.