Sorption characteristics and mechanisms of organic contaminant to carbonaceous biosorbents in aqueous solution

A series of carbonaceous biosorbents was prepared by pyrolyzing pine needles, a model biomass, at various temperatures (100–700°C) under an oxygen-limited condition for 6 h. The elemental compositions and the specific surface areas (BET-N₂) of the biosorbents were analyzed. Sorption properties of 4-nitrotoluene to the biosorbents and their mechanisms were investigated, and then correlated with the structures of the biosorbents. The result shows that with the increase of the pyrolytic temperature, the aromaticity of the carbonaceous biosorbents increases dramatically and the polarity (the (N+O)/C atomic ratio) decreases sharply. Correspondingly, conformations of the organic matter in the biosorbents transform gradually from a “soft-state” to a “hard-state” and the specific surface areas of the resultant biosorbents extend rapidly. The sorption isotherms fit well with the Freundlich equation. The regression parameters (i.e., N and IgK _f) are linearly related to the aromaticity indices (the H/C atomic ratio). Contributions of adsorption and partition to total sorption of the carbonaceous biosorbents are quantified. The adsorption of the carbonaceous biosorbents increases quickly with the increase of the pyrolytic temperature. The saturated adsorption amounts (Q _max) increase linearly with the increase of the specific surface areas (SA) of the biosorbents. For the carbonaceous biosorbents with hard-state carbon, the calculated normalized-Q _max values by SA are comparable to the theoretical estimation (2.45 μmol/m²). In comparison, for the carbonaceous sorbents with soft-state carbon, the calculated normalized-Q _max values by SA are much higher than the theoretical estimation. The partition coefficients (K _om) increase with the decrease of the polarity of the biosorbents, reaching a maximum, and then decrease sharply with further decreasing the polarity, suggesting that partition mechanism be dominated by the compatibility and accessibility of the sorbent medium with organic pollutant. These observations will provide a theoretical and practical reference to design a cost-effective and high-efficient sorbent, and to accurately predict sorption properties and mechanisms of a given sorbent. Supported by the National Natural Science Foundation of China (Grant No. 20577041), and the Program for New Century Excellent Talents in University (Grant No. NCET-05-0525)