为准确了解生物修复过程中多环芳烃(PAHs)的生物吸附行为,采用化学方法(脱蜡、皂化)分离白腐真菌样品并制得3个组分,探讨了白腐真菌组分的结构特征.同时,用批量平衡法研究了菲和芘在白腐真菌样品上的生物吸附-脱附行为及共存重金属Cu2+对吸附作用的影响,探讨了PAHs生物吸附的作用机制及构-效关系.结果表明,菲和芘在白腐真菌体上的等温吸附-脱附曲线均呈线性(Freundlich,N=1),为可逆吸附过程,其生物吸附机理为PAHs在白腐真菌体上的分配作用;经脱蜡和皂化后,菲在白腐真菌体上的分配系数Kp(F1)分别为Kp(F2)和Kp(F3)的4.5倍和7.5倍,芘的分配系数Kp(F1)则分别为Kp(F2)和Kp(F3)的3.8倍和7.2倍,表明主要分配介质为白腐真菌体上的脂类和聚酯类物质;PAHs的有机碳标化的分配系数Koc值与白腐真菌体的极性指数(O+N)/C呈反比.共存Cu^2+离子促进白腐真菌体对菲的生物吸附,随着Cu^2+浓度的增加,菲的生物吸附作用逐渐增强;增强吸附机制为Cu^2+通过配合作用吸附到白腐真菌体上中和微生物表面的负电荷,降低白腐真菌体表面的亲水性,进而提高其疏水性分配作用;同时,吸附态Cu^2+与菲之间形成阳离子-π键等特殊作用,其作用大小随白腐真菌体的极性指数(O+N)/C增大而降低.
White-rot fungi biomass and its fractions were isolated by chemical methods including de-waxing and saponification. The elemental compositions,polarity index [(O+N)/C atomic ratio] and functional groups of three white-rot fungi fractions were characterized by elemental analysis and Fourier transform infrared spectrometry. To elucidate the biosorption of organic pollutants for bioremediation,the biosorption-desorption behavior of phenanthrene and pyrene to the isolated white-rot fungi fractions were investigated using a batch equilibration technique,and the effects of co-existing Cu^2+ on the biosorption of phenanthrene were also compared. The correlation of sorption properties with the structural characterization is discussed. The sorption-desorption isotherms of phenanthrene and pyrene to the sorbents were linear (Freundlich,N=1) and had the characteristics of a reversible process,suggesting that the biosorption mechanism to white-rot fungi fractions is dominated by partitioning into white-rot fungi biomass. The partition coefficients (Kp) of white-rot fungi decreased significantly after de-waxing and saponification,i.e.,by 4.5-and 7.5-fold for phenanthrene,and by 3.8-and 7.2-fold for pyrene,indicating that the partition medium is attributed to the extractable lipids and polymeric lipids. Polarity apparently played a regulating role in the biosorption of phananthrene and pyrene. The carbon-normalized biosorption coefficient (Koc ) was negatively correlated with the polarity index of the white-rot fungi fractions. The biosorption of phenanthrene to white-rot fungi fractions was promoted by coexisting heavy metal ions such as Cu^2+ at the environmental level (0-32 μg·mL^-1),and the sorption enhancement (△Kp) increased with the concentration of Cu^2+,and decreased with the polarity index of the sorbent. Binding of Cu^2+ neutralized the negative charge of the fungi surface,making it less hydrophilic and enhancing hydrophobic partitioning of phenanthrene. A specific interaction m