对干酪根样品(OS)进行了活化和氧化处理(ZnCl2(Z)和KOH(K)活化,H2O2(H)和NaClO(N)氧化),利用元素分析、傅里叶红外光谱(FTIR)及CO2气体吸附法对其进行表征,并对比研究其对非极性和极性有机污染物菲(Phen)和壬基酚(NP)的吸附行为.结果表明,样品的比表面积(SSA)和纳米孔体积(Vo)分别为76.57-104.00 m2·g^-1和30.68-41.67μL·g^-1,与有机碳含量呈显著正相关关系.吸附实验表明,所有样品对菲和壬基酚的吸附均为典型的非线性吸附,对菲的吸附非线性因子n值(0.678-0.797)都大于对壬基酚吸附的n值(0.530-0.748),且对壬基酚的吸附容量(K'F为1358-3750μg·g^-1)都大于对菲的吸附容量(K'F为435-1297μg·g^-1).此外,样品对菲和壬基酚的吸附容量与O/C和(N+O)/C呈显著负相关关系.纳米孔填充模型拟合表明,菲的吸附机理主要是纳米孔填充机制,但对壬基酚的吸附超过对菲的吸附这一现象与氢键作用有关.在KH(KOH活化+H2O2氧化,其余类同)、ON、KN处理组合上NP的纳米孔填充体积都有明显的提高,这一方面与纳米孔径大小的变化有关,另一方面与NP与表面—OH、—COOH、—NH2等基团形成氢键有关.
A bulk kerogen( OS) was activated by using Zn Cl2( Z) and KOH( K),followed by the oxidation with H2O2( H) and Na Cl O( N),respectively. The treated samples were characterized by using elemental analysis,Fourier transformed infrared spectroscopy( FTIR),and CO2 gas adsorption techniques,to investigate the aqueous adsorption behaviors of phenanthrene and nonylphenol. The CO2 gas adsorption results show that specific surface areas( SSA) and nanopore volumes( Vo) of the samples were 76.57-104.00 m2·g^-1and 30.68 - 41.67 μL·g^-1,respectively,and were positively correlated with contents of organic carbon. The aqueous sorption experiments show that all the samples were typically nonlinear for phenanthrene and nonylphenol,and the nonlinear sorption factor( n) of phenanthrene( 0.678 - 0.797) was greater than the n value of nonylphenol( 0.530 - 0.748),and the sorption affinity of nonylphenol( K'F为 1358 - 3750 μg·g^-1) was larger than that of phenanthrene( K'F为 435 - 1297 μg·g^-1). Moreover,the sorption affinity of phenanthrene and nonylphenol was negatively correlated with O/C and( N + O)/C values. The nanopore filling models showe that microporous filling mechanism was the main mechanism for the adsorption of phenanthrene. However,the higher sorption affinity of nonylphenol than of phenanthrene suggests other possible specific interaction such as hydrogen bonding. With the combined treatments of KH,ON,KN,the nanopore-filling volume of nonylphenol is related to nanopore size variation and hydrogen bonding of nonylphenol on —OH、—COOH、—NH2 functional groups.