Liang Xinmiao, Xu Feng, Lin Bingcheng, Su Fan, Schramm Karl-Werner, Kettrup Antonius
Dalian Institute of Chemical Physics, Chinese Academy of Sciences.
Chemosphere. 2002 Nov;49(6):569-74. doi: 10.1016/s0045-6535(02)00308-9.
To study the transport mechanism of hydrophobic organic chemicals (HOCs) and the energy change in soil/solvent system, a soil leaching column chromatographic (SLCC) experiment at an environmental temperature range of 20-40 degrees C was carried out, which utilized a reference soil (SP 14696) packed column and a methanol-water (1:4 by volume ratio) eluent. The transport process quickens with the increase of column temperature. The ratio of retention factors at 30 and 40 degrees C (k'30/k'40) ranged from 1.08 to 1.36. The lower enthalpy change of the solute transfer in SLCC (from eluent to soil) than in conventional reversed-phase liquid chromatography (e.g., from eluent to C18) is consistent with the hypothesis that HOCs were dominantly and physically partitioned between solvent and soil. The results were also verified by the linear solvation energy relationships analysis. The chief factor controlling the retention was found to be the solute solvophobic partition, and the second important factor was the solute hydrogen-bond basicity, while the least important factors were the solute polarizability-dipolarity and hydrogen-bond acidity. With the increase of temperature, the contributions of the solute solvophobic partition and hydrogen-bond basicity gradually decrease, and the latter decreases faster than the former.
为研究疏水性有机化合物(HOCs)的传输机制以及土壤/溶剂体系中的能量变化,在20 - 40摄氏度的环境温度范围内进行了土壤淋溶柱色谱(SLCC)实验,该实验采用了填充有参考土壤(SP 14696)的柱体和甲醇 - 水(体积比1:4)洗脱液。传输过程随着柱温的升高而加快。30和40摄氏度下保留因子的比值(k'30/k'40)在1.08至1.36之间。与传统反相液相色谱(例如从洗脱液到C18)相比,SLCC中溶质转移(从洗脱液到土壤)的焓变较低,这与HOCs主要在溶剂和土壤之间进行物理分配的假设一致。线性溶剂化能关系分析也验证了该结果。发现控制保留的主要因素是溶质的疏溶剂分配,第二个重要因素是溶质的氢键碱性,而最不重要的因素是溶质的极化率 - 偶极矩和氢键酸度。随着温度的升高,溶质疏溶剂分配和氢键碱性的贡献逐渐降低,且后者比前者降低得更快。