Stipicević Sanja, Fingler Sanja, Drevenkar Vlasta
Institute for Medical Research and Occupational Health, Zagreb, Croatia.
Arh Hig Rada Toksikol. 2009 Mar;60(1):43-52. doi: 10.2478/10004-1254-60-2009-1898.
This article compares the sorption behaviour of 2,4,6-trichlorophenol, 2,3,4,6-tetrachlorophenol, pentachlorophenol, chlorotriazine atrazine, methylthiotriazine ametryn, methoxytriazine atratone, hydroxyatrazine, and didelakylated atrazine in a topsoil and an aquifer sediment before and after removal of sorbent organic matter and in humic acid. Freundlich isotherm coefficients Kf and 1/n and free energy change (deltaG degrees ) were calculated for all compounds in all sorbents. According to sorbent pH values, chlorophenolate anions and uncharged triazine species dominated in all sorption experiments with topsoil and aquifer sediment. In experiments with humic acid, chlorophenols, atrazine, and didealkylated atrazine existed almost completely as neutral species, whereas protonated species dominated for hydroxyatrazine, atratone, and ametryn. In addition to a hydrophobic partition, sorption of all compounds in native soil and sediment sorbents includes specific, more polar interactions, which greatly depend on sorbate acidity/basicity, specific properties of the sorbent organic matter and of mineral surface, as well as on the system pH. A significantly greater sorption intensity of all compounds in "organic-free" than in the native aquifer sediment confirmed the importance and possible dominance of mineral surface in the sorption process. Sorption intensity of chlorophenol and triazine compounds in humic acid was closely related to compound hydrophobicity. Greater sorption of almost completely protonated hydroxyatrazine than of the more hydropohobic but uncharged atrazine indicated different humic acid reaction sites for two compounds and consequently different sorption mechanisms.
本文比较了2,4,6-三氯酚、2,3,4,6-四氯酚、五氯酚、氯代三嗪阿特拉津、甲基硫代三嗪莠灭净、甲氧基三嗪莠去通、羟基阿特拉津和去二烷基阿特拉津在去除吸附剂有机物前后的表土和含水层沉积物以及腐殖酸中的吸附行为。计算了所有化合物在所有吸附剂中的弗伦德利希等温线系数Kf和1/n以及自由能变化(ΔG°)。根据吸附剂的pH值,在所有表土和含水层沉积物吸附实验中,氯酚盐阴离子和不带电荷的三嗪类物质占主导。在腐殖酸实验中,氯酚、阿特拉津和去二烷基阿特拉津几乎完全以中性物种存在,而质子化物种在羟基阿特拉津、莠去通和莠灭净中占主导。除了疏水分配外,所有化合物在天然土壤和沉积物吸附剂中的吸附还包括特定的、极性更强的相互作用,这在很大程度上取决于吸附质的酸度/碱度、吸附剂有机物和矿物表面的特定性质以及体系pH值。“无有机”状态下所有化合物的吸附强度明显高于天然含水层沉积物,这证实了矿物表面在吸附过程中的重要性和可能的主导作用。氯酚和三嗪化合物在腐殖酸中的吸附强度与化合物的疏水性密切相关。几乎完全质子化的羟基阿特拉津比疏水性更强但不带电荷的阿特拉津具有更强的吸附作用,这表明两种化合物在腐殖酸上的反应位点不同,因此吸附机制也不同。