Department of Chemistry and Biochemistry, School of Medicine, University of Rijeka, Rijeka, Croatia.
J Environ Sci Health B. 2012 Sep;47(8):779-94. doi: 10.1080/03601234.2012.676413.
Sorption-desorption behavior of imidacloprid in six soils collected from five coastal regions in Croatia at 20, 30 and 40°C was investigated using batch equilibrium technique. Isothermal data were applied to Freundlich, Langmuir and Temkin equations, and the thermodynamic parameters ΔH°, ΔG°, ΔS° were calculated. The sorption isotherm curves were non-linear and may be classified as L-type, suggesting a relatively high sorption capacity for imidacloprid. Our results showed that the K( sor ) ( F ) values decreased for all the tested soils as the temperature increased, indicating that the temperature strongly influences the sorption. Values of ΔG° were negative (-4.65 to -2.00 kJ/mol) indicating that at all experimental temperatures the interactions of imidacloprid with soils were spontaneous processes. The negative and small ΔH° values (-19.79 to -8.89 kJ/mol) were in the range of weak forces, such as H-bonds, consistent with interactions and partitioning of the imidacloprid molecules into soil organic matter. The ΔS° values followed the range of -57.12 to -14.51 J/molK, suggesting that imidacloprid molecules lose entropy during transition from the solution phase to soil surface. It was found that imidacloprid desorption from soil was concentration and temperature-dependent, i.e. at lower imidacloprid concentrations and temperature, lower desorption percentage occurred. Desorption studies revealed that hysteretic behavior under different temperature treatments existed, and it was more pronounced at 20°C in the soils with higher OC content. The study results emphasize the importance of thermodynamic parameters in controlling soil pesticide mobility in different geographical locations, seasons and greenhouse conditions.
采用批量平衡技术研究了 20、30 和 40°C 时从克罗地亚五个沿海地区采集的六种土壤中吡虫啉的吸附-解吸行为。等温数据应用于 Freundlich、Langmuir 和 Temkin 方程,并计算了热力学参数ΔH°、ΔG°、ΔS°。吸附等温线曲线呈非线性,可归类为 L 型,表明吡虫啉具有较高的吸附能力。我们的结果表明,随着温度的升高,所有测试土壤的 K( sor )(F) 值均降低,表明温度强烈影响吸附。ΔG°值为负值(-4.65 至-2.00 kJ/mol),表明在所有实验温度下,吡虫啉与土壤的相互作用均为自发过程。负且较小的ΔH°值(-19.79 至-8.89 kJ/mol)处于较弱力的范围内,如氢键,与吡虫啉分子进入土壤有机质的相互作用和分配一致。ΔS°值遵循-57.12 至-14.51 J/molK 的范围,表明吡虫啉分子在从溶液相到土壤表面的转变过程中失去熵。研究发现,吡虫啉从土壤中的解吸与浓度和温度有关,即在较低的吡虫啉浓度和温度下,解吸百分比较低。解吸研究表明,在不同温度处理下存在滞后行为,在 OC 含量较高的土壤中,20°C 时更为明显。研究结果强调了热力学参数在控制不同地理位置、季节和温室条件下土壤中农药迁移性方面的重要性。