Pateiro-Moure Miriam, Pérez-Novo Cristina, Arias-Estévez Manuel, López-Periago Eugenio, Martínez-Carballo Elena, Simal-Gandara Jesús
Soil and Agricultural Science Group, Plant Biology and Soil Science Department, and Nutrition and Bromatology Group, Analytical and Food Chemistry Department, Faculty of Food Science and Technology, University of Vigo, Ourense Campus, 32400 Ourense, Spain.
J Agric Food Chem. 2007 Jul 25;55(15):6219-26. doi: 10.1021/jf071122e. Epub 2007 Jul 4.
Retention of the cationic herbicides paraquat (PQ), diquat (DQ), and difenzoquat (DFQ) in two vineyard soils with a different management history and retention capacity was examined. The influence of copper on the ability of the soils to retain the herbicides was determined by comparing the results of adsorption and desorption tests on untreated and Cu-enriched soil samples, and also on soils that were previously treated with EDTA to extract native copper. The three herbicides were strongly adsorbed by both soils. Soil 1 exhibited linear adsorption isotherms for PQ and DFQ with partition coefficients, KD, of 1.28 x 103 and 1.37 x 103 L kg-1, respectively, and a Freundlich-type isotherm for DQ with a linearized partition coefficient, KD*, of 1.01 x 103 L kg-1. On the other hand, soil 2 exhibited curved isotherms and smaller KD* values (viz. 106, 418, and 28 L kg-1 for PQ, DQ, and DFQ, respectively). Using EDTA to extract copper from the soils released new sites for the herbicides to bind. The three herbicides exhibited strong hysteresis in the adsorption-desorption process. Extracting copper decreased the percent desorption of PQ and DQ; on the other hand, it decreased the affinity of DFQ for the resulting vacant adsorption sites. Similarly, competitive adsorption tests with copper and the herbicides revealed that the metal was only capable of displacing DFQ from adsorption sites. The behavior of this herbicide in the soils was consistent with a specific adsorption model. The disparate behavior of the two soils toward the herbicides was a result of the adsorption sites in soil 1 being less extensively occupied than those of soil 2 in the adsorption tests. The effect of copper on the adsorption of DFQ in the two soils was acceptably reproduced by an adsorption model involving Coulombic and specific sorption with competition from the metal.
研究了阳离子除草剂百草枯(PQ)、敌草快(DQ)和地芬诺喹(DFQ)在两种具有不同管理历史和吸附能力的葡萄园土壤中的吸附情况。通过比较未处理和富铜土壤样品以及先前用乙二胺四乙酸(EDTA)处理以提取天然铜的土壤的吸附和解吸试验结果,确定了铜对土壤吸附除草剂能力的影响。这三种除草剂在两种土壤中均被强烈吸附。土壤1对PQ和DFQ表现出线性吸附等温线,分配系数KD分别为1.28×10³和1.37×10³ L kg⁻¹,对DQ表现出Freundlich型等温线,线性化分配系数KD为1.01×10³ L kg⁻¹。另一方面,土壤2表现出曲线等温线且KD值较小(分别为PQ、DQ和DFQ的106、418和28 L kg⁻¹)。用EDTA从土壤中提取铜释放出了除草剂可结合的新位点。这三种除草剂在吸附 - 解吸过程中表现出强烈的滞后现象。提取铜降低了PQ和DQ的解吸百分比;另一方面,它降低了DFQ对产生的空吸附位点的亲和力。同样,铜与除草剂的竞争吸附试验表明,该金属仅能将DFQ从吸附位点上置换下来。这种除草剂在土壤中的行为符合特定吸附模型。两种土壤对除草剂的不同行为是由于在吸附试验中土壤1中的吸附位点比土壤2中的吸附位点占据程度更低。涉及库仑和特定吸附以及金属竞争的吸附模型可以较好地再现铜对两种土壤中DFQ吸附的影响。