Delolme Cécile, Hébrard-Labit Céline, Spadini Lorenzo, Gaudet Jean-Paul
Laboratoire des Sciences de l'Environnement, Ecole Nationale des Travaux Publics de l'Etat, Rue Maurice Audin, 69518 Vaulx-en-Velin Cedex, France.
J Contam Hydrol. 2004 Jun;70(3-4):205-24. doi: 10.1016/j.jconhyd.2003.09.002.
Nowadays, it is necessary to understand and identify the reactions governing the fate of heavy metals introduced into the environment with low complexing organic compounds, particularly when they are transferred through soils in urban areas. In this work the concomitant influence of pH and acetate on the fate of zinc on siliceous sand was studied in batch and non-saturated column experiments. Total zinc concentrations varied between 2 and 20 mg/l, and total acetate concentrations were fixed at 22, 72, 132, and 223 mM to obtain solution pHs of 4, 5, 6 and 7, respectively. Natural sand (diameter, 0.3-2 mm), mainly constituted of silica, was used. In batch adsorption experiments, zinc adsorption is insignificant at pH 4, low and linear at pH 5, and increasingly nonlinear, of the Langmuir type, at pH 6 and 7 indicating near-saturation conditions of surface sites at these high pH values. In column experiments, Zn retardation increases and the maximum outlet concentration of Zn decreases with rising pH and acetate concentrations. Previous column tracer experiments revealed the occurrence of regionalized water transport in the column. Modeling these data was based on a non-electrostatic approach. Batch and column data modeling was based on the PHREEQC code that allows concomitant resolution of chemical speciation and regionalized water transport. The speciation calculation indicates that the ZnAcetate+ species is the dominant Zn species in the solutions used. Batch experimental curves are correctly modeled assuming the formation of the three surface species triple bond SiOZn+, triple bond SiOH-Zn Acetate+ and triple bond SiO-Zn(Acetate)2-. The column data could be adequately modeled assuming a two-region water transport and the formation of the same three species with the same thermodynamic constants determined in the batch experiments. The hypothesis of the modeling leads to a slight overestimation of the quantities of zinc eluted (10%) at pH 6 and 7, mostly in the desorption phase. These results show that the methodology used facilitates the correct modeling of both batch and transport experiments and formulation of the hypothesis on the interactions between the low reactive sand and a complex solution.
如今,了解和识别控制低络合有机化合物引入环境中重金属归宿的反应很有必要,特别是当它们在城市地区通过土壤转移时。在这项工作中,通过批次和非饱和柱实验研究了pH值和乙酸盐对锌在硅质砂中归宿的协同影响。总锌浓度在2至20mg/L之间变化,总乙酸盐浓度固定为22、72、132和223mM,分别获得pH值为4、5、6和7的溶液。使用主要由二氧化硅组成的天然砂(直径0.3 - 2mm)。在批次吸附实验中,锌在pH 4时吸附不显著,在pH 5时较低且呈线性,在pH 6和7时呈越来越非线性的朗缪尔型,表明在这些高pH值下表面位点接近饱和状态。在柱实验中,随着pH值和乙酸盐浓度的升高,锌的阻滞作用增强,锌的最大出口浓度降低。先前的柱示踪实验揭示了柱中存在区域化水流。对这些数据进行建模基于非静电方法。批次和柱数据建模基于PHREEQC代码,该代码允许同时解析化学形态和区域化水流。形态计算表明,乙酸锌离子(ZnAcetate+)是所用溶液中的主要锌物种。假设形成三种表面物种:三键SiOZn+、三键SiOH-Zn Acetate+和三键SiO-Zn(Acetate)2-,批次实验曲线得到了正确建模。假设区域化水流分为两个区域,并形成与批次实验中确定的相同的三种具有相同热力学常数的物种,可以对柱数据进行充分建模。建模假设导致在pH 6和7时锌洗脱量略有高估(10%),主要在解吸阶段。这些结果表明,所使用的方法有助于对批次和传输实验进行正确建模,并有助于提出关于低活性砂与复杂溶液之间相互作用的假设。