pH influence on sorption characteristics of heavy metal in the vadose zone

Sorption is an important process in the modelling and prediction of the movement of heavy metals in unsaturated clay barriers. This experimental study investigates the effect of pH changes in the acidic range on the sorption characteristics of heavy metals such as: lead, copper and zinc in an unsaturated soil. A series of one-dimensional coupled solute and moisture leaching column tests, using different heavy metal solutions, were conducted on an unsaturated illitic soil at varying pH values. Variations of volumetric water content (VWC) with distance were measured for different time durations, and concentrations of heavy metals in the liquid and solid phases were analysed. Partitioning coefficient profiles of contaminants along the soil column were determined for each individual layer in the soil.

Results from column leaching tests showed that the sorption characteristics of heavy metals are controlled by many factors which should be taken into consideration, i.e. the VWC, time of wetting, soil pH, and the influent heavy metal concentrations. Simplification of K_d as a constant and of the VWC as a linear function cannot be considered a good assumption and may lead to an improper evaluation of the sorption phenomena and also to serious errors in predicting contaminant transport through unsaturated soils.     

南方典型丘陵区酸性土壤重金属地球化学分布特征及来源分异解析

本文采用基于多元统计的APCS-MLR和基于GIS技术的地统计学相结合的方法,以广西南宁市郊区典型丘陵水稻种植区酸性土壤为例,有效的对土壤重金属的空间分布特征和来源分异进行了解析和验证。结果表明:(1)研究区8种重金属中除部分样点的Cd以外,其它元素含量均未超过国家土壤环境质量的二级标准。研究区土壤大部分未受到污染,少部分受到了轻污染,其中Cd处于轻污染的样品数最多;(2)重金属在不同岩性岩石中的含量差异较大;(3)研究区水稻产区农田土壤重金属来源主要包括土壤母质继承和农田施肥,其中值得注意的是农田施肥中引入较多的重金属为Hg和Cd。此外,研究区主要的岩石类型碳酸盐岩中含有较高含量的Cd和Hg;(4)本文研究结果对于南方丘陵区酸性土壤重金属污染的特征与防治的研究具有重要的参考意义。同时,本文所提出的绝对主成分得分(APCS)与GIS相结合的方法能够有效的对主成分分析的结果进行有效的补充和有力的验证,对于相关研究具有一定的示范意义。     

土壤溶解性有机质对植物吸收-输送-贮存重金属的影响研究现状与进展

土壤溶解性有机质对重金属生物地球化学循环中的生物可利用性起着重要作用。近年来,在土壤溶解性有机质对植物吸收、输送和贮存重金属过程的影响研究领域,国际上主要聚焦于以下三个探索方向:①土壤溶解性有机质与重金属形成配位体,改变重金属在土壤中的迁移性和植物根际环境的作用机理研究;②土壤溶解性有机质可突破植物细胞内重金属吸附点位的限制,通过控制植物细胞壁-重金属复合体的形态及重金属在细胞壁内外的吸收平衡,来干预重金属穿过细胞壁进入植物体的动力学过程研究;③土壤溶解性有机质-重金属的络合形态影响重金属在植物体内的输送和贮存作用过程与机理研究。本文基于研究溶解性有机质和重金属的植物过程中,水体溶解性有机质研究多而土壤溶解性有机质研究少的现状,针对溶解性有机质异质性的研究难点和溶解性有机质与植物亚细胞结构的配位特征的复杂性与局限性,从极性、官能团、配位结构等角度,分析并评述了土壤溶解性有机质和重金属生物地球化学中,植物吸收、输送和贮存重金属过程的研究现状和未来发展趋势。     

A study on the adsorption characteristics of cadmium and zinc onto acidic and alkaline soils

The adsorption of cadmium (Cd) and zinc (Zn) with similar chemical properties is examined onto three soil samples: one is alkaline and the others are acidic. The distribution coefficient (K _d) and the Freundlich constant (K _F) for Zn are slightly higher than those for Cd, implying that the adsorption affinity of Zn is a little greater and less mobile. However, Cd and Zn usually show comparable results in the kinetic, isotherm, and envelope experiments. The adsorption of the heavy metals is relatively rapid and the reaction is almost completed within 15 min. The kinetics for both Cd and Zn are very well explained by the parabolic diffusion model. The maximum adsorption of the heavy metals is obtained at high pH, high temperature, and low ionic strength. The adsorption capacity on the alkaline soil is more significantly affected by the temperature as compared to the acidic soil. It is found that the adsorption affinity of the two heavy metals is mainly affected by the soil properties, such as pH, pH_PZC, organic matter, and total carbon. It is also confirmed that the chemical properties of the heavy metals are important factors in their adsorption onto soil. The adsorption isotherms of Cd and Zn are well described in both Freundlich and Langmuir models at the usual pH (soil pH). Under acidic and alkaline pHs, however, only the Freundlich model describes the adsorption of both heavy metals satisfactorily.     

地下水系统中镍污染和天然胶体共迁移特征

为了对地下水系统中天然胶体与Ni²⁺的共迁移特征进行研究，通过静态吸附实验和石英砂模拟含水层介质柱实验研究了土壤胶体对Ni²⁺在地下水中运移的影响，以及pH、离子强度（IS）、有机质等对土壤胶体吸附Ni²⁺的影响。结果表明：随着pH值升高，土壤胶体对Ni²⁺的吸附量增加；离子强度的增加会显著地降低土壤胶体吸附Ni²⁺的能力；腐殖酸（HA）的存在会增强胶体对Ni²⁺的吸附能力；在有胶体的情况下，Ni²⁺穿透砂柱的时间会缩短，吸附能力增强，吸附量增加，但当离子强度增加时，虽然Ni²⁺穿透砂柱的时间也被缩短，但是吸附量却降低。     

德兴铜矿地区土壤的基本特征及其对重金属元素的吸附研究

本文首先分析了江西德兴铜矿区周围土壤的微量元素和矿物组成特征,结果显示该地区重金属元素富集,且表层土中重金属元素含量与粘土矿物相对含量变化具有较好的一致性。室内土柱淋滤实验结果表明,当总淋滤时间为451 h时,土壤对Pb²⁺的总吸附量为2 584.75 mg/kg,淋滤实验的前半期存在多种竞争吸附机制,后半期土壤对Pb²⁺的吸附基本达到动态平衡。淋滤后土壤矿物的相对质量分数发生了改变,粘土矿物有所减少。粘土矿物在不同土壤层对Pb²⁺的吸附能力也各异。     

GIS支持下的土壤重金属污染预测预警研究

面对日益严重的土壤重金属污染问题,必须采用快速高效的方法对污染趋势做出预测预警。本研究建立了土壤重金属污染预警模型和土壤重金属污染超标年限预测模型,并在GIS技术支持下,开发了基于ArcView GIS的预警预测程序模块,实现了对土壤重金属污染的预警预测。最后以北京市及其近郊区为实例,对该区重金属污染进行了预警并对Pb元素超标年限进行了预测,取得了较好的预警预测结果。     

离心实验在污染物迁移研究中的应用

离心实验模拟以其可以获得与原型一致的应力水平并且能够大大缩短原型历时而被应用于污染物迁移实验研究。在离心相似理论及离心实验模拟的相似基础上,重点回顾了离心机在饱和带水分、非饱和带水分、保守性溶质、NAPLs、重金属、核素迁移以及污染场地修复方面的实验应用。最后讨论了离心模拟中土壤预制和加速度选择的问题,并简单介绍了离心监测方法。可以得出结论:离心机能够成功用于各类物质迁移的实验研究中,离心实验模拟能够为理论和数值等分析方法快速提供真实可靠的参数依据,但离心实验的理论基础和监测方法需要进一步完善,此外也应积极开展更接近实际情况下的离心实验模拟研究。     

Experimental and Modelling Approaches for the Assessment of Chemical Impacts of Leachate Migration from Landfills: A Case Study of a Site on the Triassic Sandstone Aquifer in the UK East Midlands

Current risk-based methods for assessing the effects of landfill leachate migration on groundwater resources are conservative and generalised. Cost-effective and practical strategies are required which can robustly determine the potential for contaminant attenuation on a site-specific basis. In this paper laboratory column experiments and reactive transport modelling are evaluated as a combined approach for assessing the chem’ical impact of leachate migration in the Triassic Sandstone aquifer. The results are compared with field data for a landfill in the East Midlands. Columns of aquifer sandstone were flushed sequentially with groundwater, followed by acetogenic or methanogenic leachate to simulate chemical interactions occurring during leachate loading episodes. The key contaminants in leachate (NH₄, heavy metals, organic fractions) were attenuated by ion exchange, redox reactions, sorption and degradation. These processes produce a consistent hydrochemical signature which may help identify the extent of leachate migration in the aquifer. The laboratory results largely replicate those found in the field system, and the behaviour of inorganic contaminants during leachate flushing of the aquifer columns can be described by the reactive transport model. The experimental and modelling approach presented represents a powerful tool for risk assessment and prediction of leachate contaminant fate at unlined and lined landfills.     

The development of a multi-surface soil speciation model for Cd (II) and Pb (II): Comparison of two approaches for metal adsorption to clay fractions

The mobility of toxic metals in soils or sediments is of great concern to scientists and environmentalists since it directly affects the bioavailability of metals and their movement to surface and ground waters. In this study, a multi-surface soil speciation model for Cd (II) and Pb (II) was developed to predict the partition of metals on various soil solid components (e.g. soil organic matter (SOM), oxide mineral, and clay mineral). In previous study, the sorption of metal cations on SOM and oxide minerals has been evaluated by thermodynamically based surface complexation model. However, metal binding to soil clay fractions was normally treated in a simplistic manner: only cation exchange reactions were considered and exchange coefficient was assumed unity. In this study, the binding of metals onto clays was described by a two-site surface sorption model (a basal surface site and an edge site). The model was checked by predicting the adsorption behavior of Cd (II) and Pb (II) onto three selected Chinese soils as a function of pH and ionic strengths. Results showed that the proposed model more accurately predicted the metal adsorption on soils under studied condition, especially in low ionic strength condition, suggesting that adsorption of metals to soil clay fractions need to be considered more carefully when modeling the partition of trace elements in soils. The developed soil speciation model will be useful when evaluating the movement and bioavailability of toxic metals in soil environment.     

天然有机质存在条件下的纳米颗粒与重金属协同行为研究

纳米颗粒与重金属元素相结合发生反应,可能产生一系列相互作用关系。这些作用过程是取决于多个环境条件共同作用的复杂过程,尤其是在土壤这种复杂的典型非均质环境介质中。这些作用关系可分为协同促进和拮抗抑制两大类关系。对于土壤中的重金属元素离子而言,纳米态粒子对其环境有效性究竟是协同促进还是拮抗抑制作用,关键取决于纳米粒子的表面修饰特性、二者间的界面反应以及反应后重金属元素的最终赋存状态这三个方面。协同促进或拮抗抑制作用与否则最终决定了这些污染重金属离子的生物可利用性和生态毒性响应。本文对近年来纳米颗粒-重金属共环境行为国内外研究现状进行综述讨论。纳米-重金属界面吸附解吸和土壤中迁移持留过程研究涉及多个热力学、动力学解析方法,科学家结合静态批实验和动态迁移实验等实验室模拟手段,对纳米颗粒、重金属离子、有机质三因子在土壤介质中的相互作用影响和共行为方式展开深入探讨。在重金属离子-纳米颗粒表面吸附机制、赋存形态以及重金属纳米吸附态土壤迁移固定机制研究中,多种定性表征方法的综合应用,如透射电镜(TEM)、X射线衍射(XRD)、X射线光电子能谱(XPS)、傅里叶变换红外光谱(FTIR)、X射线吸收近边结构光谱/扩展X射线吸收精细结构光谱(XANES/EXAFS)等方法相结合,被公认是揭示这一系列过程机制的重要技术手段。针对不同土壤环境中有机质存在条件,正确评价纳米态物质对重金属的迁移性及生物可利用性的影响作用,将为纳米环境效应评估和纳米修复技术等相关应用提供重要的数据支持和机理依据。     

不同地下水补给条件下非饱和砂壤土冻结试验及模拟

为研究土壤冻融过程中不同地下水位对土壤的补给规律,在室内进行了两组不同地下水边界条件下的土柱冻结试验: A组无地下水补给,土柱高度60cm;B组地下水维持在距土柱表层60cm深度处。土壤在冻结过程中水分及盐分均呈向上运移趋势,稳定浅地下水补给会加剧水分及盐分向上运移,造成上层土壤盐分的聚积,影响土壤剖面的热量平衡,引起剖面温度的重新分布,从而减缓冻结锋的推进速度。运用HYDRUS-1D冻融模块对不同地下水埋深（0.5m,1.0m,1.5m,2.0m,2.5m）情况下冻结过程中水分运移规律进行了模拟。模拟结果表明:累积补给量在埋深小于1.5 m时随埋深增加而有所增加,而当地下水埋深大于1.5 m时,累积补给量随着埋深增加而有所减小,甚至保持不变。     

Pesticide transport and transformation modeling in soil column and groundwater contamination prediction

Pesticide transport and transformation were modeled in soil column from the soil surface to groundwater zone. A one dimensional dynamic mathematical and computer model is formulated to simulate two types of pesticides namely 2,4-dichlorophenoxy acetic acid and 1,2-dibromo 3-chloro propane in soil column. This model predicts the behavior and persistence of these pesticides in soil column and groundwater. The model is based on mass balance equation, including convective transport, dispersive transport and chemical adsorption in the phases such as solid, liquid and gas. The mathematical solution is obtained by finite difference implicit method. The model was verified with experimental measurements and also with analytical solution. The simulation results are in good agreement with measured values. The major findings of this research are the development of the model which can calculate and predict the concentration of pesticides in soil profiles, as well as groundwater after 4, 12, 31 days of pesticide application under steady state and unsteady water flow condition. With the results of this study, the distribution of various types of pesticides in soil column to groundwater table can be predicted.     

Potential of natural bed soil in adsorption of heavy metals in industrial waste landfill

Development of higher welfare could not be realized unless by energy consumption and other natural resources. Growth of industrial complexes has shown an unprecedented trend during recent years. Many of these towns have no treatment systems for the industrial wastes leachates. Besides, the chemical composition of wastes in such complexes varies considerably due to the different kinds of industries. It is endeavored in the present work to study the natural potential of soil to treat leachate of such industrial wastes. For this purpose, the Aliabad industrial complex in Tehran — Garmsar road was selected as the study area. The potential of adsorption of elements such as nickel, copper, cadmium, zinc, chromium, lead and manganese was investigated. The results indicated that the soil potential to adsorb heavy metals (except for manganese) was very high (95 %) in the adsorption of heavy metals (except for manganese). Further, chemical partitioning studies revealed that heavy metals are associated with various soil phases such as loosely bonded ions, sulfide and organics to various extents. Among the mentioned soil phases, one can deduce that major portion of metal contaminants is absorbed as loosely bonded ions. Organic bond and sulfide bond are in the 2^nd and 3^rd positions of metal contaminants adsorption, respectively. The results of the present study apparently showed that soil column had ample capacity to adsorb metal contaminants. Thus, determination of soil potential in adsorption of heavy metals during site selection is as important criteria.     

Capability of vis-NIR spectroscopy and Landsat 8 spectral data to predict soil heavy metals in polluted agricultural land (Iran)

Heavy metals are toxic elements that have hazardous effect on the environment. They cause soil pollution as a result of their toxicity, potential reactivity, and mobility in soils. There are so many methods for the measurement of heavy metal concentrations in soils and aquatic systems. The traditional methods used for detecting heavy metal distribution in soil involve laboratory analysis and raster sampling. Both of them are expensive and time-consuming for large areas. Remote sensing techniques are used for obtaining the earth’s surface information, and these techniques have been used in the investigations of heavy metal distributions in preliminary analysis of soils as a rapid method. Today, near-infrared reflectance spectroscopy (NIRS) of soil characteristics has been of interest as a significant object. The present investigation is focused on the detection of heavy metals in contaminated soils by the application of reflectance spectroscopy in the spectral range of 350 to 2500 nm. This study also discusses the circumstances of the applied current methods for the detection and estimation of arsenic (As), cadmium (Cd), nickel (Ni), and lead (Pb) in contaminated agricultural soils. In the first part of laboratory spectroscopy, estimations were done using heavy metal reflectance spectroscopy and partial least square regression (PLSR) approaches, while in the second part, the heavy metal estimations were done using soil organic carbon reflectance spectroscopy through the PLSR approaches. Similar to the tasks above, estimations of As, Cd, Ni, and Pb by using Landsat 8 images were done in the forms of direct and indirect methods and the distribution of heavy metals in the study area was determined. Finally, the results obtained using direct and indirect methods were compared with the wet chemical measurements of heavy metals and organic carbon. It was found that although the direct detection of heavy metals using the images of Landsat 8 produced more accurate results than the indirect detections, the results obtained from laboratory spectroscopy corresponded more with the results from atomic adsorption spectroscopy. On the other hand, based on the fact that the soil has a complex content, the use of nonlinear methods, such as artificial neural networks in predicting soil heavy metal contents, could be regarded as a trusted method.     

有效参数的幂平均算法对农田尺度阿特拉津淋溶动态数值模拟的影响

以模拟农田尺度降雨入渗—重分布条件下阿特拉津(atrazine)在非饱和土壤中的淋溶动态为数值算例,通过在北京东郊的一块27m×27m的农田采集100个土壤样品,测定其主要理化性质,间接计算获得各土壤样品的van Genuchten型水力学参数、溶质运移的弥散度及atrazine在土壤中吸附的分配系数,进而基于柱模型假设,运用HY DRUS 1D软件得到不同时刻采样区内土壤水负压和atrazine浓度的平均分布。在此基础上,重点探讨了应用幂平均算法计算不同的等价有效参数对农田尺度下土壤水负压和atrazine浓度平均分布的数值模拟精度的影响。就所设计的降雨入渗—重分布条件下atrazine淋溶的算例而言,土壤水力学参数、溶质运移参数和吸附特性参数取几何平均或调和平均作为有效参数值,空间平面上呈正态分布的土壤水负压的初值采用算术平均值作为流场模拟的初始条件,可以获得满意的数值模拟结果。     

Partitioning of heavy metals on soil samples from column tests

In this study, column tests were used to determine the retention capability of three types of estuarine alluvia collected adjacent to landfill sites in South Wales. Selective sequential extraction (SSE) was used to study the retention mechanisms of heavy metals in the soil columns obtained from leaching experiments. Acid digestion was later used to check the validity of the SSE results. Breakthrough curves show good retention of heavy metal ions (Pb, Cu, and Zn) by all soils, where almost 99% of heavy metals were retained with the C_e/C_o values in the order of 10⁻³. The retention strength of these soils was observed to be constant up to five pore volumes (PV). This corresponds with the pH of the effluents and pore water of soil slices, which also show good buffering capacity against very acidic leachate up to 5PV. The heavy metal extraction profiles from SSE show very similar trends with the retention profiles from the leaching experiments, where heavy metals were retained mainly at the top part where the leachate entered the column. SSE indicates qualitatively that heavy metals precipitated with carbonates and amorphous materials (oxides/hydroxides) are higher than heavy metal retention via exchangeable mechanisms. The mass balance calculation gives range of deviation of 1–16% of the total soil extraction. The distribution of the heavy metals with various soil constituents are ranked in the following order: Carbonates>Amorphous oxides hydroxides>Organic matter>Exchangeable phases.     

A Review of Study on Fe-C Interaction and Their Adsorption Properties to Soil Heavy Metal

Nowadays, the Fe-C coprecipitate mechanism is recognized by more and more scholars and becomes the hot topic in the environmental science. On the basis of discussing the interaction between iron oxide and organic matter, and the adsorption research progress of Fe-C complexes on heavy metals, the immobilization potential of Fe-C complexes on heavy metals in polluted soil were illustrated. The surface properties and physical characterizations of iron oxide are changed regularly with the interaction of organic matter, which lead to the higher adsorption capacity of Fe-C complexes in contrast to single iron oxide. Besides, the influences of pH values, organic matter types and surface properties of iron oxides on the adsorption capacity of Fe-C complexes on heavy metals were discussed. The excellent adsorption performance of Fe-C complexes in certain conditions will provide important theoretical basis for contaminated soil remediation.     

汞等重金属元素在黄浦江中迁移富集研究

为了探讨生物膜对重金属元素的富集,以及生物膜在水-沉积物交换过程中的影响和贡献,研究了生物膜和沉积物对于汞等重金属的吸附以及吸附前后汞形态的变化.结果表明沉积物中的汞和大部分重金属元素以残渣态为主,可交换态、有机质结合态、碳酸盐结合态百分含量相对较少.生物膜中有机质含量很高,生长时间,光照,季节都是影响生物膜中重金属元素含量的重要因素.可以推断,光照越强,温度越高,生长时间越长,生物膜中重金属元素含量越高.     

应用连续混合器模型模拟非饱和土壤盐分淋洗过程

尽管连续混合器模型已经广泛应用于土壤中溶质迁移转化规律计算,但却仅限于饱和土壤条件。通过采用Kostiakov公式描述非稳定入渗过程,并结合活塞假设计算入渗过程中土壤水分的运动和分布规律,将连续混合器模型扩展应用于非饱和土壤的盐分淋洗过程计算,并求出了模型的解析解。分析发现,在一定的土壤质地、初始含水率剖面和初始含盐量剖面下,模型的计算结果会受到土层划分厚度的影响,而合理的土层厚度又与饱和导水率和溶质弥散系数之间存在量纲一的函数关系。当土层厚度选取合理时,连续混合器模型与HYDRUS-1D的计算结果十分接近,采用该模型模拟试验土壤盐分淋洗过程,显示了较好的计算精度。