Removal of Heavy Metals from Calcareous Contaminated Soils by EDTA Leaching

The performance of EDTA for the treatment of calcareous soils contaminated with heavy metals from mining and smelting activities was evaluated in this study. Soil samples containing variable levels of contamination, from 500 to 35 000 mg kg^-1 Pb and 700 to 20 000 mg kg^-1 Zn, were subjected to EDTA treatment and the extraction of heavy metals was found to vary, ranging between 50 and 98% for Pb and 50 to 100% for Zn. Total residual concentrations were above the limits set by regulatory authorities; leachable metals, however, were efficiently removed and treated soils were all acceptable in terms of toxicity. The effect of EDTA concentration and pulp density was studied on a soil sample containing 12 000 mg kg^-1 Pb and 10 000 mg kg^-1 Zn. Heavy metals removal was improved at low pulp densities and when EDTA concentration was increased from 0.025 to 0.25 M. The tetrasodium salt Na₄-EDTA was found to be less effective for metals removal compared to the disodium salt Na₂-EDTA, though applied at higher concentrations. This experimental work has also demonstrated the great importance of soil matrix for the overall evaluation of the EDTA leaching as a cost effective remedial option. The simultaneous dissolution of calcite was found to consume approximately 90% of the available EDTA. It was thus concluded that for the treatment of calcareous soils the design criteria and cost estimations should be based on the calcite content of the soil.     

EDTA和柠檬酸对污染土壤中重金属的解吸动力学及其形态的影响

利用批处理振荡解吸平衡法研究了0.05 mol/L的乙二胺四乙酸钠(EDTA)和柠檬酸对污染土壤中Cd,Pb,Cu,Zn的解吸动力学特征,并采用优化的BIER(European Community Bureau of Reference)连续提取法分析了EDTA和柠檬酸处理前后土壤中重金属形态和生物有效性的变化.结果表明,污染土壤中重金属Cd,Pb,Cu,Zn的解吸率随着解吸时间的延长而不断增加,但解吸速率随解吸时间的延长而不断降低.EDTA对Pb,Cu的解吸能力显著大于柠檬酸,柠檬酸对Zn的解吸能力显著大于EDTA,柠檬酸和EDTA对Cd的解吸能力相差不大.EDTA和柠檬酸对4种重金属解吸能力的顺序分别为:Pb＞Cd＞Zn＞Cu和CA＞Zn＞Pb＞Cu.双常数方程是描述污染土壤中Cd,Pb,Cu,Zn解吸动力学过程的最佳方程.EDTA去除的重金属主要以酸提取态和可还原态存在,柠檬酸去除的重金属主要以酸提取态存在.EDTA和柠檬酸处理后.污染土壤中Cd,Pb,Cu,Zn的生物有效性降低.     

Removal of Heavy Metals from Soils using Enhanced Electrokinetic Soil Processing

In order to remediate contaminated land, a new process of electrokinetic purging of heavy metals from saturated soil is examined by laboratory experiments. Electrokinetic soil remediation is one of the most promising soil decontamination processes as it has high removal efficiency and time-effectiveness in low permeability soils such as clay. Being combined with several mechanisms-electromigration, electroosmosis, diffusion and electrolysis of water, electrokinetic soil processing can remove non-polar organics as well as ionic contaminants. This study suggests that the removal efficiencies for Pb and Cd are significantly influencedby applied voltage and current, type of purging solutions, soilpH, permeability and zeta potential of soil. The removal efficiencies for Pb and Cd were 75–85% for the kaolinite soil and 50–70% for the tailing soil over the duration of 4 days. For heavy metals, their adsorption capacities on the soil surface and mobilities in soil have significant effects on the removal efficiency.     

Removal of Heavy Metals from Soil Components and Soils by Natural Chelating Agents. Part II. Soil Extraction by Sugar Acids

Aqueous solutions of the natural chelatingagents D-gluconic acid and D-glucaric acid (D[+]-saccharic acid) were tested for their ability to remove heavy metals (Cd, Cr, Cu,Ni, Pb, Zn) from a soil polluted by long-term application of sewage sludge. Batch equilibrium experiments were performed undervariation of fundamental process parameters, i.e. pH value, sugaracid concentration, batch solution volume, solid:liquid ratioand number of treatment cycles.The extractability of heavy metals was low under near-neutral andslightly basic pH conditions. It increased drastically between pH12.0 and 13.0. Pb and Cu were preferentially extracted metals.Compared with the extraction efficiency of pH adequate puresodium hydroxide solutions, the sugar acids enhanced thesolubilisation of Pb and Cr especially. The metal depletion fromsoil was the highest when applying 20 or 50 g L^-1 solutionsof the chelating agents. Under strongly basic conditions solid:liquid ratios of 1:10 or 1:20 were proofed to be advantageous.Except Ni, multi-step extraction improved the metal removalstrongly. This effect was the greatest for Cr extraction. Underoptimised conditions the following metal extraction degrees wereachieved with strongly alkaline D-gluconic acid solutions: Ni 43%%, Cr 60%%, Cd 63%%,Zn 70%%, Pb 80%%, and Cu 84%%.     

Role of Different Soil Fractions in Copper Sorption by Soils

Abstract

To evaluate contributions of organic matter, oxides, and clay fraction to copper (Cu) adsorption in six characterized soils, adsorption isotherms and distribution coefficients were obtained by a batch experimental method. Copper adsorption isotherms from untreated soil, organic matter removed from samples, and organic‐matter‐ and oxide‐removed samples were compared with curve patterns and correlated to Langmuir and Freundlich models. Copper sorption data on untreated soils described L or H‐curves, whereas in soils deprived of any component, their curves were S‐type. Distribution coefficients allowed knowing Cu adsorption capacity of untreated soil and of organic matter, oxides, and clay fraction. Soil organic matter is the main component that affects Cu adsorption as long as soil pH is near neutrality. At acid pH, oxides are the main component that affects Cu adsorption, although to a much smaller extent than organic matter near neutral conditions. Soil pH is the main soil factor that determines Cu adsorption.     

EDTA对土壤渗滤液中TOC和重金属动态变化的影响

通过盆栽试验研究了EDTA对土壤渗滤液中总有机碳(TOC)和重金属动态变化的影响.结果表明,施用EDTA极显著地增加了土壤渗滤液中TOC含量,土壤渗滤液中TOC含量随淋洗量呈指数曲线下降.在加入EDTA 48天后,土壤渗滤液中TOC含量仍然高于对照处理.施用EDTA大幅度地增加了土壤渗滤液中Cd、Ni的浓度,其浓度在1个月内迅速下降,以后趋于稳定.用EDTA强化重金属污染土壤的修复存在淋溶迁移的环境风险.防止因EDTA施用而引起地下水污染的关键时期在EDTA施入后的2周内.     

土壤重金属复合污染的化学固定修复研究

本文研究糠醛渣、磷矿粉、风化煤3 种修复剂对重金属复合污染土壤的化学固定修复效果.结果表明:糠醛渣、磷矿粉、风化煤3 种修复剂都可一定程度地降低复合污染土壤中的Cu、Zn、Pb、Cd含量,其中以风化煤降低土壤有效态Zn、Cu的效果较好,在风化煤添加量为80 g/kg时土壤有效态Zn的含量降低了37.22%,土壤有效态Cu的含量降低了31.22%;磷矿粉处理修复Pb的效果比糠醛渣、风化煤好,在磷矿粉添加量为80 g/kg时,土壤有效态Pb的含量降低了23.79%;3 种修复剂都能显著降低土壤有效态Cd,在磷矿粉添加量为40 g/kg时,土壤有效态Cd的含量降低最显著,较对照降低了83.09%.在本试验条件下,3 种修复剂对4 种重金属复合污染土壤的修复效果,以Cd 较好,其次是Zn,对Pb的修复效果较差.     

土壤重金属形态对径流中重金属流失的影响

土壤重金属的积累可促进地表径流中重金属的流失,流失量与土壤中重金属的形态有关。田间观测和室内模拟淋洗试验的结果都表明,径流或淋出液中重金属主要来源于土壤的交换态(包括水可溶态)重金属;土壤重金属总量与径流中重金属浓度相关不明显;用稀盐(0.01mol/LCaCl2)和1mol/LNH4OAc提取的土壤重金属量与径流和淋出液中重金属浓度都呈显著的相关,可较好地表征土壤中重金属流失潜力。     

混合试剂在不同电解质条件下对土壤重金属淋洗效果的影响

为了得出不同电解质(CaCl2和KCl)对混合试剂(EDTA和柠檬酸)去除土壤重金属的影响,对重金属污染土壤进行盆栽淋洗实验.结果表明,含电解质CaC12的混合试剂有利于去除酸性污染土壤中重金属;而含KC1的混合试剂有利于去除中性污染土壤中重金属.含电解质CaC12和KC1混合试剂[EDTA-+-CA+ 1/2(CaC12+KCl)]对土壤重金属的淋洗效果不明显;但电解质用量的增加(如EDTA+ CA+ CaCl2+KCl)提高了酸性土壤中Cd、Zn、Pb和Cu的去除率,提高幅度分别达22％,16％,18％和9％.Cd和Zn污染的酸性土壤,可用CA+ CaCl2+KCl混合试剂淋洗;但Pb和Cu的去除还要靠EDTA.中性重金属污染土壤可采用EDTA+ CaCl2+ KCl混合试剂淋洗.     

Phytotoxicity of Heavy Metals in Contaminated Podzolic Soils of Different Fertility Levels

Eurasian Soil Science - We have compared the impact of heavy metals (HMs: Cu 660 + Zn 1100 + Pb 650 mg/kg) on agrosoddy-podzolic soils (Albic Retisols (Loamic, Aric, Cutanic, Ochric)) of two arable...     

Kinetics of Desorption of Heavy Metals from Polluted Soils: Influence of Soil Type and Metal Source

Kinetics of desorption of heavy metal ions (Cd, Cu, Ni and Zn) from the surface (0–15 cm) samples of an acidic soil (Inceptisol) and a neutral soil (Mollisol) spiked with inorganic salts of these metals or through an acidic sludge were studied by the column method. The rate of desorption of soil applied heavy metals was initially rapid and gradually declined with time. In general, the release of heavy metals from soils polluted by inorganic or sludge sources conformed to a multi-site model of first order kinetics; however, the release of Cd and Ni applied through inorganic sources to the neutral soil could be adequately accounted for by single-site model. The double-site model could adequately explain the release of Cd from sludge amended acidic soil and the release of Zn applied though inorganic salt or sludge to the neutral soil. In acidic soil, the apparent desorption rate coefficients of heavy metals applied through inorganic sources were higher than those for the sludge source. In neutral soil, however, the apparent desorption rate coefficients of heavy metals added through sludge were higher than for inorganic sources. Among the heavy metals, the higher apparent desorption coefficient value and percent desorption of Cd indicated a higher potential of this metal for leaching and ground water contamination. The results also suggested that the acidic soil pH might reduce the ability of the soil to naturally sequester heavy metal cations and lead to their leaching.     

高光谱在土壤重金属信息提取中的应用与实现

以建设一套基于光谱数据的土壤重金属信息提取系统为研究目标,总结了土壤重金属指标及其光谱学机理。在软件技术和数据库技术支持下,实现了土壤重金属光谱信息管理、处理、分析和应用。研究表明:土壤重金属元素在其特征波段上所显示的光谱特性,经过光谱预处理、变换和定量化提取,能够为建模提供理论依据。在计算光谱统计特征量基础上,采用光谱分析法,自动检索土壤重金属光谱特征位置。以东北黑土地机载高光谱CASI和SASI数据为例,计算了硒、锰和铁等元素的含量,最高硒元素含量达到了80.767 mg kg~(-1)。随着植被覆盖率的提升,硒、锰、锡和锌元素的含量随之升高,说明水稻吸收了部分金属元素,对特征波段反射率产生了影响。     

不同土壤改良剂对大豆富集重金属的影响

在广西环江开展了土壤改良剂对大豆富集重金属的影响研究,结果表明:土壤改良剂(煤灰、菌渣、蚕沙)均能在大豆苗期、结荚期和成熟期有效降低大豆中重金属含量。菌渣对大豆苗期重金属抑制效果最好,蚕沙对成熟期重金属吸收的抑制效果最佳,而煤灰在结荚期抑制重金属效果优于其他的改良剂,并且对减少大豆籽粒中重金属含量作用效果最好。     

Sequentially Extracted Arsenic from Different Size Fractions of Contaminated Soils

Five soils from Austria that have high contents of arsenic (As)due to anthropogenic and/or geogenic sources were separated intosand, silt, and clay fractions. The distribution of As among theparticle-size fractions was clay >> silt > sand. Theparticle-size fractions were analysed according to an 8-stepsequential extraction procedure (SEP) designed to assess theprimary reservoirs and extractability of As. Steps 1 and 2,(i.e. NH₄NO₃ and (NH₄)₂SO₄) extractedthe least As, while considerably greater amounts were extractedin steps 3, 4 and 5 (i.e. NH₄H₂PO₄,NH₂OH-HCl, and NH₄F). The greatest amounts of As wereextracted in steps 6 and 7, both NH₄-oxalate extractantstargeting the amorphous and crystalline oxide fractions. Theresidual fraction (step 8) was typically low. The extraction ofthe clays contained generally more As in steps 3 to 8, while Asrelease in the first two steps was typically highest in the sandand silt fractions. These findings are in accord with factoranalysis indicating that the extractants of the SEP areseparated into weak (steps 1 and 2) and strong (steps 3 to 8)extractants. SEP data along with microprobe analyses (X-raymicroanalyses) indicate that most As is associated with Fe andis therefore not readily mobile. Anyhow, As could be releasedupon changes in redox potential or pH. The greaterextractability of As from sand fractions using weak extractantsmay explain the higher toxicity of As in coarse-textured soils,as found in previous studies.     

低分子有机酸去除土壤中重金属条件的研究

采用化学萃取实验,以湖南郴州柿竹园和湖南衡阳水口山矿区的重金属污染农田土壤为研究对象,采用柠檬酸、草酸、酒石酸作为低分子有机酸萃取剂,在一定的条件下对污染土壤中重金属进行萃取实验,确定各个单因素的适宜条件。结果表明,对于湖南郴州和衡阳两个污染地区土壤运用化学萃取技术萃取重金属来进行土壤修复是实际可行的;柠檬酸、酒石酸、草酸对各种土壤中的重金属都表现出了良好的萃取能力,是高效的土壤重金属萃取剂;单因素的适宜萃取条件为100mmol·L^-1有机酸溶液,固液比1∶5,恒定温度35℃,pH为3,反应时间24h,且萃取率随着电解质浓度的增大而提高;土壤中重金属存在形态与萃取效果有一定的相关性,稳定态（残渣态、硫化物和有机结合态、铁-锰氧化物结合态）金属含量高,表现为较低的萃取率;反之,萃取率高;柠檬酸、草酸、酒石酸3种萃取剂均能有效地降低衡阳污染土壤中的重金属浓度,3种萃取剂的萃取效率依次为酒石酸〉草酸〉柠檬酸。     

石灰水对混合试剂洗脱土壤重金属淋洗效果的影响

为了探索石灰水对混合试剂(MC)洗脱后土壤中重金属的淋洗效果,对重金属污染土壤进行了盆栽淋洗试验研究。结果表明:石灰水淋洗MC洗脱土壤,淋出液中Cd、Zn、Pb和Cu浓度均显著高于去离子水淋洗MC洗脱土壤,这主要由于石灰水提高土壤pH,释放土壤所吸附的络合态重金属,这种现象在酸性污染土壤中表现更明显。对于酸性污染土壤,可采用MC+石灰水+去离子水依次进行淋洗处理,其Cd和Zn去除率与MC+去离子水+去离子水依次淋洗处理相比提高22.6%和28.8%;对于中性重金属污染土壤,两处理间重金属去除率差异不显著。石灰水淋洗可提高土壤重金属去除率,并提高土壤pH,改善MC洗脱对土壤的酸化,有利于淋洗后土壤的农业利用。     

Small Scale Heterogeneity of Soil Chemical Properties. II. Fractions of Aluminum and Heavy Metals

Soil aggregates from nine horizons of five forest sites in Bavaria were mechanically separated into an aggregate surface fraction and an aggregate core fraction. Seven operationally defined fractions of AI, Cd, Cu, Cr, Ni, Pb, and Zn were determined by a sequential extraction procedure within both aggregate fractions. The CEC, C_org, and oxides of Mn and Fe also were measured. The differences in metal concentrations between surface and core fractions were small but consistent: mainly lithogenic metals (Al, and, within a serpentine derived soil, Ni and Cr) showed lower total concentrations in the surface than in the core fraction. Metals originating primarily from atmospheric deposition form two groups. Cadmium, Pb, and Zn usually showed higher total concentrations in the surface fraction whereas Cu, Cr, and Ni showed no uniform trends. In general, lower proportions of the total metal concentration could be extracted by the residual extraction step (mainly bound within silicates) in the surface than in the core fraction. Accordingly, higher proportions could be extracted by the sum of all other steps (bound to cation exchangers, organic matter, and oxides) in the surface fraction, although in the aggregate surface fraction the concentrations of organic matter and oxides as well as the CEC were lower than in the core fraction. The fact that the sorption capacity of the surface is lower than of the core fraction has to be considered for the identification of external metal inputs. Based on these results, a new method to identify external inputs is proposed.     

有机物料对污染土壤上水稻重金属吸收的调控效应

采用重金属污染水稻土开展盆栽试验,研究施用有机碳源、菜籽饼和猪粪对不同水稻(汕优63,简称“SY63”;中浙优1号,简称“ZZY1”)重金属吸收的调控效应.结果表明,在重金属污染土壤上ZZY1具有一定的耐性,相同处理时ZZY1糙米、砻糠、秸秆中重金属含量均低于SY63品种,糙米中Cd含量较SY63低57.5％ ～ 83.8％,Cu含量低37.8％ ～ 69.1％,Zn含量低0.88％ ～ 31.7％,食物链风险较SY63品种低.3种有机物料中,施用菜籽饼使两水稻品种糙米中重金属含量明显低于其他处理;与对照相比,施用菜籽饼使SY63糙米中Cd、Cu和Zn含量降低73.5％、52.6％和32.1％,ZZY1糙米Cd含量降低30.5％.在供试重金属污染土壤上可选择具有一定重金属耐性的水稻品种ZZY1进行粮食生产,同时施用适量的菜籽饼以增强其抵御重金属毒害的能力,降低糙米中Cd、Cu和Zn含量及其食物链污染风险.     

Relationships of Heavy Metals in Natural Lake Waters with Physico-chemical Characteristics of Waters and Different Chemical Fractions of Metals in Sediments

The relationships between heavy metal concentrations and physico-chemical properties of natural lake waters and also with chemical fractions of these metals in lake sediments were investigated in seven natural lakes of Kumaun region of Uttarakhand Province of India during 2003–2004 and 2004–2005. The concentrations of Cr, Mn, Fe, Ni, Cu, Zn, Cd and Pb in waters of different lakes ranged from 0.29–2.39, 10.3–38.3, 431–1407, 1.0–6.6, 5.3–12.1, 12.6–166.3, 0.7–2.7 and 3.9–27.1 μg l^?1 and in sediments 14.3–21.5, 90.1–197.5, 5,265–6,428, 17.7–45.9, 13.4–32.0, 40.0–149.2, 11.1–14.6 and 88.9–167.4 μg g^?1, respectively. The concentrations of all metals except Fe in waters were found well below the notified toxic limits. The concentrations of Cr, Mn, Ni, Cu, Zn, Cd and Pb were positively correlated with pH, electrical conductivity, biological oxygen demand, chemical oxygen demand and alkalinity of waters, but negatively correlated with dissolved oxygen. The concentrations of Cr, Ni, Zn, Cd and Pb in waters were positively correlated with water soluble + exchangeable fraction of these metals in lake sediments. The concentrations of Zn, Cd and Pb in waters were positively correlated with carbonate bound fraction of these metals in lake sediments. Except for Ni, Zn and Cd, the concentrations of rest of the heavy metals in waters were positively correlated with organically bound fraction of these metals in lake sediments. The concentrations of Cr, Mn, Ni, Cu and Zn in waters were positively correlated with reducible fraction of these metals in lake sediments. Except for Cd, the concentrations of rest of the metals in waters were positively correlated with residual fraction and total content of these heavy metals in lake sediments.     

不同种类有机物对污染农田土壤重金属活性的影响

为了解施用不同种类有机物对污染农田土壤重金属行为的影响,布设了田间小区试验,观察研究施用6种不同类型有机物对土壤水溶性重金属和农作物对重金属吸收等的影响。试验设7个处理,分别为对照(不施有机肥)、施新鲜水稻秸秆、新鲜鸡粪、鸡粪堆肥、新鲜猪粪、猪粪堆肥和商品有机肥,动态检测土壤中水溶性重金属含量、田面水中重金属浓度及收获水稻籽粒中重金属含量的变化。结果表明,与不施有机物的对照处理比较,施用各类有机物在试验前期均可明显提高土壤中水溶性重金属和田面水中重金属的含量,总体上以施用新鲜猪粪的最高,其次为新鲜鸡粪,施用商品有机肥的最低。土壤中水溶性重金属含量随试验时间增长逐渐下降。施用各类有机物对水稻籽粒中重金属的积累影响不明显。土壤中水溶性重金属及田面水中重金属含量均与相应的水溶性碳(DOC)浓度呈显著相关性,表明因有机物施用增加土壤中DOC浓度可能是土壤中水溶性重金属含量增加的主要原因;而不同有机物对土壤重金属活性影响的差异可能与有机物本身的分解程度及可释放DOC大小有关。但施用有机物引起的农田土壤水溶性重金属含量的增加是暂时的,对水稻生长后期籽粒中重金属积累的影响不明显。