农田土壤重金属淋洗剂筛选与效应分析

为分析不同淋洗剂在不同淋洗条件下对重金属淋洗效果的影响,采用振荡淋洗法对比研究4种淋洗剂(柠檬酸(CA)、酒石酸(TA)、乙二胺四乙酸二钠盐(EDTA)和氨三乙酸三钠盐(NTA))不同浓度、淋洗时间、pH和固液比对重金属复合污染农田土壤中Pb、Cd、Cu和Zn的淋洗效果及单因素最佳淋洗条件下土壤淋洗前后重金属不同形态含量的变化。结果表明,CA和TA的最佳淋洗浓度为0.3mol/L,EDTA和NTA为0.05mol/L;CA和NTA的最佳淋洗时间为480min,EDTA和TA为720min;4种淋洗剂的最佳淋洗pH均为3,最佳固液比均为1∶20。单因素最佳淋洗条件下,EDTA对土壤重金属去除效果最佳,对Pb、Cd、Zn和Cu的去除率分别为67.4%,61.0%,13.8%和76.0%;NTA效果次之,去除率分别为41.6%,42.4%,9.9%和54.3%。土壤重金属去除率随淋洗剂pH的降低而升高,随固液比的增加而增加,随淋洗剂CA与TA浓度增大而增大。淋洗剂对土壤重金属的解吸动力学曲线符合准二级动力学模型,解吸过程为化学解吸,且解吸反应速率受土壤重金属含量与淋洗剂浓度控制。土壤重金属在淋洗剂作用下的解吸速率为Cd>Pb≈Zn≈Cu。EDTA和NTA淋洗显著降低土壤中Pb、Cd、Zn和Cu铁锰氧化态和有机结合态的含量,CA和TA显著降低Pb、Cd、Zn和Cu铁锰氧化态的含量。淋洗剂对重金属的去除效率为EDTA>NTA>CA>TA。     

EDTA对Cu污染农田土壤的淋洗实验研究

为了解鄂西南地区土壤铜的赋存形态及其污染修复,采用Tessier连续提取法测定土壤铜的赋存形态,采用振荡淋洗法研究了乙二胺四乙酸二钠(EDTA)在提取时间、淋洗浓度、固液比、p H等四个因素作用下对重金属铜(Cu)去除效果的影响。结果表明:农田土壤中铜的赋存形态依次表现为残渣态(4.26 mg kg-1)铁锰氧化物结合态(3.29 mg kg-1)硫化物及有机结合态(2.29 mg kg-1)可交换态(2.10 mg kg-1)碳酸盐结合态(1.63 mg kg-1);在EDTA修复Cu高污染土壤时,单因素实验分析表明当提取时间、淋洗浓度、固液比、p H分别为18 h、0.01 mol L-1、1∶10和7时为最佳实验条件,最佳单因素组合后对Cu的去除率为20.14%,将之应用于农田土壤,重金属Cu的去除率略有降低,可达18.29%。EDTA对土壤Cu处理前后对其赋存形态分析表明,土壤中重金属Cu交换态、碳酸盐结合态和铁锰氧化物结合态去除效果明显,但不能有效去除土壤中有机及硫化物态和残渣态。     

茶皂素对潮土重金属污染的淋洗修复作用

为了探讨茶皂素淋洗修复土壤重金属污染的可行性,该文采用振荡提取和土柱淋洗的方法,研究了茶皂素对污染土壤中重金属的去除作用。结果表明,茶皂素溶液的浓度和土壤的pH值对重金属去除率有明显影响。土柱淋洗试验中,采用质量分数7%茶皂素溶液作淋洗液,pH 5.0±0.1、土液质量体积比1：4为最佳淋洗修复条件,此时,Pb、Cd、Zn、Cu的去除率分别为6.74%、42.38%、13.07%、8.75%,去除率的大小顺序为Cd＞Zn＞Cu＞Pb。茶皂素淋洗能有效去除酸溶态和可还原态的重金属,从而大大降低了重金属的环境风险,同时说明茶皂素用于土壤重金属污染淋洗修复有较大潜力。     

GLDA淋洗参数对污泥中重金属去除效率的影响及其动力学分析

采用GLDA作为淋洗剂对工业污水污泥进行淋洗,确定淋洗的最优参数,为治理工业污泥提供参考依据。通过振荡淋洗研究了GLDA浓度（0.5% ~ 20%）、pH（2 ~ 10）、液固比（10∶1 ~ 80∶1）和淋洗时间（0 ~ 24 h）对污泥中重金属去除率的影响,利用动力学方程对实验数据进行拟合。结果表明,降低pH、增加液固比和延长淋洗时间均可提升重金属的淋洗效率,在pH为2,浓度5%,液固比60∶1,淋洗时间480 min时,GLDA对污泥中的重金属淋洗率达到最优,镍（Zn）、镍（Ni）、镉（Cd）和铬（Cr）的去除率分别为91.21%、76.34%、69.56%和65.01%。准二级动力学方程可以较好的拟合GLDA对4种重金属的淋洗过程,说明重金属淋洗过程以化学淋洗为主。综上所述,在进行淋洗参数优化的基础上,GLDA可用于工业污水污泥中重金属的去除。     

淋洗法修复铬渣污染场地实验研究

铬渣污染场地已经列为我国土壤污染重点治理对象,急需修复铬渣污染土壤的关键技术。本文通过室内模拟实验,采用振荡淋洗的方法研究了水、EDTA、EDDS、柠檬酸、草酸、盐酸、磷酸、环糊精和十二烷基苯磺酸钠等淋洗剂对铬渣污染场地Cr的淋洗效果,探讨了淋洗剂浓度、淋洗时间、土水比、淋洗次数等对淋洗效果的影响,并研究了不同淋洗剂复合对Cr的淋洗效果以及不同浓度柠檬酸淋洗前后重金属形态的变化。结果表明：水、EDTA、EDDS、环糊精和十二烷基苯磺酸钠对Cr的去除率较低,柠檬酸在浓度为0.5mol·L-1、土水比1：20、反应时间为24h、淋洗次数为2次的条件下可以达到最佳淋洗效果,Cr的去除率可达到82.8%;SDBS、EDTA与柠檬酸单独组合顺序或者混合淋洗,都没有增加柠檬酸对Cr的去除率。重金属形态分析表明,柠檬酸淋洗有效地改变了Cr的形态从而达到较高的修复效果。当柠檬酸浓度小于0.25mol·L-1时,对铬的去除主要以C（rⅥ）为主;当柠檬酸浓度大于0.25mol·L-1时,对铬的去除主要以C（rⅢ）为主。本文的研究结果为异位淋洗修复铬渣污染土壤提供理论依据。     

四种生物质材料水浸提液淋洗镉污染土壤及其废水处理研究

采用八角金盘、枳椇子、空心莲子草和赤胫散4种生物质材料的水浸提液进行Cd污染土壤的批量淋洗试验,结果表明:4种生物质材料浸提液对污染土壤中的Cd均有一定去除作用,且差异显著(P0.05)。4种材料的Cd淋洗率随其浸提液浓度的增加呈对数、幂函数或倒数变化;赤胫散的Cd淋洗率随淋洗液p H增加呈线性上升,而其余3种生物质材料Cd淋洗率则随淋洗液p H增加呈线性、倒数或幂函数下降。[0]时间和淋洗量的关系以二级动力学模型(R~20.994)和Elovich方程(R~20.803)拟合效果较优。液土比增加能够促进Cd的淋洗。淋洗3次后,八角金盘、枳椇子、空心莲子草和赤胫散的Cd累积淋洗率分别达到78.31%、53.88%、47.59%和27.98%。此外,采用4种生物质材料浸提液淋洗后,土壤可交换态、碳酸盐结合态和铁锰氧化物结合态Cd含量显著降低(P0.05),土壤钾素含量略有增加,其他养分及有机质则下降。浸提残渣能够有效吸附淋洗废水中的Cd,用其处理后的废水达到国家排放标准。由此,兼顾Cd的淋洗率及对土壤性质的影响,八角金盘是一种修复Cd污染土壤的潜力材料。     

工业废弃地多金属污染土壤组合淋洗修复技术研究

采用批量淋洗实验方法,对比了采用人工螯合剂乙二胺四乙酸二钠盐(EDTA-Na2)和天然有机酸草酸(oxalic acid,OX)对工业废弃地污染土壤中重金属的去除效果,并采用不同浓度草酸和EDTA组合的两步淋洗法研究多金属污染土壤的最佳淋洗方式。结果表明,EDTA淋洗剂对土壤中Zn、Pb、Cu、Ni去除效果较好,而对Cr去除效果较差,实验条件下,EDTA对金属的去除率并未随着浓度增加而增加;相反,草酸对Cr去除效果较好,且去除率随着淋洗剂浓度的增加而增加,而对Zn、Cu、Ni的去除效果随着淋洗剂浓度增加而降低,对Pb的去除率非常低;采用先以0.20 mol L-1草酸提取2 h,再以0.01 mol L-1EDTA提取2 h的两步淋洗法可以达到对多金属同时去除,且对Zn、Cu、Cr、Ni的去除率明显高于单用草酸和EDTA,总去除率分别为Zn 75.21%、Pb 21.30%、Cu 59.81%、Cr 60.72%和Ni 62.10%,更为有意义的是两步淋洗法对非残渣态金属去除效果分别高达Zn 91.93%、Pb 57.75%、Cu 75.33%、Cr 73.94%、Ni 77.99%。利用不同化学淋洗剂对金属去除能力的差异进行组合的多步淋洗法是一种较为高效的去除工业废弃地污染土壤中重金属的化学淋洗修复方法。     

酶强化茶皂素修复重金属污染土壤的研究

以多种重金属污染的土壤为材料,研究了生物酶、茶皂素和两者组合等处理方式对重金属的去除效果。结果表明:酶和茶皂素对土壤中重金属有良好的去除效果,起到协同、互补作用。采用响应面法优化反应条件,得到p H值4.0、反应温度35℃、茶皂素溶液和酶溶液配比3∶1的最佳淋洗修复条件,此时Cd、Cr、Cu、Ni、Zn去除率分别为88.87%、81.64%、43.33%、47.16%、62.03%,去除率的大小顺序为CdCrZnNiCu。酶与茶皂素组合淋洗液能有效去除酸提取态、可还原态和可氧化态的重金属,表明组合液在重金属污染土壤修复方面具有较好的应用前景。     

不同pH值混合螯合剂对土壤重金属淋洗及植物提取的影响

为了得出混合螯合剂（MC）淋洗去除重金属的最佳pH值以及对后续植物提取重金属的影响,用Ca(OH)2将pH值为2.75的MC提高至pH值5、7和9,对重金属污染土壤进行了盆栽淋洗试验,而后种植东南景天（Sedum Alfredii）,测定淋出液及植物重金属含量。另外,通过浸提试验研究了含有不同阳离子的MC对重金属淋洗效果的影响。结果表明,pH值为5和7的MC显著提高了Cd、Pb和Cu的淋出率。与Na+、K+离子相比,Ca2+的存在能够提高MC对重金属的淋洗去除。pH值7和9的MC淋洗土壤后提高了东南景天的生物量,但是降低东南景天中Cd和Zn的浓度,导致其植物提取率低于无淋洗剂对照。在化学淋洗+植物提取联合技术中,Cd和Zn主要靠植物提取去除,植物提取率分别可达土壤Cd的30%～40%和土壤Zn的6.5%～6.9%;而Pb和Cu主要靠混合螯合剂淋洗去除,去除率分别为2.3%～2.6%和1.6%～2.0%。综合来说,如果需要同时去除Cd、Zn、Pb和Cu,降低土壤重金属有效态含量,用pH值9的MC淋洗土壤联合植物提取较为合适。     

4A沸石对土壤铅浓度及形态的影响

采用室内土柱淋洗培养法研究了4A沸石对土壤重金属铅浓度与形态变化的影响。结果表明,4A沸石对土壤重金属铅具有一定的钝化效果,可有效抑制土壤铅的迁移及生态有效性。未添加4 A沸石土壤经过淋洗培养后土壤铅的可交换态、碳酸盐结合态和铁锰氧化态铅浓度上升,有机结合态和残渣态铅浓度显著下降,37 d淋洗培养后土壤中铅以可交换态为主,所占比例为52.9%;而添加4 A沸石可有效降低土壤可交换态、碳酸盐结合态和铁锰氧化态铅的浓度,土壤铅以残渣态为主,其占比例44.8%～59.2%。     

Mixed chelators of EDTA,GLDA, and citric acid as washing agent effectively remove Cd,Zn, Pb,and Cu from soils

Purpose

Soil washing with chelators is a viable treatment alternative for remediating multi-contaminated soils. The aim of this study was to investigate the removal efficiencies of Cd, Zn, Pb, and Cu in alkaline and acid multi-metal-contaminated soils by washing with the mixed chelators (MC).

Materials and methods

The batch experiments were carried out to evaluate the removal efficiencies of heavy metals in contaminated soils by the MC with different molar ratios of EDTA, GLDA, and citric acid, and evaluated the washing factors, including contact time, pH, MC concentration, and single and multiple washings at the same MC dose, on the removal efficiencies.

Results and discussion

Results showed that the removal efficiencies for Cd, Zn, Pb, and Cu by the MC (the molar ratio of EDTA, GLDA, and citric acid was 1:1:3) were as much as those of the only EDTA washing from both soil at the same application dose of total chelators; moreover, the application dose of EDTA decreased by 80%. For the alkaline-contaminated soil, the removal efficiencies of Cd, Zn, Pb, and Cu decreased with the increasing of the solution pH, which was opposite to acid-contaminated soil. This was attributed to that the metal-ligand complex could be obviously re-adsorbed on the soil surface sites, particularly in low pH values. The removal efficiencies of Cd, Zn, Pb, and Cu depended on MC concentration. A higher MC concentration led to a more effective removal of Cd, Zn, Pb, and Cu in alkaline-contaminated soil; however, their changes were slightly increased in acid-contaminated soil. At the same dose of MC, single washing with higher MC concentration might be favorable to remove heavy metals, moreover, with much less wastewater generation.

Conclusions

The MC (the molar ratio of EDTA, GLDA, and citric acid was 1:1:3) may be a useful, environmentally friendly, and cost-effective chelators to remediate heavily multi-metal-contaminated soil.

     

Feasibility of a counter-current extraction procedure for the removal of heavy metals from contaminated soils

Effective remediation and sanitation technologies for soils contaminated with heavy metals are limited. We investigated the feasibility of a counter-current metal extraction procedure for the removal of selected heavy metals (Cd, Cu, Ph, and Zn) from two contaminated soils. The process involved a decarbonation (removal of carbonates), acid solubilisation, washing, and liming step. Results from batch equilibration experiments simulating the counter-current process showed more than 85% of the Cd present to be removed. Removal efficiencies for Cu and Pb were limited to approximately 15%, this mainly due to resorption of these elements during the decarbonation step. As most Zn was found to be present in a more difficult acid-extractable solid phase, its extractability accounted for only 25%. While reaction (pH) conditions of both decarbonation and solubilisation determined removal efficiencies, washing the extracted soil with deionized water only slightly increased the amount of metals removed. Metal distribution among solid phases — exchangeable, carbonate, reducible, organically bound, and residual — was affected by the different treatments. The amount of metals contained in the exchangeable and residual fractions determined their extractability. Except for Cu, the reducible and organically bound fractions were less important. After solubilisation 13 to 70% of the metals were present in an exchangeable solid phase. This implicates that washing the solubilized soil with a salt may increase the extractability of metals, especially for Zn and Pb. Based on our results the process is critically evaluated and possibilities for optimization formulated.     

工业和农业污染稻田土壤重金属的赋存形态及水稻吸收运移比较

[目的]稻田土壤重金属污染是当前农产品安全生产关注的重要问题.本文比较分析工业和农业污染源稻田土壤重金属的赋存形态及水稻吸收运移,以期为稻田土壤重金属污染控制提供参考.[方法]在长江中下游地区调查选取工业源和农业源重金属污染稻田各27块,在水稻成熟期使用抖根法采集根际土壤及水稻根系和籽粒样品,采用Tessier七步提取...     

冻融-化学淋洗法协同修复重金属Cd和Pb污染黏性土

针对质地黏重、低渗透性黏性土的淋洗效率低下,该文提出冻融协同化学淋洗的修复方案,并以某冶炼厂受Cd、Pb污染场地黏性土为研究对象,选用乙二胺四乙酸二钠(ethylene diaminetetraacetic acid disodium salt,EDTA)为淋洗剂,进行了冻融-淋洗土柱的实证试验。结果表明,土体的反复冻融(冻胀-吸水、融沉-排水)破坏土体颗粒原有结构,有助于淋洗液与污染物充分接触,淋洗效果明显,经7次冻融后,Cd、Pb去除率分别达到77.24%、37.78%。采用改进的BCR(European Communities Bureau of Reference)连续提取法分析了土柱中Cd、Pb的赋存特征,经7次冻融后,土壤中弱酸提取态、可还原态、残渣态结合的Cd质量分数较淋洗前分别降低了41.46%、63.02%、26.33%,而土壤中可还原态和残渣态结合的Pb质量分数分别降低了32.32%、67.36%。冻融协同化学淋洗修复技术的淋洗剂用量远小于传统淋洗法,为今后利用寒区冻融交替现象,大规模对季冻区重金属污染土壤的异位修复提供了新的思路。     

重金属污染土壤清洗导致几种营养元素流失的研究

通过HCl、柠檬酸、EDTA这3种提取剂对Pb、Cd、Cu、Zn污染土壤的漫提试验，研究了土壤清洗洗脱重金属的效果，并探讨了土壤清洗导致K、Ca、Mg、Fe、Mn这几种营养元素的流失和有效性的改变。试验结果表明，土壤清洗能有效地洗脱土壤中的Ph、Cd、Cu、Zn，伺时也造成了土壤中K、Ca、Mg、Fe、Mn的流失，降低了其中部分营养元素的有效性。EDTA对重金属的洗脱能力大于HCl和柠檬酸。HCl漫提造成的K、Ca、Mg的流失量大于柠檬酸和EDTA，柠檬酸浸提造成的Fe流失量大于HCl和EDTA，EDTA漫提造成的Mn流失量大于HCl和柠檬酸。HCl和柠檬酸浸提降低了土壤K、Ca、Mg的有效性EDTA浸提提高了土壤K的有效性。降低了土壤Ca的有效性。在高浓度时（50mmol／L），EDTA显著地降低了土壤Mg的有效性。HCl漫提导致土壤K的有效性下降比柠檬酸严重，高浓度的EDTA浸提导致土壤Ca的有效性下降比HCl和柠檬酸严重。HCl、柠檬酸、EDTA浸提都能提高土壤中Fe的有效性．且EDTA的效应大于其它2种萃取剂；在低浓度时，3种提取剂都能提高土壤中Mn的有效性，且以柠檬酸的作用最为明显，当提取剂浓度增加时，Mn的有效性有所回落。     

Removal of trace and major metals by soil washing with Na<Subscript>2</Subscript>EDTA and oxalate

Background, aim, and scope  

Various metals such as cationic metals (Cu, Pb, Zn) and anionic metals (As, Cr) often coexist in real soils, and normal soil washing techniques for the removal of cationic metals with a single-washing reagent make it rather difficult to simultaneously remove all of them. Oxalate could effectively remove anionic As and EDTA could effectively remove the cationic metals, so it was possible to remove all coexisting cationic and anionic metals by washing with the combination of Na₂EDTA and oxalate. The objective of this study was to (1) discuss the possibility of removing five metals, As, Cd, Cu, Pb, and Zn, effectively from the soil by washing with Na₂EDTA-combined oxalate; (2) optimized through the consecutive washing.     

开封黑岗口引黄灌区稻麦轮作下农田土壤剖面重金属分布特征

引黄灌区是我国重要的农业生产基地,其土壤重金属赋存状况直接关系到农业的可持续发展。本研究以黑岗口引黄灌区开封北郊稻麦轮作下农田土壤为研究对象,采集了耕作层(0~15 cm与15~30 cm)与剖面(0~100 cm)土壤样品,对其土壤剖面主要性质与重金属Pb、Cd、Cu和Zn的积累特征进行了分析。结果表明:(1)长期引黄灌溉及稻麦轮作下,开封北郊农业土壤主要性质在剖面上表现出明显的分异特征:总有机碳(TOC)与全氮(TN)含量主要分布在耕作层土壤,而30 cm以下的土层其含量明显降低;全磷(TP)含量在各土壤层中无明显差异;在部分土壤剖面中CaCO3呈现出明显的淀积层。(2)耕作层(0~30 cm)土壤中重金属Pb、Cu、Zn的含量与研究区背景值相当,而Cd含量显著高于背景值。除少部分剖面含量超标外,Cd、Pb、Cu、Zn的平均含量均未超出WHO限值,且远低于我国农业土壤环境质量标准。因子分析源解析表明:引黄灌区土壤中Pb、Cu和Zn具有相似的来源和迁移特性,而Cd的来源和迁移特性具有特殊性,它可能与当地的化肥施用等农业活动有关。(3)土壤剖面中Cu和Zn具有明显的表聚现象,Pb的表聚作用不明显,而Cd在剖面各层土壤含量具有较大变异性,这与重金属的自身属性、土壤剖面性质和当地的耕作条件有较大相关性。(4)Cu和Zn在土壤剖面主要以有机结合态和残余态形式存在;Pb的残余态、有机态以及铁锰氧化态含量也较高,且Pb的全量与有机结合态含量百分比变化呈现出一定的相似性;而Cd具有较高的碳酸盐结合态和离子交换态,表明Cd在土壤中具有较强的移动性,预示Cd的潜在健康风险较高。     

泉州走马埭典型土壤重金属的赋存形态分析

采用改进的Tessier连续萃取方法研究了泉州走马埭国家农田示范保护区典型土壤中重金属(Cr、Ni、Cu、Zn、Cd、Pb)的化学形态分布,通过土壤重金属的赋存形态分析比较了6种重金属的生物可利用性。研究结果表明,土壤中不同重金属元素化学形态分布具有不同的特点:Cr和Ni主要以残渣态存在,其余形态所占的比例很小;Cu以残渣态含量最高,碳酸盐结合态含量最低;Zn以残渣态为主,可交换态含量最低;Cd以可交换态和碳酸盐结合态为主,水溶态含量最低;Pb以残渣态和铁锰氧化物结合态为主,水溶态含量最低。土壤中除Cd外,Zn、Cu、Cr、Pb、Ni在正常自然条件下相对比较稳定。     

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%%.