Immobilization of lead in anthropogenic contaminated soils using phosphates with/without oxalic acid

Understanding the effects of oxalic acid (OA) on the immobilization of Pb(II) in contaminated soils by phosphate materials, has considerable benefits for risk assessment and remediation strategies for the soil. A series of phosphate amendments with/without oxalic acid were applied to two anthropogenic contaminated soils. We investigated the immobilization of Pb(II) by KH₂PO₄, phosphate rock (PR), activated phosphate rock (APR) and synthetic hydroxyapatite (HAP) at different phosphate:Pb (P:Pb) molar ratios (0, 0.6, 2.0 and 4.0) in the presence/absence of 50 mmol oxalic acid/kg soil, respectively. The effects of treatments were evaluated using single extraction with deionized water or CaCl₂, Community Bureau of Reference (BCR) sequential extraction and toxicity characteristic leaching procedure (TCLP) methods. Our results showed that the concentration of water extractable, exchangeable and TCLP-Pb all decreased with incubation time. The concentration of water-extractable Pb after 120 days was reduced by 100% when soils were amended with APR, HAP and HAP + OA, and the TCLP-Pb was <5 mg/L for the red soil at P:Pb molar ratio 4.0. Water-soluble Pb could not be detected and the TCLP-Pb was <5 mg/L at all treatments applied to the yellow-brown soil. BCR results indicated that APR was most effective, although a slight enhancement of water-soluble phosphate was detected at the P:Pb molar ratio 4.0 at the beginning of incubation. Oxalic acid activated phosphates, and so mixing insoluble phosphates with oxalic acid may be a useful strategy to improve their effectiveness in reducing Pb bioavailability.     

磷矿粉和腐熟水稻秸秆对土壤铅污染的钝化

通过室内培养试验研究了磷矿粉和草酸活化磷矿粉与腐熟水稻秸秆配施及不同水分处理对土壤基本性质和铅形态变化的影响.结果表明,施用3种钝化材料都能提高土壤p H值、有效磷、交换性钙、阳离子交换量,其中活化磷矿粉效果最佳;与保持70%田间持水量相比,淹水处理增加p H、提高交换性钙效果更好,但有效磷较低.施用3种钝化材料能使可交换态铅减少,促进其向生物难利用态转变,活化磷矿粉对铅的钝化效果优于未活化的磷矿粉,两者最高分别可使交换态与对照相比降低40.3%和24.2%,且钝化效果与施用量呈正相关;腐熟水稻秸秆能增加土壤有机结合态铅;淹水处理可促使交换态铅向铁锰氧化物和残渣态转化.     

不同阴离子对水溶性磷酸盐稳定污染土壤中重金属的影响

在重金属污染土壤中加入磷酸盐是稳定重金属的有效方法.本研究的目的是探讨不同阴离子对水溶性磷酸盐稳定污染土壤铅、镉和锌的影响.在重金属复合污染土壤(全铅、镉和锌的含量分别为2337、21.4和391 mg·kg^-1)中按P:Pb=2:1 (mol:mol)加入磷酸二氢钙,之后按P:阴离子=3:1或3:2 (mol:mol)加入盐酸、氯化钠、硫酸、硫酸钠或氟化钠,并设置只加磷酸盐、不加其它试剂的对照,培养55 d,之后测定土壤性质.结果表明,与对照相比,HCl处理、2HCl处理、NaCl处理和2NaCl处理土壤DTPA-Pb含量下降比例依次为5.72%、9.29%、6.38%和8.80%(p<0.05),加入硫酸、硫酸钠的处理土壤DTPA-Pb含量与对照无显著差异(p>0.05),而加入氟化钠的处理升高4.70%(p<0.05).加入盐酸或氯化钠的处理土壤镉有效性显著高于对照(升高5.24%~12.8%)(p<0.05),其它处理对DTPA-Cd含量无显著影响(p>0.05).各处理对土壤DTPA-Zn含量和pH影响较小,但均引起土壤电导率明显升高.以上结果表明,氯离子可促进水溶性磷酸盐对土壤铅的稳定,但可促进镉有效性.氯磷酸铅的生成是加氯情况下磷酸盐稳定铅的重要机制.     

钙、氯对磷酸盐稳定污染土壤中铅的促进作用研究

为探讨促进磷酸盐稳定污染土壤中铅的方法,在全铅含量为517 mg·kg-1的铅冶炼污染土壤中加入5 mmol·kg-1磷酸盐,同时加入10mmol·kg-1硝酸钙或5 mmol·kg-1氯化钾,在15%或30%的含水率下培养40 d,之后种植黑麦草.结果表明,与单独施用磷酸盐相比,采用磷酸盐与钙、氯结合或增加培养期间的土壤含水率后,土壤DTPA-Pb含量下降3.92%~26.1%;对于同一添加剂处理,培养期间土壤含水率从15%增加到30%,土壤有效铅(DTPA-Pb)含量下降8.83%~24.4%.增加土壤含水率后,土壤有效磷(Olsen-P)含量均显著升高(p0.05).土壤铅的EXAFS分析表明,与未施用磷酸盐的对照相比,土壤中加入磷酸盐后矿物态铅的比例由57%上升至81%,加施钙、氯或增加土壤含水率后,多数处理矿物态铅的比例有所下降,而有机结合态铅比例上升.与对照相比,污染土壤中施用磷酸盐后,植物产量大幅增加,但施用钙、氯或增加培养期间含水率后,部分处理植物产量有所下降.以上结果表明,在铅冶炼污染土壤中加入磷酸盐时,加入钙、氯或者增加土壤含水率均有利于铅的稳定,但以上措施可能对植物生长产生不利影响.     

磷酸盐、腐殖酸与粉煤灰联合钝化处理模拟铅镉污染土壤

本研究利用过磷酸钙、腐殖酸、粉煤灰及其复配组合钝化处理人工模拟Pb、Cd污染土壤,并采用CaCl_2浸取法、三乙三胺五乙酸(DTPA)浸取法以及BCR形态分级实验评价钝化效果,利用X射线衍射仪(XRD)和扫描电子显微镜能谱(SEMEDS)分析土壤表面微观形态与结构,进一步探究其钝化机制.结果表明,除了腐殖酸单一处理,其他不同钝化处理均能降低土壤CaCl_2和DTPA提取态Pb、Cd含量,其中先添加过磷酸钙和腐殖酸,然后再添加粉煤灰的联合处理实验组效果最佳.土壤pH值与CaCl_2、DTPA提取态Pb含量存在微弱的正相关关系,与CaCl_2、DTPA提取态Cd含量存在负相关关系,速效磷含量与二者都存在显著的负相关关系,说明速效磷含量是控制土壤Pb、Cd活性的主要因素.施用磷酸盐、腐殖酸和粉煤灰可以促进Pb、Cd由活性较高的弱酸提取态向活性低的残渣态转化,从而有效降低Pb、Cd的迁移能力.XRD和SEM-EDS分析表明,过磷酸钙钝化重金属的机制主要是通过离子交换作用将重金属转化为难溶的Ca-重金属混合磷酸盐,3种钝化剂联合作用机制主要通过溶解/沉淀以及表面吸附作用将重金属转化为稳定的磷酸铅沉淀[Pb_3(PO_4)_2]或者混合重金属矿物[PbFe_3(SO_4)(PO_4)(OH)_6],从而有效钝化重金属.     

外源添加磷和有机酸模拟铅污染土壤钝化效果及产物的稳定性研究

有机酸可提高土壤磷有效性,且能影响对重金属的固定,其在磷活化和重金属钝化方面具有非常复杂的功能.本研究以模拟铅污染土壤为对象,外源添加磷和柠檬酸,采用BCR三步连续提取法、0.01 mol·L-1CaCl2提取和毒性淋溶提取法(TCLP)评价有机酸存在下磷对模拟铅污染土壤的钝化效果;以苹果酸、NaNO3溶液为解吸剂探讨磷-柠檬酸-铅体系的稳定性.结果表明,无柠檬酸时,酸提取态Pb含量随磷浓度的增加而降低;加磷100 mg·kg-1、400 mg·kg-1时,酸提取态Pb含量随柠檬酸浓度增加而显著增加.残渣态Pb与酸提取态Pb的变化趋势相反,说明磷能降低土壤铅的生物有效性,柠檬酸则作用相反.有机酸浓度一定时,随磷浓度增加,0.01 mol·L-1CaCl2提取和TCLP提取的铅含量均呈降低趋势,表明磷具有钝化铅污染土壤的效果;但磷浓度一定时,它们提取铅含量随柠檬酸浓度增加表现出相反的变化趋势.土壤铅的解吸率随苹果酸浓度增加、pH值减小、离子强度增加而提高,且只添加磷处理的土壤铅解吸量较添加磷和柠檬酸共同处理的土壤少,前者钝化的铅稳定性更高.     

蜂窝煤灰渣对酸性和石灰性污染土壤中重金属的稳定研究

本研究的目的是探讨不同洗涤蜂窝煤灰渣在不同酸碱性土壤中对重金属的稳定效果.在酸性的淳安土壤(铅、镉、铜、锌污染)和石灰性的济源土壤(铅、镉污染)中以4%用量加入灰渣,培养60 d后测定土壤性质.结果表明,灰渣对淳安土壤pH和EC值的增加效果要大于对济源土壤的影响.原灰渣、硫酸洗灰渣和盐酸洗灰渣加入淳安土壤均可显著降低土壤DTPA提取态铅、镉、铜和锌的含量(p0.05),灰渣对济源土壤DTPA提取态重金属的含量影响较小.对于济源土壤,硫酸洗和盐酸洗灰渣与磷酸盐结合施用后土壤DTPA-Pb含量分别下降20.9%和33.1%.对于淳安土壤,加入3类灰渣后土壤DTPA-Pb含量下降26.8%~41.8%;对于淳安土壤,不论是单独施用还是与磷酸盐结合施用,硫酸洗灰渣对铜、锌稳定效果均强于盐酸洗灰渣.以上结果说明,蜂窝煤灰渣在酸性土壤中对重金属有更强的稳定作用,硫酸洗灰渣和盐酸洗灰渣对土壤重金属的稳定作用存在差异.     

淋洗修复后残留土壤中重金属的再释放及环境风险

淋洗修复后残留土壤中的重金属会因外界环境的改变可能会发生再释放过程而使环境风险增加,淹水是农田土壤常见的管理模式之一,然而淹水介导的土壤环境条件的改变对淋洗修复后残留农田土壤中重金属的再释放和环境风险的变化影响尚不清楚.因此,本研究开展了持续淹水培养（180 d）对经柠檬酸（CA）、EDTA、FeCl₃和HCl淋洗修复后残留土壤中Cd、Pb和Zn的有效性、形态分配和环境风险的影响研究.结果表明随着培养时间的延长,经CA、EDTA和HCl淋洗后土壤中有效态Cd含量呈先增加后减少的趋势,有效态Pb含量增加,有效态Zn含量减少.经FeCl₃淋洗后土壤中有效态Cd、Pb和Zn含量随培养时间延长而增加.形态分析结果表明,淹水会使土壤E_h降低而致使铁锰氧化物的溶解,因此导致可还原态Pb含量向弱酸提取态Pb转移是有效态Pb含量增加的原因;土壤弱酸提取态Cd含量变化与土壤有效态Cd含量变化基本一致;淹水对淋洗修复后Zn形态的影响较小.基于改进的潜在生态风险指数法评价结果表明淹水使CA、EDTA和HCl淋洗后土壤Cd、Zn环境风险和重金属环境总风险减少,使Pb的环境风险增加.淹水后FeCl₃淋洗后土壤Cd、Pb和Zn环境风险及重金属环境总风险增加.由于FeCl₃淋洗后的土壤重金属污染状况较低且环境总风险（低风险）明显小于其它3种淋洗剂淋洗的土壤,因此,FeCl₃可成为Cd-Pb-Zn复合污染土壤的淋洗剂选择,但是需关注其淋洗修复后残留土壤中重金属的再释放并采取调控措施.本研究结果可为农田重金属污染土壤合适淋洗剂的选择和淋洗法修复重金属污染农田土壤的效果评估提供更为合理的指导思路.     

Field demonstration of in situ immobilization of soil Pb using P amendments

A long-term field-scale demonstration project on the feasibility of using P to immobilize Pb in a Pb-contaminated urban soil was conducted. Phosphate was applied at an average rate of 3040 mg P/kg soil based on a P/Pb molar ration of 4.0, with four treatments: T₀, no P application; T₁, H₃PO₄ only; T₂, 1/2 H₃PO₄+1/2 CaH₂PO₄; and T₃, 1/2 H₃PO₄+1/2 phosphate rock. Soil samples were collected and analyzed 220 days after the P applications. For all P treatments, toxicity characteristic leaching procedure (TCLP) extractable Pb levels in surface soils (0-10 cm) were reduced to below 5.0 mg Pb/l, with T₂ also effective in reducing the TCLP Pb level in subsurface soils (10-30 cm, <4.63 mg/l). Sequential extraction analysis indicates that P was effective in transforming soil Pb from non-residual fractions to a residual fraction. Such a transformation was mainly through dissolution of Pb associated with carbonate fraction and precipitation of pyromorphite-like minerals, which were confirmed using X-ray diffraction (XRD). Among these three treatments, T₃ was the most effective in reducing Pb mobility and minimizing P and Pb leaching in the soil. Our research clearly demonstrates that P amendments were effective in immobilizing Pb in contaminated soil.     

Colonization of Penicillium oxalicum SL2 in Pb-contaminated paddy soil and its immobilization effect on soil Pb

Penicillium oxalicum SL2 (SL2) is a previously screened Pb-tolerant fungus that can promote crops growth. The relationship between SL2 colonization and Pb immobilization was studied to provide a theoretical basis for microbial remediation of Pb-contaminated paddy soil. In this study, green fluorescent protein (GFP) labeled SL2 was inoculated into different Pb-contaminated paddy soils (S1-S6). The Pb extracted from the soil by HNO₃, EDTA and CaCl₂ were used to characterize the available Pb. The results showed that the colonization of SL2 was divided into lag phase (0-7 days), growth phase (7-30 days), and mortality phase (30-90 days). SL2 colonized well in sandy soils rich in clay and total phosphorus with initial pH of 4.5-7.0. In addition, SL2 increased soil pH and decreased soil Eh, which was beneficial to immobilize Pb. In different soils, the highest percentages of CaCl₂-Pb, EDTA-Pb, and HNO₃-Pb immobilized by SL2 were 34.34%-40.53%, 17.05%-20.11%, and 7.39%-15.62%, respectively. Pearson correlation analysis showed that the percentages of CaCl₂-Pb and EDTA-Pb immobilized by SL2 were significantly positively correlated with the number of SL2 during the growth phase. SL2 mainly immobilized Pb in the growth phase and a higher peak number of SL2 was beneficial to the immobilization of Pb.     

低分子有机酸对土壤中Cu化学形态的影响

向石英砂岩坡积物发育的红壤中添加系列浓度CuSO4模拟土壤Cu污染,然后加入不同浓度的低分子量有机酸培养,采用改进的BCR连续提取法评价低分子有机酸对重金属Cu形态的影响.结果表明,对不同程度的Cu污染(Cu 0～400mg·kg-1)土壤,随着有机酸添加浓度的升高,最具活性的弱酸溶解态Cu含量均有不同程度的提高,土壤重金属Cu得到活化;Cu活化效果随柠檬酸浓度升高而升高,随酒石酸和草酸浓度升高呈先上升后基本不变趋势;整体活化效果是柠檬酸>酒石酸≈草酸.可还原态Cu随着有机酸浓度的增加而减少,其中添加柠檬酸的处理减少最明显.当有机酸浓度为10 mmol·kg-1、20 mmol·kg-1时,酒石酸和草酸、柠檬酸活化Cu效果分别达到最优.     

氯和磷对土壤中水溶-可交换态铅的影响

在实验室培养条件下研究了氯离子(C1-)对含磷物质KH2PO4降低污染土壤中铅毒作用的影响.结果表明,在铅锌矿污染土壤中添加KH2P04显著降低了土壤中铅(Pb)的水溶-可交换态含量,降低幅度为92.0%-95.1%,显著降低了铅的生物有效性.数据统计分析表明, KH2PO4用量在P/Pb摩尔比为0.6时已足够修复土壤的铅毒,并且在此磷添加量水平时,加氯与不加氯比较,显著降低了土壤中Pb的水溶-可交换态含量,说明了添加氯对含磷物质降低铅毒有促进作用运.用Visual MINTEQ模型模拟计算的结果表明,添加磷和氯处理土壤后,土壤中Pb的活度主要受P的控制,尤其是磷氯铅矿[pyromorphite, Pb5(PO4)3 Cl]沉淀.在使用含磷物质修复铅污染土壤技术时,添加适量的氯,以达到最佳修复效果.     

不同磷源对土壤镉有效性的影响

本研究采用湖北省具有代表性的黄棕壤和潮土进行室内培养试验,研究了5种磷源和5个施磷量（0、0.1、0.2、0.4、0.8g.kg-1,以每kg土中有效态P2O5含量计）对土壤镉（Cd）有效性的影响.结果表明,培养8周后,随着磷酸氢二铵（DAP）、磷酸二氢铵（MAP）和过磷酸钙（SSP）施入量的增加,两种土壤的pH均显著...     

Screening hydroxyapatite for cadmium and lead immobilization in aqueous solution and contaminated soil: The role of surface area

Hydroxyapatite (HAP) has been widely used to immobilize many cationic metals in water and soils. The specific reason why an increase in the surface area of HAP enhances cadmium (Cd) uptake, but has no effect on lead (Pb) uptake, is not clear. The aim of this study was to determine the factors causing the differences in sorption behavior between Cd and Pb by evaluating HAPs with different surface areas. We synthesized HAPs with two different surface areas, which were characterized by X-ray diffraction, N₂ adsorption, and scanning electron microscopy, and then evaluated them as sorbents for Cd and Pb removal by testing in single and binary systems. The sorption capacity of large surface area HAP (1.85 mmol/g) for Cd in the single-metal system was higher than that of small surface area HAP (0.64 mmol/g), but there were no differences between single- and binary-metal solutions containing Pb. After the Cd experiments, the HAP retained a stable structure and intact morphology, which promotes the accessibility of reactive sites for Cd. However, a newly formed precipitate covered the surface and blocked the channels in the presence of Pb, which reduced the number of potential adsorption sites on HAP for Cd and Pb. Remediation experiments using Cd- and Pb-contaminated soil produced similar results to the solution tests. These results indicate that alterations of the structure and morphology during the reaction is an important factor influencing metal sorption to HAP.     

针铁矿-富里酸复合材料对铅镉污染土壤的钝化修复性能

珠三角地区作为粤港澳大湾区的重要经济区域,工矿企业多,土壤重金属污染状况较为严重,且多以铅镉复合污染为主,研发安全高效的重金属修复材料与技术对保障区域环境质量和人居安全具有重要意义.本文拟采用钝化修复技术,以南方红壤中典型矿物针铁矿为主体,制备了针铁矿-富里酸复合材料,并将其应用于铅镉复合污染土壤的钝化修复.结果表明,复合材料中富里酸所占的质量分数越高,对铅镉钝化作用效果越好;土壤中铅镉的钝化率(IE)随钝化时间的延长而增加,并趋于稳定;钝化修复后可交换态及碳酸盐结合态Pb含量降低,残渣态Pb含量增加,土壤中Cd可交换态含量降低,铁锰氧化态及残渣态含量显著增加;钝化修复后土壤CEC、速效钾及铵态氮含量均有所提高;综合评价认为针铁矿-富里酸复合材料应用于红壤铅镉钝化修复有效可行.     

磷酸盐对铅镉复合污染土壤的钝化修复研究

通过模拟实验,研究磷酸二氢钾、磷酸二氢钙和磷酸二氢铵3种磷酸盐对铅镉复合污染土壤的钝化效果,采用重金属形态分析和X-射线衍射法(XRD)探讨了钝化剂的修复机制。结果表明:3种磷酸盐处理可使土壤TCLP提取态Pb、Cd含量显著降低,其中磷酸二氢钙钝化效果最好,且随着投加量的增加,在n(P)/n(Pb+Cd)=5∶1时,钝化效率最高,对Pb、Cd的钝化率分别达到69.81%、35.18%。施加磷酸盐可使污染土壤中Pb、Cd从可交换态和碳酸盐结合态向残渣态转化,显著降低Pb、Cd的生物可利用性。X-射线衍射仪(XRD)检测发现,钝化后的土壤中有羟基磷铅矿、磷酸铅、磷酸镉等矿物晶体生成,表明3种磷酸盐对土壤中铅镉的钝化机理主要是生成难溶性磷酸盐沉淀和羟基磷铅镉矿物。     

新型杂化材料钝化修复镉铅复合污染土壤的效应与机制研究

采用盆栽实验,研究了新型杂化材料及其与磷酸盐复配使用对镉铅复合污染土壤的钝化修复效果,并通过重金属形态分析、吸附平衡实验以及X射线光电子能谱(XPS)探讨了杂化材料钝化修复重金属污染土壤的机制.结果表明,杂化材料单一处理对油菜生长没有明显的促进作用,而杂化材料与磷酸盐复合处理则能显著提高油菜地上部和根部生物量,分别比对...     

淋洗剂对多金属污染尾矿土壤的修复效应及技术研究

以我国南方某多金属复合污染尾矿土壤为研究对象,对土壤中重金属全量和各形态含量进行分析.通过系列振荡淋洗试验研究了蒸馏水、草酸、柠檬酸、乙酸、硝酸和EDTA对污染土壤的淋洗效果,筛选合适的淋洗剂及其最佳的液土比、液洗时间、淋洗次数等技术参数,并提出利用综合毒性消减指数来综合评价淋洗剂对污染土壤的修复效果.结果表明,该土壤以Cd和Pb污染最为严重,含量分别达52.2 mg.kg-1和4 836.5 mg.kg-1;淋洗剂对土壤中不同重金属元素的淋洗效果差异明显,其中对Cr的去除率最高仅为2.7%,而最多能去除约60%的Cd和Pb;蒸馏水对重金属几乎没有脱除效果,去除率都在0.1%以下,草酸和乙酸对重金属的去除率也较低,0.1 mol.L-1的EDTA是适合的高效淋洗剂;基于综合毒性消减指数和经济成本,选择在1∶6土水比2次淋洗3 h的技术条件.     

不同添加剂对铅冶炼污染土壤中铅、镉稳定效果的研究

为了研究铅冶炼形成的重金属复合污染石灰性土壤中重金属的稳定方法,在污染土壤(Pb、Cd含量分别为2337和21.4mg·kg-1)中分别加入磷酸二氢钾、磷酸二氢钙、石灰、盐酸、磷酸,通过盆栽试验探讨了不同添加剂对土壤重金属有效性和黑麦草(Lolium perenne L.cv.Rainbow)性状的影响.结果表明,加入石灰显著降低了土壤中DTPA-Cd含量,但对DTPA-Pb含量无显著影响;加入盐酸显著增加了土壤DTPA-Cd含量,对DTPA-Pb含量无明显影响.磷酸二氢钾、磷酸二氢钾与盐酸配合、磷酸二氢钙和磷酸均显著降低了土壤DTPA-Pb(降低幅度为39.5%～47.8%)和DTPA-Cd含量(降低幅度为10.5%～19.4%)(p<0.05),且磷酸二氢钾和盐酸配合处理与单独加入磷酸二氢钾处理相比,土壤DTPA-Pb含量下降了12.6%(p<0.05).磷酸二氢钾和盐酸配合处理土壤的Olsen-P含量和pH均显著低于单独加入磷酸二氢钾处理.加入石灰和盐酸处理的植物产量显著低于除对照外的其它处理,其余处理地上部产量比对照增加了100%～140%.加入盐酸显著增加了植物地上部镉含量,各处理均显著降低了植物地上部铅含量(p<0.05).     

A porous biochar supported nanoscale zero-valent iron material highly efficient for the simultaneous remediation of cadmium and lead contaminated soil

Risk associated with heavy metals in soil has been received widespread attention.In this study,a porous biochar supported nanoscale zero-valent iron（BC-nZVI） was applied to immobilize cadmium（Cd） and lead（Pb） in clayey soil.Experiment results indicated that the immobilization of Cd or Pb by BC-nZVI process was better than that of BC or nZVI process,and about 80% of heavy metals immobilization was obtained in BC-nZVI process.Addition of BC-nZVI could increase soil pH and organic matter（SOM）.Cd or...