磷灰石等改良剂对重金属铜镉污染土壤的田间修复研究

通过田间小区试验,研究了磷灰石、石灰、木炭、猪粪、铁粉5种改良剂对Cu、Cd复合污染土壤的改良效果。结果表明,石灰、磷灰石、木炭、猪粪降低了土壤溶液中重金属Cu、Cd的含量,提高了土壤溶液的pH,但改良效果随着时间的推移不断降低。磷灰石、石灰、木炭的加入显著降低了有效态Cu含量,但对有效态Cd含量影响较小。与猪粪相比,磷灰石、石灰、木炭显著增加了黑麦草生物量,提高了对重金属Cu、Cd的吸收能力,对该污染土壤的修复具有实践应用价值。     

纳米羟基磷灰石对重金属污染土壤Cu/Cd形态分布及土壤酶活性影响

通过室内培养实验,研究了纳米羟基磷灰石对重金属污染土壤Cu/Cd形态分布及土壤酶活性的影响。结果表明,施加纳米羟基磷灰石显著提高了土壤pH,其中3%和5%添加剂量处理60 d后使土壤pH分别提高了1.23个和1.35个单位;纳米羟基磷灰石显著减少了毒性较强的离子交换态Cu/Cd的含量,增加了毒性中等的碳酸盐结合态、铁锰氧化物结合态、有机结合态及毒性最低的残留态Cu/Cd含量,使Cu/Cd由植物可利用态向潜在可利用态转变;纳米羟基磷灰石不同程度地提高了土壤过氧化氢酶、脲酶和酸性磷酸酶活性。3种酶活性与Cu/Cd形态分布的相关性表明,过氧化氢酶和酸性磷酸酶对土壤重金属Cu/Cd活性变化比较敏感,可以作为重金属Cu/Cd污染土壤的评价指标。     

巨大芽孢杆菌LY02对黑麦草修复重金属污染土壤的影响

采用盆栽试验方法,研究了接种巨大芽孢杆菌LY02对黑麦草修复Cd、Cu污染土壤以及二者复合污染土壤效果的影响。结果表明:在Cd、Cu污染土壤及复合污染土壤中接种巨大芽孢杆菌LY02,可显著提高黑麦草地上部生物量,增幅达65.0%~108.3%;促进了黑麦草在3种污染土壤中对重金属的吸收,其中对Cd污染土壤中黑麦草吸收Cd的影响最为显著,地上部Cd吸收量较对照组增加了45.8%(P0.05);3种污染土壤中黑麦草根际土壤有效磷含量显著升高,较对照组分别增加了18.2%,26.7%,16.2%;黑麦草根际土壤中有效态Fe含量显著提高,Cu单一污染土壤中增幅最大,达到152.5%;3种污染土壤中有效态重金属含量升高,在Cu污染土壤中,有效态Cu增幅达到49.7%(P0.05)。综上所述,巨大芽孢杆菌LY02通过增加污染土壤中生物可利用态P和Fe,促进黑麦草生长;通过提高有效态Cd和Cu的含量,增加黑麦草对其吸收,从而提高了黑麦草对Cu、Cd污染土壤的修复效率。     

6种固化剂对土壤Pb Cd Cu Zn的固化效果

通过在重金属污染土壤中分别施加沸石、石灰石、硅藻土、羟基磷灰石、膨润土和海泡石6种固化剂,研究了这6种固化剂对土壤中Pb、Cd、Cu、Zn的固化效果,筛选出几种效果较好的固化剂。实验结果表明：沸石、石灰石和羟基磷灰石均能够有效地降低土壤中交换态Pb、Cd的含量,并且明显减少了土壤中Pb、Cd的毒性浸出量,其中沸石最多降低土壤中交换态Pb、Cd含量分别达到48.7%和56.2%,减少土壤中Pb、Cd的毒性浸出量达到37.1%和30.1%;沸石、石灰石均能够有效降低土壤中交换态Cu的含量,降低量分别高达68.1%和85.2%,膨润土能有效减少土壤中Cu的毒性浸出量,减少量最高达到66.51%;石灰石对土壤中Zn有着良好的固化效果。     

生物炭对铜矿区污染土壤微生物活性及香根草富集铜、镉、铅的影响

矿区土壤易发生重金属污染,是土地资源利用和维护的一大难题。以铜矿区污染土壤为研究对象,按质量比添加0,1%,2%,4%,10% (w/w)的生物炭,进行香根草室内盆栽试验。研究添加生物炭对土壤pH和微生物活性、香根草富集与转运重金属的影响,探明重金属形态含量与生物炭、微生物活性的相关性,旨在为生物炭与香根草联合修复矿区重金属污染土壤提供理论参考。结果表明:生物炭的添加能提高土壤pH,显著提高土壤FDA水解酶、蔗糖酶和脲酶活性,显著促进土壤基础呼吸,但对土壤微生物量碳无显著影响;生物炭的添加使香根草生物量显著增大,降低土壤Cu和Pb的有效态占比,Cd的变化与此相反;添加生物炭促进香根草对Cd和Pb的富集,降低香根草对Cu的富集,减少Cu、Cd和Pb在香根草体内的转运,因此香根草可作为Cu、Cd和Pb的稳定化植物。土壤蔗糖酶活性与香根草叶片Cu、Cd和Pb含量、有效态和残渣态Cu含量呈显著正相关,土壤基础呼吸与叶片Cu、Cd和Pb含量、有效态Cu、Pb含量呈显著负相关,而与有效态Cd含量呈显著正相关。总之,生物炭可减弱矿区土壤重金属对香根草生长的毒害作用,并促进香根草对重金属的富集,两者结合可改善铜矿区污染土壤的理化性质和微生物活性,有利于重金属污染土壤修复,改善土壤质量。     

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.     

羟基磷灰石–植物联合修复对Cu/Cd污染植物根际 土壤微生物群落的影响

针对江西贵溪Cu、Cd重金属污染土壤,通过田间试验,比较无机生物材料羟基磷灰石及3种植物(海州香薷、巨菌草、伴矿景天)与羟基磷灰石联合修复对土壤总Cu、Cd的吸收及对活性Cu、Cd的钝化吸收能力差异。采用磷脂脂肪酸(PLFA)分析法,比较不同修复模式对土壤微生物群落结构的影响,以评估土壤微生态环境对不同修复措施的响应。研究结果表明:羟基磷灰石的施加可显著提高土壤pH,并有效钝化土壤活性Cu、Cd含量,但对土壤总Cu、Cd的含量影响较小。植物与羟基磷灰石的联合修复在显著降低土壤活性Cu、Cd(P0.05)的同时,减少了植物根际土壤总Cu、Cd的含量(P0.05)。不同修复措施对土壤微生物群落组成影响差异明显。单独施加羟基磷灰石与土壤真菌群落呈显著正相关,使土壤真菌生物量提高,从而引起真菌/细菌(F/B)的升高。植物与羟基磷灰石的联合修复可有效缓解土壤真菌化的趋势,其中巨菌草与羟基磷灰石的联合修复可有效提高土壤革兰氏阳性、革兰氏阴性细菌生物量及多样性,降低F/B值,从而降低土壤真菌病害的风险。不同植物根系活性代谢引起有机质的积累促进植物与羟基磷灰石处理中根际有机碳含量显著提高。聚类增强树(Aggregated boosted tree,ABT)分析结果表明:不同修复模式是影响土壤微生物群落的重要因素,其次土壤pH和Cu的含量及活性也是改变重金属污染区域微生物群落的因子。该研究从微生物群落结构角度解释了植物与羟基磷灰石联合修复对土壤微生态体系的作用,为开展Cu、Cd等重金属污染地植物与无机生物材料的联合修复方式的筛选及实施提供可靠的理论依据。     

油葵和苦荬菜根际土壤中镉和锌的活化机制及修复潜力比较

  目的  研究油葵和苦荬菜根际土壤固、液相对镉（Cd）和锌（Zn）的活化机制,比较两种植物在轻、中度复合污染农田的修复潜力。  方法  通过大田试验种油葵和苦荬菜,测定成熟期土壤的pH值、有机酸、重金属总量及其生物有效性;测定土壤溶液中的溶解性有机质（DOM）、主要离子、水溶态重金属及其形态分布;测定植物各部位中重金属的浓度及形态,通过计算重金属在植物中的富集系数（BCF）和转运系数（TF）,比较两种植物对土壤重金属污染的修复潜力。  结果  油葵和苦荬菜根系分泌的低分子有机酸均使根际土壤pH值下降明显,显著低于非根际土壤（P < 0.05）;苦荬菜根际土中低分子有机酸及DOM的浓度显著高于油葵根际土（P < 0.05）。两种植物根际土壤溶液中的Cd以离子态和DOM结合态为主,Zn以离子态为主;两种植物根际土壤中有效态的Cd差异不显著,油葵根际有效态Zn显著高于苦荬菜;两种植物根际土壤的Zn和Cd有效态与土壤溶液中Cd-DOM和Zn-DOM呈显著相关。苦荬菜根对重金属的富集能力较强,但油葵地上部分能吸收转运更多的Cd和Zn,并在叶中以毒性较低的不溶性磷酸盐结合态和草酸结合态富集。  结论  两种植物根际分泌的有机酸可以增加根际土壤中的Cd-DOM和Zn-DOM的浓度,提高土壤中的Cd和Zn的有效性,苦荬菜根际对重金属有较强的活化能力,但油葵地上部分对Cd和Zn的吸收转运能力更强。两种植物都具有较强的土壤重金属修复潜力,但从经济角度出发,油葵更适合现阶段我国农田重金属污染的修复。     

不同钝化剂和培养时间对Cd污染土壤中可交换态Cd的影响

原位化学钝化技术是修复重金属污染土壤的重要途径之一,通过施入一些钝化剂以降低土壤中重金属有效态含量,从而减少其迁移及对植物的毒害。选取羟基磷灰石（HA）、磷矿粉（PRX和PRH）、沸石、赤泥、新鲜植物残体、玉米秸秆粉末以及相应的处理共21种钝化剂,在同一培养条件和添加浓度下,比较其对人工Cd污染土壤中可交换态Cd含量的影响,并分析了其在不同培养时间对钝化效果的时间效应,试验的结果对于筛选Cd污染土壤钝化剂有着重要的意义。结果表明,纳米化赤泥、羟基磷灰石和纳米化酸洗赤泥可显著降低土壤中可交换态Cd含量,钝化比例高达35%-55%;赤泥、酸洗赤泥、沸石达15%-25%;富含巯基植物蒜苗、油菜、大葱植物残体也可达20%-25%。磷矿粉、大葱粉末、玉米秸秆和巯基化玉米秸秆的钝化效果相对较差;HA、铵型沸石、纳米赤泥、酸洗纳米赤泥、干油菜粉末、酸洗赤泥对可交换态Cd的钝化效果的时间效应不明显;赤泥、大葱残体、特别是玉米秸秆和巯基玉米秸秆随时间增长钝化效果增加显著,在8周和16周时段钝化效果较好。     

石灰石和海泡石组配对水稻糙米重金属积累的影响

为了研究组配改良剂(石灰石+海泡石,LS)对于重金属Pb、Cd、Cu和Zn复合污染稻田的修复效果,在湘南某矿区附近稻田中进行了组配改良剂的田间试验。结果表明:施用0~1.8 kg m-2的组配改良剂LS使土壤pH和CEC显著增加,使土壤中Pb、Cd、Cu和Zn交换态含量显著降低。土壤Pb、Cd、Cu和Zn交换态含量的降低是pH升高,土壤胶体的CEC增加及土壤吸附能力增强的共同作用。施用组配改良剂LS显著降低了3个水稻品种(黄华占、丰优9号、Ⅱ优93)糙米中Pb、Cd和Cu的累积量,最大降幅分别为55.8%、66.9%、37.4%,而对糙米中Zn的含量没有明显影响。当LS施用量为1.8 kg m-2时,能使丰优9号糙米中Cd含量(0.195 mg kg-1)达到国家食品中污染物限量标准(0.20 mg kg-1)以下。土壤中交换态Pb、Cd和Cu含量的降低是糙米中重金属累积量减少的原因。土壤交换态Pb、Cd和Cu含量的对数值(lnC交换态)与其糙米中含量(lnC糙米)的对数值之间存在显著的线性相关关系。     

Sustainability of in situ remediation of Cu- and Cd-contaminated soils with one-time application of amendments in Guixi,China

Purpose

In situ immobilization of heavy metal-contaminated soils with the repeated incorporation of amendments can effectively reduce the bioavailability of soil heavy metals. However, the long-term application of amendments would lead to the destruction of soil structure and accumulation of soil toxic elements, ultimately affecting food security and quality. Thus, the sustainability of the amendments in a heavy metal-contaminated soil was evaluated from 2010 to 2012.

Materials and methods

Batch field experiments were conducted in the soils, which were amended with apatite (22.3 t ha^?1), lime (4.45 t ha^?1), and charcoal (66.8 t ha^?1), respectively. The amendments were applied only one time in 2009, and ryegrass was sown each year. Ryegrass and setaria glauca (a kind of weed) were harvested each year. Concentrations of copper (Cu) and cadmium (Cd) were determined by batch experiments. Five fractions of Cu and Cd were evaluated by a sequential extraction procedure.

Results and discussion

Ryegrass grew well in the amended soils in the first year, but it failed to grow in all the soils in the third year. However, setaria glauca could grow with higher biomass in all the amended soils. The treatment of apatite combined with plants was more effective than lime and charcoal treatments in removing Cu and Cd from the contaminated soils by taking biomass into account. Apatite had the best sustainable effect on alleviating soil acidification. The Cu and Cd concentrations of CaCl₂-extractable and exchangeable fractions decreased with the application of amendments. Moreover, apatite and lime could effectively maintain the bioavailability of Cu and Cd low.

Conclusions

Apatite had a better sustainable effect on the remediation of heavy metal-contaminated soils than lime and charcoal. Although all the amendment treated soils did not reduce soil total concentrations of Cu and Cd, they could effectively reduce the environmental risk of the contaminated soils. The findings could be effectively used for in situ remediation of heavy metal-contaminated soils.

     

磷灰石和石灰稳定化修复对污染土壤铜和镉垂直迁移的影响

大量改良材料被用于重金属污染土壤的稳定化修复,但是不同用量的改良材料长期田间修复后重金属总量和有效态在不同土层的垂直分布特征鲜有研究涉及。本研究采集不同剂量的磷灰石和石灰稳定化修复的0~13、13~30和30~50 cm土层污染土壤,考察铜和镉总量及有效态含量在不同土层的分布特征。结果表明:随着磷灰石和石灰用量的增加,显著降低了0~13 cm土层土壤交换性酸和交换性铝,增加了土壤全钙的含量,且磷灰石处理提高了土壤全磷和速效磷含量。0~13 cm土层土壤pH、总铜和总镉含量均随着磷灰石和石灰用量的增加而逐渐增加,但是降低了13~30和30~50 cm土层土壤总铜和总镉含量。3个土层中铜和镉有效态含量均随着磷灰石和石灰用量的增加而显著降低,其中23.2 g/kg磷灰石处理和4 g/kg石灰处理土壤有效态铜含量降低85.1%和92.0%,有效态镉降低18.8%和23.5%。相关性分析表明,土壤pH和铜镉总量是影响铜镉有效性的主要因素。可见,磷灰石和石灰的应用使铜和镉较好地固定在土壤表层,减少铜和镉向下层土壤的淋溶,降低了铜和镉的有效性。     

不同改良剂对黑麦草在铜矿尾矿砂上生长的影响

Montmorillonite, rice straw, organic manure and chemical fertilizer were used as amendment materials for copper mine tailings, and their effects on mine tailing pH, nutrients and metal availability to ryegrass were investigated. Chemical fertilization was the most effective one in improving ryegrass growth in mine tailings among the amendment materials examined. It was found that montmorillonite raised biomass of ryegrass at the 1st and 2nd cuts, but it did not give further positive effects at the 3rd and 4th cuts. The effect of organic materials on ryegrass growth was not so good as expected, mainly due to their slow decomposition in mine tailings with less soil microorganisms. Available Cu and Zn contents in mine tailings decreased in the presence of montmorillonite but increased when rice straw and organic manure were used as amendments. Cu and Zn contents in ryegrass decreased with increasing the rate of montmorillonite application but increased with the rate of rice straw. Zn showed much stronger mobility from soil to ryegrass than Cu, and almost all the available N and P in mine tailings, except for the treatments with organic manure, were completely consumed after ryegrass had grown in mine tailings for more than four months and been harvested for four times. Owing to its large biomass and high metal uptake, ryegrass is a potential plant for remediation of metal contaminated soils in practice.     

铅镉高污染土壤的钝化材料筛选及其修复效果初探

本研究以重金属高污染农田土壤(全Pb含量为1 277 mg/kg,全Cd含量为39.0 mg/kg)为研究对象,通过土培试验和玉米苗期盆栽试验,探讨海泡石、石灰、腐植酸、钙镁磷肥、磷矿粉、生物质炭等常用稳定材料不同剂量及复配组合对高污染土壤重金属的钝化修复效应。土培试验结果表明,石灰对Pb和Cd钝化效果最好,其次是海泡石,但两者表现为较高添加量处理间没有显著差异;而低剂量生物质炭和腐植酸显著增加土壤有效态Pb和Cd含量,高剂量生物质炭具有较好的钝化效果。盆栽试验表明,海泡石与石灰配施钝化效果较好,与对照相比,土壤氯化钙提取态Pb、Cd含量分别降低了97.5%、81.4%;玉米根和地上部Cd含量分别降低48.5%、34.0%,Pb含量分别降低35.6%、29.6%;但海泡石与磷材料配施显著增加玉米根Pb含量,对玉米Cd吸收没有显著影响。以上结果表明,重金属高污染农田土壤添加合适的改良剂,可较大幅度降低土壤重金属有效性和植物重金属吸收性。     

石灰与生物炭配施对不同浓度镉污染土壤修复

通过室内培养试验,研究生物炭与石灰不同用量配施对镉污染土壤pH和镉赋存形态的影响。结果表明,生物炭与石灰配施能够明显提高污染土壤pH,且随着施入量的增加pH提升效果显著。随着石灰和生物炭配施用量的增加,土壤交换态镉降低比例逐渐增大。培养60天后,镉污染浓度为5mg/kg的土壤交换态镉含量同对照处理相比依次减少36.80%,49.12%和57.38%;而土壤镉污染浓度为20mg/kg的土壤交换态镉含量较对照相比分别降低29.27%,31.68%和39.03%。2个浓度中土壤碳酸盐结合态镉、铁锰氧化物结合态镉和有机结合态镉均有所增加,残渣态镉虽有所增加,但在不同浓度之间存在差异。总体来看,本试验用量条件下,石灰和生物炭配施对污染浓度为5mg/kg的土壤镉钝化效果优于污染浓度为20mg/kg的土壤。     

土壤钝化剂对黑土中铜的原位固定作用

采用盆栽试验研究3种钝化剂(粉煤灰、磷灰石和膨润土)对黑土中铜(Cu)的化学形态、生物积累和有效性的影响。结果表明:3种钝化剂能显著降低Cu污染黑土中水提取态(DW)、TCLP提取态和二乙基三胺五乙酸-三乙醇胺(DTPA-TEA)提取态Cu含量,其中以膨润土的效果最为明显;Tessier连续提取测定发现,3种钝化剂显著降低非残留态Cu(水溶态和交换态、碳酸盐结合态、铁锰氧化物结合态和有机结合态)含量(p<0.01),增加残留态Cu含量,表明3种钝化剂通过改变黑土中Cu的化学形态,降低了黑土中Cu的可淋失性和生物有效性;与对照相比,添加钝化剂能显著降低水稻地上部分的Cu含量(p<0.01),如在400Cu mg/kg处理的土壤上,添加2.5%的粉煤灰、磷灰石和膨润土使米粉中的Cu含量分别降低21.8%,22.7%和31.9%。土壤中可淋失态和生物有效态Cu的分析表明,钝化剂主要是通过改变土壤中Cu的化学形态,降低土壤中Cu的生物有效性,以降低Cu在水稻中的积累;试验表明,Cu污染土壤中施用钝化剂可以修复Cu污染,降低水稻Cu污染风险。     

蚓粪对黑麦草吸收污染土壤重金属铜的影响

在长江冲积物形成的高沙土中加入CuSO4.5H2O模拟土壤污染,使Cu污染浓度分别为200、400、600 mg kg-1,并设置加蚓粪(15%)和加原土(15%)处理,二处理各设种植黑麦草(Lolium multiflorum)和不种黑麦草培养试验,研究蚓粪对黑麦草生长及对Cu吸收的影响,以揭示蚓粪在Cu污染土壤植物修复中的作用。结果表明:蚓粪显著增加了黑麦草的地上部和地下部的生物量(p<0.001**)以及根系的长度、表面积、体积和根尖数(p<0.05*),在Cu浓度为200 mg kg-1时促进作用最大;蚓粪还显著提高了黑麦草地上部Cu的浓度及累积量,但显著降低了地下部的Cu浓度(p<0.05*),而对地下部的铜累积量没有影响,显示蚓粪能促进Cu从根系向地上部的运移及在地上部的富集。通过对土壤的pH和Cu的形态特征分析,发现种植黑麦草处理降低了土壤的pH并增加了可交换态铜的含量,而且这种作用在加入蚓粪后更加明显。推测蚓粪主要通过促进黑麦草根系的生长和活性而影响根系周围环境,提高重金属铜的生物有效性进而增加植物对铜的吸收。     

氧化节杆菌生物降解苯并芘

A pot experiment was conducted with multi-metal (Pb, Cd, Cu, and Zn) contaminated acidic soil to investigate changes in available metal burden resulting from the application of industrial wastes (fly ash and steel slag). The efficiency of amendments-induced metal stabilization was evaluated by diffusive gradients in thin films (DGT), sequential extraction, and plant uptake. The stability of remediation was assessed by an acidification test and by chemical equilibrium modeling. Addition of fly ash (20 g kg-1 ) and steel slag (3 g kg-1 ) resulted in similar increase in soil pH. Both amendments significantly decreased the concentrations of metals measured with DGT (C DGT) and the metal uptake by Oryza sativa L. Significant correlations were found between C DGT and the concentration of a combination of metal fractions (exchangeable, bound to carbonates, and bound to Fe/Mn oxides), unraveling the labile species that participate in the flux of metal resupply. The capability of metal resupply, as reflected by the R (ratio of C DGT to pore water metal concentration) values, significantly decreased in the amended soils. The C DGT correlated well with the plant uptake, suggesting that DGT is a good indicator for bioavailability. Acidification raised the extractable metal concentration in amended soil but the concentration did not return to the pre-amendment level. Equilibrium modeling indicated that the soil amendments induced the precipitation of several Fe, Al and Ca minerals, which may play a positive role in metal stabilization. Chemical stabilization with alkaline amendments could be an effective and stable soil remediation strategy for attenuating metal bioavailability and reducing plant metal uptake.     

Immobilization of Cu and Cd in a contaminated soil: one- and four-year field effects

Purpose

Many amendments have been applied to immobilize heavy metals in soil. However, little information is available on the changes of immobilization efficiencies of heavy metals in contaminated soils over time. This work investigated the immobilization efficiencies of copper (Cu) and cadmium (Cd) in contaminated soils in situ remediated with one-time application of three amendments for 1 year and 4 years.

Materials and methods

Apatite, lime, and charcoal were mixed with the topsoil of each plot with the amounts of 22.3, 4.45, and 66.8 t/ha, respectively. Soil chemical properties and fractions of Cu and Cd were examined after in situ remediation for 1 year and 4 years. Soil sorption and retention capacities and desorption proportions for Cu and Cd were investigated by batch experiments.

Results and discussion

The addition of amendments significantly increased soil pH, but decreased exchange acid and aluminum (Al). The amendments significantly decreased the CaCl₂ extractable Cu and Cd and transformed them from active to inactive fractions. After the application of amendments for 1 year, the maximum sorption capacities ranged from 35.6 to 38.8 mmol/kg for Cu and from 14.4 to 17.0 mmol/kg for Cd, which were markedly higher than those of the application of amendments for 4 years (Cu, 29.6–34.7 mmol/kg; Cd, 10.9–16.4 mmol/kg). Desorption proportions (D) of Cu and Cd using three extractants followed the order of \( {D}_{{\mathrm{NaNO}}_3}<{D}_{{\mathrm{CaCI}}_2}<{D}_{{\mathrm{MgCI}}_2} \) . Moreover, the retention capacities (R) of Cu and Cd both increased and followed the order of R _apatite?>?R _lime?>?R _charcoal, resulting in higher Cu and Cd in the amended soils than the untreated soil.

Conclusions

Apatite, lime, and charcoal increased the soil sorption and retention capacities of Cu and Cd and resulted in higher immobilization efficiencies in the amended soils than the untreated soil. However, the immobilization efficiencies of Cu and Cd decreased with the decrease of sorption capacities after 4 years. It was concluded that apatite had the best effect on the long-term stability of immobilized Cu and Cd and can be applied to immobilize heavy metals in contaminated soils.