重金属Cd、Zn、Pb复合污染对土壤酶活性的影响

采用回归正交设计方案 ,研究了潮褐土中Cd、Zn、Pb复合污染对 4种土壤酶活性 (过氧化氢酶、脲酶、碱性磷酸酶、转化酶 )的影响 .结果表明 ,在复合效应影响中 ,重金属对土壤酶活性的抑制效应顺次为Cd >Zn >Pb ;同时 ,Cd、Zn、Pb复合污染对 4种土壤酶活性的影响效应存在着明显差异 .其复合污染对脲酶表现出协同抑制负效应的特征 ;对过氧化氢酶表现出一定的屏蔽作用 ;对转化酶和碱性磷酸酶活性影响则主要随着Cd浓度的增加而显著降低 .离子冲量与土壤脲酶活性之间呈显著负相关 ,用脲酶活性作为预测土壤重金属Cd、Zn、Pb复合污染程度的主要生化指标具有一定的可行性     

施肥对老化污染土壤中PAHs可提取态浓度的影响

采用温室模拟试验,施用农业生产中广泛使用的无机氮肥和有机肥,以花红苋菜为典型叶菜类蔬菜,研究了不同施肥对老化污染土壤中PAHs可提取态浓度的影响.结果表明,有机肥处理与无机氮肥处理相比较,土壤中菲、荧蒽和苯并(b)荧蒽的可提取态浓度显著降低(p<0.05);在相同的采样时间及处理下,3种PAHs的可提取浓度与其在老化污染土壤中初始浓度的比值顺序为:苯并(b)荧蒽<荧蒽<菲(p<0.05),说明不同PAHs与土壤组分之间的吸附因其不同的理化特性而存在差异;裸土处理中3种PAHs的可提取浓度均显著高于根际土壤中的对应浓度(p<0.05).     

株洲城郊农田土壤重金属污染特征与Pb同位素示踪

通过采集湖南株洲城郊农田区表层土壤（A层）,并分析其Cd、Hg、Pb、Zn等重金属元素含量,研究了土壤中重金属元素的污染特征.为示踪这些金属元素的来源,选择农田区典型土壤样品及湘江沉积物、污染源区土壤样品,进行重金属元素含量和Pb同位素组成测定.结果表明,农田区A层土壤受到不同程度的重金属污染,其中,Cd、Hg、Pb、Zn含量最高,分别为21.71、24.52、261.49、577.94 mg·kg^-1,且Cd、Pb、Zn元素之间显著相关,而研究区附近湘江水体和沉积物中这些元素含量没有增高,说明这些重金属不是来自湘江,而是可能主要来自冶炼厂;铅同位素显示,冶炼厂附近A层土壤²⁰⁶Pb/²⁰⁷Pb值（1.150~1.164）低于周边区域A层土壤（1.164~1.169）,²⁰⁸Pb/²⁰⁶Pb值（2.108~2.122）高于周边地区（2.106~2.119）,说明受到人为污染的影响.从污染区分布空间位置和铅同位素源解析的结果看,农田区土壤中Cd、Hg、Pb、Zn等重金属的主要污染源是冶炼厂的冶炼烟气粉尘及与农耕活动有关的其他人为污染.     

胡敏酸改性膨润土钝化污染土壤Pb&Cd及机理

通过盆栽试验,探讨了胡敏酸改性膨润土对重金属铅、镉污染土壤的钝化效果及机理。结果表明,铅、镉污染土壤中施加胡敏酸改性膨润土能显著降低小白菜中Pb、Cd的含量,在添加Cd(3 mg/kg)/Pb(250 mg/kg)污染土壤和Cd(1 0 mg/kg)/Pb(5 00 mg/kg)污染土壤上小白菜地上部分Pb含量分别比对照降低19.08%和47.91%,Cd含量分别比对照降低9.79%和14.89%。土壤本身对添加的重金属Pb/Cd有一定的耐受力和自我净化能力,在添加重金属后,添加的Pb/Cd元素大部分直接转化为较为稳定的碳酸盐结合态和铁锰氧化结合态。相关性分析显示小白菜的鲜重与小白菜Pb/Cd含量极显著负相关,进一步说明胡敏酸改性膨润土是通过提高小白菜的生物量,从而降低Pb/Cd在小白菜中的含量。     

典型Pb/Zn矿区土壤重金属污染特征与Pb同位素源解析

以我国典型的铅锌矿区——湖南水口山铅锌矿区及其周围地区为研究对象,分析自然土壤(A层和C层)样品中不同重金属(Pb、Zn、Cr、Cu、Cd、Hg)的污染特征和Pb同位素组成.结果表明,受铅锌选矿和冶炼活动的影响,研究区域A层土壤明显受到重金属的污染,尤其是在中心区域(水口山矿区),土壤中Pb、Zn、Cr、Cu、Cd、Hg含量最高达3966.88、 2086.25、 135.31、 185.63、 56.15、 16.434 mg/kg;受原生地质环境的影响,C层土壤重金属含量虽然变化很大,但基本反映土壤背景值.土壤中不同重金属的潜在生态危害大小顺序为Cd>Hg>Pb>Cu>Zn=Cr.中心区域多重金属综合潜在生态危害明显高于周围区域,其34%、 33%、 11%、 22%的采样点分别属于轻微、中等、强和很强生态危害,而周围区域属于轻微、中等、强和很强生态危害的采样点比例分别为68%、 16%、 10%、 6%.与C层Pb同位素相比(²⁰⁶Pb/²⁰⁷Pb为1.168～1.246,²⁰⁸Pb/²⁰⁶Pb为2.014～2.130),由于人为Pb源的污染A层土壤中²⁰⁶Pb/²⁰⁷Pb值(1.166～1.226)低而²⁰⁸Pb/²⁰⁶Pb值(2.043～2.135)高.与铅锌选矿、冶炼废水和烟尘中Pb同位素比值对比表明,A层土壤铅污染主要来自于冶炼厂烟气粉尘的沉降.     

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).     

不同环境材料对Pb、Cd污染土壤的淋溶效应

为了探索环境材料对土壤中重金属的去除效果,采用土柱淋溶方法研究了不同环境材料（腐植酸HA、高分子材料SAP、粉煤灰FM及沸石FS）对污染土壤（单一Pb污染土壤、单一Cd污染土壤和Pb-Cd复合污染土壤）中铅（Pb）、镉（Cd）的淋溶效应。结果表明：添加不同环境材料处理的淋出液pH值呈现先上升后降低再上升的趋势,均为弱碱性。添加FM和复合N1（HA+SAP+FM+FS）、N2（HA+SAP+FM）处理淋出液的电导率（EC）明显高于其他。FM和复合N1、N2对单一Pb污染土壤中Pb达到显著固定作用;单一Cd污染土壤中,添加单一SAP处理所淋溶出的Cd量小于CK（未加任何环境材料）,淋溶出的Cd量为CK的63.68%,对Cd起到一定的固定作用;Pd-Cd复合污染土壤中,HA对Pb达到显著固定作用,淋出Pb量仅为CK的40.6%。SAP及复合N3对Cd的固定作用明显,淋溶出的Cd量分别为CK的55.32%、78.13%。可见,采用的环境材料对重金属淋溶能起到一定的抑制作用。     

土壤改良剂及其组合原位钝化果园土壤中的Pb、Cd

采用土壤改良剂及其组合,研究了重庆市金果园2个园区土壤中Pb、Cd的原位钝化效果.实验包括8种处理:对照、生石灰、过磷酸钙、有机肥、生石灰+过磷酸钙、生石灰+有机肥、过磷酸钙+有机肥、生石灰+过磷酸钙+有机肥.结果表明,除单施过磷酸钙外,其它改良剂处理都能降低枇杷园和桃园土壤酸度.与对照比较,单施生石灰可显著提高枇杷园和桃园土壤pH,处理120 d时土壤pH分别提高0.93和0.79个单位.改良剂处理均能降低土壤中Pb、Cd的生物有效性,进而降低果品中的Pb、Cd含量.配施生石灰和过磷酸钙可显著降低枇杷园和桃园土壤有效态Pb含量,处理150 d时分别下降3.46%和3.56%,枇杷和桃子中Pb含量分别下降18.3%和14.44%.单施生石灰可显著降低枇杷园土壤有效态Cd含量,处理150 d时下降10.95%;配施生石灰、过磷酸钙和有机肥能显著降低桃园土壤有效态Cd含量,处理150 d时下降7.09%.施加改良剂可进一步降低枇杷中的Cd含量,单施生石灰使枇杷和桃子中的Cd含量分别下降30.91%和24.62%.     

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.     

应用in vitro法评估土壤性质对土壤中Pb的生物可给性的影响

选取22种典型土壤样品,应用2种in vitro(体外模拟)试验方法——SBET法(simple bioaccessibility extraction test,生物有效性简化提取法)和PBET法(physiologically-based extraction test,生物原理提取法),定量阐明土壤性质对Pb的生物可给性的影响. 结果表明:①SBET法中Pb的生物可给性为18.78%~77.08%,平均值为44.14%;PBET法中Pb的生物可给性为0.72%~50.51%,平均值为13.77%. 除赤红壤和贵州黄壤外,其余20种土壤样品均表现为SBET法中Pb的生物可给性显著高于PBET法,并且随着土壤pH的增长,2种方法的差距更加显著. ②逐步回归分析结果表明,在SBET法中,对土壤Pb的生物可给性影响最大的因子是土壤中w(黏粒),其次为pH,二者可以解释69.49%的Pb的生物可给性的变化;在PBET法中,对土壤Pb的生物可给性影响最大的因子是pH,其次为w(黏粒),二者可以解释73.65%的Pb的生物可给性的变化. 研究结果说明,污染土壤中Pb的生物可给性可以根据土壤pH和w(黏粒)进行预测.      

有机磷和无机磷材料修复铅污染土壤

近年来,城市工业污染场地严重威胁着人居环境安全,其中土壤铅污染问题比较突出。为加强对铅污染土壤的风险管控,采取磷酸氢二钠（DSP）和植酸（PA）钝化处理铅污染土壤,采用BCR形态分析法和固体废物浸出毒性浸出方法-醋酸缓冲溶液法（HJ/T 300—2007）评价土壤铅赋存化学形态和浸出毒性。结果表明：DSP与PA对污染土壤pH的影响差异比较明显,但均能有效降低污染土壤的铅浸出浓度,并满足生活垃圾填埋场入场标准限值（0.25 mg?L^?1）;随添加比例增加,DSP与PA均能促使土壤中铅元素由活泼态（酸可提取态和可还原态）向稳定态（残渣态）转变,且PA钝化效果优于DSP;两种磷材料处理后的土壤浸出毒性与酸可提取态均表现出显著相关性,同样地,PA优于DSP。可见,PA对铅污染土壤具有良好的固铅作用。     

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.     

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 APRwasmost effective, although a slight enhancement of water-soluble phosphate was detected at the P:Pbmolar 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.     

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 Ca Cl2, 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 after120 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.     

砒砂岩修复晋陕蒙能源区铅污染土壤的研究

寻找合适的材料来修复晋陕蒙地区因煤炭、石油和天然气开发导致的土壤重金属污染是该区域环境治理的重要措施.砒砂岩具有较强的吸附性,是可以用于土壤重金属污染修复的潜在材料.本研究通过室内模拟实验来研究土壤中添加砒砂岩对铅形态分布、毒性溶出量(TCLP)的影响及其对土壤孔隙度、pH、田间持水量、土壤酶活性的影响.结果表明,砒砂岩可显著降低土壤弱酸提取态铅含量,增加可还原态与残渣态铅含量;随土壤中砒砂岩添加量的增加,高活性态铅的降幅越大低活性态铅的增幅越大.砒砂岩显著降低了土壤铅毒性溶出量,降低程度与砒砂岩添加量成正比.砒砂岩的较强吸附特性及可以提高土壤pH是固化土壤重金属铅的重要因素.此外,砒砂岩对土壤理化性质的改善一定程度上对污染土壤起着改良作用.     

磷肥对铅锌矿污染土壤中铅毒的修复作用

用连续提取法研究了不同磷肥对铅锌矿污染土壤中铅化学形态的影响、磷肥降低铅毒性的机理以及磷肥的有效使用条件.结果表明,3种磷肥都具有显著降低铅的各种非残渣形态含量的作用.磷肥用量在P/Pb摩尔比为7.0时已经足够修复土壤的铅毒,并且在该磷肥用量水平时,从非残渣形态铅总量的降低幅度上看,3种磷肥修复铅污染的效果顺序为：过磷酸钙（85%）、钙镁磷肥（83%）〉〉磷矿粉（16%）;把铅的形态与其生物有效性联系起来比较,3种磷肥修复铅污染效果顺序为：钙镁磷肥（94%）、过磷酸钙（92%）＞磷矿粉（61%）.磷肥具有原位修复铅污染土壤的潜能,其主要机理是通过磷肥中的磷与各种非残渣形态铅反应形成溶解度极小的磷（氯/羟基/氟）铅矿沉淀,从而降低铅的溶解性的结果,3种磷肥中以磷矿粉最为经济.     

Does the long-term application of calcium superphosphate lead to an increase of the soil rare earth element contents?

In order to test whether the long-term application of calcium superphosphate leads to an increase of the soil rare earth element contents, superphosphate fertilized soils were sampled and compared with superphosphate-free soils. Spectrophlame inductively coupled argon plasma atomic emission spectrophotometer （ICP-AES） was applied to quantify the rare earth elements （REEs）. The total rare earth element contents in calcium superphosphate from Zhijin County, west part of Guizhou Province, China （produced by the sulphuric acid treatment of the apatites） are about 2.54 mg/g. Between 38 and 189 gREEs/hm^2 per year （available for plants, estimated by 2% citric acid） will be introduced into the soil solution when applying 320 kg superphosphate/hm^2 per year. The long-term application of the latter will increase the REE content by about 18% in the soil surface layer in these areas. A statistically significant increase of the content of the rare earths in some cultivated soils should not be neglected.     

EDTA-enhanced phytoremediation of lead contaminated soil by Bidens maximowicziana

Phytoremediation is a potential cleanup technology for the removal of heavy metals from contaminated soils.Bidens maximowicziana is a new Pb hyperaccumulator,which not only has remarkable tolerance to Pb but also extraordinary accumulation capacity for Pb.The maximum Pb concentration was 1509.3 mg/kg in roots and 2164.7 mg/kg in overground tissues.The Pb distribution order in the B. maximowicziana was:leaf>stem>root.The effect of amendments on phytoremediation was also studied.The mobility of soil Pb and the Pb concentrations in plants were both increased by EDTA application.Compared with CK(control check),EDTA application promoted translocation of Pb to overground parts of the plant.The Pb concentrations in overground parts of plants was increased from 24.23-680.56 mg/kg to 29.07-1905.57 mg/kg.This research demonstrated that B.maximowicziana appeared to be suitable for phytoremediation of Pb contaminated soil,especially,combination with EDTA.