组配固化剂的研制及其对土壤重金属的固化效果
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摘要
通过对衡阳某地、郴州某地和株洲某地土壤的采样和调查,了解当地耕作土壤的重金属污染状况。在实验室向衡阳某地和郴州某地的重金属污染土壤添加单一固化剂和组配固化剂,添加浓度均为6g·kg-1。通过毒性浸出实验(TCLP),研究单一固化剂和组配固化剂对土壤Pb、Cd、Cu、Zn浸出量的影响,评价两类固化剂的固化效果,筛选出固化效果最好的固化剂,并进行浓度梯度试验。同时在株洲某地新马村建立径流场,向径流场内的土壤添加固化剂,添加浓度为6g·kg-1,以人工泼水的方式模拟降雨,收集地表径流水和渗漏水,分析地表径流水和渗漏水中重金属含量。试验主要结果如下：
(1)在衡阳某地采集的耕作土壤样品中,Pb、Cd、Zn含量均超过了土壤环境质量三级标准；在郴州某地采集的土壤样品中,Pb、Cd含量超过了土壤环境质量三级标准,土壤Zn含量超过一级标准；在株洲某地采集的耕作土壤样品中Cd含量超过了土壤环境质量三级标准,Pb和Zn含量均超过了土壤环境质量一级标准。
(2)在单一固化剂中,石灰石对土壤重金属的综合固化效果最好,相比对照,Pb、Cd、Cu、Zn的土壤浸出量分别下降了29.5%、100%、68.6%、49.6%；在组配固化剂中,组配比例为1：2的固化剂Ⅱ(硅藻土、石灰石)的综合固化效果最好,相比对照,Pb、Cd, Cu、Zn在衡阳某地供试土壤中的浸出量分别下降了54.3%、100%、27.3%、63.8%,在郴州某地供试土壤中的浸出量分别下降了100%、48.4%、64.8%、71.2%。
(3)对组配比例为1：2的固化剂Ⅱ(硅藻土、石灰石)进行浓度梯度筛选,结果发现,添加浓度为6g·kg-1的固化效果最好,相比对照,其土壤Pb、Cd、 Cu、Zn的浸出量分别下降了54.3%、100%、27.3%、63.8%。
(4)无论是从经过单一固化剂处理过的径流区域收集的地表径流水和渗漏水,还是从未经任何处理的对照径流区域收集的地表水和渗漏水,都无法检测到重金属的含量。
In order to understand heavy metal pollution of planting soils, sampling and surveys of soil samples were conducted in someplace in Hengyang, someplace in Chenzhou, someplace in Zhuzhou. Single curing agents and group matching curing agents with a concertration of6g·kg-1were added to the soils of heavy metal contaminated in Hengyang and Chenzhou in the laboratory. Research on effects of single curing agents and group matching curing agents addition on the leaching contents of soil Pb, Cd, Cu and Zn, evaluation the effects of two types of curing agents on stabilization of soil heavy metals, selection of curing agents which had the best curing effect, conduction of concentration gradient test were conducted through extraction procedure for leaching toxicity (TCLP). A runoff field was established in Zhuzhou, in which curing agents were added to the soils with a concentration of6g·kg-1, rainfall was simulated in the way of artificial splashing, surface runoff water and seepage water were collected and analyzed for the contents of heavy metals. The primary results of the experiments were as follows:
(1) In the farming soil samples collected from Hengyang, Pb, Cd and Zn contents were higher than the third level of soil environmental quality standard (SEQS). In the soils from Shihupu village in Chenzhou, Pb and Cd content were higher than the third level of SEQS,.Zn contents higher than the first level of SEQS. Cd content was higher than the third level of SEQS in the soils from Zhuzhou, and Pb and Zn contents exceeded the first level of SEQS.
(2) Compared to the control, limestone was the best curing agent to stabilize soil heavy metals among six single curing agents, and decreased the leaching contents of Pb, Cd, Cu and Zn from the soils by29.5%,100%,68.6%, and49.6%, respectively. For group matching curing agents, the best curing effects for soil heavy metals showed for curing agent II with a ratio of1:2for diatomite and limestone. Compared to the control, this curing agent reduced the leaching contents of Pb, Cd, Cu and Zn by54.3%,100%,27.3%, and63.8%from the soils in Hengyang, and by100%,48.4%, 64.8%, and71.2%from the soils in Chenzhou, respectively.
(3) As a result of concentration gradient test for curing agent II with a ratio of1:2for diatomite and limestone, the best curing effects for stabilization of soil heavy metals were showed for the addition of this curing agent with the concentration of6g-kg-1compared to the control, and the leaching contents of Pb, Cd, Cu and Zn from the soils were decreased by54.3%,100%,27.3%and63.8%, respecti vely.
(4) Heavy metals were not detected either for the surface runoff waters or for the seepage waters from the runoff field in Zhuzhou no matter the soils treated with single curing agents or not.
(1)在衡阳某地采集的耕作土壤样品中,Pb、Cd、Zn含量均超过了土壤环境质量三级标准；在郴州某地采集的土壤样品中,Pb、Cd含量超过了土壤环境质量三级标准,土壤Zn含量超过一级标准；在株洲某地采集的耕作土壤样品中Cd含量超过了土壤环境质量三级标准,Pb和Zn含量均超过了土壤环境质量一级标准。
(2)在单一固化剂中,石灰石对土壤重金属的综合固化效果最好,相比对照,Pb、Cd、Cu、Zn的土壤浸出量分别下降了29.5%、100%、68.6%、49.6%；在组配固化剂中,组配比例为1：2的固化剂Ⅱ(硅藻土、石灰石)的综合固化效果最好,相比对照,Pb、Cd, Cu、Zn在衡阳某地供试土壤中的浸出量分别下降了54.3%、100%、27.3%、63.8%,在郴州某地供试土壤中的浸出量分别下降了100%、48.4%、64.8%、71.2%。
(3)对组配比例为1：2的固化剂Ⅱ(硅藻土、石灰石)进行浓度梯度筛选,结果发现,添加浓度为6g·kg-1的固化效果最好,相比对照,其土壤Pb、Cd、 Cu、Zn的浸出量分别下降了54.3%、100%、27.3%、63.8%。
(4)无论是从经过单一固化剂处理过的径流区域收集的地表径流水和渗漏水,还是从未经任何处理的对照径流区域收集的地表水和渗漏水,都无法检测到重金属的含量。
In order to understand heavy metal pollution of planting soils, sampling and surveys of soil samples were conducted in someplace in Hengyang, someplace in Chenzhou, someplace in Zhuzhou. Single curing agents and group matching curing agents with a concertration of6g·kg-1were added to the soils of heavy metal contaminated in Hengyang and Chenzhou in the laboratory. Research on effects of single curing agents and group matching curing agents addition on the leaching contents of soil Pb, Cd, Cu and Zn, evaluation the effects of two types of curing agents on stabilization of soil heavy metals, selection of curing agents which had the best curing effect, conduction of concentration gradient test were conducted through extraction procedure for leaching toxicity (TCLP). A runoff field was established in Zhuzhou, in which curing agents were added to the soils with a concentration of6g·kg-1, rainfall was simulated in the way of artificial splashing, surface runoff water and seepage water were collected and analyzed for the contents of heavy metals. The primary results of the experiments were as follows:
(1) In the farming soil samples collected from Hengyang, Pb, Cd and Zn contents were higher than the third level of soil environmental quality standard (SEQS). In the soils from Shihupu village in Chenzhou, Pb and Cd content were higher than the third level of SEQS,.Zn contents higher than the first level of SEQS. Cd content was higher than the third level of SEQS in the soils from Zhuzhou, and Pb and Zn contents exceeded the first level of SEQS.
(2) Compared to the control, limestone was the best curing agent to stabilize soil heavy metals among six single curing agents, and decreased the leaching contents of Pb, Cd, Cu and Zn from the soils by29.5%,100%,68.6%, and49.6%, respectively. For group matching curing agents, the best curing effects for soil heavy metals showed for curing agent II with a ratio of1:2for diatomite and limestone. Compared to the control, this curing agent reduced the leaching contents of Pb, Cd, Cu and Zn by54.3%,100%,27.3%, and63.8%from the soils in Hengyang, and by100%,48.4%, 64.8%, and71.2%from the soils in Chenzhou, respectively.
(3) As a result of concentration gradient test for curing agent II with a ratio of1:2for diatomite and limestone, the best curing effects for stabilization of soil heavy metals were showed for the addition of this curing agent with the concentration of6g-kg-1compared to the control, and the leaching contents of Pb, Cd, Cu and Zn from the soils were decreased by54.3%,100%,27.3%and63.8%, respecti vely.
(4) Heavy metals were not detected either for the surface runoff waters or for the seepage waters from the runoff field in Zhuzhou no matter the soils treated with single curing agents or not.
引文
[1]董悦,刘晓群,李翠兰,等.土壤重金属污染研究进展[J].现代农业科技,2009,37(4)：142-143.
[2]刘素纯,萧浪涛,王惠群,等.植物对重金属的吸收机制与植物修复技术[J].湖南农业大学学报(自然科学版),2004,30(5)：493-498.
[3]Ford R C, Sparks D L. The nature of Zn precipitates formed in the presence of pyrophyllite [J]. Environ Sci Technol,2000,34:2479-2483.
[4]何宏乎,郭九皋.蒙脱石、高岭石、伊利石对重金属离子吸附容量的实验研究[J].岩石矿物学志,2001,20(4)：573-578.
[5]Ryan J A, Zhang P C, Hesterberg D, Sayers D E, Chou J. Formation of chloropyromorphite in a lead-contaminated soil amended with hydroxyapatite [J]. Environ Sci Technol,2001,35:3798-3803.
[6]Tessier A, Campbell P G C, Bisson M. Sequential extraction procedure for the speciation of particulate trace metals. Analy Chem,1979,51(7):844-851.
[7]李波,林玉锁,张孝飞,等.沪宁高速公路两侧土壤和小麦重金属污染状况[J].农村生态环境,2005,21(3)：50-53.
[8]Davidovits J. Recent progresses in concretes for nuclear waste and uranium waste containment [J]. Concrete Internat,1994,16(12):53-58.
[9]Davidovits J. Geopolymeric concretes for environmental protection [J]. Concrete Internat,1990,12(7):30-40.
[10]顾继光,周启星,王新.土壤重金属污染的治理途径及其研究进展[J].应用基础与工程科学学报,2003,11(2)：143-151.
[11]安志装,王校常,施卫明,等.重金属与营养元素交互作用的植物生理效应[J].土壤与环境,2002,11(4)：392-396.
[12]刘珺,秦善.层状硅酸盐矿物对重金属污染的防治[J].岩石矿物学杂志,2001,20(4)：66-71.
[13]Garcia S A, Alvarez A E and Jimenez de B O. Sorption of heavy metals from industrial waste water by low-cost mineral silicates [J]. Clay Miner,1999,34(3): 469-477.
[14]Misaelides P, Godelitsas A, Charistos V. Heavy metal uptake by zeoliferous rocks form Metaxades, Thrace, Greece, exploratory study [J]. J Radioanal Nucl Chem,1994: 159-166.
[15]王湖坤,龚文琪.累脱石改性研究及应用研究[J].非金属矿,2007,30(4)：53-55.
[16]王学锋,朱桂芬.重金属Cd, Pb, Zn在青菜中的富集和分布[C].北京：第三届环境模拟与污染防治学术研讨会论文,2003：25-27.
[17]李双文.重金属进入人体的渠道[J].百科知识,2011,6(1)：32-34.
[18]郝秀珍,周东美.沸石在土壤改良中的应用研究进展[J].土壤,2003,35(2)：133-138.
[19]张超兰,李忠义,邓超冰,等.铅锌矿区农田土壤重金属的统计分析及空间分布研究[J].上海环境科学,2009,28(6)：253-25.
[20]Halim M, Conte P, Piccolo A. Potential availability of heavy metals to phytoextraction from contaminated soils induced by exogenous humic substances [J]. Chemosphere,2003,52:265-275.
[21]贺菊香.治理水口山铅冶炼烟气污染的方案探讨[J].湖南有色金属,2000,16(4)：22-24.
[22]孙树青,胡国华,王勇泽,等.湘江干流水环境健康风险评价[J]. 安全与环境学报,2006,6(2)：12-15.
[23]雷鸣,秦普丰,铁柏清.湖南湘江流域重金属污染的现状与分析[J].农业环境与发展,2010,27(2)：62-65.
[24]郭朝晖,朱永官.典型矿冶周边地区土壤重金属污染及有效性含量[J].生态环境,2004,13(4)：553-555.
[25]郭朝晖,肖细元,陈同斌.湘江中下游农田土壤和蔬菜的重金属污染[J].地理学报,2008,63(1)：3-11.
[26]崔妍,丁永生,公维民,等.土壤中重金属化学形态与植物吸收的关系[J].大连海事大学学报,2005,31(2)：59-63.
[27]蔡保松,陈同斌,廖晓勇,等.土壤砷污染对蔬菜砷含量及食用安全性的影响 [J].生态学报,2004,24(4)：711-716.
[28]曾敏,廖柏寒,曾清如,等.湖南郴州、石门、冷水江3个矿区As污染状况的初步调查[J].农业环境科学学报,2006,25(2)：418-421.
[29]雷鸣,曾敏,郑袁明,等.湖南采矿区和冶炼区水稻土重金属污染及其潜在风险评价[J].环境科学学报,2008,28(6)：1212-1220.
[30]梁佳妮,马友华,周静.土壤重金属污染现状与修复技术研究[J].农业环境与发展,2009,26(4)：45-46.
[31]李选统,卢维盛,李谦,等.土壤重金属污染的修复[J].现代农业科技,2011,39(24)：295-296.
[32]崔德杰,张玉龙.土壤重金属污染现状与修复技术研究进展[J].土壤通报,2004,35(6)：366-370.
[33]Probstein R F, Hick R E. Removal of contaminants from soils by electric fields [J]. Science,1993,260:498-503.
[34]Kawachi T, Kubo H. Model experimental study on the migrationbehavior of heavy metals in electtokinetic remediation process for contaminated soil [J]. Soil Sci Plant Nutr,1999,45(2):259-268.
[35]郑喜坤,鲁安怀,高翔,等.土壤中重金属污染现状与防治方法[J].土壤与环境,2002,11(1)：79-84.
[36]吴龙华,骆永明,黄焕忠,等.铜污染土壤修复的有机调控研究Ⅰ可容性有机物和EDTA对污染土壤的释放作用[J].土壤,2000,32(2)：62-70.
[37]Pichtel J, Pichtel, T M. Comparison of solvents for ex situ removal of chromium and lead from contaminated soil [J]. Environ Engin Sci,1997,14(2):97-104.
[38]曾敏,廖柏寒,曾清如.等.3种萃取剂对土壤重金属的去除及其对重金属有效性的影响[J].农业环境科学学报,2006,25(4)：979-982.
[39]Irving H, Williams RP.1953. The stability of transition-metal complexes [J]. Chem Soc,1953:3192-3210.
[40]廖敏,谢正苗,黄昌勇.镉在土水系统中的迁移特征[J].土壤学报,1998,35(2)：179-184.
[41]陈怀满.土壤—植物系统中的重金属污染[M].北京：科学出版社,1996：71-85.
[42]曾敏CaCO3对土壤Cd污染及Cd与酸雨复合污染的治理研究[D].长沙：湖南农业大学,2004.
[43]曾敏,廖柏寒,张永,等CaCO3对黄豆生长过程中Cd毒害的缓解效应[J].湖南农业大学学报(自然科学版),2004,10(5)：453-456.
[44]江伟武,雷恒毅,张小红.沸石分子筛处理含汞废水研究[J].广东工业大学学报,2000,17(3)：97-100.
[45]蒙冬柳,宋波.沸石在重金属污染土壤修复中的应用进展[J].吉林农业,2011,22(3)：200.
[46]詹树林,林俊雄,方明辉.硅藻土在工业污水处理中的应用研究进展[J].工业水处理,2006,26(9)：10-13.
[47]杨宇翔,王鹏,陈荣三.硅藻土比表面的研究[J].南京大学学报,1991,27(4)：706-714.
[48]颜酉斌,叶艳华,张洪林,等.改性海泡石对有机污染物氯苯的吸附研究[J].中国非金属矿工业导刊,2009,79(6)：42-44.
[49]Raquel S, Blanca C, Malcolm Y, et al. Microwave decomposition of aehlorinated pesticide (Lindane) supported on modified sepiolites [J]. Appl Clay Sci, 2002,22(3): 103-113.
[50]林大松,徐应明,孙国红,等.海泡石黏土矿物对Cu2+的吸附动力学研究[J].环境化学,2009,28(1)：58-61.
[51]徐应明,梁学峰,孙国红,等.海泡石表面化学特性及其对重金属Pb2+、Cd2+、Cu2+吸附机理研究[J].农业环境科学学报,2009,28(10)：2057-2063.
[52]王亮,陈盂林,何星存.改性海泡石对亚甲基蓝的吸附性能[J].过程工程学报,2009,9(6)：1095-1097.
[53]杨飞华,王肇嘉.粘土矿物在环境治理中的应用[J].矿产保护与利用,2005,24(5)：24-27.
[54]Khan A G, Kuek C, Chaudhry T M et al. Role of plants, mycorrhizae and phytochelators in heavy metal contaminated land remediation [J]. Chemosphere,2000, 41(1/2):197-207.
[55]Brigatri M F, Lugli C, Poppi L. Kinetics of heavy-metal removal and recovery in sepiolite [J]. Appl Clay Sci,2000,16(1/2):45-57.
[56]Barbirr F, Duc G, Petit-ramel M. Adsorption of lead and cadmium ions from aqueous solution to the montmorillonite:water interface [J]. Colloids and Surfaces, A: Physicochemical and Engineering Aspects,2000,166(1/3):153-159.
[57]李明德,童潜明,汤海涛,等.海泡石对Cd污染土壤改良效果的研究[J].土壤肥料,2005,41(1)：42-44.
[58]罗惠华,钟康年,刘羽.羟基磷灰石吸附剂去除铬黄工业废水中铅离子的研究[J].岩石矿物学杂志,2001,20(4)：587-589.
[59]刘羽,胥焕岩,黄志良,等.羟基磷灰石吸附水溶液中Cd2+的影响因素的研究[J].岩石矿物学杂志,2001,20(4)：583-586.
[60]李育华,康轩,邓启发,等.土壤重金属污染修复措施研究进展[J].现代农业科技,2011,6(17)：246-248.
[61]金枫,王翠,林海建,等.植物重金属转运蛋白研究进展[J].应用生态学报,2010,21(7)：1875-1882.
[62]刘小宁,马剑英,张慧文,等.植物修复技术在土壤重金属污染中应用的研究进展[J].中国沙漠,2009,29(5)：859-865.
[63]俞协治,成杰民.蚯蚓对土壤中铜、镉生物有效性的影响[J].生态学报,2003,23(5)：922-928.
[64]蒋先军.土壤重金属污染的植物提取修复技术及其应用前景[J].农业环境保护,2000,19(3)：179-183.
[65]张涪平,曹凑贵,李苹,等.藏中矿区重金属污染土壤的微生物活性变化[J].生态学报,2010,30(16)：4452-4459.
[66]崔斌,王凌,张国印,等.土壤重金属污染现状与危害及修复技术研究进展[J].安徽农业科学,2012,40(1)：373-375.
[67]丁园.重金属污染土壤的治理方法[J].环境与开发,2000,15(2)：25-28.
[68]王新.不同作物对重金属复合污染物吸收特征研究[J].农业环境保护,1998,17(5)：193-196.
[69]蒋玉根.农艺措施对降低污染土壤重金属活性的影响[J].土壤,2002,34(3)：145-147.
[70]向言词,黄璜,彭秀花.作物间作对油菜积累镉与铅的影响[J].水土保持学 报,2010,24(3)：50-55.
[71]乔冬梅,齐学斌,庞鸿宾,等.不同pH值对重金属Pb2+形态的影响研究[J].水土保持学报,2010,24(6)：173-176.
[72]荣湘民,宋海星,何增明,等.几种重金属钝化剂及其不同添加比例对猪粪堆肥重金属(As,Cu,Zn)形态转化的影响[J].水土保持学报,2009,23(4)：136-140.
[73]韩晓日,王颖,杨劲峰,等.长期定位施肥对土壤中镉含量的影响及其时空变异研究[J].水土保持学报,2009,23(1)：107-110.
[74]丁凌云,蓝崇钰,林建平,等.不同改良剂对重金属污染农田水稻产量和重金属吸收的影响[J].生态环境,2006,15(6)：1204-1208.
[75]李瑞美,王果,方玲.钙镁磷肥与有机物料配施对作物镉铅吸收的控制效果[J].土壤与环境,2002,11(4)：348-351.
[76]杜玉成,叶力佳,刘燕琴.硅藻土吸附重金属离子Cd2+的动力学研究[J].中国非金属矿工业导刊,2004,38(1)：38-40.
[77]沈岩柏,朱一民,王忠安,魏德洲.硅藻土对水相中Pb2+的吸附[J].东北大学学报(自然科学版),2003,24(10)：982-985.
[78]沈岩柏,朱一民,魏德洲.硅藻土对锌离子的吸附特性[J].东北大学学报(自然科学版),2003,24(9)：907-910.
[79]叶力佳.硅藻土对废水中重金属离子的吸附性能研究[D].北京：北京工业大学,2003：8.
[80]袁笛,王莹,李国宏,等硅藻土吸附工业废水中汞离子的研究[J].环境保护科学,2005,30(2)：27-29.
[81]王秀春,丁志斌,都的箭.沸石的性能及其在水处理中的应用[J].解放军理工大学学报,2001,2(4)：74-77.
[82]Paola C, Laura S, Pietro M. Heavy metal immobilization by chemical amendments in a polluted soil and influence on white lupin growth[J]. Chemosphere, 2005,60:365-371.
[83]Querol X, Alastuey A, Moreno N, et al. Immobilization of heavy metals in polluted soils by the addition of zeolite material synthesized from coal fly ash [J]. Chemosphere,2006,62:171-180.
[84]张乃娴.黏土矿物研究方法[M].北京：科学出版社,1990：72-75.
[85]冯秀娟,王海宁,普红平.改性海泡石在环境污染治理中的应用[J].环境污染治理技术与设备,2004,5(4)：80-83.
[86]孙胜龙,龙振永,蔡保丰.非金属矿物修复环境机理研究现状[J].地球科学进展,1999,13(5)：475-477.
[87]鲁安怀.环境矿物材料在土壤、水体、大气污染治理中的利用[J].岩石矿物杂志,1999,17(4)：295-299.
[88]章燕豪.吸附作用[M].上海：上海科学技术文献出版社,1987：3-7,46-47.
[89]Ma L Q, Ran G N. Aqueous Pb reduction in Pb-contaminated soil by Florida phosphate rocks [J]. Water Air Soil Pollut,1999,110:1-16.
[2]刘素纯,萧浪涛,王惠群,等.植物对重金属的吸收机制与植物修复技术[J].湖南农业大学学报(自然科学版),2004,30(5)：493-498.
[3]Ford R C, Sparks D L. The nature of Zn precipitates formed in the presence of pyrophyllite [J]. Environ Sci Technol,2000,34:2479-2483.
[4]何宏乎,郭九皋.蒙脱石、高岭石、伊利石对重金属离子吸附容量的实验研究[J].岩石矿物学志,2001,20(4)：573-578.
[5]Ryan J A, Zhang P C, Hesterberg D, Sayers D E, Chou J. Formation of chloropyromorphite in a lead-contaminated soil amended with hydroxyapatite [J]. Environ Sci Technol,2001,35:3798-3803.
[6]Tessier A, Campbell P G C, Bisson M. Sequential extraction procedure for the speciation of particulate trace metals. Analy Chem,1979,51(7):844-851.
[7]李波,林玉锁,张孝飞,等.沪宁高速公路两侧土壤和小麦重金属污染状况[J].农村生态环境,2005,21(3)：50-53.
[8]Davidovits J. Recent progresses in concretes for nuclear waste and uranium waste containment [J]. Concrete Internat,1994,16(12):53-58.
[9]Davidovits J. Geopolymeric concretes for environmental protection [J]. Concrete Internat,1990,12(7):30-40.
[10]顾继光,周启星,王新.土壤重金属污染的治理途径及其研究进展[J].应用基础与工程科学学报,2003,11(2)：143-151.
[11]安志装,王校常,施卫明,等.重金属与营养元素交互作用的植物生理效应[J].土壤与环境,2002,11(4)：392-396.
[12]刘珺,秦善.层状硅酸盐矿物对重金属污染的防治[J].岩石矿物学杂志,2001,20(4)：66-71.
[13]Garcia S A, Alvarez A E and Jimenez de B O. Sorption of heavy metals from industrial waste water by low-cost mineral silicates [J]. Clay Miner,1999,34(3): 469-477.
[14]Misaelides P, Godelitsas A, Charistos V. Heavy metal uptake by zeoliferous rocks form Metaxades, Thrace, Greece, exploratory study [J]. J Radioanal Nucl Chem,1994: 159-166.
[15]王湖坤,龚文琪.累脱石改性研究及应用研究[J].非金属矿,2007,30(4)：53-55.
[16]王学锋,朱桂芬.重金属Cd, Pb, Zn在青菜中的富集和分布[C].北京：第三届环境模拟与污染防治学术研讨会论文,2003：25-27.
[17]李双文.重金属进入人体的渠道[J].百科知识,2011,6(1)：32-34.
[18]郝秀珍,周东美.沸石在土壤改良中的应用研究进展[J].土壤,2003,35(2)：133-138.
[19]张超兰,李忠义,邓超冰,等.铅锌矿区农田土壤重金属的统计分析及空间分布研究[J].上海环境科学,2009,28(6)：253-25.
[20]Halim M, Conte P, Piccolo A. Potential availability of heavy metals to phytoextraction from contaminated soils induced by exogenous humic substances [J]. Chemosphere,2003,52:265-275.
[21]贺菊香.治理水口山铅冶炼烟气污染的方案探讨[J].湖南有色金属,2000,16(4)：22-24.
[22]孙树青,胡国华,王勇泽,等.湘江干流水环境健康风险评价[J]. 安全与环境学报,2006,6(2)：12-15.
[23]雷鸣,秦普丰,铁柏清.湖南湘江流域重金属污染的现状与分析[J].农业环境与发展,2010,27(2)：62-65.
[24]郭朝晖,朱永官.典型矿冶周边地区土壤重金属污染及有效性含量[J].生态环境,2004,13(4)：553-555.
[25]郭朝晖,肖细元,陈同斌.湘江中下游农田土壤和蔬菜的重金属污染[J].地理学报,2008,63(1)：3-11.
[26]崔妍,丁永生,公维民,等.土壤中重金属化学形态与植物吸收的关系[J].大连海事大学学报,2005,31(2)：59-63.
[27]蔡保松,陈同斌,廖晓勇,等.土壤砷污染对蔬菜砷含量及食用安全性的影响 [J].生态学报,2004,24(4)：711-716.
[28]曾敏,廖柏寒,曾清如,等.湖南郴州、石门、冷水江3个矿区As污染状况的初步调查[J].农业环境科学学报,2006,25(2)：418-421.
[29]雷鸣,曾敏,郑袁明,等.湖南采矿区和冶炼区水稻土重金属污染及其潜在风险评价[J].环境科学学报,2008,28(6)：1212-1220.
[30]梁佳妮,马友华,周静.土壤重金属污染现状与修复技术研究[J].农业环境与发展,2009,26(4)：45-46.
[31]李选统,卢维盛,李谦,等.土壤重金属污染的修复[J].现代农业科技,2011,39(24)：295-296.
[32]崔德杰,张玉龙.土壤重金属污染现状与修复技术研究进展[J].土壤通报,2004,35(6)：366-370.
[33]Probstein R F, Hick R E. Removal of contaminants from soils by electric fields [J]. Science,1993,260:498-503.
[34]Kawachi T, Kubo H. Model experimental study on the migrationbehavior of heavy metals in electtokinetic remediation process for contaminated soil [J]. Soil Sci Plant Nutr,1999,45(2):259-268.
[35]郑喜坤,鲁安怀,高翔,等.土壤中重金属污染现状与防治方法[J].土壤与环境,2002,11(1)：79-84.
[36]吴龙华,骆永明,黄焕忠,等.铜污染土壤修复的有机调控研究Ⅰ可容性有机物和EDTA对污染土壤的释放作用[J].土壤,2000,32(2)：62-70.
[37]Pichtel J, Pichtel, T M. Comparison of solvents for ex situ removal of chromium and lead from contaminated soil [J]. Environ Engin Sci,1997,14(2):97-104.
[38]曾敏,廖柏寒,曾清如.等.3种萃取剂对土壤重金属的去除及其对重金属有效性的影响[J].农业环境科学学报,2006,25(4)：979-982.
[39]Irving H, Williams RP.1953. The stability of transition-metal complexes [J]. Chem Soc,1953:3192-3210.
[40]廖敏,谢正苗,黄昌勇.镉在土水系统中的迁移特征[J].土壤学报,1998,35(2)：179-184.
[41]陈怀满.土壤—植物系统中的重金属污染[M].北京：科学出版社,1996：71-85.
[42]曾敏CaCO3对土壤Cd污染及Cd与酸雨复合污染的治理研究[D].长沙：湖南农业大学,2004.
[43]曾敏,廖柏寒,张永,等CaCO3对黄豆生长过程中Cd毒害的缓解效应[J].湖南农业大学学报(自然科学版),2004,10(5)：453-456.
[44]江伟武,雷恒毅,张小红.沸石分子筛处理含汞废水研究[J].广东工业大学学报,2000,17(3)：97-100.
[45]蒙冬柳,宋波.沸石在重金属污染土壤修复中的应用进展[J].吉林农业,2011,22(3)：200.
[46]詹树林,林俊雄,方明辉.硅藻土在工业污水处理中的应用研究进展[J].工业水处理,2006,26(9)：10-13.
[47]杨宇翔,王鹏,陈荣三.硅藻土比表面的研究[J].南京大学学报,1991,27(4)：706-714.
[48]颜酉斌,叶艳华,张洪林,等.改性海泡石对有机污染物氯苯的吸附研究[J].中国非金属矿工业导刊,2009,79(6)：42-44.
[49]Raquel S, Blanca C, Malcolm Y, et al. Microwave decomposition of aehlorinated pesticide (Lindane) supported on modified sepiolites [J]. Appl Clay Sci, 2002,22(3): 103-113.
[50]林大松,徐应明,孙国红,等.海泡石黏土矿物对Cu2+的吸附动力学研究[J].环境化学,2009,28(1)：58-61.
[51]徐应明,梁学峰,孙国红,等.海泡石表面化学特性及其对重金属Pb2+、Cd2+、Cu2+吸附机理研究[J].农业环境科学学报,2009,28(10)：2057-2063.
[52]王亮,陈盂林,何星存.改性海泡石对亚甲基蓝的吸附性能[J].过程工程学报,2009,9(6)：1095-1097.
[53]杨飞华,王肇嘉.粘土矿物在环境治理中的应用[J].矿产保护与利用,2005,24(5)：24-27.
[54]Khan A G, Kuek C, Chaudhry T M et al. Role of plants, mycorrhizae and phytochelators in heavy metal contaminated land remediation [J]. Chemosphere,2000, 41(1/2):197-207.
[55]Brigatri M F, Lugli C, Poppi L. Kinetics of heavy-metal removal and recovery in sepiolite [J]. Appl Clay Sci,2000,16(1/2):45-57.
[56]Barbirr F, Duc G, Petit-ramel M. Adsorption of lead and cadmium ions from aqueous solution to the montmorillonite:water interface [J]. Colloids and Surfaces, A: Physicochemical and Engineering Aspects,2000,166(1/3):153-159.
[57]李明德,童潜明,汤海涛,等.海泡石对Cd污染土壤改良效果的研究[J].土壤肥料,2005,41(1)：42-44.
[58]罗惠华,钟康年,刘羽.羟基磷灰石吸附剂去除铬黄工业废水中铅离子的研究[J].岩石矿物学杂志,2001,20(4)：587-589.
[59]刘羽,胥焕岩,黄志良,等.羟基磷灰石吸附水溶液中Cd2+的影响因素的研究[J].岩石矿物学杂志,2001,20(4)：583-586.
[60]李育华,康轩,邓启发,等.土壤重金属污染修复措施研究进展[J].现代农业科技,2011,6(17)：246-248.
[61]金枫,王翠,林海建,等.植物重金属转运蛋白研究进展[J].应用生态学报,2010,21(7)：1875-1882.
[62]刘小宁,马剑英,张慧文,等.植物修复技术在土壤重金属污染中应用的研究进展[J].中国沙漠,2009,29(5)：859-865.
[63]俞协治,成杰民.蚯蚓对土壤中铜、镉生物有效性的影响[J].生态学报,2003,23(5)：922-928.
[64]蒋先军.土壤重金属污染的植物提取修复技术及其应用前景[J].农业环境保护,2000,19(3)：179-183.
[65]张涪平,曹凑贵,李苹,等.藏中矿区重金属污染土壤的微生物活性变化[J].生态学报,2010,30(16)：4452-4459.
[66]崔斌,王凌,张国印,等.土壤重金属污染现状与危害及修复技术研究进展[J].安徽农业科学,2012,40(1)：373-375.
[67]丁园.重金属污染土壤的治理方法[J].环境与开发,2000,15(2)：25-28.
[68]王新.不同作物对重金属复合污染物吸收特征研究[J].农业环境保护,1998,17(5)：193-196.
[69]蒋玉根.农艺措施对降低污染土壤重金属活性的影响[J].土壤,2002,34(3)：145-147.
[70]向言词,黄璜,彭秀花.作物间作对油菜积累镉与铅的影响[J].水土保持学 报,2010,24(3)：50-55.
[71]乔冬梅,齐学斌,庞鸿宾,等.不同pH值对重金属Pb2+形态的影响研究[J].水土保持学报,2010,24(6)：173-176.
[72]荣湘民,宋海星,何增明,等.几种重金属钝化剂及其不同添加比例对猪粪堆肥重金属(As,Cu,Zn)形态转化的影响[J].水土保持学报,2009,23(4)：136-140.
[73]韩晓日,王颖,杨劲峰,等.长期定位施肥对土壤中镉含量的影响及其时空变异研究[J].水土保持学报,2009,23(1)：107-110.
[74]丁凌云,蓝崇钰,林建平,等.不同改良剂对重金属污染农田水稻产量和重金属吸收的影响[J].生态环境,2006,15(6)：1204-1208.
[75]李瑞美,王果,方玲.钙镁磷肥与有机物料配施对作物镉铅吸收的控制效果[J].土壤与环境,2002,11(4)：348-351.
[76]杜玉成,叶力佳,刘燕琴.硅藻土吸附重金属离子Cd2+的动力学研究[J].中国非金属矿工业导刊,2004,38(1)：38-40.
[77]沈岩柏,朱一民,王忠安,魏德洲.硅藻土对水相中Pb2+的吸附[J].东北大学学报(自然科学版),2003,24(10)：982-985.
[78]沈岩柏,朱一民,魏德洲.硅藻土对锌离子的吸附特性[J].东北大学学报(自然科学版),2003,24(9)：907-910.
[79]叶力佳.硅藻土对废水中重金属离子的吸附性能研究[D].北京：北京工业大学,2003：8.
[80]袁笛,王莹,李国宏,等硅藻土吸附工业废水中汞离子的研究[J].环境保护科学,2005,30(2)：27-29.
[81]王秀春,丁志斌,都的箭.沸石的性能及其在水处理中的应用[J].解放军理工大学学报,2001,2(4)：74-77.
[82]Paola C, Laura S, Pietro M. Heavy metal immobilization by chemical amendments in a polluted soil and influence on white lupin growth[J]. Chemosphere, 2005,60:365-371.
[83]Querol X, Alastuey A, Moreno N, et al. Immobilization of heavy metals in polluted soils by the addition of zeolite material synthesized from coal fly ash [J]. Chemosphere,2006,62:171-180.
[84]张乃娴.黏土矿物研究方法[M].北京：科学出版社,1990：72-75.
[85]冯秀娟,王海宁,普红平.改性海泡石在环境污染治理中的应用[J].环境污染治理技术与设备,2004,5(4)：80-83.
[86]孙胜龙,龙振永,蔡保丰.非金属矿物修复环境机理研究现状[J].地球科学进展,1999,13(5)：475-477.
[87]鲁安怀.环境矿物材料在土壤、水体、大气污染治理中的利用[J].岩石矿物杂志,1999,17(4)：295-299.
[88]章燕豪.吸附作用[M].上海：上海科学技术文献出版社,1987：3-7,46-47.
[89]Ma L Q, Ran G N. Aqueous Pb reduction in Pb-contaminated soil by Florida phosphate rocks [J]. Water Air Soil Pollut,1999,110:1-16.