污灌土壤中重金属形态及化学治理研究
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摘要
近年来，由于人口急剧增长和工业迅猛发展，固体废物向土壤表面堆放倾倒、有害废水向土壤中渗透、大气中的有害气体及飘尘不断随雨水降落在土壤中及大量引用工业污水灌溉致使土壤污染日益严重化，土壤污染问题已成为一个亟待重视和解决的问题。土壤污染的类型大致可以分为重金属污染、农药和有机物污染、放射性污染、病原菌污染等。重金属污染是造成土壤环境质量下降的重要原因之一，和其他类型的污染物相比，重金属污染的特殊性在于它很难被土壤微生物降解而从环境中彻底消除，当其在土壤中积累到一定程度时，就会对土壤—植物系统产生毒害和破坏作用。重金属污染物难降解、易积累、毒性大，并且具有隐蔽性、长期性和不可逆转性的特点，是影响生态系统安全的一类重要污染物质。并且由于重金属存留于表层土壤中容易使农作物吸收，并通过食物链对人体造成严重的危害，使重金属污染的治理研究早已成为国际论坛及科研的焦点。
长期以来，由于我国单纯注重经济的发展，对环境污染持有先污染后治理的态度，因而忽略了对环境的保护，导致环境质量日益下降。而今，人类生存与发展一刻也离不开环境，可持续发展的战略的提出使人类保护生态环境的认识提高到一个新的高度，要求在满足当代人的需求的同时，不影响后代人生存的能力。由此，针对白银地区污灌土壤重金属污染的特点，应用相适应的科学手段，提出可行的治理措施以降低重金属生物有效性和毒性是十分必要的。
第一章土壤重金属污染状况及化学治理技术
文中较为详细地介绍了我国和白银地区重金属污染状况及危害、相关土壤中重金属形态与生物有效性的研究，以及污染土壤中重金属的化学固定及淋洗的研究进展，并对已有的土壤固定剂和冲洗剂进行了评述，共引用文献75篇。
第二章腐殖酸对污灌土壤中Cu、Cd、Pb、Zn形态的影响研究
土壤中过量的有毒重金属如Cu、Cd、Pb、Zn对农作物生长及人类的健康都有极大的危害，它们在土壤中的不同形态也直接影响其在环境中的迁移转化及毒性。腐殖酸(Humic acid简称HA)是地球生态环境中分布最为广泛的天然有机物，约占土壤有机质60％，由于其复杂的结构和多种官能团的高反应活性，对重金属进入土壤环境后的毒性及生物有效性有着重要的影响和调控作用。本章选择腐殖酸以及柠檬酸、乙酸和EDTA为土壤添加物，对比研究了不同添加量及不同pH值条件时，腐殖酸等对污灌土壤中Cu、Cd、Pb、Zn不同形态的影响。结果显示：在污灌土壤中添加腐殖酸可以改变土壤对重金属离子各形态的吸持能力，使具有直接毒性的重金属可溶态急剧减少60—80％，同时使重金属氧化物结合态、碳酸盐结合态及有机结合态增加，降低重金属在土壤中的流动性、活性和生物可利用性。
第三章腐殖酸对Cd在黄土上吸附特性影响的研究
腐殖酸是土壤环境中的重要天然有机物，含有较多的活性基团和具有特殊结构，使其与金属离子能够发生离子交换、表面吸附、配位和凝结等作用。近年来土壤中存在的天然可溶有机物对重金属迁移转化的影响引起了研究者们极大兴趣，但主要集中于天然有机物对重金属吸附解吸的研究。本章研究了腐殖酸对Cd在西部黄土上的吸附特征的影响，并对其它相关影响因素进行了研究。结果显示：无论是否加入腐殖酸，Cd的吸附都能够较好地符合Freundlich方程，25℃时加入10ml 55mg·L~(-1)的腐殖酸使土样对Cd的饱和吸附量由29.22mmol·kg~(-1)增加到了31.39mmol·kg~(-1)，并且吸附量随温度升高而降低，表明吸附为放热过程。加入与不加腐殖酸相比，吸附标准自由能改变量分别为△G_2~θ=-0.9497kJ·mol~(-1)和△G_1~θ=-0.8885kJ·mol~(-1)，不加腐殖酸时，描述Cd在供试土样上的吸附动力学最优方程为Elovich方程，其次为双常数方程；加入腐殖酸溶液后，其吸附动力学最优方程改变为双常数方程，且Cd的吸附平衡时间缩短。随着加入腐殖酸量的增加，土壤样品对Cd的吸附量明显增加；随pH值的增加，加入腐殖酸降低了土壤对Cd的吸附增加量。
第四章表面活性剂强化EDTA络合洗脱污灌土壤中的重金属
土壤冲洗技术在淋洗液中加入有机或无机酸降低土壤pH值、加入无污染的电解质溶液交换解吸和加入有机配体生成水溶性配合物等以释放存留于土壤固相的重金属。其中有机配体如EDTA由于对土壤性质影响较小，对多种重金属有较好的络合溶解能力，已有较为深入的研究。现应用表面活性剂对有毒有机污染物增溶洗脱的研究较多，但对于表面活性剂应用于重金属的解吸及与螯合剂复合解吸研究相对较少。
本章选用白银地区污灌土壤为供试样品，以两种表面活性剂与EDTA复合应用于重金属Cd和Pb的解吸，以补偿单一解吸剂使用时的缺点，同时根据复合解吸前后土壤样品中Cd、Pb形态的变化情况，综合评价复合洗脱的效果。结果显示：加入表面活性剂SDS可使EDTA对Cd的解吸量由61.67％增加到79.68％，对Pb的解吸量由57.25％增加到89.65％。在EDTA浓度较小时，加入SDS对Cd、Pb的解吸产生拮抗作用，抑制了EDTA对污染土样中Cd、Pb的解吸；随着EDTA浓度的不断增加，加入SDS与EDTA产生明显的协同增溶作用；表面活性剂Brij35具有相同的增溶作用，且增溶效果SDS＞Brij35。比较复配解吸前后重金属形态变化，可溶态、碳酸盐结合态较解吸前减少60％-90％，大大降低了污灌土壤中重金属的毒性和生物可利用性。
第五章皂角苷络合洗脱污灌土壤中重金属的研究
生物表面活性剂具有低毒性、生物可降解性和表面活性等优点，并可回收加以重复利用，具有较高的经济价值，并且其在环境治理方面的应用也引起了研究者的关注。
本章选用白银地区污灌土壤为供试样品，采用生物表面活性剂皂角苷对土样中重金属进行解吸研究，同时根据解吸前后土壤样品中重金属形态的变化情况，综合评价皂角苷洗脱的效果。实验结果显示：随皂角苷浓度增加，土样中Cu、Cd、Pb、Zn的解吸率也不断增加，在皂角苷浓度为3％时，Cu、Cd、Pb、Zn解吸量分别达到43.87％95.11％、83.54％和20.34％，而单独用水冲洗各重金属解吸量最大不超过5％；并且发现随土壤pH值增加，重金属解吸量逐渐减小。同时实验结果显示离子强度对Pb、Zn影响不大，而Cu、Cd随离子强度增大解吸量减小。比较冲洗前后重金属形态的变化，发现Cu、Cd、Pb、Zn的可溶态、碳酸盐结合态减少在50％以上，而氧化物结合态和残渣态含量略有减少。表明皂角苷与重金属形成稳定的可溶性的络合物，大大降低土壤对重金属的吸附作用，从而降低了土壤中重金属的毒性和生物可利用性，因此生物表面活性剂皂角苷对污灌土样中重金属具有较好的冲洗去除效果。
There are currently many sites that contain soils contaminated with heavy metals because of incresement of population, rapid development of industry, leacheat and run off from waste solids on soil surface, hazardous material in atmosphere fall on the ground and irrigated by sewage water, et, al. Heavy metal-contaminated soil is one of most common problem and much need of recognition and settlement. There are mainly five kinds of soil pollution: heavy metal-contaminated soil, rdionclides of metal, pesticides and hazardous organic compounds and biologic containment. It is not only hard to degrade and also retain in surface of soil, which easy to assimilate by crop, and tranfer in food chain. Heavy metal pollution is the important reasons for degrading of soil quality, and comparing with orther pollutants the particularity of metal pollution is that it is hard to biotic degrad and etire died away. When reached a high concentration, it can be detrimental and destroy the soil-plant system.
It was only focus on developing of our national economy in long-term, and people hold viewpoint of contamination first, then remediation on environmental pollution. So the environmental protect against pollution has been ignored, which lead to reduce of environmental quality. Nowdays survive and development of people maintain close ties with the environment and the proposition of sustainable development strategy is to enhance the knowledge that human protect the ecological environment to a new height, it is also required that doesn't influence the survival ability of offspring while meeting contemporary people's demands. So it is necessary for us to take effect measure to effectively increase the resistance to bioavailability and toxicity of heavy metals in sewage farm in the light of situaion of metal-contaminated soil in Baiyin.
Chapter 1.
Situation of soils contaminated by heavy metals and the chemicalremediation technology by solidification and solubilization
A review with 75 references is given on characteristics and current situation of contaminated by heavy metals and the relation between species and bioavailability of heavy metals in soil. There are two main type of remediation for metal contaminated soil: solidification/stabilization and desorption/solubilization, which mainly are discussed. In addition, some kinds of agents for solidification and desorption of heavy metals in soil also dicussed in these section.
Chapter 2.The effect of humic acid on species of Cu、Cd、Pb、Zn in sewage farm.
The superfluous heavy metals are harm for health of human being and the different speciation of heavy metals has direct influence on tranfer and transform and toxicity of heavy metals in soils. Humic acid is the most common natural organic matter in soil, and it is about 60% in soil organic matter. It has an important influence on toxicity and bioavailability of heavy metals in soil environment because of its complex structure and high activity of functional groups. Although, natural organic matter and its effect on tranfer and tranform of heavy metals have been studied, it mainly about sorption and desorption of heavy metals, but the effect of humic acid on speciation of heavy metals has not studied in previous work. To investigate the effects of humic acid on the speciations of heavy metals, such as Cu, Pb, Zn and Cd in sewage farm in Baiyin, four kinds of organic matters including humic acid, EDTA, citric acid and acetic acid were added, respectively, in polluted soil with a method of successive extraction performed to determine the species of heavy metals. The results showed that humic acid could remarkably decrease the content of soluble heavy metals with about60—80 %, while increase the fractions of Fe+Al+MnO_x and carbonate, which demonstrated clearly that huimc substance, under certain conditions, could effectively increase the resistance to bioavailability and toxicity of heavy metals in sewage farm.
Chapter 3.Study on sorption of Cd on loess soil affected by humic acid.
Humic acid is the most common natural organic matter in soil, and it has some engernic groups. It can be sorption and complexing with heavy metals because of its special structure and high activity of functional groups. Natural organic matter and its effect on tranfer and tranform of heavy metals has been studied, mainly about sorption and desorption of heavy metals, In this section vibration-centrifuge experiments were chosen to study on adsorption isotherms and adsorption thermodynamics of Cd on loess soil affected by humic acid in order to study the tranfer and transform regulation of heavy metal in soil. The results showed that the adsorption of Cd on loess soils fitted well with Freundlich isothermal equation no matter with or without humic acid, and the adsorption capacity of Cd increased from 29.22 mmol·kg~(-1) to 31.39 mmol·kg~(-1) by adding 10ml 55mg·L~(-1) humic acid solution at 25°C, The adsorption quantity of Cd were reduced with increasing of environmental temperature, which indicated that adsorption of Cd was an excergic process, meanwhile, the respective adsorption standard free energy were△G_2~θ=-0.9497kJ·mol~(-1) and△G_1~θ=-0.8885kJ·mol~(-1) with or without humic acid. The adsorption kinetics of Cd fitted with Evolich kinetics equation the best, and then was Double constant equation, but it changed to Double constant equation at present of humic acid. The adsorption speed of Cd is faster then no humic acid at present. The adsorption capability of Cd increased with an increase in the humic acid concentration and the solution pH. The adsorption quantity of Cd was high at low pH then high pH.
Chapter 4.Surfactants enhanced soils washing efficiency of heavy metal with EDTA.
Soil washing is common used to treat soils contaminated with heavy metal that separated heavy from soils in an aqueous-based system. The wash water may be augmented with a basic leaching agent, acid, surfactant, pH adjustments, or chealting agents in order to separate heavy metals that absorbed on soil surface. The most common chelating agent studied in the literature is ethylenediamine-tetraacetic acid (EDTA) because of its strong chelation nature, and little influence on soil nature. Meanwhile, the most study on desorption of organic pollutants in soils by surfactants carried out, but not mainly about heavy metals desorption. In this section, the effects of sodium dodecyl sulfate(SDS)、laural polooxyethylene ether(Brij35) and Ethylenediaminetetraacetic acid(EDTA) on desorption of Cd and Pb from the soil contaminated by the wastewater irrigation are studied in laboratory, respectively, while the influence of adding SDS and Brij35 on EDTA desorption capacity is certified. The changes of the heavy metal's species before and after desorption in the soil matrix are certified too. The experimental results show that the removal of Cd from the soil increases from 61.67% by using EDTA alone to 79.68% if adding SDS, meantime, the removal of Pb increases from 57.25% to 79.68%. However, the addition of the surfactants could restrain the desorption capacity of EDTA, if EDTA has a lower concentration. SDS can significantly enhance the synergetic solubilization of Cd and Pb by an increase of EDTA concentrations. Brij35 has the same effect on the enhanced solubilization of Cd and Pb, but its efficiency appears to be little weaker than SDS. With a comparison of the changes of the heavy metal species in the desorption processes, the contents of soluble and carbonate species were decreased by 60-90% compared to that measured before desorption. It is said that bioavailability and toxicity of heavy metals in sewage farm have been decreased. The research results not only could theoretically provide the approach how to use surfactants to enhance the complexing capacity of EDTA for desorption of heavy metals from soil media, but also could extensively be used in the in-situ flushing technique for heavy metal contaminated soils. The research results not only could theoretically provide the approach how to use surfactants to enhance the complexing capacity of EDTA for desorption of heavy metals from soil media, but also could extensively be used in the in-situ flushing technique for heavy metal contaminated soils.
Chapter 5.Study on desorption of heavy metal in sewage-irrigated soil bycomplexing with saponin.
Biosurfactant which contains a hydrophobic portion and a hydrophilic group from qullaja bark seemed to be an attractive cleaning agent in environmental applications for researchers because of its biodegradability, low loxicity, possibility of reuse, and high economic value.
In this section, the vibration-centrifuge experiments were performed to evaluate the feasibility of using saponin for the removal of heavy metals from the soil contaminated by the wastewater irrigation in laboratory, respectively, the sequential extraction procedure were selected to determine the speciation of heavy metal, at the same time, recovery of heavy metals and recycle of used saponin were also studied as a method for decreasing the costs of remediation processes. The results showed that desorption efficiency could be enhanced with the increase of the added Saponin concentrations, and could finally reach 43.9%, 95.1%, 83.5% and 20.7% for Cu、Cd、Pb、and Zn, respectively, by adding 3.0% of Saponin, while desorption by water alone was less than 5%. It was also found that the desorbed amount gradually decreased with the increase of pH values of the soil, which indicated that the high removal only take place in the week acidic environment. The ionic strength slightly had a negative influence on the desorption of Cd、Cu, but no efforts on Pb、Zn. Comparing the spices transformation of heavy metals before and after desorption in the soil matrix by Tesseri method, it was evident that soluble spices and carbonated fractions of Cu、Cd、Pb、Zn adsorbed on the soil surfaces were washed away tremendously but oxidant-combined and residual spices only reduced little. As a result, the toxicity and bio-reusability of the heavy metals were significantly decreased.
长期以来，由于我国单纯注重经济的发展，对环境污染持有先污染后治理的态度，因而忽略了对环境的保护，导致环境质量日益下降。而今，人类生存与发展一刻也离不开环境，可持续发展的战略的提出使人类保护生态环境的认识提高到一个新的高度，要求在满足当代人的需求的同时，不影响后代人生存的能力。由此，针对白银地区污灌土壤重金属污染的特点，应用相适应的科学手段，提出可行的治理措施以降低重金属生物有效性和毒性是十分必要的。
第一章土壤重金属污染状况及化学治理技术
文中较为详细地介绍了我国和白银地区重金属污染状况及危害、相关土壤中重金属形态与生物有效性的研究，以及污染土壤中重金属的化学固定及淋洗的研究进展，并对已有的土壤固定剂和冲洗剂进行了评述，共引用文献75篇。
第二章腐殖酸对污灌土壤中Cu、Cd、Pb、Zn形态的影响研究
土壤中过量的有毒重金属如Cu、Cd、Pb、Zn对农作物生长及人类的健康都有极大的危害，它们在土壤中的不同形态也直接影响其在环境中的迁移转化及毒性。腐殖酸(Humic acid简称HA)是地球生态环境中分布最为广泛的天然有机物，约占土壤有机质60％，由于其复杂的结构和多种官能团的高反应活性，对重金属进入土壤环境后的毒性及生物有效性有着重要的影响和调控作用。本章选择腐殖酸以及柠檬酸、乙酸和EDTA为土壤添加物，对比研究了不同添加量及不同pH值条件时，腐殖酸等对污灌土壤中Cu、Cd、Pb、Zn不同形态的影响。结果显示：在污灌土壤中添加腐殖酸可以改变土壤对重金属离子各形态的吸持能力，使具有直接毒性的重金属可溶态急剧减少60—80％，同时使重金属氧化物结合态、碳酸盐结合态及有机结合态增加，降低重金属在土壤中的流动性、活性和生物可利用性。
第三章腐殖酸对Cd在黄土上吸附特性影响的研究
腐殖酸是土壤环境中的重要天然有机物，含有较多的活性基团和具有特殊结构，使其与金属离子能够发生离子交换、表面吸附、配位和凝结等作用。近年来土壤中存在的天然可溶有机物对重金属迁移转化的影响引起了研究者们极大兴趣，但主要集中于天然有机物对重金属吸附解吸的研究。本章研究了腐殖酸对Cd在西部黄土上的吸附特征的影响，并对其它相关影响因素进行了研究。结果显示：无论是否加入腐殖酸，Cd的吸附都能够较好地符合Freundlich方程，25℃时加入10ml 55mg·L~(-1)的腐殖酸使土样对Cd的饱和吸附量由29.22mmol·kg~(-1)增加到了31.39mmol·kg~(-1)，并且吸附量随温度升高而降低，表明吸附为放热过程。加入与不加腐殖酸相比，吸附标准自由能改变量分别为△G_2~θ=-0.9497kJ·mol~(-1)和△G_1~θ=-0.8885kJ·mol~(-1)，不加腐殖酸时，描述Cd在供试土样上的吸附动力学最优方程为Elovich方程，其次为双常数方程；加入腐殖酸溶液后，其吸附动力学最优方程改变为双常数方程，且Cd的吸附平衡时间缩短。随着加入腐殖酸量的增加，土壤样品对Cd的吸附量明显增加；随pH值的增加，加入腐殖酸降低了土壤对Cd的吸附增加量。
第四章表面活性剂强化EDTA络合洗脱污灌土壤中的重金属
土壤冲洗技术在淋洗液中加入有机或无机酸降低土壤pH值、加入无污染的电解质溶液交换解吸和加入有机配体生成水溶性配合物等以释放存留于土壤固相的重金属。其中有机配体如EDTA由于对土壤性质影响较小，对多种重金属有较好的络合溶解能力，已有较为深入的研究。现应用表面活性剂对有毒有机污染物增溶洗脱的研究较多，但对于表面活性剂应用于重金属的解吸及与螯合剂复合解吸研究相对较少。
本章选用白银地区污灌土壤为供试样品，以两种表面活性剂与EDTA复合应用于重金属Cd和Pb的解吸，以补偿单一解吸剂使用时的缺点，同时根据复合解吸前后土壤样品中Cd、Pb形态的变化情况，综合评价复合洗脱的效果。结果显示：加入表面活性剂SDS可使EDTA对Cd的解吸量由61.67％增加到79.68％，对Pb的解吸量由57.25％增加到89.65％。在EDTA浓度较小时，加入SDS对Cd、Pb的解吸产生拮抗作用，抑制了EDTA对污染土样中Cd、Pb的解吸；随着EDTA浓度的不断增加，加入SDS与EDTA产生明显的协同增溶作用；表面活性剂Brij35具有相同的增溶作用，且增溶效果SDS＞Brij35。比较复配解吸前后重金属形态变化，可溶态、碳酸盐结合态较解吸前减少60％-90％，大大降低了污灌土壤中重金属的毒性和生物可利用性。
第五章皂角苷络合洗脱污灌土壤中重金属的研究
生物表面活性剂具有低毒性、生物可降解性和表面活性等优点，并可回收加以重复利用，具有较高的经济价值，并且其在环境治理方面的应用也引起了研究者的关注。
本章选用白银地区污灌土壤为供试样品，采用生物表面活性剂皂角苷对土样中重金属进行解吸研究，同时根据解吸前后土壤样品中重金属形态的变化情况，综合评价皂角苷洗脱的效果。实验结果显示：随皂角苷浓度增加，土样中Cu、Cd、Pb、Zn的解吸率也不断增加，在皂角苷浓度为3％时，Cu、Cd、Pb、Zn解吸量分别达到43.87％95.11％、83.54％和20.34％，而单独用水冲洗各重金属解吸量最大不超过5％；并且发现随土壤pH值增加，重金属解吸量逐渐减小。同时实验结果显示离子强度对Pb、Zn影响不大，而Cu、Cd随离子强度增大解吸量减小。比较冲洗前后重金属形态的变化，发现Cu、Cd、Pb、Zn的可溶态、碳酸盐结合态减少在50％以上，而氧化物结合态和残渣态含量略有减少。表明皂角苷与重金属形成稳定的可溶性的络合物，大大降低土壤对重金属的吸附作用，从而降低了土壤中重金属的毒性和生物可利用性，因此生物表面活性剂皂角苷对污灌土样中重金属具有较好的冲洗去除效果。
There are currently many sites that contain soils contaminated with heavy metals because of incresement of population, rapid development of industry, leacheat and run off from waste solids on soil surface, hazardous material in atmosphere fall on the ground and irrigated by sewage water, et, al. Heavy metal-contaminated soil is one of most common problem and much need of recognition and settlement. There are mainly five kinds of soil pollution: heavy metal-contaminated soil, rdionclides of metal, pesticides and hazardous organic compounds and biologic containment. It is not only hard to degrade and also retain in surface of soil, which easy to assimilate by crop, and tranfer in food chain. Heavy metal pollution is the important reasons for degrading of soil quality, and comparing with orther pollutants the particularity of metal pollution is that it is hard to biotic degrad and etire died away. When reached a high concentration, it can be detrimental and destroy the soil-plant system.
It was only focus on developing of our national economy in long-term, and people hold viewpoint of contamination first, then remediation on environmental pollution. So the environmental protect against pollution has been ignored, which lead to reduce of environmental quality. Nowdays survive and development of people maintain close ties with the environment and the proposition of sustainable development strategy is to enhance the knowledge that human protect the ecological environment to a new height, it is also required that doesn't influence the survival ability of offspring while meeting contemporary people's demands. So it is necessary for us to take effect measure to effectively increase the resistance to bioavailability and toxicity of heavy metals in sewage farm in the light of situaion of metal-contaminated soil in Baiyin.
Chapter 1.
Situation of soils contaminated by heavy metals and the chemicalremediation technology by solidification and solubilization
A review with 75 references is given on characteristics and current situation of contaminated by heavy metals and the relation between species and bioavailability of heavy metals in soil. There are two main type of remediation for metal contaminated soil: solidification/stabilization and desorption/solubilization, which mainly are discussed. In addition, some kinds of agents for solidification and desorption of heavy metals in soil also dicussed in these section.
Chapter 2.The effect of humic acid on species of Cu、Cd、Pb、Zn in sewage farm.
The superfluous heavy metals are harm for health of human being and the different speciation of heavy metals has direct influence on tranfer and transform and toxicity of heavy metals in soils. Humic acid is the most common natural organic matter in soil, and it is about 60% in soil organic matter. It has an important influence on toxicity and bioavailability of heavy metals in soil environment because of its complex structure and high activity of functional groups. Although, natural organic matter and its effect on tranfer and tranform of heavy metals have been studied, it mainly about sorption and desorption of heavy metals, but the effect of humic acid on speciation of heavy metals has not studied in previous work. To investigate the effects of humic acid on the speciations of heavy metals, such as Cu, Pb, Zn and Cd in sewage farm in Baiyin, four kinds of organic matters including humic acid, EDTA, citric acid and acetic acid were added, respectively, in polluted soil with a method of successive extraction performed to determine the species of heavy metals. The results showed that humic acid could remarkably decrease the content of soluble heavy metals with about60—80 %, while increase the fractions of Fe+Al+MnO_x and carbonate, which demonstrated clearly that huimc substance, under certain conditions, could effectively increase the resistance to bioavailability and toxicity of heavy metals in sewage farm.
Chapter 3.Study on sorption of Cd on loess soil affected by humic acid.
Humic acid is the most common natural organic matter in soil, and it has some engernic groups. It can be sorption and complexing with heavy metals because of its special structure and high activity of functional groups. Natural organic matter and its effect on tranfer and tranform of heavy metals has been studied, mainly about sorption and desorption of heavy metals, In this section vibration-centrifuge experiments were chosen to study on adsorption isotherms and adsorption thermodynamics of Cd on loess soil affected by humic acid in order to study the tranfer and transform regulation of heavy metal in soil. The results showed that the adsorption of Cd on loess soils fitted well with Freundlich isothermal equation no matter with or without humic acid, and the adsorption capacity of Cd increased from 29.22 mmol·kg~(-1) to 31.39 mmol·kg~(-1) by adding 10ml 55mg·L~(-1) humic acid solution at 25°C, The adsorption quantity of Cd were reduced with increasing of environmental temperature, which indicated that adsorption of Cd was an excergic process, meanwhile, the respective adsorption standard free energy were△G_2~θ=-0.9497kJ·mol~(-1) and△G_1~θ=-0.8885kJ·mol~(-1) with or without humic acid. The adsorption kinetics of Cd fitted with Evolich kinetics equation the best, and then was Double constant equation, but it changed to Double constant equation at present of humic acid. The adsorption speed of Cd is faster then no humic acid at present. The adsorption capability of Cd increased with an increase in the humic acid concentration and the solution pH. The adsorption quantity of Cd was high at low pH then high pH.
Chapter 4.Surfactants enhanced soils washing efficiency of heavy metal with EDTA.
Soil washing is common used to treat soils contaminated with heavy metal that separated heavy from soils in an aqueous-based system. The wash water may be augmented with a basic leaching agent, acid, surfactant, pH adjustments, or chealting agents in order to separate heavy metals that absorbed on soil surface. The most common chelating agent studied in the literature is ethylenediamine-tetraacetic acid (EDTA) because of its strong chelation nature, and little influence on soil nature. Meanwhile, the most study on desorption of organic pollutants in soils by surfactants carried out, but not mainly about heavy metals desorption. In this section, the effects of sodium dodecyl sulfate(SDS)、laural polooxyethylene ether(Brij35) and Ethylenediaminetetraacetic acid(EDTA) on desorption of Cd and Pb from the soil contaminated by the wastewater irrigation are studied in laboratory, respectively, while the influence of adding SDS and Brij35 on EDTA desorption capacity is certified. The changes of the heavy metal's species before and after desorption in the soil matrix are certified too. The experimental results show that the removal of Cd from the soil increases from 61.67% by using EDTA alone to 79.68% if adding SDS, meantime, the removal of Pb increases from 57.25% to 79.68%. However, the addition of the surfactants could restrain the desorption capacity of EDTA, if EDTA has a lower concentration. SDS can significantly enhance the synergetic solubilization of Cd and Pb by an increase of EDTA concentrations. Brij35 has the same effect on the enhanced solubilization of Cd and Pb, but its efficiency appears to be little weaker than SDS. With a comparison of the changes of the heavy metal species in the desorption processes, the contents of soluble and carbonate species were decreased by 60-90% compared to that measured before desorption. It is said that bioavailability and toxicity of heavy metals in sewage farm have been decreased. The research results not only could theoretically provide the approach how to use surfactants to enhance the complexing capacity of EDTA for desorption of heavy metals from soil media, but also could extensively be used in the in-situ flushing technique for heavy metal contaminated soils. The research results not only could theoretically provide the approach how to use surfactants to enhance the complexing capacity of EDTA for desorption of heavy metals from soil media, but also could extensively be used in the in-situ flushing technique for heavy metal contaminated soils.
Chapter 5.Study on desorption of heavy metal in sewage-irrigated soil bycomplexing with saponin.
Biosurfactant which contains a hydrophobic portion and a hydrophilic group from qullaja bark seemed to be an attractive cleaning agent in environmental applications for researchers because of its biodegradability, low loxicity, possibility of reuse, and high economic value.
In this section, the vibration-centrifuge experiments were performed to evaluate the feasibility of using saponin for the removal of heavy metals from the soil contaminated by the wastewater irrigation in laboratory, respectively, the sequential extraction procedure were selected to determine the speciation of heavy metal, at the same time, recovery of heavy metals and recycle of used saponin were also studied as a method for decreasing the costs of remediation processes. The results showed that desorption efficiency could be enhanced with the increase of the added Saponin concentrations, and could finally reach 43.9%, 95.1%, 83.5% and 20.7% for Cu、Cd、Pb、and Zn, respectively, by adding 3.0% of Saponin, while desorption by water alone was less than 5%. It was also found that the desorbed amount gradually decreased with the increase of pH values of the soil, which indicated that the high removal only take place in the week acidic environment. The ionic strength slightly had a negative influence on the desorption of Cd、Cu, but no efforts on Pb、Zn. Comparing the spices transformation of heavy metals before and after desorption in the soil matrix by Tesseri method, it was evident that soluble spices and carbonated fractions of Cu、Cd、Pb、Zn adsorbed on the soil surfaces were washed away tremendously but oxidant-combined and residual spices only reduced little. As a result, the toxicity and bio-reusability of the heavy metals were significantly decreased.
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