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CN104550210A - Method for continuously remediating soil cadmium contamination by using chelating agent EDDS and ramie - Google Patents

Method for continuously remediating soil cadmium contamination by using chelating agent EDDS and ramie Download PDF

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CN104550210A
CN104550210A CN201410718494.7A CN201410718494A CN104550210A CN 104550210 A CN104550210 A CN 104550210A CN 201410718494 A CN201410718494 A CN 201410718494A CN 104550210 A CN104550210 A CN 104550210A
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soil
ramie
edds
chelating agent
repaired
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殷宪强
孙慧敏
陈卫民
韦革宏
刘金
彭绍远
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Northwest A&F University
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Abstract

本发明属于土壤污染治理技术领域,具体涉及一种螯合剂EDDS和苎麻连续修复土壤重金属污染的方法,包括以下步骤:将苎麻植入待修复的土壤中;待苎麻存活后,再向土壤中施入生物可降螯合剂EDDS,施用量为75-300kg/亩;每隔30天,用浓度为0.005-0.015mol/L,的EDDS溶液灌溉一次,其余时间正常灌溉;定期收割苎麻地上部分的茎秆和叶,地下部分留在土壤中继续繁育生长。本发明的修复方法,较之现有技术,其修复效果更好,更加环保,且操作方便,具有一定的经济效益,推广前景广阔。

The invention belongs to the technical field of soil pollution control, and specifically relates to a method for continuously repairing soil heavy metal pollution by chelating agent EDDS and ramie, comprising the following steps: implanting ramie into the soil to be repaired; Add the biodegradable chelating agent EDDS, and the application rate is 75-300kg/mu; every 30 days, use the EDDS solution with a concentration of 0.005-0.015mol/L to irrigate once, and irrigate normally in the rest of the time; regularly harvest the stems of the ramie above ground stems and leaves, and the underground part remains in the soil to continue to reproduce and grow. Compared with the prior art, the repairing method of the present invention has better repairing effect, is more environmentally friendly, is convenient to operate, has certain economic benefits, and has broad promotion prospects.

Description

螯合剂EDDS和苎麻连续修复土壤镉污染的方法A method for continuous remediation of soil cadmium pollution by chelating agent EDDS and ramie

技术领域technical field

本发明属于土壤污染治理技术领域,具体涉及一种螯合剂EDDS和苎麻连续修复土壤重金属污染的方法。The invention belongs to the technical field of soil pollution control, and in particular relates to a method for continuously repairing soil heavy metal pollution with chelating agent EDDS and ramie.

背景技术Background technique

土壤重金属污染引发的土壤生态功能破坏和农产品等问题日益受到大众的关注,重金属不仅直接毒害土壤生物和植物,破坏土壤结构,还可以通过食物链迁移转化,危害人类健康。近年来我国已经发生多起重大的重金属污染事件,严重威胁人民群众的生命健康。土壤重金属污染与农产品安全息息相关,并通过土气、土水界面与大气环境和水环境相关联,所以如何修复重金属污染土壤和保障农产品安全是当前的重要环境问题。开展土壤重金属污染的修复技术研究,对于促进农产品质量安全,保障广大人民群众的生命健康具有重大意义。The destruction of soil ecological functions and agricultural products caused by heavy metal pollution in soil have attracted increasing public attention. Heavy metals not only directly poison soil organisms and plants, destroy soil structure, but can also migrate and transform through the food chain, endangering human health. In recent years, there have been many major heavy metal pollution incidents in my country, which have seriously threatened the lives and health of the people. Soil heavy metal pollution is closely related to the safety of agricultural products, and is related to the atmospheric environment and water environment through the soil atmosphere and soil-water interface. Therefore, how to repair heavy metal-contaminated soil and ensure the safety of agricultural products is an important environmental issue at present. Carrying out the research on remediation technology of heavy metal pollution in soil is of great significance to promote the quality and safety of agricultural products and protect the lives and health of the general public.

重金属污染土壤的修复与治理当前主要围绕固化和活化清除进行,主要是通过物理、化学和生物的方法,切断重金属向食物链的迁徙。物理上的工程治理方法(淋溶法或客土法等)是比较经典的土壤重金属污染治理措施,它具有彻底、稳定的优点,但实施工程量大、投资费用高,破坏土体结构,引起土壤肥力下降,并且还要对换出的污土进行堆放或处理。化学修复就是利用化学试剂、化学反应或化学原理来降低土壤中重金属的迁移性、生物可利用率,减少甚至去除土壤中的重金属,从而达到土壤的治理和修复。化学修复主要包括淋洗,淋洗提取法、固化法、电化学方法和施用改良剂法等方法。化学修复法优点是简单易行,但它只是改变了重金属在土壤中的存在形态,金属元素仍保留在土壤中,很容易再度活化危害植物。The remediation and treatment of heavy metal-contaminated soil is currently mainly carried out around solidification and activation removal, mainly through physical, chemical and biological methods to cut off the migration of heavy metals to the food chain. The physical engineering treatment method (leaching method or alien soil method, etc.) is a relatively classic soil heavy metal pollution control measure. It has the advantages of thoroughness and stability, but it has a large amount of engineering, high investment costs, damage to the soil structure, and causes Soil fertility is reduced, and the replaced dirty soil must be stacked or disposed of. Chemical remediation is to use chemical reagents, chemical reactions or chemical principles to reduce the mobility and bioavailability of heavy metals in soil, reduce or even remove heavy metals in soil, so as to achieve soil governance and restoration. Chemical restoration mainly includes leaching, rinsing extraction, curing, electrochemical methods, and application of modifiers. The advantage of the chemical remediation method is that it is simple and easy to implement, but it only changes the existing form of heavy metals in the soil, and the metal elements remain in the soil, which is easy to reactivate and harm plants.

植物修复简单易行,成本较低,而且不破坏土壤的生态环境,具有良好的经济和生态效益,具有广泛的应用前景。但植物对重金属的修复效率有限,影响重金属污染土壤植物吸取修复效率的限制因素主要包括:土壤重金属溶解度低、迁移能力差以及重金属从植物根向地上部转运的效率低等因素,而且土壤中重金属大都难以被植物吸收。加入植物修复剂可以提高重金属的生物有效性,促进植物对重金属的吸收;而且施用植物修复剂还可以增强植物对重金属的耐性,提高植物对重金属土壤的修复能力。目前研究过的植物修复剂包括有机螯合剂、酸碱调节剂、微生物菌剂和有机废弃物等。Phytoremediation is simple, low cost, and does not damage the ecological environment of the soil, has good economic and ecological benefits, and has broad application prospects. However, the remediation efficiency of plants to heavy metals is limited, and the limiting factors affecting the uptake and remediation efficiency of heavy metal-contaminated soils by plants mainly include: low solubility of heavy metals in soil, poor migration ability, and low transport efficiency of heavy metals from plant roots to shoots, and heavy metals in soil Most of them are difficult to be absorbed by plants. The addition of phytoremediation agents can increase the bioavailability of heavy metals and promote the absorption of heavy metals by plants; and the application of phytoremediation agents can also enhance the tolerance of plants to heavy metals and improve the ability of plants to repair heavy metal soils. The currently studied phytoremediation agents include organic chelating agents, acid-base regulators, microbial agents and organic wastes.

螯合剂可增加金属离子的溶解度但降低离子的活度,表面活性剂对微量重金属阳离子具有增溶作用和增流作用,与重金属结合后,能显著提高土壤中重金属的溶解。向土壤施加螯合剂、表面活性剂能提高植物对金属的吸收和富集,提高植物修复效率,甚至常规植物都可能用于土壤的植物修复。添加有机螯合剂提高植物对土壤中重金属的吸收,可能存在2种机制:一是活化土壤中的重金属离子,提高其生物有效性;二是促进植物对重金属的吸收及向地上部转移。土壤中重金属总含量较高,但通常其生物有效性较低,植物能够吸收的数量有限,即使转运能力很强的超富集植物往往也是如此。添加螯合剂能够促使重金属离子解吸和溶解,提高其生物有效性。螯合剂与重金属形成能被植物吸收的螯合物,从而降低重金属对植物的毒性,有利于植物吸收富集重金属。Chelating agents can increase the solubility of metal ions but reduce the activity of ions. Surfactants can solubilize and increase the flow of trace heavy metal cations. After combining with heavy metals, they can significantly improve the dissolution of heavy metals in soil. Applying chelating agents and surfactants to the soil can improve the absorption and enrichment of metals by plants, and improve the efficiency of phytoremediation. Even conventional plants may be used for phytoremediation of soil. Adding organic chelating agents to improve the absorption of heavy metals in the soil by plants may have two mechanisms: one is to activate heavy metal ions in the soil and improve their bioavailability; the other is to promote the absorption of heavy metals by plants and their transfer to the aboveground. The total content of heavy metals in the soil is high, but their bioavailability is usually low, and the amount that plants can take up is limited, even if the hyperaccumulator plants with strong transport capacity are often the same. The addition of chelating agents can promote the desorption and dissolution of heavy metal ions and improve their bioavailability. Chelating agents and heavy metals form chelates that can be absorbed by plants, thereby reducing the toxicity of heavy metals to plants and facilitating the absorption and enrichment of heavy metals by plants.

目前,常用螯合剂和表面活性剂有EDTA(乙二胺四乙酸)、HEDTA(羟乙基乙二胺三乙酸)、DTPA(二乙基三胺五乙酸)、EGTA(乙二醇二乙醚二胺四乙酸)、NTA(氮川三乙酸)、EDDHA(乙二胺二邻苯基乙酸)、CyDTA(环己二胺四乙酸)等,应用较多的是EDTA和DTPA。当前用于植物提取研究的螯合剂主要是以EDTA为代表的非生物可降解螯合剂。众多研究表明EDTA、HEDTA、DTPA、EGTA、EDDHA、HEIDA、NTA等均可以提高镉、砷、铅、铜等重金属的生物有效性。虽然目前已有使用螯合剂EDTA和植物进行土壤修复的技术,但是上述以EDTA为代表的络合剂属于非降解类络合剂,大量施用对地表水容易带来二次污染,目前EDTA、NTA的环境污染问题已经受到关注,当前欧洲已禁止在清洁剂中使用EDTA。在市政污水系统中,EDTA可与重金属离子螯合,对饮用水供应构成潜在威胁。此外,德国限制在印刷书写纸中使用EDTA,欧盟明令禁止在复写纸漂白工艺中使用EDTA。At present, commonly used chelating agents and surfactants are EDTA (ethylenediaminetetraacetic acid), HEDTA (hydroxyethylethylenediaminetriacetic acid), DTPA (diethyltriaminepentaacetic acid), EGTA (ethylene glycol diethyl ether di amine tetraacetic acid), NTA (nitrilotriacetic acid), EDDHA (ethylenediamine di-o-phenylacetic acid), CyDTA (cyclohexanediamine tetraacetic acid), etc. EDTA and DTPA are more widely used. Chelating agents currently used in plant extraction research are mainly non-biodegradable chelating agents represented by EDTA. Many studies have shown that EDTA, HEDTA, DTPA, EGTA, EDDHA, HEIDA, NTA, etc. can increase the bioavailability of heavy metals such as cadmium, arsenic, lead, and copper. Although there are existing technologies for soil remediation using chelating agent EDTA and plants, the above-mentioned complexing agents represented by EDTA are non-degradable complexing agents, and a large amount of application is likely to cause secondary pollution to surface water. At present, EDTA, NTA The problem of environmental pollution has been concerned, and the use of EDTA in cleaning agents has been banned in Europe. In municipal wastewater systems, EDTA can chelate heavy metal ions, posing a potential threat to drinking water supplies. In addition, Germany restricts the use of EDTA in printing and writing paper, and the European Union explicitly prohibits the use of EDTA in the bleaching process of carbon paper.

因此开发选择适宜的环境友好型的螯合剂,并选用合适的修复植物,对于植物修复土壤重金属污染的推广应用具有重大意义。Therefore, the development and selection of suitable environment-friendly chelating agents and the selection of suitable remediation plants are of great significance for the popularization and application of phytoremediation of soil heavy metal pollution.

发明内容Contents of the invention

本发明实施例的目的是针对上述现有技术的缺陷,提供一种效果更好,更加环保的螯合剂EDDS和苎麻连续修复土壤镉(Cd)污染的方法。The purpose of the embodiments of the present invention is to address the defects of the above-mentioned prior art, and provide a method for continuously remediating soil cadmium (Cd) pollution with better effect and more environment-friendly chelating agent EDDS and ramie.

为了实现上述目的本发明采取的技术方案是:The technical scheme that the present invention takes in order to realize the above object is:

一种螯合剂EDDS和苎麻连续修复土壤镉污染的方法,包括以下步骤:A kind of method that chelating agent EDDS and ramie repair soil cadmium pollution continuously, comprises the following steps:

将苎麻植入待修复的土壤中;Plant ramie into the soil to be repaired;

待苎麻存活后,再向土壤中施入生物可降螯合剂EDDS,施用量为75-300kg/亩;After the ramie survives, apply the biodegradable chelating agent EDDS to the soil at an application rate of 75-300kg/mu;

每隔30天,用浓度为0.005-0.015mol/L的EDDS溶液灌溉一次,其余时间正常灌溉;Every 30 days, irrigate once with EDDS solution with a concentration of 0.005-0.015mol/L, and irrigate normally for the rest of the time;

定期收割苎麻地上部分的茎秆和叶,地下部分留在土壤中继续繁育生长。The stalks and leaves of the aboveground part of ramie are harvested regularly, and the underground part is left in the soil to continue to breed and grow.

进一步的,前述螯合剂EDDS和苎麻连续修复土壤镉污染的方法,植入的苎麻为培育好的苎麻幼苗,其高长为35-45cm。Further, in the method for continuously remediating soil cadmium pollution by the aforementioned chelating agent EDDS and ramie, the ramie to be implanted is a cultivated ramie seedling with a height of 35-45 cm.

进一步的,前述螯合剂EDDS和苎麻连续修复土壤镉污染的方法,用NaOH调节所述EDDS溶液的PH值与待修复土壤的PH值相同。Further, in the method for continuously remediating soil cadmium pollution by the aforementioned chelating agent EDDS and ramie, NaOH is used to adjust the pH value of the EDDS solution to be the same as the pH value of the soil to be remediated.

进一步的,前述螯合剂EDDS和苎麻连续修复土壤镉污染的方法,苎麻地上部分的茎秆和叶每年收割2~3次。Furthermore, in the aforementioned method of continuously remediating soil cadmium pollution with the chelating agent EDDS and ramie, the stems and leaves of the aerial part of ramie are harvested 2 to 3 times a year.

进一步的,前述螯合剂EDDS和苎麻连续修复土壤镉污染的方法,植入土壤的苎麻,每2-3年后连同地下部分全部收割,再重新植入新的苎麻苗,直至土壤镉染污修复完毕。Further, the aforementioned method of chelating agent EDDS and ramie to continuously remediate soil cadmium pollution, the ramie implanted in the soil, after every 2-3 years, all the underground parts are harvested, and then new ramie seedlings are reimplanted until the soil cadmium pollution is repaired complete.

进一步的,前述螯合剂EDDS和苎麻连续修复土壤镉污染的方法,所述EDDS溶液的浓度为0.009mol/L。Further, the aforementioned chelating agent EDDS and ramie continuously repair soil cadmium pollution method, the concentration of the EDDS solution is 0.009mol/L.

进一步的,前述螯合剂EDDS和苎麻连续修复土壤镉污染的方法,所述EDDS向待修复土壤中的施入量为225kg/亩。Further, the aforementioned chelating agent EDDS and ramie continuously repair soil cadmium-polluted method, the amount of EDDS applied to the soil to be repaired is 225kg/mu.

进一步的,前述螯合剂EDDS和苎麻连续修复土壤镉污染的方法,所述螯合剂EDDS的施用方法为:Further, the method for continuously remediating soil cadmium pollution by the aforementioned chelating agent EDDS and ramie, the application method of the chelating agent EDDS is:

均匀撒施或沟施;Spread evenly or furrow;

或将所述螯合剂EDDS溶解在水中,1次或平均分为2-3次随灌水施入待修复土壤中。Alternatively, the chelating agent EDDS is dissolved in water, and applied once or divided into 2-3 times on average into the soil to be repaired along with watering.

进一步的,前述螯合剂EDDS和苎麻连续修复土壤镉污染的方法,苎麻植入前,向待修复土壤中施入底肥,所述底肥为(NH4)2SO4,KH2PO4,K2SO4Further, the aforementioned method of chelating agent EDDS and ramie to continuously remediate soil cadmium pollution, before the ramie is planted, apply base fertilizer to the soil to be repaired, the base fertilizer is (NH 4 ) 2 SO 4 , KH 2 PO 4 , K 2 SO 4 .

进一步的,前述螯合剂EDDS和苎麻连续修复土壤镉污染的方法,所述底肥的施用量为:(NH4)2SO4:45kg/亩,KH2PO4:30kg/亩,K2SO4:45kg/亩。Further, the method for continuously repairing soil cadmium pollution by the aforementioned chelating agent EDDS and ramie, the application amount of the base fertilizer is: (NH 4 ) 2 SO 4 : 45kg/mu, KH 2 PO 4 : 30kg/mu, K 2 SO 4 : 45kg/mu.

与现有技术相比,本发明的土壤镉污染修复方法具有以下有益效果:Compared with the prior art, the soil cadmium pollution remediation method of the present invention has the following beneficial effects:

1、本发明修复方法中选用的生物可降解螯合剂EDDS(乙二胺二琥珀酸),最初是从一种放线菌中分离得到的,是一种天然物质;与EDTA相比,其生物毒性,包括对植物和土壤微生物的毒性都低于EDTA,同时EDDS又具有生物可降解性,其半衰期依施用量不同而介于3.8与7.5天之间,而EDTA最小半衰期为36天。因此,EDDS的环境污染风险相对EDTA小得多,因此更环保。1, the biodegradable chelating agent EDDS (ethylenediamine disuccinic acid) that selects in the restoration method of the present invention, is to obtain from a kind of actinomycetes isolation at first, is a kind of natural substance; Compared with EDTA, its biological The toxicity, including the toxicity to plants and soil microorganisms, is lower than EDTA, while EDDS is biodegradable, and its half-life is between 3.8 and 7.5 days depending on the application amount, while the minimum half-life of EDTA is 36 days. Therefore, the environmental pollution risk of EDDS is much smaller than that of EDTA, so it is more environmentally friendly.

2、本发明修复方法中选用的苎麻,具有以下优点:1、作为修复植物苎麻是一种能耐受多种重金属(如Pb、Zn和Cd)的非食用性多年生经济作物,分布广,适应各种土壤条件,易于大面积繁殖,能同时耐受和吸收Pb、Zn和Cd,其地上部能高富集Pb、Zn和Cd等重金属,且多年生,根系发达,生长快,生物量高;2、荨麻科苎麻属多年生宿根性草本,其茎内的韧皮纤维可用作纺织原料,是重要的纤维作物,具有非常好的经济价值,潜在经济效益可观,容易推广应用;3、不进入食物链,不会对人体产生任何潜在的重金属危害;4、荨麻科苎麻属多年生宿根性草本植物,为多年生长植物,可以只收割其地上部的茎和叶,地下部可继续生长,从而实现连续的土壤修复。2, the ramie selected in the repair method of the present invention has the following advantages: 1, as the repair plant ramie is a kind of non-edible perennial economic crop that can tolerate multiple heavy metals (such as Pb, Zn and Cd), it is widely distributed and adapts to Various soil conditions, easy to reproduce in a large area, can tolerate and absorb Pb, Zn and Cd at the same time, its aerial parts can be highly enriched in heavy metals such as Pb, Zn and Cd, and it is perennial, with well-developed root system, fast growth and high biomass; 2. Urticaceae ramie is a perennial herb. The bast fibers in its stems can be used as textile raw materials. It is an important fiber crop with very good economic value and considerable potential economic benefits. It is easy to popularize and apply; 3. Entering the food chain, it will not cause any potential heavy metal hazards to the human body; 4. Urticaceae ramie is a perennial herbaceous plant, which is a perennial plant. You can only harvest the stems and leaves of the aboveground part, and the underground part can continue to grow, thereby Achieve continuous soil remediation.

3、以EDDS为螯合剂,并且采用发明公开的施用浓度和施用方法,土壤中重金属易被植物吸收的酸可提取态(弱酸提取态,如碳酸盐结合态)的含量显著增加,而植物很难利用的可氧化态(有机态)和残余态(残渣态)含量显著减少。每隔30天用浓度0.005-0.015mol/L的EDDS溶液灌溉,可以有效配合苎麻的生长周期,补充降解的EDDS,显著促进苎麻根部不断地吸收螯合剂EDDS活化的重金属,苎麻根、茎、叶中的重金属含量都有所增加,极大地增强了苎麻对重金属污染土壤的修复能力。同时,土壤中重金属含量显著减少,EDDS也被生物降解,减少了螯合剂和重金属可能造成二次污染的风险。同时,与EDTA对比,施加相同浓度的EDDS,对苎麻造成的不良胁迫更小。3. With EDDS as the chelating agent, and adopt the application concentration and application method disclosed in the invention, the content of the acid extractable state (weak acid extraction state, such as carbonate binding state) that heavy metals are easily absorbed by plants in the soil increases significantly, and the plant The content of oxidizable (organic) and residual (residue) forms which are difficult to utilize is significantly reduced. Irrigation with EDDS solution with a concentration of 0.005-0.015mol/L every 30 days can effectively match the growth cycle of ramie, replenish degraded EDDS, and significantly promote the continuous absorption of heavy metals activated by chelating agent EDDS in ramie roots. The content of heavy metals in ramie has increased, which greatly enhanced the ability of ramie to repair heavy metal-contaminated soil. At the same time, the content of heavy metals in the soil is significantly reduced, and EDDS is also biodegraded, reducing the risk of secondary pollution that may be caused by chelating agents and heavy metals. At the same time, compared with EDTA, the same concentration of EDDS caused less adverse stress to ramie.

4、本发明所公开的修复方法,螯合剂EDDS不需进行包膜或其他复杂工艺处理,以灌溉添加的方法更加便捷。4. In the restoration method disclosed in the present invention, the chelating agent EDDS does not need to be coated or processed by other complicated processes, and the method of adding by irrigation is more convenient.

5、本发明所公开的修复方法,EDDS的施用浓度和施用时间是经过对土壤中重金属的形态影响多次试验后得出的优化浓度,EDDS在土壤中的加入量应该与土壤中重金属含量形成合理配置,在本发明所公开的修复方法推荐的范围内选取,具有适用于实际大面积土壤修复的应用价值。5. For the restoration method disclosed in the present invention, the application concentration and application time of EDDS are the optimized concentrations obtained after many tests on the form of heavy metals in the soil. Reasonable configuration, selected within the range recommended by the restoration method disclosed in the present invention, has application value applicable to actual large-area soil restoration.

6、本发明所提供的修复方法相比其他物理、化学类修复方法,成本低,绿色环保,操作简单,修复后后续处理简单,所收获的地上部分进行集中安全填埋或焚烧,不会造成二次污染,同时修复时不破坏土壤生态系统,有助于减少土壤质量退化和生产力下降的风险。6. Compared with other physical and chemical restoration methods, the restoration method provided by the present invention is low in cost, environmentally friendly, simple in operation, and simple in follow-up treatment after restoration. Secondary pollution, while remediating without disrupting the soil ecosystem, helps to reduce the risk of soil quality degradation and reduced productivity.

附图说明Description of drawings

图1是EDDS对土壤镉形态的作用效果对照图;Fig. 1 is a comparison chart of the effect of EDDS on the form of soil cadmium;

图2修复后苎麻各部分镉含量对照图;Fig. 2 Comparison chart of cadmium content in various parts of ramie after restoration;

图3修复后土壤中镉含量对照图;Figure 3 is a comparison chart of cadmium content in the soil after remediation;

图4EDTA处理与EDDS处理的苎麻叶中丙二醛含量对照图;Fig. 4 EDTA is processed and the malondialdehyde content contrast figure in the ramie leaf of EDDS processing;

具体实施方式Detailed ways

为使本发明的目的、技术方案和优点更加清楚,下面将结合附图对本发明实施方式作进一步地详细描述。In order to make the object, technical solution and advantages of the present invention clearer, the implementation manner of the present invention will be further described in detail below in conjunction with the accompanying drawings.

本发明的螯合剂EDDS和苎麻连续修复土壤镉污染的方法,包括以下步骤:The method that chelating agent EDDS of the present invention and ramie repair soil cadmium pollution continuously may further comprise the steps:

将培育好的高度为35-45cm的苎麻幼苗,植入待修复的土壤中;The ramie seedlings with a height of 35-45cm that have been cultivated are implanted in the soil to be repaired;

待苎麻存活后,再向土壤中施入生物可降螯合剂EDDS,施用量为75-300kg/亩,施用方式为均匀撒施或沟施,随后灌水溶解冲入土壤,或将所述螯合剂EDDS溶解在水中,1次或平均分为2-3次随大田灌水施入待修复土壤中;After the ramie survives, apply the biodegradable chelating agent EDDS to the soil, the application rate is 75-300kg/mu, the application method is uniform spreading or furrow application, and then the water is dissolved and washed into the soil, or the chelating agent is washed into the soil. EDDS is dissolved in water, once or divided into 2-3 times on average, and applied to the soil to be repaired with field irrigation;

每隔30天,用浓度为0.005-0.015mol/L的EDDS溶液灌溉一次,其余时间根据大田苎麻生长的需要进行正常灌溉,所述EDDS溶液的pH值可用NaOH调节至与待修复土壤的pH值相同或相近;Every 30 days, irrigate once with the EDDS solution of 0.005-0.015mol/L with a concentration, and carry out normal irrigation according to the needs of field ramie growth in the rest of the time, and the pH value of the EDDS solution can be adjusted to the pH value of the soil to be repaired with NaOH same or similar;

每隔2-3个月即可收割一次苎麻地上部分的茎秆和叶,地下部分留在土壤中继续繁育生长;The stalks and leaves of the aboveground part of ramie can be harvested every 2-3 months, and the underground part is left in the soil to continue to breed and grow;

每次植入土壤的苎麻,在2-3年后可以连同地下部分全部收割,如果需要继续修复土壤时,可再重新植入新的苎麻苗,直至土壤镉染污修复完毕。The ramie planted into the soil can be harvested together with the underground part after 2-3 years. If the soil needs to be repaired, new ramie seedlings can be replanted until the soil cadmium pollution is repaired.

苎麻植入前,可以向待修复土壤中施入底肥,所述底肥为(NH4)2SO4:45kg/亩,KH2PO4:30kg/亩,K2SO4:45kg/亩。Before the ramie is planted, base fertilizer can be applied to the soil to be repaired. The base fertilizer is (NH 4 ) 2 SO 4 : 45kg/mu, KH 2 PO 4 : 30kg/mu, K 2 SO 4 : 45kg/mu.

本发明选用的可降解螯合剂为EDDS(乙二胺二琥珀酸),其CAS号为20846-91-7。分子式:C10H16N2O8。分子量:292.24。中文同义词有:N,N'-乙二胺二琥珀酸;N,N'-(1,2-乙烷二基)双天冬氨酸;N,N'-(1,2-乙烷二基)双天冬氨酸。英文名称为TRISODIUMETHYLENEDIAMINE DISUCCINATE。英文同义词:L-Asparticacid,N-1,2-ethanediylbis-;2-[2-(1,2-dicarboxyethylamino)ethylamino]butanedioic acid;N,N'-ethylenediamine disuccinic acid;1-Ethylenediaminedisuccinic acid;Aspartic acid,N,N'-ethylenedi-(7CI);Aspartic acid,N,N'-ethylenedi-,1,1-(8CI);N,N'-1,2-ethanediylbis-1-Aspartic acid;n,n'-1,2-ethanediylbis-l-aspartic acid。The degradable chelating agent selected by the present invention is EDDS (ethylenediamine disuccinic acid), and its CAS number is 20846-91-7. Molecular formula: C10H16N2O8. Molecular weight: 292.24. Chinese synonyms are: N,N'-ethylenediamine disuccinic acid; N,N'-(1,2-ethanediyl)bispartic acid; N,N'-(1,2-ethanediyl) base) bis-aspartic acid. The English name is TRISODIUMETHYLENEDIAMINE DISUCCINATE. English synonyms: L-Asparticacid, N-1,2-ethanediylbis-; 2-[2-(1,2-dicarboxyethylamino)ethylamino]butanedioic acid; N,N'-ethylenediamine discuccinic acid; 1-Ethylenediaminedisuccinic acid; Aspartic acid, N,N'-ethylenedi-(7CI); Aspartic acid, N,N'-ethylenedi-,1,1-(8CI); N,N'-1,2-ethanediylbis-1-Aspartic acid; n,n' -1,2-ethanediylbis-l-aspartic acid.

EDDS配合能力强、易生物降解,与过渡金属有很强的螯合作用,最初是从一种放线菌中分离得到的,是一种天然物质,与EDTA相比,其生物毒性包括对植物和土壤微生物的毒性都低于EDTA,又具有生物可降解性,EDDS的半衰期依施用量不同而介于3.8与7.5天之间,而EDTA最小半衰期为36天。因此,EDDS的环境风险相对EDTA非常小。EDDS has strong coordination ability, easy biodegradation, and strong chelating effect with transition metals. It was originally isolated from an actinomycete and is a natural substance. Compared with EDTA, its biological toxicity includes to plants The toxicity of EDDS and soil microorganisms is lower than that of EDTA, and it is biodegradable. The half-life of EDDS is between 3.8 and 7.5 days depending on the amount of application, while the minimum half-life of EDTA is 36 days. Therefore, the environmental risk of EDDS is very small compared with EDTA.

选用可降解的EDDS作为植物修复土壤的螯合剂,并且采用发明公开的施用浓度和施用方法,土壤中重金属易被植物吸收的酸可提取态(弱酸提取态,如碳酸盐结合态)的含量显著增加,而植物很难利用的可氧化态(有机态)和残余态(残渣态)含量显著减少。每隔30天用浓度0.005-0.015mol/L的EDDS溶液灌溉,可以有效配合苎麻的生长周期,补充降解的EDDS,显著促进苎麻根部不断地吸收螯合剂EDDS活化的重金属,苎麻根、茎、叶中的重金属含量都有所增加,极大地增强了苎麻对重金属污染土壤的修复能力。同时,土壤中重金属含量显著减少,EDDS也被生物降解,减少了螯合剂和重金属可能造成二次污染的风险。同时,与EDTA对比,施加相同浓度的EDDS,对苎麻造成的不良胁迫更小,对苎麻有更好的亲和性。同时,EDDS作为螯合剂不需进行包膜或其他复杂工艺处理,灌溉添加方法更加便捷。Select degradable EDDS as the chelating agent for phytoremediation soil, and adopt the application concentration and application method disclosed in the invention, the content of acid extractable state (weak acid extraction state, such as carbonate binding state) in the soil where heavy metals are easily absorbed by plants Significantly increased, while the oxidizable state (organic state) and residual state (residue state) content that is difficult for plants to use decreased significantly. Irrigation with EDDS solution with a concentration of 0.005-0.015mol/L every 30 days can effectively match the growth cycle of ramie, replenish degraded EDDS, and significantly promote the continuous absorption of heavy metals activated by chelating agent EDDS in ramie roots. The content of heavy metals in ramie has increased, which greatly enhanced the ability of ramie to repair heavy metal-contaminated soil. At the same time, the content of heavy metals in the soil is significantly reduced, and EDDS is also biodegraded, reducing the risk of secondary pollution that may be caused by chelating agents and heavy metals. At the same time, compared with EDTA, applying the same concentration of EDDS caused less adverse stress to ramie and had better affinity to ramie. At the same time, as a chelating agent, EDDS does not need to be coated or other complicated processes, and the method of adding irrigation is more convenient.

本发明所提供的修复方法采用的苎麻有一定的经济价值,不进入食物链,潜在经济效益可观,容易推广应用。选择苎麻作为修复植物是因为苎麻是能耐受多种重金属(如Pb、Zn和Cd)的非食用性多年生经济作物,苎麻地上部能高富集Pb、Zn和Cd等重金属。它是荨麻科苎麻属多年生宿根性草本。其茎内的韧皮纤维可用作纺织原料,是重要的纤维作物。苎麻作为植物修复材料具有如下几大优点:1.分布广,适应各种土壤条件,能同时耐受和吸收Pb、Zn和Cd;2.具有重大经济价值并且不经过食物链;3.荨麻科苎麻属多年生宿根性草本植物,为多年生长植物,可以只收割其地上部的茎和叶,地下部可继续生长,从而实现连续的土壤修复,其根系发达,生长快,生物量高;4.易于大面积繁殖。The ramie used in the restoration method provided by the invention has certain economic value, does not enter the food chain, has considerable potential economic benefits, and is easy to popularize and apply. Ramie was chosen as the restoration plant because ramie is a non-edible perennial economic crop that can tolerate a variety of heavy metals (such as Pb, Zn and Cd), and the shoots of ramie can be highly enriched in heavy metals such as Pb, Zn and Cd. It is a perennial herb of the genus Ramie of the family Urticaceae. The bast fibers in its stems can be used as textile raw materials and are important fiber crops. As a phytoremediation material, ramie has the following advantages: 1. It is widely distributed, adapts to various soil conditions, and can tolerate and absorb Pb, Zn and Cd at the same time; 2. It has great economic value and does not go through the food chain; 3. Urticaceae Ramie is a perennial herbaceous plant. It is a perennial plant. It can only harvest the stems and leaves of the aboveground part, and the underground part can continue to grow, so as to realize continuous soil restoration. Its root system is well developed, fast growing, and high in biomass; 4. Easy to reproduce in large areas.

本发明所提供的修复方法,相比其他物理、化学类修复方法,成本低,绿色环保,操作简单,修复后后续处理简单,所收获的地上部分进行集中安全填埋或焚烧,不会造成二次污染,同时修复时不破坏土壤生态系统,有助于减少土壤质量退化和生产力下降的风险。Compared with other physical and chemical restoration methods, the restoration method provided by the present invention has low cost, environmental protection, simple operation, and simple follow-up treatment after restoration. Remediation without disrupting soil ecosystems helps reduce the risk of soil quality degradation and reduced productivity.

下面通过具体实施例对本发明做进一步的说明:The present invention will be further described below by specific embodiment:

实施例1Example 1

本发明螯合剂EDDS和苎麻连续修复土壤镉污染的方法,包括以下步骤:The method for chelating agent EDDS of the present invention and ramie to continuously restore soil cadmium pollution may further comprise the steps:

将苎麻植入待修复的土壤中;Plant ramie into the soil to be repaired;

待苎麻存活后,再向土壤中施入生物可降螯合剂EDDS,施用量为300kg/亩,一次性撒施到待修复土壤表层后立即灌水,溶解后冲入土壤;After the ramie survives, apply the biodegradable chelating agent EDDS to the soil at an application rate of 300kg/mu, and sprinkle it on the surface of the soil to be repaired at one time, and then immediately water it, dissolve it and wash it into the soil;

每隔30天,用浓度为0.009mol/L的EDDS溶液灌溉一次,其余时间根据大田苎麻生长的需要进行正常灌溉;Every 30 days, irrigate once with the EDDS solution of 0.009mol/L with concentration, and carry out normal irrigation according to the needs of field ramie growth in the rest of the time;

每隔3个月即可收割一次苎麻地上部分的茎秆和叶,地下部分留在土壤中继续繁育生长;The stalks and leaves of the aerial part of ramie can be harvested every 3 months, and the underground part can be left in the soil to continue to breed and grow;

每次植入土壤的苎麻,在3年后可以连同地下部分全部收割,如果需要继续修复土壤时,可再重新植入新的苎麻苗,直至土壤镉染污修复完毕。Every time the ramie is planted into the soil, it can be harvested together with the underground part after 3 years. If it is necessary to continue to restore the soil, new ramie seedlings can be replanted until the soil cadmium pollution is repaired.

实施例2Example 2

将培育好的高度为40cm的苎麻幼苗,植入待修复的土壤中;The ramie seedling that the height that will cultivate is 40cm is implanted in the soil to be repaired;

待苎麻存活后,再向土壤中施入生物可降螯合剂EDDS,施用量为150kg/亩,一次性开沟施入待修复土壤表层后立即灌水,溶解后冲入土壤;After the ramie survives, apply the biodegradable chelating agent EDDS to the soil at an application rate of 150kg/acre, ditch it once and apply it to the surface of the soil to be repaired, and immediately irrigate it, dissolve it and wash it into the soil;

每隔30天,用浓度为0.015mol/L的EDDS溶液灌溉一次,其余时间根据大田苎麻生长的需要进行正常灌溉,所述EDDS溶液的pH值用NaOH调节至与待修复土壤的pH值相同。Every 30 days, the EDDS solution with a concentration of 0.015mol/L was irrigated once, and the rest of the time was normally irrigated according to the needs of field ramie growth. The pH value of the EDDS solution was adjusted to be the same as the pH value of the soil to be repaired with NaOH.

每隔2个月即可收割一次苎麻地上部分的茎秆和叶,地下部分留在土壤中继续繁育生长;The stalks and leaves of the aerial part of ramie can be harvested every 2 months, and the underground part can be left in the soil to continue to breed and grow;

每次植入土壤的苎麻,在2年后可以连同地下部分全部收割,如果需要继续修复土壤时,可再重新植入新的苎麻苗,直至土壤镉染污修复完毕。Every time the ramie is planted into the soil, it can be harvested together with the underground part after 2 years. If it is necessary to continue to repair the soil, new ramie seedlings can be replanted until the soil cadmium pollution is repaired.

实施例3Example 3

向待修复土壤中施入底肥,所述底肥为(NH4)2SO4,KH2PO4,K2SO4,施用可视苎麻的生长合理需要确定;Apply base fertilizer to the soil to be repaired, the base fertilizer is (NH 4 ) 2 SO 4 , KH 2 PO 4 , K 2 SO 4 , and the application can be determined according to the reasonable needs of the growth of ramie;

将培育好的高度为45cm的苎麻幼苗,选择长势良好相近的苎麻进行移栽,植入待修复的土壤中,;The ramie seedling that the height that will cultivate is 45cm, selects the good similar ramie of growing way to transplant, and implants in the soil to be repaired;

待苎麻存活后,再向土壤中施入生物可降螯合剂EDDS,施用量为75kg/亩,将所述螯合剂EDDS溶解在水中,在灌溉时一次性随灌溉水施入待修复土壤中;After the ramie survives, apply the biodegradable chelating agent EDDS to the soil again, the application rate is 75kg/mu, dissolve the chelating agent EDDS in water, and apply it to the soil to be repaired with the irrigation water at one time during irrigation;

每隔30天,用浓度为0.005mol/L的EDDS溶液灌溉一次,其余时间根据大田苎麻生长的需要进行正常灌溉,所述EDDS溶液的pH值用NaOH调节至与待修复土壤的pH值相同。Every 30 days, the EDDS solution with a concentration of 0.005mol/L was irrigated once, and the rest of the time was normally irrigated according to the needs of field ramie growth. The pH value of the EDDS solution was adjusted to be the same as the pH value of the soil to be repaired with NaOH.

每隔2.5个月即可收割一次苎麻地上部分的茎秆和叶,地下部分留在土壤中继续繁育生长;The stalks and leaves of the aboveground part of ramie can be harvested every 2.5 months, and the underground part is left in the soil to continue to breed and grow;

每次植入土壤的苎麻,在两年半后可以连同地下部分全部收割,如果需要继续修复土壤时,可再重新植入新的苎麻苗,直至土壤镉染污修复完毕。Every time the ramie is planted into the soil, it can be harvested together with the underground part after two and a half years. If it is necessary to continue repairing the soil, new ramie seedlings can be replanted until the soil cadmium pollution is repaired.

实施例4Example 4

向待修复土壤中施入底肥,所述底肥为(NH4)2SO4:45kg/亩,KH2PO4:30kg/亩,K2SO4:45kg/亩;Apply base fertilizer to the soil to be repaired, the base fertilizer is (NH 4 ) 2 SO 4 : 45kg/mu, KH 2 PO 4 : 30kg/mu, K 2 SO 4 : 45kg/mu;

将培育好的高度为35cm的苎麻幼苗,选择长势良好相近的苎麻进行移栽,植入待修复的土壤中;With the ramie seedling that the height that cultivates is 35cm, select the good similar ramie of growing way to transplant, implant in the soil to be repaired;

待苎麻存活后,再向土壤中施入生物可降螯合剂EDDS,施用量为225kg/亩,将所述螯合剂EDDS溶解在水中,平均分为2次,随灌溉水施入待修复土壤中;After the ramie survives, apply the biodegradable chelating agent EDDS to the soil again, the application rate is 225kg/mu, dissolve the chelating agent EDDS in water, divide it into 2 times on average, and apply it in the soil to be repaired with the irrigation water ;

每隔30天,用浓度为0.010mol/L的EDDS溶液灌溉一次,其余时间根据大田苎麻生长的需要进行正常灌溉,所述EDDS溶液的pH值用NaOH调节至与待修复土壤的pH值相同;Every 30 days, use the EDDS solution irrigation of 0.010mol/L with concentration once, carry out normal irrigation according to the needs of field ramie growth in the rest of the time, the pH value of described EDDS solution is adjusted to be identical with the pH value of the soil to be repaired with NaOH;

每隔3个月即可收割一次苎麻地上部分的茎秆和叶,地下部分留在土壤中继续繁育生长;The stalks and leaves of the aerial part of ramie can be harvested every 3 months, and the underground part can be left in the soil to continue to breed and grow;

每次植入土壤的苎麻,在两年半后可以连同地下部分全部收割,如果需要继续修复土壤时,可再重新植入新的苎麻苗,直至土壤镉染污修复完毕。Every time the ramie is planted into the soil, it can be harvested together with the underground part after two and a half years. If it is necessary to continue repairing the soil, new ramie seedlings can be replanted until the soil cadmium pollution is repaired.

实施例5Example 5

向待修复土壤中施入底肥,所述底肥为(NH4)2SO4:45kg/亩,KH2PO4:30kg/亩,K2SO4:45kg/亩;Apply base fertilizer to the soil to be repaired, the base fertilizer is (NH 4 ) 2 SO 4 : 45kg/mu, KH 2 PO 4 : 30kg/mu, K 2 SO 4 : 45kg/mu;

将培育好的高度为30cm的苎麻幼苗,选择长势良好相近的苎麻进行移栽,植入待修复的土壤中;The ramie seedling that the height that will cultivate is 30cm, selects the good similar ramie of growing way to transplant, and implants in the soil to be repaired;

待苎麻存活后,再向土壤中施入生物可降螯合剂EDDS,施用量为200kg/亩,将所述螯合剂EDDS溶解在水中,平均分为3次,随灌溉水施入待修复土壤中;After the ramie survives, apply the biodegradable chelating agent EDDS to the soil again, the application rate is 200kg/mu, dissolve the chelating agent EDDS in water, divide it into 3 times on average, and apply it in the soil to be repaired with the irrigation water ;

每隔30天,用浓度为0.009mol/L的EDDS溶液灌溉一次,其余时间根据大田苎麻生长的需要进行正常灌溉,所述EDDS溶液的pH值用NaOH调节至与待修复土壤的pH值相同;Every 30 days, use the EDDS solution irrigation that concentration is 0.009mol/L once, carry out normal irrigation according to the needs of field ramie growth in the rest of the time, the pH value of described EDDS solution is adjusted to be identical with the pH value of soil to be repaired with NaOH;

每隔2.5个月即可收割一次苎麻地上部分的茎秆和叶,地下部分留在土壤中继续繁育生长;The stalks and leaves of the aboveground part of ramie can be harvested every 2.5 months, and the underground part is left in the soil to continue to breed and grow;

每次植入土壤的苎麻,在3后可以连同地下部分全部收割,如果需要继续修复土壤时,可再重新植入新的苎麻苗,直至土壤镉染污修复完毕。The ramie implanted into the soil can be harvested together with the underground part after 3 days. If it is necessary to continue to repair the soil, new ramie seedlings can be re-implanted until the soil cadmium pollution is repaired.

为进一步验证本发明所公开的修复方法对土壤镉污染的修复效果,发明人做了多次验证实施,现对部分实验细述如下。In order to further verify the remediation effect of the remediation method disclosed in the present invention on soil cadmium pollution, the inventor has conducted multiple verification implementations, and some experiments are described in detail as follows.

试验实例1:EDDS对土壤镉形态的作用效果实验Experimental example 1: Effect experiment of EDDS on soil cadmium form

1、本次试验选择重金属污染的土壤,采取0-20cm土层的土壤。1. In this test, the soil polluted by heavy metals is selected, and the soil in the 0-20cm soil layer is taken.

土壤采自某锌冶炼厂区外农田,土壤基本性质及元素含量:镉95.2mg·kg-1,铅241mg·kg-1,含氮量1.32g/kg,含磷量1.12g/kg,钾含量17.56g/kg,pH7.8。The soil was collected from a farmland outside a zinc smelting plant. The basic properties and element contents of the soil were: cadmium 95.2mg kg-1, lead 241mg kg-1, nitrogen 1.32g/kg, phosphorus 1.12g/kg, potassium 17.56g/kg, pH7.8.

2、使用生物可降解螯合剂EDDS对土壤中形态的作用效果。2. The effect of using biodegradable chelating agent EDDS on the morphology in soil.

将土样磨碎过筛后,分别称取20.00g镉污染土壤样品,置于50mL带盖聚乙烯塑料瓶中。将EDDS以不同施用水平(CK,1.5mmol/kg土,3mmol/kg土,6mmol/kg土,9mmol/kg土),分别加入20.00g污染土壤样品中,常温下进行土壤培养30天,保持土壤湿度为70%左右。然后,用BCR连续提取浸提测定土壤中镉的形态和含量,探究EDDS对各种形态镉的影响情况。BCR法是欧洲参考交流局(European Community Bureau of Reference)提出的较新的划分方法,将镉的形态分为4种,即:酸溶态(弱酸提取态,如碳酸盐结合态)、可还原态(如铁锰氧化物态)、可氧化态(如有机态)、残渣态。After the soil samples were ground and sieved, 20.00g of cadmium-contaminated soil samples were weighed and placed in 50mL polyethylene plastic bottles with lids. EDDS was added to 20.00 g of contaminated soil samples at different application levels (CK, 1.5 mmol/kg soil, 3 mmol/kg soil, 6 mmol/kg soil, 9 mmol/kg soil), and the soil was cultivated at room temperature for 30 days. Humidity is around 70%. Then, the form and content of cadmium in the soil were determined by continuous extraction and leaching by BCR, and the influence of EDDS on various forms of cadmium was explored. The BCR method is a relatively new division method proposed by the European Community Bureau of Reference, which divides the form of cadmium into four types, namely: acid-soluble state (weak acid extraction state, such as carbonate-bound state), Reduction state (such as iron manganese oxide state), oxidizable state (such as organic state), residue state.

参见图1,EDDS对土壤镉形态的作用效果对照图,结果表明:与对照相比,施加EDDS后,土壤中重金属易被植物吸收的酸可提取态(弱酸提取态,如碳酸盐结合态)的含量显著增加,而植物很难利用的可氧化态(有机态)和残余态(残渣态)含量显著减少,其中EDDS施用量为9mmol/kg土时效果最佳。Referring to Fig. 1, EDDS is to the control figure of the action effect of soil cadmium form, the result shows: compared with contrast, after applying EDDS, the acid extractable state (weak acid extractable state, such as carbonate binding state) of heavy metals in the soil is easily absorbed by plants ) content increased significantly, while the oxidizable (organic) and residual (residual) content, which was difficult for plants to use, decreased significantly, and the effect was the best when the application rate of EDDS was 9 mmol/kg soil.

试验实例2:EDDS和苎麻联合修复重金属污染土壤效果Experimental example 2: The effect of EDDS and ramie combined remediation of heavy metal polluted soil

1、本次试验选择重金属污染的土壤,采取0-20cm土层的土壤。1. In this test, the soil polluted by heavy metals is selected, and the soil in the 0-20cm soil layer is taken.

土壤采自某锌冶炼厂区外农田,土壤基本性质及元素含量:镉95.2mg·kg-1,铅241mg·kg-1,含氮量1.32g/kg,含磷量1.12g/kg,钾含量17.56g/kg,pH7.8。The soil was collected from a farmland outside a zinc smelting plant. The basic properties and element contents of the soil were: cadmium 95.2mg kg-1, lead 241mg kg-1, nitrogen 1.32g/kg, phosphorus 1.12g/kg, potassium 17.56g/kg, pH7.8.

2、向污染土壤中加入底肥(NH4)2SO4:0.3g·kg-1,KH2PO4:0.2g·kg-1,K2SO4:0.3g·kg-1用作盆栽土壤;2. Add base fertilizer (NH 4 ) 2 SO 4 : 0.3g·kg-1, KH 2 PO 4 : 0.2g·kg-1, K 2 SO 4 : 0.3g·kg-1 to the polluted soil for potting soil ;

选取株高40cm左右,长势良好相近的苎麻进行移栽;Select about 40cm of plant height, and the ramie that grows well and similarly is transplanted;

待苎麻存活后,再向土壤中加入占土壤重0.05%,0.10%,0.15%,0.20%的生物可降螯合剂EDDS;After the ramie survives, add 0.05%, 0.10%, 0.15%, and 0.20% of the biodegradable chelating agent EDDS to the soil;

每隔30天,用浓度0.009mol/L的EDDS溶液灌溉一次,其余时间正常灌溉;Every 30 days, irrigate once with EDDS solution with a concentration of 0.009mol/L, and irrigate normally for the rest of the time;

在移栽64天后的成熟期,将苎麻株取出用自来水和蒸馏水洗净,测定株高、茎粗和分蘖数,然后将根、茎、叶分开,测定各部位的生物量,晾干后先在105℃下杀青30min,然后在80℃下烘干至恒重,粉碎后分别测定苎麻根、茎、叶中的重金属含量;At the maturity stage after 64 days of transplanting, the ramie plants were taken out and washed with tap water and distilled water, and the plant height, stem diameter and tiller number were measured, and then the roots, stems and leaves were separated to measure the biomass of each part, and after drying, the Fix the greens at 105°C for 30 minutes, then dry at 80°C to constant weight, and measure the heavy metal content in ramie roots, stems, and leaves after crushing;

土壤自然风干后,过0.15mm(100目)尼龙筛,用王水—高氯酸消煮—原子吸收光谱法,对土样镉含量进行测定。After the soil was naturally air-dried, it was passed through a 0.15mm (100 mesh) nylon sieve, digested with aqua regia-perchloric acid-atomic absorption spectrometry, and the cadmium content of the soil samples was determined.

参见图2,修复后苎麻各部分镉含量对照图,结果表明:用本方法修复后,苎麻根、茎、叶各部分镉的含量都有显著增加,其中根部增加量最大,在施用浓度为0.15%~0.20%下,可达到70%,施用浓度为0.05%时,地上部分含量有所减小,但土壤中镉含量依然减小显著,说明此浓度下地上部分整体生物累积量依然增加,对镉吸收效果较好。苎麻各部分吸收镉的含量关系为:根中镉含量>茎重镉含量>叶中镉含量。See Figure 2, the comparison chart of cadmium content in various parts of ramie after restoration. The results show that after repairing with this method, the cadmium content in each part of ramie roots, stems and leaves has increased significantly, and the root has the largest increase, when the application concentration is 0.15 % to 0.20%, it can reach 70%. When the application concentration is 0.05%, the content of cadmium in the aboveground part is reduced, but the content of cadmium in the soil is still significantly reduced, indicating that the overall bioaccumulation of the aboveground part is still increasing at this concentration. Cadmium absorption effect is better. The relationship of cadmium uptake in each part of ramie was: cadmium content in roots>weight cadmium content in stems>cadmium content in leaves.

参见图3,修复后土壤中镉含量对照图;相比修复前,用本方法修复后,土壤中镉的含量均有显著降低,分别下降了38%~40%,修复效果得到了很好的提现。See Figure 3, the comparison chart of cadmium content in the soil after remediation; compared with before remediation, after remediation by this method, the content of cadmium in the soil has been significantly reduced, respectively decreased by 38% to 40%, and the remediation effect has been very good withdraw.

试验实例3:EDDS与EDTA施用对苎麻胁迫作用比较Test example 3: Comparison of EDDS and EDTA application on ramie stress

用本方法的EDDS和相同浓度EDTA和苎麻联合修复方法对比,具体实验方法同试验实例2中操作步骤,处理方面添加EDTA不同浓度的处理。收获前10天,采集苎麻新鲜叶片,测定叶片中丙二醛(MDA)含量。因为植物器官衰老或在逆境下遭受伤害,往往发生膜脂过氧化作用,丙二醛(MDA)是膜脂过氧化的最终分解产物,其含量可以反映植物遭受逆境伤害的程度。实验对比发现,在施用量为各个浓度下,苎麻叶片中丙二醛的含量,都是EDTA>EDDS,说明EDTA对苎麻产生的不良胁迫更大,EDDS对苎麻本身的不良胁迫较小,对修复植物苎麻有更高的亲和性。验证了EDDS的环境友好性高于EDTA,有更大的推广使用价值。The EDDS of this method is compared with the joint restoration method of EDTA and ramie at the same concentration. The specific experimental method is the same as the operation steps in Experimental Example 2. In terms of treatment, different concentrations of EDTA are added. Ten days before harvest, fresh leaves of ramie were collected, and the content of malondialdehyde (MDA) in the leaves was determined. Membrane lipid peroxidation often occurs because plant organs are aging or damaged under adversity. Malondialdehyde (MDA) is the final decomposition product of membrane lipid peroxidation, and its content can reflect the degree of adversity damage to plants. Experimental comparison found that at various concentrations of application, the content of malondialdehyde in ramie leaves was EDTA>EDDS, indicating that EDTA had greater adverse stress on ramie, and EDDS had less adverse stress on ramie itself. Plant ramie has a higher affinity. It has been verified that EDDS is more environmentally friendly than EDTA, and has greater promotion and use value.

为进一步验证本发明所述实施例所公开的修复方法对土壤镉污染的修复效果,发明人做了多次大田验证实施。大田实验依照试验实例2的具体方法,将EDDS、EDDS溶液和底肥的施用量,换算成大田施用量,施用量的换算采用土壤学中惯用的每亩耕作层土壤总重15万kg的重量计,换算成大田亩用量,即向待修复土壤中施入底肥为(NH4)2SO4:45kg/亩,KH2PO4:30kg/亩,K2SO4:45kg/亩;向土壤中施入生物可降螯合剂EDDS,施用量为75kg/亩、150kg/亩、225kg/亩、300kg/亩。按照试验实例2的具体操作步骤,进行大田实验。最后收获苎麻、并取土测定。大田实验的结果与盆栽实验结果相差不大,本方法对土壤镉污染的修复效果极好,而且更加环保。In order to further verify the remediation effect of the remediation method disclosed in the embodiments of the present invention on soil cadmium pollution, the inventor has conducted several field verification implementations. In the field experiment, according to the specific method of Test Example 2, the application amount of EDDS, EDDS solution and base fertilizer was converted into field application amount. , converted into the amount per mu of the field, that is, the base fertilizer applied to the soil to be repaired is (NH 4 ) 2 SO 4 : 45kg/mu, KH 2 PO 4 : 30kg/mu, K 2 SO 4 : 45kg/mu; Apply biodegradable chelating agent EDDS, the application rate is 75kg/mu, 150kg/mu, 225kg/mu, 300kg/mu. According to the specific operation steps of the test example 2, the field experiment was carried out. Finally, the ramie was harvested and soil was taken for determination. The results of the field experiment are not much different from those of the pot experiment. This method has an excellent effect on remediating soil cadmium pollution and is more environmentally friendly.

以上所述仅为本发明的较佳实施例,并不用以限制本发明,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。The above descriptions are only preferred embodiments of the present invention, and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included in the protection of the present invention. within range.

Claims (10)

1.一种螯合剂EDDS和苎麻连续修复土壤镉污染的方法,其特征在于,包括以下步骤:1. a method for chelating agent EDDS and ramie to continuously repair soil cadmium pollution, is characterized in that, may further comprise the steps: 将苎麻植入待修复的土壤中;Plant ramie into the soil to be repaired; 待苎麻存活后,再向土壤中施入生物可降螯合剂EDDS,施用量为75-300kg/亩;After the ramie survives, apply the biodegradable chelating agent EDDS to the soil at an application rate of 75-300kg/mu; 每隔30天,用浓度为0.005-0.015mol/L的EDDS溶液灌溉一次,其余时间正常灌溉;Every 30 days, irrigate once with EDDS solution with a concentration of 0.005-0.015mol/L, and irrigate normally for the rest of the time; 定期收割苎麻地上部分的茎秆和叶,地下部分留在土壤中继续繁育生长。The stalks and leaves of the aboveground part of ramie are harvested regularly, and the underground part is left in the soil to continue to breed and grow. 2.根据权利要求1所述的螯合剂EDDS和苎麻连续修复土壤镉污染的方法,其特征在于,2. the method for chelating agent EDDS according to claim 1 and ramie continuous repair soil cadmium pollution is characterized in that, 植入的苎麻为培育好的苎麻幼苗,其高长为35-45cm。The implanted ramie is a cultivated ramie seedling, and its height is 35-45cm. 3.根据权利要求1所述的螯合剂EDDS和苎麻连续修复土壤镉污染的方法,其特征在于,3. the method for chelating agent EDDS according to claim 1 and ramie continuous repair soil cadmium pollution is characterized in that, 用NaOH调节所述EDDS溶液的pH值与待修复土壤的pH值相同。The pH value of the EDDS solution is adjusted with NaOH to be the same as the pH value of the soil to be repaired. 4.根据权利要求1所述的螯合剂EDDS和苎麻连续修复土壤镉污染的方法,其特征在于,4. the method for chelating agent EDDS according to claim 1 and ramie continuous restoration soil cadmium pollution is characterized in that, 苎麻地上部分的茎秆和叶每年收割2~3次。The stems and leaves of the aerial part of ramie are harvested 2 to 3 times a year. 5.根据权利要求1所述的螯合剂EDDS和苎麻连续修复土壤镉污染的方法,其特征在于,5. the method for chelating agent EDDS according to claim 1 and ramie continuous restoration soil cadmium pollution is characterized in that, 植入土壤的苎麻,每2-3年后连同地下部分全部收割,再重新植入新的苎麻苗,直至土壤镉染污修复完毕。The ramie implanted in the soil shall be harvested together with the underground part after every 2-3 years, and then replanted with new ramie seedlings until the soil cadmium pollution is repaired. 6.根据权利要求1所述的螯合剂EDDS和苎麻连续修复土壤镉污染的方法,其特征在于,6. the method for chelating agent EDDS according to claim 1 and ramie continuous repair soil cadmium pollution is characterized in that, 所述EDDS溶液的浓度为0.009mol/L。The concentration of the EDDS solution is 0.009mol/L. 7.根据权利要求1所述的螯合剂EDDS和苎麻连续修复土壤镉污染的方法,其特征在于,7. the method for chelating agent EDDS according to claim 1 and ramie continuous repair soil cadmium pollution is characterized in that, 所述EDDS向待修复土壤中的施入量为225kg/亩。The amount of EDDS applied to the soil to be repaired is 225kg/mu. 8.根据权利要求1所述的螯合剂EDDS和苎麻连续修复土壤镉污染的方法,其特征在于,8. the method for chelating agent EDDS according to claim 1 and ramie continuous remediation soil cadmium pollution is characterized in that, 所述螯合剂EDDS的施用方法为:The application method of described chelating agent EDDS is: 均匀撒施或沟施;Spread evenly or furrow; 或将所述螯合剂EDDS溶解在水中,1次或平均分为2-3次随灌水施入待修复土壤中。Alternatively, the chelating agent EDDS is dissolved in water, and applied once or divided into 2-3 times on average into the soil to be repaired along with watering. 9.根据权利要求1所述的螯合剂EDDS和苎麻连续修复土壤镉污染的方法,其特征在于,9. the method for chelating agent EDDS according to claim 1 and ramie continuous restoration of soil cadmium pollution, is characterized in that, 苎麻植入前,向待修复土壤中施入底肥,所述底肥为(NH4)2SO4,KH2PO4,K2SO4Before the ramie is planted, a base fertilizer is applied to the soil to be repaired, and the base fertilizer is (NH 4 ) 2 SO 4 , KH 2 PO 4 , K 2 SO 4 . 10.根据权利要求8所述的螯合剂EDDS和苎麻连续修复土壤镉污染的方法,其特征在于,10. the method for chelating agent EDDS according to claim 8 and ramie continuous remediation soil cadmium pollution is characterized in that, 所述底肥的施用量为:(NH4)2SO4:45kg/亩,KH2PO4:30kg/亩,K2SO4:45kg/亩。The application rate of the base fertilizer is: (NH 4 ) 2 SO 4 : 45kg/mu, KH 2 PO 4 : 30kg/mu, K 2 SO 4 : 45kg/mu.
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CN106069038A (en) * 2016-06-21 2016-11-09 重庆市中药研究院 A kind of pollution containing plantation river, cadmium soil party plant is intervened and land method
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CN109647876B (en) * 2018-12-04 2021-09-14 浙江清华长三角研究院 Method for restoring farmland soil polluted by low-concentration mercury by using ramie single cropping
CN111153737A (en) * 2020-01-10 2020-05-15 广西绿浪生物技术有限公司 Efficient composite water-soluble fertilizer and preparation method and application thereof
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