CN102989753A - Method for assisting vegetable crops to restore Cd-Zn-Pb composite contaminated soil by EDTA (Ethylene Diamine Tetraacetic Acid) - Google Patents
Method for assisting vegetable crops to restore Cd-Zn-Pb composite contaminated soil by EDTA (Ethylene Diamine Tetraacetic Acid) Download PDFInfo
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- CN102989753A CN102989753A CN2012105139399A CN201210513939A CN102989753A CN 102989753 A CN102989753 A CN 102989753A CN 2012105139399 A CN2012105139399 A CN 2012105139399A CN 201210513939 A CN201210513939 A CN 201210513939A CN 102989753 A CN102989753 A CN 102989753A
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Abstract
The invention relates to vegetable restoration of heavy metal composite contaminated soil, and in particular relates to a method for restoring Cd-Zn-Pb composite contaminated soil by virtue of strengthening measures. The method comprises the following steps of planting vegetable crops such as green soy beans and spinach in soil to be restored in successions according to seasons; adding a chelating agent EDTA to the soil when the green soy beans and spinach grow to a mature period; integrally removing the vegetables after the crops grow for 10-15 days to achieve the purpose of restoring Cd-Zn-Pb composite contaminated soil. According to the method provided by the invention, EDTA is applied, so that not only can heavy metal contaminants in the soil be activated, but also the restoring effect of the vegetable crops to Cd-Zn-Pb can be remarkably improved so as to accelerate a process of restoring the Cd-Zn-Pb composite contaminated soil by the plants. The method has the advantages of low restoring cost, high restoring efficiency, strong operability and low environment risk, and the like.
Description
Technical field
The vegetable crop that the present invention relates to heavy-metal composite pollution soil is repaired, specifically a kind of method of utilizing enhancements to repair the Cd-Zn-Pb combined contamination soil.
Background technology
Heavy metal pollution problem is day by day serious in China, and according to statistics, China has 1.3 ten thousand hm approximately at present
2The arable land is subject to the heavy metal pollutions such as Cd, Pb, reaches 1,000 ten thousand t[document 1: Yang Shujing because heavy metal pollution causes grain drop in production, Zhang Aiping, poplar generation figured woven silk material, Deng. Agriculture Non-point Source Pollution analysis and domestic and international progress [J]. Chinese agriculture is meteorological, 2009,30:82-85].Heavy metal in soil suppresses its growth after by plant absorbing, cause crop failure even total crop failure, and finally enter harm health [document 2:Maeda S by food chain, Kawachi T, Unami K.Controlling wasteloads from pointand nonpoint sources to river byGIS-aid-ed epsilon robust optimization mode[J] .Journal of Hydro-EnvironmentResearch, 2010,4 (1): 27-36; Document 3:Singh Vijay P.Computer Models of Watershed Hydrology[M] .Highlands Ranch, Colorado, USA:Water Resources Publications, 1995].At occurring in nature, heavy metal pollution seldom separately exists in a certain environment, normally multiple pollutant entered environment and coexistence, namely the detection device for multi metallic elements combined pollution [document 4: Xi Danli. environmental project handbook: environmental monitoring volume [M]. Beijing: Higher Education Publishing House, 1998:683-684; Document 5: Chongqing City statistics bureau, Chongqing investigation army unit of State Statistics Bureau. Chongqing statistical yearbook, 2009[K]. Beijing: China Statistics Press, 2009].Since the sixties in 20th century, the heavy-metal composite pollution such as Cd, Pb has caused the extensive concern of Chinese scholars, studies show that, during the detection device for multi metallic elements coexistence, its compound action can change toxic action [document 6: Cao Yanlong, the Li Chongming of single heavy metal on plants greatly, Guo Jingsong, Deng. Three Gorge Reservoir Region in Chongqing agricultural nonpoint source pollution source analysis and load calculate [J]. Chongqing Univ. of Architecture's journal, 2007,29 (4): 1-5].Therefore, the reparation of research heavy-metal composite pollution soil has definite meaning to the improvement of combined pollution, and the improvement that can be combined pollution provides scientific theory foundation and reference.
At present, the technology that can be used for the repairing heavy metal in soil pollution is a lot, but method with low cost is rare.Phytoremediation (phytoremediation) technology that occurs in recent years, as the green recovery technique of a kind of original position, have expense cheap, not welding, be easy to be the advantages such as people are accepted, become the research and application focus of environmental science.With the reparation of vegetables for heavy metal soil soil, plant by pressing the crop rotation in season, but both repairing heavy metal in soil pollutes, and can guarantee quality of vegetable again, the assurance economic benefit is killed two birds with one stone when obtaining environmental effect.
In recent years, the phytoremediation of heavy metal pollution of soil cheap take its expense, not the damage field ground structure, beautify the environment, be easy to be obtained attention by society such as accepts at the advantage.But because the target heavy metal activity is lower in a lot of soil to be repaired, the most poor growth of enriching plant of finding, biomass is little, and the enriching plant that growth is rapid, biomass is large generally is difficult to absorb the heavy metal of enrichment high concentration, brings a lot of difficulties to actual repair.
Summary of the invention
The method that the object of the present invention is to provide a kind of efficient, economic, safe enhancements to repair the Cd-Zn-Pb combined contamination soil.
For achieving the above object, technology contents of the present invention is: the vegetable crop green soy bean, the spinach that have the Cd-Zn-Pb accumulation ability in soil to be repaired by crop rotation plantation in season, when treating green soy bean, spinach growth to the maturity period, in soil, add chelating agent EDTA, after regrowth 10-15 days vegetable crop integral body is removed, thereby reach the purpose of repairing the Cd-Zn-Pb combined contamination soil, wherein the addition of chelating agent is 2.5-7.5mmol in every kilogram of soil.Can use according to fertility state in the soil simultaneously the azophoska of an amount of Promoting plant growth.In soil, add the heavy metal in the chelating agent activating soil, improve biological effect, promote plant to the absorption of heavy metal, improve the efficient of phytoremediation.In the chelating agent that uses, EDTA generally uses, and heavy metal is had stronger sequestering power.The at present use of chelating agent, bring plurality of advantages to restoration of soil polluted by heavy metal: (1) can activate the Heavy Metals in Contaminated Soils activity by adding chelating agent, is easier to the heavy metal in the plants enriched soil.(2) applying of chelating agent improved the efficient of phytoremediation contaminated soil, reduces rehabilitation cost.(3) apply the absorption that chelating agent has also promoted plant in the soil, be beneficial to the production of plant, improve its output.
Described chelating agent is ethylenediamine tetra-acetic acid (EDTA).Described plantation green soy bean, spinach refer to high 2-5cm or contain green soy bean that the 2-3 sheet launches true leaf, spinach seedling replanting in the Cd-Zn-Pb combined contamination soil.The green soy bean of planting in the Cd-Zn-Pb combined contamination soil, spinach are adopted outdoor planting, regularly water, and make soil moisture content remain on 60% ~ 80% of field capacity.Adopt the mode of crop rotation to plant green soy bean, spinach crop at the Cd-Zn-Pb combined contamination soil, namely when first batch of green soy bean crop grows to the maturity period, green soy bean integral body is shifted out from contaminated soil, plant again second batch of spinach crop, repeat said process, until the heavy metal Cd in the soil-Zn-Pb content reaches the environmental standard value.
The advantage that the present invention has:
(1) the present invention cooperates chelating agent EDTA enhancements on the basis of vegetable crop rehabilitating soil, has both guaranteed higher remediation efficiency, has reduced again rehabilitation cost and environmental risk.
(2) green soy bean, the spinach selected of the present invention is all stronger to patience and the accumulation ability of Cd, Zn, Pb, cultivation management is easier, and fast growth can guarantee again the kind of vegetable crop, has good environment, economic benefit when repairing the Cd-Zn-Pb combined contamination soil.
(3) the present invention adopts the plant home position strengthening to repair the measure of Cd-Zn-Pb combined contamination soil, compares with traditional Remediation of Contaminated Soil, has that small investment, quantities are little, a specification requirement advantages of higher not.
The specific embodiment
The present invention is described in more detail below by instantiation.
Embodiment 1
The pot experiment place the Wujin of Changzhou rice research the solarium in, this place is on the Wujin District farm, do not have pollution sources around the experimental site, is the uncontaminated district of heavy metal, organic matter.Pot experiment soil pick up from the Wujin of Changzhou rice research in the topsoil (0 ~ 20cm) of pollution-free area.
4 concentration have been set in experiment altogether, be respectively contrast (CK, do not add Cd, Zn, Pb) and 3 different Cd, Zn, Pb adds the concentration experiment, Cd adds concentration: 2.0mg/kg(T1), 6.0mg/kg(T2), 10.0mg/kg(T3), Zn adds concentration: 1000mg/kg(T1), 3000mg/kg(T2), 5000mg/kg(T3), Pb adds concentration: 1000mg/kg(T1), 3000mg/kg(T2), 5000mg/kg(T3), be respectively China standard of soil environment quality (GB15618,195) 2 of grade III Standard, 6,10 times, the Heavy Metals that adds is CdCl
22.5H
2O, ZnSO
47H
2O, Pb (NO
3)
2, join respectively in the soil, abundant mixing, balance is stand-by after half a year.
This was tested spring, and the green soy bean seed is grown seedlings indoor.The green soy bean seed is placed the seedling-raising box of pre-installing sandy soil, and sand: soil=1:3 when treating the long high 2-5cm of arriving of seedling, selects the consistent seedling of growth to be transplanted into respectively respectively and processes in the basin.Every basin young plant each years 3 repeats 3 times.According to soil lack of water situation in the basin, irregularly water running water (not containing Cd, Zn, Pb in the water), make soil moisture content often remain on about 60% ~ 80% of field capacity, after the plant maturation, gather in the crops, plant again the second crop spinach, the same green soy bean of the processing of spinach.
Repeatedly rinse well with running water after the vegetables results, use at last rinsed with deionized water 3 times, with blotting paper surface water is blotted, bright sample ground the 0.129mm sieve after 85 ℃ of lower oven dry, vegetable sample is bottled for subsequent use.Take by weighing to dry under 105 ℃ to the sample 0.5g of constant weight and place conical flask, add the 5mL water-wet, add again red fuming nitric acid (RFNA) 3mL and perchloric acid 2mL, low-temperature heat is cleared up, when treating that solution reduces volume to 2 ~ 3mL, improve digestion condition to solution and seethe with excitement, behind boiling 40 ~ 50min, stopped heating when treating that container implants powder becomes white solid or viscous liquid makes it cooling.Add the salpeter solution of 1mL10% in the cooled conical flask, and add suitable quantity of water, low-temperature heat makes dissolution of solid in the conical flask, be transparence liquid, then filter by quantitative filter paper, and be settled to 50mL, make into liquid to be measured, carry out the mensuration of Cd, Cu, Pb with Atomic Absorption Spectrometer.
Experimental result
Table 1 has provided under different Cd, Zn, the Pb concentration treatment conditions, the variation of green soy bean, spinach the upperground part biomass.Variance analysis shows, compared with the control, it is 2.0mg/kg, 6.0mg/kg that green soy bean, spinach are added concentration at Cd, and it is in the processing of 1000mg/kg, 3000mg/kg that Zn, Pb add concentration, all significantly decline of the upperground part biomass (p〉0.05), show stronger patience.But add when dense at Cd, Zn, Pb, be that Cd interpolation concentration is 10.0mg/kg, it is 5000mg/kg that Zn, Pb add concentration, green soy bean, spinach the upperground part biomass all significantly descend (p＜0.05), although green soy bean, spinach are described the patience of Cd, Zn, Pb combined pollution are still had by force certain limit.
The measurement result of Cd, Zn, Pb content shows (table 1) in the vegetables body, and under Cd 2.0mg/kg, Zn, Pb 1000mg/kg level of pollution, green soy bean overground part Cd, Zn, Pb content are respectively 0.87mg/kg, 166.43mg/kg, 343.25mg/kg; Spinach overground part Cd, Zn, Pb content are respectively 1.37mg/kg, 324.5mg/kg, 203.1mg/kg; Under Cd 6.0mg/kg, Zn, Pb 3000mg/kg level of pollution, green soy bean overground part Cd, Zn, Pb content are respectively 1.26mg/kg, 487.51mg/kg, 565.63mg/kg; Spinach overground part Cd, Zn, Pb content are respectively 1.54mg/kg, 546.2mg/kg, 532.6mg/kg; Under Cd 10.0mg/kg, Zn, Pb 5000mg/kg level of pollution, green soy bean overground part Cd, Zn, Pb content are respectively 1.57mg/kg, 668.45mg/kg, 725.35mg/kg; Spinach overground part Cd, Zn, Pb content are respectively 1.61mg/kg, 688.3mg/kg, 654.8mg/kg.Can find out that green soy bean, spinach have stronger enrichment Cd, Zn, the ability of Pb, but not reach the standard of Cd, Zn, Pb super enriching plant, can by adding chelating agent EDTA, strengthen the ability that it repairs Cd, Zn, Pb combined contamination soil.
Cd, Zn, Pb content (mg/kg) and the upperground part biomass (g/ basin) in the potted plant gradient experiment of table 1 vegetables
Embodiment 2
The Cd that adds in the soil, Zn, Pb content are respectively 6mg/kg, 3000mg/kg, 3000mg/kg, and the Heavy Metals that adds is CdCl
22.5H
2O, ZnSO
47H
2O, Pb (NO
3)
2, be added in the soil, abundant mixing, balance is stand-by after half a year.Select the Glycine max Seedling consistent with embodiment 1 growth to transplant, in green soy bean front 2 weeks of results, near the root district of upper soll layer, apply EDTA, the artificial disposable adding of chelating agent, each is processed and repeats 3 times, and green soy bean 2 weeks after processing gather in the crops, plantation spinach seedling in soil, the same green soy bean of spinach processing method.The specific embodiment sees Table 2.
Table 2 chelating agent EDTA applies concentration
Experimental result shows (table 3, table 4), 2 all disposable chelating agent EDTA that apply can improve remediation efficiency before results, although green soy bean, spinach the upperground part biomass descend to some extent, but vegetable field top Cd, Zn, Pb content significantly increase, so that the total amount of green soy bean, spinach enrichment Cd, Zn, Pb significantly increases.EDTA to the activation effect of Cd, Zn, Pb all clearly, but can produce certain toxic action to vegetable growth, reduce green soy bean, spinach the upperground part biomass, along with concentration raises, vegetables the upperground part biomass descends, and vegetables reached maximum to Cd, Zn, Pb accumulation (accumulation refers to overground part and underground part sum) when EDTA was 5mmol/kg.
Green soy bean is absorbed the EDTA of table 3 variable concentrations and the impact of enrichment Cd, Zn, Pb
Spinach is absorbed the EDTA of table 4 variable concentrations and the impact of enrichment Cd, Zn, Pb
Embodiment 3
The Cd that adds in the soil, Zn, Pb content are respectively 6mg/kg, 3000mg/kg, 3000mg/kg, and the Heavy Metals that adds is CdCl
22.5H
2O, ZnSO
47H
2O, Pb (NO
3)
2, be added in the soil, abundant mixing, balance is stand-by after half a year., select the Glycine max Seedling consistent with embodiment 1 growth to transplant, but manually chelating agent EDTA add at twice, press the described time adding of table 5, wherein said maturation is results the last fortnight, the specific embodiment sees Table 5.
Table 5EDTA applies sequentially and concentration
Experimental result shows (table 6, table 7): apply EDTA when ripe, to apply the EDTA effect best the last week for results, make green soy bean reach respectively 5.8 times, 3.0 times, 7.5 times of contrast to the cumulant of Cd, Zn, Pb, spinach reaches respectively 6.8 times, 3.25 times, 4.9 times of contrast to the cumulant of Cd, Zn, Pb.
Process 3 effects that are better than disposable employed EDTA in the example 2, the further remediation efficiency that improved is used in gradation, the murder by poisoning of plant has been reduced the secondary pollution that reduction may produce vegetable crop, underground water etc.It is more to process 3 Cd, Zn, the Pb total amounts of extracting from soil than green soy bean and the spinach of processing 2.
Table 6 gradation applies EDTA absorbs and accumulate Cd, Zn, Pb on green soy bean impact
Table 7 gradation applies EDTA absorbs and accumulate Cd, Zn, Pb on spinach impact
Claims (6)
1. method of utilizing enhancements to repair the Cd-Zn-Pb combined contamination soil, it is characterized in that: crop rotation plantation green soy bean, spinach in the Cd-Zn-Pb combined contamination soil, then in soil, add chelating agent, thereby reach the purpose of repairing the Cd-Zn-Pb combined contamination soil.
2. the method for utilizing enhancements to repair the Cd-Zn-Pb combined contamination soil according to claim 1, it is characterized in that: described chelating agent is ethylenediamine tetra-acetic acid (EDTA).
3. the method for utilizing enhancements to repair the Cd-Zn-Pb combined contamination soil according to claim 1, it is characterized in that: the addition of described chelating agent EDTA is 2.5-7.5mmol in every kilogram of soil.
4. the method for utilizing enhancements to repair the Cd-Zn-Pb combined contamination soil according to claim 1 is characterized in that: the vegetable crop of described plantation refers to high 2-5cm or contains green soy bean that the 2-3 sheet launches true leaf, spinach seedling replanting in the Cd-Zn-Pb combined contamination soil.
5. the method for utilizing enhancements to repair the Cd-Zn-Pb combined contamination soil according to claim 1, it is characterized in that: in the Cd-Zn-Pb combined contamination soil, plant, crop adopts outdoor planting, regularly water, make soil moisture content remain on 60% ~ 80% of field capacity.
6. the method for utilizing enhancements to repair the Cd-Zn-Pb combined contamination soil according to claim 1, it is characterized in that: in the Cd-Zn-Pb combined contamination soil, press crop rotation in season planting vegetable crop green soy bean, spinach, namely first batch of green soy bean length during to the maturity period, in soil, add chelating agent, after regrowth 10-15 days, plant integral body is shifted out from combined contamination soil, plant again the second crop spinach, spinach growth is during to the maturity period, in soil, add chelating agent, after regrowth 10-15 days, plant integral body is shifted out from combined contamination soil; Repeat said process, until the Cd-Zn-Pb content in the soil reaches environmental safety standard.
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| CN107999535A (en) * | 2017-12-18 | 2018-05-08 | 新乡学院 | A kind of method using herbaceous plant cadmium pollution soil repair |
| CN114226435A (en) * | 2021-11-29 | 2022-03-25 | 中山大学 | Remediation method of heavy metal-organic matter composite contaminated soil |
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Application publication date: 20130327 |