CN109777443A - A kind of heavy metal pollution of soil renovation agent - Google Patents

A kind of heavy metal pollution of soil renovation agent Download PDF

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Publication number
CN109777443A
CN109777443A CN201910204345.1A CN201910204345A CN109777443A CN 109777443 A CN109777443 A CN 109777443A CN 201910204345 A CN201910204345 A CN 201910204345A CN 109777443 A CN109777443 A CN 109777443A
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soil
saccharomycete
heavy metal
nanoscale iron
metal pollution
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石国荣
肖苗
李小雨
杨贻皖
李香君
林炜琪
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Hunan Agricultural University
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Hunan Agricultural University
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Abstract

The present invention provides a kind of heavy metal pollution of soil renovation agent, the Nanoscale Iron including yeast vector and its load, wherein Nanoscale Iron is that the saccharomycete of boron hydride preparation is replaced to carry Nanoscale Iron with waste tobacco leaf extract.It is mixed well withed the soil, the lead and cadmium that can promote in soil are converted into residual form, achieve the purpose that the biological effectiveness for reducing lead and cadmium in soil.The saccharomycete carries Nanoscale Iron preparation and does not need any toxic reagent, just can be completed using conventional instrument at room temperature, at a normal.It is not only able to achieve the resource utilization of waste tobacco leaf, reduces the preparation cost of Nanoscale Iron, it is environmental-friendly, and can increase soil organic matter content while repairing heavy metal in soil pollutes, improve the yield and quality of crops.The in-situ immobilization that can be widely used for lead, cadmium pollution soil belongs to heavy metal pollution recovery technique field.

Description

A kind of heavy metal pollution of soil renovation agent
Technical field
The present invention provides a kind of heavy metal pollution of soil renovation agent, the Nanoscale Iron including yeast vector and its load, In, Nanoscale Iron is that the saccharomycete of boron hydride preparation is replaced to carry Nanoscale Iron with waste tobacco leaf extract, for lead-contaminated soil and The reparation of cadmium pollution soil.Belong to heavy metal pollution of soil recovery technique field.
Background technique
In recent years, crop heavy metal over-standard phenomenon happens occasionally, and the heavy metal pollution of soil is one of the main reasons for this. Heavy metal pollution renovation agent is applied, by changing the occurrence patterns of heavy metal, reducing its migration and biology in the soil has Effect property is one of the effective way of repairing heavy metal in soil pollution.
The high reproducibility of nano zero valence iron and excellent absorption property become a kind of soil huge sum of money for having much application potential Belong to pollution amelioration agent.Currently, the preparation of Nanoscale Iron is mostly using sodium borohydride or potassium borohydride as reducing agent, not only toxicity is big, and And plus polymer or surfactant is needed to make the coating agent or stabilizer of Nanoscale Iron, there are certain environmental risks, and with The plant extracts such as tealeaves, eucalyptus leaves, dried peppermint leaf, sorghum bran, orange peel and citrus are that prepare Nanoscale Iron not only at low cost for reducing agent It is honest and clean and environmentally protective.Patent CN201710245090.4 disclose it is a kind of with 80 DEG C of water extract green-tea extract for reduction The method that agent, dispersing agent and screening agent prepare nanometer iron powder, for pitch it is anti-aging and reduction road surface heavy metal ion;Patent CN201610274411.9 discloses a kind of utilization tea free aqueous extract synthesis Nanoscale Iron removal p, the method for p '-DDT;Patent CN201510824709.8 and CN201510824685.6 individually discloses a kind of utilization green tea aqueous extract synthesis nano zero-valence Iron nickel bimetal and nano zero-valence iron-copper bi-metal material and its for the hexavalent chromium polluted side in rehabilitating soil and underground water Method, both bimetallic materials require addition surfactant and are modified.In addition, patent CN201410112823.3 and CN201310141406.7 then individually discloses a kind of hot water extracting solution green syt that leaf is liked using mangosteen peel and monkey The method of Nanoscale Iron.
Saccharomycete has porous network structure and amino abundant, hydroxyl, carboxyl and phosphate group, is a kind of natural life Object adsorbent.The Nanoscale Iron that waste tobacco leaf extract restores ferrous salt or molysite preparation is loaded on saccharomycete, yeast is made Bacterium carries Nanoscale Iron, not only can be reduced the reunion between nano iron particles, but also can play the suction-operated and nanometer of saccharomycete simultaneously The reduction of iron improves the utilization rate of Nanoscale Iron.The prior art yeast that disclosure is prepared not yet with waste tobacco leaf extract Bacterium carries the method that Nanoscale Iron is used for repairing heavy metal in soil pollution.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of heavy metal pollution of soil renovation agent, including yeast vector and Its Nanoscale Iron loaded, the Nanoscale Iron are to replace boron hydride with waste tobacco leaf extract, the ferrous salt that saccharomycete is adsorbed Or molysite in-situ reducing, obtained saccharomycete carry Nanoscale Iron.By adjusting the mass ratio of yeast vector and ferrous salt or molysite, And/or the dosage by adjusting leaf tobacco extract, and/or by adjusting reaction time, and/or by adjusting stirring or oscillation speed It spends to control the reactivity of Nanoscale Iron.
Therefore, the first purpose of the invention is to provide a kind of heavy metal pollution of soil renovation agents, including yeast vector It is that boron hydride is replaced with waste tobacco leaf extract with the Nanoscale Iron of its load, the ferrous salt of saccharomycete absorption or molysite is former Position reduction gained.
Heavy metal pollution of soil reparation is prepared using waste tobacco leaf extract a second object of the present invention is to provide a kind of The method of agent, comprising the following steps:
(1) tobacco leaf is handled: it after the tobacco natural for having washed off impurity is dried, dried at 50 DEG C, crushed 200 meshes, Sealing is stand-by;
(2) prepared by leaf tobacco extract: by tobacco leaf powder obtained in above-mentioned steps (1) and Extraction solvent according to quality volume Than for 1:5~1:40 (unit gmL-1), it is added in 250mL conical flask, 10~40min of ultrasonic extraction or shaken at room temperature mention 1~8h is taken, after centrifuge separation, clear liquid Rotary Evaporators are concentrated into 10mL at 38 DEG C or less;
(3) prepared by yeast vector: carrying out saccharomycete Liquid Culture according to a conventional method, resulting saccharomycete is centrifuged, is washed After washing, it is freeze-dried to obtain yeast vector;
(4) ferrous salt or molysite aqueous solution yeast vector absorption ferrous salt or molysite: are added to what step (3) obtained In yeast vector, in 50~200rmin-10.5~2h of lower stirring or oscillation obtains being adsorbed with ferrous salt after centrifugation, washing Or the saccharomycete of molysite;
(5) Nanoscale Iron prepare: it is lasting stirring or oscillation under conditions of, toward step (4) obtain be adsorbed with ferrous salt or The leaf tobacco extract that step (2) obtain is added in the saccharomycete of molysite, continues stirring or oscillating reactions 0.5h~8h, then consolidated Liquid separation, solid carry Nanoscale Iron after freeze-drying grinding with second distillation water washing 3 times up to saccharomycete.
Preferably, the saccharomycete is Saccharomyces cerevisiae or saccharomyces cerevisiae.
Preferably, tobacco leaf powder described in step (2) is 1.0g, and Extraction solvent is 25mL 0~80% (volume ratio) Ethanol solution.
Preferably, yeast vector quality described in step (4) is 0.02~1.0g, the ferrous salt or molysite with The mass ratio of yeast vector is 1:2~30.
Preferably, step (5) is while stirring or oscillation with 0.5~0.8mLmin-1Gas supply speed toward described molten Lead to N in liquid2, the separation of solid and liquid is in 3000~5000rmin-15~10min is centrifuged under revolving speed.
Third object of the present invention is to provide carry out heavy-metal contaminated soil using the heavy metal pollution of soil renovation agent The method of reparation.
The restorative procedure of heavy-metal contaminated soil is as follows: applying heavy metal pollution of soil reparation into heavy-metal contaminated soil Agent, after mixing well, routinely earth culture method is managed.Timing sampling, by BCR method (Tanta, 2006,70:973-978) Measure the content of various forms heavy metal in soil.
In a specific embodiment, the soil preferably repaired is lead-contaminated soil.
In another specific embodiment, the soil preferably repaired is cadmium pollution soil.
Technical effect
(1) biologically effective of lead and cadmium in soil can be effectively reduced in heavy metal pollution of soil renovation agent prepared by the present invention Property, promote lead and cadmium in soil to be converted into inactive residual form.Nanoscale Iron load significantly improves saccharomycete to soil weight The passivation ability of metal: saccharomycete carries ferment of the ability than unsupported Nanoscale Iron that Nanoscale Iron converts the lead in soil to residual form Female bacterium is high by 24.9%, and the ability that the cadmium in soil is converted residual form by it is higher than the saccharomycete of unsupported Nanoscale Iron by 12.4 Times.
(2) saccharomycete carries the rice husk carbon-supported nanometer that Nanoscale Iron is above equivalent to the passivation ability of lead and cadmium in soil Iron.The ability that the lead in soil is converted residual form by saccharomycete load Nanoscale Iron is higher by 15.3% than rice hull carbon load Nanoscale Iron, will be native Cadmium is converted into the ability of residual form than rice hull carbon to carry Nanoscale Iron strong by 155.8% in earth.
(3) with waste tobacco leaf extract replace toxic boron hydride prepare saccharomycete carry Nanoscale Iron, do not need using appoint What toxic reagent, just can be completed using conventional instrument at room temperature, at a normal, not only be able to achieve the resource utilization of waste tobacco leaf, The preparation cost of Nanoscale Iron is reduced, it is environmental-friendly, and the soil organism can be increased while repairing heavy metal in soil pollutes Content improves the yield and quality of crops.
Detailed description of the invention
Fig. 1 is that heavy metal pollution of soil renovation agent handles the influence to form lead content each in lead-contaminated soil in 3 months.
Fig. 2 is that heavy metal pollution of soil renovation agent handles the influence to form cadmium content each in cadmium pollution soil in 2 months.
Specific embodiment
In the following, the present invention will be further detailed with embodiment, but its any for being not limited to these examples A or similar example.
Embodiment 1:
(1) tobacco leaf is handled: after the tobacco natural for having washed off impurity is dried, being dried at 50 DEG C, be crushed 200 meshes;
(2) prepared by leaf tobacco extract: tobacco leaf powder obtained in 1.0g above-mentioned steps (1) is weighed in 250mL conical flask, Be added 25mL50% ethanol solution (volume ratio) ultrasonic extraction 30min, after centrifuge separation, clear liquid Rotary Evaporators 38 DEG C with Under be concentrated into 10mL;
(3) prepared by yeast vector: saccharomycete Liquid Culture is conventionally carried out, saccharomycete is collected and wash, it is cold It is lyophilized dry;
(4) saccharomycete adsorbs ferrous salt: yeast vector obtained in 0.050g step (3) is weighed in 100mL beaker, 3.0mL 16.5gL is added-1FeSO4·7H2O solution is placed in 25 DEG C of water-baths with 200rmin-1Revolving speed stirring 30min, in 3000rmin-1It is centrifuged 10min under revolving speed, obtains the yeast vector for being adsorbed with ferrous salt;
(5) prepared by Nanoscale Iron: under lasting stirring or oscillating condition, the ferment for being adsorbed with ferrous salt that obtains toward step (4) The leaf tobacco extract that step (2) obtain is added in female bacterium, continues stirring or oscillating reactions 3h, in 3000rmin-1Under the conditions of from Heart 5min, solid carry Nanoscale Iron after freeze-drying grinding with second distillation water washing 3 times up to saccharomycete.
Embodiment 2:
Tobacco leaf processing, leaf tobacco extract and yeast vector preparation, saccharomycete absorption ferrous salt and Nanoscale Iron preparation step With embodiment 1, in addition to weighed yeast vector is 0.020g in step (4).
Embodiment 3:
Tobacco leaf processing, leaf tobacco extract and yeast vector preparation, saccharomycete absorption ferrous salt and Nanoscale Iron preparation step With embodiment 1, in addition to weighed yeast vector is 0.100g in step (4).
Embodiment 4:
Tobacco leaf processing, leaf tobacco extract and yeast vector preparation, saccharomycete absorption ferrous salt and Nanoscale Iron preparation step With embodiment 1, in addition to weighed yeast vector is 0.200g in step (4).
Embodiment 5:
Tobacco leaf processing, leaf tobacco extract and yeast vector preparation, saccharomycete absorption ferrous salt and Nanoscale Iron preparation step With embodiment 1, in addition to weighed yeast vector is 0.300g in step (4).
Embodiment 6:
Tobacco leaf processing, leaf tobacco extract and yeast vector preparation, saccharomycete absorption ferrous salt and Nanoscale Iron preparation step With embodiment 1, in addition to weighed quality of tobacco is 0.20g in step (2).
Embodiment 7:
Tobacco leaf processing, leaf tobacco extract and yeast vector preparation, saccharomycete absorption ferrous salt and Nanoscale Iron preparation step With embodiment 1, in addition to weighed quality of tobacco is 0.30g in step (2).
Embodiment 8:
Tobacco leaf processing, leaf tobacco extract and yeast vector preparation, saccharomycete absorption ferrous salt and Nanoscale Iron preparation step With embodiment 1, in addition to weighed quality of tobacco is 0.40g in step (2).
Embodiment 9:
Tobacco leaf processing, leaf tobacco extract and yeast vector preparation, saccharomycete absorption ferrous salt and Nanoscale Iron preparation step With embodiment 1, in addition to what is be added in step (2) is 10mL50% ethanol solution.
Embodiment 10:
Tobacco leaf processing, leaf tobacco extract and yeast vector preparation, saccharomycete absorption ferrous salt and Nanoscale Iron preparation step With embodiment 1, in addition to what is be added in step (2) is 20mL50% ethanol solution.
Embodiment 11:
Tobacco leaf processing, leaf tobacco extract and yeast vector preparation, saccharomycete absorption ferrous salt and Nanoscale Iron preparation step With embodiment 1, in addition to what is be added in step (2) is 40mL50% ethanol solution.
Embodiment 12:
Tobacco leaf processing, leaf tobacco extract and yeast vector preparation, saccharomycete absorption ferrous salt and Nanoscale Iron preparation step With embodiment 1, in addition to the time of ultrasonic extraction in step (2) is 10min.
Embodiment 13:
Tobacco leaf processing, leaf tobacco extract and yeast vector preparation, saccharomycete absorption ferrous salt and Nanoscale Iron preparation step With embodiment 1, in addition to the time of ultrasonic extraction in step (2) is 20min.
Embodiment 14:
Tobacco leaf processing, leaf tobacco extract and yeast vector preparation, saccharomycete absorption ferrous salt and Nanoscale Iron preparation step With embodiment 1, in addition to the time of ultrasonic extraction in step (2) is 40min.
Embodiment 15:
Tobacco leaf processing, leaf tobacco extract and yeast vector preparation, saccharomycete absorption ferrous salt and Nanoscale Iron preparation step With embodiment 1, in addition to being to be shaken in 40 DEG C of water-baths and extract 1h instead of ultrasonic extraction 30min in step (2).
Embodiment 16:
Tobacco leaf processing, leaf tobacco extract and yeast vector preparation, saccharomycete absorption ferrous salt and Nanoscale Iron preparation step With embodiment 1, in addition to being to be shaken in 40 DEG C of water-baths and extract 4h instead of ultrasonic extraction 30min in step (2).
Embodiment 17:
Tobacco leaf processing, leaf tobacco extract and yeast vector preparation, saccharomycete absorption ferrous salt and Nanoscale Iron preparation step With embodiment 1, in addition to being to replace 50% ethanol solution with 80% ethyl alcohol (volume ratio) in step (2).
Embodiment 18:
Tobacco leaf processing, leaf tobacco extract and yeast vector preparation, saccharomycete absorption ferrous salt and Nanoscale Iron preparation step With embodiment 1, in addition to being to replace 50% ethanol solution with water in step (2).
Embodiment 19:
Tobacco leaf processing, leaf tobacco extract and yeast vector preparation, saccharomycete absorption molysite and Nanoscale Iron preparation step are same Embodiment 1, in addition to being with FeCl in step (4)3·6H2O solution replaces FeSO4·7H2O solution.
Application Example 1:
Heavy metal pollution of soil renovation agent is used for lead-contaminated soil reparation.
The restorative procedure of lead-contaminated soil is as follows: surface layer 0-20cm Tobacco-rice rotation topsoil is taken, after natural air drying, 2mm sieve is crossed, by 500mg Pb2+·kg-1Soil is added, and after conventional method aging 1 month, is separately added into 5% soil weight Metallic pollution renovation agent, the rice hull carbon load Nanoscale Iron of using similar approach preparation and the saccharomycete and rice husk of unsupported Nanoscale Iron Charcoal fills basin after mixing, each processing is repeated 3 times, and routinely earth culture method is managed at room temperature.It is sampled after 3 months, it is natural Air-dry after, measure soil in weak acid extractable, can reduction-state, oxidable state and residual form lead content.Soil physics and chemistry substantially Matter is as shown in table 1.
Table 1 is for trying soil labile organic matter
Compared with the control group for not applying renovation agent, apply 5% saccharomycete carry Nanoscale Iron repair process 3 months after, lead In contaminated soil weak acid extractable with can reduction-state lead content respectively lower than control group 52.52% and 15.03%, and oxidable state It is higher than control group by 15.29% and 86.56% respectively with residual form lead content;And after applying saccharomycete 3 months of 5%, lead contamination In soil weak acid extractable with can reduction-state lead content respectively lower than control group 50.05% and 12.00%, oxidable state and residue State lead content is higher than control group by 0.15% and 69.28% respectively, sees attached drawing 1.
Show that saccharomycete and saccharomycete carry the biological effectiveness that lead in soil can be effectively reduced in Nanoscale Iron by comparing, Promote soil in lead be converted into low activity oxidable state and inactive residual form, saccharomycete carry Nanoscale Iron will be in soil The ability that lead is converted into residual form is 1.25 times of saccharomycete, and Nanoscale Iron load significantly improves saccharomycete to Lead Pollution in Soil Passivation ability.
The rice hull carbon of addition 5% carries after Nanoscale Iron carries out repair process 3 months, weak acid extractable in lead-contaminated soil, can Lower than control group 36.85%, 7.56% and 13.42%, residual form lead content compare respectively for reduction-state and oxidable state lead content It is high by 75.05% according to organizing;And after adding rice hull carbon repair process 3 months of 5%, weak acid extractable in lead-contaminated soil can restore State and oxidable state lead content lower than control group 43.85%, 7.45% and 3.45% respectively, residual form lead content is higher than control group 31.92%.
Show that saccharomycete carries Nanoscale Iron and receives the ability that the lead in soil is converted into residual form than rice hull carbon load by comparing It is stronger than rice hull carbon load Nanoscale Iron to the passivation ability of Lead Pollution in Soil to illustrate that saccharomycete carries Nanoscale Iron by meter Tie Gao 15.3%.
Application Example 2:
Heavy metal pollution of soil renovation agent rehabilitating soil cadmium pollution.
The restorative procedure of cadmium pollution is as follows in soil: surface layer 0-20cm Tobacco-rice rotation topsoil is taken, through natural air drying Afterwards, 2mm sieve is crossed, by 2mg Cd2+·kg-1Soil is added, and after conventional method aging 1 month, is separately added into 1% soil Heavy metal pollution renovation agent, the rice hull carbon load Nanoscale Iron of using similar approach preparation and saccharomycete and the rice of unsupported Nanoscale Iron Shell charcoal fills basin after mixing, each processing is repeated 3 times, and routinely earth culture method is managed at room temperature.It is sampled after 2 months, from So air-dry after, measure soil in weak acid extractable, can reduction-state, oxidable state and residual form cadmium content.Soil is managed substantially It is as shown in table 1 to change property.
After the saccharomycete of application 1% carries Nanoscale Iron 2 months, weak acid extractable and can reduction-state cadmium content in cadmium pollution soil Respectively lower than control group 31.45% and 9.79%, oxidable state and residual form cadmium content 2.71% He higher than control group respectively 63.09%;And after applying saccharomycete 2 months of 1%, weak acid extractable in cadmium pollution soil, can reduction-state and oxidable state cadmium Content lower than control group 26.01%, 8.21% and 2.38% respectively, residual form cadmium content is higher than control group by 4.71%, sees attached drawing 2。
Show that saccharomycete and saccharomycete carry the biological effectiveness that cadmium in soil can be effectively reduced in Nanoscale Iron by comparing, Saccharomycete carries 13.4 times that the ability that cadmium in soil is converted into residual form is saccharomycete by Nanoscale Iron, and Nanoscale Iron load significantly improves Passivation ability of the saccharomycete to Cadmium Pollution in Soils.
After the rice hull carbon and rice hull carbon of addition 1% carry Nanoscale Iron progress repair process 2 months, weak acid is mentioned in cadmium pollution soil Take state cadmium content respectively lower than control group 9.08% and 9.91%, and residual form cadmium content 15.86% He higher than control group respectively 24.66%.
Show that saccharomycete carries Nanoscale Iron and converts the ability of residual form than rice husk carbon-supported nanometer for cadmium in soil by comparison Iron is strong by 155.8%, and it is stronger than rice hull carbon load Nanoscale Iron to the passivation ability of Cadmium Pollution in Soils to illustrate that saccharomycete carries Nanoscale Iron.

Claims (8)

1. a kind of heavy metal pollution of soil renovation agent, which is characterized in that the Nanoscale Iron including yeast vector and its load, In, Nanoscale Iron is that the saccharomycete of boron hydride preparation is replaced to carry Nanoscale Iron with waste tobacco leaf extract.It is mixed well withed the soil, it can Promote lead and cadmium in soil to be converted into residual form, achievees the purpose that the biological effectiveness for reducing lead and cadmium in soil.
2. the preparation method of heavy metal pollution of soil renovation agent described in claim 1, which is characterized in that including preparing step as follows It is rapid:
(1) tobacco leaf is handled: after the tobacco natural for having washed off impurity is dried, being dried at 50 DEG C, be crushed 200 meshes, seals For use;
(2) prepared by leaf tobacco extract: being according to mass volume ratio by tobacco leaf powder obtained in above-mentioned steps (1) and Extraction solvent 1:5~1:40 (unit gmL-1), it is added in 250mL conical flask, 10~40min of ultrasonic extraction or shaken at room temperature extract 1 ~8h, after centrifuge separation, clear liquid Rotary Evaporators are concentrated into 10mL at 38 DEG C or less;
(3) prepared by yeast vector: resulting saccharomycete is centrifuged by culture yeasts bacterium according to a conventional method, after washing, freeze-drying Obtain yeast vector;
(4) saccharomycete absorption ferrous salt or molysite: ferrous salt or molysite aqueous solution are added to the saccharomycete that step (3) obtains and carried In body, in 50~200rmin-10.5~2h of lower stirring or oscillation after centrifugation, washing, obtains being adsorbed with ferrous salt or molysite Saccharomycete;
(5) prepared by Nanoscale Iron: under conditions of lasting stirring or oscillation, being adsorbed with ferrous salt or molysite toward what step (4) obtained Saccharomycete in step (2) obtained leaf tobacco extract is added, continue stirring or oscillating reactions 0.5h~8h, then carry out solid-liquid point From solid carries Nanoscale Iron after freeze-drying grinding with second distillation water washing 3 times up to saccharomycete.
3. the preparation method of heavy metal pollution of soil renovation agent according to claim 2, which is characterized in that the saccharomycete For Saccharomyces cerevisiae or saccharomyces cerevisiae.
4. the preparation method of heavy metal pollution of soil renovation agent according to claim 2, which is characterized in that in step (2) The Extraction solvent is the ethanol solution of 0~80% (volume ratio).
5. the preparation method of heavy metal pollution of soil renovation agent according to claim 2, which is characterized in that in step (4) The yeast vector quality is that the mass ratio of 0.02~1.0g, the ferrous salt or molysite and yeast vector is 1:2 ~30.
6. the preparation method of heavy metal pollution of soil renovation agent according to claim 2, which is characterized in that step (5) exists With 0.5~0.8mLmin while stirring or oscillation-1Gas supply speed into the solution lead to N2, the separation of solid and liquid is In 3000~5000rmin-15~10min is centrifuged under revolving speed.
7. heavy metal pollution of soil renovation agent described in claim 1, or pass through side described in any one of claim 2~6 The heavy metal pollution of soil renovation agent that method is prepared is used for the reparation of lead-contaminated soil.
8. heavy metal pollution of soil renovation agent described in claim 1, or pass through side described in any one of claim 2~6 The heavy metal pollution of soil renovation agent that method is prepared is used for the reparation of cadmium pollution soil.
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Application publication date: 20190521