CN112646587A - Soil remediation composition, preparation method thereof and soil bioremediation method - Google Patents
Soil remediation composition, preparation method thereof and soil bioremediation method Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/40—Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds
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- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01B—SOIL WORKING IN AGRICULTURE OR FORESTRY; PARTS, DETAILS, OR ACCESSORIES OF AGRICULTURAL MACHINES OR IMPLEMENTS, IN GENERAL
- A01B79/00—Methods for working soil
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01B—SOIL WORKING IN AGRICULTURE OR FORESTRY; PARTS, DETAILS, OR ACCESSORIES OF AGRICULTURAL MACHINES OR IMPLEMENTS, IN GENERAL
- A01B79/00—Methods for working soil
- A01B79/02—Methods for working soil combined with other agricultural processing, e.g. fertilising, planting
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
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- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
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- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
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- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
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Abstract
The application relates to the field of soil remediation, and particularly discloses a soil remediation composition, a preparation method thereof and a soil bioremediation method, wherein the soil remediation composition is prepared from the following raw materials in parts by weight: 50-60 parts of phosphorylated chitosan, 400 parts of sodium chloride, 10-15 parts of soluble organic matter (DOM), 80-100 parts of charcoal, 80-100 parts of water-retaining agent and 80-100 parts of biological bacterial fertilizer; the preparation method comprises the following steps: uniformly mixing the components in parts by weight to prepare a soil remediation composition; the soil bioremediation method comprises the following steps: the soil is treated by the soil remediation composition, then the super-enriched plants are planted, and the super-enriched plants are harvested after the super-enriched plants grow vigorously. The composition can be used for phytoremediation polluted by heavy metal soil, and has the advantage of enhancing the remediation effect on the soil.
Description
Technical Field
The application relates to the field of soil remediation, in particular to a soil remediation composition, a preparation method thereof and a soil bioremediation method.
Background
The metal mineral resources in China are rich, the mining intensity of the mineral resources is getting larger and larger in recent years, and the harmful elements are transferred into the soil by the waste rocks generated by mineral mining, the tailings generated by mineral separation and the smelting waste residues (containing harmful elements such as Pb, Cd and the like) through weathering leaching, so that the quality of the soil is reduced, meanwhile, the crops are polluted, and finally, the harmful elements enter the human body through a food chain, and the health of human beings is influenced. Once the soil environment is polluted, the self-remediation is difficult only by a method of cutting off a pollution source, so that the soil remediation can eliminate the pollution only by adopting various effective granulation technologies.
The soil remediation method comprises a physical remediation method, a chemical remediation method and a biological remediation method, wherein the physical remediation method is high in cost and limited in use due to the destruction of soil biological diversity; the chemical reagents used in the chemical remediation method may cause secondary pollution to the soil; therefore, the bioremediation method is widely used, and comprises a plant remediation technology, a microbial remediation technology and an animal remediation technology, wherein the plant remediation technology is to plant hyper-enriched plants on polluted soil, and transfer, contain or transform toxic and harmful pollutants in an environmental medium by using the plants, so that the polluted soil is remedied and treated.
The phytoremediation is limited by the biological effectiveness and water solubility of pollutants, has the defects of low remediation speed, long remediation time and the like, and measures for enhancing the phytoremediation effect and improving the phytoremediation efficiency are always the research hotspots of the bioremediation.
Disclosure of Invention
In order to enhance the soil remediation effect of plants, the application provides a soil remediation composition, a preparation method thereof and a soil bioremediation method.
In a first aspect, the present application provides a soil remediation composition, using the following technical scheme:
the soil remediation composition is prepared from the following raw materials in parts by weight: 50-60 parts of phosphorylated chitosan, 380 parts of sodium chloride, 10-15 parts of soluble organic matter (DOM), 80-100 parts of charcoal, 80-100 parts of water-retaining agent and 80-100 parts of biological bacterial fertilizer;
the hypophosphorous chitosan is prepared by performing phosphonomethylation modification on chitosan by using phosphorous acid and formaldehyde.
By adopting the technical scheme, when the soil of the abandoned mine is repaired by utilizing the hyper-enrichment plants, the plants can only absorb the heavy metals in the liquid phase of the soil, and the proportion occupied by the heavy metals is small, so that the effect of repairing the soil polluted by the heavy metals by the plants is poor.
The phosphorous acid and formaldehyde are used for modifying chitosan, on one hand, the water solubility of the chitosan can be improved, on the other hand, ligands on the chitosan are increased, the chelation effect of the chitosan on heavy metals is enhanced, after the phosphorous acid chitosan enters soil, the ligands contained in the phosphorous acid chitosan are combined with heavy metal ions in a soil solution to form a chelate, the concentration of the heavy metal ions in a soil liquid phase is reduced, the balance of the heavy metal ions between the soil liquid phase and a soil solid phase is maintained, the adsorption of soil minerals on the heavy metals is reduced, the bioavailability of the heavy metals is improved, and the heavy metals are absorbed and utilized by plants, so that the migration of the heavy metals in the soil to plants is enhanced, and the repairing effect of the.
The back in the sodium chloride gets into soil, dissolve in the soil liquid phase for plant roots department forms electrolyte solution, can lead to the internal osmotic adjustment of plant to produce the change on the one hand, and the salt stresses the internal osmotic substance accumulation of plant and increases down, can promote the accumulation of heavy metal in the plant, and on the other hand can also change plant roots's metabolite, thereby improves plant roots's biological activation to heavy metal, improves the biological validity of heavy metal, further improves plant roots's absorption to heavy metal ion.
Soluble organic matter (DOM) can be complexed with heavy metal to prevent the heavy metal from being adsorbed on the solid phase surface, or compete with the heavy metal for the adsorption point position on the solid phase surface, so that the solubility of the heavy metal is increased, meanwhile, the DOM can also change the surface property of a soil adsorbent, reduce the adsorption effect of the soil on the heavy metal ions, and further improve the absorption effect of a plant root system on the heavy metal ions.
The DOM changes the surface property of the soil adsorbent, and reduces the adsorption effect of the soil on heavy metal ions; the phosphorylating chitosan, sodium chloride, DOM all can make in the soil heavy metal to the conversion of biological effective performance, improve the biological effectiveness who improves the heavy metal, simultaneously, the osmotic substance accumulation in the plant body increases under the sodium chloride coercion, promotes the accumulation of heavy metal in the plant body, and the three cooperation improves the adsorption of plant to heavy metal in the soil from soil, heavy metal and the three aspect of plant.
The biochar, the water-retaining agent and the biological bacterial fertilizer are used as soil conditioners and added into soil, the biological bacterial fertilizer provides nutrients for plant growth, on one hand, the biochar can improve the organic carbon content of the soil, improve the water retention and fertilizer retention performance of the soil and reduce the nutrient loss, on the other hand, the biochar can be used as a synergistic carrier of the biological bacterial fertilizer, the release of the nutrients of the biological bacterial fertilizer in the soil is delayed, the nutrient loss is reduced, the nutrient utilization rate of the biological bacterial fertilizer is improved, the water-retaining agent can effectively guarantee the moisture in the soil, and the vegetation survival rate is.
Preferably, the preparation method of the phosphorylated chitosan comprises the following steps:
A1. dissolving 10-15 parts of chitosan in 750 parts of 1% acetic acid 500-750 parts, uniformly stirring, and heating to 60-70 ℃ to obtain a chitosan solution for later use;
A2. dissolving 10-15 parts of phosphorous acid in 20-30 parts of water to obtain a phosphorous acid solution, adding the phosphorous acid solution into the chitosan solution obtained from A1, and uniformly stirring;
A3. adding 15-20 parts of 40% formaldehyde solution into the solution obtained from A2, and uniformly stirring to obtain a mixed solution;
A4. and (2) reacting the mixed solution obtained in the step A3 at a constant temperature of 60-70 ℃ for 5-6h, cooling, pouring into absolute ethyl alcohol to separate out a precipitate, performing suction filtration to the utmost extent, washing the precipitate obtained by suction filtration to be neutral, then washing the precipitate with absolute ethyl alcohol, and finally drying the precipitate in vacuum at 40-45 ℃ for 7-8h to obtain the phosphorylated chitosan.
According to the technical scheme, the phosphonic acid and formaldehyde are used for performing phosphonomethylation modification on chitosan, phosphonic acid groups are added to chitosan molecules to add ligands to the chitosan, and the phosphonous chitosan mainly performs chelation between amino groups and phosphonic acid groups and heavy metals to enhance chelation of the chitosan to the heavy metals, so that the exchangeable heavy metal content in soil is remarkably increased.
Preferably, the formaldehyde solution is added dropwise at a rate of (0.5-1.5) d/s when the formaldehyde solution is added to the solution obtained in A2 in the step A3.
By adopting the technical scheme, as the chitosan molecules are more beaten than the formaldehyde molecules, if the formaldehyde is added at one time, the formaldehyde molecules can not be fully combined with the chitosan molecules under the shielding effect of the chitosan molecules, and the chitosan is slowly dripped, so that the formaldehyde molecules and the chitosan molecules can be ensured to be fully reacted.
Preferably, the DOM is DOM (domc) extracted from chicken manure.
By adopting the technical scheme, the DOMc can obviously improve the content of heavy metal in the rhizosphere soil solution, and improve the proportion of organic complex heavy metal in the total soluble heavy metal content, thus being beneficial to enhancing the absorption effect of plants on the heavy metal, and the chicken manure raw material is pollution-free and cheap.
Preferably, the preparation method of the DOMc comprises the following steps: naturally air-drying the chicken manure, crushing, sieving by a 0.2-0.25mm sieve, and mixing the chicken manure with the raw materials in percentage by weight: adding deionized water into the chicken manure according to the proportion of 1 (20-25), and oscillating the mixed solution of the chicken manure and the deionized water at the constant temperature of 20-25 ℃ for 23-24h (200--1) Then fermenting at constant temperature of 25-27 deg.C for 6-7d, centrifuging for 20-25min (9000--1) And immediately performing air suction filtration on the centrifuged supernatant by using a 0.45-0.5 mu m sterile microporous filter membrane to obtain filtrate DOMc.
By adopting the technical scheme, no extra chemical substance is added in the process of preparing DOMc, and the chicken manure after extracting the DOMc can also be used as a fertilizer, so that the energy waste is reduced.
Preferably, the sodium chloride is 320-380 parts.
By adopting the technical scheme, the concentration of sodium chloride in the root system soil solution is too high due to too much sodium chloride content, the water loss of plant root system cells can be caused due to too high sodium chloride solubility, the growth of plants is not facilitated, and the sodium chloride is 320 plus 380 parts, so that the sodium chloride can play a role in promoting the accumulation of heavy metals in plants and the water loss of the plant cells is not easily caused.
In a second aspect, the present application provides a method for preparing a soil remediation composition, using the following technical scheme:
uniformly mixing the phosphorylate chitosan, sodium chloride, soluble organic matters, biochar, a water-retaining agent and biological bacterial fertilizer in parts by weight.
By adopting the technical scheme, the preparation of the soil remediation composition can be completed only under the physical mixing action, the preparation method is simple in process and simple to operate, and the waste of energy can be effectively reduced.
In a third aspect, the present application provides a soil bioremediation method of a soil remediation composition, which adopts the following technical scheme:
s1, loosening soil of soil to be repaired; after loosening the soil, adding a soil remediation composition into the soil, and turning over the soil to uniformly mix the soil remediation composition with the soil, wherein the adding amount of the soil remediation composition is 30-35 kg/mu;
s2, leveling the soil, and standing for 36-48 h;
s3, watering the leveled soil, and then planting hyper-enriched plants;
s4, harvesting the hyper-enriched plants after the growth of the hyper-enriched plants is in a vigorous period.
By adopting the technical scheme, the soil and the soil remediation composition are mixed firstly, then stand still, the soil remediation composition is given enough reaction time to play a role, then the hyperaccumulator plants are planted, the hyperaccumulator plants absorb heavy metals in the soil, finally the hyperaccumulator plants are harvested and then are treated in a centralized manner, and the soil remediation is completed.
Preferably, during the S2 standing process, after standing for 24 hours, the soil needs to be turned over, and then the soil is leveled and kept standing.
By adopting the technical scheme, the soil remediation composition can be settled in the process of standing in the soil, the soil is turned over after standing for 24 hours, the probability of reducing the concentration of the soil remediation composition in the surface soil caused by settlement of the soil remediation composition under the action of self gravity is reduced, the content of heavy metals in the surface soil is relatively high, and the sufficient soil remediation composition in the surface soil is ensured, so that the adsorption effect of plants on the heavy metals is ensured.
Preferably, in the step S4, in the growth vigorous period of the hyper-enriched plant, calcium thiosulfate is dissolved in water and uniformly sprayed into the soil around the root system of the hyper-enriched plant, the dosage of the calcium thiosulfate is 7-9 kg/mu, and the hyper-enriched plant is harvested 4-6 days after the calcium thiosulfate is added.
By adopting the technical scheme, a certain amount of heavy metal is enriched in the plant body, when the plant reaches the vigorous growth stage, the more metabolites are secreted by the plant root system, the stronger the absorption effect on the heavy metal is, the sodium thiosulfate is added, has a reduction effect on the heavy metal, accelerates the leaching of heavy metal ions from soil, and is beneficial to the absorption of the plant on the heavy metal.
In summary, the present application has the following beneficial effects: (Note: the effect of the exclusive right will usually be noted first, and then the effect from the technical solution that contributes to the innovativeness of the present case will be further described)
1. Because this application adopts the cooperation of phosphorylating chitosan, sodium chloride, soluble organic matter to improve the adsorption of plant to heavy metal in the soil from three aspect of soil, heavy metal and plant, be favorable to improving the restoration effect of plant to soil.
2. The method has the advantages that DOMc is preferably adopted, so that the content of heavy metal in the rhizosphere soil solution can be obviously improved, the proportion of organic complex heavy metal in the total soluble heavy metal content is improved, and the method is favorable for enhancing the absorption effect of plants on the heavy metal.
3. According to the soil bioremediation method, the sodium thiosulfate is added in the growth vigorous period of the hyper-enriched plants, so that the absorption of the plants and the medium heavy metals is facilitated.
Detailed Description
The present application will be described in further detail with reference to examples.
Examples of preparation of raw materials and/or intermediates
Raw materials
The chitosan has an average molecular weight of 15000, is purchased from Biotechnology Limited of Hebei Chuang and has a content of 99%;
acetic acid cargo number 64-19-7 was purchased from Ji south Guo Wei industries chemical Co., Ltd, content 99%;
phosphorous acid cargo number 13598-36-2 was purchased from Shandong Laya chemical Co., Ltd, content 99%;
formaldehyde was purchased from jonan Chuangtong chemical ltd;
absolute ethanol was purchased from Shandong Ju and Biotechnology, Inc.;
sodium chloride was purchased from salt housekeeper salt industry ltd of henyang city;
the biochar is purchased from Jiangsu Huafeng agricultural bioengineering company Limited;
the water-retaining agent is purchased from new materials of Zhuhai de mi, Inc.;
the biological bacterial fertilizer is purchased from Shijiazhuang nongxing Fei Co Ltd;
the chicken manure is purchased from wood organic fertilizer commercial businesses in Yangxi county;
calcium thiosulfate was purchased from wuhantai ruixin chemical ltd.
Preparation example
Preparation example 1
The preparation method of the phosphorylating chitosan comprises the following steps:
A1. dissolving 10kg of chitosan in 500kg of 1% acetic acid, uniformly stirring, and heating to 60 ℃ to obtain a chitosan solution for later use;
A2. dissolving 10kg of phosphorous acid in 20kg of water to obtain a phosphorous acid solution, adding the phosphorous acid solution into the chitosan solution obtained from A1, and uniformly stirring;
A3. dropwise adding 15kg of 40% formaldehyde solution into the solution obtained from A2 at a dropwise rate of 0.5d/s, and uniformly stirring to obtain a mixed solution;
A4. and (2) reacting the mixed solution obtained in the step A3 at a constant temperature of 60 ℃ for 5h, cooling, pouring the cooled mixed solution into absolute ethyl alcohol to separate out a precipitate, performing suction filtration, washing the precipitate obtained by suction filtration to be neutral, then washing the precipitate with absolute ethyl alcohol, and finally, performing vacuum drying on the precipitate at a temperature of 40 ℃ for 7h to obtain the phosphorylated chitosan.
Preparation example 2
The preparation method of the phosphorylating chitosan comprises the following steps:
A1. dissolving 13kg of chitosan in 625kg of 1% acetic acid, uniformly stirring, and heating to 65 ℃ to obtain a chitosan solution for later use;
A2. dissolving 13kg of phosphorous acid in 25kg of water to obtain a phosphorous acid solution, adding the phosphorous acid solution into the chitosan solution obtained from A1, and uniformly stirring;
A3. dripping 17kg of 40% formaldehyde solution into the solution obtained from A2 at a dripping rate of 1d/s, and uniformly stirring to obtain a mixed solution;
A4. and (2) reacting the mixed solution obtained in the step A3 at the constant temperature of 65 ℃ for 5.5h, cooling, pouring the cooled mixed solution into absolute ethyl alcohol to separate out a precipitate, performing suction filtration, washing the precipitate obtained by suction filtration to be neutral, then washing the precipitate with absolute ethyl alcohol, and finally, drying the precipitate at 42.5 ℃ in vacuum for 7.5h to obtain the phosphorylated chitosan.
Preparation example 3
The preparation method of the phosphorylating chitosan comprises the following steps:
A1. dissolving 15kg of chitosan in 750kg of 1% acetic acid, uniformly stirring, and heating to 70 ℃ to obtain a chitosan solution for later use;
A2. dissolving 15kg of phosphorous acid in 30kg of water to obtain a phosphorous acid solution, adding the phosphorous acid solution into the chitosan solution obtained from A1, and uniformly stirring;
A3. dripping 20kg of 40% formaldehyde solution into the solution obtained from A2 at a dripping rate of 1.5d/s, and uniformly stirring to obtain a mixed solution;
A4. and (2) reacting the mixed solution obtained in the step A3 at a constant temperature of 70 ℃ for 6h, cooling, pouring the cooled mixed solution into absolute ethyl alcohol to separate out a precipitate, performing suction filtration, washing the precipitate obtained by suction filtration to be neutral, then washing the precipitate with absolute ethyl alcohol, and finally, performing vacuum drying on the precipitate at a temperature of 45 ℃ for 8h to obtain the phosphorylated chitosan.
Preparation example 4
The preparation method of the DOMc comprises the following steps:
naturally drying chicken manure, grinding, sieving with 0.2mm sieve, adding 800kg deionized water into 40kg chicken manure, and shaking the mixture at 20 deg.C for 23h (200 r.min)-1) Fermenting at 25 deg.C for 6d, and centrifuging for 20min (9000r min)-1) And immediately performing air suction filtration on the centrifuged supernatant by using a 0.45-micron sterile microporous filter membrane to obtain filtrate which is DOMc.
Preparation example 5
The preparation method of the DOMc comprises the following steps:
naturally drying chicken manure, grinding, sieving with 0.23mm sieve, adding 900kg deionized water into 40kg chicken manure, and shaking the mixture at 22.5 deg.C for 23.5h (210 r.min)-1) Fermenting at 26 deg.C for 6.5d, and centrifuging for 23min (9500 r.min)-1) And immediately performing air suction filtration on the centrifuged supernatant by using a 0.47 mu m sterile microporous filter membrane to obtain filtrate which is DOMc.
Preparation example 6
The preparation method of the DOMc comprises the following steps:
naturally drying chicken manure, grinding, sieving with 0.25mm sieve, adding 1000kg deionized water into 40kg chicken manure, and shaking the mixture at 25 deg.C for 24 hr (220 r.min)-1) Fermenting at 27 deg.C for 7d, and centrifuging for 25min (10000 r.min)-1) And immediately pumping and filtering the centrifuged supernatant by using a 0.5 mu m sterile microporous filter membrane to obtain filtrate which is DOMc.
Examples
Example 1
Uniformly mixing 50kg of phosphorylated chitosan, 400kg of sodium chloride, DOMc10kg, 100kg of biochar, 80kg of water-retaining agent and 100kg of biological bacterial fertilizer to obtain a soil remediation composition;
wherein the phosphorylate chitosan is obtained in preparation example 2, and DOMc is obtained in preparation example 5;
the soil bioremediation method comprises the following steps:
s1, loosening soil of soil to be repaired; after loosening the soil, adding a soil remediation composition into the soil, and turning over the soil to uniformly mix the soil remediation composition with the soil, wherein the adding amount of the soil remediation composition is 30 kg/mu;
s2, leveling the soil, standing for 24 hours, turning over the soil again, and standing for 24 hours;
s3, watering the leveled soil, and then planting Indian mustard;
s4, dissolving calcium thiosulfate in water in the vigorous growth period of the India mustard, uniformly spraying the calcium thiosulfate to soil around the root system of the India mustard, wherein the using amount of the calcium thiosulfate is 7 kg/mu, and harvesting the India mustard 6 days after the calcium thiosulfate is added.
Example 2
Uniformly mixing 55kg of phosphorylated chitosan, 350kg of sodium chloride, DOMc12.5kg, 90kg of biochar, 90kg of water-retaining agent and 90kg of biological bacterial fertilizer to obtain a soil remediation composition;
wherein the phosphorylate chitosan is obtained in preparation example 2, and DOMc is obtained in preparation example 5;
the soil bioremediation method comprises the following steps:
s1, loosening soil of soil to be repaired; after loosening the soil, adding a soil remediation composition into the soil, and turning over the soil to uniformly mix the soil remediation composition with the soil, wherein the adding amount of the soil remediation composition is 30 kg/mu;
s2, leveling the soil, standing for 24 hours, turning over the soil again, and standing for 18 hours;
s3, watering the leveled soil, and then planting Indian mustard;
s4, dissolving calcium thiosulfate in water in the vigorous growth period of the hyper-enriched plants, uniformly spraying the calcium thiosulfate to soil around the root system of the Indian mustard, wherein the using amount of the calcium thiosulfate is 8 kg/mu, and harvesting the Indian mustard 6 days after the calcium thiosulfate is added.
Example 3
Uniformly mixing 60kg of phosphorylate chitosan, 300kg of sodium chloride, DOMc15kg, 80kg of biochar, 100kg of water-retaining agent and 80kg of biological bacterial fertilizer to obtain a soil remediation composition;
wherein the phosphorylate chitosan is obtained in preparation example 2, and DOMc is obtained in preparation example 5;
the soil bioremediation method comprises the following steps:
s1, loosening soil of soil to be repaired; after loosening the soil, adding a soil remediation composition into the soil, and turning over the soil to uniformly mix the soil remediation composition with the soil, wherein the adding amount of the soil remediation composition is 35 kg/mu;
s2, leveling the soil, standing for 24 hours, turning over the soil again, and standing for 12 hours;
s3, watering the leveled soil, and then planting Indian mustard;
s4, dissolving calcium thiosulfate in water in the vigorous growth period of the India mustard, uniformly spraying the calcium thiosulfate to soil around the root system of the India mustard, wherein the using amount of the calcium thiosulfate is 8 kg/mu, and harvesting the India mustard 4 days after the calcium thiosulfate is added.
Example 4
In contrast to example 2, the phosphitylated chitosan was obtained from preparation 1 and DOMc was obtained from preparation 5.
Example 5
In contrast to example 2, the phosphitylated chitosan was obtained from preparation 3 and DOMc was obtained from preparation 5.
Example 6
In contrast to example 2, the phosphitylated chitosan was obtained from preparation 2 and DOMc was obtained from preparation 4.
Example 7
In contrast to example 2, the phosphitylated chitosan was obtained from preparation 2 and DOMc was obtained from preparation 6.
Example 8
In contrast to example 2, 320kg of sodium chloride was used.
Example 9
In contrast to example 2, 380kg of sodium chloride was used.
Example 10
In contrast to example 2, the calcium thiosulfate was replaced by the same amount of biological bacterial manure.
Comparative example
Comparative example 1
Loosening soil of soil to be repaired, watering, directly planting Indian mustard, and harvesting the Indian mustard after the growing period of the Indian mustard is over.
Comparative example 2
In contrast to example 2, the phosphorylated chitosan was replaced by an equal amount of chitosan.
Comparative example 3
In contrast to example 2, 175kg of biochar and 175kg of biofertilizer were used instead of sodium chloride.
Performance test
Detection method/test method
And (4) determining the content of lead and cadmium in the soil according to' trial implementation of soil pollution risk management and control standards (GB15618-2018) of soil environment quality agricultural land.
TABLE 1 Performance test results
| Lead (mg/kg) | Cadmium (mg/kg) | |
| Initial content | 180 | 0.50 |
| Blank control | 178 | 0.50 |
| Example 1 | 125 | 0.35 |
| Example 2 | 120 | 0.30 |
| Example 3 | 130 | 0.37 |
| Example 4 | 135 | 0.40 |
| Example 5 | 128 | 0.36 |
| Example 6 | 130 | 0.38 |
| Example 7 | 134 | 0.41 |
| Example 8 | 126 | 0.37 |
| Example 9 | 132 | 0.39 |
| Example 10 | 140 | 0.43 |
| Comparative example 1 | 160 | 0.52 |
| Comparative example 2 | 150 | 0.48 |
| Comparative example 3 | 145 | 0.45 |
The initial content in the table is the content of lead and cadmium in the soil before remediation.
The blank control is that the soil is not subjected to any remediation measures, but is tested synchronously with other examples, namely the remediation is carried out by virtue of the self-cleaning capacity of the soil.
In combination with examples 1 to 10 and comparative example 1, and table 1, it can be seen that the lead content and cadmium content in the soil are significantly reduced compared to the initial content and blank control in the soil remediation composition and soil bioremediation method of examples 1 to 10, which indicates that the soil remediation composition and soil bioremediation method of the present application can achieve better soil remediation effect.
In combination with examples 1 to 3 and table 1, it can be seen that the soil remediation composition and the soil bioremediation method of examples 1 to 3 can achieve a better remediation effect on soil, and the soil remediation composition and the soil bioremediation method of example 2 are better in proportion.
By combining the example 2 and the comparative example 2 and the table 1, the content of lead and cadmium in the soil in the example 2 is lower, which shows that the hypophosphorylated chitosan prepared by performing phosphonomethylation modification on chitosan by phosphorous acid and formaldehyde has better chelating and activating effects on lead and cadmium in the soil than untreated chitosan, and the absorption effect of the brassica juncea on lead and cadmium in the soil is improved, so that the soil remediation effect is improved.
By combining the example 2 and the comparative example 3 and combining the table 1, the content of lead and cadmium in the soil in the example 2 is lower, and the sodium chloride and the phosphorous chitosan are used together to further improve the absorption effect of the indian mustard on the lead and cadmium in the soil, so that the soil remediation effect is improved.
By combining the examples 2 and 4-5 and the table 1, it can be seen that the soil remediation compositions of the examples 2 and 4-5 can achieve a better remediation effect on soil, wherein the proportion of the soil remediation composition of the example 2 is better, that is, the proportion and the method for preparing the phosphorylated chitosan in the preparation example 2 are better.
By combining the example 2 with the examples 6 to 7 and combining the table 1, it can be seen that the soil remediation compositions of the examples 2 and 6 to 7 can achieve better remediation effects on soil, wherein the proportion of the soil remediation composition of the example 2 is better, that is, the proportion and the method for preparing DOMc in the preparation example 5 are better.
Combining example 2 with examples 8-9 and combining Table 1, it can be seen that 400kg of NaCl can achieve the effect of promoting the absorption of the soil lead and cadmium by the Indian mustard, wherein 380kg of NaCl has 320 content, and the absorption of the soil lead and cadmium by the Indian mustard is better, probably because the negative effect of the NaCl in the range on the growing process of the Indian mustard is smaller.
By combining example 2 with example 10 and table 1, it can be seen that the lead content and cadmium content in the soil are lower in example 2, which indicates that the absorption of lead and cadmium in the soil by the brassica juncea can be promoted by treating the brassica juncea root system soil with calcium thiosulfate during the vigorous growth period of the brassica juncea.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (10)
1. The soil remediation composition is characterized by being prepared from the following raw materials in parts by weight: 50-60 parts of phosphorylated chitosan, 400 parts of sodium chloride, 10-15 parts of soluble organic matter (DOM), 80-100 parts of charcoal, 80-100 parts of water-retaining agent and 80-100 parts of biological bacterial fertilizer;
the hypophosphorous chitosan is prepared by performing phosphonomethylation modification on chitosan by using phosphorous acid and formaldehyde.
2. A soil remediation composition according to claim 1, wherein: the preparation method of the phosphorylated chitosan comprises the following steps:
A1. dissolving 10-15 parts of chitosan in 750 parts of 1% acetic acid 500-750 parts, uniformly stirring, and heating to 60-70 ℃ to obtain a chitosan solution for later use;
A2. dissolving 10-15 parts of phosphorous acid in 20-30 parts of water to obtain a phosphorous acid solution, adding the phosphorous acid solution into the chitosan solution obtained from A1, and uniformly stirring;
A3. adding 15-20 parts of 40% formaldehyde solution into the solution obtained from A2, and uniformly stirring to obtain a mixed solution;
A4. and (2) reacting the mixed solution obtained in the step A3 at a constant temperature of 60-70 ℃ for 5-6h, cooling, pouring into absolute ethyl alcohol to separate out a precipitate, performing suction filtration, washing the precipitate obtained by suction filtration to be neutral, then washing the precipitate with absolute ethyl alcohol, and finally, performing vacuum drying on the precipitate at a temperature of 40-45 ℃ for 7-8h to obtain the phosphorylated chitosan.
3. A soil remediation composition according to claim 2, wherein: when the formaldehyde solution is added to the solution obtained in step A2 in the step A3, the formaldehyde solution is added dropwise at a rate of (0.5-1.5) d/s.
4. A soil remediation composition according to claim 1, wherein: the DOM is DOM (domc) extracted from chicken manure.
5. A soil remediation composition according to claim 4, wherein: the preparation method of the DOMc comprises the following steps: naturally air-drying the chicken manure, crushing, sieving by a 0.2-0.25mm sieve, and mixing the chicken manure with the raw materials in percentage by weight: adding deionized water into the chicken manure according to the proportion of 1 (20-25), and oscillating the mixed solution of the chicken manure and the deionized water at the constant temperature of 20-25 ℃ for 23-24h (200--1) Then fermenting at constant temperature of 25-27 deg.C for 6-7d, centrifuging for 20-25min (9000--1) Immediately filtering the centrifuged supernatant with 0.45-0.5 μm sterile microporous membrane under suction to obtain filtrateNamely DOMc.
6. A soil remediation composition according to claim 1, wherein: the sodium chloride is 320-380 parts.
7. A soil remediation composition according to any one of claims 1 to 6 prepared by:
uniformly mixing the phosphorylate chitosan, sodium chloride, soluble organic matters, biochar, a water-retaining agent and biological bacterial fertilizer in parts by weight.
8. A soil bioremediation method of a soil remediation combination according to any one of claims 1 to 7 including:
s1, loosening soil of soil to be repaired; after loosening the soil, adding a soil remediation composition into the soil, and turning over the soil to uniformly mix the soil remediation composition with the soil, wherein the adding amount of the soil remediation composition is 30-35 kg/mu;
s2, leveling the soil, and standing for 36-48 h;
s3, watering the leveled soil, and then planting hyper-enriched plants;
s4, harvesting the hyper-enriched plants after the growth of the hyper-enriched plants is in a vigorous period.
9. A soil bioremediation method of a soil remediation combination according to claim 8, wherein: in the S2 standing process, the soil needs to be turned over after standing for 24 hours, and then the soil is leveled and continuously kept standing.
10. A soil bioremediation method of a soil remediation combination according to claim 8, wherein: in the step S4, calcium thiosulfate is dissolved in water and uniformly sprayed into the soil around the root system of the hyper-enriched plant in the vigorous growth period of the hyper-enriched plant, the dosage of the calcium thiosulfate is 7-9 kg/mu, and the hyper-enriched plant is harvested 4-6 days after the calcium thiosulfate is added.
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Application publication date: 20210413 |