CN117965173B - Cadmium-polluted soil restoration agent and preparation method thereof, composite cadmium-polluted soil restoration agent and preparation method thereof, and soil restoration method - Google Patents
Cadmium-polluted soil restoration agent and preparation method thereof, composite cadmium-polluted soil restoration agent and preparation method thereof, and soil restoration method Download PDFInfo
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- 238000000034 method Methods 0.000 title claims description 21
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 73
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 72
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims abstract description 72
- 229910010272 inorganic material Inorganic materials 0.000 claims abstract description 72
- 239000011147 inorganic material Substances 0.000 claims abstract description 72
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
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- 238000010438 heat treatment Methods 0.000 claims description 9
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- 241000196324 Embryophyta Species 0.000 abstract description 30
- 241000209082 Lolium Species 0.000 abstract description 30
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 9
- 239000011575 calcium Substances 0.000 abstract description 9
- 229910052791 calcium Inorganic materials 0.000 abstract description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 7
- 238000010521 absorption reaction Methods 0.000 abstract description 7
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- 239000010703 silicon Substances 0.000 abstract description 7
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 6
- 239000011777 magnesium Substances 0.000 abstract description 6
- 229910052749 magnesium Inorganic materials 0.000 abstract description 6
- 239000002086 nanomaterial Substances 0.000 abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 238000002386 leaching Methods 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 description 29
- 229910001385 heavy metal Inorganic materials 0.000 description 17
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- 241000238631 Hexapoda Species 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
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- 241000607479 Yersinia pestis Species 0.000 description 2
- MMDJDBSEMBIJBB-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] MMDJDBSEMBIJBB-UHFFFAOYSA-N 0.000 description 2
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 2
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- 230000008569 process Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
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- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
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- 239000003463 adsorbent Substances 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/02—Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only
- C09K17/06—Calcium compounds, e.g. lime
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Soil Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Processing Of Solid Wastes (AREA)
- Soil Conditioners And Soil-Stabilizing Materials (AREA)
Abstract
The invention provides a preparation method of a cadmium-polluted soil restoration agent, which comprises the following steps: and soaking the mineral fiber blanket in a phosphoric acid buffer solution, drying and crushing to obtain calcium-silicon composite inorganic material particles. The calcium-silicon composite Inorganic Material (IM) provided by the invention is a novel environment-friendly inorganic material, contains abundant soluble calcium, magnesium and silicon elements as measured under leaching conditions, can promote the growth of ryegrass on cadmium-polluted soil, improve the cadmium resistance of ryegrass under cadmium stress, and strengthen the absorption of ryegrass to the soil cadmium, thereby reducing the effective cadmium content of the soil. Carbon quantum dots (CDs) are a kind of carbon nanomaterial, and in recent years, CDs have been studied and applied as exogenous substances in improving stress resistance of plants. CDs play an important role in relieving plant cadmium stress and improving plant remediation cadmium pollution, and the combination of the IM and the nanomaterial CDs prepares the CDs and IM mixed type cadmium polluted soil remediation agent with better cadmium polluted soil remediation effect.
Description
Technical Field
The invention relates to the technical field of soil heavy metal pollution remediation, in particular to a cadmium-polluted soil remediation agent and a preparation method thereof, a composite cadmium-polluted soil remediation agent and a preparation method thereof and a soil remediation method.
Background
Heavy metal pollution of soil is one of the common environmental pollution problems, and the heavy metal pollution refers to the fact that the content of heavy metal elements in the soil exceeds a standard and exceeds a limit value of bearing the soil, so that the self-circulation capacity of the soil is seriously affected. Heavy metals are severely harmful to the ecological environment and human health because of their greater toxicity, difficulty in being normally degraded by organisms, and easy accumulation along with the food chain. Cadmium (Cd) is a heavy metal with serious harm, has strong migration and transformation characteristics in soil environment, has large toxicity and wide pollution range, is serious to human health, is listed as a toxic substance endangering human health, has higher mobility and potential toxicity compared with other heavy metals, and is easily absorbed, transferred and accumulated by animals, plants and microorganisms in soil, thereby influencing the physicochemical properties of the soil and the life activities of the organisms in the soil.
The soil Cd pollution restoration technology has two main approaches, one is to fix Cd, so that the Cd is converted into a more stable form, and the migration and the effectiveness of the Cd in the soil, namely passivation, are reduced; and the other is to remove Cd, and reduce the Cd content in the soil by different methods so as to achieve the purpose of restoration. According to the two approaches, the method for repairing Cd-polluted soil mainly comprises physical repair, chemical repair, biological repair, new material repair and joint repair.
The chemical restoration technology is mainly characterized in that restoration agents are added into soil to enable heavy metals and the restoration agents to react chemically, so that toxicity or bioavailability of heavy metal Cd is reduced, and the purpose of restoring heavy metal pollution of the soil is achieved. Phytoremediation refers to the utilization of the combined action of certain plants capable of accumulating and enriching heavy metal elements and root microorganisms thereof to absorb, enrich or decompose heavy metal pollutants in soil, and the content of the heavy metal elements in the soil can be reduced below a threshold value through repeated planting. However, the existing super-enriched plants have the problems of small biomass and long growth cycle, and the conventional plants have the problems of poor Cd tolerance, small accumulation and the like, so that the soil restoration efficiency can be improved by adopting the combination of chemical restoration and plant restoration. However, the method for adding the soil restoration agent in the chemical restoration technology has the problems of high cost, low efficiency, possibility of changing the soil texture and the like, so that the proper low-cost, high-efficiency and environment-friendly Cd-polluted soil restoration agent is needed to be found at present, and the restoration efficiency of the cadmium pollution of the soil is improved jointly by combining with phytoremediation.
The calcium-silicon composite inorganic material has the characteristic of multiple pores, has good adsorptivity, can possibly adsorb cadmium in a cultivation medium, and reduces the content of effective cadmium in the medium; the main components of the calcium-silicon composite inorganic material are SiO 2, caO and MgO, and the calcium and the silicon can promote the plant growth on the cadmium-polluted soil and improve the cadmium resistance of the plant. The carbon quantum dot is a carbon nanomaterial, and researches show that the carbon quantum dot can adsorb and retain trace cadmium, can reduce the cadmium concentration in sediment, and is gradually paid attention to in recent years in the application of the agricultural field.
At present, the research on the calcium-silicon composite inorganic material as a cadmium polluted soil restoration agent is less, particularly, the combination of the calcium-silicon composite inorganic material and carbon quantum dots is not reported at present, the application research of the two materials in the aspect of soil heavy metal restoration is in a starting stage, and the related theory and application research need to be enhanced.
Disclosure of Invention
In view of the above, the technical problem to be solved by the invention is to provide a cadmium-polluted soil restoration agent, which can reduce the soil restoration cost and improve the soil restoration efficiency.
The invention provides a preparation method of a cadmium-polluted soil restoration agent, which comprises the following steps:
and soaking the mineral fiber blanket in a phosphoric acid buffer solution, drying and crushing to obtain calcium-silicon composite inorganic material particles.
Preferably, the phosphate buffer is 0.1 mol/L phosphate buffer with pH of 6.0; the soaking time is 20-24 hours.
Preferably, the drying temperature is 65-75 ℃;
the crushing is specifically crushing to a particle size smaller than 2mm.
The invention provides a cadmium-polluted soil restoration agent, which is prepared by the preparation method according to any one of the technical schemes.
The invention provides a composite cadmium-polluted soil restoration agent, which comprises the soil restoration agent and carbon quantum dots.
The invention provides a preparation method of a composite cadmium-polluted soil restoration agent, which comprises the following steps:
The soil restoration agent according to the technical scheme is placed into a disc granulator, a certain amount of carbon quantum dot solution is uniformly sprayed on the surface of the soil restoration agent which rotates under the conditions that the inclination angle of a rotary disc is 49 degrees and the rotating speed is 30 r/min (the mass ratio of the soil restoration agent to the carbon quantum dots is 45:4-63:4), the soil restoration agent is rotated and sprayed for 5 minutes, the composite material is taken out, and the oven is dried for 50-60 minutes by blowing at the low temperature of 40 ℃ to obtain the carbon quantum dot and calcium silicon composite inorganic material mixed cadmium pollution soil restoration agent.
Preferably, the preparation method of the carbon quantum dot specifically comprises the following steps:
Dissolving citric acid and cysteine in water, heating, cooling, dissolving in water again, centrifuging, and filtering.
Preferably, the carbon quantum dot is 0.9g/mL, and the specification is 3-5 nm;
the heating time is 4-8 min; and the centrifugation is carried out at 8000-9000 rpm for 10 min.
The invention provides a soil remediation method, which is characterized in that the soil remediation agent prepared by any one of the preparation methods, the soil remediation agent, the composite soil remediation agent or the composite soil remediation agent prepared by any one of the preparation methods is mixed with soil containing heavy metals to be remediated.
Preferably, the addition amount of the cadmium-polluted soil restoration agent is controlled as follows: the volume ratio of the repairing agent to the soil is 1-5: 100;
the addition amount of the carbon quantum dots in the soil is 500-700 mg/kg;
the heavy metal includes cadmium.
Compared with the prior art, the invention provides a preparation method of a cadmium-polluted soil restoration agent, which comprises the following steps: and soaking the mineral fiber blanket in a phosphoric acid buffer solution, drying and crushing to obtain calcium-silicon composite inorganic material particles. The invention provides a calcium-silicon composite inorganic material, which is a novel environment-friendly inorganic material and is formed by high-temperature melting and filament-throwing of pure inorganic materials such as calcium stone powder, wollastonite powder, magnesia and the like. The calcium-silicon composite inorganic material measured under leaching conditions contains rich soluble calcium, magnesium and silicon elements, and the calcium, magnesium and silicon are used as beneficial nutrient elements required by plant growth, so that the growth of ryegrass on cadmium-polluted soil can be promoted, the cadmium resistance of ryegrass can be improved, the absorption of ryegrass to the soil cadmium can be enhanced, and the effective cadmium content of the soil can be reduced. The calcium-silicon composite inorganic material has the advantages of light weight, large porosity, strong fertilizer and water retention capacity and the like, has good adsorptivity, and has the potential of adsorbing cadmium in a cultivation medium and reducing the content of effective cadmium in the medium.
The invention also provides a composite cadmium-polluted soil restoration agent, which comprises the soil restoration agent and the carbon quantum dots.
The preparation method of the composite cadmium-polluted soil restoration agent is preferably as follows: and uniformly spraying the carbon quantum dots on the surface of the soil restoration agent through a disc granulator under the conditions of a certain inclination angle and a certain rotating speed, taking out and drying to obtain the soil restoration agent.
The two soil restoration agents are combined with phytoremediation for use, so that the soil restoration efficiency can be further improved. Sowing ryegrass on the cadmium polluted soil, strengthening the absorption of ryegrass to the effective cadmium in the soil, and further reducing the content of the effective cadmium in the soil.
The invention aims to prepare a calcium-silicon composite inorganic material soil restoration agent and a carbon quantum dot and calcium-silicon composite inorganic material blended soil restoration agent, and the prepared green environment-friendly soil restoration agent has the advantages of simple processing process, low cost and environmental friendliness, combines plant restoration, and improves the restoration efficiency of cadmium-polluted soil.
Detailed Description
The invention provides a preparation method and an application method of a cadmium-polluted soil restoration agent, and a person skilled in the art can refer to the content of the cadmium-polluted soil restoration agent and properly improve the technological parameters. It is expressly noted that all such similar substitutions and modifications will be apparent to those skilled in the art, and they are intended to be within the scope of the present invention. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those skilled in the relevant art that the invention can be practiced and practiced with modification and alteration and combination of the methods and applications herein without departing from the spirit and scope of the invention.
The calcium-silicon composite inorganic material is a novel environment-friendly inorganic material, and is formed by high-temperature melting and filament-throwing of pure inorganic materials such as calcium stone powder, wollastonite powder, magnesia and the like. The calcium-silicon composite inorganic material measured under leaching conditions contains rich soluble calcium, magnesium and silicon elements, and the calcium, magnesium and silicon are used as beneficial nutrient elements required by plant growth, so that the growth of ryegrass on cadmium-polluted soil can be promoted, the cadmium resistance of ryegrass under cadmium stress can be improved, the absorption of the ryegrass to the soil cadmium can be enhanced, and the effective cadmium content of the soil can be reduced. The calcium-silicon composite inorganic material has the advantages of light weight, large porosity, strong fertilizer and water retention capacity and the like, has good adsorptivity, and has the potential of adsorbing cadmium in a cultivation medium and reducing the content of effective cadmium in the medium. Carbon quantum dots (CDs) are a kind of carbon nanomaterial, and in recent years, CDs have been studied and applied as exogenous substances in improving stress resistance of plants. CDs have the advantages of simple preparation, good water solubility, low cytotoxicity, environmental friendliness, wide raw material sources, strong stability, low cost, good biocompatibility and the like, and can be used as a high-performance adsorbent for retaining trace cadmium. The carbon quantum dots play an important role in relieving plant cadmium stress and improving plant remediation cadmium pollution, and the calcium-silicon composite inorganic material particles and the nano material carbon quantum dots are combined to prepare the carbon quantum dots and calcium-silicon composite inorganic material doped cadmium pollution soil restoration agent with better cadmium pollution soil restoration effect.
The invention provides a preparation method of a cadmium-polluted soil restoration agent, which comprises the following steps:
and soaking the mineral fiber blanket in a phosphoric acid buffer solution, drying and crushing to obtain calcium-silicon composite inorganic material particles.
The mineral fiber blanket of the present invention is commercially available from Lu Yang company as an "aluminum silicate fiber blanket"; or a soluble mineral fiber blanket prepared by the method disclosed in CN 113582536.
The preparation method of the cadmium-polluted soil restoration agent provided by the invention comprises the steps of firstly soaking a mineral fiber blanket in a phosphate buffer solution.
According to the invention, the phosphate buffer is 0.1 mol/L phosphate buffer with the pH value of 6.0; the soaking time is 20-24 hours.
In the invention, the phosphate buffer is 0.1 mol/L phosphate buffer with the pH value of 6.0; the soaking time is 24 hours.
Soaking and drying; the drying temperature is 65-75 ℃;
Preferably, the drying temperature is 67-73 ℃.
And drying and crushing to obtain the calcium-silicon composite inorganic material particles.
Preferably, the crushing is specifically crushing to a particle size of less than 2mm.
The invention provides a cadmium-polluted soil restoration agent, which is prepared by the preparation method according to any one of the technical schemes.
The present invention has been clearly described with respect to the above preparation method, and will not be described in detail herein.
According to the invention, the addition amount of the cadmium-polluted soil restoration agent is controlled as follows: the volume ratio of the repairing agent to the soil is 1-5: 100.
The invention provides a composite cadmium-polluted soil restoration agent, which comprises the cadmium-polluted soil restoration agent and carbon quantum dots.
According to the invention, the mass ratio of the soil restoration agent to the carbon quantum dots is 45:4-63:4.
The invention provides a preparation method of a composite cadmium-polluted soil restoration agent, which comprises the following steps:
spraying the carbon quantum dots into the cadmium polluted soil restoration agent according to the technical scheme.
According to the invention, the preparation method of the carbon quantum dot specifically comprises the following steps:
Dissolving citric acid and cysteine in water, heating, cooling, dissolving in water again, centrifuging, and filtering.
In the invention, the preparation method of the carbon quantum dot specifically comprises the following steps:
mixing and dissolving citric acid and cysteine with certain mass in water, heating for a certain time by a microwave oven, cooling to room temperature until colorless and clear, dissolving the obtained material in deionized water, centrifuging, and filtering by a needle filter to obtain the carbon quantum dot for the test. And uniformly spraying the prepared carbon quantum dots to the prepared cadmium-polluted soil restoration agent according to the required amount to prepare the cadmium-polluted soil restoration agent by mixing the carbon quantum dots with the calcium-silicon composite inorganic material.
Wherein the mixing mass ratio of the citric acid to the cysteine is 50:19;
Preferably, the mass of citric acid and cysteine used to prepare 10 ml of 0.9 g/ml carbon quantum dots are 1.5 g and 0.57 g, respectively.
The heating of the microwave oven is specifically heating for 4-8 min until the material is colorless and clear.
According to the invention, the carbon quantum dot is 0.9g/mL, and the specification is 3-5 nm;
The heating time is 3-5 min;
preferably, the centrifugation is 10 min at 8000-9000 rpm.
Preferably, the centrifugation parameters are specifically: 9000 Centrifuge at 10 min at rpm.
According to some preferred embodiments of the invention, the carbon quantum dots in the composite soil remediation agent are added in the following manner: the soil remediation agent according to the technical scheme is placed into a disc granulator, and carbon quantum dot solution is uniformly sprayed onto the surface of the rotating soil remediation agent under the conditions that the dip angle of a rotating disc is 49 degrees and the rotating speed is 30 r/min; and (5) rotating and spraying for 5 minutes, taking out the composite material, and drying the composite material by blowing at a low temperature of 40 ℃ for 50-60 minutes in an oven to obtain the carbon quantum dot and calcium-silicon composite inorganic material doped cadmium polluted soil restoration agent. Wherein the mass ratio of the soil restoration agent to the carbon quantum dots is 45:4-63:4.
The invention provides a soil remediation method, which is characterized in that the cadmium-polluted soil remediation agent prepared by any one of the preparation methods, the cadmium-polluted soil remediation agent, the composite soil remediation agent or the composite soil remediation agent prepared by any one of the preparation methods is mixed with the soil containing cadmium to be remediated.
Preferably, the addition amount of the cadmium-polluted soil restoration agent is controlled as follows: the volume ratio of the repairing agent to the soil is 1-5: 100;
Specifically, the addition amount of the cadmium-polluted soil restoration agent is controlled as follows: the volume ratio of the repairing agent to the soil is 1: 100. 2: 100. 3: 100. 4:100 or 5:100.
The addition amount of the carbon quantum dots in the soil is 500-700 mg/kg.
The invention also provides a blending type cadmium-polluted soil restoration agent, which comprises the cadmium-polluted soil restoration agent and the carbon quantum dots. And uniformly spraying the carbon quantum dots on the surface of the soil restoration agent through a disc granulator under the conditions of a certain inclination angle and a certain rotating speed, taking out and drying to obtain the soil restoration agent. The two cadmium-polluted soil restoration agents are combined with phytoremediation for use, so that the soil restoration efficiency can be further improved. Sowing ryegrass on the cadmium polluted soil, strengthening the absorption of ryegrass to the effective cadmium in the soil, and further reducing the content of the effective cadmium in the soil.
The invention aims to prepare a cadmium-polluted soil restoration agent of a calcium-silicon composite inorganic material and a cadmium-polluted soil restoration agent of a carbon quantum dot and calcium-silicon composite inorganic material, and the prepared green environment-friendly soil restoration agent has the advantages of simple processing process, low cost and environmental friendliness, combines plant restoration, and improves the restoration efficiency of cadmium-polluted soil.
The application method is simple and convenient, the soil can be directly added into cadmium-polluted soil to be uniformly mixed, flooding is not needed, and the soil can be still used in the repairing period;
The raw materials used for the cadmium-polluted soil restoration agent, the carbon quantum dot and the calcium-silicon composite inorganic material blended soil restoration agent, namely the calcium-silicon composite inorganic material, are rich in mineral nutrients such as calcium, magnesium, silicon and the like, are beneficial elements for plant growth, and can promote the growth of plants on the cadmium-polluted soil;
the cadmium-polluted soil restoration agent has the characteristics of multiple pores, adsorbability and the like, can increase the porosity of soil, can play a role in water retention after water absorption, and can improve the soil texture to a certain extent.
The invention can repair the chemical repair combined plants, and jointly improves the repair efficiency of the cadmium-polluted soil. The calcium-silicon composite inorganic material soil restoration agent, the carbon quantum dots and the calcium-silicon composite inorganic material blended soil restoration agent are added to cadmium polluted soil, and simultaneously combine with phytoremediation, so that the growth of plants on cadmium pollution can be promoted, the absorption and extraction of ryegrass to the soil cadmium can be enhanced, and the cadmium removal efficiency can be improved.
The preparation method of the cadmium-polluted soil restoration agent provided by the invention is simple and convenient, does not need a complex production instrument, and the used raw material calcium-silicon composite inorganic material is low in cost and degradable, and belongs to an environment-friendly soil restoration agent.
In order to further illustrate the invention, the following describes in detail the cadmium-contaminated soil restoration agent, the preparation method thereof and the soil restoration method thereof according to the embodiments. The percentages in the examples are mass percentages unless otherwise indicated.
The application technology of the cadmium-polluted soil restoration agent comprises the following steps:
And screening the optimal addition amount of the cadmium-polluted soil restoration agent according to the plant growth condition and the effective cadmium content of the soil on the cadmium-polluted soil, and performing an application test of the soil heavy metal cadmium-polluted restoration agent. The test uses ryegrass as a plant material to be tested to respectively carry out application example illustration of the cadmium-polluted soil restoration agent of the calcium-silicon composite inorganic material and the application example illustration of the carbon quantum dot and calcium-silicon composite inorganic material mixed soil restoration agent. Of course, the described examples are only some embodiments of the invention, and not all examples. Based on the present invention, other examples obtained by those skilled in the art without an innovative breakthrough are within the scope of the invention.
Example 1: preparation and application of cadmium-polluted soil restoration agent of calcium-silicon composite inorganic material
The first step: soaking the novel mineral fiber blanket block in 0.1 mol/L phosphoric acid buffer solution with the pH value of 6.0 for 24 h, and improving the pH value of the material; and a second step of: soaking, taking out, and then placing into an oven to be dried at 65-75 ℃; and a third step of: crushing the material blocks into particles, and sieving the particles with a2 mm sieve for standby to prepare the cadmium-polluted soil restoration agent of the calcium-silicon composite inorganic material; fifth step: the method comprises the steps of (1) in potting, mixing a cadmium-polluted soil restoration agent of a calcium-silicon composite inorganic material with cadmium-polluted soil according to the volume ratio of 1:100, uniformly mixing for later use; sixth step: and sowing ryegrass on the cadmium polluted soil to be used.
Example 2:
The volume ratio of the cadmium-polluted soil restoration agent and the cadmium-polluted soil of the calcium-silicon composite inorganic material in the embodiment 1 is changed to 2:100, uniformly mixing for later use;
example 3:
the volume ratio of the cadmium-polluted soil restoration agent and the cadmium-polluted soil of the calcium-silicon composite inorganic material in the embodiment 1 is changed to 3:100, uniformly mixing for later use;
Example 4:
The volume ratio of soil remediation agent to cadmium contaminated soil in example 1 was changed to 4:100, uniformly mixing for later use;
Example 5:
the volume ratio of soil remediation agent to cadmium contaminated soil in example 1 was changed to 5:100, uniformly mixing for later use;
example 6:
the first step: 1.5 g citric acid and 0.57 g cysteine were fixed in 10 mL deionized water, then transferred to a microwave oven and heated for 4-8 minutes to colorless clarify, and cooled to room temperature. And a second step of: dissolving the obtained material in 10 mL deionized water, centrifuging at 9000 rpm for 10min, and filtering with a needle filter to obtain carbon quantum dots for test (synthetic carbon quantum dots 0.9 g/ml,3-5 nm). And a third step of: adding the prepared carbon quantum dots into cadmium polluted soil, and uniformly mixing to ensure that the concentration of the carbon quantum dots in the soil is 600 mg/kg; fourth step: and sowing ryegrass on the cadmium polluted soil to be used.
Example 7: preparation and application of carbon quantum dot and calcium-silicon composite inorganic material doped cadmium-polluted soil restoration agent
The first step: soaking the novel mineral fiber blanket block in 0.1 mol/L phosphoric acid buffer solution with the pH value of 6.0 for 24 h, and improving the pH value of the material; and a second step of: soaking, taking out, and then placing into an oven to be dried at 65-75 ℃; and a third step of: crushing the materials into particles, and sieving with a 2mm sieve to prepare the cadmium-polluted soil restoration agent of the calcium-silicon composite inorganic material; and a third step of: screening out the optimal addition amount of the cadmium-polluted soil restoration agent of the calcium-silicon composite inorganic material in examples 1-5 (screening out example 5); fourth step: preparing the carbon quantum dots used in the example 6; fifth step: and (3) placing the calcium-silicon composite inorganic material soil restoration agent into a disc granulator, uniformly spraying a certain amount of carbon quantum dot solution onto the surface of the rotating soil restoration agent under the conditions that the dip angle of a rotary disc is 49 degrees and the rotating speed is 30 r/min (wherein the mass ratio of the calcium-silicon composite inorganic material soil restoration agent to the carbon quantum dot is 105:8, so that the concentration of the carbon quantum dot in the soil is 600 mg/kg), rotating and spraying for 5 minutes, taking out the composite material, and drying the composite material by using a blast oven at a low temperature of 40 ℃ for 50-60 minutes to obtain the carbon quantum dot and calcium-silicon composite inorganic material doped cadmium polluted soil restoration agent. Sixth step: adding the prepared carbon quantum dot and calcium-silicon composite inorganic material blended cadmium-polluted soil restoration agent into cadmium-polluted soil, and uniformly mixing; seventh step: and sowing ryegrass on the cadmium polluted soil to be used.
Application example 1: application example of cadmium-polluted soil restoration agent of calcium-silicon composite inorganic material
1. Test soil and plants
Potted plant tests are synchronously carried out on Shandong agricultural university resources, environmental college and a greenhouse of a Zibo source technology innovation development limited company, and test soil is taken from a pollution-free test field. Basic properties of tested soil: the soil type is brown soil, ammonium nitrogen is 6.00 mg/kg, nitrate nitrogen is 13.01 mg/kg, quick-acting phosphorus is 28.93 mg/kg, quick-acting potassium is 76.39 mg/kg, pH is 6.88, conductivity is 54 mu S/cm, and total Cd content is 0.16 mg/kg. The artificial contaminated soil preparation of this test: dissolving CdCl 2·2.5H2 O (M=228.4) in distilled water to prepare a solution of 3.81 g/L, spraying 20. 20mL into 750. 750 g air-dried soil (750. 750 g soil per pot in the test), uniformly mixing to prepare the tested Cd-polluted soil with the Cd element content of 50 mg/kg, and sowing after balancing for 1 week.
Test plants: tetraploid ryegrass. And selecting ryegrass seeds which are uniform in size and free of plant diseases and insect pests, and carrying out 0.1% of NaClO disinfection treatment to seed the ryegrass seeds.
2. Test design
The experiment was performed with 7 treatments, CK: test soil free of Cd pollution; cd: the content of Cd element is 50 mg/kg; cd+im1: cadmium-polluted soil restoration agent of calcium-silicon composite inorganic material with the volume ratio of 1% provided in the example 1 is added into Cd-polluted soil; cd+im2: cadmium-polluted soil restoration agent of calcium-silicon composite inorganic material with the volume ratio of 2% provided in the example 1 is added into Cd-polluted soil; cd+im3: cadmium-polluted soil restoration agent of calcium-silicon composite inorganic material with 3 percent of volume ratio provided in the example 1 is added into Cd-polluted soil; cd+im4: cadmium-polluted soil restoration agent of calcium-silicon composite inorganic material with the volume ratio of 4% provided in the example 1 is added into Cd-polluted soil; cd+im5: cadmium-polluted soil restoration agent of calcium-silicon composite inorganic material with the volume ratio of 5% provided in example 1 is added into Cd-polluted soil. The base fertilizer is a compound fertilizer: 15% N,15% P 2O5,15%K2 O. The plastic pot for the test is used, the fertilizer consumption of each pot is 225 mg, each pot is sown with 2. 2g, and finally 80 seedlings are left.
3 Times of repetition are carried out for each treatment design, and the calcium-silicon composite inorganic material cadmium-polluted soil restoration agent is applied into soil at one time in the test design, and after 30 d times of treatment, various indexes of plants and soil are harvested and measured.
TABLE 1 influence of different additions of cadmium-contaminated soil remediation agents of calcium-silicon composite inorganic materials on growth characteristics of ryegrass on Cd-contaminated soil
TABLE 2 influence of cadmium-contaminated soil remediation agents of calcium-silicon composite inorganic materials with different addition amounts on cadmium content of plants, cadmium accumulation amount and effective cadmium content of soil
From the test results, the cadmium contaminated soil is added with the calcium-silicon composite inorganic material cadmium contaminated soil restoration agent with the volume ratio of 1% -5% provided in the example 1, so that the fresh weight, dry weight, plant height and SPAD of ryegrass on the cadmium contaminated soil can be obviously improved, the cadmium accumulation of plants is increased, the effective cadmium content of the soil is reduced, and the calcium-silicon composite inorganic material cadmium contaminated soil restoration agent with the addition amount of 5% has the most obvious effect of reducing the effective cadmium of the soil.
Application example 2: application example of carbon quantum dot and calcium-silicon composite inorganic material mixed cadmium-polluted soil restoration agent
1. Test soil and plants
Potted plant tests are synchronously carried out on Shandong agricultural university resources, environmental college and a greenhouse of a Zibo source technology innovation development limited company, and test soil is taken from a pollution-free test field. Basic properties of tested soil: the soil type is brown soil, ammonium nitrogen is 6.00 mg/kg, nitrate nitrogen is 13.01 mg/kg, quick-acting phosphorus is 28.93 mg/kg, quick-acting potassium is 76.39 mg/kg, pH is 6.88, conductivity is 54 mu S/cm, and total cadmium content is 0.16 mg/kg. The artificial contaminated soil preparation of this test: dissolving CdCl 2·2.5H2 O (M=228.4) in distilled water to prepare a solution of 3.81 g/L, spraying 20. 20mL into 750. 750 g air-dried soil (750. 750 g soil per pot in the test), uniformly mixing to prepare the tested Cd-polluted soil with the Cd element content of 50 mg/kg, and sowing after balancing for 1 week.
Test plants: tetraploid ryegrass. And selecting ryegrass seeds which are uniform in size and free of plant diseases and insect pests, and carrying out 0.1% of NaClO disinfection treatment to seed the ryegrass seeds.
2. Test design
The test consisted of 5 treatments, CK: test soil free of Cd pollution; cd: the content of Cd element is 50 mg/kg; cd+im: adding 5% by volume of the cadmium-polluted soil restoration agent of the calcium-silicon composite inorganic material provided in the example 1 into Cd-polluted soil; cd+cds: adding the carbon quantum dots provided in the example 6 into Cd-polluted soil to ensure that the soil concentration range is 600 mg/kg; cd+im+cds: adding the carbon quantum dot calcium-silicon composite inorganic material doped cadmium-polluted soil restoration agent provided in the example 7 into Cd-polluted soil; the base fertilizer is a compound fertilizer: 15% N,15% P 2O5,15%K2 O. The plastic pot for the test is used, the fertilizer consumption of each pot is 225 mg, each pot is sown with 2. 2 g, and finally 80 seedlings are left. And 3 times of repetition are carried out for each treatment, and the carbon quantum dot and calcium-silicon composite inorganic material doped cadmium polluted soil restoration agent is applied to soil at one time in the test design, and after 30 d times of treatment, various indexes of plants and soil are harvested and measured.
TABLE 3 influence of different soil remediation agents on fresh and Dry weight of ryegrass on Cd contaminated soil
TABLE 4 Effect of different soil remediation agents on cadmium accumulation in plants and soil effective cadmium content
As can be seen from the test results, compared with CK, the growth of ryegrass on Cd-polluted soil can be inhibited, and the cadmium-polluted soil restoration agent of the calcium-silicon composite inorganic material, the carbon quantum dots, the cadmium-polluted soil restoration agent of the carbon quantum dots and the calcium-silicon composite inorganic material are independently added into the Cd-polluted soil, so that the growth of ryegrass on the cadmium-polluted soil can be promoted, the Cd accumulation amount of the overground part of ryegrass can be increased, and the content of effective Cd in the soil can be reduced. Compared with a calcium-silicon composite inorganic material soil restoration agent and carbon quantum dots, the restoration effect of the cadmium-polluted soil restoration agent mixed by the carbon quantum dots and the calcium-silicon composite inorganic material on Cd-polluted soil is better.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (6)
1. The composite cadmium-polluted soil restoration agent is characterized by comprising carbon quantum dots and cadmium-polluted soil restoration agent; the mass ratio of the soil restoration agent to the carbon quantum dots is 45:4-63:4;
the preparation method of the cadmium-polluted soil restoration agent comprises the following steps:
soaking, drying and crushing the mineral fiber blanket by adopting a phosphoric acid buffer solution to obtain calcium-silicon composite inorganic material particles;
The phosphate buffer solution is 0.1 mol/L phosphate buffer solution with the pH value of 6.0; the soaking time is 20-24 hours;
the temperature of the drying is 65-75 ℃;
the crushing is specifically crushing to a particle size smaller than 2mm.
2. A method for preparing the composite cadmium-contaminated soil restoration agent according to claim 1, comprising:
Spraying the carbon quantum dots into the cadmium polluted soil restoration agent to obtain the carbon quantum dot.
3. The preparation method of the composite cadmium-polluted soil restoration agent according to claim 2, which is characterized in that the preparation method of the carbon quantum dots specifically comprises the following steps:
Dissolving citric acid and cysteine in water, heating, cooling, dissolving in water again, centrifuging, and filtering.
4. The method for preparing the composite cadmium-polluted soil restoration agent according to claim 3, wherein the carbon quantum dots are 0.9g/mL and have a specification of 3-5 nm;
The heating time is 4-8 min; and the centrifugation is carried out at 8000-9000 rpm for 10 min.
5. A soil restoration method is characterized in that,
The composite cadmium-polluted soil restoration agent of claim 1 or the composite cadmium-polluted soil restoration agent prepared by the preparation method of any one of claims 2-4 is mixed with the soil containing cadmium to be restored.
6. The soil remediation method of claim 5 wherein the amount of cadmium contaminated soil remediation agent added is controlled to be: the volume ratio of the repairing agent to the soil is 1-5: 100;
The addition amount of the carbon quantum dots in the soil is 500-700 mg/kg.
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