CN114289492A - Application method of phosphate soil conditioner in farmland carbon sequestration cooperative regulation and control of cadmium pollution - Google Patents
Application method of phosphate soil conditioner in farmland carbon sequestration cooperative regulation and control of cadmium pollution Download PDFInfo
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- CN114289492A CN114289492A CN202111636000.7A CN202111636000A CN114289492A CN 114289492 A CN114289492 A CN 114289492A CN 202111636000 A CN202111636000 A CN 202111636000A CN 114289492 A CN114289492 A CN 114289492A
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- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 229910052793 cadmium Inorganic materials 0.000 title claims abstract description 72
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 63
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 62
- 239000010452 phosphate Substances 0.000 title claims abstract description 61
- 239000003516 soil conditioner Substances 0.000 title claims abstract description 58
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 43
- 230000009919 sequestration Effects 0.000 title claims abstract description 23
- 230000033228 biological regulation Effects 0.000 title claims abstract description 20
- 239000002689 soil Substances 0.000 claims abstract description 127
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims abstract description 35
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims abstract description 35
- 244000063299 Bacillus subtilis Species 0.000 claims abstract description 30
- 235000014469 Bacillus subtilis Nutrition 0.000 claims abstract description 30
- 239000000243 solution Substances 0.000 claims abstract description 18
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
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- 239000011259 mixed solution Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- TYJOJLOWRIQYQM-UHFFFAOYSA-L disodium;phenyl phosphate Chemical compound [Na+].[Na+].[O-]P([O-])(=O)OC1=CC=CC=C1 TYJOJLOWRIQYQM-UHFFFAOYSA-L 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims description 15
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- XZKIHKMTEMTJQX-UHFFFAOYSA-N 4-Nitrophenyl Phosphate Chemical compound OP(O)(=O)OC1=CC=C([N+]([O-])=O)C=C1 XZKIHKMTEMTJQX-UHFFFAOYSA-N 0.000 claims description 3
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 3
- 230000007480 spreading Effects 0.000 claims description 3
- 238000003892 spreading Methods 0.000 claims description 3
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 17
- 230000000694 effects Effects 0.000 abstract description 12
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- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000009630 liquid culture Methods 0.000 description 4
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- 229910052791 calcium Inorganic materials 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 2
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- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 1
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- Soil Conditioners And Soil-Stabilizing Materials (AREA)
Abstract
The invention relates to the technical field of farmland soil remediation, in particular to an application method of a phosphate soil conditioner in farmland carbon sequestration cooperative regulation and control of cadmium pollution. According to the invention, a mixed solution of disodium phenylphosphate and calcium chloride is added into a bacillus subtilis solution for reaction, and the bacillus subtilis is used for assisting in synthesizing hydroxyapatite under mild conditions. The phosphate soil conditioner disclosed by the invention can effectively promote the generation of soil aggregates, increase the pH value and water storage performance of soil, and simultaneously cause the negative excitation effect of soil organic carbon, thereby being beneficial to the carbon fixation of farmland soil; and the adsorption capacity of soil colloid on heavy metal cadmium can be improved, so that the adsorbed cadmium is not easy to release to the environment again, and the soil colloid has good remediation effect in the farmland polluted by medium and light cadmium. The phosphate soil conditioner obtained by the invention has long-term development prospect in the field of farmland carbon fixation cooperative regulation and control of medium and light cadmium pollution.
Description
Technical Field
The invention relates to the technical field of farmland soil remediation, in particular to an application method of a phosphate soil conditioner in farmland carbon sequestration cooperative control of cadmium pollution, and more particularly relates to an application method of the phosphate soil conditioner in farmland carbon sequestration cooperative control of moderate and light cadmium pollution.
Background
As a heavy metal element, cadmium (Cd) has the characteristics of strong chemical activity, high mobility, lasting toxicity, easy absorption by crops and the like in a soil environment. It is an enrichment through the food chain, endangering human health. May induce renal decay, arthritis and other diseases. Effective control and improvement of cadmium pollution in farmland soil is a global problem concerning food safety and human health. At present, the soil improvement and restoration ideas are divided into two categories, namely pollution removal and stabilization. The method respectively corresponds to two repairing modes, namely ectopic repairing and in-situ repairing. For farmland soil, the in-situ remediation has the absolute advantages of simple operation and no delay of crop production. Therefore, the in-situ repair is a better choice for guaranteeing the grain safety. The selection of a proper improver is the key of the problem, and various improvers are not all suitable for farmland soil with medium and light cadmium pollution. For example, if the amendment containing phosphorus is applied to farmlands, the eutrophication of surrounding water bodies can be caused after soil irrigation; a single alkaline substance modifier is applied, so that soil hardening is possibly caused; waste residues and waste materials are applied, and the normal growth of crops can be influenced. For farmland soil with medium and light cadmium pollution, an improved material which is low in price, trace in quantity, high in efficiency and eco-friendly is needed.
The theoretical composition of the hydroxyapatite is Ca10(PO4)6(OH)2Ca/P of 1.67, also known as hydroxyapatite and basic calcium phosphate, is calcium apatite (Ca5(PO4)3(OH)) in natural mineralization. The crystal is a hexagonal ionic crystal. The surface of the hydroxyapatite has two calcium ions (Ca (I) and Ca (II)),the molar ratio of the two is 2: and 3, the two calcium environments correspond to two adsorption positions, when the hydroxyapatite is in an aqueous solution, the calcium on the surface of the hydroxyapatite crystal can form a vacancy at a certain moment, and the radius of cadmium atoms is similar to that of calcium atoms, so that the positions of calcium ions are easily replaced by cadmium ions, and the hydroxyapatite has a good adsorption effect on heavy metal cadmium. At present, the preparation method of hydroxyapatite has many ways, which can be divided into a wet method and a dry method. The wet method includes a precipitation method, a hydrothermal synthesis method and the like, and the dry method is a solid reaction method and the like. The methods have the defects of low purity of the obtained product, high price of raw materials, high toxicity of organic solvents, environmental pollution and the like, so that the method is limited in practical engineering application.
Disclosure of Invention
In order to solve the problems, the invention aims to provide an application method of a phosphate soil conditioner in farmland carbon sequestration cooperative regulation and control of cadmium pollution; wherein the phosphate modifying agent is hydroxyapatite; cadmium pollution especially refers to medium and light cadmium pollution.
The accumulation of heavy metal cadmium in soil and the complexity of soil structure make the remediation of the heavy metal cadmium in farmland soil extremely difficult. The bacillus subtilis has the characteristics of strong reproductive capacity and low requirement on growth environment, and extracellular polymers secreted by the metabolism of microorganisms can influence the pH value of soil, so that the form of heavy metal cadmium is changed, and the mutual transformation among the forms of cadmium is promoted. The method for synthesizing the phosphate soil conditioner by using the auxiliary agent under mild conditions has the advantages of low cost and simple and convenient operation. Therefore, the scheme of selecting the hydroxyapatite synthesized by the assistance of the microorganisms as the modifier to repair the farmland soil polluted by the heavy metal cadmium is beneficial to controlling the pollution risk of the heavy metal cadmium, can ensure the safe production of crops, and promotes the sustainable development of land agriculture.
The phosphate soil conditioner is sprayed into farmland soil, and the material has rich pore structure and large specific surface area, so that the storage capacity and pH value of soil water can be improved, and carbonic acid (CO) in the soil is promoted2+H2O) to produce bicarbonate radical (HCO)3 -) And carbonate radical(CO3 2-) Further to remove CO from the atmosphere/soil2Dissolving the organic carbon in the soil solution in the form of dissolved inorganic carbon, and utilizing and fixing the organic carbon by indigenous microorganisms in the soil; meanwhile, the phosphate soil conditioner influences the composition and symbiotic network relationship of the soil indigenous microbial community, and reduces the catabolic activity of the phosphate soil conditioner on organic matters and the soil respiratory entropy, thereby promoting the immobilization of soil organic carbon. The phosphate soil conditioner of the invention has larger specific surface area on one hand, so that the phosphate soil conditioner is easier to be combined with active functional groups of the conditioner, such as hydroxyl ions (-OH), phosphate ions (PO)4 3-) And (3) reacting, and on the other hand, extracellular polymers secreted by the metabolism of the bacillus subtilis can also absorb cadmium ions, so that the migration capacity of the cadmium in the soil is reduced. Therefore, the phosphate soil conditioner has better carbon fixation and cadmium pollution regulation and control effects.
According to the invention, a mixed solution of disodium phenylphosphate and calcium chloride is added into a bacillus subtilis solution for reaction, and the bacillus subtilis is used for assisting in synthesizing hydroxyapatite under mild conditions. The phosphate soil conditioner disclosed by the invention can effectively promote the generation of soil aggregates, increase the pH value and water storage performance of soil, and simultaneously cause the negative excitation effect of soil organic carbon, thereby being beneficial to the carbon fixation of farmland soil; and the adsorption capacity of soil colloid on heavy metal cadmium can be improved, so that the adsorbed cadmium is not easy to release to the environment again, and the soil colloid has good remediation effect in the farmland polluted by medium and light cadmium. The phosphate soil conditioner obtained by the invention has long-term development prospect in the field of farmland carbon fixation cooperative regulation and control of medium and light cadmium pollution.
The purpose of the invention can be realized by the following technical scheme:
the invention aims to provide an application method of a phosphate soil conditioner in farmland carbon sequestration cooperative regulation and control of cadmium pollution, which comprises the following steps:
spreading a phosphate soil conditioner into the soil to be improved, and then fully and uniformly mixing the phosphate soil conditioner and the soil to be improved for treatment;
the phosphate soil conditioner is hydroxyapatite.
In one embodiment of the invention, the hydroxyapatite is synthesized from calcium chloride and disodium p-nitrophenylphosphate induced by bacillus subtilis.
In one embodiment of the present invention, the hydroxyapatite is prepared as follows:
(1) mixing a disodium phenylphosphate solution and a hydrogen chloride solution to obtain a first mixed solution;
(2) and (2) adding the first mixed solution obtained in the step (1) into bacillus subtilis liquid for reaction, and performing post-treatment to obtain the phosphate soil conditioner.
In one embodiment of the invention, the hydroxyapatite has a specific surface area higher than 100m2/g。
In one embodiment of the invention, after the phosphate soil conditioner is fully and uniformly mixed with the soil to be improved, mixed soil is obtained; keeping the water content of the mixed soil to be 60-80%;
preferably, the water content of the mixed soil is maintained at 70%.
In one embodiment of the invention, the pH of the soil to be improved is 7 to 9.
In one embodiment of the invention, the cadmium concentration in the soil to be improved is between 0.6 and 2 mg/kg.
In one embodiment of the invention, the content of available cadmium in the soil to be improved is higher than 0.58 mg/kg.
In one embodiment of the invention, the dosage ratio of the phosphate soil conditioner to the soil to be improved is 80mg-2100 mg: 1 kg.
In one embodiment of the invention, the treatment time is 10 to 20 days;
preferably, the treatment time is 14 days.
In one embodiment of the invention, the phosphate soil conditioner has the following functions at the same time:
(1) increasing the content of organic carbon in soil;
(2) the disturbance to the pH value of the soil is lower than 5 percent;
(3) the content of the heavy metal cadmium in the effective state of the soil is effectively reduced.
In one embodiment of the present invention, the phosphate soil conditioner may be applied to any one of the following applications:
(1) the application in improving the carbon sequestration capacity of farmland soil or promoting the conversion of a carbon source to a carbon sink of a farmland soil ecosystem;
(2) the application in alkaline (pH value is 7-9) soil;
(3) the application in improving farmland soil with medium and light cadmium pollution (0.6-2mg/kg), or in soil with effective cadmium content higher than 0.58 mg/kg.
In one embodiment of the invention, soil samples of 7d, 14d, 52d and 104d after treatment are respectively collected, the improvement effect test is carried out, the pH value of the improved soil is measured, and the concentration of the available cadmium in the improved soil is measured and the removal rate is calculated.
In one embodiment of the invention, the method for determining the concentration of available cadmium in the soil is a calcium chloride method.
In one embodiment of the invention, the calcium chloride method is used for extracting and measuring the concentration of cadmium in the effective state in the soil according to the research on the determination method of the extractable state (effective state) of heavy metal in the soil provided by Nanjing environmental science institute of environmental protection.
Compared with the prior art, the invention has the following beneficial effects:
(1) the method for synthesizing the hydroxyapatite by using the paranitrophenyldisodium phosphate to provide a phosphorus source and the calcium chloride induced by the bacillus subtilis and the paranitrophenyldisodium phosphate has the advantages of simple operation, mild preparation conditions, suitability for large-scale industrial production, easy realization of engineering application, no toxic action on farmland soil environment and good ecological environmental benefit.
(2) The microbial-assisted synthetic phosphate soil conditioner has good carbon sequestration and emission reduction effects, effectively promotes the generation of soil aggregates by applying hydroxyapatite with multiple pores and large specific surface area, increases the stability of the soil aggregates, and is beneficial to the carbon sequestration of farmland soil.
(3) The microbial-assisted synthetic phosphate soil conditioner has good long-term effect of repairing, improves the adsorption capacity of soil colloid to heavy metal cadmium by adding an alkaline substance, namely hydroxyapatite, and ensures that the adsorbed heavy metal cadmium is not easy to be released into the environment again.
Drawings
FIG. 1 is a field emission scanning electron microscope image of hydroxyapatite prepared in example 2 of the present invention; wherein (a) is a macroscopic scanning electron micrograph; (b) is a high-power scanning electron microscope picture;
fig. 2 is a fourier infrared spectrum of hydroxyapatite prepared in example 2 of the present invention.
FIG. 3 is a line graph showing the pH values of soils 7d, 14d, 52d and 104d after application of the phosphate soil conditioner of example 3 of the present invention to the soil to be improved.
Detailed Description
The invention aims to provide an application method of a phosphate soil conditioner in farmland carbon sequestration cooperative regulation and control of cadmium pollution, which comprises the following steps:
spreading a phosphate soil conditioner into the soil to be improved, and then fully and uniformly mixing the phosphate soil conditioner and the soil to be improved for treatment;
the phosphate soil conditioner is hydroxyapatite.
In one embodiment of the invention, the hydroxyapatite is synthesized from calcium chloride and disodium p-nitrophenylphosphate induced by bacillus subtilis.
In one embodiment of the present invention, the hydroxyapatite is prepared as follows:
(1) mixing a disodium phenylphosphate solution and a hydrogen chloride solution to obtain a first mixed solution;
(2) and (2) adding the first mixed solution obtained in the step (1) into bacillus subtilis liquid for reaction, and performing post-treatment to obtain the phosphate soil conditioner.
In one embodiment of the invention, the hydroxyapatite has a specific surface area higher than 100m2/g。
In one embodiment of the invention, after the phosphate soil conditioner is fully and uniformly mixed with the soil to be improved, mixed soil is obtained; keeping the water content of the mixed soil to be 60-80%;
preferably, the water content of the mixed soil is maintained at 70%.
In one embodiment of the invention, the pH of the soil to be improved is 7 to 9.
In one embodiment of the invention, the cadmium concentration in the soil to be improved is between 0.6 and 2 mg/kg.
In one embodiment of the invention, the content of available cadmium in the soil to be improved is higher than 0.58 mg/kg.
In one embodiment of the invention, the dosage ratio of the phosphate soil conditioner to the soil to be improved is 80mg-2100 mg: 1 kg.
In one embodiment of the invention, the treatment time is 10 to 20 days;
preferably, the treatment time is 14 days.
In one embodiment of the invention, the phosphate soil conditioner has the following functions at the same time:
(1) increasing the content of organic carbon in soil;
(2) the disturbance to the pH value of the soil is lower than 5 percent;
(3) the content of the heavy metal cadmium in the extractable state of the soil is effectively reduced.
In one embodiment of the present invention, the phosphate soil conditioner may be applied to any one of the following applications:
(1) the application in improving the carbon sequestration capacity of farmland soil or promoting the conversion of a carbon source to a carbon sink of a farmland soil ecosystem;
(2) the application in alkaline (pH value is 7-9) soil;
(3) the application in improving farmland soil with medium and light cadmium pollution (0.6-2mg/kg), or in soil with effective cadmium content higher than 0.58 mg/kg.
In one embodiment of the invention, soil samples of 7d, 14d, 52d and 104d after treatment are respectively collected, the improvement effect test is carried out, the pH value of the improved soil is measured, and the concentration of the extractable heavy metal cadmium in the improved soil is measured and the removal rate is calculated.
In one embodiment of the invention, the method for determining the concentration of available cadmium in the soil is a calcium chloride method.
In one embodiment of the invention, the calcium chloride method is used for extracting and measuring the concentration of cadmium in the effective state in the soil according to the research on the determination method of the extractable state (effective state) of heavy metal in the soil provided by Nanjing environmental science institute of environmental protection.
The invention is described in detail below with reference to the figures and specific embodiments.
The various starting materials used in the examples are all commercially available unless otherwise specified.
Example 1
This example provides a method for activating Bacillus subtilis spore powder.
(1) Putting all experimental articles (except strains), pipettors, sterilized culture media, gun heads and other articles into a clean bench, opening an ultraviolet lamp of the clean bench for sterilization for more than 15min, closing the ultraviolet lamp after sterilization is finished, simultaneously opening a fan of the clean bench, and putting the strains into the clean bench.
(2) Before inoculating bacteria, placing the mouth and the stopper of the conical flask filled with the culture medium at the outer flame of an alcohol lamp for burning for 5-10 seconds, and sterilizing again.
(3) 0.5mL of bacillus subtilis liquid (from China center for culture Collection of industrial microorganisms, number: 23587), 9g of LB medium powder and 500mL of distilled water are sucked to prepare a medium, the medium is subpackaged in 300mL conical flasks, each conical flask is 100mL, when in inoculation, the conical flasks are opened, and the weighed spore powder is poured into the sterilized liquid medium.
(4) The flask to which the spore powder was added was placed on a shaker at 30 ℃ and 200rpm with shaking for 12 h. After the bacillus subtilis grows, the liquid culture medium becomes turbid, and the bacillus subtilis culture solution is obtained.
(5) And (3) taking the bacillus subtilis culture solution obtained in the step (4) as a seed solution, inoculating the bacillus subtilis culture solution into a fresh sterile culture medium by using the inoculation amount of 5% (v/v), namely 100ml of fresh sterile culture medium, and adding 5ml of the bacillus subtilis culture solution to obtain a bacillus subtilis first-generation liquid.
(6) And (3) taking 5ml of the first-generation bacillus subtilis liquid obtained in the step (5), adding the first-generation bacillus subtilis liquid into a sterile liquid culture medium, placing the conical flask in a shaking table, and oscillating the conical flask at 35 ℃ and 180rpm for 6 hours to obtain the second-generation bacillus subtilis liquid.
(7) And (4) taking 5ml of the bacillus subtilis second-generation bacterial liquid obtained in the step (6), adding the bacillus subtilis second-generation bacterial liquid into a sterile liquid culture medium, placing the conical flask in a shaking table, and oscillating for 6 hours at 35 ℃ and 180rpm to obtain the bacillus subtilis third-generation bacterial liquid.
Through detection: the bacillus subtilis third-generation liquid obtained in the embodiment enables a liquid culture medium to be turbid, and the bacillus subtilis is activated.
Example 2
The embodiment provides a preparation method of a phosphate soil conditioner.
(1) Preparing a chemical solution of 50ml of 0.10 mol/L calcium chloride solution and 0.06mol/L disodium phenylphosphate, and sterilizing to obtain a first mixed solution.
(2) Mixing 10ml of activated bacillus subtilis third generation liquid and the first mixed solution prepared in the step (1) in a super clean bench, and carrying out shaking culture at 37 ℃, wherein the shaking frequency is 100rpm, and the reaction lasts for 32 h.
(3) Adjusting the pH value of the solution obtained in the step (2) to 9.0-9.5.
(4) And (4) carrying out shaking culture on the solution obtained in the step (3) at the temperature of 30 ℃, wherein the shaking frequency is 120rpm, and reacting for 24 hours.
(5) And (5) carrying out suction filtration and drying on the solution obtained in the step (4), wherein the drying temperature is 100 ℃, and the drying time is 12h, so as to obtain the phosphate soil conditioner: hydroxyapatite.
Through detection: this example prepared porous hydroxyapatite having a specific surface area of 117.42m2The porosity consists of lamellar nanoparticles, which are interwoven to exhibit a microporous structure (FIG. 1), and hyphae are observed (FIG. 1A). Analysis according to fourier infrared spectroscopy (fig. 2) reveals that: the-OH peak appears at 3448cm-1The peak of C ═ O appeared at 1653cm-1Asymmetric elongation of P-OThe contraction vibration peak appears at 1039cm-1The peak of O-P-O bending vibration appears at 603cm-1And 563cm-1Therefore, the substance can be determined to be hydroxyapatite.
Example 3
The embodiment provides an application method of a phosphate soil conditioner in farmland carbon sequestration cooperative regulation and control of cadmium pollution.
(1) This example sets up 12 treatment groups, mixes hydroxyapatite with cadmium contaminated soil, where the concentration of hydroxyapatite is 0% (0mg/kg), 0.008% (80mg/kg), 0.013% (1300mg/kg), 0.021% (2100mg/kg), and collects 7d, 14d, 52d, and 104d soil samples.
(2) The specific experimental steps are as follows: the method comprises the steps of weighing the hydroxyapatite prepared in the example 2 in proportion, adding hydroxyapatite powder into actual cadmium-polluted farmland soil (the cadmium content is 1.39mg/kg), fully mixing the hydroxyapatite powder with the soil, keeping the water content of the soil at 70%, culturing for 7 days, 14 days, 52 days and 104 days, then sampling, drying and grinding a soil sample, sieving the soil sample by a sieve of 10 meshes and 100 meshes for later use, finally measuring the pH value of the soil, the organic carbon content of the soil and the content of the effective cadmium, and calculating the removal rate of the content of the effective cadmium.
(3) And (3) measuring the pH value of the soil: accurately weighing 10g of air-dried soil sample, placing the air-dried soil sample in a centrifugal tube, adding 25ml of pure water, placing the centrifugal tube in an oscillator for oscillation for 1h, taking out the centrifugal tube and standing the centrifugal tube for 30min, completely separating the supernatant from the soil sample to be measured, taking out the supernatant, inserting a pH meter into the supernatant, and recording the pH value after the reading is stable.
(4) Determination of soil organic carbon: accurately weighing a proper amount of air-dried soil sample, placing the air-dried soil sample in a digestion glass tube, adding a reagent, carrying out digestion, cooling and volume fixing, taking out and standing for 1h, centrifuging for 10min at the rotating speed of 2000rpm, taking supernatant liquid, measuring absorbance, recording the absorbance value after reading is stable, and finally calculating the organic carbon content of soil.
(5) And (3) determination of the content of cadmium in an effective state extracted from calcium chloride in soil: the determination of the effective cadmium content of the soil adopts a calcium chloride extraction method. Accurately weighing 1g of air-dried soil sample, placing the air-dried soil sample in a centrifugal tube, adding 10ml of 0.01mol/L calcium chloride, screwing a tube cover, placing the tube cover in an oscillator, horizontally oscillating for 120min at 180rpm at a constant temperature of 20 ℃, taking out the tube cover, placing the tube cover in the centrifuge, centrifuging for 10min under a centrifugal force of 1000g, filtering through a 0.45 mu m filter membrane, and measuring by an inductively coupled plasma emission spectrometer.
And (4) analyzing results: applying the microbial-assisted synthetic phosphate soil conditioner of the invention: the organic carbon content of the soil after hydroxyapatite is increased (table 1), the pH value of the soil is increased (figure 3), the cadmium removal rate is increased along with the increase of the applied concentration, and the removal rate is fluctuated along with the increase of the passivation time (table 2). The proper increase of the pH value of the soil can fix carbon dioxide in air/soil, and can cause the change of soil microbial communities, thereby achieving the purpose of changing the carbon source of the soil to the carbon sink; but also can reduce the mobility and bioavailability of cadmium in soil. Therefore, the method has important effects of increasing the carbon holding effect of the soil, reducing the effectiveness, the migration capacity and the like of the heavy metal cadmium in the soil by regulating and controlling the pH value of the soil and the soil aggregation structure.
TABLE 1 organic carbon content of soil 7 days and 104 days after 0.021% additive remediation application
| Time | 7 days | 104 days |
| Organic carbon content | 18.83g/kg | 20.74g/kg |
TABLE 2 soil effective cadmium removal rates 7, 14, 52 and 104 days after remediation application
The embodiments described above are intended to facilitate the understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. An application method of a phosphate soil conditioner in farmland carbon sequestration cooperative regulation and control of cadmium pollution is characterized by comprising the following steps:
spreading a phosphate soil conditioner into the soil to be improved, and then fully and uniformly mixing the phosphate soil conditioner and the soil to be improved for treatment;
the phosphate soil conditioner is hydroxyapatite.
2. The application method of the phosphate soil conditioner in farmland carbon sequestration cooperative regulation and control of cadmium pollution, according to claim 1, is characterized in that the hydroxyapatite is synthesized from calcium chloride induced by bacillus subtilis and disodium p-nitrophenylphosphate.
3. The application method of the phosphate soil conditioner in farmland carbon sequestration cooperative regulation and control of cadmium pollution according to claim 2, characterized in that the preparation process of the hydroxyapatite is as follows:
(1) mixing a disodium phenylphosphate solution and a hydrogen chloride solution to obtain a first mixed solution;
(2) and (2) adding the first mixed solution obtained in the step (1) into bacillus subtilis liquid for reaction, and performing post-treatment to obtain the phosphate soil conditioner.
4. The method of claim 2The application method of the phosphate soil conditioner in farmland carbon sequestration cooperative regulation and control of cadmium pollution is characterized in that the specific surface area of the hydroxyapatite is higher than 100m2/g。
5. The application method of the phosphate soil conditioner in farmland carbon sequestration cooperative regulation and control of cadmium pollution, which is characterized in that the phosphate soil conditioner is fully and uniformly mixed with soil to be improved to obtain mixed soil; keeping the water content of the mixed soil to be 60-80%;
preferably, the water content of the mixed soil is maintained at 70%.
6. The application method of the phosphate soil conditioner in farmland carbon sequestration cooperative regulation of cadmium pollution, which is characterized in that the pH value of the soil to be modified is 7-9.
7. The application method of the phosphate soil conditioner in farmland carbon sequestration cooperative regulation and control of cadmium pollution, as claimed in claim 1, is characterized in that the cadmium concentration in the soil to be modified is 0.6-2 mg/kg.
8. The application method of the phosphate soil conditioner in farmland carbon sequestration cooperative regulation and control of cadmium pollution, as claimed in claim 1, is characterized in that the content of available cadmium in the soil to be modified is higher than 0.58 mg/kg.
9. The application method of the phosphate soil conditioner in farmland carbon sequestration cooperative regulation and control of cadmium pollution, which is characterized in that the dosage ratio of the phosphate soil conditioner to the soil to be modified is 80-2100 mg: 1 kg.
10. The application method of the phosphate soil conditioner in farmland carbon sequestration cooperative regulation and control of cadmium pollution, which is characterized in that the treatment time is 10-20 days;
preferably, the treatment time is 14 days.
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