CN113508728B - Method for reducing cadmium and nickel content in rice - Google Patents
Method for reducing cadmium and nickel content in rice Download PDFInfo
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- CN113508728B CN113508728B CN202110847100.8A CN202110847100A CN113508728B CN 113508728 B CN113508728 B CN 113508728B CN 202110847100 A CN202110847100 A CN 202110847100A CN 113508728 B CN113508728 B CN 113508728B
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- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
- A01G22/00—Cultivation of specific crops or plants not otherwise provided for
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- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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Abstract
The invention relates to the technical field of soil treatment, and discloses a method for reducing cadmium and nickel contents in rice, which comprises the following steps: (1) the heavy metal compound conditioner is scattered in the soil polluted by cadmium and nickel and is uniformly mixed with the soil, a basic fertilizer is scattered, and then the rice is transplanted or scattered; the heavy metal composite conditioner is porous biomass carbon particles loaded with calcium magnesium phosphate fertilizer and calcium oxide; (2) spraying a leaf surface control agent from the tillering stage to the flowering stage of the rice; (3) watering and fertilizer supplementing are carried out according to the water and fertilizer conditions of the soil, and the rice is planted according to a conventional method. The invention adopts the organic-inorganic composite heavy metal composite conditioner and combines the foliage resistance control, can obviously reduce the cadmium and nickel content in the rice and improve the rice yield.
Description
Technical Field
The invention relates to the technical field of soil treatment, in particular to a method for reducing cadmium and nickel contents in rice.
Background
According to the report of national soil pollution condition survey bulletin in 2014, the national total soil exceeding rate is 16.1%, and the pollution type is mainly inorganic type and accounts for 82.8% of the total exceeding rate. And in the case of the standard exceeding of the point position of the inorganic pollutant, the standard exceeding of heavy metals such as cadmium, nickel, mercury and the like is higher. The highest cadmium pollution is cadmium pollution, the point position exceeding rate is as high as 7%, and the point position exceeding rate is increased year by year. Once the soil environment is polluted by heavy metals, the microbial activity of the soil is reduced, thereby affecting the yield and quality of crops, and the soil enters human bodies or animal bodies through food chains to be accumulated. In the reports of harm caused by cadmium and nickel to human in recent years, the fact that excessive cadmium taken by human is very easy to cause serious and even difficult-to-cure diseases such as prostate cancer, kidney cancer, stomach cancer, pain and the like is shown; nickel compounds are also listed in 2017 by the world health organization international agency for research on cancer in a list of carcinogens. Therefore, the treatment of cadmium and nickel pollution is urgent.
In order to reduce heavy metal pollution of agricultural products from soil, scientists have developed a large number of soil remediation technical researches including physical methods, chemical methods and biological methods. The common methods include soil-moving method, solvent leaching method, soil discharging method, bioremediation method, distillation extraction method, electric remediation method and the like. However, the current soil remediation methods cannot be popularized and used in the field due to the defects of large project amount, high cost, reduced soil fertility, damaged soil structure or secondary pollution and the like. In addition, the pollution control is mainly directed to cadmium pollution, and no technology is available for the reduction and control of nickel pollution.
The in-situ passivation technology has low cost and quick response, can realize simultaneous treatment and production, and has good application prospect for quickly and efficiently treating the acid soil with medium and light heavy metal pollution. The prior common soil heavy metal passivation conditioning type has various yields, most passivation conditioners have single components and action mechanisms, and certain defects exist when the passivation conditioners are used for fixing the soil heavy metals; and long-term application of a single passivating conditioner also tends to create new soil and environmental problems or be cost prohibitive. For example, lime as a passivator is not applied to soil for a long time and needs to be applied frequently, and the long-term application of a large amount of lime can cause excessive calcification of soil and soil hardening, and can also cause the problems of crop yield reduction and the like; the cost of using biomass charcoal alone is too high, about 1000 and 2000 yuan/mu, and the reduction amplitude is not high. Therefore, the development of a novel efficient, durable and environment-friendly soil heavy metal passivation conditioner has important practical significance and application prospect.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for reducing the content of cadmium and nickel in rice. In addition, the heavy metal composite conditioner has stronger durability.
The specific technical scheme of the invention is as follows: a method for reducing the content of cadmium and nickel in rice comprises the following steps:
(1) the heavy metal compound conditioner is scattered in the soil polluted by cadmium and nickel and is uniformly mixed with the soil, a basic fertilizer is scattered, and then the rice is transplanted or scattered; the heavy metal composite conditioner is porous biomass carbon particles loaded with calcium magnesium phosphate fertilizer and calcium oxide.
(2) Spraying a leaf surface control agent from the tillering stage to the flowering stage of the rice.
(3) Watering and fertilizer supplementing are carried out according to the water and fertilizer conditions of the soil, and the rice is planted according to a conventional method.
The invention adopts the organic-inorganic composite heavy metal composite conditioner and combines the foliage resistance control, can obviously reduce the cadmium and nickel content in the rice and improve the rice yield. Specifically, the method comprises the following steps: the main components of the heavy metal composite conditioner are lime (calcium oxide), biomass charcoal and calcium magnesium phosphate fertilizer. The lime has the main function of being beneficial to increasing negative charges of soil, so that adsorption, complexation and even precipitation of Cd and Ni ions in the soil by soil particles are improved. The surface of the biomass charcoal has a plurality of oxygen-containing functional groups such as carboxyl, hydroxyl and the like and negative charges, and can be matched with lime to adsorb and complex heavy metal ions such as Cd, Ni and the like in a solution together and even form precipitates, so that the mobility of the biomass charcoal is reduced. The calcium magnesium phosphate fertilizer can generate insoluble phosphate precipitation with heavy metals such as Cd, Ni and the like through chemical action to passivate the heavy metals, thereby reducing the mobility and the biological effectiveness of the heavy metals in soil.
In the prior art, lime, biomass charcoal and other conditioning agents such as calcium magnesium phosphate fertilizer are generally applied singly or after being simply and physically mixed. However, the team of the invention discovers that lime, calcium magnesium phosphate fertilizer and the like are easy to transform or lose after being applied into soil, so that the effect cannot be lasting, the lime and the calcium magnesium phosphate fertilizer need to be applied frequently, and the problems of excessive soil calcification, soil hardening, crop yield reduction and the like caused by long-term large-amount lime application can also be caused. Therefore, the lime, the calcium magnesium phosphate fertilizer and the biomass charcoal are compounded in a special mode, so that the continuous effectiveness of the heavy metal compound conditioner can be obviously improved, and a better soil treatment effect is further obtained. Specifically, calcium oxide and a calcium magnesium phosphate fertilizer are loaded in the pore channels of the biomass charcoal in a special mode. After the biological carbon fertilizer is applied to soil, under the action of slow water absorption of the biological carbon, calcium oxide reacts with water to generate calcium hydroxide. In this process: on one hand, the generation of calcium hydroxide can improve the alkalinity of soil, increase the quantity of negative charges in the soil, and is beneficial to the adsorption, complexation and even precipitation formation of Cd and Ni ions in the soil. On the other hand, local heat is generated in the conversion process, so that the calcium magnesium phosphate fertilizer can be promoted to be dissolved into soil from the inside of the biomass charcoal pore canal, and the effect is exerted. On the last hand, along with the slow progress of the reaction, more and more calcium oxide is converted into calcium hydroxide to form colloid with larger volume, and the pore diameter of the pore canal inside the biomass charcoal can be reduced to a certain extent by the volume change, so that the calcium magnesium phosphate fertilizer can be prevented from being dissolved out from the biomass charcoal in a large amount in the early stage, and the long-acting slow release effect is achieved.
In addition, on the basis of applying the heavy metal composite conditioner, the invention also sprays the foliage resistance and control agent in the key period (from the tillering stage to the flowering stage) of rice growth. Silicon fertilizer and the like are sprayed on the leaf surfaces of rice, silicon absorbed by the leaf surfaces is conveyed to the root systems, and the adsorption and fixation capacity of the cell walls of the root systems of the rice to Cd and Ni can be improved, so that the Cd and Ni are inhibited from being transported to the overground part and seeds from the root systems. Meanwhile, the silicon fertilizer sprayed on the leaf surface can reduce the migration of Cd and Ni by reducing the transpiration rate of the plants (the invention finds that the higher the transpiration rate is, the faster the migration of heavy metal elements in the plants is). It should be noted that the Cd must be spread from the tillering stage to the flowering stage of the rice because part of the Cd absorbed by the root system from the soil directly enters the seeds through the cob during the growth of the rice, the other part is transferred to the leaves and stored, and enters the seeds through the cob during the grain filling stage of the rice, and the Cd transfer by the leaves and the cob can be effectively reduced by spraying the foliar silicon fertilizer during the tillering to the flowering stage, so that the Cd content in the seeds can be reduced.
In conclusion, the heavy metal compound conditioner is applied to soil, and the foliage resistance and control agent is sprayed in the key growth period of rice, so that the content of Cd and Ni in rice grains can be synergistically and effectively reduced, and the rice yield is improved.
Preferably, in the step (1), the preparation method of the heavy metal complex conditioner is as follows: adding a solubilizer into ice water, stirring for dissolving, then adding a calcium magnesium phosphate fertilizer and hydrated lime under the stirring condition until the calcium magnesium phosphate fertilizer and the hydrated lime are saturated, and uniformly dispersing to obtain a saturated suspension; dispersing porous biomass carbon particles into a saturated suspension liquid placed in an ice water bath, repeatedly adsorbing for many times under an oscillation condition until the particles are saturated and adsorbed, and drying to obtain porous biomass carbon particles loaded with calcium magnesium phosphate fertilizer and hydrated lime; calcining at the temperature of 600 ℃ in the nitrogen atmosphere and 550-.
Because lime is converted into calcium hydroxide after meeting water, the lime cannot be directly loaded into the pore channels of the biomass charcoal through a common impregnation and adsorption mode. Therefore, the invention skillfully loads the calcium hydroxide in the pore canal of the biomass charcoal, and then realizes the loading in a mode of converting the calcium hydroxide into calcium oxide by calcining. Under the conditions of calcination and oxygen-free at the temperature of 550-600 ℃, calcium hydroxide is pyrolyzed into calcium oxide. It should be noted that the calcination temperature should not be too low or too high. If the temperature is too low, the calcium hydroxide cannot be fully decomposed, and if the temperature is too high, all oxygen-containing functional groups carried on the surface of the biomass charcoal are pyrolyzed, so that the binding capacity of the biomass charcoal to heavy metal elements is reduced.
In addition, the effect of the biomass charcoal is influenced because a part of active functional groups on the surface of the biomass charcoal are removed in the calcining process. Therefore, microwave activation treatment is designed after calcination, so that the activity of the active functional groups remained on the surface of the biomass charcoal can be further excited, and the binding capacity with heavy metal elements is improved.
Preferably, the temperature of the ice water and the ice water bath is 0-5 ℃.
The solubility of calcium hydroxide is higher in this temperature range.
Preferably, the solubilizer is polysorbate, and the addition concentration is 0.1-0.5 wt%.
The solubility of calcium hydroxide is further enhanced by the solubilizer due to its lower solubility.
Preferably, the particle size of the porous biomass carbon particles and the particle size of the porous biomass carbon particles loaded with calcium magnesium phosphate fertilizer and calcium oxide are 0.5-2 mm.
Preferably, the dosage ratio of the porous biomass carbon particles to the saturated suspension is 300-500 g/L.
Preferably, the calcination time is 1-3 h; the microwave activation temperature is 90-110 deg.C, and the activation time is 5-15 min.
The activation effect under the above conditions is good.
Preferably, in the step (1), the spreading amount of the heavy metal composite conditioner is 500-800 kg/mu.
Preferably, in the step (1), the base fertilizer is applied 7-10 days after the heavy metal compound conditioner is applied.
Preferably, in the step (2), the foliage resistance and control agent is a water-soluble foliage silicon fertilizer solution (the concentration of silicon element is more than or equal to 85g/L) added with 0.5-1.5wt% of bletilla striata extract; spraying for 2-3 times from tillering stage to flowering stage at interval of 7-10 days; the dosage is 250-500 mL/mu/time.
In order to enable the foliage resistance and control agent to better reduce the transpiration rate of rice after being sprayed, bletilla striata extract is specially added into the foliage resistance and control agent. Research shows that the bletilla striata extract is added into the foliage resistance and control agent, so that the attachment capacity of liquid on the foliage can be effectively improved, and the liquid can be prevented from being washed away by rainwater; in addition, the bletilla striata extract can form a layer of film on the leaf surface at the later stage of spraying, the effect of semi-closing leaf pores can be achieved to a certain extent, and the absorption and the transfer of heavy metal cadmium in soil by rice plants and the activation and the reutilization of accumulated cadmium of the plants can be reduced by reducing the transpiration strength of the leaves.
Compared with the prior art, the invention has the beneficial effects that:
(1) the main components of the heavy metal composite conditioner are lime (calcium oxide), biomass charcoal and calcium magnesium phosphate fertilizer. The lime has the main function of being beneficial to increasing negative charges of soil, so that adsorption, complexation and even precipitation of Cd and Ni ions in the soil by soil particles are improved. The surface of the biomass charcoal has a plurality of oxygen-containing functional groups and negative charges, and can be matched with lime to adsorb and complex heavy metal ions such as Cd, Ni and the like in a solution together, even form precipitates, so that the mobility of the biomass charcoal is reduced. The calcium magnesium phosphate fertilizer can generate insoluble phosphate precipitation with heavy metals such as Cd, Ni and the like through chemical action to passivate the heavy metals, thereby reducing the mobility and the biological effectiveness of the heavy metals in soil.
(2) The lime and the calcium magnesium phosphate fertilizer in the heavy metal composite conditioner are applied in a form of being loaded in a biomass charcoal pore channel. Compared with simple physical mixing and compounding, the sustained effectiveness of the heavy metal composite conditioner can be obviously improved.
(3) On the basis of applying the heavy metal compound conditioner, the invention also sprays the leaf surface control agent in the key period (from tillering period to flowering period) of rice growth. The adsorption and fixation capacity of the rice root system cell walls to Cd and Ni can be improved, and the Cd and Ni are inhibited from being transported to the overground part and the grains from the root system. Meanwhile, the migration of Cd and Ni can be reduced by reducing the plant transpiration rate.
(4) The invention adopts heavy metal composite conditioner combined with leaf surface resistance control, can obviously reduce the cadmium and nickel content in rice and improve the rice yield.
Drawings
FIG. 1 is a graph showing the comparison of cadmium and nickel contents in rice after different treatments;
FIG. 2 is a graph showing a comparison of rice yields after different treatments.
Detailed Description
The present invention will be further described with reference to the following examples.
General examples
A method for reducing the content of cadmium and nickel in rice comprises the following steps:
(1) spreading the heavy metal compound conditioner in the cadmium and nickel polluted soil according to the spreading amount of 500-800 kg/mu, uniformly mixing the heavy metal compound conditioner with the soil, spreading a base fertilizer after 7-10 days, and then transplanting or spreading the rice; the heavy metal composite conditioner is porous biomass carbon particles loaded with calcium magnesium phosphate fertilizer and calcium oxide.
(2) Spraying 2-3 times of foliar control agent (water-soluble foliar silicon fertilizer solution containing 0.5-1.5wt% of bletilla striata extract (the concentration of silicon element is more than or equal to 85g/L) from the tillering stage to the flowering stage of rice), wherein the spraying interval is 7-10 days, and the dosage is 500 mL/mu/time.
(3) Watering and fertilizer supplementing are carried out according to the water and fertilizer conditions of the soil, and the rice is planted according to a conventional method.
The preparation method of the heavy metal composite conditioner comprises the following steps: adding 0.1-0.5wt% of solubilizer polysorbate into ice water at 0-5 deg.C, and stirringStirring for dissolving, and adding calcium magnesium phosphate (P) under stirring2O5≥12wt％，CaO≥45wt％，SiO2Not less than 20 wt%, MgO not less than 12 wt%) and hydrated lime until saturated, and dispersing uniformly to obtain saturated suspension; dispersing porous biomass carbon particles with the particle size of 0.5-2mm into a saturated suspension liquid in an ice water bath at the temperature of 0-5 ℃ according to the dosage ratio of 300-500g/L, repeatedly adsorbing for many times under the oscillation condition until saturated adsorption, and drying to obtain porous biomass carbon particles loaded with calcium magnesium phosphate fertilizer and hydrated lime; calcining for 1-3h at the temperature of 550-600 ℃ in the nitrogen atmosphere, finally performing microwave activation for 5-15min at the temperature of 90-110 ℃, and sieving to obtain porous biomass carbon particles which are 0.5-2mm in particle size and are loaded with calcium magnesium phosphate fertilizer and calcium oxide.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The field plot experiment is adopted, and the experimental base is selected in the city and city. The rice variety tested is Yongyou 15.
Summary of the test: city-crossing Mashan Zhen rice base: the pH value of the soil is 5.57-5.94, Cd is 0.35-0.40mg/kg, and Ni is 30.0-35.6 mg/kg; the rice base of Zhongji city depressed paddy: the soil pH is 5.34-5.49, Cd is 0.36-0.41mg/kg, and Ni is 31.4-36.2 mg/kg.
The experiment set up 6 treatments:
comparison: blank, do not apply;
processing one: lime is applied singly, 300 kg/mu;
and (5) processing: lime and biomass charcoal (lime: biomass charcoal 1: 1, 600 kg/mu);
and (3) treatment III: lime, biomass charcoal and calcium magnesium phosphate fertilizer (lime, biomass charcoal and calcium magnesium phosphate fertilizer are 1: 0.5, 600 kg/mu);
and (4) treatment: lime, biomass charcoal and calcium magnesium phosphate fertilizer (lime, biomass charcoal and calcium magnesium phosphate fertilizer are 1: 0.5, 600 kg/mu), and leaf surface resistance control agent (90g/L silicon);
and (5) processing: porous biomass carbon particles (600 kg/mu) loaded with calcium magnesium phosphate fertilizer and calcium oxide and a foliar resistance and control agent (90g/L silicon).
And (6) treatment six: porous biomass charcoal particles (600 kg/mu) loaded with calcium magnesium phosphate fertilizer and calcium oxide and a foliar resistance and control agent (90g/L silicon and 1 wt% bletilla striata extract).
The specific application mode is as follows:
(1) and (3) scattering the heavy metal conditioner in the soil, uniformly mixing the heavy metal conditioner with the soil, scattering a base fertilizer after 10 days, and then transplanting the rice.
(2) Spraying the leaf surface control agent for 3 times from the tillering stage to the flowering stage of the rice, wherein the spraying interval is 10 days; the dosage is 300 mL/mu/time. This step is only for processing four to six.
(3) Watering and fertilizer supplementing are carried out according to the water and fertilizer conditions of the soil, and the rice is planted according to a conventional method.
The preparation method of the heavy metal composite conditioner for treating the fifth and sixth heavy metals comprises the following steps: adding 0.3 wt% of solubilizer polysorbate into ice water at the temperature of 1 ℃, stirring and dissolving, then adding calcium magnesium phosphate fertilizer and slaked lime under the stirring condition until the mixture is saturated, and uniformly dispersing to obtain saturated suspension; dispersing porous biomass carbon particles with the particle size of 1-2mm into a saturated suspension liquid in an ice water bath at the temperature of 1 ℃ according to the dosage ratio of 400g/L, repeatedly adsorbing for 5 times under the oscillation condition, and drying to obtain porous biomass carbon particles loaded with calcium magnesium phosphate fertilizer and hydrated lime; calcining for 2h at 580 ℃ in a nitrogen atmosphere, finally activating for 10min by microwave at 100 ℃ and sieving to obtain the porous biomass carbon particles which are 1-2mm in particle size and loaded with calcium magnesium phosphate fertilizer and calcium oxide.
Results and analysis
(1) The influence of different treatments on the cadmium and nickel contents of the edible parts of rice grains is as follows: as can be seen from fig. 1, the content of heavy metals cadmium and nickel in the brown rice is significantly reduced in each treatment group compared with the control group, wherein the comprehensive effect of treating the second (lime + biomass charcoal) is better than that of treating the first (lime application alone); compared with the second treatment, the third treatment (lime, biomass charcoal and calcium magnesium phosphate fertilizer) has better comprehensive effect; the effect of treating the fourth (lime, biomass charcoal, calcium magnesium phosphate fertilizer and leaf surface resistance control agent) is better than that of treating the third, which shows that the heavy metal content can be further reduced by matching with the leaf surface resistance control agent. Compared with the fourth treatment, the fifth treatment adopts the composite heavy metal conditioner in a special form, so that the effect is further improved; compared with the fifth treatment, the sixth treatment has the best effect because the bletilla striata extract is added into the leaf surface resistance and control agent on the basis of the fifth treatment, and the effect of reducing rice transpiration is more effective.
(2) Effect of different treatments on rice yield: in different treatments, the yield of rice is not affected and slightly increased, and after the conditioner is adopted, the yield is increased obviously (figure 2), and compared with a control, the yield of two places is increased by 10.9-25.6 percent respectively.
The raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalents of the above embodiments according to the technical spirit of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (9)
1. A method for reducing the content of cadmium and nickel in rice is characterized by comprising the following steps:
(1) the heavy metal compound conditioner is scattered in the soil polluted by cadmium and nickel and is uniformly mixed with the soil, basic fertilizer is scattered, and then the rice is transplanted or scattered; the heavy metal compound conditioner is porous biomass carbon particles loaded with calcium magnesium phosphate fertilizer and calcium oxide;
(2) spraying a leaf surface control agent from the tillering stage to the flowering stage of the rice; the foliage resistance and control agent is a water-soluble foliage silicon fertilizer solution added with 0.5-1.5wt% of bletilla striata extract, and the concentration of silicon element is more than or equal to 85 g/L;
(3) watering and fertilizer supplementing are carried out according to the water and fertilizer conditions of the soil, and rice is planted according to a conventional method;
in the step (1), the preparation method of the heavy metal composite conditioner comprises the following steps: adding a solubilizer into ice water, stirring for dissolving, then adding a calcium magnesium phosphate fertilizer and hydrated lime under the stirring condition until the calcium magnesium phosphate fertilizer and the hydrated lime are saturated, and uniformly dispersing to obtain a saturated suspension; dispersing porous biomass carbon particles into a saturated suspension liquid placed in an ice water bath, repeatedly adsorbing for many times under an oscillation condition until the particles are saturated and adsorbed, and drying to obtain porous biomass carbon particles loaded with calcium magnesium phosphate fertilizer and hydrated lime; calcining at the temperature of 600 ℃ in the nitrogen atmosphere and 550-.
2. The method of claim 1, wherein the temperature of the ice water and the ice water bath is 0-5 ℃.
3. The method of claim 1, wherein the solubilizing agent is polysorbate at an added concentration of 0.1-0.5 wt%.
4. The method of claim 1, wherein the porous biomass charcoal particles and the porous biomass charcoal particles loaded with calcium magnesium phosphate and calcium oxide have a particle size of 0.5-2 mm.
5. The method as claimed in claim 1, wherein the amount ratio of the porous biomass carbon particles to the saturated suspension is 300-500 g/L.
6. The method of claim 1, wherein the calcination time is from 1 to 3 hours; the microwave activation temperature is 90-110 deg.C, and the activation time is 5-15 min.
7. The method as claimed in any one of claims 1 to 6, wherein the amount of the heavy metal complex conditioner applied in step (1) is 500-800 kg/mu.
8. The method of claim 1, wherein in step (1), the base fertilizer is broadcast 7-10 days after the heavy metal complex conditioner is broadcast.
9. The method of claim 1, wherein in the step (2), the foliar drag-control agent is sprayed 2-3 times from the tillering stage to the flowering stage of rice, with an interval of 7-10 days; the dosage is 250-500 mL/mu/time.
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| CN113083254A (en) * | 2021-04-09 | 2021-07-09 | 江苏大学 | Preparation method and application of functionalized biomass carbon-based adsorbent |
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| CN104817382A (en) * | 2015-04-20 | 2015-08-05 | 广东大众农业科技股份有限公司 | Garden waste biomass charcoal-based calcium magnesium phosphate fertilizer and preparation method thereof |
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