Organic selenium soil heavy metal degradation agent and application thereof

Abstract

The invention provides an organic selenium soil heavy metal degradation agent and application thereof, and belongs to the field of agricultural planting. The organic selenium soil heavy metal degradation agent is prepared from the following raw materials: organic selenium, selenoprotein, amino acid, high-purity peptide, a biological insecticidal bacterium agent and an organic silicon additive. By adding the organic selenium, changing the occurrence form of the heavy metal, forming an organic compound of the organic selenium and the heavy metal, or replacing a selenium element in the organic selenium with the heavy metal in an ionic state, forming the organic compound of the heavy metal, so that the activity of the heavy metal pollutants is reduced, small molecules of the heavy metal pollutants are converted, and protein selenium is synthesized and enzymolyzed; therefore, the heavy metal decomposition effect is achieved. According to the present invention, the national selenium-rich agricultural product standard can be met after the rice is applied once, the cadmium accumulation in the rice can be reduced, the pesticide residue can be reduced, the soil can be improved, the fungi, the bacteria, the virus bacteria and the fusarium in the soil can be well solved, the soil can be dried without pollution, and the selenium-rich healthy high-quality functional agricultural product can be obtained.

Description

Technical Field

[0001] The invention belongs to the field of agricultural planting, and particularly relates to an organic selenium soil heavy metal degrading agent and application thereof. Background Art

[0002] Selenium is a trace element found in nature and in the human body. While tiny, it's extremely important to human health. A lack of it can lead to a variety of illnesses. Selenium is considered crucial for vision and can also boost the immune system. As a trace element, selenium is not only essential for animals but also plays a vital role in plants and microorganisms, serving as a vital element for crops.

[0003] Organic selenium, a compound formed by combining selenium with organic molecules (such as amino acids), has high bioavailability and low toxicity. It has been studied for its antioxidant and anti-aging effects, immune regulation, cardiovascular protection, and neuroprotection, and has attracted significant attention in nutrition, medicine, and agriculture. Furthermore, organic selenium can reduce the presence of heavy metals such as lead, mercury, cadmium, chromium, and arsenic, improve soil fertility, and increase crop yields.

[0004] The impact of heavy metal pollution on the environment is becoming increasingly severe and its scope is constantly expanding, involving areas such as environmental water bodies, soil, and the atmosphere. Heavy metal pollution of soil includes heavy metals that enter the soil with atmospheric deposition, heavy metals that enter the soil with sewage irrigation, and heavy metals that enter the soil with solid waste. Representative pollutants include arsenic, lead, cadmium, chromium, etc. Heavy metal pollution will suddenly enter the human body through foods such as rice and wheat along the food chain, posing a serious threat to human health. The inventor once studied an organic selenium fertilizer (ZL202011402692.4) that can reduce heavy metals in agricultural products and help increase agricultural production. After repeated tests on rice, the results showed that it did not meet the standards in the first test, only just met the standards in the second year, and only met the national green food standards in the third year. This shows that the organic selenium fertilizer has a long effective time, and the rice grown after multiple applications meets the green standards.

[0005] To address these issues, this application aims to provide a fertilizer that is fast-acting, simple to operate, and can produce agricultural products that meet green food standards with just one application. It also increases selenium content in agricultural products and reduces heavy metal contamination. It improves soil quality, effectively combating fungi, bacteria, viruses, and Fusarium, leaving the soil clean and pollution-free, allowing the growth of selenium-rich, healthy, high-quality, functional agricultural products. Summary of the Invention

[0006] The purpose of the present invention is to provide a selenium-rich fertilizer that has a fast effect, a simple operation method, and can produce agricultural products that meet green food standards after only one spraying. At the same time, it can also degrade heavy metal pollution in the soil.

[0007] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0008] An organic selenium soil heavy metal degrader comprises the following raw materials: 15,000 to 25,000 ppm of organic selenium, 8,000 to 12,000 ppm of selenoprotein, 55 to 65 g of amino acids, 55 to 65 mL of high-purity peptides, 90 to 110 g of a biological insecticide, and 25 to 35 mL of an organosilicon additive.

[0009] Preferably, the preparation method of the organic selenium is:

[0010] S1. Inoculate brewer's yeast on a slant surface on a solid culture medium and culture;

[0011] S2. The solid culture medium containing brewer's yeast after culture in step S1 is added to the liquid culture medium and fermented to obtain a liquid culture;

[0012] S3. Inoculate the liquid bacterial strain slant into the solid culture medium and continue culturing to obtain the organic selenium.

[0013] Preferably, the preparation process of the solid bacterial culture medium in step S1 is: mixing the cooked inorganic selenium powder and fig powder with tryptophan, valine and brown sugar; bottling and sterilizing;

[0014] The liquid culture medium in step S2 is prepared by mixing cooked inorganic selenium powder and fig powder with tryptophan, valine, brown sugar, glucose and yeast powder, sterilizing the mixture and then adding Bacillus subtilis or Trichoderma to obtain a liquid culture medium;

[0015] The solid culture medium in step S3 is prepared by uniformly mixing the cooked fig powder with tryptophan, valine, brown sugar and glucose; bottling and sterilizing.

[0016] Preferably, the amino acid is one or more of tryptophan, methionine, threonine, valine, lysine, histidine or leucine.

[0017] Preferably, the preparation method of the high-purity peptide is: after crushing the soybeans, adding water, fermenting at 28-32°C for 7 days, then adding water at a ratio of 5 kg of water per kg of soybean fermentation, stirring, and hydrolyzing, and obtaining the high-purity peptide after the hydrolysis is completed.

[0018] The present invention provides a preparation method of the organic selenium soil heavy metal degrader, comprising mixing organic selenium, selenoprotein, amino acid, high-purity peptide, biological insecticide and organosilicon adjuvant, and performing fully enclosed fermentation at a fermentation temperature of 27-29° C. for 5-10 days.

[0019] The present invention also provides the use of the organic selenium soil heavy metal degrading agent in degrading soil heavy metals and / or planting selenium-rich agricultural products.

[0020] Preferably, the application amount of the organic selenium soil heavy metal degrader is 1800-2200 mL / mu, and when used, it is diluted with water at a volume ratio of 1:10-20 and then sprayed on the soil surface.

[0021] Beneficial effects

[0022] The present invention changes the occurrence form of heavy metals by adding organic selenium to form organic compounds of organic selenium and heavy metals, or uses ionic heavy metals to replace the selenium element in organic selenium to form organic compounds of heavy metals, thereby reducing the activity of heavy metal pollutants. It can also cause small molecule conversion and enzymatic hydrolysis of protein selenium, thereby achieving the effect of decomposing heavy metals.

[0023] Compared with the prior art, the present invention has at least the following beneficial effects:

[0024] (1) The present invention is improved on the basis of the previous invention, so that it can meet the national selenium-rich agricultural product standards with just one application, and can be used as an organic selenium supplement or organic selenium nutrient. In addition to organic selenium, the organic selenium soil heavy metal degrader prepared by the present invention also includes more than 30 small molecular substances such as amino acids, organic acids, sugars, nucleotides and lipids, which have a significant promoting effect on increasing rice yield.

[0025] (2) The heavy metal cadmium content in the rice grown by the present invention meets the national green agricultural product standard, namely GB 2762 standard;

[0026] (3) The present invention has the effect of increasing production and value, and can obtain selenium-rich high-quality agricultural products;

[0027] (4) The invention has a killing rate of underground insects ≥ 98%, mainly including mole crickets, white grubs, wireworms, cutworms, root maggots, root bugs, root aphids, seed flies, onion flies, cabbage flies, etc.;

[0028] (5) The present invention can reduce pesticide residues and meet green food standards.

[0029] (6) The present invention has the function of improving the soil, which can clean up the pathogenic bacteria in the soil at one time, so that crops can grow fresh capillary roots, and reduce the problems of yellowing, yellowing leaves, and yellowing seedlings in crops. In addition to rice, the present invention can also be applied to crops such as wheat, potatoes, citrus, or used to grow high-quality vegetables.

[0030] (7) After many tests, it was found that the use of drones for spraying is fast, efficient and of good quality. It only costs 5 yuan per acre (667 square meters), which greatly reduces the cost of pesticide application for farmers and reduces planting costs. It is welcomed and supported by the general public. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 The selenium content test results of rice in the 2023 planting experiment in Example 2;

[0032] Figure 2 This is a site map of the test acceptance by the expert group of the Provincial Department of Agriculture at the planting base in 2024 in Example 2;

[0033] Figure 3 The selenium and cadmium content test results of rice in the 2024 planting experiment in Example 2;

[0034] Figure 4 This is a report on the field demonstration of the organic selenium soil heavy metal degrader on rice in Experiment 1;

[0035] Figure 5 This is the cadmium content test result of the treatment group of Experimental Example 1;

[0036] Figure 6 The cadmium content test results of rice in Test Example 3 are as follows;

[0037] Figure 7 The test results of pesticide residues (BCH and DDT) in rice in Test Example 4 are as follows;

[0038] Figure 8 This is the test result of the pesticide residue (deltamethrin) in rice in Test Example 4. DETAILED DESCRIPTION

[0039] The technical solutions provided by the present invention are described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0040] Example 1

[0041] An organic selenium soil heavy metal degrader contains 20,000 ppm of organic selenium, 10,000 ppm of selenoprotein, 60 g of amino acids (tryptophan, methionine, threonine, valine, lysine and histidine added in equal proportions), 60 mL of high-purity peptide, 100 g of biological insecticide (purchased from Cangzhou Zhengxing Biopesticide Co., Ltd.), and 30 mL of organosilicon additive per liter of water. After preparation, the mixture is fully enclosed for fermentation at a temperature of 28° C. for 8 days.

[0042] The preparation method of the organic selenium (reference patent CN 112457117 B - a culture medium composition, synthesis method and application for synthesizing organic selenium) is specifically as follows:

[0043] Step .S1 solid culture medium culture:

[0044] (1) The raw material composition of the solid bacterial culture medium is: 91% fig nanopowder, 2% tryptophan, 1.5% valine, 3.5% brown sugar, and 2% inorganic selenium powder; here, the inorganic selenium powder is sodium selenite;

[0045] (2) Weighing raw materials according to the ratio; cooking inorganic selenium powder and fig powder; mixing the cooked inorganic selenium powder and fig powder with tryptophan, valine, and brown sugar, and stirring evenly;

[0046] (3) The mixed material was bottled and sterilized; the slant was inoculated with brewer's yeast for bacterial culture; the culture temperature was 45°C, the pH value was 7.2, and the culture time was 3 days;

[0047] Step S2. Liquid culture medium culture:

[0048] (1) The raw materials of the liquid culture medium are composed of culture medium and Bacillus subtilis. 500 g of Bacillus subtilis is added to every 40 L of culture medium.

[0049] Among them, the culture medium is calculated by weight: 30L of water, 2000g of fig nanopowder, 500g of tryptophan, 250g of valine, 500g of brown sugar, 500g of glucose, 200g of inorganic selenium powder, and 20g of yeast powder.

[0050] (2) Weighing raw materials according to the ratio; cooking inorganic selenium powder and fig powder; mixing the cooked inorganic selenium powder and fig powder with tryptophan, valine, brown sugar, glucose, and yeast powder, and stirring evenly to obtain a culture medium; and then adding Bacillus subtilis to the culture medium.

[0051] The inorganic selenium powder is sodium selenite, and the water is nano water.

[0052] (3) placing the liquid culture medium in a liquid fermentation tank, adding the solid culture medium cultured in step 1 into the liquid fermentation tank, and mixing the solid culture medium with the liquid culture medium for fermentation; the fermentation temperature is 25° C., the pH value is 6.5, and the culture time is 8 days;

[0053] Step S3. Solid medium culture:

[0054] (1) The raw material composition of the solid culture medium is: 96.5% fig nanopowder, 1% tryptophan, 0.5% valine, 1% brown sugar, 1% glucose, and each 500g of fig nanopowder contains 300μg of organic selenium.

[0055] (2) Weighing raw materials according to the ratio; cooking the fig powder; mixing the cooked fig powder with tryptophan, valine, brown sugar, and glucose; bottling and sterilizing; inoculating the liquid culture obtained in step 2 into a solid culture medium with a slant to perform solid culture.

[0056] (3) The solid culture medium culture temperature was set to 25°C, the pH value was set to 7.0, and the culture time was set to 10 days; and organic selenium was finally obtained.

[0057] Among them, fig nanopowder is made by adding inorganic selenium to figs when they are germinating. The inorganic selenium is converted into organic selenium in the figs, and the fig nanopowder containing 300μg of organic selenium per 500g is obtained.

[0058] The preparation method of the high-purity peptide is as follows: soybeans are crushed and passed through a No. 2 sieve, and then water is added at a mass ratio of 1:1 and fermented at 28-32°C for 7 days. After the fermentation is completed, water is added at a ratio of 5 kg of water per kilogram of soybean fermentation material and stirred. The stirred raw materials are added into an extraction machine for controlled extraction, and alkaline protease is added for enzymatic hydrolysis at an enzyme dosage of 10,000 u / g. The enzymatic hydrolysis is carried out at a pH of 9 and 50°C for 5 hours. After the hydrolysis is completed, the high-purity peptide is obtained.

[0059] Example 2

[0060] Method for using the organic selenium soil heavy metal degrader in rice fields:

[0061] After the paddy field is drained, a tractor is used to select a flat surface in the field, select it into mud, level the four sides of the field, and there must be no uneven surface with high and low sides. The ground plane is leveled. Every mu of land (667 square meters of standard calculation) is diluted with 2L of the organic selenium soil heavy metal degrader described in Example 1 (not diluted with water). During manual spraying, it is diluted with water at a volume ratio of 1:20 and evenly sprayed on the surface water surface of the paddy field. After spraying, the water on the paddy field ground plane must not be released to ensure that the organic selenium is in the local plot and will not be lost. After spraying for 12 hours, rice seedlings are planted. The local plot cannot be watered within 20 hours to ensure that the organic selenium is absorbed by the local plot soil.

[0062] In 2023, 1,600 mu of rice was used with organic selenium soil heavy metal degrader. After maturity, the rice was sampled by the Agricultural Bureau and sent to the designated inspection unit for testing. The test report is as follows: Figure 1 As shown, the selenium content in rice is 0.161 mg / kg.

[0063] In 2024, 5,000 mu of rice was used with organic selenium soil heavy metal degrader. After the rice matured, it was sampled by the Agricultural Bureau and sent to the designated inspection unit for testing. The acceptance site was as follows: Figure 2 , test report such as Figure 3 The cadmium content in rice is 0.0351 mg / kg, which is far below the national limit (≤0.2 mg / kg), and the selenium content is 0.211 mg / kg.

[0064] Example 3

[0065] Method for using the organic selenium soil heavy metal degrader in rice fields:

[0066] Use 2L of organic selenium soil heavy metal degrader per mu, add 15kg of dry sand, mix into a wet shape, grab it in your hand, and it will spread when you let go. After mixing, spread it evenly in the newly planted rice seedling field. When using organic selenium soil heavy metal degrader, keep water in the rice seedling field, the water depth is 3 to 5 centimeters, and water can be added to the local plot after 20 hours.

[0067] Example 4

[0068] Different from Example 2, this example uses a drone for spraying, and the organic selenium soil heavy metal degrader is diluted with water at a ratio of 1:10.

[0069] Test Example 1

[0070] A planting experiment was conducted using the method of Example 2. The experimental unit was Tashui Dajia Family Farm (Chunlin Village, Tashui Town), with an experimental area of ​​10 mu. The experimental rice variety was Rongkangyou 37. A treatment group using the organic selenium soil heavy metal degrader described in Example 1 and a control group not using organic selenium were set up. Other management was the same, and the rice was sent for inspection after harvest.

[0071] Rice field demonstration report shows that ( Figure 4 ), organic selenium soil heavy metal degrader is used on rice, and the rice yield per mu increases by about 15%, which is more than the conventional fertilizer control value. It can promote the development of the root system, increase the number of panicles, and significantly increase the yield and quality. On average, it increases the yield per mu by about 15% compared with the local conventional fertilizer control. The heavy metal content meets the national green agricultural product standards, namely GB2762 standards: meets the selenium-rich agricultural product standards; underground insect killing rate ≧98%; rice per kilogram increases by 0.3 yuan, and the rice septum content in the treatment group is 0.0144 mg / kg (test results are as follows Figure 5The cadmium content of rice in the control group was 0.404 mg / kg, which confirmed that the product of the present invention could meet the cadmium reduction standard in rice and the pesticide residue test results were up to standard.

[0072] Test Example 2

[0073] The present invention conducted planting experiments in Dongbai Village, Tianzhu Village, and Chunlin Village in Xiushui Town, respectively. Two treatment groups were set up, each treated with an organic selenium soil heavy metal degrader, and a control group was set up without organic selenium. The cadmium content in the rice was measured after harvest. The results are shown in Table 1:

[0074] Table 1 Statistics of cadmium content in rice after harvest at different experimental bases

[0075]

[0076] The cadmium content in rice in different treatment groups was lower than that in the control group, indicating that the organic selenium soil heavy metal degrader provided by the present invention can effectively reduce the accumulation of cadmium in rice.

[0077] Test Example 3

[0078] Using the method of Example 2, a planting experiment was conducted at Lvkun Family Farm in Shidi Town, Mianzhu City. The cadmium content in rice was detected after harvest. The test results were as follows: Figure 6 As shown, the cadmium content in the rice is 0.0118 mg / kg, which is up to the standard. This shows that the present invention can ensure that the cadmium content in the rice is far lower than the national standard.

[0079] Test Example 4

[0080] Using the method of Example 2, a planting experiment was conducted in Changhe Village, Tuanjie Street, Pidu District, Chengdu City, spraying pesticides in the middle of rice growth;

[0081] One group was sprayed with BHC and DDT. The ratio of BHC, DDT and water was 100ml:100ml:15L. After adding water, 30L per mu was sprayed on the crop leaves. The insect death rate reached 95% 20 hours after application.

[0082] Another group was sprayed with deltamethrin. The ratio of deltamethrin to water was 100ml:15L. After adding water, 30L per mu was sprayed on the crop leaves. The insect death rate reached 98% 20 hours after application.

[0083] When the rice is mature, it is harvested and sent for inspection. The results of the 666 and DDT tests are as follows: Figure 7 As shown in the following table, the test results of deltamethrin are as follows: Figure 8 As shown, no pesticide residues such as BCH, DDT, and deltamethrin were detected in the samples tested, indicating that the present invention can effectively prevent the accumulation of pesticide residues in the soil in rice plants.

[0084] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as within the scope of protection of the present invention.

Claims

1. An organic selenium soil heavy metal degrader, characterized in that The organic selenium soil heavy metal degrader comprises the following raw materials: 15,000 to 25,000 ppm of organic selenium, 8,000 to 12,000 ppm of selenoprotein, 55 to 65 g of amino acids, 55 to 65 mL of high-purity peptides, 90 to 110 g of biological insecticides, and 25 to 35 mL of organosilicon additives.

2. The organic selenium soil heavy metal degradation agent according to claim 1, characterized in that The preparation method of the organic selenium is: S1. Inoculate brewer's yeast on a slant surface on a solid culture medium and culture; S2. The solid culture medium containing brewer's yeast after culture in step S1 is added to the liquid culture medium and fermented to obtain a liquid culture; S3. Inoculate the liquid bacterial strain slant into the solid culture medium and continue culturing to obtain the organic selenium.

3. The organic selenium soil heavy metal degradation agent according to claim 2, characterized in that The preparation process of the solid bacterial culture medium in step S1 is as follows: evenly mixing the cooked inorganic selenium powder and fig powder with tryptophan, valine, and brown sugar; bottling and sterilizing; The preparation process of the liquid culture medium in step S2 is as follows: the cooked inorganic selenium powder and fig powder are mixed with tryptophan, valine, brown sugar, glucose and yeast powder, and after bottling and sterilization, Bacillus subtilis or Trichoderma is added to obtain the liquid culture medium; The solid culture medium in step S3 is prepared by uniformly mixing the cooked fig powder with tryptophan, valine, brown sugar and glucose; bottling and sterilizing.

4. The organic selenium soil heavy metal degrading agent according to claim 3, characterized in that The amino acid is one or more of tryptophan, methionine, threonine, valine, lysine, histidine or leucine.

5. The organic selenium soil heavy metal degrading agent according to claim 4, characterized in that The preparation method of the high-purity peptide is as follows: soybeans are crushed, water is added, and fermented at 28-32° C. for 7 days, and then water is added at a ratio of 5 kg of water per kg of soybean fermentation material, stirred, and hydrolyzed. After the hydrolysis is completed, the high-purity peptide is obtained.

6. The method for preparing the organic selenium soil heavy metal degrading agent according to any one of claims 1 to 5, characterized in that: Organic selenium, selenoprotein, amino acid, high-purity peptide, biological insecticide and organosilicon additive are mixed and fermented in a fully closed manner at a fermentation temperature of 27-29° C. for 5-10 days.

7. Use of the organic selenium soil heavy metal degrader according to any one of claims 1 to 5 or the organic selenium soil heavy metal degrader prepared by the preparation method according to claim 6 in degrading heavy metals in soil and / or growing selenium-rich agricultural products.

8. The use according to claim 7, characterized in that The application amount of the organic selenium soil heavy metal degrader is 1800-2200 mL / mu, and when used, it is diluted with water at a volume ratio of 1:10-20 and then sprayed on the soil surface.

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