A fertilizer and pesticide integrated cadmium absorption control agent, a preparation method and application thereof
By using a dispersion system of nano-silica and surfactants in foliar inhibitors, combined with ZnSO4 and the pesticide abamectin·indoxacarb, an integrated fertilizer and pesticide cadmium absorption inhibitor was prepared. This solved the problem of crop yield reduction caused by the reaction between foliar inhibitors and pesticides, and achieved efficient cadmium reduction and disease suppression with a single application.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- JIANGSU ACAD OF AGRI SCI
- Filing Date
- 2024-04-29
- Publication Date
- 2026-06-12
AI Technical Summary
Existing foliar inhibitors are prone to reacting with pesticides, leading to crop yield reduction. Furthermore, multiple applications are costly and have limited cadmium reduction efficiency.
A fertilizer-pesticide integrated cadmium absorption inhibitor was prepared by using nano-silica and surfactant as a dispersion system, combined with ZnSO4 and the pesticide abamectin·indoxacarb, adjusting the pH to 6.0-7.0, and then ultrasonically treating it to ensure uniform dispersion of the components and avoid reaction.
It achieves an effective combination of cadmium-blocking components and pesticides, providing two effects with a single application: reducing cadmium absorption by crops, preventing yield reduction, increasing willingness to use, and possessing good economic value.
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Figure CN118420402B_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of environmental protection and agricultural product quality and safety technology, specifically relating to a fertilizer-pesticide integrated cadmium absorption inhibitor, its preparation method, and its application. Background Technology
[0002] Cadmium (Cd) is widely recognized as one of the most toxic heavy metals posing a significant threat to humans due to its high mobility and toxicity. Rice is an important food crop, and cadmium accumulates in large quantities in its roots, stems, leaves, and grains, affecting not only rice yield and quality and the entire farmland ecosystem but also endangering human health through the food chain. To address cadmium (Cd) pollution in farmland soils, researchers have proposed various remediation measures to reduce cadmium accumulation in edible parts of crops. Among these, the use of foliar inhibitors to reduce or even block the migration of heavy metals to edible parts of crops has become an important technical means for the safe production of crops in moderately to mildly Cd-contaminated soils due to its advantages such as ease of operation, rapid absorption, low cost, and good heavy metal inhibition effect.
[0003] The mechanism of action of foliar cadmium (Cd) inhibitors is as follows: microelements such as zinc, silicon, and selenium can antagonize and chelate with Cd, competing with Cd for metal ion transport channels within the plant, thus reducing the absorption and transport of Cd by crops, or depositing Cd in plant cell walls and vacuoles, thereby reducing the translocation of Cd to edible parts of crops. However, compared with technologies such as soil passivation, the cadmium reduction efficiency of foliar inhibitors is still quite limited and needs further improvement. Multiple applications can increase the cadmium reduction efficiency of foliar inhibitors, but this increases the cost of application significantly. Developing integrated fertilizer-pesticide foliar inhibitors can achieve one-time application of pesticides and foliar inhibitors, reducing application costs. However, foliar inhibitors have complex compositions and are prone to reacting with pesticides, which not only reduces pesticide efficacy and leads to crop yield reduction, but also affects the dispersion of the active ingredients in the foliar inhibitor and the adhesion of the inhibitor to the leaves. Therefore, developing highly efficient integrated fertilizer-pesticide inhibitors to reduce cadmium absorption has become an urgent problem to be solved in agricultural production. Summary of the Invention
[0004] To address the problems in the prior art, this invention provides a cadmium absorption inhibitor that integrates fertilizer and pesticide application, along with its preparation method and application. This cadmium absorption inhibitor not only prevents the reaction between the cadmium-blocking component and the pesticide, thus avoiding crop yield reduction, but also effectively combines the cadmium-blocking component and the pesticide, achieving two effects with a single application, thereby increasing users' willingness to use it.
[0005] To achieve the above objectives, the present invention adopts the following technical solution:
[0006] A fertilizer-pesticide integrated cadmium absorption inhibitor includes an inhibitor and a pesticide, wherein the inhibitor comprises components at the following concentrations:
[0007] Nano-silica 0.1–0.4 wt%,
[0008] Surfactant 0.1–0.4 wt%,
[0009] The concentration of ZnSO4, calculated as Zn elemental, is 50–150 mg / L.
[0010] pH adjuster
[0011] The remainder is water;
[0012] The pH of the control agent is 6.0–7.0.
[0013] The final concentration of the pesticide is 2 wt.%.
[0014] Preferably, the pesticide is abamectin-indoxacarb.
[0015] Preferably, the surfactant is a nonionic surfactant or a mixture of a nonionic surfactant and anionic surfactant.
[0016] Preferably, the nonionic surfactant is Tween 80.
[0017] Preferably, in the mixture of nonionic surfactant and anionic surfactant, the mass ratio of the anionic surfactant to the nonionic surfactant is 4:1 to 2:1.
[0018] Preferably, the pH adjuster is NaOH or HCl.
[0019] The present invention also provides a method for preparing the above-mentioned fertilizer-pesticide integrated cadmium absorption inhibitor, comprising the following steps:
[0020] (1) The nano-silica, surfactant and ZnSO4 are uniformly mixed and the pH is adjusted to 6.0-7.0. Then, the mixture is ultrasonically treated to obtain the resistance control agent.
[0021] (2) Add pesticide to the control agent to the application concentration, and then treat it with ultrasound to obtain the product.
[0022] Preferably, the temperature of the ultrasonic treatment is 15-30°C, and the time of the ultrasonic treatment is 15-30 minutes.
[0023] The present invention also provides the application of the above-mentioned fertilizer-pesticide integrated cadmium absorption control agent.
[0024] Preferably, the application is in the application of cadmium barrier in rice.
[0025] Nanoparticles combine small particle size with excellent biocompatibility, increasing the adhesion of spray solutions to plant leaves. By loading functional trace elements, nanoparticles can prevent the stress of trace element ions on crops caused by water evaporation and promote the migration of functional elements between the aqueous and solid phases. However, due to the low solubility of nanoparticles in water, they are prone to aggregation and deposition. Therefore, this invention employs anionic or nonionic surfactants to improve the dispersibility of nanoparticles in the solution system.
[0026] The addition of pesticides to the fertilizer-pesticide integrated cadmium absorption control agent may change the original dispersion characteristics of the functional elements loaded on the nanoparticles. Therefore, based on the properties of the nanoparticles, functional trace elements and pesticides, this invention selects a suitable dispersion system to ensure the disease suppression and cadmium reduction efficiency of the fertilizer-pesticide integrated cadmium absorption control agent.
[0027] The beneficial effects of this invention are as follows:
[0028] This invention prepares a uniformly dispersed fertilizer-pesticide integrated cadmium absorption inhibitor, which not only avoids the reaction between the cadmium inhibitor and the pesticide, thus preventing crop yield reduction, but also effectively combines the cadmium inhibitor and the pesticide, achieving two effects with a single application, increasing users' willingness to use it, and has good economic value. Attached Figure Description
[0029] Figure 1 This refers to the solution state of the fertilizer-pesticide integrated foliar inhibitor in different dispersion systems in the test examples of this invention. The correspondence between numbers 1-6 and the examples and comparative examples is shown in Table 2.
[0030] Figure 2 This invention relates to the effect of the fertilizer-pesticide integrated foliar inhibitor on the cadmium content of rice grains in the test examples.
[0031] Figure 3 This is the effect of the fertilizer-pesticide integrated foliar inhibitor on rice yield in the test examples of this invention. Detailed Implementation
[0032] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.
[0033] Comparative Example 1
[0034] Formulation of a fertilizer-pesticide integrated foliar inhibitor based on nano-hydroxyapatite (nHAP) and a dispersion system of anionic surfactant (sodium citrate (SC)):
[0035] Accurately weigh 3g of nHAP and dissolve it in 1L of 0.3wt.% sodium citrate solution (3g of sodium citrate dissolved in 1L of deionized water), and stir until homogeneous;
[0036] Add 0.44 g ZnSO4·7H2O (100 mg / L Zn) to the solution, and simultaneously add deionized water to make the final dispersion reach 100 wt.%.
[0037] The pH of all dispersions was determined by using 3 mol·L⁻¹ -1 HCl solution and 1 mol·L -1 The NaOH solution was uniformly adjusted to 6.5.
[0038] Leaf surface inhibition agents with different treatments were prepared by ultrasonication at 25℃ for 15 min.
[0039] Take 50 mL of the control agent and add it to the colorimetric tube. Add abamectin·indoxacarb (Y) to the foliar control agent solution according to the application amount to make the final concentration 2 wt% of the application concentration. After sonication at 25℃ for 15 min, the fertilizer-pesticide integrated foliar control agent is obtained.
[0040] Comparative Example 2
[0041] Formulation of a foliar inhibitor for fertilizer and pesticide integration based on nano-hydroxyapatite (nHAP) and a dispersion system containing nonionic surfactant (Tween 80 (TW)):
[0042] Accurately weigh 3g of nHAP and dissolve it in 1L of 0.1wt.% Tween 80, stirring until homogeneous;
[0043] Add 0.44 g ZnSO4·7H2O (100 mg / L Zn) to the solution, and simultaneously add deionized water to make the final dispersion reach 100 wt.%.
[0044] The pH of all dispersions was determined by using 3 mol·L⁻¹ -1 HCl solution and 1 mol·L -1 The NaOH solution was uniformly adjusted to 6.5.
[0045] Leaf surface inhibition agents with different treatments were prepared by ultrasonication at 25℃ for 15 min.
[0046] Take 50 mL of the control agent and add it to the colorimetric tube. Add abamectin and indoxacarb to the foliar control agent solution according to the application amount to make the final concentration 2 wt% of the application concentration. After sonication at 25℃ for 15 min, the fertilizer-pesticide integrated foliar control agent is obtained.
[0047] Comparative Example 3
[0048] The formulation of a foliar inhibitor integrating fertilizer and pesticide based on nano-hydroxyapatite (nHAP) and a dispersion system consisting of anionic and nonionic surfactants (sodium citrate + Tween 80):
[0049] Accurately weigh 3g of nHAP and dissolve it in 1L of 0.3wt.% sodium citrate solution (3g of sodium citrate dissolved in 1L of deionized water), and stir until homogeneous;
[0050] Add 0.44 g ZnSO4·7H2O (100 mg / L Zn) to the solution, and simultaneously add deionized water to make the final dispersion reach 100 wt.%.
[0051] The pH of all dispersions was determined by using 3 mol·L⁻¹ -1 HCl solution and 1 mol·L -1 The NaOH solution was uniformly adjusted to 6.5 and sonicated at 25℃ for 15 minutes;
[0052] Transfer 250 mL of the above solution into a beaker, add 0.25 g of Tween 80 (0.1 wt.%), and stir until homogeneous;
[0053] Take 50 mL of the above solution and add it to a colorimetric tube. Add abamectin and indoxacarb to the foliar control agent solution according to the application amount to make the final concentration 2 wt% of the application concentration. After sonication at 25℃ for 15 min, the fertilizer-pesticide integrated foliar control agent is obtained.
[0054] Example 1
[0055] Formulation of a foliar inhibitor combining fertilizer and pesticide based on nano-silica (nSiO2) and a dispersion system of anionic surfactant (sodium citrate):
[0056] Accurately weigh 1g of nSiO2 and dissolve it in 1L of 0.3wt.% sodium citrate solution (3g of sodium citrate dissolved in 1L of deionized water), and stir until homogeneous;
[0057] Add 0.44 g ZnSO4·7H2O (100 mg / L Zn) to the solution, and simultaneously add deionized water to make the final dispersion reach 100 wt.%.
[0058] The pH of all dispersions was determined by using 3 mol·L⁻¹ -1 HCl solution and 1 mol·L -1 The NaOH solution was uniformly adjusted to 6.5.
[0059] Leaf barrier agents with different treatments were prepared by ultrasonication at 25℃ for 15 min.
[0060] Add 50 mL of the control agent to the colorimetric tube, and add the pesticide abamectin·indoxacarb to the foliar control agent solution according to the application amount, so that the final concentration is 2 wt% of the application concentration. Sonicate at 25℃ for 15 min.
[0061] Example 2
[0062] Formulation of a foliar inhibitor combining fertilizer and pesticide based on nano-silica (nSiO2) and a dispersion system of nonionic surfactant (Tween 80):
[0063] Accurately weigh 1g of nSiO2 and dissolve it in 1L of 0.1wt.% Tween 80 and stir until homogeneous;
[0064] Add 0.44 g ZnSO4·7H2O (100 mg / L Zn) to the solution, and simultaneously add deionized water to make the final dispersion reach 100 wt.%.
[0065] The pH of all dispersions was determined by using 3 mol·L⁻¹ -1 HCl solution and 1 mol·L -1 The NaOH solution was uniformly adjusted to 6.5.
[0066] Leaf barrier agents with different treatments were prepared by ultrasonication at 25℃ for 15 min.
[0067] Add 50 mL of the control agent to the colorimetric tube, and add the pesticide abamectin·indoxacarb to the foliar control agent solution according to the application amount, so that the final concentration is 2 wt% of the application concentration. Sonicate at 25℃ for 15 min.
[0068] Example 3
[0069] The formulation of a foliar inhibitor integrating fertilizer and pesticide based on nano-silica (nSiO2) and a dispersion system consisting of anionic and nonionic surfactants (sodium citrate + Tween 80):
[0070] Accurately weigh 1g of nSiO2 and dissolve it in 1L of 0.1wt.% Tween 80 and stir until homogeneous;
[0071] Add 0.44 g ZnSO4·7H2O (100 mg / L Zn) to the solution, and simultaneously add deionized water to make the final dispersion reach 100 wt.%.
[0072] The pH of all dispersions was determined by using 3 mol·L⁻¹ -1 HCl solution and 1 mol·L -1 The NaOH solution was uniformly adjusted to 6.5 and sonicated at 25℃ for 15 minutes;
[0073] Transfer 250 mL of the above solution into a small beaker, add 0.75 g of sodium citrate (0.3 wt.%), and stir well;
[0074] Add 50 mL of the above solution to a colorimetric tube, and add the pesticide abamectin·indoxacarb to the foliar control agent solution according to the application amount, so that the final concentration is 2 wt% of the application concentration. Sonicate at 25℃ for 15 min.
[0075] Example 4
[0076] The formulation of a foliar inhibitor integrating fertilizer and pesticide based on nano-silica (nSiO2) and a dispersion system consisting of anionic and nonionic surfactants (sodium citrate + Tween 80):
[0077] Accurately weigh 4g of nSiO2 and dissolve it in 1L of 0.1wt.% Tween 80 and stir until homogeneous;
[0078] Add 0.22 g ZnSO4·7H2O (50 mg / L Zn) to the solution, and simultaneously add deionized water to make the final dispersion reach 100 wt.%.
[0079] The pH of all dispersions was determined by using 3 mol·L⁻¹ -1 HCl solution and 1 mol·L -1 The NaOH solution was uniformly adjusted to 6.0, and sonicated at 15℃ for 30 min;
[0080] Transfer 250 mL of the above solution into a small beaker, add 0.75 g of sodium citrate (0.2 wt.%), and stir well;
[0081] Add 50 mL of the above solution to a colorimetric tube, and add the pesticide abamectin·indoxacarb to the foliar control agent solution according to the application amount, so that the final concentration is 2 wt% of the application concentration. Sonicate at 25℃ for 15 min.
[0082] Example 5
[0083] The formulation of a foliar inhibitor integrating fertilizer and pesticide based on nano-silica (nSiO2) and a dispersion system consisting of anionic and nonionic surfactants (sodium citrate + Tween 80):
[0084] Accurately weigh 1g of nSiO2 and dissolve it in 1L of 0.02wt.% Tween 80, then stir until homogeneous.
[0085] Add 0.66 g ZnSO4·7H2O (150 mg / L Zn) to the solution, and simultaneously add deionized water to make the final dispersion reach 100 wt.%.
[0086] The pH of all dispersions was determined by using 3 mol·L⁻¹ -1 HCl solution and 1 mol·L -1 The NaOH solution was uniformly adjusted to 7.0 and sonicated at 30℃ for 15 minutes;
[0087] Transfer 250 mL of the above solution into a small beaker, add 0.75 g of sodium citrate (0.08 wt.%), and stir until well mixed;
[0088] Add 50 mL of the above solution to a colorimetric tube, and add the pesticide abamectin·indoxacarb to the foliar control agent solution according to the application amount, so that the final concentration is 2 wt% of the application concentration. Sonicate at 25℃ for 15 min.
[0089] Test case
[0090] (1) Characterization of dispersion state and stability test of foliar inhibitors for fertilizer-pesticide integration:
[0091] The particle size distribution of particles in a dispersion system can characterize its dispersion state to some extent. The particle size and dispersibility index (PDI) of the leaf barrier agent components in the solutions prepared in Examples 1-3 and Comparative Examples 1-3, as well as Comparative Examples 4 and 5 (without pesticides), were measured using a nanoparticle size potentiometer to determine the effect of pesticide addition on the degree of particle dispersion in different dispersion systems. The measurement temperature was 20℃, and each sample was measured six times. The concentrations of each sample component are shown in Table 1.
[0092] Table 1. Comparison of Sample Component Concentrations
[0093]
[0094] The particle size distribution and PDI of different fertilizer-pesticide integrated foliar inhibitors are shown in Table 2.
[0095] Table 2. Particle size distribution of foliar inhibitors with different components that combine fertilizer and pesticide.
[0096]
[0097]
[0098] It can be seen that when the foliar inhibitor loaded with Zn using nHAP is supplemented with abamectin and indoxacarb, both the particle size and PDI increase significantly. However, in the treatment with anionic + nonionic surfactant as the dispersion system (Comparative Example 3), the solution particle size decreases significantly to 248.8±8.2 nm, and the solution PDI decreases significantly to 0.419±0.007. This shows that the foliar inhibitor loaded with Zn using nHAP and abamectin and indoxacarb have good dispersibility in the anionic + nonionic surfactant dispersion system. Therefore, this system can be used to formulate an nHAP-based fertilizer-pesticide integrated foliar inhibitor.
[0099] After adding abamectin and indoxacarb to the foliar inhibitor loaded with Zn using nSiO2, the particle size in the solution was significantly reduced, and the PDI of the solution also showed a downward trend. In the treatment with nonionic surfactant as the dispersion system (Example 2), the particle size of the solution was significantly reduced to 755.9±15.0 nm, and the PDI of the solution was significantly reduced to 0.650±0.004. It can be seen that the foliar inhibitor loaded with Zn using nSiO2 and abamectin and indoxacarb have good dispersibility in the nonionic surfactant dispersion system. Therefore, this system is used to formulate an integrated fertilizer and pesticide foliar inhibitor based on nSiO2.
[0100] (2) Field efficacy verification of foliar inhibitors that combine fertilizer and pesticide application:
[0101] The experiment was conducted from April to October 2023 at a cadmium-contaminated farmland in Gaochun District, Nanjing City, Jiangsu Province. A completely randomized block design was used, dividing the experimental area into 20 plots, each with an area of 9 m². 2 (3m×3m) Each small section was divided by artificial embankments, with a protective row at each end. Foliar control treatments are shown in Table 3, with four replicates per treatment group. The foliar control agent was applied twice: once during the jointing stage and again during the early grain-filling stage of the rice, at a rate of 50L / mu. Other field management practices for rice followed the local large-scale field production model.
[0102] Table 3 shows the information on the treatment groups in the field experiment of this invention.
[0103]
[0104]
[0105] Rice samples were harvested at maturity in early October 2023, and the yield of rice in each plot was determined. Rice from each treatment was collected, and the grains were manually separated. The grains were then soaked in a 1% acetic acid solution for 2 minutes, followed by rinsing with tap water and deionized water to ensure no residual fertilizer-pesticide inhibitors remained on the grain surface. The rice grains were blanched at 105℃ for 30 minutes, then dried at 70℃ to constant weight and weighed. After pulverizing, the grains were passed through a 100-mesh sieve and left for digestion and cadmium content determination. The results are as follows: Figure 2 As shown.
[0106] Analysis of cadmium content in rice grains under different treatments showed that the application of foliar inhibitors loaded with Zn nanomaterials and abamectin-indoxacarb, either separately or in combination, could effectively reduce cadmium content in rice grains by 31.67%-44.38%.
[0107] To evaluate the effects of the combined fertilizer-pesticide foliar control agent formulation on the efficacy of the pesticide abamectin·indoxacarb and on rice yield, two treatments were established: combined fertilizer-pesticide application and separate fertilizer and pesticide application. Rice yield was then measured. The results are as follows: Figure 3 As shown, only the YHS2 and YHST2 treatments (nHAP+SC+Y fertilizer-pesticide integrated application and nHAP+SC+TW+Y fertilizer-pesticide integrated application) significantly reduced rice yield by 16.7%-17.64%. This may be because the Zn element loaded in nHAP interacts with abamectin and indoxacarb in the dispersion system, affecting the functional structure of abamectin and indoxacarb, thus affecting its efficacy. In contrast, the foliar control agent based on Zn element loaded in nSiO2 and abamectin and indoxacarb has no significant effect on rice yield.
[0108] Therefore, considering both the cadmium reduction capacity of rice grains and the impact on rice yield, the best foliar control agent, which combines nSiO2-loaded zinc with a nonionic surfactant (Tween 80) and abamectin·indoxacarb, is the most effective. It can not only effectively reduce the absorption and translocation of cadmium in rice, resulting in a significant 41.04% reduction in cadmium in rice grains, but also does not affect the efficacy of pesticides or significantly change rice yield. It can be applied to cadmium-contaminated farmland, achieving the integration of foliar control agent and insecticide in a single application.
Claims
1. A fertilizer-pesticide integrated cadmium absorption inhibitor, characterized in that, It includes a control agent and a pesticide, wherein the control agent comprises components at the following concentrations: Nano-silica 0.1~0.4wt%, Surfactant 0.1~0.4wt%, The concentration of ZnSO4, calculated as Zn element, is 50~150 mg / L. pH adjuster The remainder is water; the pH of the control agent is 6.0~7.
0. The final concentration of the pesticide is 2 wt%. The pesticide in question is abamectin·indoxacarb.
2. The fertilizer-pesticide integrated cadmium absorption inhibitor according to claim 1, characterized in that, The surfactant is a nonionic surfactant or a mixture of a nonionic surfactant and anionic surfactant.
3. The fertilizer-pesticide integrated cadmium absorption inhibitor according to claim 2, characterized in that, The nonionic surfactant is Tween 80.
4. The fertilizer-pesticide integrated cadmium absorption inhibitor according to claim 2, characterized in that, In a mixture of nonionic and anionic surfactants, the mass ratio of the anionic surfactant to the nonionic surfactant is 4:1 to 2:
1.
5. The fertilizer-pesticide integrated cadmium absorption inhibitor according to claim 1, characterized in that, The pH adjuster is NaOH or HCl.
6. The preparation method of the fertilizer-pesticide integrated cadmium absorption inhibitor according to any one of claims 1 to 5, characterized in that, Includes the following steps: (1) The nano-silica, surfactant and ZnSO4 are uniformly mixed and the pH is adjusted to 6.0~7.
0. Then the mixture is ultrasonically treated to obtain the resistance control agent. (2) Add pesticide to the control agent to the final concentration, and then treat it with ultrasound to obtain the final product.
7. The preparation method according to claim 6, characterized in that, The ultrasonic treatment temperature is 15~30℃, and the ultrasonic treatment time is 15~30 min.
8. The application of the fertilizer-pesticide integrated cadmium absorption inhibitor as described in any one of claims 1 to 5.
9. The application according to claim 8, characterized in that, The application is in the cadmium barrier of rice.