阅读说明：本技术 一种减少水稻中锑积累的叶面肥 (Foliar fertilizer for reducing antimony accumulation in rice ) 是由 谷泳 雷鸣 苗旭峰 谷红伟 于 2021-09-01 设计创作，主要内容包括：本发明公开了一种减少水稻中锑积累的叶面肥,属于肥料加工技术领域,其制备包括如下步骤：(1)将0.3415g MnSO-(4)·H-(2)O和0.5434g K-(2)S-(2)O-(8)加入到50mL 50％的H-(2)SO-(4)溶液中,在室温下用磁力搅拌器搅拌10min,形成均匀溶液后将溶液转移至100mL的高压反应釜内衬中；(2)将高压反应釜置于电热鼓风干燥箱中,在110℃下反应6h后取出,冷却至室温,离心3次收集沉淀物质,每次离心后除去上层清液,并用超纯水洗涤产物直至pH为7；(3)在真空干燥箱中60℃干燥8h,得到黑色纳米MnO-(2)粉末。本发明技术方案科学合理,经过反复试验证明,其在降低稻米中重金属Sb元素的含量的同时还能增加稻米中铁锰元素的含量,同时还能有效增加水稻产量。(The invention discloses a foliar fertilizer for reducing the accumulation of antimony in rice, which belongs to the technical field of fertilizer processing and comprises the following steps: (1) 0.3415g of MnSO 4 ·H 2 O and 0.5434g K 2 S 2 O 8 50mL of 50% H was added 2 SO 4 Stirring the solution for 10min by a magnetic stirrer at room temperature to form a uniform solution, and transferring the solution to a 100mL high-pressure reaction kettle lining; (2) placing the high-pressure reaction kettle in an electric heating forced air drying box, reacting for 6 hours at 110 ℃, taking out, cooling to room temperature, centrifuging for 3 times, collecting precipitate, centrifuging each time, removing supernatant, and washing the product with ultrapure water until the pH is 7; (3) drying in a vacuum drying oven at 60 deg.C for 8 hr to obtain blackColor nano MnO 2 And (3) powder. The technical scheme of the invention is scientific and reasonable, and repeated tests prove that the content of heavy metal Sb in rice can be reduced, the content of ferrum and manganese in rice can be increased, and the rice yield can be effectively increased.)

1. A foliar fertilizer for reducing the accumulation of antimony in rice is characterized by comprising the following steps:

(1) 0.3415g of MnSO₄·H₂O and 0.5434g K₂S₂O₈50mL of 50% H was added₂SO₄Stirring the solution for 10min by a magnetic stirrer at room temperature to form a uniform solution, and transferring the solution to a 100mL high-pressure reaction kettle lining;

(2) placing the high-pressure reaction kettle in an electric heating forced air drying box, reacting for 6 hours at 110 ℃, taking out, cooling to room temperature, centrifuging for 3 times, collecting precipitate, centrifuging each time, removing supernatant, and washing the product with ultrapure water until the pH is 7;

(3) drying for 8h at 60 ℃ in a vacuum drying oven to obtain black nano MnO₂And (3) powder.

2. A method of using a foliar fertilizer for reducing the accumulation of antimony in rice, which comprises using the foliar fertilizer for reducing the accumulation of antimony in rice according to claim 1: adding nano MnO₂The powder is diluted by water by 1000 times and is evenly vibrated by ultrasonic waves to prepare the nano MnO₂Suspending liquid, namely selecting a windless and sunny morning at the early stage of rice heading, and using a handheld spray can to spray nano MnO₂The turbid liquid is uniformly sprayed on the rice leaves to ensure that the rice leaves are full of liquid drops, if raining occurs within four hours after spraying, the turbid liquid needs to be re-sprayed, the time period of direct and violent sunlight and the time period of water carrying of the rice leaves are avoided during spraying, and the spraying time is preferably before 9 am or after 4 pm.

Technical Field

The invention belongs to the technical field of fertilizer processing, and particularly relates to a foliar fertilizer for reducing antimony accumulation in rice.

Background

Antimony (Sb) is a carcinogenic element in humans and has been the priority pollutant in the last 70 th century. In uncontaminated soils or sediments, the Sb content is very low: (<0.2mg·kg^-1). However, due to Sb's associated use and mining activities, uncontrolled Sb is released into the environment, resulting in increased concentrations of Sb in soils, sediments, water and animals and plants. China has the most abundant Sb ore resource reserves in the world, and accounts for 52 percent of the total amount of the world. Hunan is the province with the largest resource reserves of Sb ores in China, wherein the cold river tin mine is the largest Sb ore in the world, and the Sb yield accounts for one third of the whole country. According to previous investigation, the concentration range of Sb in the soil around Sb ore of tin mine in Hunan province is 100-5054 mg-kg^-1。

Sb can enter the human body through the food chain. One survey indicated that in the vicinity of antimony ore in tin mines, the main contaminant constituting a health risk to residents through dietary exposure was antimony, rather than arsenic (an analog of arsenic). Furthermore, rice has been reported to be a major dietary intake source of Sb in the human body, however, in Sb mines, people use rice as a major food. The rice has strong capacity of absorbing and enriching Sb, and the condition that the rice needs long-term flooding in actual production is favorable for absorbing and enriching Sb in rice plants^-1And 5.79mg kg^-1. Planting rice on soil contaminated with Sb may increase human health risks compared to other crops.

At present, the research on the role of Sb in the soil-plant system is mainly focused on: 1) the physicochemical behavior of Sb in soil, including the adsorption and desorption mechanisms of Sb in soil and factors that influence these processes; 2) the toxic mechanism of Sb in soil-dwelling animals; 3) processes of absorption, enrichment, transport, isolation and toxic response in plants. Therefore, the development of a technology for relieving the toxicity of Sb to plants and reducing the Sb accumulation of rice is of great importance, and the exposure risk caused by eating rice containing antimony by human is reduced.

Disclosure of Invention

The invention aims to provide a foliar fertilizer for reducing the accumulation of antimony in rice aiming at the existing problems.

The invention is realized by the following technical scheme:

a foliar fertilizer for reducing the accumulation of antimony in rice is prepared by the following steps:

(1) 0.3415g of MnSO₄·H₂O and 0.5434g K₂S₂O₈50mL of 50% H was added₂SO₄Stirring the solution for 10min by a magnetic stirrer at room temperature to form a uniform solution, and transferring the solution to a 100mL high-pressure reaction kettle lining;

(2) placing the high-pressure reaction kettle in an electric heating forced air drying box, reacting for 6 hours at 110 ℃, taking out, cooling to room temperature, centrifuging for 3 times, collecting precipitate, centrifuging each time, removing supernatant, and washing the product with ultrapure water until the pH is 7;

(3) drying in vacuum drying oven (DZF-6021, Shanghai flying apparatus Co., Ltd.) at 60 deg.C for 8 hr to obtain black nanometer MnO₂And (3) powder.

A method of using a foliar fertilizer for reducing the accumulation of antimony in rice, which comprises the use of a foliar fertilizer for reducing the accumulation of antimony in rice as claimed in claim 1: adding nano MnO₂The powder is diluted by water by 1000 times and is evenly vibrated by ultrasonic waves to prepare the nano MnO₂Suspending liquid, namely selecting a windless and sunny morning at the early stage of rice heading, and using a handheld spray can to spray nano MnO₂The turbid liquid is uniformly sprayed on the rice leaves to ensure that the rice leaves are full of liquid drops, if raining occurs within four hours after spraying, the turbid liquid needs to be re-sprayed, the time period of direct and violent sunlight and the time period of water carrying of the rice leaves are avoided during spraying, and the spraying time is preferably before 9 am or after 4 pm.

Compared with the prior art, the invention has the following advantages:

1. spraying nano MnO on leaf surface₂The rice yield can be improved;

2. spraying nano MnO on leaf surface₂The chlorophyll content of the rice leaves can be increased, and the photosynthesis of the rice leaves is enhanced;

3. spraying nano MnO on leaf surface₂Lipid peroxidation of rice leaf cells can be relieved, and the content of antioxidant kinase can be improved;

4. spraying nano MnO on leaf surface₂Can reduce the Sb content in rice leaves, stems and brown rice; the contents of Fe and Mn in rice leaves, stems and brown rice are increased.

5. The invention relates to a foliar fertilizer for reducing Sb accumulation in rice, which is prepared by spraying nano MnO on the leaf surface₂And the content of Sb in the rice leaves, stems and brown rice is reduced. So as to relieve the toxic action of Sb on rice and reduce the health risk of rice planted in Sb-polluted soil to human beings.

6. The technical scheme of the invention is scientific and reasonable, and repeated tests prove that the content of heavy metal Sb in rice can be reduced, the content of ferrum and manganese in rice can be increased, and the rice yield can be effectively increased.

Drawings

FIG. 1 shows the rice yield of the test field of the present application;

FIG. 2 shows the chlorophyll content in rice leaves according to the present application;

FIG. 3 shows the P in rice leaf_nThe content of (A);

FIG. 4 shows the rice leaf G of the present application_sThe content of (A);

FIG. 5 shows the leaf C of rice of the present application_iThe content of (A);

FIG. 6 shows the rice leaf pitch T of the present application_rThe content of (A);

FIG. 7 shows the MDA content in rice leaves according to the present application;

FIG. 8 shows the CAT content in rice leaves according to the present application;

FIG. 9 shows the SOD content in rice leaves according to the present application;

FIG. 10 shows the POD content in rice leaves according to the present invention.

Detailed Description

A foliar fertilizer for reducing the accumulation of antimony in rice is prepared by the following steps:

(1) 0.3415g of MnSO₄·H₂O and 0.5434g K₂S₂O₈50mL of 50% H was added₂SO₄Stirring the solution for 10min by a magnetic stirrer at room temperature to form a uniform solution, and transferring the solution to a 100mL high-pressure reaction kettle lining;

(2) placing the high-pressure reaction kettle in an electric heating forced air drying box, reacting for 6 hours at 110 ℃, taking out, cooling to room temperature, centrifuging for 3 times, collecting precipitate, centrifuging each time, removing supernatant, and washing the product with ultrapure water until the pH is 7;

(3) drying in vacuum drying oven (DZF-6021, Shanghai flying apparatus Co., Ltd.) at 60 deg.C for 8 hr to obtain black nanometer MnO₂And (3) powder.

A method of using a foliar fertilizer for reducing the accumulation of antimony in rice, which comprises the use of a foliar fertilizer for reducing the accumulation of antimony in rice as claimed in claim 1: adding nano MnO₂The powder is diluted by water by 1000 times and is evenly vibrated by ultrasonic waves to prepare the nano MnO₂Suspending liquid, namely selecting a windless and sunny morning at the early stage of rice heading, and using a handheld spray can to spray nano MnO₂The turbid liquid is uniformly sprayed on the rice leaves to ensure that the rice leaves are full of liquid drops, if raining occurs within four hours after spraying, the turbid liquid needs to be re-sprayed, the time period of direct and violent sunlight and the time period of water carrying of the rice leaves are avoided during spraying, and the spraying time is preferably before 9 am or after 4 pm.

For further explanation of the present invention, reference will now be made to the following specific examples.

1 materials and methods

1.1 overview of the study region

The test site is a hoeing base (E113 degrees 04 '52', N28 degrees 04 '52') of Hunan agricultural university of Hunan, Changsha, Hunan, and belongs to subtropical monsoon climate areas. The soil of the test field was collected from a farmland near the cold water river tin mine of Hunan province, and the basic physicochemical properties of the surface soil before rice planting and in the mature period are shown in Table 1Wherein the total Sb (157 mg kg. multidot. kg) of soil before rice planting and in mature period^-1、157.43mg·kg^-1) The contents of the above-mentioned materials exceed the corresponding threshold values (10 mg. kg) in GB 15618-2008 & lt & gt soil environmental quality Standard (revision) & gt^-1)。

TABLE 1 basic physicochemical Properties of soil in test fields before Rice planting and at maturity¹⁾

1) The data in the table above are the average of all test cell soil samples.

1.2 design of the experiment

In 2019, in 7-11 months, a field test is carried out in a hoeing base of the Hunan agricultural university, and the field is divided into 2.0m multiplied by 2.0m cells. Ridge is formed around the cells and covered by plastic films, and drainage ditches with the width of 30.0cm are arranged between adjacent cells to avoid mutual influence among the treatments. The tested rice variety is Yunquyou 1211, the field management measures are the same as the mode in local production, and the chemical herbicide is applied to treat weeds.

In the middle 9 th month of 2019, the rice is in the early stage of heading. Separately weighing 1.0 and 5.0g of nano MnO₂Dissolving the powder in 1.0L deionized water containing 1% Tween 80, stirring, and making into nanometer MnO with mass fractions of 0.1% and 0.5%₂And (4) suspending the solution. In a windless and sunny morning, 2 concentrations of nano MnO are sprayed by a handheld spray can₂The turbid liquid is uniformly sprayed on the rice leaves, so that the rice leaves are full of liquid drops. Control group was sprayed with 2.0L of deionized water containing 1% Tween 80. The 3 treatments were repeated 3 times and randomly distributed for a total of 9 cells.

1.3 sample Collection and analysis

1.3.1 determination of Rice leaf chlorophyll and photosynthetic characteristic parameters

Chlorophyll and photosynthetic parameters were determined on site in the field. Spraying nano MnO on leaf surface₂One week later, 10 functional leaves of rice were randomly selected in each plot, and chlorophyll (SPAD) in rice leaves was measured using a portable chlorophyll measuring instrument (SPAD-502Plus, Konica Minolta)Value), net photosynthesis rate (Pn, stomatal conductance (Gs), intercellular carbon dioxide concentration (intercellular CO2 concentration, Ci, and transpiration rate (Tr) of rice leaf were measured using a portable plant photosynthesis meter (Li-6400, Li-Cor Biosciences).

1.3.2 determination of lipid peroxidation of Rice leaves and antioxidant stress enzyme content

Spraying nano MnO on leaf surface₂One week later, 10 functional leaves of rice were randomly collected in each cell, stored in liquid nitrogen, transported to a laboratory, and stored in an ultra-low temperature refrigerator for later use. The content of Malondialdehyde (MDA) in rice leaves is measured by a spectrophotometric method, the content of catalase (CATase, CAT) in the rice leaves is measured by an ultraviolet spectrophotometer method, the content of Peroxidase (POD) in the rice leaves is measured by a colorimetric method, and the content of superoxide dismutase (SOD) in the rice leaves is measured by a spectrophotometric method.

1.3.3 soil samples

Before planting and in the mature period of rice, 5 pieces of topsoil (0 cm-20 cm) are collected by each test cell according to a five-point sampling method to be mixed into a sample. The collected soil sample is air-dried in a cool place indoors, impurities are removed, the soil sample is ground by a mortar and then passes through nylon sieves of 10 meshes, 20 meshes and 100 meshes respectively, and the soil sample is stored in a plastic package bag for later use. The pH value of the soil is leached by adopting a water-soil ratio of 2.5:1 and is measured by a pH meter (Seven Compact S220, Mettler Toledo); the organic matter is measured by a high-temperature external thermogravimetric potassium chromate titration method; the Cation Exchange Capacity (CEC) was measured by ammonium acetate exchange. A soil sample is digested by a aqua regia-HClO 4 wet method, the contents of Sb, Mn and Fe in a digestion solution are measured by inductively coupled plasma emission spectroscopy (ICP-OES iptima 8300, Perkinelmer), quality control is carried out by soil GB 07457, the recovery rate is 86.6-100.2%, and a blank test is carried out in the whole process.

1.3.4 plant samples

In the mature period of the rice, 5 roots of rice are collected by each test cell according to a five-point sampling method to be mixed into a sample, the sample is packaged by a nylon mesh bag, and then the rest rice is harvested, threshed and weighed. Washing a rice sample with deionized water, dividing the sample into 4 parts of roots, stems, leaves and grains, drying the grains in the sun outdoors, taking part of the roots, freeze-drying the part of the roots in a freeze dryer (FD-1A-50, Beijing Bo Yi kang laboratory instruments Co., Ltd.), putting the rest parts in an electric heating blowing drying oven, deactivating enzyme at 105 ℃ for 2h, and drying at 60 ℃ to constant weight. Separating rice hull and brown rice with rice huller, pulverizing all rice parts with miniature pulverizer, and storing.

The iron-manganese glue film on the surface of the rice roots is extracted by a DCB method. Plant samples are subjected to wet digestion by HNO3-HClO4 (volume ratio is 4:1), the contents of Ca, Zn, Mn and Fe in leaching liquor and digestion liquor are measured by inductively coupled plasma emission spectroscopy (ICP-OES iptima 8300, Perkinelmer), the content of Cd is measured by inductively coupled plasma mass spectrometry (ICP-MS7500a, Agilent Technologies), quality control is carried out by shrub branches and leaves GBW 07603 and rice GBW 100348, the recovery rates are respectively 88.7-104.4% and 92.5-104.9%, and blank tests are carried out in the whole process.

1.4 data processing

All data for this experiment were data-collated using Microsoft Excel 2010 software, statistically analyzed using SPSS 24.0 software, and plotted using GraphPad Prism 8 software. Differences between treatments were determined using one-way anova and LSD multiple comparison analysis, where P <0.05 indicated statistical significance. And obtaining a correlation coefficient through a Pearson correlation coefficient in the bivariate correlation.

2 results and analysis

2.1 foliar spray of Nano MnO₂Influence on Rice yield

After the rice is ripe, harvesting the rice, and measuring the grain weight of the test cell on site. As shown in FIG. 1, nano MnO with concentration of 0.1% and 0.5% was sprayed on the leaf surface₂The later rice yields were (3.44. + -. 0.22) and (3.58. + -. 0.35) kg. cell^-1The yield of the control cell is compared with that of the control cell (3.28 +/-0.51) kg. cell^-1Respectively increased by 5.8%, 6.4% and 6.7%, but the yield-increasing effect is not significant (P)>0.05), namely spraying the nano MnO with different concentrations on the leaf surface₂The difference of the rice yield increase is not significant (P)>0.05)。

The different lower case letters in the figure indicate that the difference reaches a significant level (P < 0.05). The same applies below.

2.2 foliar spray of Nano MnO₂Influence on chlorophyll of rice leaves

As shown in figure 2, nano MnO with concentration of 0.1% and 0.5% is sprayed on the leaf surface₂Has no obvious influence on the chlorophyll content of rice leaves (P)>0.05)。

2.3 foliar spray of Nano MnO₂Influence on rice photosynthetic characteristic parameters

As shown in FIG. 3, FIG. 4, FIG. 5, and FIG. 6, the nano MnO was sprayed to the leaf surface compared to CK₂Pn, Gs, Ci and Tr influence on rice leaves are different, but no significant difference is observed (P)>0.05)。

2.4 foliar spray of Nano MnO₂Influence on MDA, CAT, POD and SOD content in rice leaf

As shown in figure 7, figure 8, figure 9 and figure 10, the nano MnO is sprayed on the leaf surface₂The MDA content in the rice leaf is reduced to different degrees, and compared with CK, the MDA content in the rice leaf is obviously reduced after 0.5 percent of treatment (P)<0.05). The leaf surface treatment can increase the content of CAT, POD and SOD in rice leaves, and compared with CK, the content of CAT and POD in the rice leaves under the two treatments is obviously increased (P)>0.05), no obvious difference in SOD content (P)<0.05). To sum up, the nano MnO is sprayed on the leaf surface₂Can relieve lipid peroxidation of rice leaf cells and improve the content of antioxidant kinase.

2.5 foliar spray of Nano MnO₂Influence on Sb, Mn and Fe contents in different parts of rice

As shown in table 2, Sb is mainly concentrated in the root of rice, and the Sb content difference between different parts is large, and the distribution rule of Sb content in each part of rice under different treatments is: root of herbaceous plant>Stem of a tree>Leaf of Chinese character>Brown rice. The Sb content in the brown rice was reduced in both treatments compared to CK, but the difference was not significant (P)>0.05), the two treatments can obviously reduce the Sb content (P) in the rice leaves and stems<0.05). To sum up, the nano MnO is sprayed on the leaf surface₂Can reduce the Sb content in rice leaves, stems and brown rice, and has the following Sb reduction effects in different treatments: 0.5 percent>0.1％。

Mn is highest in rice leaves, and secondlyIs the stem followed by the root, the least of the brown rice. The leaf surface treatment can increase the Mn content of the rice roots to different degrees, wherein the Mn content of the roots treated with 0.5 percent is obviously increased compared with CK (P)<0.05), 0.5% treatment the Mn content in the roots was significantly higher than 0.3% treatment (P)<0.05). Compared with CK, the leaf surface treatment can obviously increase the Mn content (P) in the rice stems and leaves<0.05), wherein the Mn increasing effect is best when the treatment is 0.1%. The Mn content in the leaf-treated brown rice is obviously higher than CK (P)<0.05). To sum up, the nano MnO is sprayed on the leaf surface₂Can increase the Mn content in each part of the rice, and the Mn increasing effect by different treatments is as follows: 0.5 percent>0.1％。

Fe is mainly enriched at the root of the rice, the Fe content difference among different parts is large, and the distribution rule of the Fe content in each part of the rice under different treatments is as follows: root of herbaceous plant>Stem of a tree>Leaf of Chinese character>And (4) rice. Compared with CK, 5% of nano MnO is sprayed on the leaf surface₂Can obviously increase the Fe content (P) of the rice root<0.05), has little influence on the Fe content in the rice stem (P)<0.05). The leaf surface treatment reduced the Fe content in rice leaves and brown rice, and significantly reduced the Fe content (P) in rice leaves and brown rice as compared with CK<0.05)。

TABLE 2 contents of elements in different parts of rice¹⁾/mg·kg^-1

1) Different lower case letters in the same column indicate that the within-group difference reached a significant level (P <0.05) and n is 3.

2.7 foliar spray of Nano MnO₂Influence on content of each element in iron-manganese adhesive film on rice root surface

As shown in Table 3, the leaf surface was sprayed with 0.5% of nano MnO compared to CK₂The content of Sb and Mn in the back iron-manganese adhesive film is obviously increased (P)<0.05). The iron content in the root surface ferro-manganese glue film is slightly increased after the leaf surface treatment (P)>0.05)。

TABLE 3 iron manganese coating on the surface of rice root¹⁾/mg.kg^-1

1) Different lower case letters in the same column indicate that the within-group difference reached a significant level (P <0.05) and n is 3.

2.8 correlation coefficient between Sb content and other element content at different parts of rice

The correlation coefficients between the Sb content and the content of the elements (Mn, Fe) to be measured in different parts of rice were different (table 4). The content of Sb in the brown rice is in negative correlation with the content of Mn (P >0.05), the content of Sb in the brown rice is in obvious positive correlation with the content of Fe (P <0.05), and the content of Mn in the brown rice is in extremely obvious negative correlation with the content of Fe (P < 0.01). The Sb content in the rice leaves is obviously negative relative to the Mn content (P <0.05), the Mn content is obviously positive relative to the Fe content (P <0.05), and the Mn content is obviously negative relative to the Fe content (P < 0.05). The Sb content and Mn content in the rice stem are obviously in negative correlation, and the Mn content and the Fe content are in negative correlation (P is more than 0.05). The Sb content in the rice roots is positively correlated with Fe and Mn, wherein Mn is obviously positively correlated (P <0.05), and Mn content is obviously positively correlated with Fe content (P < 0.05).

TABLE 4 correlation coefficients of Sb, Mn and Fe contents at different parts of rice¹⁾

1) Indicates significant correlation at the 0.01 level (two-tailed), indicates significant correlation at the 0.05 level (two-tailed); n is 9.