CN113234445A - Regulating agent suitable for alkaline soil heavy metal cadmium pollution remediation, preparation method and application - Google Patents

Regulating agent suitable for alkaline soil heavy metal cadmium pollution remediation, preparation method and application Download PDF

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CN113234445A
CN113234445A CN202110354000.1A CN202110354000A CN113234445A CN 113234445 A CN113234445 A CN 113234445A CN 202110354000 A CN202110354000 A CN 202110354000A CN 113234445 A CN113234445 A CN 113234445A
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soil
heavy metal
cadmium
metal cadmium
alkaline
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徐应明
王雅乐
黄青青
孙约兵
王林
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Agro Environmental Protection Institute Ministry of Agriculture
Agro Environmental Protection Institute Ministry of Agriculture and Rural Affairs
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K17/00—Soil-conditioning materials or soil-stabilising materials
    • C09K17/02—Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only
    • C09K17/06—Calcium compounds, e.g. lime
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09C—RECLAMATION OF CONTAMINATED SOIL
    • B09C1/00—Reclamation of contaminated soil
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09C—RECLAMATION OF CONTAMINATED SOIL
    • B09C1/00—Reclamation of contaminated soil
    • B09C1/08—Reclamation of contaminated soil chemically
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
    • C05D3/00—Calcareous fertilisers
    • C05D3/02—Calcareous fertilisers from limestone, calcium carbonate, calcium hydrate, slaked lime, calcium oxide, waste calcium products
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
    • C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
    • C05G3/80—Soil conditioners
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09C—RECLAMATION OF CONTAMINATED SOIL
    • B09C2101/00—In situ
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2101/00—Agricultural use
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2109/00—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE pH regulation

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Soil Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Environmental & Geological Engineering (AREA)
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  • Pest Control & Pesticides (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Processing Of Solid Wastes (AREA)
  • Soil Conditioners And Soil-Stabilizing Materials (AREA)

Abstract

The invention relates to a regulating agent suitable for repairing heavy metal cadmium pollution in alkaline soil, which consists of calcined skarn powder, vivianite powder, zinc sulfate and manganese salt. The conditioner disclosed by the invention has the advantages of wide sources of raw materials for preparation, low price, low application amount, simple application method, ingenious and reasonable product formula design, obvious regulation and control effect and the like, can be used for efficiently repairing the heavy metal cadmium pollution of alkaline soil, can effectively control the heavy metal cadmium pollution of the alkaline soil in northern China and guarantees the safe production of agricultural products. Directly spreading the conditioner and the heavy metal cadmium polluted soil into the heavy metal cadmium polluted alkaline soil according to the mass ratio of 1:200-1:500, uniformly ploughing, and sowing.

Description

Regulating agent suitable for alkaline soil heavy metal cadmium pollution remediation, preparation method and application
Technical Field
The invention belongs to the technical field of soil heavy metal pollution remediation, and particularly relates to a regulating agent suitable for alkaline soil heavy metal cadmium pollution remediation, a preparation method and an application.
Background
In recent 30 years, with the rapid development of industrialization and urbanization in China, the problem of heavy metal pollution of soil is more and more prominent, and according to the survey bulletin on the condition of soil pollution in China issued by the environmental protection department and the national soil resource department in 2014, the standard exceeding rate of soil point positions in cultivated land in China is 19.4%, wherein the standard exceeding rate of the point position of heavy metal cadmium is 7.0%, and the soil point position is the first of eight heavy metal elements, so that the soil is widely concerned by the whole society. Cadmium is considered as a heavy metal with the highest toxicity to human health, can damage the kidney function of a human body, can weaken bone, can cause osteodynia of the human body, can improve the carcinogenicity of the human body, and can cause kidney cancer, bladder cancer, breast cancer and prostate cancer. Therefore, the repair and treatment of the heavy metal cadmium polluted soil are enhanced, and the safe production of agricultural products and the health of human bodies are ensured.
In the last decade, because the cadmium pollution of the acid paddy field in south China is serious, the attention on the cadmium pollution of heavy metal in the farmland is focused on the prevention and treatment of the cadmium pollution of the acid paddy field in south China, a large amount of prevention and treatment technical researches are developed, and a plurality of research results are obtained; meanwhile, as the soil of the wheat field in the northern area belongs to alkaline soil and is planted in dry land, the effective cadmium content of the soil can not be regulated and controlled by adjusting the pH value of the soil, managing water and other agronomic measures like acid rice fields in the southern area, the cadmium absorption accumulation amount of wheat grains is reduced, a large number of materials, products, technologies and the like with remarkable control effects in the cadmium pollution of the acid rice fields in the southern area are not suitable for the control of the cadmium pollution of the soil in the alkaline wheat field in the northern area, and the added wheat grains have strong absorption accumulation capacity on the cadmium in the soil, so that the control difficulty of the cadmium pollution of the alkaline wheat field is high. Wheat is one of three staple grains in China, and sowing areas of the wheat are mainly distributed in Henan, Hebei, Shandong, Shanxi, inner Mongolia and other places in the North of China. In recent years, with the exposure of the cadmium pollution phenomenon of wheat grains in local areas of northern major wheat producing areas, the serious attention of national and local governments on the cadmium pollution of wheat field soil is aroused. Therefore, the method further enhances the research on the prevention and treatment technology of the cadmium pollution of the alkaline soil in northern areas of China, and has important significance for ensuring the safe production of large crops such as wheat and the like.
At present, the most common farmland soil heavy metal cadmium pollution prevention and treatment technology comprises the following steps: agronomic regulation measures, such as water and fertilizer management, foliage spraying conditioner separation, farming measures and the like; in-situ passivation repair, plant extraction repair and the like. The in-situ passivation repair technology is characterized in that a passivation material is added into soil to have physical and chemical effects with cadmium in the soil, so that the effective cadmium is converted into a chemically inactive form, the migration and biological effectiveness of the cadmium in the soil are reduced, the absorption of the cadmium in the soil by crop root systems is reduced, and the accumulation amount of the cadmium in edible parts of crops is reduced. Currently, common passivation materials include: calcium silicate materials (sodium silicate, potassium silicate, magnesium silicate, calcium oxide, calcium hydroxide, calcium carbonate, etc.), clay mineral materials (sepiolite, palygorskite, bentonite, montmorillonite, kaolin, etc.), phosphorus-containing materials (calcium superphosphate, calcium magnesium phosphate fertilizer, hydroxyapatite, etc.), biomass charcoal, metal oxides (iron oxide, ferrous sulfate, ferric sulfate, manganese oxide, manganese potash ore, etc.), organic materials (humic acid, peat, pig manure, cow manure, chicken manure, etc.), etc. The passivation restoration technology has the characteristics of simple operation, good restoration effect, high restoration speed, strong stability, lower cost, simultaneous restoration and production and the like, and is widely applied to restoration and treatment of heavy metal cadmium polluted farmland soil, but researches show that the regulation and control agent with good restoration effect in the south acidic cadmium polluted paddy field is as follows: many materials in the silicon-calcium material, the clay material, the phosphorus-containing material, the biomass charcoal, the metal oxide and the organic material have unobvious passivation and repair effects in the northern alkaline cadmium polluted soil, and the regulating agent capable of meeting the repair and treatment requirements of the northern alkaline cadmium polluted soil is few; in addition, the water and fertilizer management measures cannot be suitable for the production of crops in northern dry land, the leaf surface spraying of the conditioner has low blocking effect, poor stability and low general effect of cultivation measures, and only as an auxiliary measure, the hyper-enriched plant extraction and restoration are performed in the northern alkaline soil cadmium pollution, and the alkaline soil cadmium pollution restoration requirements cannot be met due to low extraction efficiency and long restoration time. Therefore, the research and development of a regulating agent suitable for preventing and treating the cadmium pollution of the alkaline soil in northern China are urgently needed, and the safe production of agricultural products and the health of human bodies are guaranteed.
Through searching, the following patent publications related to the patent application of the invention are found:
1. a clay mineral-based microelement regulator (CN106590678A) for the treatment of cadmium pollution in paddy fields, which comprises: 8-16 parts by weight of chelated manganese (EDTA-Na 2 Mn); 0.5-3 parts by weight of silicon dioxide; 24-32 parts of zinc sulfate; 1-5 parts by weight of magnesium sulfate; 0.4-1.2 parts by weight of ferrous sulfate; 0.6-1.4 parts by weight of calcium oxide; 80-160 parts by weight of clay mineral. The invention relates to a novel technology for treating cadmium pollution of a rice field based on environmental geochemistry and antagonism principles, which reduces the bioavailability of cadmium in soil by improving the pH value of the soil and changing the occurrence form of cadmium in the soil, and ensures the remediation effect and efficiency by reducing the absorption of cadmium in rice through element antagonism under double control.
2. A passivation antagonistic regulator for reducing cadmium pollution of winter wheat and a preparation method thereof (CN107523309B) are composed of the following raw materials: by adopting the method, on one hand, the occurrence form of the cadmium in the soil is changed and the bioavailability of the cadmium in the soil is reduced by improving the adsorption and precipitation of the soil, and on the other hand, the absorption of the cadmium in the wheat is reduced by element antagonism, so that the repairing effect and efficiency are ensured under two conditions.
3. A rhizosphere regulating agent for improving plant repair efficiency and application thereof (CN102827613A), wherein the rhizosphere regulating agent comprises the following raw materials: the weathered coal nitro humic acid fertilizer comprises 25-26 parts by weight of weathered coal nitro humic acid, nitrogen fertilizer, phosphate fertilizer and potash fertilizer: 5-7: 4-5: 4 to 5. The invention reduces the pH value of the soil through the rhizosphere regulating agent, complexes or chelates the cadmium in the soil, increases the bioavailability of the cadmium in the soil, achieves the aim of improving the phytoremediation efficiency of the cadmium-polluted farmland soil, has no pollution to the environment, and is suitable for commercial application and large-area demonstration and popularization.
By contrast, the present patent application is substantially different from the above patent publications.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a regulating agent suitable for alkaline soil heavy metal cadmium pollution remediation, a preparation method and application.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a regulating agent suitable for alkaline soil heavy metal cadmium pollution remediation is composed of calcined skarn powder, wustite powder, zinc sulfate and manganese salt.
Further, the mass ratio of the skarn powder to the vivianite powder to the zinc sulfate to the manganese salt is 1:1:0.5: 1.5-1: 1:3: 4.
Further, the median particle size of the skarn powder and the vivianite powder is 5-10 mu m, and the maximum content of particles with the particle size larger than 30 mu m is not more than 0.1%;
or the manganese salt is one or more than two of manganese sulfate, manganese acetate, manganese chloride and manganese nitrate.
Furthermore, the purity of the zinc sulfate and the manganese salt is industrial grade, and no secondary pollution is caused.
Further, the preparation steps of the calcined skarn powder are as follows:
calcining skarn ore at 800-1000 ℃ for 2-3 h, and grinding to obtain calcined skarn powder.
The preparation method of the regulating agent suitable for the alkaline soil heavy metal cadmium pollution remediation comprises the following steps:
and uniformly mixing the calcined skarn powder, the vivianite powder, the zinc sulfate and the manganese salt to obtain the regulating agent suitable for preventing and treating the heavy metal cadmium pollution of the alkaline soil.
The use method of the regulating agent suitable for preventing and controlling the heavy metal cadmium pollution of the alkaline soil comprises the following steps:
regulating agent according to the following ratio: the heavy metal cadmium-polluted soil is directly applied to the heavy metal cadmium-polluted alkaline soil in a mass ratio of 1:200-1:500, and the soil can be sown after being uniformly ploughed.
The regulating agent suitable for preventing and controlling the heavy metal cadmium pollution of the alkaline soil is applied to the regulation of the heavy metal cadmium polluted soil.
Further, the soil is cadmium-polluted alkaline edible crop field soil; or the soil is weakly alkaline or alkaline cadmium-polluted soil; or the pH value of the soil is not less than 7, and the soil is dry land.
Further, the edible crop is wheat, corn, vegetables or soybean.
Furthermore, the mass ratio of the addition amount of the regulating agent to the heavy metal cadmium-polluted soil is 1:200-1: 500.
The invention has the advantages and positive effects that:
1. the conditioner has the advantages of wide sources of raw materials for preparing the conditioner, low price, low application amount, simple application method, ingenious and reasonable product formula design, obvious regulation and control effect and the like, can be used for efficiently repairing the heavy metal cadmium pollution of alkaline soil, can effectively control the heavy metal cadmium pollution of the soil of the alkaline wheat field in north China, and ensures the safe production of agricultural products (such as wheat). Directly spraying the conditioner and the heavy metal cadmium polluted soil into the heavy metal cadmium polluted alkaline soil according to the mass ratio of 1:200-1:500, uniformly ploughing, and sowing.
2. The regulating agent has wide raw material source and low cost, the skarn material and the vivianite material in the raw material components have abundant reserves in the nature, the calcination process of the skarn material is simple, the purification process of magnesium oxide and calcium oxide is omitted, and meanwhile, zinc sulfate and manganese salt can adopt industrial-grade products, so that the production cost is greatly reduced.
3. The regulating agent has no secondary pollution, is green and environment-friendly, is simple to produce and prepare, reduces energy consumption, and does not discharge waste water, waste and greenhouse gas.
4. The regulating agent can effectively passivate/stabilize the cadmium pollution of the heavy metal in the alkaline soil, realize the remediation of the cadmium polluted alkaline soil, promote the content of trace elements necessary for the growth of plants such as magnesium, silicon, calcium, zinc, manganese, iron, phosphorus, sulfur and the like in the remedied soil, and effectively improve the soil fertility.
5. The preparation method is simple to operate and can be used for large-scale and industrial production.
6. Skarn is a metamorphic rock, which is mainly composed of calcium-rich or magnesium-rich silicate minerals. The mineral components mainly include garnet, pyroxene and other silicate minerals. Mainly distributed in Anhui, Jiangxi, Gansu, Qinghai, Tibet, Hebei, Hunan, Fujian and other provinces, and the reserves are extremely rich. So that the raw materials of the regulating agent are extremely easy to obtain. The skarn decomposition product contains MgO and Fe by high-temperature calcination3(BO3)O2、Ca3Si3O9And (4) and the like. A phosphate of ferrihydrite water of the formula Fe3(PO4)2·8H2O, the main components are: p2O528.30％，FeO43.0％，H2O28.7 percent. Generally columnar, flat, spherical, flaky, radial, fibrous, soil-like, etc., and has a specific gravity of 2.68. + -. 0.01. Therefore, the regulating agent is a mixture containing magnesium oxide, lime, phosphate, zinc, manganese and sulfur. Hydration of activated magnesium oxide to produce brucite (Mg (OH)2) The layered crystal structure of the hydrate can limit heavy metal cadmium ions between layers, thereby achieving the purpose of fixing and passivating the heavy metal cadmium in the soil. In addition, the calcium and magnesium elements are a large number of elements required by plant growth, and can compete with cadmium ions for ion absorption sites and transport channels on plant root systems, inhibit the absorption and transport of cadmium in soil by the crop root systems, and reduce the accumulation of cadmium in the overground parts and edible parts of crops. Phosphate ions in the phosphate can be combined with cadmium ions in the soil to form precipitates, so that the bioavailability of cadmium in the soil is reduced. Zinc is a trace element necessary for plant growth, cadmium toxicity can be relieved through zinc/cadmium antagonism by applying a zinc fertilizer on cadmium-polluted soil, and meanwhile, zinc and cadmium can compete for operationAbsorption sites on the cell membrane surface of the root system and transport proteins in cells inhibit the absorption and transport of cadmium in soil by the root system of crops, and reduce the accumulation of cadmium in the overground part and the edible part of the crops. The manganese element contained in the manganese salt plays an important role in the processes of photosynthesis, lipid biosynthesis, oxidative stress and the like of plants. Cadmium is a non-essential element for plant growth, and no special transport protein and ion channel exist in plants. Numerous studies have shown that proteins of the Nramp family of proteins in plants are not only involved in the transport of manganese ions, but are also accompanied by the uptake of cadmium ions. Increase the effectiveness of manganese plants in soils and plants, and also inhibit cadmium uptake by plants through manganese and cadmium antagonism. The increase of the content of the available sulfur in the soil can promote the synthesis of sulfur compounds in plants, and the combination of sulfur protein and cadmium in the plants can further inhibit the transport process of the cadmium to seeds in the plants and reduce the absorption accumulation amount of the cadmium in edible parts.
Magnesium oxide and calcium ions generated by calcining the skarn material are effective components of the regulating agent, and phosphate contained in the vivianite material is also the effective component of the regulating agent, so that the effect of the effective components in natural minerals can be fully utilized, and the preparation cost of the regulating agent is reduced.
After the skarn material is calcined, components containing Mg, Fe, B, Si, Ca and the like are generated, and different proportions of Mg, Fe, B and Si in the calcined product can be obtained by adopting different calcination temperatures. In addition, the calcination temperature has certain influence on the activity of MgO, the MgO activity generated by the lower calcination temperature is higher, but the lower calcination temperature also causes the lower CaO content, and the pH value of the soil after hydration is lower, which is not beneficial to the excitation effect on the vivianite material.
In order to ensure the activity of MgO in the calcined product, the preferred calcination temperature of the skarn material is 800-1000 ℃, and the calcination time is 2-3 h.
Detailed Description
The following detailed description of the embodiments of the present invention is provided for the purpose of illustration and not limitation, and should not be construed as limiting the scope of the invention.
The raw materials used in the invention are conventional commercial products unless otherwise specified; the methods used in the present invention are conventional in the art unless otherwise specified.
A regulating agent suitable for alkaline soil heavy metal cadmium pollution remediation is composed of calcined skarn powder, wustite powder, zinc sulfate and manganese salt.
Preferably, the mass ratio of the skarn powder to the vivianite powder to the zinc sulfate to the manganese salt is 1:1:0.5: 1.5-1: 1:3: 4.
The skarn and vivianite materials of the present invention may include skarn and vivianite materials of various purities and varieties.
Preferably, the median particle size of the skarn powder and the vivianite powder is 5-10 mu m, and the maximum content of particles with the particle size larger than 30 mu m is not more than 0.1%;
or the manganese salt is one or more than two of manganese sulfate, manganese acetate, manganese chloride and manganese nitrate.
Preferably, the purity of the zinc sulfate and the manganese salt is industrial grade, and no secondary pollution is caused.
Preferably, the calcined skarn powder is prepared by the steps of:
calcining skarn ore at 800-1000 ℃ for 2-3 h, and grinding to obtain calcined skarn powder.
The preparation method of the regulating agent suitable for the alkaline soil heavy metal cadmium pollution remediation comprises the following steps:
and uniformly mixing the calcined skarn powder, the vivianite powder, the zinc sulfate and the manganese salt to obtain the regulating agent suitable for the heavy metal cadmium pollution remediation of the alkaline soil.
The use method of the regulating agent suitable for the alkaline soil heavy metal cadmium pollution remediation comprises the following steps:
regulating agent according to the following ratio: the heavy metal cadmium-polluted soil is directly applied to the alkaline soil polluted by the heavy metal cadmium in a mass ratio of 1:200-1:500, and the soil can be sown after being uniformly ploughed.
The regulating agent suitable for the alkaline soil heavy metal cadmium pollution remediation is applied to the regulation of the heavy metal cadmium polluted soil.
Preferably, the soil is cadmium-polluted alkaline edible crop field soil; or the soil is weakly alkaline or alkaline cadmium polluted soil, the pH value of the soil is not less than 7 generally, and the soil is dry land.
Preferably, the edible crop is wheat, corn, vegetables or soybean.
Furthermore, the mass ratio of the addition amount of the regulating agent to the heavy metal cadmium-polluted soil is 1:200-1: 500.
Specifically, the preparation and detection are as follows:
example 1 preparation of modulators:
weighing a proper amount of the skarn powder material, placing the skarn powder material in a crucible, placing the crucible in a muffle furnace, and starting heating at a heating rate of 10 ℃/min. And (3) keeping the temperature for 2 hours when the temperature of the muffle furnace is raised to 900 ℃, cooling to obtain a calcined skarn powder material, grinding, and sieving to obtain a sample with the median particle size of 5-10 mu m and the maximum content of particles with the particle size larger than 30 mu m of not more than 0.1% for later use. Mixing the calcined skarn powder material with zinc sulfate and manganese salt according to a certain mass ratio, and stirring for more than 5 minutes by using a stirrer to ensure uniform mixing to prepare the conditioning agent # 1.
Example 2 preparation of modulators:
crushing a vivianite material by a high-speed crusher, sieving to obtain a sample with a median particle size of 5-10 mu m and a maximum particle content of not more than 0.1% with a particle size of more than 30 mu m, mixing the vivianite powder material with zinc sulfate and manganese salt according to a certain mass ratio, stirring for more than 5 minutes by using a stirrer to ensure uniform mixing, and preparing into a regulating agent No. 3.
Example 3 preparation of modulators:
the calcined skarn powder material was mixed with the vivianite powder material, zinc sulfate and manganese salt that had been sieved with a 200 mesh sieve at a certain mass ratio, and stirred with a stirrer for 5 minutes or more to ensure uniform mixing, as in example 1, to prepare control agent # 3.
Example 4 potting experiment:
in order to better verify the regulation and control effect of the regulation and control agent on the cadmium pollution of the alkaline soil, the cadmium pollution degree of the soil is medium, and the soil type is clay, and the cadmium pollution soil of the alkaline wheat field is selected to carry out test verification. In the example, soil of a cadmium-polluted wheat field in a place in Henan province is selected, and the soil type is clay. The planted wheat variety is Shijiazhuang No. 8. The basic physicochemical properties of the soil tested are shown in Table 1.
Table 1 example 4 basic physicochemical properties of soil for potting experiments
Figure BDA0003002995470000071
Example 4
1. Experiment design:
the control agents 1#, 2# and 3# are respectively applied to 5kg of potted soil according to the dosage of 3.0g/kg (soil), 1L of distilled water is added after the control agents are fully and uniformly mixed, soil culture is carried out, the control agents are respectively marked as H1, H2 and H3, 3 repetitions are set for each treatment, a blank control CK is set, 3 repetitions are also set, and the planted wheat variety is Shijiazhuang No. 8. After soil culture for 14 days, wheat seeds are sown in each pot, and after 240 days of growth, wheat is harvested. Respectively collecting a soil sample and a wheat grain sample after the wheat is mature for analysis.
2. And (3) sample analysis:
the effective cadmium content of the soil adopts 0.1M CaCl2The extraction method is used for determining, the content of effective manganese and zinc in the soil is determined by adopting a DTPA extraction method, the total content of cadmium, manganese and zinc in the soil is determined by adopting a nitric acid and hydrofluoric acid digestion method, the effective sulfur in the soil is determined by adopting a barium sulfate turbidimetry method, and the content of cadmium, manganese and zinc in the wheat grains is determined by adopting a nitric acid digestion method. And measuring the extracting solution and the digestion solution obtained after the sample is treated by ICP-MS, and performing quality control on detection data by setting a blank and a standard sample. The regulation effect of the soil regulator on cadmium in wheat grains is determined through pot experiment design.
3. The application effect is as follows:
the pH value of the soil, the effective cadmium, the effective manganese, the effective zinc and the effective sulfur content of the harvested wheat are shown in the table 2. The control treated soil had an average pH of 8.56 and was alkaline, with the pH of the soil being increased to various degrees after the conditioning agents were applied. Compared with a blank control, the content of the cadmium in the effective state of the soil is gradually reduced under the treatment of H1, H2 and H3, wherein the reduction of the content of the cadmium in the effective state of the soil is most obvious under the treatment of H3; the effective manganese content and the effective zinc content of the soil are obviously increased, but the change among H1, H2 and H3 treatments is not obvious; the effective sulfur content of the soil is obviously increased, but the change among H1, H2 and H3 treatments is not obvious and regular.
TABLE 2 soil pH and available cadmium, zinc, manganese and sulfur content after application of control agents
Figure BDA0003002995470000081
The change of cadmium content in the wheat grains in the pot experiment is shown in table 3. In the potting soil without the regulator, the cadmium content of the wheat grains is 0.55 mg/kg; under the treatment of H1, H2 and H3, the cadmium content in the wheat grains is 0.39mg/kg, 0.42mg/kg and 0.25mg/kg respectively, and the reduction rate of the cadmium content is 29.09%, 23.64% and 54.55% respectively, wherein under the treatment of H3, the cadmium content in the wheat grains is obviously reduced compared with that of the wheat grains treated by H2 and H3. Under the treatment of H1, H2 and H3, the zinc content in the wheat grains is obviously increased compared with the control, but the manganese content is not obviously different from that of the blank control. Experimental results prove that the cadmium content in the wheat grains can be effectively reduced after the regulating agent is applied to the alkaline cadmium-polluted soil, the zinc content in the wheat grains is increased, and the wheat quality is improved. The test results of this example demonstrate the reliability of the results of example 3.
TABLE 3 variation of cadmium, Zinc and manganese content in wheat grain after application of conditioning agents
Figure BDA0003002995470000082
Example 5
1. Pot experiment:
in order to better verify the control effect of the alkaline soil cadmium pollution regulating agent on the absorption and accumulation of cadmium in wheat grains, cadmium-polluted alkaline soil of a certain polluted irrigation farmland in Tianjin is continuously selected, and the influence of the regulating agent on the content change of heavy metal cadmium in the soil and the cadmium content of the wheat grains is researched through a pot experiment. The cadmium-polluted alkaline farmland soil of a certain polluted irrigation farmland in Tianjin city selected in the example is tested and tested, and the soil type is moisture soil. The wheat variety planted was Bainong 207. The physicochemical properties of the soil tested are shown in Table 4.
TABLE 4 Pot culture test basic physicochemical properties of soil in certain pollution irrigation area of Tianjin City
Figure BDA0003002995470000083
2. Experiment design:
the control agents 1#, 2# and 3# are respectively applied to 5kg of potted soil according to the dosage of 3.0g/kg (soil), 1L of distilled water is added after the control agents are fully and uniformly mixed, soil culture is carried out, the control agents are respectively marked as T1, T2 and T3, 3 repetitions are set for each treatment, a blank control CK is set, 3 repetitions are also set, and the variety of the planted wheat is Shijiazhuang No. 8. After soil culture for 14 days, wheat seeds are sown in each pot, and after 240 days of growth, wheat is harvested. Respectively collecting a soil sample and a wheat grain sample after the wheat is mature for analysis.
3. And (3) sample analysis:
the effective cadmium content of the soil adopts 0.1M CaCl2The extraction method is used for determining, the content of manganese and zinc in the soil in an effective state is determined by adopting a DTPA extraction method, the total content of cadmium, manganese and zinc in the soil is determined by adopting a nitric acid and hydrofluoric acid digestion method, the soil effective sulfur is determined by adopting a barium sulfate turbidimetry method, and the content of cadmium, manganese and zinc in the wheat grains is determined by adopting a nitric acid digestion method. And measuring the extracting solution and the digestion solution obtained after the sample is treated by ICP-MS, and performing quality control on detection data by setting a blank and a standard sample. The regulation and control effect of the soil regulator on cadmium in wheat grains is determined through pot experiment design.
4. The application effect is as follows:
the pH value of the soil, the effective cadmium, the effective manganese, the effective zinc and the effective sulfur content of the harvested wheat are shown in Table 5. The control treated soil had an average pH of 8.26 and was alkaline, and the pH of the soil was increased to various degrees after the control was applied. Compared with a blank control, the content of the cadmium in the effective state of the soil is gradually reduced under the treatment of T1, T2 and T3, the reduction rate respectively reaches 21.43 percent, 15.87 percent and 38.10 percent, wherein the content of the cadmium in the effective state of the soil is reduced most obviously under the treatment of T3; the effective manganese content and the effective zinc content of the soil are obviously increased, but the change among the T1 treatment, the T2 treatment and the T3 treatment is not obvious; the effective sulfur content of the soil is also obviously increased, but the change among the T1, the T2 and the T3 treatments is also not obviously regular.
TABLE 5 soil pH and cadmium, zinc, manganese and sulfur active state content after application of the conditioning agent
Figure BDA0003002995470000091
The change of cadmium content in the wheat grains of the pot experiment is shown in the table 6. In the potting soil without the regulator, the cadmium content of the wheat grains is 0.32 mg/kg; under the treatment of T1, T2 and T3, the cadmium content in the wheat grains is 0.21mg/kg, 0.24mg/kg and 0.15mg/kg respectively, and the reduction rate of the cadmium content is 34.38%, 25.00% and 53.55% respectively, wherein under the treatment of T3, the cadmium content in the wheat grains is obviously reduced compared with the treatment of T2 and T3. Under the treatment of T1, T2 and T3, the zinc content in the wheat grains is obviously increased compared with the control, but the manganese content is also not obviously different from that of the blank control. Experimental results further verify that the cadmium content in the wheat grains can be effectively reduced after the regulating agent is applied to the alkaline cadmium-polluted soil, meanwhile, the zinc content in the wheat grains is increased, and the wheat quality is improved. The test results of this example further demonstrate the reliability of the results of example 3.
TABLE 6 wheat grain cadmium, Zinc and manganese content changes after application of the conditioning agent
Figure BDA0003002995470000101
The main action mechanism of the soil regulator of the invention which can effectively reduce the cadmium content of wheat grains is as follows:
(1) the regulating agent is applied, so that the contents of magnesium ions, silicon ions, manganese ions, zinc ions, iron ions and phosphate ions in the soil are increased, and the content of effective cadmium capable of being absorbed by the root system of wheat in the soil is effectively reduced;
(2) competitive absorption of magnesium ions, manganese ions, zinc ions and cadmium ions in the soil in the root system of the wheat further reduces the absorption capacity and the absorption amount of the root system of the wheat on the effective cadmium in the soil;
(3) the increase of the effective sulfur content of the soil promotes the synthesis of sulfur-containing compounds in the wheat body, and the combination of sulfur protein and cadmium in the wheat body further inhibits the transport process of cadmium to grains in the wheat body, thereby reducing the cadmium accumulation amount in the wheat grains.
Although the embodiments of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that: various substitutions, changes and modifications are possible without departing from the spirit and scope of the invention and the appended claims, and therefore the scope of the invention is not limited to the embodiments disclosed.

Claims (10)

1. A regulating agent suitable for alkaline soil heavy metal cadmium pollution remediation is characterized in that: the regulating agent consists of calcined skarn powder, vivianite powder, zinc sulfate and manganese salt.
2. The regulator applicable to alkaline soil heavy metal cadmium pollution remediation according to claim 1, wherein: the mass ratio of the skarn powder to the vivianite powder to the zinc sulfate to the manganese salt is 1:1:0.5: 1.5-1: 1:3: 4.
3. The regulator applicable to alkaline soil heavy metal cadmium pollution remediation according to claim 1, wherein: the median particle size of the skarn powder and the vivianite powder is 5-10 mu m, and the maximum content of particles with the particle size larger than 30 mu m is not more than 0.1%;
or the manganese salt is one or more than two of manganese sulfate, manganese acetate, manganese chloride and manganese nitrate.
4. The regulator applicable to alkaline soil heavy metal cadmium pollution remediation according to claim 1, wherein: the purity of the zinc sulfate and the manganese salt is industrial grade, and no secondary pollution is caused.
5. The regulator for repairing heavy metal cadmium polluted by alkaline soil according to any one of claims 1 to 4, wherein the regulator comprises the following components in percentage by weight: the preparation steps of the calcined skarn powder are as follows:
calcining skarn ore at 800-1000 ℃ for 2-3 h, and grinding to obtain calcined skarn powder.
6. A preparation method of the regulator applicable to the remediation of the heavy metal cadmium polluted by the alkaline soil according to any one of claims 1 to 5, wherein the preparation method comprises the following steps: the method comprises the following steps:
and uniformly mixing the calcined skarn powder, the vivianite powder, the zinc sulfate and the manganese salt to obtain the regulating agent suitable for the remediation of the heavy metal cadmium pollution of the alkaline soil.
7. The use method of the regulator applicable to the remediation of heavy metal cadmium polluted by alkaline soil as claimed in any one of claims 1 to 5, wherein the regulator comprises the following steps: the method comprises the following steps:
regulating agent according to the following ratio: the heavy metal cadmium-polluted soil is directly applied to the alkaline soil polluted by the heavy metal cadmium in a mass ratio of 1:200-1:500, and the soil can be sown after being uniformly ploughed.
8. The use of the regulating agent for the remediation of alkaline soil polluted by heavy metal cadmium as claimed in any one of claims 1 to 5 for regulating soil polluted by heavy metal cadmium.
9. Use according to claim 8, characterized in that: the soil is cadmium-polluted alkaline edible crop soil; or the soil is weakly alkaline or alkaline cadmium-polluted soil; or the pH value of the soil is not less than 7, and the soil is dry land.
10. Use according to claim 8 or 9, characterized in that: the mass ratio of the addition amount of the regulating agent to the heavy metal cadmium-polluted soil is 1:200-1: 500.
CN202110354000.1A 2021-04-01 2021-04-01 Regulating agent suitable for alkaline soil heavy metal cadmium pollution remediation, preparation method and application Pending CN113234445A (en)

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