CN112226234A - Soil remediation agent for heavy metal pollution and preparation and use methods thereof - Google Patents

Soil remediation agent for heavy metal pollution and preparation and use methods thereof Download PDF

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CN112226234A
CN112226234A CN202011170172.5A CN202011170172A CN112226234A CN 112226234 A CN112226234 A CN 112226234A CN 202011170172 A CN202011170172 A CN 202011170172A CN 112226234 A CN112226234 A CN 112226234A
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soil
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soil remediation
remediation agent
heavy metal
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张锦琇
张文洁
张文博
寇军胜
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Shaanxi Sanwei Zhike Ecological Industry Co ltd
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Shaanxi Sanwei Zhike Ecological Industry Co ltd
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K17/00Soil-conditioning materials or soil-stabilising materials
    • C09K17/40Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B09DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09CRECLAMATION OF CONTAMINATED SOIL
    • B09C1/00Reclamation of contaminated soil
    • B09C1/08Reclamation of contaminated soil chemically
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B09DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09CRECLAMATION OF CONTAMINATED SOIL
    • B09C1/00Reclamation of contaminated soil
    • B09C1/10Reclamation of contaminated soil microbiologically, biologically or by using enzymes
    • B09C1/105Reclamation of contaminated soil microbiologically, biologically or by using enzymes using fungi or plants
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2101/00Agricultural use

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Abstract

The invention discloses a soil remediation agent for heavy metal pollution and preparation and use methods thereof, belongs to the technical field of soil remediation, and aims to solve the problems of high cost and poor treatment effect in the treatment process of heavy metal polluted soil. The soil remediation agent comprises the following raw materials: complex microbial inoculum, complex biological enzyme; the preparation method of the soil remediation agent comprises the steps of culturing the compound microbial inoculum, preparing the compound biological enzyme, preparing the mixed material and fermenting and hydrolyzing; the soil remediation agent is used in an amount of 0.5-1% by weight of the soil. The preparation method can ensure the matching effect of the raw materials to the greatest extent, so that the finally produced soil remediation agent can restore heavy metal pollution, has a cleaning function and improves soil activity; the use is convenient and quick, and the economic and ecological benefits are achieved; has great popularization prospect.

Description

Soil remediation agent for heavy metal pollution and preparation and use methods thereof
Technical Field
The invention belongs to the technical field of soil remediation, and particularly relates to a heavy metal contaminated soil remediation agent and preparation and use methods thereof.
Background
According to the survey bulletin of national soil pollution status published by the ministry of environmental protection and the ministry of national resources 2014: the national environment condition is not optimistic, the soil pollution of partial areas is heavy, the quality of the cultivated land soil environment is great, and the environmental problem of industrial and mining waste soil is prominent. The artificial activities of the industrial and mining industry, the agriculture and the like and the high background value of the soil environment are main causes of soil pollution or exceeding standards.
The total overproof rate of national soil pollution is 16.1%, wherein the proportion of slightly, moderately and severely polluted points is 11.2%, 2.3%, 1.5% and 1.1% respectively. The pollution type is mainly inorganic type, organic type is secondary, the specific gravity of the composite type pollution is small, and the number of the exceeding standard points of the inorganic pollutants accounts for 82.8 percent of the exceeding standard points of China.
The current common pollution mode is heavy metal pollution, and the main pollutants are cadmium, nickel, copper, arsenic, mercury, lead and the like. The heavy metal pollution sources of soil are wide, including mining, smelting, chemical industry, leather making, dye and other industrial three wastes and automobile exhaust emission, the heavy metal pollutants are generated and discharged by agriculture of sewage irrigation, sludge, municipal garbage and the like, and enter surface water, underground water and the atmosphere, and finally are collected in the soil, so that the heavy metal content in the soil is overhigh, and the heavy metal pollution of the soil is caused.
Fundamentally, the main approaches to contaminated soil remediation may include: (1) changing the existing form of the pollutants in the soil or combining the pollutants with the soil, and reducing the mobility and bioavailability of the pollutants in the environment, namely stabilizing; (2) the concentration of toxic substances in the soil is reduced.
Different treatment measures and methods have been created around these two approaches: namely engineering treatment measures (soil improvement method, electrochemical method and washing complexation method) and agronomic control measures (pH value increase, EH adjustment, organic fertilizer application and ion antagonism). The heavy metal pollution of the soil is treated by engineering, the soil with heavy pollution and small area has the advantages of obvious and rapid treatment effect, but the farmland polluted soil with large pollution area, light degree and wide range needs to consume a large amount of manpower and financial resources, and the damage of the soil structure and the reduction of the soil fertility are easily caused. Therefore, the development of a low-cost, simple, efficient and environment-friendly soil remediation agent is of great significance.
The soil restoration agents in the market are roughly divided into chemical restoration agents and composite restoration agents, the chemical restoration agents can only restore heavy metals, but the soil polluted by the heavy metals is saline-alkaline and relatively barren, and after the single chemical restoration agent is applied, the soil needs to be ploughed and fertilized; the composite repairing agent is formed by adding some raw materials with fertility on the basis of the chemical repairing agent and is approved by the combination of the chemical repairing agent and the biological organic fertilizer; however, microbial products such as microbial agents, decomposition agents and bacterial fertilizers in a large number of bio-organic fertilizers in domestic markets are simply applied to normal soil, the survival of the bacterial strains in the polluted soil and the polluted soil in the repairing process is not considered, the used bacterial strains are single, even if two or three kinds of bacteria are simply mixed, the microbial products are far from insufficient in the adaptability aspect of special soil environments, if the survival problem cannot be solved after the bacterial strains are applied, the important expectations for improving the soil fertility and improving the quality and the efficiency in the composite repairing agent are all in a null line, so how to scientifically mix the bacterial strains can be well adapted and survive in the polluted soil and the polluted soil in the repairing process is the key for realizing the heavy metal pollution repairing and the soil fertility improvement of the composite repairing agent.
Disclosure of Invention
The invention aims to provide a soil remediation agent for heavy metal pollution, and aims to solve the problems of high cost and single treatment effect in the soil treatment process of the existing soil remediation agent.
The invention also aims to provide the soil remediation agent for heavy metal pollution and a preparation and use method thereof, so as to solve the problems of long fermentation period, difficult control of fermentation degree and long use and remediation period of the existing soil remediation agent.
In order to solve the problems, the technical scheme of the invention is as follows:
the soil remediation agent for heavy metal pollution comprises the following raw materials: complex microbial inoculum, complex biological enzyme; the compound microbial inoculum comprises: 15-20 parts of bacillus cereus, 20-25 parts of copper green pseudomonas, 15-20 parts of lactobacillus bulgaricus, 15-20 parts of lactobacillus acidophilus, 15-20 parts of pasteurella and 15-20 parts of pseudomonas reptilis; the compound biological enzyme comprises: 10-15 parts of solid amylase, 10-15 parts of solid laccase, 25-35 parts of solid cellulase, 20-25 parts of solid urease and 20-25 parts of solid phytase.
Furthermore, the raw materials of the soil remediation agent also comprise mixed materials; the mixed material comprises: 60-75 parts of attapulgite powder, 15-25 parts of phytochemicals, 15-20 parts of livestock and poultry manure and 5-10 parts of ammonium sulfate.
Further, the soil remediation agent comprises the following composite bacteria agent, composite biological enzyme and mixed materials in percentage by weight: 0.5%: 0.03%: 1.
furthermore, the livestock manure is any one or any combination of pig manure, sheep manure and poultry manure, and the water content of the livestock manure is 20-35%.
Further, the phytochemicals comprise any one or any combination of soybean meal, bran, rice bran and rapeseed meal.
Furthermore, the soil repairing agent contains water, and the water content is 20-30 percent of the water content.
The preparation method of the soil remediation agent for heavy metal pollution comprises the following steps:
step A, culturing a complex microbial inoculum;
the formula of the lactobacillus bulgaricus culture medium is as follows: 5.3g to 5.6g of glucose, 0.8g to 1.1g of peptone, 0.4g to 0.7g of dipotassium hydrogen phosphate, 100mL of distilled water and 6.4 to 6.6 of PH value; sterilizing at 118 deg.C for 15 min; inoculating with an inoculation amount of 2%, and culturing at a constant temperature of 37 ℃ for 24 h;
the bacillus cereus culture medium comprises the following components in percentage by weight: 2.5 to 3.5 percent of soluble starch, 1.5 to 2.5 percent of bean cake powder, 0.25 to 0.35 percent of dipotassium hydrogen phosphate, MgSO4 & 7H20.01 to 0.03 percent of O and CaCl20.01% -0.02%; pH7.2, the culture temperature is 25 ℃, the rotating speed is 250r/min, and the inoculation amount is 7 percent;
the formula of the copper green pseudomonas culture medium is as follows: gelatin peptone 15.5-16.5 g, tryptone 9.0-11.0 g, K2SO49.5g-10.6g,MgCl21.2g to 1.6g, 0.15g to 0.25g of hexadecyl trimethylamine bromide and 1000mL of distilled water; sterilizing at 121 deg.C for 15min at pH of 7.1 + -0.2; culturing at 36 + -1 deg.C for 40-48 h;
the culture medium formula of the acidophilic lactobacillus comprises: 3 to 5 percent of corn steep liquor, 1 to 2 percent of beef extract and 0.5 to 1.5 percent of lactose; culturing at 34 deg.C for 20 h;
the culture medium formula of the pasteurella comprises: 38g-44g of mannitol, 22g-28g of soyabean peptone, 2.0g-3.5g of ammonium chloride, 9.5g-10.5g of sodium chloride and 1000mL of distilled water; the pH is 8.0, the optimum culture condition is 30 ℃, the rotating speed of a shaking table is 200r/min, the inoculation amount is 4.0% (V/V), and the bottling amount is 75mL/250 mL;
the culture medium formula of the reptile pseudomonas is as follows: 15.5-16.5 g of gelatin peptone, 9-11 g of tryptone and K2SO49.5g-10.6g,MgCl21.2g to 1.6g, 0.15g to 0.25g of hexadecyl trimethylamine bromide and 1000mL of distilled water; final pH7.1 + -0.2;
step B, preparing compound biological enzyme;
respectively taking 10-15 parts of solid amylase, 10-15 parts of solid laccase, 25-35 parts of solid cellulase, 20-25 parts of solid urease and 20-25 parts of solid phytase according to parts by weight, and mixing the components to prepare the composite biological enzyme;
step C, preparing a mixed material;
respectively taking 60-75 parts of attapulgite powder, 15-25 parts of phytochemicals, 15-20 parts of livestock and poultry manure and 5-10 parts of ammonium sulfate according to the parts by weight, and dry-mixing the materials uniformly by using a power mixer to obtain a mixed material;
step D, adding water to prepare a raw material of the soil remediation agent;
taking the compound biological enzyme accounting for 0.03 percent of the weight of the mixed material and the compound microbial inoculum accounting for 0.5 percent of the weight of the mixed material, and adding the taken compound biological enzyme and the compound microbial inoculum into the mixed material; adding a proper amount of water, and fully and uniformly mixing by using a dynamic mixer, wherein the water content in the uniformly mixed material is kept between 30 and 40 percent to form a raw material of the soil remediation agent;
step E, fermentation and enzymolysis;
and D, pouring the raw material of the soil remediation agent obtained in the step D into a fermentation tank for enzymolysis and fermentation, wherein after the continuous enzymolysis and fermentation is carried out for 21-25 days, the temperature begins to decrease, and when the temperature is reduced to be lower than 45 ℃, the enzymolysis and fermentation are completed, so that the soil remediation agent is obtained.
And further, controlling the internal enzymolysis and fermentation temperature of the raw material of the soil remediation agent in the step E at 45-60 ℃, and turning and cooling when the internal temperature of the raw material of the soil remediation agent exceeds 60 ℃.
Further, the soil remediation agent and the heavy metal contaminated soil are turned and mixed evenly, and remediation of the heavy metal contaminated soil is completed after 25-30 days.
The soil repairing agent is used in an amount of 0.5-1% by weight based on the weight of the soil.
The invention has the following beneficial effects:
(1) the invention utilizes the biological action of the compound microbial inoculum and the compound biological enzyme, wherein the compound biological bacteria can decompose various mineral substances in soil, release more than 20 medium trace elements necessary for plants such as nitrogen, phosphorus, potassium, calcium, magnesium, sulfur, iron, manganese, boron, copper, zinc, molybdenum, chlorine and the like and nutrients required by plants such as magnesium aluminum silicate, turquoise, silicic acid and the like, increase the soil fertility, and activate the self-regulation function of the soil to form a healthy nutrient cycle supply system, thereby achieving healthy ecological soil and ensuring the plant growth to be in the optimal state; in the enzymolysis and fermentation process, compound biological enzyme is added, the aim is to break the cell and tissue structure of organic matters, decompose macromolecular substances such as crude fiber, lignin, semi-fiber, protein and the like into micromolecular organic matters convenient for microorganisms to absorb and utilize, and can promote the adsorption and decomposition functions of the microorganisms, thereby shortening the fermentation time in preparation; meanwhile, the process reduces or removes the organic waste and the heavy metal ions in the soil, completes the soil remediation and prevents the crops planted in the soil from being affected by the heavy metal pollution.
(2) The microorganism in the composite microbial inoculum in the repairing agent has strong affinity to heavy metals, heavy metal ions can be distributed at different parts in cells after entering the cells, Metallothionein (MT) can be synthesized in the cells, and the MT is low molecular weight protein with strong affinity and has the functions of enriching and inhibiting toxicity to the heavy metals; meanwhile, microorganisms in the composite microbial inoculum in the repairing agent can disturb the chemical form of the metal elements by releasing inorganic and organic acids to the surrounding environment outside the cells, and the organic compound outside the cells contains low molecular weight organic matters with a multifunctional group molecular structure, which can change the form of soluble metal ions and make the soluble metal ions precipitate;
in particular, the copper green pseudomonas and the reptile pseudomonas have strong enrichment effect on cadmium (Cd), lead (Pb) and zinc (Zn); the copper green pseudomonas can reduce Hg2+ into Hg to form harmless vapor which is volatilized to the atmosphere to reduce the toxicity of ionic mercury to the soil environment; bacillus cereus, Lactobacillus bulgaricus and Pasteurella have strong enrichment effect on cadmium (Cd), nickel (Ni) and cobalt (Co); acidophilic lactobacillus can oxidize ferrous iron, low-valent sulfur and the like;
meanwhile, the five enzymes in the formula of the soil conditioner play a role in catalyzing the process, so that the applied compound microbial inoculum and the compound biological enzyme can adapt to and survive in the polluted soil, the basic effects of common components of soil conditioners such as attapulgite, phytochemicals, livestock and poultry manure, ammonium sulfate and the like can be fully exerted, the compound microbial inoculum and the compound biological enzyme generate a synergistic effect, and the remarkable effects of efficiently repairing heavy metal pollution and quickly improving the soil fertility are achieved.
(3) The repairing agent releases beneficial ions through the ion exchange effect, absorbs heavy metal ions into the attapulgite, loses the activity of harmful heavy metal elements, is prevented from transferring to crops, reduces the activity of heavy metals, and improves the soil production capacity.
(4) Compared with the traditional repairing agent preparation mechanism and the effect thereof, the preparation method disclosed by the invention is simple, the raw materials are easy to obtain, the cost is low, the preparation is simple and easy, and the popularization and application values are extremely high.
(5) The preparation method can ensure the matching effect of the raw materials to the greatest extent, so that the finally produced soil remediation agent can restore heavy metal pollution, has a cleaning function and improves soil activity; the compound biological enzyme plays an important role in the enzymolysis process and the nutrient releasing process, releases elements such as phosphorus, potassium, calcium, iron and the like fixed in soil for crops to absorb through synergistic effects such as decomposition, complexation, covalent modification and the like after entering the soil, provides nutrient elements for farmlands, greatly reduces the using amount of chemical fertilizers, greatly reduces the soil repairing cost, and has economic and ecological benefits; further leading farmers to more willingly use the soil remediation agent which can plant green products with real meaning, and having great popularization prospect.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all embodiments of the present invention.
Thus, the following detailed description of embodiments of the invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention.
Example 1
Firstly, the soil remediation agent for heavy metal pollution described in the present example was prepared as follows.
Step A, culturing a complex microbial inoculum;
lactobacillus bulgaricus culture medium: 5.43g of glucose, 0.98g of peptone, 0.59g of dipotassium phosphate, 100mL of distilled water and 6.4-6.6 of PH value; sterilizing at 118 deg.C for 15 min; inoculating with an inoculation amount of 2%, and culturing at a constant temperature of 37 ℃ for 24 h;
bacillus cereus culture medium: 3.0% of soluble starch, 2.0% of bean cake powder, 0.3% of dipotassium phosphate, MgSO4 & 7H2O0.02% and CaCl20.01%; pH7.2, culture temperature 25 deg.C, rotation speed 250r/min, and inoculum size 7%.
Copper green pseudomonas culture medium: 16.0g of gelatin peptone, 10.0g of tryptone, 10.0g of K2SO410.0g of MgCl21.4g of agar, 0.2g of hexadecyl trimethylamine bromide and 1000mL of distilled water; sterilizing at 121 deg.C for 15min at pH of 7.1 + -0.2; culturing at 36 + -1 deg.C for 40-48 h.
Culture medium of acidophilic lactobacillus: 3% of corn steep liquor, 1% of beef extract and 1% of lactose; culturing at 34 deg.C for 20 h.
Pasteur bacillus culture medium: 40g of mannitol, 25g of soybean peptone, 3g of ammonium chloride, 10g of sodium chloride and 1000mL of distilled water; the pH is 8.0, the optimum culture condition is 30 ℃, the rotating speed of a shaking table is 200r/min, the inoculation amount is 4.0% (V/V), and the bottling amount is 75mL/250 mL.
A reptile-feeding pseudomonas culture medium: formulation (per liter): 16.0g of gelatin peptone, 10.0g of tryptone, 10.0g of K2SO410.0g of MgCl21.4g of cetyltrimethylammonium bromide; final pH 7.1. + -. 0.2.
Step B, preparing compound biological enzyme;
respectively taking 12 parts of solid amylase, 13 parts of solid laccase, 30 parts of solid cellulase, 23 parts of solid urease and 22 parts of solid phytase according to the parts by weight, and mixing the components to prepare the composite biological enzyme.
Secondly, preparing the mixed material for the heavy metal polluted soil remediation agent;
68 parts of attapulgite powder, 20 parts of phytochemicals, 18 parts of livestock and poultry manure and 8 parts of ammonium sulfate are respectively taken according to the parts by weight and are mixed uniformly by a power mixer to form a mixed material.
Thirdly, preparing a raw material of the soil remediation agent for heavy metal pollution;
taking the compound biological enzyme accounting for 0.03 percent of the weight of the mixed material and the compound microbial inoculum accounting for 0.5 percent of the weight of the mixed material, and adding the taken compound biological enzyme and the compound microbial inoculum into the mixed material; adding a proper amount of water, and fully and uniformly mixing by using a dynamic mixer, wherein the water content in the uniformly mixed materials is kept about 30-40 percent, so as to form the raw material of the soil remediation agent.
Fourthly, preparing the soil remediation agent for heavy metal pollution, which is disclosed by the embodiment;
pouring the raw materials of the soil remediation agent into a fermentation tank for enzymolysis and fermentation, after the continuous enzymolysis and fermentation is carried out for 21-25 days, the temperature begins to drop, when the temperature is reduced to be lower than 45 ℃, the enzymolysis and fermentation are finished, and the soil remediation agent is obtained, in the process, the internal enzymolysis and fermentation temperature of the raw materials of the soil remediation agent is controlled to be 45-60 ℃, and when the internal temperature of the raw materials of the soil remediation agent exceeds 60 ℃, the soil remediation agent is turned over and cooled.
Fifthly, the soil remediation agent for heavy metal pollution, which is provided by the embodiment, is used
(1) The laboratory repair process:
the test soil is collected from a heavy metal pollution area of a tailing pond, the content of heavy metals in the surface layer of the soil in the area is higher than the agricultural land soil pollution risk control value of soil environment quality agricultural land soil pollution risk control standard (GB15618-2018), and specific data are shown in table 1.
Repairing according to the actual condition of pollution.
Performing a leaching test on the soil by adopting an overturning oscillator according to a leaching toxicity leaching method sulfuric acid-nitric acid method (HJ/T299-2007) of the original soil waste, and detecting the heavy metal concentration of the soil before and after remediation; a group of blank experiments without using the soil remediation agent are carried out at the same time in the above experiments, and the same experiment conditions are kept to be used as a control group.
Test groups: weighing 500g of 10-mesh test heavy metal polluted air-dried soil sample, fully mixing the soil remediation agent and the soil to be tested after the application amount of the soil remediation agent is 1% of the weight of the dry soil (the amount of the soil to be converted into the field is 150 kg/mu), putting the mixture into a plastic cup, adding 122mL of deionized water, simulating and keeping the field water holding capacity to be about 70% in the whole experiment process, sealing the plastic cup with a preservative film, forming small holes in the plastic cup, putting the plastic cup into a constant-temperature incubator, and keeping the temperature to be 25 ℃.
After 30 days of co-cultivation, the soil was taken out and the contents of heavy metal ions- -copper, cadmium, zinc, lead and arsenic- -in the test soil were measured again, and the results are shown in Table 1.
TABLE 1 comparison table of contents of heavy metal ions before and after soil remediation in laboratory
Figure RE-DEST_PATH_IMAGE001
Table 1 shows: after the soil remediation agent is used in a laboratory in a quantitative manner, the concentration of heavy metal ions is remarkably reduced, and the soil remediation agent has a remarkable heavy metal polluted soil remediation effect.
(2) The field repairing process comprises the following steps:
selecting a test field I located in a new Lanzhou area, wherein the heavy metal content in the soil surface layer of the test field is higher than the agricultural land soil pollution risk control value of soil environment quality agricultural land soil pollution risk control standard (GB15618-2018), and the specific data are shown in Table 1.
Repairing according to the actual condition of pollution.
Test groups: according to the water content measurement of a test field, 150 kg/mu of soil remediation agent is used in the test field (the application amount is 1 percent of the weight of dry soil), the soil remediation agent is ploughed by 15cm-25cm after being used, the water retention is ensured in the whole experiment process, the field water retention is kept about 70 percent, and the temperature is kept to be about 25 +/-3 ℃ by matching with a plastic greenhouse.
A group of blank experiments without using the soil remediation agent are simultaneously carried out beside the test field, and the same test conditions are kept to be used as a control group.
After the soil samples are repaired for 45 days, the soil samples are sampled randomly and divided, and the contents of heavy metal ions, namely copper, cadmium, zinc, lead and arsenic, in the test soil are measured again after the samples are dried, sieved and prepared, and the results are shown in table 2.
Table 2 heavy metal ion type and nutrient content comparison table before and after field soil remediation
Figure 28591DEST_PATH_IMAGE002
Table 2 shows: after the soil remediation agent is used in a large field according to a certain amount, the concentration of heavy metal ions is also obviously reduced, and the fertilizer efficiency is obviously improved.
The soil remediation agent has the advantages of stable remediation effect, simple and easy application in the field, fertilizer effect and excellent popularization prospect.
Example 2
Firstly, the soil remediation agent for heavy metal pollution described in the present example was prepared as follows.
Step A, culturing a complex microbial inoculum;
the formula of the lactobacillus bulgaricus culture medium is as follows: 5.3g of glucose, 0.8g of peptone, 0.4g of dipotassium hydrogen phosphate, 100mL of distilled water and 6.4 of PH value; sterilizing at 118 deg.C for 15 min; inoculating with 2% of inoculum size, and culturing at 37 deg.C for 24 hr.
The bacillus cereus culture medium comprises the following components in percentage by weight: 2.5 percent of soluble starch, 1.5 percent of bean cake powder, 0.25 percent of dipotassium hydrogen phosphate, MgSO4 & 7H2O0.01% and CaCl20.01 percent; pH7.2, culture temperature 25 deg.C, rotation speed 250r/min, and inoculum size 7%.
The formula of the copper green pseudomonas culture medium is as follows: gelatin peptone 15.5g, tryptone 9.0g, K2SO49.5gg,MgCl21.2g, 0.15gg of hexadecyl trimethylamine bromide and 1000mL of distilled water; sterilizing at 121 deg.C for 15min at pH of 7.1 + -0.2; culturing at 36 +/-1 deg.C for 40 hr.
The culture medium formula of the acidophilic lactobacillus comprises: 3% of corn steep liquor, 1% of beef extract and 0.5% of lactose; culturing at 34 deg.C for 20 h.
The culture medium formula of the pasteurella comprises: 38g of mannitol, 22g of soybean peptone, 2.0g of ammonium chloride, 9.5g of sodium chloride and 1000mL of distilled water; the pH is 8.0, the optimum culture condition is 30 ℃, the rotating speed of a shaking table is 200r/min, the inoculation amount is 4.0% (V/V), and the bottling amount is 75mL/250 mL.
The culture medium formula of the reptile pseudomonas is as follows: gelatin peptone 15.5g, tryptone 9g, K2SO49.5g,MgCl21.2g, 0.15g of hexadecyl trimethylamine bromide and 1000mL of distilled water; final pH 7.1. + -. 0.2.
Secondly, preparing the mixed material for the heavy metal polluted soil remediation agent;
60 parts of attapulgite powder, 15 parts of phytochemicals, 15 parts of livestock and poultry manure and 5 parts of ammonium sulfate are respectively taken according to the parts by weight and are mixed uniformly by a power mixer to form a mixed material.
Thirdly, preparing a raw material of the soil remediation agent for heavy metal pollution;
taking the compound biological enzyme accounting for 0.03 percent of the weight of the mixed material and the compound microbial inoculum accounting for 0.5 percent of the weight of the mixed material, and adding the taken compound biological enzyme and the compound microbial inoculum into the mixed material; adding a proper amount of water, and fully and uniformly mixing by using a dynamic mixer, wherein the water content in the uniformly mixed materials is kept about 30-40 percent, so as to form the raw material of the soil remediation agent.
Fourthly, preparing the soil remediation agent for heavy metal pollution, which is disclosed by the embodiment;
pouring the raw materials of the soil remediation agent into a fermentation tank for enzymolysis and fermentation, after the continuous enzymolysis and fermentation is carried out for 21-25 days, the temperature begins to drop, when the temperature is reduced to be lower than 45 ℃, the enzymolysis and fermentation are finished, and the soil remediation agent is obtained, in the process, the internal enzymolysis and fermentation temperature of the raw materials of the soil remediation agent is controlled to be 45-60 ℃, and when the internal temperature of the raw materials of the soil remediation agent exceeds 60 ℃, the soil remediation agent is turned over and cooled.
Fifthly, the soil remediation agent for heavy metal pollution, which is provided by the embodiment, is used
(1) The laboratory repair process:
the test soil is collected from a heavy metal pollution area of a tailing pond, the content of heavy metals in the surface layer of the soil in the area is higher than the agricultural land soil pollution risk control value of soil environment quality agricultural land soil pollution risk control standard (GB15618-2018), and specific data are shown in table 3.
Repairing according to the actual condition of pollution.
Performing a leaching test on the soil by adopting an overturning oscillator according to a leaching toxicity leaching method sulfuric acid-nitric acid method (HJ/T299-2007) of the original soil waste, and detecting the heavy metal concentration of the soil before and after remediation; a group of blank experiments without using the soil remediation agent are carried out at the same time in the above experiments, and the same experiment conditions are kept to be used as a control group.
Test groups: weighing 500g of 10-mesh test heavy metal polluted air-dried soil sample, fully mixing the soil remediation agent and the soil to be tested after the application amount of the soil remediation agent is 1% of the weight of the dry soil (the amount of the soil to be converted into the field is 150 kg/mu), putting the mixture into a plastic cup, adding 122mL of deionized water, simulating and keeping the field water holding capacity to be about 70% in the whole experiment process, sealing the plastic cup with a preservative film, forming small holes in the plastic cup, putting the plastic cup into a constant-temperature incubator, and keeping the temperature to be 25 ℃.
After 30 days of co-cultivation, the soil was taken out and the contents of heavy metal ions- -copper, cadmium, zinc, lead and arsenic- -in the test soil were measured again, and the results are shown in Table 3.
Table 3 comparison table of contents of heavy metal ions before and after soil remediation in laboratory
Figure RE-DEST_PATH_IMAGE003
Table 1 shows: after the soil remediation agent is used in a laboratory in a quantitative manner, the concentration of heavy metal ions is remarkably reduced, and the soil remediation agent has a remarkable heavy metal polluted soil remediation effect.
(2) The field repairing process comprises the following steps:
selecting a test field II in a new Lanzhou region, wherein the heavy metal content in the soil surface layer of the test field is higher than the agricultural land soil pollution risk control value of soil environment quality agricultural land soil pollution risk control standard (GB15618-2018), and the specific data are shown in Table 3.
Repairing according to the actual condition of pollution.
Test groups: according to the water content measurement of a test field, 150 kg/mu of soil remediation agent is used in the test field (the application amount is 1 percent of the weight of dry soil), the soil remediation agent is ploughed by 15cm-25cm after being used, the water retention is ensured in the whole experiment process, the field water retention is kept about 70 percent, and the temperature is kept to be about 25 +/-3 ℃ by matching with a plastic greenhouse.
A group of blank experiments without using the soil remediation agent are simultaneously carried out beside the test field, and the same test conditions are kept to be used as a control group.
After the soil samples are repaired for 45 days, the soil samples are sampled randomly and divided, and the contents of heavy metal ions, namely copper, cadmium, zinc, lead and arsenic, in the test soil are measured again after the samples are dried, sieved and prepared, and the results are shown in table 4.
Table 4 heavy metal ion type and nutrient content comparison table before and after field soil remediation
Figure 309181DEST_PATH_IMAGE004
Table 4 shows: after the soil remediation agent is used in a large field according to a certain amount, the concentration of heavy metal ions is also obviously reduced, and the fertilizer efficiency is obviously improved.
The soil remediation agent has the advantages of stable remediation effect, simple and easy application in the field, fertilizer effect and excellent popularization prospect.
Example 3
Firstly, the soil remediation agent for heavy metal pollution described in the present example was prepared as follows.
Step A, culturing a complex microbial inoculum;
the formula of the lactobacillus bulgaricus culture medium is as follows: 5.6g of glucose, 1.1g of peptone, 0.7g of dipotassium hydrogen phosphate, 100mL of distilled water and 6.6 of PH value; sterilizing at 118 deg.C for 15 min; inoculating with 2% of inoculum size, and culturing at 37 deg.C for 24 hr.
The bacillus cereus culture medium comprises the following components in percentage by weight: 3.5 percent of soluble starch, 2.5 percent of bean cake powder, 0.35 percent of dipotassium phosphate, MgSO4 & 7H2O0.03% and CaCl20.02 percent; pH7.2, culture temperature 25 deg.C, rotation speed 250r/min, and inoculum size 7%.
Culture medium for copper green pseudomonasThe formula is as follows: gelatin peptone 16.5g, tryptone 11.0g, K2SO410.6g,MgCl21.6g, 0.25g of hexadecyl trimethylamine bromide and 1000mL of distilled water; sterilizing at 121 deg.C for 15min at pH of 7.1 + -0.2; culturing at 36 +/-1 deg.C for 48 hr.
The culture medium formula of the acidophilic lactobacillus comprises: 5% of corn steep liquor, 2% of beef extract and 1.5% of lactose; culturing at 34 deg.C for 20 h.
The culture medium formula of the pasteurella comprises: 44g of mannitol, 28g of soybean peptone, 3.5g of ammonium chloride, 10.5g of sodium chloride and 1000mL of distilled water; the pH is 8.0, the optimum culture condition is 30 ℃, the rotating speed of a shaking table is 200r/min, the inoculation amount is 4.0% (V/V), and the bottling amount is 75mL/250 mL.
The culture medium formula of the reptile pseudomonas is as follows: gelatin peptone 16.5g, tryptone 11g, K2SO410.6g,MgCl21.6g, 0.25g of hexadecyl trimethylamine bromide and 1000mL of distilled water; final pH 7.1. + -. 0.2.
Secondly, preparing the mixed material for the heavy metal polluted soil remediation agent;
respectively taking 75 parts of attapulgite powder, 25 parts of phytochemicals, 20 parts of livestock and poultry manure and 10 parts of ammonium sulfate according to the parts by weight, and dry-mixing the attapulgite powder, the phytochemicals, the livestock and poultry manure and the ammonium sulfate uniformly by using a power mixer to obtain a mixed material.
Thirdly, preparing a raw material of the soil remediation agent for heavy metal pollution;
taking the compound biological enzyme accounting for 0.03 percent of the weight of the mixed material and the compound microbial inoculum accounting for 0.5 percent of the weight of the mixed material, and adding the taken compound biological enzyme and the compound microbial inoculum into the mixed material; adding a proper amount of water, and fully and uniformly mixing by using a dynamic mixer, wherein the water content in the uniformly mixed materials is kept about 30-40 percent, so as to form the raw material of the soil remediation agent.
Fourthly, preparing the soil remediation agent for heavy metal pollution, which is disclosed by the embodiment;
pouring the raw materials of the soil remediation agent into a fermentation tank for enzymolysis and fermentation, after the continuous enzymolysis and fermentation is carried out for 21-25 days, the temperature begins to drop, when the temperature is reduced to be lower than 45 ℃, the enzymolysis and fermentation are finished, and the soil remediation agent is obtained, in the process, the internal enzymolysis and fermentation temperature of the raw materials of the soil remediation agent is controlled to be 45-60 ℃, and when the internal temperature of the raw materials of the soil remediation agent exceeds 60 ℃, the soil remediation agent is turned over and cooled.
Fifthly, the soil remediation agent for heavy metal pollution, which is provided by the embodiment, is used
(1) The laboratory repair process:
the test soil is collected from a heavy metal pollution area of a tailing pond, the content of heavy metals in the surface layer of the soil in the area is higher than the agricultural land soil pollution risk control value of soil environment quality agricultural land soil pollution risk control standard (GB15618-2018), and specific data are shown in table 1.
Repairing according to the actual condition of pollution.
Performing a leaching test on the soil by adopting an overturning oscillator according to a leaching toxicity leaching method sulfuric acid-nitric acid method (HJ/T299-2007) of the original soil waste, and detecting the heavy metal concentration of the soil before and after remediation; a group of blank experiments without using the soil remediation agent are carried out at the same time in the above experiments, and the same experiment conditions are kept to be used as a control group.
Test groups: weighing 500g of 10-mesh test heavy metal polluted air-dried soil sample, fully mixing the soil remediation agent and the soil to be tested after the application amount of the soil remediation agent is 1% of the weight of the dry soil (the amount of the soil to be converted into the field is 150 kg/mu), putting the mixture into a plastic cup, adding 122mL of deionized water, simulating and keeping the field water holding capacity to be about 70% in the whole experiment process, sealing the plastic cup with a preservative film, forming small holes in the plastic cup, putting the plastic cup into a constant-temperature incubator, and keeping the temperature to be 25 ℃.
After 30 days of co-cultivation, the soil was taken out and the contents of heavy metal ions- -copper, cadmium, zinc, lead and arsenic- -in the test soil were measured again, and the results are shown in Table 5.
TABLE 5 comparison table of contents of heavy metal ions before and after soil remediation in laboratory
Figure RE-DEST_PATH_IMAGE005
Table 5 shows: after the soil remediation agent is used in a laboratory in a quantitative manner, the concentration of heavy metal ions is remarkably reduced, and the soil remediation agent has a remarkable heavy metal polluted soil remediation effect.
(2) The field repairing process comprises the following steps:
selecting a test field III located in a new Lanzhou area, wherein the heavy metal content in the soil surface layer of the test field is higher than the agricultural land soil pollution risk control value of soil environment quality agricultural land soil pollution risk control standard (GB15618-2018), and the specific data are shown in Table 5.
Repairing according to the actual condition of pollution.
Test groups: according to the water content measurement of a test field, 150 kg/mu of soil remediation agent is used in the test field (the application amount is 1 percent of the weight of dry soil), the soil remediation agent is ploughed by 15cm-25cm after being used, the water retention is ensured in the whole experiment process, the field water retention is kept about 70 percent, and the temperature is kept to be about 25 +/-3 ℃ by matching with a plastic greenhouse.
A group of blank experiments without using the soil remediation agent are simultaneously carried out beside the test field, and the same test conditions are kept to be used as a control group.
After the soil samples are repaired for 45 days, the soil samples are sampled randomly and divided, and the contents of heavy metal ions, namely copper, cadmium, zinc, lead and arsenic, in the test soil are measured again after the samples are dried, sieved and prepared, and the results are shown in table 6.
TABLE 6 heavy metal ion type and nutrient content comparison table before and after field soil remediation
Figure 151235DEST_PATH_IMAGE006
Table 6 shows: after the soil remediation agent is used in a large field according to a certain amount, the concentration of heavy metal ions is also obviously reduced, and the fertilizer efficiency is obviously improved.
The soil remediation agent has the advantages of stable remediation effect, simple and easy application in the field, fertilizer effect and excellent popularization prospect.
Limited by the space of the specification, only 3 representative examples are listed, but the soil remediation agent of the invention achieves excellent results on the improvement of the soil polluted by heavy metal in the test fields of Lanzhou new districts and the test fields of elms, and the improved test fields are all put into cultivation and are used for the test fields of the fertilizer efficiency of organic fertilizers of related companies.

Claims (10)

1. A soil remediation agent for heavy metal contamination, characterized by: the soil remediation agent comprises the following raw materials: complex microbial inoculum, complex biological enzyme;
the complex microbial inoculum comprises: 15-20 parts of bacillus cereus, 20-25 parts of copper green pseudomonas, 15-20 parts of lactobacillus bulgaricus, 15-20 parts of lactobacillus acidophilus, 15-20 parts of pasteurella and 15-20 parts of pseudomonas reptilis;
the compound biological enzyme comprises: 10-15 parts of solid amylase, 10-15 parts of solid laccase, 25-35 parts of solid cellulase, 20-25 parts of solid urease and 20-25 parts of solid phytase.
2. The soil remediation agent for heavy metal contamination of claim 1, wherein: also comprises a mixed material;
the mixed material comprises: 60-75 parts of attapulgite powder, 15-25 parts of phytochemicals, 15-20 parts of livestock and poultry manure and 5-10 parts of ammonium sulfate.
3. The soil remediation agent for heavy metal contamination of claim 2, wherein: the soil remediation agent comprises the following components in percentage by weight: 0.5%: 0.03%: 1.
4. the soil remediation agent for heavy metal contamination of claim 2, wherein: the livestock and poultry manure is any one or any combination of pig manure, sheep manure and poultry manure, and the water content of the livestock and poultry manure is 20-35%.
5. The soil remediation agent for heavy metal contamination of claim 2, wherein: the phytochemicals comprise one or more of soybean meal, bran, rice bran and rapeseed meal.
6. The soil remediation agent for heavy metal contamination of any one of claims 3-5, wherein: the soil restoration agent contains water, and the water content is 20-30%.
7. The method of claim 6, wherein said method comprises the steps of:
the method comprises the following steps:
step A, culturing a complex microbial inoculum;
the formula of the lactobacillus bulgaricus culture medium is as follows: 5.3g to 5.6g of glucose, 0.8g to 1.1g of peptone, 0.4g to 0.7g of dipotassium hydrogen phosphate, 100mL of distilled water and 6.4 to 6.6 of PH value; sterilizing at 118 deg.C for 15 min; inoculating with an inoculation amount of 2%, and culturing at a constant temperature of 37 ℃ for 24 h;
the bacillus cereus culture medium comprises the following components in percentage by weight: 2.5 to 3.5 percent of soluble starch, 1.5 to 2.5 percent of bean cake powder, 0.25 to 0.35 percent of dipotassium hydrogen phosphate, MgSO4 & 7H20.01 to 0.03 percent of O and CaCl20.01% -0.02%; pH7.2, the culture temperature is 25 ℃, the rotating speed is 250r/min, and the inoculation amount is 7 percent;
the formula of the copper green pseudomonas culture medium is as follows: gelatin peptone 15.5-16.5 g, tryptone 9.0-11.0 g, K2SO49.5g-10.6g,MgCl21.2g to 1.6g, 0.15g to 0.25g of hexadecyl trimethylamine bromide and 1000mL of distilled water; sterilizing at 121 deg.C for 15min at pH of 7.1 + -0.2; culturing at 36 + -1 deg.C for 40-48 h;
the culture medium formula of the acidophilic lactobacillus comprises: 3 to 5 percent of corn steep liquor, 1 to 2 percent of beef extract and 0.5 to 1.5 percent of lactose; culturing at 34 deg.C for 20 h;
the culture medium formula of the pasteurella comprises: 38g-44g of mannitol, 22g-28g of soyabean peptone, 2.0g-3.5g of ammonium chloride, 9.5g-10.5g of sodium chloride and 1000mL of distilled water; the pH is 8.0, the optimum culture condition is 30 ℃, the rotating speed of a shaking table is 200r/min, the inoculation amount is 4.0% (V/V), and the bottling amount is 75mL/250 mL;
the culture medium formula of the reptile pseudomonas is as follows: 15.5-16.5 g of gelatin peptone, 9-11 g of tryptone and K2SO49.5g-10.6g,MgCl21.2g to 1.6g, 0.15g to 0.25g of hexadecyl trimethylamine bromide and 1000mL of distilled water; final pH7.1 + -0.2;
step B, preparing compound biological enzyme;
respectively taking 10-15 parts of solid amylase, 10-15 parts of solid laccase, 25-35 parts of solid cellulase, 20-25 parts of solid urease and 20-25 parts of solid phytase according to parts by weight, and mixing the components to prepare the composite biological enzyme;
step C, preparing a mixed material;
respectively taking 60-75 parts of attapulgite powder, 15-25 parts of phytochemicals, 15-20 parts of livestock and poultry manure and 5-10 parts of ammonium sulfate according to the parts by weight, and dry-mixing the materials uniformly by using a power mixer to obtain a mixed material;
step D, adding water to prepare a raw material of the soil remediation agent;
taking the compound biological enzyme accounting for 0.03 percent of the weight of the mixed material and the compound microbial inoculum accounting for 0.5 percent of the weight of the mixed material, and adding the taken compound biological enzyme and the compound microbial inoculum into the mixed material; adding a proper amount of water, and fully and uniformly mixing by using a dynamic mixer, wherein the water content in the uniformly mixed material is kept between 30 and 40 percent to form a raw material of the soil remediation agent;
step E, fermentation and enzymolysis;
and D, pouring the raw material of the soil remediation agent obtained in the step D into a fermentation tank for enzymolysis and fermentation, wherein after the continuous enzymolysis and fermentation is carried out for 21-25 days, the temperature begins to decrease, and when the temperature is reduced to be lower than 45 ℃, the enzymolysis and fermentation are completed, so that the soil remediation agent is obtained.
8. The method of claim 7, wherein said method comprises the steps of: and step E, controlling the internal enzymolysis and fermentation temperature of the raw materials of the soil remediation agent to be 45-60 ℃, and turning and cooling when the internal temperature of the raw materials of the soil remediation agent exceeds 60 ℃.
9. The method of using a soil remediation agent for heavy metal contamination of claim 8, wherein: the soil remediation agent and the heavy metal contaminated soil are turned and mixed evenly, and the remediation of the heavy metal contaminated soil is completed after 25-30 days.
10. The method of using a soil remediation agent for heavy metal contamination of claim 9, wherein: the using weight of the soil remediation agent is 0.5-1% of the weight of the soil.
CN202011170172.5A 2020-10-28 2020-10-28 Soil remediation agent for heavy metal pollution and preparation and use methods thereof Pending CN112226234A (en)

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Application publication date: 20210115