CN110918640A - Method for repairing halohydrocarbon contaminated soil by using industrial iron powder - Google Patents
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Abstract
The invention relates to a method for restoring halohydrocarbon polluted soil by utilizing industrial iron powder, which utilizes the protective effect of a passivation layer on the surface of the industrial iron powder on high-activity zero-valent iron, inhibits the activity of endogenous microorganisms in soil by heating, directly injects passivated zero-valent iron and exogenous thermophilic iron reducing bacteria into the soil to be restored, realizes the controllable removal of the passivation layer of the zero-valent iron by regulating the activity of the thermophilic reducing bacteria, exposes the high-activity zero-valent iron, and realizes the controllable reduction of halohydrocarbon in the soil.
Description
Technical Field
The invention relates to a method for restoring soil polluted by halohydrocarbon by using industrial iron powder.
Background
Halogenated hydrocarbons have a "three-fold" effect, and their control and remediation in soils is of great interest. Chemical reduction is a common halohydrocarbon polluted soil remediation technology, and zero-valent iron is a reducing agent widely used at present due to the advantages of strong reaction activity, environmental protection and the like. However, zero-valent iron still faces some problems during use. The zero-valent iron is unstable in air and is easily oxidized to form a passivation layer, so that the electron transfer between the zero-valent iron and the halogenated hydrocarbon is blocked, and the reduction performance is influenced. The reduction and passivation of zero-valent iron can be enhanced through the iron reducing bacteria, and the degradation efficiency of the chlorinated hydrocarbon is improved. However, exogenous iron reducing bacteria are directly added into soil, and are difficult to survive and exert a reducing effect, because the soil environment is complex, endogenous microorganisms in the soil often generate an inhibiting effect on the growth of the exogenous iron reducing bacteria through nutrition competition, so that the exogenous iron reducing bacteria are difficult to effectively remove a passivation layer of zero-valent iron, high-activity zero-valent iron is difficult to effectively release, and the removal effect on halogenated hydrocarbon pollutants in the soil is limited.
Disclosure of Invention
Aiming at the defects in the prior art, the invention discloses a method for repairing halohydrocarbon polluted soil by utilizing industrial iron powder, which inhibits the metabolic activity of endogenous microorganisms by heating and raising the temperature of the soil and provides proper temperature conditions for exogenous thermophilic reducing bacteria. The activity of the thermophilic reducing bacteria is regulated and controlled by regulating and controlling the temperature and the nutritional conditions of the thermophilic reducing bacteria, so that the iron powder passivation layer can be removed controllably; exposing high-activity zero-valent iron to realize the controllable reduction of halogenated hydrocarbon in the soil; after the remediation goal is achieved, exogenous microorganisms are inactivated and endogenous microorganisms in the soil are allowed to act again by restoring the original temperature of the soil.
The method specifically comprises the following steps:
(1) the soil is heated to inhibit the metabolic activity of endogenous microorganisms, so that the activity and the competitiveness of exogenous microorganism thermophilic iron reducing bacteria in a field are enhanced;
(2) preparing biochar by taking biomass materials as raw materials, and mixing the biochar with industrial iron powder to obtain a biochar-iron powder composite material;
(3) the biochar-iron powder composite material and the thermophilic iron reducing bacteria are injected into soil, the metabolic activity of the thermophilic iron reducing bacteria is regulated and controlled through a nutrient, the exposure rate of active zero-valent iron is controlled, and the controllable reduction of halogenated hydrocarbons in the soil is realized; the growth environment of the thermophilic iron reducing bacteria is regulated and controlled by the nutrient, the metabolic activity of the thermophilic iron reducing bacteria is improved, and the exposure rate of zero-valent iron can be further enhanced. Thus, the thermophilic iron reducing bacteria can be in required reaction activity, and the exposure rate of active zero-valent iron is controlled.
(4) After the remediation goal is achieved, exogenous microorganisms are inactivated and endogenous microorganisms in the soil are allowed to act again by restoring the original temperature of the soil.
The thermophilic iron reducing bacteria in the step (1) are anaerobic bacteria, are thermophilic and can show activity at 40-65 ℃, and comprise Caldanaeerovra acetiginens, Bacillus infernus, Thermoterrabacter ferrerium reducens, Thermoanaerobumferrivorum or Ferroglobisplaceus and the like.
The soil heating temperature in the step (1) can inhibit the metabolic activity of endogenous microorganisms, so that the activity and the competitiveness of exogenous microorganism thermophilic iron reducing bacteria in a field are enhanced. The soil heating temperature is 40-65 ℃.
The biomass material in the step (2) comprises straw, fruit shell, pig manure and the like. The biochar and the iron powder are subjected to ball milling to obtain the biochar-iron powder composite material.
The halogenated hydrocarbon in the step (3) comprises at least one of halogenated aromatic hydrocarbon, aliphatic hydrocarbon and the like.
The addition amount of the biochar-iron powder composite material is 0.2-4% of the mass of the polluted soil. The addition amount of the biochar is less than 10% of that of the biological-iron powder composite material.
Compared with the prior art, the invention has the beneficial effects that:
the invention utilizes heating to inhibit the activity of soil endogenous microorganisms and provides proper temperature conditions for exogenous thermophilic reducing bacteria. The activity of the exogenous thermophilic microorganisms is controlled by changing the growth conditions of the exogenous thermophilic microorganisms, such as a nutrient and the environmental temperature, so that the removal process of the zero-valent iron passivation layer is regulated and controlled, and the controllable reduction of the halogenated hydrocarbon in the soil is realized. The method uses cheap industrial iron powder, changes the harm into the benefit through the activity control of thermophilic reducing bacteria, changes a passivation layer which has the effect of hindering the activity of high-activity zero-valent iron into a protective layer for protecting the zero-valent iron, ensures that the iron powder reaches a target point position and exerts high activity, and reduces the repair cost.
The invention adopts a chemical reduction method to remove halogenated hydrocarbon substances, actually is the reduction dehalogenation process of zero-valent iron to halogenated hydrocarbon, the added thermophilic reducing bacteria play a role in regulating and controlling the exposure of high-activity zero-valent iron, can be used for removing high-concentration halogenated hydrocarbon, and has the advantages of high reaction rate and high efficiency compared with a simple microbial degradation mode.
After the restoration target is achieved, the activity of the endogenous microorganisms in the soil can be restored by restoring the soil temperature, and the exogenous thermophilic iron reducing bacteria are inactivated to restore the original state of the ecological system.
The iron powder, the carbonaceous material and the exogenous microorganisms are combined to play a synergistic effect among the iron powder, the carbonaceous material and the exogenous microorganisms, so that the efficient controllable reduction of the halogenated hydrocarbons in the soil is realized.
Detailed Description
In order to better understand the contents of the present invention, the following examples are given to further illustrate the present invention, but the scope of the present invention is not limited by the examples.
Example 1
Collecting carbon tetrachloride (80mg/kg) polluted soil of a certain pesticide factory in Tianjin City. The contaminated soil is heated to 60 ℃ to inhibit the activity of endogenous microorganisms in the soil. Thermophilic reducing bacteria, a biochar-iron powder composite material and tap water are added into the polluted soil, the adding amount of the biochar-iron powder composite material is 0.5 percent of the mass of the soil, and a stirrer is used for stirring to fully mix the biochar-iron powder composite material, the thermophilic reducing bacteria and soil particles. Then, a nutrient (namely a culture medium) is injected to ensure that the thermophilic reducing bacteria fully exert the activity, and the biochar-iron powder composite material fully reacts with carbon tetrachloride in soil for 3 days, so that the carbon tetrachloride is reduced. After the implementation of the embodiment, the content of carbon tetrachloride in the soil is reduced to 0.5 mg/kg. After the restoration is finished, the soil temperature is restored, the growth of exogenous microorganisms is inhibited, and the original ecological environment of the soil is restored.
Culturing thermophilic reducing bacteria: the desired strain, Thermoterrabacter ferrireducens, was purchased. The Erlenmeyer flask containing 1L of the medium was inoculated with Thermoterrabacter ferrireducens and incubated at 120rpm for 72 hours at 60 ℃ with shaking. The culture medium comprises: glycerol (40mmol/L), sodium lactate (20mmol/L), 1, 2-propanediol (20mmol/L), glycerate (20mmol/L), pyruvate (20mmol/L) and yeast powder (5 g/L).
Preparing a biochar-iron powder composite material: taking air-dried corn straws as a raw material, crushing the air-dried corn straws to be less than 2mm by a crusher, placing the crushed air-dried corn straws in a muffle furnace for anaerobic heating at 350 ℃ for 2 hours to obtain corn straw biochar; the biochar-iron powder composite material is obtained by the ball milling method of the biochar and the iron powder, and the biochar accounts for 2% of the total mass of the composite material.
Example 2
Collecting carbon tetrachloride (80mg/kg) polluted soil of a certain pesticide factory in Tianjin City. The contaminated soil was heated to 60 ℃ to inhibit endogenous microbial activity. Thermophilic reducing bacteria, a biochar-iron powder composite material and tap water are added into the polluted soil, the adding amount of the biochar-iron powder composite material is 0.3 percent of the mass of the soil, and a stirrer stirs the materials to ensure that the biochar-iron powder composite material, the thermophilic reducing bacteria and soil particles are completely mixed. And (4) injecting a nutrient, and stirring by a stirrer to ensure that the thermophilic reducing bacteria fully exert the activity. The biochar-iron powder composite material fully reacts with carbon tetrachloride in soil for 5 days, so that the carbon tetrachloride is reduced. After the implementation of the embodiment, the content of carbon tetrachloride in the soil is reduced to 7 mg/kg. After the restoration is finished, the soil temperature is restored, the growth of exogenous microorganisms is inhibited, and the original ecological environment of the soil is restored.
Culturing thermophilic reducing bacteria: the desired strain, Thermoterrabacter ferrireducens, was purchased. The Erlenmeyer flask containing 1L of the medium was inoculated with Thermoterrabacter ferrireducens and incubated at 120rpm for 72 hours at 50 ℃ with shaking. The culture medium comprises: glycerol (40mmol/L), sodium lactate (20mmol/L), 1, 2-propanediol (20mmol/L), glycerate (20mmol/L), pyruvate (20mmol/L) and yeast powder (5 g/L).
Preparing a biochar-iron powder composite material: taking air-dried pig manure as a raw material, crushing the pig manure by a crusher to be less than 2mm, placing the crushed pig manure in a muffle furnace for anaerobic heating at 350 ℃ for 2h to obtain the pig manure biochar. The biochar-iron powder composite material is obtained by the ball milling method of the biochar and the iron powder, and the proportion of the biochar is 2%.
Example 3
Collecting the soil polluted by trichloroethylene (94 mg/kg). The contaminated soil was heated to 55 ℃ to inhibit the growth of endogenous microorganisms. Thermophilic reducing bacteria, a biochar-iron powder composite material and tap water are added into the polluted soil, the adding amount of the biochar-iron powder composite material is 0.5 percent of the mass of the soil, and a stirrer stirs the materials to ensure that the biochar-iron powder composite material, the thermophilic reducing bacteria and soil particles are completely mixed. And (3) injecting a nutrient, stirring by a stirrer to enable the thermophilic reducing bacteria to fully exert activity, and fully reacting the biochar-iron powder composite material with the trichloroethylene in the soil for 4 days so as to reduce the trichloroethylene. After the implementation of the embodiment, the content of the trichloroethylene in the soil is reduced to 9 mg/kg. After the restoration is finished, the soil temperature is restored, the growth of exogenous microorganisms is inhibited, and the original ecological environment of the soil is restored.
Culturing thermophilic reducing bacteria: the desired strain, Thermoterrabacter ferrireducens, was purchased. The Erlenmeyer flask containing 1L of the medium was inoculated with Thermoterrabacter ferrireducens and incubated at 120rpm and 55 ℃ for 72 hours with shaking. The culture medium comprises: glycerol (40mmol/L), sodium lactate (20mmol/L), 1, 2-propanediol (20mmol/L), glycerate (20mmol/L), pyruvate (20mmol/L) and yeast powder (5 g/L).
Preparing a biochar-iron powder composite material: taking air-dried pig manure as a raw material, crushing the pig manure by a crusher to be less than 2mm, placing the crushed pig manure in a muffle furnace for anaerobic heating at 350 ℃ for 2h to obtain the pig manure biochar. The biochar-iron powder composite material is obtained by the ball milling method of the biochar and the iron powder, and the proportion of the biochar is 2%.
Example 4
Collecting the soil polluted by certain trichloroethylene (90 mg/kg). The contaminated soil was heated to 55 ℃ to inhibit the growth of endogenous microorganisms. Thermophilic reducing bacteria, a biochar-iron powder composite material and tap water are added into the polluted soil, and the adding amount of the biochar-iron powder composite material is 0.3 percent of the soil mass. And stirring by a stirrer to completely mix the biochar-iron powder composite material, the thermophilic reducing bacteria and the soil particles. Injecting a nutrient, stirring by a stirrer to enable thermophilic reducing bacteria to fully exert activity, and fully reacting the biochar-iron powder composite material with trichloroethylene in soil for 4 days so as to reduce the trichloroethylene. After the implementation of the embodiment, the content of the trichloroethylene in the soil is reduced to 5 mg/kg. After the restoration is finished, the soil temperature is restored, the growth of exogenous microorganisms is inhibited, and the original ecological environment of the soil is restored.
Culturing thermophilic reducing bacteria: the desired strain, Thermoterrabacter ferrireducens, was purchased. The Erlenmeyer flask containing 1L of the medium was inoculated with Thermoterrabacter ferrireducens and incubated at 120rpm and 55 ℃ for 72 hours with shaking. The culture medium comprises: glycerol (40mmol/L), sodium lactate (20mmol/L), 1, 2-propanediol (20mmol/L), glycerate (20mmol/L), pyruvate (20mmol/L) and yeast powder (5 g/L).
Preparing a biochar-iron powder composite material: taking air-dried pig manure as a raw material, crushing the pig manure by a crusher to be less than 2mm, placing the crushed pig manure in a muffle furnace for anaerobic heating at 550 ℃ for 2h to obtain the pig manure biochar. The biochar-iron powder composite material is obtained by the ball milling method of the biochar and the iron powder, and the proportion of the biochar is 1.5%.
Example 5
Some polychlorinated biphenyl (PCB-52) (5.5mg/kg) contaminated soil was collected. The contaminated soil was heated to 55 ℃ to inhibit the growth of endogenous microorganisms. Thermophilic reducing bacteria, a corn straw biochar-zero-valent iron composite material and tap water are added into the polluted soil, the adding amount of the biochar-iron powder composite material is 0.5 percent of the mass of the soil, and a stirrer stirs the materials to ensure that the biochar-iron powder composite material, the thermophilic reducing bacteria and soil particles are completely mixed. And (3) injecting a nutrient, stirring by a stirrer to enable the thermophilic reducing bacteria to fully exert activity, and fully reacting the biochar-iron powder composite material with the polychlorinated biphenyl in the soil for 5 days so as to reduce the polychlorinated biphenyl. After the implementation of the embodiment, the content of the PCB-52 in the soil is reduced to 1.2 mg/kg. After the restoration is finished, the soil temperature is restored, the growth of exogenous microorganisms is inhibited, and the original ecological environment of the soil is restored.
Culturing thermophilic reducing bacteria: the desired strain, Caldanaeerovrga acegignens, was purchased. Erlenmeyer flasks containing 1L of medium were inoculated with Caldanarovorga acetignens and shake-cultured at 55 ℃ for 72h at 120 rpm. The culture medium comprises: KH (Perkin Elmer)2PO4(0.272g/L)，NH4Cl(0.5g/L)，(NH4)2SO4(0.5g/L)，NaHCO3(1.5g/L), N-tris (hydroxymethyl) methyl-3-aminopropanesulfonic acid buffer (2.43g/L), MgCl2(0.02g/L)，CaCl2(0.015g/L), 1mL vitamin solution and 1mLNa2SeO3-Na2WO3And (3) solution.
Preparing a biochar-iron powder composite material: taking air-dried corn straws as raw materials, crushing the raw materials to be less than 2mm by a crusher, placing the crushed materials in a muffle furnace to be anaerobic and heated for 2 hours at 350 ℃ to obtain the corn straw biochar. The biochar-iron powder composite material is obtained by the ball milling method of the biochar and the iron powder, and the proportion of the biochar is 2%.
Example 6
Collecting some polybrominated diphenyl ether contaminated soil (the concentrations of BDE-47, BDE-153, BDE-183 and BDE-209 are 1mg/kg, 0.8mg/kg and 5mg/kg respectively). The polybrominated diphenyl ether contaminated soil is heated to 55 ℃ to inhibit the growth of endogenous microorganisms. Thermophilic reducing bacteria, a corn straw biochar-iron powder composite material and tap water are added into the polluted soil, the adding amount of the biochar load-iron powder composite material is 0.5 percent of the mass of the soil, and a stirrer stirs the materials to ensure that the biochar-iron powder composite material, the thermophilic reducing bacteria and soil particles are completely mixed. And (3) injecting a nutrient, stirring by a stirrer to enable thermophilic reducing bacteria to fully exert activity, and fully reacting the biochar-iron powder composite material with the polybrominated diphenyl ethers in the soil for 5 days so as to reduce the polybrominated diphenyl ethers. After this example was performed, the concentrations of BDE-47, BDE-153, BDE-183 and BDE-209 in the soil were reduced to 0.04mg/kg, 0.05mg/kg, 0.04mg/kg and 0.2 mg/kg. After the restoration is finished, the soil temperature is restored, the growth of exogenous microorganisms is inhibited, and the original ecological environment of the soil is restored.
Culturing thermophilic reducing bacteria: the desired strain, Caldanaeerovrga acegignens, was purchased. Erlenmeyer flasks containing 1L of medium were inoculated with Caldanarovorga acetignens and shake-cultured at 55 ℃ for 72h at 120 rpm. The culture medium comprises: KH (Perkin Elmer)2PO4(0.272g/L)，NH4Cl(0.5g/L)，(NH4)2SO4(0.5g/L)，NaHCO3(1.5g/L), N-tris (hydroxymethyl) methyl-3-aminopropanesulfonic acid buffer (2.43g/L), MgCl2(0.02g/L)，CaCl2(0.015g/L), 1mL vitamin solution and 1mLNa2SeO3-Na2WO3And (3) solution.
Preparing a biochar-iron powder composite material: taking the air-dried fruit shell as a raw material, crushing the fruit shell into the particle size of less than 2mm by a crusher, placing the crushed fruit shell in a muffle furnace to be anaerobic and heated for 2 hours at 350 ℃ to obtain the fruit shell biochar. The biochar-iron powder composite material is obtained by the ball milling method of the biochar and the iron powder, and the proportion of the biochar is 2%.
Example 7
Collecting carbon tetrachloride (80mg/kg) polluted soil of a certain pesticide factory in Tianjin City. Heating the carbon tetrachloride-polluted soil to 40 ℃, and inhibiting the activity of endogenous microorganisms in the soil; adding the obtained thermophilic reducing bacteria, the biochar-iron powder composite material and tap water into the polluted soil, wherein the adding amount of the biochar-iron powder composite material is 0.5 percent of the mass of the soil, and stirring by a stirrer to fully mix the biochar-iron powder composite material, the thermophilic reducing bacteria and soil particles. And then raising the temperature of the soil, injecting a nutrient to gradually activate the thermophilic iron reducing bacteria, raising the temperature of the soil to 60 ℃ and keeping the temperature so that the thermophilic iron reducing bacteria fully exert the activity, and fully reacting the biochar-iron powder mixed material with carbon tetrachloride in the soil for 3 days so as to reduce the carbon tetrachloride. The activity is gradually generated at the target site, the dosage of the medicament is reduced, and meanwhile, the embodiment can obviously reduce the energy consumption. After the implementation of this example, the carbon tetrachloride in the soil was reduced to 0.5 mg/kg. After the restoration is finished, the soil temperature is restored, the growth of exogenous microorganisms is inhibited, and the original ecological environment of the soil is restored.
Culturing thermophilic reducing bacteria: the desired strain, Thermoterrabacter ferrireducens, was purchased. The Erlenmeyer flask containing 1L of the medium was inoculated with Thermoterrabacter ferrireducens and incubated at 120rpm for 72 hours at 60 ℃ with shaking. The culture medium comprises: glycerol (40mmol/L), sodium lactate (20mmol/L), 1, 2-propanediol (20mmol/L), glycerate (20mmol/L), pyruvate (20mmol/L) and yeast powder (5 g/L).
Biochar-iron powder composite: taking air-dried corn straws as a raw material, crushing the air-dried corn straws to be less than 2mm by a crusher, placing the crushed air-dried corn straws in a muffle furnace for anaerobic heating at 350 ℃ for 2 hours to obtain corn straw biochar; the biochar-iron powder composite material is obtained by the ball milling method of the biochar and the iron powder, and the biochar accounts for 2% of the total mass of the composite material.
The method is used for soil remediation, utilizes the protective effect of the passivation layer on the surface of iron powder on high-activity zero-valent iron, directly injects passivated zero-valent iron and exogenous thermophilic iron reducing bacteria into soil to be remedied by heating and inhibiting the activity of endogenous microorganisms in the soil, changes the injection rate of nutrients, regulates and controls the activity of thermophilic reducing bacteria, controls the removal process of the passivation layer on the surface of iron, realizes the controllable removal of the passivation layer of the zero-valent iron, exposes the high-activity zero-valent iron, and realizes the controllable reduction of halogenated hydrocarbons in the soil.
Nothing in this specification is said to apply to the prior art.
Claims (8)
1. A method for repairing halohydrocarbon polluted soil by using industrial iron powder has an inhibiting effect on the growth of soil endogenous microorganisms through heat treatment, and provides a proper temperature condition for exogenous thermophilic iron reducing bacteria; the activity of thermophilic reducing bacteria is regulated and controlled by regulating and controlling the nutritional conditions, so that the iron powder passivation layer can be removed controllably; the exposed high-activity zero-valent iron realizes the controllable reduction of the halogenated hydrocarbon in the soil; after the restoration goal is achieved, the exogenous microorganisms are inactivated by restoring the original temperature of the soil, and the endogenous microorganisms of the soil play a role again.
2. The method for remediating halogenated hydrocarbon contaminated soil using industrial iron powder as claimed in claim 1, wherein the method comprises the steps of:
(1) the soil is heated to inhibit the metabolic activity of endogenous microorganisms, so that the activity and the competitiveness of exogenous thermophilic iron reducing bacteria in a field are enhanced;
(2) preparing biochar by taking biomass materials as raw materials, and mixing the biochar with industrial iron powder to obtain a biochar-iron powder composite material;
(3) the biochar-iron powder composite material and the thermophilic iron reducing bacteria are injected into soil, the metabolic activity of the thermophilic iron reducing bacteria is regulated and controlled through a nutrient, the exposure rate of active zero-valent iron is controlled, and the controllable reduction of halogenated hydrocarbons in the soil is realized;
(4) after the restoration goal is achieved, the original temperature of the soil is restored, so that the exogenous microorganisms are inactivated, the endogenous microorganisms of the soil play a role again, and the original ecological system of the soil is restored.
3. The method for remediating halogenated hydrocarbon contaminated soil using industrial iron powder as claimed in claim 2, wherein said thermophilic iron-reducing bacteria of step 1 are anaerobic bacteria, are thermophilic, and exhibit activity at 40-65 ℃, and include Caldanaeerovirgaacetiginens, Bacillus inferus, Thermoterabacter ferricerides, Thermovinabaum ferriganovorum or Ferroglobisplacecidus, etc.
4. The method for remediating halogenated hydrocarbon contaminated soil by using industrial iron powder as claimed in claim 2, wherein the soil heating temperature in the step (1) is 40-65 ℃.
5. The method for remediating halogenated hydrocarbon contaminated soil by using industrial iron powder as claimed in claim 2, wherein the biomass material in the step (2) comprises at least one of straw, fruit shell or pig manure.
6. The method for remediating halogenated hydrocarbon contaminated soil with industrial iron powder as claimed in claim 2, wherein the halogenated hydrocarbon in the step (3) comprises at least one of halogenated aromatic hydrocarbon and halogenated aliphatic hydrocarbon.
7. The method for remediating halogenated hydrocarbon contaminated soil by using industrial iron powder as claimed in claim 2, wherein the addition amount of the biochar-iron powder composite material is 0.2-5% of the contaminated soil by mass; the addition amount of the biochar is less than 10% of that of the biochar-iron powder composite material.
8. The method for remediating halocarbon-contaminated soil using industrial iron powder as claimed in claim 2, wherein the metabolic activity of the thermophilic iron-reducing bacteria is gradually increased by gradually adding a nutrient required for the growth of the thermophilic iron-reducing bacteria after the biochar-iron powder composite and the thermophilic iron-reducing bacteria are injected into the soil in the step (3).
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| CN115338245A (en) * | 2022-07-19 | 2022-11-15 | 广州珠矶科技有限公司 | Method for removing soil organic matter by efficiently catalyzing sodium persulfate |
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| CN114921388B (en) * | 2022-04-11 | 2023-09-15 | 河北工业大学 | Iron-reducing flora and application thereof |
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