CN115156279B - Method for killing iron sulfur oxidizing bacteria in pyrite mountain acid soil by utilizing biogas slurry and reconstructing mine soil microorganism population - Google Patents

Method for killing iron sulfur oxidizing bacteria in pyrite mountain acid soil by utilizing biogas slurry and reconstructing mine soil microorganism population Download PDF

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CN115156279B
CN115156279B CN202210724287.7A CN202210724287A CN115156279B CN 115156279 B CN115156279 B CN 115156279B CN 202210724287 A CN202210724287 A CN 202210724287A CN 115156279 B CN115156279 B CN 115156279B
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biogas slurry
soil
pyrite
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mountain
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CN115156279A (en
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董滨
陈思思
孙相娟
徐祖信
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Tongji University
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    • 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

Abstract

The invention relates to a method for killing iron sulfur oxidizing bacteria in pyrite mountain acid soil by utilizing biogas slurry and reconstructing mine soil microorganism population, which comprises the following steps: pretreatment of biogas slurry: removing impurities, quenching and tempering pretreatment and deodorization treatment are carried out on the biogas slurry to obtain biogas slurry A, and then a compound stabilizer is added to obtain biogas slurry B; and (3) sterilization period treatment: loosening soil on the surface layer of the pyrite mountain, spraying biogas slurry B, simultaneously turning and mixing, and then maintaining; oxygen consumption period treatment: loosening the soil on the surface layer of the pyrite mountain, spraying biogas slurry B, simultaneously turning and mixing, and then naturally maintaining; consolidation period treatment: spraying biogas slurry A, covering the surface layer with charcoal, and naturally maintaining to finish the treatment. Compared with the prior art, the method can solve the problem of acidic wastewater of the pyrite mountain, can recover nitrogen, phosphorus, amino acid and other resources from the acidic wastewater, improves the structure and fertility of the soil of the pyrite mountain, is beneficial to plant growth, and is convenient for subsequent ecological greening of the pyrite mountain.

Description

Method for killing iron sulfur oxidizing bacteria in pyrite mountain acid soil by utilizing biogas slurry and reconstructing mine soil microorganism population
Technical Field
The invention relates to ecological restoration of mines and sludge recycling treatment, in particular to a method for killing iron-sulfur oxidizing bacteria in pyrite mountain acid soil by using biogas slurry and reconstructing a mine soil microorganism population.
Background
After mining, the ecological environment of the land is seriously destroyed, and natural disasters such as landslide, debris flow and the like frequently occur. In particular, pyrite mountain mining is also constantly producing acidic mine wastewater (Acid mine drainage, AMD) containing large amounts of sulfate and heavy metal ions. AMD can permanently affect the environment, especially soil, water resources and aquatic communities, even under extreme conditions where heavy metals can enter the food chain, threatening animal, plant and human health. Thus, the ecological restoration of mine land, especially the blocking of AMD in sulfur-containing mine soil, is unprecedented. AMD is produced by oxidation of sulphide minerals in the presence of oxygen, water and microorganisms (iron sulphur oxidising bacteria such as thiobacillus thiooxidans, thiobacillus ferrooxidans etc.). Thus, reducing contact of metal sulfide minerals with water and air or inhibiting microbial activity can greatly reduce the production of AMD, reduce the acidity and heavy metal concentration of AMD, and thereby reduce pollution. Killing iron-sulfur oxidizing bacteria, creating low-oxygen environment and inhibiting the metabolic activity of iron-sulfur oxidizing bacteria plays a key role in blocking AMD pollution.
The biogas slurry is a liquid formed by fermenting organic substances, and contains abundant nitrogen, phosphorus, potassium and other macronutrient elements and zinc and other trace nutrient elements, amino acid, active enzyme, auxin and the like. Because the nutrient elements basically exist in the form of available nutrients, the biogas slurry has strong available nutrient capacity in theory, is a multi-element available compound fertilizer, and can be used for seed soaking, foliage fertilizer spraying, nutrient soil mixing, flower and fruit preserving agents, soilless culture mother liquor, flower planting and the like. However, a series of problems exist in the practical application of biogas slurry in engineering, such as the concentration of ammonia nitrogen and the concentration of volatile fatty acid are too high, the seedlings are easy to burn, and the seedlings need to be retted in advance before application; the biogas slurry contains a large amount of substances which emit odor, and large-area odor pollution is formed during application; the biogas slurry contains new pollutants such as pathogenic bacteria, antibiotics and the like, and can cause ecological environment pollution when used for cultivated lands and urban forest lands.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for killing iron-sulfur oxidizing bacteria in the acidic soil of the pyrite mountain by utilizing biogas slurry and reconstructing a mine soil microorganism population. Not only can solve the problem of acid wastewater of the pyrite mountain, but also can synchronously solve the treatment and disposal of biogas slurry, recover nitrogen, phosphorus, amino acid and other resources from the biogas slurry, improve the structure and fertility of the soil of the pyrite mountain, ensure that the soil is favorable for the growth of plants and is convenient for the subsequent ecological greening of the mine.
The aim of the invention can be achieved by the following technical scheme:
a method for killing iron sulfur oxidizing bacteria in acid soil of a pyrite mountain by utilizing biogas slurry and reconstructing a mine soil microorganism population, comprising the following steps:
pretreatment of biogas slurry: removing impurities, quenching and tempering pretreatment and deodorization treatment are carried out on the biogas slurry to obtain biogas slurry A, and then a compound stabilizer is added to obtain biogas slurry B;
and (3) sterilization period treatment: loosening soil on the surface layer of the pyrite mountain, spraying biogas slurry B, simultaneously turning and mixing, and then maintaining;
oxygen consumption period treatment: loosening the soil on the surface layer of the pyrite mountain, spraying biogas slurry B, simultaneously turning and mixing, and then naturally maintaining;
consolidation period treatment: spraying biogas slurry A, covering the surface layer with charcoal, and naturally maintaining to finish the treatment.
Further, the biogas slurry is obtained by anaerobic digestion of urban organic matters, and the urban organic matters comprise municipal sludge, kitchen waste, straw or livestock manure as a single matrix or a mixed matrix.
Further, the specific steps of impurity removal are as follows: adding 0.5-1% of humic acid into fresh biogas slurry, stirring for 30-60min under 50-100r/min, standing for 15-30min, and collecting supernatant.
Further, the tempering pretreatment specifically refers to low-temperature concentration or dilution of ammonia and volatile fatty acid in biogas slurry, so that the pH value of the biogas slurry is=6-8, the ammonia nitrogen concentration is 2500-4000mg/L, the volatile fatty acid concentration is 300-600mg/L, and the specific steps are as follows: analyzing the concentration of ammonia nitrogen and the concentration of volatile fatty acid in the biogas slurry, concentrating at 60-70 ℃ by adopting a low-temperature concentrator if the concentration of ammonia nitrogen and the concentration of volatile fatty acid in the biogas slurry are lower than a set value, and diluting by adding water if the concentration of ammonia nitrogen and the concentration of volatile fatty acid in the biogas slurry are higher than the set value.
Further, the specific steps of the deodorization treatment are as follows: adding sodium hypochlorite powder until the concentration of sodium hypochlorite is 100-200mg/L and stirring for 15-30min under the condition of 50-100r/min, so that the concentration of volatile phenol in biogas slurry A is lower than 1mg/L, the concentration of hydrogen sulfide is lower than 0.01mg/L and the concentration of indole is lower than 0.1mg/L.
Further, the components and the formulated weight ratio of the compound stabilizer are as follows: guar gum, borax and dimethylpyrazole phosphate, nitrogen pyridine or dicyandiamide=1 (0.01-0.05): (0.01-0.05), and the addition amount of the compound stabilizer is 0.1-1% of the mass of biogas slurry A.
Further, the pH value of the pyrite mountain soil is 2-5, the sulfur content is 1000-10000mg/kg dry basis, the iron content is 500-2000mg/kg dry basis, the ferrous ion content is 200-500mg/kg dry basis, and the pyrite mountain soil contains other heavy metals such as copper, mercury, lead and cadmium composite minerals, wherein the iron sulfur oxidizing bacteria comprise sulfur oxidizing rods (Thiobacillus thiooxidans), ferrous thiobacillus (Thiobacillus ferrooxidans and Acidithiobacillus ferrooxidan), and the total content of the iron sulfur oxidizing bacteria is 1 multiplied by 10 measured by adopting a plate counting method 4 -1×10 9 On a dry basis.
Further, the sterilization period treatment comprises the following specific steps: loosening the soil with 0-0.5m of the surface layer of pyrite mountain to make the porosity reach 40-50%, spraying biogas slurry B with the spraying amount of 30-50L/m 2 The soil is turned and mixed while spraying, so that the water content of the soil at the depth of 0.5m is consistent with the water content of the soil at the depth of 0m, the maintenance is carried out for 5-10d, and the iron sulfur oxidizing bacteria count in the depth of 0-0.5m of the soil is reduced by more than 99% compared with that before biogas slurry application.
Further, the oxygen consumption period treatment comprises the following specific steps: soil with 0-0.3m of ploughing and loosening, the porosity reaches 40-50%, biogas slurry B is sprayed, and the spraying amount is 10-20L/m 2 The soil is turned and mixed while spraying, so that the water content of the soil at the depth of 0.3m is consistent with the water content of the soil at the depth of 0m, natural maintenance is carried out for 20-30d, the oxygen content of the soil at the depth of 0.3-0.5m is reduced to 5-10%, and the iron-sulfur oxidizing bacteria count in the depth of 0-0.5m of the soil is reduced by more than 99.99% compared with that before biogas slurry application.
Further, the specific steps of the consolidation period treatment are as follows: spraying biogas slurry A with a spraying amount of 5-10L/m 2 Covering the surface layer with biochar, and naturally maintaining for 30-60d, wherein the biochar is prepared from biogas residue with an amount of 0.5-2kg/m 2 After the consolidation period treatment, the iron-sulfur oxidizing bacteria count in the depth of 0-0.5m of the soil is reduced by more than 99.99 percent compared with that before biogas slurry application, the pH value of 0-0.3m of the soil is restored to 5-7, and the volatile fatty acid content in the soil of 0-0.3m of the soil is reduced to 5mg/kg dry basis or below.
The working principle of the invention is as follows: the biogas slurry obtained by anaerobic digestion of urban organic matters contains a large amount of ammonia nitrogen and volatile fatty acid, and the substances have cytotoxicity to iron sulfur oxidizing bacteria in the soil of the pyrite mountain at high concentration, and can kill the iron sulfur oxidizing bacteria when applied; meanwhile, the volatile fatty acid in the biogas slurry can consume a large amount of oxygen in the soil, can create a low-oxygen environment and inhibit the sulfuric acid production metabolism of the iron-sulfur oxidizing bacteria; by utilizing the dual effects, iron sulfur oxidizing bacteria in the soil of the sulfur iron mine can be inhibited, and the generation of AMD can be blocked. In general biogas slurry, the concentration of ammonia nitrogen and volatile fatty acid is difficult to reach the range which can kill iron-sulfur oxidizing bacteria and is suitable for plant growth, and the biogas slurry contains odor substances, and when the biogas slurry is directly applied to urban soil, seedlings are burned, odor pollution is brought, and when the biogas slurry is directly applied to mine soil, the activity of the iron-sulfur oxidizing bacteria is not sufficiently inhibited, so that a series of targeted treatments including concentration or dilution tempering pretreatment, sodium hypochlorite addition, compound stabilizer addition and the like are carried out according to the characteristics of the biogas slurry, and the aims of blocking AMD, utilizing nutrient substances in the biogas slurry, avoiding pollution brought by the biogas slurry and facilitating the re-greening of the mine are fulfilled. After being applied, the soil is covered with a layer of biochar to lock ammonia and micromolecular nutrient substances in the soil, so that the mine soil can recover fertility conveniently.
When the compound medicament is prepared, the guar gum, borax, dimethylpyrazole phosphate or the mixture of nitrogen pyridine or dicyandiamide is selected, and the principle is that the guar gum is adopted to increase the viscosity of biogas slurry, increase the adhesive capacity of the biogas slurry on the surface of mine soil and reduce the overflow and the loss of the biogas slurry through surface runoff, rainwater sand flushing and the like; the borax is adopted for preventing insect pest generation in mine soil and supplementing necessary boron element in the soil; the purpose of adopting dimethylpyrazole phosphate or nitrogen pyridine or dicyandiamide is to serve as a nitrification inhibitor, so that ammonia nitrogen concentration is prevented from being reduced by rapid nitrification after high-concentration ammonia nitrogen is applied, and the killing capacity of the dimethylpyrazole phosphate or nitrogen pyridine or dicyandiamide to iron-sulfur oxidizing bacteria is reduced.
In the invention, the pH value of the biogas slurry defined after a series of pretreatment is carried out on the biogas slurry in the biogas slurry pretreatment step, and the concentration of ammonia nitrogen, the concentration of volatile fatty acid, the concentration of volatile phenol, the concentration of hydrogen sulfide and the concentration of indole are key parameters for inhibiting iron-sulfur oxidizing bacteria when the biogas slurry is applied to the soil of the pyrite mountain. The concentration of ammonia nitrogen and volatile fatty acid is too low to form a killing effect on iron-sulfur oxidizing bacteria in soil, and too high to concentrate biogas slurry requires high cost; when the concentration of volatile phenol, hydrogen sulfide and indole is too high, odor pollution is formed, and hygienic application of biogas slurry is affected.
In the invention, the spraying quantity and the maintenance time of the biogas slurry type (A or B) in the sterilization period, the oxygen consumption period and the consolidation period are key parameters for inhibiting iron-sulfur oxidizing bacteria by the biogas slurry and improving the quality of mine soil after the biogas slurry is applied. The sterilization period is long, the spraying biogas slurry amount is large, the depth is large, the compound stabilizer is added, and the maintenance time is short, so that iron-sulfur oxidizing bacteria in mine soil can be effectively and fully killed; the oxygen consumption period is short, the spraying biogas slurry amount is small, the depth is shallow, the compound stabilizer is added, the maintenance time is prolonged, so that the oxygen in the mine surface soil is fully consumed, the iron-sulfur oxidizing bacteria in the mine soil are further killed, and the oxidation acid-producing activity of the iron-sulfur oxidizing bacteria is inhibited; the consolidation period is short in biogas slurry spraying amount, surface spraying is performed, a compound stabilizer is not added, the maintenance time is longer, the sterilization and oxygen consumption effects are further consolidated, volatile fatty acids in the biogas slurry are removed through oxidization, at the moment, aerobic microorganisms in soil are rebuilt, biochar is covered after spraying, ammonia and micromolecular nutrient substances in the soil are locked, and mine soil fertility recovery is facilitated.
Compared with the prior art, the invention has the following advantages:
(1) The invention adopts a pretreatment method of innovative organic biogas slurry. The concentration of volatile fatty acid, ammonia nitrogen, volatile phenol, hydrogen sulfide and indole in the biogas slurry obtained by dewatering anaerobic digestion products is controlled by means of concentration or dilution tempering pretreatment, sodium hypochlorite addition, compound medicament addition and the like, so that the process not only controls the odor of the biogas slurry, but also ensures that the biogas slurry has the characteristics of killing iron sulfur oxidizing bacteria in pyrite mountain soil and creating a low-oxygen environment, and simultaneously avoids the overflow and loss of the applied biogas slurry through surface runoff, rainwater sand washing and the like, and the reduction of the ammonia nitrogen concentration in the biogas slurry through nitrification.
(2) In the invention, the concentration of ammonia nitrogen and volatile fatty acid in the biogas slurry applied to the pyrite mountain soil is far higher than the concentration of ammonia nitrogen and volatile fatty acid which are required to be controlled when the biogas slurry is applied to agriculture and forestry (the seedling burning is avoided, no killing effect on iron-sulfur oxidizing bacteria is caused), and the unique concentration can synchronously kill the iron-sulfur oxidizing bacteria in the pyrite mountain soil, block the generation of AMD and recover the resources in the biogas slurry, thus being a great innovation different from the traditional application concentration;
(3) The invention adopts an application method of innovative organic biogas slurry. The biogas slurry is applied for three times, and the sterilization period is long, the spraying biogas slurry is large in volume and depth, the compound stabilizer is added, and the maintenance time is short, so that the iron-sulfur oxidizing bacteria in mine soil can be effectively and fully killed; the oxygen consumption period is short, the spraying biogas slurry amount is small, the depth is shallow, the compound stabilizer is added, the maintenance time is prolonged, so that the oxygen in the mine surface soil is fully consumed, the iron-sulfur oxidizing bacteria in the mine soil are further killed, and the oxidation acid-producing activity of the iron-sulfur oxidizing bacteria is inhibited; the consolidation period is short in biogas slurry spraying amount, surface spraying is performed, a compound stabilizer is not added, the maintenance time is longer, the sterilization and oxygen consumption effects are further consolidated, volatile fatty acids in the biogas slurry are sufficiently oxidized and removed, at the moment, aerobic microorganisms in the soil are rebuilt, biochar is covered after spraying, ammonia and micromolecular nutrient substances in the soil are locked, and the mine soil is convenient to recover fertility. The three-stage application can efficiently achieve the effects of killing iron-sulfur oxidizing bacteria, preventing excessive scattering caused by one-time application, consuming oxygen in the surface layer of the soil and avoiding the excessive concentration of volatile fatty acid in the soil, and the effect has durability.
Detailed Description
The following describes in detail the examples of the present invention, which are implemented on the premise of the technical solution of the present invention, and detailed embodiments and specific operation procedures are given, but the scope of protection of the present invention is not limited to the following examples.
A method for killing iron sulfur oxidizing bacteria in acid soil of a pyrite mountain by utilizing biogas slurry and reconstructing a mine soil microorganism population, comprising the following steps:
pretreatment of biogas slurry: removing impurities and deodorizing the biogas slurry to obtain biogas slurry A, and adding a compound stabilizer to obtain biogas slurry B; the biogas slurry is obtained by anaerobic digestion of urban organic matters, wherein the urban organic matters comprise municipal sludge, kitchen waste, straw or livestock and poultry manure as a single matrix or a mixed matrix. The specific steps of impurity removal are as follows: adding 0.5-1% of humic acid into fresh biogas slurry, stirring for 30-60min under 50-100r/min, standing for 15-30min, and collecting supernatant. The specific steps of deodorization treatment are as follows: adding sodium hypochlorite powder until the concentration of sodium hypochlorite is 100-200mg/L and stirring for 15-30min under the condition of 50-100r/min, so that the concentration of volatile phenol in biogas slurry A is lower than 1mg/L, the concentration of hydrogen sulfide is lower than 0.01mg/L and the concentration of indole is lower than 0.1mg/L. Concentrating or diluting ammonia and volatile fatty acid in the biogas slurry at low temperature before deodorization treatment to ensure that the pH value of the biogas slurry is=6-8, the ammonia nitrogen concentration is 2500-4000mg/L, and the volatile fatty acid concentration is 300-600mg/L, and specifically comprises the following steps: analyzing the concentration of ammonia nitrogen and the concentration of volatile fatty acid in the biogas slurry, concentrating at 60-70 ℃ by adopting a low-temperature concentrator if the concentration of ammonia nitrogen and the concentration of volatile fatty acid in the biogas slurry are lower than a set value, and diluting by adding water if the concentration of ammonia nitrogen and the concentration of volatile fatty acid in the biogas slurry are higher than the set value. The components of the compound stabilizer and the weight ratio of the compound stabilizer are as follows: guar gum, borax and dimethylpyrazole phosphate, nitrogen pyridine or dicyandiamide=1 (0.01-0.05): (0.01-0.05), and the addition amount of the compound stabilizer is 0.1-1% of the mass of biogas slurry A.
And (3) sterilization period treatment: loosening soil on the surface layer of the pyrite mountain, spraying biogas slurry B, simultaneously turning and mixing, and then maintaining; the pH value of the pyrite mountain soil is 2-5, the sulfur content is 1000-10000mg/kg dry basis, the iron content is 500-2000mg/kg dry basis, the ferrous ion content is 200-500mg/kg dry basis, and the pyrite mountain soil contains other heavy metals such as copper, mercury, lead and cadmium complex minerals, wherein the iron sulfur oxidizing bacteria comprise sulfur oxidizing rods (Thiobacillus thiooxidans) and ferrous sulfur oxidizing bacilli (Thiobacillus ferrooxidans and Acidithiobacillus ferrooxidan), and the total content of the iron sulfur oxidizing bacteria is 1 multiplied by 10 measured by adopting a plate counting method 4 -1×10 9 On a dry basis. The sterilization period treatment comprises the following specific steps: loosening the soil with 0-0.5m of the surface layer of pyrite mountain to make the porosity reach 40-50%, spraying biogas slurry B with the spraying amount of 30-50L/m 2 Turning and mixing while spraying to make the water content of soil at 0.5m depth consistent with that at 0m, maintaining for 5-10d, and maintaining the soilThe iron-sulfur oxidizing bacteria count in the depth of 0-0.5m is reduced by more than 99% compared with that before biogas slurry application.
Oxygen consumption period treatment: loosening the soil on the surface layer of the pyrite mountain, spraying biogas slurry B, simultaneously turning and mixing, and then naturally maintaining; the oxygen consumption period treatment comprises the following specific steps: soil with 0-0.3m of ploughing and loosening, the porosity reaches 40-50%, biogas slurry B is sprayed, and the spraying amount is 10-20L/m 2 The soil is turned and mixed while spraying, so that the water content of the soil at the depth of 0.3m is consistent with the water content of the soil at the depth of 0m, natural maintenance is carried out for 20-30d, the oxygen content of the soil at the depth of 0.3-0.5m is reduced to 5-10%, and the iron-sulfur oxidizing bacteria count in the depth of 0-0.5m of the soil is reduced by more than 99.99% compared with that before biogas slurry application.
Consolidation period treatment: spraying biogas slurry A, covering the surface layer with charcoal, and naturally maintaining to finish the treatment. The consolidation period treatment comprises the following specific steps: spraying biogas slurry A with a spraying amount of 5-10L/m 2 Covering the surface layer with biochar, and naturally maintaining for 30-60d, wherein the biochar is prepared from biogas residue with an amount of 0.5-2kg/m 2 After the consolidation period treatment, the iron-sulfur oxidizing bacteria count in the depth of 0-0.5m of the soil is reduced by more than 99.99 percent compared with that before biogas slurry application, the pH value of 0-0.3m of the soil is restored to 5-7, and the volatile fatty acid content in the soil of 0-0.3m of the soil is reduced to 5mg/kg dry basis or below.
Example 1
A method for killing iron sulfur oxidizing bacteria in pyrite mountain acid soil by utilizing biogas slurry and reconstructing mine soil microorganism population comprises the following steps:
(1) Taking biogas slurry obtained by anaerobic digestion of municipal sludge, adding humic acid with the biogas slurry amount of 0.5 into fresh biogas slurry, stirring for 30min under the condition of 50 rpm, standing for 15min, and taking out supernatant, wherein the concentrations of ammonia nitrogen and volatile fatty acid in the biogas slurry are respectively 800mg/L and 200mg/L;
(2) Concentrating the supernatant by adopting a low-temperature concentrator at 60-70 ℃ to obtain biogas slurry with the pH value of 8, the ammonia nitrogen concentration of 2000mg/L and the volatile fatty acid concentration of 300mg/L, then adding sodium chloride to the concentration of 100mg/L, and stirring for 15min under the condition of 50 revolutions per minute to ensure that the concentration of volatile phenol is lower than 1mg/L, the concentration of hydrogen sulfide is lower than 0.01mg/L and the concentration of indole is lower than 0.1mg/L, wherein the biogas slurry is biogas slurry A.
(3) The compound stabilizer is added into the biogas slurry A, and the components and the weight ratio of the compound stabilizer are as follows: guar gum: borax; dimethylpyrazole phosphate or azopyridine or dicyandiamide=1: 0.01:0.01, wherein the addition amount of the compound stabilizer is 0.1% of the mass of the biogas slurry, and the compound stabilizer is uniformly stirred to obtain biogas slurry B;
(4) The pH value of the pyrite mountain soil is 4, the content of sulfur is 1000mg/kg dry basis, the content of iron is 500mg/kg dry basis, the content of ferrous ions is 200mg/kg dry basis, and the pyrite mountain soil contains other heavy metals such as copper, mercury, lead, cadmium and other composite minerals, and the total content of iron-sulfur oxidizing bacteria is 1 multiplied by 10 7 On a dry basis. Sterilization period: loosening soil with 0-0.5m of pyrite mountain surface layer, and spraying biogas slurry B with porosity of 40% and spraying amount of 30L/m 2 Turning and mixing are carried out while spraying, so that the water content of the soil at the depth of 0.5m is consistent with the water content of the soil at the depth of 0m, curing is carried out for 5 days, and the count of iron-sulfur oxidizing bacteria in the depth of 0-0.5m of the soil is reduced by 99.9% compared with that before biogas slurry is applied;
(5) Oxygen consumption period: after the step (4) is finished, soil with 0-0.3m is ploughed and loosened, the porosity reaches 40%, biogas slurry B is sprayed, and the spraying amount is 10L/m 2 The soil is turned and mixed at the same time of spraying, so that the water content of the soil at the depth of 0.3m is consistent with the water content of the soil at the depth of 0m, natural maintenance is carried out for 20d, the oxygen content of the soil at the depth of 0.3-0.5m is reduced to 5%, and the count of iron-sulfur oxidizing bacteria in the depth of 0-0.5m of the soil is reduced by 99.999% compared with that before biogas slurry is applied;
(6) Consolidation period: after the step (5) is finished, spraying biogas slurry A with the spraying amount of 5L/m 2 Then covering the surface layer with biological carbon prepared from biogas residue with the dosage of 0.5kg/m 2 And (5) naturally curing for 30d. Compared with the counting of iron sulfur oxidizing bacteria before biogas slurry application, the obtained iron sulfur oxidizing bacteria in the depth of 0-0.5m of the pyrite mountain soil is reduced by 99.999 percent, the pH value of 0-0.3m is restored to 7, and the volatile fatty acid content in the soil of 0-0.3m is reduced to 4mg/kg dry basis.
Example 2
(1) Taking biogas slurry obtained by anaerobic digestion of livestock and poultry manure, adding 1% of humic acid in the fresh biogas slurry, stirring for 60min under the condition of 100 rpm, standing for 30min, and taking out supernatant, wherein the concentrations of ammonia nitrogen and volatile fatty acid in the biogas slurry are 6000mg/L and 900mg/L respectively.
(2) Adding water for dilution to obtain biogas slurry with pH value of 6, ammonia nitrogen concentration of 4000mg/L and volatile fatty acid concentration of 600mg/L, adding sodium chlorate to concentration of 200mg/L, stirring for 30min under the condition of 100 rpm to make the concentration of volatile phenol lower than 1mg/L, the concentration of hydrogen sulfide lower than 0.01mg/L and the concentration of indole lower than 0.1mg/L, wherein the biogas slurry is biogas slurry A.
(3) The compound stabilizer is added into the biogas slurry A, and the components and the weight ratio of the compound stabilizer are as follows: guar gum: borax; dimethylpyrazole phosphate or azopyridine or dicyandiamide=1: 0.05:0.05, wherein the addition amount of the compound stabilizer is 1% of the mass of the biogas slurry, and stirring uniformly to obtain biogas slurry B;
(4) The pH value of the pyrite mountain soil is 2, the content of sulfur is 10000mg/kg dry basis, the content of iron is 2000mg/kg dry basis, the content of ferrous ions is 500mg/kg dry basis, and the pyrite mountain soil contains other heavy metals such as copper, mercury, lead, cadmium and other composite minerals, and the content of iron-sulfur oxidizing bacteria is 1 multiplied by 10 9 On a dry basis. Sterilization period: loosening soil with 0-0.5m of pyrite mountain surface layer, and spraying biogas slurry B with porosity of 50L/m 2 Turning and mixing are carried out while spraying, so that the water content of the soil at the depth of 0.5m is consistent with the water content of the soil at the depth of 0m, curing is carried out for 10 days, and the count of iron-sulfur oxidizing bacteria in the depth of 0-0.5m of the soil is reduced by 99.2% compared with that before biogas slurry is applied;
(5) Oxygen consumption period: after the step (4) is finished, soil with 0-0.5m is ploughed and loosened, the porosity reaches 50%, biogas slurry B is sprayed, and the spraying amount is 20L/m 2 The soil is turned and mixed at the same time of spraying, so that the water content of the soil at the depth of 0.5m is consistent with the water content of the soil at the depth of 0m, natural maintenance is carried out for 30d, the oxygen content of the soil at the depth of 0.3-0.5m is reduced to 10%, and the count of iron-sulfur oxidizing bacteria in the depth of 0-0.5m of the soil is reduced by 99.992% compared with that before biogas slurry application;
(6) Consolidation period: after the step (5) is finished, spraying biogas slurry A with the spraying amount of 10L/m 2 Then covering the surface layer with biochar prepared from biogas residues with the dosage of 2kg/m 2 And (5) naturally curing for 60d. The obtained pyrite mountain soilCompared with the counting of the iron sulfur oxidizing bacteria before biogas slurry application, the counting of the iron sulfur oxidizing bacteria in the depth of 0-0.5m of the soil is reduced by 99.995 percent, the pH value of the soil in the depth of 0-0.3m is restored to 5, and the volatile fatty acid content in the soil in the depth of 0-0.3m is reduced to 4.8mg/kg dry basis or below.
Comparative example 1
Compared with the example 1, the difference is that the pretreatment means is not adopted to directly apply the biogas slurry, the pH value of the biogas slurry is 7, the ammonia nitrogen concentration is 800mg/L, the volatile fatty acid concentration is 200mg/L, the volatile phenol concentration is 2.5mg/L, the hydrogen sulfide concentration is 0.05mg/L, and the indole concentration is 0.3mg/L. After 10d of the first spraying maintenance, the oxygen content of the soil at the depth of 0.3-0.5m is 20%, after 20d of the second spraying maintenance, the content of iron-sulfur oxidizing bacteria in the depth of 0-0.5m of the soil is reduced by 40% compared with the count before biogas slurry application, after 60d of the third spraying maintenance, the pH value of 0-0.3m of the soil is 5, the content of volatile fatty acid in the soil at the depth of 0-0.3m is reduced by 45% compared with the count before biogas slurry application, and the content of volatile fatty acid in the soil at the depth of 0-0.3m is 4.5mg/kg of dry basis. The iron sulfur oxidizing bacteria in the soil of the pyrite mountain are not killed, the pH value of the iron sulfur oxidizing bacteria is not recovered, and the iron sulfur oxidizing bacteria emit large-area odor when being applied.
Comparative example 2
In comparison with example 1, the difference is that the first spray quantity is 20L/m 2 After curing for 5d after spraying, the oxygen content of the soil at the depth of 0.3-0.5m is 15%, and the second spraying amount is 5L/m 2 After curing for 5d after spraying, the iron-sulfur oxidizing bacteria in the depth of 0-0.5m of the soil is reduced by 10 percent compared with the counting before biogas slurry application, and the third spraying amount is 5L/m 2 After 5d of curing after spraying, the pH value of the depth of 0-0.3m is 4.5, the count of the iron-sulfur oxidizing bacteria in the depth of 0-0.5m is reduced by 20 percent compared with the count before biogas slurry application, and the volatile fatty acid content in the soil of the depth of 0-0.3m is 10mg/kg dry basis. The iron sulfur oxidizing bacteria in the pyrite mountain soil are not killed, the pH value is not recovered, and the concentration of volatile fatty acid is beyond the expected value.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the invention in any way, and any person skilled in the art may make modifications or alterations to the disclosed technical content to the equivalent embodiments. However, any simple modification, equivalent variation and variation of the above embodiments according to the technical substance of the present invention still fall within the protection scope of the technical solution of the present invention.

Claims (3)

1. The method for killing iron sulfur oxidizing bacteria in the acidic soil of the pyrite mountain by utilizing the biogas slurry and reconstructing a mine soil microorganism population is characterized by comprising the following steps of:
pretreatment of biogas slurry: removing impurities, quenching and tempering pretreatment and deodorization treatment are carried out on the biogas slurry to obtain biogas slurry A, and then a compound stabilizer is added to obtain biogas slurry B;
and (3) sterilization period treatment: loosening soil on the surface layer of the pyrite mountain, spraying biogas slurry B, simultaneously turning and mixing, and then maintaining;
oxygen consumption period treatment: loosening the soil on the surface layer of the pyrite mountain, spraying biogas slurry B, simultaneously turning and mixing, and then naturally maintaining;
consolidation period treatment: spraying biogas slurry A, covering the surface layer with charcoal, and naturally curing to finish treatment;
the specific steps of impurity removal are as follows: adding 0.5-1% of humic acid into fresh biogas slurry, stirring for 30-60min under the condition of 50-100r/min, standing for 15-30min until flocculent precipitate appears in biogas slurry, and taking out supernatant;
the tempering pretreatment specifically refers to low-temperature concentration or dilution of ammonia and volatile fatty acid in biogas slurry, so that the pH value of the biogas slurry is=6-8, the ammonia nitrogen concentration is 2500-4000mg/L, the volatile fatty acid concentration is 300-600mg/L, and the specific steps are as follows: analyzing the concentration of ammonia nitrogen and the concentration of volatile fatty acid in the biogas slurry, concentrating by adopting a low-temperature concentrator at 60-70 ℃ if the concentration of ammonia nitrogen and the concentration of volatile fatty acid in the biogas slurry are lower than a set value, and diluting by adding water if the concentration of ammonia nitrogen and the concentration of volatile fatty acid in the biogas slurry are higher than the set value;
the specific steps of the deodorization treatment are as follows: adding sodium hypochlorite powder until the concentration of sodium hypochlorite is 100-200mg/L and 50-100r/min, and stirring for 15-30min to ensure that the concentration of volatile phenol in biogas slurry A is lower than 1mg/L, the concentration of hydrogen sulfide is lower than 0.01mg/L and the concentration of indole is lower than 0.1 mg/L;
the components and the weight ratio of the compound stabilizer are as follows: guar gum, borax and dimethylpyrazole phosphate, nitrogen pyridine or dicyandiamide=1, (0.01-0.05): (0.01-0.05), and the addition amount of the compound stabilizer is 0.1-1% of the mass of biogas slurry A;
the sterilization period treatment comprises the following specific steps: loosening the soil with 0-0.5-m of pyrite mountain surface layer to make the porosity reach 40-50%, spraying biogas slurry B with a spraying amount of 30-50L/m 2 The soil is turned and mixed at the same time of spraying, so that the water content of the soil at the depth of 0.5-m is consistent with the water content of the soil at the depth of 0m, the maintenance is carried out for 5-10d, and the iron-sulfur oxidizing bacteria count in the depth of 0-0.5-m of the soil is reduced by more than 99% compared with that before biogas slurry application;
the oxygen consumption period treatment comprises the following specific steps: soil with 0-0.3 of m of ploughed pine has porosity of 40-50%, and is sprayed with biogas slurry B with a spraying amount of 10-20L/m 2 The soil is turned and mixed while spraying, so that the water content of the soil at the depth of 0.3-m is consistent with that of the soil at the depth of 0m, the soil is naturally maintained for 20-30d, the oxygen content of the soil at the depth of 0.3-0.5-m is reduced to 5-10%, and the iron sulfur oxidizing bacteria count in the depth of 0-0.5-m of the soil is reduced by more than 99.99% compared with that before biogas slurry application;
the consolidation period treatment comprises the following specific steps: spraying biogas slurry A with a spraying amount of 5-10L/m 2 Covering the surface layer with biochar (0.5-2 kg/m) prepared from biogas residue, and naturally maintaining for 30-60d 2 After the consolidation period treatment, the iron-sulfur oxidizing bacteria count in the depth of 0-0.5 and m of the soil is reduced by more than 99.99 percent compared with that before biogas slurry application, the pH value of 0-0.3 and m is recovered to 5-7, and the volatile fatty acid content in the soil of 0-0.3 and m is reduced to below 5mg/kg dry basis.
2. The method for killing iron sulfur oxidizing bacteria in acidic soil of pyrite and reconstructing microbial population of mine soil by utilizing biogas slurry according to claim 1, wherein the biogas slurry is obtained by anaerobic digestion of urban organic matters, and the urban organic matters comprise municipal sludge, kitchen waste, straw or livestock manure as a single matrix or a mixed matrix.
3. The method for killing iron sulfur oxidizing bacteria in acidic soil of pyrite mountain and reconstructing microbial population of mine soil by utilizing biogas slurry as claimed in claim 1, wherein the pH value range of the pyrite mountain soil is 2-5, the sulfur content is 1000-10000mg/kg dry basis, the iron content is 500-2000mg/kg dry basis, the ferrous ion content is 200-500mg/kg dry basis, and the biogas slurry contains other heavy metal compound minerals, wherein the iron sulfur oxidizing bacteria comprise sulfur oxidizing rods and ferrous sulfur oxidizing bacteria, and the total content of the iron sulfur oxidizing bacteria is 1 x 10 measured by adopting a plate counting method 4 -1×10 9 On a dry basis.
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