CN109127712B - Method for repairing heavy metal polluted tailings by using chemistry and microorganisms - Google Patents
Method for repairing heavy metal polluted tailings by using chemistry and microorganisms Download PDFInfo
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- CN109127712B CN109127712B CN201811101421.8A CN201811101421A CN109127712B CN 109127712 B CN109127712 B CN 109127712B CN 201811101421 A CN201811101421 A CN 201811101421A CN 109127712 B CN109127712 B CN 109127712B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/10—Reclamation of contaminated soil microbiologically, biologically or by using enzymes
Abstract
The invention relates to a method for repairing tailings polluted by heavy metals by using chemistry and microorganisms, wherein tailings with the particle size of 0.04-500 mu m are selected, soil dressing with the thickness of 5-10 cm is paved on the surface layer of the tailings, organic manure is applied, and the surface layer of the tailings is ploughed and leveled; inoculating a microbial inoculum, and irrigating to ensure that the water holding rate is 60%; planting artemisia scoparia and leymus chinensis; adding rhamnolipid and ethylenediamine disuccinic acid repairing agent water solution at the early stage of harvesting Artemisia sphaerocephala and Leymus chinensis. The fertility of the tailings is improved by adopting the organic manure, the microbial inoculum is inoculated to promote the growth of plants, and the rhamnolipid and the ethylenediamine disuccinic acid are added to resolve heavy metals in the tailings in the early stage of plant harvest to promote the plants to super-absorb and accumulate the heavy metals in a short period. The invention has the advantages of good repairing effect, simple operation, biodegradable repairing agent and no secondary pollution.
Description
Technical Field
The invention relates to the technical field of heavy metal polluted iron tailings restoration, in particular to a method for restoring heavy metal polluted tailings by using chemistry and microorganisms.
Background
The tailings are byproducts of mine beneficiation and are high-moisture-content solid wastes which have no strength, contain pollutants and are easy to liquefy and flow. China is a big country with abundant metal mine resources, the development and utilization intensity of mines is high, a large amount of tailings can be generated every year, according to statistics, the existing tailings in China exceed billions of tons, and the existing tailings are increased at the speed of hundreds of millions of tons every year, but the comprehensive utilization rate of the tailings is low, and most of the tailings are not comprehensively utilized but are directly stockpiled. The heavy metal content in the tailings is often too high, and the tailings are piled up without loose coverage, so that the piled tailings are easy to erode, the water and soil loss is aggravated, and the heavy metal pollutants can pollute water sources and farmlands along with the water and soil loss in heavy rain.
At present, the modes of treating tailings at home and abroad mainly comprise physical, chemical and ecological restoration and the like. Physical methods such as construction and fixation by using cement and chemical methods such as adding a chemical chelating agent to reduce the activity of heavy metals in tailings, but the physical and chemical methods do not fundamentally eliminate the risk of environmental pollution. Ecological restoration is considered to be the most effective way for solving the environmental problem of the waste tailings land, but due to the severe environment caused by mining, the metal waste land has extreme ecological conditions and a plurality of conditions which are not beneficial to vegetation growth, such as low organic matter content in tailings, extremely low comprehensive fertility status of soil, extremely poor nutrient elements of various soils, almost no microorganisms and the like.
The inventor conducts experimental research for several years, and finally finds a method for repairing the heavy metal polluted tailings by using chemistry and microorganisms.
Disclosure of Invention
The invention aims to provide a method for repairing heavy metal polluted tailings by using chemistry and microorganisms.
The purpose of the invention is realized by the following technical scheme:
the method for repairing the tailings polluted by the heavy metals by using the chemicals and the microorganisms is characterized by comprising the following steps of:
(1) selecting tailings with the particle size of 0.04-500 um, paving a layer of additional soil with the thickness of 5-10 cm on the surface of the tailings, applying organic manure with the additional soil amount of 6-9%, turning over the surface of the tailings with the depth of 10-20 cm to enable the ratio of the tailings to the additional soil to be 1:1, and flattening the surface layer of the tailings soil;
(2) spraying the microbial inoculum 0-5 cm away from the surface layer of the tailing soil, wherein the inoculation ratio is 800-1200 g/m2Leveling and irrigating to ensure that the water holding rate of the tailing soil is 60 percent;
(3) planting artemisia sphaerocephala and leymus chinensis, wherein the number of the artemisia sphaerocephala and the leymus chinensis is 1:1, and the planting density is 400-600 plants/m2；
(4) Watering the planting area, managing uniformly, adding rhamnolipid and ethylenediamine disuccinic acid repairing agent aqueous solution with the mass concentration of 1.2-2 g/kg into the plants 10-15 days before the harvest of the artemisia lasiocarpa and the leymus chinensis, adding 100-200 mL into each 3-5 plants, wherein the mass ratio of the rhamnolipid to the ethylenediamine disuccinic acid is 3: 1.
According to the method for repairing the heavy metal polluted tailings by using the chemicals and the microorganisms, the microbial inoculum strains formed by mixing the fungal spores and the exohyphae are as follows: the matrix for the infection and propagation of the moxidectin sacculus (Glomus mossea), the root inner sacculus (Glomus intraradics), the surface sacculus (Glomus versiforme), the clump of the sacculus (Glomus aggregatum) and the photic sacculus (Glomus diaphanum) is as follows: sand and soil in a weight ratio of 1: 1.
The microorganism of the invention is commercially available: mossbisporus (Glomus mosseae), BGC HUN01A, Glomus intraradices BGC AH01, Glomus versiforme CGMCC No.8775, Glomus agglomerans BGC BJ07, Glomus diaphanum BGC XJ 04A; wherein, BGC is China arbuscular mycorrhizal fungi germplasm resource Bank (Bank of Glomales in China), CGMCC is China General Microbiological Culture Collection Center (China General Microbiological Culture Collection Center).
The preparation method of the microbial inoculum comprises the following steps:
respectively inoculating primary seeds of a strain in a culture medium under an aseptic condition, and performing activation culture independently under a separation condition at the culture temperature of 23-27 ℃ for 7-10 days to obtain secondary seeds of the strain; digging small blocks, and inoculating the small blocks into a large glass round culture dish for propagation culture at the culture temperature of 30-32 ℃ for 5-8 days, and the pH value of 6-7; collecting and diluting to 1-9 × 107CFU/ml bacterial liquid, and mixing the bacterial liquids in equal volumes to obtain the bacterial liquid.
The activating and propagation culture medium is prepared into a nitrogen source: 1-3 g/L, carbon source: 1-3 g/L, yeast extract: 1-3 g/L, peptone: 2-5 g/L, dipotassium hydrogen phosphate: 0.5-1 g/L, magnesium sulfate: 0.03-0.05 g/L.
Experimental research shows that active and effective soil improvement measures are taken in a tailing pond, and a microorganism inoculation method is adopted for plant planting, so that the inoculated microorganisms can not only improve the survival rate of plants, but also promote the growth of the plants to enable the plants to have larger biomass. The method of the invention is to utilize organic manure, strengthen soil microorganisms, apply chemical repairing agent and plant planting method. The organic manure used is cow dung. The chemical repairing agent is a chelating agent: ethylenediamine disuccinic acid and surfactant: rhamnolipids. The rhamnolipid has long carbon chain, the structures of hydrophilic group and hydrophobic group in the molecular structure are complex, and the complex stability constant of the rhamnolipid and heavy metal is large, so that the rhamnolipid has strong desorption capacity to heavy metal in soil; the ethylenediamine disuccinic acid can increase the solubility of heavy metals in the soil and desorb the heavy metals from the soil surface; moreover, the heavy metals in the soil can be converted from an insoluble state to a soluble state by the aid of the two methods, the heavy metals in the soil are activated, the absorption of plants is enhanced, and the plants can enrich the heavy metals in a short time, so that tailings can be repaired; the two can be biodegraded without causing secondary pollution.
The method belongs to a chemical and microbial combined remediation method, has good remediation effect and simple operation, and can be widely applied to remediation of the iron tailings polluted by heavy metals. The environment quality of the repaired tailing soil meets the requirement of a secondary standard value of soil environment quality standard (GB 156181995) in China, the content of organic matters in the soil can be improved, and the repaired soil body can be directly used as planting soil.
Detailed Description
The following examples are provided for illustrative purposes only and are not intended to limit the scope of the claims, and other alternatives that may occur to those skilled in the art from consideration of the specification are intended to be within the scope of the claims.
Collecting samples: the tailings used in the test are taken from 0-20 cm of the surface layer of an iron ore tailing pond in northeast China, small stones are removed after the tailings are collected, the tailings are naturally dried in a fume hood, and the tailings are sieved by a 2mm nylon sieve; the content of heavy metal in the tailings is respectively determined as follows: the content of Pd is 506.95mg/kg, Cd is 2.087mg/kg, Zn is 547mg/kg, and Cu is 212.5mg/kg, and the heavy metal content is determined by chemical treatment and atomic absorption spectrophotometer; the content of fluoride is 341 mg/kg; the pH was 8.67; the effective nitrogen is 9.027mg/kg, and the organic matter content is 1.15%; the available phosphorus is below the detection range.
The preparation method of the microbial inoculum provided by the embodiment of the invention comprises the following steps:
inoculating in culture medium under aseptic conditionThe first-stage seeds of the strains are obtained by independently culturing the culture medium under the separation condition, wherein the culture temperature is 25-26 ℃, and the culture time is 8-9 days; digging small blocks, and inoculating the small blocks into a large glass round culture dish for amplification culture, wherein the culture temperature is 30-31 ℃, the culture time is 6-7 days, and the pH is 6-7; collecting and diluting to 1-1.5 × 107CFU/ml bacterial liquid, and mixing the bacterial liquids in equal volumes to obtain the bacterial liquid.
The activating and propagation culture medium is prepared into a nitrogen source: 2g/L, carbon source: 2g/L, yeast extract: 2g/L, peptone: 4g/L, dipotassium hydrogen phosphate: 0.8g/L, magnesium sulfate: 0.05 g/L.
In the places with luxuriant plant growth, such as tamarix chinensis, lactuca sativa, kochia scoparia, robinia pseudoacacia, salix matsudana and the like, around the tailings, a certain amount of loess samples are collected at the rhizosphere of the plants, the loess samples are filled into sterile bags and are brought back to a laboratory under the condition of refrigeration to identify the types of microorganisms, and the dominant strains are Glomus mosseae, Glomus intraradicis, Glomus versiforme and Glomus aggregatum photic cocci (Glomus diaphanum).
The microorganism of the embodiment of the invention is the same as the commercial China arbuscular mycorrhizal fungi germplasm resource library BGC (Bank of Glomales in China) in the following strains: mossbisporus (Glomus mosseae), BGCHUN01A, Glomus intraradices BGC AH01, Glomus versiforme CGMCC No.8775, Glomus agglomerans BGC BJ07, Glomus diaphanum BGC XJ 04A.
The soil for planting the artificial soil is obtained from loess in a dense vegetation growing area around a tailing pond, the loess passes through a 2mm nylon sieve, is sterilized in a pressure steam sterilization pot at the temperature of 120 ℃ for 2 hours, and is filled into a plastic pot after being sterilized, wherein the specification of the pot is 160mm by 110mm by 140 mm. The method comprises the steps of carrying out infection propagation on a microbial inoculum strain formed by mixing identified fungal spores and external hyphae with artemisia sphaerocephala and leymus chinensis, wherein the propagation matrix is sand and soil, the ratio of the sand to the soil is 1:1, and taking rhizosphere soil containing the fungal spores, the external hyphae and infected parasitic artemisia sphaerocephala and leymus chinensis root sections as the microbial inoculum after propagation.
Example 1
Weighing 1100g of tailings in each pot into a plastic pot (160mm 110mm 140mm), wherein the thickness is about 6cm, covering foreign soil on the pot is 800g, the thickness is 6cm, the foreign soil is taken from the periphery of a tailing pond, weighing 105g of cow dung on a plastic film, adding a H436 wetting agent into the plastic pot, pouring the tailings and soil in the plastic pot onto the film for placing the cow dung, fully mixing the tailings and the soil uniformly, and filling the mixture into the plastic pot; inoculating 30g of a microbial inoculum formed by mixing fungal spores and external root hyphae at a position 3cm away from the surface layer, and adding a sterilizing microbial inoculum with the same mass into a control group without inoculating the microbial inoculum; watering until the water capacity of the tailings is 60%, and statically culturing for 3-5 days; respectively selecting seeds of artemisia widescripta and leymus chinensis with full and uniform seeds in two beakers, soaking the seeds in 10% hydrogen peroxide solution for 10 minutes, then respectively and completely washing the seeds with tap water and distilled water, placing the washed seeds in a culture dish paved with wet filter paper, accelerating germination at a constant temperature of 25 ℃, periodically supplementing water to keep the filter paper wet, selecting the seeds with consistent growth vigor after the seeds germinate, sowing the seeds in pots, and placing 5 plants of artemisia widescripta or leymus chinensis in each pot. The pots are placed in a greenhouse, seedlings are thinned after emergence of seedlings, 3 plants are reserved in each pot, and management is carried out in the growth period according to a common farmland management method. And (4) harvesting a plant sample after 60 days, and analyzing the biomass of the plant, the content of heavy metal in the plant body and the content of heavy metal in a tailing soil sample.
After the artemisia lasiocarpa and the leymus chinensis grow for 60 days, the result of comparison between the inoculated bacterium agent treatment and the control group is as follows:
the biomass of the overground parts of the artemisia lasiocarpa and the leymus chinensis is respectively increased by 213.7 percent and 229.2 percent, and the biomass of the underground parts is respectively increased by 208.53 percent and 216.7 percent;
the contents of heavy metals Pd, Cd, Zn and Cu in the overground part of the artemisia scoparia are respectively increased by 24.3%, 6.8%, 17.3% and 10.2%;
the contents of heavy metals Pd, Cd, Zn and Cu on the overground part of the leymus chinensis are respectively increased by 9.6 percent, 15.3 percent, 30.6 percent and 11.3 percent;
the contents of heavy metals Pd, Cd, Zn and Cu in the underground part of the artemisia sphaerocephala are respectively increased by 16.3%, 3.74%, 20.9% and 18.6%;
the contents of heavy metals Pd, Cd, Zn and Cu in the underground part of the leymus chinensis are respectively increased by 12.5%, 8.64.3%, 31.6% and 21.3%;
the contents of Pd, Cd, Zn and Cu in the tailing soil sample are respectively reduced by 10.3%, 7.6%, 12.17% and 9.4%.
Example 2
Weighing 1100g of tailings in each pot in a plastic pot (160mm 110mm 140mm), wherein the thickness is about 6cm, covering foreign soil on the pot is 800g, the thickness is 6cm, and the foreign soil is taken from the periphery of a tailing pond; weighing 105g of cow dung on a plastic film, adding a H436 wetting agent in the sea, pouring tailings and soil in a plastic pot on the film for placing the cow dung, fully and uniformly mixing, then placing the mixture into the plastic pot, inoculating 30g of a microbial inoculum formed by mixing fungal spores and hyphae outside roots at a position 3cm away from the surface layer, watering until the water capacity of the tailings is 60%, and statically culturing for 3-5 days; respectively selecting seeds of artemisia widescripta and leymus chinensis with full seeds and uniform individuals in two beakers, soaking the seeds in 10% hydrogen peroxide solution for 10 minutes, then respectively and completely washing the seeds with tap water and distilled water, placing the washed seeds in a culture dish paved with wet filter paper, accelerating germination at a constant temperature of 25 ℃, periodically supplementing water to keep the filter paper wet, after the seeds germinate, selecting the seeds with consistent growth vigor, sowing the seeds in pots, and placing 5 plants of artemisia widescripta or leymus chinensis in each pot; the pots are placed in a greenhouse, thinning is carried out after seedling emergence, 3 plants are respectively reserved in each pot, and management is carried out in the growth period according to a common farmland management method; when artemisia lasiocarpa and leymus chinensis grow for 50 days, 200mL of rhamnolipid and ethylenediamine disuccinic acid repairing agent aqueous solutions with different mass concentrations are respectively added into different plant pots, the pots are in parallel, the mass concentrations of the repairing agent aqueous solutions are respectively 0g/kg, 1.2g/kg and 2g/kg, and the mass ratio of the rhamnolipid to the ethylenediamine disuccinic acid is 3: 1.
And (4) harvesting a plant sample after the plant grows for 60 days, and analyzing the biomass of the plant, the content of heavy metal in the plant body and the content of heavy metal in a tailing soil sample.
Results of comparison with the control group after 60 days of growth of artemisia lasiocarpa and leymus chinensis:
the biomass difference between the control group and the artemisia lasiocarpa and the leymus chinensis added with the rhamnolipid and the ethylenediamine disuccinic acid repairing agent aqueous solution with the mass concentration of 1.2g/kg is not obvious; the aboveground biomass of the artemisia sphaerocephala in the control group is 3.21g, the underground biomass is 0.76g, the aboveground biomass is 3.18g and the underground biomass is 0.79g in the treatment of the ethylenediamine disuccinic acid repairing agent aqueous solution; the aboveground biomass of the guinea grass in the control group was 3.98g, the underground biomass was 1.02g, the aboveground biomass was 4.01g and the underground biomass was 0.98g in the treatment with the aqueous solution of ethylenediamine disuccinic acid remediation agent.
Adding the mixture with the mass concentration of 2g/kg, and respectively reducing the biomass of the overground part and the underground part of the artemisia stolonifera by 7.8 percent and 5.57 percent; the biomass of the overground part and the underground part of the leymus chinensis is respectively reduced by 10.1 percent and 6.5 percent;
adding the solution with the mass concentration of 1.2g/kg, wherein the contents of Pd, Cd, Zn and Cu in the overground part of the artemisia rupestris are respectively increased by 80.9 percent, 120.7 percent, 105 percent and 38.6 percent; the contents of Pd, Cd, Zn and Cu in the overground part of the leymus chinensis are respectively increased by 68.4%, 79.3%, 94.7% and 53.2%;
the mass concentration is added to be 2g/kg, and the contents of Pd, Cd, Zn and Cu in the overground part of the artemisia rupestris are respectively increased by 200.3%, 420%, 109.7% and 247%; the contents of Pd, Cd, Zn and Cu in the overground part of the leymus chinensis are respectively increased by 213%, 380%, 197.4% and 158.8%;
the mass concentration of the added raw materials is 1.2g/kg, and the contents of Pd, Cd, Zn and Cu in the underground part of the artemisia lasiocarpa are respectively increased by 34.6%, 89.4%, 123.1% and 65%; the contents of Pd, Cd, Zn and Cu in the underground part of the leymus chinensis are respectively increased by 78%, 32.5%, 108% and 29.7%;
the mass concentration of the added substances is 2g/kg, and the contents of Pd, Cd, Zn and Cu in the underground part of the artemisia lasiocarpa are respectively increased by 154.4%, 292%, 79.6% and 158%; the contents of Pd, Cd, Zn and Cu in the underground part of the leymus chinensis are respectively increased by 153.2%, 89.6%, 143% and 67.2%.
The mass concentration of the added solution is 1.2g/kg, and the contents of heavy metals Pd, Cd, Zn and Cu in a tailing soil sample are respectively reduced by 17.51%, 19%, 32.9% and 15.92%;
the mass concentration of the added heavy metals Pd, Cd, Zn and Cu in the tailing soil sample is reduced by 41.2%, 59.8%, 47.2% and 34.2% respectively.
Claims (2)
1. A method for repairing heavy metal polluted tailings by using chemistry and microorganisms is characterized by comprising the following steps:
(1) selecting tailings with the particle size of 0.04-500 um, paving a layer of additional soil with the thickness of 5-10 cm on the surface of the tailings, applying organic manure with the additional soil amount of 6-9%, turning over the surface of the tailings with the depth of 10-20 cm, enabling the ratio of the tailings to the additional soil to be 1:1, and leveling the surface of the soil of the tailings;
(2) spraying the microbial inoculum 0-5 cm away from the surface layer of the tailing soil, wherein the inoculation ratio is 800-1200 g/m2Leveling and irrigating to ensure that the water holding rate of the tailing soil is 60 percent;
(3) planting artemisia sphaerocephala and leymus chinensis, wherein the number of the artemisia sphaerocephala and the leymus chinensis is 1:1, and the planting density is 400-600 plants/m2；
(4) Watering a planting area, managing uniformly, adding rhamnolipid and ethylenediamine disuccinic acid repairing agent aqueous solution with the mass concentration of 1.2-2 g/kg into plants 10-15 days before cutting artemisia lasiocarpa and leymus chinensis, adding 100-200 mL into each 3-5 plants, wherein the mass ratio of the rhamnolipid to the ethylenediamine disuccinic acid is 3: 1;
wherein the microbial inoculum is prepared by respectively activating, propagating and diluting the strains to 1-9 × 107CFU/ml bacterial liquid, and mixing the bacterial liquid in equal volume to obtain the final product.
2. The method for repairing the tailings polluted by the heavy metals by using the chemicals and the microorganisms according to claim 1, wherein the matrix for the inoculation and the propagation of the artemisia lasiocarpa and the leymus chinensis is as follows: sand and soil in a weight ratio of 1: 1.
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| CN112410265A (en) * | 2020-12-09 | 2021-02-26 | 鞍钢集团矿业有限公司 | Microbial agent and method for planting plants to improve tailing sand |
| CN114713618B (en) * | 2022-06-08 | 2022-08-23 | 河北协同化学有限公司 | Phytoremediation promoter for treating heavy metal pollution based on phytoremediation technology |
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| CN102764757A (en) * | 2012-08-02 | 2012-11-07 | 大连民族学院 | Bioremediation method for heavy-metal contaminated soil of mining area |
| CN106077056A (en) * | 2016-08-06 | 2016-11-09 | 天津市滨海新区聚荣科技有限公司 | A kind of Bioremediation method for heavy-metal contaminated soil of mining area |
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| CN102764757A (en) * | 2012-08-02 | 2012-11-07 | 大连民族学院 | Bioremediation method for heavy-metal contaminated soil of mining area |
| CN106077056A (en) * | 2016-08-06 | 2016-11-09 | 天津市滨海新区聚荣科技有限公司 | A kind of Bioremediation method for heavy-metal contaminated soil of mining area |
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