CN114160558A - Contaminated soil in-situ chemical barrier material and preparation and application thereof - Google Patents
Contaminated soil in-situ chemical barrier material and preparation and application thereof Download PDFInfo
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- CN114160558A CN114160558A CN202111352751.6A CN202111352751A CN114160558A CN 114160558 A CN114160558 A CN 114160558A CN 202111352751 A CN202111352751 A CN 202111352751A CN 114160558 A CN114160558 A CN 114160558A
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- 239000002689 soil Substances 0.000 title claims abstract description 113
- 239000000126 substance Substances 0.000 title claims abstract description 113
- 239000000463 material Substances 0.000 title claims abstract description 107
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 46
- 239000011149 active material Substances 0.000 claims abstract description 40
- 239000002734 clay mineral Substances 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 230000003204 osmotic effect Effects 0.000 claims abstract description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 20
- 229910052799 carbon Inorganic materials 0.000 claims description 14
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- 230000035699 permeability Effects 0.000 claims description 13
- 230000000087 stabilizing effect Effects 0.000 claims description 11
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- 235000015097 nutrients Nutrition 0.000 claims description 10
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- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 10
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- 230000000903 blocking effect Effects 0.000 claims description 8
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
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- 239000011572 manganese Substances 0.000 claims description 4
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- 239000004113 Sepiolite Substances 0.000 claims description 3
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- 239000008103 glucose Substances 0.000 claims description 3
- 229910052900 illite Inorganic materials 0.000 claims description 3
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 3
- VGIBGUSAECPPNB-UHFFFAOYSA-L nonaaluminum;magnesium;tripotassium;1,3-dioxido-2,4,5-trioxa-1,3-disilabicyclo[1.1.1]pentane;iron(2+);oxygen(2-);fluoride;hydroxide Chemical compound [OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[F-].[Mg+2].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].[K+].[Fe+2].O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2 VGIBGUSAECPPNB-UHFFFAOYSA-L 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 229910052624 sepiolite Inorganic materials 0.000 claims description 3
- 235000019355 sepiolite Nutrition 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 239000004343 Calcium peroxide Substances 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- 229960000892 attapulgite Drugs 0.000 claims description 2
- LHJQIRIGXXHNLA-UHFFFAOYSA-N calcium peroxide Chemical group [Ca+2].[O-][O-] LHJQIRIGXXHNLA-UHFFFAOYSA-N 0.000 claims description 2
- 235000019402 calcium peroxide Nutrition 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical group O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052625 palygorskite Inorganic materials 0.000 claims description 2
- 238000010186 staining Methods 0.000 claims 1
- 239000011159 matrix material Substances 0.000 abstract description 9
- 239000002131 composite material Substances 0.000 abstract description 6
- 238000012954 risk control Methods 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 5
- 230000009467 reduction Effects 0.000 abstract description 5
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- FMMWHPNWAFZXNH-UHFFFAOYSA-N Benz[a]pyrene Chemical compound C1=C2C3=CC=CC=C3C=C(C=C3)C2=C2C3=CC=CC2=C1 FMMWHPNWAFZXNH-UHFFFAOYSA-N 0.000 description 50
- 229910052785 arsenic Inorganic materials 0.000 description 20
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 20
- 239000000243 solution Substances 0.000 description 17
- 238000002386 leaching Methods 0.000 description 16
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
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- WQHONKDTTOGZPR-UHFFFAOYSA-N [O-2].[O-2].[Mn+2].[Fe+2] Chemical compound [O-2].[O-2].[Mn+2].[Fe+2] WQHONKDTTOGZPR-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
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- TXVHTIQJNYSSKO-UHFFFAOYSA-N BeP Natural products C1=CC=C2C3=CC=CC=C3C3=CC=CC4=CC=C1C2=C34 TXVHTIQJNYSSKO-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
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Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/002—Reclamation of contaminated soil involving in-situ ground water treatment
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C2101/00—In situ
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Soil Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention belongs to the technical field of in-situ risk control and restoration of polluted soil, and particularly relates to an in-situ chemical barrier material for heavy metal, organic and composite polluted soil, a preparation method of the in-situ chemical barrier material, and application of cooperative control and restoration treatment of polluted soil and underground water. The material comprises 50-95% of polluted area in-situ soil and 5-50% of clay mineral in percentage by weight. The chemical barrier layer material provided by the invention has multiple advantages of convenient material taking, multiple functions, durable performance, convenient operation, wide application and the like. The soil that cleans soil or reaches the landfill and handle the standard with place normal position is as main matrix material, saves material economic cost, adds the clay mineral in the separation material simultaneously, is showing the osmotic coefficient that reduces the separation mixed material, and in addition, the application of active material carries out effective control and supplementary reduction to the pollution factor in the mixed material to realize the normal position risk management and control and the processing target in pollution place through multiple functional characteristic.
Description
Technical Field
The invention belongs to the technical field of in-situ risk control and restoration of polluted soil, and particularly relates to an in-situ chemical barrier material for heavy metal, organic and composite polluted soil, a preparation method of the in-situ chemical barrier material, and application of cooperative control and restoration treatment of polluted soil and underground water.
Background
The site polluted soil is from the production operation activities of factories in petrochemical industry, coking and smelting, electronic pharmacy and other industries operated in early stage and for a long time. With the increasing attention on ecological environment protection, the environmental protection supporting measures of industrial enterprises in the production process are continuously perfected, the supervision of important industrial enterprises related to environmental interference is continuously expanded, and the pollution problem of new sites is effectively controlled and reduced. However, the problem of the pollution site left over in history still exists at present, and particularly for large-scale industrial enterprises, the current situations of high upgrading and upgrading cost of production process, difficulty in relocation and serious pollution problem exist, so that the urban development and expansion and economic development are greatly restricted, land waste is caused, potential human health risks are brought to the lives of people around, and efficient and reasonable pollution disposal, development and reutilization are urgently needed.
In view of a plurality of factors such as historical remnants, pollution characteristics, geographical positions and development planning, the treatment of a large pollution site has the problems of large volume, heavy disposal burden, long period, secondary pollution diffusion and the like. Particularly, how to realize low-carbon, economic and efficient disposal of the pollution site under the background of global advocation of carbon peak reaching and carbon emission reduction becomes one of the key and core problems aiming at treatment of large pollution sites.
The existing general technical strategy for treating the polluted site usually comprises two modes of restoration treatment and risk management and control, but practice shows that the cost for carrying out thorough heterotopic removal and restoration on the polluted soil in the site is high, the period is long, and experience combined with site later-stage planning and construction shows that the phenomenon of restoration redundancy exists. Therefore, on the premise of ensuring that the planned construction risk reaches the standard, the combination of restoration treatment and risk management and control measures is a pollution site dominant treatment mode for effectively realizing carbon emission reduction, volume reduction, cost reduction and efficiency improvement in the treatment process.
In the existing risk control measures, the ectopic landfill and the in-situ barrier are mainly used, and the ectopic landfill needs to occupy space resources and management cost of a landfill site, so the in-situ barrier measures have more economic advantages. The existing in-situ barrier measures mainly aim at the physical anti-seepage barrier of polluted soil through two films, and mainly aim at underground water by building a waterproof curtain and a barrier wall. But the drawback of in-situ barrier control lies in that the pollution factor content is not effectively reduced, the risk of damage and pollution exposure exists, and the construction of site follow-up planning is restricted to a certain extent. Therefore, how to further realize gradual pollutant concentration reduction while implementing separation control, and minimize the operation contradiction with site later development and construction, and ensure long-term up-to-standard control effect will be an important breakthrough for improving the comprehensive disposal efficiency of the polluted site.
In view of the above, for satisfying the above-mentioned demand of dealing with to the normal position of large-scale contaminated site, this patent provides an in situ chemical barrier material that can apply place contaminated soil and preparation method and application mode to the high-efficient risk management and control of pollution factor is dealt with and is reduced the restoration with the pollution factor is cooperateed in realizing the place, and reduces the construction degree of difficulty for the development construction of place later stage, continuously ensures the safe utilization in contaminated site for a long time.
Disclosure of Invention
The invention aims to provide an in-situ chemical barrier material for heavy metal, organic and composite polluted soil, a preparation method thereof and application of cooperative management and control and restoration treatment for polluted soil and underground water.
In order to achieve the purpose, the invention adopts the technical scheme that:
an in-situ chemical barrier material for polluted soil is prepared from (by weight) polluted area in-situ soil 50-95% and clay mineral 5-50%.
Adding an active material into the in-situ chemical barrier material of the polluted soil; wherein the active material is a heavy metal stabilized active material and/or a biostimulating active material.
The heavy metal stabilizing active material is an oxide of iron and/or manganese; the biostimulation active material is a nutrient salt agent, an organic carbon source and a slow-release oxygen agent;
wherein, the heavy metal stabilizing active material accounts for 0.5 to 3 percent of the material dosage of the total chemical barrier layer;
the dosage of the nutrient salt agent in the biostimulation active material accounts for 0.1-0.3 percent of the total material of the chemical barrier layer, the dosage of the organic carbon source accounts for 1-5 percent of the total material of the chemical barrier layer, and the dosage of the slow-release oxygen agent accounts for 1-3 percent of the total material of the chemical barrier layer.
The clay mineral is one or more of montmorillonite, illite, sepiolite, bentonite and attapulgite; the amount of clay mineral applied is the percentage (W) of each type of clay mineral in the total chemical barrier material mass, which is related to the mixture permeability coefficient (k):
k＝f(W)，W∈(WML,WLL,WSL,WMT,WAT)
wherein ,WML、WLL、WSL、WMT、WATThe dosage proportion of the clay mineral is determined according to the functional relation of k-W, and the dosage proportion of one or more types of clay minerals which need to be doped when the target osmotic coefficient is reached is determined.
The permeability coefficient (k) of the mixed material is less than or equal to 1 multiplied by 10 after the barrier layer material is laid in an in-situ mode-6～1×10-7cm/s。
The in-situ soil of the polluted area is clean soil dug out from a polluted site or soil which reaches the landfill standard after being treated.
The standard for achieving landfill is that the content of organic pollutants in leachate of treated soil reaches the comprehensive sewage discharge standard (DB21/1627-2008) and the content of heavy metals in soil reaches the IV-type standard in the quality standard of surface water (GB3838-2002), and the filler can be used for preparing the chemical barrier layer filler.
The iron oxide is ferric oxide (Fe)2O3) And/or ferrous sulfate (FeSO)4) (ii) a The manganese oxide is pyrolusite (beta-MnO)2) And/or manganite (Mn)3+O(OH))；
The nutrient salt agent comprises the following components: NH (NH)4NO3,15％～20％，MgSO4,20％～25％，NaCl,10％～15％，K2HPO4,5％～10％，KH2PO4,5％～10％，CaCl2,20％～45％；
The organic carbon source is industrial glucose and/or bran;
the slow-release oxygen agent is a calcium peroxide preparation embedded by polyvinyl alcohol.
Preparation of an in-situ chemical barrier material for contaminated soil:
aiming at the heavy metal contaminated soil, the contaminated soil in-situ chemical barrier material is formed by mixing in-situ soil, clay minerals and heavy metal stabilizing active materials;
aiming at the organic polluted soil, the in-situ chemical barrier material of the polluted soil is the mixture of in-situ soil, clay minerals and biostimulation active materials;
aiming at the heavy metal/organic matter compound contaminated soil, the in-situ chemical barrier material of the contaminated soil is formed by mixing in-situ soil, clay minerals, heavy metal stabilizing active materials and biostimulation active materials.
The application of the in-situ chemical barrier material for the polluted soil is used as a barrier layer covered by the in-situ polluted soil to realize the common management and control and repair of the in-situ polluted soil and underground water.
The in-situ chemical barrier material of the polluted soil horizontally and/or vertically covers the in-situ soil body; when the chemical blocking layer is not soaked in underground water, the thickness of the chemical blocking layer can be set to be 30-100 cm; when the laying position is deep or the groundwater level is shallow, and the blocking layer is possibly soaked in groundwater, the thickness of the chemical blocking layer can be set to be 60-100 cm.
The invention has the advantages that:
1) the chemical barrier layer material provided by the invention has multiple advantages of convenient material taking, multiple functions, durable performance, convenient operation, wide application and the like. The method has the advantages that the site in-situ clean soil or the soil meeting the landfill disposal standard is used as a main matrix material, the economic cost of materials is saved, meanwhile, clay minerals are added into the barrier material, the permeability coefficient of the barrier mixed material is obviously reduced, the adsorption characteristic of the material matrix is increased, in addition, the application of active materials in the mixed material is effectively controlled and assisted to reduce pollution factors, and therefore the in-situ risk control and disposal target of the polluted site is achieved through various functional characteristics;
2) in the chemical barrier layer material provided by the invention, different types of active materials can be selectively applied aiming at different types of polluted soil, and specific treatment can be respectively carried out aiming at heavy metal polluted soil, organic polluted soil and composite polluted soil, for example, functional materials such as strong chemical adsorption iron manganese oxide and the like are added for heavy metal pollution factors, biostimulation functional materials are added for organic pollution factors, and the stimulation effect on the biological degradation activity of the pollution factors is realized by utilizing, improving and strengthening indigenous microorganisms in-situ soil matrix and induced metabolic functions of the indigenous microorganisms, obtained by long-term pollutant domestication, aiming at the pollution factors;
3) the clay mineral provided by the invention can be selected from multiple feasible types, the alternative mineral types have the characteristics of low permeability and strong chemical adsorption, and the heavy metal ions can be captured through chemical bonds such as hydrogen bonds, coordination bonds and the like, so that the stabilization process of the heavy metal ions is realized;
4) the invention provides a reasonable parameter range of total clay mineral application amount in a chemical barrier layer material, but the application amount of each type of clay mineral needs to be accurately determined in the construction design process, and accordingly, the invention further provides a method for realizing quantitative calculation of the application amount of each clay mineral by constructing a functional relation between the total osmotic coefficient of the barrier layer material and the application amount ratio of each type of clay mineral, so that material parameters are accurately determined;
5) the chemical barrier layer provided by the invention can be applied in situ to soil and underground water at the same time, the water and soil co-treatment process is realized, meanwhile, the application of the chemical barrier layer can overcome the defects that the traditional physical barrier layer is damaged due to long-term use or the barrier layer is exposed due to site subsequent development piling construction and the like, and is difficult to repair, the barrier layer can be repaired in a mode of refilling materials when the traditional physical barrier layer is damaged, and the method is convenient and quick and has no residual leakage points.
Drawings
Fig. 1 is a schematic view of a chemical barrier material according to an embodiment of the present invention.
FIG. 2 is a graph of the permeability coefficient (k) of the chemical barrier bulk material as a function of the content of each type of mineral component according to an embodiment of the present invention.
Fig. 3 is a schematic view of a small test of management and control treatment of a chemical barrier layer of SVOCs and heavy metal arsenic contaminated soil according to an embodiment of the present invention.
Fig. 4 is a graph showing the change of the effective state content of heavy metal arsenic in the material in the small-test chemical barrier layer according to the embodiment of the present invention.
FIG. 5 is a graph showing the change in the content of benzo [ a ] pyrene in SVOCs in soil outside the chemical barrier layer of the pilot test provided by the embodiment of the present invention.
FIG. 6 is a graph showing the variation of benzo (a) pyrene content in barrier layer material according to the leaching period
Fig. 7 is a schematic view of disposing a chemical barrier layer on a complex contaminated site of a chemical plant according to an embodiment of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and examples.
Aiming at the risk management and control treatment of heavy metal and organic matter polluted sites, the chemical barrier material provided by the invention and the chemical barrier layer constructed by the chemical barrier material are adopted to carry out barrier treatment on pollutants in the site soil, so that the safe utilization of the ground space of the polluted site is realized. The preparation of the chemical barrier material and the application thereof to barrier control of a polluted site are respectively illustrated by the results of a small-scale experiment and a site-site pilot test.
The in-situ chemical barrier material for the polluted soil is prepared by uniformly mixing in-situ soil and clay minerals in a polluted area, and can be added with an active material, wherein the in-situ soil accounts for 50-95% and the clay minerals accounts for 5-50% of the chemical barrier material. Wherein the clay mineral is selected from montmorillonite, illite, sepiolite, bentonite, and attapulgiteOne or more of the soil; the active material comprises a heavy metal stabilized active material, namely iron manganese oxide, and a biostimulating active material, namely a mixture of a nutrient salt agent, an organic carbon source and a slow-release oxygen agent. The clay mineral composition content in the mixed material is quantitatively determined according to the functional relationship between the permeability coefficient of the mixed material and the ratio of the clay mineral usage amount of each type, and the permeability coefficient of the prepared chemical barrier layer material after being laid is less than or equal to 1 multiplied by 10-6～1×10-7cm/s. The in-situ chemical barrier layer made of the chemical barrier material can be respectively used for in-situ control and restoration of heavy metal contaminated soil, organic contaminated soil and composite contaminated soil, effectively solves the problems that the barrier layer is damaged by natural corrosion or piling operation in the traditional physical barrier mode, so that pollutants are exposed and the like, has the function of cooperative disposal of soil and underground water, and has good demonstration effect and popularization and application prospect.
Example 1 preparation of chemical Barrier layer Material for contaminated sites
The embodiment is directed at the application of in-situ barrier control of heavy metal and organic pollutant combined contaminated soil:
accordingly, the chemical barrier material is composed of in-situ soil, clay minerals, heavy metal stabilizing active materials and biostimulation active materials, the schematic diagram of the chemical barrier material is shown in fig. 1, and the components of the material are shown in table 1.
1) Preparation of chemical barrier material
Firstly, in-situ soil is taken as a chemical barrier material matrix, the in-situ soil is dug from a polluted site of a certain northern chemical plant, the pollution characteristics of the soil in the site are that heavy metal arsenic exceeds the screening values (arsenic 60mg/kg and benzo [ a ] pyrene 1.5mg/kg) of the two types of construction sites in soil pollution risk control standard of soil environment quality construction sites (GB 36600-2018), the average total amount of arsenic in the soil reaches 75.3mg/kg, and meanwhile, the average content of benzo [ a ] pyrene in the soil reaches 15.87 mg/kg. In contrast, a heavily polluted area is avoided, a suspected lightly polluted and non-polluted soil area is selected for dredging, the average content of heavy metal arsenic in the excavated soil is detected to be 18.96mg/kg, the average content of benzo [ a ] pyrene is detected to be 2.87mg/kg, furthermore, a leaching experiment is carried out on the soil by adopting a solid waste leaching toxicity leaching method acetic acid buffer solution method (HJT300-2007), the content of heavy metal arsenic and benzo [ a ] pyrene in a leaching solution is detected, the total amount of arsenic in the solution is 0.082mg/L, the IV standard in the surface water quality standard (GB3838-2002) is met, the content of benzo [ a ] pyrene in the solution is 0.00016mg/L, and the comprehensive sewage discharge standard (DB 21/1627-.
Secondly, bentonite (MT) is selected as a clay mineral component to be added to the chemical barrier matrix filler to reduce the overall permeability of the material. In order to accurately determine the relation between the clay mineral addition proportion and the target permeability of the mixed material, k-W is carried out in advanceMTConstructing a relation model, namely performing k-W by respectively adopting series of addition proportions of 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt% and 40 wt% and corresponding permeability coefficients of the mixed materialsMTRelationship determination, the resulting relationship model is shown in fig. 2, resulting in the following relationship:
y＝0.002833e-21.6299x
when the target permeability coefficient y is 9.2 × 10-7Amount of bentonite added (W) in cm/sMT) The amount was 37%, and the addition ratio of the clay mineral component was determined. Correspondingly, the proportion of the soil matrix to the total mixed material is 63%.
Thirdly, adding a chemical barrier layer active material into the mixed material of the in-situ soil matrix and the clay mineral for stabilizing and degrading pollutants. The pollution-oriented field provided in the embodiment is the heavy metal and organic matter combined pollution, so that the chemical barrier active material is respectively designed for heavy metal passivation and organic matter biodegradation.
Aiming at the stabilization treatment of heavy metal, the active material is selected from iron oxide (Fe)2O3) And pyrolusite (beta-MnO)2) The mixture of (1) and (0) is composed of iron oxide, pyrolusite and manganese oxide, wherein the iron oxide accounts for 1% of the total material, the pyrolusite accounts for 0.5% of the total material, and the total iron and manganese oxide accounts for 1.5% of the total material.
Aiming at the biodegradation treatment of organic pollutants, the used active materials are biostimulation active materials, and comprise a nutrient salt agent, an organic carbon source and a slow-release oxygen agent. Wherein the total addition amount of the nutrient salt agent is 0.2%, the total addition amount of the organic carbon source is 3%, and the addition amount of the slow-release oxygen agent is 2%.
The components of the nutrient salt agent are as follows: NH (NH)4NO3,20％，MgSO4,25％，NaCl,15％，K2HPO4,10％，KH2PO4,10％，CaCl2,20％；
The used organic carbon source is industrial glucose, and the total addition amount is 3%;
the slow-release oxygen agent is prepared by embedding polyvinyl alcohol, and the total addition amount is 2%.
And (3) homogenizing and mixing the in-situ soil, the clay mineral, the heavy metal stabilizing active material and the biostimulation active material to prepare the chemical barrier material.
TABLE 1
2) Barrier control of chemical barrier layer for heavy metal arsenic and benzo [ a ] pyrene combined contaminated soil
In order to verify the application effect of the chemical barrier layer in the barrier control of the heavy metal and organic compound contaminated soil, a small-scale barrier experiment is adopted for verification and evaluation. The chemical barrier layer evaluation was performed by solution leaching using a bench-scale leaching apparatus (fig. 3). The device is internally divided into a pollutant solution loading chamber, a chemical barrier material chamber, a glass bead liquid distribution chamber, a collecting groove and a filtrate collecting bottle from top to bottom.
The used polluted solution is a polluted solution containing arsenic and benzo [ a ] pyrene with series concentrations, the initial content of As in the solution is respectively 0.5, 1, 2, 5 and 10mg/L, and the initial content of benzo [ a ] pyrene is 0.5, 1.0, 2.5, 5.0 and 10mg/kg (table 2); the overall diameter of the test device is 36mm, the total height is 127mm, the thickness of the chemical barrier layer filling chamber is 30mm, and the chemical barrier material is the material provided in the step 1).
The whole experiment is carried out in a two-stage process, water is firstly added to saturate the chemical barrier material with water, then the polluted solution is added every 12 hours to carry out leaching, the leaching capacity is 50mL each time, and the total leaching frequency of the one-stage experiment is 6 times. After the polluted solution is completely sprayed on the chemical barrier layer made of the chemical barrier material, the content of heavy metal arsenic pollutants in filtrate in a collecting bottle at the bottom end of the experimental device is detected. And after the first-stage experiment is finished, carrying out rinsing on the polluted solution once every 15 days, carrying out rinsing treatment for 4 times in total, storing the rinsed chemical barrier layer for 120 days, sampling once every 15 days, carrying out content detection on benzo [ a ] pyrene in the chemical barrier layer material, and finishing the second-stage experiment.
The detection results of the experiments are shown in fig. 4 and 5, aiming at the leaching of the polluted solution with the initial arsenic content of 0.5-5 mg/L, the arsenic content is less than 0.1mg/L in all the leacheate sampled for 6 times, and the arsenic content is more than 0.1mg/L in the leacheate sampled for 5-6 times under the condition of the initial high-concentration solution of 10mg/L, which is caused by the adsorption saturation of the chemical barrier layer filler; aiming at the leaching of the polluted solution with the benzo [ a ] pyrene content of 0.5-2.5 mg/L, in all 6 times of sampled leacheate, the benzo [ a ] pyrene content is less than 0.0003mg/L, and when the initial content is greater than 5.0mg/L, the benzo [ a ] pyrene content in the leacheate begins to be greater than 0.0003mg/L, which indicates that the adsorption of the chemical barrier layer is saturated. The results show that the chemical barrier layer has good adsorption and passivation effects on heavy metals of arsenic and benzo [ a ] pyrene under the condition of certain initial content. Secondly, in a second-stage experiment, aiming at the detection of benzo [ a ] pyrene, the determination of benzo [ a ] pyrene in a barrier layer material is carried out for 15 days, 30 days, 45 days, 60 days, 75 days, 90 days, 105 days and 120 days respectively (figure 6), and the result shows that after leaching treatment of different initial content of pollution solutions, pollutant accumulation with different degrees is generated in the barrier layer material, the content of benzo [ a ] pyrene is gradually increased along with the increase of leaching times, but the content detected each time is obviously lower than the accumulation amount of the added benzo [ a ] pyrene, particularly in a sample sampled and detected at 120 days, even if the benzo [ a ] pyrene sample is 10mg/kg in the initial pollution solution, the total pollutant removal rate still reaches 72.7 percent. Therefore, the chemical barrier layer made of the chemical barrier material has good adsorption barrier activity on heavy metal arsenic and organic benzo [ a ] pyrene, and has good degradation performance on benzo [ a ] pyrene, so that barrier control and degradation of pollutants are realized while treatment is carried out.
TABLE 2
| Initial content of leacheate | 1 | 2 | 3 | 4 | 5 |
| As(mg/L) | 0.5 | 1 | 2 | 5 | 10 |
| Benzo [ a ]]Pyrene (mg/kg) | 0.5 | 1 | 2.5 | 5 | 10 |
Example 2 application of chemical barrier layer to Pilot plant field barrier control of heavy metal arsenic contaminated soil
According to the treatment result of the chemical barrier layer verified by the bench test in the step 2) of the example 1, an area with the length of 5m and the width of 5m is selected from the sampling place (the pollution place of a certain chemical plant in the north) of the polluted soil sample in the chemical barrier material matrix prepared in the step 1) of the example 1 to carry out the bench test on the polluted soil barrier. In the construction process, firstly, a polluted target area is dug, a flat-bottom foundation pit (figure 7) with the length of 7m, the width of 7m and the depth of 800mm is dug, then the chemical barrier material prepared in the step 1) of the embodiment 1 is used as a chemical barrier layer, the thickness of the barrier layer is designed to be 0.5m, and the total amount of filling materials of the barrier layer is 44.1 t. After the chemical barrier layer is filled and paved, in-situ clean soil with the thickness of about 300mm is paved above the chemical barrier layer. And a surface soil sampling area is arranged in the central area of the chemical barrier control area, the surface soil sampling depth is 10cm, sample collection is carried out once every 30 days, and the total sampling period is 1 year. And (3) carrying out leaching experiment detection on the extracted soil sample, and analyzing the contents of heavy metal arsenic and organic benzo [ a ] pyrene in the leaching solution. Experimental results show that in soil samples above 12 analyzed chemical barrier layers, the total amount of arsenic and benzo [ a ] pyrene in the samples meets the screening value of the second-class construction land in the soil pollution risk control standard for soil environmental quality construction land (GB 36600-2018), and the contents of heavy metal arsenic and benzo [ a ] pyrene in leachate respectively meet the IV-class standard in the ground surface water quality standard (GB3838-2002) and the comprehensive sewage discharge standard (DB21/1627-2008), so that the safety control and utilization of the chemical barrier layer material for the heavy metal and organic matter composite pollution field under the pilot test condition are realized.
Claims (10)
1. An in-situ chemical barrier material for polluted soil, which is characterized in that: the material comprises 50-95% of polluted area in-situ soil and 5-50% of clay mineral in percentage by weight.
2. The in-situ chemical barrier material for contaminated soil as claimed in claim 1, wherein: adding an active material into the in-situ chemical barrier material of the polluted soil; wherein the active material is a heavy metal stabilized active material and/or a biostimulation active material;
the heavy metal stabilizing active material is an oxide of iron and/or manganese; the biostimulation active material is a nutrient salt agent, an organic carbon source and a slow-release oxygen agent;
wherein, the heavy metal stabilizing active material accounts for 0.5 to 3 percent of the material dosage of the total chemical barrier layer;
the dosage of the nutrient salt agent in the biostimulation active material accounts for 0.1-0.3 percent of the total material of the chemical barrier layer, the dosage of the organic carbon source accounts for 1-5 percent of the total material of the chemical barrier layer, and the dosage of the slow-release oxygen agent accounts for 1-3 percent of the total material of the chemical barrier layer.
3. The in-situ chemical barrier material for contaminated soil as claimed in claim 1, wherein:
the clay mineral is one or more of montmorillonite, illite, sepiolite, bentonite and attapulgite; the amount of clay mineral applied is the percentage (W) of each type of clay mineral in the total chemical barrier material mass, which is related to the mixture permeability coefficient (k):
k＝f(W)，W∈(WML,WLL,WSL,WMT,WAT)
wherein ,WML、WLL、WSL、WMT、WATThe dosage proportion of the clay mineral is determined according to the functional relation of k-W, and the dosage proportion of one or more types of clay minerals which need to be doped when the target osmotic coefficient is reached is determined.
4. The in-situ chemical barrier material for contaminated soil as claimed in claim 3, wherein: the permeability coefficient (k) of the mixed material is less than or equal to 1 multiplied by 10 after the barrier layer material is laid in an in-situ mode-6～1×10-7cm/s。
5. The in-situ chemical barrier material for contaminated soil as claimed in claim 1, wherein: the in-situ soil of the polluted area is clean soil dug out from a polluted site or soil which reaches the landfill standard after being treated.
6. The in-situ chemical barrier material for contaminated soil as claimed in claim 5, wherein: the standard for achieving landfill is that the content of organic pollutants in leachate of treated soil reaches the comprehensive sewage discharge standard (DB21/1627-2008) and the content of heavy metals in soil reaches the IV-type standard in the quality standard of surface water (GB3838-2002), and the filler can be used for preparing the chemical barrier layer filler.
7. The in-situ chemical barrier material for contaminated soil as claimed in claim 2, wherein:
the iron oxide is ferric oxide (Fe)2O3) And/or ferrous sulfate (FeSO)4) (ii) a The manganese oxide is pyrolusite (beta-MnO)2) And/or manganite (Mn)3+O(OH))；
The nutrient salt agent comprises the following components: NH (NH)4NO3,15％～20％，MgSO4,20％～25％，NaCl,10％～15％，K2HPO4,5％～10％，KH2PO4,5％～10％，CaCl2,20％～45％；
The organic carbon source is industrial glucose and/or bran;
the slow-release oxygen agent is a calcium peroxide preparation embedded by polyvinyl alcohol.
8. Preparation of the in-situ chemical barrier material for contaminated soil according to claim 1, wherein:
aiming at the heavy metal contaminated soil, the contaminated soil in-situ chemical barrier material is formed by mixing in-situ soil, clay minerals and heavy metal stabilizing active materials;
aiming at the organic polluted soil, the in-situ chemical barrier material of the polluted soil is the mixture of in-situ soil, clay minerals and biostimulation active materials;
aiming at the heavy metal/organic matter compound contaminated soil, the in-situ chemical barrier material of the contaminated soil is formed by mixing in-situ soil, clay minerals, heavy metal stabilizing active materials and biostimulation active materials.
9. The application of the in-situ chemical barrier material for the polluted soil as claimed in claim 1, wherein the in-situ chemical barrier material comprises the following components: the in-situ chemical barrier material for the polluted soil is used as a barrier layer for covering the in-situ polluted soil, so that the application of common control and restoration of the in-situ polluted soil and underground water is realized.
10. The use of the soil-staining in-situ chemical barrier material as claimed in claim 9, wherein: the in-situ chemical barrier material of the polluted soil horizontally and/or vertically covers the in-situ soil body; when the chemical blocking layer is not soaked in underground water, the thickness of the chemical blocking layer can be set to be 30-100 cm; when the laying position is deep or the groundwater level is shallow, and the blocking layer is possibly soaked in groundwater, the thickness of the chemical blocking layer can be set to be 60-100 cm.
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