CN111957734B - Method for in-situ remediation of soil heavy metal pollution - Google Patents
Method for in-situ remediation of soil heavy metal pollution Download PDFInfo
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- CN111957734B CN111957734B CN202010637291.0A CN202010637291A CN111957734B CN 111957734 B CN111957734 B CN 111957734B CN 202010637291 A CN202010637291 A CN 202010637291A CN 111957734 B CN111957734 B CN 111957734B
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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
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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
- B09C1/02—Extraction using liquids, e.g. washing, leaching, flotation
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- C09K17/32—Prepolymers; Macromolecular compounds of natural origin, e.g. cellulosic materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
The invention provides a method for in-situ remediation of soil heavy metal pollution, which comprises the following steps: (1) soaking and washing: pouring the heavy metal dissolving agent into the heavy metal contaminated soil to dissolve out the heavy metal; (2) adsorption: adding modified hair containing at least partial sulfydryl into soil, intermittently stirring, and adsorbing heavy metal. In the method for in-situ remediation of heavy metal pollution in soil, the combined soil cleaning technology of the lead adsorption material and the soil cleaning method is invented, so that the secondary pollution of the soil is effectively avoided while the in-situ soil cleaning with low cost is realized, and the safety of the soil, the food safety and the ecological environment safety are ensured.
Description
Technical Field
The invention belongs to the technical field of soil pollution control, and particularly relates to a method for in-situ remediation of heavy metal pollution in soil.
Background
At present, there are many physical, chemical and biological methods for treating soil pollution internationally. The physical method is an engineering measure for treating the heavy metal pollution of soil by a physical (mechanical) and physical-chemical method. Mainly comprises the steps of soil dressing, surface soil removal, ploughing, isolation, soil washing, thermal desorption, electric restoration, vitrification and the like, and the methods have good effects but high cost. Biological measures, which refer to the removal or degradation of contaminants in soil by certain animals, plants or microorganisms. Bioremediation is generally popular with the scientific community and government departments because of its advantages of low cost, good effect, environmental friendliness, convenient operation, etc. But has poor biological adaptability, difficult collection and small biomass, and the heavy metal in the body can be absorbed and metabolized and released into soil through death and metabolism. The chemical method is to inactivate heavy metals in the soil by chemical reaction (promotion of precipitation, addition of inhibitors or adsorbents, antagonism between elements, etc.) between the reagents and the heavy metal ions. The chemical remediation method is quick, simple, economical and practical, but the soil is still not clean. Even if the heavy metals in the soil are temporarily inactivated, leaving the heavy metals in the soil is still dangerous.
From another perspective, soil remediation is divided into in situ remediation and ex situ remediation. The in-situ repair cost is lower than that of ex-situ repair, and the engineering quantity is small. International soil remediation technologies tend to: (1) green and environment-friendly bioremediation technology; (2) a combined repair technique; (3) and (3) in-situ repair technology.
At present, several existing remediation technologies capable of cleaning soil, such as leaching method, heat treatment method, electric remediation method, biological remediation method and the like, have great limitations, wherein the leaching method is to clean soil by using leacheate, so that heavy metals in the polluted soil enter the leacheate, and then collect the leacheate for recycling. Soil cleaning is one of the few permanent treatment methods for removing metal contaminants from soil, particularly in connection with remediation of metal contaminated soils, and may be used alone or in combination with other treatment techniques. Because of its low cost, good effect and high speed, it has been widely used in developed countries such as the netherlands, germany, sweden, norway, belgium, canada, usa, but has not been widely used in the field control.
Disclosure of Invention
The invention aims to provide a method for in-situ remediation of heavy metal pollution in soil, which can effectively adsorb and remove heavy metals in the heavy metal polluted soil only by using a simple and environment-friendly heavy metal dissolving agent and modified hair.
The technical scheme adopted by the invention is as follows:
a method for in-situ remediation of soil heavy metal pollution comprises the following steps:
(1) soaking and washing: pouring the heavy metal dissolving agent into the heavy metal contaminated soil to dissolve out the heavy metal;
(2) adsorption: adding modified hair containing at least partial sulfydryl into soil, intermittently stirring, and adsorbing heavy metal.
Preferably, in the method for in-situ remediation of heavy metal pollution in soil, the step (2) may also be: and (2) collecting the supernatant in the step (1), adding modified hair containing at least partial sulfydryl, intermittently stirring, and adsorbing heavy metal. Then returning the clear liquid to the field.
Preferably, in the method for in-situ remediation of heavy metal pollution in soil, the heavy metal leaching agent is poured into a plough layer of the heavy metal polluted soil, and generally, the soil layering can be divided into: the soil layer, the subsoil layer and the bottom soil layer, wherein the thickness of the topsoil layer, namely a plough layer, is about 20cm, a plough layer with the thickness of 6-8 cm is arranged below the topsoil layer, the soil quality is compact, the water permeability is poor, and more than 60 percent of root systems which can adsorb heavy metals are concentrated in the plough layer. Therefore, in the method for in-situ remediation of heavy metal pollution in soil, the heavy metal leaching agent is selected to be poured into the plough layer of the soil, so that heavy metal can be leached out, the heavy metal in a leaching state can not migrate to the soil layer due to the compact soil texture and poor water permeability of the plough layer, and secondary pollution is effectively avoided.
Preferably, in the method for in-situ remediation of heavy metal pollution in soil, the mass ratio of the heavy metal leaching agent to the soil to the modified hair is as follows: 250:125: 1-10.
Preferably, in the method for remediating heavy metal pollution in situ in soil, the heavy metal-dissolving agent in step (1) is at least one selected from natural organic acids such as citric acid, tartaric acid, lactic acid, ascorbic acid, malic acid, oxalic acid, acetic acid, pyruvic acid, ketoglutaric acid, gluconolactone, ethylenediaminetetraacetic acid, diethyltriaminepentaacetic acid, and the like.
Preferably, in the method for in-situ remediation of heavy metal pollution in soil, the molar concentration of the heavy metal leaching agent is 0.01-0.1 mol.L-1。
Preferably, in the method for repairing heavy metal pollution in soil in situ, the preparation method of the modified hair comprises the following steps:
(1) the hair is treated at a concentration of 0.3 to 0.8 mol.L-1Soaking in NaOH aqueous solution for 4-10 h, washing to be neutral, and filtering to obtain pretreated hair;
(2) adding 2-mercaptoethanol into the pretreated hair, and then adding 2-6 mol.L-1The urea is decanted and placed for 4-10 hours.
Preferably, in the method for in-situ remediation of heavy metal pollution in soil, the mass-to-volume ratio of the pretreated hair to the 2-mercaptoethanol is 1g: 0.7-3 mL.
The invention has the beneficial effects that:
1. in the method for in-situ remediation of heavy metal pollution in soil, the heavy metal leaching agent of the natural chelating agent or the biosurfactant is used, so that the method has the advantages of stable performance, good biodegradability, environmental friendliness and high leaching efficiency of the heavy metal.
2. The hair is selected as the heavy metal treatment material, is easy to obtain, stable, environment-friendly and easy to recover, can treat Pb or other biotoxic heavy metal elements independently or simultaneously, and does not cause loss of nutrient elements or trace elements in the soil cleaning solution.
3. According to the characteristics of each layer of the soil layer, the plough layer is selected for leaching, the combined soil cleaning technology of the lead adsorption material and the soil cleaning method is invented, the secondary pollution of the soil is effectively avoided while the quick and low-cost in-situ soil cleaning is realized, and the soil safety, the food safety and the ecological environment safety are ensured.
Drawings
Fig. 1 shows the adsorption amounts of the modified hair to the respective coexisting heavy metal ions.
Detailed Description
In order to make the objects, technical solutions and technical effects of the present invention more clear, the present invention will be described in further detail with reference to specific embodiments. It should be understood that the detailed description and specific examples, while indicating the preferred embodiment of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention. The specific process parameters and the like of the following examples are also only one example of suitable ranges, and the skilled person can make a selection within the suitable ranges through the description herein, and are not limited to the specific data of the following examples. The starting materials used in the examples are, unless otherwise specified, commercially available from conventional sources.
In the following examples, modified hair was prepared by the following method:
(1) the hair is treated at 0.5 mol.L-1Soaking in NaOH aqueous solution for 6h, washing to neutrality, and filtering to obtain pretreated hair;
(2) the mass concentration of the added pretreated hair is 0.02 mol.L-12-mercaptoethanol, 4 mol. L-1The urea was decanted and allowed to stand for 6 h.
Example 1: a method for in-situ remediation of soil heavy metal pollution comprises the following steps:
(1) soaking and washing: 0.05 mol.L-1The citric acid solution is poured into a plough layer of the heavy metal polluted soil, wherein the mass volume ratio of the soil to the citric acid solution is 1g to 2mL, and the heavy metal is fully dissolved out;
(2) adsorption: adding modified hair containing at least partial sulfydryl into soil, wherein the mass volume ratio of the citric acid solution to the soil to the modified hair is 250mL to 125g to 1g, intermittently stirring, and fully adsorbing heavy metals.
Example 2: a method for in-situ remediation of soil heavy metal pollution comprises the following steps:
(1) soaking and washing: 0.1 mol/L-1The citric acid solution is poured into a plough layer of the heavy metal polluted soil, wherein the mass volume ratio of the soil to the citric acid solution is 1g to 2mL, and the heavy metal is fully dissolved out;
(2) adsorption: and (2) collecting the supernatant obtained in the step (1), adding modified hair containing at least partial sulfydryl, wherein the mass-volume ratio of the citric acid solution to the soil to the modified hair is 250mL to 125g to 8g, and stirring intermittently to fully adsorb heavy metal. Then returning the clear liquid to the field.
Example 3: a method for in-situ remediation of soil heavy metal pollution comprises the following steps:
(1) soaking and washing: 0.08 mol/L-1The citric acid solution is poured into a plough layer of the heavy metal polluted soil, wherein the mass volume ratio of the soil to the citric acid solution is 1g to 2mL, and the heavy metal is fully dissolved out;
(2) adsorption: adding modified hair containing at least partial sulfydryl into soil, wherein the mass volume ratio of the citric acid solution to the soil to the modified hair is 250mL to 125g to 5g, intermittently stirring, and fully adsorbing heavy metals.
Comparative example 1: a method for remedying soil polluted by heavy metal comprises the following steps:
(1) soaking and washing: 0.05 mol.L-1The citric acid solution is poured into a plough layer of the heavy metal polluted soil, wherein the mass body of the soil and the citric acid solutionThe volume ratio is 1g to 2mL, and heavy metals are fully dissolved out;
(2) adsorption: adding unmodified hair into the soil, wherein the mass volume ratio of the citric acid solution to the soil to the unmodified hair is 250mL to 125g to 1g, intermittently stirring, and fully adsorbing heavy metals.
Test example: analysis of heavy metal content and soil quality of the soil treated in examples 1-3 and comparative example 1
The soil samples before and after 2h treatment in example 1 were subjected to assay analysis, and the results are shown in table 1:
TABLE 1 elemental content of soil samples before and after 2h of treatment in example 1
| Content of soil elements | All Pb (g.kg)-1) | Available Pb (g.kg)-1) |
| Before treatment | 5.25 | 1.49 |
| After treatment | 5.14 | 1.08 |
As can be seen from Table 1, after one treatment by the method of the present invention, the Pb content in the soil was reduced by 2%, from 5.25 g.kg before the treatment-1Reduced to 5.14 g.kg-1The effective Pb content in the soil was 1.49 g/kg before treatment-1Reduced to 1.08 g.kg-1。
The soil samples before and after 2h treatment in comparative example 1 were subjected to assay analysis, and the results are shown in table 2:
TABLE 2 elemental content of soil samples before and after 2h treatment in comparative example 1
| Content of soil elements | All Pb (g.kg)-1) | Available Pb (g.kg)-1) |
| Before treatment | 5.25 | 1.49 |
| After treatment | 5.15 | 1.39 |
As can be seen from Table 2, the total Pb content in the soil was reduced by about 2%, from 5.25 g/kg before treatment-1Reduced to 5.15 g.kg-1The effective Pb content in the soil is 1.49 g/kg before treatment-1Reduced to 1.39 g.kg-1。
Comparing table 1 and table 2 shows that the modified hair has better adsorption capacity for Pb than the unmodified hair.
To further analyze the quality of the soil after the treatment according to the method of the present invention, the soil samples of example 2 before and after 2 hours of treatment were subjected to assay analysis, and the results are shown in tables 3 to 6:
table 3 example 2 basic chemistry of soil samples before and after 2h of treatment
| Nature of the soil | pH | Organic matter (g.kg)-1) | Cation exchange capacity (cmol. kg)-1) |
| Before treatment | 7.23 | 26.1 | 9.33 |
| After treatment | 7.74 | 28.2 | 9.60 |
As can be seen from Table 3, the pH, the organic matter content and the cation exchange capacity of the soil treated by the method for in-situ remediation of heavy metal pollution in soil are all improved.
Table 4 example 2 nutrient elements of soil samples before and after 2h treatment
As can be seen from Table 4, the contents of available nutrient elements, available N and available K, in the soil treated by the method for in-situ remediation of heavy metal pollution in the soil are reduced by about 3%, the full P is reduced by about 8%, and the others are all increased, which indicates that the method is favorable for maintaining the content of the available nutrients in the soil.
Table 5 example 2 mineral elements of soil samples before and after 2h treatment
As can be seen from Table 5, the contents of the effective mineral elements in the soil of the soil treated by the method for in-situ remediation of heavy metal pollution in the soil are all increased, which indicates that the method is favorable for improving the effective contents of the mineral elements in the soil.
Table 6 example 2 micro-elements of soil samples before and after 2h treatment
As can be seen from Table 6, the contents of effective trace elements in the soil of the soil treated by the method for in-situ remediation of heavy metal pollution in the soil are all increased, which indicates that the method is favorable for improving the effective contents of the trace elements in the soil.
Comparing tables 3-6, it is demonstrated that the method of the present invention is beneficial to improving soil quality.
Due to Pb in the soil eluate2+Usually with Cr3+、Cd2+、Cu2+、Zn2+The plasma coexists, thereby weakening the adsorption capacity of the modified hair for Pb. Whether or not to selectively remove Pb in such a complicated environment2+Is a serious challenge to the treatment method. Therefore, to analyze the selective removal performance of the modified hair on Pb heavy metal in the method of the invention, 25mL of the modified hair containing Cr is taken3+、Ni2+、Cu2+、Zn2+、、Cd2+、Pb2+The initial mass concentration of each ion in the solution of (1) is 1 mmol. multidot.L-1The results of an adsorption experiment performed on 100mg of the modified hair of the present invention at 25 ℃ and a statistical analysis of the amount of adsorption after standing for 6 hours are shown in FIG. 1.
As can be seen from FIG. 1, the modified hair used in the method for in-situ remediation of soil heavy metal pollution according to the present invention has a higher adsorption capacity for Pb than other ions, which means that the modified hair preferentially adsorbs Pb in a solution containing multiple metal ions, further indicating that the modified hair of the present invention can selectively remove heavy metal Pb in a complex metal element coexisting solution.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (3)
1. A method for in-situ remediation of soil heavy metal pollution comprises the following steps:
(1) soaking and washing: pouring the heavy metal dissolving agent into the heavy metal contaminated soil to dissolve out the heavy metal;
(2) adsorption: adding modified hair containing at least partial sulfydryl into soil, intermittently stirring, and adsorbing heavy metal;
the mass ratio of the heavy metal stripping agent to the soil to the modified hair is 250:125: 1-10;
the heavy metal dissolving agent in the step (1) is at least one selected from citric acid, tartaric acid, lactic acid, ascorbic acid, malic acid, oxalic acid, acetic acid, pyruvic acid, ketoglutaric acid, gluconolactone, ethylenediamine tetraacetic acid and diethyltriamine pentaacetic acid;
the molar concentration of the heavy metal stripping agent is 0.01-0.1 mol.L-1；
The preparation method of the modified hair comprises the following steps:
(1) the hair is treated at a concentration of 0.3 to 0.8 mol.L-1Soaking in NaOH aqueous solution for 4-10 h, washing to be neutral, and filtering to obtain pretreated hair;
(2) adding 2-mercaptoethanol into the pretreated hair, and then adding 2-6 mol.L-1Decanting the urea and standing for 4-10 h;
in the preparation method of the modified hair, in the step (2), the mass volume ratio of the pretreated hair to the 2-mercaptoethanol is 1g: 0.7-3 mL;
the heavy metal contaminated soil is soil containing heavy metal lead.
2. The method for in-situ remediation of soil contaminated with heavy metals according to claim 1, wherein: the step (2) is replaced by the following steps: collecting the supernatant in the step (1), adding modified hair containing at least partial sulfydryl, intermittently stirring, adsorbing heavy metal, and returning the supernatant to the field.
3. The method for in-situ remediation of soil contaminated with heavy metals according to claim 1, wherein: and (1) pouring the heavy metal stripping agent into a plough layer of the heavy metal contaminated soil.
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