CN115074136A - Heavy metal contaminated soil remediation agent and soil remediation method - Google Patents
Heavy metal contaminated soil remediation agent and soil remediation method Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/40—Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01B—SOIL WORKING IN AGRICULTURE OR FORESTRY; PARTS, DETAILS, OR ACCESSORIES OF AGRICULTURAL MACHINES OR IMPLEMENTS, IN GENERAL
- A01B79/00—Methods for working 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
- B09C1/08—Reclamation of contaminated soil chemically
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0836—Compounds with one or more Si-OH or Si-O-metal linkage
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/11—Compounds covalently bound to a solid support
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- Environmental & Geological Engineering (AREA)
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Abstract
The invention provides a heavy metal contaminated soil remediation agent and a soil remediation method. The heavy metal contaminated soil remediation agent comprises the following components: selenite and a silane coupling agent are used for modifying the biochar. The heavy metal contaminated soil remediation agent provided by the invention not only can reduce the mercury content of plants, but also can reduce the absorption of cadmium by the plants, and has good remediation effect on mercury and cadmium contaminated soil.
Description
Technical Field
The invention belongs to the technical field of heavy metal pollution treatment, and particularly relates to a heavy metal polluted soil repairing agent and a soil repairing method.
Background
Soil heavy metal pollution is an increasingly serious environmental problem in recent years, which is not only harmful to ecosystems and agricultural production, but also poses a serious threat to human health. Among these heavy metal pollutants, mercury (Hg) and cadmium (Cd) are widely spotlighted because of their high toxicity and many adverse effects on humans, animals and plants. The comprehensive prevention and treatment plan for heavy metal pollution also considers the two heavy metal elements as key pollutants for treatment.
The toxicity of mercury is closely related to the chemical form of mercury, most mercury compounds have toxicity, and mercury in soil can be converted into methyl mercury which has higher toxicity and is easier for biological enrichment, and can also be volatilized into the atmosphere and then absorbed by plant leaves. Methylmercury is a mercury compound with the strongest toxicity, and has high neurotoxicity, carcinogenicity, cardiovascular toxicity, reproductive toxicity, immune system effect, renal toxicity and the like. The water error in Japan in the 20 th century is a typical case of human methyl mercury poisoning.
Cadmium in industrial waste gas diffuses around along with wind direction and is accumulated in soil around a factory through natural sedimentation, and the other mode is that cadmium-containing industrial waste water irrigates farmlands to cause the soil to be polluted by the cadmium. Early renal damage from chronic cadmium poisoning is manifested by the presence of low molecular weight proteins (β 2 microglobulin, vitamin a binding protein, lysozyme, ribonuclease, etc.) in the urine, and may also be manifested by diabetes mellitus, hyperaminouria, and hyperphosphaturia. Chronic renal failure occurs in patients with advanced stages. Japan reports that chronic cadmium poisoning caused by ingestion of a cadmium-contaminated water source is called "pain disease". The clinical manifestations are back and leg pain, abdominal distension and dyspepsia, and severe patients suffer from multiple pathological fractures.
Therefore, aiming at the severe pollution condition of heavy metals Hg and Cd in the soil, the pollution of Hg and Cd is treated by adopting a proper means, and the effective soil remediation is particularly important.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a heavy metal contaminated soil remediation agent and a soil remediation method. The heavy metal contaminated soil remediation agent provided by the invention has a good passivation effect on mercury and cadmium, and can reduce the content of cadmium in plants while reducing the content of mercury in plants.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a heavy metal contaminated soil remediation agent, which comprises the following components: selenite and a silane coupling agent are used for modifying the biochar.
In some embodiments of the invention, the mass ratio of the selenite to the silane coupling agent modified biochar is 1 (7500-15000); for example, it may be 1:7500, 1:8000, 1:8500, 1:9000, 1:9500, 1:10000, 1:11000, 1:12000, 1:13000, 1:14000 or 1: 15000.
In some embodiments of the invention, the silane coupling agent modified biochar comprises silane coupling agent in an amount of 0.5 to 1.5 wt%; for example, it may be 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 1 wt%, 1.2 wt%, 1.3 wt%, 1.5 wt%, or the like.
In some embodiments of the invention, the selenite is sodium selenite.
In some embodiments of the invention, the silane coupling agent is gamma-mercaptopropyltrimethoxysilane (KH590) or gamma-methacryloxypropyltrimethoxysilane (KH 570).
In some embodiments of the invention, the biochar is selected from one or more of straw-based biochar, shell-based biochar, wood-based biochar, tobacco rod biochar, and pine cone biochar.
The pine cone biochar (PBC) has a large surface area, high porosity and rich oxygen-containing functional groups, and compared with other biochar, the pine cone biochar has a relatively strong capacity of fixing mercury and cadmium through a pore structure. The pinecone biochar contains C, N and O elements, and also contains a small amount of K, Ca, Mg metal elements and Cl elements, so that the pinecone biochar can provide nutrient elements for rice growth while reducing heavy metal pollution. Therefore, the biochar in the invention is preferably pinecone biochar.
In some embodiments of the present invention, the silane coupling agent modified biochar is prepared by the following method:
and soaking the biochar in a silane coupling agent solution, performing ultrasonic dispersion, then standing for reaction, filtering after the reaction is finished, and drying a filter cake to obtain the silane coupling agent modified biochar.
Wherein the concentration of the silane coupling agent solution is preferably 3 to 4 wt%.
The solvent of the silane coupling agent solution is preferably methanol.
The time of ultrasonic dispersion is preferably 15-30 min; for example, it may be 15min, 18 min, 20min, 22min, 25min, 28min or 30 min.
The time of the standing reaction is preferably 4-6 h; for example, it may be 4h, 4.2h, 4.5h, 4.8h, 5h, 5.2h, 5.5h, 5.8h or 6h, etc.
In a second aspect, the invention provides the use of a heavy metal contaminated soil remediation agent as described in the first aspect for remediation of mercury and cadmium contaminated soil.
In a third aspect, the invention provides a method for remediating heavy metal contaminated soil, which comprises the following steps: the heavy metal contaminated soil remediation agent of the first aspect is applied to soil in an amount of 1-2% by mass (e.g., 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, etc.) of the soil.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, selenite and silane coupling agent modified biochar are adopted as a heavy metal contaminated soil remediation agent, and the synergistic cooperation of the selenite and the silane coupling agent is utilized, so that the mercury content of plants can be reduced, the absorption of cadmium by the plants can be reduced, and the remediation effect on mercury and cadmium contaminated soil is good.
Drawings
FIG. 1A is a graph showing the total mercury content of rice stems in different concentrations of sodium selenite-treated groups in a potting experiment according to the present invention;
FIG. 1B is a graph showing the total mercury content of rice stems of different biochar-treated groups in a potting experiment according to the present invention;
FIG. 1C is a graph showing the total mercury content of rice stems in a modified biochar in combination with sodium selenite treatment group in a potting experiment according to the present invention;
FIG. 2A is a graph showing the total mercury content in rice leaves of different sodium selenite concentration treatment groups in the potting experiment of the present invention;
FIG. 2B is a graph showing the total mercury content of rice leaves of different biochar-treated groups in the potting experiment of the present invention;
FIG. 2C is a graph showing the total mercury content in rice leaves of modified charcoal combined with sodium selenite treatment groups in a potting experiment according to the present invention;
FIG. 3A is a graph showing the total mercury content of rice hulls from sodium selenite treated groups of different concentrations in a potting experiment of the present invention;
FIG. 3B is a graph showing the total mercury content of rice hulls from different biochar treatment groups in a potting experiment according to the present invention;
FIG. 3C is a graph showing the total mercury content of modified biochar in combination with sodium selenite treatment of rice hulls in a potting experiment according to the present invention;
FIG. 4 is a graph showing the total mercury content of each group of rice seeds in the potting experiment of the present invention;
FIG. 5 is a graph showing the total cadmium content of rice seeds of each group in the potting experiment of the present invention.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings. It should be understood by those skilled in the art that the specific embodiments are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a heavy metal contaminated soil remediation agent, which consists of sodium selenite and gamma-methacryloxypropyltrimethoxysilane modified pinecone biochar (KH570-PBC) in a mass ratio of 1: 15000;
the preparation method of the KH570-PBC comprises the following steps:
cleaning stains such as soil on the surface of the collected pinecone with clear water, and then air-drying for 24 hours; drying the air-dried pinecone in an oven at 80 ℃ for 10h, crushing by using a crusher, and screening by using a 16-mesh sieve;
placing crushed pinecone particles in a program temperature control muffle furnace, carbonizing for 8 hours at 400 ℃ under an anaerobic condition, cooling to room temperature, taking out powder, soaking for 12 hours by using 1mol/L hydrochloric acid, filtering, washing to be neutral by using deionized water, and drying for 10 hours in an oven at 80 ℃ to obtain pinecone biochar;
preparing a methanol solution of KH570 with the concentration of 3.5 wt%, completely soaking the pinecone biochar into the solution, performing ultrasonic treatment for 20min at room temperature, standing for 5h after ultrasonic treatment, filtering, drying the filtrate in an oven at 80 ℃ for 4h to obtain KH570-PBC, and calculating the content of KH570 in the KH570-PBC to be 1.5 wt% according to the mass change of the pinecone biochar before and after modification.
Example 2
The embodiment provides a heavy metal contaminated soil remediation agent, which consists of sodium selenite and gamma-methacryloxypropyltrimethoxysilane modified pinecone biochar (KH570-PBC) in a mass ratio of 1: 10000; the preparation method of KH570-PBC is the same as that of example 1.
Example 3
The embodiment provides a heavy metal contaminated soil remediation agent, which consists of sodium selenite and gamma-methacryloxypropyltrimethoxysilane modified pinecone biochar (KH570-PBC) in a mass ratio of 1: 7500; the preparation method of KH570-PBC is the same as that of example 1.
Example 4
The comparative example provides a heavy metal contaminated soil remediation agent, which consists of sodium selenite and gamma-mercaptopropyltrimethoxysilane modified pinecone biochar (KH590-PBC) according to the mass ratio of 1: 15000; among them, KH590-PBC was prepared by a method different from that of KH570-PBC of example 1 only in that KH570 was replaced with KH590 of the same mass, and KH590-PBC was prepared with a KH590 content of 1.5 wt%.
Example 5
The comparative example provides a heavy metal contaminated soil remediation agent, which consists of sodium selenite and gamma-mercaptopropyltrimethoxysilane modified pinecone biochar (KH590-PBC) according to the mass ratio of 1: 10000; among them, the preparation method of KH590-PBC is different from that of KH570-PBC in example 1 only in that KH570 is replaced by KH590 of the same mass.
Example 6
The comparative example provides a heavy metal contaminated soil remediation agent, which consists of sodium selenite and gamma-mercaptopropyltrimethoxysilane modified pinecone biochar (KH590-PBC) according to the mass ratio of 1: 7500; among them, KH590-PBC was prepared by a method different from that of KH570-PBC of example 1 only in that KH570 was replaced with KH590 of the same mass.
Experiment of potting
The potting soil used in the research is collected from the mountainous area of cupren city, Guizhou province, and the collection point is 27.5725 degrees N109.2428 degrees E. The soil to be tested is taken from a soil layer of 0-20 cm, the mercury content of the soil is 68.35mg kg-1, the cadmium content is 2.09mg kg-1, the selenium content is 2.65mg kg-1, and the pH value is 7.68.
The sieved soil was potted (using pots 17cm diameter and 25cm height) with 4.5 kg of soil per pot, and after potting, remediation materials were added according to the groups and addition levels shown in table 1, three replicates per sample were designed. After the repairing materials are added into the groups 2-7, the soil keeps 60% of water holding capacity at room temperature and is stable for 20 days; and adding the modified biochar into groups 8-13, keeping 60% of water holding capacity at room temperature, stabilizing for 10 days, and then adding the sodium selenite solution, and stabilizing for 10 days.
TABLE 1
After the soil is stabilized, 1 rice (the tested rice variety is Liangyou Huazhan), the soil keeps 60% of water holding capacity, the experiment is stopped after 150 days, and a soil sample and a rice sample are collected.
Collecting and processing a soil sample:
and (4) taking a soil sample of the part around the rice rhizosphere, and uniformly sampling. The soil sample after gathering transports to clean and ventilate well indoor and dry, avoids the sample to insolate. After most of the water in the sample is evaporated, the sample is transferred to an oven to be dried to constant weight, and the temperature of the oven is set below 35 ℃. The dried samples were ground and sieved through 100 mesh and 200 mesh sieves, sealed and stored with polyethylene self-sealing bags for handling tests.
Collecting and processing rice samples:
collecting potted rice, washing the sludge on the surface of rice with tap water, and washing with deionized water for more than three times. The cleaned rice samples were placed in a clean and well ventilated room for air drying. All samples were then oven dried, setting the temperature below 35 ℃. After the sample is dried to constant weight, dividing the rice sample into four parts of root, stem, leaf and rice ear, further processing the rice ear part, taking rice hull and rice part, removing bran of the rice by a bran remover, and taking polished rice (seed). All samples were crushed with a non-polluting crusher and stored sealed for handling tests.
The total mercury (THg) content of the above collected samples was determined using a mercury analyzer (Millestone DMA-80, Beijinglabo Tyco Instrument Co., Ltd.) and the total cadmium (TCd) content of the above collected samples was determined using ICP-MS.
Wherein the total mercury content of the rice stem, leaf, shell and seed is shown in FIGS. 1A-1C, 2A-2C, 3A-3C and 4 respectively. The total cadmium content of each group of rice seeds is shown in FIG. 5.
As can be seen from the experimental results of FIGS. 1A to 1C, FIGS. 2A to 2C, FIGS. 3A to 3C and FIG. 4, the THg contents of the rice stem, leaf, husk and seed of the original soil control group (CK) were 18.09. + -. 1.91. mu.g/kg, 53.27. + -. 1.70. mu.g/kg, 26.62. + -. 1.94. mu.g/kg and 48.17. + -. 2.34. mu.g/kg, respectively. Compared with the original soil control group, the THg content of the rice stems, leaves, shells and seeds of the treatment groups (1-Se, 1.5-Se and 2-Se) added with sodium selenite with different concentrations is respectively reduced by 0-23%, 14-16% and 24-26%. THg contents of stems, leaves, shells and seeds of the rice in different concentrations of sodium selenite (1-Se, 1.5-Se, 2-Se) + KH570-PBC treatment groups are respectively reduced by 26-41%, 21-27%, 0-28% and 26-60%. The THg content of the stems, leaves, shells and seeds of the rice in the sodium selenite (1-Se, 1.5-Se, 2-Se) + KH590-PBC treatment groups with different concentrations is reduced by 42-50%, 22-27%, 31-54% and 53-60% respectively. The heavy metal contaminated soil remediation agent provided by the invention can obviously reduce the mercury content of plants, and has a good mercury passivation effect.
As can be seen from the experimental results of FIG. 5, the TCd content of the rice seeds of the original soil control group (CK) was 8.39. + -. 1.54. mu.g/kg. Compared with the original soil control group, the TCd content of the rice seeds of the treatment groups (1-Se, 1.5-Se and 2-Se) added with sodium selenite with different concentrations is respectively increased by 34.15%, 6.82% and 6.58%, which shows that selenium cannot reduce the absorption of cadmium by plants, but can lead to the increase of cadmium content in plants.
KH 570-the TCd content of the rice seeds of PBC-treated group decreased by 10%. The TCd content of rice seeds of sodium selenite (1-Se, 1.5-Se, 2-Se) + KH570-PBC treatment groups with different concentrations is respectively reduced by 15%, 23% and 19%, and the reduction ratio is greater than the sum of the sodium selenite treatment group and the KH570-PBC treatment group.
KH 590-the TCd content of the rice seeds of PBC-treated group was reduced by 38%. While the TCd content of the rice seeds in the sodium selenite (1-Se, 1.5-Se, 2-Se) + KH590-PBC treatment groups with different concentrations is respectively reduced by 35 percent, 34 percent and 44 percent, and the reduction ratio is greater than the sum of the sodium selenite treatment group and the KH590-PBC treatment group.
Therefore, the silane coupling agent modified biochar is combined with selenite, so that the effect of synergistically reducing the cadmium content of plants is achieved, and an unexpected technical effect is achieved.
Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that many modifications and improvements can be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (10)
1. The heavy metal contaminated soil remediation agent is characterized by comprising the following components: selenite and a silane coupling agent are used for modifying the biochar.
2. The heavy metal contaminated soil remediation agent of claim 1, wherein the mass ratio of said selenite to said silane coupling agent-modified biochar is 1 (7500-15000).
3. The heavy metal contaminated soil remediation agent of claim 1 or 2, wherein said silane coupling agent-modified biochar comprises silane coupling agent in an amount of 0.5-1.5 wt%.
4. The heavy metal contaminated soil remediation agent of any one of claims 1-3, wherein said selenite is sodium selenite.
5. The heavy metal contaminated soil remediation agent of any one of claims 1 to 4, wherein said silane coupling agent is gamma-mercaptopropyltrimethoxysilane or gamma-methacryloxypropyltrimethoxysilane.
6. The heavy metal contaminated soil remediation agent of any one of claims 1 to 5, wherein said biochar is selected from one or more of straw-based biochar, shell-based biochar, wood-based biochar, tobacco-stem biochar and pine cone biochar, preferably pine cone biochar.
7. The heavy metal contaminated soil remediation agent of any one of claims 1-6, wherein said silane coupling agent modified biochar is prepared by the following method:
and soaking the biochar in a silane coupling agent solution, performing ultrasonic dispersion, then standing for reaction, filtering after the reaction is finished, and drying a filter cake to obtain the silane coupling agent modified biochar.
8. The heavy metal contaminated soil remediation agent of claim 7, wherein said silane coupling agent solution is present at a concentration of 3-4 wt%;
preferably, the solvent of the silane coupling agent solution is methanol;
preferably, the time of ultrasonic dispersion is 15-30 min;
preferably, the standing reaction time is 4-6 h.
9. The use of the heavy metal contaminated soil remediation agent of any one of claims 1-8 for remediation of mercury and cadmium contaminated soil.
10. A method for remediating heavy metal contaminated soil, comprising: the heavy metal contaminated soil remediation agent of any one of claims 1-8 applied to soil at an add-on level of 1-2% of soil mass.
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