CN111909703A - Low-degree heavy metal pollution in-situ remediation agent for greenhouse vegetable field, preparation method and application method - Google Patents
Low-degree heavy metal pollution in-situ remediation agent for greenhouse vegetable field, preparation method and application method Download PDFInfo
- Publication number
- CN111909703A CN111909703A CN201911419382.0A CN201911419382A CN111909703A CN 111909703 A CN111909703 A CN 111909703A CN 201911419382 A CN201911419382 A CN 201911419382A CN 111909703 A CN111909703 A CN 111909703A
- Authority
- CN
- China
- Prior art keywords
- soil
- shrimp
- heavy metal
- low
- agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- 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
-
- 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
- A01B79/02—Methods for working soil combined with other agricultural processing, e.g. fertilising, planting
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
-
- 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
-
- 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
- C09K2101/00—Agricultural use
-
- 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
- C09K2109/00—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE pH regulation
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Soil Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Inorganic Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Environmental Sciences (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention provides an in-situ restoration agent for low-degree heavy metal contaminated soil of a facility vegetable field, and a preparation method and an application method thereof, belonging to the technical field of in-situ restoration of soil. The invention mainly aims at the characteristic of low heavy metal pollution intensity of facility vegetable fields in China, and provides the special in-situ restoration agent for the low heavy metal pollution facility vegetable field soil, which has the advantages of rich raw materials, low cost, simple production process, high restoration efficiency and no secondary pollution, and the preparation and application methods thereof.
Description
Technical Field
The invention relates to the technical field of soil in-situ remediation, in particular to an in-situ remediation agent for low-degree heavy metal contaminated soil of a facility vegetable field and a preparation method and an application method thereof.
Background
The current situation of heavy metal pollution of farmland soil in partial areas of China is serious, so that the heavy metal content of agricultural products exceeds the standard, and the human health is harmed. Meanwhile, China has more people and less land, and in order to ensure the safety of grains, the farmland is still required to be safely polluted by medium and light degrees, and safe agricultural products are produced. In 2016, the State Council issued the action plan for soil pollution control, and the safety utilization rate of the polluted cultivated land reaches about 90% and more than 95% respectively by 2020 and 2030. Therefore, the remediation and the control of the heavy metals in the soil of the moderately and slightly polluted farmland become the hot point of the scientific research of the agricultural environment in recent years.
The heavy metal pollution of the soil refers to pollution caused by excessive accumulation of heavy metals in the soil. The heavy metals in the polluted soil comprise elements with remarkable biological toxicity, such As Cd, Pb, Hg, Cr and As, and elements with certain toxicity, such As Cu, Zn and Ni. The pollution range is wide, the duration is long, the pollution is hidden, the soil can not be biologically degraded, the yield and the quality of crops are reduced, and surface water and underground water are polluted by runoff and leaching loss.
The national environmental protection agency monitors 30 ten thousand hectares of soil in a basic farmland protection area in a sampling way, and finds that 3.6 thousand hectares of soil have excessive heavy metals, and the excessive rate reaches 12.1 percent. According to the information of the ministry of land resources, more than 10 percent of the cultivated land area in China is polluted by heavy metal, about 1.5 hundred million mu, 3250 ten thousand mu of the cultivated land is polluted by sewage irrigation, solid wastes are accumulated to occupy land and destroy the land by 200 ten thousand mu, and most of the solid wastes are concentrated in relatively economically developed areas.
The remediation technology of heavy metal contaminated soil can be classified into two types: one is to remove heavy metal pollutants from soil by utilizing engineering measures and plant extraction means, but the engineering measures (such as soil dressing, soil replacement and the like) are not suitable for the pollution of cultivated land with large area and small pollution intensity, the plant restoration efficiency is lower, the period is long, especially, the cultivated land with more cultivated land of our country is less, the existing cultivated land can not be completely treated by not producing grains, but utilizing the plant restoration technology to treat for a long time; the second type is an in-situ passivation repair technology, which mainly changes the form of heavy metal in soil by adding a passivating agent, reduces the mobility and bioavailability of the heavy metal, and thus reduces the absorption of plants on the heavy metal. Aiming at the current situation that the basic condition of heavy metal pollution of farmlands in China is large in pollution area but low in pollution degree, for example, the general total Cd content is less than or equal to 1.0mg k-1The total Pb content is less than or equal to 500mg kg-1Therefore, the soil remediation agent is practical, the activity of heavy metal ions in soil is passivated, the transfer and enrichment of the heavy metal ions of crops are prevented and controlled, the aim of safe production is fulfilled, and the technology has great practical significance.
The traditional fixing substance mainly takes phosphate, lime and biosolids as materials, has higher cost, has more obvious repairing effect on single heavy metal contaminated soil in the repairing process, and has no outstanding treating effect on the pollution phenomenon associated with several elements. The traditional fixing agent has single component and poor buffering performance in soil, the stability is influenced when the soil condition is changed, and meanwhile, soil nutrients cannot be timely supplemented in the repairing process.
The shrimp and crab shells are byproducts of marine fishery products, the main inorganic components of the shrimp and crab shells are calcium carbonate and chitin, and the shrimp and crab shells have unique biological evolution microstructures. However, the utilization of the shrimp and crab shells is limited at present, most of the shrimp and crab shells are treated as garbage, which has potential harm to the environment in the long term and generates serious waste of resources; part of methods for recycling crab shells also only use calcium carbonate in the crab shells to convert hydroxyapatite or only use chitin as an effective component to convert chitosan, so that the effective component in the crab shells cannot be fully utilized. If the calcium carbonate and the chitin in the crab shells can be simultaneously utilized through a simple and effective conversion mode, and the residual protein and grease in the shrimp and crab shells can be effectively recycled, so that the pollution to the environment can be reduced, the effective utilization of resources can be realized, and the green and environment-friendly effects are realized.
Disclosure of Invention
The invention aims to provide an in-situ repairing agent for low-degree heavy metal polluted soil of facility vegetable lands, and provides a preparation method and an application method of the special repairing agent for low-degree heavy metal polluted soil of facility vegetable lands, which have the advantages of rich raw materials, low cost, simple production process, high repairing efficiency and no secondary pollution, and mainly aims at the characteristic of low heavy metal pollution intensity of facility vegetable lands in China.
The invention aims to provide an in-situ restoration agent for low-concentration heavy metal contaminated soil in a facility vegetable field, which is prepared by mixing, heating, reacting and drying shrimp and crab shell extracts and alum paste powder.
As a further technical scheme, the shrimp and crab shell extract is prepared by taking shrimp shells and crab shells as raw materials and sequentially carrying out acid washing and alkali washing processes.
The second purpose of the invention is to provide a preparation method of the in-situ remediation agent for low-concentration heavy metal contaminated soil of the facility vegetable field,
(1) preparing alum paste powder;
(2) preparation of shrimp and crab shell extract
A1, pretreatment, removing impurities such as meat, dirt and the like of shrimp and crab shells, washing with water and drying;
a2, acid washing, namely putting the pretreated shrimp and crab shells into dilute hydrochloric acid for reaction, and then filtering and washing the shrimp and crab shells to be neutral;
a3, performing an alkali washing process, namely placing the shrimp and crab shells subjected to acid washing in a sodium hydroxide solution for reaction;
a4, filtering, washing with water to neutrality, and oven drying to obtain solid extract of shrimp and crab shell;
(3) mixed heating reaction
S1, mixing the shrimp and crab shell extract obtained in the step (2) with water and acid, controlling the reaction temperature to be 40-60 ℃ under the protection of nitrogen, and continuously heating for 1.5-3 h;
s2 addition of H after completion of the reaction at S12O2；
S3, adding the alum slurry powder prepared in the step (1), and fully stirring to prepare paste;
s4: standing overnight, filtering, and vacuum drying to constant weight to obtain the repairing agent.
As a further technical solution, it is proposed that,
the concentration of hydrochloric acid in the acid washing process is 5% -10%, and the pickling process is performed for 2-4 hours at room temperature.
As a further technical solution, it is proposed that,
the alkali washing process specifically comprises the steps of putting the shrimp and crab shells subjected to acid washing into a 10% sodium hydroxide solution, and boiling for 2 hours at the temperature of 100 +/-5 ℃.
As a further technical solution, the step (3) specifically includes:
s1, mixing 1g of the shrimp and crab shell extract obtained in the step (2) with 100mL of deionized water and 1mL of acid, controlling the reaction temperature to be 50 ℃ under the protection of nitrogen, and continuously heating for 2 hours;
s2 addition of 20 ml of 30% H after completion of the reaction at S12O2；
S3, adding 20g of alum slurry powder prepared in the step (1), and fully stirring to prepare paste;
s4: standing overnight, filtering, and vacuum drying to constant weight to obtain the repairing agent.
As a further technical scheme, the step (1) comprises the following specific steps; drying Alumen pulp, grinding, and placing in muffle furnace at 5 deg.C for min-1And raising the temperature to 800 ℃ at a constant speed, roasting for 1-2 h, naturally cooling, washing with water to be neutral, drying, grinding and sieving with a 80-mesh sieve to obtain the alum slurry powder.
The third purpose of the invention is to provide an application method of the in-situ remediation agent for the low-concentration heavy metal contaminated soil of the facility vegetable field, which comprises the following steps: the method comprises the steps of applying the repairing agent prepared by the method to the ground surface at the dosage of 50-100 kilograms per mu after vegetables are harvested in soil to be repaired, deeply ploughing, watering, keeping the soil moist for 2 weeks, planting and managing crops according to a conventional method, and applying no chemical fertilizer during the period of applying the repairing agent.
Compared with the prior art, the in-situ restoration agent for the low-degree heavy metal contaminated soil of the facility vegetable field has the following technical advantages:
the in-situ restoration agent for low-degree heavy metal contaminated soil of facility vegetable fields provided by the invention can restore the range that the Cd content is not more than 1.0mg/kg and the Pb content is not more than 500mg/kg in the contaminated soil.
The in-situ restoration agent for low-degree heavy metal contaminated soil of the facility vegetable field has good restoration effect, and is an exogenous substance added into the contaminated soil to reduce the bioavailability of the heavy metal in the soil; in particular to a fixing agent for reducing the mobility of metal ions in soil and reducing the toxicity to organisms in the in-situ remediation technology of heavy metal contaminated soil. After the exogenous additive is thrown into the soil, on one hand, the migration activation performance of metal ions can be changed through the influence on the pH value in the soil environment; on the other hand, through the physical and chemical properties of the fixing agent, free metal ions can be captured from the soil environment, and the metal ions are adsorbed and fixed in the additive and generate new conformations. Thereby achieving the effects of passivating the activity of metal ions and reducing the restoration effect of the metal ions migrating from the soil environment to plants and underground water systems; has good effect on non-point source pollution caused by the pollution of agricultural soil.
The in-situ remediation agent for low-concentration heavy metal contaminated soil of the facility vegetable field provided by the invention is low in cost. The invention adopts an artificial synthesis method, takes organic and inorganic materials as carriers, and generates a mixture after modification. The fixative produced by the invention has low synthesis cost, wide material source, easy acquisition and stable and reliable preparation process, and is suitable for the treatment of heavy metal polluted soil of different types; the investment is low.
The in-situ restoration agent for low-degree heavy metal contaminated soil of the facility vegetable field has wide application range. The fixing agent disclosed by the invention is mainly applied to the in-situ remediation process of heavy metal contaminated soil, can be applied to large-area agricultural soil, has a remarkable effect on compound pollution caused by different heavy metal elements, and has the characteristics of low price, no secondary pollution, environmental friendliness and the like.
The in-situ remediation agent for the low-degree heavy metal contaminated soil of the facility vegetable field provided by the invention has high remediation efficiency. The fixing agent has large adsorption capacity on various heavy metal ions and wide application environment range, and particularly has the effect of simultaneously fixing various metal ions; the agricultural straws are used as an organic carrier of the fixing agent, can be used for assisting in adsorption and fixation in the repairing process, and can supplement a large amount of nutrients for soil in time and supplement fertility for the soil environment.
Drawings
FIG. 1 is a process flow diagram of the present invention.
FIG. 2 is a flow chart of the process for preparing shrimp and crab shell extract in FIG. 1.
FIG. 3 shows the contents (mg/kg) of heavy metals Cd and Pb in the edible part of the vegetable without the addition of the repairing agent.
FIG. 4 shows the contents (mg/kg) of heavy metals Cd and Pb in the edible part of the vegetable with the repairing agent.
FIG. 5 different treatment of organ biomass dry weight (g/pot) of amaranthus viridis.
FIG. 6 shows different treatment of Cd content (mg/kg) in aerial parts of amaranthus viridis.
Detailed Description
The present invention will be described in further detail below with reference to specific embodiments and with reference to the attached drawings.
Example 1
An in-situ restoration agent for low-degree heavy metal contaminated soil of a facility vegetable field is prepared by mixing, heating, reacting and drying shrimp and crab shell extracts and alum paste powder. The shrimp and crab shell extract is prepared by taking shrimp shells and crab shells as raw materials and sequentially carrying out acid washing and alkali washing processes.
A preparation method of an in-situ remediation agent for low-degree heavy metal contaminated soil of a facility vegetable field comprises the following steps:
(1) preparing alum paste powder;
(2) preparing shrimp and crab shell extract;
a1, pretreatment, removing impurities such as meat, dirt and the like of shrimp and crab shells, washing with water and drying;
a2, acid washing, namely putting the pretreated shrimp and crab shells into dilute hydrochloric acid for reaction, and then filtering and washing the shrimp and crab shells to be neutral;
a3, performing an alkali washing process, namely placing the shrimp and crab shells subjected to acid washing in a sodium hydroxide solution for reaction;
a4, filtering, washing with water to neutrality, and oven drying to obtain solid extract of shrimp and crab shell;
(3) mixed heating reaction
S1, mixing the shrimp and crab shell extract obtained in the step (2) with water and acid, controlling the reaction temperature to be 40-60 ℃ under the protection of nitrogen, and continuously heating for 1.5-3 h;
s2 addition of H after completion of the reaction at S12O2；
S3, adding the alum slurry powder prepared in the step (1), and fully stirring to prepare paste;
s4: standing overnight, filtering, and vacuum drying to constant weight to obtain the repairing agent.
As a further technical scheme, the concentration of hydrochloric acid in the pickling process is 5% -10%, and the pickling process is performed for 2-4 hours at room temperature.
As a further technical scheme, the alkali washing process specifically comprises the steps of putting the shrimp and crab shells subjected to acid washing into a 10% sodium hydroxide solution, and boiling for 2 hours at the temperature of 100 +/-5 ℃.
As a further technical solution, the step (3) specifically includes:
s1, mixing 1g of the shrimp and crab shell extract obtained in the step (2) with 100mL of deionized water and 1mL of acid, controlling the reaction temperature to be 50 ℃ under the protection of nitrogen, and continuously heating for 2 hours;
s2 addition of 20 ml of 30% H after completion of the reaction at S12O2；
S3, adding 20g of alum slurry powder prepared in the step (1), and fully stirring to prepare paste;
s4: standing overnight, filtering, and vacuum drying to constant weight to obtain the repairing agent.
As a further technical scheme, the step (1) comprises the following specific steps; drying Alumen pulp, grinding, and placing in muffle furnace at 5 deg.C for min-1And raising the temperature to 800 ℃ at a constant speed, roasting for 1-2 h, naturally cooling, washing with water to be neutral, drying, grinding and sieving with a 80-mesh sieve to obtain the alum slurry powder.
Example 2: the effect of applying the in-situ repairing agent in the field to produce the cherry tomatoes
With reference to example 1, the application method of the in-situ remediation agent for low-concentration heavy metal contaminated soil in the facility vegetable field comprises the following steps: after the current-crop vegetables are harvested in the soil to be repaired, the repairing agent is applied to the soil in the greenhouse of the greenhouse at the dosage of 50 kilograms per mu, deep ploughing and watering are carried out, the soil is kept moist for 2 weeks, and chemical fertilizer cannot be applied during the period of applying the repairing agent. After two weeks, the crops can be planted and managed according to a conventional method, and the cherry tomatoes are planted, and experimental results show that the heavy metals (Cd, Pb, Zn, Cu and Ni) in the cherry tomato fruits are all lower than the Chinese food pollutant limit standard value (the food pollutant limit standard GB 2762-2012) so as to achieve the purpose of safe production.
Example 3: effect of applying in-situ repairing agent in field for producing cucumber
With reference to example 1, the application method of the in-situ remediation agent for low-concentration heavy metal contaminated soil in the facility vegetable field comprises the following steps: after the current-crop vegetables are harvested in the soil to be repaired, the repairing agent is applied to the soil of a greenhouse for planting cucumbers according to the dosage of 80 kilograms per mu, deep ploughing and watering are carried out, the soil is kept moist for 2 weeks, and chemical fertilizer cannot be applied during the period of applying the repairing agent. After two weeks, crops and cucumbers can be planted and managed according to a conventional method, and experimental results show that the heavy metals (Cd, Pb, Zn, Cu and Ni) in the cucumbers are all lower than the Chinese food pollutant limit standard value (the food pollutant limit standard GB 2762-2012) so as to achieve the purpose of safe production.
Example 4: comparative tests with and without application of a repair agent according to the invention
The experiments were performed in a greenhouse in a potting manner. The experimental pot is a PVC pot with the diameter of 30 cm and the height of 30 cm, a 20-mesh nylon net is padded at the bottom of the pot to prevent soil leakage, and 12 kg (dry weight) of soil is filled in the experimental pot. The contents of Cd and Pb in the soil are respectively 0.54mg/kg and 358mg/kg, and the soil belongs to the second class of soil according to the soil environment quality standard (the content of Cd is 0.38 mg/kg, and the content of Pb is 376.9 mg/kg). The experimental arrangement is as follows, 6 kinds of vegetables, 2 kinds of heavy metals, 1 treatment and 0.5% of the repairing agent (calculated by dry soil) are added, a control (without the repairing agent) is designed, the growth process is uniformly managed, and each treatment is repeated for 3 times under the same water and fertilizer conditions.
Sowing about 20 seeds in each pot, watering the soil every 1-2 days, keeping the soil moist, thinning the seedlings for the first time when the seedlings grow to about 2 cm after the seeds bud, thinning the seedlings according to the growth condition, and finally fixing 5 plants. The edible parts are harvested successively according to the growth period of each vegetable, and the heavy metal content in the vegetables is respectively tested, and the results show that in the treatment of adding the soil remediation agent, the heavy metal Cd content in six vegetables except amaranth reaches the limit value of the hygiene standard of heavy metal element food in the vegetables in China (0.2 mg/kg), and the heavy metal Pb content in all the vegetables reaches the limit value of the hygiene standard of heavy metal element food in the vegetables in China (0.3 mg/kg), so that the aim of safe production is fulfilled.
Example 5: comparative test of applying the repairing agent of the invention and applying the conventional repairing agent (hydrated lime)
The research adopts a greenhouse potting method, and compares the influence of applying the repairing agent and lime in the invention on reducing the absorption amount of Cd in the amaranthus viridis. The experiments were performed in a greenhouse in a potted manner. The experimental PVC basin is filled with 5 kg of dry soil in each basin, and a nylon net with 20 meshes is padded at the bottom of the basin to prevent the soil from leaking. Then cadmium solution (3 CdSO) was added to the pot4·8H2O) until the Cd content in the soil is 1 mg/kg, and adding water until the water content in the field is 60 percent. And then, carrying out dry-wet circulation of watering for many times until the field water capacity is reached, then naturally air-drying, pouring all the soil out of the pot after the soil is aged for 90 days, removing weed seeds, uniformly mixing, and then re-potting. The soil remediation agent and the hydrated lime are added in an amount of 1.0 percent of the total amount of the soil. And provided with pairs without additivesAnd (CK) processing. Each treatment was repeated 4 times. Soil restoration agent and hydrated lime are respectively applied into the pots, about 20 grains are sowed in each pot, and then the soil is covered by about 1 cm. Thinning the seedlings for the first time when the seedlings grow to about 2 cm, thinning the seedlings according to the growth condition, and finally fixing 5 plants. Harvesting is carried out 60 days after sowing, soil samples are collected at the same time, and relevant parameters are determined.
(1) Effect of different remediation agent treatments on the Biomass of Amaranthus viridis
The results showed that the aerial biomass of amaranthus viridis was much greater than the root biomass (FIG. 2), and in the control treatment, the leaf biomass was 13.6 g/pot, the stem biomass was 11.2 g/pot, and was about 4.0 and 3.16 times the root biomass (3.54 g/pot), respectively. The biomass of the green leaf amaranth is greatly reduced by lime application, the biomass of leaves, stems and roots is respectively 7.56 g/pot, 6.17 g/pot and 2.58 g/pot, and the biomass of the green leaf amaranth is respectively reduced by 44.4 percent, 44.9 percent and 27.1 percent compared with a control group. The treatment with the repairing agent of the invention has little influence on the green leaf amaranth biomass, and the leaf and root biomass is similar to that of the control. From the observation of growth, the application of lime causes the color of the leaves to become lighter, which affects the photosynthesis of the leaves and thus the biomass of the amaranthus viridis.
(2) Influence of different treatments on Cd content in aerial parts of amaranthus viridis
In the three cases, the heavy metal Cd content of the aerial parts of the amaranthus viridis was leaf > stem (FIG. 3). The content of Cd in the green amaranth leaves can be greatly reduced by applying lime, and the reduction amplitude is 38.4%. Wherein, when lime is not applied, the Cd content of the green amaranth leaf is 2.74 mg/kg, and when lime is applied, the Cd content is only 1.69 mg/kg; correspondingly, the content of Cd in the control is 2.19 mg/kg, the content of Cd in the control is 0.77 mg/kg after lime application, and the reduction is 64.7%. The application of the repairing agent in the patent can greatly reduce the Cd content in the stem and the leaf of the amaranthus viridis, and the Cd content in the leaf is reduced by 47.1 percent compared with the control and is only 1.45 mg/kg; the content of Cd in the stem is reduced by 47.8 percent compared with the control, and is 1.15 mg/kg.
Therefore, the application of lime and a soil remediation agent can greatly reduce the absorption of Cd by the amaranthus viridis, and compared with a control, the reduction is more than 30%, but the application of lime reduces the biomass of the amaranthus viridis by about half. The application of the repairing agent has no obvious influence on the biomass of the green amaranth, so that the application of the repairing agent can effectively reduce the absorption of the green amaranth to Cd, does not influence the biomass of the green amaranth, and further does not cause loss in production.
Example 6
Selecting a facility vegetable land with the service life of 5 years in the Hangzhou region in Hangzhou city of Zhejiang, and respectively collecting the surface soil (0-20 cm) of the facility vegetable land and the adjacent open vegetable land, and measuring the heavy metal content, wherein the result shows that the heavy metal content in the facility vegetable land soil is obviously higher than that in the adjacent open vegetable land (table 1) and is light heavy metal polluted soil.
TABLE 1 heavy metal content (mg/kg) in the soil of the vegetable field of the facility under test and the surface soil of the adjacent open vegetable field
| Cd | Pb | Zn | Cu | |
| Soil for greenhouse vegetable field | 0.58 | 30.7 | 88.6 | 42.8 |
| Soil of open vegetable field | 0.12 | 13.9 | 43.5 | 20.1 |
Respectively collecting soil on the surface layers of the facility vegetable land and the adjacent open vegetable land, bringing the facility vegetable land and the adjacent open vegetable land back to a laboratory, air-drying and crushing the soil, uniformly mixing the soil and the soil, and then loading the soil into a PVC (polyvinyl chloride) basin for planting experiments. Lightly contaminated facility vegetable field soil without any remediation agent added was recorded as treatment 1; the surface soil of the open vegetable field is planted as treatment 2, 20kg of the repairing agent in the embodiment 1 of the invention is applied into slightly polluted facility vegetable field soil in the amount of 667 square meters, and the treatment is recorded as treatment 3; 40kg of the remediation agent of example 1 of the present invention was applied to lightly contaminated facility vegetable field soil in terms of per 667 square meters, which treatment was recorded as treatment 4; each treatment was 3 replicates. Under the condition of ensuring that all planting and management conditions are the same, 4 small green vegetables (Shanghai green) are planted in each pot, and the overground parts of the small green vegetables are harvested after 30 days for heavy metal content analysis.
The experimental results show that in the whole planting process, the growth vigor of the small green vegetables has no obvious difference among treatments, and the heavy metal content in the small green vegetables is shown in table 2. As can be seen from Table 2, in the treatment 1, the facility vegetable field soil is slight Cd and Pb polluted soil, the heavy metals Cd and Pb of the small vegetables planted in the treatment exceed the limit value of pollutant Limit in food (Pb is less than or equal to 0.30, Cd is less than or equal to 0.20)), and the contents of other heavy metals do not exceed the standard; the addition of the repairing agent can ensure that the heavy metal content of the overground part of the small green vegetables planted in the treatment 3 and the treatment 4 can reach the limit value of pollutant limit in food below, thereby realizing the aim of safe production.
TABLE 2 Effect of different treatments on the heavy Metal content of the aerial parts of Brassica chinensis
| Cd | Pb | | Cu | ||
| Process | |||||
| 1 | Soil for greenhouse vegetable field | 0.211 | 0.351 | 3.078 | 6.037 |
| |
Soil of open vegetable field | 0.053 | 0.207 | 1.519 | 5.019 |
| |
Facility vegetable land soil and 20kg of repairing agent | 0.118 | 0.106 | 2.109 | 4.325 |
| |
Facility vegetable land soil and 40kg of repairing agent | 0.105 | 0.135 | 2.127 | 4.001 |
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (8)
1. The in-situ restoration agent for the low-degree heavy metal contaminated soil of the facility vegetable field is characterized by being prepared by mixing, heating, reacting and drying shrimp and crab shell extracts and alum slurry powder.
2. The in-situ restoration agent for low-concentration heavy metal contaminated soil of facility vegetable lands as claimed in claim 1, wherein the shrimp and crab shell extract is prepared from shrimp shells and crab shells as raw materials by acid washing and alkali washing processes in sequence.
3. The preparation method of the in-situ remediation agent for the low-degree heavy metal contaminated soil of the facility vegetable field is characterized by sequentially comprising the following steps of:
preparing alum paste powder;
preparing shrimp and crab shell extract;
a1, pretreatment, removing impurities such as meat, dirt and the like of shrimp and crab shells, washing with water and drying;
a2, acid washing, namely putting the pretreated shrimp and crab shells into dilute hydrochloric acid for reaction, and then filtering and washing the shrimp and crab shells to be neutral;
a3, performing an alkali washing process, namely placing the shrimp and crab shells subjected to acid washing in a sodium hydroxide solution for reaction;
a4, filtering, washing with water to neutrality, and oven drying to obtain solid extract of shrimp and crab shell;
mixed heating reaction
S1, mixing the shrimp and crab shell extract obtained in the step (2) with water and acid, controlling the reaction temperature to be 40-60 ℃ under the protection of nitrogen, and continuously heating for 1.5-3 h;
s2 addition of H after completion of the reaction at S12O2 ；
S3, adding the alum slurry powder prepared in the step (1), and fully stirring to prepare paste;
s4: standing overnight, filtering, and vacuum drying to constant weight to obtain the repairing agent.
4. The method for preparing in-situ remediation agent for low-grade heavy metal contaminated soil of facility vegetable land as claimed in claim 3, wherein the hydrochloric acid concentration in the acid pickling process is 5% -10%, and the soil is soaked at room temperature for 2-4 h.
5. The method for preparing in-situ remediation agent for low-grade heavy metal contaminated soil of facility vegetable land as claimed in claim 3, wherein the alkali washing process comprises placing the shrimp and crab shells subjected to acid washing in 10% sodium hydroxide solution, and boiling for 2h at 100 ± 5 ℃.
6. The method for preparing in-situ remediation agent for soil contaminated by low-grade heavy metals in greenhouse vegetable areas as claimed in claim 3, 4 or 5, wherein the step (3) is specifically as follows:
s1, mixing 1g of the shrimp and crab shell extract obtained in the step (2) with 100mL of deionized water and 1mL of acid, controlling the reaction temperature to be 50 ℃ under the protection of nitrogen, and continuously heating for 2 hours;
s2 addition of 20 ml of 30% H after completion of the reaction at S12O2；
S3, adding 20g of alum slurry powder prepared in the step (1), and fully stirring to prepare paste;
s4: standing overnight, filtering, and vacuum drying to constant weight to obtain the repairing agent.
7. The facility vegetable low-grade weight of claim 3The preparation method of the in-situ repairing agent for the metal contaminated soil is characterized in that the step (1) comprises the following specific steps; drying Alumen pulp, grinding, and placing in muffle furnace at 5 deg.C for min-1And raising the temperature to 800 ℃ at a constant speed, roasting for 1-2 h, naturally cooling, washing with water to be neutral, drying, grinding and sieving with a 80-mesh sieve to obtain the alum slurry powder.
8. The application method of the in-situ remediation agent for the low-degree heavy metal contaminated soil of the facility vegetable field comprises the following steps: the method is characterized in that the method comprises the repairing agent prepared by the method of any one of claims 1-7, after the current vegetable is harvested from the soil to be repaired, the repairing agent is applied to the ground surface at the dosage of 50-100 kilograms/acre, deep ploughing and watering are carried out, the soil is kept wet for 2 weeks, then the crops can be planted and managed according to the conventional method, and the fertilizer cannot be applied during the application of the repairing agent.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2019102547792 | 2019-03-31 | ||
| CN201910254779 | 2019-03-31 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111909703A true CN111909703A (en) | 2020-11-10 |
Family
ID=73242483
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911419382.0A Pending CN111909703A (en) | 2019-03-31 | 2019-12-31 | Low-degree heavy metal pollution in-situ remediation agent for greenhouse vegetable field, preparation method and application method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111909703A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102962250A (en) * | 2012-12-17 | 2013-03-13 | 浙江省农业科学院 | Method for remedying cadmium (Cd) and lead (Pb) polluted soil by alum pulp in situ |
| CN103274872A (en) * | 2013-04-24 | 2013-09-04 | 陆玉 | Bio-organic fertilizer with shrimp shell powder as main material, and preparation method thereof |
| CN103288531A (en) * | 2013-05-17 | 2013-09-11 | 安徽三星化工有限责任公司 | Slow-release fertilizer specially used for briquette slag soybean |
| CN103402624A (en) * | 2010-12-06 | 2013-11-20 | 科学与工业研究委员会 | Organic-inorganic composite material for removal of anionic pollutants from water and process for the preparation thereof |
| CN104496629A (en) * | 2014-10-29 | 2015-04-08 | 季克丰 | Strawberry special-purpose compound selenium-nucleic acid-containing modified bamboo fiber-coated fertilizer and preparation method thereof |
| CN104591913A (en) * | 2013-10-30 | 2015-05-06 | 烟台纳克环保科技有限公司 | Multielement nutritious fertilizer |
-
2019
- 2019-12-31 CN CN201911419382.0A patent/CN111909703A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103402624A (en) * | 2010-12-06 | 2013-11-20 | 科学与工业研究委员会 | Organic-inorganic composite material for removal of anionic pollutants from water and process for the preparation thereof |
| CN102962250A (en) * | 2012-12-17 | 2013-03-13 | 浙江省农业科学院 | Method for remedying cadmium (Cd) and lead (Pb) polluted soil by alum pulp in situ |
| CN103274872A (en) * | 2013-04-24 | 2013-09-04 | 陆玉 | Bio-organic fertilizer with shrimp shell powder as main material, and preparation method thereof |
| CN103288531A (en) * | 2013-05-17 | 2013-09-11 | 安徽三星化工有限责任公司 | Slow-release fertilizer specially used for briquette slag soybean |
| CN104591913A (en) * | 2013-10-30 | 2015-05-06 | 烟台纳克环保科技有限公司 | Multielement nutritious fertilizer |
| CN104496629A (en) * | 2014-10-29 | 2015-04-08 | 季克丰 | Strawberry special-purpose compound selenium-nucleic acid-containing modified bamboo fiber-coated fertilizer and preparation method thereof |
Non-Patent Citations (5)
| Title |
|---|
| 周安娜等: ""一步法"壳聚糖制备新工艺", 《食品工业科技》 * |
| 王静妍: "《优质苹果科学无公害栽培技术指南》", 30 April 2008, 农村科技出版社 * |
| 董学畅等: "从虾蟹壳制备甲壳素及壳聚糖的研究", 《云南化工》 * |
| 郑国璋: "《农业土壤重金属污染研究的理论与实践》", 31 May 2007, 中国环境科学出版社 * |
| 郑晓冬: "小龙虾虾壳及其仿生合成物对污水中重金属的吸附特性与机理研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105344708B (en) | A kind of restorative procedure of alkaline land soil heavy metal pollution | |
| CN107695088B (en) | Method for restoring As-Cd combined polluted farmland soil by utilizing hyper-enriched plant biomass charcoal combined system | |
| CN107790491B (en) | A method of using making restoring cadmium polluted farmland between corn and Sedum alfredii Hance | |
| CN105127187B (en) | The method that oil-heavy-metal contaminated soil is repaired in a kind of animals and plants-charcoal collaboration | |
| CN101758068B (en) | Method for continuously repairing heavy metal in soil by using chelating agent | |
| CN108856282B (en) | Composite remediation method for heavy metal contaminated farmland soil | |
| CN105170623B (en) | A kind of method of charcoal and plant combined restoration of soil polluted by heavy metal | |
| Montemurro et al. | MSW compost application on tomato crops in Mediterranean conditions: effects on agronomic performance and nitrogen utilization | |
| CN105170622B (en) | A kind of restorative procedure of acidity-heavy-metal contaminated soil | |
| CN107470334B (en) | Compound repairing agent for cleaning petroleum-polluted soil | |
| CN109777428B (en) | Composite modified diatomite heavy metal passivator and application thereof | |
| CN111330970A (en) | Method for reducing bioavailability of heavy metal composite contaminated soil in agricultural land | |
| CN113210411B (en) | Heavy metal composite contaminated site soil remediation method | |
| CN110038887A (en) | Heavy metal decomposition method in soil | |
| CN108097711A (en) | A kind of method for repairing Grown In Zinc Contaminated Soil using penicillium janthinellum joint Indian mustard | |
| CN102441562A (en) | Method for promoting broad bean in restoring and treating cadmium-polluted soil by using citric acid | |
| CN112567920A (en) | Method for improving cadmium-polluted soil restoration capacity of hybrid pennisetum alopecuroides | |
| CN101560018B (en) | Method for bioremediating waste water containing copper by common dayflower | |
| CN106576809A (en) | Method for lowering heavy-metal lead-cadmium content of Ipomoea aquatica | |
| CN113366945B (en) | Intercropping method for safely planting corn while repairing farmland with moderate and mild cadmium pollution | |
| CN111909703A (en) | Low-degree heavy metal pollution in-situ remediation agent for greenhouse vegetable field, preparation method and application method | |
| CN115572187A (en) | Microbial compound fertilizer and method for repairing heavy metal contaminated soil by using same | |
| CN101186535A (en) | Method for repairing heavy metal pollution in town domestic refuse compost by dicotyledonous ruderal | |
| CN113185345A (en) | Amino acid organic fertilizer and preparation method and application thereof | |
| CN108265010B (en) | Method for repairing cadmium-polluted soil by using aspergillus versicolor and Indian mustard |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20201110 |