CN114014504A - Biological/ultrasonic enhanced adsorption removal system for nitrate pollution of underground water and application thereof - Google Patents
Biological/ultrasonic enhanced adsorption removal system for nitrate pollution of underground water and application thereof Download PDFInfo
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Abstract
The invention discloses a biological/ultrasonic enhanced adsorption removal system for nitrate pollution of underground water and application thereof, wherein the system comprises the following structures: the system comprises field soil, an in-situ observation well, a permeable reactive barrier, an ultrasonic observation well, a repaired observation well, an ultrasonic electrode, an ultrasonic plate, a water pump and filling soil; the permeable reactive barrier is arranged in the soil of the field; the in-situ observation well is arranged on the upstream of the permeable reactive barrier; the repaired observation well is arranged at the downstream of the permeable reactive barrier; the filling soil covers the upper part of the repair field; the water suction pump is connected with the in-situ observation well, the ultrasonic observation well and the repaired observation well; the ultrasonic observation wells are uniformly distributed in the permeable reactive wall and are connected to the ultrasonic plate and the ultrasonic electrode, the ultrasonic generator is connected with the ultrasonic electrode, and ultrasonic waves are transmitted to the permeable reactive wall through the ultrasonic electrode, the ultrasonic plate and the side wall of the ultrasonic observation well. The denitrifying bacteria loaded on the surface of the resin takes nitrate as an electron acceptor, and removes microbial metabolites on the surface of the resin through ultrasonic enhancement, so that a permeable reactive wall channel is dredged, an adsorption-biological regeneration system is constructed, the service life of the resin is prolonged, frequent replacement of fillers is avoided, and long-term and efficient operation of the permeable reactive wall is realized.
Description
Technical Field
The invention belongs to the field of groundwater pollution remediation and risk management and control, and particularly relates to a system and a method for biologically enhanced adsorption removal of groundwater nitrate pollution.
Technical Field
Nitrate in underground water is continuously accumulated due to the large use of nitrogen fertilizer in farmland, over-standard discharge of livestock and poultry breeding wastewater, unreasonable irrigation of sewage and leakage of leachate of refuse landfill, so that the use value and ecological value of the underground water are seriously influenced. Strengthening the work of preventing and controlling the pollution of the underground water and repairing the polluted underground water are tasks to be completed urgently at present. The Permeable Reactive Barrier (PRB) technology has the advantages of high treatment efficiency, small disturbance to water environment, low operation cost, mature application and the like, and is widely applied in recent years. The key to PRB technology is the choice of filler. Currently, the mechanisms of PRB technology for removing nitrate from groundwater mainly include biological and non-biological. The biological method can permanently remove the nitrate in the underground water by utilizing the metabolic action of denitrifying bacteria, has low operation and maintenance cost, and is a green restoration technology. However, there are some problems in the actual operation: firstly, denitrifying bacteria and organic carbon sources in underground water are fewer and need to be supplemented additionally; secondly, a nitrogen source with higher concentration is needed for the growth of denitrifying bacteria, and nitrate in underground water is dispersed, so that the activity of the denitrifying bacteria is not high, and the rate of degrading the nitrate is slower; thirdly, the packing layer is easy to block, and the effluent quality is influenced; fourth, the carbon source release rate is difficult to control. The abiotic method is the most common adsorption method, and is to fill an adsorption material into a permeable reactive barrier wall body and remove nitrate through adsorption. The method has stable operation, quick response and no secondary pollution, but has some problems in the operation process: firstly, nitrate can only be enriched, nitrate cannot be converted into harmless substances, and the risk of desorption exists; secondly, the adsorbent has limited adsorption capacity and needs to be replaced in time after saturated adsorption.
Disclosure of Invention
Aiming at the problems of frequent filler replacement, easy blockage of the filler layer, low activity of denitrifying bacteria and the like in the existing permeable reactive barrier technology, the invention provides a biological/ultrasonic enhanced adsorption removal system and method for underground water nitrate pollution, so as to prolong the service life of an adsorbent, improve the activity of denitrifying bacteria, dredge the filler layer and promote the stable operation of the system.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a biological/ultrasonic enhanced adsorption removal system and method for nitrate pollution of underground water are characterized by comprising the following structures: the method comprises the following steps of 1, in-situ observation wells 2, permeable reactive walls 3, ultrasonic observation wells 4, repaired observation wells 5, ultrasonic electrodes 6, ultrasonic plates 7, water pumps 8 and filling 9; the in-situ observation well 2 is arranged at the upstream of the permeable reactive barrier 3 and is used for monitoring the quality of the inlet water; the repaired observation well 5 is arranged at the downstream of the permeable reactive barrier 3 and used for monitoring the quality of the effluent; the filling soil 9 covers the upper part of the repair site; the water suction pump 8 is connected with the in-situ observation well 2, the ultrasonic observation well 4 and the repaired observation well 5 and is used for periodically pumping water samples, so that the water suction pump is multipurpose, and can periodically pump underground water at corresponding positions for detection and analysis, and dynamically know the water quality conditions of different positions; the ultrasonic observation wells are uniformly distributed in the permeable reactive wall 3 and are connected to the ultrasonic plate 7 and the ultrasonic electrode 6, the ultrasonic generator is connected with the ultrasonic electrode, ultrasonic waves are transmitted to the permeable reactive wall 3 through the ultrasonic electrode 6, the ultrasonic plate 7 and the side wall of the ultrasonic observation well 4, and the metabolic products of denitrifying bacteria are separated through resonance. Specifically, the permeable reactive barrier 3 is arranged in the field soil 1 and is used for adsorbing and degrading nitrate in underground water.
Specifically, the ultrasonic observation wells 4 are arranged in 9 numbers and are uniformly distributed in the permeable reactive barrier 3.
Specifically, the permeable reactive barrier 3 is composed of resin, denitrifying bacteria, a carbon source, a pH regulator and nutrient substances.
Further, the resin is strong base type anion exchange resin with 1 or more functional groups of dimethylamine, trimethylamine and triethylamine.
Further, the denitrifying bacteria are composed of one or more mixed strains of Pseudomonas, Bacteroides and Alischewanella.
Further, the carbon source is one or more of sodium acetate, acetic acid, glucose and a slow-release carbon source.
Further, the slow-release carbon source material is one or more of starch, straw, loofah sponge, wood chips, sawdust, cotton and cassava vinasse.
Further, the nutrient substance is (NH)4)6Mo7O24.4H2O, ZnCl2, H3BO3, FeCl2.4H2O, CoCl2.6H2O, MnCl2.6H2O, NiCl2.6H2O, MgSO4A mixture of any two or more thereof.
The pH regulator is one or more of dipotassium hydrogen phosphate trihydrate, sodium hydroxide and sodium bicarbonate in any combination.
Specifically, the ultrasonic observation well 4 is also a well for adding the biodegradation accelerator, the biodegradation accelerator is added in a proper amount at proper time according to the specific condition of pollution, and the biodegradation accelerator is added through the ultrasonic observation well 4 in a special environment with weak biological activity or too high concentration of nitrate at the entrance, so that the biological denitrification process is enhanced, and the denitrification efficiency is improved;
specifically, the ultrasonic observation well 4 can also promote the slow-release carbon source material to release the carbon source through the resonance effect of the well wall, enhance the activity of denitrifying bacteria, and improve the degradation capability of the instantaneously increased nitrate.
The use method of the biological/ultrasonic enhanced adsorption removal system for the nitrate pollution of underground water comprises the following steps:
firstly, determining the flow direction of polluted groundwater and pollution feather, arranging a repairing area at the downstream of the pollution feather, digging a pit filled with soil 9 above the repairing area, and arranging a slope of 30-60 degrees in front of the pit;
digging a pit of the permeable reactive barrier 3 below the slope for filling resin and reagent;
arranging ultrasonic observation wells 4 in the pits of the permeable reactive barrier 3, uniformly distributing the ultrasonic observation wells in the permeable reactive barrier 3, and being used as a water quality monitoring system, an ultrasonic transmission system, a biodegradation accelerator adding system and a slow-release carbon source increasing and releasing system;
inoculating denitrifying bacteria on the surface of the resin;
filling the loaded resin into the permeable reactive barrier, and adding a carbon source, nutrient substances and a pH regulator;
sixthly, nitrate in the groundwater flows through the wall and is removed through physical adsorption and biodegradation;
and seventhly, after the operation is carried out for a period of time, periodically starting an ultrasonic system and adding a denitrification promoter, and carrying out ultrasonic treatment on the permeable reactive barrier by utilizing the ultrasonic resonance effect of the well body of the ultrasonic observation well 4 to ensure the permeability of the permeable reactive barrier 3, promote the release of a carbon source in the slow-release carbon source material and enhance the denitrification.
Has the advantages that:
(1) denitrifying bacteria are attached to the resin in advance, so that the denitrifying bacteria do not need to be inoculated additionally, and the operation flow is simplified; a physical adsorption-biodegradation system is constructed, adsorption and regeneration are realized, the service life of the filler is prolonged, and frequent replacement of the filler is avoided.
(2) An ultrasonic technology is introduced to remove microbial metabolites on the surface of the resin, so that adsorption channels are dredged, and poor nitrate treatment effect caused by bed layer blockage is avoided.
(3) The ultrasonic observation well is multipurpose, and is used as an observation well for monitoring the nitrate pollution conditions of different positions of the permeable reactive wall; as an ultrasonic transmission system, removing the redundant metabolite loaded on the surface of the resin and promoting the slow-release carbon source to release carbon; the biological degradation promoter is added into the well as the material at proper time to improve the activity of denitrifying bacteria.
Drawings
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
FIG. 1 is a schematic structural diagram of a biological enhanced adsorption removal system for nitrate pollution in underground water.
FIG. 2 is a graph of residual nitrate concentration over time for different nitrate treatment systems.
Description of the symbols:
the method comprises the following steps of 1 site soil, 2 in-situ observation wells, 3 permeable reactive walls, 4 ultrasonic observation wells, 5 repaired observation wells, 6 ultrasonic electrodes, 7 ultrasonic plates, 8 water pumps and 9 filling.
Detailed Description
The technical solution of the present invention will be described in detail and clearly with reference to the embodiments of the present invention. It should be noted that the embodiments of the present invention are only preferred embodiments of the present invention, and all other embodiments obtained by those skilled in the art without any inventive work are within the scope of the present invention.
Example 1 Structure and working principle of biological/ultrasonic enhanced adsorption removal system for nitrate pollution in underground water
With reference to fig. 1, the biological/ultrasonic enhanced adsorption removal system for nitrate pollution of underground water comprises field soil 1, an in-situ observation well 2, a permeable reactive barrier 3, an ultrasonic observation well 4, a repaired observation well 5, an ultrasonic electrode 6, an ultrasonic plate 7, a water pump 8 and filling soil 9.
The permeable reactive barrier 3 is arranged in the field soil 1 and is used for filling resin and a biodegradation accelerator and removing nitrate through physical adsorption and biodegradation; the in-situ observation well 2 is arranged at the upstream of the permeable reactive barrier 3 and is used for monitoring the quality of the inlet water; the repaired observation well 5 is arranged at the downstream of the permeable reactive barrier 3 and used for monitoring the quality of the effluent; the filling soil 9 covers the upper part of the repair site; the water suction pump 8 is connected with the in-situ observation well 2, the ultrasonic observation well 4 and the repaired observation well 5 and is used for periodically pumping water samples; the number of the ultrasonic observation wells 4 is 9, the ultrasonic observation wells are uniformly distributed in the permeable reactive wall 3 and are connected to the ultrasonic plate 7 and the ultrasonic electrode 6, the ultrasonic generator is connected with the ultrasonic electrode, ultrasonic waves are transmitted to the permeable reactive wall 3 through the ultrasonic electrode 6, the ultrasonic plate 7 and the side wall of the ultrasonic observation well 4, microbial metabolites such as mucus, capsules, protein, polysaccharide, fulvic acid and the like attached to the surface of the resin are removed, and the permeable reactive wall is dredged.
EXAMPLE 2 preparation of resin packed in permeable reactive barrier
Mixed denitrifying bacteria containing Pseudomonas, Bacteroides and Alischewanella are inoculated into denitrifying culture medium containing resin in a ratio of 2%, and the formula of the culture medium is as follows: 2.7 g/L of dipotassium phosphate trihydrate, 3.85 g/L of anhydrous sodium acetate, 0.42 g/L of sodium nitrate, 0.6 g/L of sodium bicarbonate and nutrient elements (MgSO)42g/L, (NH4)6Mo7O24.4H2O2g/L, ZnCl20.05g/L, H3BO30.3g/L, FeCl2.4H2O1.5g/L, CoCl2.6H2O10 g/L, MnCl2.6H2O0.03g/L, NiCl2.6H2O0.03 g/L) 1 ml/L, and culturing at 25 deg.C and 150 r/min under constant temperature shaking for 24 hr to make denitrifying bacteriaIs carried on the surface of the resin.
EXAMPLE 3 treatment of nitrate with denitrifying bacteria-loaded resin
After solid-liquid separation, the resin carrying the denitrifying bacteria is reserved, 100 mL of 300mg/L nitrate solution is added, and a carbon source (anhydrous sodium acetate), a pH regulator (sodium bicarbonate, dipotassium hydrogen phosphate trihydrate) and nutrient elements are added according to the formula of the culture medium in the example 2, the control group 1 is a pure adsorption process, uses resin without denitrifying bacteria, does not add substances required by the growth of microorganisms, the control group 2 used a resin carrying denitrifying bacteria, but no substances required for the growth of microorganisms were added to the system, performing constant temperature shaking culture at 25 deg.C and 150 r/min, sampling at regular intervals, passing through C18 column and 0.22 μm filter membrane, determining residual nitrate content, the specific data is shown in FIG. 2, after the operation is carried out for more than 15 hours, the bioaugmentation adsorption and denitrification show obvious advantages, and the nitrate concentration in the solution is not detected after 28 hours.
FIG. 2 is a graph showing the time-dependent change of the concentration of residual nitrate in the system of pure adsorption, adsorption after loading and bioaugmentation adsorption. In the pure adsorption process, the removal efficiency of the resin on the nitrate in the system can reach 51.67 percent, and in comparison, the removal efficiency of the resin with the denitrifying bacteria on the nitrate in the system is reduced by 6.56 percent, which shows that the adsorption performance of the resin with the denitrifying bacteria is influenced but the influence degree is not large. According to the biological enhanced adsorption curve, the removal rate of nitrate by the resin is lower than that of a control group within 0-10 h, mainly the adsorption effect is taken as the main factor, after 10h, the activity of denitrifying bacteria loaded on the surface of the resin is improved, the residual nitrate on the resin and in the system is degraded, after 28h, the residual nitrate is basically not in the system, and the removal rate of nitrate in the system by the biological enhanced adsorption reaches 100%. Generally, the biologically enhanced adsorption integrates adsorption and degradation, the removal efficiency of the nitrate is high, the feasibility of treating the nitrate-polluted underground water by using the biologically enhanced adsorption as the filler of the permeable reactive barrier is high, the service life of the resin can be prolonged, and the frequent replacement of the filler is avoided.
Example 4 Effect of ultrasound on carbon Release Performance of Slow-Release carbon Source Material
To evaluate the effect of ultrasound on the carbon release performance of the slow-release carbon source, the following test was performed. Adding a certain amount of slow-release carbon source material (starch) into the reactor, injecting 1L of pure water, periodically starting the ultrasonic generator, and measuring the chemical oxygen demand in the solution after 12 h. For reference, in another reactor, the same slow-release carbon source material and pure water were added without sonication, and chemical oxygen demand was measured after 12 h. Experimental results show that the chemical oxygen demand is 105 mg/L under the condition of no ultrasound, and the chemical oxygen demand is increased to 143 mg/L after ultrasound, which shows that the ultrasound can promote the carbon release of the slow-release carbon source material.
EXAMPLE 5 specific use of the biological/ultrasonic enhanced adsorption removal System for groundwater nitrate contamination according to the invention
Filling a certain amount of resin loaded with denitrifying bacteria in the permeable reactive wall, adding a carbon source, a nutrient substance and a pH regulator according to the formula in the embodiment 2 to meet the growth and propagation of the denitrifying bacteria, enabling nitrate-polluted underground water (300 mg/L) to flow through the permeable reactive wall, removing the nitrate through the physical adsorption of the resin and the biodegradation of the denitrifying bacteria, and detecting the nitrate concentration in the range of 0-15.18 mg/L every day from 1-29 days. The system runs for about 1 month, and the permeable reactive wall is blocked due to the accumulation of metabolites of denitrifying bacteria, which is mainly shown in the following two aspects: on one hand, the liquid level of the water inlet well is obviously increased before the liquid level of the water inlet well, on the other hand, the concentration of the nitrate in the outlet water is obviously increased and has large variation amplitude, and the concentration of the nitrate in the outlet water detected for many times in the 30 th day is within the range of 20.43-156.87 mg/L. And starting an ultrasonic generator to transmit ultrasonic waves to the permeable reactive wall through the side wall of the ultrasonic observation well. Through ultrasonic, the yellow metabolite attached to the surface of the resin falls off, and the liquid level at the water inlet end drops, which indicates that the pores of the filler layer are dredged by ultrasonic. After the ultrasonic treatment is finished for a period of time, the effluent quality is detected and analyzed every day from 31 th to 40 th days, the detected nitrate concentration is obviously reduced and is in the range of 0-19.18 mg/L, and the ultrasonic treatment can promote the long-acting operation of the system.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (12)
1. The biological/ultrasonic enhanced adsorption removal system for nitrate pollution of underground water is characterized by comprising the following structures: the system comprises field soil (1), an in-situ observation well (2), a permeable reactive wall (3), an ultrasonic observation well (4), a repaired observation well (5), an ultrasonic electrode (6), an ultrasonic plate (7), a water pump (8) and filling soil (9); the permeable reactive barrier (3) is arranged in the field soil (1); the in-situ observation well (2) is arranged at the upstream of the permeable reactive barrier (3); the repaired observation well (5) is arranged at the downstream of the permeable reactive barrier (3); the filling soil (9) covers the upper part of the repair site; the water suction pump (8) is connected with the in-situ observation well (2), the ultrasonic observation well (4) and the repaired observation well (5); the ultrasonic observation wells are uniformly distributed in the permeable reactive wall (3) and connected to the ultrasonic plate (7) and the ultrasonic electrode (6), and the ultrasonic generator is connected with the ultrasonic electrode and transmits ultrasonic waves to the permeable reactive wall (3) through the ultrasonic electrode (6), the ultrasonic plate (7) and the side wall of the ultrasonic observation well (4).
2. The biological/ultrasonic enhanced adsorption removal system for underground water nitrate pollution according to claim 1, characterized in that 9 ultrasonic observation wells (4) are arranged and uniformly distributed in the permeable reactive wall (3).
3. The biological/ultrasonic enhanced adsorption removal system for nitrate contamination of underground water as claimed in claim 1, wherein the permeable reactive wall (3) contains resin, denitrifying bacteria, carbon source, nutrient substances, pH regulator.
4. The bio/ultrasonic enhanced adsorption removal system for nitrate contamination of underground water of claim 3, wherein the resin is a strong base anion exchange resin with 1 or more functional groups of dimethylamine, trimethylamine, triethylamine.
5. The biological/ultrasonic enhanced adsorption removal system for nitrate contamination of underground water as claimed in claim 3, wherein the denitrifying bacteria is composed of a mixture strain of one or more of Pseudomonas, Bacteroides, and Alischewanella.
6. The biological/ultrasonic enhanced adsorption removal system for underground water nitrate pollution according to claim 3, wherein the carbon source is one or more of sodium acetate, acetic acid, glucose and a slow-release carbon source.
7. The biological/ultrasonic enhanced adsorption removal system for nitrate contamination of underground water of claim 3, wherein the nutrient is (NH)4)6Mo7O24.4H2O, ZnCl2, H3BO3, FeCl2.4H2O, CoCl2.6H2O, MnCl2.6H2O, NiCl2.6H2O, MgSO4A mixture of any two or more thereof.
8. The biological/ultrasonic enhanced adsorption removal system for nitrate contamination of underground water of claim 3, wherein the pH regulator is one or more of dipotassium hydrogen phosphate trihydrate, sodium hydroxide and sodium bicarbonate in any combination.
9. The biological/ultrasonic enhanced adsorption removal system for nitrate contamination of underground water as claimed in claim 1, wherein the ultrasonic observation well (4) is a well to which a biodegradation accelerator is added, wherein the biodegradation accelerator is a carbon source, a nutrient substance, a pH regulator.
10. The biological/ultrasonic enhanced adsorption removal system for underground water nitrate pollution according to claim 1, wherein the ultrasonic observation well (4) can transmit ultrasonic waves to the slow-release carbon source to promote the slow-release carbon source to release carbon.
11. The biological/ultrasonic-enhanced adsorption removal system for nitrate pollution of underground water as claimed in claim 1, wherein the permeable reactive barrier can be added with a slow-release carbon source material in addition to the carbon source, specifically one or more of starch, straw, loofah sponge, wood chips, sawdust, cotton and cassava vinasse.
12. The method of using the biological/ultrasonic enhanced adsorption removal system for nitrate contamination of underground water as claimed in claim 1, comprising the steps of:
determining the flow direction of polluted underground water and pollution feather, arranging a repairing area at the downstream of the pollution feather, digging a pit filled with soil (9) above the repairing area, and arranging a slope of 30-60 degrees in front of the pit;
digging a pit of the permeable reactive barrier (3) below the slope for filling resin and reagent;
arranging the ultrasonic observation wells (4) in pits of the permeable reactive barrier (3) and uniformly distributing the ultrasonic observation wells in the permeable reactive barrier (3);
inoculating denitrifying bacteria on the surface of the resin;
filling the loaded resin into the permeable reactive barrier, and adding a carbon source, nutrient substances and a pH regulator;
nitrate in the underground water flows through the wall and is removed through physical adsorption and biodegradation;
after the operation is carried out for a period of time, the ultrasonic system is periodically started and the denitrification accelerant is added, the ultrasonic resonance effect of the well body of the ultrasonic observation well (4) is utilized to carry out ultrasonic treatment on the permeable reactive barrier, so that the permeability of the permeable reactive barrier (3) is ensured, the release of the carbon source in the slow-release carbon source material is promoted, and the denitrification effect is enhanced.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116329264A (en) * | 2023-03-24 | 2023-06-27 | 江苏省环境科学研究院 | Anti-blocking type biological strengthening removing device for treating nitrate pollution of underground water |
| CN117602742A (en) * | 2023-12-15 | 2024-02-27 | 广东省环境科学研究院 | Groundwater pollution restoration system and restoration method |
| CN117602742B (en) * | 2023-12-15 | 2024-06-04 | 广东省环境科学研究院 | Groundwater pollution restoration system and restoration method |
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| CN104150613A (en) * | 2014-09-01 | 2014-11-19 | 南京大学 | Permeable reactive filler for removing nitrate organisms from underground water, system and filling method thereof |
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| CN214611726U (en) * | 2020-10-27 | 2021-11-05 | 北京高能时代环境技术股份有限公司 | PRB construction system for repairing polluted underground water |
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| CN104150613A (en) * | 2014-09-01 | 2014-11-19 | 南京大学 | Permeable reactive filler for removing nitrate organisms from underground water, system and filling method thereof |
| CN107746101A (en) * | 2017-11-27 | 2018-03-02 | 天津工业大学 | A kind of construction method that the PRB in-situ remediation systems for selecting factory are discarded for lead zinc |
| CN110723813A (en) * | 2019-10-18 | 2020-01-24 | 浙江建投环保工程有限公司 | Back-washing system for ferro-sulphur coupling device |
| CN111054743A (en) * | 2019-12-31 | 2020-04-24 | 上海弼好环境科技有限公司 | Soil remediation system based on electric auxiliary infiltration technology |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116329264A (en) * | 2023-03-24 | 2023-06-27 | 江苏省环境科学研究院 | Anti-blocking type biological strengthening removing device for treating nitrate pollution of underground water |
| CN116329264B (en) * | 2023-03-24 | 2024-04-09 | 江苏省环境科学研究院 | Anti-blocking type biological strengthening removing device for treating nitrate pollution of underground water |
| CN117602742A (en) * | 2023-12-15 | 2024-02-27 | 广东省环境科学研究院 | Groundwater pollution restoration system and restoration method |
| CN117602742B (en) * | 2023-12-15 | 2024-06-04 | 广东省环境科学研究院 | Groundwater pollution restoration system and restoration method |
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