A carbon-based adsorption / microbial anaerobic degradation risk control composite material and its application

Abstract

The present invention discloses a carbon-based adsorption / microbial anaerobic degradation risk control composite material and its application, belonging to the technical field of groundwater remediation. The composite material is composed of a corrinoid-providing bacterial shell and a halogenated hydrocarbon repair functional core to form a core-shell structure. The shell is composed of biphenylophilic Rhodococcus that provides the cofactor corrinoid vitamin B12, and is fixed to the surface of the core by light-curing gelatin; the functional material of the core is composed of humic acid material, anaerobic dehalogenating bacteria and biochar, which are fixed by sodium alginate and calcium chloride. The composite material constructs an anaerobic habitat for dehalogenating bacteria in a groundwater environment, and uses aerobic bacteria to provide the anaerobic dehalogenating bacteria with the cofactor VB that cannot be synthesized. 12 , improve the survival ability and reduction dechlorination activity of dehalogenating bacteria, and avoid the loss of dehalogenation activity caused by the strict requirements of dehalogenating microorganisms for oxygen and cofactors. The present invention can be applied to the remediation of groundwater contaminated by halogenated hydrocarbons, and has the advantages of high efficiency, long-term effect, low cost, no secondary pollution, and simple preparation.

Description

Technical Field

[0001] The present invention relates to the field of groundwater remediation, and more particularly to a carbon-based adsorption / microbial anaerobic degradation risk management composite material and its application in the remediation of halogenated hydrocarbon-contaminated water bodies. Background Art

[0002] In the process of urbanization and industrialization, groundwater pollution is widespread and is getting worse. Organic pollution is a difficult problem in groundwater pollution control, which seriously affects the quality of groundwater. Due to the large-scale aggregation of chemical parks and the long history of some enterprises, there are serious problems of organic groundwater pollution around the parks. Halogenated hydrocarbons are very common organic pollutants in groundwater of chemical raw material manufacturing enterprises. Due to its concealment, complexity, and difficulty in control and treatment, groundwater pollution is very difficult to control and restore once it is polluted, and the cost of repair is huge.

[0003] A biobarrier is a method of groundwater pollution treatment and site pollution control that fills a permeable barrier with biological materials to degrade or transform and detoxify pollutants. At present, the research and practical application cases of biobarriers are mainly concentrated in the reduction and remediation of groundwater nitrates and high-valent toxic heavy metals. It is widely used abroad with good application effects, and there are very few demonstration and application studies in China. In general, there are relatively few studies and applications of biobarriers for the remediation of organic pollutants and site risk control. For organic pollutants such as halogenated hydrocarbons, it is suitable to use a reduction biobarrier.

[0004] The primary material of the biological reaction wall is the adsorption material. Since the time of microbial reaction is longer than that of chemical reaction, the adsorption material is needed to adsorb the pollutants on the microbial coexistence matrix to form a microbial reactor for degradation or transformation. For the reduction biological reaction wall, microorganisms reduce, transform and detoxify halogenated hydrocarbons through anaerobic dehalogenation. In addition to anaerobic dehalogenating bacteria, the required materials also include electron donor matrix, carbon source, nitrogen source, phosphorus source and nutrient matrix such as corrinoid cofactors. At present, the reduction biological reaction wall materials used in actual groundwater are insufficient. In the long-term operation process, the adsorption materials of the biological reaction wall have short-term problems such as easy adsorption saturation and blockage caused by secondary mineral formation. Therefore, the strategy of combining microorganisms with adsorption materials can effectively solve this bottleneck. Summary of the invention

[0005] In view of the short-term effectiveness problems of reduction and dehalogenation biological reaction wall materials, such as lack of corrinoid cofactors and easy inactivation of dehalogenating bacteria dehalogenase, the present invention provides a carbon-based adsorption / microbial anaerobic degradation risk management composite material, which has a significant removal and control effect on halogenated hydrocarbons in groundwater.

[0006] The technical solutions specifically adopted in the present invention are as follows:

[0007] In the first aspect, the present invention provides a carbon-based adsorption / microbial anaerobic degradation risk management composite material, wherein the composite material is a core-shell spherical structure composed of a corrinoid-providing bacterial shell and a halogenated hydrocarbon repair functional core;

[0008] The corrinoids provide the bacterial coat by providing the cofactor corrinoid vitamin B 12 (VB 12 ) is composed of aerobic biphenylophilic Rhodococcus, which is fixed on the outer surface of the halogenated hydrocarbon repair function core by light-cured gelatin;

[0009] The halogenated hydrocarbon repair functional core is composed of humic acid, anaerobic dehalogenating bacteria and biochar as functional materials, and is fixed by sodium alginate and calcium chloride to form a microsphere core.

[0010] As a preferred embodiment of the first aspect, the biochar is obtained by subjecting sawdust raw materials to oxygen-limited pyrolysis at 650-750° C. for 5-7 hours.

[0011] As a preferred embodiment of the first aspect, the aerobic rhodococcus biphenylophilus has been deposited in the General Microbiology Center of China Microbiological Culture Collection Administration, the deposit address is No. 3, Yard 1, Beichen West Road, Chaoyang District, Beijing, Institute of Microbiology, Chinese Academy of Sciences, the deposit date is October 8, 2014, and the deposit number is CGMCC No.1.12975.

[0012] As a preferred embodiment of the first aspect, the anaerobic dehalogenating bacteria is Dehalococcoides mccartyi strain 195 (Dhc 195), with ATCC catalog number BAA-2266.

[0013] As a preference of the first aspect above, the particle size of the core-shell spherical structure is 0.1 to 0.2 cm.

[0014] In a second aspect, the present invention provides a method for preparing a carbon-based adsorption / microbial anaerobic degradation risk management composite material as described in any one of the schemes of the first aspect, comprising:

[0015] S1, using 1wt.% sodium alginate solution at 40-50°C as the mother solution, adding 200mg / L humic acid (HA), 50g / L biochar and 10 6 CFU / mL of anaerobic dehalogenating bacteria were mixed, and the mixed solution was added dropwise to a 1wt.% CaCl2 solution through a droplet forming device under anaerobic conditions to form microspheres in the solution;

[0016] S2, using 3wt.% gelatin solution as the mother solution, according to the final concentration of 10 7CFU / mL is added to the logarithmic phase aerobic biphenylophilic Rhodococcus and mixed evenly, and then the microspheres are added to make a layer of bacteria-containing gelatin solution evenly adhere to the surface of the microspheres, and then taken out for light curing to obtain a core-shell spherical structure composite material with the microspheres as the halogenated hydrocarbon repair function core and the core wrapped with corrinoids to provide a bacterial shell.

[0017] In a third aspect, the present invention provides a carbon-based adsorption / microbial anaerobic degradation risk management composite material prepared by the preparation method described in the second aspect above.

[0018] In a fourth aspect, the present invention provides a bioreactor wall, which uses the carbon-based adsorption / microbial anaerobic degradation risk control composite material described in any one of the first or third aspects as filler.

[0019] In a fifth aspect, the present invention provides an application of the reduction and dehalogenation type bioreactor wall composite material as described in any one of the schemes of the first aspect or the third aspect in the restoration of halogenated hydrocarbon contaminated water bodies.

[0020] As a preferred embodiment of the fifth aspect above, the water body is groundwater.

[0021] The present invention provides a carbon-based adsorption / microbial anaerobic degradation risk control composite material, which adopts a core-shell structure. The outer shell is composed of biphenylophilic Rhodococcus that provides cofactor corrinoid vitamin B12, and the functional material of the inner core is composed of humic acid material, anaerobic dehalogenating bacteria and biochar. The composite material constructs an anaerobic habitat for dehalogenating bacteria in a groundwater environment, and uses aerobic bacteria to provide anaerobic dehalogenating bacteria with cofactors that cannot be synthesized. 12 , improve the survival ability and reduction dechlorination activity of dehalogenating bacteria, and avoid the loss of dehalogenation activity caused by the stringent requirements of dehalogenating microorganisms for oxygen and cofactors. The carbon-based adsorption / microbial anaerobic degradation risk control composite material of the present invention has a significant removal effect on halogenated hydrocarbons in groundwater. The composite material and the single carbon-based material have the purification capacity of typical halogenated organic pollutants on the site of 96.0 mg / g and 72.0 mg / g respectively. Therefore, the carbon-based adsorption / microbial anaerobic degradation risk control composite material has a 33.3% improvement in the purification capacity of typical halogenated organic pollutants on the site compared with a single carbon-based material. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 The morphology of the composite material prepared in the embodiment of the present invention.

[0023] Figure 2 The change of the outer layer of the core-shell structure material of the present invention over time.

[0024] Figure 3 The changes in the activities of the outer layer of red coccus and the inner layer of dehalogenating bacteria in the core-shell structure material of the present invention.

[0025] Figure 4 The core-shell structure material of the present invention has a removal effect on trichloroethylene in simulated groundwater. DETAILED DESCRIPTION

[0026] The present invention is further described in detail below in conjunction with the accompanying drawings, which are intended to explain the present invention rather than to limit it. The methods used in the following examples are all conventional methods unless otherwise specified, and the reagents used can all be existing commercially available products unless otherwise specified.

[0027] The two microbial strains involved in the following embodiments of the present invention are both existing strains. Among them, the aerobic biphenylophilic Rhodococcus is a biological material that the applicant has deposited in the early stage, which is recorded in the published Chinese patent application, and the deposit information is: deposit institution: General Microbiological Center of China Microbiological Culture Collection Administration, deposit address: No. 3, Yard No. 1, Beichen West Road, Chaoyang District, Beijing, Institute of Microbiology, Chinese Academy of Sciences, deposit date: October 8, 2014, deposit number: CGMCC No.1.12975, referred to as TG9 in the following embodiments. In addition, the anaerobic dehalogenating bacteria is Dehalococcoides mccartyi strain 195 (referred to as Dhc 195 in the following embodiments), which is a commercially available bacterial agent, and the corresponding ATCC catalog number is ATCC BAA-2266.

[0028] The specific preparation process and application effect of the above-mentioned carbon-based adsorption / microbial anaerobic degradation risk management composite material of the present invention are demonstrated through examples below.

[0029] Embodiment 1:

[0030] In this embodiment, the preparation process of a carbon-based adsorption / microbial anaerobic degradation risk management composite material according to the present invention is mainly demonstrated, as follows:

[0031] (1) Culture of bacterial strains

[0032] Cultivation of aerobic biphenylophilic Rhodococcus TG9: The strain TG9 with the aforementioned accession number of CGMCC No.1.12975 was inoculated into 20 mL of LB medium at a 1% inoculation rate (v / v), and placed in a dark shaker at 30°C for recovery culture at a speed of 180 rpm; after culturing for 24 to 48 hours, the recovery solution was inoculated into a new medium at a 1% inoculation rate (v / v), and placed in a dark shaker at 30°C for expansion culture at a speed of 180 rpm. The strain TG9 was cultured with LB medium until its OD 600 Reach 1.7~1.8.

[0033] It should be noted that the LB medium formula used in this embodiment is as follows: 10.0 g tryptone, 5.0 g yeast extract, 10.0 g sodium chloride, add 1000 mL of distilled water to dissolve, adjust pH=7, and sterilize at high temperature and high pressure. The LB medium formula used in subsequent embodiments is also the same and will not be repeated here.

[0034] Culture of Dhc 195: Dhc 195 was cultured in a 120 mL serum bottle containing 50 mL of liquid anaerobic culture medium. The culture medium used was an anaerobic mineral salt culture medium, and the culture medium preparation process was as follows: 1) Prepare inorganic salt stock solution (100×), selenium and tungsten element stock solution (1000×), and trace element stock solution (1000×) for use; 2) Prepare vitamin stock solution (1000×), adjust the pH to 7.5, sterilize through a 0.22 μm filter membrane, transfer to a sterile serum bottle, seal it, remove O2 in the vitamin stock solution by repeated vacuuming and N2, and wrap the bottle with aluminum foil. Protect from light and store at 4°C for future use; 3) Mix 800 mL of deionized water, 10 mL of inorganic salt stock solution (100×), 1 mL of selenium and tungsten stock solution (1000×), 1 mL of trace element stock solution (1000×), 2.292 g of biological buffer Tris ethanesulfonic acid, 0.25 mL of redox indicator 0.1% (w / w) resazurin solution, and carbon source sodium lactate or sodium acetate (final concentration 10 mM) evenly, and then dilute the solution to 1 L with deionized water.

[0035] (2) Preparation process of carbon-based adsorption / microbial anaerobic degradation risk control composite materials

[0036] In this embodiment, the carbon-based adsorption / microbial anaerobic degradation risk control composite material is a core-shell spherical structure material, which is composed of a corrinoid-provided bacterial shell and a halogenated hydrocarbon repair function core. The applicant found through research that Dhc 195 is a nutritionally deficient strain that lacks the corrinoid VB necessary for growth. 12 The biosynthesis pathway of Dhc 195 is mediated by the biphenylophilic Rhodococcus TG9, which can provide corrinoid VB for Dhc 195. 12 No need to add corrinoid VB to the material 12 The addition of humic acid (HA) can increase the dehalogenase activity of Dhc 195 and promote dehalogenation. Therefore, the principle adopted in the design of the composite material in this embodiment is based on: (1) Rhodococcus has VB 12 The synthetic pathway can provide the nutrients necessary for the growth of Dhc 195; (2) Humic acid (HA) can improve the dechlorination effect by increasing the activity of dehalogenase. In the final prepared carbon-based adsorption / microbial anaerobic degradation risk control composite material, the dehalogenation active ingredient is Dhc 195.

[0037] The preparation of the core-shell spherical structure of the composite material in this embodiment is described in detail below:

[0038] (2.1) Preparation of halogenated hydrocarbon repair functional core: First, prepare a 1 wt.% sodium alginate solution at 40-50°C as a mother solution, add 200 mg / L humic acid (HA), 50 g / L biochar and 10 6 CFU / mL of anaerobic dehalogenating bacteria Dhc195 were mixed to form a mixed solution. Under anaerobic conditions, the mixed solution was added dropwise to a 1wt.% CaCl2 solution through a droplet forming device to form microspheres.

[0039] The biochar used above is obtained by oxygen-limited pyrolysis of sawdust at 700°C for 6 hours. The specific method is: the dried sawdust is put into a crucible and compacted, the crucible is covered with a lid and cracked in a muffle furnace, the temperature is increased to 700°C at a rate of 5°C / min, and the constant temperature is maintained for carbonization for 6 hours, then the heating is stopped, the grayish white part of the surface of the cracked sample is removed, and the carbonaceous component is retained to obtain the biochar.

[0040] (2.2) Corrinoids provide bacterial shell preparation:

[0041] The microspheres prepared as above were used as the core of the halocarbon repair function, and a layer of corrinoid VB was further fixed on the surface of the microspheres by photocuring gelatin. 12 The specific preparation method is as follows: using 3wt.% gelatin solution as the mother solution, and mixing it according to the final concentration of 10 7 CFU / mL was added into the logarithmic phase aerobic biphenylophilic Rhodococcus TG9 and mixed evenly, and then the above microspheres were added into the bacteria-containing gelatin solution, so that a layer of bacteria-containing gelatin solution was evenly attached to the surface of the microspheres, and then taken out for light curing, thereby obtaining a core-shell spherical structure composite material with a halogenated hydrocarbon repair function core wrapped with a corrinoid-provided bacterial shell, and the particle size was 0.1-0.2 cm.

[0042] In this embodiment, the prepared core-shell spherical structure composite material is a composite material of Dehalogenococcus + HA + corrinoid providing bacteria, and its morphology under an optical microscope is as follows: Figure 1 As shown, it can be seen that the material presents an obvious core-shell multilayer structure, and a large amount of aerobic Rhodococcus biphenylophilus TG9 is fixed in the shell. The immobilized material can build an anaerobic habitat for dehalogenating bacteria in groundwater environments, and aerobic Rhodococcus biphenylophilus TG9 can provide the anaerobic dehalogenating bacteria Dhc195 with the cofactor VB that cannot be synthesized. 12 , improve the survival ability and reduction dechlorination activity of dehalogenating bacteria, and overcome the loss of dehalogenation activity caused by the stringent requirements of dehalogenating microorganisms for oxygen and cofactors. The effect will be described in Example 2 later.

[0043] Embodiment 2:

[0044] In this example, the carbon-based adsorption / microbial anaerobic degradation risk management composite material with a core-shell spherical structure prepared in Example 1 was applied to the remediation of trichloroethylene (TCE) contamination in groundwater to demonstrate its specific application effect.

[0045] This example simulates and tests the actual petroleum hydrocarbon contaminated groundwater remediation experiment to investigate the removal ability and kinetics of TCE by the Dehalogenococcus + HA + corrinoid-donating bacteria composite material in Example 1. The results are as follows: Figure 2 to Figure 4 shown.

[0046] In this example, SYTO9 staining combined with laser confocal microscopy was used to characterize the distribution of microorganisms on the microspheres. Figure 2 The laser confocal characterization of the core-shell structure of the composite material of Dehalogenococcus + HA + corrinoid-providing bacteria and the changes of TG9 Rhodococcus in the outer layer of the composite material over time are shown. In the figure, green is the corrinoid-providing bacteria, B1, B3, and B5 are the composite material morphologies under the laser confocal bright field on the 0th, 4th, and 16th days, respectively, and B2, B4, and B6 are the composite material morphologies corresponding to the laser confocal green fluorescence field on the 0th, 2nd, and 8th days, respectively. The results show that the outer layer of the composite material shows obvious green colony characteristics, while there are almost no green colonies in the inner core area of ​​the microspheres (B2). The microspheres were added to simulate the actual TCE-contaminated groundwater for cultivation experiments to investigate the morphological changes of the material. The results show that the number of green colonies on the outer layer of the microspheres gradually decreases with the extension of the cultivation time, and the green colonies gradually disappear (B4 and B6).

[0047] Single cell Raman spectroscopy can well reflect the material composition of cells. When combined with isotope labeling, the water utilization process of Dehalococcoides and corrinoid-providing bacteria cells can be judged by the change of Raman peak position. In a medium containing heavy water, the metabolic activity of cells is accompanied by the participation of heavy water. In this example, the activity of corrinoid-providing bacteria on the surface of microspheres was investigated by incubating the composite material with heavy water. Figure 3 The Raman spectra were used to characterize the activity changes of single-cell corrinoid-providing bacteria and dehalogenococcus in simulated groundwater using a composite material of dehalogenococcus + HA + corrinoid-providing bacteria. T0, T4, T8, and T16 were the Raman spectra of single-cell corrinoid-providing bacteria on the 0th, 4th, 8th, and 16th days, respectively. The corrinoid-providing bacteria without heavy water incubation were used as negative controls, and the logarithmic corrinoid-providing bacteria incubated with 50% heavy water were used as positive controls. The Raman shift in the figure is 2800-3100cm -1 represents CH peak), Raman shift 2040-2300cm -1 Represents the CD peak. Figure 3It can be found that the corrinoid-providing bacteria on the surface of the microspheres have an obvious D peak, with a CD ratio of 31.7%. At the same time, the characteristic D peak of the dehalogenating coccidioides cells also appears in the anaerobic system, with a CD ratio of 23.2%. The above shows that the dehalogenating coccidioides cells will be slowly released from the microspheres into the solution for the dechlorination process. The above results show that the corrinoid-providing bacteria are mainly distributed on the outer surface of the microspheres and have good activity, and the dehalogenating coccidioides are mainly distributed in the inner core area of ​​the microspheres. The dehalogenating coccidioides also have good activity after release.

[0048] At the same time, single-cell Raman spectroscopy showed that on the 4th and 16th days of incubation, the CD ratio of corrinoid-providing bacteria on the surface of the microspheres also gradually decreased, from 31.7% on the 0th day to 8.9% on the 16th day. The above results show that in simulated TCE-contaminated groundwater, the activity of corrinoid-providing bacteria gradually decreased and gradually died. Single-cell Raman spectroscopy in the solution showed that from the 0th day to the 16th day of incubation, the CD ratio of dehalococcoides in the solution of the composite material of dehalococcoides + HA + corrinoid-providing bacteria also gradually increased, from 23.2% on the 0th day to 34.9% on the 16th day. The above results show that in simulated TCE-contaminated groundwater, dehalococcoides can be slowly released into the solution, and the activity of dehalococcoides gradually increases with the dechlorination activity.

[0049] This example simulates and tests the remediation of groundwater contaminated by halogenated hydrocarbons to investigate the removal capacity and kinetics of TCE by the composite material of Dehalococcus + HA + corrinoid-providing bacteria. In order to achieve control, this example uses Dehalococcus + HA + corrinoid-providing bacteria as the composite material, the same amount of biochar as the experimental group, and the simulated groundwater without any material added as the control group. Figure 4 The removal effect of the composite material of dehalogenated coccidioides + HA + corrinoids on trichloroethylene in simulated TCE-contaminated groundwater in the present invention. Through calculation, it can be seen that the composite material prepared in Example 1 and the single carbon-based material have the purification capacity of typical halogenated organic pollutants on the site of 96.0 mg / g and 72.0 mg / g respectively, and the trichloroethylene removal rate of the carbon-based adsorption / microbial anaerobic degradation risk control composite material in groundwater on the 16th day is 38.1%, and the purification capacity of typical halogenated organic pollutants on the site is 33.3% higher than that of the single carbon-based material.

[0050] In addition, it should be noted that the reduction dehalogenation type bioreactor wall composite material prepared by the present invention can be applied to the restoration of any halogenated hydrocarbon contaminated water body. In addition to groundwater, the water body to be restored can also be other water bodies other than groundwater, such as lakes, rivers, landscape water bodies, etc., without limitation. It can be directly added to the water body to be restored, or it can be used as a filler for the bioreactor wall, so as to utilize the anaerobic dehalogenating coccidioides in the material to dehalogenate halogenated hydrocarbons and realize the restoration of halogenated hydrocarbon contaminated groundwater.

[0051] The above-described embodiment is only a preferred solution of the present invention, but it is not intended to limit the present invention. A person skilled in the relevant technical field may make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, any technical solution obtained by equivalent replacement or equivalent transformation falls within the protection scope of the present invention.

Claims

1. A carbon-based adsorption / microbial anaerobic degradation risk management composite material, characterized in that: The composite material is a core-shell spherical structure composed of a corrinoid-providing bacterial shell and a halogenated hydrocarbon repairing functional core; The corrinoids provide the bacterial coat by providing the cofactor corrinoid vitamin B 12 (VB 12 ) is composed of aerobic biphenylophilic Rhodococcus, which is fixed on the outer surface of the halogenated hydrocarbon repair function core by light-cured gelatin; The halogenated hydrocarbon repair functional core is composed of humic acid, anaerobic dehalogenating bacteria and biochar as functional materials, and is fixed by sodium alginate and calcium chloride to form a microsphere core; The biochar is obtained by pyrolysis of sawdust raw materials at 650-750°C with limited oxygen for 5-7 hours; The aerobic biphenylophilic Rhodococcus has been deposited in the General Microbiological Center of China Microbiological Culture Collection Administration, with the deposit address at No. 3, Yard No. 1, Beichen West Road, Chaoyang District, Beijing, Institute of Microbiology, Chinese Academy of Sciences, on October 8, 2014, with the deposit number CGMCC No. 1.12975; The anaerobic dehalogenating bacteria is Dehalogenating Coccidioides Dehalococcoides mccartyi strain 195 ( Dh 195), ATCC catalog number BAA-2266; The preparation method of the carbon-based adsorption / microbial anaerobic degradation risk management composite material comprises: S1, using 1 wt.% sodium alginate solution at 40-50 °C as the mother solution, adding 200 mg / L humic acid (HA), 50 g / L biochar and 10 6 CFU / mL of anaerobic dehalogenating bacteria mixed ， Under anaerobic conditions, the mixed solution was added dropwise to a 1 wt.% CaCl2 solution through a droplet forming device to form microspheres in the solution; S2, using 3 wt.% gelatin solution as the mother solution, according to the final concentration of 10 7 CFU / mL is added to the logarithmic phase aerobic biphenylophilic Rhodococcus and mixed evenly, and then the microspheres are added to make a layer of bacteria-containing gelatin solution evenly adhere to the surface of the microspheres, and then taken out for light curing to obtain a core-shell spherical structure composite material with the microspheres as the halogenated hydrocarbon repair function core and the core wrapped with corrinoids to provide a bacterial shell.

2. The carbon-based adsorption / microbial anaerobic degradation risk management composite material according to claim 1, characterized in that: The particle size of the core-shell spherical structure is 0.1-0.2 cm.

3. A method for preparing the carbon-based adsorption / microbial anaerobic degradation risk management composite material as claimed in claim 1 or 2, characterized in that: include: S1, using 1 wt.% sodium alginate solution at 40-50 °C as the mother solution, adding 200 mg / L humic acid (HA), 50 g / L biochar and 10 6 CFU / mL of anaerobic dehalogenating bacteria mixed ， Under anaerobic conditions, the mixed solution was added dropwise to a 1 wt.% CaCl2 solution through a droplet forming device to form microspheres in the solution; S2, using 3 wt.% gelatin solution as the mother solution, according to the final concentration of 10 7 CFU / mL is added to the logarithmic phase aerobic biphenylophilic Rhodococcus and mixed evenly, and then the microspheres are added to make a layer of bacteria-containing gelatin solution evenly adhere to the surface of the microspheres, and then taken out for light curing to obtain a core-shell spherical structure composite material with the microspheres as the halogenated hydrocarbon repair function core and the core wrapped with corrinoids to provide a bacterial shell.

4. A biological reaction wall, characterized in that: The carbon-based adsorption / microbial anaerobic degradation risk management composite material as claimed in claim 1 is used as filler.

5. An application of the carbon-based adsorption / microbial anaerobic degradation risk management composite material as claimed in claim 1 in the remediation of halogenated hydrocarbon-contaminated water bodies.

6. The use according to claim 5, characterized in that: The water body is groundwater.

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