A method for in-situ remediation or control of contaminated soil and groundwater using a combination of ozone aeration and microorganisms

Abstract

The present invention relates to an in-situ remediation or control method for contaminated soil and groundwater using a combination of ozone aeration and microorganisms, comprising the following steps: S1: injecting ozone micro-nano bubbles of a first particle size into the soil or groundwater, aerating continuously for 1 to 5 days, with an aeration time of 6 to 10 hours per day, wherein the first particle size is nanometer-level; S2: injecting ozone micro-nano bubbles of a second particle size into the soil or groundwater, aerating continuously for 1 to 5 days, with an aeration time of 6 to 10 hours per day, wherein the second particle size is larger than the first particle size, and is micrometer-level; S3: injecting air micro-nano bubbles or oxygen micro-nano bubbles of a third particle size into the soil or groundwater 2 to 9 days after step S2 is completed, aerating continuously for 1 to 4 days, with an aeration time of 6 to 10 hours per day, wherein the third particle size is nanometer-level; S4: injecting a composite microbial agent 12 to 24 hours after step S3 is completed.

Description

Technical Field

[0001] The present invention relates to the field of contaminated soil and groundwater treatment, and in particular to an in-situ remediation or control method for contaminated soil and groundwater using a combination of ozone aeration and microorganisms. Background Art

[0002] Ozone is a strong oxidant that can quickly decompose organic pollutants. After the oxidation reaction is completed, it will decompose into oxygen and usually does not cause secondary pollution. However, ozone has limited solubility and a short half-life, and requires continuous supply and injection to maintain an effective oxidation reaction. Therefore, the application of ozone in pollutant control needs further research.

[0003] Microbial remediation is green, environmentally friendly, energy-saving, can be repaired in situ, is cost-effective, and can adapt to the environment and continue to repair for a long time. However, when it is applied to the treatment of contaminated soil and sewage, the pollutants in the contaminated soil and sewage are often highly toxic to them and are difficult to use directly. Summary of the Invention

[0004] The technical problem to be solved by the present invention is to provide a new in-situ remediation or control method for contaminated soil and groundwater by combining ozone aeration and microorganisms.

[0005] In order to solve the above technical problems, the technical solution adopted in the first aspect of the present invention is:

[0006] A method for in-situ remediation or control of contaminated soil and groundwater using a combination of ozone aeration and microorganisms, comprising the following steps:

[0007] S1. Injecting ozone micro-nano bubbles of a first particle size into the soil or groundwater for continuous aeration for 1 to 5 days, with a daily aeration time of 6 to 10 hours, wherein the first particle size is nanometer-level;

[0008] S2: injecting ozone micro-nano bubbles of a second particle size into the soil or groundwater for continuous aeration for 1 to 5 days, with an aeration time of 6 to 10 hours per day, wherein the second particle size is larger than the first particle size and is in the micron level;

[0009] S3: 2 to 9 days after step S2, injecting air micro-nano bubbles or oxygen micro-nano bubbles of a third particle size into the soil or groundwater for continuous aeration for 1 to 4 days, with an aeration time of 6 to 10 hours per day, wherein the third particle size is nanometer-level;

[0010] S4: 12 to 24 hours after step S3 is completed, inject the composite microbial agent.

[0011] In some specific embodiments, in step S1 , aeration is continued for 1 day, 2 days, 3 days, 4 days or 5 days.

[0012] In some specific embodiments, in step S2, aeration is continued for 1 day, 2 days, 3 days, 4 days or 5 days.

[0013] In some specific embodiments, in step S3, air micro-nano bubbles or oxygen micro-nano bubbles of a third particle size are injected into the soil or groundwater 2 days, 3 days, 4 days, 5 days, 6 days, 7 days, 8 days or 9 days after step S2 is completed.

[0014] In some specific embodiments, in step S3, aeration is continued for 1 day, 2 days, 3 days or 4 days.

[0015] In some specific embodiments, in step S4, the composite microbial agent is injected 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, 17 hours, 18 hours, 19 hours, 20 hours, 21 hours, 22 hours, 23 hours or 24 hours after step S2 is completed.

[0016] In some specific embodiments, in step S1 , the aeration time is 6 h, 7 h, 8 h, 9 h or 10 h per day.

[0017] In some specific embodiments, in step S2, the aeration time is 6 hours, 7 hours, 8 hours, 9 hours or 10 hours per day.

[0018] In some specific embodiments, in step S3, the aeration time is 6 hours, 7 hours, 8 hours, 9 hours or 10 hours per day.

[0019] In one embodiment, the first particle size range is 90-120 nm, and / or the second particle size range is 8-12 μm.

[0020] In one embodiment, the first particle size range is 95-110 nm, and / or the second particle size range is 9-11 μm.

[0021] In one embodiment, the microbial strains in the composite microbial agent are all aerobic bacteria.

[0022] In one embodiment, the composite microbial agent is used to treat chlorinated hydrocarbon pollutants, and / or the composite microbial agent is used to treat petroleum hydrocarbon pollutants.

[0023] In one embodiment, the composite microbial agent comprises Pseudomonas, Sphingomonas, Rhodococcus, Bacillus, and Burkholderia, and the viable cell count ratio thereof is 1-3:1-3:1-3:1-3:1-2:1.

[0024] In one embodiment, the composite microbial agent comprises Pseudomonas, Cupriavidus, Comamonas, Achromobacter, and Variovorax, and the ratio of viable bacteria counts thereof is 3-8:1-3:1-2:1-2:1.

[0025] In one embodiment, the composite microbial agent comprises Rhodococcus, Sphingobium, Arthrobacter, Stenotrophomonas, and Mycobacterium, and the ratio of viable bacteria counts thereof is 2-6:2-4:2-4:1-2:1.

[0026] In one embodiment, the composite microbial agent comprises Bacillus, Alcaligenes, Ochrobactrum, Methylobacterium, and Dechloromonas, and the ratio of viable bacteria counts thereof is 4-10:2-4:1-3:1-2:1.

[0027] In one embodiment, the composite microbial agent comprises Pseudomonas, Paenibacillus, Hyphomicrobium, Nocardia, and Flavobacterium, and the ratio of viable bacteria counts thereof is 3-8:1-3:1-2:1-2:1.

[0028] In one embodiment, the composite microbial agent comprises Pseudomonas, Rhodococcus, Bacillus, Alcaligenes, and Acinetobacter, and the ratio of viable bacteria counts thereof is 4-10:2-4:1-3:1-2:1.

[0029] In one embodiment, the composite microbial agent comprises Sphingomonas, Mycobacterium, Burkholderia, Streptomyces, and Paracoccus, and the ratio of viable bacteria counts thereof is 2-6:2-4:2-4:1-2:1.

[0030] In one embodiment, the composite microbial agent comprises Pseudomonas, Rhodococcus, Bacillus, Acinetobacter, and Arthrobacter, and the ratio of viable bacteria counts thereof is 1-3:1-3:1-3:1-3:1-2:1.

[0031] In one embodiment, the viable bacterial count of the composite microbial agent is not less than 1×10 9 CFU / mL.

[0032] In one embodiment, the micro-nano bubbles and the composite microbial agent are injected at the same point; or, the composite microbial agent is injected downstream of the micro-nano bubbles and is less than or equal to 1 meter from the micro-nano bubble injection point. Downstream is defined relative to the direction of the groundwater field.

[0033] In one embodiment, the pollutants that contaminate the soil or groundwater are one or more of chlorinated hydrocarbons, benzene series, polychlorinated biphenyls, organic pesticides, and phenols.

[0034] In one embodiment, the pollutants that contaminate the soil or groundwater exist in the form of non-aqueous oil (NAPL), and the non-aqueous oil includes light non-aqueous liquid (LNAPL) and heavy non-aqueous liquid (DNAPL).

[0035] In one embodiment, the pollutant content of the groundwater is 0.4-2000 ug / L 60-135 days after step S4.

[0036] In one embodiment, the pollutant content in the soil is less than 560 mg / kg 45 to 135 days after step S4.

[0037] In one embodiment, the soil or groundwater is formed into a unit at a depth of 5 m. In step S1, the ozone micro-nano bubbles of the first particle size are injected into each of the units at a depth of 4 to 6 m, and / or in step S2, the ozone micro-nano bubbles of the second particle size are injected into each of the units at a depth of 4 to 6 m, and / or in step S3, the air micro-nano bubbles or oxygen micro-nano bubbles of the third particle size are injected into each of the units at a depth of 4 to 6 m.

[0038] In one embodiment, when the remediation object is the groundwater, the pollutant concentration is less than 200 mg / L 0 to 24 hours after step S3 is completed.

[0039] In one embodiment, when the remediation object is the groundwater, the pollutant concentration is less than 150 mg / L 0 to 24 hours after step S3 is completed.

[0040] In one embodiment, when the remediation object is the groundwater, the pollutant concentration is less than 100 mg / L 0 to 24 hours after step S3 is completed.

[0041] In one embodiment, when the remediation object is the groundwater, 0 to 24 hours after step S3 is completed, the microbial biomass is less than 2×10 6 CFU / ml.

[0042] In one embodiment, when the remediation object is the groundwater, 0 to 24 hours after step S3 is completed, the microbial biomass is less than 1×10 6 CFU / ml.

[0043] In one embodiment, when the remediation object is the groundwater, the redox potential is less than 300 mV 0 to 24 hours after step S3 is completed.

[0044] In one embodiment, when the remediation object is the groundwater, the redox potential is less than 250 mV 0 to 24 hours after step S3 is completed.

[0045] In one embodiment, when the remediation object is the groundwater, the redox potential is greater than 200 mV 0 to 24 hours after step S3 is completed.

[0046] In one embodiment, when the remediation object is the soil, the concentration of refractory pollutants is less than 1000 mg / kg 0 to 24 hours after step S3 is completed.

[0047] In one embodiment, when the remediation object is the soil, the concentration of refractory pollutants is less than 800 mg / kg 0 to 24 hours after step S3 is completed.

[0048] In one embodiment, when the remediation object is the soil, 0 to 24 hours after step S3 is completed, the microbial biomass is less than 1.5×10 8 CFU / g.

[0049] In one embodiment, when the remediation object is the soil, 0 to 24 hours after step S3 is completed, the microbial biomass is less than 1×10 8 CFU / g.

[0050] In one embodiment, the soil environment is one or more of silt, clay, silt clay, silt sand, or sand.

[0051] In order to solve the above technical problems, the technical solution adopted in the second aspect of the present invention is:

[0052] A method for in-situ remediation or control of contaminated soil and groundwater using a combination of ozone aeration and microorganisms, characterized by comprising the following steps:

[0053] S1. Injecting ozone micro-nano bubbles of a first particle size into the soil or groundwater for continuous aeration for 1 to 5 days, with a daily aeration time of 6 to 10 hours, wherein the first particle size is nanometer-level;

[0054] S2: injecting ozone micro-nano bubbles of a second particle size into the soil or groundwater for continuous aeration for 1 to 5 days, with an aeration time of 6 to 10 hours per day, wherein the second particle size is larger than the first particle size and is in the micron level;

[0055] S3: 12 to 24 hours after step S2 is completed, inject the composite microbial agent.

[0056] In one embodiment, the first particle size range is 90-120 nm, and / or the second particle size range is 8-12 μm.

[0057] In one embodiment, the composite microbial agent is aerobic bacteria and / or anaerobic bacteria.

[0058] Due to the application of the above technical solution, the present invention has the following advantages compared with the prior art:

[0059] 1. By setting up ozone micro-nano bubbles, the oxidizing properties and solubility of ozone are enhanced, and the residence time of ozone in contaminated soil or groundwater is increased; the properties of ozone micro-nano bubbles are used to treat pollutants; the bactericidal properties of ozone and the oxygen generated after ozone reaction are used to regulate the environmental conditions of contaminated soil or groundwater and enhance / activate microorganisms;

[0060] 2. By combining ozone micro-nano bubbles with microorganisms, microorganisms can be used for continuous environmental remediation or pollution source reduction risk control, making the treatment of pollutants in soil or groundwater more thorough;

[0061] 3. By sequentially injecting ozone micro-nano bubbles of a first nanometer particle size and ozone micro-nano bubbles of a second micrometer particle size, and specifically setting the aeration time and interval time, a compound microbial agent delivery point is formed. This delivery point not only uses ozone micro-nano bubbles to remove some microorganisms and pollutants in contaminated soil or groundwater, but also prevents residual ozone from affecting the activity of subsequently delivered compound microbial agents, allowing the subsequent compound microbial agents to survive and reproduce smoothly;

[0062] 4. By rationally setting the release sequence, aeration time and interval time of ozone micro-nano bubbles of different particle sizes, the pre-treatment time of contaminated soil or groundwater before the release of the composite microbial agent is shortened to the maximum extent, thereby improving the treatment efficiency of contaminated soil or groundwater. DETAILED DESCRIPTION

[0063] In one embodiment, the in-situ remediation or control method for contaminated soil and groundwater using ozone aeration and microbial combination of the present invention includes the following steps:

[0064] S1: Inject ozone micro-nano bubbles of the first particle size into the soil or groundwater for continuous aeration for 1 to 5 days, with a daily aeration time of 6 to 10 hours. The first particle size is nanometer-level.

[0065] S2: inject ozone micro-nano bubbles of the second particle size into the soil or groundwater for continuous aeration for 1 to 5 days, with an aeration time of 6 to 10 hours per day. The second particle size is larger than the first particle size and is in the micron level.

[0066] S3: 2 to 9 days after step S2, injecting air micro-nano bubbles or oxygen micro-nano bubbles of a third particle size into the soil or groundwater for continuous aeration for 1 to 4 days, with an aeration time of 6 to 10 hours per day, wherein the third particle size is nanometer-sized;

[0067] S4: 12 to 24 hours after step S3 is completed, inject the composite microbial agent.

[0068] Furthermore, the microbial strains in the composite microbial inoculant are aerobic bacteria. That is, in this embodiment, air micro-nano bubbles or oxygen micro-nano bubbles aeration is performed in step S3 after step S2, which is suitable for the living environment of aerobic bacteria.

[0069] Furthermore, aerobic bacteria can be divided into two categories according to the different target pollutants they target: chlorinated hydrocarbon aerobic bacteria used to treat chlorinated hydrocarbon pollutants and petroleum hydrocarbon aerobic bacteria used to treat petroleum hydrocarbon pollutants.

[0070] Chlorohydrocarbon aerobic bacteria can have the following combinations:

[0071] Combination 1: Pseudomonas, Sphingomonas, Rhodococcus, Bacillus, Burkholderia, with a viable cell count ratio of 1-3:1-3:1-3:1-3:1-2:1;

[0072] Combination 2: Pseudomonas, Cupriavidus, Comamonas, Achromobacter, and Variovorax, with a viable cell count ratio of 3-8:1 to 3:1 to 2:1 to 2:1;

[0073] Combination 3: Rhodococcus, Sphingobium, Arthrobacter, Stenotrophomonas, Mycobacterium, with a viable cell count ratio of 2-6:2-4:2-4:1-2:1;

[0074] Combination 4: Bacillus, Alcaligenes, Ochrobactrum, Methylobacterium, Dechloromonas, with a viable cell count ratio of 4-10:2-4:1-3:1-2:1;

[0075] Combination 5: Pseudomonas, Paenibacillus, Hyphomicrobium, Nocardia, and Flavobacterium, with a live cell count ratio of 3~8:1~3:1~2:1~2:1.

[0076] Petroleum hydrocarbon aerobic bacteria can be combined in the following ways:

[0077] Combination 1: Pseudomonas, Rhodococcus, Bacillus, Alcaligenes, Acinetobacter, with a viable cell count ratio of 4-10:2-4:1-3:1-2:1;

[0078] Combination 2: Sphingomonas, Mycobacterium, Burkholderia, Streptomyces, Paracoccus, with a viable cell count ratio of 2-6:2-4:2-4:1-2:1;

[0079] Combination three: Pseudomonas, Rhodococcus, Bacillus, Acinetobacter, and Arthrobacter, with a live cell count ratio of 1~3:1~3:1~3:1~2:1.

[0080] Commonalities of compound microbial agent combinations:

[0081] (1) Common characteristics of chlorinated hydrocarbon aerobic bacteria: They rely on oxygen as an electron acceptor and catalyze the oxidation of chlorinated hydrocarbons through monooxygenase or dioxygenase, cleaving the C-Cl bond and generating low-toxic intermediates (such as chloroethanol and chloroacetic acid). They also require co-metabolizing substrates (such as toluene and phenol) to induce the expression of dechlorinase, and coenzymes (NADH / FADH2) provide reducing power to drive the reaction. In addition, they are good at degrading low-chlorinated aliphatic hydrocarbons (such as ethyl chloride) and aromatic hydrocarbons (chlorobenzene) and have strong tolerance to highly chlorinated compounds (such as tetrachloroethylene). They secrete lipase to assist in the degradation of hydrophobic pollutants.

[0082] (2) Common characteristics of petroleum hydrocarbon aerobic bacteria: They can usually rely on oxygenases (such as CYP450, AlkB monooxygenase, and PAH dioxygenase) to oxidize alkanes and aromatic hydrocarbons (such as n-alkanes and polycyclic aromatic hydrocarbons (PAHs)). They can also decompose long-chain hydrocarbons into acetyl-CoA through the β-oxidation pathway, which enters the tricarboxylic acid (TCA) cycle and is completely mineralized into CO2 and H2O. In addition, they can secrete biosurfactants (such as rhamnolipids and trehalose lipids) to emulsify petroleum and improve its bioavailability. They can also form biofilms by secreting extracellular polysaccharides (EPS), enhancing their attachment and degradation efficiency at the oil-water interface.

[0083] In one embodiment, the in-situ remediation or control method for contaminated soil and groundwater using ozone aeration and microbial combination of the present invention includes the following steps:

[0084] S1: Inject ozone micro-nano bubbles of the first particle size into the soil or groundwater for continuous aeration for 1 to 5 days, with a daily aeration time of 6 to 10 hours. The first particle size is nanometer-level.

[0085] S2: inject ozone micro-nano bubbles of the second particle size into the soil or groundwater for continuous aeration for 1 to 5 days, with an aeration time of 6 to 10 hours per day. The second particle size is larger than the first particle size and is in the micron level.

[0086] S3: 12 to 24 hours after step S2 is completed, inject the composite microbial agent.

[0087] Furthermore, the microbial strains in the composite microbial agent are aerobic bacteria and / or anaerobic bacteria. That is, in this embodiment, it is not necessary to perform air micro-nano bubble aeration or oxygen micro-nano bubble aeration after step S2. Compared with performing air micro-nano bubble aeration or oxygen micro-nano bubble aeration after step S2, this embodiment is suitable for the case where the microbial strains in the composite microbial agent are anaerobic bacteria, or the microbial strains in the composite microbial agent are aerobic bacteria, and the environment itself has a high oxygen content, such as shallow contaminated soil or sandy soil.

[0088] The present invention will be further described below with reference to the examples. However, the present invention is not limited to the following examples. The implementation conditions used in the examples can be further adjusted according to the different requirements of specific use. The implementation conditions not specified are conventional conditions in the industry. The technical features involved in the various embodiments of the present invention can be combined with each other as long as they do not conflict with each other. Unless otherwise specified, the reagents in this application can be purchased commercially or prepared by methods known in the art.

[0089] Examples 1-2: The in-situ remediation or control method for contaminated soil and groundwater using ozone aeration and microbial combination according to Example 1 comprises the following steps:

[0090] S1: Inject ozone micro-nano bubbles of the first particle size into groundwater through a single point, with an injection depth of 5m, and aerate continuously for 3 days, with an aeration time of 8h per day. The first particle size is 100nm;

[0091] S2: Ozone micro-nano bubbles of the second particle size were injected into the groundwater through a single point, with an injection depth of 5 m, and aerated continuously for 3 days, with an aeration time of 8 h per day. The second particle size was 100 μm.

[0092] S3: Seven days after step S2, injecting air micro-nano bubbles of a third particle size into the groundwater through a single point for continuous aeration for 3 days, with an aeration time of 8 hours per day, wherein the third particle size is 100 nm;

[0093] S4: 24 hours after step S3, a composite microbial agent is injected at a single point. The specific composite microbial agent consists of Pseudomonas, Sphingomonas, Rhodococcus, Bacillus, and Burkholderia. The viable cell count ratio is 2:2:2:1:1, and the viable cell count concentration is 1×10 9 CFU / mL. Specifically, the composite microbial agent is a composite microbial fermentation broth, obtained by mixing the fermentation broths of the above strains. During use, the fermentation broth is diluted 10-fold, and approximately 200 L of the diluted bacterial broth is injected into each site. In this embodiment, the injection point for the micro-nano bubbles in steps S1 to S3 is the same as the injection point for the composite microbial agent in step S4.

[0094] The in-situ remediation or control method for contaminated soil and groundwater using a combination of ozone aeration and microorganisms of Example 2 comprises the following steps:

[0095] S1: Inject ozone micro-nano bubbles of the first particle size into the contaminated soil through a single point, with an injection depth of 5m, and aerate continuously for 3 days, with an aeration time of 8h per day. The first particle size is 100nm;

[0096] S2: Ozone micro-nano bubbles of the second particle size were injected into the contaminated soil through a single point, with an injection depth of 5m, and aerated continuously for 3 days, with an aeration time of 8h per day. The second particle size was 100μm.

[0097] S3: Seven days after step S2, injecting air micro-nano bubbles of a third particle size into the contaminated soil through a single point, and aerating the soil continuously for three days, with an aeration time of 8 hours per day, wherein the third particle size is 100 nm;

[0098] S4: 24 hours after step S3, a composite microbial agent is injected at a single point, specifically Pseudomonas, Sphingomonas, Rhodococcus, Bacillus, and Burkholderia, with a viable cell count ratio of 2:2:2:1:1 and a viable cell count concentration of 1×10 9 CFU / mL, specifically, the composite microbial agent is a composite microbial fermentation broth, which is obtained by mixing the fermentation broths of the above strains. When used, the fermentation broth is diluted 10 times, and about 200L of the diluted bacterial broth is injected into each site.

[0099] The main difference between Example 2 and Example 1 is that compared with Example 1, which treats groundwater pollution, Example 2 treats contaminated soil.

[0100] The aeration equipment in Examples 1 and 2 is a micro-nano bubble generating integrated device, the RJN-MN-1100 engineering model (including an ozone generator) manufactured by Shanghai Rujing Environmental Protection Technology Co., Ltd. The specific parameters of the machine are as follows:

[0101] Bubble water output: 1.8 T / h; working pressure: 0.4 ~ 0.5 MPa; air flow rate: 0.1 ~ 2.5 L / min (standard condition). Using gas-liquid dissolution technology and precise shearing of the nozzle to generate bubble water, it can produce micro-nano bubbles with a minimum median particle size of 120 ~ 90 nm, and the bubble concentration can reach 2 ~ 5 × 10 8 / mL, the standard oxygen mass transfer efficiency SOTE can reach 82~85%, the nanobubble potential is -58.4~-59.6mV, and the nanobubble properties are stable.

[0102] Supplementary parameters of the ozone generator: The ozone generation concentration is 35~70mg / L, and the generation volume meets the intake flow requirements.

[0103] The soil in Examples 1 and 2 was surveyed and found to be mainly composed of clayey soil, silt, and silt sand. The characteristics are described as follows from top to bottom:

[0104] ① Plain fill: mainly light grey to light grey-yellow silt, very wet, slightly dense, with occasional small amounts of gravel, uneven composition and density, and poor structural properties. This layer is distributed locally, with a thickness of 1.00 to 3.40 m, averaging 1.99 m.

[0105] ②Silty soil layer: light grayish yellow to light gray, soft and plastic, medium density, dull cross-section, low dry strength and toughness, and obvious water release upon shaking. This layer is distributed throughout the site, with a thickness of 16.90 to 18.70 m, averaging 17.97 m.

[0106] Layer 3: Silt: Blue-gray, saturated, medium-dense to dense. Its primary mineral components are quartz and feldspar, with mica flakes. Its particles are sub-rounded and angular, with poor particle gradation. It has no dry strength or toughness and reacts quickly to shaking. This layer is distributed throughout the site.

[0107] Pilot test results

[0108] Sampling: The contaminated soil and groundwater treated by the in-situ remediation or control method of sewage using ozone aeration and microbial composite in Examples 1 to 2 were sampled. The sampling points of each example were 1 m and 5 m horizontally from the aeration point. Sampling was conducted 7 times in total, and the sampling times were 0 d (before aeration), 3 d (the day after completing step S1), 6 d (the day after completing step S2), 9 d (3 d after completing step S2), 13 d (7 d after completing step S2), 16 d (the day after completing step S3), and 17 d (1 d after completing step S3, the point before the composite microbial agent was added).

[0109] Detection indicators: There are four types of detection indicators for Example 1, namely, the concentration of difficult-to-degrade pollutants, microbial biomass, dissolved oxygen concentration and oxidation-reduction potential (ORP). There are two types of detection indicators for Example 2, namely, the concentration of difficult-to-degrade pollutants and microbial biomass.

[0110] Among them, the method for detecting the concentration of difficult-to-degrade pollutants is: purge and trap / gas chromatography-mass spectrometry. The difficult-to-degrade pollutant detected in Examples 1 and 2 is o-dichlorobenzene. In Example 1, the determination is specifically carried out according to the "Determination of Volatile Organic Compounds by Purge and Trap / Gas Chromatography-Mass Spectrometry" (HJ639-2012), and in Example 2, the determination is specifically carried out according to the "Determination of Volatile Organic Compounds by Purge and Trap / Gas Chromatography-Mass Spectrometry" (HJ605-2011).

[0111] The method for detecting the amount of microorganisms is the plate count method. In Examples 1 and 2, the determination is performed specifically according to the "Determination of the Total Bacterial Quantity in Water - Plate Count Method" (HJ1000-2018).

[0112] The dissolved oxygen concentration is detected by an electrochemical probe method. In Example 1, the determination is performed according to the "Electrochemical Probe Method for Determination of Dissolved Oxygen in Water" (HJ506-2009).

[0113] The method for detecting the oxidation-reduction potential (ORP) is potentiometric measurement. In Example 1, the measurement is performed according to SL 94-1994 Determination of oxidation-reduction potential (potentiometric measurement).

[0114] The specific test results are as follows:

[0115]

[0116]

[0117]

[0118]

[0119]

[0120]

[0121] Pilot test conclusion

[0122] 1. Initial oxidation of refractory pollutants

[0123] It can be seen from Table 1-1 and Table 1-2 that the pollution concentration was relatively high on day 0; the concentrations at 1m and 5m decreased on day 3, with the decrease at 1m being greater; the pollution concentrations at 1m and 5m further decreased to the same level on day 6, and then the concentration in Example 1 rebounded, while the concentration in Example 2 continued to decrease.

[0124] In Example 1, the pollutant concentration was treated to a level of 100 mg / L after 6 days, and in Example 2, the pollutant concentration was treated to a level of 900 mg / kg after 6 days, which basically met the pollution concentration range for efficient microbial treatment.

[0125] The pollutant concentration of Example 1 at 17 days increased slightly compared with the pollutant concentration at 6 days, but was still maintained below 150 mg / L. The pollutant concentration of Example 2 at 17 days decreased slightly compared with the pollutant concentration at 6 days, and was maintained below 800 mg / kg.

[0126] 2. Inhibition of in situ microorganisms

[0127] As shown in Table 2-1 and Table 2-2, the in-situ microbial biomass was high at 0 days; at 3 days, the microbial biomass at 1m and 5m decreased, with the decrease at 1m being greater, indicating a significant antibacterial effect; at 6 days, the microbial biomass at 1m and 5m further decreased to the same level, and then (at 13 days) the microbial biomass in Example 1 was basically stable at 3×10 5 CFU / ml level, the microbial biomass in Example 2 was basically stable at 8×10 7 CFU / g level.

[0128] The ozone micro-nano bubble aeration in Examples 1 and 2 has an excellent inhibitory effect on in-situ microorganisms. The microbial biomass of Example 1 can be basically controlled to 5×10 5 CFU / ml level, the microbial biomass of Example 2 was controlled at 10×10 7 Due to the short observation period, no significant rebound in microbial biomass was observed.

[0129] The microbial count of Example 1 at 17 days increased slightly compared to the pollutant concentration at 13 days, but still maintained at 20×10 5 CFU / ml, the microbial count of Example 2 at 17 days was slightly higher than the pollutant concentration at 13 days, and was maintained at 10×10 7 Below the CFU / g level.

[0130] 3. Construction of aerobic environment

[0131] As shown in Table 3, the in-situ environment was anaerobic on day 0; the oxygen content at both 1 m and 5 m increased on day 3, with the increase at 1 m being greater; the oxygen content at both 1 m and 5 m further increased to the same level on day 6, and then gradually decreased; and the oxygen content increased on day 16 due to the completion of the aeration of air micro-nano bubbles or oxygen micro-nano bubbles in step S3.

[0132] 4. Ozone residual time

[0133] As shown in Table 4, the in-situ environment was slightly oxidizing at 0 d; the oxidizing properties at 1 m and 5 m increased at 3 d, with the increase at 1 m being greater; the oxidizing properties at 1 m and 5 m further increased to the same level at 6 d, reaching a maximum of 860 mV; and then gradually decreased, returning to 250 mV at 13 d.

[0134] Ozone micro- and nano-bubble aeration exhibits a significant degree of pollutant oxidation within a short period of time after completion, namely on day 6. However, this duration is short, and it can be assumed that only a minimal amount of residual ozone remains by day 17, when the composite microbial inoculant is added. This is primarily due to the design of ozone micro- and nano-bubble aeration in steps S1 and S2, which aims to avoid adverse effects on subsequent processes (such as the addition of exogenous composite microbial inoculant). This is reflected in the reduction of the oxidizing properties (ORP value) within the environment to a certain level within a controlled timeframe.

[0135] Examples 3-4 and Comparative Examples 1-2: The steps of the in-situ remediation or control method for contaminated soil and groundwater composited with ozone aeration and microorganisms in Example 3 are exactly the same as those in Example 1, and the steps of the in-situ remediation or control method for contaminated soil and groundwater composited with ozone aeration and microorganisms in Example 4 are exactly the same as those in Example 2. The difference between the steps of the in-situ remediation or control method for contaminated soil and groundwater composited with ozone aeration and microorganisms in Comparative Example 1 and Example 3 is that: steps S1 and S2 in Comparative Example 1 are changed to: injecting ozone micro-nano bubbles of a first particle size into the groundwater through a single point, the injection depth is 5 m, and the aeration is continuous for 6 days, the aeration time is 8 h per day, and the first particle size is 100 nm. The difference between the steps of the in-situ remediation or control method for contaminated soil and groundwater composited with ozone aeration and microorganisms in Comparative Example 2 and Example 4 is that: steps S1 and S2 in Comparative Example 2 are changed to: injecting ozone micro-nano bubbles of a first particle size into the contaminated soil through a single point, the injection depth is 5 m, the aeration is continuous for 6 days, the aeration time is 8 h per day, and the first particle size is 100 nm.

[0136] Result detection

[0137] Sampling: The results of the sewage treated by the in-situ remediation or control method of sewage with ozone aeration and microbial composite in Examples 3 to 4 and Comparative Examples 1 to 2 were sampled. The sampling points of each embodiment were 1 m and 5 m horizontally away from the aeration point. A total of 7 samplings were conducted, and the sampling times were 13 d (7 d after completing step S2), 16 d (the same day after completing step S3), 20 d (3 days after completing step S4), 32 d (15 days after completing step S4), 47 d (30 days after completing step S4), 62 d (45 days after completing step S4), 92 d (75 days after completing step S4), 122 d (105 days after completing step S4), and 152 d (135 days after completing step S4).

[0138] Detection indicators: There are three types of detection indicators in Example 3 and Comparative Example 1, namely, the concentration of difficult-to-degrade pollutants, the amount of microorganisms, and the oxidation-reduction potential (ORP). There are two types of detection indicators in Example 4 and Comparative Example 2, namely, the concentration of difficult-to-degrade pollutants and the amount of microorganisms. The detection method is the same as that in Examples 1 and 2.

[0139] The specific test results are as follows:

[0140]

[0141]

[0142]

[0143]

[0144]

[0145] Pilot test conclusion

[0146] 1. Value-added of compound microbial agents

[0147] It can be seen from Tables 5-1 and 5-2 that the in-situ microbial biomass was low before the injection of the composite microbial agent (13d and 16d). The microbial biomass on 16d showed that even after the subsequent three-day air micro-nano bubble aeration, the antibacterial effect of the comparative example 1 point was still higher than that of the example 3 point, and the antibacterial effect of the comparative example 2 point was still higher than that of the example 4 point. This shows that considering only the antibacterial effect, the comparative example 1 scheme is better than the example 3, and the comparative example 2 scheme is better than the example 4.

[0148] However, a comparison of the data in Table 5-1 from 20 days to 152 days after the injection of the composite microbial inoculant reveals that the microbial growth process at the site in Comparative Example 1 did not begin immediately after injection, but rather was delayed for a period of time. Combined with the changes in groundwater ORP values (residual ozone from the reaction) in Table 7, it is speculated that the residual ozone at the site in Comparative Example 1, while continuing to inhibit the in-situ microorganisms, also inhibited the exogenously added composite microbial inoculant. This resulted in a biochemical shock during the initial addition of the composite microbial inoculant, thus affecting the initial growth and competition of the exogenous microorganisms. Over the longer term (122 days and 152 days), this effect did not reduce the peak microbial biomass, but rather significantly delayed it. Specifically, the time required for the exogenous microbial biomass to reach the same value in Comparative Example 1 was significantly longer than in Example 3.

[0149] Comparing the data in Table 5-2 from 20 days to 152 days after the composite microbial inoculum injection, we find that the microbial growth process at the site in Comparative Example 2 did not begin immediately after injection, but was delayed for a period of time. It is speculated that while the residual ozone at the site in Comparative Example 1 continued to inhibit the in-situ microorganisms, it also inhibited the exogenously added composite microbial inoculum, resulting in a biochemical shock during the initial addition of the composite microbial inoculum, thus affecting the initial growth and competition of the exogenous microorganisms. Looking at the longer term (92 days, 122 days, and 152 days), this effect did not reduce the peak microbial biomass, but significantly delayed it. The peak microbial biomass in Example 3 occurred around 92 days, while that in Comparative Example 2 occurred after 152 days. In other words, the time required for the exogenous microbial biomass to reach the same value in Comparative Example 2 was significantly longer than that in Example 4.

[0150] To prevent disturbance of groundwater or soil before injection of the composite microbial agent, the microbial biomass at 17 days in Examples 3 and 4 was not detected. Based on the microbial biomass data from 13 days to 17 days in Examples 1 and 2, it is inferred that the microbial biomass before injection of the composite microbial agent in step S4 of Examples 3 and 4 (17 days) was slightly increased or basically the same as that from 13 days to 16 days.

[0151] 2. Microbial treatment of difficult-to-degrade pollutants

[0152] Table 6-1 demonstrates that the in-situ remediation or control method for contaminated soil and groundwater using a combination of ozone aeration and microorganisms has a significant impact on groundwater treatment. In Example 3, the pollutant concentration dropped below 2.0 mg / L (Class IV water standard) between 122 and 152 days, reaching 0.6 mg / L (Class III water standard) by 152 days. However, in Comparative Example 1, the concentration still did not reach below 2.0 mg / L by 152 days. Due to the short experimental time, the point at which Comparative Example 1 reached the Class IV water standard was not observed. It is speculated that this point may have occurred between 182 and 212 days.

[0153] As shown in Table 6-2, the in-situ remediation or control method for contaminated soil and groundwater using a combination of ozone aeration and microorganisms according to the present invention does have a significant impact on contaminated soil treatment. In Example 4, the pollutant concentration dropped below 560 mg / kg (the screening value for Class I land use) between 47 and 62 days. However, in Comparative Example 2, the concentration still did not fully reach below 560 mg / kg by 92 days, but only dropped below 560 mg / kg (the screening value for Class I land use) between 92 and 122 days.

[0154] The reason for this is that the initial impact of residual ozone causes a biochemical shock to the added composite microbial inoculum, resulting in a subsequent decrease in survival rate and instantaneous effective concentration. This means that the actual initial concentration and initial proliferation rate of the composite microbial inoculum at the site of Comparative Example 1 were lower than those at the site of Example 3, and lower than those at the site of Comparative Example 2. The decrease in remediation efficiency in Comparative Example 1 compared to Example 3, and in Comparative Example 2 compared to Example 4, is due to the impact on the microbial proliferation rate and the accumulation time after the microorganisms reach their peak.

[0155] In order to prevent disturbance of groundwater or soil before injection of the composite microbial agent, the difficult-to-degrade pollutants at 17 days in Examples 3 and 4 were not detected. Based on the data of difficult-to-degrade pollutants at 13 days to 17 days in Examples 1 and 2, it is inferred that the difficult-to-degrade pollutants before injection of the composite microbial agent in step S4 of Examples 3 and 4 (17 days) were slightly reduced or basically the same as those at 13 days to 16 days.

[0156] Examples 5-6: The main difference between the steps of the in-situ remediation or control method for contaminated soil and groundwater using ozone aeration and microorganisms in Example 5 and Example 1 is that steps S1-3 of Example 5 are: S1 Injecting ozone micro-nano bubbles of a first particle size into the groundwater through a single point, with an injection depth of 5 m, continuous aeration for 1 day, and an aeration time of 8 hours per day, and the first particle size is 100 nm; S2 Injecting ozone micro-nano bubbles of a second particle size into the groundwater through a single point, with an injection depth of 5 m, continuous aeration for 1 day, and an aeration time of 8 hours per day, and the second particle size is 100 μm; S3 Four days after step S2 is completed, injecting air micro-nano bubbles or oxygen micro-nano bubbles of a third particle size into the groundwater, continuously aerating for 2 days, with an aeration time of 6-10 hours per day, and the third particle size is 100 nm.

[0157] The main difference between the steps of the in situ remediation or control method of contaminated soil and groundwater combined with ozone aeration and microorganisms in Example 6 and Example 2 is that steps S1 to 3 of Example 6 are: S1. Ozone micro-nano bubbles of a first particle size are injected into the contaminated soil through a single point, the injection depth is 5m, and aeration is continuous for 1 day, the aeration time is 8h per day, and the first particle size is 100nm; S2. Ozone micro-nano bubbles of a second particle size are injected into the contaminated soil through a single point, the injection depth is 5m, and aeration is continuous for 1 day, the aeration time is 8h per day, and the second particle size is 100μm; S3. Four days after step S2 is completed, air micro-nano bubbles or oxygen micro-nano bubbles of a third particle size are injected into the soil, and aeration is continuously carried out for 2 days, the aeration time is 6 to 10h per day, and the third particle size is 100nm.

[0158] The soil in Examples 5 and 6 was surveyed. The soil was sandy and its characteristics were described from top to bottom as follows:

[0159] ① Layer of plain fill soil: grayish yellow, wet, loose, with more plant roots on the surface, mainly composed of clay, uneven soil, and generally distributed.

[0160] ② Layer of silty clay: gray, saturated, plastic, locally interspersed with a small amount of thin silt layers (single layer thickness varies from 3 to 5 cm), slightly glossy, no shaking reaction, medium dry strength, medium toughness, uneven soil quality, and widespread distribution.

[0161] ③ Layer of sandy silt: gray, wet to very wet, slightly dense to medium dense, with a small amount of clay strips (single layer thickness 1-20mm) and silt lumps, low dry strength, low toughness, no gloss reaction, rapid shaking reaction, uneven soil quality, and local distribution.

[0162] ④ Layer of silt: gray, saturated, medium-dense to dense, mainly composed of quartz, mica and feldspar,

[0163] The particle gradation is relatively uniform, with clumps of silt, and the soil is uneven and widely distributed.

[0164] ⑤ Layer of sandy silt: gray, wet, medium dense, with a small amount of clay strips (single layer thickness 1-20mm) and silt lumps, low dry strength, low toughness, no gloss reaction, rapid shaking reaction, uneven soil quality, and widespread distribution.

[0165] ⑥ Layer of silt sand: gray, saturated, dense, mainly composed of quartz, mica and feldspar, with relatively uniform particle grading, interspersed with silt clumps, and uneven soil quality.

[0166] Pilot test results

[0167] Sampling: The contaminated soil and groundwater treated by the in situ remediation or control method of contaminated soil and groundwater combined with ozone aeration and microorganisms of Examples 5 to 6 were sampled. The sampling points of each example were 1 m and 5 m horizontally from the aeration point. A total of 6 samplings were conducted, and the sampling times were 0 d (before aeration), 1 d (the day after completing step S1), 2 d (the day after completing step S2), 6 d (4 d after completing step S2), 8 d (the day after completing step S3), and 9 d (1 d after completing step S3, the point before the composite microbial agent was added).

[0168] Detection indicators: The detection indicators of Example 5 are the concentration of difficult-to-degrade pollutants, microbial biomass, dissolved oxygen concentration and redox potential (ORP). The detection indicators of Example 6 are two types, namely the concentration of difficult-to-degrade pollutants and microbial biomass. The detection method is the same as that of Examples 1 and 2.

[0169] The specific test results are as follows:

[0170]

[0171]

[0172]

[0173]

[0174]

[0175]

[0176] Pilot test conclusion

[0177] 1. Initial oxidation of refractory pollutants

[0178] It can be seen from Table 8-1 and Table 8-2 that the pollution concentration was relatively high on day 0; on day 1, the concentrations at 1m and 5m decreased, with the decrease at 1m being greater; on day 2, the pollution concentrations at 1m and 5m further decreased to the same level, and then the concentration rebounded.

[0179] In Example 5, the pollutants were treated to a level below 100 mg / L within 2 days, and in Example 6, the pollutants were treated to a level below 900 mg / kg within 2 days, which basically met the pollution concentration range for efficient microbial treatment. Comparing Examples 5 and 6 with Examples 1 and 2, for sandy soil sites, when similar pollutant treatment effects were achieved, the time required for aeration in steps S1 to S3 was shorter than that for powdery clay sites.

[0180] The pollutant concentration of Example 5 at 9 days increased slightly compared with the pollutant concentration at 4 days, but was still maintained below 100 mg / L. The pollutant concentration of Example 6 at 9 days decreased slightly compared with the pollutant concentration at 4 days, and was maintained below 750 mg / kg.

[0181] 2. Inhibition of in situ microorganisms

[0182] As shown in Table 9-1 and Table 9-2, the in-situ microbial biomass was high at 0 days; at 1 day, the microbial biomass at 1m and 5m decreased, with the decrease at 1m being greater, indicating a significant antibacterial effect; at 2 days, the microbial biomass at 1m and 5m further decreased, and then (at 6 days) the microbial biomass in the groundwater of Example 5 was basically stable at 2×10 5 CFU / ml level, the microbial biomass in the contaminated soil of Example 6 was basically stable at 8×10 7 CFU / g level.

[0183] It can be seen that ozone micro-nano aeration has an excellent inhibitory effect on in-situ microorganisms, and can basically control the groundwater microbial biomass to 3×10 5CFU / ml level, and control the soil microbial biomass to 10×10 7 Below the CFU / g level, when comparing Examples 5-6 with Examples 1-2, for sandy soil sites, when achieving similar microbial biomass control effects, the time required for aeration in Steps S1 to S3 is shorter than that for powdery clay sites.

[0184] The microbial count of Example 5 at 9 days increased slightly compared to the pollutant concentration at 6 days, but still maintained at 3×10 5 CFU / ml, the microbial count of Example 6 at 9 days was slightly higher than the pollutant concentration at 6 days, and was maintained at 15×10 7 Below the CFU / g level.

[0185] 3. Ozone residual time

[0186] From the ORP value change trend in Table 11, it can be seen that the in-situ environment was slightly oxidizing on day 0; on day 1, the oxidizing properties at both 1m and 5m increased, with the increase at 1m being greater; on day 2, the oxidizing properties at both 1m and 5m further increased to the same level, reaching a maximum of 884mV; and then gradually decreased, returning to 200mV on day 6.

[0187] Ozone micro- and nano-bubble aeration drastically oxidizes pollutants for a short period of time (2 days) after aeration is completed, but this effect is short-lived, and only a minimal amount of residual ozone remains after 9 days. This is primarily due to the design of ozone micro- and nano-bubble aeration in steps S1 and S2, which aims to avoid adverse effects on subsequent processes (such as the addition of exogenous composite microbial inoculants). This is reflected in the reduction of the oxidizing properties (ORP value) within the environment to a certain level within a controlled timeframe.

[0188] Comparing Examples 1 and 2, Examples 5 and 6 show a shorter ozone residual time and a faster ORP drop. This is because the sandy soil in Examples 5 and 6 has better permeability, making the residual ozone concentration more easily diluted by the air / oxygen micro-nano bubble water in step S3. Therefore, the ORP value used to determine the residual ozone can be higher. This means that in Examples 5 and 6, the pretreatment can be considered complete 2 to 4 days after step S2, and step S3 (air / oxygen micro-nano aeration stage) can be entered. This is because the soil properties in Examples 5 and 6 lead to an optimized process effect and reduced time.

[0189] The above embodiments are intended only to illustrate the technical concepts and features of the present invention. Their purpose is to enable those skilled in the art to understand the contents of the present invention and implement them accordingly. They are not intended to limit the scope of protection of the present invention. Any equivalent changes or modifications made in accordance with the spirit of the present invention are intended to be covered by the scope of protection of the present invention.

Claims

1. A method for in-situ remediation or control of contaminated soil and groundwater using a combination of ozone aeration and microorganisms, characterized in that: The following steps are involved: S1. Injecting ozone micro-nano bubbles of a first particle size into the soil or groundwater for continuous aeration for 1 to 5 days, with a daily aeration time of 6 to 10 hours, wherein the first particle size is nanometer-level; S2: injecting ozone micro-nano bubbles of a second particle size into the soil or groundwater for continuous aeration for 1 to 5 days, with an aeration time of 6 to 10 hours per day, wherein the second particle size is larger than the first particle size and is in the micron level; S3: 2 to 9 days after step S2, injecting air micro-nano bubbles or oxygen micro-nano bubbles of a third particle size into the soil or groundwater for continuous aeration for 1 to 4 days, with an aeration time of 6 to 10 hours per day, wherein the third particle size is nanometer-level; S4: 12 to 24 hours after step S3 is completed, a compound microbial agent delivery point is formed and the compound microbial agent is injected.

2. The in-situ remediation or control method for contaminated soil and groundwater using a combination of ozone aeration and microorganisms according to claim 1, characterized in that: The first particle size range is 90-120 nm, and / or the second particle size range is 8-12 μm.

3. The in-situ remediation or control method for contaminated soil and groundwater using a combination of ozone aeration and microorganisms according to claim 1, characterized in that: The microbial strains in the composite microbial agent are all aerobic bacteria.

4. The in-situ remediation or control method for contaminated soil and groundwater using a combination of ozone aeration and microorganisms according to claim 3 is characterized by: The viable bacterial count concentration of the composite microbial agent is not less than 1×10 9 CFU / mL.

5. The in-situ remediation or control method for contaminated soil and groundwater using a combination of ozone aeration and microorganisms according to claim 1, characterized in that : The micro-nano bubbles and the composite microbial agent are injected through the same point; or, the injection point of the composite microbial agent is downstream of the injection point of the micro-nano bubbles and is less than or equal to 1m away from the injection point of the micro-nano bubbles.

6. The in-situ remediation or control method for contaminated soil and groundwater using a combination of ozone aeration and microorganisms according to claim 1, characterized in that: The pollutants that contaminate the soil or groundwater are one or more of chlorinated hydrocarbons, benzene series, polychlorinated biphenyls, organic pesticides, and phenols.

7. The in-situ remediation or control method for contaminated soil and groundwater using a combination of ozone aeration and microorganisms according to claim 1, characterized in that: The groundwater has a pollutant content of 0.4 to 2000 ug / L 60 to 135 days after step S4.

8. The in-situ remediation or control method for contaminated soil and groundwater using a combination of ozone aeration and microorganisms according to claim 1, characterized in that: 45 to 135 days after step S4, the pollutant content in the soil is less than 560 mg / kg.

9. The in-situ remediation or control method for contaminated soil and groundwater using a combination of ozone aeration and microorganisms according to claim 1, characterized in that: The soil or groundwater is formed into a unit at a depth of 5 m. In step S1, the ozone micro-nano bubbles of the first particle size are injected into each of the units at a depth of 4 to 6 m, and / or in step S2, the ozone micro-nano bubbles of the second particle size are injected into each of the units at a depth of 4 to 6 m, and / or in step S3, the air micro-nano bubbles or oxygen micro-nano bubbles of the third particle size are injected into each of the units at a depth of 4 to 6 m.

10. The in-situ remediation or control method for contaminated soil and groundwater using a combination of ozone aeration and microorganisms according to claim 1, characterized in that: When the remediation object is the groundwater, the pollutant concentration is less than 200 mg / L 0 to 24 hours after step S3 is completed.

11. The in-situ remediation or control method for contaminated soil and groundwater using a combination of ozone aeration and microorganisms according to claim 1, characterized in that: When the remediation object is the groundwater, 0 to 24 hours after step S3 is completed, the microbial biomass is less than 2×10 6 CFU / ml.

12. The in-situ remediation or control method for contaminated soil and groundwater using a combination of ozone aeration and microorganisms according to claim 1, characterized in that: When the remediation object is the groundwater, the redox potential is less than 300 mV 0 to 24 hours after step S3 is completed.

13. The in-situ remediation or control method for contaminated soil and groundwater using a combination of ozone aeration and microorganisms according to claim 1, characterized in that: When the remediation object is the soil, 0 to 24 hours after step S3 is completed, the concentration of refractory pollutants is less than 1000 mg / kg.

14. The in-situ remediation or control method for contaminated soil and groundwater using a combination of ozone aeration and microorganisms according to claim 1, characterized in that: When the remediation object is the soil, 0 to 24 hours after step S3 is completed, the microbial biomass is less than 1.5×10 8 CFU / g.

15. The in-situ remediation or control method for contaminated soil and groundwater using a combination of ozone aeration and microorganisms according to claim 1, characterized in that: The soil environment is one or more of silt, clay, silt clay, silt sand or sandy soil.

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