WO2005118171A1

WO2005118171A1 - Additive for use to restore polluted soil, groundwater or bottom sediment soil

Info

Publication number: WO2005118171A1
Application number: PCT/JP2005/010187
Authority: WO
Inventors: Shrihari Chandraghatgi; Shingo Maeda; Kaoru Nogawa; Hideki Himi
Original assignee: Ecocycle Corporation
Priority date: 2004-06-02
Filing date: 2005-06-02
Publication date: 2005-12-15
Also published as: JPWO2005118171A1; JP3834580B2

Abstract

[PROBLEMS] To provide an additive that is capable of restoring various geological polluted sites and can realize low-cost restoration work, and that is used in biological restoration of soil, groundwater or bottom sediment soil polluted by organic halogenated compounds, especially organic chlorinated compounds. [MEANS FOR SOLVING PROBLEMS] An additive comprising a substance capable of formation/activation of microbial consortiums, a substance capable of accelerating reductive dehalogenation by anaerobic microbes and a substance capable of generating anaerobic condition is added to soil, groundwater or bottom sediment soil polluted by organic chlorinated compounds. As a result, native microbial consortiums consume oxygen to thereby create an anaerobic atmosphere (anaerobic condition) in the restoration object. In the created anaerobic atmosphere, anaerobic microbes decompose organic halogenated compounds as electron acceptors, finally to inorganic halides, through reductive dehalogenation using a supplied electron donor or an electron donor produced by decomposition of supplied other additive.

Description

Additives used to repair contaminated soil, groundwater or sediment

[0001] The present invention relates to an organic halogenated compound, particularly to an additive used for repairing soil, groundwater or sediment soil contaminated with an organic chlorine compound.

Background art

[0002] In recent years, soil, groundwater or sediment soil is seriously contaminated by organic halogenated compounds represented by organic chlorine compounds such as tetrachloroethylene, trichloroethylene, dichloroethylene, dioxins, and polychlorinated biphenyls. Has become a problem.

[0003] At present, as a restoration technique for soil, groundwater or sediment soil contaminated by such an organic halogenated compound, after pumping contaminated groundwater, activated carbon or resin is injected into the pumped groundwater. Physical treatment methods such as adsorption of contaminants due to the contamination and volatilization and removal of the contaminated soil by air drying have been considered effective (for example, see Non-Patent Document 1). However, neither is a fundamental solution because it is not a technology to completely detoxify pollutants with high initial capital investment and high power costs. Therefore, the development of a bioremediation technology that utilizes microorganisms to decompose hard-to-decompose harmful substances contained in soil, groundwater or sedimentary soil to remove contamination is expected.

[0004] Noremediation (bioremediation method) is a technology that biologically decomposes harmful organic compounds and converts them into harmless substances such as carbon dioxide, methane, water, inorganic salts, and biomass. It is. More recently, the concept of bioremediation has been extended to techniques for repairing hazardous waste and contaminated soil, groundwater or sediment. Under such circumstances, research and development using aerobic microorganisms has been conducted on bioremediation of black-mouthed carbon pollution in Japan.

[0005] The neurostimulation (bioactivity method) is a method that inhabits the site of contamination and promotes the decomposition and removal of contamination by growing and activating certain aerobic microorganisms. This is a method of supplying necessary carbon sources such as methane, air or pure oxygen, and nutrients from the outside. [0006] Neuroregulation (biological addition method) is a method of cultivating a large amount of a single microorganism with excellent resolution and injecting it together with an oxidant into the basement of the contamination site to decompose the contamination. · It is a method to remove.

[0007] In particular, as a means for decomposing organic chlorine compounds, there is reductive dechlorination by anaerobic microorganisms (for example, see Non-Patent Document 1). When an anaerobic microorganism is supplied with an electron donor such as an organic acid, the anaerobic microorganism decomposes the organic chlorine compound by reductive dechlorination using the organic chlorine compound as an electron acceptor. Therefore, if this process is applied to the remediation of pollution by organochlorine compounds, it is necessary to provide a means to make the contaminated area anaerobic.

[0008] In this connection, Patent Document 1 discloses a method in which a distilled liquor waste liquid is applied to soil to purify soil and Z or groundwater contaminated by an organochlorine compound using the action of anaerobic microorganisms. It is disclosed that the distillation residue waste liquid contains organic acids such as lactic acid, acetic acid, citric acid, and succinic acid, sugars such as maltose, glucose, and fructose, and amino acids in a well-balanced manner. ing. Patent Document 2 discloses a method in which an organochlorine compound is decomposed by an organochlorine-decomposing microorganism present in soil and Z or groundwater by adding an amino acid and an electron donor to the source. Lactic acid, sucrose and the like are listed. Further, Patent Document 3 discloses that, in soil and Z or groundwater contaminated with tetrachloroethylene or the like, a carbon source necessary for the growth and survival of microorganisms in the soil, an inorganic reducing agent, a polymer water-absorbing resin and Z or It is disclosed that a water-retaining resin is injected and mixed, and as a carbon source, for example, lactic acid, polypeptone, a sugar-containing organic substance, or the like is described as a nutrient source of a sulfate-reducing microorganism.

Patent Document 1: Japanese Patent Application Laid-Open No. 2002-224658

Patent Document 2: JP 2003-145131 A

Patent Document 3: JP-A-11-2622751

Non-patent document 1: Environmental purification technology Vol. 1, No. 1 (pp. 80-84)

Disclosure of the invention

Problems to be solved by the invention

[0010] However, these methods have the following problems. Biostimulation is

The introduction of oxidizers and large volumes of air requires significant capital and repair costs. there were. In addition, the neuroregulation has a problem that the resolution of microorganisms depends on the environment of the contaminated area where the microorganisms are injected, and the ability of the injected microorganisms is not always sufficiently exhibited. In addition, reductive dechlorination by anaerobic microorganisms has a problem that means for making the area to be restored an anaerobic state in order to utilize anaerobic microorganisms having the resolution of organic halogenated compounds is not considered. Was. As described above, all of the no-remediation technologies that have been developed up to now contain problems, and there is a need for the development of repair technologies that resolve them.

[0011] Further, although the methods according to Patent Documents 1 to 3 have some effects, there has been a strong demand for further improvement in the effects. In other words, there has been a demand for the development of additives that exhibit more remarkable effects.

[0012] The present invention has been made in view of the above-described problems in the conventional art, and is an organic halogen compound, particularly an organic halogen compound that can repair various soil contamination sites and can perform low-cost repair work. The aim of the present invention is to provide additives for biological remediation of soil, groundwater or sediment contaminated by organochlorine compounds.

Means for solving the problem

[0013] The inventors of the present application have conducted research on additives having a remarkable effect, and have found that a substance that activates a microorganism consortium, a substance that promotes reductive dehalogenation of anaerobic microorganisms, and an anaerobic state. An additive which has three kinds of material strengths with the material forming the material has been found.

[0014] That is, the additive used for repairing soil, groundwater or sediment soil contaminated with the organic halogenated conjugate of the present invention is a substance that forms and activates a microbial consortium and reductive removal of anaerobic microorganisms. It is characterized by comprising a substance that promotes halogenation and a substance that creates an anaerobic state.

[0015] The substance that forms and activates the microbial consortium is peptone, and the substance that promotes reductive dehalogenation of the anaerobic microorganism is propionic acid, butyric acid, lactic acid, and their salt power. Characterized in that the substance forming the anaerobic state is at least one substance selected from the group consisting of glucose, galactose, fructose, ratatose, sucrose, and maltosca.

[0016] In addition, soil, groundwater or sediment contaminated by the organic halogenated compound of the present invention The restoration method for restoring soil is characterized by adding a substance that creates and activates a microbial consortium, a substance that promotes reductive dehalogenation of anaerobic microorganisms, and a substance that creates an anaerobic state.

[0017] The substance that forms and activates the microbial consortium is peptone, and the substance that promotes reductive dehalogenation of the anaerobic microorganism is propionic acid, butyric acid, lactic acid, and their salt power. Characterized in that the substance forming the anaerobic state is at least one substance selected from the group consisting of glucose, galactose, fructose, ratatose, sucrose, and maltosca.

[0018] Further, the method for repairing soil, groundwater or sediment soil contaminated with the organohalide ligated compound of the present invention is as follows: peptone is added to form a microbial consortium; Lactic acid, and their salt powers. At least one selected substance is added to promote the reductive dehalogenation of anaerobic microorganisms, from the group consisting of glucose, galactose, fructose, ratatose, sucrose, and maltose. An anaerobic state is created by adding at least one selected substance.

[0019] The additive used for the restoration of soil, groundwater or sediment soil contaminated with the organic halogenated conjugate according to the invention of the present application has a substance that forms and activates a microbial consortium as described above. It is characterized by. A microbial consortium refers to the entire indigenous group of microorganisms, including both aerobic and anaerobic, and various anaerobic microorganisms! The substance that forms and activates the microbial consortium is a substance that is effective for the formation, that is, propagation, of both aerobic and anaerobic microorganisms.

[0020] In order to restore the soil, groundwater or sedimentary soil of an area contaminated with an organic halogenated compound, particularly an organic chlorine compound, microorganisms having a plurality of different properties can be effectively used. It is effective.

[0021] If a substance that creates and activates a microbial consortium is added to soil, groundwater, or sedimentary soil, indigenous aerobic microorganisms or facultative anaerobic microorganisms degrade the substances contained in the additives. By utilizing the electron donor generated by the decomposition, nitrate ions, sulfate ions, and the like existing in soil and the like are consumed as electron acceptors. At the same time, it consumes oxygen as an electron acceptor and puts soil, groundwater or sediment under anaerobic conditions. [0022] When the object to be repaired becomes anaerobic, it becomes possible for the absolute anaerobic microorganisms to decompose the organic halogen compound, particularly the organic chlorine compound, as an electron acceptor. For example, ethylene tetrachloride is converted into trichloroethylene and then dichloroethylene by successive reductive dechlorination reactions, which are eventually decomposed into stable inorganic salts.

[0023] As described above, by supplying the substance that creates and activates the entire microbial consortium, an environment in which anaerobic microorganisms perform reductive dehalogenation quickly is provided, and repair work is efficiently performed. proceed.

[0024] That is, the harmful intermediate products generated by the anaerobic microorganisms in the process of reductive dechlorination include those that cannot always be decomposed effectively by these anaerobic microorganisms (Shiiro Bul monomer, cis monomer). There is also 1,2-dichloroethylene), but once the entire microbial consortium is activated, other types of microorganisms that make up the microbial consortium can effectively decompose these substances. Therefore, harmful intermediate products are unlikely to remain during repair work using anaerobic microorganisms.

[0025] As described above, in order to decompose an organic halogenated compound, in particular, an organic chlorine compound, it is necessary to activate the entire indigenous group of microorganisms including both aerobic and anaerobic to bring them into an anaerobic state. Is particularly important.

[0026] Further, the additive used for repairing soil, groundwater or sediment soil contaminated with the organic halogenated conjugate according to the present invention has a substance that promotes reductive dehalogenation of anaerobic microorganisms. It is characterized by the following.

[0027] The function of the anaerobic microorganism is effectively exerted by supplying a substance that promotes the anaerobic microorganism to dehalogenate the organic halogenated compound, particularly the organic chlorine compound.

[0028] Further, the additive used for restoring soil, groundwater or sediment soil contaminated with the organic halogenated conjugate according to the present invention has a feature of forming a substance that forms an anaerobic state.

[0029] In addition to a substance that forms and activates the entire microbial consortium, a substance that forms an anaerobic state, that is, a substance that can effectively propagate oxygen-consuming microorganisms such as aerobic microorganisms is also actively supplied. This allows the repair target to be more efficiently Soon become anaerobic.

[0030] As described above, in consideration of the function of the entire microbial consortium involved in the process of decomposing an organic halogen compound, particularly an organic chlorine compound, it is possible to supply a plurality of types of substances having different functions as additives. This makes it possible to use a no-remediation method that is efficient and hardly causes harmful substances to remain. Furthermore, since the microorganisms used for restoration are anaerobic, no oxidizing agent or air supply is required, and restoration work can be performed at low cost.

[0031] Further, the substance used for repairing soil, groundwater or sediment soil contaminated with the organic halogenated conjugate according to the present invention is a substance that activates a microbial consortium by peptone. I do.

[0032] Peptone is a generic name of various proteins obtained by enzymatic degradation or hydrolysis with an acid. The main components are amino acids and oligopeptides, and polypeptides are also mixed as components. All of these components are water-soluble, and when injected into groundwater as an additive, can be easily diffused into the area to be purified. Is a substance. Further, peptone is a desired substance as an organic nitrogen source for growing a large number of microorganisms because peptone is a decomposition product of protein and contains a large amount of nitrogen. In addition, peptone is mainly composed of low-molecular substances with a small number of amino acids, and is easily used as a nutrient source even by microorganisms with low protease (proteolytic enzyme) activity, and activates many types of microorganisms. Therefore, it is a desirable substance as a nutrient source for activating a microbial consortium. Amino acids and vitamins produced by the decomposition of peptone by microorganisms are also nutrients of microorganisms constituting the microorganism consortium, and the microbial consortium is effectively activated. Due to the activation of the microbial consortium, the object to be repaired quickly becomes anaerobic, and harmful substances hardly remain in the object to be repaired.

[0033] In addition, propionic acid is a substance that promotes reductive dehalogenation of anaerobic microorganisms in an additive used for repairing soil, groundwater or sediment soil contaminated with the organic halogenated conjugate according to the present invention. , Butyric acid, lactic acid, and salts thereof. [0034] Propionic acid, butyric acid, lactic acid, and salts thereof have excellent electron donating properties and serve as a source of hydrogen in the dehalogenation reaction of the organic halide conjugate. Moreover, they are available stably and at low cost. Therefore, it is a particularly desirable substance as the fatty acid salt used in the present invention.

[0035] In addition, the substance that creates an anaerobic state in an additive used for repairing soil, groundwater, or sediment soil contaminated with the organic halogenated conjugate according to the present invention includes dalucose, galactose, fructose, ratatose, and sucrose. , And at least one substance selected from the group consisting of maltose.

Glucose, galactose, fructose, ratatose, sucrose, and maltose

It is a kind of saccharide that is an effective nutrient for aerobic microorganisms. Among them, it is easily decomposed, and can be obtained stably and at low cost.

[0036] The restoration effect can be enhanced by setting the compounding ratio of each substance constituting the additive according to the soil to be restored. The restoration target in the present invention is an organic halogenated compound, particularly soil, groundwater or sediment soil contaminated with an organic chlorine compound. The organic halogenated compound is a substance in which hydrogen of an aliphatic or aromatic hydrocarbon is substituted with halogen (such as fluorine and chlorine). For example, aliphatic organochlorine compounds such as tetrachlorethylene, trichlorethylene and dichloroethylene, dioxins such as polychlorinated dibenzodioxin (PCDD) and polychlorinated dibenzofuran (PCDF), PCBs such as cobraner polychlorinated biphenyl and the like. Aromatic organochlorine compounds such as black benzene correspond to this category. The above description is an example, and the restoration target and the chemical substance to be removed in the present invention are not limited by the description.

The invention's effect

According to the present invention, in repairing groundwater, soil or sediment soil contaminated with an organic halogen compound, particularly an organic chlorine compound, it is possible to carry out a repair work in which harmful substances hardly remain, and Short-term rehabilitation work can be realized, so low-cost rehabilitation work is possible.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, embodiments of the present invention will be described. In the present embodiment, a microcosm study in the laboratory determines a proper microbial community in the contaminated area, that is, an appropriate mixing ratio of the electron donor according to the microbial consortium. Microcosms are formed from soil, groundwater or sediment collected from contaminated areas. The additives are mixed in various ratios, mixed into microcosms and cultured at a constant temperature. Under anaerobic conditions, soil or water is periodically sampled for microcosm power to observe the concentration of organic chlorine compounds, methane, vinyl chloride, chloride ions, dissolved oxygen, redox potential, nitrate ion, and sulfate ion. Organochlorine compounds, methane, vinyl chloride and chloride ions are used to confirm the concentrations of contaminants and their decomposition products. The dissolved oxygen amount and the oxidation reduction potential are for confirming that the microcosm is in an absolutely anaerobic atmosphere. When these become 0.5mgZL and -50mV respectively, it is an absolute anaerobic condition. Nitrate ion and sulfate ion are involved in the reduction reaction of anaerobic microorganisms! It is consumed in preference to organic chlorine compounds. Therefore, by measuring the concentrations of nitrate ion and sulfate ion, it can be confirmed that the reduction reaction in the microcosm was started. Based on the results of experiments for a certain period of time, usually about one to two months, the optimal additive ratio for the remediation target in the contaminated area is determined.

[0039] The additive is added to soil, groundwater or sediment in the contaminated area. The form of the additive may be solid, liquid, slurry, etc., and is determined based on the geological condition of the geological layer in the contaminated area and the contamination status in the contaminated area.

[0040] The microbial consortium consumes dissolved oxygen in soil, groundwater or sedimentary soil by decomposing substances contained in additives and using electron donors generated by the decomposition, The environment to be restored is set to an anaerobic state, which is an anaerobic atmosphere. At this time, electron acceptors that originally exist in the contaminated area, such as ion nitrate and sulfate ions, are also consumed. The anaerobic microorganisms contained in the microbial consortium reduce the organochlorine compounds, which are electron acceptors, in the created anaerobic state by using the electron donors supplied or generated as decomposition products. Decomposes by dechlorination. Decomposition of organochlorine compounds by dechlorination of anaerobic microorganisms occurs sequentially with high chlorination number compounds and eventually decomposes to inorganic chlorides.

(Example) Examples of the present invention will be described below.

A laboratory-scale microcosm experiment was conducted to demonstrate the effect of the additive of the present invention in promoting the purification of groundwater contaminated by organochlorine compounds. Groundwater used for the experiment was collected anaerobically at sites contaminated with organochlorine compounds such as trichloroethylene (hereinafter referred to as TCE) and cis 1,2-dichloroethylene (hereinafter referred to as CDCE). . Groundwater was filled into 2,190 lOOmL brown glass containers, previously sterilized, until full and transported to the laboratory while refrigerated at 4 ° C.

[0042] Next, 73 types of additives shown in Tables 1 and 2 were added to the collected groundwater to compare the effects of the purification. Under anaerobic conditions, one type of additive was added to 2,190 groundwater samples and mixed with 30 groundwater samples, and the air in the headspace of each vessel was replaced with nitrogen gas. Later sealed.

[Table 1]

Number of days of purification below the lower limit of quantification

Sugar organic acid salt

Lower limit of quantification Lower limit of quantification Lower limit of quantification Example Peptone Glucose Sodium Propionate Pt Pose Glucose Frobion Toro Calcium Day Date Day P Day Peptone Glucose Sodium Butyrate Date P P Pt Glucose Calcium Butyrate P P P After the day After the day After the day After the day After the day After the day After the day After the day After the day After the day After the day After the day After the day After the day After the day After the day After the day After the day After the day After the day After the day After the day After Peptone Fruc! Sodium Monosulfonate Date After Phrase Peptone Fruc! Sodium Butyrate Ptton Fructos Sodium Lactate Peptone Fructose Sodium Lactate Date Ptp Pak Rak! Sodium Lactate Day After Day After Day After Day Peptone Lac! Calcium Spropionate After The Day After Peptone Lactose Sodium Sodium Lactate After Day After Day After The Day Peptone Lac!-Calcium Sulfate Postscript Postscript Postscript Postscript Peptone Lactose Calcium Lactate Day Postscript Postscript Postscript Peptone Sucrose Sodium Probiate Sodium Postscript Postscript Postscript Postscript Postscript Postscript Sodium Butyl Sucrose Sodium Butyrate Postscript Postscript Postscript Postscript Sodium Lactone Sucrose Sodium Lactate Postscript Postscript Sodium lactate Peptone Mal! Sodium propionate Sodium butyrate Peptone Mal! Sodium butyrate Sodium lactate Peptone Maru! Sodium lactate Sodium lactate Peptone Glucose Probiate Calcium Later Later Later After Peptone Glucose Sodium Butyrate After Repeat Unpurified Peptone Glucose Butyrate After Repeat After Unpurified Peptone Glucose Sodium Lactate After Repeat After Repeat After Peptone Glucose Lactate After Repeat After Peptone Lac! Sodium Onate Day After Day After Day Peptone Lac! Calcium Supionate After After Day After Peptone Lactose Sodium Sulfate Sodium After Sodium Peptone Lak! Calcium Butyrate After Sodium Lactone Sodium Lactate After the day After the day After the peptone Lac! Calcium lactate After the after The after peptone Glucose sodium sodium probiate Day after the day After the galaxy

Peptone gelcoose sodium arsenate

Peptone Glucose Sodium Prosuccinate

Peptone Glucose Sodium propionate Postscript Postscript Postscript Sucrose

Peptone Glucose Sodium Prohionate

ぺ Buton Galactose Sodium Propitanate Day After Day After Purification

Peptone easy! Sodium butyrate

No. 1 Carapella 43 in Table 1 relates to a case where the additive of the present invention was prepared, and was changed from Example to Example 43. Nos. 1 to 29 in Table 2 show that some of the components of the present invention are not Or, when additives different from those of the invention of the present application were added, comparative examples 1 to 29 were used. No. 30 in Table 2 is a control sample in which no additive was added, and Comparative Example 30 was used.

[0045] Next, in order to measure the concentration of the organochlorine compound before the purification treatment, immediately before the start of the culture, a total of 365 specimens, each of which had 5 specimens for each treatment, were selected from the 2,190 specimens. The samples were analyzed by gas chromatography for the organochlorine compounds, the salt-forming butyl monomer and ethylene, and the initial concentration for each treatment was determined from the average value of the five samples.

[0046] The remaining 1,825 samples were cultured in the dark at 25 ° C for 90 days. Then, every 30 days after the start of the cultivation, every 15 days after the start of the culture, the concentrations of the organic chlorine compounds, the salty butyl monomer and the ethylene contained in the total of 365 samples for each treatment were measured by gas chromatography. From the average value of the three samples, the concentrations of organochlorine compounds and ethylene for each treatment at each time point and for each treatment were determined. Figure 1 to Figure 73 show changes in the concentrations of organochlorine compounds and ethylene contained in the samples subjected to 73 types of treatment.

The results of FIGS. 1 to 73 will be verified. In the case of Examples 1 to 43 in which the additive of the present application was added, TCE with a large chlorination number was purified to the lower limit of quantification (less than 0.002 mgZ) in 30 days and 75 days. In 90 days, DCE has been purified to below the lower limit of quantitation (0.004 mg ZL) in 90 days.Shiridani vinyl monomer (hereinafter referred to as VC) which is a problem in the purification of organochlorine compounds (Except for Examples 27 and 28 and Examples 42 and 43), the quantification was reduced to below the lower limit of quantification (0.001 mg ZL) within 90 days of the test period. , 28, 42 and 43, although they could be purified to below the lower limit of quantification, the unpurified components were 0.1mg / L, 0.1mg / L, 0.3mg / L, 0mg respectively. It was extremely low at 3 mg / L.

[0048] On the other hand, in the case of Comparative Examples 1 to 30 which are not the present invention, in most cases, TCE remains in the system even after 90 days, and the same applies to C-DCE and VC. I understand that.

[0049] Specifically, in Comparative Example 1, only peptone was added as an additive.

TCE, C—DCE, and VC remained unpurified and remained in the system.

[0050] Comparative Examples 2 to 7 contain peptone and the saccharide according to claim 1, and contain an organic acid salt. In this case, TCE, C-DCE, and VC remained unpurified and remained in the system.

[0051] Comparative Examples 8 to 13 show the power obtained when peptone and the organic acid salt according to claim 1 are used, but no saccharides. In this case also, TCE, C-DCE, and VC are purified. The system remained.

[0052] Comparative Examples 14 to 19 each include a saccharide according to claim 1 and an organic acid salt according to claim 1 and a force that does not include peptone. In this case also, TCE, C-DCE, and VC was not purified and remained in the system.

[0053] Comparative Examples 20 to 23 each include peptone, a saccharide, and an organic hydrochloric acid, but have a saccharide having a force different from the component described in claim 1. In this case, TCE is 7

In 5 days or 90 days, it was purified to below the lower limit of quantification. C-CDE and VC remained unpurified.

[0054] Comparative Examples 24 to 26 include peptone, saccharides, and organic hydrochloric acid, but the organic hydrochloric acid is a component different from the component according to claim 1. The force is TCE, CDCE , And VC were not purified and remained in the system.

[0055] Comparative Examples 27 to 29 each include peptone, a saccharide, and an organic hydrochloric acid, but each of the saccharides and the organic hydrochloric acid is different from the component according to claim 1. , C—DCE, and VC remained unpurified and remained in the system.

[0056] Comparative Example 30 was a case in which nothing was added. In this case, TCE and C-CDE were not purified and remained in the system. In addition, it was not detected about VC.

[0057] From the above results, when the additive of the present invention is used in purifying organic chlorine compounds, both contaminants such as TCE and harmful substances generated during purification such as CDCE and VC are purified. The purification effect was remarkably excellent as compared with the case where an additive in which some components were different from the present invention was used. That is, three types of substances according to claim 1 of the present invention, a substance that creates and activates a microbial consortium, a substance that promotes reductive dehalogenation of anaerobic microorganisms, and a substance that creates an anaerobic state It was shown that, in the additive consisting of, not only the combination of the specific three components had a remarkable effect, but also that the combination had an excellent effect as compared with other combinations. Industrial applicability

[0058] The additive according to the present application can be used for the restoration work of soil, groundwater or sediment soil contaminated with an organic halogen compound.

Brief Description of Drawings

FIG. 1 is a graph showing changes in the concentrations of an organic chlorine compound, a salt-doping butyl monomer, and ethylene in Example 1.

FIG. 2 is a graph showing changes in the concentration of an organic chlorine compound, a salt-doping butyl monomer, and ethylene in Example 2.

FIG. 3 is a graph showing changes in the concentration of an organic chlorine compound, a salt-forming butyl monomer, and ethylene in Example 3.

FIG. 4 is a graph showing changes in the concentration of an organic chlorine compound, a salt-doping butyl monomer, and ethylene in Example 4.

FIG. 5 is a graph showing changes in the concentration of an organic chlorine compound, a salt-doping butyl monomer, and ethylene in Example 5.

FIG. 6 is a graph showing changes in the concentration of an organic chlorine compound, a salt-doping butyl monomer, and ethylene in Example 6.

FIG. 7 is a graph showing changes in the concentrations of an organic chlorine compound, a salt-doping butyl monomer, and ethylene in Example 7.

FIG. 8 is a graph showing changes in the concentration of an organic chlorine compound, a salt-doping butyl monomer, and ethylene in Example 8.

FIG. 9 is a graph showing changes in the concentration of an organic chlorine compound, a salt-doping butyl monomer, and ethylene in Example 9.

FIG. 10 is a graph showing changes in the concentration of an organic chlorine compound, a salt-forming butyl monomer, and ethylene in Example 10.

FIG. 11 is a graph showing changes in the concentration of an organic chlorine compound, a salt-doping butyl monomer and ethylene in Example 11.

FIG. 12 is a graph showing changes in the concentration of an organic chlorine compound, a salt-doping butyl monomer, and ethylene in Example 12. [13] FIG. 13 is a graph showing changes in the concentrations of an organic chlorine compound, a salt-doping butyl monomer, and ethylene in Example 13.

[14] Fig. 14 is a graph showing changes in the concentration of an organic chlorine compound, a salt-doping butyl monomer and ethylene in Example 14.

[15] FIG. 15 is a graph showing changes in the concentration of an organic chlorine compound, a salt-doping butyl monomer, and ethylene in Example 15.

[16] Fig. 16 is a graph showing changes in the concentration of an organic chlorine compound, a salt-doping butyl monomer, and ethylene in Example 16.

[17] Fig. 17 is a graph showing changes in the concentration of an organic chlorine compound, a salt-doping butyl monomer, and ethylene in Example 17.

[18] FIG. 18 is a graph showing changes in the concentration of an organic chlorine compound, a salt-doping butyl monomer, and ethylene in Example 18.

[19] Fig. 19 is a graph showing changes in the concentration of an organic chlorine compound, a salt-doping butyl monomer, and ethylene in Example 19.

[20] Fig. 20 is a graph showing changes in the concentration of an organic chlorine compound, a salt-doping butyl monomer, and ethylene in Example 20.

[21] Fig. 21 is a graph showing changes in the concentration of an organic chlorine compound, a salt-doping butyl monomer and ethylene in Example 21.

[22] Fig. 22 is a graph showing changes in the concentration of an organic chlorine compound, a salt-doping butyl monomer and ethylene in the case of Example 22.

[23] FIG. 23 is a graph showing changes in the concentration of an organic chlorine compound, a salt-doping butyl monomer, and ethylene in Example 23.

[24] Fig. 24 is a graph showing changes in the concentration of an organic chlorine compound, a salt-doping butyl monomer, and ethylene in Example 24.

[25] FIG. 25 is a graph showing changes in the concentration of an organic chlorine compound, a salt-doping butyl monomer, and ethylene in Example 25.

[26] Fig. 26 is a graph showing changes in the concentration of an organic chlorine compound, a salt-doping butyl monomer, and ethylene in Example 26. [27] FIG. 27 is a graph showing changes in the concentration of an organic chlorine compound, a salt-doping butyl monomer, and ethylene in Example 27.

[28] Fig. 28 is a graph showing changes in the concentration of an organic chlorine compound, a salt-doping butyl monomer, and ethylene in Example 28.

[29] Fig. 29 is a graph showing changes in the concentration of an organic chlorine compound, a salt-doping butyl monomer and ethylene in Example 29.

[30] Fig. 30 is a graph showing changes in the concentration of an organic chlorine compound, a salt-doping butyl monomer, and ethylene in Example 30.

[31] Fig. 31 is a graph showing changes in the concentration of an organic chlorine compound, a salt-doping butyl monomer, and ethylene in Example 31.

[32] Fig. 32 is a graph showing changes in the concentration of an organic chlorine compound, a salt-doping butyl monomer, and ethylene in Example 32.

[33] Fig. 33 is a graph illustrating changes in the concentrations of an organic chlorine compound, a salt-doping butyl monomer, and ethylene in Example 33.

[34] Fig. 34 is a graph showing changes in the concentration of an organic chlorine compound, a salt-doping butyl monomer, and ethylene in Example 34.

[35] Fig. 35 is a graph showing changes in the concentration of an organic chlorine compound, a salt-doping butyl monomer, and ethylene in Example 35.

[36] Fig. 36 is a graph showing changes in the concentration of an organic chlorine compound, a salt-forming bulle monomer and ethylene in the case of Example 36.

[37] Fig. 37 is a graph showing changes in the concentration of an organic chlorine compound, a salt-doping butyl monomer and ethylene in the case of Example 37.

[38] Fig. 38 is a graph showing changes in the concentration of an organic chlorine compound, a salt-doping butyl monomer, and ethylene in Example 38.

[39] Fig. 39 is a graph showing changes in the concentration of an organic chlorine compound, a salt-doping butyl monomer and ethylene in the case of Example 39.

FIG. 40 is a graph showing changes in the concentration of an organic chlorine compound, a salt-doping butyl monomer, and ethylene in Example 40. FIG. 41 is a graph showing changes in the concentration of an organic chlorine compound, a salt-doping butyl monomer, and ethylene in Example 41.

FIG. 42 is a graph showing changes in the concentration of an organic chlorine compound, a salt-doping butyl monomer and ethylene in the case of Example 42.

FIG. 43 is a graph showing changes in the concentrations of an organic chlorine compound, a salt-doping butyl monomer and ethylene in Example 43.

FIG. 44 is a graph showing a change in the concentration of an organic chlorine compound, a salt-doping butyl monomer and ethylene in the case of Comparative Example 1.

FIG. 45 is a graph showing changes in the concentration of an organic chlorine compound, a salt-doping butyl monomer, and ethylene in Comparative Example 2.

FIG. 46 is a graph showing changes in the concentration of an organic chlorine compound, a salt-doping butyl monomer, and ethylene in Comparative Example 3.

FIG. 47 is a graph showing changes in the concentration of an organic chlorine compound, a salt-doping butyl monomer, and ethylene in Comparative Example 4.

FIG. 48 is a graph showing changes in the concentrations of an organic chlorine compound, a salt-doping butyl monomer, and ethylene in Comparative Example 5.

FIG. 49 is a graph showing changes in the concentrations of an organic chlorine compound, a salt-doping butyl monomer, and ethylene in Comparative Example 6.

FIG. 50 is a graph showing changes in the concentrations of an organic chlorine compound, a salt-doping butyl monomer and ethylene in Comparative Example 7.

FIG. 51 is a graph showing changes in the concentration of an organic chlorine compound, a salt-doping butyl monomer and ethylene in the case of Comparative Example 8.

FIG. 52 is a graph showing changes in the concentration of an organic chlorine compound, a salt-doping butyl monomer, and ethylene in Comparative Example 9.

FIG. 53 is a graph showing a change in the concentration of an organic chlorine compound, a salt-doping butyl monomer and ethylene in the case of Comparative Example 10.

FIG. 54 is a graph showing changes in the concentration of an organic chlorine compound, a salt-doping butyl monomer and ethylene in the case of Comparative Example 11. [55] FIG. 55 is a graph illustrating changes in the concentrations of an organic chlorine compound, a salt-doping butyl monomer, and ethylene in Comparative Example 12.

[56] FIG. 56 is a graph illustrating changes in the concentrations of an organic chlorine compound, a salt-doping butyl monomer, and ethylene in Comparative Example 13.

[57] FIG. 57 is a graph showing changes in the concentration of an organic chlorine compound, a salt-doping butyl monomer and ethylene in the case of Comparative Example 14.

[58] Fig. 58 is a graph showing changes in the concentration of an organic chlorine compound, a salt-doping butyl monomer and ethylene in the case of Comparative Example 15.

[59] Fig. 59 is a graph showing changes in the concentration of an organic chlorine compound, a salted butyl monomer and ethylene in Comparative Example 16.

[60] FIG. 60 is a graph showing changes in the concentration of an organic chlorine compound, a salt-doping butyl monomer, and ethylene in Comparative Example 17.

[61] Fig. 61 is a graph showing changes in the concentrations of an organic chlorine compound, a salt-doping butyl monomer, and ethylene in Comparative Example 18.

[62] FIG. 62 is a graph illustrating changes in the concentrations of an organic chlorine compound, a salt-doping butyl monomer, and ethylene in Comparative Example 19.

[63] This is a graph showing changes in the concentration of an organic chlorine compound, a salt-doping butyl monomer, and ethylene in Comparative Example 20.

[64] Fig. 64 is a graph illustrating changes in the concentration of an organic chlorine compound, a salt-doping butyl monomer, and ethylene in the case of Comparative Example 21.

[65] Fig. 65 is a graph showing changes in the concentrations of an organic chlorine compound, a salt-doping butyl monomer, and ethylene in Comparative Example 22.

[66] Fig. 66 is a graph showing changes in the concentration of an organic chlorine compound, a salt-doping butyl monomer, and ethylene in Comparative Example 23.

[67] FIG. 67 is a graph illustrating changes in the concentrations of an organic chlorine compound, a salt-doping butyl monomer, and ethylene in Comparative Example 24.

[68] Fig. 68 is a graph illustrating changes in the concentration of an organic chlorine compound, a salt-doping butyl monomer, and ethylene in Comparative Example 25. FIG. 69 is a graph showing changes in the concentrations of an organic chlorine compound, a salt-doping butyl monomer and ethylene in Comparative Example 26.

FIG. 70 is a graph showing changes in the concentration of an organic chlorine compound, a salt-doping butyl monomer and ethylene in the case of Comparative Example 27.

FIG. 71 is a graph showing changes in the concentrations of an organic chlorine compound, a salt-doping butyl monomer and ethylene in Comparative Example 28.

FIG. 72 is a graph showing changes in the concentrations of an organic chlorine compound, a salt-doping butyl monomer, and ethylene in Comparative Example 29.

FIG. 73 is a graph showing changes in the concentrations of an organic chlorine compound, a salt-doping butyl monomer, and ethylene in Comparative Example 30.

Claims

The scope of the claims

[1] Contaminated with an organic halogen compound characterized by being composed of a substance that forms and activates a microbial consortium, a substance that promotes reductive dehalogenation of anaerobic microorganisms, and a substance that forms an anaerobic state Additives used to repair soil, groundwater or sediment.

[2] The substance that forms and activates the microbial consortium is peptone, and the substance that promotes reductive dehalogenation of the anaerobic microorganism is propionic acid, butyric acid, lactic acid, and their salt power. Group strength is at least one substance selected, and the substance forming the anaerobic state is at least one substance selected from glucose, galactose, fructose, ratatose, sucrose, and maltosca. An additive for repairing soil, groundwater or sediment contaminated with the organic halogenated conjugate according to claim 1.

[3] A soil contaminated with an organic halogen compound by adding a substance that creates and activates a microbial consortium, a substance that promotes reductive dehalogenation of anaerobic microorganisms, and a substance that creates an anaerobic state, Restoration method to restore groundwater or sediment.

[4] The substance that forms and activates the microbial consortium is peptone, and the substance that promotes reductive dehalogenation of the anaerobic microorganism is propionic acid, butyric acid, lactic acid, and their salt power. Group strength is at least one substance selected, and the substance forming the anaerobic state is at least one substance selected from glucose, galactose, fructose, ratatose, sucrose, and maltosca. A method for repairing soil, groundwater or sediment soil contaminated with the organic halogenated conjugate according to claim 3.

[5] Peptone is added to form and activate a microbial consortium, and anaerobic microorganisms are reduced by adding propionic acid, butyric acid, lactic acid, and at least one substance selected from the group consisting of salt and salt. An organic halogen compound characterized by promoting the objective dehalogenation and forming an anaerobic state by adding at least one substance selected from the group consisting of glucose, galactose, fructose, lactose, sucrose, and maltose. How to remediate contaminated soil, groundwater or sediment.