WO2001038267A1

WO2001038267A1 - Method of decomposing halogenated substance, method of detecting decomposition of harmful substance, and kit for detecting decomposition of harmful substance

Info

Publication number: WO2001038267A1
Application number: PCT/JP2000/008184
Authority: WO
Inventors: Hiroshi Kashihara
Original assignee: Kukita, Takeshi
Priority date: 1999-11-22
Filing date: 2000-11-20
Publication date: 2001-05-31
Also published as: AU1417801A

Abstract

A halogenated substance such as a dioxin, a polybiphenyl chloride compound, e.g., PCB, a halogenated organic agricultural chemical, a halogenated organic compound, or a haloethylene compound is reacted with a substance which is chemically equivalent to the halogenated substance in decomposition and is lowly toxic or nontoxic, with the aid of a chemical substance such as an acid, alkali, or reducing agent, e.g., lithium aluminum hydride, a biological means such as a microorganism or an enzyme, or a physical means such as ultraviolet or ultrasonic. Thus, the halogenated substance can be dehalogenated and decomposed. Whether the halogenated substance has been decomposed can be easily detected or ascertained by thin-layer chromatography or UV irradiation.

Description

aft ^ Consider

Haguchigen decomposition method and

Hazardous substance decomposition detection method and toxic substance decomposition detection kit

The present invention particularly relates to a halogenated substance decomposition method for decomposing halogenated substances which are harmful substances. More specifically, the present invention relates to harmful substances causing serious problems as environmental pollution, in particular, halogenated harmful substances which are hardly decomposable compounds, for example, dioxins, P

A halogenated substance decomposition method that can safely, easily and efficiently decompose polychlorinated biphenyl compounds such as CBs, organic halogen-based pesticides, organic halogen compounds, and haloethylene compounds. The present invention relates to a method for decomposing a halogenated substance by chemical conversion. The present invention also relates to a harmful substance decomposition detection method capable of safely and easily detecting and confirming the decomposition of the harmful substance including the halogenated substance, and a kit for detecting the harmful substance decomposition. Background art

In recent years, harmful substances such as polychlorinated biphenyl compounds such as dioxins and PCBs, organic halogen-based pesticides, organic halogen compounds, and haloethylene compounds are dehalogenated and decomposed by dehalogenation. Research has been done and a number of decomposition methods have been developed. Among these hagen-forming substances, methods for treating polychlorinated biphenyl compounds such as PCBs have been put into practical use, and examples thereof include a high-temperature incineration method, an alkali dechlorination method, and a supercritical water oxidation method. High temperature incineration has the difficult problem of burning at high temperatures. Alkali dechlorination, unlike incineration, has the advantage that no gas is generated by the reaction and no by-products of dioxins are generated.Difficulty based on the reactivity of the alcohol used. Is the problem. In addition, the supercritical water oxidation method has a drawback in that the treatment is performed at a high temperature and a high pressure. In addition to these methods, a number of methods have been used or proposed, but all of them use high temperatures, high pressures, etc., and are extremely difficult to handle and manage. And various issues such as the need to improve safety aspects.

In addition, there are various environments where harmful substances such as polychlorinated biphenyl compounds such as dioxins and PCBs, organic halogen-based pesticides, organic halogen compounds, and haloethylene compounds are distributed, so find a suitable decomposition method for each environment. Is important. For example, there is a need for the development of decomposition methods suitable for each environment, such as in an incinerator, in the air, in soil, and in water such as rivers and wells. Therefore, it is extremely useful to develop a method that can decompose such harmful substances, which are harmful substances, by decomposing them at normal temperature and pressure. Until now, such halogenated substances have been extremely difficult to decompose as hardly decomposable substances, and can only be decomposed under severe conditions such as high temperature and high pressure.

Further, it is extremely dangerous to conduct an experiment using such a harmful substance in searching for a method for decomposing a halogenated substance. For example, it is very important to construct an experimental device for preventing such a hazard. Need investment. In such a situation, the means for detecting the decomposition of such harmful substances Replacement sheet (Rule 26) At present, it is not possible to easily carry out research to search for such information. Therefore, it is possible to conduct an experiment to find a substance, means, and method for decomposing such a harmful substance without any risk of the harmful substance, and to detect the decomposition of such a harmful substance which is safe, inexpensive, and easy to operate. There is a demand for the development of means and methods that can do this. Disclosure of the invention

The present inventor has conducted intensive studies on various possibilities from this viewpoint, and found that dioxins, polychlorinated biphenyl compounds such as PCBs, organic halogenated pesticides, organic halogenated compounds, halogenated substances such as haloethylene compounds, etc. The inventors have found that such a halogenated substance can be decomposed by irradiating ultrasonic waves using a reductive decomposing agent, and completed the present invention.

In addition, the present inventor has found that it is possible to confirm whether or not such a harmful substance is decomposed without directly using the harmful substance by applying the above finding, and completed the present invention. did.

Accordingly, the present invention provides a halide decomposition method comprising decomposing a halogenated substance by using such a halogenated substance with a reductive decomposing agent and using physical means such as ultraviolet rays and ultrasonic waves. It is intended to be.

In one aspect of the present invention, the decomposition of a harmful substance is performed using a chemically equivalent compound that is substantially chemically equivalent to the harmful substance without actually using the harmful substance. An object of the present invention is to provide a useful and easy method for detecting harmful substance decomposition for detection. Further, another object of the present invention is to provide a kit for detecting harmful substance decomposition capable of performing an experiment for detecting the decomposition of such harmful substance without actually using the harmful substance.

In order to achieve the above object, the present invention relates to polychlorinated biphenyl compounds such as dioxins and PCBs, which are hardly decomposable halogenated substances, organic parogen-based pesticides, organic halogenated compounds, and haloethylene compounds. Provided is a method for decomposing a halogenated substance, which comprises decomposing a harmful substance by physical means such as ultraviolet rays or ultrasonic waves using a reductive decomposing agent.

In a preferred embodiment of the method for decomposing a halogenated substance according to the present invention, examples of the reductive decomposer used include a metal hydride and an organometallic compound. Since this method for decomposing a halogenated substance can be performed substantially at normal temperature and normal pressure, the operation is very simple, and it can be carried out inexpensively, safely and efficiently with simple equipment. Further, in order to achieve another object of the present invention, a chemically equivalent compound that is substantially chemically equivalent to a harmful substance is decomposed by a sample for investigating whether or not it contains a harmful substance, and Provided is a method for detecting the decomposition of harmful substances, which comprises detecting the decomposition of harmful substances by qualitative and quantitative determination of the decomposition of a valence compound.

Further, the present invention provides a method for detecting and decomposing harmful substances, which comprises a chemical equivalent compound which is substantially chemically equivalent to a harmful substance, a thin layer chromatography tool, and an ultrasonic or ultraviolet ray generating tool. Provide kit for use. In the present invention, by using the method for detecting harmful substance decomposition and the kit for detecting harmful substance decomposition, an experiment for finding a substance, a means, and a method for decomposing such harmful substance is conducted. It can be performed in a completely non-existent state, and can safely, inexpensively and easily operate and detect the decomposition of harmful substances.

In a preferred embodiment of the present invention, the chemical equivalent compounds used in the method for detecting harmful substance decomposition and the kit for detecting harmful substance decomposition include polychlorinated biphenyl compounds such as dioxins and PCBs, organic halogen-based pesticides, and organic halogens. Chemically equivalent compounds with low or no toxicity that are substantially chemically equivalent to hazardous substances that are halogenated compounds such as compounds and haloethylene compounds are used. Therefore, this makes it possible to detect and confirm that the harmful substance has been decomposed extremely safely, inexpensively, and easily.

As described above, in addition to the above-mentioned effects, the present invention provides a method that does not directly use harmful substances such as polychlorinated biphenyl compounds such as dioxins and PCBs, organic halogen-based pesticides, organic halogen compounds, and haloethylene compounds. And, it is possible to confirm the decomposition of harmful substances safely. In another preferred embodiment of the present invention, a halogenobenzene derivative or an organic halogen compound containing a benzene derivative or the like is used as a chemical equivalent compound used in the method for detecting harmful substance decomposition and the kit for detecting harmful substance decomposition. ing.

Further, according to this preferred embodiment of the present invention, in addition to the above-mentioned effects, in particular, the decomposition of chlorine-based harmful substances can be confirmed safely without directly using chlorine-based harmful substances. In another preferred embodiment of the present invention, as a specimen, for example, such a halogenated substance is decomposed by a chemical substance such as an acid, an alkali, or a reducing agent, an enzyme, a microorganism, or a physical means such as ultraviolet rays or ultrasonic waves. Can be detected. Further, according to this preferred embodiment of the present invention, in addition to the above-described effects, it can be safely, inexpensively, and easily detected whether or not such a specimen can decompose such a harmful substance.

Furthermore, the present invention provides a method for detecting and decomposing harmful substances by using such a kit for detecting harmful substance decomposition, which confirms whether or not a specimen or a substance contained in the specimen can decompose such harmful substance. For another purpose.

In order to achieve another object of the present invention, the present invention relates to a chemical equivalent compound which is substantially chemically equivalent to such a harmful substance, a thin layer chromatography tool, and an ultrasonic or ultraviolet ray generating tool. The present invention provides a method for detecting the decomposition of harmful substances, comprising detecting the decomposition of harmful substances using the kit for detecting the decomposition of harmful substances.

In this embodiment of the present invention, in the method for detecting the decomposition of harmful substances, the chemical equivalent compounds include harmful substances such as polychlorinated biphenyl compounds such as dioxins and PCBs, organic halogen-based pesticides, organic halogen compounds, and haloethylene compounds. Uses chemical equivalents that are substantially chemically equivalent to and have low or no toxicity.

By using the method for detecting the decomposition of harmful substances according to this aspect of the present invention, an experiment for finding a substance, a means, and a method for decomposing such harmful substances can be performed without any direct danger from the harmful substances. At the same time, it becomes possible to detect the decomposition of such harmful substances inexpensively and easily. In a preferred embodiment of the present invention, the chemical equivalent of the kit for detecting harmful substances used in the present detection method includes polychlorinated biphenyl compounds such as dioxins and PCBs, organic halogen-based pesticides, organic halogen compounds, and haloethylene compounds. Uses chemical equivalents that are substantially chemically equivalent to harmful substances such as halogenated substances and have low or no toxicity. According to this preferred embodiment of the present invention, in addition to the above effects, harmful substances such as polychlorinated biphenyl compounds such as dioxins and PCBs, organic halogen-based pesticides, organic halogen compounds, and ethylene oxide compounds are not directly used. In addition, the decomposition of harmful substances can be confirmed safely and safely. In another preferred embodiment of the present invention, a benzene derivative or an organic halogen compound is used as a chemically equivalent compound of the kit for detecting the decomposition of harmful substances used in the present detection method. Further, according to this preferred embodiment of the present invention, in addition to the above-mentioned effects, in particular, it is possible to safely confirm the decomposition of chlorine-based harmful substances without directly using the chlorine-based harmful substances.

In another preferred embodiment of the present invention, as the specimen used in the present detection method, for example, chemical substances such as acids, alkalis, and reducing agents, enzymes, microorganisms, and physical means such as ultraviolet rays and ultrasonic waves are used. Then, it can be detected whether or not such a harmful substance is decomposed.

Further, according to this preferred embodiment of the present invention, in addition to the above-mentioned effects, it is possible to safely, inexpensively and easily detect whether or not such a specimen can decompose such a harmful substance. Other objects, features and advantages of the present invention will become apparent from the description of the following specification with reference to the accompanying drawings. BRIEF DESCRIPTION OF THE FIGURES

Figure 1 shows the standard GC-MS peak pattern of KC300.

Figure 2 shows the GC-MS peak pattern as a result of treating KC300 for 1 minute.

FIG. 3 is a GC-MS peak pattern obtained by treating KC300 for 10 minutes.

Figure 4 shows the standard GC-MS peak pattern for KC400.

Figure 5 shows the GC-MS peak pattern of KC400 treated for 1 minute.

FIG. 6 shows a GC-MS peak pattern obtained by treating KC400 for 10 minutes.

FIG. 7 is a GC-MS peak pattern obtained by further processing the result of FIG. 2 with Pseudomonas pseudoalcaligenes KF707 (FERM P-8297).

Fig. 8 shows the results of Fig. 5 in addition to the pseudomonas. Pseudoalkagenes KF707 (FE

RM P-829 This is the GC-MS peak pattern as a result of further processing in 7). BEST MODE FOR CARRYING OUT THE INVENTION

Examples of the halogenated substance that can be decomposed by dehalogenation by the method for decomposing a halogenated substance according to the present invention include polychlorinated biphenyl compounds such as dioxins and PCBs, organic halogen-based pesticides, organic halogenated compounds, and ethylene compounds in the mouth. And other harmful substances. However, what should be particularly noted in the present invention is the method for decomposing a halogenated substance according to the present invention. Is not limited to the compounds exemplified above, but can be widely applied to halogenated compounds, and is not limited to the above compounds at all.

One such hapogen compound that can be decomposed by the hapogen-decomposing method according to the present invention includes dioxins, and the dioxins are represented by the general formula (I):

(Wherein X represents a halogen atom;

a means 0 or 1;

m l and n l are the same or different and are 0 or

Means an integer from 1 to 4, where m l and n 1 are not both 0

And dioxins represented by

Another such halogenated compound which can be decomposed by the method for decomposing a halogenated substance according to the present invention includes a polychlorinated biphenyl compound. As such a polychlorinated biphenyl compound, a compound represented by the general formula (II):

X ^^-^ Xn, "

(Wherein X represents a halogen atom;

m 2 and n 2 are the same or different and are each 0 or

Means an integer from 1 to 5, provided that both m 2 and n 2 are not 0 and one of them is an integer other than 0)

And a polychlorinated biphenyl compound containing PCBs represented by the following formula:

Examples of the halogenated compound that can be decomposed by dehalogenation according to the present invention include organic halogen-based pesticides. Examples of the organic halogen-based pesticides include insecticides, fungicides, and herbicides having an organic halogen-based structure. And various halogen-containing organic pesticides such as a pesticide and a plant growth regulator.

One example of such an organohalogen pesticide is, for example, a compound represented by the following general formula (III):

(Wherein R is a hydrogen atom, a hydroxyl group, a hydroxymethyl group, an unsubstituted or substituted amino group, b

Amide, thioamide, nitro, carboxyl, alkyl, alkoxy, oxyacetic acid residues, nitrile, nitrophenoxy, butyl, phosphorothioate, unsubstituted or substituted phenoxy or pyrethrin Means residue,

X represents a halogen atom,

b means an integer from 1 to 5)

And a halobenzene derivative represented by Examples of powerful halobenzene derivatives include PCNB, CNA, chloroneb, HCB, 2,4-D, 2,4-DP, MCPB, 4-CPA, Swep, MDBA, TCTP, DCMU, Nonuron, Actinol, and diclobenil. , DCBN, DC PA, Purpizamide, CVP, CVMP, Profenophos, ECP, Protiphos, Tonocloclophosmethinole, Nono, Noreffenprox, Chloronitrophen, Bifuenox, Nitrophen, Etobenzanide, Aromatic halogens such as Tefluthrin, Cyfluthrin System, phenoxy system, olebamate system, aromatic nitro system, aromatic nitrile system, urea system, organic phosphorus system, diphenyl ether system, pyrethrin system and the like.

Other examples of such organohalogen-based pesticides include Ziha-mouth substituted carbocyclic compounds, such as, for example, dicophor, bromopropylate, Tecguchi phthalam, hunoresurfuamide, funoretranil, MCPCA, tefur Benzulene, chlorfensone, chlorbenzilate, tetradiphone, dienochlor, difluvenzuron and the like. Further, another example of such an organic halogen-based pesticide includes a halogen-containing heterocyclic compound. Examples thereof include triclopyr, picloram, chlorpyrifos, fluazinam, chlorfluazuron, dithiopyr, and triflumi. Zol, prochloraz, fipronil, benzophenap, birazoxifene, pyrazolate, iprodione, fenarimol, triforine, diclomedine, imibenconazole, diphenoconazol, propiconazol, hexaconazole, oxaziazone, ecloclozone Pyridine, imidazole, pyrazole, imidazolidine, pyrimidine, piperazine, such as anilazine, vinclozolin, and kink mouth lac, Examples thereof include pyridazine, triazole, oxaziazolidine, thiadiazole, tetrazole, triazine, oxazolidine, and quinoline.

Furthermore, such an organic halogen-based pesticide has a general formula (IV):

[IV]

(Where c represents 0 or 1)

In addition to the halo condensed polycyclic compound represented by the formula, there may be mentioned halo condensed polycyclic compounds such as heptachlor, heptachlor epoxide, nepin and the like.

Further, another haptic compound which can be decomposed by the method for decomposing a halogenated substance according to the present invention. An organic halogen compound represented by the general formula (V): X

R l- C -R 3

I

R2

(Wherein X represents a halogen atom;

Rl, R2 and R3 are the same or different and are each water

A hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group, and Rl, R2 and R3 may form a monocyclic ring or a bicyclic ring Good)

And an organic halogen compound represented by the formula:

Further, the haloethylene compound which is another hapogen compound which can be decomposed by the hapogen-decomposing method according to the present invention includes a general formula (VI):

A a, y c

_{X b} ^{C = C} \ _{X d} ^[VI ]

(Where X a, X b, (: 1 (1 is the same or different,

Xa, Xb, Xc

And at least one of X d represents a halogen atom)

And a haloethylene compound represented by

In the above general formula, the halogen atom includes a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Further, in the above general formula, the alkyl group means a linear or branched monovalent saturated aliphatic hydrocarbon group having 1 to 8 carbon atoms, for example, a methyl group, Ethyl group, n-propyl group, i-propyl group, n_butyl group, i-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, n_hexynole group, n-heptinole group, n-octyl group and the like. Further, in the above general formula, a cycloalkyl group means a monovalent saturated alicyclic hydrocarbon group having 3 to 7 carbon atoms and, for example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, Examples include a cyclohexyl group and a cycloheptyl group.

Furthermore, in the above general formula, the aralkyl group is a linear or branched monovalent saturated aliphatic hydrocarbon having 7 to 11 carbon atoms and substituted with an unsubstituted or substituted aromatic ring. And benzyl, o-methylbenzyl, m-methylbenzyl, p-methylbenzyl, phenethyl, o-methylphenethyl, m-methylphenyl, p-methylphenyl, phenylpropyl Group, o-methylphenylpropyl group, m-methylphenylpropyl group, p-methylphenylpropyl group, phenylbutyl group, ct-naphthylmethyl group, and 3-naphthylmethyl group. Further, in the above general formula, an aryl group is a monovalent unsubstituted or substituted aromatic hydrocarbon group having 7 to 10 carbon atoms, such as a phenyl group, an o-tolyl group, _m -tolyl group, p-tolyl group, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, 3,4- Dimethinolephenyl group, 3,5-dimethylphenyl group, 2,3,4-trimethylphenyl group, 2,3,5_trimethylphenyl group, 2,3,6-trimethylphenyl group, 3, Examples thereof include 4,5-trimethylphenyl group, 3,4,6-trimethylphenyl group, 2,4,6-trimethylphenyl group, α-naphthyl group, and β-naphthyl group.

In the organic halogen compound represented by the general formula (V), when Rl, R2 and R3 are linked together to form a single ring, the single ring may be, for example, dimethylene (CH ₂ ) ₂ , trimethylene (CH ₂ ) ₃ , tetramethylene (CH ₂ ) ₄ , pentamethylene (CH ₂ ) ₅ , hexamethylene (CH ₂ ) ₆ groups and the like.

When Rl, R2 and R3 are linked together to form a bicyclic ring, examples of such a bicyclic ring include a bicyclo [1. 1. 0] butane ring and a bicyclo [1 1. 1. 1] pentane ring, bicyclo [2. 1. 0] pentane ring, bicyclo [2. 2. 0] hexane ring, bicyclo [3. 1. 0] hexane ring, bicyclo [2.1.1] ] Hexane ring, bicyclo [2.2.1] heptane ring, bicyclo [3. 2. 0] heptane ring, bicyclo [4. 2. 0] octane ring, bicyclo [3. 3. 0] octane ring, Bicyclo [3.2.1] octane ring.

Examples of the compound represented by the above general formula (I) include the following as typical compounds.

Examples of the compound represented by the above general formula (II) include the following as typical compounds.

The following are typical examples of the compound represented by the general formula (III). It is mentioned.

Examples of the compound represented by the above general formula (IV) include the following as typical compounds.

As examples of the compound represented by the above general formula (V), the following are mentioned as typical compounds.

CH, F CH, C 1 CH, Br CH, I _{C H2} F ₂

CH ₂ C 1 ₂ CH 2 Br 2 CH ₂ I ₂ CHF, CH CI ₃

CH B r, CH I, CF ₂ CI, CC l ₂ B r ₂ CB r ₂ I ₂ CC 1 ₂ I ₂ CFC 1, CCIB r, CB r I ₃ CC I

CFCC 1 CB r CI CH, CH ₂ F

CH, CH ₂ CI CH, CH ₂ Br CH, CH ₂ I P h CH ₂ FP h CH _Z CIP h CH ₂ B r P h CH ₂ IP h FP h C l P h B r P hi

In the above structural formula, Ph means a ferul group.

Examples of the compound represented by the above general formula (VI) include the following as typical compounds.

C then C = C C C "C = CHC 1

C 1 H C = CH C I (c i s) C I H C = CHC I (t r a n s)

C 1 HC = CH ₂ C 1 ₂ C- CB r 2 C "C = CF ₂ CI, C = CI ₂ C l HC = CHF (cis) C 1 HC = CHF (trane)

C l HC = CH B r (c is s) C 1 HC = CH B r (t r a n s)

C 1 H C = CH I (c is) C 1 H C = CH I (t r a n s)

C then C = CC l Br C 1 ₂ C = CC 1 FC 1 ₂ C = CC 1 [BT 2 C = CB r ₂ F ₂ C = CF ₂ I ₂ C = CI ₂

C 1 F C = C C 1 F (Z) C 1 F C = C C 1 F (E)

C l B r C = CCIB r (Z) C l B r C = CC l B r (E) CIIC = CC 1 I (Z) CIIC = CC 1 I (E) Examples of the reductive decomposer used in the present invention include the above-mentioned metal hydrides and organometallic compounds. Preferred examples of the reductive decomposer include the above-mentioned metal hydrides. Particularly preferred are, for example, lithium aluminum hydride, aluminum hydride, lithium hydride, sodium hydride, potassium hydride, and calcium hydride. , Borohydride, borohydride, sodium borohydride, potassium borohydride and the like.

The amount of the reductive decomposing agent can be appropriately changed, but is preferably used in a range of about 1 to 50 equivalents based on the raw material (eg, a halogen group).

The method for decomposing a halogenated substance according to the present invention is preferably carried out in an ether-based solvent such as THF, and the amount of the solvent can be changed as appropriate. It is preferable to use it in the range of about 30 to 300 times mol. The irradiation time of UV or ultrasonic waves is preferably, for example, in the range of 1 minute to 1 hour. Irradiation such as UV or ultrasonic waves is preferably performed at room temperature.

In the method for decomposing a halogenated substance according to the present invention, depending on the halogenated substance, it may not be possible to eliminate all halogen groups substituted by the halogenated substance. For example, when a mixture of biphenyl dichloride, biphenyl trichloride, biphenyl tetrachloride, and biphenyl pentachloride is dechlorinated by the method for decomposing a halogenated substance according to the present invention, the decomposed product obtained is Sometimes a mixture of mono- or tri-chloride substances is detected. However, if these mixtures have no adverse effects on the environment or the human body, no further decomposition is necessary. Therefore, it is natural that the present invention is included in the scope of the present invention even if it is only partially decomposed. Similarly, in the method for decomposing a halogenated substance according to the present invention, for example, 2,3,7,8-tetrabenzodibenzo-p-dioxin (2,3,7,8- (TCDD), the dehalogenation of the product can be converted into a product with extremely low toxicity by dehalogenation, and the product is converted into a substance that no longer has an adverse effect on the environment or the human body. Can be.

However, when it is necessary to further dehalogenate and decompose a partially decomposed product in which a halogen group remains partially, the above decomposition method can be repeated. In addition, it was found that, besides repeating the above-mentioned decomposition method, the microorganisms can be further de-halogenated and decomposed. As a strain that can be preferably used for this purpose, for example, Pseudomonas pseudoalcal igenes KF707 (FERMP-82997) and the like can be used. By culturing the partially decomposed solution at room temperature for a predetermined period of time, for example, all day and night, using such a strain, dehalogenation further occurs to accelerate the decomposition. The strain used here can dehalogenate particularly well a halogenated substance having a relatively small number of halogen groups.

Next, a method for detecting harmful substance decomposition and a kit for detecting harmful substance decomposition according to the present invention will be described.

Hazardous substances that can be decomposed and detected by the harmful substance decomposition detection method and the harmful substance decomposition detection kit according to the present invention are, for example, halogenated substances such as dioxins, organic halogen pesticides, and polychlorinated biphenyl compounds. The kit for detecting harmful substances according to the present invention comprises a chemically equivalent compound which is substantially chemically equivalent to a halogenated substance, a thin layer chromatography tool, and an ultrasonic or ultraviolet ray generating tool. .

Examples of the chemically equivalent compound that is substantially chemically equivalent to the harmful substance used in the harmful substance decomposition detection method and the harmful substance decomposition detection kit according to the present invention include dioxins,

Compared with harmful substances such as polychlorinated biphenyl compounds such as PCBs, organic halogen-based pesticides, organic halogenated compounds, and ethylene oxide compounds, they have chemical equivalents in decomposition reactions and have no or extremely low toxicity. If there is no danger in handling, it can be used. It is preferable that such a chemical equivalent compound has a lower toxicity or no toxicity, and it is sufficient that the experiment can be performed safely without causing any harm to the experimenter in the decomposition detection experiment.

Among such chemically equivalent compounds, examples of chemically equivalent compounds having chemical equivalents in the decomposition reaction as compared with dioxins include, for example, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene Mouth benzene, 4-chloroaesonolle, 1-chloronaphthalene, 2-chloronaphthalene, 1,2,3-trichlorobenzene, 1,2,4-trichlorobenzene, 1,3,5-trichloro Benzene derivatives such as benzene. Among the chemical equivalent compounds, benzyl chloride, benzyl, and the like are particularly useful as chemical equivalents having chemical equivalents in the decomposition reaction as compared with pesticides of chlorinated pesticides or organic halogenated compounds. Organic halogen compounds including alkyl halides such as fluoralkyl, benzyl bromide, benzyl chloride and the like, hexinochloride, hexyl fluoride, hexyl bromide, and hexino leo-dide.

As the thin-layer chromatography tool and the ultraviolet ray generation tool, which are the other elements constituting the kit for detecting harmful substances according to the present invention, use any of those commonly used in chemical experiments and the like. be able to. The kit can be appropriately selected according to the situation in which the kit for detecting harmful substances according to the present invention is used.For example, when the decomposition can be easily confirmed at a sample collection site or the like, a portable type can be used. It is good to use the equipment. It is convenient to use, for example, a handy UV device as an ultraviolet ray generating tool, and even if the wavelength of the UV light is used, it is conventionally used to generate a UV light having a wavelength of a harmful substance whose decomposition is to be confirmed. UV light generating equipment can be used.

Next, the harmful substance decomposition detection method according to the present invention will be described. The method for detecting the decomposition of a harmful substance according to the present invention comprises decomposing a chemically equivalent compound which is substantially equivalent to the harmful substance in a decomposition reaction thereof by a sample for examining whether or not the harmful substance to be detected is contained. The method for detecting the harmful substance according to the present invention is carried out by using a kit for detecting harmful substance decomposition which is another aspect of the present invention. Is preferred.

That is, in a preferred embodiment of the method for detecting the decomposition of harmful substances according to the present invention, the kit for detecting the decomposition of harmful substances of the present invention has a chemical equivalence in the decomposition reaction as compared with a harmful substance, using the kit. And the ability to degrade low or non-toxic chemically equivalent compounds Or not, and confirm its decomposition.

In order to detect whether a sample can degrade such a chemical equivalent compound according to the present invention, for example, a chemical decomposition method, a physical decomposition method, a biological decomposition method, and a method combining them are used. Used.

In the chemical decomposition method according to the present invention, whether or not a sample can chemically degrade a chemically equivalent compound having low or non-toxicity in a decomposition reaction as compared with a harmful substance, and This is a method of detecting and confirming its decomposition. In this chemical decomposition method, for example, a sample such as an alkali metal such as sodium hydroxide, an acid such as hydrochloric acid, a reducing agent such as sodium borohydride, or a sample containing them is a particularly chemically equivalent compound. The method can be carried out by detecting whether or not a halogenobenzene derivative or an organic halogen compound including a kuguchiguchi benzene derivative can be decomposed.

To decompose harmful substances based on this chemical decomposition method, for example, a sample obtained by dissolving a sample such as an alkali, an acid or a reducing agent in a solvent such as hexane, tetrahydrofuran, or purified water is used, for example, For example, a halogenobenzene derivative or organic halogen compound containing a benzene derivative, which is a chemically equivalent compound, dissolved in an organic solvent such as hexane. The reaction can be carried out by stirring for 24 hours to cause a decomposition reaction of the chemically equivalent compound. Further, anhydrous sodium sulfate or anhydrous magnesium sulfate can be used as a drying agent for the solvent.

For the decomposition of harmful substances based on the physical decomposition method, for example, is physical means such as ultraviolet rays or ultrasonic waves chemically equivalent to harmful substances in the decomposition reaction and less toxic? Alternatively, it is a method of decomposing non-toxic chemically equivalent compounds. That is, for example, while irradiating a hexane solution such as a black benzene derivative or an organic halogen compound with changing conditions such as ultraviolet rays or ultrasonic waves, at room temperature or under heating conditions for a predetermined time, for example, 1 minute to 2 minutes. This can be done by stirring for 4 hours to cause a decomposition reaction of the force, a chemically equivalent compound.

Furthermore, the decomposition of harmful substances based on the biological decomposition method involves the decomposition of various microorganisms, including molds and fungi, or various enzymes such as oxidoreductases and hydrolases, in comparison with harmful substances. Is a method of decomposing chemically equivalent compounds that have chemical equivalency and have low or no toxicity. That is, for example, various microorganisms including molds, fungi and the like or various enzymes such as oxidoreductases and hydrolases are added to a solution of a benzene derivative or an organic halogen compound, and the microorganisms and enzymes are added. It can be carried out by causing a decomposition reaction of such a chemically equivalent compound. Examples of the power and such microorganisms include microorganisms such as power bacteria or fungi resistant to black benzene derivatives, and microorganisms such as power halogen or fungi resistant to organic halogen compounds. Various enzymes such as oxidoreductases and hydrolases can also be used. In such reactions using microorganisms and enzymes, it is often necessary to use a solvent or a solubilizing agent. As the solvent, for example, 0.1 M phosphate buffer (pH 7) is preferably used, and acetone and the like can be used as the solvent and the solubilizing agent. This biodegradation method involves dissolving such microorganisms, such as molds, fungi, etc., or acetone in an aqueous solution of the enzyme. It can be carried out by adding the undiluted benzene derivative or the organohalogen compound with stirring and stirring or leaving the mixture at a temperature of 20 to 40 ° C for 1 to 2 weeks.

On the other hand, the decomposition of harmful substances based on the chemico-physical decomposition method combines the above-mentioned chemical decomposition method and physical decomposition method to provide a chemical equivalent to the decomposition reaction in comparison with harmful substances. It is a method of decomposing chemically equivalent compounds having low toxicity or non-toxicity. In other words, the decomposition of harmful substances based on the chemical-physical decomposition method involves, for example, subjecting a sample such as an alkali, an acid or a reducing agent or a sample containing the same to UV light against a hexane solution such as a benzene derivative or an organic halogen compound. Alternatively, the specimen is decomposed by stirring for a predetermined time, for example, 24 hours at room temperature or under heating conditions while irradiating with ultrasonic waves under different conditions.

In addition, the decomposition of harmful substances based on the biochemical decomposition method combines the above-mentioned biological decomposition method and chemical decomposition method, and has chemical equivalent in the decomposition reaction compared to harmful substances. Secondly, it is a method to degrade low-toxic or non-toxic chemical equivalents. In other words, the decomposition of harmful substances based on the biochemical decomposition method includes, for example, a specimen such as an alkali, an acid or a reducing agent or a specimen containing the same, and various microorganisms or oxidoreductases and hydrolases including molds and fungi. A sample consisting of various enzymes such as benzene is added to a chemically equivalent compound such as a benzene derivative or an organic halide, and the chemically equivalent compound such as a benzene derivative or an organic halogen compound is decomposed. This is done by: For example, to an aqueous solution of a microorganism or an enzyme such as a fungus or a bacterium or the like, a benzene derivative or an organic halogen compound dissolved in acetone, for example, is added with stirring, and an alkali, an acid or a reducing agent is added. Decomposition can be carried out by stirring or standing at a temperature of 0 to 40 ° C for 1 to 2 weeks.

Furthermore, the decomposition of harmful substances based on the biophysical decomposition method combines the above-mentioned biological decomposition method and physical decomposition method, and has chemical equivalence in the decomposition reaction as compared with harmful substances, It is a method of breaking down chemically equivalent compounds with low or no toxicity. In other words, the decomposition of harmful substances based on the biophysical decomposition method is based on the analysis of various microorganisms including bacteria, bacteria, etc. or various enzymes such as oxidoreductase, hydrolase, etc. By adding to a chemical equivalent compound such as an organic halogen compound, and irradiating with ultraviolet light or ultrasonic waves under different conditions, stirring or leaving at a temperature of 20 to 40 ° C for 1 to 2 weeks Decomposition can be performed.

Furthermore, the decomposition of harmful substances based on the biochemical physical decomposition method combines the biological decomposition method, the chemical decomposition method, and the physical decomposition method as described above, and the decomposition reaction of the harmful substance is compared with the harmful substance. It is a method of decomposing chemically equivalent compounds with low chemical toxicity and low toxicity or non-toxicity. That is, the decomposition of harmful substances based on this biochemical physical decomposition method includes, for example, a specimen of alkali, an acid or a reducing agent or a specimen containing the same, and various microorganisms or oxidoreductases including molds, fungi, etc. Specimens composed of various enzymes such as hydrolases are added to chemically equivalent compounds such as chlorobenzene derivatives and organic halogen compounds, and irradiated with ultraviolet light or ultrasonic waves under different conditions. 1 to 2 weeks at a temperature of ~ 40 ° C, The stirring or standing is performed by decomposing the chemically equivalent compounds such as the above-mentioned benzene derivatives and organic halogen compounds.

The method for analyzing whether or not the chemical equivalents such as the chlorobenzene derivative and the organic halogen compound have been decomposed as described above is performed by using the chemical equivalent compound (raw material) such as the chlorobenzene derivative and the organic halogen compound. By thin-layer chromatographic analysis with the reaction solution (product), it is possible to confirm the decomposition and determine the degree of decomposition by comparing the R f values of those spots. Spots with relatively strong UV absorption can be easily identified by UV irradiation with a handy UV lamp (254 nra). Those with low UV absorption can be easily checked by immersing them in a solution of a coloring agent such as potassium permanganate or vanillin sulfate to develop color.

Needless to say, when conducting an experiment for detection of harmful substance decomposition using the kit for detecting harmful substance decomposition according to the present invention, in addition to the above-mentioned components, it is usually necessary to carry out a chemical experiment. It is obvious to those skilled in the art that the necessary experimental tools, for example, instruments, devices, reagents, and the like, are necessary, and thus will not be described in detail here. Examples of such experimental tools include an Erlenmeyer flask, magnetic stirrer (automatic stirrer), stirrer, thermometer, funnel, filter paper, absorbent cotton, pit, rubber cap, precision balance (with weight), Packaging paper, spatula, safety glasses, silicone rubber stopper, sample bottle, separating funnel, developing tank, etc. When using the biodegradation method, a water bath or constant temperature bath can be used if necessary. On the other hand, when a physical decomposition method is used, an ultraviolet lamp (for reaction), an ultrasonic generator, or the like can be used. Industrial applicability

The method for decomposing a haptic compound according to the present invention comprises reacting a halogenated substance such as dioxins, a polychlorinated biphenyl compound, an organic halogen-based pesticide, an organic halogen compound, or a haloethylene compound with a reductive decomposing agent, It can be dehalogenated and decomposed in a very short time of about 1 minute at room temperature and pressure using physical means such as ultraviolet light. Therefore, the method for decomposing harmful substances according to the present invention is an extremely useful method for decomposing halogenated substances, which can decompose halogenated substances safely, effectively, simply and in a short time.

In addition, even if the partially decomposed material is still partially toxic according to the method for decomposing a halogenated substance according to the present invention, if such partially decomposed substance is still toxic, a microorganism is used. This has the great advantage that the halogen can be further desorbed and decomposed to make it non-toxic. Moreover, even in the method using this microorganism, since the culture is performed in a controlled environment, there is an advantage that harmful partial decomposition substances can be decomposed safely, efficiently, and in a short time.

Further, it should be particularly noted in the present invention that the method for decomposing a halogenated substance according to the present invention is a method for harmful halogens such as dioxins, polychlorinated biphenyl compounds, organic halogen-based pesticides, organic halogenated compounds, and haloethylene compounds. It is not limited to halogenated compounds, but can be applied to halogenated compounds in general.

Further, by the method for detecting harmful substance decomposition and the kit for detecting harmful substance decomposition according to the present invention, Decomposition of harmful substances such as polychlorinated biphenyl compounds such as dioxins and PCBs, and organic halogen-based pesticides, organic halogen compounds, and haloethylene compounds, which are extremely dangerous to remove. Experiments can be safely and easily attempted, and decomposition can be easily detected and confirmed.

The method for detecting the decomposition of harmful substances and the kit for detecting the decomposition of harmful substances according to the present invention include a chemically equivalent compound that is substantially chemically equivalent to a harmful substance, a thin-layer chromatography tool, and an ultrasonic or ultraviolet light generation tool. This makes it possible to safely and easily carry out experiments to decompose harmful substances that are extremely dangerous in handling, without directly taking them. There is a great advantage that detection and confirmation can be performed. In a method for detecting harmful substance decomposition and a kit for detecting harmful substance decomposition according to a preferred embodiment of the present invention, the chemical equivalent compound is a polychlorinated biphenyl compound such as dioxins and PCBs, an organic halogen-based pesticide, and an organic halogen. The kit of the present invention is characterized by being substantially chemically equivalent to harmful substances such as compounds and haloethylene compounds. In addition to the above advantages, the kit of the present invention is particularly suitable for dioxins, pesticide residues, polychlorinated bifuunil compounds, and organic halogens. It also has the advantage of being able to safely and easily detect the degradation of harmful substances such as compounds.

In a further preferred embodiment of the method for detecting harmful substance decomposition and the kit for detecting harmful substance decomposition according to the present invention, the chemical equivalent compound is substantially chemically combined with a halogenobenzene derivative including a chlorobenzene derivative or an organic halogen compound. In addition to the above advantages, the kit of the present invention is particularly suitable for halogen-based harmful substances including chlorine-based substances such as dioxins, residual agricultural chemicals, polychlorinated biphenyl compounds, and organic halogen compounds. It also has the great advantage that decomposition can be detected safely and easily.

In the method for detecting harmful substance decomposition and the kit for detecting harmful substance decomposition according to a preferred embodiment of the present invention, the sample may be a chemical substance such as an acid, an alkali or a reducing agent; an enzyme such as an oxidoreductase; It is characterized by being a microorganism or physical means such as ultraviolet light or ultrasonic waves, and in addition to the above advantages, a great advantage that it can detect substances that decompose such harmful substances from a wide range of fields from the chemical field to the physical field. There is.

Furthermore, it should be particularly noted here that, in the present invention, in order to detect and confirm whether or not a harmful substance can be decomposed, a chemical equivalent substance which is chemically equivalent to the harmful substance and its decomposition reaction is used. The basic concept of the present invention, which is to use a chemical compound, is that it can be applied not only to the harmful substances exemplified in the present application but also to any other chemical substances. By using this basic concept, for example, when it is difficult to directly decompose a substance whose decomposition is to be confirmed, by using a chemically equivalent substance whose decomposition reaction is equivalent to that of such a substance. However, the decomposition of such a substance can be confirmed.

The present invention will be described in detail with reference to examples. It should be understood that the following examples do not limit the present invention in any way and are described only for the purpose of illustrating the present invention.

(Example) Example 1: Experiment by chemical decomposition method

In an Erlenmeyer flask, 143 mg (1 mmol) of 4-chloroazoline and 4 ml of tetrahydrofuran were added, and 38 mg (1 mmol) of lithium aluminum hydride was added thereto with stirring, followed by stirring at room temperature for 24 hours. The reaction solution was filtered, and the filtrate was subjected to thin-layer chromatography analysis (irradiation with 254 nm UV light). In addition to undecomposed 4-chloroazolyl, compounds in which chlorine was reductively decomposed

(Showing the same R f value as the Aesole sample).

Example 2: Experiment by chemical physical decomposition method

A halogenobenzene derivative (lmmol) and tetrahydrofuran (4 to 20 ml) are placed in an Erlenmeyer flask, and lithium aluminium hydride (38 to 38 Omg (1 to: lOmmol)) is added thereto with stirring. Stirred for minutes to 1 hour. The reaction wave was filtered, and the filtrate was subjected to thin-layer chromatography analysis (irradiation with 254 nm UV). In most cases, halogenobenzene derivatives were completely decomposed, and compounds in which halogens were reductively decomposed (anisole or naphthalene) Rf values that were completely the same as those of the reduction products such as the standard) were confirmed. Example 3: Experiment by biological decomposition method

An Erlenmeyer flask was charged with 144 mg (1 mmol) of 4-chloroanisole and 50 Oml of a culture solution of Maitake (Grifola frondosa 30661), stirred, and allowed to stand at 30 ° C. for 1 week. The reaction mixture was extracted with hexane (10 ml X 3), and the extract was subjected to thin-layer chromatography analysis (UV irradiation at 254 nm). In addition to undecomposed 4-chloroacesol, degraded products were considered. Was confirmed.

Example 4: Experiment by biophysical decomposition method

In an Erlenmeyer flask were placed 4-chloroanisole (143 mg, lmmol) and an ultrasonically stimulated culture of Maitake (Grifola frondosa 30661) (500 ml), and the mixture was stirred and left at 30 ° C for 1 week. The reaction mixture was extracted with hexane (10 ml X 3), and thin-layer chromatography analysis (irradiation at 254 nm) was performed on the extract. Two or three spots that seemed to be objects could be confirmed.

The experimental results of Examples 1 to 4 are shown in Tables 1 to 5 below. In the table, the decomposition rate was calculated from the peak area ratio by HPLC (high performance liquid chromatography) analysis. The results correlated well with the results of thin layer chromatography. In the case of Example 2, the reaction temperature was at room temperature in all experiments, but rose to about 50 ° C when the ultrasonic irradiation time reached 1 hour. Ultrasonic irradiation was not performed in Example 1, but was performed for 1 hour in Example 2 (Tables 1 and 2). table

Table 2

Replacement form (Rule 26) Table 3

Table 4

Replacement form (Rule 26)

Among the above examples, in the ultrasonic irradiation reaction using lithium aluminum hydride shown in Example 2, a violent reductive decomposition reaction occurred for all halogenobenzene derivatives, resulting in a high decomposition rate. Gave. Furthermore, it was found that when an excessive amount of lithium aluminum hydride and a sufficient amount of THF solvent were used, a high decomposition rate was exhibited even when the irradiation time was extremely short. In particular, when a 5-fold molar amount of lithium aluminum hydride is used, it is possible to decompose 100% of 1-chloronaphthalene even when the irradiation time is about 5 minutes. It was found that even if the irradiation time was only about 1 minute, 100% of chloronaphthalene was decomposed. Under these conditions, it was found that even the most difficult to decompose in the nu- and gen-bribers and the fluo mouth (eg, 11-fluoro-naphthalene) can be almost completely decomposed by ultrasonic treatment for about 1 minute. Therefore, by the method according to the present invention, toxic substances such as dioxins, pesticide residues, polychlorinated biphenyl compounds (PCB, etc.), organic halogen compounds, phthalene compounds, and chloroethylenes are extremely practically decomposed. You can do it. Further, the decomposition method according to the present invention provides a high industrial advantage, judging from the simplicity of the treatment, the low cost, and the industrial use of the decomposition product.

Example 5:

As a PCB sample, 1 O mg (0.0388 mmol) of KC300 (trademark "Kanechlor": Kanegafuchi Chemical Industry Co., Ltd .: mixture of biphenyl compounds containing biphenyl trichloride as a main component) The mixture was placed in a dry triangular flask, and 2.3 ml of dry THF was added to dissolve. Thereafter, 44 mg (1.164 mmol) of lithium aluminum hydride was added to the solution, which was then stoppered with a silicone rubber and stirred gently two or three times. Next, it was placed in an ultrasonic generator containing water and irradiated with ultrasonic waves for one minute. Examination of the peak pattern donates decomposition solution irradiated with ultrasonic waves to GC-MS, the peak pattern was as shown in ^FIG. Fig. 1 shows the GC-MS peak pattern of KC300 as a control.

Example 6:

In the same manner as in Example 5, the K C 300 decomposition solution when the ultrasonic irradiation time was set to 10 minutes.

Replacement form (Rule 26) Figure 3 shows the GC-MS peak pattern.

Example 7:

KC 400 (trademark “Kanechlor”: Kanegafuchi Chemical Industry Co., Ltd.): A mixture of biphenyl compounds containing biphenyl tetrachloride as a main component. Was added and dissolved. Thereafter, 44 mg (1.026 mol) of lithium aluminum hydride was added to the solution, and the mixture was stoppered with silicon rubber and stirred slowly a few times. Next, it was placed in an ultrasonic generator containing water and irradiated with ultrasonic waves for one minute. The digested solution irradiated with ultrasonic waves was supplied to GC-MS to examine the peak pattern. The peak pattern was as shown in Fig. 5. FIG. 4 shows the GC-MS peak pattern of KC400 as a control. Example 8:

FIG. 6 shows the GC-MS peak pattern of the K C400 decomposition solution when the treatment was performed in the same manner as in Example 7 and the ultrasonic irradiation time was set to 10 minutes.

Example 9:

In Example 5, the KC300 decomposed liquid obtained by decomposing by irradiating ultrasonic waves for 1 minute was decomposed by microorganisms. As a microorganism, Pseudomonas pseudoalcaligenes KF707 (FERMP-8297) was used.

30 ml of the bacterium of the KF707 strain was added to the above-mentioned KC300 digestion solution. After culturing for 24 hours, the mixture was extracted with ethyl acetate. After concentration, it was supplied to GC-MS, and the GC-MS peak pattern was examined. Fig. 7 shows the GC-MS peak pattern.

Example 10:

FIG. 8 shows a GC-MS peak pattern of a KC400 decomposed solution obtained by treating the KC400 decomposed solution irradiated with ultrasonic waves for 1 minute in Example 7 in the same manner as in Example 9.

From the results obtained in Examples 5 to 8, remarkable dechlorination was confirmed for both KC300 and KC400. In addition, since there was almost no difference in the ultrasonic irradiation time, it was confirmed that an irradiation time of 1 minute was sufficient. Further, after being decomposed by ultrasonic waves, when Pseudomonas pseudoalcaligenes KF707 (F ERM P-8297) was used as a microorganism, the results are shown in FIGS. 7 and 8. It was confirmed that it was almost completely decomposed as shown in FIG.

Claims

The scope of the claims

1. A method for decomposing a halogenated substance, comprising mixing a halogenated substance with a reductive decomposing agent and irradiating ultraviolet rays or ultrasonic waves to dehalogenate and decompose the halogenated substance.

2. The method for decomposing a halogenated substance according to claim 1, wherein the halogenated substance is a dioxin, a polychlorinated biphenyl compound, an organic halogen-based pesticide, an organic halogenated compound, or a haloethylene compound. Halogenated substance decomposition method.

3. The method for decomposing a halogenated substance according to claim 1 or 2, wherein the organic halogen-based pesticide, the organic halogen compound or the haloethylene compound is a chlorine compound.

4. In the method for decomposing haptic substances according to any one of claims 1 to 3, wherein the halogenated substance is represented by the general formula (I):

(Wherein X represents a halogen atom;

a means 0 or 1;

m l and n l are the same or different and are 0 or

Means an integer from 1 to 4, where m l and n 1 are not both 0

Or a dioxin represented by the general formula (II):

χ ^^^ ^ "

(Wherein X represents a halogen atom;

m 2 and η 2 are the same or different and are each 0 or

Means an integer of 1 to 5, where both m 2 and η 2 are not 0, and one of them is an integer other than 0)

A polychlorinated biphenyl compound containing PCBs represented by the formula: or a general formula (III))

(Wherein R is a hydrogen atom, a hydroxyl group, a hydroxymethyl group, an unsubstituted or substituted amino group, Amide, thioamide, nitro, carboxyl, alkyl, alkoxy, oxyacetic acid residues, nitrile, nitrophenoxy, vinyl, phosphorothioate, unsubstituted or substituted phenoxy or Means pyrethrin residue,

X represents a halogen atom,

b means an integer from 1 to 5)

A halobenzene derivative, a disubstituted carbocyclic compound, a halogen-containing heterocyclic compound, or a general formula (IV):

(Where c represents 0 or 1)

Or an organohalogen-based pesticide or a halo-condensed polycyclic compound represented by the general formula (V):

X

R l- C -R 3 [V]

R 2

(Wherein X represents a halogen atom;

R l R 2 and R 3 are the same or different and are each water

A hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group, and R 1 R 2 and R 3 may be combined to form a monocyclic or bicyclic ring )

An organic halogen compound represented by the general formula (VI): [VI]

(Where X a X b X c and X d are the same or different,

A hydrogen atom, a hydrogen atom, and a halogen atom,

At least one of X a X b X c and X d means a halogen atom)

A method for decomposing a halogenated substance, which is a haloethylene compound represented by the formula:

5. The method for decomposing a halogenated substance according to any one of claims 1 to 4, wherein the reductive decomposing agent is a metal hydride or an organometallic compound. Disassembly method.

6. The method for decomposing a halogenated substance according to any one of claims 1 to 5, wherein the reductive decomposing agent is the metal hydride, and the metal hydride is lithium aluminum hydride, hydrogen, or hydrogen. A method for decomposing a halogenated substance, which is sodium hydride or sodium borohydride.

7. Partially decomposed substances that have been partially decomposed by partial dehalogenation according to the method for decomposing lipogenated substances according to any one of claims 1 to 6 are further decomposed by microorganisms. A method for decomposing a halogenated substance.

8. The method for decomposing a halogenated substance according to claim 7, wherein the microorganism is Pseudomonas pseudoalcal igenes KF707 (FERP-82997). Halogenated substance decomposition method.

8. A harmful substance characterized by decomposing a chemical equivalent compound that is substantially chemically equivalent to a harmful substance using a sample, and detecting the decomposition of the harmful substance based on the presence or absence of the decomposition of the chemical equivalent compound. Quality degradation detection method.

9. The method for detecting the decomposition of harmful substances according to claim 8, wherein a kit for detection of decomposition of harmful substances comprising the chemical equivalent compound, a tool for thin-layer chromatography, and a tool for generating ultrasonic or ultraviolet light is used. A method for detecting the decomposition of harmful substances, comprising detecting the decomposition of harmful substances.

10. The method for detecting the decomposition of harmful substances according to claim 8 or 9, wherein the chemically equivalent compound is substantially a dioxin, a pesticide residue, a polychlorinated biphenyl compound or an organic halide. A method for detecting the decomposition of harmful substances, which is chemically equivalent.

11. The harmful substance decomposition detection method according to any one of claims 8 to 10, wherein the chemical equivalent compound is a halogenobenzene derivative or an organic halogen compound. Material decomposition detection method.

12. The method for detecting harmful substances according to any one of claims 8 to 11, wherein the specimen is a chemical substance, an enzyme, a microorganism, or a physical means. Decomposition detection method.

13. In the method for detecting harmful substances according to any one of claims 8 to 12, the specimen is an acid, alkali, reducing agent, microorganism, enzyme, ultraviolet light or ultrasonic wave. A method for detecting harmful substances by decomposition.

1 4. For detection of decomposition of harmful substances, which is composed of a chemical equivalent compound that is substantially chemically equivalent to harmful substances, one tool for thin layer chromatography, a tool for generating ultrasonic waves, and a tool for generating ultraviolet rays. kit.

15. The kit for detecting harmful substances according to claim 14, wherein the chemically equivalent compound is substantially a dioxin, a polychlorinated biphenyl compound, an organic halogen-based pesticide, an organic halogen compound or a halothylene compound. A kit for detecting the decomposition of harmful substances, which is chemically equivalent to:

16. The kit for detecting harmful substances according to claim 14 or 15, wherein the chemically equivalent compound is a halogenobenzene derivative or an organic halogen compound. Kit.

17. The kit for detecting harmful substance degradation according to any one of claims 14 to 16, wherein the sample is a chemical substance, an enzyme, a microorganism, or a physical means. Kit for detecting harmful substances.

18. The kit for detecting harmful substances according to any one of claims 14 to 17, wherein the specimen is an acid, an alkali, a reducing agent, a microorganism, an enzyme, ultraviolet light, or ultrasonic waves. A kit for detection of decomposition of harmful substances, characterized in that: