JP2001286576A - Decomposing method for endocrine disrupting chemicals - Google Patents

Abstract

PROBLEM TO BE SOLVED: To efficiently and economically decompose endocrine disrupting chemicals. SOLUTION: According to this method, the endocrine disrupting chemicals are decomposed by working singlet oxygen generated by applying visible light beams such as sunlight beams or the like on a water system containing an organic pigment and dissolved oxygen which is put in the triplet excitation state by absorbing light on the endocrine disrupting chemicals.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for decomposing and rendering harmful environmental hormones which disrupt hormonal action of a living body.

[0002]

2. Description of the Related Art As a method for decomposing environmental hormones, methods such as thermal decomposition, ultraviolet light, ozone, hydrogen peroxide, and titanium oxide / ultraviolet light have been known. However, each of these conventional methods has a strong oxidizing or decomposing action, so that various side reactions are induced, and the harmfulness of products due to these side reactions is problematic. There was a drawback that the residual toxicity of the drug became a new problem.

[0003]

DISCLOSURE OF THE INVENTION The present invention provides a method capable of easily and economically decomposing environmental hormones with less side effects than these conventional methods.

[0004]

Means for Solving the Problems The present invention relates to a singlet oxygen produced by irradiating visible light to a solution system containing an environmental hormone, an organic dye capable of entering a triplet excited state by light absorption, and dissolved oxygen. Is a method of decomposing environmental hormones.

[0005]

The present inventors have proposed various treatment methods using active oxygen in JP-A-11-199490 and JP-A-10-249364. As described in these specifications, singlet oxygen generated by applying visible light to a dye that can be in a triplet excited state has a relatively weak oxidizing effect, and has a lifetime of 3.3 × 10 ^−. Since it is extremely short, ⁶ seconds, it disappears quickly after oxidizing the target substance, and does not flow out or remain outside the reaction system.
This is an extremely safe treatment method. The present inventors have found that environmental hormones harmful to the human body can be easily and economically decomposed using the characteristics of singlet oxygen.

The environmental hormones of the present invention include compounds having a hydroxyl group, a halogen group, a double bond,
For example, alkylphenols (nonylphenols, bisphenol A), dioxins, DDT, BHC
, PCBs, organotins, phthalates and the like.

The dye that can be used in the present invention may be any dye that can absorb visible light and enter a triplet excited state. Examples of the dyes preferably used in the present invention include, for example, methylene blue, thionin, rose bengal, erythrosin, eosin Y, fluorescein, proflavin, fluorenone, rhodamine B, tetraphenylporphyrin, chlorophyll (chlorophyll) s, chlorophyllin, There are organic dyes such as hemoglobins and hemin and derivatives thereof. For the purpose of effectively utilizing these dyes and preventing them from leaking into the environment, the dyes were previously converted to natural fibers,
Plastics, ceramics, glass, metal, rock,
It is desirable to use it supported on the surface of a carrier such as concrete. In addition, in order to increase the light use efficiency, it is preferable to use a transparent or nearly white material as the carrier. Water is usually used as the liquid phase, but alcohol or the like can be used as necessary.

As the visible light used in the present invention, sunlight can be used most economically. In particular, as a means for treating a trace amount of environmental hormones contained in a large amount of water, a large-area water tank is used outdoors. It only needs to be installed, consumes little energy, and is an ideal light source for large volume water treatment. In addition, incandescent lamps, discharge lamps, lasers, and the like can be used as necessary.

[0009]

【Example】

Embodiment 1 A singlet oxygen generator is shown in FIG. A sample 2 is placed in a cylindrical quartz cell 1 and a 50 W metal halide arc lamp 4 is blown while blowing oxygen gas from a pipe 3.
Irradiation. A heat ray cut filter 5 is provided between the quartz cell 1 and the lamp 4 to prevent the reaction liquid from evaporating, and a Y43, Y48 colored glass is used to cut light having a wavelength of 430 nm or 480 nm or less and irradiate visible light. Filters 6 and 7 were inserted with a lens 8 to reduce irradiation light. For the sample, a stock solution of a dye and a stock solution of an environmental hormone were prepared in advance, and these were diluted with methanol before use. The stock solution of the dye was prepared by adding methanol
Then, the mixture was dissolved by adding ml (hereinafter referred to as RB stock solution). Stock solutions of environmental hormones were prepared by the following methods. The stock solution of bisphenol A is bisphenol A 2.56m
g was dissolved in 10 ml of methanol. The stock solution of nonylphenol was dissolved by adding 10 ml of methanol to 5.38 mg of nonylphenol. The stock solution of DDT is D
To 4.52 mg of DT, 10 ml of methanol was added and dissolved. The stock solution of PCBs was dissolved by adding 10 ml of methanol to 7.1 mg of PCBs. Degradation of environmental hormones by singlet oxygen was performed by the following method. Dilute environmental hormone stock solution 100 times with methanol, put 10 ml into cylindrical quartz cell 1, add 0.2 ml RB stock solution, cool to 0 ° C, and irradiate with lamp 4 while blowing oxygen gas to generate singlet oxygen The endocrine disruptors were broken down. The reaction solution was collected every hour, and the product was analyzed by HPLC.
As a result, the raw material of bisphenol A was completely decomposed in 12 hours as shown in FIG. Nonylphenol decomposed 93.4% of the raw material in 48 hours. DDT decomposed 92.7% of the raw material in 264 hours. The reaction solution faded during the irradiation.
After 42 hours, 110 μg and 20 μg were added, respectively.

[0010]

EXAMPLE 2 1.1 mg of Rose Bengal was added to 120 mg
The mixture was sterilized at 2 ° C. and 2 atm and dissolved in 500 ml of seawater filtered through a membrane filter to obtain a rose bengal seawater solution. 1.0 mg of 4-nonylphenol was dissolved in 3.0 ml of a 1 M aqueous sodium hydroxide solution, and 7.0 ml of a Rose Bengal sea aqueous solution (2.16 × 10 ⁻⁶ M) was added thereto.
Was added to make a stock solution. This stock solution was put into a Pyrex test tube, oxygen gas was blown at 0 ° C., and light was irradiated using the apparatus shown in FIG. 1 to generate singlet oxygen, and the change over time in the concentration of nonylphenol was measured. As a result, nonylphenol was decomposed with a half life of 35 minutes.

[0011]

As is clear from the above description, the method for decomposing environmental hormones of the present invention consumes less energy,
An object of the present invention is to provide a method capable of easily treating a large amount of water in which a trace amount of environmental hormone is dissolved without producing harmful by-products.

[Brief description of the drawings]

FIG. 1 is a conceptual diagram showing an example of an apparatus used in the method of the present invention.

FIG. 2 is a graph showing the rate of environmental hormone degradation by the method of the present invention.

[Explanation of symbols]

 1: Cylindrical quartz cell 2: Sample 3: Pipe 4: Metal halide arc lamp 5: Heat ray cut filter 6, 7: Color glass filter 8: Lens

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (Reference) C07C 39/16 C07C 39/16 (72) Inventor Kenya Ozawa Fairwater, Sweetwater, Tennessee, United States Circle, address 732 F term (reference) 2E191 BA11 BC01 BC05 BD11 BD17 4G075 AA37 AA70 BA04 BA05 CA32 CA80 4H006 AA05 AC13 BA95 BE30 EA22 FC52 FE13

Claims (2)

[Claims] The present invention is characterized in that a singlet oxygen generated by irradiating visible light to a solution system containing an organic dye and dissolved oxygen that can be brought into a triplet excited state by light absorption is caused to act on an environmental hormone. , Environmental hormone decomposition method. 2. The method according to claim 1, wherein the environmental hormone is at least one member selected from the group consisting of a hydroxyl group, a halogen group and a compound having a double bond.