JP2001337080A - Phenols analyzing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To analyze bisphenol A, chlorophenols, and alkylphenols by one analysis by a chromatography device and to prevent the occurrence of variations in the results of analysis by the chromatography device even if the amount of sample to be introduced and the speed of water passage vary when extracting a solid phase. SOLUTION: By performing analysis by the chromatography after extraction by a solid-phase extracting method, a plurality of types of phenols contained in sample water are analyzed. The extraction is performed through the use of two types of solid-phase extractants or more selected from among a silica gel with the organic functional group styrene-divinylbenzene copolymer, styrene- divinylbenzene copolymer with the anion exchange group, silica gel with the anion exchange group, and activated carbon.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for analyzing a plurality of types of phenols contained in a sample water by performing extraction with a solid phase extraction method and then performing analysis with a chromatography device.

[0002]

2. Description of the Related Art In recent years, some phenols have been expressed in μg / l.
It has been reported that at low levels, hormone-like effects are exerted, especially on germ cells in animals, with severe effects on ecosystems. Such a substance is called "exogenous endocrine disrupting chemical substance (environmental hormone)" and attracts attention. Therefore, from the viewpoint of environmental problems, it is required to establish a technique for trace analysis of such substances at an early stage.

[0003] In fact, in October 1998, the Environment Agency issued a "Temporary Manual for Investigation of Exogenous Endocrine Disrupters (hereinafter abbreviated as a provisional manual)". According to this provisional manual, it is possible to analyze phenols contained in water at concentrations of μg / l to ng / l. As a method for analyzing phenols contained in water, which is described in this provisional manual, the method most frequently used at present is a method using a liquid-liquid extraction method.

In this method, first, phenols in a sample water are extracted with dichloromethane (liquid-liquid extraction), and this extract is concentrated by a rotary evaporator or the like. Then, the contaminants contained in the concentrate are further removed by column chromatography. That is, 5
The phenols contained in the concentrate are adsorbed on silica gel by passing through a column packed with silica gel containing water, and the adsorbed phenols are recovered with acetone. Thereafter, the collected liquid is analyzed by gas chromatography-mass spectrometry.

[0005] By using this method, phenols in water can be usually analyzed at a recovery rate of 70% to 130%, and the relative standard deviation when the analysis is repeated five times can be kept within 20%. . However, this liquid-liquid extraction method has the disadvantages that it takes a long time for pretreatment, is difficult to automate, is expensive because it is performed manually, and requires the use of a large amount of a harmful solvent such as dichloromethane.

Although the use of the solid phase extraction method can improve such disadvantages, the solid phase extraction method described in the interim manual separates the analysis of alkylphenols from the analysis of bisphenol A and chlorophenols. Need to be done. Therefore, when analyzing both bisphenol A and / or chlorophenols and alkylphenols, there is a problem that the analysis takes a long time.

As a method for shortening the time required for analysis, there has been proposed a method using an apparatus in which a solid phase extraction apparatus and a chromatography apparatus are connected online. For example, Japanese Patent Application Laid-Open No. 11-344777 discloses that a quantitative sample collecting device, a solid phase extracting device for solid-phase extraction of trace harmful substances from a collected sample, and a solid-phase extracting device are provided in a drain line of a harmful organic substance decomposition treatment device. A wastewater monitoring device is described in which a chromatography device for analyzing and processing a phase-extracted substance is connected online. This publication also describes that when a phenol is a target substance, collection and concentration are performed using a solid phase cartridge formed using a benzenedivinylbenzene-based polymer.

In addition, O. Jauregui, M .; T. G
alceran, “Anal. Chim. Act.
a, 340 (1997), p191-199 ", describes that the measurement of phenols in water is carried out by a method using a solid phase extraction device and a liquid chromatography device connected online. In this method, a disk-type solid phase extractant made of poly (styrene-divinylbenzene) is used. As the liquid chromatography device, high performance liquid chromatography (HPLC) equipped with an electrochemical detector is used. In this way,
13 kinds of phenols such as nitrophenol and chlorophenol are measured at the detection limit of 0.01 to 0.1 μg / l.

[0009]

However, the method described in Japanese Patent Application Laid-Open No. H11-344377 and the method described in O.I. Ja
There is a question as to whether the method by Uregui et al. is an effective method with high recovery when analyzing both alkylphenols and bisphenol A and / or chlorophenols.

In particular, O.D. According to the literature by Jauregui et al., Some components of the 13 phenols are:
It is described that the recovery rate varies depending on the amount of sample introduced during solid phase extraction. For example, o-chlorophenol is
It is described that when the amount of sample introduced is more than 150 ml, the recovery rate by analysis becomes smaller than 80%. The present invention has been made in view of such a point, and by performing analysis with a chromatography device after performing extraction by solid phase extraction, it is possible to reduce a plurality of types of phenols contained in sample water. In the analysis method, both bisphenol A and / or chlorophenols and alkylphenols can be analyzed by a single analysis using a chromatographic apparatus, and the amount and flow rate of a sample to be introduced during solid phase extraction. It is an object of the present invention to provide a method in which an analysis result by a chromatography apparatus does not change even if the value changes.

[0011]

In order to solve the above-mentioned problems, the present invention provides a method for extracting a plurality of types of water contained in a sample water by performing an extraction with a solid phase extraction method and then performing an analysis with a chromatography apparatus. In the method for analyzing phenols, the extraction is performed by using a silica gel having an organic functional group (non-polar type), a styrene-divinylbenzene copolymer, a styrene-divinylbenzene copolymer having an anion exchange group, Silica gel having an ion exchange group,
And a method for analyzing phenols, wherein the method is performed using two or more solid phase extractants selected from activated carbon (graphite carbon).

The method of the present invention is particularly suitable when the phenols to be analyzed are bisphenol A and / or chlorophenols and alkylphenols. As the functional group of the solid phase extractant, an octadecyl group,
Octyl, ethyl, methyl, cyclohexyl,
Examples include a butyldimethyl group, a phenyl group, a cyanopropyl group, and the like. Examples of the solid phase extractant and the anion exchange group include a primary amine group, a secondary amine group, a quaternary ammonium group, a diethylaminopropyl group, and a trimethylaminopropyl group.

The form of the solid phase extractant is a disk type (a film-like solid phase extractant cut out into a disk shape and used by being fixed to a frame made of glass or the like) and a cartridge. It may be of any type (a particulate or powdery solid phase extractant filled in a syringe or the like container). In the method of the present invention, extraction is performed using two or more solid phase extractants selected from the following. Therefore, in the case of a disk type, two or more kinds of membrane-shaped solid phase extractors are prepared, and these are stacked and fixed to a frame for use. Alternatively, two or more types of commercially available disk-type solid phase extractants composed of one kind of membrane-like solid phase extractant are prepared, and these are stacked and set in the extraction device.

In the case of the cartridge type, a container in which particles of two or more kinds of solid phase extractants are filled in a container is used. Alternatively, a commercially available cartridge filled with particles of one type of solid phase extractant is used after being filled with another type of solid phase extractant. In this case, the particles of two or more solid phase extractants in the container may be in a mixed state or in a separated state.

The extraction of phenols by the solid phase extraction method is as follows:
This is performed as follows. First, phenols in the sample water are adsorbed on the solid phase extractant by passing the sample water through the solid phase extractant. Next, by passing a solvent capable of eluting phenols through the solid phase extractant, an extract in which phenols are eluted is obtained. Solvents that can elute phenols include methanol, acetone, acetonitrile, methyl acetate, dichloromethane, and a concentration of 0.001 to 0.00.
5 mol / l mixed solution of hydrochloric acid and methanol, 2-4%
It is preferable to use a mixed solution of ammonia water and methanol at a concentration. The amount of the solvent used is, for example, 2 to 10
ml.

The obtained extract is concentrated first, and then
If necessary, a treatment for derivatizing phenols is performed, and then the phenols are introduced into a chromatography device. The derivatization treatment of phenols is performed by reacting a derivatization reagent with a hydroxyl group of phenol. Examples of the method for derivatizing phenols include trimethylsilylation (TMS), alkylation, fluorescent derivatization, halogenated acylation, and halogenated benzylation.

When performing trimethylsilylation (TMS conversion), the concentrated extract is first dehydrated with anhydrous sodium sulfate or the like, and a silylating agent is added to the dehydrated extract to cause a reaction. As the silylating agent, one or a mixture of two or more selected from the following substances is used. N, O-bis (trimethylsilyl) trifluoroacetamide (abbreviated as "BSTFA"), N, O-bis (trimethylsilyl) acetamide, hexamethyldisilazane, dimethyldichlorosilane, trimethylchlorosilane, N-trimethylsilylacetamide, N-methyl- Trimethylsilylacetamide, N-methyl-trimethylsilyltrifluoroacetamide, N-trimethylsilyldimethylamine, N-trimethylsilyldiethylamine, N-trimethylsilylimidazole, tetramethyldisilazane, tert-butyldimethylchlorosilane, N-methyl-N- (tert-butyldimethyl Silyl) trifluoroacetamide, dichloromethyltetramethyldisilazane, chloromethyldimethylchlorosilane, and bromomethyldisilane Chill chlorosilane.

Of these silylating agents, BMSFA is preferably used to carry out TMS conversion by reacting phenols in the extract after dehydration with BSTFA at room temperature for about 1 hour. When performing alkylation, the concentrated extract is first dehydrated with anhydrous sodium sulfate or the like, and an alkylating agent is added to the dehydrated extract to cause a reaction. As the alkylating agent, one selected from the following substances is used.
Use a mixture of two or more types. Dimethyl sulfate, diethyl sulfate, di-n-propyl sulfate, di-n-butyl sulfate, N, N-dimethylformamide dialkyl acetate, 3-alkyl-1-p-tolyl triazene.

Using diethyl sulfate among these alkylating agents, a mixed solution of diethyl sulfate, ethanol and an aqueous alkali solution is added to the extract after dehydration, and phenols and diethyl sulfate in the extract are separated. It is preferable to carry out the alkylation by a method of reacting at room temperature for about 1 hour. When performing fluorescent derivatization, the extract after concentration is first dehydrated with anhydrous sodium sulfate or the like, and a fluorescent derivatizing agent is added to the dehydrated extract and reacted. As the fluorescent derivatizing agent, one or a mixture of two or more selected from the following substances is used.

Dansyl chloride, 4-chloro-7-nitro-2,1,3-benzoxadiazole, 4-fluoro-7-nitrobenzofurazan, 4-bromomethyl-
7-methoxycoumarin, 9-bromomethylacridine,
3-bromomethyl-6,7-dimethoxy-1-methyl-
2 (1H) -quinoxaline, naphthacyl bromide (2-
Bromoacetonaphthone), p- (anthroyloxy)
Phenacyl bromide (panacyl bromide), 1-bromoacetylpyrene, 9-chloromethylanthracene, 9-
Anthryldiazomethane.

Using dansyl chloride among these fluorescent derivatizing agents, a mixed solution of dansyl chloride, acetone and an alkaline aqueous solution is added to the dehydrated extract,
It is preferable to carry out fluorescent derivatization by a method in which phenols and dansyl chloride in this extract are reacted at 60 ° C. for about 30 minutes. When performing halogenated acylation and halogenated benzylation, the concentrated extract is first dehydrated with anhydrous sodium sulfate or the like, and the dehydrated extract is added with a halogenated acylating agent and a halogenated benzylating agent. And react. As the halogenated acylating agent and the halogenated benzylating agent, one or a mixture of two or more selected from the following substances is used.

Trifluoroacetic anhydride, pentafluoropropionic anhydride, heptafluorobutyric anhydride, pentafluorobenzoyl chloride, trichloroacetic anhydride, pentafluorobenzyl bromide, difluorobenzyl bromide, difluorobenzyl chloride, trifluorobenzyl bromide, trifluorobenzyl chloride , Pentafluorobenzyl chloride, trifluoroacetylimidazole, heptafluorobutylylimidazole, pentafluoropropionylimidazole.

The analysis using a chromatography device is performed using a gas chromatography device or a liquid chromatography device. When using a gas chromatography device, use a device equipped with a flame ionization detector or an electron capture detector as a detector, or a device combining a gas chromatography device and a mass spectrometer (GC-MS). Is appropriate. In particular, it is preferable to use GC-MS.

When a liquid chromatography device is used, a device equipped with an electrochemical detector as a detector, a mass spectrometer, an ultraviolet / visible absorption spectrophotometer, or a fluorescence spectrometer is connected to the liquid chromatography device. It is appropriate to use a device that has been adapted. In particular, it is preferable to use a device in which a liquid chromatography device is combined with a mass spectrometer or a fluorescence spectrometer.

In order to shorten the time required for analysis, it is preferable to use an automatic solid-phase extraction device for automatically performing solid-phase extraction. Further, if an apparatus in which an automatic solid-phase extraction apparatus and a chromatography apparatus are connected online is used, the time required for analysis can be further reduced. As an automatic solid phase extraction device, for example, a holder for setting a solid phase filler, an inlet for sample water, and a container for storing a solvent, and after setting the solid phase filler, the sample water is injected into the inlet. After the sample water has passed through the solid phase packing material, phenols are automatically recovered by the solvent, and the recovered solution is automatically injected into the sample inlet of the chromatography device. Use the one marked with. In the case of performing the derivatization treatment, it is preferable to use an automatic solid-phase extraction device having a container for storing the derivatization reagent in addition to the above-described configuration and in which the derivatization treatment is also performed automatically.

As an automatic solid-phase extraction device, for example, a product called "ASPEC-XLi" is commercially available from Gilson. For the quantification of each component, a calibration curve is prepared in advance using a standard reagent, the area value of each peak is determined from the obtained chromatogram, and the quantitative value is determined from the area value and the calibration curve. The method of preparing a calibration curve includes an absolute calibration curve method, an internal standard method, an internal standard addition method, and the like, and it is preferable to prepare a calibration curve by the internal standard method. When the internal standard method is used, for example, naphthalene, phenanthrene, pyrene, acenaphthene, fluoranthene, chrysene, perylene, benzopyrene, or a deuterated product thereof is used as the internal standard. A known amount of the internal standard is added, and a quantitative value is determined from the ratio of the area ratio of the sample to the weight of the internal standard added.

In the present invention, phenols are compounds having an aromatic ring in the molecule and a hydroxyl group directly bonded to the aromatic ring. If it has this hydroxyl group, it may have a substituent such as an alkyl group, a phenyl group, an amino group, a halogen or sulfur in the molecule. Examples of phenols other than phenol are shown below. 2-ter
t-butylphenol, 4-tert-butylphenol, 4-sec-butylphenol, 4-n-pentylphenol, 4-hydroxybiphenyl, 4,4'-dihydroxybiphenyl, 4-ethylphenol, 4-propylphenol, 3-tert- Butylphenol,
Isopentylphenol, 4-tert-octylphenol, 5-octylphenol, 4-nonylphenol, 2,4-dichlorophenol, pentachlorophenol, 4-butoxyphenol, 4-hexyloxyphenol, 4-n-hexylphenol, 4-n Heptylphenol, bisphenol A, 2,4-dichlorophenol, pentachlorophenol, α-naphthol, β-naphthol, 2-phenylphenol, 4-phenylphenol, estriol, ethinylestradiol, 17β-estradiol and estrone. Or their isomers.

[0028]

Embodiments of the present invention will be described below. Environmental Agency's “Environmental Hormone Strategic Plan (SPEE)
D98)). 4-tert-butylphenol, 4-n-
Pentylphenol, 4-n-hexylphenol, 4
-Tert-octylphenol, 4-n-heptylphenol, 4-n-octylphenol, nonylphenol, bisphenol A, 2,4-dichlorophenol, and pentachlorophenol. As these phenols, those commercially available from Kanto Chemical Co., Ltd. or Tokyo Chemical Industry Co., Ltd. were used.

Sample water was obtained by adding these 10 phenols to pure water so that the concentration of each phenol would be 100 to 1000 ng / l, and adjusting the pH to 3. Using this sample water, all ten phenols were analyzed by the following methods. [Example 1] A disk-type solid phase extractant made of a styrene divinylbenzene copolymer having a sulfonic acid group ("Mpore Disc SDB-RP" manufactured by 3M) was placed in a suction filter.
S ", diameter 47 mm) and a disk-type solid phase extractant made of a styrene divinylbenzene copolymer (" Mpore Disc SDB-XD "manufactured by 3M, diameter 47 mm) were mounted so as to overlap in the flow channel direction. . "Empore Disk S
"DB-RPS" was arranged on the upstream side of "Empore disc SDB-XD". The suction filter was assembled using a suction manifold for empore disc manufactured by GL Sciences Inc. and glassware. A collection container was installed in the manifold.

Sample water was placed in the upper vessel (glass funnel) of the suction filter, and a vacuum pump connected to the manifold was operated to allow 500 ml of sample water to flow at a water flow rate of 100 ml / min. As a result, the phenols in the sample water were adsorbed to the two solid-phase extractants of the styrene divinyl benzene copolymer and the styrene divinyl benzene copolymer having a sulfonic acid group.

Next, 10 ml of methyl acetate was passed through the two solid phase extracting agents by putting methyl acetate into the upper container and operating a vacuum pump. Next, 10 ml of methanol was passed through the two solid phase extracting agents by putting methanol in the upper container and operating a vacuum pump. Thereby, the extract in which phenols were eluted in methyl acetate and methanol was collected in the collection container.

After the obtained extract was concentrated, hexane was added to the concentrated extract to perform liquid-liquid extraction. Next, the extract obtained by the liquid-liquid extraction was dehydrated with anhydrous sodium sulfate, and then concentrated until the liquid volume became about 0.1 ml. These concentrations were performed by spraying nitrogen purified with an activated carbon column. An ethanol solution of potassium hydroxide (concentration of about 1 mol) is placed in a container containing the concentrated solution.
/ L) was added, and then diethyl sulfate was further added, and the mixture was kept at room temperature for 60 minutes. As a result, the phenol was alkylated, and a precipitate was formed in the container. Next, an ethanol solution of potassium hydroxide (concentration of about 1 m) was placed in this container.
ol / l), pure water was further added to dissolve the precipitate in the container.

Next, the solution in this container was diluted with 1 m of hexane.
1) Phenanthrene deuteride 10 as an internal standard
Liquid-liquid extraction was performed with a solution to which 0 ng was added. Next, the extract obtained by the liquid-liquid extraction was injected into a chromatography device and analyzed. As the chromatography device, a device in which a gas chromatography device and an electron ionization type mass spectrometer were combined was used. The gas chromatography apparatus is “HP6890” of Hewlett-Packard Company, and the mass spectrometer is “JMS-AMSUN” of JEOL.

From the results of the analysis, the recoveries (values obtained by dividing the quantitative value obtained by the analysis by the added amount and multiplying by 100) were calculated for each of the ten phenols in the sample water, and the results were obtained from 91%. The value was up to 105%. This value indicates that a good analysis was performed. In addition, when the reproducibility was examined by repeating extraction and analysis by the above procedure five times, the relative standard deviation was within 10%, and sufficient reproducibility (analysis accuracy) was obtained. The total time required for extraction and analysis by the above procedure was about 6 hours.

The flow rate of the sample water at the time of solid phase extraction is 2,000 m
l, the water flow rate was 100 ml / min, and all other points were extracted and analyzed by the above procedure. The recovery rate was in the range of 89% to 104%. Almost never. The flow rate of the sample water during solid phase extraction was set to 500 ml, and the flow rate was set to 300 ml.
/ Min, and extraction and analysis of all other points by the above procedure showed that the recovery was in the range of 93% to 105%, and there was almost no change in the recovery due to the water flow rate. Furthermore, the relative standard deviations when performing five repeated measurements by these methods were all within 10%, and the reproducibility (analysis accuracy) was sufficient.

When the measurement of the standard sample used at the time of preparing the calibration curve was repeated five times and the detection limit was three times the standard deviation obtained from the result, the detection limit in this example was 2 ng / l. As mentioned above,
According to the method of this embodiment, the analysis of bisphenol A and both chlorophenols and alkylphenols can be performed by a single analysis using a chromatographic apparatus. Even if the speed fluctuated, there was no fluctuation in the analysis result by the chromatography apparatus. [Example 2] Phenols contained in sample water were analyzed in the same manner as in Example 1 except for the following points, by performing extraction by a solid phase extraction method and analysis by a chromatographic apparatus. .

After solid-phase extraction of the sample water, fluorescence derivatization was performed in place of the alkylation treatment of phenols. Fluorescence derivatization was performed as follows. 50 μl of an aqueous solution of sodium hydrogen carbonate (concentration: 1 mol / l) was placed in a container containing the concentrated liquid concentrated to a volume of about 0.1 ml;
Acetone solution of dansyl chloride (concentration 1mg / m
l) was added, and the mixture was kept at 60 ° C for 30 minutes. Thereby, fluorescent derivatization of phenols was performed. Next, an aqueous sodium hydroxide solution (concentration 0.5
mol / l) was added.

[0038] The solution in this container was
Liquid-liquid extraction was performed with a solution in which 100 ng of phenanthrene deuteride was added as an internal standard substance to 1 ml of hexane to obtain a liquid to be injected into the chromatography device. As the chromatography device, a device in which a liquid chromatography device and a fluorescence detector were combined ("LC-10 series" manufactured by Shimadzu Corporation) was used.

From the results of the analysis, the recovery rate was calculated for each of the ten phenols in the sample water, and the values were 87% to 108%. This value is
It means that a good analysis was performed. When the reproducibility was examined by repeating the extraction and analysis by the above procedure five times, the relative standard deviation was within 15%, and sufficient reproducibility (analysis accuracy) was obtained. The total time required for extraction and analysis by the above procedure was about 6 hours.

The flow rate of the sample water during the solid phase extraction was 2,000 m
1 and the water flow rate was 100 ml / min. Extraction and analysis of all other points by the above procedure showed no change in the recovery rate. The flow rate of the sample water during the solid phase extraction was set to 500 ml, the flow rate was set to 300 ml / min,
All other points were extracted and analyzed by the above procedure, and there was no change in the recovery rate. Furthermore, the relative standard deviation when performing five repeated measurements by these methods is:
All were within 15%, and the reproducibility (analysis accuracy) was sufficient.

When the measurement of the standard sample used at the time of preparing the calibration curve was repeated five times and the detection limit was set to a value three times the standard deviation obtained from the result, the detection limit in this example was 10 ng / day. l. As described above, according to the method of this example, it is possible to analyze both bisphenol A and chlorophenols and alkylphenols by a single analysis using a chromatographic apparatus, and furthermore, the sample introduced during solid phase extraction. The results of analysis by the chromatography apparatus did not fluctuate even when the amount of water and the flow rate varied. [Example 3] The phenols contained in the sample water were analyzed in the same manner as in Example 1 except that the extraction by the solid phase extraction method and the analysis by the chromatographic apparatus were performed in the same manner as in Example 1. .

After the solid phase extraction of the sample water, benzyl halide was used instead of the alkylation treatment of phenols.
Halogenated benzylation was performed as follows. 100 μl of pentafluorobenzyl bromide was placed in a container containing a concentrated liquid concentrated until the liquid volume became about 0.1 ml.
and 20 mg of potassium carbonate, then 10 ml of acetone was further added, and the mixture was refluxed at 70 ° C. for 3 hours. As a result, the phenol was subjected to halogenated benzylation. Next, after cooling the liquid after reflux, 50 ml of diethyl ether, 2 ml of ethyl acetate, and 1 ml of pure water were added to the liquid and shaken. After removing the aqueous layer generated by shaking, anhydrous sodium sulfate was added to the organic layer, and the mixture was concentrated using a rotary evaporator.

To a concentrate obtained by this concentration, a mixed solution of acetone, diethyl ether and hexane (diethyl ether: acetone: hexane = 1: 1: 98) was added.
Then, 100 ng of phenanthrene deuteride was added as an internal standard to obtain a liquid to be injected into the chromatography apparatus. As the chromatography device, a device in which a gas chromatography device and a negative ion chemical ionization type mass spectrometer were combined was used. The gas chromatography apparatus is “HP6890” of Hewlett-Packard Company, and the mass spectrometer is “JMS-AMSUN” of JEOL.

From the results of the analysis, the recovery rate was calculated for each of the ten phenols in the sample water and found to be between 80% and 112%. This value is
It means that a good analysis was performed. When the reproducibility was examined by repeating the extraction and analysis by the above procedure five times, the relative standard deviation was within 15%, and sufficient reproducibility (analysis accuracy) was obtained. The total time required for extraction and analysis by the above procedure was about 9 hours.

The flow rate of the sample water during the solid phase extraction was 2,000 m
1 and the water flow rate was 100 ml / min. Extraction and analysis of all other points by the above procedure showed no change in the recovery rate. The flow rate of the sample water during the solid phase extraction was set to 500 ml, the flow rate was set to 300 ml / min,
All other points were extracted and analyzed by the above procedure, and there was no change in the recovery rate. Furthermore, the relative standard deviation when performing five repeated measurements by these methods is:
All were within 15%, and the reproducibility (analysis accuracy) was sufficient.

When the measurement of the standard sample used at the time of preparing the calibration curve was repeated five times, and the detection limit was three times the standard deviation obtained from the result, the detection limit in this example was 0.1. It was 2 ng / l. As described above, according to the method of this example, it is possible to analyze both bisphenol A and chlorophenols and alkylphenols by a single analysis using a chromatographic apparatus, and furthermore, the sample introduced during solid phase extraction. The results of analysis by the chromatography apparatus did not fluctuate even when the amount of water and the flow rate varied. Example 4 Phenols contained in sample water were analyzed in the same manner as in Example 1 except that the extraction by the solid phase extraction method and the analysis by a chromatographic apparatus were performed in the same manner as in Example 1. .

After the solid phase extraction of the sample water, TMS was carried out instead of the phenol alkylation treatment. TMS conversion was performed as follows. BSTFA is placed in a container containing the concentrated liquid concentrated to a volume of about 0.1 ml.
0 μl was added and kept at room temperature for 1 hour. This allows
Phenols were converted to TMS. To the liquid after TMS conversion, 1 phenanthrene deuteride was used as an internal standard.
By adding 00 ng, a liquid to be injected into the chromatography device was obtained.

From the results of the analysis, the recovery rate was calculated for each of the ten phenols in the sample water, and the values were between 88% and 109%. This value is
It means that a good analysis was performed. In addition, when the reproducibility was examined by repeating extraction and analysis by the above procedure five times, the relative standard deviation was within 10%, and sufficient reproducibility (analysis accuracy) was obtained. The total time required for extraction and analysis by the above procedure was about 6 hours.

The water flow rate of the sample water during the solid phase extraction was 2,000 m
1 and the water flow rate was 100 ml / min. Extraction and analysis of all other points by the above procedure showed no change in the recovery rate. The flow rate of the sample water during the solid phase extraction was set to 500 ml, the flow rate was set to 300 ml / min,
All other points were extracted and analyzed by the above procedure, and there was no change in the recovery rate. Furthermore, the relative standard deviation when performing five repeated measurements by these methods is:
All were within 10%, and the reproducibility (analysis accuracy) was sufficient.

When the measurement of the standard sample used at the time of preparing the calibration curve was repeated five times, and the detection limit was set to a value three times the standard deviation obtained from the result, the detection limit in this example was 4 ng / kg. l. As mentioned above,
According to the method of this embodiment, the analysis of bisphenol A and both chlorophenols and alkylphenols can be performed by a single analysis using a chromatographic apparatus. Even if the speed fluctuated, there was no fluctuation in the analysis result by the chromatography apparatus. Example 5 Phenols contained in the sample water were analyzed in the same manner as in Example 1 except that the extraction by the solid phase extraction method and the analysis by the chromatographic apparatus were performed in the same manner as in Example 1. .

In the same suction filter as in Example 1, a disk-type solid phase extractant made of silica gel having an octadecyl group (reverse phase system C18) (“Epore Disc C1” manufactured by 3M) was used.
8 ") and a disk-type solid phase extractant (" Mpore Disc SDB-XD "manufactured by 3M) made of a styrene divinylbenzene copolymer were mounted so as to overlap in the channel direction. "Empore Disk C18" was arranged upstream of "Empore Disk SDB-XD". Example 1
In the above, 10 ml of ethyl acetate and 10 ml of methanol were used as the recovery solvent, but here, 10 ml of ethyl acetate and 10 ml of dichloromethane were used.

From the results of the analysis, the recovery rate was calculated for each of the ten phenols in the sample water, and the values were between 82% and 121%. This value is
It means that a good analysis was performed. When the reproducibility was examined by repeating the extraction and analysis by the above procedure five times, the relative standard deviation was within 15%, and sufficient reproducibility (analysis accuracy) was obtained. The total time required for extraction and analysis by the above procedure was about 6 hours.

The flow rate of the sample water during the solid phase extraction was 2,000 m
1 and the water flow rate was 100 ml / min. Extraction and analysis of all other points by the above procedure showed no change in the recovery rate. The flow rate of the sample water during the solid phase extraction was set to 500 ml, the flow rate was set to 300 ml / min,
All other points were extracted and analyzed by the above procedure, and there was no change in the recovery rate. Furthermore, the relative standard deviation when performing five repeated measurements by these methods is:
All were within 15%, and the reproducibility (analysis accuracy) was sufficient.

When the measurement of the standard sample used at the time of preparing the calibration curve was repeated five times and the detection limit was set to a value three times the standard deviation obtained from the result, the detection limit in this example was 2 ng / l. As mentioned above,
According to the method of this embodiment, the analysis of bisphenol A and both chlorophenols and alkylphenols can be performed by a single analysis using a chromatographic apparatus. Even if the speed fluctuated, there was no fluctuation in the analysis result by the chromatography apparatus. In this example, dichloromethane was used as a recovery solvent, but the amount used was 10 ml.
And a small amount (1/10 or less of Comparative Example 2 described later). Example 6 As a solid phase extractant, a cartridge type styrene divinylbenzene copolymer ("EN" manufactured by Spelco)
VI-ChromP ": 0.5 g of styrene divinylbenzene copolymer particles (filled in a syringe) and a styrene divinylbenzene copolymer having a sulfonic acid group (" CXP "manufactured by Spelco Co.) 0.5 g was prepared. Using these, the particles made of a styrene divinyl benzene copolymer and the particles made of a styrene divinyl benzene copolymer having a sulfonic acid group are placed in the syringe at the outlet of the syringe. On the side, a cartridge-type solid phase extractant packed separately was obtained.

The obtained cartridge-type solid phase extractant was
Automated solid-phase extraction device (ASPEC-XL by Gilson)
i "). A liquid chromatography-mass spectrometer was connected online to this apparatus. This mass spectrometer is "LCQ" (electrospray ionization type mass spectrometer) manufactured by ThermoQuest. Liquid chromatography is based on Hewlett-Packard's HP1
100 ".

First, after conditioning, the apparatus was operated, and the flow rate of 500 ml of sample water was 15 m.
Water was passed at 1 / min. As a result, the phenols in the sample water were adsorbed to the two solid-phase extractants of the styrene divinyl benzene copolymer and the styrene divinyl benzene copolymer having a sulfonic acid group. Next, 2 ml of acetone and 2 ml of methanol were continuously flown into the automatic solid-phase extraction device. As a result, an extract in which phenols were eluted in acetone and methanol was recovered. The obtained extract is concentrated in an automatic solid-phase extraction device by a flow of nitrogen gas until the liquid volume becomes about 1 ml. The concentrated extract was automatically injected into a liquid chromatography-mass spectrometer for analysis.

From the results of the analysis, the recovery rate was calculated for each of the ten phenols in the sample water, and the values were between 92% and 113%. This value is
It means that a good analysis was performed. In addition, when the reproducibility was examined by repeating extraction and analysis by the above procedure five times, the relative standard deviation was within 7%, and sufficient reproducibility (analysis accuracy) was obtained. The total time required for extraction and analysis by the above procedure was about 3 hours.

The flow rate of the sample water during the solid phase extraction was 2,000 m
1 and the water flow rate was 15 ml / min. All other points were extracted and analyzed by the above procedure, and there was no change in the recovery rate. In addition, when the flow rate of the sample water at the time of the solid phase extraction was 500 ml, the flow rate was 25 ml / min, and all other points were extracted and analyzed by the above procedure, the recovery rate did not change. Furthermore, the relative standard deviations when performing five repeated measurements by these methods were all within 7%, and the reproducibility (analysis accuracy) was sufficient.

When the measurement of the standard sample used at the time of preparing the calibration curve was repeated five times and the detection limit was set to a value three times the standard deviation obtained from the result, the detection limit in this example was 10 ng / day. l. As described above, according to the method of this example, it is possible to analyze both bisphenol A and chlorophenols and alkylphenols by a single analysis using a chromatographic apparatus, and furthermore, the sample introduced during solid phase extraction. The results of analysis by the chromatography apparatus did not fluctuate even when the amount of water and the flow rate varied. [Comparative Example 1] The phenols contained in the sample water were analyzed by the same method as in Example 1 except that the extraction by the solid phase extraction method and the analysis by the chromatographic apparatus were performed in the same manner as in Example 1. .

The same suction filter as in Example 1 was equipped only with a disk-type solid phase extractant ("Mpore Disc SDB-XD" manufactured by 3M) comprising a styrenedivinylbenzene copolymer. From this analysis result, the recovery rate was calculated for each of the ten types of phenols in the sample water, and the values were from 75% to 110%. From the value of the recovery rate, it is understood that the analysis result by the method of Comparative Example 1 is slightly inferior to the results of Examples 1 to 6.

Further, the extraction and analysis by the above procedure
When the reproducibility was examined by repeating this process twice, the relative standard deviation was within 10%, and sufficient reproducibility (analysis accuracy) was obtained. The total time required for extraction and analysis by the above procedure was about 6 hours. The flow rate of the sample water during the solid phase extraction was set to 2000 ml, and the flow rate was set to 100
When the extraction and analysis were performed by the above procedure for all other points, there was no change in the recovery rate. In addition, when the flow rate of the sample water at the time of the solid phase extraction was 500 ml, the flow rate was 300 ml / min, and all other points were extracted and analyzed by the above procedure, the recovery rate did not change. Furthermore, the relative standard deviations when performing five repeated measurements by these methods were all within 10%, and the reproducibility (analysis accuracy) was sufficient.

When the measurement of the standard sample used at the time of preparing the calibration curve was repeated five times and the detection limit was three times the standard deviation obtained from the result, the detection limit in this comparative example was 2 ng / kg. l. Comparative Example 2 Sample water was analyzed according to the method described in the provisional manual, in which extraction by liquid-liquid extraction and analysis by gas chromatography-mass spectrometer were performed. The analysis of alkylphenols and the analysis of bisphenol A and chlorophenols were performed separately.

From the results of the analysis, the recovery rate was calculated for each of the ten phenols in the sample water, and the values were from 75% to 114%. From the value of the recovery rate, it is understood that the analysis result by the method of Comparative Example 1 is slightly inferior to the results of Examples 1 to 6. In addition, when the reproducibility was examined by repeating extraction and analysis by the above procedure five times, the relative standard deviation was within 10%, and sufficient reproducibility (analysis accuracy) was obtained. The time required for extraction and analysis by the above procedure was about 8 hours for each analysis.

The total amount of dichloromethane required for analyzing the ten phenols was 200 ml. The measurement of the standard sample used at the time of preparing the calibration curve was repeated five times, and the detection limit was 4 ng / l in this comparative example, assuming that a value three times the standard deviation obtained from the result was used as the detection limit. Was.

From the results of the above Examples and Comparative Examples, according to the method of the present invention, a low concentration of phenol at the ng / l level can be prepared without using a large amount of harmful solvent, dichloromethane, in a provisional manual. It can be understood that the analysis can be performed in a shorter time than the method of performing extraction by the liquid-liquid extraction method described in (1). Further, by using a device in which the automatic extraction device and the chromatography device are connected online, analysis can be performed in a shorter time.

[0066]

As described above, according to the method of the present invention, a plurality of types of phenols contained in the sample water can be obtained by performing the extraction with the solid phase extraction method and then performing the analysis with the chromatography device. In the method of analyzing phenol, bisphenol A and / or both chlorophenols and alkylphenols can be analyzed by a single analysis using a chromatographic apparatus, and the amount and flow rate of the sample to be introduced during solid phase extraction. Can be prevented from fluctuating in the analysis result by the chromatography device even if the value fluctuates. Further, phenols at a low concentration of ng / l can be analyzed in a short time without using a large amount of harmful solvents.

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Claims (2)

[Claims] 1. A method for analyzing a plurality of types of phenols contained in a sample water by performing an analysis with a chromatography device after performing an extraction by a solid phase extraction method, wherein the extraction is performed by using an organic functional group. Two or more solid-phase extractants selected from silica gel having a group, styrene-divinylbenzene copolymer, styrene-divinylbenzene copolymer having an anion exchange group, silica gel having an anion exchange group, and activated carbon A method for analyzing phenols, characterized in that the method is performed by using the method. 2. The method for analyzing phenols according to claim 1, wherein the phenols to be analyzed are bisphenol A and / or chlorophenols and alkylphenols.