WO2013024518A1 - 酸化ハロゲン酸分析方法 - Google Patents
酸化ハロゲン酸分析方法 Download PDFInfo
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- WO2013024518A1 WO2013024518A1 PCT/JP2011/068456 JP2011068456W WO2013024518A1 WO 2013024518 A1 WO2013024518 A1 WO 2013024518A1 JP 2011068456 W JP2011068456 W JP 2011068456W WO 2013024518 A1 WO2013024518 A1 WO 2013024518A1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/72—Mass spectrometers
- G01N30/7233—Mass spectrometers interfaced to liquid or supercritical fluid chromatograph
- G01N30/724—Nebulising, aerosol formation or ionisation
- G01N30/7266—Nebulising, aerosol formation or ionisation by electric field, e.g. electrospray
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/96—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation using ion-exchange
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/29—Chlorine compounds
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
- G01N2030/8809—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample
- G01N2030/8872—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample impurities
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/26—Conditioning of the fluid carrier; Flow patterns
- G01N30/28—Control of physical parameters of the fluid carrier
- G01N30/34—Control of physical parameters of the fluid carrier of fluid composition, e.g. gradient
Definitions
- the present invention relates to a halogenated acid analysis method for analyzing halogenated acid such as perchloric acid, chloric acid, bromic acid and iodic acid with high sensitivity.
- bromic acid has a problem of carcinogenicity.
- regulations on the content of bromic acid in tap water have been strengthened in Japan. With such stricter regulations or growing concerns about pollution of the living environment such as river water, higher sensitivity and higher accuracy are required for quantitative analysis of halogen oxides.
- halogen oxyhalide exists as a halogen oxyhalide ion in a solution such as water
- Ion chromatography using an electric conductivity detector as a detector has been conventionally used for quantitative analysis (Patent Document 1, etc.). reference).
- Ion chromatography is a separation method that uses a column with an ion exchange resin or the like as a stationary phase and an electrolyte solution as a mobile phase.
- Various ion ions in the sample solution can exchange ions with the ion exchange resin ( Each ion is separated and eluted from the column according to the difference in the selection factor.
- it is difficult to quantify a very small amount of halogen oxyhalic acid with such a conventional analysis method and the measurement accuracy is not sufficient.
- pretreatment such as concentration for increasing the concentration of the analysis target component in the sample is essential, and it is difficult to increase the analysis throughput.
- Non-Patent Document 1 proposes a method for analyzing halogen oxyacid by ion chromatography using an electrospray ionization (ESI) mass spectrometer as a detector.
- FIG. 3 is a schematic configuration diagram of an analyzer based on the proposed method.
- the mobile phase (potassium hydroxide) sucked from the mobile phase container 11 by the liquid feed pump 12 is sent to the ion exchange column 14 through the injector 13.
- a sample containing bromine, bromic acid, chloric acid, perchloric acid or the like is introduced from the injector 13 into the mobile phase, these components are separated and eluted when passing through the ion exchange column 14.
- a suppressor 15 is inserted between the ion exchange column 14 and the mass spectrometer 17 in order to avoid introduction of this into the mass spectrometer 17. .
- the background noise can be reduced and the clogging of the ESI spray nozzle due to the salt derived from the mobile phase can be prevented.
- methanol at a constant flow rate is added to the mobile phase in the methanol addition unit 16 in order to increase the ionization efficiency.
- the mass spectrometer 17 acquires a mass chromatogram (extracted ion chromatogram) corresponding to each component by executing MRM measurement in the negative ionization mode.
- the target component is utilized by utilizing the difference in mass-to-charge ratio. Only can be detected.
- the mass spectrometer 17 and the suppressor 15 in combination the target component can be detected with higher sensitivity than in the case of detection using an electrical conductivity detector.
- potassium hydroxide used as a mobile phase is a substance that requires careful handling as specified by the Japanese law as a deleterious substance.
- the use of such a substance as a mobile phase is also an effective analytical task. It becomes an obstacle.
- the present invention has been made to solve the above-mentioned problems, and its main purpose is to make use of a general high-performance liquid chromatograph mass spectrometer that is simpler and more versatile than the above-described conventional method.
- An object of the present invention is to provide a method for analyzing halogen oxyacid that can quantitatively analyze halogen oxyacid with high sensitivity and high accuracy.
- the above-described combination of a mobile phase having a high non-volatile salt concentration, an ion exchange column, and a mass spectrometer can achieve high detection sensitivity, but it is inevitable to use a suppressor that removes unwanted ions.
- the present inventor replaced the ion exchange column as a column, and with respect to hydrophobicity, the inventor has characteristics almost equal to or close to those of a general reverse phase column (reverse phase chromatography column), while having high ionicity.
- the inventors came up with the use of a column with an ion exchange function so that polar substances can be retained.
- the halogenated oxyacid analysis method according to the present invention has been made based on the above knowledge, and is a halogenated oxyacid analysis method for quantitatively analyzing a halogenated oxyacid in a sample, Using a liquid chromatograph mass spectrometer in which a high-performance liquid chromatography column and an atmospheric pressure ionization mass spectrometer are connected, and using a reverse phase column having an ion exchange function as the column, an organic acid or an organic acid salt buffer It is characterized in that a mixed liquid of a liquid and an organic solvent is used as a mobile phase to detect various components including halogen oxyacid in the sample after separation.
- organic acids are acetic acid, formic acid, oxalic acid, lactic acid, tartaric acid, and citric acid. These are carboxylic acids containing trifluoroacetic acid and the like, and as the organic acid salt buffer, for example, ammonium formate buffer or ammonium acetate buffer may be used.
- the organic solvent is not particularly limited, but typically acetonitrile can be used.
- the mobile phase can be a mixed solution of ammonium formate buffer and acetonitrile. At that time, it is preferable to perform a gradient analysis in which the ammonium formate concentration is increased over time.
- ammonium formate contains positively charged ammonium ions and negatively charged formate ions, and contributes to the action of retaining halogen oxide ions in the sample by the ion exchange function of the stationary phase in the column.
- an organic acid salt buffer such as ammonium formate is a volatile salt, even if it is introduced into, for example, an ESI ion source of a mass spectrometer, problems such as precipitation hardly occur.
- an organic solvent such as acetolitol is a polar solvent, which contributes to the hydrophobic interaction (that is, reverse phase function) of the stationary phase in the column, and further ionizes sample molecules efficiently in, for example, an ESI source of a mass spectrometer. It also contributes.
- reverse phase column having an ion exchange function a column in which an ODS (OctaDecylSylyl) group and an ion acceptor are introduced on the surface and a carrier such as porous silica as a stationary phase can be used.
- a column packed with a mixture of a carrier for reverse phase chromatography having an ODS group introduced on its surface and a carrier for ion chromatography (or ion exchange chromatography) such as an ion exchange resin can be used.
- the column has both a component separation function by ion exchange and a component separation function in reverse phase mode, so that not only ions derived from halogen oxyacid, which is a strong ionic compound, but also nonionic compounds in the sample are separated. Is done.
- the halogen oxyacid analysis method of the present invention it is not necessary to provide a suppressor between the column and the mass spectrometer, and it is also necessary to mix an organic solvent in the flow path between the suppressor and the mass spectrometer. Therefore, the analysis can be performed with an apparatus configuration of a very general high performance liquid chromatograph mass spectrometer. Therefore, even when analyzing substances other than halogen oxyacids, it is not necessary to change the apparatus configuration one by one, and the analysis work is not complicated, which is advantageous for improving the throughput. In addition, since a general mobile phase that is easy to handle can be used, the analysis work is also simple in this respect.
- FIG. 1 is a schematic configuration diagram of an example of HPLC / MS for carrying out the analysis method according to the present invention.
- the first liquid feed pump 2 sucks the mobile phase A from the first mobile phase container 1 and sends it out at a predetermined flow rate
- the second liquid feed pump 4 sucks the mobile phase B from the second mobile phase container 3. Then, it is sent out at a predetermined flow rate.
- Mobile phase A and mobile phase B are mixed by a mixer 5 and sent to a column 7 via an injector 6.
- a liquid sample to be analyzed is injected into the mobile phase using a microsyringe or the like, and the liquid sample is sent to the column 7 along the flow of the mobile phase.
- Various components in the sample are separated when passing through the column 7 and are eluted from the outlet of the column 7 with a time difference.
- the eluate from the column 7 is sent to a mass spectrometer 8 as a detector and sprayed from the spray nozzle of the ESI ion source 81 into a substantially atmospheric pressure atmosphere, and the component molecules contained in the eluate are ionized.
- the generated ions are converged by the ion lens 82, separated by the quadrupole mass filter 83 according to the mass-to-charge ratio, and reach the ion detector 84 to be detected.
- the type of component contained in the eluate that is, the type of component used for mass spectrometry, changes with time.
- the quadrupole mass filter 83 is driven in an ion selection (SIM) mode so as to detect ions having one or more preset mass-to-charge ratios.
- SIM ion selection
- the detection signal obtained by the ion detector 84 reflects each component, and a data chromatogram corresponding to the target component oxyhalic acid compound is created based on the detection signal by a data processing unit (not shown).
- the target component is qualitatively and quantitatively determined based on the peak appearing in the chromatogram.
- the ion source of the mass spectrometer 8 is not limited to the one based on ESI, but may be based on the atmospheric pressure chemical ionization method (APCI) or the atmospheric pressure photoionization method (APPI).
- the mass separator may not be a quadrupole mass filter, and may be a time-of-flight mass analyzer, for example.
- a mass spectrometer capable of MS / MS analysis or MS n analysis, such as a triple quadrupole mass spectrometer, may be used.
- the column 7 and the mass spectrometer 8 are directly connected, and there is no apparatus for performing any treatment on the solution such as a suppressor in between.
- the HPLC column 7 is not an ion exchange column, but a column packed with a stationary phase having both an ion exchange function and a component separation function by a reverse phase mode (that is, a component separation function by hydrophobic interaction).
- the Scherzo C18 series manufactured by Intact see ⁇ URL: http://www.imtakt.com/jp/Products/Scherzo/index.htm>) can be used.
- a column packed with a mixture of a carrier for reverse phase chromatography having an ODS group introduced on the surface thereof and a carrier for ion chromatography such as an ion exchange resin can be used.
- an organic acid salt buffer such as ammonium formate buffer or ammonium acetate buffer
- a mobile phase mixed with an organic solvent such as acetonitrile
- a gradient analysis is performed in which the concentration of the organic acid salt buffer is changed over time.
- a mixed phase of ammonium formate having a concentration sufficiently higher than the ammonium formate concentration of mobile phase A and acetonitrile is used as mobile phase A, and a mixture of mobile phase B is used as mobile phase B.
- Gradient analysis is performed by gradually increasing the ratio from a low ratio, for example, 0%.
- the halogenated halide ions in the sample are retained in the ion acceptor of the column 7 and further differ as the ammonium formate concentration increases. Due to the large difference in the retention capacity for the different types of halogen oxide ions, different types of halogen oxides are eluted from the column 7 with sufficient temporal differences. On the other hand, nonionic compounds contained in the sample are separated by the hydrophobic interaction of ODS. Therefore, the combination of the mobile phase and the column 7 separates various components contained in the sample, including different types of halogen oxyacids and nonionic compounds.
- FIG. 2 shows a mass chromatogram obtained by measuring and detecting a perchloric acid standard product (10 ppb) and a bromic acid standard product (100 ppb) under the above analysis conditions. From FIG. 2, it can be seen that perchloric acid and bromic acid are detected with a sufficient holding time difference, and that a background that hinders quantification hardly appears. This is the result of the measurement data using a triple quadrupole mass spectrometer, which is due to the high selectivity of the MRM measurement of the triple quadrupole mass spectrometer. From this result, it can be confirmed that sufficient performance for quantifying bromic acid, perchloric acid, etc. contained in tap water or river water can be ensured.
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Abstract
Description
高速液体クロマトグラフィのカラムと大気圧イオン化質量分析計とを接続した液体クロマトグラフ質量分析計を使用し、前記カラムとしてイオン交換機能を持たせた逆相カラムを用いるとともに、有機酸又は有機酸塩緩衝液と有機溶媒との混合液を移動相として、試料中の酸化ハロゲン酸を含む各種成分を分離した上で検出することを特徴としている。
分析条件は次の通りである。
・装置:LCMS-8030(島津製作所製)
・カラム:インタクト社製 Scherzo SM-C18(内径2.0mm、長さ50mm、充填物粒子径3μm)
・移動相A:1mM 蟻酸アンモニウム緩衝液
・移動相B:100mM 蟻酸アンモニウム緩衝液+アセトニトリル(混合比 1:9)
・カラム流速:0.25mL/min
・グラジエント時間プログラム:0%(0分)-60%(6.0分)移動相B
・カラム温度:35℃
また、質量分析計8でのイオン化法はネガティブイオンモードである。
2…第1送液ポンプ
3…第2移動相容器
4…第2送液ポンプ
5…混合器
6…インジェクタ
7…カラム
8…質量分析計
81…ESIイオン源
82…イオンレンズ
83…四重極マスフィルタ
84…イオン検出器
Claims (3)
- 試料中の酸化ハロゲン酸を定量分析する酸化ハロゲン酸分析方法であって、
高速液体クロマトグラフィのカラムと大気圧イオン化質量分析計とを接続した液体クロマトグラフ質量分析計を使用し、前記カラムとしてイオン交換機能を持たせた逆相カラムを用いるとともに、有機酸又は有機酸塩緩衝液と有機溶媒との混合液を移動相として、試料中の酸化ハロゲン酸を含む各種成分を分離した上で検出することを特徴とする酸化ハロゲン酸分析方法。 - 請求項1に記載の酸化ハロゲン酸分析方法であって、
前記カラムは表面にODS基とイオン受容体とを導入した担体を固定相としたものであることを特徴とする酸化ハロゲン酸分析方法。 - 請求項1又は2に記載の酸化ハロゲン酸分析方法であって、
前記移動相は蟻酸アンモニウム緩衝液とアセトニトリルとの混合液であり、時間経過に伴い蟻酸アンモニウム濃度を上昇させるグラジエント分析を行うことを特徴とする酸化ハロゲン酸分析方法。
Priority Applications (3)
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US14/238,228 US20140179018A1 (en) | 2011-08-12 | 2011-08-12 | Method for analyzing halogen oxoacids |
JP2013528852A JP5696787B2 (ja) | 2011-08-12 | 2011-08-12 | 酸化ハロゲン酸分析方法 |
PCT/JP2011/068456 WO2013024518A1 (ja) | 2011-08-12 | 2011-08-12 | 酸化ハロゲン酸分析方法 |
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PCT/JP2011/068456 WO2013024518A1 (ja) | 2011-08-12 | 2011-08-12 | 酸化ハロゲン酸分析方法 |
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WO2013024518A1 true WO2013024518A1 (ja) | 2013-02-21 |
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PCT/JP2011/068456 WO2013024518A1 (ja) | 2011-08-12 | 2011-08-12 | 酸化ハロゲン酸分析方法 |
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US (1) | US20140179018A1 (ja) |
JP (1) | JP5696787B2 (ja) |
WO (1) | WO2013024518A1 (ja) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2017067658A (ja) * | 2015-09-30 | 2017-04-06 | 東ソー株式会社 | イオン化合物のイオン変換方法及びイオン変換装置 |
JP2017067660A (ja) * | 2015-09-30 | 2017-04-06 | 東ソー株式会社 | イオン化合物のイオン変換方法及びイオン変換装置 |
JP2017067661A (ja) * | 2015-09-30 | 2017-04-06 | 東ソー株式会社 | イオン化合物のイオン変換方法及びイオン変換装置 |
EP3141894A4 (en) * | 2014-05-08 | 2017-11-15 | Showa Denko K.K. | Method, column, and device for analyzing organic acid by mass spectrometry |
CN109154291A (zh) * | 2016-09-26 | 2019-01-04 | 株式会社岛津制作所 | 切换阀、二元泵以及具备该二元泵的液相色谱仪 |
US20220026404A1 (en) * | 2018-11-28 | 2022-01-27 | Shimadzu Corporation | Analyzing method for azo compound |
Citations (3)
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JP2002249517A (ja) * | 2000-12-19 | 2002-09-06 | Showa Denko Kk | 多孔質重合体粒子、耐アルカリ性陰イオン交換体、その製造方法、イオンクロマトグラフィー用カラム、及び陰イオン測定方法 |
JP2006242944A (ja) * | 2005-02-04 | 2006-09-14 | Showa Denko Kk | イオンクロマトグラフィー用充填剤 |
WO2010137132A1 (ja) * | 2009-05-27 | 2010-12-02 | 株式会社島津製作所 | 陰イオン測定方法 |
-
2011
- 2011-08-12 JP JP2013528852A patent/JP5696787B2/ja active Active
- 2011-08-12 WO PCT/JP2011/068456 patent/WO2013024518A1/ja active Application Filing
- 2011-08-12 US US14/238,228 patent/US20140179018A1/en not_active Abandoned
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JP2002249517A (ja) * | 2000-12-19 | 2002-09-06 | Showa Denko Kk | 多孔質重合体粒子、耐アルカリ性陰イオン交換体、その製造方法、イオンクロマトグラフィー用カラム、及び陰イオン測定方法 |
JP2006242944A (ja) * | 2005-02-04 | 2006-09-14 | Showa Denko Kk | イオンクロマトグラフィー用充填剤 |
WO2010137132A1 (ja) * | 2009-05-27 | 2010-12-02 | 株式会社島津製作所 | 陰イオン測定方法 |
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Title |
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KAZUAKI ITO ET AL.: "Enhanced Detection of Iodide in Seawater by Ion Chromatography Using an ODS Column Coated with Cetyltrimethylammonium", ANALYTICAL SCIENCES, vol. 17, no. 5, May 2001 (2001-05-01), pages 579 - 581 * |
T.TAKEUCHI ET AL.: "Indirect Fluorometric Detection in Micro High- Performance Liquid Chromatography", CHROMATOGRAPHIA, vol. 25, no. 12, December 1988 (1988-12-01), pages 1072 - 1074 * |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3141894A4 (en) * | 2014-05-08 | 2017-11-15 | Showa Denko K.K. | Method, column, and device for analyzing organic acid by mass spectrometry |
JP2017067658A (ja) * | 2015-09-30 | 2017-04-06 | 東ソー株式会社 | イオン化合物のイオン変換方法及びイオン変換装置 |
JP2017067660A (ja) * | 2015-09-30 | 2017-04-06 | 東ソー株式会社 | イオン化合物のイオン変換方法及びイオン変換装置 |
JP2017067661A (ja) * | 2015-09-30 | 2017-04-06 | 東ソー株式会社 | イオン化合物のイオン変換方法及びイオン変換装置 |
CN109154291A (zh) * | 2016-09-26 | 2019-01-04 | 株式会社岛津制作所 | 切换阀、二元泵以及具备该二元泵的液相色谱仪 |
CN109154291B (zh) * | 2016-09-26 | 2019-12-13 | 株式会社岛津制作所 | 切换阀、二元泵以及具备该二元泵的液相色谱仪 |
US20220026404A1 (en) * | 2018-11-28 | 2022-01-27 | Shimadzu Corporation | Analyzing method for azo compound |
Also Published As
Publication number | Publication date |
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JPWO2013024518A1 (ja) | 2015-03-05 |
JP5696787B2 (ja) | 2015-04-08 |
US20140179018A1 (en) | 2014-06-26 |
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