JP6133563B2 - Method and apparatus for measuring haloacetic acid - Google Patents
Method and apparatus for measuring haloacetic acid Download PDFInfo
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- JP6133563B2 JP6133563B2 JP2012210431A JP2012210431A JP6133563B2 JP 6133563 B2 JP6133563 B2 JP 6133563B2 JP 2012210431 A JP2012210431 A JP 2012210431A JP 2012210431 A JP2012210431 A JP 2012210431A JP 6133563 B2 JP6133563 B2 JP 6133563B2
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- 239000002253 acid Substances 0.000 title claims description 93
- 238000000034 method Methods 0.000 title claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 74
- DFPAKSUCGFBDDF-UHFFFAOYSA-N Nicotinamide Chemical compound NC(=O)C1=CC=CN=C1 DFPAKSUCGFBDDF-UHFFFAOYSA-N 0.000 claims description 38
- 239000012670 alkaline solution Substances 0.000 claims description 28
- 238000010438 heat treatment Methods 0.000 claims description 23
- 239000000126 substance Substances 0.000 claims description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 229960003966 nicotinamide Drugs 0.000 claims description 19
- 235000005152 nicotinamide Nutrition 0.000 claims description 19
- 239000011570 nicotinamide Substances 0.000 claims description 19
- 150000001450 anions Chemical class 0.000 claims description 17
- 239000003513 alkali Substances 0.000 claims description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 13
- 230000005284 excitation Effects 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 6
- 125000000524 functional group Chemical group 0.000 claims description 6
- 238000004401 flow injection analysis Methods 0.000 claims description 3
- 150000003141 primary amines Chemical class 0.000 claims description 3
- 150000003335 secondary amines Chemical class 0.000 claims description 3
- 150000003512 tertiary amines Chemical class 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims 1
- 238000005349 anion exchange Methods 0.000 description 37
- 239000007788 liquid Substances 0.000 description 20
- 238000001514 detection method Methods 0.000 description 18
- JXTHNDFMNIQAHM-UHFFFAOYSA-N dichloroacetic acid Chemical compound OC(=O)C(Cl)Cl JXTHNDFMNIQAHM-UHFFFAOYSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- 238000011088 calibration curve Methods 0.000 description 11
- SIEILFNCEFEENQ-UHFFFAOYSA-N dibromoacetic acid Chemical compound OC(=O)C(Br)Br SIEILFNCEFEENQ-UHFFFAOYSA-N 0.000 description 10
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 10
- 238000005259 measurement Methods 0.000 description 8
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 7
- 229960005215 dichloroacetic acid Drugs 0.000 description 7
- 238000010586 diagram Methods 0.000 description 6
- 229910021642 ultra pure water Inorganic materials 0.000 description 6
- 239000012498 ultrapure water Substances 0.000 description 6
- 239000002699 waste material Substances 0.000 description 6
- UCZDDMGNCJJAHK-UHFFFAOYSA-N 2,2-dibromo-2-chloroacetic acid Chemical compound OC(=O)C(Cl)(Br)Br UCZDDMGNCJJAHK-UHFFFAOYSA-N 0.000 description 5
- XSWVFEQKZFUULO-UHFFFAOYSA-N 2-bromo-2,2-dichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Br XSWVFEQKZFUULO-UHFFFAOYSA-N 0.000 description 5
- HLHNOIAOWQFNGW-UHFFFAOYSA-N 3-bromo-4-hydroxybenzonitrile Chemical compound OC1=CC=C(C#N)C=C1Br HLHNOIAOWQFNGW-UHFFFAOYSA-N 0.000 description 5
- GEHJBWKLJVFKPS-UHFFFAOYSA-N bromochloroacetic acid Chemical compound OC(=O)C(Cl)Br GEHJBWKLJVFKPS-UHFFFAOYSA-N 0.000 description 5
- 238000000691 measurement method Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 238000002189 fluorescence spectrum Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- -1 MBAA Chemical compound 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000005341 cation exchange Methods 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000005264 electron capture Effects 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- DFPAKSUCGFBDDF-ZQBYOMGUSA-N [14c]-nicotinamide Chemical compound N[14C](=O)C1=CC=CN=C1 DFPAKSUCGFBDDF-ZQBYOMGUSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 231100000135 cytotoxicity Toxicity 0.000 description 1
- 230000003013 cytotoxicity Effects 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 231100000025 genetic toxicology Toxicity 0.000 description 1
- 230000001738 genotoxic effect Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000008236 heating water Substances 0.000 description 1
- 210000004962 mammalian cell Anatomy 0.000 description 1
- 231100000350 mutagenesis Toxicity 0.000 description 1
- 238000002703 mutagenesis Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Description
本発明は、試料水中のハロ酢酸濃度を測定するハロ酢酸の測定方法および測定装置に関するものである。 The present invention relates to a haloacetic acid measurement method and a measurement apparatus for measuring a haloacetic acid concentration in a sample water.
ハロ酢酸は、主に塩素処理において有機物と塩素とが反応することによって生成される消毒副生成物であり、発がん性が疑われている物質である。このため、水道水質基準では、モノクロロ酢酸（ＭＣＡＡ）、ジクロロ酢酸（ＤＣＡＡ）、およびトリクロロ酢酸（ＴＣＡＡ）の基準濃度がそれぞれ２０μｇ／Ｌ、４０μｇ／Ｌ、および２００μｇ／Ｌ以下に定められている。このうち、ＴＣＡＡについては、基準濃度を５倍程度強化することが検討されている（非特許文献１参照）。また、臭素系のハロ酢酸は塩素系のハロ酢酸より毒性が強いことが報告されているために（非特許文献２参照）、将来的には９種類のハロ酢酸（ＭＣＡＡ、ＤＣＡＡ、ＴＣＡＡ、モノブロモ酢酸（ＭＢＡＡ）、ジブロモ酢酸（ＤＢＡＡ）、トリブロモ酢酸（ＴＢＡＡ）、ブロモクロロ酢酸（ＢＣＡＡ）、ブロモジクロロ酢酸（ＢＤＣＡＡ）、ジブロモクロロ酢酸（ＤＢＣＡＡ））が規制の対象になることも考えられる。 Haloacetic acid is a disinfection by-product produced mainly by the reaction between organic substances and chlorine in chlorination, and is a substance suspected of carcinogenicity. Therefore, in the tap water quality standards, the standard concentrations of monochloroacetic acid (MCAA), dichloroacetic acid (DCAA), and trichloroacetic acid (TCAA) are set to 20 μg / L, 40 μg / L, and 200 μg / L or less, respectively. Among these, for TCAA, it has been studied to reinforce the reference concentration by about 5 times (see Non-Patent Document 1). In addition, bromine-based haloacetic acid has been reported to be more toxic than chlorine-based haloacetic acid (see Non-Patent Document 2), so in the future, nine types of haloacetic acid (MCAA, DCAA, TCAA, monobromo) Acetic acid (MBAA), dibromoacetic acid (DBAA), tribromoacetic acid (TBAA), bromochloroacetic acid (BCAA), bromodichloroacetic acid (BDCAA), dibromochloroacetic acid (DBCAA)) may be subject to regulation.
従来までは、試料水中のハロ酢酸濃度はガスクロマトグラフ／電子捕獲型検出器（Gas Chromatography - Electron Capture Detector : GC-ECD）を利用して測定されていた。しかしながら、ＧＣ−ＥＣＤを構成する分析機器は高額であるために、ＧＣ−ＥＣＤを利用してハロ酢酸濃度を安価に測定することは難しい。また、ＧＣ−ＥＣＤを利用してハロ酢酸濃度を測定する場合、誘導体化処理などの複雑な前処理が必要になるために、ハロ酢酸濃度の測定に技術と時間とを要し、ハロ酢酸濃度を迅速に測定することが困難である。このような背景から、試料水中のハロ酢酸濃度を迅速、且つ、安価に測定可能な技術の提供が期待されていた。 Until now, the concentration of haloacetic acid in sample water was measured using a gas chromatograph / electron capture detector (GC-ECD). However, since the analytical instruments constituting the GC-ECD are expensive, it is difficult to measure the haloacetic acid concentration at low cost using the GC-ECD. In addition, when measuring the haloacetic acid concentration using GC-ECD, a complicated pretreatment such as a derivatization treatment is required. Therefore, the measurement of the haloacetic acid concentration requires technology and time. Is difficult to measure quickly. From such a background, provision of a technique capable of measuring the haloacetic acid concentration in the sample water quickly and inexpensively has been expected.
本発明は、上記課題に鑑みてなされたものであって、その目的は、試料水中のハロ酢酸濃度を安価、且つ、迅速に測定可能なハロ酢酸の測定方法および測定装置を提供することにある。 The present invention has been made in view of the above problems, and an object of the present invention is to provide a measurement method and a measurement apparatus for haloacetic acid capable of measuring the haloacetic acid concentration in a sample water at low cost and quickly. .
上記課題を解決し、目的を達成するために、本発明に係るハロ酢酸の測定方法は、ハロ酢酸を含む試料水にニコチン酸アミドとアルカリとを添加する第１ステップと、前記第１ステップ後の前記試料水を所定時間加熱する第２ステップと、前記第２ステップ後の前記試料水を冷却する第３ステップと、前記第３ステップ後の前記試料水に含まれる蛍光物質の蛍光強度を測定する第４ステップと、前記蛍光強度から前記ハロ酢酸の濃度を算出する第５ステップと、を含むことを特徴とする。 In order to solve the above problems and achieve the object, a method for measuring haloacetic acid according to the present invention includes a first step of adding nicotinamide and an alkali to sample water containing haloacetic acid, and after the first step. A second step of heating the sample water for a predetermined time, a third step of cooling the sample water after the second step, and measuring a fluorescence intensity of a fluorescent substance contained in the sample water after the third step And a fifth step of calculating the concentration of the haloacetic acid from the fluorescence intensity.
本発明に係るハロ酢酸の測定方法は、上記発明において、前記第４ステップが、励起波長および蛍光波長をそれぞれ３６５ｎｍおよび４５５ｎｍとして前記蛍光物質の蛍光強度を測定するステップを含むことを特徴とする。 The method for measuring haloacetic acid according to the present invention is characterized in that, in the above-mentioned invention, the fourth step includes a step of measuring the fluorescence intensity of the fluorescent substance by setting the excitation wavelength and the fluorescence wavelength to 365 nm and 455 nm, respectively.
本発明に係るハロ酢酸の測定方法は、上記発明において、前記アルカリが、水酸化ナトリウム又は水酸化カリウムであることを特徴とする。 The method for measuring haloacetic acid according to the present invention is characterized in that, in the above invention, the alkali is sodium hydroxide or potassium hydroxide.
本発明に係るハロ酢酸の測定方法は、上記発明において、前記試料水の加熱温度が９０℃、前記所定時間が３０分以上６０分以下の時間であることを特徴とする。 The method for measuring haloacetic acid according to the present invention is characterized in that, in the above invention, the heating temperature of the sample water is 90 ° C., and the predetermined time is 30 minutes or more and 60 minutes or less.
本発明に係るハロ酢酸の測定方法は、上記発明において、前記第１ステップが、ハロ酢酸を選択的に吸着する陰イオン交換体に前記試料水を通水するステップと、前記試料水を通水した後に陰イオン交換体にアルカリ溶液を通水するステップと、前記陰イオン交換体を通過したアルカリ溶液にニコチン酸アミドを添加するステップと、を含むことを特徴とする。 In the method for measuring haloacetic acid according to the present invention, in the above invention, the first step is a step of passing the sample water through an anion exchanger that selectively adsorbs haloacetic acid; And a step of passing an alkaline solution through the anion exchanger and a step of adding nicotinamide to the alkaline solution that has passed through the anion exchanger.
本発明に係るハロ酢酸の測定方法は、上記発明において、前記陰イオン交換体が、１級アミン、２級アミン、若しくは３級アミンを官能基に有する弱陰イオン交換体、又は、４級アンモニウム塩を官能基に有する強陰イオン交換体であることを特徴とする。 The method for measuring haloacetic acid according to the present invention is the above-mentioned invention, wherein the anion exchanger is a weak anion exchanger having a primary amine, secondary amine, or tertiary amine as a functional group, or quaternary ammonium. It is a strong anion exchanger having a salt as a functional group.
本発明に係るハロ酢酸の測定方法は、上記発明において、前記第１ステップが、前記陰イオン交換体に前記試料水を通水する前に該試料水をＡｇ／Ｈカラムに通水するステップを含むことを特徴とする。 In the haloacetic acid measurement method according to the present invention, in the above invention, the first step includes a step of passing the sample water through an Ag / H column before passing the sample water through the anion exchanger. It is characterized by including.
本発明に係るハロ酢酸の測定方法は、上記発明において、前記第１〜第４ステップが、フローインジェクション法を利用して前記蛍光物質の蛍光強度を測定するステップを含むことを特徴とする。 The method for measuring haloacetic acid according to the present invention is characterized in that, in the above invention, the first to fourth steps include a step of measuring the fluorescence intensity of the fluorescent substance using a flow injection method.
上記課題を解決し、目的を達成するために、本発明に係るハロ酢酸の測定装置は、ハロ酢酸を含む試料水にニコチン酸アミドとアルカリとを添加する手段と、ニコチン酸アミドとアルカリとが添加された前記試料水を所定時間加熱する手段と、前記所定時間加熱された前記試料水を冷却する手段と、冷却後の前記試料水に含まれる蛍光物質の蛍光強度を測定する手段と、前記蛍光強度から前記ハロ酢酸の濃度を算出する手段と、を備えることを特徴とする。 In order to solve the above-mentioned problems and achieve the object, a measuring apparatus for haloacetic acid according to the present invention comprises means for adding nicotinamide and alkali to sample water containing haloacetic acid, and nicotinamide and alkali. Means for heating the added sample water for a predetermined time; means for cooling the sample water heated for the predetermined time; means for measuring the fluorescence intensity of the fluorescent substance contained in the sample water after cooling; Means for calculating the concentration of the haloacetic acid from the fluorescence intensity.
本発明に係るハロ酢酸の測定方法および測定装置によれば、試料水中のハロ酢酸濃度を安価、且つ、迅速に測定することができる。 According to the measuring method and measuring apparatus for haloacetic acid according to the present invention, the haloacetic acid concentration in the sample water can be measured inexpensively and rapidly.
以下、図面を参照して、本発明の一実施形態であるハロ酢酸の測定方法について説明する。 Hereinafter, a method for measuring haloacetic acid according to an embodiment of the present invention will be described with reference to the drawings.
〔本発明の概念〕
本発明の発明者らは、鋭意研究を重ねてきた結果、ハロ酢酸を含む試料水にニコチン酸アミドとアルカリ（水酸化ナトリウム（ＮａＯＨ）又は水酸化カリウム（ＫＯＨ））とを添加した後、試料水を加熱、冷却することによって蛍光物質が生成されることを知見した。また、本発明の発明者らは、蛍光物質の励起蛍光スペクトルを測定したところ、図１に示すように、励起波長（ＥＸ）および蛍光波長（ＥＭ）がそれぞれ３６５ｎｍおよび４５５ｎｍの位置を中心としたピークを有することを知見した。なお、図１は、ＴＣＡＡを１０００μｇ／Ｌ含む試料水から得られた蛍光物質の励起蛍光スペクトルを示している。以上の知見から、本発明の発明者らは、励起波長および蛍光波長をそれぞれ３６５ｎｍおよび４５５ｎｍとして蛍光物質の蛍光強度を測定し、予め作成しておいた蛍光強度とハロ酢酸濃度との関係を示す検量線と測定された蛍光強度とを比較することによって、試料水中のハロ酢酸濃度を算出できるとの技術思想を想到するに至った。
[Concept of the present invention]
As a result of intensive studies, the inventors of the present invention have added nicotinamide and alkali (sodium hydroxide (NaOH) or potassium hydroxide (KOH)) to sample water containing haloacetic acid, It has been found that a fluorescent substance is produced by heating and cooling water. Further, the inventors of the present invention measured the excitation fluorescence spectrum of the fluorescent substance, and as shown in FIG. 1, the excitation wavelength (EX) and the fluorescence wavelength (EM) were centered at the positions of 365 nm and 455 nm, respectively. It was found to have a peak. FIG. 1 shows an excitation fluorescence spectrum of a fluorescent material obtained from a sample water containing 1000 μg / L of TCAA. Based on the above knowledge, the inventors of the present invention measure the fluorescence intensity of the fluorescent substance with the excitation wavelength and the fluorescence wavelength being 365 nm and 455 nm, respectively, and show the relationship between the fluorescence intensity and the haloacetic acid concentration prepared in advance. The technical idea that the haloacetic acid concentration in the sample water can be calculated by comparing the calibration curve with the measured fluorescence intensity has been conceived.
〔ハロ酢酸の測定方法〕
次に、図２を参照して、上記本発明の概念に基づいた本発明の一実施形態であるハロ酢酸の測定方法について説明する。図２は、本発明の一実施形態であるハロ酢酸の測定方法の流れを示すフローチャートである。
[Measurement method of haloacetic acid]
Next, a method for measuring haloacetic acid, which is an embodiment of the present invention based on the concept of the present invention, will be described with reference to FIG. FIG. 2 is a flowchart showing a flow of a method for measuring haloacetic acid according to an embodiment of the present invention.
図２に示すように、本発明の一実施形態であるハロ酢酸の測定方法では、始めに、試料水にニコチン酸アミドとアルカリ（ＮａＯＨ又はＫＯＨ）とを添加する（ステップＳ１）。なお、試料水の総量が６ｍＬである場合、濃度８〜４０％、好ましくは濃度４０％のニコチン酸アミドを１０ｍＬ添加し、濃度０．４〜１０ｍｏｌ／Ｌ、好ましくは濃度１ｍｏｌ／ＬのＮａＯＨ又はＫＯＨを４ｍＬ添加するとよい。 As shown in FIG. 2, in the method for measuring haloacetic acid according to an embodiment of the present invention, first, nicotinamide and alkali (NaOH or KOH) are added to sample water (step S1). When the total amount of sample water is 6 mL, 10 mL of nicotinamide having a concentration of 8 to 40%, preferably 40%, is added, and a concentration of 0.4 to 10 mol / L, preferably 1 mol / L of NaOH or Add 4 mL of KOH.
試料水にニコチン酸アミドとアルカリとを添加すると、次に、試料水を加熱する（ステップＳ２）。図３は、ＭＣＡＡ、ＤＣＡＡ、およびＴＣＡＡをそれぞれ１０００μｇ／Ｌ含む試料水について、加熱時間に伴う蛍光物質の蛍光強度の変化を評価した結果を示す図である。図３に示すように、蛍光物質の蛍光強度は加熱時間の増加に伴い増加し、加熱時間が３０分以上で平衡に達する。また、図示していないが、ＭＢＡＡ、ＤＢＡＡ、ＴＢＡＡ、ＢＣＡＡ、ＢＤＣＡＡ、およびＤＢＣＡＡをそれぞれ含む試料水においても、加熱時間が３０分以上で蛍光物質の蛍光強度が平衡に達した。このことから、試料水の加熱時間は３０〜６０分程度にするとよい。 Once nicotinamide and alkali are added to the sample water, the sample water is then heated (step S2). FIG. 3 is a diagram showing the results of evaluating the change in fluorescence intensity of the fluorescent substance with heating time for sample water containing 1000 μg / L each of MCAA, DCAA, and TCAA. As shown in FIG. 3, the fluorescence intensity of the fluorescent material increases as the heating time increases, and reaches an equilibrium after the heating time of 30 minutes or more. Moreover, although not shown in figure, also in the sample water each containing MBAA, DBAA, TBAA, BCAA, BDCAA, and DBCAA, the fluorescence intensity of the fluorescent substance reached an equilibrium after heating time of 30 minutes or more. Therefore, the heating time of the sample water is preferably about 30 to 60 minutes.
試料水の加熱が完了すると、次に、試料水を冷却する（ステップＳ３）。試料水を所定時間加熱した後に直ちに冷却することにより、蛍光物質の生成量を加熱完了時の蛍光物質の生成量に保持できる。次に、励起波長および蛍光波長をそれぞれ３６５ｎｍおよび４５５ｎｍとして蛍光物質の蛍光強度を測定する（ステップＳ４）。そして最後に、予め作成しておいた蛍光強度とハロ酢酸濃度との関係を示す検量線と測定された蛍光強度とを比較することによって、試料水中のハロ酢酸濃度を算出する（ステップＳ５）。 When the heating of the sample water is completed, the sample water is then cooled (step S3). By immediately cooling the sample water after heating it for a predetermined time, the amount of the fluorescent substance produced can be maintained at the amount of the fluorescent substance produced when the heating is completed. Next, the fluorescence intensity of the fluorescent material is measured by setting the excitation wavelength and the fluorescence wavelength to 365 nm and 455 nm, respectively (step S4). Finally, the haloacetic acid concentration in the sample water is calculated by comparing a calibration curve prepared in advance showing the relationship between the fluorescence intensity and the haloacetic acid concentration with the measured fluorescence intensity (step S5).
なお、ＭＣＡＡ、ＤＣＡＡ、ＴＣＡＡ、ＭＢＡＡ、ＤＢＡＡ、ＴＢＡＡ、ＢＣＡＡ、ＢＤＣＡＡ、およびＤＢＣＡＡの各ハロ酢酸について、蛍光物質の蛍光強度とハロ酢酸濃度との関係を示す検量線を作成したところ、図４（ａ）〜（ｃ）に示すように、ハロ酢酸濃度５０〜１０００μｇ／Ｌの範囲で直線性が高い検量線が得られた。このことから、予め作成しておいた蛍光強度とハロ酢酸濃度との関係を示す検量線と測定された蛍光強度とを比較することによって、ハロ酢酸濃度を精度高く測定できる。図４に示す検量線を作成する際には、アルカリとして１ｍｏｌ／ＬのＮａＯＨを試料水に添加し、試料水の加熱時間は６０分とした。 For each haloacetic acid of MCAA, DCAA, TCAA, MBAA, DBAA, TBAA, BCAA, BDCAA, and DBCAA, a calibration curve showing the relationship between the fluorescence intensity of the fluorescent substance and the haloacetic acid concentration was prepared. As shown in a) to (c), a calibration curve with high linearity was obtained in the haloacetic acid concentration range of 50 to 1000 μg / L. From this, it is possible to measure the haloacetic acid concentration with high accuracy by comparing a calibration curve indicating the relationship between the fluorescence intensity and the haloacetic acid concentration prepared in advance with the measured fluorescence intensity. When preparing the calibration curve shown in FIG. 4, 1 mol / L NaOH was added to the sample water as an alkali, and the heating time of the sample water was 60 minutes.
以上の説明から明らかなように、本発明の一実施形態であるハロ酢酸の測定方法では、ハロ酢酸を含む試料水にニコチン酸アミドとアルカリとを添加し、ニコチン酸アミドとアルカリとが添加された試料水を所定時間加熱した後、冷却し、冷却後の試料水に含まれる蛍光物質の蛍光強度を測定し、測定された蛍光強度からハロ酢酸の濃度を算出する。このような測定方法によれば、ガスクロマトグラフ／電子捕獲型検出器を利用することなく試料水中のハロ酢酸濃度を測定できるので、試料水中のハロ酢酸濃度を安価、且つ、迅速に測定することができる。 As is clear from the above description, in the method for measuring haloacetic acid according to one embodiment of the present invention, nicotinamide and alkali are added to sample water containing haloacetic acid, and nicotinamide and alkali are added. The sample water is heated for a predetermined time, cooled, the fluorescence intensity of the fluorescent substance contained in the cooled sample water is measured, and the concentration of haloacetic acid is calculated from the measured fluorescence intensity. According to such a measuring method, since the haloacetic acid concentration in the sample water can be measured without using a gas chromatograph / electron capture detector, the haloacetic acid concentration in the sample water can be measured inexpensively and quickly. it can.
なお、ハロ酢酸濃度を測定する際には、例えば図５に示すような測定装置を用いてハロ酢酸を分離、濃縮することが望ましい。図５は、ハロ酢酸の測定装置の構成を示す模式図である。図５に示すように、ハロ酢酸の測定装置１は、前処理部１０と、反応部２０と、検出部３０と、を主な構成要素として備えている。前処理部１０は、アルカリ溶液を貯留する容器１１ａと、ハロ酢酸を含む試料水を貯留する容器１１ｂと、任意のハロ酢酸濃度に調製した標準試料水を貯留する容器１１ｃと、超純水を貯留する容器１１ｄと、本発明に係る陰イオン交換体として機能する陰イオン交換カラム１２と、Ａｇ／Ｈカラム１３と、を備えている。 When measuring the haloacetic acid concentration, it is desirable to separate and concentrate the haloacetic acid using, for example, a measuring apparatus as shown in FIG. FIG. 5 is a schematic diagram showing the configuration of a measuring apparatus for haloacetic acid. As shown in FIG. 5, the haloacetic acid measurement apparatus 1 includes a pretreatment unit 10, a reaction unit 20, and a detection unit 30 as main components. The pretreatment unit 10 contains a container 11a for storing an alkaline solution, a container 11b for storing sample water containing haloacetic acid, a container 11c for storing standard sample water prepared to have an arbitrary haloacetic acid concentration, and ultrapure water. The container 11d to store, the anion exchange column 12 which functions as an anion exchanger based on this invention, and the Ag / H column 13 are provided.
容器１１ａと陰イオン交換カラム１２とは配管１４ａを介して接続されている。配管１４ａには、陰イオン交換カラム１２へのアルカリ溶液の供給／停止を制御する電磁弁１６ａと、容器１１ａ内のアルカリ溶液を陰イオン交換カラム１２に圧送するポンプ１５ａとが配設されている。 The container 11a and the anion exchange column 12 are connected via a pipe 14a. The pipe 14a is provided with an electromagnetic valve 16a that controls supply / stop of the alkaline solution to the anion exchange column 12, and a pump 15a that pumps the alkaline solution in the container 11a to the anion exchange column 12. .
容器１１ｂ，１１ｃ，１１ｄと陰イオン交換カラム１２とは配管１４ｂ〜１４ｄと配管１４ｅとを介して接続されている。配管１４ｂ〜１４ｄにはそれぞれ、配管１４ｅへの液体の供給／停止を制御する電磁弁１６ｂ〜１６ｄが配設されている。配管１４ｅには、配管１４ｂ〜１４ｄのいずれかから供給された液体を陰イオン交換カラム１２に圧送するポンプ１５ｂと、陰イオン交換カラム１２に圧送される液体中に含まれる塩類を除去するＡｇ／Ｈカラム１３とが配設されている。Ａｇ／Ｈカラム１３は、銀型陽イオン交換カラムと水素型陽イオン交換カラムとを組み合わせたカラムによって構成され、通水された液体中に含まれるハロゲンを吸着する機能を有している。陰イオン交換カラム１２の前にＡｇ／Ｈカラム１３を配設することにより、液体中の塩類が陰イオン交換カラム１２へのハロ酢酸の吸着率を低下させることを抑制できる。 The containers 11b, 11c, 11d and the anion exchange column 12 are connected via pipes 14b to 14d and a pipe 14e. Solenoid valves 16b to 16d for controlling the supply / stop of the liquid to the pipe 14e are disposed in the pipes 14b to 14d, respectively. The pipe 14e includes a pump 15b that pumps the liquid supplied from any of the pipes 14b to 14d to the anion exchange column 12, and an Ag / that removes salts contained in the liquid pumped to the anion exchange column 12. An H column 13 is provided. The Ag / H column 13 is composed of a combination of a silver-type cation exchange column and a hydrogen-type cation exchange column, and has a function of adsorbing halogen contained in the liquid that has passed through. By disposing the Ag / H column 13 in front of the anion exchange column 12, it is possible to suppress the salt in the liquid from lowering the adsorption rate of haloacetic acid to the anion exchange column 12.
陰イオン交換カラム１２は、トリハロメタンとハロ酢酸とを選択的に吸着する機能を有している。本実施形態では、陰イオン交換カラム１２は、ポリマーを母体とし、１級アミン、２級アミン、若しくは３級アミンを官能基に有する弱陰イオン交換カラム、又は、シリカを母体とし、４級アンモニウム塩を官能基に有する強陰イオン交換カラムによって構成されている。陰イオン交換カラム１２の液体流出側には配管１４ｆが接続されている。配管１４ｆには、陰イオン交換カラム１２から排出された液体を外部に排出する廃液用配管１４ｇと、陰イオン交換カラム１２から排出された液体を反応部２０に供給する検出用配管１４ｈとが接続されている。 The anion exchange column 12 has a function of selectively adsorbing trihalomethane and haloacetic acid. In this embodiment, the anion exchange column 12 is a weak anion exchange column having a polymer as a base and a primary amine, secondary amine, or tertiary amine as a functional group, or silica as a base, and a quaternary ammonium. It is comprised by the strong anion exchange column which has a salt in a functional group. A pipe 14 f is connected to the liquid outflow side of the anion exchange column 12. Connected to the pipe 14f are a waste liquid pipe 14g for discharging the liquid discharged from the anion exchange column 12 to the outside and a detection pipe 14h for supplying the liquid discharged from the anion exchange column 12 to the reaction unit 20. Has been.
反応部２０は、ニコチン酸アミドを貯留する容器２１と、容器２１内のニコチン酸アミドを検出用配管１４ｈに圧送するポンプ２２と、検出用配管１４ｈ内の液体を所定温度に加熱して検出部３０に供給する加熱部２３と、を備えている。 The reaction unit 20 includes a container 21 that stores nicotinamide, a pump 22 that pumps the nicotinamide in the container 21 to the detection pipe 14h, and a liquid in the detection pipe 14h that is heated to a predetermined temperature. And a heating unit 23 to be supplied to 30.
検出部３０は、液体の蛍光強度を測定する装置である。具体的には、検出部３０は、加熱部２３から供給された液体を冷却する熱交換器３２と、冷却された液体の蛍光強度を測定し、測定が終了した液体を廃液用配管１４ｇに排出する光学検出器３１を備えている。フローインジェクション法によって蛍光強度を測定することにより、液体の蛍光強度を連続的、且つ、自動的に測定することができる。なお、蛍光強度の測定精度を一定に制御するために、検出部３０には熱交換器３２が配設されている。また、蛍光強度の測定精度を一定に制御するために、検出部３０内の配管に超純水を導入し、測定の度毎に検出部３０内の配管を超純水で洗浄してもよい。 The detection unit 30 is a device that measures the fluorescence intensity of the liquid. Specifically, the detection unit 30 measures the fluorescence intensity of the cooled liquid and the heat exchanger 32 that cools the liquid supplied from the heating unit 23, and discharges the measured liquid to the waste liquid piping 14g. An optical detector 31 is provided. By measuring the fluorescence intensity by the flow injection method, the fluorescence intensity of the liquid can be continuously and automatically measured. Note that a heat exchanger 32 is disposed in the detection unit 30 in order to control the measurement accuracy of the fluorescence intensity to be constant. In addition, in order to control the measurement accuracy of the fluorescence intensity to be constant, ultrapure water may be introduced into the piping in the detection unit 30 and the piping in the detection unit 30 may be washed with ultrapure water for each measurement. .
このような構成を有するハロ酢酸の測定装置１では、以下のようにして試料水のハロ酢酸濃度を測定する。すなわち、試料水のハロ酢酸濃度を測定する際には、始めに、電磁弁１６ｄを開状態とした後、ポンプ１５ｂを駆動することによって、容器１１ｄ内の超純水をＡｇ／Ｈカラム１３を介して陰イオン交換カラム１２に通水し、陰イオン交換カラム１２を通過した超純水を廃液用配管１４ｇに排出する。次に、ポンプ１５ｂの駆動を停止して電磁弁１６ｄを閉状態とした後、電磁弁１６ａを開状態とし、ポンプ１５ａを駆動ことによって、アルカリ溶液を陰イオン交換カラム１２に通水し、陰イオン交換カラム１２を通過したアルカリ溶液を反応部２０に供給する。反応部２０は、アルカリ溶液にニコチン酸アミドを添加した後、アルカリ溶液を所定時間加熱し、所定時間加熱した後のアルカリ溶液を検出部３０に供給する。検出部３０は、冷却したアルカリ溶液の蛍光強度を測定することによって、ハロ酢酸濃度が０μｇ／Ｌである時の蛍光強度を検出することができる（ゼロ点校正）。 In the haloacetic acid measuring apparatus 1 having such a configuration, the haloacetic acid concentration of the sample water is measured as follows. That is, when measuring the haloacetic acid concentration of the sample water, first, after opening the solenoid valve 16d, the pump 15b is driven, so that the ultrapure water in the container 11d is removed from the Ag / H column 13. Then, the water is passed through the anion exchange column 12, and the ultrapure water that has passed through the anion exchange column 12 is discharged into the waste liquid pipe 14g. Next, after the pump 15b is stopped and the solenoid valve 16d is closed, the solenoid valve 16a is opened, and the pump 15a is driven to pass the alkaline solution through the anion exchange column 12, thereby The alkaline solution that has passed through the ion exchange column 12 is supplied to the reaction unit 20. The reaction unit 20 adds nicotinamide to the alkaline solution, then heats the alkaline solution for a predetermined time, and supplies the alkaline solution after heating for a predetermined time to the detection unit 30. The detection unit 30 can detect the fluorescence intensity when the haloacetic acid concentration is 0 μg / L by measuring the fluorescence intensity of the cooled alkaline solution (zero point calibration).
次に、ポンプ１５ａの駆動を停止し、電磁弁１６ａを閉状態とした後、電磁弁１６ｃを開状態とし、ポンプ１５ｂを駆動することによって、容器１１ｃ内の標準試料水をＡｇ／Ｈカラム１３を介して陰イオン交換カラム１２に通水し、陰イオン交換カラム１２を通過した標準試料水を廃液用配管１４ｇに排出する。この処理によって、標準試料水中のハロ酢酸は、陰イオン交換カラム１２に吸着し、分離、濃縮される。次に、ポンプ１５ｂの駆動を停止して電磁弁１６ｃを閉状態とした後、電磁弁１６ａを開状態とし、ポンプ１５ａを駆動ことによって、アルカリ溶液を陰イオン交換カラム１２に通水し、陰イオン交換カラム１２を通過したアルカリ溶液を反応部２０に供給する。この処理によって、陰イオン交換カラム１２に吸着した標準試料水中のハロ酢酸は、アルカリ溶液に溶出し、反応部２０に供給される。反応部２０は、アルカリ溶液にニコチン酸アミドを添加した後、アルカリ溶液を所定時間加熱し、所定時間加熱した後のアルカリ溶液を検出部３０に供給する。検出部３０は、冷却したアルカリ溶液の蛍光強度を測定することによって、標準試料水のハロ酢酸濃度に対応する蛍光強度を検出することができる。その後、ポンプ１５ａの駆動を停止し、電磁弁１６ａを閉状態とする。 Next, the drive of the pump 15a is stopped, the electromagnetic valve 16a is closed, the electromagnetic valve 16c is opened, and the pump 15b is driven, whereby the standard sample water in the container 11c is supplied to the Ag / H column 13 The standard sample water that has passed through the anion exchange column 12 is discharged to the waste liquid pipe 14g. By this treatment, the haloacetic acid in the standard sample water is adsorbed on the anion exchange column 12 and separated and concentrated. Next, after the pump 15b is stopped and the solenoid valve 16c is closed, the solenoid valve 16a is opened and the pump 15a is driven to pass the alkaline solution through the anion exchange column 12, thereby The alkaline solution that has passed through the ion exchange column 12 is supplied to the reaction unit 20. By this treatment, the haloacetic acid in the standard sample water adsorbed on the anion exchange column 12 is eluted into the alkaline solution and supplied to the reaction unit 20. The reaction unit 20 adds nicotinamide to the alkaline solution, then heats the alkaline solution for a predetermined time, and supplies the alkaline solution after heating for a predetermined time to the detection unit 30. The detection unit 30 can detect the fluorescence intensity corresponding to the haloacetic acid concentration of the standard sample water by measuring the fluorescence intensity of the cooled alkaline solution. Thereafter, the driving of the pump 15a is stopped and the electromagnetic valve 16a is closed.
次に、検出部３０は、ハロ酢酸濃度が０μｇ／Ｌである時の蛍光強度と標準試料水のハロ酢酸濃度に対応する蛍光強度とからハロ酢酸濃度と蛍光強度との対応関係を示す検量線を作成する。なお、この検量線を作成するまでの処理は、予め実行しておいてもよいし、試料水のハロ酢酸濃度を測定する度毎に実行してもよい。 Next, the detection unit 30 uses a calibration curve indicating the correspondence between the haloacetic acid concentration and the fluorescence intensity from the fluorescence intensity when the haloacetic acid concentration is 0 μg / L and the fluorescence intensity corresponding to the haloacetic acid concentration of the standard sample water. Create Note that the processing until the calibration curve is created may be executed in advance, or may be executed every time the haloacetic acid concentration of the sample water is measured.
検量線の作成が完了すると、次に、電磁弁１６ｂを開状態とし、ポンプ１５ｂを駆動することによって、容器１１ｂ内の試料水をＡｇ／Ｈカラム１３を介して陰イオン交換カラム１２に通水し、陰イオン交換カラム１２を通過した試料水を廃液用配管１４ｇに排出する。この処理によって、試料水中のハロ酢酸は、陰イオン交換カラム１２に吸着し、共存物質と分離、濃縮される。次に、ポンプ１５ｂの駆動を停止して電磁弁１６ｂを閉状態とした後、電磁弁１６ａを開状態とし、ポンプ１５ａを駆動することによって、アルカリ溶液を陰イオン交換カラム１２に通水し、陰イオン交換カラム１２を通過した溶出液を反応部２０に供給する。この処理によって、陰イオン交換カラム１２に吸着した試料水中のハロ酢酸は、アルカリ溶液に溶出し、反応部２０に供給される。一方、陰イオン交換カラム１２に吸着したトリハロメタンは、陰イオン交換カラム１２から脱離せずに残留する。反応部２０は、アルカリ溶液にニコチン酸アミドを添加した後、アルカリ溶液を所定時間加熱し、所定時間加熱した後のアルカリ溶液を検出部３０に供給する。検出部３０は、冷却したアルカリ溶液の蛍光強度を測定し、検量線に基づいて測定された蛍光強度に対応するハロ酢酸濃度を算出する。以上の流れにより、試料水のハロ酢酸濃度を測定することができる。 When the creation of the calibration curve is completed, next, the electromagnetic valve 16b is opened and the pump 15b is driven to pass the sample water in the container 11b through the Ag / H column 13 to the anion exchange column 12. Then, the sample water that has passed through the anion exchange column 12 is discharged to the waste liquid pipe 14g. By this treatment, the haloacetic acid in the sample water is adsorbed on the anion exchange column 12, and separated from the coexisting substances and concentrated. Next, after stopping the driving of the pump 15b and closing the electromagnetic valve 16b, the electromagnetic valve 16a is opened and the pump 15a is driven to pass the alkaline solution through the anion exchange column 12, The eluate that has passed through the anion exchange column 12 is supplied to the reaction unit 20. By this treatment, the haloacetic acid in the sample water adsorbed on the anion exchange column 12 is eluted into the alkaline solution and supplied to the reaction unit 20. On the other hand, trihalomethane adsorbed on the anion exchange column 12 remains without desorbing from the anion exchange column 12. The reaction unit 20 adds nicotinamide to the alkaline solution, then heats the alkaline solution for a predetermined time, and supplies the alkaline solution after heating for a predetermined time to the detection unit 30. The detection unit 30 measures the fluorescence intensity of the cooled alkaline solution, and calculates the haloacetic acid concentration corresponding to the fluorescence intensity measured based on the calibration curve. With the above flow, the haloacetic acid concentration of the sample water can be measured.
〔実施例〕
市販の３種類（WAX,MA-2,X-AW）の陰イオン交換カラムについて、４種類のトリハロメタン（CHCl3：57 mg/L、CHBrCl2：68 mg/L、CHBr2Cl：73 mg/L、CHBr3：75 mg/L）が添加された超純水に対するトリハロメタンの吸着率及び溶出液を流した際のトリハロメタンの回収率を評価した。評価結果を以下の表１に示す。表１に示すように、どの陰イオン交換カラムも、トリハロメタンに対し高い吸着率を示し、また溶出液を流した際のトリハロメタンの回収率が低かった。以上のことから、トリハロメタンは、陰イオン交換カラムに吸着されるが、溶出液を流しても溶出せずに陰イオン交換カラム内に留まることが確認された。これにより、陰イオン交換カラムを用いることによってトリハロメタンとハロ酢酸とを分離できることが知見された。
〔Example〕
Four types of trihalomethanes (CHCl 3 : 57 mg / L, CHBrCl 2 : 68 mg / L, CHBr 2 Cl: 73 mg /) for three types of commercially available anion exchange columns (WAX, MA-2, X-AW) L, CHBr 3 : 75 mg / L) was added to evaluate the adsorption rate of trihalomethane to ultrapure water and the recovery rate of trihalomethane when flowing the eluate. The evaluation results are shown in Table 1 below. As shown in Table 1, every anion exchange column showed a high adsorption rate with respect to trihalomethane, and the recovery rate of trihalomethane when the eluate was passed was low. From the above, it was confirmed that trihalomethane was adsorbed on the anion exchange column, but remained in the anion exchange column without being eluted even when the eluate was passed. Thus, it was found that trihalomethane and haloacetic acid can be separated by using an anion exchange column.
以上、本発明者によってなされた発明を適用した実施の形態について説明したが、本実施形態による本発明の開示の一部をなす記述および図面により本発明は限定されることはない。すなわち、本実施形態に基づいて当業者などによりなされる他の実施の形態、実施例、および運用技術などは全て本発明の範疇に含まれる。 Although the embodiment to which the invention made by the present inventor is applied has been described above, the present invention is not limited by the description and the drawings that form a part of the disclosure of the present invention according to this embodiment. That is, other embodiments, examples, operational techniques, and the like made by those skilled in the art based on the present embodiment are all included in the scope of the present invention.
１ ハロ酢酸の測定装置
１０ 前処理部
１１ａ〜１１ｄ，２１ 容器
１２ 陰イオン交換カラム
１３ Ａｇ／Ｈカラム
１４ａ〜１４ｆ 配管
１４ｇ 廃液用配管
１４ｈ 検出用配管
１５ａ，１５ｂ，２２ ポンプ
１６ａ〜１６ｄ 電磁弁
２０ 反応部
２３ 加熱部
３０ 検出部
３１ 光学検出器
３２ 熱交換器
DESCRIPTION OF SYMBOLS 1 Measurement apparatus of haloacetic acid 10 Pretreatment part 11a-11d, 21 Container 12 Anion exchange column 13 Ag / H column 14a-14f Piping 14g Waste liquid piping 14h Detection piping 15a, 15b, 22 Pump 16a-16d Electromagnetic valve 20 Reaction unit 23 Heating unit 30 Detection unit 31 Optical detector 32 Heat exchanger
Claims (8)
前記第１ステップ後の前記試料水を所定時間加熱する第２ステップと、
前記第２ステップ後の前記試料水を熱交換器で直ちに所定の温度まで冷却する第３ステップと、
前記第３ステップ後の前記試料水に含まれる蛍光物質の蛍光強度を測定する第４ステップと、
前記蛍光強度から前記ハロ酢酸の濃度を算出する第５ステップと、
を含み、
前記第１ステップは、ハロ酢酸を選択的に吸着する陰イオン交換体に前記試料水を通水するステップと、前記試料水を通水した後に陰イオン交換体にアルカリ溶液を通水するステップと、前記陰イオン交換体を通過したアルカリ溶液にニコチン酸アミドのみを添加するステップと、を含むことを特徴とするハロ酢酸の測定方法。 A first step of adding nicotinamide and alkali to sample water containing haloacetic acid;
A second step of heating the sample water after the first step for a predetermined time;
A third step of immediately cooling the sample water after the second step to a predetermined temperature with a heat exchanger;
A fourth step of measuring the fluorescence intensity of the fluorescent substance contained in the sample water after the third step;
A fifth step of calculating the concentration of the haloacetic acid from the fluorescence intensity;
Including
The first step includes passing the sample water through an anion exchanger that selectively adsorbs haloacetic acid; passing the alkaline solution through the anion exchanger after passing the sample water; Adding only nicotinamide to the alkaline solution that has passed through the anion exchanger, and a method for measuring haloacetic acid.
ニコチン酸アミドとアルカリとが添加された前記試料水を所定時間加熱する手段と、
前記所定時間加熱された前記試料水を一定の温度まで直ちに冷却する熱交換器と、
冷却後の前記試料水に含まれる蛍光物質の蛍光強度を測定する手段と、
前記蛍光強度から前記ハロ酢酸の濃度を算出する手段と、
を備え、
前記添加する手段は、ハロ酢酸を選択的に吸着する陰イオン交換体に前記試料水を通水し、前記試料水を通水した後の陰イオン交換体にアルカリ溶液を通水し、前記陰イオン交換体を通過したアルカリ溶液にニコチン酸アミドのみを添加することを特徴とするハロ酢酸の測定装置。 Means for adding nicotinamide and alkali to sample water containing haloacetic acid;
Means for heating the sample water to which nicotinamide and alkali are added for a predetermined time;
A heat exchanger that immediately cools the sample water heated for a predetermined time to a certain temperature;
Means for measuring the fluorescence intensity of the fluorescent substance contained in the sample water after cooling;
Means for calculating the concentration of the haloacetic acid from the fluorescence intensity;
With
The means for adding comprises passing the sample water through an anion exchanger that selectively adsorbs haloacetic acid, passing an alkaline solution through the anion exchanger after passing through the sample water, and An apparatus for measuring haloacetic acid, wherein only nicotinamide is added to an alkaline solution that has passed through an ion exchanger .
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