JPH0695074B2 - Analyzer for trace iron or manganese in water - Google Patents
Analyzer for trace iron or manganese in waterInfo
- Publication number
- JPH0695074B2 JPH0695074B2 JP5178492A JP5178492A JPH0695074B2 JP H0695074 B2 JPH0695074 B2 JP H0695074B2 JP 5178492 A JP5178492 A JP 5178492A JP 5178492 A JP5178492 A JP 5178492A JP H0695074 B2 JPH0695074 B2 JP H0695074B2
- Authority
- JP
- Japan
- Prior art keywords
- manganese
- column
- iron
- water
- analyzer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims description 36
- 229910052742 iron Inorganic materials 0.000 title claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 18
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims description 12
- 229910052748 manganese Inorganic materials 0.000 title claims description 12
- 239000011572 manganese Substances 0.000 title claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 27
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 24
- 229910001447 ferric ion Inorganic materials 0.000 claims description 21
- 239000003480 eluent Substances 0.000 claims description 18
- 239000013535 sea water Substances 0.000 claims description 16
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 claims description 13
- HWYHZTIRURJOHG-UHFFFAOYSA-N luminol Chemical compound O=C1NNC(=O)C2=C1C(N)=CC=C2 HWYHZTIRURJOHG-UHFFFAOYSA-N 0.000 claims description 12
- 239000013522 chelant Substances 0.000 claims description 8
- 238000012856 packing Methods 0.000 claims description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 9
- 229910001437 manganese ion Inorganic materials 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000004020 luminiscence type Methods 0.000 description 5
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 4
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- -1 seawater Chemical class 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 229910001448 ferrous ion Inorganic materials 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 230000009920 chelation Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000011002 quantification Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- 238000006193 diazotization reaction Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- ZXZKYYHTWHJHFT-UHFFFAOYSA-N quinoline-2,8-diol Chemical compound C1=CC(=O)NC2=C1C=CC=C2O ZXZKYYHTWHJHFT-UHFFFAOYSA-N 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 210000003462 vein Anatomy 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、水中の微量鉄とマンガ
ンの分析装置に関し、特に海水中の微量の第２鉄イオン
の分析装置に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an analyzer for trace amounts of iron and manganese in water, and more particularly to an analyzer for trace amounts of ferric ion in seawater.
【０００２】[0002]
【従来の技術】従来は、水中の微量の鉄とマンガンを分
析する装置として、水中の微量の鉄またはマンガンをイ
オン交換樹脂で濃縮した後、これを溶離液を用いて溶出
し、原子吸光法など一般に用いられている水中の鉄また
はマンガンを分析する方法で分析している。2. Description of the Related Art Conventionally, as an apparatus for analyzing a trace amount of iron and manganese in water, after concentrating a trace amount of iron or manganese in water with an ion exchange resin, this is eluted with an eluent and then subjected to an atomic absorption method. It is analyzed by a commonly used method for analyzing iron or manganese in water.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、上記従
来技術では、溶解塩の少ない水中の鉄またはマンガンイ
オンは濃縮できるが、海水のように溶解塩の多い水は溶
解塩、海水の場合はナトリウムイオンに妨害され、微量
の鉄またはマンガンイオンは定量的に濃縮されないとい
う問題がある。また濃縮された溶離液を分析する原子吸
光法などの分析方法は、一般に０．１〜１０ｐｐｍ程度
の分析精度しかないという問題がある。However, in the above-mentioned prior art, iron or manganese ions in water containing a small amount of dissolved salts can be concentrated, but water containing a large amount of dissolved salts such as seawater, or sodium ions in the case of seawater. However, there is a problem that a trace amount of iron or manganese ion is not quantitatively concentrated. In addition, analysis methods such as the atomic absorption method for analyzing a concentrated eluent generally have a problem that the analysis accuracy is only about 0.1 to 10 ppm.
【０００４】しかしながら、環境水中の鉄またはマンガ
ン、特に海水中の第２鉄イオンの濃度をさらに低濃度ま
で分析するという要求は強く、また最近は海水中の有効
鉱脈の探索などに海水中の微量重金属の分析の必要性が
大きくなってきている。However, there is a strong demand to analyze the concentration of iron or manganese in environmental water, especially ferric ion in seawater, to a lower concentration, and recently, a trace amount in seawater has been used for searching effective veins in seawater. The need for heavy metal analysis is growing.
【０００５】本発明の目的は、水中の微量の鉄とマンガ
ン、特に海水中の第２鉄イオンを１０ｐｐｔ程度の分析
精度で分析できる装置を提供することである。An object of the present invention is to provide an apparatus capable of analyzing a trace amount of iron and manganese in water, especially ferric ion in seawater with an analysis accuracy of about 10 ppt.
【０００６】[0006]
【課題を解決するための手段】本発明は、オキシンを固
定化した充填物のカラムに水を導き、鉄またはマンガン
をキレート反応によって濃縮した後、これを溶離液で溶
出し、ルミノール化学発光反応試薬と反応させて発光
し、この発光強度を光電子増倍管で検出することを特徴
とする水中の微量鉄およびマンガンの分析装置である。According to the present invention, water is introduced into a column of a packing in which oxine is immobilized, iron or manganese is concentrated by a chelate reaction, and then this is eluted with an eluent to carry out a luminol chemiluminescence reaction. An analyzer for trace amounts of iron and manganese in water, which is characterized in that it reacts with a reagent to emit light, and the emission intensity is detected by a photomultiplier tube.
【０００７】また本発明は、オキシンを固定化した充填
物のカラムに海水を導き、第２鉄イオンをキレート反応
によって濃縮した後、これを溶離液で溶出し、ルミノー
ル化学発光反応試薬と反応させて発光し、この発光強度
を光電子増倍管で検出することを特徴とする。In the present invention, seawater is introduced into a column of a packing in which oxine is immobilized, ferric ions are concentrated by a chelate reaction, and then this is eluted with an eluent to react with a luminol chemiluminescent reaction reagent. It is characterized in that the emitted light is emitted by a photomultiplier tube.
【０００８】[0008]
【作用】本発明に従えば、鉄またはマンガンとキレート
反応をするオキシンを固定化した充填物をカラムに充填
し、試料水をこのカラムに一定量通す。カラムでは試料
水の分析目的重金属だけがキレート反応によって濃縮さ
れ、他の金属はカラムを素通りする。濃縮操作が終わる
と、溶離液で濃縮された分析目的重金属を溶出し、この
濃縮溶離液をルミノール化学発光反応試薬と反応させ、
発光強度を高電子増倍管で測定して、海水中の微量重金
属の量を１０ｐｐｔ程度まで精確に分析できる。According to the present invention, a column is filled with a packing material on which oxine which undergoes a chelate reaction with iron or manganese is immobilized, and a fixed amount of sample water is passed through this column. In the column, only heavy metals for the purpose of analysis of the sample water are concentrated by the chelation reaction, and other metals pass through the column. When the concentration operation is completed, the heavy metal for analysis concentrated in the eluent is eluted, and the concentrated eluent is reacted with the luminol chemiluminescent reaction reagent,
The emission intensity can be measured with a high electron multiplier, and the amount of trace heavy metals in seawater can be accurately analyzed up to about 10 ppt.
【０００９】[0009]
【実施例】以下実施例でもって、本発明にかかる水中の
微量の鉄またはマンガンの分析装置をより具体的に説明
するが、本発明はこれに限定されるものではない。EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.
【００１０】図１は、本発明の一実施例の全体図であ
り、海水中の微量の第２鉄イオン（Ｆｅ3+）を分析する
場合について説明する。本分析装置１の中心となるオキ
シンを固定化したカラム５は、次の方法で製造する。FIG. 1 is an overall view of an embodiment of the present invention, and a case of analyzing a trace amount of ferric ion (Fe 3+ ) in seawater will be described. The column 5 on which oxine is immobilized, which is the center of the analyzer 1, is manufactured by the following method.
【００１１】アミノガラスビーズ（２００メッシュ、ポ
ア径１００Å）をベンゾイル化した後、チオ硫酸ナトリ
ウムで還元する。次に亜硝酸ナトリウムでジアゾ化した
後、エタノール中でオキシン（８−ヒドロキシキノリノ
ール）をジアゾカップリングする。このオキシンを固定
化したアミノガラスビーズを内径６ｍｍ長さ４０ｍｍの
テフロン製カラムに充填する。Amino glass beads (200 mesh, pore size 100Å) are benzoylated and then reduced with sodium thiosulfate. Next, after diazotization with sodium nitrite, oxine (8-hydroxyquinolinol) is diazo coupled in ethanol. The oxine-immobilized amino glass beads are packed in a Teflon column having an inner diameter of 6 mm and a length of 40 mm.
【００１２】試料Ｓを試料容器２に入れ、試料中の第２
鉄イオンとオキシンとがキレート反応をするｐＨ３に調
整し、本分析装置１にセットする。試料Ｓはポンプ３に
よって吸引加圧され、フィルタ４で懸濁物を濾過され、
管路７および３方弁Ｖ１を通ってカラム５に送られる。
ここで試料中の微量の第２鉄イオンは、鉄（ＩＩＩ）オ
キシムキレートを生成し、カラム中の充填物に捕捉され
る。第２鉄イオンを含まない液は、カラム５から管路８
および３方弁Ｖ２を通って、流量計６で計量され、本分
析装置１外へ排出される。またカラム５内でキレート反
応を完全に行わせるために、試料は一定の流速５ｍｌ／
ｍｉｎで通す。試料が規定量たとえば５００ｍｌ通過す
れば、３方弁Ｖ１，Ｖ２を切換え、ポンプ３を停止す
る。The sample S is placed in the sample container 2 and the second sample
The pH is adjusted to pH 3 at which iron ions and oxine undergo a chelating reaction, and the pH is set in the analyzer 1. The sample S is suction-pressurized by the pump 3, the suspension is filtered by the filter 4,
It is sent to the column 5 through the line 7 and the three-way valve V1.
Here, a trace amount of ferric ion in the sample forms an iron (III) oxime chelate and is captured by the packing material in the column. The liquid containing no ferric ion is supplied from the column 5 to the conduit 8
Then, through the three-way valve V2, the flow rate is measured by the flow meter 6, and is discharged to the outside of the analyzer 1. Further, in order to completely carry out the chelation reaction in the column 5, the sample has a constant flow rate of 5 ml /
Pass with min. If the sample passes a prescribed amount, for example 500 ml, the three-way valves V1 and V2 are switched and the pump 3 is stopped.
【００１３】次に溶離液９をポンプ１０によって吸引加
圧し、管路８および３方弁Ｖ２を通してカラム５に送
る。溶離液９は、キレート結合した第２鉄を溶離するも
のであればよいが、一般には塩酸でｐＨ１に調整した液
を用いる。第２鉄イオンを含んだ溶離液は、カラム５か
ら３方弁Ｖ１を通って流量計１１で計量される。溶離液
は、カラム５中の鉄（ＩＩＩ）オキシムキレートを完全
に溶離して、第２鉄イオンが溶出するように、１ｍｌ／
ｍｉｎの定流速で行う。溶離液の流量はカラム５、管路
７，８の容量などを考えて、たとえば５ｍｌと決める。
溶離液は、同量の１ｍｍｏｌ／ｌルミノール水溶液１１
および４４０ｍｍｏｌ／ｌ過酸化水素水液１２とともに
２８℃の反応セル１４に導く。ここでルミノールは、第
２鉄イオンおよび過酸化水素と反応して発光する。発光
量は、ルミノールと過酸化水素が充分に存在するので第
２鉄イオンの量に比例する。この発光量を光電子増倍管
１３で検出し、増幅器１６で増幅して表示する。Next, the eluent 9 is suction-pressurized by the pump 10 and sent to the column 5 through the conduit 8 and the three-way valve V2. The eluent 9 may be any that can elute the chelate-bonded ferric iron, but generally a liquid adjusted to pH 1 with hydrochloric acid is used. The eluent containing ferric ions is measured by the flow meter 11 from the column 5 through the three-way valve V1. The eluent was 1 ml / ml so that the iron (III) oxime chelate in column 5 was completely eluted and ferric ion was eluted.
Perform at a constant flow rate of min. The flow rate of the eluent is set to, for example, 5 ml in consideration of the volumes of the column 5 and the pipes 7 and 8.
The eluent is the same amount of 1 mmol / l luminol aqueous solution 11
And 440 mmol / l hydrogen peroxide solution 12 are introduced into the reaction cell 14 at 28 ° C. Here, luminol reacts with ferric ion and hydrogen peroxide to emit light. The amount of luminescence is proportional to the amount of ferric ion because luminol and hydrogen peroxide are sufficiently present. The amount of emitted light is detected by the photomultiplier tube 13, amplified by the amplifier 16, and displayed.
【００１４】ルミノールの発光反応は、非常に鋭敏であ
り、これの発光量を高感度の光電子増倍管で検出するこ
とによって、従来一般に用いられている原子吸光法の定
量下限の１／１０００まで定量でき、さらにキレート反
応を使って１００倍に濃縮することによって、定量下限
は１０ｐｐｔ（part per trillion，１兆分の１）まで
にできる。Luminol's luminescence reaction is extremely sensitive, and by detecting the amount of luminescence from this with a highly sensitive photomultiplier tube, up to 1/1000 of the lower limit of quantification of the atomic absorption method generally used in the past. It can be quantified, and by concentrating 100 times using the chelate reaction, the lower limit of quantification can be made up to 10 ppt (part per trillion, one trillionth).
【００１５】なお、第２鉄イオンとオキシンとの反応は
次式で表される。The reaction between ferric ion and oxine is represented by the following equation.
【００１６】[0016]
【化１】 [Chemical 1]
【００１７】この反応式で左方向の矢印はｐＨ１以下で
進み、右方向の矢印はｐＨ３以上で進む。In this reaction formula, the arrow pointing left moves at pH 1 or lower, and the arrow pointing right moves at pH 3 or higher.
【００１８】同一の装置を使って、第２鉄イオンと同様
に第１鉄イオンおよびマンガンイオンが定量できる。Ｌ
１は第２鉄イオン、Ｌ２は第１鉄イオン、Ｌ３はマンガ
ンイオンがオキシンを固定化したカラムによって捕捉お
よび溶離されるｐＨを図３を示す。縦軸は、オキシンを
固定化したカラムに各金属の５００ｎｇ／ｌ（５００ｐ
ｐｔ）濃度の水溶液を通したとき、オキシンを固定化し
たカラムに捕捉される各金属の割合を表す。これによっ
て第２鉄イオンは、ｐＨ３で捕捉し、ｐＨ１で溶離すれ
ばよく、第１鉄イオンはｐＨ５で捕捉し、ｐＨ３で溶離
すればよく、マンガンイオンはｐＨ７で捕捉し、ｐＨ４
で溶離すればよいことがわかる。Using the same apparatus, ferrous ions and manganese ions as well as ferric ions can be quantified. L
FIG. 3 shows the pH at which 1 is ferric ion, L2 is ferrous ion, and L3 is manganese ion captured and eluted by a column on which oxine is immobilized. The vertical axis represents 500 ng / l of each metal (500 p
The ratio of each metal captured on the column on which oxine is immobilized when the aqueous solution of pt) concentration is passed through. As a result, ferric ions may be captured at pH 3 and eluted at pH 1, ferrous ions may be captured at pH 5 and eluted at pH 3, manganese ions may be captured at pH 7, pH 4
It is understood that it is sufficient to elute with.
【００１９】図２は光電子増倍管１５の原理を説明する
ための図である。過酸化水素とルミノールと第２鉄イオ
ンとの反応で発光した光は、入光窓２１から光電子増倍
管１５に入り、光電面２２で光電変換により電子に交換
する。光電面２２には負の高電圧（−ＨＶ）がかけてあ
るので陰極として作用し、陽極２５へ進むが、途中に電
圧分割回路によって作られるダイオードと呼ばれる電極
２３１，２３２，…，２３ｎで増倍される。陽極に集ま
った電子は、電流となって増幅器１６に入り、電圧に変
換されて増幅される。これによって微弱な発光も検出で
きる。FIG. 2 is a diagram for explaining the principle of the photomultiplier tube 15. The light emitted by the reaction of hydrogen peroxide, luminol, and ferric ions enters the photomultiplier tube 15 through the light entrance window 21 and is exchanged into electrons by photoelectric conversion at the photocathode 22. Since a negative high voltage (-HV) is applied to the photocathode 22, the photocathode 22 acts as a cathode and proceeds to the anode 25, but is increased by electrodes 231, 232, ..., 23n called diodes formed by a voltage dividing circuit on the way. Doubled. The electrons collected at the anode become a current, enter the amplifier 16, are converted into a voltage, and are amplified. This makes it possible to detect weak light emission.
【００２０】１試料の分析が終われば、３方弁Ｖ１，Ｖ
２を切換えて試料容器２を洗浄液容器に替えて、ポンプ
３を使って洗浄液をフィルタ４、カラム５内に入れ内部
を洗浄し、流量計６を通して排出し、また、３方弁Ｖ１
を切換えて、流量計１１、反応器１４を洗浄し、次の試
料の分析を行う。When analysis of one sample is completed, three-way valves V1, V
2 is switched to replace the sample container 2 with a cleaning liquid container, and the cleaning liquid is put into the filter 4 and the column 5 using the pump 3 to clean the inside, and is discharged through the flow meter 6, and the three-way valve V1
Are switched to wash the flow meter 11 and the reactor 14, and the next sample is analyzed.
【００２１】図４は、これらの一連の操作を自動的に行
う自動分析計の一例を示す全体図である。構成は、図１
に示す実施例の構成と類似であり、同一の部分には同一
の参照符を付す。本自動分析計３０では、ｐＨ調整され
た試料は、ｎ個たとえば１６個までＳ１，Ｓ２，…，Ｓ
ｎの位置に取付けられ、３方切換弁ＶＳ１，ＶＳ２，
…，ＶＳｎによって、Ｓ１から順に分析される。図示し
ていないコンピュータからの指令に基づき、第１試料Ｓ
１のカラムへの送液、溶離液９による溶離、発光反応を
前述の手順で自動的に行い第１試料の分析を終えれば、
洗浄液３１によってカラム５と流量計１１、反応コイル
１４などとを洗浄し、第２試料の分析に移る。なお発光
反応は、２８℃のウォータバス３３中の反応コイル１４
で行い、反応が終わればセル３４に導かれ、ここで発光
し、光が光電子増倍管１５に送られる。試料中の目的成
分をカラム５で捕捉するのは一般に長時間を要するの
で、この間コンピュータによって高電圧供給装置３５を
停止し、必要な時だけ、光電子増倍管１５、増幅器１６
および記録計３６を作動させる。また１ｍｍｏｌ／ｌル
ミノール水溶液と４４０ｍｍｏｌ／ｌ過酸化水素水溶液
は、コンピュータによって制御される電磁弁３２によっ
て必要な時同時に溶離液に混ぜられる。FIG. 4 is an overall view showing an example of an automatic analyzer for automatically performing the series of operations described above. The configuration is shown in Figure 1.
The configuration is similar to that of the embodiment shown in, and the same portions are denoted by the same reference numerals. In this automatic analyzer 30, the number of pH-adjusted samples is n, for example up to 16, S1, S2, ..., S
It is mounted at the position of n and is a three-way switching valve VS1, VS2.
.., VSn, which is analyzed in order from S1. Based on a command from a computer (not shown), the first sample S
When the analysis of the first sample is completed by automatically performing the liquid feeding to the column of 1, the elution by the eluent 9 and the luminescence reaction in the above-mentioned procedure,
The column 5, the flow meter 11, the reaction coil 14 and the like are washed with the washing liquid 31, and the second sample is analyzed. The luminescence reaction was performed by the reaction coil 14 in the water bath 33 at 28 ° C.
When the reaction is completed, the light is guided to the cell 34, where it emits light and the light is sent to the photomultiplier tube 15. Since it generally takes a long time to capture the target component in the sample in the column 5, the high voltage supply device 35 is stopped by the computer during this period, and only when necessary, the photomultiplier tube 15, the amplifier 16 are provided.
And activate recorder 36. Further, the 1 mmol / l luminol aqueous solution and the 440 mmol / l hydrogen peroxide aqueous solution are simultaneously mixed with the eluent by a solenoid valve 32 controlled by a computer when necessary.
【００２２】図５は、本実施例の分析装置を使って、海
水中の５０ｐｐｔ（Ｓ１，Ｓ２）および１００ｐｐｔ
（Ｓ３，Ｓ４）の第２鉄イオンを分析したときのチャー
トである。縦軸は増幅器１６から出力された電圧で、こ
れらによって作った検量線を図６に示す。FIG. 5 shows that 50 ppt (S1, S2) and 100 ppt in seawater are obtained by using the analyzer of this embodiment.
It is a chart when ferric ion of (S3, S4) is analyzed. The vertical axis represents the voltage output from the amplifier 16, and the calibration curve created by these is shown in FIG.
【００２３】[0023]
【発明の効果】以上のように本発明によれば、水中の鉄
またはマンガンイオンをオキシンを固定化した充填物の
カラムによって濃縮し、溶離液を用いて濃縮液を得、こ
の濃縮液中の鉄またはマンガンイオンをルミノール化学
発光反応試薬によって発光させ、その発光量を高感度の
光電子増倍管で検出することによって、水中の微量の鉄
またはマンガンイオンを検出できる。特に、海水中の第
２鉄イオンを１０ｐｐｔ程度まで定量できる。As described above, according to the present invention, iron or manganese ions in water are concentrated by a column of a packing in which oxine is immobilized, and a concentrated solution is obtained by using an eluent. A small amount of iron or manganese ion in water can be detected by causing iron or manganese ion to emit light with a luminol chemiluminescence reaction reagent and detecting the amount of emitted light with a highly sensitive photomultiplier tube. In particular, ferric ion in seawater can be quantified up to about 10 ppt.
【図１】本発明の一実施例に全体図である。FIG. 1 is an overall view of an embodiment of the present invention.
【図２】本発明に用いる光電子増倍管の原理を説明する
ための図である。FIG. 2 is a diagram for explaining the principle of the photomultiplier tube used in the present invention.
【図３】本発明の一実施例にも用いるオキシンを固定化
した充填物のカラムによる第２鉄、第１鉄およびマンガ
ンの各イオンが捕捉されまたは溶離されるｐＨを示すグ
ラフである。FIG. 3 is a graph showing a pH at which ferric iron, ferrous iron, and manganese ions are trapped or eluted by a column of a packing in which oxine is immobilized, which is also used in an embodiment of the present invention.
【図４】本発明の原理を用いた自動分析計３０の全体図
である。FIG. 4 is an overall view of an automatic analyzer 30 using the principle of the present invention.
【図５】本発明によって、海水中に５０ｐｐｔおよび１
００ｐｐｔ含む第２鉄イオンを分析したときのチャート
である。FIG. 5: According to the present invention, 50 ppt and 1 in seawater.
It is a chart when analyzing the ferric ion containing 00 ppt.
【図６】本発明による海水中の微量第２鉄を分析するた
めの検量線のグラフである。FIG. 6 is a graph of a calibration curve for analyzing a trace amount of ferric iron in seawater according to the present invention.
２ 試料容器 ４ フィルタ ５ カラム ６ 流量計 ９ 溶離液 １４ 反応容器 １５ 光電子増倍管 １６ 増幅器 2 sample container 4 filter 5 column 6 flow meter 9 eluent 14 reaction container 15 photomultiplier tube 16 amplifier
Claims (2)
水を導き、鉄またはマンガンをキレート反応によって濃
縮した後、これを溶離液で溶出し、ルミノール化学発光
反応試薬と反応させて発光し、この発光強度を光電子増
倍管で検出することを特徴とする水中の微量鉄およびマ
ンガンの分析装置。1. After introducing water to a column of a packing in which oxine is immobilized and concentrating iron or manganese by a chelate reaction, this is eluted with an eluent and reacted with a luminol chemiluminescence reaction reagent to emit light, An analyzer for trace amounts of iron and manganese in water, characterized by detecting this emission intensity with a photomultiplier tube.
海水を導き、第２鉄イオンをキレート反応によって濃縮
した後、これを溶離液で溶出し、ルミノール化学発光反
応試薬と反応させて発光し、この発光強度を光電子増倍
管で検出することを特徴とする請求項１記載の海水中の
微量第２鉄イオンの分析装置。2. Seawater is introduced into a column of a packing in which oxine is immobilized, ferric ions are concentrated by a chelate reaction, which is then eluted with an eluent and reacted with a luminol chemiluminescence reaction reagent to emit light. The analyzer for trace amounts of ferric ion in seawater according to claim 1, wherein the emission intensity is detected by a photomultiplier tube.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5178492A JPH0695074B2 (en) | 1992-03-10 | 1992-03-10 | Analyzer for trace iron or manganese in water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5178492A JPH0695074B2 (en) | 1992-03-10 | 1992-03-10 | Analyzer for trace iron or manganese in water |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06194314A JPH06194314A (en) | 1994-07-15 |
| JPH0695074B2 true JPH0695074B2 (en) | 1994-11-24 |
Family
ID=12896577
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5178492A Expired - Lifetime JPH0695074B2 (en) | 1992-03-10 | 1992-03-10 | Analyzer for trace iron or manganese in water |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0695074B2 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100476340B1 (en) * | 2002-08-27 | 2005-03-15 | 임흥빈 | method of analyzing a sample material and apparatus of performing the same |
| JP2006317354A (en) * | 2005-05-13 | 2006-11-24 | Miyagi Prefecture | Iron analysis method, fish quality evaluation method and kit |
| JP5206120B2 (en) * | 2008-05-28 | 2013-06-12 | 株式会社Ｓｕｍｃｏ | Metal analysis method and semiconductor wafer manufacturing method |
| JP6626686B2 (en) * | 2015-10-27 | 2019-12-25 | 三菱重工エンジニアリング株式会社 | Acid gas recovery method and system, and iron ion analysis method and system |
| US10942096B2 (en) * | 2017-09-07 | 2021-03-09 | Elemental Scientific, Inc. | Automated system for remote inline concentration of ultra-low concentrations in pure chemicals |
| DE112019006354T9 (en) * | 2018-12-21 | 2021-12-23 | Elemental Scientific, Inc. | AUTOMATED SYSTEM FOR REMOTE INLINE CONCENTRATION AND HOMOGENIZATION OF EXTREMELY LOW CONCENTRATIONS IN PURE CHEMICALS |
| JP7367602B2 (en) * | 2020-04-24 | 2023-10-24 | 三浦工業株式会社 | Quantification method |
| JP7643855B2 (en) * | 2020-10-09 | 2025-03-11 | 三菱重工業株式会社 | Management system, management method, and management program |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6348313B2 (en) | 2014-03-31 | 2018-06-27 | 株式会社ニューギン | Game machine |
-
1992
- 1992-03-10 JP JP5178492A patent/JPH0695074B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6348313B2 (en) | 2014-03-31 | 2018-06-27 | 株式会社ニューギン | Game machine |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06194314A (en) | 1994-07-15 |
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