JP4656508B2 - Determination of selenium by chemical form - Google Patents
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本発明は、Ｓｅ（０）、Ｓｅ（IV）及びＳｅ（VI）のそれぞれの濃度を測定可能なセレンの化学形態別定量法に関する。 The present invention relates to a method for quantifying selenium by chemical form, which can measure the respective concentrations of Se (0), Se (IV), and Se (VI).
水道水などの上水や各種排水などの水質基準においてはセレン濃度が規定されており、種々の方法によって各種溶液中のセレンの定量が実施されている。従来、溶液中に存在するセレンは通常４価及び６価と考えられており、４価及び６価セレンの分別定量法が考えられている。４価及び６価セレンの分別定量法として、例えばＪＩＳ Ｋ０１０２に記載された方法、又は引用文献１（特許文献１参照）に記載された方法が挙げられる。 The selenium concentration is defined in water quality standards such as tap water such as tap water and various effluents, and selenium in various solutions is quantified by various methods. Conventionally, selenium present in a solution is generally considered to be tetravalent and hexavalent, and fractional quantification methods of tetravalent and hexavalent selenium are considered. Examples of the method for fractional quantification of tetravalent and hexavalent selenium include the method described in JIS K0102, or the method described in Cited Document 1 (see Patent Document 1).
しかしながら、従来から用いられているセレンの化学形態別定量法は、金属セレン（以下Ｓｅ（０））の存在を考慮しておらず、Ｓｅ（０）がＳｅ（VI）として定量されている虞があった。また、セレンの処理を行う際にはＳｅ（IV）とＳｅ（VI)それぞれに最適とされる処理条件で処理を行っており、通常、Ｓｅ（IV）は凝集沈殿させた後にろ過などの固液分離を行うことで取り除き、Ｓｅ（VI）は一度還元剤を用いてＳｅ（IV）に還元してから凝集沈殿、固液分離を行うことにより取り除いている。そのため、Ｓｅ（０）がＳｅ（VI）として定量されることにより、必要量以上の還元剤が使われてしまうという虞があった。また、水に不溶であるＳｅ（０）が、ろ過できない微粒子で存在している場合は除去できず、Ｓｅ（０）は排水に流されている虞があった。 However, the conventional quantification method for selenium by chemical form does not consider the presence of metal selenium (hereinafter, Se (0)), and Se (0) may be quantified as Se (VI). was there. In addition, when selenium is treated, it is treated under the optimum processing conditions for Se (IV) and Se (VI). Usually, Se (IV) is coagulated and precipitated, and then solidified by filtration or the like. It is removed by liquid separation. Se (VI) is once reduced to Se (IV) using a reducing agent and then removed by coagulation precipitation and solid-liquid separation. For this reason, Se (0) is quantified as Se (VI), so that there is a possibility that a reducing agent more than a necessary amount is used. Further, when Se (0) that is insoluble in water is present as fine particles that cannot be filtered, it cannot be removed, and Se (0) may flow into the waste water.
本発明は、このような事情に鑑み、Ｓｅ（IV）及びＳｅ（VI）だけではなく、Ｓｅ（０）も定量できるセレンの化学形態別定量法を提供することを課題とする。 In view of such circumstances, it is an object of the present invention to provide a selenium quantification method by chemical form that can quantify not only Se (IV) and Se (VI) but also Se (0).
本発明の第１の態様は、Ｓｅ（０）、Ｓｅ（IV）及びＳｅ（VI）のそれぞれの定量を行うセレンの化学形態別定量法であって、定量対象となる試料を溶かした溶液を、そのまま処理して含有セレンをセレン化水素に変化させた後、誘導結合プラズマ発光分光分析を行うことによりＳｅ（IV）量を測定してＳｅ（IV）濃度を求める第１の工程と、前記溶液について別途、有機物分解処理及びＳｅ（VI）をＳｅ（IV）に還元するがＳｅ（IV）をＳｅ（０）に還元しない条件で還元処理を順次行い、次いで含有セレンをセレン化水素に変化させた後、誘導結合プラズマ発光分光分析を行うことによりＳｅ（IV）量を測定して全セレン濃度を求める第２の工程と、前記溶液について別途、Ｓｅ（０）をＳｅ（IV）に酸化するがＳｅ（IV）をＳｅ（VI）に酸化しない条件下で酸分解処理し、次いで含有セレンをセレン化水素に変化させた後、誘導結合プラズマ発光分光分析を行うことによりＳｅ（IV）量を測定してＳｅ（０）及びＳｅ（IV）の総濃度を求める第３の工程と、前記第２の工程で求めた全セレン濃度と前記第３の工程で求めたＳｅ（０）及びＳｅ（IV）の総濃度との差からＳｅ（VI）濃度を求める第４の工程と、前記第１の工程で求めたＳｅ（IV）濃度と前記第３の工程で求めたＳｅ（０）及びＳｅ（IV）の総濃度との差からＳｅ（０）濃度を求める第５の工程とを具備することを特徴とするセレンの化学形態別定量法にある。
The first aspect of the present invention is a selenium chemical form quantification method for quantifying Se (0), Se (IV), and Se (VI), wherein a solution in which a sample to be quantified is dissolved. The first step of determining the Se (IV) concentration by measuring the amount of Se (IV) by performing inductively coupled plasma emission spectroscopic analysis after changing the selenium contained into hydrogen selenide by treatment as it is, Separately, the solution is subjected to organic substance decomposition treatment and reduction treatment under the condition that Se (VI) is reduced to Se (IV) but Se (IV) is not reduced to Se (0), and then the selenium contained is changed to hydrogen selenide. Then, inductively coupled plasma emission spectrometry is performed to measure the amount of Se (IV) to obtain the total selenium concentration, and separately separate Se (0) into Se (IV) for the solution. But Se (IV) is oxidized to Se (VI) The amount of Se (IV) is measured by performing inductively coupled plasma emission spectrometry after acid decomposition treatment under no conditions, and then changing the selenium contained to hydrogen selenide, and then performing Se (IV) and Se (IV) From the difference between the third step for determining the total concentration of selenium, the total selenium concentration determined in the second step and the total concentrations of Se (0) and Se (IV) determined in the third step, Se (VI ) Se (IV) from the difference between the fourth step for obtaining the concentration and the Se (IV) concentration obtained in the first step and the total concentration of Se (0) and Se (IV) obtained in the third step. And (5) a selenium chemical form quantification method characterized by comprising a fifth step of determining the concentration.
本発明の第２の態様は、第１の態様において、前記酸分解処理が前記溶液に少なくとも硝酸を含む酸性溶液を加え、加熱濃縮することによって行われることを特徴とするセレンの化学形態別定量法にある。 According to a second aspect of the present invention, in the first aspect, the acid decomposition treatment is performed by adding an acidic solution containing at least nitric acid to the solution, followed by heating and concentration. Is in the law.
本発明の第３の態様は、第２の態様において、前記硝酸の濃度が前記溶液に対して０．６％以上であることを特徴とするセレンの化学形態別定量法にある。
本発明の第４の態様は、第１又は第２の態様において、前記有機物分解処理及び前記還元処理がＪＩＳ Ｋ０１０２の方法に準じて行われることを特徴とするセレンの化学形態別定量法にある。
According to a third aspect of the present invention, in the second aspect, the selenium chemical form quantification method is characterized in that the concentration of the nitric acid is 0.6% or more based on the solution.
According to a fourth aspect of the present invention, in the first or second aspect, the organic substance decomposition treatment and the reduction treatment are performed according to the method of JIS K0102, characterized in that the selenium is determined by chemical form. .
本発明によれば、Ｓｅ（IV）及びＳｅ（VI）だけではなく、Ｓｅ（０）も定量できるセレンの化学形態別定量法を提供できる。 ADVANTAGE OF THE INVENTION According to this invention, the quantification method according to the chemical form of selenium which can quantify not only Se (IV) and Se (VI) but also Se (0) can be provided.
以下、本発明の実施形態を詳細に説明する。 Hereinafter, embodiments of the present invention will be described in detail.
図１は、本発明の一実施形態に係るセレンの化学形態別定量法を示す図である。図１に示すように、本発明の定量方法は、定量対象となる試料を溶かした溶液である試料１について、そのまま処理して含有セレンをセレン化水素に変化させた後、誘導結合プラズマ発光分光分析を行う水素化物発生‐誘導結合プラズマ発光分光分析２によりＳｅ（IV）量を測定してＳｅ（IV）濃度６を求める第１の工程と、試料１について別途、有機物分解処理３及び還元処理４を順次行い、次いで水素化物発生‐誘導結合プラズマ発光分光分析２によりＳｅ（IV）量を測定して全セレン（Ｔ−Ｓｅ）濃度７を求める第２の工程と、試料１について別途、Ｓｅ（０）をＳｅ（IV）に酸化するがＳｅ（IV）をＳｅ（VI）に酸化しない条件下で酸分解処理５を行い、次いで水素化物発生‐誘導結合プラズマ発光分光分析２によりＳｅ（IV）量を測定してＳｅ（０）及びＳｅ（IV）の総濃度８を求める第３の工程と、第２の工程で求めた全セレン濃度７と第３の工程で求めたＳｅ（０）及びＳｅ（IV）総濃度８との差からＳｅ（VI）濃度９を求める第４の工程と、第１の工程で求めたＳｅ（IV）濃度６と第３の工程で求めたＳｅ（０）及びＳｅ（IV）の総濃度８との差からＳｅ（０）濃度１０とを求める第５の工程とを具備する。
FIG. 1 is a diagram illustrating a selenium quantitative determination method according to one embodiment of the present invention. As shown in FIG. 1, in the quantification method of the present invention, sample 1 which is a solution in which a sample to be quantified is dissolved, and the selenium contained therein is changed to hydrogen selenide, and then inductively coupled plasma emission spectroscopy is performed. Analysis of hydride generation-Inductively coupled
本発明の第１の工程においては、定量対象となる試料を溶かした溶液を、そのまま処理して含有セレンをセレン化水素に変化させ、誘導結合プラズマ発光分光分析を行うことよりＳｅ（IV）量を測定する。セレンをセレン化水素に変化させて行う誘導結合プラズマ発光分光分析は、例えばＪＩＳ Ｋ０１０２の方法に準じて行えばよい。ここで、Ｓｅ（０）、Ｓｅ（IV）及びＳｅ（VI）の中で、セレン化水素に変化するのは、Ｓｅ（IV）のみであり、Ｓｅ（０）、Ｓｅ（VI）はセレン化水素にはならない。したがって、Ｓｅ（IV）をセレン化水素に変化させて誘導結合プラズマ発光分光分析を行うことで、Ｓｅ（IV）量のみが求められる。これよりＳｅ（IV）濃度を求める。 In the first step of the present invention, the amount of Se (IV) is obtained by treating a solution in which a sample to be quantified is treated as it is, changing the contained selenium to hydrogen selenide, and performing inductively coupled plasma emission spectrometry. Measure. The inductively coupled plasma emission spectroscopic analysis performed by changing selenium to hydrogen selenide may be performed, for example, according to the method of JIS K0102. Here, among Se (0), Se (IV) and Se (VI), only Se (IV) is changed to hydrogen selenide, and Se (0) and Se (VI) are selenized. It does not become hydrogen. Therefore, only the amount of Se (IV) can be obtained by performing inductively coupled plasma emission spectroscopic analysis by changing Se (IV) to hydrogen selenide. From this, the Se (IV) concentration is obtained.
本発明の第２の工程においては、定量対象となる試料を溶かした溶液について、まず有機物分解処理を行い、誘導結合プラズマ発光分光分析の妨害となる溶液中の有機物を排除する。この有機物分解処理は、例えばＪＩＳ Ｋ０１０２の方法に準じて行えばよく、具体的には定量対象となる試料を溶かした溶液に硫酸及び硝酸を加え、加熱濃縮する。加熱温度はセレンが気化しない温度であればよい。ここで、Ｓｅ（０）がＳｅ（IV）に酸化され、場合によっては、Ｓｅ（IV）がＳｅ（VI）に酸化される。 In the second step of the present invention, the organic substance decomposition treatment is first performed on the solution in which the sample to be quantified is dissolved, and the organic substance in the solution that interferes with inductively coupled plasma emission spectrometry is excluded. This organic substance decomposition treatment may be performed according to, for example, the method of JIS K0102, and specifically, sulfuric acid and nitric acid are added to a solution in which a sample to be quantified is dissolved, and the mixture is heated and concentrated. The heating temperature may be any temperature at which selenium does not vaporize. Here, Se (0) is oxidized to Se (IV), and in some cases, Se (IV) is oxidized to Se (VI).
本発明の第２の工程では次に還元処理を行う。還元処理は、例えばＪＩＳ Ｋ０１０２の方法に準じて行えばよく、具体的には前処理を行った定量対象の試料を溶かした溶液に、水、塩酸及び臭化カリウム溶液を加え、一定の時間加熱する。加熱温度はセレンが気化しない温度であればよい。この還元処理は、定量対象の試料中に元々存在する、又は有機分解処理により酸化されたＳｅ（VI）を、Ｓｅ（IV）に還元するものであるが、Ｓｅ（IV）をＳｅ（０）に還元しない条件で行う必要がある。 In the second step of the present invention, a reduction process is performed next. The reduction treatment may be performed according to, for example, the method of JIS K0102, and specifically, water, hydrochloric acid and potassium bromide solution are added to a solution in which the sample to be quantified which has been pretreated is dissolved, and heated for a certain period of time. To do. The heating temperature may be any temperature at which selenium does not vaporize. In this reduction treatment, Se (VI) originally present in the sample to be quantified or oxidized by the organic decomposition treatment is reduced to Se (IV). Se (IV) is reduced to Se (0). It is necessary to carry out under conditions that do not reduce the amount.
本発明の第２の工程では最後にＳｅ（IV）をセレン化水素に変化させ、誘導結合プラズマ発光分光分析を行うことより、Ｓｅ（IV）量を求める。有機物分解処理及び還元処理により、定量対象となる試料を溶かした溶液中のセレンはすべてＳｅ（IV）となっているため、このＳｅ（IV）をセレン化水素に変化させ、誘導結合プラズマ発光分光分析を行うことで、定量対象となる試料を溶かした溶液中の全セレンの量がわかる。これより全セレン濃度を求める。 In the second step of the present invention, Se (IV) is finally changed to hydrogen selenide, and the amount of Se (IV) is determined by performing inductively coupled plasma emission spectroscopic analysis. Since all the selenium in the solution in which the sample to be quantified is dissolved by the organic substance decomposition treatment and the reduction treatment is Se (IV), this Se (IV) is changed to hydrogen selenide, and inductively coupled plasma emission spectroscopy is performed. By performing the analysis, the amount of total selenium in the solution in which the sample to be quantified is dissolved is known. From this, the total selenium concentration is determined.
本発明の第３の工程においては、定量対象となる溶液について、まず酸分解処理を行う。この酸分解処理は、Ｓｅ（０）をＳｅ（IV）に酸化するがＳｅ（IV）をＳｅ（VI）に酸化しない条件下で処理することで、Ｓｅ（０）をＳｅ（IV）に酸化する。かかる酸分解処理は、具体的には硝酸を少なくとも含む酸性溶液を、定量対象となる溶液に加え、加熱濃縮することにより行う。ここでの加熱温度はセレンが気化しない温度であればよい。また、酸分解処理で用いる酸性溶液は、硝酸を含有していればよく、硝酸に加えて塩酸や硫酸などの強酸をさらに含有していてもよい。また、酸性溶液の添加量は、定量対象となる試料を溶かした溶液に対して硝酸濃度が０．６％以上であればよい。 In the third step of the present invention, first, an acid decomposition treatment is performed on a solution to be quantified. In this acid decomposition treatment, Se (0) is oxidized to Se (IV) by treating Se (0) to Se (IV) but not Se (IV) to Se (VI). To do. Specifically, the acid decomposition treatment is performed by adding an acidic solution containing at least nitric acid to the solution to be quantified and concentrating with heating. The heating temperature here may be a temperature at which selenium does not vaporize. Moreover, the acidic solution used by an acid decomposition process should just contain nitric acid, and may contain further strong acids, such as hydrochloric acid and a sulfuric acid, in addition to nitric acid. Moreover, the addition amount of an acidic solution should just have a nitric acid density | concentration of 0.6% or more with respect to the solution which melt | dissolved the sample used as fixed quantity.
本発明の第３の工程では最後に溶液中のＳｅ（IV）をセレン化水素に変化させ、誘導結合プラズマ発光分光分析を行うことより、Ｓｅ（IV）量を求める。このとき、酸分解処理によってＳｅ（０）はＳｅ（IV）に変化しているので、Ｓｅ（０）及びＳｅ（IV）の総量がわかる。これよりＳｅ（０）及びＳｅ（IV）の総濃度を求める。 In the third step of the present invention, Se (IV) in the solution is finally changed to hydrogen selenide, and inductively coupled plasma emission spectroscopic analysis is performed to determine the amount of Se (IV). At this time, Se (0) is changed to Se (IV) by the acid decomposition treatment, so that the total amount of Se (0) and Se (IV) is known. From this, the total concentration of Se (0) and Se (IV) is obtained.
本発明の第４の工程においては、第２の工程において求めた全セレン濃度と、第３の工程において求めたＳｅ（０）及びＳｅ（IV）の総濃度との差よりＳｅ（VI）濃度を求める。 In the fourth step of the present invention, the Se (VI) concentration is determined from the difference between the total selenium concentration determined in the second step and the total concentration of Se (0) and Se (IV) determined in the third step. Ask for.
本発明の第５の工程においては、第１の工程において求めたＳｅ(IV）濃度と、第３の工程において求めたＳｅ（０）及びＳｅ（IV）の総濃度との差よりＳｅ（０）濃度を求める。 In the fifth step of the present invention, Se (0) is obtained from the difference between the Se (IV) concentration obtained in the first step and the total concentration of Se (0) and Se (IV) obtained in the third step. ) Find the concentration.
なお、本発明の第１〜第５の工程は、必ずしもこの順番に行う必要はなく、本発明の目的を達成できる範囲で適宜変更可能であり、第４の工程が第２の工程及び第３の工程の後であり、第５の工程が第１の工程及び第３の工程の後であれば特に限定されない。 It should be noted that the first to fifth steps of the present invention are not necessarily performed in this order, and can be appropriately changed as long as the object of the present invention can be achieved, and the fourth step is the second step and the third step. There is no particular limitation as long as the fifth step is after the first step and the third step.
本発明は、Ｓｅ（０）の定量も行うことができるため、Ｓｅ（０）、Ｓｅ（IV）及びＳｅ（VI）のそれぞれの濃度を正確に定量することができる。また、Ｓｅ（０）、Ｓｅ（IV）及びＳｅ（VI）のそれぞれを適切な処理を行うことができるようになった。 Since the present invention can also quantify Se (0), the respective concentrations of Se (0), Se (IV), and Se (VI) can be accurately quantified. In addition, each of Se (0), Se (IV), and Se (VI) can be appropriately processed.
以下、本発明の詳細を実施例に基づいて説明する。 Hereinafter, details of the present invention will be described based on examples.
（実施例１）
Ｓｅ（０）粉末を用いて、Ｓｅ（０）濃度が１．０ｍｇ／ｌになるように調製した溶液を試料とした。この試料１０ｍｌについてそのままＳｅ（IV）をセレン化水素に変化させ、誘導結合プラズマ発光分光分析を行うことよりＳｅ（IV）量を測定してＳｅ（IV）濃度を求めた。（本発明の第１の工程）
Example 1
A solution prepared using Se (0) powder so that the Se (0) concentration was 1.0 mg / l was used as a sample. Se (IV) was changed to hydrogen selenide as it was for 10 ml of this sample, and the Se (IV) concentration was determined by measuring the amount of Se (IV) by performing inductively coupled plasma optical emission spectrometry. (First step of the present invention)
この試料１０ｍｌに硝酸１．０ｍｌ（濃度６０％，有害金属測定用）を加え、１６０℃で加熱濃縮を行った。室温まで冷やした後、Ｓｅ（IV）をセレン化水素に変化させ、誘導結合プラズマ発光分光分析を行い、Ｓｅ（IV）量を測定してＳｅ（０）及びＳｅ（IV）総濃度を求めた。（本発明の第３の工程） To 10 ml of this sample, 1.0 ml of nitric acid (concentration 60%, for toxic metal measurement) was added and concentrated by heating at 160 ° C. After cooling to room temperature, Se (IV) was changed to hydrogen selenide, inductively coupled plasma optical emission spectrometry was performed, and the Se (IV) amount was measured to determine the total concentration of Se (0) and Se (IV). . (Third step of the present invention)
本実施例においては、定量対象の試料中に含まれるセレンがＳｅ（０）のみであることがあらかじめわかっているので、本発明の第２の工程を省き、第１の工程と第３の工程の差からＳｅ（０）の濃度を求めた。（本発明の第５の工程）この結果を図２に示す。 In this example, since it is known in advance that the selenium contained in the sample to be quantified is only Se (0), the second step of the present invention is omitted, and the first step and the third step. From the difference, the concentration of Se (0) was determined. (Fifth step of the present invention) The results are shown in FIG.
（実施例２）
硝酸１．０ｍｌの代わりに硝酸１．０ｍｌ及び硫酸１．０ｍｌを加えた以外は実施例１と同様の操作を行った。この結果を図２に示す。
(Example 2)
The same operation as in Example 1 was performed except that 1.0 ml of nitric acid and 1.0 ml of sulfuric acid were added instead of 1.0 ml of nitric acid. The result is shown in FIG.
（実施例３）
硝酸１．０ｍｌの代わりに硝酸１．０ｍｌ及び塩酸１．０ｍｌを加えた以外は実施例１と同様の操作を行った。この結果を図２に示す。
(Example 3)
The same operation as in Example 1 was performed except that 1.0 ml of nitric acid and 1.0 ml of hydrochloric acid were added instead of 1.0 ml of nitric acid. The result is shown in FIG.
（実施例４）
硝酸１．０ｍｌの代わりに硝酸０．１ｍｌ及び塩酸１．０ｍｌを加えた以外は実施例１と同様の操作を行った。この結果を図２に示す。
Example 4
The same operation as in Example 1 was performed except that 0.1 ml of nitric acid and 1.0 ml of hydrochloric acid were added instead of 1.0 ml of nitric acid. The result is shown in FIG.
（比較例１）
硝酸１．０ｍｌの代わりに硫酸１．０ｍｌを加えた以外は実施例１と同様の操作を行った。この結果を図２に示す。
(Comparative Example 1)
The same operation as in Example 1 was performed except that 1.0 ml of sulfuric acid was added instead of 1.0 ml of nitric acid. The result is shown in FIG.
（比較例２）
硝酸１．０ｍｌの代わりに塩酸１．０ｍｌを加えた以外は実施例１と同様の操作を行った。この結果を図２に示す。
(Comparative Example 2)
The same operation as in Example 1 was performed except that 1.0 ml of hydrochloric acid was added instead of 1.0 ml of nitric acid. The result is shown in FIG.
（実施例１〜４及び比較例１及び２の結果のまとめ）
実施例１〜４のように硝酸を加えて加熱濃縮を行ったものはＳｅ（０）の定量が可能であったのに対し、比較例１及び２のように硝酸を加えずに、他の強酸のみを加えて加熱濃縮を行ったものはＳｅ（０）の定量を行うことができなかった。これより、硝酸を加えていない条件においては、酸性条件下であってもＳｅ（０）をＳｅ（IV）に酸化しないことがわかる。
(Summary of results of Examples 1 to 4 and Comparative Examples 1 and 2)
As in Examples 1 to 4, the nitric acid was added and the mixture was heated and concentrated, while Se (0) could be quantified, while the nitric acid was not added as in Comparative Examples 1 and 2, and the other. Se (0) could not be quantified when heating and concentrating by adding only a strong acid. This shows that Se (0) is not oxidized to Se (IV) even under acidic conditions under conditions where nitric acid is not added.
（実施例５）
ＳｅＯ２を用いて、ＳｅＯ２濃度が１．０ｍｇ／ｌ（Ｓｅ（IV）濃度が１．０ｍｇ／ｌ）になるように調製した溶液を試料とした。
(Example 5)
A solution prepared using SeO 2 so that the SeO 2 concentration was 1.0 mg / l (Se (IV) concentration was 1.0 mg / l) was used as a sample.
この試料１０ｍｌについてそのままＳｅ（IV）をセレン化水素に変化させ、誘導結合プラズマ発光分光分析を行うことよりＳｅ（IV）量を測定してＳｅ（IV）濃度を求めた。（本発明の第１の工程） Se (IV) was changed to hydrogen selenide as it was for 10 ml of this sample, and the Se (IV) concentration was determined by measuring the amount of Se (IV) by performing inductively coupled plasma emission spectroscopic analysis. (First step of the present invention)
また、別途試料１０ｍｌを用意し、これに硝酸（濃度６０％，有害金属測定用）と硫酸（濃度９６％，有機金属測定用）をそれぞれ１．０ｍｌ加え、加熱濃縮させ、室温まで放冷した。その後、水、塩酸（ＪＩＳＫ８１８０）及び臭化カリウム溶液（１ｍｏｌ／ｌ）をそれぞれ同体積加え、９０℃で２０分加熱し、室温まで冷やし、Ｓｅ（IV）をセレン化水素に変化させ、誘導結合プラズマ発光分光分析を行うことよりＳｅ（IV）量を測定して全セレン濃度を求めた。（本発明の第２の工程） Separately, 10 ml of a sample was prepared, and 1.0 ml of nitric acid (concentration 60%, for toxic metal measurement) and sulfuric acid (concentration 96%, for organometallic measurement) were added to each sample, concentrated by heating, and allowed to cool to room temperature. . Thereafter, water, hydrochloric acid (JISK8180) and potassium bromide solution (1 mol / l) are added in the same volume, heated at 90 ° C. for 20 minutes, cooled to room temperature, Se (IV) is changed to hydrogen selenide, and inductively coupled. The total selenium concentration was determined by measuring the amount of Se (IV) by performing plasma emission spectroscopic analysis. (Second step of the present invention)
さらに別途試料１０ｍｌを用意し、これに硝酸（濃度６０％，有害金属測定用）１．０ｍｌを加え、加熱濃縮させ、室温まで放冷した。その後、Ｓｅ（IV）をセレン化水素に変化させ、誘導結合プラズマ発光分光分析を行うことよりＳｅ（IV）量を測定してＳｅ（０）及びＳｅ（IV）総濃度を求めた。（本発明の第３の工程） Furthermore, 10 ml of a sample was separately prepared, 1.0 ml of nitric acid (concentration 60%, for toxic metal measurement) was added thereto, the mixture was heated and concentrated, and allowed to cool to room temperature. Thereafter, Se (IV) was changed to hydrogen selenide, and the Se (IV) amount was measured by performing inductively coupled plasma emission spectroscopic analysis to determine the total concentration of Se (0) and Se (IV). (Third step of the present invention)
第２の工程で求めた全セレン濃度と第３の工程で求めたＳｅ（０）及びＳｅ（IV）濃度との差からＳｅ（VI）濃度を求め、第１の工程で求めたＳｅ（IV）濃度と第３の工程で求めたＳｅ（０）及びＳｅ（IV）総濃度との差からＳｅ（０）濃度を求めた。（本発明の第４の工程及び本発明の第５の工程） The Se (VI) concentration is obtained from the difference between the total selenium concentration obtained in the second step and the Se (0) and Se (IV) concentrations obtained in the third step, and Se (IV obtained in the first step is obtained. ) Se (0) concentration was determined from the difference between the concentration and the total concentration of Se (0) and Se (IV) determined in the third step. (Fourth step of the present invention and fifth step of the present invention)
（実施例６）
ＳｅＯ２の代わりにＮａ２ＳｅＯ４を用いて試料（Ｓｅ（VI）濃度が１．０ｍｇ／ｌ）を調製した以外は実施例５と同様の操作で各セレンの濃度を求めた。
(Example 6)
The concentration of each selenium was determined in the same manner as in Example 5 except that Na 2 SeO 4 was used instead of SeO 2 to prepare a sample (Se (VI) concentration was 1.0 mg / l).
（実施例７）
ＳｅＯ２の代わりにＳｅ（０）粉末を用いて試料（Ｓｅ（０）濃度が１．０ｍｇ／ｌ）を調製した以外は実施例５と同様の操作で各セレンの濃度を求めた。
(Example 7)
The concentration of each selenium was determined in the same manner as in Example 5 except that a sample (Se (0) concentration was 1.0 mg / l) was prepared using Se (0) powder instead of SeO 2 .
（比較例３）
第３の工程の操作を省いた以外は実施例５と同様の操作で各セレンの濃度を求めた。
(Comparative Example 3)
The concentration of each selenium was determined in the same manner as in Example 5 except that the operation in the third step was omitted.
（比較例４）
第３の工程の操作を省いた以外は実施例６と同様の操作で各セレンの濃度を求めた。
(Comparative Example 4)
The concentration of each selenium was determined in the same manner as in Example 6 except that the operation in the third step was omitted.
（比較例５）
第３の工程の操作を省いた以外は実施例７と同様の操作で各セレンの濃度を求めた。
(Comparative Example 5)
The concentration of each selenium was determined in the same manner as in Example 7 except that the operation in the third step was omitted.
（実施例５〜７及び比較例３〜５の結果のまとめ)
実施例５〜７及び比較例３〜５で求めた各セレン濃度を図３に示す。それぞれ、０価、４価、６価のそれぞれの濃度をわけて表示した。
(Summary of results of Examples 5 to 7 and Comparative Examples 3 to 5)
Each selenium density | concentration calculated | required in Examples 5-7 and Comparative Examples 3-5 is shown in FIG. The respective concentrations of 0, 4 and 6 were separately displayed.
実施例７及び比較例５で用いたＳｅ（０）粉末は０価のセレンであるが、比較例５においては６価のセレンとして測定された。従来から用いられている４価及び６価セレンの分別定量法では、比較例３及び４に示すように４価及び６価のセレンは測定できるが、比較例５に示すように０価のセレンは６価として測定されることがわかった。これに対し、本発明に基づいて行った実施例５〜７では、４価及び６価のセレンはそれぞれ４価及び６価として測定され、さらに０価のセレンも０価として測定される。よって、Ｓｅ（０）、Ｓｅ（IV）及びＳｅ（VI）のそれぞれの濃度を正確に定量することができる。 The Se (0) powder used in Example 7 and Comparative Example 5 was zero-valent selenium, but in Comparative Example 5, it was measured as hexavalent selenium. Conventional fractional determination of tetravalent and hexavalent selenium can measure tetravalent and hexavalent selenium as shown in Comparative Examples 3 and 4, but zero-valent selenium as shown in Comparative Example 5. Was measured as hexavalent. On the other hand, in Examples 5 to 7 performed based on the present invention, tetravalent and hexavalent selenium are measured as tetravalent and hexavalent, respectively, and zero-valent selenium is also measured as zero-valent. Therefore, the respective concentrations of Se (0), Se (IV), and Se (VI) can be accurately quantified.
（実施例８）
ＳｅＯ２濃度が１．０ｍｇ／ｌである代わりにＳｅ（０）、Ｓｅ（IV）及びＳｅ（VI）のそれぞれ０．５ｍｇ／lを混合した溶液を用いた以外は実施例５と同様の操作で各セレンの濃度を求めた。
(Example 8)
The same operation as in Example 5 except that a solution in which 0.5 mg / l each of Se (0), Se (IV) and Se (VI) was mixed instead of the SeO 2 concentration being 1.0 mg / l was used. The concentration of each selenium was determined.
（比較例６）
第３の工程の操作を省いた以外は実施例８と同様の操作で各セレンの濃度を求めた。
(Comparative Example 6)
The concentration of each selenium was determined in the same manner as in Example 8 except that the operation in the third step was omitted.
（実施例８及び比較例６の結果のまとめ）
実施例８及び比較例６で求めた各セレン濃度を図４に示す。
(Summary of results of Example 8 and Comparative Example 6)
The selenium concentrations obtained in Example 8 and Comparative Example 6 are shown in FIG.
比較例６においては、０価のセレンが６価として測定された。これに対し、実施例８においては、０価のセレンは０価として測定されており、計算値との差はわずかであった。本発明の定量方法を用いるとＳｅ（０）、Ｓｅ（IV）及びＳｅ（VI）のそれぞれの濃度を正確に定量することができることが確認できた。 In Comparative Example 6, zero-valent selenium was measured as hexavalent. On the other hand, in Example 8, zero-valent selenium was measured as zero-valent, and the difference from the calculated value was slight. It was confirmed that the concentrations of Se (0), Se (IV) and Se (VI) can be accurately quantified by using the quantification method of the present invention.
１ 試料
２ 水素化物発生‐誘導結合プラズマ発光分光分析
３ 有機物分解処理
４ 還元処理
５ 酸分解処理
６ Ｓｅ（IV）
７ 全セレン（Ｔ−Ｓｅ）
８ Ｓｅ（０）＋Ｓｅ（IV）
９ Ｓｅ（VI）
１０ Ｓｅ（０）
1
7 Total selenium (T-Se)
8 Se (0) + Se (IV)
9 Se (VI)
10 Se (0)
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| JP5053342B2 (en) * | 2009-08-27 | 2012-10-17 | 株式会社日立ハイテクノロジーズ | Method and system for fractional quantitative analysis of arsenic, selenium and antimony |
| JP5752564B2 (en) * | 2011-11-01 | 2015-07-22 | 一般財団法人電力中央研究所 | Method for analyzing water-soluble selenium |
| JP5752563B2 (en) * | 2011-11-01 | 2015-07-22 | 一般財団法人電力中央研究所 | Water-soluble selenium analysis system |
| JP6141668B2 (en) * | 2013-03-29 | 2017-06-07 | 一般財団法人電力中央研究所 | Determination of selenium by chemical form |
| JP6128523B2 (en) * | 2013-06-24 | 2017-05-17 | 国立大学法人 熊本大学 | Method for chemiluminescence analysis of water-soluble selenium |
| CN104655603B (en) * | 2015-02-10 | 2017-10-24 | 中国农业科学院农产品加工研究所 | A kind of discrimination method of selenium-rich rice |
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| JPH11142387A (en) * | 1997-11-05 | 1999-05-28 | Mitsubishi Heavy Ind Ltd | Method for separating determining quadrivalent selenium from hexavalent selenium in solution |
| JP2003268457A (en) * | 2002-03-15 | 2003-09-25 | Mitsubishi Materials Corp | Method for dissolving substance containing selenium and platinum group element |
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| JPH11142387A (en) * | 1997-11-05 | 1999-05-28 | Mitsubishi Heavy Ind Ltd | Method for separating determining quadrivalent selenium from hexavalent selenium in solution |
| JP2003268457A (en) * | 2002-03-15 | 2003-09-25 | Mitsubishi Materials Corp | Method for dissolving substance containing selenium and platinum group element |
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