JP2005134277A - Method of regulating liquid sample for fluorescent x-ray analysis - Google Patents

Method of regulating liquid sample for fluorescent x-ray analysis Download PDF

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JP2005134277A
JP2005134277A JP2003371655A JP2003371655A JP2005134277A JP 2005134277 A JP2005134277 A JP 2005134277A JP 2003371655 A JP2003371655 A JP 2003371655A JP 2003371655 A JP2003371655 A JP 2003371655A JP 2005134277 A JP2005134277 A JP 2005134277A
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liquid sample
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JP3823156B2 (en
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Takao Moriyama
孝男 森山
Naeko Toma
苗子 東馬
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Rigaku Corp
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Rigaku Industrial Corp
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<P>PROBLEM TO BE SOLVED: To provide a regulation method for a liquid sample for fluorescent X-ray analysis allowing the fluorescent X-ray analysis by a spot method, even in arsenic or the like of a heavy metal of a positive ion vaporized easily when dried, and a fluoride ion of a negative ion. <P>SOLUTION: Since a valency of the positive ion of the heavy metal is brought into a valency stable against a liquid absorbent 4 by oxidation reaction of the spotted heavy metal in a solution with nitric acid, the heavy metal is immobilized to prevent vaporization so as to allow the fluorescent X-ray analysis by the spot method for the heavy metal of the positive ion easily vaporized when dried. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

本発明は、河川水などの環境分析に係る液体試料に含まれる分析対象元素（含有成分）を蛍光Ｘ線分析するときに使用される、点滴法による蛍光Ｘ線分析用液体試料の調整方法に関するものである。   The present invention relates to a method for preparing a liquid sample for X-ray fluorescence analysis by the drip method, which is used when X-ray fluorescence analysis is performed on an analysis target element (containing component) contained in a liquid sample for environmental analysis such as river water. Is.

従来から、液体試料を前処理して含有成分を蛍光Ｘ線分析するための技術として、ろ紙に液体試料を滴下して乾燥させることにより含有成分を濃縮し、かつ保持させる点滴法が知られている。   Conventionally, as a technique for fluorescent X-ray analysis of contained components by pretreatment of a liquid sample, a drip method is known in which the contained components are concentrated and retained by dropping the liquid sample onto a filter paper and drying. Yes.

ところで、液体試料に含まれる分析対象元素が揮散しやすいもの、例えば、ＨＣｌ（塩酸）溶液中の塩素やＨ２ＳＯ４（硫酸）溶液中の硫黄の場合には、ろ紙への点滴後に乾燥させてから蛍光Ｘ線強度を測定するときに、前記塩素や硫黄が揮散してしまい、正確な分析が困難なことから、ろ紙に点滴される塩素や硫黄に反応して不揮発性生成物を作る安定化剤をろ紙に点滴させることが知られている（例えば、特許文献１）。
特開平７−３１１１３１号公報 By the way, in the case where the element to be analyzed contained in the liquid sample is easily volatilized, for example, chlorine in HCl (hydrochloric acid) solution or sulfur in H 2 SO 4 (sulfuric acid) solution, it is dried after instilling on the filter paper. When measuring the X-ray fluorescence intensity, the chlorine and sulfur are volatilized and accurate analysis is difficult. It is known to drip the agent on filter paper (for example, Patent Document 1).
JP-A-7-311131

しかし、例えば河川水などの環境分析に係る液体試料に含まれる分析対象元素が、乾燥時に揮散しやすい＋イオンの重金属のヒ素（Ａｓ）などや−イオンのフッ素（Ｆ）である場合に、現状では、点滴法による蛍光Ｘ線分析用液体試料の安定な調整方法は実現されていない。   However, for example, when the analysis target element contained in a liquid sample related to environmental analysis such as river water is arsenic (As) of a + ion heavy metal that is easily volatilized during drying, or -ion fluorine (F). However, a stable adjustment method of a liquid sample for fluorescent X-ray analysis by the drip method has not been realized.

他方、液体試料が飛散するのを防止するために、試料室内などをＨｅ置換することも知られているが、分析の度にＨｅ置換する必要があり、分析作業が煩雑になる。   On the other hand, in order to prevent the liquid sample from scattering, it is also known to perform He substitution in the sample chamber and the like, but it is necessary to perform He substitution for each analysis, which complicates the analysis work.

本発明は、前記の問題点を解決して、乾燥時に揮散しやすい＋イオンの重金属のヒ素などや−イオンのフッ素であっても、点滴法により蛍光Ｘ線分析できる蛍光Ｘ線分析用液体試料の調整方法を提供することを目的としている。   The present invention solves the above-mentioned problems, and a liquid sample for fluorescent X-ray analysis that can be analyzed by fluorescent X-ray analysis by the drip method even if it is + ion heavy metal arsenic or -ion fluorine that is easily volatilized during drying. The purpose is to provide an adjustment method.

前記目的を達成するために、本発明の一構成は、液体試料を液体吸収材に点滴し乾燥させて含有成分を蛍光Ｘ線分析するための蛍光Ｘ線分析用液体試料を調整する方法であって、乾燥時に揮散しやすい＋イオンの重金属のヒ素（Ａｓ）、鉛（Ｐｂ）またはクロム（Ｃｒ）の溶液である液体試料を前記液体吸収材に点滴すると同時に、硝酸溶液を滴下して、溶液乾燥時に前記＋イオンの重金属の揮散を防止するものである。   In order to achieve the above object, one configuration of the present invention is a method of preparing a liquid sample for fluorescent X-ray analysis for instilling a liquid sample onto a liquid absorbent material and drying it to perform X-ray fluorescence analysis of the contained components. In addition, a liquid sample which is a solution of ionic heavy metal arsenic (As), lead (Pb) or chromium (Cr), which is easily volatilized at the time of drying, is dropped on the liquid absorbent, and at the same time, a nitric acid solution is dropped. It prevents volatilization of the heavy metal of the + ions during drying.

この構成によれば、点滴された重金属を含んでいる溶液に対して、強い酸化作用のある濃硝酸を滴下することにより、重金属の＋イオンの価数をより大きな価数にすることができる。この反応により、液体吸収材上で乾燥時に揮散しにくい＋イオンを生成させる。したがって、点適法では問題であった乾燥時の揮散を防ぎ、蛍光Ｘ線により重元素の分析を安定に行うことができる。   According to this configuration, by adding concentrated nitric acid having a strong oxidizing action to a solution containing heavy metal that has been instilled, the valence of + ions of heavy metal can be increased. By this reaction, + ions that are difficult to be volatilized when dried on the liquid absorbent material are generated. Therefore, volatilization at the time of drying, which was a problem in the point application method, can be prevented, and analysis of heavy elements can be performed stably by fluorescent X-rays.

本発明の他の構成は、液体試料を液体吸収材に点滴し乾燥させて含有成分を蛍光Ｘ線分析するための蛍光Ｘ線分析用液体試料を調整する方法であって、乾燥時に揮散しやすい−イオンのフッ素（Ｆ）の溶液である液体試料を前記液体吸収材に点滴すると同時に、水酸化ナトリウム溶液を滴下して、溶液乾燥時に前記−イオンのフッ素の揮散を防止するものである。   Another configuration of the present invention is a method of preparing a liquid sample for X-ray fluorescence analysis for instilling a liquid sample onto a liquid absorbent and drying to analyze the contained components by X-ray fluorescence analysis, and is easy to evaporate during drying. -A liquid sample, which is a solution of ionic fluorine (F), is dropped on the liquid absorbent, and at the same time, a sodium hydroxide solution is dropped to prevent volatilization of the-ion fluorine during solution drying.

この構成によれば、点滴された溶液中のフッ素（Ｆ）と水酸化ナトリウム（ＮａＯＨ）とが化学反応して不揮発性生成物であるＮａＦをつくるので、フッ素を固定化させてその揮散を防止することができるから、乾燥時に揮散しやすいフッ素を点滴法により蛍光Ｘ線分析できる。   According to this configuration, fluorine (F) and sodium hydroxide (NaOH) in the instilled solution are chemically reacted to form a non-volatile product NaF, so that fluorine is fixed to prevent its volatilization. Therefore, X-ray fluorescence analysis can be performed by drip method on fluorine which is easily volatilized during drying.

好ましくは、前記蛍光Ｘ線分析用液体試料の調整方法を前記液体吸収材を保持する試料保持具を用いて行うものであって、前記試料保持具は、輪状の台座と、その台座に保持される周辺部およびＸ線を透過させるための透過部を有する厚さ１０μｍ未満の疎水性フィルムと、その疎水性フィルムの透過部に貼付された厚さ１μｍ以上１００μｍ以下のシート状の液体吸収材とを備え、その液体吸収材に前記液体試料および溶液が滴下されて乾燥されることにより、前記含有成分を保持してなるものである。   Preferably, the method for preparing the liquid sample for X-ray fluorescence analysis is performed using a sample holder that holds the liquid absorbent, and the sample holder is held on a ring-shaped base and the base. A hydrophobic film having a thickness of less than 10 μm having a peripheral part and a transmission part for transmitting X-rays, and a sheet-like liquid absorbent material having a thickness of 1 μm or more and 100 μm or less attached to the transmission part of the hydrophobic film; The liquid sample and the solution are dropped onto the liquid absorbent material and dried to hold the contained component.

この場合には、１次Ｘ線が照射される疎水性フィルムおよび液体吸収材はいずれも十分に薄いので、散乱線を減少させてバックグラウンドを抑制できる一方、疎水性フィルムに貼付された適切な厚さの液体吸収材で、十分な量の液体試料を保持して均一に凝縮できるので、より大きい強度の蛍光Ｘ線を均一に発生させることができる。これにより、液体試料中の含有成分が微量であっても検出感度を十分に向上できる。   In this case, since both the hydrophobic film and the liquid absorbent that are irradiated with the primary X-rays are sufficiently thin, the background can be suppressed by reducing the scattered radiation, while the appropriate film attached to the hydrophobic film is used. Since a sufficient amount of liquid sample can be held and condensed uniformly with the liquid absorbent material having a thickness, fluorescent X-rays with higher intensity can be generated uniformly. Thereby, even if the content component in a liquid sample is a trace amount, detection sensitivity can fully be improved.

以下、本発明の実施形態を図面に基づいて説明する。図１は、本発明の第１実施形態に係る蛍光Ｘ線分析用液体試料の調整方法を示す構成図である。この蛍光Ｘ線分析用液体試料の調整方法は、河川水の環境分析に係る液体試料１を試料保持具７に設けられた液体吸収材４に点滴し乾燥させて含有成分を蛍光Ｘ線分析するために用いられるものである。   Hereinafter, embodiments of the present invention will be described with reference to the drawings. FIG. 1 is a configuration diagram illustrating a method for preparing a fluorescent X-ray analysis liquid sample according to the first embodiment of the present invention. In this method of preparing a liquid sample for fluorescent X-ray analysis, the liquid sample 1 relating to the environmental analysis of river water is instilled on the liquid absorbent 4 provided in the sample holder 7 and dried to perform X-ray fluorescence analysis of the contained components. It is used for this purpose.

液体試料１は、乾燥時に揮散しやすい３価のヒ素（Ａｓ３＋）のような＋イオンをもつ重金属の溶液（例えば、Ａｓ２Ｏ３溶液）である。図１に示すように、この調整方法は、例えば５００μｌの液体試料１を液体吸収材４に点滴するのと同時に、例えば３０μｌの硝酸溶液５を滴下する。液体試料１と硝酸溶液５を滴下することにより、液体吸収材４上で混合液体試料１０となる。混合液体試料１０の硝酸濃度は例えば５〜１０ｗｔ％である。 The liquid sample 1 is a heavy metal solution (for example, an As 2 O 3 solution) having + ions such as trivalent arsenic (As 3+ ) that is easily volatilized during drying. As shown in FIG. 1, in this adjustment method, for example, 500 μl of the liquid sample 1 is dropped on the liquid absorbent material 4, and at the same time, for example, 30 μl of the nitric acid solution 5 is dropped. By dropping the liquid sample 1 and the nitric acid solution 5, the mixed liquid sample 10 is formed on the liquid absorbent 4. The nitric acid concentration of the mixed liquid sample 10 is, for example, 5 to 10 wt%.

点滴された混合液体試料１０中でヒ素と硝酸とが混合し、硝酸の酸化作用により３価のヒ素（Ａｓ３＋）をより大きな価数の５価のヒ素（Ａｓ５＋）にすることができる。そうすると、液体吸収材４に対してヒ素が安定し固定化するので、点滴後の溶液乾燥時にヒ素の揮散を防止することができる。 Arsenic and nitric acid are mixed in the infused mixed liquid sample 10, and trivalent arsenic (As 3+ ) can be converted into pentavalent arsenic (As 5+ ) having a higher valence by the oxidizing action of nitric acid. Then, since arsenic is stabilized and fixed to the liquid absorbent material 4, volatilization of arsenic can be prevented when the solution is dried after the drip.

図３は、本調整方法でなされたヒ素（１ｐｐｍ含有）の試料について蛍光Ｘ線分析したときの定性スペクトルを示すもので、本調整方法によるヒ素溶液と硝酸溶液を同時に滴下した場合が図示αである。図示βはヒ素溶液のみを滴下した場合、図示γは原子吸光用標準溶液であって当初から揮散しないように処理したものを滴下した場合である。図示αの定性スペクトルは図示βの定性スペクトルとほぼ同一であり、ヒ素の揮散が防止されていることがわかる。   FIG. 3 shows a qualitative spectrum when a fluorescent X-ray analysis is performed on a sample of arsenic (containing 1 ppm) made by the present adjustment method, and the case where an arsenic solution and a nitric acid solution are dropped simultaneously by the present adjustment method is shown in FIG. is there. In the figure, β is when only an arsenic solution is dropped, and in the figure, γ is a standard solution for atomic absorption, which is treated so as not to be volatilized from the beginning. The qualitative spectrum of α shown in the figure is almost the same as the qualitative spectrum of β shown in the figure, and it can be seen that volatilization of arsenic is prevented.

このように、ヒ素と硝酸による酸化反応により、ヒ素を安定させ固定化させてその揮散を防止することができるから、乾燥時に揮散しやすいヒ素を点滴法により蛍光Ｘ線分析できる。   Thus, the arsenic and nitric acid can be stabilized and immobilized to prevent volatilization of the arsenic, so that arsenic that is easily volatilized during drying can be analyzed by the fluorescent X-ray analysis by the drip method.

この実施形態では、＋イオンの重金属としてヒ素（Ａｓ）を用いているが、鉛（Ｐｂ）、クロム（Ｃｒ）等であってもよい。   In this embodiment, arsenic (As) is used as the heavy metal of + ions, but lead (Pb), chromium (Cr), or the like may be used.

この調整方法は図１に示す試料保持具７を用いて行われる。この試料保持具７は、疎水性フィルムを安定に保持するための例えばポリエチレン、ポリスチレンなどの樹脂材料からなる輪状の台座２と、その台座２に保持される周辺部３ａおよびＸ線を透過させるための透過部３ｂを有する厚さ１０μｍ未満の疎水性フィルム３と、その疎水性フィルムの透過部３ｂに貼付された厚さ１μｍ以上１００μｍ以下のシート状の液体吸収材４とを備え、その液体吸収材４に液体試料１と硝酸溶液５が滴下されて乾燥されることにより、液体試料１の含有成分Ａｓを濃縮し、保持する。   This adjustment method is performed using the sample holder 7 shown in FIG. This sample holder 7 is used to transmit a ring-shaped pedestal 2 made of a resin material such as polyethylene or polystyrene, and a peripheral portion 3a held on the pedestal 2 and X-rays for stably holding the hydrophobic film. A hydrophobic film 3 having a thickness of less than 10 μm and a sheet-like liquid absorbent material 4 having a thickness of 1 μm or more and 100 μm or less attached to the transmission part 3b of the hydrophobic film. The liquid sample 1 and the nitric acid solution 5 are dropped onto the material 4 and dried, thereby concentrating and holding the contained component As of the liquid sample 1.

図２に図１の縦断面図を示すが、ここでは、疎水性フィルム３は、厚さ１．５μｍのポリエチレンテレフタレートからなり、直径が台座２の外径とほぼ同径の円形（図示と理解の容易のため、図では小さめに表している）で、周辺部３ａが台座２に密着して保持されている。周辺部３ａを除いた部分は、Ｘ線を透過させるための透過部３ｂである。図１では、台座２の内周は、疎水性フィルム３の下に隠れるので破線で示しているが、実際には透けて見える。また、ここでは、液体吸収材４は、あぶらとり紙のようにタルクを含有する厚さ数μｍの紙からなり、直径１．８ｃｍの円形で、例えばスプレーのり（成分はアクリルゴム（１０％）、有機溶剤（５４％）およびイソヘキサンガス（３６％）で、噴射用高圧ガスはジメチルエーテル）を液体吸収材４の裏に吹き付けて、疎水性フィルム３の中央部に貼付する。貼付に用いる接着剤は、このスプレーのりに限らず、分析の障害とならないものであればよい。   FIG. 2 shows a longitudinal sectional view of FIG. 1. Here, the hydrophobic film 3 is made of polyethylene terephthalate having a thickness of 1.5 μm, and the diameter is a circle having the same diameter as the outer diameter of the base 2 (as shown and understood). The peripheral portion 3a is held in close contact with the pedestal 2 in the figure. The part excluding the peripheral part 3a is a transmission part 3b for transmitting X-rays. In FIG. 1, the inner periphery of the base 2 is hidden under the hydrophobic film 3, so that it is indicated by a broken line. Further, here, the liquid absorbent material 4 is made of paper having a thickness of several μm containing talc, such as oil blotting paper, and has a circular shape with a diameter of 1.8 cm, for example, spray glue (component is acrylic rubber (10%) Then, an organic solvent (54%) and isohexane gas (36%), and the high-pressure gas for injection is dimethyl ether) are sprayed on the back of the liquid absorbent material 4 and attached to the center of the hydrophobic film 3. The adhesive used for sticking is not limited to this spray paste, and any adhesive that does not hinder analysis can be used.

図１のように液体吸収材４に液体試料１と硝酸溶液５を滴下すると、液体吸収材４の下および周囲には、疎水性フィルム３があるので、液体試料１と硝酸溶液５が混合された混合液体試料１０は、液体吸収材４から下方や周囲に染み出すことがなく、かつ表面張力を利用して２００μｌ以上６００μｌ程度まで滴下することができる。そして、液体試料１と硝酸溶液５を滴下した試料保持具７を乾燥させることにより、液体試料１の含有成分Ａｓを液体吸収材４に吸着させて保持させる。この状態の試料保持具７を、従来のろ紙と同様に試料ホルダ（従来用いられているＡl またはＴi 製の中空カップで、下地からの散乱線の影響がないもの）に装着し、液体吸収材４の部位に１次Ｘ線を照射して蛍光Ｘ線分析を行う。   When the liquid sample 1 and the nitric acid solution 5 are dropped onto the liquid absorbent material 4 as shown in FIG. 1, the liquid sample 1 and the nitric acid solution 5 are mixed because the hydrophobic film 3 exists under and around the liquid absorbent material 4. Furthermore, the mixed liquid sample 10 does not bleed out from the liquid absorbent material 4 or around it, and can be dropped to about 200 μl or more and about 600 μl using the surface tension. Then, by drying the sample holder 7 to which the liquid sample 1 and the nitric acid solution 5 are dropped, the component As of the liquid sample 1 is adsorbed and held on the liquid absorbent material 4. The sample holder 7 in this state is attached to a sample holder (a conventional Al or Ti hollow cup that is not affected by scattered rays from the base) in the same manner as a conventional filter paper, and a liquid absorbent material X-ray fluorescence analysis is performed by irradiating 4 sites with primary X-rays.

このように、この試料保持具７を用いることにより、１次Ｘ線が照射される疎水性フィルム３および液体吸収材４がいずれも十分に薄いので、散乱線を減少させてバックグラウンドを抑制できる。一方、疎水性フィルム３に貼付された適切な厚さの液体吸収材４で、十分な量の液体試料１を保持して均一に凝縮できるので、より大きい強度の蛍光Ｘ線を均一に発生させることができる。したがって、液体試料１中の含有成分Ａｓが微量であっても検出感度を十分に向上できる。   Thus, by using this sample holder 7, since both the hydrophobic film 3 and the liquid absorbent material 4 irradiated with the primary X-rays are sufficiently thin, the scattered radiation can be reduced and the background can be suppressed. . On the other hand, since a sufficient amount of the liquid sample 1 can be held and condensed uniformly with the liquid absorbent material 4 of an appropriate thickness attached to the hydrophobic film 3, higher-intensity fluorescent X-rays are uniformly generated. be able to. Therefore, even if the contained component As in the liquid sample 1 is very small, the detection sensitivity can be sufficiently improved.

なお、液体吸収材４は、疎水性フィルム３に貼り付けられることにより常に一定のテンションがかかっているので、例えば含有成分がきわめて微量である場合に、滴下、乾燥を繰り返して含有成分を多く凝縮させても、均一かつ安定に保持できる。また、従来の小面積の蒸着膜では、結晶化などにより十分均一に含有成分を凝縮させることは容易でないが、この試料保持具７では、適切な厚さ、面積のシート状の液体吸収材４により、含有成分を十分均一に凝縮させることができるので、後述するフッ素（Ｆ）のような軽元素についても十分安定した定量分析が可能である。   In addition, since the liquid absorbent 4 is always applied with a certain tension by being attached to the hydrophobic film 3, for example, when the amount of the contained component is very small, the dripping and drying are repeated to condense much of the contained component. Even if it makes it, it can hold uniformly and stably. Further, in the conventional small-area deposited film, it is not easy to condense the contained components sufficiently uniformly by crystallization or the like. However, in this sample holder 7, the sheet-like liquid absorbent 4 having an appropriate thickness and area. Therefore, it is possible to condense the contained components sufficiently uniformly, so that sufficiently stable quantitative analysis is possible even for light elements such as fluorine (F) described later.

次に、第２実施形態に係る蛍光Ｘ線分析用液体試料の調整方法について説明する。この蛍光Ｘ線分析用液体試料を調整する方法は、第１実施形態と異なり、乾燥時に揮散しやすい−イオンのフッ素（Ｆ）の溶液（例えば、ＨＦ溶液等）である液体試料の例えば５００μｌを液体吸収材４に点滴するのと同時に、例えば３０μｌの１ｗｔ％の水酸化ナトリウム（ＮａＯＨ）溶液を滴下して、溶液乾燥時に前記−イオンのフッ素の揮散を防止する。その他の構成は第１実施形態と同様である。   Next, a method for preparing a liquid sample for fluorescent X-ray analysis according to the second embodiment will be described. Unlike the first embodiment, this method of preparing a liquid sample for X-ray fluorescence analysis is easy to evaporate at the time of drying-for example, 500 μl of a liquid sample that is a solution of ionic fluorine (F) (for example, HF solution). At the same time that the liquid absorbent material 4 is instilled, for example, 30 μl of a 1 wt% sodium hydroxide (NaOH) solution is dropped to prevent volatilization of the − ion fluorine during solution drying. Other configurations are the same as those of the first embodiment.

点滴された溶液中のフッ素（Ｆ）と水酸化ナトリウム（ＮａＯＨ）とは、ＮａＯＨ＋ＨＦ→ＮａＦ＋Ｈ２Ｏのように化学反応して、不揮発性生成物であるＮａＦをつくり、液体吸収材４上に沈殿する。この際、水酸化ナトリウムをやや過多に入れることにより反応がより促進する。その後、乾燥されて蛍光Ｘ線分析用の試料となる。 Fluorine (F) and sodium hydroxide (NaOH) in the instilled solution chemically react like NaOH + HF → NaF + H 2 O to produce non-volatile product NaF, which is precipitated on the liquid absorbent 4 To do. At this time, the reaction is further promoted by adding a little excess of sodium hydroxide. Thereafter, it is dried to become a sample for fluorescent X-ray analysis.

図４は、本調整方法でなされたフッ素の試料についてフッ素０〜１００ｐｐｍ含有における定性スペクトルの各ピークをプロットしたときの検量線を示す。図４のように、定量分析に十分に使用できる検量線を作成できたことから、フッ素の揮散が防止されていることがわかる。   FIG. 4 shows a calibration curve when plotting each peak of the qualitative spectrum at a fluorine content of 0 to 100 ppm for a fluorine sample made by this adjustment method. As shown in FIG. 4, since a calibration curve that can be used sufficiently for quantitative analysis was created, it can be seen that volatilization of fluorine was prevented.

このように、フッ素と水酸化ナトリウムとの化学反応により、フッ素を安定させ固定化させてその揮散を防止することができるから、乾燥時に揮散しやすいフッ素を点滴法により蛍光Ｘ線分析できる。   Thus, the chemical reaction between fluorine and sodium hydroxide can stabilize and immobilize the fluorine to prevent its volatilization, so that fluorine that tends to volatilize during drying can be analyzed by fluorescent X-ray analysis by the drip method.

本発明の第１実施形態に係る蛍光Ｘ線分析用液体試料の調整方法を示す構成図である。It is a block diagram which shows the adjustment method of the liquid sample for a fluorescent X-ray analysis which concerns on 1st Embodiment of this invention. 図１の一部縦断面図である。It is a partial longitudinal cross-sectional view of FIG. 第１実施形態の調整方法でなされた分析による定性スペクトルを示す特性図である。It is a characteristic view which shows the qualitative spectrum by the analysis made with the adjustment method of 1st Embodiment. 第２実施形態の調整方法でなされた試料を用いた検量線を示す特性図である。It is a characteristic view which shows the calibration curve using the sample made with the adjustment method of 2nd Embodiment.

符号の説明Explanation of symbols

１：液体試料
４：液体吸収材
５：硝酸溶液
７：試料保持具 1: Liquid sample 4: Liquid absorbent material 5: Nitric acid solution 7: Sample holder

Claims (3)

液体試料を液体吸収材に点滴し乾燥させて含有成分を蛍光Ｘ線分析するための蛍光Ｘ線分析用液体試料を調整する方法であって、
乾燥時に揮散しやすい＋イオンの重金属のヒ素（Ａｓ）、鉛（Ｐｂ）またはクロム（Ｃｒ）の溶液である液体試料を前記液体吸収材に点滴すると同時に、硝酸溶液を滴下して、溶液乾燥時に前記＋イオンの重金属の揮散を防止する蛍光Ｘ線分析用液体試料の調整方法。 A method of preparing a liquid sample for fluorescent X-ray analysis for instilling a liquid sample onto a liquid absorbent and drying to analyze the contained components by fluorescent X-ray analysis,
A liquid sample, which is a ionic arsenic (As), lead (Pb) or chromium (Cr) solution that easily evaporates during drying, is instilled into the liquid absorbent, and at the same time, a nitric acid solution is added dropwise. A method for preparing a liquid sample for X-ray fluorescence analysis which prevents volatilization of the heavy metal of the + ion. 液体試料を液体吸収材に点滴し乾燥させて含有成分を蛍光Ｘ線分析するための蛍光Ｘ線分析用液体試料を調整する方法であって、
乾燥時に揮散しやすい−イオンのフッ素（Ｆ）の溶液である液体試料を前記液体吸収材に点滴すると同時に、水酸化ナトリウム溶液を滴下して、溶液乾燥時に前記−イオンのフッ素の揮散を防止する蛍光Ｘ線分析用液体試料の調整方法。 A method of preparing a liquid sample for fluorescent X-ray analysis for instilling a liquid sample onto a liquid absorbent and drying to analyze the contained components by fluorescent X-ray analysis,
Easy to volatilize during drying-Drop a liquid sample, which is a solution of ionic fluorine (F), onto the liquid absorbent and simultaneously drop a sodium hydroxide solution to prevent volatilization of the-ion fluorine during solution drying. A method for preparing a liquid sample for fluorescent X-ray analysis. 請求項１または２に記載の蛍光Ｘ線分析用液体試料の調整方法を前記液体吸収材を保持する試料保持具を用いて行うものであって、
前記試料保持具は、輪状の台座と、その台座に保持される周辺部およびＸ線を透過させるための透過部を有する厚さ１０μｍ未満の疎水性フィルムと、その疎水性フィルムの透過部に貼付された厚さ１μｍ以上１００μｍ以下のシート状の液体吸収材とを備え、その液体吸収材に前記液体試料および溶液が滴下されて乾燥されることにより、前記含有成分を保持してなるものである蛍光Ｘ線分析用液体試料の調整方法。




The method for preparing a liquid sample for fluorescent X-ray analysis according to claim 1 or 2 is performed using a sample holder that holds the liquid absorbent,
The sample holder is attached to a ring-shaped pedestal, a peripheral part held by the pedestal, a hydrophobic film having a thickness of less than 10 μm having a transmission part for transmitting X-rays, and a transmission part of the hydrophobic film. And a liquid absorbent material in the form of a sheet having a thickness of 1 μm or more and 100 μm or less, and the liquid sample and the solution are dropped onto the liquid absorbent material and dried to hold the contained components. A method for preparing a liquid sample for fluorescent X-ray analysis.




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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008122144A (en) * 2006-11-09 2008-05-29 Rigaku Industrial Co Specimen drip substrate for total-reflection fluorescence x-ray analysis, total reflection fluorescent x-ray analyzer, and total reflection fluorescent x-ray analysis method
JP2020118673A (en) * 2019-01-21 2020-08-06 ブルーカー ダルトニック ゲーエムベーハー Method for controlling sample on sample support for spectrum analysis

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008122144A (en) * 2006-11-09 2008-05-29 Rigaku Industrial Co Specimen drip substrate for total-reflection fluorescence x-ray analysis, total reflection fluorescent x-ray analyzer, and total reflection fluorescent x-ray analysis method
JP4537367B2 (en) * 2006-11-09 2010-09-01 株式会社リガク Sample reflection substrate for total reflection X-ray fluorescence analysis, total reflection X-ray fluorescence analyzer, and total reflection X-ray fluorescence analysis method
JP2020118673A (en) * 2019-01-21 2020-08-06 ブルーカー ダルトニック ゲーエムベーハー Method for controlling sample on sample support for spectrum analysis
US11802819B2 (en) 2019-01-21 2023-10-31 Bruker Daltonik Gmbh Method of sample preparation on a spectrometric sample support

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