JP4523805B2 - X-ray fluorescence analysis method for trace elements in water, column and system used in the method - Google Patents

Description

  The present invention relates to a method for fluorescent X-ray analysis of trace elements contained in a liquid such as a test solution obtained from a soil sample, and a column and a system used in the method.

  Harmful elements such as lead, arsenic, and hexavalent chromium have strict environmental standards for soil and groundwater because even a trace amount can adversely affect the human body and the environment. For example, according to the environmental standards related to soil contamination (Environment Agency Notification No. 46), when lead or arsenic is contained in a test solution prepared from soil, the concentration thereof is 10 μg / L or less. It is supposed to be. In addition, at the site of soil excavation work, there is a regulation that, after taking into account the risk of harmful elements, the excavated soil cannot be backfilled unless harmful element analysis is performed.

  Here, publicly accepted methods for analyzing harmful elements contained in the environment are atomic absorption spectrophotometry and ICP emission spectroscopic analysis. Since these methods can detect extremely low concentrations of elements, they are suitable for analysis of soil and groundwater that require analytical ability at a level of several μg / L to several tens of μg / L. However, on the other hand, since the equipment required for the implementation is large and ancillary equipment is also necessary, it cannot be analyzed on site. Therefore, there is a problem that it takes about two weeks including the waiting time of analysis until a test solution is prepared and the analysis result is obtained. For these reasons, the conventional soil excavation work and the like required more cost and time than necessary.

  In contrast to these official methods, there is a colorimetric method and the like as a relatively simple analytical method that can be carried out in the field. However, such a simple analysis method is originally a method for wastewater management and has a high measurement limit value. Therefore, it is not suitable for analysis of trace elements at a level of several μg / L to several tens of μg / L.

  An analysis method using a fluorescent X-ray analyzer is similar to the simple analysis method. This fluorescent X-ray analyzer has the advantage that qualitative analysis and quantitative analysis of a substance can be performed quickly, and in recent years, there is a portable type. However, there is still a problem that the analytical ability is limited. The measurement object is limited to a tangible object, and when the measurement object substance is an aqueous solution, the measurement is generally performed by dropping and drying the droplet. In this case, however, it is impossible to measure heavy metals with low concentrations at the soil environmental standard level.

Here, there is a chelate-forming compound that can capture heavy metals. For example, Patent Documents 1 and 2 disclose a powdery chelate trapping material and a chelate-forming fiber into which chelate-forming functional groups are introduced, respectively, and have a trapping ability for Cu, Fe, B, and the like. Are listed. However, these documents relate to the chelate-forming compound itself for capturing metals, and there is no description or suggestion on how to apply it to soil analysis or the like.
JP 2000-169828 A JP 2001-123379 A

  As described above, harmful elements such as lead and arsenic have an adverse effect on the human body and the environment even in very small amounts, and therefore analysis at a level of several μg / L to several tens of μg / L is necessary. On the other hand, such an analytical method having high sensitivity has a problem that it is difficult to carry out in the field, and it takes a relatively long time to obtain a result.

  Therefore, the problem to be solved by the present invention is a method that enables analysis of a very small amount of harmful metal elements, etc. in a fluorescent X-ray analysis method that is capable of analysis at a soil treatment site or the like but has insufficient analytical ability. And providing a column and system for use in the method.

  In order to solve the above-mentioned problems, the inventors of the present invention have made extensive studies on a method of applying the fluorescent X-ray analysis method to the analysis of trace harmful elements contained in soil or the like. As a result, if a column packed with a chelate polymer according to the element to be analyzed is used, the element can be concentrated at the top of the column, etc. Compared to the case where the chelate polymer is adsorbed by a batch method. The present invention has been completed by finding that the detection sensitivity becomes high and trace elements can be detected.

  That is, the fluorescent X-ray analysis method for trace elements in water according to the present invention includes (1) a column packed with a chelate polymer having a functional group having a chelate-forming ability with a metal and / or a similar metal in the side chain. A step of adsorbing a metal and / or a similar metal in a liquid to be analyzed to a chelate polymer by passing the analysis liquid (hereinafter referred to as “step (1)”); (2) a metal and / or a similar metal A process of performing X-ray fluorescence elemental analysis by irradiating the adsorbed chelate polymer with fluorescent X-rays (hereinafter referred to as "process (2)"); and (3) A step (hereinafter referred to as “step (3)”).

  The fluorescent X-ray analysis method analyzes one or more elements selected from the group consisting of Pb, As, Cd, Se, B, Hg, Fe, Cu, Zn, Cr, Ni, Mo, and Sb. It is preferable that. Even if these are trace amounts, they have an adverse effect on the human body and the environment. Therefore, while the environmental standard values in the soil and the like are extremely low, there has been no method for analyzing such low-concentration elements quickly and relatively easily. Therefore, this definition has the significance of clarifying the difference between the method of the present invention and the prior art.

  The functional groups having chelating ability include iminodiacetic acid, ethylenediaminediacetic acid, ethylenediaminetriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminedisuccinic acid, glutamic acid diacetic acid, thioglycolic acid, phosphoric acid, phosphonic acid, N One or more selected from the group consisting of -methyl-D-glucamine and D-glucamine is preferred. This is because they have a track record as being capable of adsorbing the harmful elements.

  The chelate polymer is preferably in the form of fibers, fabrics, or filter paper. This is because when applied to a column, these shapes have a very high adsorption rate for trace elements, so that the trace elements to be analyzed can be easily concentrated on the top of the column. As the chelate polymer, a fibrous polymer having an aspect ratio of 20 or less and a fibrous polymer having a bulk specific gravity of 0.15 g / mL or more are suitable. According to the findings by the present inventors, it is possible to efficiently adsorb and concentrate trace elements when the bulk specific gravity is 0.15 g / mL or more, enabling more efficient analysis, This is because the bulk specific gravity can be increased when a fibrous polymer having an aspect ratio of 20 or less is used. Therefore, after the step (1), it is preferable to increase the bulk specific gravity of the chelate polymer by compressing the chelate polymer adsorbed with the metal and / or the similar metal.

  In addition, after the step (1), it is preferable to pass a water-soluble and volatile organic solvent through the column and dry the chelate polymer. This is because if the moisture remains in the sample during the fluorescent X-ray analysis, the sensitivity is slightly lowered.

  As the main skeleton of the chelate polymer, cellulose is preferable. This is because cellulose has high hydrophilicity, so that the wettability with a liquid to be analyzed is improved, and an auxiliary chelating effect by a polyvalent hydroxyl group is obtained, so that the adsorption efficiency of the target analytical element is increased.

  In the fluorescent X-ray analysis method, a column filled with a chelate polymer having a functional group having a chelate-forming ability with a metal in the side chain and a functional group having a chelate-forming ability with a similar metal are provided in the side chain. A mode in which a column filled with a chelate polymer is connected in series and a metal and a similar metal are analyzed simultaneously is preferable. By using a chelate polymer having specificity for a chelate-forming element and simultaneously analyzing a plurality of elements, a more efficient analysis is possible.

  The element concentration in the liquid to be analyzed obtained by the fluorescent X-ray analysis method may be converted into the element concentration in the soil.

  The column of the present invention is for use in the above-mentioned fluorescent X-ray analysis method, and a chelate polymer having a functional group having a chelate-forming ability with a metal and / or a similar metal in a side chain is used in the analysis solution. It is filled with a container having an inflow port and an outflow port, and is further characterized in that a filter medium having a pore diameter through which an analyte liquid can pass and which does not allow a chelate polymer to pass through is attached to the outflow port.

  In the above-described column, a filter medium that can transmit X-rays and can pass an analysis solution may be attached to the inlet. This is because the side where the metal and / or the similar metal is concentrated can be subjected to fluorescent X-ray analysis as it is, and efficient analysis becomes possible.

  The system of the present invention is for preparing a sample to be subjected to fluorescent X-ray elemental analysis in the above-mentioned fluorescent X-ray analysis method, wherein a functional group having the ability to form a chelate with a metal and / or a similar metal is added to the side chain. A liquid-feeding pump for feeding the analyte liquid, a liquid-feeding pump for feeding washing water, and a water-soluble and volatile organic solvent to the column filled with the chelate polymer Liquid pumps to be used (note that these pumps are not limited to being separate but can be shared by one or two); a suction pump for sucking the remaining liquid in the column; and A dryer for drying the chelate polymer in the column.

  According to the method of the present invention, a result can be obtained quickly and can be carried out in the field. On the other hand, a fluorescent X-ray analysis method having insufficient analytical ability can be used for analyzing harmful elements contained in trace amounts in soils and the like. Can be applied. As a result, the time required for analysis is shortened compared to the official method that can obtain the same detection sensitivity, and further, the construction period for soil excavation work that requires analysis of harmful elements can be greatly shortened. . Therefore, the method of the present invention and the column and system used in the method are extremely excellent in industry.

The fluorescent X-ray analysis method for trace elements in water according to the present invention is at least:
(1) By passing an analyte solution through a column packed with a chelate polymer having a functional group having a chelate-forming ability with a metal and / or a similar metal in the side chain, the metal in the analyte solution and / or Or a step of adsorbing a similar metal to the chelate polymer (step (1));
(2) A step of performing fluorescent X-ray elemental analysis by irradiating a chelate polymer adsorbing a metal and / or a similar metal with fluorescent X-rays (step (2)); and (3) Step of converting to element concentration in the liquid to be analyzed (Step (3));
including. Hereinafter, each of these steps will be described.

Process (1)
First, the column of the present invention will be described. In the column of the present invention, as shown in FIGS. 1 and 2, a chelate polymer having a functional group having a chelate-forming ability with a metal and / or a similar metal in the side chain has an inlet and an outlet of an analysis solution. The container is filled with a filter medium having a pore diameter that allows the analyte liquid to pass therethrough and does not allow the chelate polymer to pass therethrough.

  Select a chelate polymer that has a functional group that can form a chelate with a metal and / or a similar metal in the side chain according to the type of metal or similar metal to be analyzed. Can be used. The type is not particularly limited, but more specifically, for example, on the main skeleton such as cellulose, iminodiacetic acid, ethylenediaminediacetic acid, ethylenediaminetriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediamine disuccinic acid, glutamic acid diacetic acid, A compound having one or more selected from the group consisting of thioglycolic acid, phosphoric acid, phosphonic acid, N-methyl-D-glucamine and D-glucamine in the side chain is used.

  There are no particular limitations on the types of metals and similar metals to be analyzed in the present invention, but considering the effects of the present invention that an extremely small amount of elements can be analyzed quickly, it is listed as a harmful element in environmental standards. Analyzes are required for analysis at construction sites. Examples of such harmful elements include Pb, As, Cd, Se, B, Hg, Fe, Cu, Zn, Cr, Ni, Mo, and Sb.

  Such a chelate polymer is preferably in the form of a fiber, a cloth, or a filter paper. By filling the fibrous chelate polymer into the column as shown in FIG. 1, the element to be analyzed in the liquid to be analyzed can be reliably captured and concentrated on the top of the column. In addition, a chelate polymer in the form of a cloth or filter paper has an advantage that the treatment after the element to be analyzed is captured and concentrated is simple (see FIG. 2). The chelate polymer is preferably a fibrous polymer having a bulk specific gravity of 0.15 g / mL or more. In the present invention, the metal or the like metal in the analyte liquid passed through the column is concentrated by being adsorbed on the chelate polymer. At that time, if the chelate polymer is dense, the efficiency of adsorption of a metal or the like with respect to the moving speed of the liquid to be analyzed in the column increases, so that the analytical performance can be improved accordingly. Furthermore, if the fibrous polymer has an aspect ratio of 20 or less, the bulk specific gravity increases and the analytical performance can be improved.

  When the sample to be analyzed by the method of the present invention is a liquid such as waste water, a filtered solution or the like may be used as it is. However, when the sample is soil or the like, it is necessary to extract the element to be analyzed into water or the like. For example, a test solution may be prepared from the soil to be analyzed using the method of Environmental Agency Notification No. 46 of 1991, “Environmental Standards for Soil Contamination (Elution Amount)”.

  The liquid to be analyzed is passed through the column by a liquid feed pump. As a result, the element to be analyzed is captured by the corresponding chelate polymer and concentrated on the top of the column. It is preferable that the liquid passing speed is low. This is because the range of element adsorption in the column becomes narrower and the degree of concentration increases, resulting in improved analytical performance.

  If there are multiple analytes, use chelate polymers that have a certain degree of adsorption specificity depending on the analyte, and install a column filled with these chelate polymers in series to analyze metals and similar metals, You may analyze metals or different kinds of metals simultaneously. For example, a mode in which a column having an ability to adsorb metals and a column for similar metals is conceivable.

  Next, the column is washed by passing washing water through the liquid feed pump and further removing the washing water by suction through the suction pump. In the fluorescent X-ray analysis, a highly sensitive analysis result can be obtained even if the analysis sample contains moisture. However, in order to obtain higher sensitivity, it is preferable to dry the chelate polymer. As a preferred embodiment, after removing water by passing a water-soluble and volatile organic solvent through a liquid feed pump, the organic solvent is also removed by sending warm air or heating. Things can be mentioned.

  Regardless of the drying, the chelate polymer after adsorbing a metal or the like is preferably compressed to increase the bulk specific gravity. Again, this is to improve the sensitivity of the fluorescent X-ray analysis.

  FIG. 3 shows a system for preparing a sample to be subjected to fluorescent X-ray elemental analysis in the next step (2).

Process (2)
Next, as described above, X-ray fluorescence elemental analysis is performed by irradiating the chelate polymer adsorbing the metal and / or the similar metal with fluorescent X-rays. This step may be performed according to the existing fluorescent X-ray elemental analysis. For example, in the case of an apparatus that emits fluorescent X-rays from below, the upper part of the column (the upper part of the chelate polymer) on which metal or the like is adsorbed must be directed downward. Therefore, when the fibrous chelate polymer is packed in the column, it is necessary to cover the upper part of the column with an X-ray permeable membrane or the like so that the dried chelate polymer does not fall out. If a column with a filter paper attached to the upper part is used as the column, it may be installed in the analyzer as it is without performing such an operation.

Process (3)
The obtained fluorescent X-ray elemental analysis result (fluorescent X-ray intensity) can be converted to the element concentration in the analyzed liquid by collating with a calibration curve prepared in advance or afterwards.

  The calibration curve used here measured the fluorescent X-ray intensity of the analysis target solution having a standard element concentration under the same conditions as in the above step (1), and clarified the relationship between the element concentration and the fluorescent X-ray intensity. Is. Incidentally, the element concentration and the fluorescent X-ray intensity should be in a proportional relationship, but since there was no idea of efficiently concentrating the analysis target element in the conventional technology, a calibration curve showing a clear proportional relationship was obtained. No satisfactory analysis results could not be obtained due to a small inclination. However, according to the present invention, it is possible to obtain a calibration curve with a clear proportional relationship and a large slope, and thus it is possible to obtain a more accurate analysis result.

  Moreover, if a calibration curve showing the relationship between the concentration of the analysis target element in the soil and the fluorescent X-ray intensity is created, the result of the fluorescent X-ray elemental analysis can be converted into the elemental concentration in the soil.

  Hereinafter, the present invention will be described in more detail by way of examples, but the scope of the present invention is not limited thereto.

Example 1
The upper part is opened as an inflow port, and the lower part is provided with No. 6 on the bottom surface of a polypropylene container having an inner diameter: 7 mm, an outer diameter: 8.5 mm, and a height: 16 mm. 5A filter paper (pore size: 7 μm) is spread, iminodiacetic acid is immobilized as a chelate polymer, 0.15 g of chelate-forming fiber having a diameter of 32 μm, a length of 300 μm, and an aspect ratio of 9.4 Packed (bulk specific gravity: 0.3 g / mL) to prepare four sample columns.

  From the top of each sample column, 300 mL of a standard Pb aqueous solution having a concentration of 0, 10, 20, 50 μg / L was passed at a flow rate of 6 mL / min. When the Pb concentration in the obtained effluent was analyzed by an ICP mass spectrometer, it was 5 μg / L or less, which is the lower limit of quantification of this analyzer, so that Pb in the standard solution was a chelate-forming fiber. It was confirmed that it was adsorbed on the surface. Next, 10 mL of ion-exchanged water and then 10 mL of acetone were passed from the top of each sample column, and then the excess liquid remaining in the chelate-forming fiber packed layer was sucked from the bottom using a suction pump. Further, warm air of 60 ° C. was blown from the upper part of the sample column for 10 minutes to dry the chelate-forming fibers, and an X-ray permeable membrane was attached to the upper part of the column to prepare a sample for fluorescent X-ray analysis.

  Next, after setting in an energy dispersive X-ray fluorescence spectrometer (OURSTEX 140/12 type) manufactured by Hours Tech, with the upper part of each column facing downward, the X-ray integrated intensity (Lα ray (10.5 keV) of Pb) cps) was measured, and the relationship between the Pb concentration of the passed standard solution and the X-ray integrated intensity was plotted and shown in FIG.

  According to the result, a very good linear relationship was recognized between the Pb concentration of the standard solution passed through and the X-ray integral intensity. Furthermore, when analyzing a solution having a low Pb concentration of several μg / L to several tens of μg / L, which conventionally had to use an ICP mass analyzer or a flameless atomic absorption spectrometer, the column of the present invention is used. It was proved that quantitative analysis by a fluorescent X-ray analyzer becomes possible.

Example 2
Using the calibration curve obtained in Example 1, the actual soil sample was analyzed. First, according to the Environmental Agency Notification No. 46 of August 1991, about 300 mL of a test solution prepared from a soil sample containing Pb, after preparing an analytical sample by the same method as in Example 1, the X-ray integral intensity was It was measured. The value obtained using the above calibration curve was converted to Pb concentration, which was 15 μg / L. Moreover, when Pb density | concentration was measured using the ICP mass spectrometer about the same test solution, it was 16 micrograms / L.

  From the above results, according to the fluorescent X-ray analysis method of the present invention, the Pb analysis value equivalent to the analysis method using the ICP mass spectrometer, which is the official method, even for a low-concentration sample of tens of μg / L. Proved to be

Example 3
In the calibration curve preparation procedure of Example 1 above, after filling the container with chelate-forming fibers, No. Each standard Pb solution was passed through after attaching 5A filter paper. Further, after the chelate-forming fiber was dried, the X-ray integral intensity (cps) was measured in the same manner except that the X-ray permeable membrane was not attached to the upper part of the container. The relationship between the obtained value and each Pb concentration is shown in FIG.

  According to the results, as a method for preventing disturbance of the concentrated portion of the chelate-forming fiber adsorbed with metal or a similar metal when the container is turned upside down in order to irradiate X-rays during fluorescent X-ray analysis, Even if a filter paper is used instead of the ray permeable membrane, the X-ray intensity hardly decreases. Therefore, it has been clarified that the operation from liquid passing to X-ray irradiation can be performed more easily by using the filter paper also in the upper part of the container.

Example 4
In the calibration curve preparation procedure of Example 1 above, the chelate-forming fiber after Pb adsorption was washed with ion-exchanged water, and further sucked with a suction pump, and then washed with acetone and not dried (chelate-forming fiber). The content of water was about 50%), and other results are shown in FIG.

  As apparent from the results, when the chelate-forming fiber contains about 50% of water, the X-ray intensity was reduced to about 65% as compared with the case where the fiber was dried. However, since the linearity of the calibration curve is good, it is possible to omit the drying step in consideration of simplification of the operation procedure.

Comparative Example 1
A similar experiment was also performed when the batch processing was performed without using the column according to the present invention. That is, 300 mL of each standard Pb solution having a Pb concentration of 0, 10, 20, 50 μg / L was placed in a glass beaker, and 0.15 g of iminodiacetic acid-type chelate-forming fiber used in the above examples was further added. After stirring for 1 hour at room temperature, the chelating fibers were filtered, washed with acetone and dried. This dry chelate-forming fiber was filled in the same container as that used in Example 1, and a calibration curve was prepared in the same manner as in Example 1 thereafter. The results are shown in FIG.

  As can be seen by comparing FIG. 4 and FIG. 7, even in FIG. 7, the Pb concentration of the standard solution and the X-ray integrated intensity are linearly related, but the X-ray intensity is about 35% compared to FIG. It is falling. Therefore, although a certain effect can be obtained even by the batch adsorption method, according to the method of the present invention that is the column adsorption method, the Pb concentration contained in the test soil sample is so low that it cannot be detected by the conventional method or the batch adsorption method. Even the detection is possible, and the method of the present invention was found to be extremely excellent.

Example 5
In Example 1 above, N-methyl-D-glucamine-immobilized fiber was used as the chelate-forming fiber, and the standard Pb aqueous solution was replaced with the standard As (arsenic) (V) aqueous solution. A calibration curve of As was created. The results are shown in FIG.

  As shown in FIG. 8, very good linearity is obtained even when the analysis target element is As. Therefore, in the method of the present invention, it is possible to analyze a wide range of elements regardless of metals or similar metals by selecting the type of chelate-forming fiber that should adsorb the elements according to the element to be analyzed. Has been demonstrated.

It is a schematic diagram of the column packed with a fibrous thing as a chelate polymer. It is a schematic diagram of a column using a cloth-like or filter paper-like chelate polymer. It is a schematic diagram which shows the system for preparing the sample which performs a fluorescent X-ray elemental analysis at the process (2) of this invention. It is a calibration curve obtained by plotting the X-ray integrated intensity obtained by fluorescent X-ray analysis of a standard Pb solution and the Pb concentration by the method of the present invention. It can be seen that an X-ray integrated intensity that can be sufficiently used as a calibration curve can be obtained even with a very low concentration solution of 10 to 50 μg / L. It is a calibration curve obtained by providing a filter paper on the top of the column of the present invention to simplify the fluorescent X-ray analysis. As in FIG. 1, it can be used sufficiently in elemental analysis in soil and the like. In the method of this invention, it is a calibration curve created based on the result of fluorescent X-ray analysis performed without sufficiently removing moisture from the column. Although the slope is smaller than that of the calibration curve shown in FIGS. 1 and 2, it is sufficiently usable for elemental analysis in soil. Regardless of the method of the present invention, it is a calibration curve prepared based on the result of X-ray fluorescence analysis of Pb adsorbed on a chelate-forming fiber by a batch method. When the slope is small and it is used for actual elemental analysis in soil, detailed results may not be obtained. It is a calibration curve created by the method of the present invention, where As is the analysis target. As in the case where the analysis target is Pb, it can be seen that it can be sufficiently used for elemental analysis in soil and the like.

Explanation of symbols

1: Inlet 2: Outlet 3a: Fibrous chelate polymer 3b: Fabric-like or filter paper-like chelate polymer 4: Filter medium 5: Liquid feed pump 6: Invention column 7: Suction pump 8: Hot air generator

Claims (14)

A method for X-ray fluorescence analysis of trace elements in water,
(1) By passing an analyte solution through a column filled with a chelate polymer having a functional group having a chelate-forming ability with a metal and / or a similar metal in the side chain, the metal in the analyte solution and / or Or a step of adsorbing a similar metal to the chelate polymer (hereinafter referred to as “step (1)”);
(2) a step of performing fluorescent X-ray elemental analysis by irradiating a chelate polymer adsorbing a metal and / or a similar metal with a fluorescent X-ray in a column ; and (3) the obtained elemental analysis value is used as an analysis solution. Converting to elemental concentration in
A method for fluorescent X-ray analysis of trace elements in water, comprising:   One or more elements selected from the group consisting of Pb, As, Cd, Se, B, Hg, Fe, Cu, Zn, Cr, Ni, Mo, and Sb are analyzed as the metal and / or the similar metal. The fluorescent X-ray analysis method according to claim 1.   Examples of the functional groups having chelating ability include iminodiacetic acid, ethylenediaminediacetic acid, ethylenediaminetriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminedisuccinic acid, glutamic acid diacetic acid, thioglycolic acid, phosphoric acid, phosphonic acid, N- The fluorescent X-ray analysis method according to claim 1 or 2, wherein one or more selected from the group consisting of methyl-D-glucamine and D-glucamine is used.   The fluorescent X-ray analysis method according to claim 1, wherein a fibrous material is used as the chelate polymer.   The fluorescent X-ray analysis method according to claim 4, wherein a fibrous polymer having an aspect ratio of 20 or less is used as the chelate polymer.   The fluorescent X-ray analysis method according to claim 4 or 5, wherein a fibrous polymer having a bulk specific gravity of 0.15 g / mL or more is used as the chelate polymer.   The fluorescent X-ray analysis method according to claim 4, wherein the chelate polymer has a cloth shape or a filter paper shape.   The fluorescent X-ray according to any one of claims 1 to 7, wherein after the step (1), the bulk specific gravity of the chelate polymer is increased by compressing the chelate polymer adsorbed with the metal and / or the similar metal. Analysis method.   The fluorescent X-ray analysis method according to any one of claims 1 to 8, wherein after the step (1), a water-soluble and volatile organic solvent is passed through the column and the chelate polymer is dried.   The fluorescent X-ray analysis method according to claim 1, wherein the main skeleton of the chelate polymer is cellulose.   A column packed with a chelate polymer having a side chain with a functional group capable of forming a chelate with a metal, and a column packed with a chelate polymer having a side chain with a functional group capable of forming a chelate with a similar metal The fluorescent X-ray analysis method according to any one of claims 1 to 10, wherein the two are connected in series to simultaneously analyze a metal and a similar metal.   The fluorescent X-ray analysis method according to any one of claims 1 to 11, wherein the obtained element concentration in the liquid to be analyzed is converted into an element concentration in the soil. A column for use in the fluorescent X-ray analysis method according to any one of claims 1 to 12,
A chelate polymer having a functional group capable of forming a chelate with a metal and / or a similar metal in a side chain is filled in a container having an inlet and an outlet for an analyte solution, and A filter medium that can pass through and has a pore size that does not allow the chelate polymer to pass through is attached to the outlet, and a filter medium that can transmit X-rays and can pass the analyte is attached to the inlet . A column characterized by The fluorescent X-ray analysis method according to any one of claims 1 to 12, which is a system for preparing a sample to be subjected to fluorescent X-ray elemental analysis,
A liquid feed pump for feeding an analyte liquid, a liquid feed pump for feeding wash water, and a water-soluble and volatile organic solvent to the column according to claim 13 Feed pump;
A suction pump for aspirating residual liquid in the column; and a dryer for drying the chelate polymer in the column;
A system comprising:

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