Sample bag cell and X-ray fluorescence analysis method

Abstract

The invention provides a fluorescence X-ray analysis method and a sample bag cell, which can measure a liquid sample and can irradiate X-rays without bubbles generated in the measurement. A sample bag cell for a liquid sample, which is vertically disposed on a side-illuminated X-ray fluorescence analyzer, comprises: a first resin film disposed on the irradiation side of primary X-rays; and a second resin film in which a region other than the injection port of the liquid sample is bonded to the first resin film.

Description

Technical Field

[0001] The invention relates to a sample bag pool and a fluorescent X-ray analysis method. Background Art

[0002] As an apparatus for measuring an element contained in a sample or the concentration of the element, a fluorescent X-ray analyzer is known. Even if the sample to be analyzed is a liquid, the fluorescent X-ray analyzer can perform analysis. Among the methods for measuring liquid samples, there are a direct method of directly irradiating the liquid sample with X-rays and a spot method of irradiating a filter-dried sample with X-rays (see the following non-patent document 1).

[0003] When the direct method is used, a container for placing a liquid sample is used. For example, the following patent document 1 discloses a liquid sample container used in a downward-illuminating fluorescent X-ray analysis device. In addition, the following patent documents 2 to 4 disclose liquid sample containers used in upward-illuminating fluorescent X-ray analysis devices. The following patent document 5 discloses a drip drying filter paper used in the drip method.

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Registered Utility Model No. 2524760

[0007] Patent Document 2: Japanese Patent Application Publication No. 2005-345442

[0008] Patent Document 3: Japanese Utility Model Application Laid-Open No. 7-5047

[0009] Patent Document 4: Japanese Patent Application Publication No. 2018-205290

[0010] Patent Document 5: Japanese Utility Model Publication No. 62-019967

[0011] Non-patent literature

[0012] Non-patent document 1: Izumi Nakai, The Reality of Fluorescent X-ray Analysis (2nd edition), Asakura Shoten, published on July 10, 2016, pp. 85-86 Summary of the invention

[0013] Problems to be solved by the invention

[0014] The drop method may volatilize the elements contained in the sample, and is not suitable for measuring samples with large matrix effects or non-volatile samples. In addition, when using an upward-illuminating fluorescent X-ray analyzer, bubbles may be generated at the position of the sample irradiated with X-rays during the measurement, and the bubbles may prevent the liquid sample from being irradiated with X-rays once. Furthermore, when using a downward-illuminating fluorescent X-ray analyzer, the film that holds the sample may be damaged, causing damage or contamination inside the fluorescent X-ray analyzer. In addition, it is sometimes affected by the precipitation of sample components.

[0015] The present invention is proposed in view of the above-mentioned problems, and its purpose is to provide a fluorescent X-ray analysis method and a sample bag pool, which can measure liquid samples regardless of whether the liquid samples are volatile or non-volatile, and can irradiate X-rays without being affected by bubbles or precipitated components generated during the measurement.

[0016] Technical solutions to solve problems

[0017] (1) A sample bag cell according to one aspect of the present disclosure is a sample bag cell for liquid samples arranged upright on a side-illuminated fluorescent X-ray analysis device, characterized in that it has a first resin film arranged on the irradiation side of a primary X-ray and a second resin film bonded to the first resin film in an area other than an injection port for the liquid sample.

[0018] (2) According to the above-mentioned method of the present disclosure, it is characterized in that it also has a frame body, which has a frame-like shape surrounding the position irradiated by one X-ray, is arranged between the first resin film and the second resin film, and maintains the distance between the first resin film and the second resin film.

[0019] (3) According to the above aspect of the present disclosure, the first resin film has an analysis window that transmits X-rays once in a region overlapping with the inner side of the frame body in a plan view.

[0020] (4) According to the above aspect of the present disclosure, the analysis window is provided below the center of the first resin film, and the injection port is provided above the center of the sample bag pool.

[0021] (5) According to the above aspect of the present disclosure, the analysis window has a polyimide film, and the polyimide film is arranged in the hole provided in the first resin film.

[0022] (6) According to the above aspect of the present invention, a linear openable and closable fastener is further provided in the region where the injection port is provided.

[0023] (7) A fluorescent X-ray analysis method according to one aspect of the present disclosure is a fluorescent X-ray analysis method using a sample bag pool having a first resin film and a second resin film, and is characterized in that it includes: a step of placing a liquid sample from an injection port into the inner side of the first resin film and the second resin film bonded together in an area other than the injection port; a step of sealing the first resin film and the second resin film in an area where the injection port is provided to complete the sample bag pool; a step of vertically arranging the sample bag pool on a side-illuminated fluorescent X-ray analysis device; and a step of irradiating the sample bag pool with a single X-ray from the side surface and performing fluorescent X-ray analysis based on the emitted fluorescent X-ray.

[0024] (8) According to the above-mentioned method of the present disclosure, it is characterized in that there is also a step of configuring a frame body between the first resin film and the second resin film before completing the above-mentioned sample bag pool, and the frame body has a frame-like shape surrounding the position irradiated by one X-ray and maintains the distance between the first resin film and the second resin film.

[0025] (9) According to the above aspect of the present disclosure, the first resin film has an analysis window that transmits X-rays once in a region overlapping with the inner side of the frame body in a plan view.

[0026] (10) According to the above aspect of the present invention, the analysis window has a polyimide film, and the polyimide film is arranged in a hole provided in the first resin film.

[0027] (11) According to the above aspect of the present invention, a predetermined distance is left between the position of the liquid surface of the liquid sample and the upper end of the first resin film.

[0028] (12) According to the above-mentioned method of the present disclosure, it is characterized in that the step of performing the fluorescent X-ray analysis includes: the step of irradiating a plurality of different positions in the upper and lower directions of the sample bag pool with a single X-ray and obtaining a spectrum representing the relationship between the intensity and energy of the emitted fluorescent X-ray in each of the plurality of positions; and the step of analyzing the elements contained in the liquid sample based on the plurality of spectra obtained in each of the plurality of positions.

[0029] Effects of the Invention

[0030] According to the present invention, regardless of whether the liquid sample is volatile or non-volatile, the liquid sample can be measured, and X-rays can be irradiated while avoiding bubbles generated during the measurement. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 These are top and bottom views of the sample bag pool.

[0032] Figure 2 is a cross-sectional view of the sample bag pool.

[0033] Figure 3 It is a top view of a sample bag pool according to a modified example.

[0034] Figure 4 It is a cross-sectional view of a sample bag cell according to a modified example.

[0035] Figure 5 This is a flow chart showing a fluorescent X-ray analysis method using a sample bag cell.

[0036] Figure 6 This is a diagram showing the outline of a side-illumination type fluorescent X-ray analyzer equipped with a sample bag cell. DETAILED DESCRIPTION

[0037] Hereinafter, preferred modes for carrying out the present invention (hereinafter referred to as embodiments) will be described. Figure 1 (a) is a top view of the sample bag pool 100, Figure 1 (b) is a bottom view of the sample bag pool 100. Figure 2 (a) and Figure 2 (b) means Figure 1 (a) and Figure 1 (b) is a diagram of the II-II section. Figure 2 (a) shows the sample bag pool 100 after sealing, Figure 2 (b) shows the sample bag cell 100 in a state where bubbles are generated in the liquid sample 202. The sample bag cell 100 of this embodiment is used in a side-illumination type X-ray fluorescence analysis device 600 (described later), and includes a first resin film 102 and a second resin film 104.

[0038] The sample bag cell 100 is a sample bag cell 100 for a liquid sample 202 arranged upright on a side-illuminated fluorescent X-ray analysis device 600. In addition, "arranged upright" means arranged on the surface of the first resin film 102 and the second resin film 104 in a manner substantially located in the direction in which gravity acts, that is, in the vertical direction. In other words, it means that the liquid surface of the liquid sample 202 arranged between the first resin film 102 and the second resin film 104 is arranged substantially orthogonal to the first resin film 102 and the second resin film 104. In addition, hereinafter, the up-down direction refers to the direction perpendicular to the liquid surface of the liquid sample 202 (i.e., the vertical direction) when the sample bag cell 100 is arranged on the fluorescent X-ray analysis device 600. In addition, the down direction (lower side) is, for example, a direction pointing to the liquid side when viewed from the liquid surface with the liquid surface as a reference, and the up direction (upper side) refers to the opposite direction.

[0039] The first resin film 102 is disposed on the primary X-ray irradiation side. Specifically, for example, the first resin film 102 is a film formed of a resin such as aluminum laminate, polypropylene, polyester, etc. The material of the first resin film 102 is preferably a thermoplastic resin.

[0040] The first resin film 102 has an analysis window 108 that transmits a single X-ray at the lower center. Specifically, the shape of the first resin film 102 is, for example, rectangular, and has a circular hole. The circular hole is arranged so that the upper end is located at the lower center of the first resin film 102. An extremely thin film 106 made of a resin such as polyimide is arranged in the hole provided on the first resin film 102, and functions as the analysis window 108 during measurement. In addition, the shape of the hole provided as the analysis window 108 can be any shape. In addition, it is preferred to leave a predetermined distance between the lower end of the analysis window 108 and the lower end of the first resin film 102. Furthermore, in the case where the first resin film 102 is formed of a material that transmits a single X-ray, the first resin film 102 may not have the analysis window 108.

[0041] The second resin film 104 is a resin film disposed opposite to the first resin film 102 via the liquid sample 202. Specifically, for example, the second resin film 104 is a film formed of the same material as the first resin film 102. The second resin film 104 does not have holes, unlike the first resin film 102, but the outer shape is preferably a shape corresponding to the first resin film 102.

[0042] The second resin film 104 is bonded to the first resin film 102. Specifically, Figure 1 (a) and Figure 1 The dotted line in (b) indicates the region (bonding region 110) where the first resin film 102 and the second resin film 104 are bonded. In addition, the bonding region 110 may be provided at other locations as long as the liquid sample 202 can be held between the first resin film 102 and the second resin film 104. The bonding method is, for example, heat fusion. In the case where the first resin film 102 and the second resin film 104 are made of materials that are difficult to be heat fused, heat fusion may be performed by sandwiching a filamentary or ribbon-shaped thermoplastic resin. In addition, the first resin film 102 and the second resin film 104 may be bonded by ultrasonic fusion instead of heat fusion.

[0043] Furthermore, the first resin film 102 and the second resin film 104 may be formed integrally (from one film). In this case, the side of the folded film irradiated with one X-ray corresponds to the first resin film 102, and the opposite side corresponds to the second resin film 104.

[0044] also, Figure 1 (a) and Figure 1(b) shows the sample bag cell 100 in a state where the liquid sample 202 is arranged between the first resin film 102 and the second resin film 104 and is hermetically sealed. The first resin film 102 and the second resin film 104 before the liquid sample 202 is arranged are bonded to the first resin film 102 in a region other than the injection port for the liquid sample 202. The injection port is provided on the upper side of the center of the sample bag cell 100. The injection port is provided, for example, at the upper end of the sample bag cell 100.

[0045] Specifically, in Figure 1 (a) and Figure 1 In the dotted line shown in (b), the lower part ( Figure 1 (a) below the dotted line) and the side ( Figure 1 The left and right sides of the dotted line of (a) are bonded, and the upper part ( Figure 1 The upper side of the dotted line in (a) is not bonded and becomes the injection port. The liquid sample 202 is introduced from the injection port so that the position of the liquid surface is higher than the upper end of the analysis window 108, and a predetermined distance is left between the position of the liquid surface and the upper end of the first resin film 102. The predetermined distance is appropriately set according to the volume of bubbles generated from the liquid sample 202.

[0046] When the sample bag cell 100 is irradiated with primary X-rays, the temperature of the liquid sample 202 rises and bubbles are generated in the liquid sample 202. Since the sample bag cell 100 of this embodiment is disposed in the side-illumination type fluorescent X-ray analysis device 600, even if gas is generated in the liquid sample 202, the bubbles move to the upper side of the upper end of the analysis window 108 (see FIG. Figure 2 (a) and Figure 2 (b)). Therefore, it is possible to irradiate X-rays while avoiding bubbles generated during measurement.

[0047] The analysis window 108 of the sample bag cell 100 is arranged below the center of the first resin film 102, and a predetermined distance is left between the position of the liquid surface and the upper end of the first resin film 102. Thus, a space for bubbles generated in the sample bag cell 100 to escape can be maintained. In addition, by leaving a predetermined distance between the lower end of the analysis window 108 and the lower end of the first resin film 102, a space for retaining the precipitated sample can be ensured. Therefore, the liquid region of the sample can be irradiated with a single X-ray.

[0048] Figure 3 , Figure 4 (a) and Figure 4 (b) is a diagram for explaining a sample bag pool 100 according to a modified example of the above embodiment. Figure 3 FIG. 1 is a top view of the sample bag pool 100 . Figure 4 (a) and Figure 4 (b) means Figure 3This modification example is different from the above-described embodiment in that it includes a frame 302 for maintaining a distance between the first resin film 102 and the second resin film 104, the first resin film 102 is formed of a material that transmits X-rays, and the analysis window 108 is not provided.

[0049] The frame body 302 has a frame-like shape surrounding the position irradiated with one X-ray and has a predetermined thickness. The frame body 302 is disposed between the first resin film 102 and the second resin film 104 and maintains the distance between the first resin film 102 and the second resin film 104. Specifically, for example, Figure 3 As shown in FIG. 1 , the frame body 302 is disposed between the first resin film 102 and the second resin film 104 so that the irradiation positions 304, 306, and 308 of one X-ray are located inside the frame. In addition, since the frame body 302 has a predetermined thickness, Figure 4 (a) and Figure 4 As shown in (b) , a frame-shaped thickness distance is generated between the first resin film 102 and the second resin film 104 inside the frame body 302 .

[0050] In the case where the frame body 302 is not provided and the first resin film 102 and the second resin film 104 are bonded, the liquid sample 202 has a substantially equal thickness in the entire region surrounded by the bonding. In this case, since the thickness of the region of the sample bag pool 100 irradiated with the primary X-ray becomes thinner, the primary X-ray may pass through the second resin film 104 and the analysis accuracy is reduced. According to this modification, by maintaining the thickness by the frame body 302, the thickness of the liquid sample 202 in the region irradiated with the primary X-ray can be made at least the thickness of the frame body 302. Therefore, the reduction in the analysis accuracy can be avoided.

[0051] In this modification, the first resin film 102 is formed of a material that transmits X-rays. Therefore, if the liquid sample 202 is present in the region behind the first resin film 102, any position of the first resin film 102 can be irradiated with X-rays once and measured.

[0052] Next, a fluorescent X-ray analysis method using the sample bag cell 100 will be described. Figure 5 1 is a flow chart showing a fluorescent X-ray analysis method using the sample bag cell 100. First, a first resin film 102 and a second resin film 104 are prepared. Then, while the outer edges of the first resin film 102 and the second resin film 104 are aligned so as to overlap, the area ( Figure 3 The bottom, left and right sides of the adhesive area 110 are shown) (S502).

[0053] Next, the frame body 302 is arranged between the first resin film 102 and the second resin film 104, and the liquid sample 202 is introduced from the injection port (S504). Specifically, the frame body 302 is arranged between the first resin film 102 and the second resin film 104, which are heat-fused in the region other than the injection port. Furthermore, the liquid sample 202 is introduced from the injection port so that the liquid surface is located above the upper end of the frame body 302 between the first resin film 102 and the second resin film 104. At this time, the liquid sample 202 is introduced so that a predetermined distance is left between the liquid surface and the upper end of the first resin film 102.

[0054] Next, the first resin film 102 and the second resin film 104 are sealed at the injection port region while the air between them is exhausted, thereby completing the sample bag cell 100 ( S506 ). Specifically, the first resin film 102 and the second resin film 104 are heat-fused at the injection port region. Figure 4 (a) is a cross-sectional view showing the sample bag pool 100 after being hermetically sealed. Figure 4 As shown in (a), air may exist inside the sample bag cell 100, but it is preferable to exhaust the air and seal the sample bag cell 100 airtightly so that the amount of air contained inside the sample bag cell 100 is as small as possible.

[0055] Next, the sample bag cell 100 is placed upright on the side-illumination type X-ray fluorescence analysis device 600 ( S508 ). Figure 4 1 is a diagram showing an overview of a side-illuminated fluorescent X-ray analysis device 600 equipped with a sample bag cell 100. Figure 4 As shown, the side-illumination type fluorescent X-ray analysis device 600 includes an X-ray source 602, a spectroscopic element 604, a detector 606, a back holder 608, and a front holder 610. The sample bag pool 100 is sandwiched between the metal back holder 608 and the metal front holder 610, and the front holder 610 and the back holder 608 are fixed inside a measurement chamber (not shown). The front holder 610 is provided with a hole, and the first irradiation position 304, the second irradiation position 306, and the third irradiation position 308 are exposed from the hole.

[0056] Then, the X-ray source 602 irradiates the sample bag pool 100 with primary X-rays from the side, and performs fluorescent X-ray analysis based on the emitted fluorescent X-rays (S510). Specifically, the sample bag pool 100 is irradiated with primary X-rays at different locations in the vertical direction, and a spectrum indicating the relationship between the intensity and energy of the emitted fluorescent X-rays is obtained at each of the multiple locations. First, the X-ray source 602 irradiates the first irradiation position 304 of the sample bag pool 100 with primary X-rays. Bubbles are generated from the liquid sample 202 heated by the primary X-ray irradiation.

[0057] like Figure 4 As shown in (b), the bubble moves to the upper side of the analysis window 108, and Figure 4 (b) The upper portion of the sample bag pool 100 is Figure 4 The upper part of the sample bag pool 100 of (a) expands. In addition, in the case of long-term measurement, such as Figure 4 As shown in (b), sometimes part of the liquid sample 202 is precipitated, but the precipitated component 204 exists on the lower side of the lower end of the frame body 302. Therefore, according to the sample bag cell 100, the liquid region can be irradiated with primary X-rays without being disturbed by bubbles or precipitated components 204. Fluorescent X-rays are emitted from the liquid sample 202 irradiated with primary X-rays.

[0058] The spectroscopic element 604 spectroscopically separates the fluorescent X-rays. Specifically, for example, the spectroscopic element 604 spectroscopically separates only the fluorescent X-rays of a specific wavelength that satisfies the Bragg condition among the fluorescent X-rays of a plurality of wavelengths generated from the liquid sample 202.

[0059] The detector 606 is, for example, a scintillation counter and measures the intensity of the fluorescent X-rays, and outputs a pulse signal having a peak value corresponding to the energy of the measured fluorescent X-rays.

[0060] The spectroscopic element 604 and the detector 606 are rotated while maintaining a constant angle relationship through a goniometer (not shown). Specifically, for example, the incident angle between the traveling direction of the fluorescent X-ray generated from the liquid sample 202 and the surface of the spectroscopic element 604 is set to θ. The spectroscopic element 604 is rotated through the goniometer so that the incident angle θ of the fluorescent X-ray relative to the surface of the spectroscopic element 604 changes within a specified range. The secondary X-ray is diffracted by the spectroscopic element 604, and the fluorescent X-ray that satisfies the Bragg condition (i.e., the fluorescent X-ray as the exit angle θ) is emitted from the spectroscopic element 604. The detector 606 is moved to the position where the fluorescent X-ray emitted from the spectroscopic element 604 at the exit angle θ is incident through the goniometer.

[0061] The side-illuminated X-ray fluorescence analyzer 600 obtains a spectrum indicating the relationship between the intensity and energy of the X-ray fluorescence by counting the pulse signals output from the detector 606 according to the peak value. Based on the spectrum, the elements contained in the liquid sample 202 are analyzed. When only specific elements are analyzed, the side-illuminated X-ray fluorescence analyzer 600 does not have a goniometer, and the positions of the spectroscopic element 604 and the detector 606 may be fixed.

[0062] As described above, the analysis result of the liquid sample 202 is obtained based on the fluorescent X-ray emitted from the first irradiation position 304. Similarly, the X-ray source 602 irradiates the second irradiation position 306 and the third irradiation position 308 with a single X-ray, obtains spectra from the emitted fluorescent X-rays, and performs fluorescent X-ray analysis.

[0063] Then, by averaging the analysis results of the first irradiation position 304, the second irradiation position 306, and the third irradiation position 308, the final analysis result of the elements contained in the liquid sample 202 is obtained (S512). In addition, the above description describes the case where three measurements are performed, but the number of measurements is arbitrary. In addition, instead of performing a simple averaging process, a weighted averaging process (for example, an averaging process that increases the weight of the analysis results of the measurement site close to the center) may be performed. By obtaining the final analysis result based on the analysis results of multiple sites, an average result can be obtained even if the liquid sample 202 is uneven.

[0064] also, Figure 3 Indicates the first irradiation position 304, the second irradiation position 306, and the third irradiation position 308, which are different in the vertical direction. When the analysis result of any measurement part is affected by bubbles or precipitation, it may be greatly different from the analysis results of other measurement parts. In this case, the analysis result affected by the bubbles or precipitation can be excluded, and the final analysis result can be obtained based on the analysis results of other measurement parts.

[0065] The present disclosure is not limited to the above-mentioned embodiments and variations, and various variations are possible. For example, the region where the injection port is provided may not be bonded, and a linear openable and closable fastener may be provided in the region. Specifically, a sealed zipper may also be provided in the region where the injection port is provided. By providing an openable and closable fastener, the liquid sample 202 can be easily replaced.

[0066] In the above description, the X-ray fluorescence analyzer 600 is a wavelength dispersive X-ray fluorescence analyzer, but the X-ray fluorescence analyzer 600 may be an energy dispersive X-ray fluorescence analyzer.

[0067] Furthermore, the structure in which the analysis window 108 is provided and the structure in which the frame body 302 is arranged may be combined. In this case, it is preferable that the first resin film 102 has an analysis window that transmits X-rays once in the region overlapping with the inner side of the frame body 302 when viewed from above. Figure 1 The entire configuration of the analysis window 108 is shown in Figure 3 The inside of the dotted line of the frame body is shown. Figure 5In the fluorescent X-ray analysis method shown, in step S504 , the frame body 302 is arranged so that the inner side of the frame body 302 overlaps with the analysis window 108 in a plan view.

[0068] Description of Reference Numerals

[0069] 100 sample bag pool, 102 first resin film, 104 second resin film, 106 resin film, 108 analysis window, 110 bonding area, 202 liquid sample, 204 precipitated component, 302 frame body, 304 first irradiation position, 306 second irradiation position, 308 third irradiation position, 600 fluorescent X-ray analysis device, 602 X-ray source, 604 spectroscopic element, 606 detector, 608 back holder, 610 front holder.

Claims

1. A sample bag cell for liquid samples arranged vertically on a side-illuminated fluorescent X-ray analysis device, characterized in that: have: A first resin film disposed on a primary X-ray irradiation side; and The second resin film is bonded to the first resin film in a region other than the injection port for the liquid sample.

2. The sample bag pool according to claim 1, characterized in that: A frame body is further provided. The frame body has a frame-like shape surrounding a position irradiated with one X-ray, is arranged between the first resin film and the second resin film, and maintains a distance between the first resin film and the second resin film.

3. The sample bag pool according to claim 2, characterized in that: The first resin film has an analysis window configured to transmit X-rays once in a region overlapping with the inner side of the frame body in a plan view.

4. The sample bag pool according to claim 3, characterized in that: The analysis window is provided at a lower side of a center of the first resin film, and the injection port is provided at an upper side of a center of the sample bag pool.

5. The sample bag pool according to claim 3 or 4, characterized in that: The analysis window has a polyimide film, and the polyimide film is arranged in a hole provided in the first resin film.

6. The sample bag pool according to any one of claims 1 to 3, characterized in that: A linear openable and closable fastener is also provided in the area where the injection port is provided.

7. A fluorescent X-ray analysis method using a sample bag cell having a first resin film and a second resin film, characterized in that: include: A step of injecting a liquid sample from an injection port into the inner side of the first resin film and the second resin film bonded together except for the region other than the injection port; The step of sealing the first resin film and the second resin film in the area where the injection port is provided to complete the sample bag pool; The step of vertically arranging the sample bag pool on a side-illuminated fluorescent X-ray analysis device; as well as The step of irradiating the sample bag pool with X-rays once from the side surface thereof and performing fluorescent X-ray analysis based on the emitted fluorescent X-rays.

8. The fluorescent X-ray analysis method according to claim 7, characterized in that: The method further comprises the step of disposing a frame body between the first resin film and the second resin film before the sample bag cell is completed, the frame body having a frame-like shape surrounding a position irradiated with one X-ray and maintaining a distance between the first resin film and the second resin film.

9. The fluorescent X-ray analysis method according to claim 8, characterized in that: The first resin film has an analysis window configured to transmit X-rays once in a region overlapping with the inner side of the frame body in a plan view.

10. The fluorescent X-ray analysis method according to claim 9, characterized in that: The analysis window has a polyimide film, and the polyimide film is arranged in a hole provided in the first resin film.

11. The fluorescent X-ray analysis method according to any one of claims 7 to 10, characterized in that: A predetermined distance is left between the position of the liquid surface of the liquid sample and the upper end of the first resin film.

12. The fluorescent X-ray analysis method according to any one of claims 7 to 10, characterized in that: The steps of performing the fluorescent X-ray analysis include: The step of irradiating a plurality of locations at different vertical positions of the sample bag pool with a single X-ray and acquiring a spectrum representing a relationship between intensity and energy of emitted fluorescent X-rays at each of the plurality of locations; and A step of analyzing elements contained in the liquid sample based on the plurality of spectra acquired at each of the plurality of locations.

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