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WO2025094494A1 - Procédé de détermination d'une teneur en arsenic - Google Patents

Procédé de détermination d'une teneur en arsenic Download PDF

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Publication number
WO2025094494A1
WO2025094494A1 PCT/JP2024/030702 JP2024030702W WO2025094494A1 WO 2025094494 A1 WO2025094494 A1 WO 2025094494A1 JP 2024030702 W JP2024030702 W JP 2024030702W WO 2025094494 A1 WO2025094494 A1 WO 2025094494A1
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arsenic
sample
lead
standard samples
calibration curve
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English (en)
Japanese (ja)
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隆美 中尾
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Shimadzu Corp
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Shimadzu Corp
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
    • G01N23/22—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material
    • G01N23/223—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material by irradiating the sample with X-rays or gamma-rays and by measuring X-ray fluorescence

Definitions

  • the present disclosure relates to a method for determining the arsenic content, and more specifically, to a method for determining the arsenic content in a target sample that may contain lead.
  • Patent Document 1 discloses a technique for quantifying Pb using the intensity of Pb L ⁇ rays when a peak of As K ⁇ rays is detected in the spectrum of the sample.
  • the peak intensity of the As K ⁇ line is about 1/5 of the peak intensity of the As K ⁇ line, so quantification with high sensitivity is not possible.
  • the peak of the As K ⁇ line overlaps with the peak of the Hg L ⁇ line. Therefore, if the sample contains Hg, it is difficult to quantify As even if the peak intensity of the K ⁇ line is used.
  • This disclosure was made in light of the above-mentioned circumstances, and its purpose is to provide a technique for quantifying As with high sensitivity in target samples that may contain Pb.
  • a method is a method for determining the arsenic content in a target sample that may contain lead by using the arsenic K ⁇ line intensity in the spectrum of the target sample measured according to energy dispersive X-ray fluorescence spectrometry, a first calibration curve for arsenic, and a first correction coefficient for correcting the overlap of arsenic with lead, and the first calibration curve and the first correction coefficient are determined using multiple standard samples, including a first standard sample that does not contain arsenic.
  • a technique for quantifying As with high sensitivity in a target sample that may contain Pb.
  • FIG. 1 is a diagram showing an example of a calibration curve for As created using six types of standard samples in which Pb and As are mixed. 1 shows a spectrum measured according to energy dispersive X-ray fluorescence spectrometry of a sample.
  • FIG. 1 is a diagram showing an example of a calibration curve defined by the term “bj ⁇ Ij+cj” in formula (1) created from a plurality of standard samples containing a mixture of Pb and As. 1 is a diagram illustrating an overall configuration of an analysis system including an energy dispersive X-ray fluorescence analyzer.
  • FIG. 2 is a diagram illustrating a hardware configuration of an information processing device 20.
  • FIG. 13 is a diagram showing an example of a screen displayed when creating a correction formula.
  • FIG. 1 is a diagram showing an example of a calibration curve for As created using six types of standard samples in which Pb and As are mixed. 1 shows a spectrum measured according to energy dispersive X-ray fluorescence spectrometry of a sample.
  • FIG. 13 is a diagram showing another example of a screen displayed when creating a correction formula.
  • FIG. 13 is a diagram showing an example of a screen displaying a created correction formula.
  • 1 is a flowchart of a process performed in an information processing device 20 to quantify the As concentration in an unknown sample.
  • This disclosure primarily describes a method for identifying the As content in a target sample in which Pb and As may be mixed.
  • Figure 1 shows an example of an As calibration curve created using six types of standard samples that contain a mixture of Pb and As.
  • the horizontal axis represents the standard value (As concentration in the standard samples).
  • the vertical axis represents the measured intensity ratio for As.
  • This measured intensity ratio means, for example, the value of the NET intensity in the energy region (e.g., 10.30-10.80 keV) including the peak of the As K ⁇ line in the spectrum divided by the integrated value of the intensity in the optimal background region (e.g., 10.50-13.50 keV).
  • the NET intensity is the area value of the portion surrounded by the peak spectrum and the background.
  • the detected intensity in the background region is derived, for example, according to the Statistically sensitive Non-linear Iterative Peak Clipping (SNIP) algorithm.
  • SNIP Non-linear Iterative Peak Clipping
  • line L11 represents the calibration curve.
  • Figure 1 shows points P10 to P60, which represent the measured values of six types of standard samples used to create the calibration curve.
  • the accuracy ( ⁇ ) of the calibration curve is 1.71 ppm.
  • Some of points P10 to P60 deviate relatively significantly from the calibration curve. This is thought to be due to the fact that the Pb concentrations are not constant in the six types of standard samples. This factor will be considered in more detail with reference to Figure 2.
  • Figure 2 shows the spectrum of a sample measured according to energy dispersive X-ray fluorescence spectrometry.
  • the sample in Figure 2 contains As and Pb.
  • waveform W11 in the spectrum in Figure 1, the peak of the K ⁇ line of As and the peak of the L line of Pb overlap.
  • the As content in the target sample is determined using not only the calibration curve but also a correction coefficient corresponding to the overlap of the K ⁇ line of As and the L line of Pb.
  • the following formula (1) represents the correction formula used to determine the As content.
  • Wj bj ⁇ Ij+cj ⁇ pk ⁇ Wk...(1)
  • Wj represents the concentration of As. bj, cj, and pk represent constants.
  • Ij represents the measured intensity ratio described above.
  • Wk represents the concentration of Pb. More specifically, W represents the concentration.
  • b and c represent constants.
  • j represents As. p represents a constant.
  • k represents Pb.
  • the term "bj ⁇ Ij+cj” on the right-hand side represents a linear function of the measured intensity ratio, such as a calibration curve.
  • the term “pk ⁇ Wk” on the right-hand side represents a term that corrects for the effect of overlap with the Pb peak.
  • the term “bj ⁇ Ij+cj” constitutes an example of a first calibration curve
  • the term “pk ⁇ Wk” constitutes an example of a first correction coefficient.
  • Figure 3 shows an example of a calibration curve defined by the term "bj ⁇ Ij+cj" in formula (1) created from multiple standard samples containing a mixture of Pb and As.
  • the concentration Wj of As is derived as the value obtained by subtracting the correction term "pk ⁇ Wk” from the term "bj ⁇ Ij+cj".
  • points P20, P30, P40, P50, and P60 are each represented as a value obtained by subtracting the correction term "pk ⁇ Wk” from points P21, P31, P41, P51, and P61 on line L21.
  • the accuracy ( ⁇ ) of the calibration curve is 0.023 ppm.
  • Points P20, P30, P40, P50, and P60 are identified as the corrected points of points P21, P31, P41, P51, and P61 on line L21, respectively.
  • [Energy dispersive X-ray fluorescence analysis system] 4 is a diagram showing an overall configuration of an analysis system including an energy dispersive X-ray fluorescence analyzer.
  • the X-ray fluorescence analysis system 100 includes an X-ray fluorescence analyzer 10, an information processing device 20, a display 40, and an input unit 34.
  • the X-ray fluorescence analyzer 10 is an energy dispersive X-ray fluorescence analyzer that measures the concentration of elements contained in a sample S, and is composed of a sample chamber 1 and a measurement chamber 5.
  • the spaces inside the sample chamber 1 and measurement chamber 5 are hermetically enclosed by a housing 3, and the inside can be kept in a vacuum, helium atmosphere, or air atmosphere as necessary.
  • the sample chamber 1 has a sample stage 2 at the bottom. An opening 4 is formed in the sample stage 2.
  • the sample S is placed on the sample stage 2 so as to cover the opening 4.
  • the sample S is placed on the sample stage 2 so that the measurement position is exposed from the opening 4.
  • the XY stage 14 is configured to be able to move the sample S along the in-plane direction of the sample stage 2.
  • the drive mechanism 15 can drive the XY stage 14 in two in-plane directions that are perpendicular to each other. This makes it possible to automatically adjust the measurement position of the sample S.
  • the measurement chamber 5 is equipped with an X-ray tube 7 and a detector 8 on its wall 6.
  • the X-ray tube 7 irradiates primary X-rays towards the sample S.
  • the X-ray tube 7 has a filament that emits thermoelectrons and a target that converts the thermoelectrons into a specified primary X-ray and emits it.
  • the primary X-rays emitted by the X-ray tube 7 are irradiated onto the measurement position of the sample S through the opening 4.
  • the secondary X-rays (fluorescent X-rays) emitted by the sample S are incident on the detector 8, and the energy and intensity of the fluorescent X-rays are measured.
  • a shutter 9, a primary X-ray filter 11, a collimator 13, and an imaging unit 16 are installed in the measurement chamber 5.
  • the shutter 9, the primary X-ray filter 11, and the collimator 13 are configured to be slidable in a direction perpendicular to the plane of the paper in FIG. 1 by a drive mechanism 12.
  • the shutter 9 is made of an X-ray absorbing material such as lead, and can be inserted into the optical path of the primary X-rays to block the primary X-rays when necessary.
  • the primary X-ray filter 11 is made of metal foil selected according to the purpose, and attenuates the background components of the primary X-rays emitted from the X-ray tube 7 to improve the S/N ratio of the required characteristic X-rays.
  • multiple primary X-ray filters 11 made of different types of metal are used, and the primary X-ray filter 11 selected according to the purpose is inserted into the optical path of the primary X-ray by the drive mechanism 12.
  • the collimator 13 is an aperture with a circular opening in the center, and determines the size of the primary X-ray beam that irradiates the sample S.
  • the collimator 13 is made of an X-ray absorbing material such as lead or brass. In an actual device, multiple collimators 13 with different opening diameters are arranged side by side in a direction perpendicular to the paper surface of FIG. 1, and the collimator 13 selected according to the purpose is inserted into the primary X-ray beam line by the driving mechanism 12.
  • the imaging unit 16 is installed at the bottom of the measurement chamber 5.
  • the imaging unit 16 is configured to capture an image of the measurement position of the sample S through an opening 4 formed in the sample stage 2.
  • the imaging unit 16 includes an imaging element partitioned into multiple pixels, such as a CMOS (Complementary Metal Oxide Semiconductor) or a CCD (Charge Coupled Device).
  • the image data of the imaging unit 16 is transmitted to the information processing device 20.
  • FIG. 5 is a diagram showing a hardware configuration of the information processing device 20.
  • the information processing device 20 is mainly composed of a central processing unit (CPU) 22, which is an arithmetic processing unit.
  • the information processing device 20 may be, for example, a personal computer.
  • the information processing device 20 further has a storage unit that non-temporarily stores programs and data.
  • the information processing device 20 operates according to a program as the CPU 22 executes the program.
  • the storage unit includes a ROM (Read Only Memory) 24, a RAM (Random Access Memory) 26, and a HDD (Hard Disk Drive) 30. Note that specific examples of the storage unit are not limited to these.
  • the information processing device 20 further has an I/O (Input/Output) interface 28 and a communication interface 32.
  • the communication interface 32 is an interface for the information processing device 20 to communicate with external devices including the X-ray fluorescence analyzer 10.
  • the I/O interface 28 is an interface for input to the information processing device 20 or output from the information processing device 20. As shown in FIG. 2, the I/O interface 28 is connected to an input unit 34 and a display 40.
  • the input unit 34 is, for example, a keyboard and/or a mouse, and accepts input including instructions from the person making the measurement to the information processing device 20.
  • the information processing device 20 is connected to the X-ray tube 7, the detector 8, and the imaging unit 16.
  • the information processing device 20 controls the X-ray fluorescence analyzer 10 based on the measurement conditions input by the input unit 34. Specifically, the information processing device 20 controls the tube voltage, tube current, and irradiation time of the X-ray tube 7, and drives each of the shutter 9, primary X-ray filter 11, and collimator 13.
  • the information processing device 20 acquires the spectrum of the secondary X-rays detected by the detector 8.
  • the information processing device 20 performs quantitative analysis of each element based on the spectrum of the secondary X-rays detected by the detector 8.
  • the information processing device 20 further controls the imaging by the imaging unit 16, and automatically detects the measurement position of the sample S based on the image data acquired by the imaging unit 16 before measurement.
  • the information processing device 20 further selects the collimator 13 having the optimal aperture diameter from among the multiple collimators 13 for the detected measurement position.
  • the display 40 can display the image of the sample S imaged by the imaging unit 16 as well as the format of the report created by the information processing device 20.
  • Standard samples A to F Six types of standard samples A to F will be described below as examples of the multiple standard samples.
  • Standard sample A is ultrapure water.
  • Standard sample B is a sample prepared by diluting a reagent containing a mixture of As and Pb by a factor of 10. The As concentration is 1.5 ppm and the Pb concentration is 0.5 ppm.
  • Standard sample C is a sample prepared by diluting a mixture of As and Pb by a factor of 5.
  • the As concentration is 3.0 ppm and the Pb concentration is 1.0 ppm.
  • Standard sample E is a stock solution of a reagent containing a mixture of As and Pb.
  • the As concentration is 14.634 ppm, and the Pb concentration is 4.878 ppm.
  • Standard sample F is a solution that contains Pb but does not contain As.
  • the Pb concentration is 10.0 ppm.
  • Ij measured intensity ratio of As
  • Ij of standard samples A to C corresponds to points P10 to P30, respectively, in FIG. 3.
  • Ij of standard samples D and E corresponds to points P50 and P60, respectively, in FIG. 3.
  • Ij of standard sample F corresponds to point P40 in FIG. 3.
  • the constants bj, cj, and pk are identified by multiple regression analysis using the least squares method.
  • the identified constants bj, cj, and pk are used to create the correction equation for As shown as equation (1).
  • correction formula for Pb is also created.
  • the correction formula for Pb is expressed as the following formula (2).
  • Ik represents the measured intensity ratio for Pb.
  • This measured intensity ratio means, for example, the value of the NET intensity (peak area) in an energy region including the peak of the L ⁇ line of Pb in the spectrum (e.g., 10.32 to 10.82 keV) divided by the integrated value of the intensity in the background region of the spectrum (e.g., a part of the range of 10.50 to 15.00 keV).
  • equation (2) the term "bk ⁇ Ik+ck” constitutes an example of a second calibration curve, and the term “pj ⁇ Wj" constitutes an example of a second correction coefficient.
  • the spectra of the eight types of standard samples can also be used to create a correction equation for Pb.
  • Ik measured intensity ratio of Pb
  • Wk Pb concentration
  • Wj As concentration
  • Ik are applied to equation (2) for each of the six types of standard samples. This results in six equations with three unknown constants bk, ck, and pj.
  • the constants bk, ck, and pj are identified by multiple regression analysis using the least squares method.
  • the identified constants bk, ck, and pj are used to create the correction equation for Pb shown as equation (2).
  • FIG. 6 is a diagram showing an example of a screen displayed when creating the correction formula.
  • FIG. 7 is a diagram showing another example of a screen displayed when creating the correction formula.
  • Screen 410 in FIG. 6 includes input fields for setting various conditions related to the creation of the correction equation.
  • input field 411 is set with a method for determining constants b, c, and p.
  • multiple regression analysis is set.
  • Screen 420 in FIG. 7 includes area 421 for inputting the As concentration in each standard sample, and area 422 for inputting the Pb concentration in each standard sample.
  • the information processing device 20 acquires the As and Pb concentrations in each standard sample, as well as the spectrum of each standard sample, it identifies the measured intensity ratio from the spectrum and creates a correction equation.
  • FIG. 8 shows an example of a screen that displays the created correction equation.
  • Six points P80 to P85 that correspond to the measured intensity ratios of each of the six types of samples are shown on the calibration curve.
  • the As concentrations at points P81 to P85 are corrected according to the created correction formula.
  • the As concentrations after correction are shown as points P91 to P95.
  • [Quantitative determination of As] 9 is a flowchart of a process performed in the information processing device 20 to quantify the As concentration in an unknown sample.
  • this process is performed by the CPU 22 executing a given program.
  • the above formulas (1) and (2) are stored in the HDD 30, and the spectrum of the unknown sample is measured.
  • step S10 the information processing device 20 obtains Ij (measured intensity ratio of As) and Ik (measured intensity ratio of Pb) from the spectrum of the unknown sample.
  • step S20 the information processing device 20 calculates a provisional Wj according to the following formula (1A), which includes some of the constants in formula (1).
  • step S30 the information processing device 20 calculates a provisional Wk according to the following formula (2A) which includes some of the constants in formula (2).
  • step S40 the information processing device 20 calculates a provisional Wj according to equation (1).
  • the latest Wk (Wk calculated in step S30 or step S50, which is executed immediately before) is used.
  • step S50 the information processing device 20 calculates a provisional Wk according to formula (2).
  • the latest Wj (Wj calculated in the immediately preceding step S20 or step S40) is used.
  • step S60 the information processing device 20 determines whether the difference between the latest Wj and the previous Wj is less than a predetermined threshold d. If the information processing device 20 determines that the difference is equal to or greater than the threshold d (NO in step S60), it returns control to step S40. As a result, the controls of steps S40 to S60 are repeated until the difference becomes less than the threshold d. Then, if the information processing device 20 determines that the difference is less than the threshold d (YES in step S60), it ends the processing in FIG. 9.
  • the latest Wj is identified as the concentration of As in the unknown sample. Also, in the processing in FIG. 9, the latest Wk is identified as the concentration of Pb in the unknown sample.
  • correction formula (1) is used to determine the concentration (content) of As in an unknown sample.
  • a sample that does not contain As but contains Pb is used as one of multiple standard samples for creating correction formula (1).
  • standard sample H constitutes an example of a first standard sample.
  • the correction formula (1) includes three constants (bj, cj, pk).
  • at least three types of standard samples with different As to Pb concentration ratios are required as multiple standard samples.
  • standard samples are generally often prepared from one type of reagent with a specific As to Pb concentration ratio. When a standard sample is prepared using such a reagent, the As to Pb concentration ratio does not change between the multiple standard samples, even if multiple standard samples with different dilution factors are prepared.
  • the operator will input a fixed value as the correction coefficient (the value corresponding to the "pk ⁇ Wk” term in formula (1)) to correct the As concentration.
  • the correction coefficients to be used between multiple analytical instruments may be close to each other, but they will not necessarily be the same.
  • the correction coefficient due to the difference in the instruments becomes an analysis error and is added to the quantitative value.
  • a sample containing only Pb and no As is used as one of the multiple standard samples.
  • a standard sample containing only Pb and no As a standard sample prepared from the above reagent, and a standard sample containing neither As nor Pb, it is possible to provide highly accurate correction coefficients and correction formulas while minimizing the burden on the operator.
  • the number of standard samples used to create the correction formula can be increased without excessively increasing the burden on the operator.
  • the method determines the arsenic content in a target sample that may contain lead by using the intensity of the arsenic K ⁇ line in the spectrum of the target sample measured according to energy dispersive X-ray fluorescence spectrometry, a first calibration curve for arsenic, and a first correction coefficient for correcting the overlap of arsenic with lead, and the first calibration curve and the first correction coefficient may be determined using a plurality of standard samples, including a first standard sample that does not contain arsenic.
  • the analytical method described in paragraph 1 provides a technique for quantifying As with high sensitivity in a target sample that may contain Pb.
  • the plurality of standard samples may further include one or more standard samples containing arsenic and lead.
  • the method described in paragraph 2 makes it possible to improve the accuracy of the first calibration curve and the first correction coefficient without placing an excessive burden on the operator, thereby improving the accuracy of the determined arsenic content.
  • the plurality of standard samples may further include two or more standard samples containing arsenic and lead in equal proportions.
  • the method described in paragraph 3 makes it possible to improve the accuracy of the first calibration curve and the first correction coefficient without placing an excessive burden on the operator, thereby improving the accuracy of the determined arsenic content.
  • the plurality of standard samples may further include one or more standard samples that contain neither arsenic nor lead.
  • the method described in paragraph 4 makes it possible to improve the accuracy of the first calibration curve and the first correction coefficient without placing an excessive burden on the operator, thereby improving the accuracy of the determined arsenic content.
  • the method according to any one of paragraphs 1 to 4 may further utilize the lead content in the target sample to determine the arsenic content.
  • the method described in paragraph 5 reliably eliminates the influence of overlapping peaks of arsenic and lead in the spectrum measured according to energy dispersive X-ray fluorescence spectrometry in determining the arsenic content.
  • the method according to 5 may further include determining the lead content in the target sample using the intensity of the L ⁇ line of lead in the spectrum, a second calibration curve for lead, and a second correction coefficient for correcting for overlap with arsenic with respect to lead.
  • the method described in paragraph 6 more reliably eliminates the effect of overlapping peaks of arsenic and lead in the spectrum measured according to energy dispersive X-ray fluorescence spectrometry when determining the arsenic content.
  • 10 X-ray fluorescence analysis device 10 X-ray fluorescence analysis device, 20 information processing device, 100 X-ray fluorescence analysis system, 410, 420, 430 screen, 411 input field, 421, 422 area, 431 field.

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Abstract

L'invention concerne une technique de quantification hautement sensible d'As dans un échantillon cible dans lequel du Pb peut être mélangé. L'invention concerne un procédé de détermination de la teneur en arsenic dans un échantillon cible dans lequel du plomb peut être mélangé, ce procédé utilisant : l'intensité de la raie Kα pour l'arsenic dans le spectre d'un échantillon cible mesurée par analyse de fluorescence X à dispersion d'énergie ; une première courbe d'étalonnage pour l'arsenic ; et un premier coefficient de correction pour corriger le chevauchement avec le plomb lié à l'arsenic. La première courbe d'étalonnage et le premier coefficient de correction dans ce procédé sont obtenus à l'aide d'une pluralité d'échantillons standards qui comprennent un premier échantillon standard qui ne contient pas d'arsenic.
PCT/JP2024/030702 2023-10-30 2024-08-28 Procédé de détermination d'une teneur en arsenic Pending WO2025094494A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04204362A (ja) * 1990-11-30 1992-07-24 Shimadzu Corp 元素定量法
JP2001050918A (ja) * 1999-08-09 2001-02-23 Rigaku Industrial Co 蛍光ｘ線分析方法およびその装置
JP2019100835A (ja) * 2017-12-01 2019-06-24 一般財団法人電力中央研究所 重金属類溶出量の測定方法
JP2019203764A (ja) * 2018-05-23 2019-11-28 一般財団法人電力中央研究所 重金属類の還元方法及びそれを利用した重金属類溶出量の測定方法
JP2020186929A (ja) * 2019-05-10 2020-11-19 一般財団法人電力中央研究所 溶出方法および溶出量測定方法
CN114136726A (zh) * 2021-11-08 2022-03-04 南京农业大学 一种同时检测贝类中铅、镉和砷的方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04204362A (ja) * 1990-11-30 1992-07-24 Shimadzu Corp 元素定量法
JP2001050918A (ja) * 1999-08-09 2001-02-23 Rigaku Industrial Co 蛍光ｘ線分析方法およびその装置
JP2019100835A (ja) * 2017-12-01 2019-06-24 一般財団法人電力中央研究所 重金属類溶出量の測定方法
JP2019203764A (ja) * 2018-05-23 2019-11-28 一般財団法人電力中央研究所 重金属類の還元方法及びそれを利用した重金属類溶出量の測定方法
JP2020186929A (ja) * 2019-05-10 2020-11-19 一般財団法人電力中央研究所 溶出方法および溶出量測定方法
CN114136726A (zh) * 2021-11-08 2022-03-04 南京农业大学 一种同时检测贝类中铅、镉和砷的方法

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