JP2017161486A - Quantitative apparatus, quantitative method, control program, and storage medium - Google Patents

Abstract

PROBLEM TO BE SOLVED: To select the proper quantitative analysis value regardless of analysis apparatus.SOLUTION: A quantitative device (1) includes: a quantitative unit (101) that calculates a quantitative analysis value for each of a plurality of signals corresponding to a target element included in the analysis result data of the atomic emission analysis; and a selection unit (104) that uses as the quantitative result of the target element, the quantitative analysis value selected in accordance with the level of the difference between the quantitative analysis values among the plurality of quantitative analysis values calculated by the quantitative unit (101).SELECTED DRAWING: Figure 1

Description

  The present invention relates to atomic emission analysis such as ICP (inductively coupled plasma) emission spectroscopic analysis, and more specifically, a quantitative apparatus for calculating a quantitative analysis value of a target element using analysis result data of atomic emission analysis. About.

  ICP emission spectroscopic analysis has been widely used for qualitative and quantitative analysis of target elements contained in samples to be analyzed. In ICP emission spectroscopic analysis, it is known that quantitative analysis values are affected by various interferences, and a technique for suppressing the influence of interference has been developed.

  For example, in Patent Document 1 below, the spectral interference amount is calculated using an interference correction coefficient specific to each model of the ICP emission spectroscopic analyzer, and the effectiveness of the background correction for the spectrum intensity based on the interference amount is calculated. It is described that it is judged. And in the following Patent Document 2, the measurement accuracy at each measurement wavelength is calculated using the interference amount calculated by the method of the above Patent Document 1, and the quantitative analysis value at the measurement wavelength with the highest measurement accuracy is selected. Have been described.

JP 2006-275892 A (released on October 2, 2006) JP 2007-003428 A (published on January 11, 2007)

  Although the techniques of Patent Documents 1 and 2 can suppress the influence of spectral interference, it is necessary to use an interference correction coefficient specific to the model of the analyzer, and lack generality. In addition, since the state of the analysis apparatus changes from day to day, the interference correction coefficient that has been initially set is not always a reasonable value according to the state of the analysis apparatus at the time of analysis.

  The present invention has been made in view of the above-mentioned problems, and its purpose is to perform a reasonable quantitative analysis regardless of what analysis device the analysis result data to be quantified is obtained by. An object of the present invention is to provide a quantitative device or the like that can select a value.

  In order to solve the above problems, a quantification device according to the present invention is a quantification device that calculates a quantitative analysis value of a target element using analysis result data of atomic emission spectrometry, and is included in the analysis result data. A quantification unit that calculates a quantitative analysis value for each of a plurality of signals corresponding to the target element, and a plurality of quantitative analysis values calculated by the quantification unit are selected according to the magnitude of the difference between the quantitative analysis values. And a selection unit that uses the quantitative analysis value as a quantitative result of the target element.

  According to the above configuration, the quantitative analysis value is calculated for each of the plurality of signals corresponding to the target element. Here, since a plurality of signals for which the quantitative analysis value is calculated correspond to the same target element, if no spectral interference occurs, the quantitative analysis value calculated for any signal can be calculated theoretically. Same value above. However, in practice, the quantitative analysis value calculated from each signal is usually different due to factors such as spectral interference and variations in measurement values. That is, it is considered that the influence of spectral interference or the like is reflected in the magnitude of the difference between the calculated quantitative analysis values.

  So, according to said structure, let the quantitative analysis value selected according to the magnitude | size of the difference between the said quantitative analysis values among the calculated several quantitative analysis values be a quantitative result of an object element. This makes it possible to use a proper quantitative analysis value selected in consideration of the influence of spectral interference or the like as the quantitative result of the target element. In addition, when selecting a quantitative analysis value, it is not necessary to use an interference correction coefficient unique to the analyzer as described in Patent Documents 1 and 2 mentioned above.

  That is, according to said structure, there exists an effect that an appropriate quantitative analysis value can be selected irrespective of what kind of analyzer the analysis result data used as the object of quantification is data obtained.

  In addition, the quantification apparatus includes an index value calculation unit 103 that calculates an index value indicating the magnitude of the difference between the quantitative analysis values, and the selection unit includes a quantitative analysis value whose index value is equal to or less than a predetermined threshold value. A configuration in which a quantitative analysis value is selected from a set of

  As described above, it is considered that the influence of spectral interference or the like is reflected in the magnitude of the difference between the calculated quantitative analysis values. In particular, when spectral interference occurs, the quantitative analysis value becomes an excessive value.

  Therefore, according to the above configuration, an index value indicating the magnitude of the difference between the quantitative analysis values is calculated, and the quantitative analysis value is selected from a set of quantitative analysis values whose index value is equal to or less than a predetermined threshold value. Therefore, it is possible to select an appropriate quantitative analysis value by excluding a quantitative analysis value whose index value exceeds a predetermined threshold, that is, a quantitative analysis value highly likely to be affected by spectral interference from the selection target. it can.

  Further, the index value calculation unit is a mathematical formula of (quantitative analysis value A−quantitative analysis value B) / quantitative analysis value A when the quantitative analysis values to be calculated are the quantitative analysis values A and B. The above index value may be calculated.

  According to the above configuration, since the index value can be calculated by a simple calculation, a quantitative analysis value can be selected promptly even in a quantitative device that does not have a high processing capacity.

  Further, the analysis result data includes analysis result data obtained by analyzing the sample containing the target element at a plurality of dilution ratios, and the quantitative analysis value selected by the selection unit is outside a predetermined quantitative range. For example, the quantification unit may include a dilution factor selection unit that calculates a quantitative analysis value from analysis result data having a dilution factor different from the dilution factor used to calculate the quantitative analysis value.

  According to the above configuration, if the selected quantitative analysis value is outside the predetermined quantitative range, the quantitative analysis value is calculated from the analysis result data having a dilution factor different from the dilution factor used for calculating the quantitative analysis value. Therefore, the quantitative analysis value within the predetermined quantitative range can be automatically calculated, and the quantitative analytical value within the predetermined quantitative range can be used as the quantitative result of the target element.

  In addition, when the analysis result data is data obtained by analysis using an internal standard substance, the quantification apparatus determines whether the internal standard substance is affected by interference from the recovery rate of the internal standard substance. You may provide the internal standard determination part which determines whether or not.

  According to the above configuration, it is automatically determined whether or not the internal standard substance is affected by interference, so it is possible to avoid adopting a quantitative analysis value based on the internal standard substance affected by interference. Is possible.

  In addition, when it determines with having received the influence of interference, it is desirable to perform the process for avoiding employ | adopting the quantitative analysis value based on the internal standard substance which received the influence of interference. For example, the user may be notified that the internal standard is affected by interference, may be automatically switched to quantification using another internal standard, or quantification without using the internal standard ( It may be automatically switched to (quantitative determination by the absolute calibration curve method).

  In addition, the quantification device may include a threshold setting unit that sets the predetermined threshold corresponding to the magnitude of variation in the analysis result data.

  Here, in the analysis result data, even if the data should theoretically have the same value, the value usually varies, and the magnitude of the variation may increase or decrease depending on the data. It is normal. The predetermined threshold value is a threshold value for identifying whether or not the difference between the quantitative analysis values is a significant difference (difference due to the influence of interference exceeding the range of variation). It is preferable to set a value in accordance with.

  Therefore, according to the above configuration, the configuration includes a threshold setting unit that sets a predetermined threshold according to the magnitude of variation in the analysis result data. As a result, a predetermined threshold value is set according to the magnitude of the variation in the analysis result data, and the quantitative analysis value is selected using this threshold value, so that an appropriate selection can be made in consideration of the magnitude of the variation.

  The analysis result data may be analysis result data of ICP emission spectral analysis. In this case, an appropriate quantitative analysis value can be selected regardless of what ICP emission spectroscopic analyzer is used as the analysis result data to be quantified.

  In addition, the quantification method according to the present invention is a quantification method by the quantification apparatus 1 that calculates the quantitative analysis value of the target element using the analysis result data of the atomic emission analysis in order to solve the above-described problem. A quantitative step (S11) for calculating a quantitative analysis value for each of a plurality of signals corresponding to the target element included in the result data, and among the multiple quantitative analysis values calculated in the quantitative step, the quantitative analysis value A selection step (S15) in which the quantitative analysis value selected according to the magnitude of the difference between them is used as the quantitative result of the target element. According to this quantification method, the same effect as the above quantification device can be obtained.

  The quantification device may be realized by a computer. In this case, the quantification device is controlled by the computer by causing the computer to operate as each unit (software element) included in the quantification device. A program and a computer-readable recording medium on which the program is recorded also fall within the scope of the present invention.

  According to the present invention, there is an effect that an appropriate quantitative analysis value can be selected regardless of which analysis device is used as the analysis result data to be quantified.

It is a block diagram which shows an example of the principal part structure of the fixed_quantity | assay apparatus which concerns on one Embodiment of this invention. It is a figure which shows an example of the analysis result data input into the said fixed_quantity | assay apparatus. It is a figure which shows an example of the wavelength data which the said fixed_quantity | quantitative_assay apparatus uses. It is a figure which shows an example of the selection criteria of the wavelength which the said fixed_quantity | quantitative_assay apparatus uses. It is a flowchart which shows an example of the procedure of ICP emission spectral analysis. It is a flowchart which shows an example of the process which the said fixed_quantity | quantitative_assay apparatus performs.

  Hereinafter, embodiments of the present invention will be described in detail with reference to FIGS.

〔Device configuration〕
First, the configuration of the quantitative device of the present embodiment will be described with reference to FIG. FIG. 1 is a block diagram illustrating an example of a main configuration of the quantitative device 1. The quantitative device 1 is a device that analyzes the analysis result data of the ICP emission spectroscopic analysis, performs quantitative determination of elements from the data, and outputs the quantitative analysis value as the result. Hereinafter, among the elements included in the sample subjected to the analysis, an element to be quantified is referred to as a target element.

  As shown in the figure, the quantification apparatus 1 includes a control unit 10 that controls each unit of the quantification apparatus 1 and a storage unit 11 that stores various data used by the quantification apparatus 1. The quantitative device 1 also includes an input unit 12 that receives data input to the quantitative device 1 and a display unit 13 that displays an image in accordance with the control of the control unit 10. For example, an image showing a quantitative result is displayed on the display unit 13. Note that the storage unit 11, the input unit 12, and the display unit 13 may be devices external to the quantitative device 1 that are externally attached to the quantitative device 1.

  As illustrated, the control unit 10 includes a data acquisition unit 100, a quantification unit 101, a dilution rate selection unit 102, an index value calculation unit 103, a selection unit 104, a quantification result data generation unit 105, and a calibration curve creation unit. 106 is included. The storage unit 11 stores wavelength data 110, calibration curve data 111, and quantitative result data 112.

  The data acquisition unit 100 acquires analysis result data (spectrum) indicating the result of ICP emission analysis. The analysis result data may be data in which the wavelength and the intensity value are associated with each signal of the target element (signal corresponding to one spectral line), for example, data as shown in FIG. Also good.

  FIG. 2 is a diagram illustrating an example of analysis result data. In the example shown in the figure, an example of analysis result data obtained by performing analysis at five dilution ratios of 10 times from undiluted (× 1) to 10,000-fold diluted (× 10000) for one sample (Sample). Is shown. In the illustrated example, the wavelength of each detected signal (188, 193, 197,...) And the intensity value corresponding to that wavelength are shown for each sample at each dilution factor.

  The quantification unit 101 calculates a quantitative analysis value from the intensity value of the analysis result data. More specifically, the quantification unit 101 specifies a signal corresponding to the target element among signals included in the analysis result data with reference to wavelength data 110 described later. Then, a quantitative analysis value (specifically, a concentration value) of the target element is calculated using calibration curve data 111 (described later) corresponding to the target element.

  The dilution rate selection unit 102 selects the dilution rate of the sample. Using the concentration value of the dilution rate selected by the dilution rate selection unit 102, the index value calculation unit 103 calculates an index value indicating the magnitude of the difference between the quantitative analysis values.

  The index value calculation unit 103 calculates an index value indicating the magnitude of the difference between the plurality of quantitative analysis values calculated by the quantification unit 101. More specifically, the index value calculation unit 103 calculates an index value for the concentration value of the dilution factor selected by the dilution factor selection unit 102 among the plurality of concentration values calculated by the quantification unit 101. A method for calculating the index value will be described later.

  The selection unit 104 selects a quantitative analysis value (specifically, a concentration value) corresponding to the index value calculated by the index value calculation unit 103 from among a plurality of quantitative analysis values as a quantitative result of the target element. The selection method by the selection unit 104 will be described later.

  The quantitative result data generation unit 105 generates quantitative result data indicating the quantitative analysis value of the target element. More specifically, the quantification result data generation unit 105 generates quantification result data indicating the concentration value of the target element (concentration value selected by the selection unit 104 among the plurality of concentration values calculated by the quantification unit 101).

  The calibration curve creation unit 106 creates calibration curve data used by the quantification unit 101 for quantification of the target element. More specifically, the calibration curve creation unit 106 creates calibration curve data using the analysis result data of the standard solution of the target element, and stores the calibration curve data as the calibration curve data 111 in the storage unit 11. Note that calibration curve data corresponding to each spectral wavelength is created for the target element having a plurality of unique spectral wavelengths.

  The wavelength data 110 is data indicating a spectral wavelength unique to the target element and a priority order of the wavelength. The wavelength data 110 basically includes three wavelengths for each target element, and for these three wavelengths, “1” ˜ A priority of “3” is set. In other words, if there is no interference or the like, the accuracy of quantification using the wavelength having the priority “1” is the highest, and the accuracy of quantification is lowered as the priority is lowered. For the target elements having two types of specific spectral wavelengths, the priority order of the two types of wavelengths is set. In addition, the priority order is not set for a target element having a single specific spectral wavelength, and the single spectral wavelength is indicated in the wavelength data 110.

  The wavelength data 110 may be data as shown in FIG. 3, for example. FIG. 3 is a diagram illustrating an example of the wavelength data 110. In the illustrated example, Ag (silver) and As (arsenic) are shown as target elements. In addition, values of 328 nm, 338 nm, and 241 nm are shown as spectral wavelengths of Ag, and values of 188 nm, 193 nm, and 197 nm are shown as spectral wavelengths of As. And for each of Ag and As, the priorities “1” to “3” of the three spectral wavelengths are shown.

  Therefore, by referring to the illustrated wavelength data 110, for example, it is possible to specify that the three signals of 328 nm, 338 nm, and 241 nm in the analysis result data of FIG. 2 are all Ag signals. And among these signals, Ag can be quantified based on signals having higher priority, that is, higher detection sensitivity.

  The calibration curve data 111 is data for quantifying the target element from the intensity value of the spectrum of the target element. As described above, the calibration curve data 111 is generated by the calibration curve creation unit 106.

  The quantitative result data 112 is data indicating the quantitative result of the target element. As described above, the quantitative result data 112 is generated by the quantitative result data generation unit 105.

[Selection of wavelength]
Next, wavelength selection by the selection unit 104 will be described with reference to FIG. FIG. 4 is a diagram illustrating an example of a wavelength selection criterion. The selection unit 104 conforms to the magnitude relationship between the index values (D _1-2 , D _2-3 , D _1-3 ) calculated by the index value calculation unit 103 and a predetermined determination reference value T according to the illustrated selection criterion. The concentration corresponding to the selected wavelength is selected as the concentration of the target element.

In the following description, the concentrations of the target elements calculated from the intensity values of the spectral wavelengths having the priorities of “1” to “3” are referred to as C _{1 to} C ₃ (mg / L), respectively. In this case, the index values _D1-2 , _D2-3 , and _D1-3 are expressed by the following mathematical formulas (1) to (3).
_{D 1-2 = (C 1 -C 2} ) / C 1 ... Equation (1)
_{D 2-3 = (C 2 -C 3} ) / C 2 ... Equation (2)
_{D 1-3 = (C 1 -C 3} ) / C 1 ... Equation (3)
Here, spectral interference is a phenomenon in which the signal of the target element overlaps with the signal of a coexisting element having a wavelength close to that of the target element, and the intensity value of the signal in which spectral interference has occurred is the intensity of the signal in which spectral interference has not occurred. Larger than the value.

  For this reason, when quantification is performed for each target element from a plurality of signals having different wavelengths, a signal whose quantification result is excessive compared with other quantification results may be generated due to the influence of spectral interference. However, since the quantification results usually vary, it is preferable to determine that a signal that is excessively quantified beyond the range of variation is a signal affected by spectral interference.

  Therefore, in the selection criterion of FIG. 4, a determination criterion value T is set, and if the index value is T or less, it is considered that there is no influence of spectral interference, and if the index value is larger than T, it is affected by spectral interference. It is considered. Then, among the quantification results regarded as not affected by the spectral interference, the wavelength with the highest priority is selected.

Specifically, in the illustrated pattern a, since all of D _1-2 , D _2-3 and D _1-3 are T or less, it is considered that there is no wavelength affected by spectral interference. . Therefore, in the selection criterion of FIG. 4, the selected wavelength of the pattern a is the wavelength of “1” having the highest priority. Further, in the illustrated pattern _c, but _{D 1-2} and _{D 1-3} is less than _T, since _{D 2-3} is more than T, _{C 2} is excessive as compared with the _{C 3, C 2} to values Is considered to be affected by spectral interference. Therefore, in the selection criterion of FIG. 4, the selected wavelength of the pattern c is the wavelength of “1” having the highest priority.

On the other hand, in the illustrated pattern b, D _1-2 and D _2-3 are equal to or less than T, but D _1-3 exceeds T. Therefore, C ₁ is excessive as compared with C _3, and the value of C ₁ Is considered to be affected by spectral interference. Therefore, in the selection criterion of FIG. 4, the selected wavelength of the pattern b is set to the wavelength of “2” having the highest priority among the wavelengths of “1”. Further, in the illustrated pattern _e, but _{D 2-3} and _{D 1-3} is less than _T, since _{D 1-2} is more than T, _{C 1} is the excessive compared to the _{C 2,} the values of _{C 1} Is considered to be affected by spectral interference. In the illustrated pattern f, D _2-3 is equal to or less than T. However, since D _1-2 and D _1-3 exceed T, C ₁ is excessive as compared with C ₂ and C _3. A value of ₁ is considered to be affected by spectral interference. Therefore, for the patterns e and f, the selected wavelength is “2” as in the case of the pattern b.

In the illustrated pattern d, D _1-2 is equal to or less than T. However, since D _2-3 and D _1-3 exceed T, C ₂ is excessive as compared to C ₃ and C ₁ also because it is too large compared to C _3, the value of even value C ₂ C ₁ is also considered to be influenced by the spectral interference. Therefore, in the pattern d, both the wavelengths “1” and “2” are unsuitable, so the selected wavelength is “3”. In the illustrated pattern g, D _1-3 is equal to or less than T, but D _1-2 and D _2-3 exceed T. _Therefore , C ₁ is excessive as compared with C ₂ and C _2. also because it is too large compared to C _3, the value of even value C ₂ C ₁ is also considered to be influenced by the spectral interference. In the illustrated pattern h, since D _1-2 , D _2-3 , and D _1-3 all exceed T, C ₁ is excessive compared to C ₂ and C ₃ , and C ₂ also because it is too large compared to C _3, the value of even value C ₂ C ₁ is also considered to be influenced by the spectral interference. Therefore, for the patterns g and h, the selection wavelength is set to “3” as in the case of the pattern d.

  Hereinafter, when T = 0.5, that is, when a difference in density value exceeds 50%, a specific example in which it is considered that there is an influence of spectral interference, and when T = 0.2, that is, the density Specific examples in the case where it is considered that there is an influence of spectral interference when the value difference exceeds 20% will be sequentially shown.

(T = 0.5)
(Example 1) C ₁ = 10, C ₂ = 11, C ₃ = 6
In this example, D _1-2 = −0.1, D _2-3 = 0.45, D _1-3 = 0.4, and these values are all equal to or less than T = 0.5. Therefore, since it corresponds to the pattern a in FIG. 4, the selection unit 104 selects the wavelength “1”. That is, the concentration C ₁ = 10 corresponding to the wavelength of “1” is set as the concentration of the target element.
(Example 2) C ₁ = 10, C ₂ = 6, C ₃ = 4
In this example, D _1-2 and D _2-3 are T = 0.5 or less, but D _1-3 exceeds T = 0.5. Therefore, since the pattern b corresponds to the pattern b in FIG. 4, the selection unit 104 selects the wavelength “2”. That is, the concentration C ₂ = 6 corresponding to the wavelength of “2” is determined as the concentration of the target element.
(Example 3) C ₁ = 10, C ₂ = 20, C ₃ = 5
In this example, D _1-2 and D _1-3 are T = 0.5 or less, but D _2-3 exceeds T = 0.5. Therefore, since it corresponds to the pattern c in FIG. 4, the selection unit 104 selects the wavelength “1”. That is, the concentration C ₁ = 10 corresponding to the wavelength of “1” is set as the concentration of the target element.
(Example 4) C ₁ = 10, C ₂ = 6, C ₃ = 2
In this example, D _1-2 is T = 0.5 or less, but D _2-3 and D _1-3 exceed T = 0.5. Therefore, since it corresponds to the pattern d in FIG. 4, the selection unit 104 selects the wavelength “3”. That is, the concentration C ₃ = 2 corresponding to the wavelength “3” is set as the concentration of the target element.
(Example 5) C ₁ = 10, C ₂ = 4, C ₃ = 6
In this example, D _2-3 and D _1-3 are T = 0.5 or less, but D _1-2 is more than T = 0.5. Therefore, since it corresponds to the pattern e in FIG. 4, the selection unit 104 selects the wavelength “2”. That is, the concentration C ₂ = 4 corresponding to the wavelength of “2” is set as the concentration of the target element.
(Example 6) C ₁ = 10, C ₂ = 4, C ₃ = 3
In this example, D _2-3 is T = 0.5 or less, but D _1-2 and D _1-3 exceed T = 0.5. Therefore, since it corresponds to the pattern f in FIG. 4, the selection unit 104 selects the wavelength “2”. That is, the concentration C ₂ = 4 corresponding to the wavelength of “2” is set as the concentration of the target element.
(Example 7) C ₁ = 10, C ₂ = 4, C ₃ = 1
In this example, all of D _1-2 , D _2-3 , and D _1-3 exceed T = 0.5. Therefore, since it corresponds to the pattern h in FIG. 4, the selection unit 104 selects the wavelength “3”. That is, the concentration C ₃ = 1 corresponding to the wavelength of “3” is set as the concentration of the target element.

(T = 0.2)
(Example 8) C ₁ = 10, C ₂ = 9, C ₃ = 8
In this example, all of D _1-2 , D _2-3 , and D _1-3 are T = 0.2 or less. Therefore, since it corresponds to the pattern a in FIG. 4, the selection unit 104 selects the wavelength “1”. That is, the concentration C ₁ = 10 corresponding to the wavelength of “1” is set as the concentration of the target element.
(Example 9) C ₁ = 10, C ₂ = 8, C ₃ = 7
In this example, D _1-2 and D _2-3 are T = 0.2 or less, but D _1-3 exceeds T = 0.2. Therefore, since the pattern b corresponds to the pattern b in FIG. 4, the selection unit 104 selects the wavelength “2”. That is, the concentration C ₂ = 8 corresponding to the wavelength of “2” is set as the concentration of the target element.
(Example 10) C ₁ = 10, C ₂ = 12, C ₃ = 8
In this _{example, D 1-2} and _{D 1-3} are T = 0.2 or _{less, D 2-3} is more than T = 0.2. Therefore, since it corresponds to the pattern c in FIG. 4, the selection unit 104 selects the wavelength “1”. That is, the concentration C ₁ = 10 corresponding to the wavelength of “1” is set as the concentration of the target element.
(Example 11) C ₁ = 10, C ₂ = 8, C ₃ = 6
In this example, D _1-2 is T = 0.2 or less, but D _2-3 and D _1-3 exceed T = 0.2. Therefore, since it corresponds to the pattern d in FIG. 4, the selection unit 104 selects the wavelength “3”. That is, the concentration C ₃ = 6 corresponding to the wavelength “3” is set as the concentration of the target element.
(Example 12) C ₁ = 10, C ₂ = 7, C ₃ = 8
In this _{example, D 2-3} and _{D 1-3} are T = 0.2 or _{less, D 1-2} is more than T = 0.2. Therefore, since it corresponds to the pattern e in FIG. 4, the selection unit 104 selects the wavelength “2”. That is, the concentration C ₂ = 7 corresponding to the wavelength “2” is set as the concentration of the target element.
(Example 13) C ₁ = 10, C ₂ = 7, C ₃ = 6
In this example, D _2-3 is T = 0.2 or less, but D _1-2 and D _1-3 exceed T = 0.2. Therefore, since it corresponds to the pattern f in FIG. 4, the selection unit 104 selects the wavelength “2”. That is, the concentration C ₂ = 7 corresponding to the wavelength “2” is set as the concentration of the target element.
(Example 14) C ₁ = 10, C ₂ = 7, C ₃ = 5
In this example, all of D _1-2 , D _2-3 , and D _1-3 exceed T = 0.2. Therefore, since it corresponds to the pattern h in FIG. 4, the selection unit 104 selects the wavelength “3”. That is, the concentration C ₃ = 5 corresponding to the wavelength “3” is set as the concentration of the target element.

[ICP emission spectroscopy]
The analysis result data input to the quantification apparatus 1 may be data obtained by atomic emission analysis, and is not particularly limited. For example, data obtained by ICP emission spectroscopic analysis according to the procedure shown in FIG. 5 may be used. . FIG. 5 is a flowchart showing an example of the procedure of ICP emission spectroscopic analysis.

  First, a sample containing the target element is pretreated (S1), and a sample solution that can be analyzed by an ICP emission spectroscopic analyzer is prepared. Here, when it is expected that the sample contains organic substances, as a pretreatment, nitric acid is added and heated to about 200 ° C. to decompose organic substances and other non-analyzed substances. May be. In addition, when performing such pretreatment, the acid to be added may be any acid as long as the desired decomposition effect can be obtained. It may be a single body or a combination of these.

  Next, the pretreated sample solution is subjected to an ICP emission spectroscopic analyzer to measure ICP emission (S2). At this time, the internal standard substance may be supplied to the ICP emission spectroscopic analyzer together with the sample solution. The internal standard substance to be added is preferably an element suitable for detection of the target element.

  Then, the ICP emission spectroscopic analyzer outputs analysis result data (spectrum) (S3). The quantification apparatus 1 quantifies the target element using this analysis result data.

[Flow of processing performed by quantitative device]
Next, the process which the fixed_quantity | quantitative_assay apparatus 1 performs is demonstrated based on FIG. FIG. 6 is a flowchart showing an example of processing (quantitative method) executed by the quantitative device 1. Here, in order to simplify the explanation, it is assumed that there is one target element, and signals of three different spectral wavelengths are detected in the target element.

  First, the data acquisition unit 100 captures analysis result data (S10). Note that the analysis result data captured in S10 includes analysis result data of a standard solution for creating a calibration curve. Although not shown in the figure, the calibration curve creation unit 106 creates calibration curve data using the analysis result data of the standard solution after S10, and stores the calibration curve data in the storage unit 11 as the calibration curve data 111. As described above, the quantification apparatus 1 performs quantification by using a calibration curve created using the analysis result data of the standard solution provided for analysis together with the sample. An analytical value can be calculated.

  Next, the quantification unit 101 calculates a concentration value corresponding to each signal included in the analysis result data (S11, quantification step). Specifically, the quantification unit 101 refers to the wavelength data 110 and identifies three signals corresponding to the target element among the signals included in the analysis result data. Then, using the calibration curve data 111 of the target element, the concentration value of the target element is calculated from each of the identified three signals.

  Subsequently, the dilution rate selection unit 102 selects the dilution rate of the sample (S12). Basically, the lower the dilution factor, that is, the higher the concentration of the target element, the higher the quantification accuracy. Therefore, it is preferable that the dilution factor selection unit 102 selects the lowest dilution factor in the first selection. For example, as in the example of FIG. 2, when analysis is performed at five dilution ratios from undiluted to 10,000-fold diluted, it is preferable to select undiluted in the first selection.

Subsequently, the index value calculation unit 103 extracts a concentration value corresponding to the dilution factor selected by the dilution factor selection unit 102 from the concentration values calculated in S11 (S13). As described above, since it is assumed here that signals of three different wavelengths are detected in the target element, the concentration values (C _{1 to} C ₃ ) corresponding to these three wavelengths are respectively obtained in S13. Extracted.

In addition, the index value calculation unit 103 calculates an index value indicating the magnitude of the difference between the extracted density values (S14). Specifically, the index value calculation unit 103 calculates the index values D _1-2 , D _2-3 , and D _{1-3 according} to the above mathematical formulas (1) to (3).

Then, the selection unit 104 selects a concentration value corresponding to the index value calculated in S14 among the plurality of concentration values (C _{1 to} C ₃ ) extracted in S13 as a quantification result of the target element (S15 , Selection step). Specifically, the selection unit 104 selects a density value corresponding to one of the priority orders “1” to “3” according to the selection criterion of FIG.

  Further, the selection unit 104 determines whether or not the selected concentration value is within a predetermined quantitative range, more specifically, whether or not it is within a calibration curve range (S16). Here, when it is determined that it is outside the range of the calibration curve (NO in S16), the process returns to S12, and the dilution rate selection unit 102 sets the next dilution rate (a higher dilution rate than the previously selected dilution rate). select. On the other hand, when it is determined that it is within the range of the calibration curve (YES in S16), the selection unit 104 outputs the selected concentration value to the quantitative result data generation unit 105.

  When quantifying a plurality of target elements, the process returns to S12 when the determination is YES in S16, and the dilution factor for the next target element is selected. Alternatively, the process may return to S11 instead of S12, and the concentration value of the next target element may be calculated. Then, when quantifying a plurality of target elements, the process of S17 is performed when the quantification of all target elements is completed.

  Then, the quantification result data generation unit 105 generates and outputs quantification result data indicating that the concentration value output from the selection unit 104 is the concentration value of the target element (S17), and the illustrated process ends. The output mode of the quantitative result data is not particularly limited. For example, it may be a display output to the display unit 13, a print output, or an output of a data file including the quantitative result data. Also good. Alternatively, the data may be output to another device that is wired or wirelessly connected to the quantitative device 1.

In addition, although the example which quantifies the target element in which the signal of three different wavelengths was detected was shown above, it quantifies similarly for the target element in which the signal of two different wavelengths is detected. be able to. In this case, two density values (C ₁ , C ₂ ) are extracted in S 13, and an index value (D _1-2 ) between these density values is calculated in S 14. Then, in _S15, the value of _{D 1-2} selects _{C 1} equal to or less than _T, the value of _{D 1-2} selects the _{C 2} is greater than T.

  Further, for a target element in which signals of four or more different wavelengths are detected, it is only necessary to select three wavelengths from the higher detection sensitivity and calculate a concentration value corresponding to the wavelength. Since there is no room for selection for the target element in which only one wavelength signal is detected, the processes of S14 and S15 are omitted.

Note that the concentration value may be selected by calculating the above-described index value for signals of four or more wavelengths. For example, when calculating the above index values for signals of four wavelengths, the concentration values C _{1 to} C ₄ are calculated from each signal. Then, index values _D1-2 , _D1-3 , _D1-4 , _D2-3 , _D2-4 , and _D3-4 are calculated from the calculated density values. In this case, since the number of index values is 6, there are 64 patterns of magnitude relationships between these index values. Accordingly, by determining which density value is selected for each of the 64 patterns in the same manner as in the example of FIG. 4, among the density values that are not affected by spectral interference, the highest priority is given. A concentration value corresponding to the wavelength can be selected. Similarly, the above index values may be calculated for signals of five wavelengths. In this case, since the number of index values is 10, there are 1024 patterns of magnitude relationships between these index values.

  In addition, the analysis result data captured in S10 may include analysis results of a plurality of types of samples. In this case, after the process of S10, the user may select which sample is to be quantified, and thereafter, the processes after S11 may be performed. Thus, after the quantification of one type of sample is completed, the processing of S11 and the subsequent steps is performed again, whereby the quantification of the other sample can be performed using the previously prepared calibration curve data as it is.

[Automatic setting of reference value T]
The reference value T may be specified by the user in advance, but may be automatically set by the quantitative device 1. In this case, the control unit 10 of the quantitative device 1 may be provided with a reference value setting unit (threshold setting unit) that automatically sets the reference value T according to the magnitude of variation in the analysis result data.

  Here, as described above, in the present embodiment, if the index value (the value indicating the magnitude of the difference between the density values) calculated by the mathematical formulas (1) to (3) is equal to or smaller than the reference value T, the spectral interference. If the index value is larger than the reference value T, it is considered that the light is affected by spectral interference. Therefore, it can be said that the reference value T is a threshold value for determining whether the difference between the density values is within the range of the density value variation or due to the influence of interference.

  For example, a deviation (standard deviation) can be used as an index indicating the variation in numerical values. For example, the reference value setting unit may calculate, as the reference value T, a value indicating a range that is allowed as the deviation of the density value. In this case, the reference value setting unit calculates and calculates the standard deviation for a plurality of concentration values (concentration values corresponding to the same element and theoretically the same value) calculated by the quantification unit 101. The reference value T corresponding to the allowable range may be calculated using the standard deviation. Thereby, the reference value T proportional to the standard deviation is calculated. The allowable range may be, for example, 99.7% (3σ), 95% (2σ), or 68% (1σ).

  In addition, since a standard solution having no influence of interference is used, it is desirable to use the concentration value of the target element in the standard solution for calculating the reference value T. However, since the concentration of the target element in the standard solution and the concentration of the target element in the sample solution are usually different, when the reference value T is calculated using the concentration value of the target element in the standard solution, the target element in the standard solution It is preferable to use it for the determination of the concentration value of the target element in the sample solution after correcting by the ratio between the concentration of the target element and the concentration of the target element in the sample solution.

  In the above example, the reference value T is calculated using the concentration value. However, the reference value T can be calculated by the same calculation using the signal intensity included in the analysis result data.

  Note that the reference value setting unit only needs to set the reference value T according to the variation of the density value, and the calculated reference value is not necessarily used as it is. For example, the reference value setting unit may determine which of the predetermined reference values is used according to the calculated reference value. As a specific example, two reference values T of 50% and 20% are set in advance, and if the calculated reference value is 35% or more, 50% is adopted as the reference value T and should be less than the threshold value. For example, 20% may be adopted as the reference value T.

  Further, when the reference value calculated as described above is used as the reference value T as it is, an excessive value may be set as the reference value T, and an appropriate determination result may not be obtained. For this reason, it is preferable that the user manually set an upper limit value in advance for the reference value T and use the upper limit value as the reference value T when the calculated reference value exceeds the upper limit value.

[Appropriateness determination of internal standard substances]
When quantification is performed by the internal standard method, the signal of the internal standard substance may be an abnormal value due to the influence of interference. In such a case, it is difficult to obtain a reasonable quantitative result. Therefore, in S2 of FIG. 5, ICP luminescence measurement may be performed using a plurality of types of internal standard substances in combination. The control unit 10 of the quantification apparatus 1 may be provided with an internal standard determination unit that determines whether the internal standard substance is affected by interference.

  The internal standard determination unit calculates, for example, the recovery rate of the internal standard substance, and if the calculated recovery rate is less than a predetermined lower limit value or greater than a predetermined upper limit value, the internal standard substance is affected by interference. You may determine that you have received. The upper limit value and the lower limit value are not particularly limited. For example, the lower limit value may be 70% and the upper limit value may be 130%. The upper limit value and the lower limit value may be different values.

  And when the said internal standard determination part determines with the internal standard substance having received the influence of interference, you may alert | report to that effect by displaying a warning on the display part 13, etc. Thereby, the user can make the quantification apparatus 1 perform the quantification again after changing the internal standard substance. In addition, when the internal standard determination unit determines that the internal standard substance is affected by the interference, the internal standard determination unit may automatically perform the quantification after changing the internal standard material automatically. When it is determined that all of the plurality of internal standard substances are affected by interference, the internal standard determination unit instructs the quantification unit 101 to perform quantification without using the internal standard substance. May be. In this case, the quantification is performed by the absolute calibration curve method without correction by the internal standard substance.

[Modification]
In the above-described embodiment, an example in which quantification is performed using analysis result data of ICP emission spectroscopic analysis has been shown. Any analysis result data based on the method may be used, and the present invention is not limited to the above example. For example, it is also possible to calculate a concentration value from analysis result data of a laser excitation plasma emission spectroscopic analyzer, a solid state emission spectroscopic analyzer, a glow discharge emission spectroscopic analyzer, or the like.

  In the above embodiment, an example is shown in which the concentration value of the target element in the sample solution is calculated as the quantitative analysis value. However, the quantitative analysis value may be a value indicating the amount of the target element and is limited to the concentration value. Absent. For example, the weight of the target element in the liquid sample may be calculated as a quantitative analysis value, or the amount or density of the target element in the solid sample may be calculated as a quantitative analysis value.

  Furthermore, in the said embodiment, although the emission analysis apparatus and the fixed_quantity | assay apparatus 1 showed the example which is a different apparatus, it is good also as an integrated apparatus. That is, an emission analysis apparatus provided with the quantification apparatus 1 is also included in the category of the present invention.

In the above embodiment, an example is shown in which the density value is selected using the index values represented by the mathematical formulas (1) to (3). However, the index value used for the selection is the magnitude of the difference in the density values. Is not limited to this example. For example, C ₁ − (C ₁ + C ₂ + C ₃ ) / 3, C ₂ − (C ₁ + C ₂ + C ₃ ) / 3, C, which is a deviation from the average value of three concentration values calculated for the target element _3- (C ₁ + C ₂ + C ₃ ) / 3 may be used as the index value.

[Example of software implementation]
The control block (especially the control unit 10) of the quantitative device 1 may be realized by a logic circuit (hardware) formed in an integrated circuit (IC chip) or the like, or by software using a CPU (Central Processing Unit). It may be realized.

  In the latter case, the quantification apparatus 1 includes a CPU that executes instructions of a program that is software that realizes each function, a ROM (Read Only Memory) in which the above-described program and various data are recorded so as to be readable by a computer (or CPU) A storage device (these are referred to as “recording media”), a RAM (Random Access Memory) that expands the program, and the like are provided. And the objective of this invention is achieved when a computer (or CPU) reads the said program from the said recording medium and runs it. As the recording medium, a “non-temporary tangible medium” such as a tape, a disk, a card, a semiconductor memory, a programmable logic circuit, or the like can be used. The program may be supplied to the computer via an arbitrary transmission medium (such as a communication network or a broadcast wave) that can transmit the program. The present invention can also be realized in the form of a data signal embedded in a carrier wave in which the program is embodied by electronic transmission.

  The present invention is not limited to the above-described embodiments, and various modifications are possible within the scope shown in the claims, and embodiments obtained by appropriately combining technical means disclosed in different embodiments. Is also included in the technical scope of the present invention.

DESCRIPTION OF SYMBOLS 1 Fixed_quantity | quantitative_assay apparatus 101 The fixed_quantity | quantitative_assay part 102 The dilution rate selection part 103 Index value calculation part 104 Selection part

Claims (10)

A quantitative device for calculating a quantitative analysis value of a target element using analysis result data of atomic emission analysis,
A quantification unit for calculating a quantitative analysis value for each of a plurality of signals corresponding to the target element included in the analysis result data;
A selection unit configured to select a quantitative analysis value selected according to the magnitude of the difference between the quantitative analysis values among the plurality of quantitative analysis values calculated by the quantitative unit, as a quantitative result of the target element; A quantitative device characterized by that. An index value calculation unit that calculates an index value indicating the magnitude of the difference between the quantitative analysis values,
2. The quantitative apparatus according to claim 1, wherein the selection unit selects a quantitative analysis value from a set of quantitative analysis values in which the index value is equal to or less than a predetermined threshold value. The index value calculation unit
When the quantitative analysis values for which the index value is to be calculated are quantitative analysis values A and B,
(Quantitative analysis value A-Quantitative analysis value B) / Quantitative analysis value A
The quantification device according to claim 2, wherein the index value is calculated by the following formula. The analysis result data includes analysis result data obtained by analyzing the sample containing the target element at a plurality of dilution ratios, respectively.
If the quantitative analysis value selected by the selection unit is outside the predetermined quantitative range, the quantitative analysis value is calculated in the quantitative unit from the analysis result data of a dilution factor different from the dilution factor used for calculating the quantitative analysis value. The quantification apparatus according to claim 1, further comprising a dilution ratio selection unit for performing the selection.   When the analysis result data is data obtained by analysis using an internal standard substance, the internal standard that determines whether the internal standard substance is affected by interference from the recovery rate of the internal standard substance The determination apparatus according to claim 1, further comprising a determination unit.   The quantitative apparatus according to claim 2 or 3, further comprising a threshold setting unit configured to set the predetermined threshold according to the magnitude of variation in the analysis result data.   The quantitative analysis apparatus according to any one of claims 1 to 6, wherein the analysis result data is analysis result data of ICP emission spectral analysis. It is a quantification method by a quantification device that calculates a quantitative analysis value of a target element using analysis result data of atomic emission analysis,
A quantification step of calculating a quantitative analysis value for each of a plurality of signals corresponding to the target element included in the analysis result data;
A selection step in which a quantitative analysis value selected according to the magnitude of the difference between the quantitative analysis values among a plurality of quantitative analysis values calculated in the quantitative step is used as a quantitative result of the target element. A quantitative method characterized by   The control program for functioning a computer as a fixed_quantity | quantitative_assay apparatus of Claim 1, Comprising: The control program for functioning a computer as the said fixed_quantity | quantitative_assay part and the said selection part.   A computer-readable recording medium on which the control program according to claim 9 is recorded.

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