JP2017106747A - Analysis device, method of evaluating drift of the same, and program - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an analysis device configured to measure optical absorbance of a reaction liquid obtained by reacting a sample liquid with reagent, which is capable of eliminating time loss for checking drift and of providing an operator with an intuitively graspable check result immediately after completion of calibration.SOLUTION: In a calibration mode, calibration curve information for converting optical absorbance into concentration is produced based on a known concentration Cz of a calibration liquid Z, a known concentration Cs (Cz≠Cs) of a calibration liquid S, optical absorbance data Iz corresponding to when the calibration liquid Z is used as a sample liquid, and optical absorbance data Is corresponding to when the calibration liquid S is used as a sample liquid. Optical absorbance data of the calibration liquids acquired for calibration is converted into concentration data based on the calibration curve information produced in the previous calibration mode.SELECTED DRAWING: Figure 1

Description

  The present invention relates to an analyzer, a drift evaluation method for the analyzer, and a program. More specifically, the present invention relates to an analyzer that determines the concentration of a component in a sample solution by measuring the absorbance of a reaction solution obtained by reacting a reagent with the sample solution, a drift evaluation method for the analyzer, and a program.

  In an analyzer using an absorptiometer, in order to obtain a calibration curve indicating the relationship between the absorbance and the concentration of the component to be measured, it is necessary to periodically perform a calibration operation using a calibration solution having a known concentration. If the calibration curve fluctuates (drifts) at the time of this calibration work, there is a high possibility that some trouble such as failure of the apparatus or alteration of the reagent has occurred. For this reason, an alarm may be issued when an excessive drift occurs during calibration.

However, the alarm function alone is not so large as to give an alarm, but it cannot detect the occurrence of a drift larger than usual. In that case, it is conceivable that an absorbance history at the time of calibration is left in the apparatus so that the operator can compare with the absorbance at the time of calibration.
However, even if the operator sees the absorbance drift, it is difficult to intuitively understand how much the absorbance drift can affect the actual concentration data.
Therefore, in practice, when it is desired to confirm drift, a calibration solution is used as a sample solution to measure the concentration separately from the calibration work, and is compared with the known concentration of the calibration solution.

However, many analyzers using an absorptiometer measure not only the absorbance of a sample solution as it is, but also the absorbance of a reaction solution obtained by reacting a sample solution with a reagent.
In particular, when it takes about one hour for one measurement (for example, Patent Document 1), if a calibration solution is measured for drift confirmation, a time loss is large. For example, it takes about 2 hours to confirm both zero drift and span drift.

Japanese Patent No. 4044399

  The present invention has been made in view of the above points, and in an analyzer for measuring the absorbance of a reaction solution obtained by reacting a sample solution with a reagent, a time loss for confirming drift is eliminated, and the operator is intuitive. It is an object of the present invention to provide a drift evaluation method for an analyzer that is easy to understand and can obtain a confirmation result immediately after completion of a calibration operation, and an analyzer and a program for implementing this evaluation method.

In order to achieve the above object, the present invention employs the following configuration.
[1] A reaction part for reacting a sample solution with a reagent to obtain a reaction solution, an absorptiometer for measuring the absorbance of the obtained reaction solution,
A control unit for controlling the reaction unit and the absorptiometer and inputting the absorbance obtained by the absorptiometer,
In the calibration mode, the arithmetic control unit performs the calibration solution Z with the known concentration Cz and the calibration solution S with the known concentration Cs (where Cz ≠ Cs), the absorbance data Iz when the calibration solution Z is used as the sample solution, and the calibration solution S. Based on the absorbance data Is when the sample solution is used, the calibration curve information for converting the absorbance into the concentration is created,
An analyzer characterized by converting one or both of absorbance data Iz and absorbance data Is obtained in the current calibration mode into a concentration based on calibration curve information created in the previous calibration mode.
[2] The calculation control unit obtains a difference between the converted concentration and a known concentration in the current calibration mode for one or both of the calibration solution Z and the calibration solution S. [1] apparatus.

[3] A drift evaluation method for an analyzer that measures the absorbance of a reaction solution obtained by reacting a reagent with a sample solution to determine the concentration of the sample solution,
In the calibration mode, when the calibration solution Z has the known concentration Cz, the calibration solution S has the known concentration Cs (where Cz ≠ Cs), and the absorbance data Iz when the calibration solution Z is the sample solution and the calibration solution S is the sample solution Based on the absorbance data Is, calibration curve information for converting the absorbance into a concentration is created,
For one or both of the calibration solution Z and the calibration solution S, the absorbance data obtained in the current calibration mode is converted into a concentration based on the calibration curve information created in the previous calibration mode, and the converted concentration And a drift evaluation method for an analyzer, wherein a difference between the measured concentration and the known concentration in the current calibration mode is obtained.

[4] A reaction part for reacting a reagent with a sample solution to obtain a reaction solution, an absorptiometer for measuring the absorbance of the obtained reaction solution,
When controlling the reaction unit and the absorptiometer, and when a calibration mode is selected in an analyzer having an operation control unit to which the absorbance obtained by the absorptiometer is input,
A program for causing the arithmetic control unit to execute processing including the following steps.
[Step A1]
The reaction unit and the absorptiometer are controlled so as to obtain absorbance data of each reaction solution using each of the calibration solution Z and the calibration solution S as sample solutions,
The known concentration Cz of the calibration solution Z, the known concentration Cs of the calibration solution S (where Cz ≠ Cs), the absorbance data Iz when the calibration solution Z is the sample solution, and the absorbance data Is when the calibration solution S is the sample solution Creating calibration curve information for converting absorbance to concentration based on the above.
[Step A2]
A step of converting one or both of the absorbance data Iz and the absorbance data Is obtained in the current calibration mode into a concentration based on the calibration curve information created in the previous calibration mode.
[5] The step A2 is a step of obtaining a difference between the converted concentration and the known concentration in the current calibration mode for one or both of the calibration solution Z and the calibration solution S. [4] The program described in.

  According to the analyzer of the present invention, the drift evaluation method of the analyzer, and the program, the time loss for confirming the drift of the analyzer that measures the absorbance of the reaction liquid obtained by reacting the reagent with the sample liquid is eliminated, and the operation It is easy for a person to understand intuitively, and a confirmation result can be obtained immediately after the calibration work is completed.

It is a schematic block diagram of the analyzer which concerns on one Embodiment of this invention.

<Analyzer configuration>
An analyzer according to an embodiment of the present invention will be described with reference to FIG. The analyzer of this embodiment is an analyzer that calculates three items of total nitrogen, total phosphorus, and COD based on the JIS method. Of these three items, COD can be obtained by directly measuring the absorbance without reacting the reagent with the sample solution, but total nitrogen and total phosphorus can be obtained by reacting the reagent with the sample solution. It is determined by measuring the absorbance of the reaction solution.

The analyzer according to this embodiment includes a reaction unit 10, an absorptiometer 20, and an arithmetic control unit 30.
The reaction unit 10 includes a reaction tank 11, a thermal decomposition tank 12, a temperature sensor 13 that measures the temperature in the reaction tank 11, and a pump for introducing the reaction solution in the reaction tank 11 into the flow cell of the absorptiometer 20. 14 and a large number of flow paths.
The reaction unit 10 is provided with a pump and various valves, and the operation and control of these valves and pumps are controlled by the arithmetic control unit 30 so that the sample solution, the reagent, and the like can be appropriately moved in each channel. It has become. The thermal decomposition tank 12 of the reaction unit 10 is also controlled by the calculation control unit 30.

FIG. 1 shows main flow paths, valves, and pumps of the analyzer according to the present embodiment. The flow path L1 is a flow path for introducing the reaction solution in the reaction tank 11 into the absorptiometer 20, and the flow cell of the pump 14 and the absorptiometer 20 is provided in this flow path L1.
The flow path L2 is a sample liquid flow path, and the flow paths L3 to L5 are reagent flow paths. The flow path L3 is a flow path for sending potassium peroxodisulfate solution to the reaction tank 11, the flow path L4 is a flow path for sending sodium hydroxide solution and hydrochloric acid to the reaction tank 11, and the flow path L5 is an ammonium molybdate solution and L- This is a flow path for sending an ascorbic acid solution to the reaction tank 11. The ammonium molybdate solution is a sulfuric acid ammonium molybdate solution containing a small amount of potassium tartrate antimonate (III).

The flow path L6 is a sample decomposition flow path for measuring total nitrogen, and the flow path L7 is a sample decomposition flow path for measuring total phosphorus, both of which have a lower end inserted into the bottom of the reaction tank 11, and an upper end side is not shown. It can be connected to the pump. This pump is preferably a metering pump using an air pump and a stepping motor. In both cases, the intermediate portion of the flow path is accommodated in the thermal decomposition tank 12. A normally closed valve SV1 is provided on the reaction tank 11 side of the portion of the flow path L6 accommodated in the thermal decomposition tank 12, and a normally closed valve SV2 is provided on the opposite side of the reaction tank 11. In addition, a normally closed valve SV3 is provided on the reaction tank 11 side of the portion accommodated in the thermal decomposition tank 12 of the flow path L7, and a normally closed valve SV4 is provided on the opposite side to the reaction tank 11.
The flow path L8 is a flow path for sending pure water to the reaction tank 11, and the flow paths L9 to L10 are waste liquid flow paths.

The absorptiometer 20 includes a flow cell, a light source, and a spectroscopic detector that are not shown. The flow cell is made of quartz glass. As the light source, a deuterium lamp and a tungsten lamp are used, and these are arranged on the same optical axis. The spectroscopic detector includes a spectroscopic unit using a diffraction grating and a linear array detector.
The arithmetic control unit 30 controls the reaction unit 10 and the absorptiometer 20 and receives the absorbance obtained by the absorptiometer. The arithmetic control unit 30 incorporates the program of the present invention.

<Measurement of sample solution>
The analyzer of the present embodiment obtains three items of total nitrogen, total phosphorus, and COD of the sample solution under the control of the arithmetic control unit 30 according to the following procedure. The temperature of the thermal decomposition tank 12 is set to a residual heat state of 70 ° C. throughout the entire process except during the thermal decomposition, and is set to 120 ° C. during the thermal decomposition. The cleaning performed in each step is performed by introducing pure water into a portion that needs to be cleaned and then draining it.
In the following description, the absorbance of the sample solution or reaction solution obtained by the absorptiometer 20 is preferably a value obtained by blank correction by subtracting a blank measurement value. The blank measurement value is the absorbance when pure water is allowed to flow through the flow cell.

1. Preparation of total nitrogen sample First, a predetermined amount of sample liquid is introduced into the reaction tank 11 through the flow path L2. Here, if necessary, pure water is introduced into the reaction tank 11 from the flow path L8 to dilute the sample solution. Next, a potassium peroxodisulfate solution and a sodium hydroxide solution, which are thermal decomposition reagents for measuring total nitrogen, are introduced into the reaction tank 11 through the flow paths L3 and L4. Thereafter, a pump is connected to the flow path L6, and the sample solution and the thermal decomposition reagent are mixed by bubbling into the reaction tank 11 with the normally closed valve SV1 and the normally closed valve SV2 opened, and the total nitrogen sample solution and To do. Then, by driving the pump connected to the flow path L6, the total amount of the total nitrogen sample liquid is sucked to the portion of the flow path L6 accommodated in the thermal decomposition tank 12 (preheated state), and the normally closed valve SV1 The normally closed valve SV2 is returned to the closed state, and the process waits while the total phosphorus sample adjustment is performed.

2. Preparation of total phosphorus sample After the inside of the reaction tank 11 is washed, a predetermined amount of sample solution is introduced into the reaction tank 11 through the flow path L2. Here, if necessary, pure water is introduced into the reaction tank 11 from the flow path L8 to dilute the sample solution. Next, a potassium peroxodisulfate solution, which is a thermal decomposition reagent for measuring total phosphorus, is introduced into the reaction tank 11 through the flow path L3. Thereafter, a pump is connected to the flow path L7, and the sample solution and the thermal decomposition reagent are mixed by bubbling into the reaction tank 11 with the normally closed valve SV3 and the normally closed valve SV4 opened, and the total phosphorus sample solution and To do. Then, by driving the pump connected to the flow path L7, the entire amount of the total phosphorus sample liquid is sucked to the portion of the flow path L7 accommodated in the thermal decomposition tank 12 (preheated state), and the normally closed valve SV3. The normally closed valve SV4 is returned to the closed state.

3. Thermal decomposition and COD measurement A pump is connected to the flow path L6, air is pumped in a state where the normally closed valve SV2 is opened, and then the normally closed valve SV2 is returned to the closed state, whereby the thermal decomposition tank 12 in the flow path L6. Increase the pressure in the part housed in.
Similarly, the pressure of the part accommodated in the thermal decomposition tank 12 of the flow path L7 is raised by pumping air with the normally closed valve SV4 opened, and then returning the normally closed valve SV4 to the closed state.

Then, the temperature of the thermal decomposition tank 12 is set to 120 ° C., and the total nitrogen sample liquid in the flow path L6 and the total phosphorus sample liquid in the flow path L7 are thermally decomposed for 30 minutes, respectively. Use a thermal decomposition solution for measurement.
By the thermal decomposition, all the nitrogen compounds in the sample solution are oxidized to nitrate ions. In addition, all phosphorus compounds in the sample solution are oxidized to phosphate ions.

  The COD measurement is performed in parallel during the 30 minutes of the thermal decomposition. That is, after the inside of the reaction tank 11 is washed, a predetermined amount of sample solution is introduced into the reaction tank 11 through the flow path L2. Here, if necessary, pure water is introduced into the reaction tank 11 from the flow path L8 to dilute the sample solution. Next, the sample solution in the reaction tank 11 is sucked into the flow cell of the absorptiometer 20 by the pump 14 to measure the absorbance. After measuring the absorbance, the flow path L1 and the reaction tank 11 are washed.

  The absorbance is measured by irradiating the sample liquid in the flow cell with light having a wavelength of 254 nm by a deuterium lamp and a wavelength of 546 nm by a tungsten lamp. The light that has passed through the flow cell is spectrally separated by the spectroscopic unit, and then detected for each wavelength by the linear array detector, and the absorbance for each wavelength is obtained. The absorbance at 254 nm corresponds to COD, but is affected by the amount of turbid components. The absorbance at 546 nm corresponds to the amount of turbid components. By converting the value obtained by subtracting the absorbance at 546 nm from the absorbance at 254 nm based on the calibration curve information obtained in advance, the COD value of the sample solution is obtained.

4). Total nitrogen measurement A pump is connected to the flow path L6, the normally closed valve SV1 and the normally closed valve SV2 are opened, and the thermal decomposition solution for measuring total nitrogen in the flow path L6 is pumped back to the reaction tank 11. Here, hydrochloric acid is introduced through the flow path L4 to adjust the pH to 2 to 3 to obtain a reaction solution for measuring total nitrogen.
Next, the pump 14 sucks the reaction solution in the reaction tank 11 into the flow cell of the absorptiometer 20 and measures the absorbance. After measuring the absorbance, the flow paths L1, L6 and the reaction tank 11 are washed.

  The absorbance is measured by irradiating the sample liquid in the flow cell with light having a wavelength of 220 nm and a wavelength of 254 nm from a deuterium lamp. The light that has passed through the flow cell is spectrally separated by the spectroscopic unit, and then detected for each wavelength by the linear array detector, and the absorbance for each wavelength is obtained. The absorbance at 220 nm corresponds to the nitrate ion concentration, but is affected by the amount of turbid components. Since the absorbance at 254 nm does not absorb the nitrate ion concentration, the total nitrogen concentration of the sample solution can be obtained by converting a value obtained by subtracting the absorbance at 254 nm from the absorbance at 220 nm based on previously obtained calibration curve information.

5). Total phosphorus measurement A pump is connected to the flow path L7, the normally closed valve SV3 and the normally closed valve SV4 are opened, and the thermal decomposition solution for measuring total phosphorus in the flow path L7 is pumped back to the reaction tank 11. Here, an L-ascorbic acid solution and ammonium molybdate hydrochloride are introduced through a flow path L5 to generate molybdenum blue.
Next, the pump 14 sucks the reaction solution in the reaction tank 11 into the flow cell of the absorptiometer 20 and measures the absorbance. After measuring the absorbance, the flow paths L1, L7 and the reaction tank 11 are washed.

  Absorbance is measured by irradiating the sample liquid in the flow cell with light having a wavelength of 880 nm from a tungsten lamp. The light that has passed through the flow cell is spectrally separated by the spectroscopic section, then detected by the linear array detector, and the absorbance at a wavelength of 880 nm is obtained. By converting this absorbance based on the calibration curve information obtained in advance, the total phosphorus concentration of the sample solution is obtained.

6). Cleaning The reaction tank 11 and each flow path are cleaned. The time required for the steps so far is about 60 minutes.

<Calibration>
When the calibration mode is selected in the analyzer, the arithmetic control unit 30 executes processing including the following step A1.
The calibration mode may be selected by an input instruction from the operator, or may be selected according to a predetermined timing programmed in advance. The predetermined timing may be every certain period, or may be a time when a usage condition of the analyzer satisfies a predetermined condition such as reagent replacement.

[Step A1]
The reaction unit 10 and the absorptiometer 20 are controlled so as to obtain absorbance data of each reaction solution using each of the calibration solution Z and the calibration solution S as sample solutions,
The known concentration Cz of the calibration solution Z, the known concentration Cs of the calibration solution S (where Cz ≠ Cs), the absorbance data Iz when the calibration solution Z is the sample solution, and the absorbance data Is when the calibration solution S is the sample solution Creating calibration curve information for converting absorbance to concentration based on the above.

As the calibration solution Z, it is preferable to use a calibration solution having a concentration of the measurement target component of zero or a known concentration in which the concentration of the measurement target component is close to zero. As the calibration solution S, it is preferable to use a calibration solution having a known concentration close to the full-scale concentration or a full-scale concentration.
In this embodiment, pure water is used as the calibration liquid Z. As the calibration solution S, a mixed solution of potassium nitrate and potassium dihydrogen phosphate is used. This calibration solution S can be shared as a calibration solution for both total nitrogen and total phosphorus.
The calibration with the calibration solution Z and the calibration with the calibration solution S may each be performed once or more, but when high accuracy is required, it is preferable to perform each of the calibrations a plurality of times. For example, when the calibration with the calibration liquid Z and the calibration with the calibration liquid S are each performed three times, the time required for calibration is about 6 hours in total.

In the total nitrogen measurement, the absorbance data Iz is a value obtained by subtracting the absorbance at 254 nm from the absorbance at 220 nm when the calibration solution Z is used as the sample solution. Further, a value obtained by subtracting the absorbance at 254 nm from the absorbance at 220 nm when the calibration solution S is used as the sample solution is the absorbance data Is.
When calibration with the calibration solution Z is performed a plurality of times, the average value Iza of each absorbance data Iz is used as the absorbance data Iz for creating a calibration curve. Further, when calibration with the calibration solution S is performed a plurality of times, the average value Isa of each absorbance data Is is used as the absorbance data Is for creating a calibration curve.

A calibration curve can be created based on the absorbance data Iz and absorbance data Is, the known concentration Cz of the calibration solution Z, and the known concentration Cs of the calibration solution S. The calibration curve is a straight line passing through two points, the point (Iz, Cz) and the point (Is, Cs), when the absorbance is the X coordinate and the concentration is the Y coordinate.
The calibration curve information in the present invention may be information consisting of the absorbance data Iz and the absorbance data Is, the known concentration Cz and the known concentration Cs, or may be information of an equation indicating the calibration curve obtained from these.
By creating the calibration curve, the concentration of the measurement target component whose concentration is unknown can be obtained based on the calibration curve when the reaction liquid of the sample solution is obtained and the absorbance is measured in the measurement mode.

<Drift evaluation>
When the calibration mode is selected in the analyzer, the arithmetic control unit 30 executes a process including the following step A2 together with the step A1. Thereby, the drift evaluation method of this invention is implemented.
[Step A2]
A step of converting one or both of the absorbance data Iz and the absorbance data Is obtained in the current calibration mode into a concentration based on the calibration curve information created in the previous calibration mode.

When the calibration with the calibration solution Z is performed a plurality of times, the current absorbance data Iz converted into the concentration in step A2 may be data obtained in one of the plurality of times (for example, the first time), or a plurality of data It may be an average value. Further, when the calibration with the calibration solution S is performed a plurality of times, the current absorbance data Is converted into the concentration in step A2 may be data obtained in one of the plurality of times (for example, the first time), or a plurality of times It may be an average value of data.
For example, when using the first data, step A2 can be performed before step A1 is completed.

  In step A2, if the calibration curve information created in the previous calibration mode is stored as information consisting of the absorbance data Iz and absorbance data Is, and the known concentration Cz and known concentration Cs, based on these information, One or both of the absorbance data Iz and the absorbance data Is obtained in the calibration mode are converted into concentrations. If the calibration curve information created in the previous calibration mode is stored as an equation indicating the calibration curve, one or both of the absorbance data Iz and the absorbance data Is obtained in the current calibration mode based on this equation are stored. Convert to concentration. Hereinafter, the conversion method will be described in detail for the former case. However, even in the latter case, only a part of the following calculation is performed when preparing the calibration curve information, and there is no essential difference.

In order to distinguish the absorbance data Iz and absorbance data Is obtained in the current calibration mode from the previous one, the absorbance data Iz ′ and absorbance data Is ′ are respectively based on the previous calibration curve information. The converted concentration Dz obtained from Iz ′ and the concentration Ds obtained from the absorbance data Is ′ are represented by the following formulas (1) and (2), respectively.
Dz = (Iz′−Iz) / (Is−Iz) * (Cs−Cz) + Cz (1)
Ds = (Is′−Is) / (Is−Iz) * (Cs−Cz) + Cs (2)

When the calibration curve information is a formula indicating a calibration curve, the above formulas (1) and (2) become the following formulas (1) ′ and (2) ′.
Dz = α * Iz ′ + β (1) ′
Ds = α * Is ′ + β (2) ′
However, in the formulas (1) ′ and (2) ′,
α = (Cs−Cz) / (Is−Iz)
β = (Cz * Is−Cs * Iz) / (Is−Iz)

  When the arithmetic control unit 30 performs at least one of the equations (1) and (2), a numerical value that can be handled as a concentration, not an absorbance, is obtained. Therefore, the operator compares the converted concentration Dz obtained by the equation (1) with the known concentration Cz ′ of the calibration solution Z used in the current calibration mode, or the converted concentration obtained by the equation (2). By comparing Ds with the known concentration Cs ′ of the calibration solution S used in the current calibration mode, the drift situation can be intuitively recognized.

The arithmetic control unit 30 may perform the following formula (3) or formula (4) instead of the formula (1) and formula (2). In this case, since the drift amount can be obtained directly in terms of concentration, the operator can recognize the drift situation more intuitively.
Dz−Cz ′ = (Iz′−Iz) / (Is−Iz) * (Cs−Cz) + Cz−Cz ′
... (3)
Ds−Cs ′ = (Is′−Is) / (Is−Iz) * (Cs−Cz) + Cs−Cs ′
... (4)

If there is no change in the known concentration of the calibration solution used during the previous calibration and the current calibration (Cz = Cz ′, Cs = Cs ′), the equations (3) and (4) are expressed by the following equation (5 ) And Equation (6).
Dz−Cz = (Iz′−Iz) / (Is−Iz) * (Cs−Cz) (5)
Ds−Cs = (Is′−Is) / (Is−Iz) * (Cs−Cz) (6)
Further, as in this embodiment, when the known concentration Cz of the calibration liquid Z used at the previous calibration and the current calibration is both zero (Cz = 0), the equations (5) and (6) are as follows: (7) and (8).
Dz = (Iz′−Iz) / (Is−Iz) * Cs (7)
Ds−Cs = (Is′−Is) / (Is−Iz) * Cs (8)

Further, the arithmetic control unit 30 may perform the following formula (9) or formula (10) instead of the formula (5) and formula (6). In this case, since the drift amount is obtained as a ratio (%) in the full scale concentration (FS), the operator can more intuitively recognize the influence of the drift on the measurement value.
[Dz-Cz] (%)
= (Iz'-Iz) / (Is-Iz) * (Cs-Cz) / FS * 100 (9)
[Ds-Cs] (%)
= (Is'-Is) / (Is-Iz) * (Cs-Cz) / FS * 100 (10)
When the known concentration Cz of the calibration solution Z used at the previous calibration and the current calibration is both zero and the known concentration Cs of the calibration solution S is both full scale concentration (FS) (Cz = Cz ′ = 0, Cs = FS), Expressions (9) and (10) become Expressions (11) and (12) below.
[Dz] (%) = (Iz′−Iz) / (Is−Iz) * 100 (11)
[Ds−Cs] (%) = (Is′−Is) / (Is−Iz) * 100 (12)

  When the calculation control unit 30 performs one or more calculations of any of the above formulas (1) to (12), the drift evaluation method of the present invention is completed. However, when the calculation control unit 30 performs the calculation of either of the above formulas (1) and (2), when the calculation process is terminated, the operator compares the converted concentration with the known concentration, and the difference To complete the drift evaluation method of the present invention.

When the drift evaluation method of the present invention is completed, the operator can intuitively confirm the state of drift.
In addition, since the above calculation can be performed by directly using the data obtained for calibration, there is no need to bother the reaction between the sample solution and the reagent in order to confirm the drift.
In the calibration mode, when the calibration with the calibration liquid Z and the calibration with the calibration liquid S are each performed a plurality of times, if the above computation is performed using the data obtained by the first calibration, the entire calibration process is completed. Drift status can be confirmed without waiting.
Therefore, depending on the drift situation, it is possible to take measures such as canceling the remaining calibration process.

  In the above-described embodiment, the analysis apparatus for obtaining the three items of total nitrogen, total phosphorus, and COD according to the JIS method has been described as an example. However, the analysis target of the analysis apparatus is not limited to this, for example, total nitrogen, An analyzer that calculates two items of total phosphorus may be used. Further, an apparatus for performing an absorbance analysis by reacting a sample solution with a reagent of hexavalent chromium, total chromium, nickel manganese, copper, or the like may be used. Alternatively, a mercury measuring apparatus may be used that obtains vaporized mercury by atomic absorption spectrophotometry from a sample solution obtained by converting a mercury compound into mercury by reaction with a reagent.

  Further, the specific configuration of the reaction unit, the absorptiometer, and the analysis procedure may be appropriately changed according to the analysis target component, and there is no particular limitation.

Moreover, in the said embodiment, although the program for performing each step was taken as the aspect integrated in the calculation control part 30, a part or all of the function of the calculation control part 30 uses a communication system directly or. It may be carried by a connected external computer.
In this case, the program may be recorded in advance on a computer, or may be recorded on a computer-readable recording medium, and the program recorded on the recording medium may be read by the computer.
Further, a program recorded in advance in a computer and a program recorded in a computer-readable recording medium and read into the computer may be combined.

DESCRIPTION OF SYMBOLS 10 ... Reaction part, 11 ... Reaction tank, 12 ... Thermal decomposition tank, 13 ... Temperature sensor,
14 ... Pump, 20 ... Absorptiometer, 30 ... Calculation control unit

Claims (5)

A reaction part for reacting a reagent with a sample solution to obtain a reaction solution, an absorptiometer for measuring the absorbance of the obtained reaction solution,
A control unit for controlling the reaction unit and the absorptiometer and inputting the absorbance obtained by the absorptiometer,
In the calibration mode, the arithmetic control unit performs the calibration solution Z with the known concentration Cz and the calibration solution S with the known concentration Cs (where Cz ≠ Cs), the absorbance data Iz when the calibration solution Z is used as the sample solution, and the calibration solution S. Based on the absorbance data Is when the sample solution is used, the calibration curve information for converting the absorbance into the concentration is created,
An analyzer characterized by converting one or both of absorbance data Iz and absorbance data Is obtained in the current calibration mode into a concentration based on calibration curve information created in the previous calibration mode.   The analyzer according to claim 1, wherein the arithmetic control unit obtains a difference between the converted concentration and a known concentration in the current calibration mode for one or both of the calibration solution Z and the calibration solution S. A drift evaluation method for an analyzer that measures the absorbance of a reaction solution obtained by reacting a reagent with a sample solution to determine the concentration of the sample solution,
In the calibration mode, when the calibration solution Z has the known concentration Cz, the calibration solution S has the known concentration Cs (where Cz ≠ Cs), and the absorbance data Iz when the calibration solution Z is the sample solution and the calibration solution S is the sample solution Based on the absorbance data Is, calibration curve information for converting the absorbance into a concentration is created,
For one or both of the calibration solution Z and the calibration solution S, the absorbance data obtained in the current calibration mode is converted into a concentration based on the calibration curve information created in the previous calibration mode, and the converted concentration And a drift evaluation method for an analyzer, wherein a difference between the measured concentration and the known concentration in the current calibration mode is obtained. A reaction part for reacting a reagent with a sample solution to obtain a reaction solution, an absorptiometer for measuring the absorbance of the obtained reaction solution,
When controlling the reaction unit and the absorptiometer, and when a calibration mode is selected in an analyzer having an operation control unit to which the absorbance obtained by the absorptiometer is input,
A program for causing the arithmetic control unit to execute processing including the following steps.
[Step A1]
The reaction unit and the absorptiometer are controlled so as to obtain absorbance data of each reaction solution using each of the calibration solution Z and the calibration solution S as sample solutions,
The known concentration Cz of the calibration solution Z, the known concentration Cs of the calibration solution S (where Cz ≠ Cs), the absorbance data Iz when the calibration solution Z is the sample solution, and the absorbance data Is when the calibration solution S is the sample solution Creating calibration curve information for converting absorbance to concentration based on the above.
[Step A2]
A step of converting one or both of the absorbance data Iz and the absorbance data Is obtained in the current calibration mode into a concentration based on the calibration curve information created in the previous calibration mode.   The step A2 is a step of further obtaining a difference between the converted concentration and a known concentration in the current calibration mode for one or both of the calibration solution Z and the calibration solution S. program.

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