JP6250105B2 - Electrolyte analyzer and electrolyte analysis method - Google Patents

Description

  The present invention relates to an electrolyte analyzer for analyzing ionic components contained in a biological sample such as blood or urine.

  The electrolyte analyzer analyzes ion components such as sodium ions, potassium ions, and chlorine ions contained in biological samples such as blood and urine (hereinafter referred to as samples). One known method for detecting ions in a sample is to measure specific ions in the sample using an ion selective electrode. In the measurement using such an ion selective electrode, first, a standard sample having a known concentration is measured in advance, and a calibration curve is calculated from the measurement result. Then, the internal standard solution and the sample are alternately measured to measure the potential difference, and the concentration of specific ions in the sample is measured using the potential difference and the calibration curve.

  As such an electric field analysis apparatus, for example, Patent Document 1 (Japanese Patent Laid-Open No. 2011-122823) discloses a storage mechanism for storing a calibration result obtained by measuring a sample having a known concentration in an arbitrarily set period, and a calibration. Measurement result slope value, internal standard solution concentration value, internal standard solution electromotive force, low concentration region standard solution electromotive force, high concentration region standard solution electromotive force, and calibrator electromotive force measurement result There is disclosed an electrolyte analysis device including a mechanism for extracting and accumulating at least any feature of the fluctuation pattern.

JP 2011-122823 A

  In the above-described conventional electrolyte analyzer, an abnormality such as electrode deterioration or sample deterioration is detected from a fluctuation pattern of a calibration result periodically performed. However, the frequency of calibration is not as high as once a day at most, and opportunities for detecting an abnormality can be obtained only at the same frequency.

  On the other hand, an electrolyte analyzer is relatively short in time until a result is obtained as compared with a biochemical automatic analyzer or the like, and is often used for measurement of an urgent sample such as an emergency specimen. In the measurement of urgent specimens and the like, the influence when an abnormality occurs in the measurement result is large, and higher reliability is required in addition to the speed of measurement.

  The present invention has been made in view of the above, and an object thereof is to provide an electrolytic analysis apparatus and an electrolyte analysis method capable of improving reliability while suppressing a decrease in measurement speediness.

  In order to achieve the above object, the present invention provides an electrolyte analyzer that measures the concentration of specific ions in a sample using an ion selective electrode, and measures each of a plurality of types of ions in the sample when measuring an electromotive force. A reference value for the normal determination of bubble noise for determining bubble noise abnormality caused by bubbles mixed in the flow path through which the sample passes is set in advance, and a known ion is set in advance before and after the measurement of the sample. When the electromotive force of the internal standard solution adjusted to the concentration of the sample is measured and the difference in the measurement result of the electromotive force of the internal standard solution before and after the measurement of the sample exceeds the reference value for the normal determination of bubble noise If the measurement result of the sample is determined to be abnormal bubble noise and does not exceed the reference value for normal determination of bubble noise, the occurrence of the internal standard solution before and after measurement of the sample is performed. When the positive / negative direction of the force measurement result is the same for the plurality of types of ions and the change amount of the measurement result is within a predetermined range for the plurality of types of ions, the measurement result of the sample is It is assumed that an abnormality determination unit that determines that the bubble noise is abnormal is provided.

  According to the present invention, it is possible to improve reliability while suppressing a decrease in measurement speed.

It is a schematic block diagram of the electrolyte analyzer which concerns on this Embodiment which concerns on one embodiment. It is a flowchart which shows operation | movement of an electrolyte analyzer. It is a flowchart which shows the processing content of a bubble noise alarm process. It is a flowchart which shows the processing content of a carry over alarm process. It is a figure which shows the setting screen of ISE abnormality detection which sets various parameters etc. which are used for the electrolyte analyzer of this Embodiment. It is a figure which shows an example of the range made into the normal value of each ion concentration contained in blood or urine. It is a figure which shows an example of the change of a measurement result when a bubble mixes in an electrode flow path.

  An embodiment of the present invention will be described with reference to the drawings.

  FIG. 1 is a schematic configuration diagram of an electrolyte analyzer according to the present embodiment.

  In FIG. 1, a sample container 1 accommodates a biological sample such as blood or urine (hereinafter referred to as a sample) and dispenses a sample from a sample dispensing nozzle 2 immersed in a sample accommodated in the sample container 1. A set amount is sucked by the operation of the nozzle syringe 3 and discharged to the dilution tank 4. The diluent bottle 5 contains a diluent used for diluting the sample. The diluent is sent to the dilution tank 4 by the operation of the diluent syringe 6 and the diluent solenoid valve 7 and discharged to the dilution tank 4. Dilute the prepared sample.

  The sample diluted in the dilution tank 4 is sucked into the sodium ion selection electrode 11, the potassium ion selection electrode 12, and the chlorine ion selection electrode 13 by the operations of the sipper syringe 8, the sipper syringe solenoid valve 9, and the pinch valve 10. The The comparison electrode solution stored in the comparison electrode solution bottle 14 is sucked into the comparison electrode 16 by the operations of the comparison electrode solution solenoid valve 15, the sipper syringe 8, and the sipper syringe solenoid valve 9. And the electromotive force between the comparison electrode 16 and each ion selection electrode 11, 12, 13 is measured.

  Further, in the measurement of the internal standard solution used for obtaining the sample concentration, the internal standard solution stored in the internal standard solution bottle 17 is changed to the sample by the operation of the internal standard solution syringe 18 and the internal standard solution solenoid valve 19. Or is sent to the dilution tank 4 from which the diluent has been removed. The internal standard solution of the dilution tank 4 is sucked by the sodium ion selection electrode 11, the potassium ion selection electrode 12, and the chlorine ion selection electrode 13 by the operations of the sipper syringe 8, the electromagnetic valve 9 for the sipper syringe, and the pinch valve 10. The electromotive force between the reference electrode 16 is measured. In the following description, when simply referred to as an electromotive force, the electromotive force between the reference electrode 16 and the reference electrode 16 is indicated.

  The sodium ion selection electrode 11, the potassium ion selection electrode 12, the chlorine ion selection electrode 13, and the comparison electrode 16 are connected to the control unit 20. The control unit 20 controls the overall operation of the electrolyte analyzer. In addition to measuring the electromotive force generated between the electrodes, the syringes 3, 6, 8, 18 and the electromagnetic valves 7, 9, 10, The operation of 15, 19, etc. is also controlled. A storage unit 21, a display unit 22, and an input unit 23 are connected to the control unit 20. Based on a setting screen displayed on the display unit 22, various parameters and measurement target samples are input by the input unit 23. Information (sample type information and the like) is input and stored in the storage unit 21. In addition, the storage unit 21 stores various programs used for sample measurement, measurement results, and the like.

  Here, each ion (in the present embodiment) in the sample (including the diluting liquid) sucked by the ion selective electrodes 11, 12, 13 from the electromotive force between the respective ion selective electrodes 11, 12, 13 and the comparison electrode 16 is used. In the embodiment, the procedure for measuring the concentration of sodium ions, potassium ions, and chlorine ions) will be described in the following (1) to (3). In order to measure a sample or an internal standard solution, calibration is first performed using a standard solution with a known concentration. As calibration, the slope sensitivity is calculated and the electromotive force of the internal standard solution and the sample of known concentration is measured, and the concentration of each ion in the sample is calculated from the obtained result and the potential difference of the electromotive force of the sample. .

(1) Preparation of calibration curve using low concentration standard solution and high concentration standard solution of known concentration (calculation of slope sensitivity)
The slope sensitivity for calculating each ion concentration in the sample is calculated based on the following (Equation 1).

SL = (EMF _H -EMF _L ) / (LogC _H -LogC _L ) (1)
SL: Slope sensitivity
EMF _H : Electromotive force of known high concentration standard solution
EMF _L : Electromotive force of known low concentration standard solution
C _H : Known concentration of high concentration standard solution
C _L : Known concentration of low concentration standard solution (2) Calculation of ion concentration in internal standard solution The calculation of ion concentration in the internal standard solution is calculated based on the following (formula 2) and (formula 3).

C _IS = C _L × 10 ^a ... (Formula 2)
a = (EMF _IS -EM _FL ) / SL (Equation 3)
C _IS : Concentration of internal standard solution
EMF _IS : Electromotive force of internal standard solution (3) Calculation of ion concentration in sample Calculation of ion concentration in the sample is calculated based on the following (Formula 4) and (Formula 5).

C _S = C _IS × 10 ^b ... (Formula 4)
b = (EMF _IS -EMF _S ) / SL (Equation 5)
C _S : Sample concentration
EMF _S : Measurement Electromotive Force of Sample Next, the operation of the electrolyte analyzer in the present embodiment will be described.

  2-4 is a flowchart which shows operation | movement of the electrolyte analyzer of this Embodiment. FIG. 2 is a flowchart for determining whether or not to measure a specific sample from the potential difference of the electromotive force of the internal standard solution measured before and after the immediately preceding (one previous) sample measurement. FIG. 3 is a flowchart showing the contents of the bubble noise alarm process, and FIG. 4 is a flowchart showing the contents of the CO alarm process. The control unit 20 performs control based on these flowcharts.

  2 to 4, when the start of sample analysis is instructed by the input unit 23 or the like, the control unit 20 first performs a reset operation to create a calibration curve (calculate slope sensitivity) and the like (step S10). ). Next, the electromotive force of the internal standard solution is measured for each item relating to the ion concentration of sodium ion, potassium ion, and chlorine ion, and the measurement result is stored in the storage unit 21 (step S20). The electromotive force of the sample to be measured is measured for each item relating to the ion concentration of potassium ion and chlorine ion, the measurement result is stored in the storage unit 21 (step S30), and the electromotive force of the internal standard solution for each item. And the measurement result is stored in the storage unit 21 (step S40). Here, the difference between the measurement results of the electromotive force of the internal standard solution measured before and after the measurement of the sample is calculated and stored. That is, for each item, the difference between the measurement result of the electromotive force of the internal standard solution in step S20 and the measurement result of the internal standard solution in step S40 is calculated and stored (step S50). In addition, when step S50 is the second time or later, the measurement result in step S40 after the previous sample measurement is used as the measurement result of the internal standard solution before the sample measurement.

  Next, the specimen type information of the sample to be measured next is acquired from the storage unit 21 (step S60), and it is determined whether or not the sample to be measured next is urine (step S70). If the determination result is YES, a CO reference value (urine) is acquired from the storage unit 21 as a carryover reference value (hereinafter referred to as a CO reference value) regarding the item of potassium ion concentration (step S80), and step Proceed to S90. If the determination result in step S70 is NO, a CO reference value (serum) is acquired from the storage unit 21 as the CO reference value for the potassium ion concentration item (step S81), and the process proceeds to step S90. In step S90, the CO reference value regarding the item of sodium ion concentration and the item of chlorine ion concentration is acquired (step S90). As will be described later, the CO reference value (serum) is a stricter (lower) reference value than the CO reference value (urine).

  Next, it is determined whether or not there is an item exceeding the CO reference value for the difference (potential difference) in the measurement results calculated in step S50 (step S100). If the determination result in step S100 is NO, it is determined that normal measurement has been performed, the process proceeds to step S130, and it is determined whether there is a next sample (step S130). If there is a next sample, the process returns to step S30 to measure the next sample. If the determination result in step S100 is YES, it is determined that there is an abnormality in the measurement of the electromotive force of the internal standard solution, and the process proceeds to a determination flow for determining whether there is an abnormality due to bubble noise or an abnormality due to carryover. To do. Here, bubble noise is a measurement abnormality caused by bubbles mixed in the internal standard solution or bubbles remaining in the flow path of the internal standard solution. Carryover is a sample measured before. This is a measurement abnormality in which the internal standard solution cannot be measured correctly because the component is contained in the internal standard solution. As described above, since the measurement result of the internal standard solution is used for the measurement of the sample concentration, a correct sample concentration result cannot be obtained due to these abnormalities. Therefore, it is important to identify these abnormalities and perform appropriate processing in order to obtain correct measurement results.

  Next, the bubble noise reference value is acquired for each item from the storage unit 21 (step S110), and it is determined whether there is an item exceeding the bubble noise reference value for the difference (potential difference) in the measurement result calculated in step S50. (Step S120). When the determination result in step S120 is NO, it is determined whether the change direction (positive or negative direction) of each item is the same (step S121) and whether the change amount of each item is the same (step) S122). Here, the same amount of change means substantially the same, and can be regarded as the same as long as the error is within 10 mV. This error range may be changeable within the apparatus. If the determination result in both step S121 and S122 is YES, it is determined that the bubble noise is abnormal, and the process proceeds to the bubble noise alarm process (step S200). If at least one of the determination results is NO, It is determined that the abnormality is caused by carryover, and the process proceeds to the CO alarm process (step S300). If the determination result in step S120 is YES, it is determined that there is an abnormality caused by bubble noise, and the process proceeds to bubble noise alarm processing. If the determination result in step S130 is NO, the measurement result is output and stored (step S140), and the process ends.

  Here, FIG. 7 shows a change example of the measurement result when bubbles are experimentally injected into the electrode channel. The horizontal axis represents time, and the vertical axis represents electromotive force. The top of the figure represents chlorine ion (Cl), the bottom two of the figure represents sodium ion, and the other represents potassium ion electromotive force. As can be seen from FIG. 7, the electromotive force changes in the same direction (positive and negative directions) in the same direction in both cases when bubbles are injected during the suction of the internal standard solution and when bubbles are injected during the suction of the sample. You can see that Therefore, it can be seen from steps S121 and 122 that it is possible to determine that there is an abnormality caused by bubble noise.

  First, the bubble noise alarm process will be described. As shown in FIG. 3, when the bubble noise alarm process is instructed (step S200), the control unit 20 sets the bubble noise alarm to be added to the measurement result after the sample measured immediately before (step S210). . By setting in this way, it is possible to check the sample determined as bubble noise and the sample after the bubble noise alarm processing is performed after the analysis is completed. There is an advantage that the sample result can be easily identified.

  Next, it is determined whether or not the ISE channel prime is set (step S220). Here, the ISE channel prime is a part of maintenance, and is an operation of replacing the inside of the channel with an internal standard solution. If the determination result is NO, the process proceeds from step (A) of FIG. 2 to step S271, a bubble noise alarm is issued (step S271), the analysis operation of the electrolyte analyzer is stopped (step S272), and the process is performed. finish. On the other hand, if the determination result in step S220 is YES, the internal standard solution in the flow path is replaced (step S230). For example, the internal standard solution is replaced five times. Thereby, it can be expected that bubbles are excluded from the flow path. Subsequently, in order to confirm whether the bubbles can be removed from the flow path and returned to the normal state, the electromotive force of the internal standard solution is measured for each item, for example, 10 times (step S240). That is, the electromotive force measurement is performed 10 times while replacing the internal standard solution. In addition, it may not be 10 times, and a more accurate result can be obtained by carrying out a suitable number of times. The potential difference between each measurement result of 10 times and the measurement result of the internal standard solution two times before (electromotive force in step S20) is calculated (step S250). Since the previous measurement result is considered to be a measurement result in a normal state, by obtaining a difference from this measurement result, it can be used as an indicator of whether or not the normal state has been restored. Next, the bubble noise reference value is acquired from the storage unit 21 (step S260), and it is determined whether there is a potential difference calculated in step S250 that exceeds the flow path noise reference value (step S270). If the determination result in step S270 is NO, it is determined whether or not adjacent measurement results are within a range of ± 2 mV among the plurality of measurement results calculated in step S250 (step S280). This is because even if the reference value does not exceed the reference value in S270, if there is a certain difference between adjacent measurement results, it is assumed that the normal state has not been restored. If the determination result is YES, it is determined that the normal state has been restored, and the process proceeds from step (A) in FIG. 2 to step S130. If the determination result in step S270 is YES and the determination result in step S280 is NO, a bubble noise alarm is issued (step S271), and the analysis operation of the electrolyte analyzer is stopped ( Step S272), the process is terminated.

  Next, CO alarm processing will be described. As shown in FIG. 4, when the CO alarm process is instructed (step S300), the control unit 20 sets the CO alarm to be added to the subsequent sample measurement results (step S310). By setting in this way, it is possible to check a sample determined to have a carryover abnormality or a sample after the CO alarm processing has been performed after the analysis is completed. There is an advantage that it can be easily distinguished from the later sample result.

  Next, it is determined whether or not automatic cleaning is set (step S320). If the determination result is NO, the process proceeds from step (A) of FIG. 2 to step S130, and a CO alarm is issued (step S381). Then, the analysis operation of the electrolyte analyzer is stopped (step S382), and the process is terminated. On the other hand, if the determination result in step S320 is YES, the inside of the flow path is washed with the internal standard solution (step S330). For example, channel cleaning is performed three times. Thereby, it can be expected that components that cause carry-over are washed away from the flow path. Subsequently, in order to confirm whether or not this component has been washed away and returned to a normal state, the electromotive force of the internal standard solution is measured 10 times for each item (step S340). That is, the electromotive force measurement is performed 10 times while replacing the internal standard solution. In addition, it may not be 10 times, and a more accurate result can be obtained by carrying out a suitable number of times. The measurement result of the internal standard solution of the last time (electromotive force of step S20) is acquired (step S350), and the potential difference between the measurement result and each measurement result for 10 times is calculated (step S360). Since the previous measurement result is considered to be a measurement result in a normal state, by obtaining a difference from this measurement result, it can be used as an indicator of whether or not the normal state has been restored. Next, the CO reference value is acquired from the storage unit 21 (step S370), and it is determined whether there is any potential difference calculated in step 360 exceeding the CO reference value (step S380). If the determination result in step S280 is NO, it is determined that the normal state has been restored, and the process proceeds from step (A) in FIG. 2 to step S130. If the determination result in step S380 is YES, a CO alarm is issued (step S381), the analysis operation of the electrolyte analyzer is stopped (step S382), and the process ends.

  FIG. 5 is an ISE (Ion Selective Electrode) abnormality detection setting screen for setting various parameters used in the electrolyte analyzer of the present embodiment. The setting screen 400 is displayed on the display unit 22 and is input and set by an operation on the input unit 23 and the like.

  In FIG. 5, the ISE abnormality detection setting screen 400 includes a setting unit 410 relating to bubble noise, a setting unit 420 relating to carryover, an OK button 401 for accepting and reflecting the setting contents, and canceling the setting contents being discarded and not reflected. The button 402 is schematically configured.

  In the setting unit 410 relating to bubble noise, the setting of whether to enable or disable the bubble noise detection function is performed by selecting the setting button 411. In the case of FIG. 5, the setting button 411 is selected and the bubble noise detection function is enabled.

  Valid / invalid setting of the liquid replacement function in the flow path is performed by selecting a setting button 412. In the case of FIG. 5, the setting button 412 is selected and the bubble noise detection function is enabled. In addition, when the setting button 412 is selected, the input box 413 for the number of times of liquid replacement in the flow path and the input box 428 for the number of stability confirmations are enabled, and numerical values can be input using the input unit 23 or the like. . Based on the number-of-settings information, the control unit 20 executes the processes of steps S230 and S240.

  The threshold value of ISE (reference value for bubble noise abnormality determination) is a reference value input box 414 for the sodium ion selection electrode 11, a reference value input box 415 for the chlorine ion selection electrode 13, and a reference value for the potassium ion selection electrode 12. The input box 416 is set by inputting a numerical value using the input unit 23 or the like. In the case of FIG. 5, a case where 30 mV is set in each input box 414, 415, 416 is described as an example. Based on these set reference values, the control unit 20 acquires the bubble noise reference value in steps S110 and S260.

  In the setting unit 420 regarding carry-over, setting of enable / disable of the carry-over detection function is performed by selecting a setting button 421. In the case of FIG. 5, the setting button 421 is selected and the bubble noise detection function is enabled.

  The automatic cleaning function is enabled / disabled by selecting the setting button 422. FIG. 5 shows a case where the setting button 422 is selected and the automatic cleaning function is enabled. When the setting button 422 is selected, the automatic cleaning frequency input box 423 and the stability confirmation frequency input box 429 are enabled, and numerical values can be input using the input unit 23 or the like. Based on the number-of-settings information, the control unit 20 executes the processes of steps S330 and S340.

  The threshold value of ISE (reference value for carryover abnormality determination) includes a reference value input box 424 for the sodium ion selection electrode 11, a reference value input box 425 for the chlorine ion selection electrode 13, and a reference value for the potassium ion selection electrode 12. , CO reference value (serum) input box 426 and CO reference value (urine) input box 427 are set by inputting numerical values using input unit 23 or the like. In the case of FIG. 5, the case where 4.1 mV is set in the input box 424, 4.5 mV is set in the input box 425, 6.2 mV is set in the input box 426, and 11.0 mV is set in the input box 427 is described as an example. . Based on these set reference values, the control unit 20 acquires the CO reference value in steps S80, S81, S90, and S370.

  Here, the value of each ion component contained in blood or urine will be described.

  FIG. 6 is a diagram illustrating an example of ranges of normal values of sodium ion concentration, potassium ion concentration, and chloride ion concentration contained in blood or urine.

  Potassium ions are substances that contribute to muscle activity, nerve transmission, and suppression of hypertension caused by sodium in vivo. In normal cases, the potassium ion concentration in the blood is kept almost constant, but if it falls into an abnormal state such as hyperkalemia or hypokalemia, it may cause serious symptoms such as myocardial infarction There is. Therefore, in order to perform appropriate and prompt treatment for patients suspected of having hyperkalemia or hypokalemia, in clinical practice, it is required to measure potassium in serum accurately and in a short time. .

  As shown in FIG. 6, the potassium ion concentration contained in serum / plasma is significantly lower than the normal value range of potassium ion concentration contained in urine, and the normal value range is also narrow. As can be seen from this, the degree of carry-over, which is a problem in serum / plasma, is different from the degree of problem in urine. If the standard value of carry-over is not divided for each sample type, but judged according to the strict standard of serum / plasma, the electromotive force of the internal standard solution after urine measurement tends to be high. The number of cases judged to be larger than when the criteria are divided. If automatic washing is set when a carry-over alarm occurs, setting the reference value for each sample type (urine / serum) reduces the number of cases judged to carry over while maintaining analysis accuracy. The time required for automatic cleaning can be suppressed.

  The effect of the present embodiment configured as described above will be described.

  In the electrolyte analyzer of the prior art, abnormalities such as electrode deterioration and sample deterioration are detected from a variation pattern of a calibration result periodically performed. However, the frequency of calibration is not as high as once a day at most, and opportunities for detecting an abnormality can be obtained only at the same frequency. On the other hand, an electrolyte analyzer is relatively short in time until a result is obtained as compared with a biochemical automatic analyzer or the like, and is often used for measurement of an urgent sample such as an emergency specimen. In the measurement of urgent specimens and the like, the influence when an abnormality occurs in the measurement result is large, and high reliability is required in addition to the speed of measurement.

  In contrast, in the present embodiment, in an electrolyte analyzer that measures the concentration of specific ions in a sample using an ion selective electrode, a known ion concentration is set in advance before and after the measurement of the sample. Measure the ion concentration of the adjusted internal standard solution, and if the difference between the measurement results of the internal standard solution before and after the measurement of the sample exceeds the predetermined reference value, the measurement result of the sample is abnormal. Therefore, the reliability can be improved while suppressing a decrease in the speed of measurement.

  For example, there is a case where bubbles are mixed in the detection flow path and become noise as an abnormality that occurs suddenly in the electrolyte analyzer. The liquid in the flow path of the electrolyte analyzer is not constant because it is changed every measurement. In the measurement, the concentration of the target ions in the sample is calculated based on the electromotive force measured by each ion selective electrode. If bubbles are mixed in this flow path, noise (bubble noise) is obtained. The measured value is different from that obtained from the actual ion concentration. Possible causes of bubbles in the flow path include, for example, defective electrode attachment, loose connection, dispensing system abnormality, reagent emptying, electrode membrane failure, and the like. In addition, after measuring a high-concentration sample, the occurrence of carryover is also conceivable. These bubble noise and carry-over abnormalities sometimes do not show clear abnormal values, and it is difficult to determine that they are abnormal from the sample measurement values themselves. In addition, knowledge and experience were required to elucidate the cause.

  On the other hand, in the electrolyte analyzer of the present embodiment, abnormalities that occur suddenly at the time of sample measurement due to the inclusion of bubbles in the flow path and carryover due to the specimen are detected, and abnormalities are detected. In this case, the maintenance can be automatically performed to improve these abnormalities before the measurement is stopped, and the measurement can be continued. Can be improved.

DESCRIPTION OF SYMBOLS 1 Sample container 2 Sample dispensing nozzle 3 Syringe for sample dispensing nozzle 4 Dilution tank 5 Diluent bottle 6 Diluent syringe 7 Diluent solenoid valve 8 Shipper syringe 9 Shipper syringe solenoid valve 10 Pinch valve 11 Sodium ion selection electrode 12 Potassium ion selection electrode 13 Chlorine ion selection electrode 14 Comparison electrode solution bottle 15 Comparison electrode solution solenoid valve 16 Comparison electrode 17 Internal standard solution bottle 18 Internal standard solution syringe 19 Internal standard solution solenoid valve 20 Control unit 21 Storage unit 22 Display unit 23 Input unit

Claims (9)

In an electrolyte analyzer that measures the concentration of specific ions in a sample using an ion selective electrode,
For each of a plurality of types of ions in the sample, a reference value for normal determination of bubble noise for determining bubble noise abnormality caused by bubbles mixed in the flow path through which the sample passes when measuring the electromotive force is set in advance. ,
Before and after the measurement of the sample, the electromotive force of the internal standard solution adjusted to a known ion concentration in advance is measured, and the difference between the measurement results of the electromotive force of the internal standard solution before and after the measurement of the sample However, when the reference value for the normal determination of bubble noise is exceeded, the measurement result of the sample is determined to be abnormal bubble noise, and when the reference value for the normal determination of bubble noise is not exceeded, the measurement of the sample is performed. The positive / negative direction of the difference between the measurement results of the electromotive force of the internal standard solution before and after is the same for the plurality of types of ions, and the change amount of the measurement results is within a predetermined range for the plurality of types of ions. In some cases, an electrolyte analyzer is provided with an abnormality determination unit that determines that the measurement result of the sample is abnormal in bubble noise. The electrolyte analyzer according to claim 1,
For each of a plurality of types of ions in the sample, preset a reference value for carryover normal determination for determining that carryover has occurred,
The abnormality determination unit
When the difference in the measurement result of the electromotive force of the internal standard solution before and after the measurement of the sample exceeds the reference value of the carry-over normal determination for at least one kind of ions, the bubble noise abnormality is determined. Electrolyte analyzer. The electrolyte analyzer according to claim 2,
The abnormality determination unit
When the difference in the electromotive force measurement results of the internal standard solution before and after measurement of the sample does not exceed the reference value for the normal determination of bubble noise, the measurement of the electromotive force of the internal standard solution before and after the measurement of the sample An electrolyte characterized by determining that the measurement result of the sample is a carry-over abnormality when a positive or negative direction of a result difference is different from other types of ions for at least one type of ions of the plurality of types of ions Analysis equipment. The electrolyte analyzer according to claim 2 or 3,
The abnormality determination unit
When the difference in the electromotive force measurement results of the internal standard solution before and after measurement of the sample does not exceed the reference value for the normal determination of bubble noise, the measurement of the electromotive force of the internal standard solution before and after the measurement of the sample When the positive and negative directions of the result difference are the same for the plurality of types of ions and the change amount of the measurement results is not within a predetermined range for the plurality of types of ions, the measurement result of the sample is carried over. An electrolyte analyzer characterized by determining that it is abnormal. The electrolyte analyzer according to any one of claims 2 to 4,
An electrolyte analyzer characterized by providing different reference values for normal carryover depending on whether the type of sample to be measured is blood or urine. The electrolyte analyzer according to any one of claims 1 to 5,
An electrolyte analyzer characterized by replacing the sample or the internal standard solution in the flow path through which the sample passes when measuring the ion concentration when it is determined that the measurement result of the sample is abnormal bubble noise. The electrolyte analyzer according to any one of claims 2 to 5,
An electrolyte analyzer characterized in that, when the measurement result of the sample is determined to be a carry-over abnormality, the inside of the flow path through which the sample passes is washed when measuring the ion concentration. In an electrolyte analyzer that measures the concentration of specific ions in a sample using an ion selective electrode,
For each of a plurality of types of ions in the sample, preset a reference value for carryover normal determination for determining that the carryover of the sample has occurred,
Before and after the measurement of the sample, the electromotive force of the internal standard solution adjusted to a known ion concentration in advance is measured, and the difference between the measurement results of the electromotive force of the internal standard solution before and after the measurement of the sample is The positive / negative direction of the difference between the measurement results of the electromotive force of the internal standard solution before and after measurement of the sample exceeds the reference value for the carry-over normal determination for at least one type of ions. An abnormality determination unit that determines that the measurement result of the sample is a carry-over abnormality when at least one ion is different from other types of ions;
The abnormality determination unit has a difference in electromotive force measurement result of the internal standard solution before and after the measurement of the sample exceeds a reference value of the carryover normal determination for at least one ion, and the measurement before and after the measurement of the sample. When the positive / negative direction of the difference in the measurement result of the electromotive force of the internal standard solution is the same for the plurality of types of ions, it is determined that the measurement result of the sample is abnormal bubble noise,
An electrolyte analyzer characterized by replacing the sample or the internal standard solution in the flow path through which the sample passes when measuring the ion concentration when it is determined that the measurement result of the sample is abnormal bubble noise. In an electrolyte analysis method for measuring the concentration of a specific ion in a sample using an ion selective electrode,
For each of a plurality of types of ions in the sample, a reference value for normal determination of bubble noise for determining bubble noise abnormality caused by bubbles mixed in the flow path through which the sample passes when measuring the electromotive force is set in advance. ,
Before and after the measurement of the sample, measure the electromotive force of the internal standard solution adjusted in advance to a known ion concentration,
When the difference between the measurement results of the electromotive force of the internal standard solution before and after the measurement of the sample exceeds the reference value for the normal determination of the bubble noise, the measurement result of the sample is determined to be abnormal bubble noise, When the standard value of bubble noise normal judgment is not exceeded , the positive and negative directions of the difference in the electromotive force measurement result of the internal standard solution before and after the measurement of the sample are the same in the plurality of types of ions, and An electrolyte analysis method, wherein when the change amount of the measurement result is within a predetermined range for the plurality of types of ions, the measurement result of the sample is determined to be abnormal bubble noise.

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