JP2017032318A - Liquid sample analyzer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid sample analyzer capable of measuring component concentration of a liquid sample with high accuracy.SOLUTION: A liquid sample analyzer (100A) includes: a supply amount setting section (107A) for controlling the amount of a liquid sample and a dilution liquid supplied to a chip (102) on the basis of electric conductivity measured by an electric conductivity measurement section (115); and a measurement section (109A) for measuring the amount of light transmission of a mixed liquid of a measurement reagent, the sample liquid, and the dilution liquid so as to analyze components of the sample liquid.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a liquid sample analyzer, and more particularly to a liquid sample analyzer suitable for analyzing soil components.

  In the field of agriculture, analysis of soil components in the growing environment of crops is widely performed in order to manage the growing state of the crops.

  Generally, a liquid sample analyzer as a soil analyzer extracts a component of soil by injecting a liquid for extraction into collected soil and performing filtration. Each extracted soil extract is poured into a plurality of test tubes while measuring with a graduated dropper, and then a reagent and a diluting solution determined for each soil component are poured into the test tubes to cause color development. And it is measured by converting into a numerical value using a colorimetric table, a turbidimetric table, an absorptiometric method or the like.

  However, the measurement method described above needs to mix a reagent with each soil extract, which increases the number of repetitive operations. Moreover, it is necessary to prepare a reagent according to the soil component to be measured, and the complexity is high.

  By performing soil analysis frequently, it is possible to perform fertilization design in consideration of the influence of the previous crop by performing detailed analysis for each field and analysis for each cropping. In addition, it is possible to optimize the timing and amount of additional fertilization by periodically analyzing crops with a long growing period in a shorter span, and as a result, it is hoped that the yield will be increased and the quality will be stabilized.

  However, it is difficult to increase the frequency of analysis due to the high complexity described above.

  In recent years, in view of such problems, a method for analyzing soil components by mixing a soil extract and a reagent by a simple method has been proposed.

  FIG. 18 shows the reagent mixing and soil analysis apparatus disclosed in Patent Document 1. FIG. 18 (a) is a schematic diagram of a conventional soil analysis apparatus, and FIG. 18 (b). And (c) is a schematic diagram showing the fitting between the storage cartridge provided in the conventional soil analyzer and the extract cartridge.

  The soil analysis apparatus described in Patent Literature 1 includes a light emitting unit 7, a light receiving unit 8, and a storage cartridge 9, as shown in FIG. The storage cartridge 9 is made of a transparent material, and is provided with a plurality of cells 11 for storing a mixture of a soil extract and a reagent extracted from soil. In the soil analyzer described in Patent Document 1, light emitted from the light emitting unit 7 passes through the mixed solution in the storage cartridge 9 and is detected by the light receiving unit 8 to measure the absorbance of the mixed solution. The concentration of soil components is measured by the method.

  As shown in FIG. 18B, a predetermined amount of reagent is stored in advance in the cell 11 of the storage cartridge 9 and is sealed with a seal paper 15. Each cell 16 of the extract cartridge 14 has a dredging function as a metering and contains a soil extract. Before the measurement, the extract cartridge 14 is pushed into the storage cartridge 9 in the direction indicated by the arrow in FIGS. 18B and 18C, so that the storage cartridge 9 and the extract cartridge 14 are fitted. Thereafter, the bottom surface of the extraction liquid cartridge 14 is penetrated, and the extraction liquid is injected into the cell 11 of the storage cartridge 9 to prepare a mixed liquid.

  Thus, in the soil analyzer described in Patent Document 1, it is easy to create a mixed solution, and the concentration of soil components is measured by the absorptiometric method, so that accurate measurement can be performed. .

JP 2007-46922 A (published February 22, 2007)

  However, for example, the concentration of components contained in soil, such as soil used in fields in agricultural crop cultivation facilities, may be relatively high. In analyzing the soil component concentration, even if the soil extract extracted from the soil and the reagent are mixed and the spectrophotometric method is used as in the soil analyzer described in Patent Document 1, the reagent is used. If the concentration of the component to be analyzed is too high, the measurable range may be exceeded.

  Thus, if it exceeds a measurable range, the rate of increase / decrease in the light transmission amount of the mixed liquid mixed with the reagent becomes small with respect to increase / decrease in components of the soil extract. As a result, the measurement of the component concentration of the soil extract that is the measurement target is unsuccessful, or accurate measurement results cannot be obtained until failure occurs. There arises a problem that the storage cartridge is lost.

  The present invention has been made in view of the above problems, and an object thereof is to provide a liquid sample analyzer that can reliably and accurately measure the components of a liquid sample even when the component concentration of the liquid sample is high. It is in.

  In order to solve the above problems, a liquid sample analyzer according to one aspect of the present invention includes a sample container that stores a liquid sample, a diluent container that stores a diluent that dilutes the liquid sample, and a measurement reagent. A measuring container to be accommodated, a measuring unit for measuring the electrical conductivity of the liquid sample, a sample supply mechanism for supplying the liquid sample to the measuring container, and a diluent supplying mechanism for supplying the diluent to the measuring container Analyzing the at least one component of the liquid sample by measuring a light transmission amount of the mixed solution of the measurement reagent, the liquid sample, and the dilution liquid mixed in the measurement container; and And a control unit that controls a ratio between the amount of the liquid sample supplied by the sample supply mechanism and the amount of the diluent supplied by the diluent supply mechanism based on the measured electrical conductivity. .

  According to one aspect of the present invention, it is possible to provide a liquid sample analyzer that can reliably and accurately measure components of a liquid sample even when the component concentration of the liquid sample is high.

It is a figure which shows the outline of a structure of the liquid sample analyzer which concerns on Embodiment 1 of this invention. It is a figure which shows the outline of a structure of the light emission part with which the liquid sample analyzer shown in FIG. 1 is equipped. It is a top view which shows the outline of a structure of the filter array with which the light emission part shown in FIG. 2 is equipped. It is a figure which shows the outline of a structure of the chip | tip with which the liquid sample analyzer shown in FIG. 1 is equipped, (a) is the front view which looked at the chip | tip from upper direction, (b) And (c) is equipped with a chip | tip. It is the schematic which shows the shape of the cell obtained. It is a figure which shows the outline of a structure of the extraction liquid storage container with which the liquid sample analyzer shown in FIG. 1 is equipped. It is a figure which shows the outline of a structure of the extract supply mechanism with which the liquid sample analyzer shown in FIG. 1 is equipped. It is a figure which shows the outline of a structure of the extract liquid storage container with which the liquid sample analyzer shown in FIG. 1 is equipped, and an electrical conductivity measurement part. (A) is a top view of the chip at the time of measurement, and (b) is a cross-sectional view taken along the line CC of the chip in (a) and the liquid sample analyzer shown in FIG. The filter array and light-receiving part with which it is equipped are shown typically. It is a flowchart which shows the flow of a measurement of the liquid sample analyzer shown in FIG. It is a figure which shows the outline of a structure of the liquid sample analyzer which concerns on Embodiment 2 of this invention. It is a flowchart which shows the flow of a measurement of the liquid sample analyzer shown in FIG. It is a figure which shows the outline of a structure of the liquid sample analyzer which concerns on Embodiment 3 of this invention. It is a figure which shows the outline of a structure of the liquid sample analyzer which concerns on Embodiment 4 of this invention. It is a figure which shows the outline of a structure of the extract liquid storage container with which the liquid sample analyzer shown in FIG. 13 is equipped, an electrical conductivity measurement part, and a lower electrical conductivity measurement part. It is a flowchart which shows the flow of the waste liquid process of the liquid sample analyzer shown in FIG. It is a figure which shows the outline of a structure of the liquid sample analyzer which concerns on Embodiment 5 of this invention. It is a flowchart which shows the flow of a measurement of the liquid sample analyzer shown in FIG. (A) is a schematic diagram of a conventionally used soil analyzer, and (b) and (c) are fittings between a storage cartridge provided in the soil analyzer shown in (a) and an extract cartridge. It is a schematic diagram which shows.

Embodiment 1
Hereinafter, embodiments of a liquid sample analyzer according to the present invention will be described with reference to the drawings. In addition, the thickness, length, etc. of each structural member described in the drawings are examples, and the liquid sample analyzer according to the present invention is not limited to the illustrated thickness, length, etc. of each structural member. .

(Outline of configuration of liquid sample analyzer)
The configuration of the liquid sample analyzer 100A according to the present embodiment will be described with reference to FIGS.

  FIG. 1 is a diagram showing an outline of the configuration of a liquid sample analyzer 100A according to Embodiment 1 of the present invention. The liquid sample analyzer 100A measures a liquid sample that is a measurement target by absorptiometry. The liquid sample analyzer 100A includes a light emitting unit 101, a chip (measuring container) 102, a light receiving unit 103, a measuring unit (analyzing unit) 109A, a rotation driving unit 106, and an extraction liquid container (sample container) 112A. , An extract supply mechanism (sample supply mechanism) 120, a diluent storage container (diluent container) 113, a diluent supply mechanism 121, an electrical conductivity measurement unit (measurement unit) 115, and a control unit 111A. ing. Hereinafter, each part of the liquid sample analyzer 100A will be described in detail.

<Light emitting unit 101>
The light emitting unit 101 will be described with reference to FIGS. FIG. 2 is a diagram illustrating an outline of the configuration of the light emitting unit 101. As shown in FIG. 2, the light emitting unit 101 includes a plurality of light sources 201a, 201b, and 201c having different emission wavelengths, collimator lenses 202a, 202b, and 202c corresponding to the light sources 201a, 201b, and 201c, and a dichroic unit. Mirrors 203a and 203b, an aperture 204, and a filter array 205 are provided. The light emitting unit 101 is connected to the control unit 111A.

  The light source 201a, the collimating lens 202a, the dichroic mirrors 203a and 203b, the aperture 204, and the filter array 205 are arranged in this order along the optical axis of the light source 201a. The light source 201b, the collimating lens 202a, and the dichroic mirror 203a are arranged linearly in this order along the optical axis of the light source 201b. The light source 201c, the collimating lens 202c, and the dichroic mirror 203b are arranged linearly in this order along the optical axis of the light source 201c.

  Each of the light sources 201a to 201c is controlled in light emission, extinction, and light emission intensity by a control signal supplied from the control unit 111A. The plurality of light sources 201a to 201c are arranged so that the light emission directions are different from each other. Each of the light sources 201a to 201c is preferably an LED (Light Emitting Diode) because of its high directivity. As an example, the light source 201a is a white LED that emits white light, the light source 201b is a blue LED that emits blue light, and the light source 201c is a red LED that emits red light.

  The collimating lens 202a transmits the light emitted from the light source 201a to the dichroic mirror 203a with improved directivity. The collimating lens 202b increases the directivity and transmits the light emitted from the light source 201b to the dichroic mirror 203a. The collimator lens 202c transmits the light emitted from the light source 201c to the dichroic mirror 203b with improved directivity.

  Each of the dichroic mirrors 203a and 203b is a mirror that transmits light in a specific wavelength band and reflects light in another specific wavelength band other than the specific wavelength band. The dichroic mirror 203a transmits the light emitted from the light source 201a, while reflecting the light emitted from the light source 201b. The dichroic mirror 203b transmits the light emitted from the light source 201a and the light source 201b, and reflects the light emitted from the light source 201c.

  In the present embodiment, the dichroic mirror 203a transmits light in the wavelength band of 470 nm to 1600 nm, while reflecting light in the wavelength band of 350 nm to 430 nm. The dichroic mirror 203b transmits light having a wavelength band of 400 nm to 630 nm, and reflects light having a wavelength band of 675 nm to 850 nm.

  The aperture 204 adjusts the diameter of light emitted from the light sources 201a, 201b, and 201c and transmitted or reflected by the dichroic mirrors 203a and 203b.

  FIG. 3 is a top view of the filter array 205 shown in FIG. 2 as viewed from above. As shown in FIG. 3, the filter array 205 includes a plurality of interference filters 301 to 306 arranged on the circumference around the rotation axis 210. The interference filters 301 to 306 have different wavelength bands of transmitted light. As an example, the interference filter 301 transmits light having a peak wavelength of 420 nm, the interference filter 302 transmits light having a peak wavelength of 520 nm, the interference filter 303 transmits light having a peak wavelength of 570 nm, and the interference filter 304 has a peak. The interference filter 305 transmits light having a peak wavelength of 710 nm, and the interference filter 306 transmits light having a peak wavelength of 720 nm. The rotation operation of the filter array 205 is controlled by a control signal supplied from the control unit 111A.

  In the light emitting unit 101, a plurality of light sources 201a to 201c emit light according to a signal from the control unit 111A. Light emitted from the light sources 201a to 201c is directed by the collimator lenses 202a to 202c corresponding to the light sources 201a to 201c, and the optical paths are coupled by the dichroic mirrors 203a and 203b. Then, the beam diameter is adjusted by the aperture 204 and guided to the filter array 205. The filter array 205 is controlled to rotate around a rotation axis 210 parallel to the traveling direction of the light in synchronization with the control of the plurality of light sources 201a to 201c, and has a specific wavelength from the light that has passed through the aperture 204 Only the light of is selected and transmitted. The light that has passed through the filter array 205 is emitted from the light emitting unit 101 as light 300.

  By configuring the light emitting unit 101 as described above, light of different wavelengths can be emitted. The light sources 201a to 201c are not limited to LEDs, and for example, laser light may be used.

<Chip 102>
4 shows an outline of the chip 102. FIG. 4A is a front view of the chip 102 as viewed from above, and FIG. 4B is a diagram of the cell 400 provided in the chip 102. FIG. FIG. 4C is a schematic diagram showing an example of the shape, and FIG. 4C is a schematic diagram showing the shape of the cell 410 provided in the chip 102.

  As shown in FIG. 4A, the chip 102 has a disk shape, and a plurality of cells 400 and cells 410 are formed radially around the rotation shaft 450. In the present embodiment, six cells 400 and one cell 410 are formed on the chip 102. The cells 400 and 410 are formed at equal intervals in the circumferential direction of the chip 102. The number of cells 400 and 410 formed on the chip 102 is not particularly limited, and five or less cells 400 or seven or more cells 400 and two or more cells 410 may be formed.

  The chip 102 is preferably made of a transparent material such as silicone, glass, or plastic so as to transmit the light 300 emitted from the light emitting unit 101. In the present embodiment, the chip 102 is made of inexpensive and highly transparent polystyrene.

  Further, the cell 400 and the cell 410 are formed inside the chip 102 (see FIG. 1) and are not formed exposed on the surface of the chip 102, but in FIG. The internal structure is shown by a solid line for easy understanding.

  As shown in FIG. 4B, in each cell 400, a sample chamber 401 for injecting a soil extract (liquid sample) extracted from soil, and a reagent chamber 402 in which a reagent (measuring reagent) is stored in advance. And a reagent chamber (mixing chamber) 403 and a measuring chamber (first measuring chamber / second measuring chamber) 404 for measuring the light transmission amount of the soil extract mixed with the reagent.

  A flow path 405 is formed between the reagent chamber 403, the sample chamber 401, the reagent chamber 402, and the measurement chamber 404, and the reagent chamber 403, the sample chamber 401, the reagent chamber 402, and the measurement chamber 404 communicate with each other. ing. In addition, an opening 407 (injection port) for injecting the soil extract is formed in the sample chamber 401, and the opening 407 opens toward the upper surface of the chip 102.

  As shown in FIG. 4C, the cell 410 does not include a reagent chamber, and a sample chamber 411 and a reference chamber 414 are formed. Further, a flow path 415 is formed between the sample chamber 411 and the reference chamber 414, and the sample chamber 411 and the reference chamber 414 communicate with each other. Similar to the sample chamber 401 of the cell 400, an opening 417 for injecting a soil extract is formed in the sample chamber 411, and the opening 417 opens toward the upper surface of the chip 102.

  Here, the measurement chamber 404 of the cell 400 and the reference chamber 414 of the cell 410 are formed on the first circumference as indicated by a dashed line A in FIG. Further, the opening 407 of the cell 400 and the opening 417 of the cell 410 are formed on the second circumference as indicated by a dashed line B in FIG. That is, the measurement chamber 404 and the reference chamber 414, and the openings 407 and 417 are formed on concentric circles with the rotation axis 450 as the center, and the openings 407 and 417 are radially inward of the measurement chamber 404 and A reference chamber 414 is formed radially outward.

  An open / close valve (not shown) is provided in the flow path 405 between the reagent chamber 403 and the measurement chamber 404, and the valve is in a closed state.

  The size of the chip 102 is, for example, about 20 cm in diameter, and the size of each of the cell 400 and the cell 410 is 4 to 5 cm in the longitudinal direction of FIGS. 4B and 4C and orthogonal to the longitudinal direction. The short direction is about 2 to 3 cm.

  The reagent stored in advance in the reagent chamber 402 and the reagent chamber 403 has a light absorption rate that varies depending on the concentration of a component (for example, nitrate nitrogen) that is a measurement target of the soil extract. It is possible to measure the concentration of a component that is a measurement target of the soil extract by mixing the reagent with the soil extract and measuring the light transmission amount of the soil extract mixed with the reagent with the liquid sample analyzer 100A. It is.

  However, if the concentration of the component that is the measurement target of the soil extract is too high, the change in the light absorption rate of the reagent is saturated, and even if the concentration of the component that is the measurement target of the soil extract changes, the light absorption of the reagent The rate does not change, and the concentration of the component to be measured in the soil extract cannot be measured accurately.

  For this reason, in order to accurately measure the component concentration of the soil extract measurement target, the optimal concentration range (where the light absorption rate of the reagent changes rapidly according to the component concentration of the soil extract measurement target ( That is, it is preferable to adjust the component concentration of the measurement target of the soil extract so that the change in the light absorption rate of the reagent is sensitive to the change in the component concentration of the measurement target.

<Light receiving unit 103, measuring unit 109A, and rotation driving unit 106>
The light receiving unit 103 receives the light 300 emitted from the light emitting unit 101 and transmitted through the region on the first circumference indicated by the alternate long and short dash line A in FIG.

  The measurement unit 109 </ b> A is connected to the light receiving unit 103. 109 A of measurement parts measure the intensity | strength (light transmission amount) of the light which the light-receiving part 103 received, and compute a soil component density | concentration based on the said measurement result.

  The rotation drive unit 106 is provided below the chip 102 and drives the chip 102 to rotate about the rotation shaft 450. In this embodiment, a stepping motor capable of pulse control is used as the rotation drive unit 106. In the present embodiment, the configuration in which the rotation drive unit 106 rotationally drives the chip 102 is shown, but the present invention is not limited to this. For example, a brushless motor or the like may be used as the rotation drive unit, or a plurality of drive systems may be used in combination. Further, for example, a drive system that combines the revolving motion of the chip around the rotation shaft 450 and the rotation of the chip may be used.

<Extract liquid container 112A>
The configuration of the extract storage container 112A will be described with reference to FIG. FIG. 5 is a cross-sectional view showing the configuration of the extract storage container 112A.

  The extract storage container 112A is a container for storing the soil extract obtained by adding water to the collected soil, shaking and filtering, and is also used for measuring the electrical conductivity described later. The soil extract may be prepared in an extraction container (not shown), which is another container, and injected from the extraction container into the extract storage container 112A. Alternatively, the extract container and the extract storage container 112A may be used. And the bottom of the extraction container may be penetrated to allow the soil extract to flow into a silicon tube or the like.

  The extraction liquid container 112A is preferably formed of a highly insulating resin material, and in this embodiment, is formed of ABS (acryl butadiene styrene) resin.

  As shown in FIG. 5, the extraction liquid storage container 112 </ b> A is provided with a pair of electrodes 501 a and 501 b for electrically connecting the inside and the outside of the extraction liquid storage container 112 </ b> A. The electrodes 501a and 501b are used for measurement of electrical conductivity described later.

  The electrodes 501a and 501b are provided at a position away from the bottom surface of the extraction liquid storage container 112A by a predetermined distance. Specifically, the electrodes 501a and 501b are in a position slightly lower than the liquid level H when the minimum amount of soil extract necessary for analysis of soil components is injected into the extract storage container 112A. Provided. Thereby, when the amount of the soil extract injected into the extract storage container 112A is less than the minimum amount necessary for the analysis of the soil components, it becomes impossible to measure the electrical conductivity described later. As a result, it can be detected that the amount of the soil extract injected into the extract storage container 112A is less than the minimum amount required for the analysis of the soil components. Alternatively, it is possible to detect forgetting to inject the soil extract. The electrodes 501a and 501b may be fixed to the extraction liquid container 112A with an adhesive or the like, or may be created by insert molding.

  In addition, an opening 112a is provided on the bottom surface of the extraction liquid container 112A. By connecting a tube to the opening 112a, the extract in the extract storage container 112A can be sent.

<Diluent container 113>
As shown in FIG. 1, the diluent storage container 113 is a container for storing a diluent (for example, pure water) for diluting the soil extract when supplying the soil extract to the chip 102. . An opening 113a (see FIG. 6) is provided on the bottom surface of the diluent storage container 113. By connecting a tube to the opening 113a, the diluent in the diluent container 113 can be fed. The material of the diluent container 113 is not limited to the above-described extract container 112A, and any material may be used.

<Extract liquid supply mechanism 120 and dilution liquid supply mechanism 121>
The configuration of the extract supply mechanism 120 and the diluent supply mechanism 121 will be described with reference to FIG. FIG. 6 is a schematic diagram showing the configuration of the extract supply mechanism 120 and the diluent supply mechanism 121. In the same figure, the chip 102, the extraction liquid storage container 112A, the dilution liquid storage container 113, and the rotation drive unit 106 are also shown.

  The extract supply mechanism 120 is a mechanism that supplies the soil extract stored in the extract storage container 112 </ b> A to the sample chambers 401 and 411 through the openings 407 and 417 of the chip 102. The dilution liquid supply mechanism 121 is a mechanism that supplies the dilution liquid stored in the extraction liquid storage container 113 to the sample chambers 401 and 411 through the openings 407 and 417 of the chip 102.

  The extract supply mechanism 120 includes a pump 120a, a tube 120b, and an injection nozzle 120c. The diluent supply mechanism 121 includes a pump 121a, a tube 121b, and an injection nozzle 121c. The extract supply mechanism 120 and the diluent supply mechanism 121 have the same structure.

  The pump 120a is a pump for sending the soil extract contained in the extract containing container 112A from the opening 112a of the extract containing container 112A to the injection nozzle 120c via the tube 120b. The pump 121a is a pump for sending the diluent stored in the diluent storage container 113 from the opening 113a of the diluent storage container 113 to the injection nozzle 121c via the tube 121b.

  As an example, the pumps 120a and 121a can be tube pumps that suck, feed, and discharge liquids by pressing the tubes by rotating rollers. The pumps 120a and 121a are not limited to tube pumps, and the soil extract contained in the extract containing container 112A or the diluted solution contained in the dilute containing container 113 is used as the tube 120b. Or what is necessary is just to be able to send to the injection | pouring nozzle 120c or the injection | pouring nozzle 121c via the tube 121b.

  The tube 120b is a tube for connecting the pump 120a and the injection nozzle 120c. The tube 121b is a tube for connecting the pump 121a and the injection nozzle 121c.

  The injection nozzle 120c and the injection nozzle 121c are disposed at positions immediately above the circumference (on the second circumference) indicated by the alternate long and short dash line B in FIG. 4A where the opening 407 or the opening 417 is formed. Is done.

  With the above configuration, the extract supply mechanism 120 sends the soil extract stored in the extract storage container 112A to the injection nozzle 120c through the tube 120b by the pump 120a. Then, the extract supply mechanism 120 supplies a predetermined amount of soil extract from the injection nozzle 120 c to the sample chambers 401 and 411 through the openings 407 and 417.

  With the above configuration, the diluent supply mechanism 121 sends the diluent contained in the diluent container 113 to the injection nozzle 121c through the tube 121b by the pump 121a. The diluent supply mechanism 121 supplies a predetermined amount of the diluent from the injection nozzle 121c to the sample chambers 401 and 411 through the openings 407 and 417.

<Electrical conductivity measuring unit 115>
The configuration of the electrical conductivity measurement unit 115 will be described with reference to FIG. FIG. 7 is a schematic diagram illustrating the configuration of the electrical conductivity measurement unit 115. In addition, the extract storage container 112A is shown together in FIG.

  The electrical conductivity measurement unit 115 is connected to the electrodes 501a and 501b of the extract storage container 112A, and measures the electrical conductivity (EC) of the soil extract stored in the extract storage container 112A. .

  The electrical conductivity measuring unit 115 includes an AC power source 115a and an AC ammeter 115b.

  The AC power supply 115a is connected to the electrodes 501a and 501b provided in the extract storage container 112A, and applies a voltage to the soil extract via the electrodes 501a and 501b. The AC ammeter 115b is provided in a circuit including the AC power supply 115a and the electrodes 501a and 501b, and measures the current flowing through the circuit.

  With the above configuration, the electrical conductivity measuring unit 115 applies a voltage to the soil extract using the AC power source 115a, and measures the current flowing through the circuit using the AC ammeter 115b. Thereby, the electrical conductivity measuring unit 115 measures the electrical conductivity of the soil extract.

<Control unit 111A>
As shown in FIG. 1, the control unit 111A includes a supply amount setting unit 107A, a liquid supply control unit 104, and a measurement control unit 105. The control unit 111A is connected to the light emitting unit 101, the measurement unit 109A, the extract supply mechanism 120, the diluent supply mechanism 121, the electrical conductivity measurement unit 115, and the rotation drive unit 106, and controls the operation of each unit.

  Based on the electrical conductivity of the soil extract measured by the electrical conductivity measuring unit 115, the supply amount setting unit 107A is a ratio of the amount of the soil extract to be injected into the chip 102 and the amount of the diluted solution, that is, dilution. Set the rate. Details of setting the ratio between the amount of the soil extract and the amount of the diluent will be described later.

  The liquid supply control unit 104 controls operations of the extraction liquid supply mechanism 120, the dilution liquid supply mechanism 121, and the rotation driving unit 106.

  Specifically, the liquid supply control unit 104 controls the rotation of the chip 102 so that the position of the injection nozzle 120 c included in the extraction liquid supply mechanism 120 matches the position of the opening 407 or the opening 417 of the chip 102. In other words, the liquid supply control unit 104 controls the rotation of the chip 102 so that the position of the injection nozzle 121 c included in the diluent supply mechanism 121 matches the position of the opening 407 or the opening 417 of the chip 102.

  Then, the liquid supply control unit 104 supplies the soil extract and the diluted solution to the measurement chamber 404 through the opening 407 or the reference chamber 414 through the opening 417 at the ratio calculated by the supply amount setting unit 107A. As described above, the pump 120a and the pump 121a of each of the extract supply mechanism 120 and the diluent supply mechanism 121 are controlled.

  The measurement control unit 105 controls the electrical conductivity measurement unit 115 to determine whether or not the electrical conductivity of the soil extract can be measured. The measurement control unit 105 outputs an instruction signal to the electrical conductivity measurement unit 115 and acquires the measurement result of the electrical conductivity of the soil extract from the electrical conductivity measurement unit 115. Moreover, even when the electrical conductivity measuring unit 115 cannot measure the electrical conductivity of the soil extract, the measurement control unit 105 acquires a result to that effect from the electrical conductivity measuring unit 115.

  Furthermore, the measurement control unit 105 controls the operations of the rotation driving unit 106 and the measurement unit 109A when measuring the absorbance, and passes through the measurement chamber 404 and the reference chamber 414 of the chip 102 rotating around the rotation axis 450. Then, the intensity (light transmission amount) of the light received by the light receiving unit 103 is measured.

(Measurement operation and measurement procedure)
Next, based on FIG.8 and FIG.9, the operation | movement and measurement procedure of each part of 100 A of liquid sample analyzers at the time of the component measurement of a soil extract are demonstrated.

  FIG. 8A is a top view of the chip 102 as viewed from above when the liquid sample analyzer 100A measures the components of the soil extract. FIG. 8B is a cross-sectional view taken along the line CC of the chip 102 in FIG. 8B also shows a filter array 205 disposed above the chip 102 and a light receiving unit 103 disposed below the chip 102.

  In the following, for convenience of explanation, when distinguishing each of the six cells 400, reference numerals 400-a to 400-f are given, and when not distinguished, 400 reference numerals are given. Similarly, when the sample chamber 401, the reagent chamber 402, the reagent chamber 403, the measurement chamber 404, the flow path 405, and the opening 407 formed in the cell 400 are distinguished from each other, 401-a to Reference numerals 401-f, 402-a to 402-f, 403-a to 403-f, 404-a to 404-f, 405-a to 405-f, and 407-a to 407-f are attached.

  0.4 ml of 5 wt% salicylic acid-sulfuric acid aqueous solution is pre-injected into the reagent chamber 402-a of the cell 400-a, and 10 ml of 2 mol / l sodium hydroxide (NaOH) aqueous solution is pre-injected into the reagent chamber 403-a. . Similarly, Table 1 shows the types and amounts of the reagents previously injected into each of the reagent chambers 402-a to 402-f and 403-a to 403-f. The column indicated by “-” in Table 1 indicates that no reagent has been injected.

As shown in Table 1, different reagents (first reagent and second reagent) are injected into the reagent chamber 402 and the reagent chamber 403 of the cell 400, respectively. This is because the sample according to the soil component to be measured is injected, nitrate nitrogen (NO ₃ -N) is used in the cell 400-a, and ammonia nitrogen (NH ₄ -N) is used in the cell 400-b. Cell 400-c, absorbable phosphoric acid (P ₂ O ₅ ), cell 400-d, exchangeable potassium (K ₂ O), cell 400-e, exchangeable calcium (CaO), cell 400 In -f, exchangeable magnesium (MgO) is used as the soil component to be measured.

  FIG. 9 is a flowchart showing the measurement procedure of the liquid sample analyzer 100A.

  First, 0.4 g of soil and 100 ml of water are placed in an extraction container (not shown) by an operator, and shaking and filtration are performed in the extraction container to produce a soil extract (step S1). And the produced soil extract is inject | poured into the extract storage container 112A of 100 A of liquid sample analyzers by an operator (step S2). Next, pure water as a diluent is poured into the diluent container 113 by the operator (step S3). Then, the chip 102 is set on the liquid sample analyzer 100A by the operator (step S4).

  Next, the electrical conductivity measuring unit 115 receives the control signal from the measurement control unit 105, and measures the electrical conductivity of the soil extract contained in the extract containing container 112A (step S5).

  And the measurement control part 105 acquires the measurement result from the electrical conductivity measurement part 115, and determines whether the electrical conductivity of a soil extract is measurable from the said measurement result (step S6). .

  When the measurement control unit 105 determines that the electrical conductivity of the soil extract cannot be measured because the liquid level of the soil extract injected into the extract storage container 112A does not reach the electrodes 501a and 501b. (No in step S6), the measurement control unit 105 determines that the amount of the soil extract injected into the extract storage container 112A is less than the minimum amount necessary for the analysis of the soil components, and a buzzer, a lamp, or a liquid crystal display After sending information to that effect to warn the operator (S16), the measurement is terminated.

  In step S6, when the measurement control unit 105 determines that the electrical conductivity of the soil extract can be measured (Yes in step S6), the supply amount setting unit 107A is then used by the electrical conductivity measurement unit 115. Based on the measured electrical conductivity, the amount of the soil extract and pure water injected into each sample chamber 401, that is, the dilution rate is set (step S7).

  Here, the setting method of the dilution rate set by the supply amount setting unit 107A will be described in detail below.

  The electrical conductivity of the soil extract is used as an indicator of the salt concentration in the soil solution. That is, the electrical conductivity of the soil solution is the concentration of anions such as nitrate nitrogen, sulfate radicals, and chlorine, and ammonia nitrogen, lime, bitter soil, potassium, and so on that are not fully adsorbed by the soil colloid. It becomes higher in proportion to the cation concentration. In general, when the electrical conductivity is low, that is, when the ion concentration is low, the soil nutrients are low. On the other hand, when the electrical conductivity is high, that is, when the ion concentration is high, the soil nutrient is high. Further, when the electrical conductivity is remarkably high, that is, when the ion concentration is remarkably high, there is an increased risk of salt concentration disturbance due to salt production.

  Thus, it is known that there is a correlation between the electrical conductivity and the component concentration of the soil extract, and using an appropriate correlation function, the electrical conductivity and the component concentration of the soil extract are Can be expressed.

  Generally, in order to estimate the concentration Y (mg / 100 g) of a certain component in a liquid, the following equation (1), which is a linear function using the electrical conductivity X (mS / cm) as a correlation function Can be used.

Y = aX + b (1)
Here, the inclination a and the Y intercept b are values set for each component, and a is a value of 0 or more. Expression (1) (first correlation function) is set for each component to be measured.

  A method for setting the slope a of the correlation function for each component will be described below. Various components are contained in the liquid, and it is not known how much each component is contained. However, depending on the liquid sample to be measured, the degree of contribution of each component to the electrical conductivity may be known. In such a case, when the concentration of a component having a high degree of contribution to electrical conductivity is high, the electrical conductivity is increased. As a result, when the concentration of other components is estimated using Equation (1), it is estimated that the component concentration is higher than the actual concentration. Therefore, it is preferable to set the slope a of the correlation function for a component having a high degree of contribution to electrical conductivity and to set the slope a of the correlation function for other components to be small. By setting each inclination a in this way, it is possible to prevent the concentration of other components from being estimated to be higher than necessary even when the concentration of a component having a high degree of contribution to electrical conductivity is high. Therefore, it is possible to accurately estimate the concentration of each component contained in the liquid.

  In this embodiment, the component concentration contained in the soil is the measurement target. In such a case, it is known that nitrate nitrogen greatly contributes to electrical conductivity in a soil extract obtained from soil. Accordingly, among the correlation functions set for the components measured in each of the cells 400-a to 400-f, the correlation function for the nitrate nitrogen measured in the cell 400-a may be set to have the largest gradient. preferable. By setting each inclination a in this way, the concentration of nitrate nitrogen can be accurately estimated even when the concentration of nitrate nitrogen is high. Furthermore, it is possible to prevent the concentration of other components from being estimated to be higher than necessary. Therefore, it is possible to accurately estimate the concentration of each component contained in the soil extract.

  The supply amount setting unit 107A estimates the concentration of each component in the soil extract using the set correlation function and the electrical conductivity measured by the electrical conductivity measurement unit 115. The supply amount setting unit 107A then sets each component chamber 401 in each sample chamber 401 so that the concentration of each component in the soil extract becomes a concentration (measurement appropriate concentration) that enables later-described absorbance measurement based on the estimated component concentration. The amount of soil extract and pure water to be injected into -a to 401-f, that is, the dilution rate is set.

  Hereinafter, a method for setting the dilution rate will be described by taking the nitrate nitrogen concentration (first component) measured in the measurement chamber 404-a (first measurement chamber) as an example.

The supply amount setting unit 107A uses the following formula (2) set in advance in order to estimate the nitrate nitrogen concentration Y ₁ (mg / 100 g) in the soil extract from the electric conductivity X (mS / cm). be able to.

Y ₁ = 44X−15 (2)
Supply quantity determination unit 107A on the basis of the equation (2) (first correlation function), to estimate the nitrate nitrogen concentration _{Y 1.} Then, based on the estimated nitrate nitrogen concentration Y ₁ , the supply amount setting unit 107A sets the sample chamber 401-a so that the nitrate nitrogen concentration in the soil extract becomes a concentration at which absorbance measurement described later can be performed. The amount of the soil extract and pure water to be injected into the water, that is, the dilution rate is set. Specific setting of the dilution rate will be described based on Table 2. Table 2 is a table showing the dilution rate with respect to the electrical conductivity of the soil extract for nitrate nitrogen.

  From the relationship between the formula (2) and the measurable concentration range of nitrate nitrogen concentration, the supply amount setting unit 107A, as shown in Table 2, is the amount of soil extract and pure water injected into the sample chamber 401-a. That is, the dilution rate is calculated. Specifically, when the electrical conductivity is less than 0.3 mS / cm, only the soil extract is injected into the sample chamber 401-a, and pure water is not injected. When the electrical conductivity is 0.3 mS / cm or more and less than 1.0 mS / cm, the soil extract and pure water are supplied to the sample chamber 401-a so that the ratio of the soil extract to pure water is 1: 1. Inject. When the electrical conductivity is 1.0 mS / cm or more, the soil extract and pure water are injected into the sample chamber 401-a so that the ratio of the soil extract and pure water is 1: 2.

  In this way, by changing the dilution rate based on the electrical conductivity of the soil extract, the nitrate nitrogen concentration can be measured within the appropriate measurement range of nitrate nitrogen. As a result, it is possible to eliminate the waste of the chip 102 and the reworking of the measurement due to the measurement outside the proper measurement range of nitrate nitrogen.

  Similarly, the supply amount setting unit 107A has a correlation function (second correlation function) for a component (second component) measured in the measurement chambers 404-b to 404-f (second measurement chamber) other than the measurement chamber 404-a. ), And the concentration of each component in the soil extract is estimated based on the electrical conductivity.

For example, in order to estimate the ammonia nitrogen concentration (second component) Y ₂ (mg / 100 g) measured in the measurement chamber 404-b (second measurement chamber), the following formula (3) set in advance is used. Can do.

_{Y 2 = 8.95X-4.54 ··· (} 3)
Supply quantity setting unit 107A, based on the equation (3) (second correlation function), to estimate the ammonia nitrogen concentration _{Y 2.} Then, based on the estimated ammonia nitrogen concentration Y ₂ , the supply amount setting unit 107A sets the sample chamber 401-b so that the nitrate nitrogen concentration in the soil extract becomes a concentration at which absorbance measurement described later can be performed. The amount of the soil extract and pure water to be injected into the water, that is, the dilution rate is set.

  As described above, the supply amount setting unit 107A sets each component chamber 401-b so that the concentration of each component in the soil extract becomes a concentration at which absorbance measurement described later can be performed based on the estimated concentration of each component. The amount of soil extract and pure water to be injected into ˜401-f, that is, the dilution rate is set.

  In this way, by measuring the electrical conductivity of the soil extract and calculating the approximate concentration of each measurement component using the correlation function set for each component, a dilution rate suitable for the measurement of each component is set. can do. As a result, the concentration of each component can be reliably and accurately measured.

  The dilution rate described above is an example, and the relationship between the electrical conductivity and the dilution rate can be appropriately changed in accordance with the measurable concentration range of the reagent to be used. In addition, by setting the relationship between the electrical conductivity and the dilution rate in more detail, the component concentration can be measured with higher accuracy.

  After step S7 described above, the liquid supply control unit 104 of the control unit 111A rotates the rotation driving unit 106 so that the opening 417 of the sample chamber 411 of the cell 410 is positioned immediately below the injection nozzle 120c. 102 is rotated (step S8). The liquid sample analyzer may be configured such that the opening 417 is always located immediately below the injection nozzle 120c when the chip 102 is installed in step S4. Can omit step S8. For example, the chip 102 is provided with a notch, a chip mounting table (not shown) on which the chip 102 is placed is provided with a projecting piece, and the notch and the projecting piece are fitted with each other. By making the rotary shaft 450 connected to the driving unit 106 into a D-cut shape, the position where the chip 102 is set is uniquely positioned so that the opening 417 is always directly below the injection nozzle 120c. I can decide.

  Next, the extract supply mechanism 120 injects the soil extract into the sample chamber 411 from the opening 417 (step S9). When the injection of the soil extract into the sample chamber 411 is completed, the liquid supply control unit 104 determines that each of the openings 407-a to 407-f of the sample chambers 401-a to 401-f is directly below the injection nozzle 120c. Thus, the extractor supply mechanism is controlled so that the rotation drive unit 106 is controlled and the amount of the soil extract set by the supply amount setting unit 107A is injected into each of the sample chambers 401-a to 401-f. 120 is controlled (step S10).

  Thus, in the liquid sample analyzer 100A according to the present embodiment, the soil extract is controlled by controlling the rotation of the chip 102 so that the liquid injection position of the extract supply mechanism 120 and the positions of the openings 407 and 417 are aligned. Can be injected. As a result, the soil extract can be injected into the sample chambers 401-a to 401-f in a short time. In addition, by first injecting the soil extract into the sample chamber 411, the air in the tube between the extract storage container 112A and the pump 120a, the pump 120a, the tube 120b, and the injection nozzle 120c is pushed out, and the soil extract is used. Can be satisfied. Therefore, in the step of injecting the soil extract into each of the sample chambers 401-a to 401-f, the accuracy of injecting the soil extract can be improved, and the measurement accuracy can be improved.

  Next, the diluent supply mechanism 121 is controlled so that the amount of pure water set by the supply amount setting unit 107A is injected into each of the sample chambers 401-a to 401-f (step S11).

  Next, the procedure proceeds to the measurement of the absorbance of each cell 410, and first, the rotation drive unit 106 rotates. The rotation of the rotation drive unit 106 causes the chip 102 to rotate about the rotation axis 450, and the cell 400 and the cell 410 have the directions indicated by arrows F in FIG. 4B and FIG. 4C, respectively. Centrifugal force (inertial force) acts.

  The soil extract injected into the sample chamber 411 of the cell 410 moves to the reference chamber 414 through the flow path 415 by centrifugal force. In addition, the soil extract in the sample chamber 401 of the cell 400 and the reagent in the reagent chamber 402 move to the reagent chamber 403 through the flow path 405. Thereby, the liquid mixture of the sample and the reagent to be measured is generated in the reagent chamber 403 (step S12). Next, the liquid mixture generated in the reagent chamber 403 of the cell 400 is agitated by the rotation of the rotation driving unit 106. At this time, when the sample and the reagent react, the sample develops color according to each soil component.

  In this embodiment, the liquid mixture is agitated by the rotation of the rotation drive unit 106. The rotation of the rotation drive unit 106 may be a configuration that rotates at a constant speed, a configuration that rotates with an acceleration, or a configuration that rotates in the reverse direction. Moreover, the structure which rotates combining these may be sufficient.

  When the stirring of the mixed liquid is completed, the open / close valve provided in the flow path 405 between the reagent chamber 403 and the measurement chamber 404 is opened, and the rotation driving unit 106 is rotated again, so that the mixed liquid is centrifuged by centrifugal force. Is moved to the measurement chamber 404 (step S13).

  Note that stirring of the above-described mixed solution may be performed in the reagent chamber 403 or in the measurement chamber 404. In the present embodiment, the mixed liquid is generated and stirred for the cells 400-a to 400-f by the rotation of the rotation driving unit 106. However, the present invention is not limited to this. Instead, it may be configured to be performed individually for each of the cells 400-a to 400-f. However, from the viewpoint of shortening the processing time, a configuration in which the cells 400-a to 400-f are performed collectively is preferable.

  As shown in FIGS. 8A and 8B, after the stirring of the mixed liquid is completed, the chip 102 is rotated at a uniform speed by the rotation of the rotation driving unit 106, and the light 300 is emitted from the light emitting unit 101. , The light 300 scans the chip 102, and the light 300 transmitted through the chip 102 passes through the measurement chamber 404 and the reference chamber 414 of the chip 102 and enters the light receiving unit 103. Next, the measurement unit 109A measures the intensity (light transmission amount) of light received by the light receiving unit 103 according to an instruction from the measurement control unit 105 (step S14).

  When the light transmission amount of the soil extract is measured, the measurement unit 109B then calculates each soil component concentration based on the measured light intensity (light transmission amount) according to an instruction from the measurement control unit 105. (Step S15). Specifically, a calibration curve that has been measured and stored in advance using a known component amount, a measured value of the intensity of light (light transmission amount) that has passed through each measurement chamber 404, and was measured in advance. Using the measured value of the intensity (light transmission amount) of light that has passed through the sample of only the reagent corresponding to each cell 400-a to 400-f that does not contain soil components, the Lambert-Beer law simplifies The soil component concentration is calculated only by simple calculation.

  In addition, in this embodiment, when calculating a soil component density | concentration, the sample of the reagent only corresponding to each cell 400-a-400-f which was measured beforehand and does not contain the soil component was passed. Although the measurement value of light intensity (light transmission amount) is used, the present invention is not limited to this. The measuring unit 109A measures the difference between the intensity of light transmitted through the measurement chambers 404-a to 404-f (light transmission amount) and the intensity of light transmitted through the reference chamber 414 (light transmission amount). The structure which calculates the light absorbency of chamber 404-a-404-f and calculates a soil component density | concentration may be sufficient.

(Main advantages of the liquid sample analyzer 100A)
As described above, according to the liquid sample analyzer 100A, the electrical conductivity measurement unit 115 measures the electrical conductivity of the soil extract stored in the extract storage container 112A. Then, the supply amount setting unit 107A of the control unit 111A is supplied from the extract storage container 112A to the chip 102 by the extract supply mechanism 120 based on the electrical conductivity of the soil extract measured by the electrical conductivity measurement unit 115. The ratio (dilution ratio) between the amount of the soil extract to be performed and the amount of the diluent supplied from the diluent storage container 113 to the chip 102 by the diluent supply mechanism 121 is controlled. Thereby, in the chip 102, the soil extract diluted with the ratio controlled by the supply amount setting unit 107A and the measurement reagent are mixed. Then, the measurement unit 109A measures the light transmission amount of the diluted soil extract, which can measure the light transmission amount by mixing the measurement reagent, and at least one of the diluted soil extracts. Analyze one component.

  According to this, since the electrical conductivity measuring unit 115 measures the electrical conductivity of the soil extract contained in the extract containing container 112A, the concentration of the component is so high that the measuring unit 109A cannot measure the light transmission amount. Even when the soil extract is stored in the extract storage container 112A, the rough component concentration of the soil extract can be calculated. Then, the measurement unit 109A measures the light transmission amount of the diluted soil extract by the measurement unit 109A controlling the ratio based on the electrical conductivity of the soil extract stored in the extract storage container 112A. Can do. For this reason, the measurement unit 109A can analyze at least one component of the soil extract in an optimum concentration range in which the amount of light transmission changes rapidly according to the increase or decrease of the concentration of the component of the soil extract.

  Thus, according to the liquid sample analyzer 100A, the measurement unit 109A can prevent the analysis of the components of the soil extract from being failed or the analysis accuracy from being lowered, so that the components of the liquid sample can be prevented. Can be analyzed reliably and accurately.

  As a result, it is possible to prevent the concentration of the component of the soil extract from being too high and the measurement to fail, or the accurate concentration of the component cannot be measured without reaching the failure. Loss can be prevented.

  Here, when the dilution rate of the soil extract is diluted depending on the operator's intuition, the optimum dilution rate differs depending on the soil extract, so dilution and light transmission are measured multiple times by dry and error. Since it is necessary to do this, rework occurs, the work becomes complicated, and the loss of the reagent and the chip 102 occurs.

  On the other hand, according to the liquid sample analyzer 100A, the supply amount setting unit 107A is configured so that the extraction liquid supply mechanism 120 moves from the extraction liquid container 112A based on the electrical conductivity of the soil extract measured by the electrical conductivity measurement unit 115. The ratio of the amount of the soil extract supplied to the chip 102 and the amount of the diluent supplied from the diluent storage container 113 to the chip 102 by the diluent supply mechanism 121 is controlled. For this reason, since the rework for grasping | ascertaining the optimal dilution rate can be eliminated, work efficiency can be improved and the loss generation | occurrence | production of the reagent and the chip | tip 102 can be prevented.

  Further, according to the liquid sample analyzer 100A, the extract supply mechanism 120 supplies the soil extract via the opening 407 to the reagent chamber 403 in which the reagent is preliminarily sealed. In addition, the diluent supply mechanism 121 supplies the diluent through the opening 407 to the reagent chamber 403 in which the reagent is sealed in advance. Thereby, in the reagent chamber 403, the reagent can be mixed while diluting the soil extract with the diluent. Thus, the reagent is sealed in the reagent chamber 403 in advance. For this reason, it is not necessary to enclose the reagent in the reagent chamber 403 every time the operation of analyzing the components of the soil extract is performed. Thereby, complication of work can be prevented.

  Further, the soil extract stored in the extract storage container 112A includes a first component and a second component that are different from each other. In the chip 102, the first reagent corresponding to the first component is accommodated in one of the reagent chambers 403-a to 403-f, and the second reagent corresponding to the second component is stored in the reagent chamber 403. -A to 403-f.

  According to this, in the chip 102, the soil extract and the first reagent are mixed in one of the reagent chambers 403-a to 403-f, and the one of the reagent chambers 403-a to 403-f is mixed. In the other one, the soil extract and the second reagent are mixed. For this reason, the measurement unit 109A includes the light transmission amount in the mixed solution of the soil extract and the first reagent mixed in one of the reagent chambers 403-a to 403-f, and the reagent chambers 403-a to 403-a to 403-a to 403-f. The light transmission amount in the mixed solution of the soil extract and the second reagent mixed in the other one of 403-f can be measured. Thereby, since a plurality of components of the first component and the second component among the soil extract contained in one chip 102 can be analyzed, the components of the soil extract can be more easily and efficiently used. Can be analyzed.

  Here, the first component analyzed by the soil extract mixed with the first reagent in one of the reagent chambers 403-a to 403-f and the reagent chamber 403-a to 403-f Since the other component is different from the second component analyzed by the soil extract mixed with the second reagent in the other one, when the measurement control unit 105 and the measurement unit 109A measure the light transmission amount, The optimum concentration range differs between when measuring and when measuring the second component.

  Therefore, the measurement unit 109A determines the concentration of the first component in the chip 102 based on the electrical conductivity measured by the electrical conductivity measurement unit 115 and the first correlation function determined corresponding to the first component. And the concentration of the first component of the soil extract in one of the reagent chambers 403-a to 403-f is the first reagent in one of the reagent chambers 403-a to 403-f The amount of soil extract supplied to one of the reagent chambers 403-a to 403-f by the extract supply mechanism 120 and the reagent chamber 403-a by the diluting solution supply mechanism 121 so that the measurement appropriate concentration is obtained. Control the ratio with the amount of diluent supplied to one of ˜403-f.

  Furthermore, the measurement unit 109A determines the concentration of the second component in the chip 102 based on the electrical conductivity measured by the electrical conductivity measurement unit 115 and the second correlation function determined corresponding to the second component. And the concentration of the second component in the other one of the reagent chambers 403-a to 403-f is equal to that of the second reagent in the other one of the reagent chambers 403-a to 403-f. The amount of the soil extract supplied to the other one of the reagent chambers 403-a to 403-f by the extract supply mechanism 120 and the reagent chamber 403- Control the ratio with the amount of diluent supplied to the other one of a-403-f.

  As a result, when the measurement control unit 105 and the measurement unit 109A measure the light transmission amount of the soil extract, one of the soil extracts 403-a to 403-f and the reagent chambers 403-a to 403 are measured. The other soil extract of -f is diluted to the optimal concentration range. For this reason, 109 A of measurement parts can analyze correctly the 1st component and 2nd component which are mutually different among soil extracts.

  The first correlation function is a linear function as shown in the above formulas (1) and (2). Thereby, supply amount setting part 107A can estimate the density | concentration of the 1st component of a soil extract by simple calculation. Furthermore, the second correlation function is also preferably a linear function. Thereby, the supply amount setting unit 107A can also estimate the concentration of the second component by a simple calculation. Thereby, the soil extract supplied to each one of the reagent chambers 403-a to 403-f and the other one of the reagent chambers 403-a to 403-f can be efficiently measured with the measurement appropriate concentration. Can be diluted.

  The first component is nitrate nitrogen, and the slope of the first correlation function is preferably larger than the slope of the second correlation function.

  Here, it can be considered that the electrical conductivity measures the total of the effects of the respective concentrations of all kinds of ions dissolved in the moisture contributing to the electrical conduction. For this reason, usually, even if the electrical conductivity is measured, it cannot be accurately determined to what extent the concentration of which kind of ions contributed to the electrical conduction.

  However, the electrical conductivity of the soil extract has a strong correlation with the concentration of nitrate nitrogen. Therefore, when the soil extract is stored in the extract storage container 112A and the first component analyzed by the liquid sample analyzer 100A is nitrate nitrogen, the slope of the first correlation function is set as the slope of the second correlation function. It is preferable to make it larger. Thereby, even if it is a case where the density | concentration of nitrate nitrogen in the soil extract accommodated in 112 A of extract storage containers is too high, the density | concentration of nitrate nitrogen can be made into a measurement appropriate density | concentration.

  Thereby, 109 A of measurement parts can measure correctly the density | concentration of the nitrate nitrogen which is a 1st component among soil extracts. On the other hand, by making the slope of the second correlation function smaller than the slope of the first correlation function, the second component in the component of the soil extract is influenced by the change of nitrate nitrogen, which is the first component, and the dilution rate is increased. Unnecessary changes can be suppressed. As a result, the measurement unit 109A can accurately measure the concentrations of the first component and the second component.

[Embodiment 2]
Another embodiment of the present invention will be described below with reference to FIGS. 10 and 11. For convenience of explanation, members having the same functions as those described in the embodiment are given the same reference numerals, and descriptions thereof are omitted.

  In the liquid sample analyzer 100B according to the present embodiment, the function of the measuring unit 109B is different from the function of the measuring unit 109A of the liquid sample analyzer 100A according to the first embodiment.

  FIG. 10 is a diagram showing an outline of the configuration of the liquid sample analyzer 100B according to the present embodiment. As shown in FIG. 10, the liquid sample analyzer 100B of the present embodiment includes a measurement unit 109B in place of the measurement unit 109A included in the liquid sample analyzer 100A (see FIG. 1). Different from the sample analyzer 100A. Other configurations of the liquid sample analyzer 100B are the same as those of the liquid sample analyzer 100A.

  The measurement unit 109A of the liquid sample analyzer 100A of Embodiment 1 calculates the concentration of each component in the soil extract diluted with the diluent. On the other hand, the measurement unit 109B of the liquid sample analyzer 100B of the present embodiment calculates the concentration of each component before dilution in consideration of the dilution rate for each component.

  The measurement procedure of the liquid sample analyzer 100B will be described based on FIG. FIG. 11 is a flowchart showing a measurement procedure of the liquid sample analyzer 100B.

  In the measurement procedure of the liquid sample analyzer 100B of the present embodiment, steps S1 to S15 are the same as the measurement procedure of the liquid sample analyzer 100A.

  In step S15, when the measurement unit 109B measures the light transmission amount of the soil extract according to an instruction from the measurement control unit 105, the measured light is then referred to a calibration curve stored in advance in the measurement unit 109B. Obtain the soil component concentration associated with the amount of permeation. Thus, the measurement unit 109B calculates the soil component concentration.

  Next, in accordance with an instruction from the measurement control unit 105, the measurement unit 109B acquires information indicating the dilution rate of the soil extract set by the supply amount setting unit 107A in step S7 from the supply amount setting unit 107A. Is multiplied by the calculated soil component concentration to calculate the concentration of each soil component before dilution. Thereby, the measurement part 109B can calculate the true soil component density | concentration (namely, component density | concentration of the soil extract liquid accommodated in 112 A of extract liquid storage containers) which considered the dilution rate (S21).

  Thereafter, the measurement unit 109B may display the calculated component concentration of the soil extract to the operator, for example, by displaying it on a display unit (not shown).

  A specific method for calculating the concentration of each soil component before dilution will be described below.

  For example, the case where the dilution rate is 0.5 (that is, the soil extract and the diluted solution are mixed 1: 1) with respect to a certain component in the soil extract will be described. In this case, the measurement unit 109B calculates the concentration of each component in the soil extract diluted with the diluent, and multiplies the concentration by the reciprocal of the dilution rate, that is, each component in the soil extract diluted with the diluent. The concentration before dilution of the component is calculated by multiplying the concentration by 2 (= 1 / 0.5).

  Thus, the liquid sample analyzer 100B according to the present embodiment calculates the concentration before dilution for each component of the soil extract taking into consideration the dilution rate. Thereby, no matter what dilution rate is used, the concentration of each component before dilution can be calculated easily and accurately.

  As described above, in the liquid sample analyzer 100B, the measurement unit 109B performs the soil extraction based on the measured light transmission amount and the ratio between the amount of the soil extract and the amount of the dilution controlled by the control unit 111B. Analyze the components of the liquid. According to this, it is possible to analyze the components of the soil extract stored in the extract storage container 112A before dilution. For this reason, the component of a soil extract can be analyzed more simply and correctly.

[Embodiment 3]
Another embodiment of the present invention is described below with reference to FIG. For convenience of explanation, members having the same functions as those described in the first and second embodiments are denoted by the same reference numerals and description thereof is omitted.

  In the liquid sample analyzer 100C according to the present embodiment, the function of the supply amount setting unit 107C is different from the function of the supply amount setting unit 107A of the liquid sample analyzer 100A according to the first embodiment.

  FIG. 12 is a diagram showing an outline of the configuration of a liquid sample analyzer 100C according to Embodiment 2 of the present invention. As shown in FIG. 12, the liquid sample analyzer 100C is different from the liquid sample analyzer 100A in that a controller 111C is provided instead of the controller 111A of the liquid sample analyzer 100A (see FIG. 1). The control unit 111C includes a supply amount setting unit 107C instead of the supply amount setting unit 107A of the control unit 111A. Other configurations of the liquid sample analyzer 100C are the same as those of the liquid sample analyzer 100A.

In the liquid sample analyzer 100C of the present embodiment, as in the first embodiment, different reagents are enclosed in the reagent chamber 402 and the reagent chamber 403 for each of the cells 400-a to 400-f (see Table 1). . The soil component to be measured in the cell 400-a is nitrate nitrogen (NO ₃ —N), the soil component to be measured in the cell 400-b is ammonia nitrogen (NH ₄ —N), and the cell 400-c. The soil component to be measured in the sample is resorbable phosphoric acid (P ₂ O ₅ ), the soil component to be measured in the cell 400-d is exchangeable potassium (K ₂ O), and the sample to be measured in the cell 400-e. The soil component is exchangeable calcium (CaO), and the soil component to be measured in the cell 400-f is exchangeable magnesium (MgO).

  In order to set the dilution rate of nitrate nitrogen measured in the cell 400-a, the supply amount setting unit 107C is similar to the supply amount setting unit 107A of the first embodiment, and a correlation function that is a linear function, and electrical conductivity Using the electrical conductivity measured by the measuring unit 115, the concentration of nitrate nitrogen in the soil extract contained in the extract containing container 112A is estimated. Then, the dilution rate is set based on the estimated nitrate nitrogen concentration.

  On the other hand, the supply amount setting unit 107C does not take into account the electrical conductivity for the dilution rate of other components measured in the measurement chambers 404-b to 404-f other than the measurement chamber 404-a, and is a preset dilution. Use rate. In other words, the supply amount setting unit 107C sets the dilution rate with the coefficient of the correlation function set to zero.

  In this way, by setting the dilution rate for each component, the supply amount setting unit 107C estimates the dilution rate based on the correlation function for nitrate nitrogen as in the first embodiment. The amount of the soil extract and pure water injected into the measurement chamber 404-a, that is, the dilution rate, can be set so that the absorbance of the nitrate nitrogen concentration in the extract can be measured. On the other hand, the supply amount setting unit 107C sets the dilution rate for the other components regardless of the electrical conductivity.

  Thus, in the liquid sample analyzer 100C, the supply amount setting unit 107C performs measurement in the measurement chambers 404-b to 404-f other than the measurement chamber 404-a, assuming that the slope of the second correlation function is zero. The dilution ratio of the ingredients is set. As a result, the dilution rate of the second component is constant regardless of the electrical conductivity. As a result, it is possible to prevent the concentration of the nitrate nitrogen from affecting the dilution ratio of the second component whatever the concentration of the nitrate nitrogen in the soil extract. Therefore, it can prevent that the measurement precision of the density | concentration of a 2nd component falls.

[Embodiment 4]
The following will describe another embodiment of the present invention with reference to FIGS. For convenience of explanation, members having the same functions as those described in the embodiment are given the same reference numerals, and descriptions thereof are omitted.

  FIG. 13 is a diagram showing an outline of the configuration of the liquid sample analyzer 100D according to this embodiment. As shown in FIG. 13, the liquid sample analyzer 100D includes an extract storage container 112D and a controller 111D instead of the extract container 112A and the controller 111A provided in the liquid sample analyzer 100A (see FIG. 1). And a lower electrical conductivity measuring unit 116. Other configurations of the liquid sample analyzer 100D are the same as those of the liquid sample analyzer 100A. The control unit 111D includes a liquid supply control unit 104, a measurement control unit 105, a supply amount setting unit 107A, and a lower electrical conductivity measurement determination unit 108.

  The lower electrical conductivity measurement determination unit 108 determines whether or not the electrical conductivity can be measured from the measurement result obtained by the lower electrical conductivity measurement unit 116 measuring the electrical conductivity in the extraction liquid container 112D. .

  With reference to FIG. 14, the configuration of the extract storage container 112D and the lower electrical conductivity measurement unit 116 will be described. FIG. 14 is a diagram showing an outline of the configuration of the extraction liquid container 112D and the lower electrical conductivity measurement unit 116. As shown in FIG. In FIG. 14, the extract storage container 112 </ b> D has a cross-sectional shape.

  The extraction liquid storage container 112D is different from the extraction liquid storage container 112A (see FIG. 5) in that it further includes a pair of electrodes 502a and 502b in addition to the pair of electrodes 501a and 501b. The other configuration of the extraction liquid storage container 112D is the same as that of the extraction liquid storage container 112A.

  The electrodes 502a and 502b are provided in the lower part of the side surface of the extraction liquid storage container 112D so as to penetrate the side surface. Accordingly, the electrodes 502a and 502b can electrically connect the liquid filled in the extraction liquid storage container 112D and the lower electrical conductivity measuring unit 116 provided outside. . The electrode 502a and the electrode 502b are separated from each other.

  The lower electrical conductivity measuring unit 116 includes an AC power source 116a and an AC ammeter 116b. The lower electrical conductivity measuring unit 116 is connected to the electrodes 502a and 502b of the extraction liquid storage container 112D and is also connected to the control unit 111D. The lower electrical conductivity measuring unit 116 measures the electrical conductivity of the soil extract contained in the extract containing container 112D according to an instruction from the control unit 111D.

  The AC power source 116a is connected to the electrodes 502a and 502b provided in the extract storage container 112D, and applies a voltage to the soil extract via the electrodes 502a and 502b according to an instruction from the control unit 111D. The AC ammeter 116b is provided in a series circuit including the AC power supply 116a and the electrodes 502a and 502b, and measures the current flowing through the series circuit.

  With the above configuration, the lower electrical conductivity measuring unit 116 applies a voltage to the soil extract using the AC power source 116a, and measures the current flowing through the series circuit using the AC ammeter 116b. Thus, the lower electrical conductivity measuring unit 116 measures the electrical conductivity of the soil extract contained in the extract containing container 112A in accordance with an instruction from the control unit 111D.

  In particular, the electrodes 502a and 502b and the lower electrical conductivity measuring unit 116 are accommodated in the extract storage container 112D after the liquid sample analyzer 100D measures the concentration of the soil extract stored in the extract storage container 112D. It can be used when waste soil extract is drained.

  Next, referring to FIG. 15, the liquid sample analyzer 100D measures the concentration of the soil extract stored in the extract storage container 112D and then drains the liquid (process discharged from the extract storage container 112D). Will be described. FIG. 15 is a flowchart showing the flow of a process in which the liquid sample analyzer 100D discharges the soil extract stored in the extract storage container 112D.

  When the liquid sample analyzer 100D executes the processing from steps S1 to S15 (see FIG. 9) and the concentration measurement of the soil extract is completed, the liquid sample analyzer 100D is next moved to the chip 102 by the operator. It is taken out from the liquid sample analyzer 100D, and a waste liquid tray (not shown) is set in the liquid sample analyzer 100D (step S31). When the waste liquid tray is set, next, in response to an instruction from the liquid supply control unit 104, the extract supply mechanism 120 is driven to discharge the soil extract remaining in the extract storage container 112D to the waste liquid tray. Is started (step S32). While the extract supply mechanism 120 is discharging the soil extract from the extract storage container 112D to the waste liquid tray, the lower electrical conductivity measurement determination unit 108 measures the electrical conductivity by the lower electrical conductivity measurement unit 116. A result is acquired and it is judged from the said measurement result whether the measurement of electrical conductivity is possible (step S33).

  When the level of the soil extract is higher than the electrodes 502a and 502b, and the lower electrical conductivity measurement unit 116 measures the electrical conductivity, the electrical conductivity measurement determination unit 108 determines the electrical conductivity. Is determined to be possible (Yes in step S33), the liquid supply control unit 104 continues to drive the extract supply mechanism 120. That is, the process returns to step S32.

  In step S33, when the level of the soil extract in the extract storage container 112D becomes lower than the electrodes 502a and 502b, the lower conductivity measurement unit 116 cannot measure the conductivity. The determination unit 108 determines that the electrical conductivity cannot be measured (No in step S33), and discharges the soil extract remaining in the pump 120a and the tube 120b of the extract supply mechanism 120. The control unit 104 drives the extract supply mechanism 120 for a predetermined time (step S34).

  Since the amount of the soil extract remaining in the pump 120a and the tube 120b of the extract supply mechanism 120 is known, it is necessary to discharge the soil extract remaining in the pump 120a and the tube 120b of the extract supply mechanism 120. The time to become is also known. Therefore, the liquid supply control unit 104 can prevent the soil extract from remaining in the extract supply mechanism 120 by driving the extract supply mechanism 120 for a predetermined time. Further, the liquid supply control unit 104 can be prevented from driving the extract supply mechanism 120 more than necessary.

  Next, after the extract supply mechanism 120 discharges the soil extract in the extract supply mechanism 120, that is, after the control unit 111D determines that the electrical conductivity cannot be measured, the liquid sample analysis is performed. The device 100D notifies the operator that the waste liquid processing is completed by using a buzzer, a lamp, a liquid crystal display, or the like (S35). Thereafter, the waste liquid tray is taken out from the liquid sample analyzer 100D by the operator (S36), and the waste liquid processing of the liquid sample analyzer 100D is completed.

  As described above, the liquid sample analyzer 100D according to the present embodiment includes the extract storage container 112D and the lower electrical conductivity measuring unit 116, so that after the waste liquid treatment, the extract storage container 112D and the extract supply mechanism. The soil extract is configured not to remain in 120.

  According to said structure, it can prevent that the last soil extract remains at the time of the next density | concentration measurement. Thereby, it can prevent that a measurement precision falls at the time of the next density | concentration measurement.

[Embodiment 5]
The fifth embodiment of the present invention will be described below with reference to FIGS. 16 and 17. For convenience of explanation, members having the same functions as those described in the first to fourth embodiments are denoted by the same reference numerals and description thereof is omitted.

  FIG. 16 is a diagram showing an outline of the configuration of a liquid sample analyzer 100E according to Embodiment 5 of the present invention. As shown in FIG. 16, the liquid sample analyzer 100E includes a hydrogen ion concentration measurement unit 117 and a control instead of the lower electrical conductivity measurement unit 116 and the control unit 111D included in the liquid sample analysis device 100D (see FIG. 13). The liquid sample analyzer 100D is different from the liquid sample analyzer 100D in that the unit 111E is provided. The other configuration of the liquid sample analyzer 100E is the same as that of the liquid sample analyzer 100D. The liquid sample analyzer 100E is similar to the liquid sample analyzer 100D in that it includes an extraction liquid container 112D (see FIG. 14) that includes a pair of electrodes 502a and 502b in addition to the pair of electrodes 501a and 501b. It is.

  The control unit 111E is different from the control unit 111D in that a supply amount setting unit 107E and a measurement control unit 105E are provided instead of the supply amount setting unit 107A and the measurement control unit 105. Other configurations of the control unit 111E are the same as those of the control unit 111D.

  The liquid sample analyzer 100E according to this embodiment is that the component concentration of the soil extract is estimated based on the hydrogen ion concentration in addition to the electrical conductivity. Is different.

  The hydrogen ion concentration measurement unit 117 is connected to the electrodes 502a and 502b of the extraction liquid storage container 112D and also to the control unit 111E. The hydrogen ion concentration measurement unit 117 measures the hydrogen ion concentration of the soil extract stored in the extract storage container 112D according to an instruction from the measurement control unit 105E.

  Next, the procedure for measuring the component concentration of the soil extract in the liquid sample analyzer 100E will be described with reference to FIG. FIG. 17 is a flowchart showing a measurement procedure of the liquid sample analyzer 100E.

  Through the processes of steps S1 to S6, in step S6, the electrical conductivity measuring unit 115 measures the electrical conductivity of the soil extract contained in the extract containing container 112A, and the electrical conductivity measurement determining unit 108 acquires the electrical conductivity. If it is determined from the measurement result that the electrical conductivity can be measured (Yes in step S6), the measurement control unit 105E next sends an instruction signal for measuring the hydrogen ion concentration to the hydrogen ion concentration measuring unit 117. Output to. When the hydrogen ion concentration measurement unit 117 acquires an instruction signal for measuring the hydrogen ion concentration from the measurement control unit 105E, the hydrogen ion concentration measurement unit 117 measures the hydrogen ion concentration of the soil extract stored in the extract storage container 112A through the electrodes 502a and 502b. (Step S41). Then, the hydrogen ion concentration measurement unit 117 outputs the measurement value of the hydrogen ion concentration to the measurement control unit 105E.

  When the measurement control unit 105E acquires the measurement value of the electric conductivity measured by the electric conductivity measurement unit 115 and the measurement value of the hydrogen ion concentration measured by the hydrogen ion concentration measurement unit 117, then the supply amount setting is performed. The unit 107E sets the amount of the soil extract and pure water to be injected into each sample chamber 401, that is, the dilution rate, based on the measurement value of the electrical conductivity and the measurement value of the hydrogen ion concentration (step S42). ). Thereafter, the processing from step S8 to step S15 is performed. In addition, since the process from step S8 to step S15 is the same as that of Embodiment 1, description is abbreviate | omitted.

  Next, the setting method of the dilution rate in step S42 will be described in detail below. In the liquid sample analyzer 100A according to Embodiment 1, the measurement control unit 105 estimates the concentration of each component of the soil extract based on the electrical conductivity. This is because the nitrate nitrogen concentration contributes the most to the electrical conductivity in the soil extract. However, even if not as much as nitrate nitrogen, the hydrogen ion concentration also contributes accordingly to the electrical conductivity. For this reason, nitrate nitrogen and hydrogen ion concentrations cannot be accurately estimated only by measuring electrical conductivity.

  Therefore, in the present embodiment, the hydrogen ion concentration measurement unit 117 further measures the hydrogen ion concentration in addition to measuring the electrical conductivity in accordance with an instruction from the measurement control unit 105E. Then, the supply amount setting unit 107E calculates the dilution rate using the two parameters of the electrical conductivity and the hydrogen ion concentration measured by the hydrogen ion concentration measuring unit 117.

  Here, the hydrogen ion concentration is a so-called acid / alkaline degree, and the hydrogen ion concentration on the log scale is PH.

  Specifically, the hydrogen ion concentration measurement unit 117 measures the hydrogen ion index (PH) as the hydrogen ion concentration in addition to the electrical conductivity. Then, the supply amount setting unit 107E calculates a base saturation estimation value using the following equation (4).

Estimated value of base saturation = 35.8 × (pH + EC) −130.4 (4)
In addition, PH is a hydrogen ion index | exponent, EC is electrical conductivity (mS / cm). In the present embodiment, the supply amount setting unit 107E calculates the electrical conductivity (EC) using the formula (2). The supply amount setting unit 107E may calculate the electrical conductivity (EC) in consideration of the hydrogen ion index (PH) measured by the hydrogen ion concentration measurement unit 117 while using Equation (2).

  The supply amount setting unit 107E sets the dilution rate from the estimated base saturation obtained by the above equation (4).

  Furthermore, the supply amount setting unit 107E is configured so that, based on the base saturation estimated value, each sample in the soil extract so as to have a concentration at which absorbance measurement is possible even for components other than nitrate nitrogen. The amount of soil extract and pure water to be injected into the chambers 401-a to 401-f, that is, the dilution rate is set.

  In addition, the total value of equivalent concentrations of calcium, magnesium, and potassium is divided by the estimated value of base saturation, and multiplied by 100 to obtain a cation exchange capacity (CEC: Cation) indicating the size of the ability to adsorb and retain cations. It is known that (Exchange Capacity) can be obtained. By knowing the cation exchange capacity, it is possible to perform fertilizer design in consideration of soil fertility and to perform more accurate soil design.

  As described above, the liquid sample analyzer 100E further includes the hydrogen ion concentration measurement unit 117 that measures the hydrogen ion concentration of the soil extract stored in the extract storage container 120D, and the supply amount setting unit 107E includes the electric conductivity. Based on the electrical conductivity measured by the measurement unit 115 and the hydrogen ion concentration measured by the hydrogen ion concentration measurement unit 117, the amount of the soil extract supplied by the extract supply mechanism 120 and the dilution supply mechanism 121. To control the ratio with the amount of diluent supplied.

  Here, as described above, the hydrogen ion concentration contributes to the electrical conductivity. Therefore, according to the above configuration, the supply amount setting unit 107E is configured to supply the amount of the soil extract supplied by the extract supply mechanism 120 and supply of the diluted solution based only on the electric conductivity measured by the electric conductivity measuring unit 115. Compared with the case where the ratio with the amount of the diluent supplied by the mechanism 121 is controlled, the soil extract can be diluted more accurately so as to be in the optimum concentration range. Thereby, the component of a soil extract can further be analyzed reliably and correctly.

[Summary]
The liquid sample analyzers 100A to 100E according to the first aspect of the present invention dilute a sample container (extract liquid container 112A, 112D) that stores a liquid sample (soil extract) and the liquid sample (soil extract). A diluent container (diluent container 113) for containing a diluent, a measurement container (chip 102) for containing a measurement reagent, and a measurement unit (electric conduction) for measuring the electrical conductivity of the liquid sample (soil extract) Degree measuring unit 115), a sample supply mechanism (extraction liquid supply mechanism 120) for supplying the liquid sample (soil extract) to the measurement container (chip 102), and the dilution liquid to the measurement container (chip 102). Measure the light transmission amount of the diluted solution supply mechanism 121 to be supplied, the measurement reagent mixed in the measurement container (chip 102), the liquid sample (soil extract), and the mixed solution of the diluted solution, and The analysis unit (measurement control unit 105, measurement unit 109A, 109B) for analyzing at least one component of the body sample (soil extract) and the electrical conductivity measured by the measurement unit (electrical conductivity measurement unit 115) Based on the control unit (supply) that controls the ratio between the amount of the liquid sample (soil extract) supplied by the sample supply mechanism (extract solution supply mechanism 120) and the amount of the diluent supplied by the diluent supply mechanism 121. Quantity setting units 107A, 107C, and 107E).

  According to said structure, the said measurement part measures the electrical conductivity of the said liquid sample accommodated in the said sample container. Then, the control unit, based on the electrical conductivity measured by the measurement unit, the amount of the liquid sample that the sample supply mechanism supplies from the sample container to the measurement container, and the dilution liquid supply mechanism that is the dilution The ratio of the amount of diluent supplied from the container to the measurement container is controlled. Thereby, the liquid sample diluted with the ratio controlled by the control unit and the measurement reagent are mixed in the measurement container. The analysis unit measures at least one component of the liquid sample by measuring the light transmission amount of the liquid sample that has become possible to measure the light transmission amount by mixing the measurement reagent.

  According to this, even when a liquid sample having a high component concentration is stored in the sample container so that the analysis unit cannot measure the amount of light transmission, the measurement unit does not measure the liquid sample stored in the sample container. In order to measure the electrical conductivity, the concentration of the rough component of the liquid sample can be calculated. The analysis unit can measure the light transmission amount of the diluted liquid sample by the control unit controlling the ratio based on the electric conductivity of the liquid sample accommodated in the sample container. . For this reason, the analysis unit can analyze at least one component of the liquid sample in an optimum concentration range in which the amount of light transmission rapidly changes according to the increase or decrease of the concentration of the component of the liquid sample.

  As described above, according to the above configuration, the analysis unit can prevent the analysis of the components of the liquid sample from failing or the analysis accuracy can be prevented from being lowered. And can be analyzed accurately.

  In the liquid sample analyzers 100A to 100E according to aspect 2 of the present invention, in the above aspect 1, the measurement container (chip 102) includes a mixing chamber (reagent chamber 403) in which the measurement reagent is preliminarily sealed. An inlet (opening 407) for injecting a liquid sample (soil extract) and the diluent is formed in the measurement container (chip 102) in communication with the mixing chamber (reagent chamber 403), and The sample supply mechanism (extract solution supply mechanism 120) supplies the liquid sample (soil extract) to the mixing chamber (reagent chamber 403) in which the measurement reagent is sealed in advance via the inlet (opening 407). The diluent supply mechanism 121 is preferably configured to supply the diluent through the inlet (opening 407) to a mixing chamber (reagent chamber 403) in which the measurement reagent is sealed in advance.

  According to the above configuration, the sample supply mechanism supplies the liquid sample to the mixing chamber in which the measurement reagent is sealed in advance via the injection port. The diluent supply mechanism supplies the diluent through the inlet to a mixing chamber in which the measurement reagent is previously sealed. Thereby, the measurement reagent can be mixed in the mixing chamber while diluting the liquid sample with the diluent. Thus, the measurement reagent is sealed in the mixing chamber in advance. For this reason, it is not necessary to enclose the measurement reagent in the mixing chamber every time the component of the liquid sample is analyzed. Thereby, complication of work can be prevented.

  In the liquid sample analyzer 100B according to aspect 3 of the present invention, in the above aspect 1 or aspect 2, the analysis unit (measurement control unit 105, measurement unit 109A, 109B) includes the measured light transmission amount and the Preferably, the composition of the liquid sample is analyzed based on the ratio between the amount of the liquid sample and the amount of the diluent controlled by the control unit.

  According to the above configuration, the analysis unit calculates the components of the liquid sample based on the measured light transmission amount and the ratio between the amount of the liquid sample controlled by the control unit and the amount of the diluent. analyse. According to this, it is possible to analyze the components of the liquid sample accommodated in the sample container before dilution. For this reason, it is possible to analyze the components of the liquid sample more easily and accurately.

  Liquid sample analyzers 100A to 100E according to aspect 4 of the present invention include, in any one aspect of aspects 1 to 3, the liquid sample (soil extract) includes a first component and a second component different from each other, A measurement reagent includes a first reagent corresponding to the first component and a second reagent corresponding to the second component, and the measurement container (chip 102) contains a first measurement chamber (reagent) One of the chambers 403-a to 403-f) and a second measurement chamber (the other one of the reagent chambers 403-a to 403-f) containing the second reagent, The control unit (supply amount setting unit 107A, 107C, 107E) is configured so that the electrical conductivity measured by the measurement unit (electrical conductivity measurement unit 115) and a first correlation determined corresponding to the first component Based on the function, the sample container (extract liquid container 1 2A, 112D), and the concentration of the first component in the first measurement chamber (one of the reagent chambers 403-a to 403-f) is the first measurement chamber (2A, 112D). The sample supply mechanism (extract solution supply mechanism 120) causes the first measurement chamber (reagent chamber 403) to have an appropriate measurement concentration of the first reagent in one of the reagent chambers 403-a to 403-f. -A to 403-f) of the liquid sample (soil extract) supplied to the first measurement chamber (reagent chambers 403-a to 403-f) by the diluent supply mechanism 121. And the ratio of the amount of the diluent supplied to one of the sample containers (based on the electric conductivity and a second correlation function determined corresponding to the second component). The concentration of the second component in the chip 102) is estimated, and the second measurement chamber (reagent chamber 403- Measurement of the second reagent in the second measurement chamber (the other one of the reagent chambers 403-a to 403-f). Liquid sample (soil) supplied to the second measurement chamber (the other one of the reagent chambers 403-a to 403-f) by the sample supply mechanism (extract liquid supply mechanism 120) so as to obtain an appropriate concentration. The ratio of the amount of the extract) and the amount of the diluent supplied to the second measurement chamber (the other one of the reagent chambers 403-a to 403-f) by the diluent supply mechanism 121 is controlled. A configuration is preferred.

  According to the above configuration, the liquid sample includes a first component and a second component different from each other, and the measurement reagent includes a first reagent corresponding to the first component and a second reagent corresponding to the second component. And the measurement container has a first measurement chamber for storing the first reagent and a second measurement chamber for storing the second reagent. According to this, in the measurement container, the liquid sample and the first reagent are mixed in the first measurement chamber, and the liquid sample and the second reagent are mixed in the second measurement chamber. To do. For this reason, the analysis unit includes a light transmission amount in a liquid mixture of the liquid sample mixed in the first measurement chamber and the first reagent, and the liquid sample mixed in the second measurement chamber. The light transmission amount in the mixed solution with the second reagent can be measured. As a result, among the liquid samples contained in one measurement container, a plurality of components of the first component and the second component can be analyzed, so that the liquid sample can be more easily and efficiently obtained. Components can be analyzed.

  Here, the first component analyzed by the liquid sample mixed with the first reagent in the first measurement chamber and the second component analyzed by the liquid sample mixed with the second reagent in the second measurement chamber. Since the components are different from each other, when the analysis unit measures the light transmission amount, the optimum concentration range differs between when the first component is measured and when the second component is measured.

  Therefore, the control unit determines the concentration of the first component in the sample container based on the electrical conductivity measured by the measurement unit and the first correlation function determined corresponding to the first component. The liquid sample supplied to the first measurement chamber by the sample supply mechanism is estimated so that the concentration of the first component in the first measurement chamber becomes the appropriate measurement concentration of the first reagent in the first measurement chamber. The ratio of the amount and the amount of diluent supplied to the first measurement chamber by the diluent supply mechanism is controlled, and the second correlation function is determined corresponding to the electrical conductivity and the second component. Based on the above, the concentration of the second component in the sample container is estimated, and the concentration of the second component in the second measurement chamber is the measurement appropriate concentration of the second reagent in the second measurement chamber. The amount of liquid sample supplied to the second measurement chamber by the sample supply mechanism To control the ratio between the amount of diluent fed to the second measurement chamber by dilution liquid supply means.

  Thereby, when the analysis unit measures the light transmission amount, the liquid sample in the first measurement chamber and the liquid sample in the second measurement chamber are diluted to an optimum concentration range. For this reason, the analysis unit can accurately analyze the first component and the second component which are different from each other in the liquid sample.

  In the liquid sample analyzers 100A to 100E according to aspect 5 of the present invention, in the aspect 4, it is preferable that the first correlation function and the second correlation function are linear functions.

  According to the above configuration, since the first correlation function and the second correlation function are linear functions, the control unit estimates the concentrations of the first component and the second component of the liquid sample by a simple calculation. can do. Thereby, the liquid sample supplied to each of the first measurement chamber and the second measurement chamber can be efficiently diluted to have a measurement appropriate concentration.

  In the liquid sample analyzers 100A to 100E according to aspect 6 of the present invention, in the aspect 5, the first component is nitrate nitrogen, and the slope of the first correlation function is larger than the slope of the second correlation function. A configuration is preferred.

  Here, it can be considered that the electrical conductivity measures the total of the effects of the respective concentrations of all kinds of ions dissolved in the moisture contributing to the electrical conduction. For this reason, usually, even if the electrical conductivity is measured, it cannot be accurately determined to what extent the concentration of which kind of ions contributed to the electrical conduction.

  However, when the liquid sample is a soil extract, the electrical conductivity of the soil extract has a strong correlation with the concentration of nitrate nitrogen. Therefore, when the first component is nitrate nitrogen, the slope of the first correlation function is made larger than the slope of the second correlation function. Thereby, even if it is a case where the density | concentration of nitrate nitrogen is too high in a soil extract, the density | concentration of nitrate nitrogen can be made into a measurement appropriate density | concentration. Thereby, the said analysis part can measure the density | concentration of nitrate nitrogen which is a 1st component among the said liquid samples correctly. On the other hand, by making the slope of the second correlation function smaller than the slope of the first correlation function, the second component in the component of the liquid sample is influenced by the change of nitrate nitrogen, which is the first component, and the dilution rate is increased. Unnecessary changes can be suppressed. As a result, the concentrations of the first component and the second component can be accurately measured.

  The liquid sample analyzer 100C according to aspect 7 of the present invention may have a configuration in which the slope of the second correlation function is zero in aspect 6 described above.

  According to the above configuration, the dilution rate of the second component is constant regardless of the electric conductivity. As a result, the concentration of nitrate nitrogen in the liquid sample can be prevented from affecting the dilution rate of the second component regardless of the concentration of nitrate nitrogen. Therefore, it can prevent that the measurement precision of the density | concentration of a 2nd component falls.

  The liquid sample analyzer 100E according to Aspect 8 of the present invention is the hydrogen ion of the liquid sample (soil extract) contained in the sample container (extract liquid container 120D) in any one of the above aspects 1 to 7. The apparatus further includes a hydrogen ion concentration measurement unit 117 that measures the concentration, and the control unit (supply amount setting unit 107E) includes the electrical conductivity measured by the measurement unit (electrical conductivity measurement unit 115) and the hydrogen ion concentration. Based on the hydrogen ion concentration measured by the measurement unit 117, the amount of liquid sample (soil extract) supplied by the sample supply mechanism (extract solution supply mechanism 120) and the dilution solution supply mechanism 121 are supplied. It is preferable that the ratio is controlled with respect to the amount of the diluent.

  Here, the hydrogen ion concentration contributes to electrical conductivity. So, according to said structure, the said control part is the electrical conductivity measured by the said measurement part, and the hydrogen ion concentration of the liquid sample accommodated in the said sample container measured by the said hydrogen ion concentration measurement part. Based on the above, the ratio between the amount of the liquid sample supplied by the sample supply mechanism and the amount of the diluent supplied by the diluent supply mechanism is controlled. Accordingly, the control unit determines the ratio between the amount of the liquid sample supplied by the sample supply mechanism and the amount of the diluent supplied by the diluent supply mechanism based only on the electrical conductivity measured by the measurement unit. As compared with the case of controlling the above, the liquid sample can be diluted more accurately so as to be in the optimum concentration range. Thereby, the components of the liquid sample can be analyzed reliably and accurately.

  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. Furthermore, a new technical feature can be formed by combining the technical means disclosed in each embodiment.

  INDUSTRIAL APPLICABILITY The present invention can be used for a liquid sample analyzer, particularly a liquid sample analyzer suitable for analyzing soil components collected from a field or the like. Since the analysis of the soil supported by the data can be easily performed, it is possible to prevent excessive input and shortage of fertilizer and to perform optimum fertilization management of the field. Therefore, the effect which reduces the complexity and economic burden in an analysis of a farmer can be expected.

100A to 100E Liquid sample analyzer 101 Light emitting unit 102 Chip (measuring container)
103 Photodetector 104 Liquid supply controller 105, 105E Measurement controller (analyzer)
106 Rotation Drive Unit 107A, 107C, 107E Supply Amount Setting Unit 108 Lower Electrical Conductivity Measurement Judgment Unit 109A, 109B Measurement Unit (Analysis Unit)
111A, 111C to E Control unit 112A, 112D Extract liquid container (sample container)
113 Diluent container (diluent container)
115 Electrical conductivity measurement unit (measurement unit)
117 Hydrogen ion concentration measuring unit 120 Extract supply mechanism (sample supply mechanism)
121 diluent supply mechanism 403, 403-a to 403-f reagent chamber (mixing chamber, first measurement chamber, second measurement chamber)
407, 407-a to 407-f opening (injection port)

Claims (8)

A sample container containing a liquid sample;
A diluent container containing a diluent for diluting the liquid sample;
A measurement container containing a measurement reagent;
A measuring unit for measuring the electrical conductivity of the liquid sample;
A sample supply mechanism for supplying the liquid sample to the measurement container;
A diluent supply mechanism for supplying the diluent to the measurement container;
An analysis unit for analyzing the at least one component of the liquid sample by measuring a light transmission amount of the mixed solution of the measurement reagent, the liquid sample, and the dilution liquid mixed in the measurement container;
A controller for controlling a ratio between the amount of the liquid sample supplied by the sample supply mechanism and the amount of the diluent supplied by the diluent supply mechanism based on the electrical conductivity measured by the measurement unit; A liquid sample analyzer characterized by the above. The measurement container has a mixing chamber in which the measurement reagent is enclosed in advance,
An inlet for injecting the liquid sample and the diluent is formed in the measurement container in communication with the mixing chamber;
The sample supply mechanism supplies the liquid sample via the inlet to a mixing chamber in which the measurement reagent is preliminarily sealed,
The liquid sample analyzer according to claim 1, wherein the diluent supply mechanism supplies the diluent via the inlet to a mixing chamber in which the measurement reagent is sealed in advance.   The said analysis part analyzes the component of the said liquid sample based on the ratio of the quantity of the liquid sample controlled by the said control part, and the quantity of the liquid sample, and the quantity of a dilution liquid. The liquid sample analyzer described in 1. The liquid sample includes a first component and a second component different from each other;
The measurement reagent includes a first reagent corresponding to the first component and a second reagent corresponding to the second component;
The measurement container has a first measurement chamber that houses the first reagent, and a second measurement chamber that houses the second reagent,
The control unit estimates the concentration of the first component in the sample container based on the electrical conductivity measured by the measurement unit and a first correlation function determined corresponding to the first component. The amount of the liquid sample supplied to the first measurement chamber by the sample supply mechanism so that the concentration of the first component in the first measurement chamber becomes the appropriate measurement concentration of the first reagent in the first measurement chamber. The ratio of the dilution liquid supplied to the first measurement chamber by the dilution liquid supply mechanism is controlled, and the electrical conductivity and the second correlation function determined corresponding to the second component Based on this, the concentration of the second component in the sample container is estimated, and the sample supply is performed so that the concentration of the second component in the second measurement chamber becomes the appropriate measurement concentration of the second reagent in the second measurement chamber. The amount of liquid sample supplied to the second measurement chamber by the mechanism and the diluent Liquid sample analyzer according to any one of claims 1 to control the ratio between the amount of diluent fed to the second measurement chamber by feeding mechanism 3.   The liquid sample analyzer according to claim 4, wherein the first correlation function and the second correlation function are linear functions. The first component is nitrate nitrogen;
The liquid sample analyzer according to claim 5, wherein a slope of the first correlation function is larger than a slope of the second correlation function.   The liquid sample analyzer according to claim 6, wherein the slope of the second correlation function is zero. A hydrogen ion concentration measurement unit that measures the hydrogen ion concentration of the liquid sample contained in the sample container;
The controller controls the amount of liquid sample supplied by the sample supply mechanism and the dilution based on the electrical conductivity measured by the measuring unit and the hydrogen ion concentration measured by the hydrogen ion concentration measuring unit. The liquid sample analyzer according to any one of claims 1 to 7, which controls a ratio with respect to an amount of a diluent supplied by a liquid supply mechanism.

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