Water quality analysis system, sensor module, calibration device, and calibration method for water quality analysis system

Abstract

The present invention is a water quality analysis system (100) which performs calibration of the water quality analysis system without using organic fluorescent substances such as phenanthrene, and analyzes the measurement target components contained in a liquid sample using fluorescence spectroscopy. The water quality analysis system (100) comprises: a light irradiation unit (2) which irradiates the liquid sample with light having an excitation wavelength of the measurement target components; a light detection unit (3) which detects the fluorescence of the measurement target components from the liquid sample; a computing device (4) which uses the fluorescence intensity obtained by the light detection unit (3) to calculate the concentration of the measurement target components; and a solid fluorescent reference component (5) which is arranged in the light path between the light irradiation unit (2) and the light detection unit (3) during calibration and emits fluorescence due to the light of the light irradiation unit (2).

Description

Technical Field

[0001] The present invention relates to a water quality analysis system for detecting fluorescence generated from a measurement target component contained in a liquid sample and measuring the concentration of the measurement target component, a sensor module used in the water quality analysis system, and a calibration method for the water quality analysis system. Background Art

[0002] In order to remove sulfur oxides (SO X ), using an exhaust gas cleaning system (EGCS). The EGCS has a SO X Scrubber, from SO X The scrubber discharges scrubber wastewater containing polycyclic aromatic hydrocarbons (PAHs). Among the PAHs, phenanthrene is used as a monitoring standard according to the EGCS guidelines established by the International Maritime Organization (IMO).

[0003] As a device for measuring the concentration of phenanthrene in the scrubber wastewater, a PAH meter using fluorescence spectroscopy is used. The phenanthrene concentration obtained by the PAH meter is used as the PAH concentration equivalent to phenanthrene, and it must be below a predetermined allowable concentration value, so it is necessary to calibrate the PAH meter or perform a sensitivity check at a predetermined timing.

[0004] Conventionally, as a calibration method or a sensitivity test method of a PAH meter using fluorescence spectroscopy, a reference solution in which phenanthrene is adjusted to a predetermined concentration is used.

[0005] However, phenanthrene is difficult to dissolve in solvents (pure water for reagents), and it is difficult to prepare a reference solution with good reproducibility. In addition, phenanthrene is toxic and is not easy to use on site. Moreover, phenanthrene is an organic fluorescent substance that fades due to light, so its use time is limited and long-term continuous measurement cannot be performed. In addition, pure water for reagents is difficult to obtain on board.

[0006] Prior art literature

[0007] Patent Literature

[0008] Patent Document 1: Japanese Patent Application Publication No. 2015-137983 Summary of the invention

[0009] Technical issues

[0010] Therefore, the present invention has been made to solve the above-mentioned problems, and a main object of the present invention is to calibrate a water quality analysis system without using an organic fluorescent substance such as phenanthrene.

[0011] Technical Solution

[0012] That is, the water quality analysis system of the present invention is a water quality analysis system that uses fluorescence spectroscopy to analyze the measurement target components contained in the liquid sample, and is characterized in that it comprises: a light irradiation unit that irradiates the above-mentioned liquid sample with light having an excitation wavelength of the above-mentioned measurement target components; a light detection unit that detects the fluorescence of the above-mentioned measurement target components from the above-mentioned liquid sample; a computing device that uses the fluorescence intensity obtained by the above-mentioned light detection unit to calculate the concentration of the above-mentioned measurement target components; and a solid fluorescent reference component that is set in the light path between the above-mentioned light irradiation unit and the above-mentioned light detection unit during calibration, and emits fluorescence due to the light of the above-mentioned light irradiation unit.

[0013] According to the water quality analysis system, by setting a solid fluorescent reference component in the path of light between the light irradiation part and the light detection part during calibration, the water quality analysis system can be calibrated without using the previous reference liquid. That is, various problems caused by the use of organic fluorescent substances such as phenanthrene can be solved. Compared with organic fluorescent materials, solid fluorescent reference components do not fade, are non-toxic, have high uniformity and high heat resistance, so they can improve the operability and convenience in calibration. In addition, the storage method of the fluorescent reference component also becomes simple, and the life of the fluorescent reference component can also be ignored. Furthermore, maintenance using the fluorescent reference component can be performed simply and quickly.

[0014] The fluorescent reference component is not particularly limited as long as it is a solid component. For example, fluorescent glass formed by doping rare earth ions in glass, fluorescent resin bodies formed by doping ceramic fluorescent bodies in organic polymer materials such as acrylic acid, or components formed by coating ceramic fluorescent body powder on glass components or organic polymer material components, etc. Among them, fluorescent glass with high transparency and high optical uniformity is preferably used. In addition, the solid fluorescent reference component can also be a gel-like component.

[0015] As a specific embodiment of the water quality analysis system, it is considered to further include a sensor head, which accommodates the light irradiation unit and the light detection unit and is immersed in the liquid sample. In this structure, in order to improve the workability of calibration using the fluorescent reference component, it is preferred that the fluorescent reference component is installed in the sensor head in a detachable manner.

[0016] As a liquid sample analyzed by the water quality analysis system of the present invention, scrubber wastewater discharged from a ship can be cited. In this case, it is preferred that the light irradiation unit irradiates light having an excitation wavelength of phenanthrene contained in the scrubber wastewater, the light detection unit detects the fluorescence of the phenanthrene, and the computing device calculates a PAH concentration corresponding to the phenanthrene contained in the scrubber wastewater using the fluorescence intensity obtained by the light detection unit.

[0017] Unlike a reference solution whose concentration of a component to be measured is known, the fluorescent reference component does not have a predetermined reference value from the beginning. Therefore, it is necessary to assign a value to the fluorescent reference component using a reference solution whose concentration of a component to be measured is known.

[0018] Therefore, it is preferred that the water quality analysis system of the present invention also includes a storage unit, which stores relationship data for correction representing the relationship between the fluorescence intensity obtained using a reference solution with a known concentration of the above-mentioned measurement object component and the fluorescence intensity obtained using the above-mentioned fluorescence reference component, and the above-mentioned computing device uses the fluorescence intensity of the above-mentioned fluorescence reference component obtained by the above-mentioned light detection unit during calibration and the above-mentioned relationship data for calibration.

[0019] When a fluorescent reference component is used as in the present invention, in order to suppress the deviation of the fluorescence amount of the fluorescent reference component and make the fluorescence amount incident to the light detection unit fall within a predetermined range, it is necessary to prepare ND filters with various attenuation rates and select an ND filter with a suitable attenuation rate for use. However, the need to select an ND filter with a suitable attenuation rate makes the operation complicated. Therefore, it is preferred to further include an angle changing mechanism, which changes the inclination angle of the fluorescent reference component relative to the light irradiation unit and the light detection unit. It is a component that is applied to the situation that the amount of excited fluorescence changes due to the change in the angle of the incident excitation light in the fluorescent reference component such as fluorescent glass. By changing the inclination angle of the fluorescent reference component, the fluorescence amount detected by the light detection unit can be continuously changed. As a result, there is no need to prepare ND filters with various attenuation rates, and the fluorescence amount incident to the light detection unit can be included in a predetermined range simply by changing the angle.

[0020] In order to facilitate adjustment of the fluorescent reference member to a predetermined angle, the angle changing mechanism preferably changes the inclination angle of the fluorescent reference member in stages. In order to freely set the inclination angle of the fluorescent reference member, the angle changing mechanism preferably changes the inclination angle of the fluorescent reference member continuously.

[0021] As a specific embodiment of the angle changing mechanism, it is considered that the angle changing mechanism includes a reference member holding the fluorescent reference member, and an adapter body fixed relative to the light irradiation unit and the light detection unit during calibration and rotatably supporting the reference member holding body.

[0022] In addition, the calibration device of the present invention is used for calibrating a water quality analysis system, which uses fluorescence spectroscopy to analyze the measurement target components contained in a liquid sample, and the water quality analysis system comprises: a light irradiation unit, which irradiates the liquid sample with light having an excitation wavelength of the measurement target components; and a light detection unit, which detects the fluorescence of the measurement target components from the liquid sample, and the calibration device comprises: a solid fluorescent reference component, which emits fluorescence due to the light of the light irradiation unit; and a calibration fixture, which holds the fluorescent reference component and sets the fluorescent reference component in the path of light between the light irradiation unit and the light detection unit during calibration.

[0023] In addition, a sensor module used in a water quality analysis system that analyzes a measurement target component contained in a liquid sample using fluorescence spectroscopy is also one embodiment of the present invention. That is, the sensor module of the present invention is characterized in that it comprises: a light irradiation unit that irradiates the liquid sample with light having an excitation wavelength of the measurement target component; a light detection unit that detects the fluorescence of the measurement target component from the liquid sample; a sensor head that accommodates the light irradiation unit and the light detection unit and is immersed in the liquid sample; and a fluorescent reference component that is mounted on the sensor head during calibration and emits fluorescence due to the light of the light irradiation unit.

[0024] Furthermore, the calibration method of the water quality analysis system of the present invention is a calibration method of the water quality analysis system which utilizes fluorescence spectroscopy to analyze the measurement target components contained in the liquid sample, and is characterized in that the water quality analysis system comprises: a light irradiation unit which irradiates the liquid sample with light having an excitation wavelength of the measurement target components; a light detection unit which detects the fluorescence of the measurement target components from the liquid sample; and a computing device which uses the fluorescence intensity obtained by the light detection unit to calculate the concentration of the measurement target components, and during calibration, the calibration method performs calibration by setting a fluorescent reference component which emits fluorescence due to the light of the light irradiation unit in the light path between the light irradiation unit and the light detection unit.

[0025] As a specific correction method, it also includes a correction relationship data generating step, which generates correction relationship data representing the relationship between the fluorescence intensity of the reference liquid with a known concentration of the above-mentioned measurement object component obtained by a reference system which serves as a reference for the above-mentioned water quality analysis system and the fluorescence intensity of the above-mentioned fluorescence reference component obtained by the above-mentioned water quality analysis system. During calibration, the correction method sets the above-mentioned fluorescence reference component in the light path between the above-mentioned light irradiation part and the above-mentioned light detection part, and uses the fluorescence intensity obtained by the above-mentioned light detection part and the correction relationship data obtained in the above-mentioned correction relationship data generating step for correction.

[0026] As the above-mentioned correction relationship data generating step, it is considered to include: a first relationship data generating step, generating first relationship data representing the relationship between the fluorescence intensity of the above-mentioned reference liquid obtained by the above-mentioned reference system and the fluorescence intensity of the above-mentioned fluorescent reference component obtained by the above-mentioned reference system; and a second relationship data generating step, generating second relationship data representing the relationship between the fluorescence intensity of the above-mentioned fluorescent reference component obtained by the above-mentioned reference system and the fluorescence intensity of the above-mentioned fluorescent reference component obtained by the above-mentioned water quality analysis system. The above-mentioned correction relationship data generating step uses the first relationship data obtained in the above-mentioned first relationship data generating step and the second relationship data obtained in the above-mentioned second relationship data generating step to generate the above-mentioned correction relationship data.

[0027] In order to ensure the traceability of calibration, the light detection unit of the above-mentioned reference system is preferably calibrated by an approved calibration agency.

[0028] Effects of the Invention

[0029] According to the present invention described above, it is possible to calibrate the water quality analysis system without using organic fluorescent substances such as phenanthrene. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 It is an overall schematic diagram of a water quality analysis system according to one embodiment of the present invention.

[0031] Figure 2 Schematic diagram showing the front end portion of the sensor head and the fluorescent glass adapter according to this embodiment.

[0032] Figure 3 This is a schematic diagram showing an example of a calibration method.

[0033] Figure 4 This is a diagram for explaining the procedure of generating correction relationship data.

[0034] Figure 5 It is a cross-sectional view showing an adapter having an angle changing mechanism according to a modified embodiment.

[0035] Figure 6 This is a graph showing the indication value of the sensor when the tilt angle is changed by the angle changing mechanism.

[0036] Explanation of symbols

[0037] 100…Water quality analysis system

[0038] 2...Light irradiation part

[0039] 3…Light detection unit

[0040] 4…Computing device

[0041] 401…Concentration calculation unit

[0042] 402... Storage

[0043] 403…Correction Department

[0044] 5…Fluorescent glass (fluorescent reference component)

[0045] 6…Sensor head

[0046] 7…Signal cable

[0047] 8…Adapter

[0048] 9…ND filter

[0049] 10…Beam splitter

[0050] 11…Optical window DETAILED DESCRIPTION

[0051] Hereinafter, a water quality analysis system according to an embodiment of the present invention will be described with reference to the drawings.

[0052] <1. Device composition>

[0053] The water quality analysis system 100 of this embodiment uses fluorescence spectroscopy as a method for measuring the measurement target components contained in the liquid sample, excites the measurement target components with excitation light, detects the fluorescence from the measurement target components generated by the excitation light, and measures the concentration of the measurement target components. Here, the liquid sample is obtained from, for example, SO2 X The scrubber wastewater discharged from the scrubber is a wastewater discharged from the scrubber. The component to be measured is phenanthrene in the wastewater.

[0054] Specifically, if Figure 1 As shown, the water quality analysis system 100 comprises: a light irradiation unit 2, which irradiates the liquid sample with light having an excitation wavelength of the measurement target component; a light detection unit 3, which detects the fluorescence of the measurement target component from the liquid sample; a computing device 4, which uses the fluorescence intensity obtained by the light detection unit 3 to calculate the concentration of the measurement target component; and a solid fluorescent reference component 5, which is set in the light path between the light irradiation unit 2 and the light detection unit 3 during calibration and emits fluorescence due to the light of the light irradiation unit 2.

[0055] Each part is described below.

[0056] The light irradiation unit 2 irradiates the excitation light of the excitation wavelength (254nm) of phenanthrene as the component to be measured, and the light irradiation unit 2 has an ultraviolet light source 21 that emits light in a wavelength region including the excitation wavelength (254nm) and a wavelength selection filter 22 that transmits the light of the excitation wavelength (254nm) from the light of the ultraviolet light source. By using the wavelength selection filter 22, the deviation of the excitation wavelength can be reduced, and the deviation of the bandwidth of the excitation wavelength can also be reduced.

[0057] The light detection unit 3 detects light of the fluorescence wavelength (360 nm) of phenanthrene, and includes a light detector 31 such as a photomultiplier tube (PMT) and a wavelength selection filter 32 that transmits light of the fluorescence wavelength (360 nm) from the light from the liquid sample. By using the wavelength selection filter 32, the deviation of the fluorescence wavelength can be reduced, and the deviation of the bandwidth of the fluorescence wavelength can also be reduced.

[0058] The light detection unit 3 of the present embodiment includes a monitoring photodetector 33 for monitoring the light amount of the light irradiation unit 2. As the photodetector 33, for example, a Si photodiode or a GaN ultraviolet detection element is used.

[0059] Moreover, the light irradiation unit 2 and the light detection unit 3 of the present embodiment are housed in the sensor head 6. A part or the whole of the sensor head 6 is immersed in the liquid sample, and the light irradiation unit 2 and the light detection unit 3 are housed at the front end. In the sensor head 6, the light irradiation unit 2 and the light detection unit 3 are configured to be coaxially illuminated using a beam splitter 10, and an optical window 11 is provided at the front end surface of the sensor head 6 to transmit the excitation light irradiated to the liquid sample and the fluorescence from the liquid sample. In addition, a signal cable 7 is connected to the base end, and the signal cable 7 transmits the fluorescence intensity signal obtained by the light detector 31 to the computing device 4.

[0060] The computing device 4 includes a concentration calculation unit 401 that obtains the fluorescence intensity signal transmitted from the photodetector 31 to calculate the PAH concentration corresponding to phenanthrene contained in the scrubber wastewater. Here, the concentration calculation unit 401 of the computing device 4 corrects the fluorescence intensity obtained by the photodetector 31 using the ultraviolet intensity obtained by the photodetector 33 to calculate the PAH concentration corresponding to phenanthrene.

[0061] The fluorescent reference member 5 is a fluorescent glass formed by doping rare earth ions in glass. For example, the fluorescent glass is a blue light-emitting glass containing divalent europium ions (Eu 2+ ) as a fluorescent active element (rare earth ion) of fluorophosphate glass. This fluorescent glass will not deteriorate due to storage or ultraviolet rays, and can be used repeatedly. In addition, fluorescent glass has high heat resistance, high transparency, high optical uniformity, and no toxicity.

[0062] Here, in order to reduce the decrease in fluorescence intensity due to the internal filter effect (IFE effect), it is preferable to use a plate-shaped fluorescent reference member rather than a block-shaped fluorescent reference member as the fluorescent reference member 5. The IFE effect refers to the absorption of excitation light and fluorescence by the fluorescent reference member itself.

[0063] The fluorescent reference member 5 is detachably mounted on the sensor head 6 and held by an adapter 8 as a calibration fixture. The fluorescent reference member 5 and the adapter 8 constitute a calibration device for calibrating the water quality analysis system 100. Furthermore, by mounting the adapter 8 on the front end of the sensor head 6, as shown in FIG. Figure 2 As shown, the fluorescent reference component 5 held in the adapter 8 is arranged opposite to the optical window 11 and is provided in the path of light between the light irradiation unit 2 and the light detection unit 3. In addition, the water quality analysis system 100 is calibrated in a state where the adapter 8 is mounted on the sensor head 6. It should be noted that the ND filter 9 may also be provided in the adapter 8. The ND filter 9 can attenuate the irradiation intensity when the fluorescence intensity is strong, and the distance between the optical window of the sensor head 6 and the fluorescent reference component 5 is set short, so that the adapter 8 can be miniaturized.

[0064] Furthermore, in order to calibrate the water quality analysis system 100 using the fluorescent reference component 5, the computing device 4 has: a storage unit 402, which stores calibration relationship data, wherein the calibration relationship data represents the relationship between the fluorescence intensity obtained using a reference solution with a known concentration of the component to be measured and the fluorescence intensity obtained using the fluorescent reference component 5; and a calibration unit 403, which calibrates the water quality analysis system 100 using the fluorescence intensity of the fluorescent reference component 5 obtained by the light detector 31 during calibration and the relationship data.

[0065] <2. Calibration Method of Water Quality Analysis System 100>

[0066] Next, a calibration method of the water quality analysis system 100 according to the present embodiment will be described.

[0067] First, the generation of calibration relationship data (calibration relationship data generation step) used for calibration of the water quality analysis system 100 will be described.

[0068] The calibration relationship data indicates the relationship between the fluorescence intensity of the reference solution having a known concentration of the measurement target component obtained by the reference system 200 and the fluorescence intensity of the fluorescent reference member 5 obtained by the water quality analysis system 100 .

[0069] Here, the reference system 200 refers to a system that serves as a reference for the water quality analysis system 100 that is the object of calibration, and uses a light detector (reference detector 31X) calibrated by an approved calibration agency. The optical system of the reference system 200 is the same as that of the water quality analysis system 100, and the physical conditions such as the configuration of the light source, wavelength selection filter, etc. are the same. In addition, the reference detector 31X is a detector whose detection wavelength and detection sensitivity have been verified by an approved calibration agency. It should be noted that as an approved calibration agency, for example, an operator approved by the National Institute of Standards and Technology (NIST) of the United States, the Certification System for the Technical Foundation of Product Evaluation (ASNITE), or an operator registered by the Joint Standards and Technology Calibration Operator Registration System (JCSS), etc.

[0070] The correction relationship data generating step includes the following steps (a) and (b).

[0071] (a) Generate a fluorescence intensity (fluorescence amount Sa, Figure 3 (B)) and the fluorescence intensity (fluorescence amount G, Figure 3 The first relationship data (α=Sa / G, Figure 4 (A)) (first relationship data generation step).

[0072] (b) Generates a fluorescence intensity (fluorescence amount G, Figure 3 (A)) and the fluorescence intensity (fluorescence amount Mg, Figure 3 The second relationship data (β=Mg / G, Figure 4 (B)) (second relational data generation step).

[0073] Then, the correction relationship data is generated using the first relationship data (α=Sa / G) obtained in the first relationship data generating step and the second relationship data (β=Mg / G) obtained in the second relationship data generating step.

[0074] Specifically, in order to make the water quality analysis system 100 to be calibrated equivalent to the reference system, the coefficient K is used, and the relationship of α=β×K=(Mg / G)×K is established. According to this relationship, K=Sa / Mg. By assigning this coefficient K to the fluorescent reference component 5, the water quality analysis system 100 can be calibrated. In other words, this coefficient K becomes the calibration relationship data obtained for each fluorescent reference component 5. This calibration relationship data is stored in the storage unit 402 of the computing device 4, for example, before the product is shipped.

[0075] Using the calibration relationship data obtained as described above, the indicated value (PAH concentration equivalent to phenanthrene) of the water quality analysis system 100 is checked regularly or at a predetermined timing, and is calibrated regularly or at a predetermined timing.

[0076] Specifically, the sensor head 6 is lifted from the pipe and / or storage tank through which the liquid sample flows, and the adapter 8 is mounted on the tip of the sensor head 6. In this state, the fluorescence from the fluorescent reference member 5 irradiated with the excitation light by the light irradiation unit 2 is detected by the photodetector 31. The calibration unit 403 of the computing device 4 calibrates the water quality analysis system 100 using the fluorescence intensity obtained by the photodetector 31 and the calibration relationship data stored in the storage unit 402.

[0077] <3. Effects of the present embodiment>

[0078] According to the water quality analysis system 100 of the present embodiment constructed in this way, when calibrating the water quality analysis system 100, by setting the solid fluorescent reference component 5 in the light path between the light irradiation unit 2 and the light detection unit 3, calibration can be performed without using the previous reference liquid. That is, various problems caused by the use of organic fluorescent substances such as phenanthrene can be solved. Compared with organic fluorescent materials, the solid fluorescent reference component 5 does not fade, has no toxicity, has high uniformity, and has high heat resistance, so it can improve the operability and convenience in calibration. In addition, the storage method of the fluorescent reference component 5 also becomes simple, and the life of the fluorescent reference component 5 can also be ignored. Furthermore, maintenance using the fluorescent reference component 5 can be performed simply and quickly.

[0079] In particular, when the PAH concentration equivalent to phenanthrene is managed on board using the water quality analysis system 100, the effect of improving the operability and convenience of the present embodiment becomes significant. In addition, in the water quality analysis system 100 of the present embodiment, traceability can be established, the reliability of the PAH concentration equivalent to phenanthrene is improved, and the reliability of the submitted data through the port state control (PSC) can be improved.

[0080] <4. Other variant implementations>

[0081] It should be noted that the present invention is not limited to the above-mentioned embodiments.

[0082] For example, the fluorescent reference component 5 in the above embodiment is fluorescent glass, but it can also be a fluorescent resin body made by doping ceramic fluorescent body in organic polymer materials such as acrylic acid, or a component made by coating ceramic fluorescent body powder on a glass component or an organic polymer material component. In addition, the fluorescent reference component 5 can also be a gel-like component added with ceramic fluorescent body.

[0083] In addition, the optical system of the light irradiation part 2 and the light detection part 3 in the above-mentioned embodiment is a coaxial illumination using a beam splitter, but it can also be an optical system configured in a manner that the optical axis of the light irradiation part 2 and the optical axis of the light detection part 3 intersect with each other, or it can be an optical system in which the light irradiation part 2 and the light detection part 3 are configured opposite to each other.

[0084] Furthermore, in the above-mentioned embodiment, a single excitation wavelength of light is irradiated to detect a single fluorescence wavelength of light, but a system may also be used in which a single excitation wavelength is irradiated to detect a plurality of fluorescence wavelengths of light. In this case, the fluorescence reference component 5 may have a fluorescence spectrum including the plurality of fluorescence wavelengths, or the water quality analysis system 100 may include a plurality of fluorescence reference components 5 corresponding to the respective fluorescence wavelengths. In addition, a mechanism capable of selecting light of the respective fluorescence wavelengths may be provided on the light detection unit 3 side.

[0085] In the above-described embodiment, the fluorescent reference member 5 is held by the adapter 8 , but the fluorescent reference member 5 may be independently mounted on the water quality analysis system 100 without being held by the adapter 8 .

[0086] Furthermore, in the configuration of the above-mentioned embodiment, it is also possible to configure the fluorescent reference member 5 so as to change the inclination angle with respect to the light irradiation section 2 and the light detection section 3. Specifically, it is considered that the adapter 8 as the calibration jig includes an angle changing mechanism 12 for changing the inclination angle of the fluorescent reference member 5 with respect to the light irradiation section 2 and the light detection section 3. The angle changing mechanism 12 is configured to be able to change the inclination angle of the fluorescent reference member 5 stepwise or continuously.

[0087] Specifically, if Figure 5 As shown, the angle changing mechanism 12 includes: a reference member holding body 121 that holds the fluorescent reference member 5; and an adapter body 122 that is fixed to the light irradiation unit 2 and the light detection unit 3 during calibration and supports the reference member holding body 121 so that it can rotate. The reference member holding body 121 is cylindrical in shape, and a mounting recess 121a for storing and mounting the fluorescent reference member 5 is formed on its side wall. In addition, a storage hole 122a is formed in the adapter body 122, and the storage hole 122a stores the cylindrical reference member holding body 121 so that it can rotate. The ND filter 9 is fixed to the adapter body 122, and a communication portion 122b that communicates with the storage hole 122a is formed at the lower part of the ND filter 9. It should be noted that the reference member holder 121 can be rotated using a rotation locking portion 121b (e.g., a flat-blade screwdriver groove) formed on its end surface when housed in the adapter body 122, thereby changing the inclination angle of the fluorescent reference member 5 relative to the light irradiation unit 2 and the light detection unit 3.

[0088] The above-mentioned angle changing mechanism 12 can change the amount of fluorescence detected by the light detection unit in at least two aspects. For example, when the measurement range is small (for example, 0 to 500 ppb), the inclination angle of the reference component holder 121 is increased to reduce the amount of fluorescence, and when the measurement range is large (for example, 0 to 5000 ppb), the inclination angle of the reference component holder 121 is reduced to increase the amount of fluorescence for correction. Consider changing the inclination angle corresponding to each water quality analysis system with such different measurement ranges. In addition, after correction, the above-mentioned angle changing mechanism 12 can also be used to change the inclination angle of the reference component holder 121, and the measured value at this time can be observed to check the linearity of the measured value of the water quality analysis system 100. It should be noted that in Figure 6 2 shows the indicated value when the tilt angle is changed by the angle changing mechanism 12 .

[0089] Furthermore, a reflector may be placed on the lower surface of the fluorescent reference member 5 (fluorescent glass). In addition, the shape (area) of the reflector placed on the lower surface of the fluorescent reference member 5 (fluorescent glass) may be changed.

[0090] Furthermore, the calibration jig (adapter 8) having the above-mentioned angle changing mechanism 12 can also be used as a tester for testing a sensor having the light irradiation unit 2 and the light detection unit 3. Specifically, by changing the inclination angle of the reference member holding body 121 by the above-mentioned angle changing mechanism 12, the sensor can be tested by checking whether the indicated value of the sensor changes accordingly.

[0091] In the above-described embodiment, the PAH concentration in the scrubber wastewater is measured, but the concentration of a measurement target component such as dissolved organic matter (DOM) contained in another liquid sample may be measured.

[0092] The water quality analysis system 100 of the above embodiment is an immersion type system, but may also be a batch cell type or flow cell type system in which a liquid sample is stored in a cell for measurement.

[0093] Furthermore, various modifications and combinations of the embodiments may be made without departing from the spirit of the present invention.

[0094] Industrial Applicability

[0095] According to the present invention, the present invention can calibrate the water quality analysis system without using organic fluorescent substances such as phenanthrene.

Claims

1. A water quality analysis system, characterized in that: The water quality analysis system is configured to analyze the components to be measured contained in the liquid sample by using fluorescence spectroscopy. The system comprises: a light irradiation unit configured to irradiate the liquid sample with light having an excitation wavelength of the component to be measured; a light detection unit configured to detect fluorescence from the component to be measured in the liquid sample; a sensor head that accommodates the light irradiation unit and the light detection unit and is immersed in the liquid sample; a computing device for calculating the concentration of the component to be measured using the fluorescence intensity obtained by the light detection unit; a solid fluorescent reference member which is disposed in a light path between the light irradiation section and the light detection section during calibration and emits fluorescence due to light from the light irradiation section; as well as an angle changing mechanism that changes the inclination angle of the fluorescent reference member relative to the light irradiation section and the light detection section, The fluorescent reference member is detachably mounted on the sensor head. By changing the inclination angle of the fluorescent reference member by the angle changing mechanism, the amount of fluorescent light detected by the light detecting section changes.

2. The water quality analysis system according to claim 1, characterized in that: The fluorescent reference component is fluorescent glass.

3. The water quality analysis system according to claim 1, characterized in that: The liquid sample is the scrubber effluent discharged from the vessel, The light irradiation unit irradiates light having an excitation wavelength of phenanthrene contained in the scrubber wastewater. The light detection unit detects the fluorescence of the phenanthrene, The calculation device calculates a PAH concentration corresponding to phenanthrene contained in the scrubber wastewater using the fluorescence intensity obtained by the light detection unit.

4. The water quality analysis system according to claim 1, characterized in that: further comprising a storage unit storing calibration relationship data indicating a relationship between a fluorescence intensity obtained using a reference solution having a known concentration of the measurement target component and a fluorescence intensity obtained using the fluorescence reference member, The calculation device performs calibration using the fluorescence intensity of the fluorescence reference member obtained by the light detection unit during calibration and the relationship data.

5. The water quality analysis system according to claim 1, characterized in that: The angle changing mechanism changes the tilt angle of the fluorescent reference member in stages or continuously.

6. The water quality analysis system according to claim 1 or 5, characterized in that: The angle changing mechanism includes: a reference member holding body that holds the fluorescent reference member; and an adapter body that is fixed to the light irradiation section and the light detection section during calibration and that rotatably supports the reference member holding body.

7. A sensor module for a water quality analysis system, characterized in that: A water quality analysis system for analyzing a measurement target component contained in a liquid sample using fluorescence spectroscopy, the water quality analysis system comprising: a light irradiation unit configured to irradiate the liquid sample with light having an excitation wavelength of the component to be measured; a light detection unit configured to detect fluorescence from the component to be measured in the liquid sample; a sensor head that accommodates the light irradiation unit and the light detection unit and is immersed in the liquid sample; a fluorescent reference member which is detachably mounted on the sensor head during calibration and emits fluorescence due to the light from the light irradiation section; as well as an angle changing mechanism that changes the inclination angle of the fluorescent reference member relative to the light irradiation section and the light detection section, By changing the inclination angle of the fluorescent reference member by the angle changing mechanism, the amount of fluorescent light detected by the light detecting section changes.

8. A calibration device, characterized in that: Used for calibration of a water quality analysis system, the water quality analysis system uses fluorescence spectroscopy to analyze a measurement target component contained in a liquid sample, and the water quality analysis system comprises: a light irradiation unit that irradiates the liquid sample with light having an excitation wavelength of the measurement target component; a light detection unit that detects fluorescence of the measurement target component from the liquid sample; and a sensor head that accommodates the light irradiation unit and the light detection unit and is immersed in the liquid sample, The calibration equipment comprises: a solid fluorescent reference member that emits fluorescence due to the light from the light irradiation portion; a calibration jig that holds the fluorescent reference member and sets the fluorescent reference member in a path of light between the light irradiation section and the light detection section during calibration; as well as an angle changing mechanism that changes the inclination angle of the fluorescent reference member relative to the light irradiation section and the light detection section, By changing the inclination angle of the fluorescent reference member by the angle changing mechanism, the amount of fluorescent light detected by the light detecting section changes.

9. A calibration method for a water quality analysis system, characterized in that: The water quality analysis system uses fluorescence spectroscopy to analyze the components to be measured contained in the liquid sample. The water quality analysis system has: a light irradiation unit configured to irradiate the liquid sample with light having an excitation wavelength of the component to be measured; a light detection unit configured to detect fluorescence from the component to be measured in the liquid sample; a sensor head that accommodates the light irradiation unit and the light detection unit and is immersed in the liquid sample; as well as a computing device for calculating the concentration of the measurement target component using the fluorescence intensity obtained by the light detection unit, The calibration method performs calibration by providing a fluorescent reference component that emits fluorescence due to the light from the light irradiation section in the light path between the light irradiation section and the light detection section. The correction is performed by changing the inclination angle of the fluorescence reference member relative to the light irradiation section and the light detection section to change the amount of fluorescence detected by the light detection section.

10. The calibration method of the water quality analysis system according to claim 9, characterized in that: The method further includes generating calibration relationship data, wherein the calibration relationship data represents a relationship between the fluorescence intensity of a reference liquid having a known concentration of the component to be measured obtained by a reference system serving as a reference for the water quality analysis system and the fluorescence intensity of the fluorescent reference component obtained by the water quality analysis system. During calibration, the calibration method provides the fluorescent reference member in the path of light between the light irradiation unit and the light detection unit, and performs calibration using the fluorescence intensity obtained by the light detection unit and the calibration relationship data obtained in the calibration relationship data generation step.

11. The calibration method of the water quality analysis system according to claim 10, characterized in that: The step of generating correction relationship data comprises: A first relationship data generating step of generating first relationship data indicating a relationship between the fluorescence intensity of the reference liquid obtained by the reference system and the fluorescence intensity of the fluorescent reference member obtained by the reference system; and a second relationship data generating step of generating second relationship data indicating a relationship between the fluorescence intensity of the fluorescent reference component obtained by the reference system and the fluorescence intensity of the fluorescent reference component obtained by the water quality analysis system, The correction relationship data generating step generates the correction relationship data using the first relationship data obtained in the first relationship data generating step and the second relationship data obtained in the second relationship data generating step.

12. The calibration method of the water quality analysis system according to claim 10 or 11, characterized in that: The light detection part of the reference system is calibrated by an approved calibration agency.

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