Absorbance detector and liquid chromatograph

1. An absorbance detector comprising:

a sample cell through which a sample solution including a sample flows;

a light source for irradiating the sample cell with light;

a photo sensor for detecting intensity of light that has been transmitted through the sample;

an optical system for guiding the light emitted from the light source to the sample cell and guiding the light that has been transmitted through the sample cell to the photo sensor;

a reference signal acquirer configured to acquire a detection signal of the photo sensor when the sample solution is not flowing through the sample cell as a reference signal for each analysis of the sample;

a calculator configured to find absorbance of the sample flowing through the sample cell based on a measurement signal obtained by the photo sensor in the analysis and the reference signal acquired for the analysis when the analysis of the sample is carried out;

an analysis data storage configured to associate data of the absorbance found by the calculator in the analysis of the sample and data of the reference signal acquired for the analysis to each other for storage; and

an abnormality determiner configured to find an increasing or decreasing trend of the absorbance and an increasing or decreasing trend of the reference signal associated with an increase in number of analyses based on the absorbance of each analysis and the reference signal stored in the analysis data storage in a case where an analysis of a same sample is carried out multiple times, and determine presence or absence of an abnormality in the sample cell, the light source or the optical system based on a combination of the increasing or decreasing trend of the absorbance and the increasing or decreasing trend of the reference signal.

2. The absorbance detector according to claim 1 , comprising:

a reference value setter configured to set a reference value for determination of whether intensity of the reference signal is normal; and

a light amount determiner configured to compare the reference signal with the reference value set by the reference value setter and determine an abnormality in light amount based on whether the reference signal is equal to or larger than the reference value.

3. The absorbance detector according to claim 2 , wherein

the optical system includes a spectrometer that separates light that has been transmitted through the sample cell into wavelength components,

the photo sensor has a plurality of light receiving elements that respectively detect light of each wavelength component that is separated by the spectrometer,

the reference value setter is configured to set the reference value in regard to a specific wavelength that is selected in accordance with a mobile phase flowing through the sample cell, and

the light amount determiner is configured to determine an abnormality in light amount by comparing a reference signal of light of the specific wavelength out of reference signals of the light of wavelength components acquired by light receiving elements of the photo sensor.

4. The absorbance detector according to claim 1 , wherein

the optical system includes a spectrometer that separates light that has been transmitted through the sample cell into wavelength components,

the photo sensor has a plurality of light receiving elements that respectively detect light of each wavelength component separated by the spectrometer, and

the analysis data storage is configured to store only a reference signal of light of a partial wavelength component out of reference signals of the light of wavelength components acquired by light receiving elements of the photo sensor.

5. The absorbance detector according to claim 1 , wherein

the abnormality determiner determines that the sample cell is contaminated at a point in time at which a continuous analysis is started in a case where the absorbance shows a decreasing trend while intensity of the reference signal shows an increasing trend each time an analysis is carried out, determines that a light amount of the light source is unstable in a case where the absorbance shows an increasing trend while the intensity of the reference signal shows a decreasing trend each time an analysis is carried out, and/or determines that the optical system is contaminated in a case where the absorbance does not change while the intensity of the reference signal shows a decreasing trend each time an analysis is carried out.

6. A liquid chromatograph comprising:

a sample injector for injecting a sample into an analysis flow path through which a mobile phase flows;

a separation column that is provided at a position farther downstream than the sample injector on the analysis flow path and is to separate the sample injected into the analysis flow path by the sample injector; and

the absorbance detector according to claim 1 that is provided at a position farther downstream than the sample injector on the analysis flow path and is to detect a sample component eluted from the separation column.

7. An abnormality determination method to be performed in a liquid chromatograph, the liquid chromatograph comprising:

a sample cell through which a sample solution including a sample flows;

a light source for irradiating the sample cell with light;

a photo sensor for detecting intensity of light that has been transmitted through the sample;

an optical system for guiding the light emitted from the light source to the sample cell and guiding the light that has been transmitted through the sample cell to the photo sensor;

a reference signal acquirer configured to acquire a detection signal of the photo sensor when the sample solution is not flowing through the sample cell as a reference signal for each analysis of the sample; and

a calculator configured to find absorbance of the sample flowing through the sample cell based on a measurement signal obtained by the photo sensor in the analysis and the reference signal acquired for the analysis when the analysis of the sample is carried out, and

the abnormality determination method including:

associating data of the absorbance found by the calculator in the analysis of the sample and data of the reference signal acquired for the analysis to each other for storage; finding an increasing or decreasing trend of the absorbance and an increasing or decreasing trend of the reference signal associated with an increase in number of analyses based on the stored absorbance of each analysis and the stored reference signal in a case where an analysis of a same sample is carried out multiple times; and

determining presence or absence of an abnormality in the sample cell, the light source or the optical system based on a combination of the increasing or decreasing trend of the absorbance and the increasing or decreasing trend of the reference signal.

8. The abnormality determination method according to claim 7 , wherein

the determining presence or absence of an abnormality includes determining that the sample cell is contaminated at a point in time at which a continuous analysis is started in a case where the absorbance shows a decreasing trend while intensity of the reference signal shows an increasing trend each time an analysis is carried out, determining that a light amount of the light source is unstable in a case where the absorbance shows an increasing trend while the intensity of the reference signal shows a decreasing trend each time an analysis is carried out and/or determining that the optical system is contaminated in a case where the absorbance does not change while the intensity of the reference signal shows a decreasing trend each time an analysis is carried out.