JP2007212167A - Adhering material analyzer and analyzing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an analyzer and an analyzing method for analyzing nondestructively an adhering material on the whole surface of a specimen. <P>SOLUTION: This analyzer includes a hot wind heater 11 for heating produce 100 having an agricultural chemical on the surface, a suction pump 23 for sucking gas formed from the agricultural chemical gasified by heating, a high-temperature gas jetting device for jetting out the sucked gas, a laser beam irradiation device for irradiating the jetted gas with a laser beam having a plurality of kinds of wavelengths, a detection means for detecting the wavelength wherein molecules included in the gas are ionized by collision between the laser beam and the gas, and a laser analysis part 25 for specifying the adhering material, based on detected wavelength data. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an analysis apparatus and an analysis method for analyzing adhered substances such as agricultural chemicals remaining on the surface of agricultural products.

  At present, the food hygiene law and the Agricultural Chemicals Control Law define the allowable limit of pesticides remaining in foods. In order to ship crops, it is necessary to determine the residual amount of pesticides in crops by testing. In addition, 112 kinds of test methods called official methods are defined as tests for determining the residual amount of agricultural chemicals. However, all of these official methods are test methods to determine the amount of each residue after pre-treatment of separating the pulverized specimen (agricultural crops) with a large amount of organic solvent and separating each type of residual pesticides one by one. It is. Therefore, it took considerable time and cost to obtain the test results. Under such circumstances, an analyzer that performs a test in place of the official method has been proposed (see Patent Document 1).

  The analyzer described in Patent Document 1 is an analyzer that uses a GC-MS device and performs screening twice, first and second, for analyzing a plurality of types of agricultural chemicals at once. More specifically, the ground specimen (agricultural crops) is sampled with a large amount of an organic solvent, and primary screening is performed in the SIM mode in which a small amount of sample can be detected with high sensitivity. When it is detected in the primary screening that the pesticide remains, the concentrated sample obtained by concentrating the increased sample is subjected to the secondary screening in a scan mode for obtaining a mass spectrum. Thus, the residual amount of the residual agricultural chemical is obtained by comparing the obtained mass spectrum with the mass spectrum obtained by measuring the sample in advance.

  The analyzer performs screening to analyze multiple types of pesticides at the same time, performs primary screening in SIM mode that does not require concentration, and detects pesticides remaining in primary screening. Since only the analyzed specimen is concentrated and subjected to secondary screening, it is possible to test the residual pesticide more efficiently than any of the conventional official methods, which is considered useful. However, in the test using the analyzer, as in the official method, it is necessary to crush in order to sample the specimen, and it is not practical to cut out and crush a part from all the agricultural products to be shipped. I couldn't. In addition, although it is more efficient than the conventional official method, it is not a test method that can satisfy the user sufficiently because it does not save time for pre-processing for pulverizing the specimen to sample. It was.

An analysis method using an infrared spectrophotometer without destroying the subject has also been proposed (see Patent Document 2).
In this analysis method, infrared absorption spectrum data on the surface of a crop whose residual concentration is known is collected in advance with an infrared spectrophotometer, and the residual concentration obtained by collecting an infrared absorption spectrum on the surface of a crop whose residual concentration is unknown is known. This is an analysis method for detecting residual concentration by comparing with infrared absorption spectrum data.

  This analysis method is different from the above-described official method and the test method using the above-described analyzer that performs primary screening and secondary screening, and is a test method that eliminates the need for pretreatment and improves the efficiency of the test. Further, since it can be inspected nondestructively, it can be used for 100% inspection. However, since this analysis method analyzes the amount of pesticide residue from the infrared absorption spectrum obtained by irradiating infrared rays, for example, when there is no residual pesticide in the portion irradiated with infrared rays, many other portions Even if residual agricultural chemicals exist, it is judged that there is no residual agricultural chemicals, so that it is not practical as a test method for the above-mentioned allowable limit based on the residual amount of agricultural chemicals remaining on the entire crop surface.

JP-A-10-213567 JP-A-8-170941

  An object of the present invention is to propose an analysis apparatus and an analysis method for nondestructively analyzing the adhered substance on the entire surface of the subject.

  The present invention includes a heating unit that heats an object having an attached substance on a surface thereof, a suction unit that sucks a gas gasified by the attached substance by heating, a gas injection unit that jets the sucked gas, and an injection A laser beam irradiating apparatus that irradiates a laser beam having a plurality of types of wavelengths to the gas that has been detected; a detecting means that detects a wavelength at which molecules contained in the gas are ionized by collision of the laser beam and the gas; The adhering substance analyzing apparatus includes an adhering substance specifying unit that specifies the adhering substance based on wavelength data.

The subject includes farm products such as vegetables and fruits, or solid foods.
The adhering substance includes agrochemicals, harmful substances, harmless substances, and the like.
As a result, it is possible to identify the adhered substance on the subject in a non-destructive manner. Further, since the adhering substance adhering to the entire surface is gasified by heating and the substance is identified from the gasified adhering substance, the adhering substance on the entire surface of the subject can be identified.

As an aspect of the present invention, the time-of-flight mass detection means for detecting the time-of-flight mass data based on the time of flight of the molecular ions ionized by the molecules, the time-of-flight mass data, the wavelength data, and the amount of attached substances Based on the correspondence data based on the correspondence data from the correspondence data storage means for storing the correspondence data previously associated with the quantitative analysis data shown, the time-of-flight mass data detected by the time-of-flight mass detection means and the wavelength data, Quantification data calculation means for calculating quantification data indicating the amount of the adhered substance on the subject and calculation result output means for outputting the calculation result can be provided.
The quantitative analysis data includes mass data obtained by an official method or a test method equivalent thereto.
The quantification data includes mass data converted based on corresponding data.
Thereby, the adhesion amount of the adhering substance on the entire surface of the subject can be detected in a non-destructive manner.

  Further, as an aspect of the present invention, an extraction unit that extracts an extract from a part of the adsorbed gas, and a quantitative analysis unit that analyzes the quantitative analysis data of the extract with a quantitative analyzer can be provided.

The extraction means includes an extraction means based on an official extraction method, an extraction means based on a supercritical extraction method, an extraction means that performs purification and concentration, and the like.
The quantitative analyzer includes a gas chromatograph / mass spectrometer, a liquid chromatograph / mass spectrometer, or a gel chromatograph / mass spectrometer.

  Thereby, the quantitative analysis data used as the basis of the quantification data which show the adhesion amount of a deposit | attachment can be obtained by the quantitative analysis according to an official method.

Further, as an aspect of the present invention, threshold value registering means for registering threshold value data for determining whether or not the amount of adhesion of the adhered substance is good, threshold value comparing means for comparing the quantified data with the threshold value data, and outputting a comparison result Comparison result output means.
The threshold data includes, for example, quantification data corresponding to the allowable limit amount of the residual agricultural chemical described above.
Thereby, it is possible to output whether or not the amount of deposits is greater than or equal to the threshold data. Therefore, for example, when the threshold data is set as quantification data corresponding to the allowable limit amount of the residual agricultural chemical, it is possible to output whether or not the residual agricultural chemical amount of the subject is within the allowable limit amount.

The present invention also includes a heating step for heating an object having an adhering substance on the surface, an aspirating step for sucking a gas gasified by the adhering substance by the heating, and a gas injection step for injecting the sucked gas. A laser beam irradiation step of irradiating the jetted gas with a laser beam having a plurality of types of wavelengths, and a detection step of detecting a wavelength at which molecules contained in the gas are ionized by collision between the laser beam and the gas; And an adhering substance analysis method including an adhering substance specifying step for specifying the adhering substance based on the detected wavelength data.
As a result, it is possible to identify the adhered substance on the subject in a non-destructive manner. Further, since the adhering substance adhering to the entire surface is gasified by heating and the substance is identified from the gasified adhering substance, the adhering substance on the entire surface of the subject can be identified.

As an aspect of the present invention, the time-of-flight mass detection step of detecting time-of-flight mass data based on the time of flight of the molecular ions ionized by molecules, the time-of-flight mass data, the wavelength data, and the amount of attached substances Based on the correspondence data based on the correspondence data from the correspondence data storage step for storing the correspondence data previously associated with the quantitative analysis data shown, the time-of-flight mass data detected by the time-of-flight mass detection step, and the wavelength data, It is possible to have a quantification data calculation step for calculating quantification data indicating the amount of the adhered substance on the subject and a calculation result output step for outputting the calculation result.
Thereby, the adhesion amount of the adhering substance on the entire surface of the subject can be detected in a non-destructive manner.

In addition, as an aspect of the present invention, an extraction process for extracting an extract from a part of the adsorbed gas, and a quantitative analysis process for analyzing the quantitative analysis data of the extract with a quantitative analyzer can be provided.
Thereby, the quantitative analysis data used as the basis of the quantification data which show the adhesion amount of a deposit | attachment can be obtained by the quantitative analysis according to an official method.

  Further, as an aspect of the present invention, a threshold value registration step for registering threshold value data for determining the quality of the adhesion amount of the adhering substance, a threshold value comparison step for comparing the quantification data and the threshold value data, and outputting a comparison result And a comparison result output step.

  Thereby, it is possible to output whether or not the amount of deposits is greater than or equal to the threshold data. Therefore, for example, when the threshold data is set to quantified data corresponding to the allowable limit amount of the residual agricultural chemical, it is possible to output whether or not the residual agricultural chemical amount of the subject is within the allowable limit amount.

  Further, as an aspect of the present invention, a second heating step of heating the subject having the quantification data exceeding the threshold data, a second suction step of sucking the gas gasified by the attached substance by the heating, A second extraction step of extracting an extract from the gas, and a second quantitative analysis step of analyzing the quantitative analysis data indicating the amount of the adhered substance on the analyte with the quantitative analyzer using the extract. .

  As a result, quantitative analysis data indicating the amount of the specimen having the quantification data exceeding the threshold data in the threshold comparison step can be obtained by quantitative analysis according to the official method.

  According to the present invention, it is possible to provide an analysis apparatus and an analysis method for nondestructively analyzing the adhered substance on the entire surface of the subject.

An embodiment of the present invention will be described below with reference to the drawings.
FIG. 1 shows a block diagram of a pesticide residue analyzer 1.
The residual pesticide analysis apparatus 1 includes a laser measurement apparatus 2 and a quantitative analysis apparatus 3, and each is connected to a control apparatus 4.

  The control device 4 is a computer, a control device composed of a CPU, ROM and RAM, a storage device such as a hard disk, and a storage medium reading device that reads a storage medium such as a CD-ROM drive or FD drive (CD-ROM, FD, etc.) And a storage medium reading / writing device, an input device such as a mouse and a keyboard, and a display device 41 including a CRT, a liquid crystal screen, and the like.

The storage device (for example, a hard disk) has a wavelength program based on a control program for controlling each device of the pesticide residue analyzer 1, a registration program for registering each data, and correspondence between wavelength spectrum data and quantitative analysis data described later. A neighborhood formula calculation program for calculating a neighborhood formula for converting data into quantitative analysis data, and quantification data for calculating quantification data indicating the amount of attached substances on the subject based on wavelength spectrum data and the neighborhood formula A calculation program, a comparison program for comparing quantified data and threshold data, and the like are stored.
In addition, the control device 4 is a database (DB) 42 that stores quantification correspondence data such as neighborhood formulas for each agricultural chemical, and allowable limit amount data of the agricultural chemical amount contained in the agricultural products defined by the Food Sanitation Law or the Agricultural Chemicals Control Law. Is connected.

  The laser measuring device 2 includes a pressure vessel 10 that allows the crop 100 to be accommodated, a warm air heater 11 that heats the inside of the pressure vessel 10 with warm air, and a suction pump 23 that sucks gas (gas) inside the pressure vessel 10. The trap part 24 for adsorbing the gas sucked by the suction pump 23 to the adsorbent and the laser analysis part 25 for irradiating the gas adsorbed by the trap part 24 with a laser beam for analysis are arranged in this order. is doing. A hot air valve 12 that adjusts the supply of warm air from the hot air heater 11 into the pressure vessel 10 is disposed between the pressure vessel 10 and the hot air heater 11. Between them, a suction valve 21 for adjusting the suction amount of the suction pump 23 and a pressure gauge 22 for monitoring the suction pressure of the suction pump 23 are arranged.

The pressure vessel 10 includes a pressure-resistant door for taking in and out the crop 100 therein, and has a pressure-resistant structure that can withstand the suction pressure by the suction pump 23 in the closed state.
The warm air heater 11 has a heating capability capable of heating the inside of the pressure vessel 10 with warm air to such an extent that the agricultural chemicals remaining on the surface of the crop 100 are gasified (vaporized).

  The suction pump 23 is a pump that sucks the gas inside the pressure vessel 10 filled with the agricultural chemicals gasified by the warm air of the warm air heater 11 with a negative pressure of about −100 to 200 mmHg. Air can be supplied to the trap portion 24.

The suction valve 21 is closed in a state where the warm air valve 12 is opened and warm air is being sent from the warm air heater 11 into the pressure vessel 10, and a predetermined temperature at which the residual agricultural chemical of the crop 100 is gasified. Then, the supply of air to the hot air heater 11 is stopped, and the hot air valve 12 is opened when the suction of the suction pump 23 is closed. Further, since the suction pressure of the suction pump 23 is monitored by the pressure gauge 22, when the suction pressure does not reach the predetermined pressure, the suction pressure of the suction pump 23 can be adjusted by appropriately adjusting the opening degree. it can.
The trap portion 24 is filled with an adsorbent made of alumina or the like, can adsorb the gas sent from the suction pump 23, and can take in and out the adsorbent.

The laser analysis portion 25 uses a laser ionization mass spectrometer (manufactured by IDX, Inc .: hereinafter referred to as “RIMMPA-TOFMS”). The RIMMPA-TOFMS includes a RIMMPA portion and a flight-type mass spectrometer (hereinafter referred to as “TOF-MS”). ”).
First, a laser beam irradiation device irradiates two colors of laser beams onto a chamber unit provided in the RIMMPA unit, and the irradiated laser beams are incident on a polygon mirror unit installed in the chamber. The laser beam incident on the polygon mirror is reflected a plurality of times by the polygon mirror and converges at the center. The gas adsorbed by the trap portion 24 heated to a higher temperature (for example, 120 degrees) is jetted onto the converging portion at the center of the laser beam by the high-temperature gas injection device, and corresponds to the wavelength of the laser beam in the gas. Pesticide substances can be ionized. At this time, when the laser beam irradiation apparatus performs irradiation by changing the wavelength of the laser beam, the agricultural chemical substance corresponding to each wavelength can be ionized. Therefore, the agrochemical substance can be identified by detecting the wavelength at which the corresponding agrochemical substance is ionized among the changed wavelengths.

Furthermore, the ionized molecules of the agricultural chemical substance become ion beams, and the time of flight due to the difference in mass of each molecule can be detected by TOF-MS, and the agricultural chemical substance can be specified.
With the above configuration, the laser analysis portion 25 can detect wavelength spectrum data from the wavelength data and time-of-flight data of the agricultural chemical substance, and can transmit the wavelength spectral data of the agricultural chemical substance to the control device 4.

  The quantitative analyzer 3 shares the pressure vessel 10, the hot air heater 11, and the hot air valve 12 with the laser measuring device 2, and sucks a gas (gas) inside the pressure vessel 10, and a suction device. A trap portion 34 that adsorbs the gas sucked by the pump 33 to the adsorbent, an extraction portion 35 that extracts an object from the gas adsorbed by the trap portion 34, and an quantitative analysis of the extract extracted by the extraction portion 35 The quantitative analysis part 36 to be arranged is arranged in this order. A suction suction valve 31 for adjusting the suction amount of the suction pump 33 and a pressure gauge 32 for monitoring the suction pressure of the suction pump 33 are arranged between the pressure vessel 10 and the suction pump 33.

  The suction pump 33 is a pump that sucks the gas inside the pressure vessel 10 filled with the agricultural chemicals gasified by the warm air of the warm air heater 11 with a negative pressure, and supplies the sucked gas to the trap portion 34. can do. The suction valve 31 is closed in a state where the warm air valve 12 is opened and warm air is being sent from the warm air heater 11 into the pressure vessel 10, and a predetermined temperature at which the residual agricultural chemical of the crop 100 is gasified. Then, the supply of air to the warm air heater 11 is stopped, and the suction of the suction pump 33 after the warm air valve 12 is closed is opened. Further, since the suction pressure of the suction pump 33 is monitored by the pressure gauge 32, the suction pressure of the suction pump 23 can be adjusted.

The trap portion 34 is filled with an adsorbent made of alumina or the like, can adsorb the gas sent from the suction pump 33, and can take in and out the adsorbent.
The extraction part 35 is composed of a supercritical extraction device that extracts agrochemical components from the adsorbent adsorbing gas with a supercritical fluid. The supercritical fluid uses carbon dioxide in a supercritical state whose temperature and pressure are adjusted. In the extraction reactor provided in the extraction portion 35, the agrochemical component contained in the adsorbent is dissolved in the supercritical fluid, and the pressure of the supercritical fluid in which the agrochemical component is dissolved in the separator inside the extraction portion 35 is reduced. Thus, the carbon dioxide and the agricultural chemical component can be separated, and the extraction portion 35 can send the agricultural chemical component separated from the carbon dioxide by the separator to the quantitative analysis portion 36.

  The extraction portion 35 is not limited to the supercritical extraction device described above, and may be an extraction device defined by a conventional official method, or may be an extraction device that performs extraction by purification / concentration.

The quantitative analysis portion 36 includes a gas chromatograph / mass spectrometer (hereinafter referred to as “GC-MS”) in which a gas chromatograph (hereinafter referred to as “GC”) and a mass spectrometer (hereinafter referred to as “MS”) are connected. ing.
The GC is a device that separates a gas containing a plurality of agricultural chemical components for each component, and more specifically, when the gas as a sample passes through the inside, each component depends on the difference in adsorptivity and chemical bonding properties. This is a device that separates each component using the fact that the passage time of each is different.

  MS is a molecular ion that forms a charged molecular ion by applying electric energy to a gasified molecule in a high vacuum, and separates it according to the mass difference by applying an electric field to this molecular ion. The mass (m) and charge (z) ratio (m / z) is recorded to calculate a mass spectrum, and this mass is obtained.

Therefore, the quantitative analysis part 36 can separate the agricultural chemical components sent out from the extraction part 35 for each component by GC, and can determine the mass by MS. This analysis for determining the mass of each component is called quantitative analysis.
Further, the quantitative analysis part 36 can transmit the quantitative analysis result to the control device 4. A liquid chromatograph / mass spectrometer or gel chromatograph / mass spectrometer may be used instead of GC-MS.

The control device 4 associates the spectral area of the wavelength spectrum data of the agricultural chemical substance transmitted from the laser analysis portion 25 with the quantitative analysis result transmitted from the quantitative analysis portion 36, and converts the wavelength spectrum data for each component. A neighborhood formula to be converted into mass is created by a neighborhood formula calculation program. Moreover, the control apparatus 4 calculates the quantification data which shows the residual amount of an agrochemical substance based on the said vicinity formula with the wavelength spectrum data newly obtained by the quantification data calculation program. Further, the quantification data is compared with the registered threshold data by the comparison program or the like, and the comparison result is output to the display device 41.
Each of the suction valve 31, the pressure gauge 32, the suction pump 33, and the trap portion 34 may be configured to be shared with the suction valve 21, the pressure gauge 22, the suction pump 23, and the trap portion 24 of the laser measuring device 2. .

Next, the residual agricultural chemical analysis method using the residual agricultural chemical analysis apparatus 1 having such a configuration will be described with reference to FIGS. 2 to 5 showing flow charts of the respective analyses.
As shown in FIG. 2, this residual pesticide analysis method comprises a preparation mode and an inspection mode. In the preparation mode, in order to register threshold value data based on the proximity formula or the quantified data by the proximity formula calculation program of the control device 4 using the residual pesticide analysis device 1, the residual pesticide analysis device in advance before the main examination. 1 is a mode in which a plurality of wavelength spectrum data and quantitative analysis data are sampled and a neighborhood formula and threshold data are registered.

  The inspection mode detects the wavelength spectrum data of the crop 100 (FIG. 1) using the residual agricultural chemical analysis apparatus 1, and uses the quantified data calculation program of the control apparatus 4 to register the neighborhood formula registered in the preparation mode. This is an inspection mode in which quantified data is calculated and compared with threshold data using the above comparison program.

When this residual pesticide analysis method is started, it is first determined whether or not it is in the preparation mode. If it is in the preparation mode (step s1: Yes), a preparation process is performed (step s2), and if not (step s2) In s1: No), an inspection process is performed (step s3).
Each mode will be described below.
First, the preparation mode will be described with reference to FIG.

  In the preparation mode, the residual agricultural chemical analyzer 1 performs a preparation process. In this preparation process, first, the crop 100 is put into the pressure vessel 10, and the crop 100 is heated by the warm air heater 11 (step t1). At this time, the crop 100 is heated to approximately a predetermined temperature (for example, about 50 to 100 ° C.) by heating the inside of the pressure vessel 10, although it varies depending on the type of the crop 100 and the type of agricultural chemical used for the type. At this time, heating adjustment is performed by the hot air valve 12 while checking a thermometer that detects the temperature inside the pressure vessel 10 (not shown).

In the heating process, after the crop 100 is heated at a predetermined temperature for a predetermined time (for example, 2.5 minutes), the warm air valve 12 is closed, the suction valve 21 and the suction valve 31 are opened, and the suction pump 23 and the suction pump 33 are used. The gas filled in the pressure vessel 10 is sucked at a predetermined pressure (step t2). The suction pressure at this time varies depending on the type of agricultural chemical, but suction is performed at a negative pressure of about −100 to −200 mmHg. This suction pressure can be adjusted by the opening of the suction valve 21 and the suction valve 31 while confirming the suction pressure with the pressure gauge 22 and the pressure gauge 32, or the suction pressure itself of the suction pump 23 and the suction pump 33 can be adjusted. It can also be adjusted.
The gas sucked in the suction step is adsorbed by the adsorbent filled in the trap portion 24 and the trap portion 34 (step t3). At this time, for example, alumina is used in the present embodiment, although the adsorbent varies depending on the type of agricultural chemical.

  Subsequently, the analysis of the agrochemical component contained in the gas from the adsorbent that has adsorbed the gas in the gas adsorption process is performed in the laser analysis portion 25 (step t4). Through this analysis step, the laser analysis portion 25 detects the wavelength spectrum data of the agrochemical component and transmits it to the control device 4. In parallel with this analysis step, the agrochemical component is extracted from the adsorbent that has adsorbed the gas in the gas adsorption step by the extraction portion 35 (step t5), and the quantitative analysis data of the extract is detected by the quantitative analysis portion 36. Then, the quantitative analysis data is transmitted to the control device 4 (step t6).

  The control device 4 that has received the wavelength spectrum data from the laser analysis portion 25 and the quantitative analysis data from the quantitative analysis portion 36 registers the data in the DB 42 in association with each other (step t7). This process is repeated, and the above process is repeated to the extent that the neighborhood equation can be calculated by associating the wavelength spectrum data with the quantitative analysis data (step t8: No). If each data is registered to such an extent that the neighborhood expression can be calculated (step t8: Yes), the neighborhood spectrum calculation program converts the wavelength spectrum data into mass (quantification data) for each component. A neighborhood expression such as a function is created (step t9). Further, threshold data corresponding to the quantification data is set and registered based on the allowable limit amount data of the agrochemical amount stored in the DB 42 (step t10), and this preparation process is completed. In addition, the number of repetitions is increased, and as the number of each data increases, a neighborhood expression that approximates each data can be calculated.

Next, the inspection mode shown in FIGS. 4 and 5 will be described.
In this inspection mode, first, using the laser measurement device 2 of the residual agricultural chemical analyzer 1, the heating process (step u1), the gas suction process (step u2), and the gas are performed as in steps t1 to t4 in the preparation mode. The adsorption process (step u3) and the analysis process (step u4) are performed, and the wavelength spectrum data of the crop 100 is transmitted from the laser analysis part 25 to the control device 4.

  The control device 4 that has received the wavelength spectrum data of the crop 100 from the laser analysis section 25 uses the neighborhood formula calculated in the preparation mode, and quantifies the residual amount of the residual agricultural chemical in the crop 100 by the quantification data calculation program. Data is calculated (step u5), and the calculated quantification data is compared with threshold data registered in the DB 42 by the comparison program (step u6).

  If the comparison result does not exceed the threshold data (step u7: Yes), the residual agricultural chemical amount of the crop 100 does not exceed the allowable limit amount, and therefore the crop 100 is output to the display device 41 as an acceptable product. At the same time, the passed quantification data is registered in the DB 42 (step u8), and this inspection mode is completed.

  However, in the comparison step, when the comparison program determines that the quantification data exceeds the threshold data (step u7: No), the amount of residual agricultural chemicals in the crop 100 exceeds the allowable limit amount. It is judged that the probability is high. Therefore, the quantitative analysis apparatus 3 performs quantitative analysis on the crop 100 for which it is determined that the quantified data exceeds the threshold data. The quantitative analysis at this time is performed in the same manner as steps t1 to t3, t5, and t6 in the preparation mode, in the heating process (step u10), the gas suction process (step u11), the gas adsorption process (step u12), and the extraction process ( Step u13) and a quantitative analysis process (step u14) are performed, and quantitative analysis data of the crop 100 is transmitted from the quantitative analysis portion 36 to the control device 4.

  The control device 4 that has received the quantitative analysis data from the quantitative analysis part 36 compares the allowable limit amount registered in the DB 42 with the quantitative analysis data (step u15), and the quantitative analysis data does not exceed the allowable limit amount. In the case (step u16: Yes), since the residual agricultural chemical amount of the crop 100 does not exceed the allowable limit amount, the crop 100 is output to the display device 41 indicating that it is an acceptable product, and the passed quantitative analysis data is displayed. Registration in the DB 42 (step u17) completes this inspection mode.

  However, when it is determined in the quantitative analysis data determination step that the quantitative analysis data exceeds the allowable limit amount (step u16: No), the residual agricultural chemical amount of the crop 100 exceeds the allowable limit amount. Therefore, the crop 100 is recognized as a rejected product (step u18), and a message to that effect is output to the display device 41 to complete this inspection mode.

  In this way, in the residual pesticide analysis method using the residual pesticide analysis apparatus 1, the user first obtains the wavelength spectrum required by the laser measurement apparatus 2 for various types of agricultural chemicals of various types of crops 100, and the quantitative analysis apparatus. 3 is obtained by associating with the quantitative analysis data obtained in step 3, and the quantification data can be calculated from the wavelength spectrum of the crop 100 by the laser measuring device 2 in the inspection mode.

  Therefore, much more efficient analysis can be performed as compared with the test method in which only the quantitative analysis device 3 or the above-described official method is used for quantitative analysis to detect the amount of residual agricultural chemicals remaining on the crop 100. For example, in order to detect the residue of each of a plurality of pesticide components contained in the official method, it took about 10 days per sample including pretreatment, but the residual pesticide analysis using the residual pesticide analyzer 1 According to the method, detection can be performed in about 10 minutes per specimen.

  Further, in the case of the residual agricultural chemical analysis method using the residual agricultural chemical analysis apparatus 1, it is not necessary to pulverize the sample of the agricultural product 100 that is the specimen, so that the agricultural product 100 subjected to the residual agricultural chemical analysis is used without being discarded. it can. Therefore, it is possible to reduce the cost for the residual pesticide analysis and to perform 100% inspection by the residual pesticide analysis method using the residual pesticide analysis apparatus 1.

  Further, in the inspection mode of the pesticide residue analysis method, the quantification is performed only when the quantification data exceeds the threshold data by comparing the quantification data obtained by the neighborhood formula based on the wavelength spectrum by the laser measuring device 2 and the threshold data. Since the quantification analysis is performed by the analysis device 3, it is possible to determine the rejection of the crop 100 based on an accurate quantitative analysis result, and it is possible to perform a more accurate pass / fail determination.

  In addition, without calculating the neighborhood formula between the wavelength spectrum data collected in the preparation mode and the quantitative analysis data, the correspondence with the quantitative analysis data corresponding to the wavelength spectrum data as it is is directly registered in the DB 42 and detected in the inspection mode. Quantification data may be calculated by searching quantitative analysis data corresponding to the wavelength spectrum data.

  Moreover, although the residual pesticide analysis apparatus 1 was described as being configured by the laser measurement apparatus 2 and the quantitative analysis apparatus 3 in the residual pesticide analysis method, the residual pesticide amount of the crop 100 is determined using only the laser measurement apparatus 2. You may judge by wavelength spectrum data.

In correspondence between the configuration of the present invention and the above-described embodiment,
The adhering substance analyzer of the present invention corresponds to the residual agricultural chemical analyzer 1,
Similarly, the subject corresponds to the crop 100,
The heating means corresponds to the warm air heater 11,
The suction means corresponds to the suction pump 23 and the suction pump 33,
The adhering substance specifying means corresponds to the laser analysis portion 25,
Corresponding data storage means corresponds to DB42,
The calculation result output means corresponds to the display device 41,
The extraction means corresponds to the extraction portion 35,
The quantitative analysis means corresponds to the quantitative analysis portion 36,
The comparison result output means corresponds to the display device 41,
The heating process corresponds to step t1 and step u1,
The suction process corresponds to step t2 and step u2,
The attached substance identification process corresponds to step t4 and step u4,
The quantification data calculation process corresponds to step u5,
The extraction process corresponds to step t5,
The quantitative analysis process corresponds to step t6,
The threshold value registration process corresponds to step t10,
The threshold comparison process corresponds to step u6,
The comparison result output process corresponds to step u9,
The second heating step corresponds to step u10,
The second suction process corresponds to step u11,
The second extraction process corresponds to step u13,
The second quantitative analysis process corresponds to step u14,
Adhering substances correspond to agricultural chemicals,
The gas injection means corresponds to the hot gas injection device,
Corresponding data corresponds to the neighborhood formula,
The quantitative analyzer is compatible with gas chromatographs and mass spectrometers.
Time-of-flight mass detection means corresponds to TOF-MS,
The time-of-flight mass data and the wavelength data correspond to the wavelength spectrum,
The quantification data calculation means corresponds to the quantification data calculation program,
The threshold registration means corresponds to the registration program,
The threshold comparison means corresponds to the comparison program,
The present invention is not limited only to the configuration of the above-described embodiment, and many embodiments can be obtained.

Block diagram of a pesticide residue analyzer. Flow chart of residual pesticide analysis method. Flow chart of preparation mode. Flow chart of inspection mode. Flow chart of inspection mode

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Residual agricultural chemical analyzer 11 ... Warm air heater 23 ... Suction pump 25 ... Laser analysis part 33 ... Suction pump 35 ... Extraction part 36 ... Quantitative analysis part 41 ... Display apparatus 42 ... DB
100 ... crops

Claims (9)

Heating means for heating an object having an attached substance on the surface, suction means for sucking a gas gasified by the attached substance by heating, gas injection means for injecting the sucked gas, and the injected gas In addition, a laser beam irradiation apparatus that irradiates laser beams of a plurality of types of wavelengths, a detection unit that detects a wavelength at which molecules contained in the gas are ionized by collision of the laser beam and the gas, and based on the detected wavelength data And an adhering substance specifying device for specifying the adhering substance. Time-of-flight mass detection means for detecting time-of-flight mass data based on the time of flight of the molecular ions ionized by molecules, time-of-flight mass data, and quantitative analysis data indicating the wavelength data and the amount of adhering substances attached Based on the correspondence data from the correspondence data storage means for storing the correspondence data associated in advance, the time-of-flight mass data detected by the time-of-flight mass detection means and the wavelength data, the attached substance of the subject The attached substance analysis apparatus according to claim 1, further comprising: a quantification data calculation unit that calculates quantification data indicating the amount of adhesion; and a calculation result output unit that outputs a calculation result. The attached substance analysis apparatus according to claim 2, further comprising: an extraction unit that extracts an extract from a part of the adsorbed gas; and a quantitative analysis unit that analyzes the quantitative analysis data of the extract with a quantitative analyzer. Threshold registration means for registering threshold data for determining the adhering amount of the adhering substance, threshold comparison means for comparing the quantification data with the threshold data, and comparison result output means for outputting a comparison result The attached substance analyzing apparatus according to claim 3. A heating step of heating an object having an adhering substance on the surface; an aspirating step of sucking a gas gasified by the adhering substance by the heating; a gas injection step of injecting the sucked gas; A laser beam irradiation step of irradiating a gas with a laser beam of a plurality of wavelengths, a detection step of detecting a wavelength at which molecules contained in the gas are ionized by collision of the laser beam and the gas, and the detected wavelength data An attached substance analysis method comprising: an attached substance specifying step for identifying the attached substance based on the attached substance. A time-of-flight mass detection step of detecting time-of-flight mass data based on the time of flight of the molecular ions ionized by molecules; and time-of-flight mass data, and quantitative analysis data indicating the amount of attached substances and the wavelength data. Based on the correspondence data from the correspondence data storage step for storing the correspondence data associated in advance, the time-of-flight mass data detected by the time-of-flight mass detection step and the wavelength data, the attached substance of the subject The method for analyzing an adhering substance according to claim 5, further comprising a quantification data calculation step for calculating quantification data indicating the amount of adhesion, and a calculation result output step for outputting a calculation result. The attached substance analysis method according to claim 6, further comprising an extraction step of extracting an extract from a part of the adsorbed gas, and a quantitative analysis step of analyzing the quantitative analysis data of the extract with a quantitative analyzer. A threshold value registering step for registering threshold data for determining the adhering amount of the adhering substance, a threshold value comparing step for comparing the quantification data and the threshold data, and a comparison result output step for outputting a comparison result. The method for analyzing an adhering substance according to claim 7. A second heating step of heating the subject having the quantification data exceeding the threshold data; a second suction step of sucking a gas gasified by the attached substance by the heating; and extracting an extract from the gas The attached substance analysis method according to claim 8, further comprising: a second extraction step; and a second quantitative analysis step of analyzing the extract with quantitative analysis data indicating the amount of attached substance attached to the subject with a quantitative analyzer.

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