Low-volatility substance detector and method for quantifying low-volatility substances

Abstract

One of the objectives is to improve the accuracy of quantitative analysis of low-volatility substances, particularly in the simplified analysis of residues. Another objective is to improve the accuracy of quantitative analysis of nitro compounds using the chemiluminescence method. Furthermore, one of the objectives is to improve safety in the quantitative testing of low-volatility substances. [Solution] A low-volatility substance detector 1 for quantifying low-volatility substances using the chemiluminescence method, comprising a collection paper holder 2 for setting collection paper 9 opposite an exposed heating section 111, the collection paper holder 2 having a ventilation opening 22 in the portion facing the heating section 111.

Description

【Technical Field】 【0001】 The present invention relates to a method for quantitative analysis of low-volatile substances, and particularly to a quantitative analysis method for enhancing the measurement and quantification performance in the simple analysis of residues of low-volatile substances. 【Background Art】 【0002】 In the pharmaceutical field, food field, environmental field, etc., for understanding the effects on the body and the residue amount, chemical substance component analysis performs complex pretreatment and widely conducts trace detailed analysis using a high-sensitivity mass spectrometer, etc. On the other hand, the importance of simple analysis of the target substance components remaining at the site is increasing more and more. 【0003】 For highly volatile substances, it is widely practiced to collect and concentrate the gas using a collector and then analyze it. On the other hand, low-volatile substances are difficult to vaporize and adhere to and remain on the surface of objects. Therefore, an analysis method is used in which the low-volatile substances adhering to the surface of an object are wiped off with a detection instrument made of paper, non-woven fabric, resin, etc., and the target substance to be measured in the adherent is detected and quantified. And in this method, various methods are carried out, such as directly analyzing the target substance to be measured, derivatizing it to change it into a different substance for analysis, or decomposing it by heat, light, impact, etc. to analyze it as a simple substance. 【0004】 Here, as low-volatile substances that cannot be collected and analyzed as a gas, there are various substances such as polycyclic aromatic hydrocarbons, compounds having a hydroxyl group, compounds having a nitro group, etc. Various chemical substances such as illegal drugs containing such low-volatile substances can be measured using ion mobility spectrometry (IMS), but IMS provides a large amount of information and requires high data analysis ability. Also, although the IMS device has become more compact, since it does not directly thermally decompose the chemical substance and sends everything into the ionization section for ion selection, a separate heating ionization section is required, the device is complex, and it is not of a size that anyone can easily carry around, and maintenance is difficult. 【0005】 For example, nitro compounds are found in explosives and active proteins, and because explosive materials require quantitative analysis to detect traces of people who have handled them or on the surfaces of objects contaminated with explosives, in order to prevent them from being carried onto aircraft or to prevent terrorist attacks, quantitative analysis is necessary for these substances. Here, specific substances to be measured include nitro compounds such as picric acid, trinitrotoluene, nitroglycerin, cyclotetramethylenetetranitramine, and cyclotrimethylenetrinitramine, which are explosive materials. 【0006】 Conventionally, various methods have been used to measure nitro compounds, including thermal conduction, Raman spectroscopy, near-infrared spectroscopy, nuclear magnetic resonance spectroscopy, nuclear quadrupole resonance spectroscopy, and chemiluminescence. However, when it is necessary to perform inspections on-site at places like airports and obtain results immediately, chemiluminescence is the most suitable method because it can be easily performed using a device weighing less than 1 kg that anyone can easily carry. 【0007】 This chemiluminescence method detects substances adhering to a detection device, such as trace substances remaining on the surface of an object, by wiping the substance with a detection device made of paper, nonwoven fabric, resin, etc., and then thermally decomposing it. For example, if a nitro compound, which is an explosive substance, is used as a trace substance, it is converted to nitrogen oxide, and the luminescence intensity produced by the chemical reaction between the nitrogen oxide, which is the substance to be measured, and an alkaline aqueous solution is quantitatively detected using a photomultiplier tube or the like. The maximum value of the luminescence is monitored to perform a quantitative analysis of the trace substance. 【0008】 As a chemiluminescence-based device specifically designed for trace analysis and easy for anyone to use, the Fido X2 (manufactured by Teledyne FLIR LLC), a handheld explosive residue detector that is a type of low-volatility substance detector, is available (Non-Patent Literature 1, Non-Patent Literature 2). This explosive residue detector uses a collection paper to wipe the surface of the object to be tested, inserts it into the sample inlet of the explosive detector, and heats the collection paper. Detection is performed using the chemiluminescence method, and because it can be configured more compactly than the IMS method, it is easy to carry and suitable for on-site explosive trace analysis. 【0009】 Furthermore, on-site inspections at airports and other locations using explosive residue detection devices, a type of low-volatility substance detector, are increasingly required to be highly accurate. Therefore, at inspection sites, it is essential to check the device status and analyze standard markers used for quantitative comparison of the target substance. These standard markers serve as a benchmark for quantitative determination of the target substance, and exceeding a certain amount indicates the presence of explosive residue. Thus, the importance of threshold verification inspections is increasing. 【0010】 To obtain such a standard threshold, a conventional method has been used in which a marker sample solution containing a low-volatility substance of known concentration is drawn from a bottle using a dropper, microsyringe, or micropipette, and added to a solution cell, detection sheet, or detection unit of an explosive residue detection device. However, the process of directly drawing up the marker sample solution requires the skill to take a consistent amount, and many field personnel in explosive detection are inexperienced or novice who have never used these tools before. As a result, the accuracy of the inspections sometimes decreases because the work is not being performed by skilled personnel. [Prior art documents] [Non-patent literature] 【0011】 [Non-Patent Document 1] Fido X2 (manufactured by Teledyne FLIR LLC) webpage (https: / / www.flir.jp / products / fido-x2 / ?vertical=explosives&segment=detection) [Non-Patent Document 2] Novus Light Today's webpage "Next-Generation Explosives Detection: TrueTrace Capability for Law Enforcement" (https: / / www-novuslight-com.translate.goog / next-generation-explosives-detection-truetrace-capability-for-law-enforcement_N5822.html?_x_tr_sl=auto&_x_tr_tl=en&_x_tr_hl=en) [Overview of the project] [Problems that the invention aims to solve] 【0012】 In conventional technologies such as the explosive residue detection device described in Non-Patent Documents 1 and 2, which are a type of low-volatility substance detector, a collection paper is inserted into the sample inlet, and the sample is heated and vaporized for measurement. However, since there is only one inlet for the sample inlet, when performing continuous measurements, the vaporized sample from the previous collection paper accumulates near the sample inlet and remains there, affecting the next measurement as a blank. 【0013】 Furthermore, in the IMS method, the sample paper is not directly heated to decompose trace substances; instead, all components are sent to the ionization section, and ions corresponding to the target substance components are selected and detected. Therefore, there is no influence from blank components originating from the measuring instrument other than the target substance component, and thus it was not necessary to consider the influence of this blank. Consequently, the measuring instruments used in the IMS method did not take into account this blank originating from the measuring instrument, resulting in a large variety and quantity of blanks, and significant differences in the amount of blanks for each measuring instrument. It should be noted that the blank originating from the measuring instrument, as referred to here, includes not only the material components that make up the measuring instrument, but also material components that subsequently adhere to the measuring instrument. 【0014】 Furthermore, in actual measurements using the explosive residue detection device and method described in Non-Patent Document 1 and Non-Patent Document 2, the luminescence status of the detection instrument used was not known. The specialized paper used as conventional detection instrument had a large variety and quantity of blanks, which are factors that affect quantitative analysis, and there were also large differences in the amount of blanks from one sheet to another. 【0015】 When measuring with instruments that contain a large amount of blank components (substances originating from the measuring instrument itself, in addition to the target substance component) and where there are significant differences in the amount of blank components among different instruments, it is possible that this could affect quantitative analysis, posing a problem. However, conventional products do not perform inspections for these blank components that affect quantitative analysis, and no measures are taken to prevent contamination due to the storage conditions of the detection instruments, making it impossible to perform accurate quantitative measurements. 【0016】 Therefore, one of the objectives of the present invention is to improve the quantitative accuracy of measurements in the quantitative analysis of low-volatility substances, particularly in the simple analysis of residues. Another objective is to improve the quantitative accuracy of measurements in the quantitative analysis of nitro compounds using the chemiluminescence method. Another objective is to improve operator safety in inspections using low-volatility substance detectors, including explosive residue detection devices. Another objective is to provide a measuring instrument for the quantitative analysis of low-volatility substances that is highly safe for the human body. Another objective is to provide a measuring instrument for the quantitative analysis of low-volatility substances that has little influence on quantitative analysis by the measuring instrument used, has small differences in the amount of blank for each measuring instrument, and can perform accurate quantitative measurements. [Means for solving the problem] 【0017】 As a means to solve the above problems, the present invention provides a low-volatility substance detector for quantifying low-volatility substances using the chemiluminescence method, comprising a heating unit exposed to the outside of the low-volatility substance detector for heating the low-volatility substance, and a collection paper holder for installing collection paper for supplying the substance to be measured to the low-volatility substance detector facing the heating unit, wherein the collection paper holder has an installation opening for installing the collection paper facing the heating unit, and a ventilation opening in the part facing the heating unit. 【0018】 Furthermore, in the low-volatility substance detector described above, the area of ​​the ventilation opening is 30% or more of the area of ​​the heating plate exposed to the outside that constitutes the heating section. 【0019】 Furthermore, the low-volatility substance detector described above is a low-volatility substance detector in which a support beam is provided in the ventilation opening. 【0020】 Furthermore, in the low-volatility substance detector described above, the strut is provided on the portion of the ventilation opening opposite the sample inlet that protrudes from the heating section. 【0021】 Furthermore, in the low-volatility substance detector described above, the paper collection holder is a low-volatility substance detector that is detachably installed on the low-volatility substance detector. 【0022】 Furthermore, the present invention relates to a low-volatility substance detector for quantifying low-volatility substances using the chemiluminescence method, comprising a heating unit exposed to the outside of the low-volatility substance detector for heating the low-volatility substance, and a collection paper holder for setting collection paper opposite the heating unit to supply the substance to be measured to the low-volatility substance detector, wherein the collection paper holder has an installation opening for setting the collection paper opposite the heating unit and a ventilation opening in the part opposite the heating unit, and the low-volatility substance detector is characterized by setting the collection paper in the collection paper holder, setting the collection paper opposite the heating unit, heating the collection paper, and heating and vaporizing the low-volatility substance adhering to the collection paper. 【0023】 In addition, in the method for quantifying the low-volatile substance, after discharging the vaporized low-volatile substance from the ventilation port in the previous quantification, a new sampling paper is installed in the sampling paper holder. This is the method for quantifying the low-volatile substance. 【0024】 In addition, in the method for quantifying the low-volatile substance, the area of the ventilation port is 30% or more of the area of the heating plate that constitutes the heating part and is exposed to the outside. This is the method for quantifying the low-volatile substance. 【0025】 In addition, in the method for quantifying the low-volatile substance, a low-volatile substance detector provided with a crossbar at the ventilation port is used. This is the method for quantifying the low-volatile substance. 【0026】 In addition, in the method for quantifying the low-volatile substance, the sampling paper uses high-quality paper with a thickness of 25 to 95 μm. This is the method for quantifying the low-volatile substance. 【0027】 In addition, in the method for quantifying the low-volatile substance, the sampling paper displays a mark at the location where the measurement target substance should adhere. This is the method for quantifying the low-volatile substance. 【0028】 In addition, in the method for quantifying the low-volatile substance, before installing the sampling paper in the sampling paper holder, a process for reducing the blank amount of the sampling paper is performed. This is the method for quantifying the low-volatile substance. 【0029】 In addition, in the method for quantifying the low-volatile substance, the process for reducing the blank amount of the sampling paper is one or more processes selected from drying, depressurization, vacuum drying, heating followed by vacuum drying, or including an adsorbent that adsorbs atmospheric impurities in the container during storage. This is the method for quantifying the low-volatile substance. 【0030】 In addition, in the method for quantifying the low-volatile substance, the sampling paper is stored in a sealed container before use. This is the method for quantifying the low-volatile substance. 【0031】 Furthermore, in the above method for quantifying low-volatility substances, the sealed container is an aluminum bag with a zipper. 【0032】 Furthermore, in the above method for quantifying low-volatile substances, the sampling paper is a sampling paper that has undergone a blank test in which the blank amount is measured in advance using chromatography. 【0033】 Furthermore, the above method for quantifying low-volatile substances involves using a storage and transfer apparatus that includes a storage apparatus, which is a container for storing a marker sample solution containing the substance to be measured, and a transfer apparatus for absorbing and retaining the marker sample solution stored in the storage apparatus and transferring it to the collection paper, thereby transferring the low-volatile substance to the collection paper. 【0034】 Furthermore, in the above method for quantifying low-volatility substances, the storage and transfer equipment is an ink-embedded penetrating stamp, a liquid ink-filled pen, or a cotton swab. 【0035】 Furthermore, the above method for quantifying low-volatile substances involves using a marking pen filled with liquid ink to trace a mark on the collection paper and transfer the low-volatile substance to the collection paper. 【0036】 Furthermore, the above method for quantifying low-volatility substances is a method for quantifying low-volatility substances in which the low-volatility substance is an explosive substance, such as a nitro compound or an organic peroxide. 【0037】 Furthermore, the method for quantifying low-volatility substances involves transferring the low-volatility substance from a marker sample solution containing the low-volatility substance to the collection paper, quantifying it, and confirming the operation of the low-volatility substance detector. [Effects of the Invention] 【0038】 As described above, the present invention makes it possible to improve the quantitative accuracy of measurements in the quantitative analysis of low-volatility substances, particularly in the simple analysis of residues. It also makes it possible to improve the quantitative accuracy of measurements in the quantitative analysis of nitro compounds using the chemiluminescence method. Furthermore, it makes it possible to improve operator safety in inspections using low-volatility substance detectors containing [specific components]. Moreover, it makes it possible to provide a measuring instrument for the quantitative analysis of low-volatility substances that is highly safe for the human body. Furthermore, in the quantitative analysis of low-volatility substances, it makes it possible to provide a measuring instrument that has little influence on quantitative analysis by the measuring instrument used, has small differences in the amount of blank for each measuring instrument, and can perform accurate quantitative measurements. [Brief explanation of the drawing] 【0039】 [Figure 1] Perspective view of one embodiment of the present invention [Figure 2] Exploded perspective view of one embodiment of the present invention [Figure 3] Perspective view of the usage state of one embodiment of the present invention [Figure 4] Conceptual diagram of one embodiment of the present invention [Figure 5] Sample paper holder - one embodiment (a) Front perspective view (b) Back perspective view [Figure 6] Sample paper holder and other examples (a) Front perspective view (b) Back perspective view [Figure 7] Front view of one example of a paper collection sample [Figure 8] Diagram showing an example of storage and transfer equipment. [Figure 9] Graph showing measurement results from a low-volatility substance detector. [Figure 10] Chromatogram of blank test of sample paper [Figure 11] Chromatogram of blank test of sample paper [Figure 12] Graph showing the luminescence intensity of the blank sample paper. [Figure 13] Graph showing the relationship between the thickness of the sample paper and the amount of blank paper used to collect light, and the resulting luminescence intensity. [Figure 14] Graph showing the luminescence intensity of the printed and blank areas on the sample paper. [Figure 15]Graph showing the luminescence intensity of the blank sample paper. [Figure 16] Luminous intensity graph diagram using a storage and transfer device according to one embodiment of the present invention. [Figure 17] Paper collection holder - Conventional example (a) Front perspective view (b) Back perspective view [Modes for carrying out the invention] 【0040】 The present invention is a low-volatility substance detector that detects low-volatility substances by heating, vaporizing, and further decomposing a low-volatility substance, causing a chemiluminescence reaction in a reaction vessel, and detecting the light emitted by the chemiluminescence reaction with a photomultiplier tube. It also describes a method for quantitatively analyzing low-volatility substances by heating a measuring instrument containing the target low-volatility substance, heating, vaporizing, and decomposing the low-volatility substance, and then quantifying the low-volatility substance using the chemiluminescence method. Low-volatility substances are analyzed by wiping the surface of the object to be tested with a collection paper, or by applying a solution containing the low-volatility substance to a collection paper and heating the collection paper. 【0041】 Furthermore, the present invention provides a method for quantifying a low-volatile substance in a marker sample solution containing a low-volatile substance that is the target of quantitative analysis, by holding the marker sample solution in a measuring instrument, and heating, vaporizing, and decomposing the low-volatile substance using a chemiluminescence method. The invention also provides a method for evaluating the amount of the low-volatile substance that is the target of quantitative analysis and is the target of measurement, by comparing this quantitative value with a threshold value of the low-volatile substance that is the target of quantitative analysis and is the target of measurement, collected from the object to be tested using a sampling and detection instrument. 【0042】 In this invention, "blank" refers to substance components derived from the measuring instrument other than the substance component to be measured, and is a substance that affects quantitative analysis. Furthermore, the blank includes not only substance components that constitute the measuring instrument, but also substance components that subsequently adhere to the measuring instrument. 【0043】 Embodiments of the present invention will be described below with reference to the drawings. As shown in Figures 1 to 4, the low-volatility substance detector 1 of the present invention comprises a sample introduction unit 11 equipped with a heating unit 111 for heating and vaporizing low-volatility substances, a pyrolysis unit 112, and a sample introduction tube 113, a reaction vessel 13 containing an alkaline aqueous solution 139, a detection unit 140 equipped with a photomultiplier tube 141, a suction pump 15, a monitor 16, a control unit 19 for controlling the low-volatility substance detector 1, and a collection paper holder 2. 【0044】 A heating plate 119 for heating the collection paper 9 is exposed at one end of the low-volatility substance detector 1, forming a heating section 111 exposed to the outside of the low-volatility substance detector 1. The tip of a sample introduction tube 113 made of quartz protrudes from the heating plate 119 that constitutes the heating section 111, forming a sample inlet 118 for sending the low-volatility substance sample to the sample introduction tube 113 and the reaction vessel 13. Heaters 116 are installed on the back surface of the heating plate 119 and around the parts of the sample introduction tube 113 other than the sample inlet 118, to heat the heating plate 119 and the sample introduction tube 113. In the exposed heating section 111, the collection paper 9 to which the low-volatility substance such as explosive material has adhered is heated by the heating plate 119, vaporizing the low-volatility substance attached to the collection paper 9. The vaporized low-volatility substance is then sucked in through the sample inlet 118 by the suction pump 15 and sent inside the low-volatility substance detector 1. There, it is heated and decomposed in the sample introduction tube 113, which is connected to the reaction vessel 13. In other words, it is thermally decomposed in the thermal decomposition section 112 of the sample introduction section 11, generating nitrogen dioxide, and the sample decomposed in the sample introduction tube 113 is sent to the reaction vessel 13. In the reaction vessel 13, the nitrogen dioxide is brought into contact with an alkaline aqueous solution 139 to cause a chemiluminescence reaction, and the light K emitted by the chemiluminescence reaction is detected by the photomultiplier tube 141 to detect the low-volatility substance. The detection section 140 is equipped with a photomultiplier tube 141, as well as a signal amplification circuit 142 and a high-voltage power supply 143. The suction pump 15 is also connected to an exhaust port 159 that discharges the reacted substance to the outside. 【0045】 The control unit 19 is configured with a processing unit comprising a CPU, and a storage device comprising ROM, RAM, or memory for storing computer programs and various data, and is switched on and off by a switch 190. The control unit 19 also processes information transmitted from the detection unit 140, calculates the concentration of the detected low-volatile substance, compares the concentration of the low-volatile substance with a threshold, and these are performed by a program stored in the storage device being executed under the control of the CPU of the processing unit. 【0046】 Furthermore, the low-volatility substance detector 1 can display operating instructions and other information on the monitor 16. It can also process the detected light information transmitted from the detection unit 140, output it externally, and use separate software to plot the luminescence against time, graph the results, and monitor the results. It can detect low-volatility substances. 【0047】 The collection paper 9 is a device for heating a low-volatility substance, which is the substance to be measured, with the low-volatility substance detector 1. By heating the paper together with the held low-volatility substance, the low-volatility substance is vaporized and supplied to the low-volatility substance detector 1. The paper used for the collection paper 9 is not particularly limited, but it is preferable to use high-quality paper made from 100% chemical pulp produced from wood or grass, which has no coating on the surface and has less blank space and is good at holding low-volatility substances. The thickness of the collection paper 9 is preferably 25 to 95 μm. If it is less than 25 μm, it is too thin and difficult to handle, and if it is thicker than 95 μm, the vaporization of explosive substances that have seeped deep into the collection paper will not occur properly, making it difficult to quantify the substance. In addition, the collection paper 9 is rectangular, and it is preferable that the corners at both ends on the side that is inserted into the collection paper holder 2 (described later) are chamfered to prevent snagging and allow for smooth insertion into the collection paper holder 2. 【0048】 Furthermore, as shown in Figure 7, it is preferable to mark the surface of the collection paper 9 by printing or other means the areas that will be inserted into the collection paper holder 2 and heated, in other words, the areas where the surface of the object to be tested will be wiped, or where a marker sample solution containing a low-volatile substance will be applied to adhere to the low-volatile substance that is the substance to be measured. With this configuration, the low-volatile substance attached to the collection paper 9 can be reliably and accurately quantitatively analyzed. The mark is not limited to this, but can consist of a dotted cross mark 91 or a solid circle 92 printed on the collection paper 9. When transferring the marker sample solution, tracing the dotted line ensures that the length is constant, allowing a constant amount of marker sample solution to be attached, thereby improving the accuracy of quantitative analysis. 【0049】 On the outer front of the heating section 111, heating plate 119, and sample inlet 118 of the sample introduction tube 113 of the low-volatility substance detector 1, a collection paper holder 2 is detachably installed facing the heating section 111, heating plate 119, and sample introduction tube 113, for positioning the collection paper 9 facing the heating section 111. The collection paper holder 2 is equipped with screws 28 and pins 29, which are inserted into screw holes 191 and pin holes 192, respectively, provided on the front surface 190 of the cover 19, which covers the front and sides of the sample inlet of the low-volatility substance detector 1 and protects the operator from the heat generated by the sample introduction section, thereby fixing the collection paper holder 2 to the low-volatility substance detector 1. 【0050】 As clearly shown in Figures 5(a) and 5(b), the sample collection paper holder 2 is equipped with an installation opening 21 for positioning the sample collection paper 9 facing the heating unit 111, heating plate 119, and sample inlet 118, and is also equipped with a ventilation opening 22 with openings on the parts facing the heating unit 111 and heating plate 119. The installation opening 21 is provided at the top of the sample collection paper holder 2, and a support shelf 23 is provided below the installation opening 21 to support the lower end of the sample collection paper 9. The sample collection paper 9 is inserted through the installation opening 21 and installed while being supported by the support shelf 23. The dimensions of the installation opening 21 are configured according to the shape and dimensions of the sample collection paper 9 to be installed, but if the width of the sample collection paper 9 is 35 mm and the thickness is 65 μm, it is preferable to have a width of 37 mm and a depth of 80 to 200 μm for ease of insertion. The length from the installation opening 21 to the support shelf 23 is not particularly limited, but can be about 30 to 35 mm. 【0051】 The ventilation opening 22 is an opening for discharging low-volatile substances that remain in the sample collection paper holder 2 after vaporizing during the detection and quantification of low-volatile substances, and are not immediately drawn into the detector, to the outside of the sample collection paper holder 2. Furthermore, the ventilation opening 22 is an opening for ventilating the area around the heating section 111 and sample collection port 118 by discharging the sample from the ventilation opening 22 to prevent the sample vaporized in the previous detection and quantification of low-volatile substances from accumulating and remaining near the heating section 111 and sample collection port 118, thereby preventing it from affecting the next measurement as a blank. The shape of the ventilation opening 22 is not particularly limited and can be the same shape as the heating plate 119, and can be concentric circles centered on the sample collection port 118 when viewed from the side. 【0052】 The ventilation opening 22 is provided with a grid-like support beam 25. The support beam 25 is located on the outside of the support shelf, and when the collection paper 9 is placed in the collection paper holder 2, the heating plate 119 and the sample inlet 118 face the collection paper 9, with the collection paper 9 positioned between the heating plate 119 and the sample inlet 118 and the support beam 25. This support beam 25 prevents the worker from touching the heating plate 119 and the sample inlet 118, thus ensuring safety. The gaps between the grid-like support beams are preferably 6.3 mm or less to prevent the worker's fingers from getting caught. It is also preferable to provide a support beam 25 on the part facing the sample inlet 118. This configuration prevents the worker's fingers from coming into contact with the sample inlet 118 via the collection paper 9, making it safer, and also prevents the sample inlet 118 from being blocked and hindering the introduction of the sample. 【0053】 The area of ​​the ventilation opening 22, or the area of ​​the ventilation opening 22 in the part other than the rail 25 if a rail 25 is provided, may be the same as or different from the area of ​​the heating plate 119. However, it is preferable that the area of ​​the ventilation opening 22 be 30% or more of the area of ​​the heating plate 119, and more preferably 60% or more of the surface area of ​​the heating plate 119. This is because if it is 30% or more, sufficient ventilation can be achieved in a short time, and if it is 60% or more, even more sufficient ventilation can be achieved in an even shorter time. 【0054】 The struts 25 are installed vertically, but they may also be installed horizontally or in other orientations. Furthermore, the struts 25 are installed in a ladder-like configuration, but they may also be installed in a grid-like configuration, extending radially from the opposite side of the sample inlet 118, or in other configurations. The ventilation opening 22 may be configured to open the entire surface opposite the heating section, as shown in Figures 6(a) and 6(b). However, there is no significant difference in the measurement results between having the struts 25 and not having them, so it is preferable to have the struts 25 for the safety of the operator. Additionally, the installation opening 21 may be provided on the side of the sample paper holder 2, allowing the sample paper 9 to be inserted from the side. 【0055】 When using the low-volatility substance detector 1, by placing the collection paper 9 in the collection paper holder 2, the collection paper 9 can be placed parallel to the heating unit 111, and the entire surface of the collection paper 9 can be placed at the same distance as the heating unit 111, enabling efficient and reliable vaporization of low-volatility substances and accurate detection results. Furthermore, since the operator does not need to hold the collection paper 9 over the heating unit 111 by hand and press it, the operator will not suffer burns, ensuring safety. However, if the collection paper 9 is pressed by hand without using the collection paper holder 2, the sample inlet 118 may be blocked, or the entire surface of the collection paper 9 may not be placed at the same distance as the heating unit 111, which may prevent efficient and reliable vaporization of low-volatility substances and accurate detection results. 【0056】 Chemiluminescence is a method of detecting trace substances remaining on the surface of an object to be tested by wiping it with a detection device made of paper, nonwoven fabric, resin, etc., and then thermally decomposing the substance. For example, if a nitro compound, which is an explosive substance, is used as a trace substance, it is converted to nitrogen oxide, and the luminescence intensity produced by the chemical reaction between the nitrogen oxide, which is the substance to be measured, and an alkaline aqueous solution is quantitatively detected using a photomultiplier tube or similar device. The maximum value of the luminescence is monitored to perform a quantitative analysis of the trace substance. Objects to be tested are often human bodies, clothing, bags, and other items that have the substance to be measured attached to them. 【0057】 A method for detecting low-volatility substances using a chemiluminescence apparatus will be explained using an example with a low-volatility substance detector 1. The low-volatility substance detector 1 has threshold values ​​set and stored for each substance to be measured. The surface of the object to be tested is wiped with a collection paper 9, and the collection paper 9 is inserted into the collection paper holder 2. The collection paper 9 is then brought close to the heating section 111 of the low-volatility substance detector 1, heated, and vaporized. The vaporized sample is then drawn into the sample introduction tube 113 from the sample inlet 118 using a pump 15. In the sample introduction tube 113, it is further heated to approximately 600°C to decompose, and the resulting substance, such as nitrogen dioxide, is sent to the reaction vessel 13. Any low-volatility substances remaining in the collection paper holder 2 that are not immediately drawn into the low-volatility substance detector 1 are discharged outside the collection paper holder 2 through the ventilation port 22. In the reaction vessel 13, the nitrogen dioxide comes into contact with an alkaline aqueous solution, and the resulting light K is quantitatively detected using a photomultiplier tube 141. Then, by monitoring and / or recording the maximum luminescence, the target substance, which is a low-volatility substance such as explosive material, is quantified, and the quantified value is displayed on monitor 16. Furthermore, while observing the value displayed on monitor 16 of the low-volatility substance detector 1, the collection paper 9 is removed once it is confirmed that the peak value has decreased. 【0058】 Furthermore, the system compares a pre-recorded threshold with the quantitative value of the low-volatile substance targeted for quantitative analysis, which is collected from the object being tested, to evaluate the amount of low-volatile substance attached to the object. If the quantitative value of the low-volatile substance collected from the object is above the threshold, the system evaluates that there is trace of an explosive and issues a warning through sound, display, etc. 【0059】 When detecting low-volatility substances consecutively, after the previous measurement is completed, the sample paper 9 placed in the sample paper holder 2 during the previous quantification is removed. Any low-volatility substances that were vaporized during the previous detection and quantification and remain near the heating unit 111 and sample inlet 118 are discharged through the ventilation port 22 of the sample paper holder 2, preferably all of them, or at least only an amount that does not affect the blank remaining. After ventilating the heating unit 111 and the area around the sample inlet 118, a new sample paper 9 is placed in the sample paper holder 2, and a new detection is performed. This method prevents residual samples from the previous measurement from affecting the next measurement as a blank. 【0060】 Furthermore, prior to the detection method for low-volatility substances described above, it is also possible to verify that the low-volatility substance detector 1 is functioning correctly. A marker sample solution or measuring instrument can be used for such verification. 【0061】 A marker sample solution is a sample solution prepared by dissolving a low-volatility substance to be quantitatively analyzed in a solvent to a predetermined concentration. It consists of a solution containing the same substance as the target substance, a substance with the same functional group, a substance with a similar structure, or a detection agent used to add to the target substance, all adjusted to a specific concentration in the solvent. For example, in the case of detecting explosive traces, the marker sample solution may contain nitro compounds such as penslit (PETN), nitroglycerin, trinitrotoluene, cyclotetramethylenetetranitramine, and cyclotrimethylenetrinitramine; detection agents such as nitroglycol (ethylene glycol dinitrate) and dimethyldinitrobutane; and substances such as 2,3-dimethyl-2,3-dinitrobutane and para-mononitrotoluene. Furthermore, various organic solvents such as ethanol and isopropanol, inorganic solvents, or mixtures of these with water can be used as the solvent for the marker sample solution. The concentration of the marker sample solution only needs to be sufficient to detect the threshold, and can be adjusted to a predetermined concentration depending on the purpose. 【0062】 As measuring instruments, storage instruments, transfer instruments, detection instruments, transfer-detection instruments, storage-transfer instruments, storage-detection instruments, and sampling-detection instruments can be used. A storage instrument is a container for storing a marker sample solution containing the low-volatile substance, in other words, the substance to be measured, that is the target of quantitative analysis, collected from the object to be analyzed. A transfer instrument is an instrument for absorbing and holding the marker sample solution stored in the storage instrument and transferring it to the detection instrument. A detection instrument is an instrument for transferring the marker sample solution stored in the storage instrument using the transfer instrument and heating it while holding the low-volatile substance, thereby heating it together with the low-volatile substance and decomposing and vaporizing it. Furthermore, a transfer-detection instrument is an instrument that combines the functions of a transfer instrument and a detection instrument, a storage-transfer instrument is an instrument that combines the functions of a storage instrument and a transfer instrument, and a storage-detection instrument is an instrument that combines the functions of a storage instrument and a detection instrument. Furthermore, a sampling-detection instrument is an instrument that combines the functions of an instrument for collecting the substance to be measured from the object to be tested and an instrument for detection. 【0063】 The storage container is not particularly limited, as long as it has a lid that seals tightly and is airtight, and is not degraded by the marker sample solution stored inside, and does not degrade the marker sample solution. Polypropylene bottles are preferred because they are made of synthetic resin, are lightweight, and are resistant to water-soluble organic solvents. In addition, their airtightness helps to reduce evaporation of the marker sample solution. The capacity is not particularly limited, but 1 to 50 mL is easy to use. Since the marker sample solution is stored and used in the storage container, contamination of other testing supplies and exposure of the human body to explosives are minimal, which is preferable. 【0064】 The transfer device is not particularly limited as long as it ensures reproducibility when transferring the marker sample solution to the detection device. Known disposable cotton swabs or water-based pen tips, which have a cotton part and a stick part capable of holding a predetermined amount of solution, can be used. The size of the transfer device is not particularly limited, but it can be selected to be a size that is easy to put in and take out of storage containers such as bottles, and that can come into contact with the heating part of chemiluminescence devices, which are low-volatility substance detectors such as explosive residue detection devices. By using such storage and transfer devices, the preparation, storage, and use of marker sample solutions of different concentrations are made easy. Furthermore, the sampling and detection device can have the same configuration as the transfer device. 【0065】 The size of the cotton swab is not particularly limited, and the size of the cotton portion that absorbs and holds the marker sample solution is not particularly limited as long as it can hold a predetermined amount of solution. However, a size of approximately 2 to 10 mm in outer diameter, 5 to 15 mm in length, and 5 to 15 cm in length for the stick portion is preferable as it is easy to use with one hand and easy to store. The material of the cotton swab is not particularly limited as long as there is no elution of substances that affect quantitative analysis when heated, but a material with a melting point of 150°C or higher is preferred. Cotton swabs made of nonwoven fabric with a cotton portion, and even more preferably with a paper stick portion, are the most preferred because they are heat resistant, can be directly placed in the heating section of chemiluminescence apparatus such as low-volatility substance detectors, and have a small amount of blank material, which is a factor that affects quantitative analysis due to substances derived from the measuring instrument other than the target substance component. Synthetic resin materials such as polyester for the cotton portion or stick portion can be used as transfer instruments, but when using the cotton swab as a transfer detection instrument, it is not preferred because it has a lower melting point than cotton and melts easily when directly heated. The cotton portion of the cotton swab should preferably have sufficient surface tension to absorb and retain the marker sample solution, and ideally be able to absorb and hold 0.05g or more of the solution. General commercially available cotton swabs can also be used as they can absorb and retain about 0.25g of water. 【0066】 The transfer device absorbs and holds the marker sample solution, and instead of using the detection device, its absorption portion can be directly placed in the heating section of a low-volatility substance detector used in chemiluminescence to measure low-volatility substances. Although the transfer device may be directly placed in the heating section of the chemiluminescence device, it is preferable to transfer the marker sample solution to the detection device, as this could cause the device to deteriorate or become contaminated. 【0067】 Furthermore, the storage and transfer equipment can be detachably connected to each other, or integrally joined together to form a single integrated storage and transfer device. While not limited to these, for example, a configuration where each is detachably connected could use a bottle with an absorbent section on the lid, such as a nail polish bottle, that absorbs and holds the marker sample solution, like a brush or sponge. Since the marker sample solution is absorbed into the absorbent section integrated with the lid, it can be used as is after removing the lid, and can also be stored as is after closing the lid. Alternatively, the absorbent section can be replaced with a cotton swab. 【0068】 Furthermore, as a storage and transfer device, an integrated configuration can be used, such as a known wet cotton swab, in which the cotton portion of the swab absorbs and holds the marker sample solution, and which is individually sealed in a resealable aluminum bag or the like. Alternatively, a known unfilled liquid ink filling pen 10, as shown in Figure 8(a), can be used, which comprises a cylindrical body 11 and a pen tip 12. A predetermined marker sample solution 13 can be freely selected and stored in the cylindrical body 11, and the marker sample solution 13 stored in the cylindrical body 11 can be absorbed by the pen tip 12 and transferred to the detection device by writing on it like a pen. 【0069】 Such a liquid ink-filled pen is not particularly limited in shape, as long as the marker sample solution is filled into a cylindrical body, the marker sample solution can be sealed, and a constant amount of the marker sample solution can be supplied through the pen tip. However, as shown in Figure 8(b), the liquid ink-filled pen 10 may be configured such that a cotton swab 16 containing the marker sample solution 13 is filled into a cylindrical body 11. Alternatively, as shown in Figure 8(c), the pen tip 12 may be held in place by a spring 17 or a bellows-shaped resin to prevent leakage of the marker sample solution. Furthermore, as shown in Figure 8(d), the pen may be configured such that when the pen tip 12 is pressed, a valve 18 is pressed, and the marker sample solution 13 is supplied to the pen tip 12. Alternatively, as shown in Figure 1(d), a ball 19 may be placed inside the cylindrical body 11 to allow stirring of the marker sample solution 13. Also, as shown in Figure 8(a), it is preferable that the liquid ink-filled pen 10 is equipped with a cap 14 to prevent the marker sample solution from evaporating. The end of the cylindrical body 11 may be a dead end, or it may be equipped with a tail cap 15. Furthermore, the pen tip 12 can be selected to be core-shaped, brush-shaped, or otherwise. 【0070】 The liquid ink filling pen is convenient because, by pre-filling the cylindrical body with the marker sample solution and ensuring airtightness with a cap and tail plug, the process of transferring the marker sample solution to the detection instrument can be started simply by removing the cap at the testing site. Alternatively, the liquid ink filling pen may be used without pre-filling the cylindrical body with the marker sample solution; instead, the marker sample solution may be transferred and filled into the cylindrical body from another storage instrument at the testing site. 【0071】 Furthermore, known ink-embedded impregnation stamps can also be used as storage and transfer devices. Additionally, as storage and detection devices, cotton swabs in which the marker sample solution has been absorbed and held in the cotton portion, and which are individually sealed in resealable aluminum bags, can be used. The cotton swab can then be removed from the packaging and the cotton portion can be placed directly on the heating element of the low-volatility substance detector. 【0072】 This configuration, in which the marker sample solution is stored in a storage device and transferred to the detection device using a transfer device, is preferable because it minimizes contamination of other testing supplies and virtually eliminates exposure of the explosive to the human body. Furthermore, by using a storage and transfer device, the marker sample solution can be used without moving it from the storage device to the transfer device, making it easier for the marker sample solution to adhere to the detection device. 【0073】 Furthermore, as a detection device, to support quantitative analysis, a collection paper 9 can be used which has markings printed on it, such as the one described above, indicating where a certain amount of marker sample solution should be attached. 【0074】 Furthermore, measuring instruments such as storage instruments, transfer instruments, detection instruments, transfer detection instruments, storage transfer instruments, storage detection instruments, and sampling detection instruments should preferably be stored in airtight containers such as resealable aluminum bags before use to prevent contamination and impurity incorporation during storage and to prevent an increase in the blank quantity. While resealable aluminum bags are preferred as airtight containers, resealable synthetic resin bags can also be used. It is also preferable to store the measuring instruments under reduced pressure when placing them in the bag. Furthermore, it is preferable to dry the measuring instruments before placing them in the bag. When drying the measuring instruments, vacuum drying is preferred, and vacuum drying is not limited to this, but can be performed by heating at 50°C for 3 hours. Thus, drying, reduced pressure, or vacuum drying can be applied to the measuring instruments as a treatment to reduce the blank quantity of the measuring instruments. In addition, it is preferable to include an adsorbent such as activated carbon in the storage container. The adsorbent is not limited to activated carbon, but can be any material that absorbs and adsorbs airborne impurities, such as silica gel, molecular sieves, or phosphorus pentoxide. 【0075】 Furthermore, the blank amount of measuring instruments such as storage instruments, transfer instruments, detection instruments, transfer detection instruments, storage transfer instruments, storage detection instruments, and sampling detection instruments is preferably 10% or less of the amount of the target substance, as this has little effect on the quantitative determination of the target substance. If the blank amount of measuring instruments is large, it becomes difficult to accurately grasp the threshold that serves as the standard for evaluating the quantitative determination of low-volatile substances, making it impossible to perform accurate comparative testing and evaluation of low-volatile substances. In addition, if the blank amount of measuring instruments is large, the variation in the blank amount of each measuring instrument becomes larger, and if the blank amount is greater than 10% of the amount of the target substance, the variation in the blank amount becomes large, and in tests to confirm the threshold that serves as the standard for evaluating the quantitative determination of low-volatile substances, the threshold value will fluctuate depending on the measuring instrument, making it impossible to perform accurate comparative testing and evaluation of low-volatile substances. If a measuring instrument is composed of multiple parts, it is preferable that the blank amount of each part is 10% or less of the amount of the target substance. 【0076】 For these reasons, it is preferable to use measuring instruments such as storage instruments, transfer instruments, detection instruments, transfer detection instruments, storage transfer instruments, storage detection instruments, and sampling detection instruments that come into contact with the sample, after performing a blank test using chromatography to determine the amount of blank beforehand. The process of selecting measuring instruments by blank testing is called optimization. This configuration allows for confirmation that there is no or minimal blank, and / or no variation in the amount of blank, before providing instruments to the testing site, thereby improving the accuracy of quantitative analysis. Furthermore, it is preferable to use measuring instruments where the amount of blank is 10% or less of the target substance analysis value measured by chromatography. Therefore, in the chromatographic test, it is preferable that the area ratio of the chromatogram peaks is 10% or less of the area ratio of the blank peak compared to the peak of the target substance. Note that the pre-emptive blank test using chromatography for measuring instruments may be performed on all products, or it may be performed on a predetermined number of instruments, for example, per lot. 【0077】 Blank testing can be performed using gas chromatography or liquid chromatography, and the analytical conditions and methods are not particularly limited. For example, thermal extraction GC / MS can be used. This method involves weighing 1 to 20 mg of instrument fragments into an insert liner for a thermal extraction device such as the OPTIC-4 (Shimadzu Corporation), directly placing the liner in the insert liner, extracting at 200°C, and then subjecting the sample to GC / MS measurement. 【0078】 A method for detecting nitro compounds, which are low-volatility substances, using a chemiluminescence apparatus will be explained using an example with a low-volatility substance detector. First, to confirm that the low-volatility substance detector operates correctly at the set threshold for the target substance, the low-volatility substance in the marker sample solution is quantified. Note that the low-volatility substance detector has a threshold value set and stored for each target substance. Specifically, the method for quantifying the low-volatility substance involves transferring the marker sample solution containing the explosive substance (the target substance to be measured at the threshold concentration) from a storage and transfer device (storage and transfer device) such as a liquid ink-filling pen to a collection paper used as a detection device. Then, the collection paper 9 is inserted into the collection paper holder 2 and placed close to the heating unit 111 of the low-volatility substance detector 1, where it is heated and vaporized. The vaporized sample is then drawn into the sample introduction tube 113 from the sample inlet 118 by a pump 15, and further heated to around 600°C in the sample introduction tube 113 to decompose it, and the resulting nitrogen dioxide is sent to the reaction vessel 13. In the reaction layer 13, nitrous oxide comes into contact with an alkaline aqueous solution, and the resulting light emission is quantitatively detected using a photomultiplier tube 141. By monitoring and / or recording the maximum luminescence, the target substance, such as explosives, is quantified, and it is confirmed that the low-volatility substance detector operates correctly at the threshold concentration. If the quantitative value of the low-volatility substance exceeds the threshold, notification is given by sound, display, etc. 【0079】 Next, the low-volatility substance remaining on the surface of the object to be inspected, which is the target substance for quantitative analysis, is wiped off with a collection paper and collected. The collection paper 9 is then inserted into the collection paper holder 2 and placed close to the heating section 111 of the low-volatility substance detector 1, where it is heated and vaporized. The vaporized sample is then drawn into the sample introduction tube 113 from the sample inlet 118 by a pump 15, and further heated to around 600°C in the sample introduction tube 113 to decompose it. The resulting substance, such as nitrogen dioxide, is sent to the reaction tank 13. In the reaction tank 13, the nitrogen dioxide comes into contact with an alkaline aqueous solution and the light emitted is quantitatively detected using a photomultiplier tube 141. Then, the system compares a threshold value pre-recorded in the low-volatility substance detector with the quantitative value of the low-volatility substance targeted for quantitative analysis collected from the object being tested to evaluate the amount of low-volatility substance attached to the object. If the quantitative value of the low-volatility substance targeted for quantitative analysis collected from the object is above the threshold value, the system evaluates that there is trace of an explosive and issues a warning through sound, display, etc. 【0080】 Furthermore, another detection method for nitro compounds, which are low-volatility substances, using a chemiluminescence apparatus will be explained using an example with a low-volatility substance detector. First, the apparatus is checked to ensure it is functioning correctly, and the low-volatility substance in the marker sample solution is quantified. Note that the low-volatility substance detector does not have a set threshold value for the substance to be measured. Specifically, the marker sample solution containing the explosive substance (as the substance to be measured at the threshold concentration) is transferred from a storage and transfer device such as a liquid ink-filling pen to a collection paper used as a detection device. The collection paper 9 is then inserted into the collection paper holder 2 and placed close to the heating section 111 of the low-volatility substance detector 1, where it is heated and vaporized. The vaporized sample is then drawn into the sample introduction tube 113 from the sample inlet 118 using a pump 15, and further heated to around 600°C in the sample introduction tube 113 to decompose it, and the resulting nitrogen dioxide is sent to the reaction vessel 13. In the reaction layer 13, nitrous oxide comes into contact with an alkaline aqueous solution, and the light emitted is quantitatively detected using a photomultiplier tube 141. By monitoring and / or recording the maximum luminescence, the target substance, such as explosives, is quantified, confirming whether the low-volatility substance detector is functioning correctly and confirming the threshold value that serves as the basis for quantification. 【0081】 Next, the low-volatility substance, which is the target substance for quantitative analysis, remaining on the surface of the object to be inspected is wiped off and collected using a collection paper, which is used as a detection device. The collection paper 9 is then inserted into the collection paper holder 2 and placed close to the heating section 111 of the low-volatility substance detector 1, where it is heated and vaporized. The vaporized sample is then drawn into the sample introduction tube 113 from the sample inlet 118 using a pump 15, and further heated to around 600°C in the sample introduction tube 113 to decompose it, and the resulting nitrogen dioxide is sent to the reaction vessel 13. In the reaction vessel 13, the nitrogen dioxide comes into contact with an alkaline aqueous solution and the light emitted is quantitatively detected using a photomultiplier tube 141. The amount of low-volatility substance attached to the object to be inspected is evaluated by comparing the threshold obtained using the marker sample solution with the quantitative value of the low-volatility substance targeted for quantitative analysis collected from the object to be inspected. Specifically, if the amount of low-volatility substance exceeds the threshold, it is evaluated as an explosive trace, and a warning is issued by sound, display, etc. [Examples] 【0082】 Measurements were taken with various shapes of paper collection holders installed in front of the sample inlet of the low-volatility substance detector to confirm the effect of the paper collection holder's shape on the low-volatility substance detector's data. Paper collection holders equipped with an installation opening 21 for installing paper collection 9 were used. Examples included: Paper collection holder 20 (Example 1-1), shown in Figure 6, which had a ventilation opening 22 with an area of ​​90% of the heating plate 119 open, without any ribs on the opposite side of the heating section 118 of the low-volatility substance detector; Paper collection holder 2 (Example 1-2), shown in Figure 5, which had ribs 25 arranged in a grid pattern on the opposite side of the heating section 118 of the low-volatility substance detector, forming a ventilation opening 22 with an area of ​​60% of the heating plate 119 open; and Paper collection holder 2 (Example 1-2), shown in Figure 5, which had ribs 25 arranged in a grid pattern on the opposite side of the heating section 118 of the low-volatility substance detector, forming a ventilation opening 22 with an area of ​​60% of the heating plate 119 open. As a comparative example, paper collection holder 200 (Comparative Example 1-1), shown in Figures 17(a) and 17(b), which did not have a ventilation opening and the ventilation opening portion of the examples was covered by a plate 201. As a comparative example, measurements were also taken without installing a paper collection holder (Comparative Example 1-2). The dimensions of the paper collection holder opening were the same for both the example and the comparative example: 33.5 mm in height, 37 mm in width, and 200 μm in depth. 【0083】 A portable explosive detector (GL Sciences Co., Ltd.) was used as a low-volatility substance detector. The portable explosive detector consists of a sample introduction unit equipped with a heating unit and a pyrolysis unit, a reaction vessel containing an alkaline aqueous solution, a detection unit equipped with a photomultiplier tube, and a suction pump. In the pyrolysis unit of the sample introduction unit, a collection paper containing an explosive substance, which is a low-volatility substance, is heated to vaporize the explosive substance, which is then aspirated and pyrolyzed. The resulting nitrogen dioxide is brought into contact with the alkaline aqueous solution in the reaction vessel, and the light emitted by the chemiluminescence reaction is detected by the photomultiplier tube to detect the explosive substance. In addition, the portable explosive detector uses separate software to plot the detected light as luminescence intensity against time and graph it for monitoring. 【0084】 A 100 ppm Penslit (PETN) solution (solvent: isopropanol and acetonitrile) was prepared, and 1 μL of this solution (containing 100 ng of PETN) was dropped onto the center of the X mark on the collection paper using a microsyringe, and the collection paper was dried. This collection paper was inserted into the collection paper holder of a portable explosive detector and measured for 30 seconds. The collection paper used was high-quality paper with a thickness of 65 μm, as shown in Figure 7. The measurement results are shown in the graphs in Figures 9(a) to 9(d). 【0085】 The measurement results using the paper collection holder in Examples 1-1 and 1-2, as shown in the graphs in Figures 9(a) and 9(b), show that the baseline dropped to 1000 counts in the data measured by inserting the paper collection paper into the paper collection holder. That is, the baseline dropped to 1000 counts in 30 seconds from the start of the initial measurement. It was found that when measuring explosive material attached to different paper collection papers and continuously collecting accurate data, it takes less time than the comparative examples described later. 【0086】 Furthermore, the measurement results for Comparative Example 1-2, which did not use a paper collection holder, showed that the baseline dropped to 1000 counts in the data measured by pressing the paper collection sheet against the heating element, as shown in the graph in Figure 9(d). That is, the baseline dropped to 1000 counts in 30 seconds from the start of the initial measurement. It was found that even when measuring explosive material attached to different paper collection sheets and continuously collecting accurate data, the same amount of time as in Examples 1-1 and 1-2 is required. 【0087】 In the measurement results using the paper collection holder in Comparative Example 1-1, as shown in the graph in Figure 9(c), the baseline only dropped to 5000 counts when the paper collection was inserted into the paper collection holder. That is, the baseline only dropped to 5000 counts within 30 seconds of the start of the initial measurement. It was found that accurately collecting data continuously by measuring explosive material attached to different paper collections takes more time than in the examples. 【0088】 In the paper collection holder of Comparative Example 1-1, only an inlet for the paper collection was provided at the sample inlet of the portable explosive detector. As a result, explosive materials that adhered to the paper collection and volatilized remained in the paper collection holder without being immediately drawn into the detector. These explosive materials were not discharged outside the paper collection holder even after the paper collection was removed, but remained near the heating unit 111 and the sample inlet 118. Subsequently, they were drawn into the low-volatility substance detector over time and detected after thermal decomposition. 【0089】 On the other hand, in the paper collection holders of Examples 1-1 and 1-2, an inlet for the paper collection was provided at the sample inlet of the portable explosive detector, and an opening was also provided in the extension direction of the sample inlet. As a result, explosive substances that adhered to the paper collection and vaporized, but were not immediately drawn into the detector and remained in the paper collection holder, were discharged outside the paper collection holder through the ventilation opening 22. Furthermore, after the paper collection was removed, the explosive substances were quickly discharged outside the paper collection holder and did not remain near the heating unit 111 and the sample inlet 118. Therefore, they were not subsequently drawn into the low-volatility substance detector and were not detected. 【0090】 In the paper collection holder of Example 1-1, vertical bars were installed in the ventilation opening to create a grid-like structure. However, there was no difference in data between this and the paper collection holder of Example 1-2, which had no bars in the ventilation opening and was fully open. Furthermore, there was absolutely no difference in data between the paper collection holder of Example 1-1 rotated 90 degrees to create a grid-like structure with horizontal bars in the ventilation opening and the paper collection holder of Example 1-1. 【0091】 From the above, it was found that even when using a paper collection holder equipped with a ventilation opening, accurate data can be collected continuously in the same amount of time as when not using a paper collection holder. Furthermore, it was found that when using a paper collection holder without a ventilation opening, more measurement time is required to continuously collect accurate data compared to when using a paper collection holder with a ventilation opening. [Examples] 【0092】 In the chemiluminescence method for quantifying explosive substances, a blank test was performed on the sampling paper used as a detection instrument using thermal desorption-GC-MS. Untreated sampling paper was used as an example, and sampling paper to which 10 μL of liquid foundation (Lancôme) was dropped and dried was used as a comparative example. The sampling paper used was high-quality paper with a thickness of 65 μm, as shown in Figure 7. The liquid foundation was dropped onto the center of the X mark on the sampling paper. 8 mg of each sampling paper fragment was placed directly into the insert liner of the thermal desorption device OPTIC-4 (Shimadzu Corporation), heated at 200°C, and subjected to GC / MS measurement. 【0093】 Thermal desorption GC / MS conditions Heat desorption device: OPTIC-4 (Shimadzu Corporation) GC-MS: GCMS-QP2010 Plus (Shimadzu Corporation) Column: InertCap 5MS, 0.18mm I.D. × 15m, df=0.18μm (GL Sciences Co., Ltd.) Col.Temp.:40℃(5min)-6℃ / min-250℃ Carrier Gas:He,0.5mL / min(constant flow) Desorption: 200℃ for 3 min Cryo Trap: -120℃ Injection: 250℃ Detection:MS Scan(28.5-600 m / z) 【0094】 The results are shown in the chromatogram in Figure 10. In the untreated sample paper of the example, blank peaks were detected, but the number of blank peaks was small (Figure 10(b)). In the sample paper of the comparative example, liquid foundation was dropped onto the sample paper and dried, and many blank peaks were detected (Figure 10(a)). Furthermore, the area of ​​the blank peaks in the untreated sample paper of the example was less than 10% of the area of ​​the blank peaks in the sample paper of the comparative example. It is clear that a large number and high level of blank peaks reduces the accuracy of quantitative analysis of explosive materials. [Examples] 【0095】 Using HPLC, blank tests were performed on untreated sample paper as an example and on sample paper to which 10 μL of liquid foundation (Lancôme) was dropped and dried as a comparative example. The sample paper used was high-quality paper with a thickness of 65 μm, as shown in Figure 7. The liquid foundation was dropped onto the center of the "X" mark on the sample paper. 【0096】 8 mg of each collection paper fragment was immersed in 5 mL of ethanol in a 10 mL glass vial for 2 hours. The collection paper fragment was then removed, and the ethanol remaining in the vial was used as the HPLC sample. 【0097】 HPLC conditions HPLC: Primaide (registered trademark, Hitachi High-Tech Corporation) Column: InertSustain AQ-C18 (GL Sciences Co., Ltd.) 5 μm 100 × 4.6 mm I.D. Eluent: A) 20mM H3PO4in CH3CN B) 20 mM H3PO4in H2O A / B=10 / 90-3min-10 / 90-10min-90 / 10-3min-90 / 10-0.1min-10 / 90-3.9min hold Flow Rate: 1.0 mL / min Col.Temp.: 40℃ Injection Volume: 10 μL Detection: UV 210nm 【0098】 The results are shown in the chromatogram in Figure 11. No blank peak was detected in the untreated sample paper of the example (Figure 11(b)). Furthermore, no hydrophobic components were detected. In the sample paper of the comparative example, where liquid foundation was dropped onto the paper and dried, a blank peak was detected at the 15.5 min position (Figure 11(a)). [Examples] 【0099】 Using a chemiluminescence method to quantify explosive materials, a portable explosive detector described in Example 1 was used as a low-volatility substance detector, and a blank test of the collection paper used as the detection device was performed. Untreated collection paper was used as the example, and collection paper to which 10 μL of liquid foundation (Lancôme) was dropped and dried was used as a comparative example. The collection paper used was high-quality paper with a thickness of 65 μm, as shown in Figure 7. The liquid foundation was dropped into the center of the X mark on the collection paper. 【0100】 Each collected paper was inserted into the paper collection holder of a portable explosive detector, and measured for 30 seconds. The paper collection holder used was the one shown in Figure 3, which is the paper collection holder of Example 1-1 of Example 1. 【0101】 The results are shown in the luminescence intensity graph in Figure 12. In the untreated sample paper of the example, a low blank of 500 counts was detected, as shown in Figure 12(a). In the sample paper of the comparative example, where liquid foundation was dropped onto the paper and dried, a high blank of 2500 counts was detected, as shown in Figure 12(b). Note that although two graphs are shown in Figure 12(a), both are graphs using the same data. One is the graph of the actual data, and the other is the graph after smoothing using a moving average (32 times). The same applies to Figure 12(b). 【0102】 Comparing the results of Examples 2, 3, and 4, it was found that data for distinguishing between high-blank and low-blank sample papers can be obtained using gas chromatography, liquid chromatography, or chemiluminescence. [Examples] 【0103】 The effect of the thickness of the sample paper, which uses high-quality paper, on the chemiluminescence method for quantifying explosives as low-volatility substances was confirmed using the portable explosive detector described in Example 1 as the low-volatility substance detector. 【0104】 Three types of sample paper with varying thicknesses and printed as shown in Figure 7 were used. As examples, sample paper with a thickness of 65 μm (Example 5-1) and 95 μm (Example 5-2) was used, and as a comparative example, sample paper with a thickness of 120 μm (Comparative Example 5-1) was used. Each sample paper was inserted into the sample paper holder of a portable explosive detector and measured for 60 seconds. The sample paper holder used was the sample paper holder of Example 1-1 of Example 1, as shown in Figure 3. 【0105】 The effect of the sample paper thickness was confirmed by the following four types of measurements. Measurement 1 involved a blank test of the sample paper. Measurement 2 involved preparing a 200 ppm Penslit (PETN) solution (solvent being a mixture of isopropanol and acetonitrile), dropping 1 μL of this solution (containing 200 ng of PETN) onto the center of the X mark on the sample paper using a microsyringe, drying the sample paper, and performing the measurement. Measurement 3 involved dropping 1 μL of the above 200 ppm PETN solution onto a glass plate, wiping it once with another blank sample paper that had undergone the blank test, and performing the measurement. Measurement 4 involved wiping the remaining PETN on the glass plate again with the same sample paper and performing the measurement. 【0106】 The results are shown in the luminescence intensity graph in Figure 13. Example 5-1 is shown in Figure 13(a), Example 5-2 in Figure 13(b), and Comparative Example 5-1 in Figure 13(c). In Figure 13, Measurement 1 is indicated by reference numeral 1, Measurement 2 by reference numeral 2, Measurement 3 by reference numeral 3, and Measurement 4 by reference numeral 4. The result of Measurement 1 (reference numeral 1 in the figure) shows that the blanks of each thickness of sample paper all had a count of 1000, and low blanks were detected in all cases. It was found that the thickness of the sample paper did not affect the blanks. 【0107】 The results of Measurement 2 (indicated by symbol 2 in the figure) were affected by the thickness of the sample paper. In Example 5-1, with a thickness of 65 μm, a single sharp peak was detected. In Example 5-2, with a thickness of 95 μm, a single peak was detected, although it was wider than in the 65 μm case. In Comparative Example 5-1, with a thickness of 120 μm, the peak shape could not be maintained, indicating that quantitative determination of explosive material was difficult. This is because, as the sample paper thickness increases, it takes longer for the explosive material that has soaked into the depths of the sample paper to vaporize, and it also takes longer for the vaporized explosive material to thermally decompose. 【0108】 The results of Measurement 3 (indicated by symbol 3 in the figure) were affected by the thickness of the collection paper. In Example 5-1, with a thickness of 65 μm, one sharp peak was detected. In Example 5-2, with a thickness of 95 μm, two peaks were detected, but since the shape of each peak was sharp, it is thought that the substance adhered to two locations on the collection paper during wiping (one inside the marker (circle) on the collection paper, and the other near the edge of the marker (circle) on the collection paper), indicating that it can be used for the quantitative determination of explosive material. In Comparative Example 5-1, with a thickness of 120 μm, the peak shape was greatly distorted, making it difficult to quantify explosive material. This is because as the collection paper gets thicker, it takes longer for the explosive material that has soaked into the depths of the paper to vaporize, and it also takes longer for the vaporized explosive material to thermally decompose. 【0109】 The results of Measurement 4 (indicated by symbol 4 in the figure) showed no effect from the thickness of the collection paper. This is because the amount of PETN wiped again was minute, and when the amount of explosive material is small, the explosive material adheres only to the surface of the collection paper regardless of its thickness, and does not seep into the deeper layers of the paper. 【0110】 From these results, it was found that if the thickness of the sample paper is 95 μm or less, it is suitable for the quantitative determination of low-volatile substances, including explosives, using chemiluminescence reactions. [Examples] 【0111】 The presence or absence of markings such as the cross mark 91 and circle 92 shown in Figure 7 on the collection paper was used to confirm how it affects the chemiluminescence method for quantifying low-volatile substances, including explosives, using the portable explosive detector described in Example 1 as the low-volatile substance detector. 【0112】 As Example 6-1, a sample paper was prepared by printing an "X" mark 91 and a circle 92 on 65 μm thick high-quality paper, as shown in Figure 7. As Example 6-2, a sample paper was prepared by preparing 65 μm thick high-quality paper without any printing. Each sample paper was inserted into the sample paper holder of a portable explosive detector and measured for 60 seconds. The sample paper holder used was the sample paper holder of Example 1-1 of Example 1, as shown in Figure 3. 【0113】 The results are shown in the luminescence intensity graph in Figure 14. Compared to the sample paper of Example 6-2 ("with printing" in Figure 14), the blank count for the sample paper of Example 6-1 ("without printing" in Figure 14) increased by about 200 counts. However, this is only about one-fifth of the desirable blank count of 1000 counts, indicating that it has almost no effect on the measurement of low-volatility explosive substances. [Examples] 【0114】 The storage conditions of the collected paper were used to determine how they affect the chemiluminescence method for quantifying low-volatile substances, including explosives, by using the portable explosive detector described in Example 1 as the low-volatile substance detector. 【0115】 Sample paper was prepared by printing on 65 μm thick high-quality paper as shown in Figure 7. The sample paper was then stored as follows. (a) The collected paper was placed in a cardboard box and stored in the laboratory for one week. (b) The collected paper was placed in a cardboard box and stored in the laboratory for two months. The sample paper from (c)(b) was dried under reduced pressure at 50°C for 2 hours. (d) The collected paper was placed in a resealable aluminum bag (AS ONE Corporation), the pressure was reduced, and the bag was sealed with the zipper and stored in the laboratory for two months. (e) The collected paper was placed in a resealable aluminum bag, activated carbon was added, the pressure was reduced, and the bag was sealed with the zipper and stored in the laboratory for two months. The collected papers from (f) and (d) were placed again in a resealable aluminum bag, sealed with the zipper, and stored in the laboratory for one month. The collected papers from (g) and (e) were placed again in a resealable aluminum bag containing activated carbon, sealed with the zipper, and stored in the laboratory for one month. 【0116】 Each collected paper was inserted into the paper collection holder of a portable explosive detector, and measured for 60 seconds. The paper collection holder used was the one shown in Figure 3, Example 1-1 of Example 1. 【0117】 The results are shown in the luminescence intensity graph in Figure 15. The sample paper in Figure 15(a) had a blank count of less than 1000 counts, while the sample paper in Figure 15(b) had a blank count of approximately 1500 counts. This is because the paper box is permeable to the atmosphere, and over time, the amount of blanking agents in the laboratory adhering to the sample paper increased. The sample paper in Figure 15(c) also had a blank count of less than 1000 counts. This is because the blanking agents were removed from the sample paper by drying under reduced pressure while heating. 【0118】 The sample papers in Figures 15(d) and 15(f) had a blank count of 1000 counts or less. This is because the resealable aluminum bags are impermeable to air, so the adhesion of blank-causing substances from the laboratory to the sample papers did not increase over time. Furthermore, even after opening and exposing the papers to air, quickly placing them back into the resealable aluminum bags and sealing them tightly prevented an increase in the adhesion of blank-causing substances from the laboratory to the sample papers. 【0119】 The sample papers in Figures 15(e) and 15(g) had a blank count of 500 counts or less. This is because the resealable aluminum bag is impermeable to air, and the blank-causing substances transferred from the sample paper to the enclosed activated carbon. Furthermore, even after being opened and exposed to air, the adhesion of blank-causing substances to the sample paper did not increase by quickly placing the bag back into the resealable aluminum bag with the enclosed activated carbon and sealing it tightly. [Examples] 【0120】 In the chemiluminescence method for quantifying low-volatility explosives, experiments were conducted using the portable explosive detector described in Example 1 as the low-volatility detector for storage and transfer equipment. A cotton-filled pen container (Kuretake Co., Ltd.) was used as the liquid ink filling pen for the storage and transfer equipment. 【0121】 As the collection paper, a sheet of high-quality paper with a thickness of 65 μm was prepared by printing on it as shown in Figure 7. A 200 ppm PenSlit (PETN) solution (solvent being a mixture of isopropanol and acetonitrile) was filled into a cotton-filled pen container. Next, the dotted cross mark 91 on the collection paper was traced with the cotton-filled pen to transfer the PETN to the paper. This transfer operation was performed on two sheets of collection paper, and each sheet was inserted into the collection paper holder of a portable explosive detector and measured for 30 seconds. The collection paper holder used was the one from Example 1-1 of Example 1, shown in Figure 3. 【0122】 The results are shown in the luminescence intensity graphs in Figures 16(a) and 16(b). Comparing the data from each of the two sample papers, a high degree of similarity was observed, indicating that low-volatility explosive substances could be reproducibly transferred to the sample paper by tracing the marks on the sample paper with the liquid ink filling pen of the storage and transfer equipment. Note that although two graphs are shown in Figure 16(a), both graphs are based on the same data. One is the graph of the actual data, and the other is the graph after smoothing using a moving average (32 times). The same applies to Figure 16(b). [Examples] 【0123】 As the collection paper, a sheet of high-quality paper with a thickness of 65 μm was prepared by printing on it as shown in Figure 7. For the storage and transfer equipment in the chemiluminescence method for quantifying low-volatility explosive substances, the portable explosive detector described in Example 1 was used as the low-volatility substance detector in the experiment. 【0124】 As Example 9-1, a cotton swab (Sanyo Co., Ltd.) consisting of absorbent cotton for the cotton portion and a paper shaft for the stick portion was soaked in a 200 ppm Penslit (PETN) solution (solvent being a mixed solvent of isopropanol and acetonitrile), placed in an aluminum bag, sealed, and stored for one month. The bag was then torn open and the cotton swab was removed. Subsequently, the cotton swab was rubbed along the cross mark 91 on the collection paper to transfer the PETN to the collection paper. The collection paper after this transfer operation was inserted into the collection paper holder of a portable explosive detector and measured for 60 seconds. The collection paper holder used was the collection paper holder of Example 1-1 of Example 1, as shown in Figure 3. 【0125】 In Example 9-2, a 200 ppm PenSlit (PETN) solution (solvent being a mixed solvent of isopropanol and acetonitrile) was filled into an ink-embedded pen-type stamp. Subsequently, the ink-embedded pen-type stamp was pressed into the circular mark 92 on the collection paper to transfer the PETN to the collection paper. The collection paper after this transfer operation was inserted into the collection paper holder of a portable explosive detector and measured for 60 seconds. The collection paper holder used was the collection paper holder of Example 1-1 of Example 1, as shown in Figure 3. 【0126】 Whether using cotton swabs or ink-embedded penetrating stamps as storage and transfer devices, peaks were detected that were comparable in both peak shape and peak height to those detected in the liquid ink-filling pen used in Example 8. [Industrial applicability] 【0127】 As described above, the present invention enables safe, rapid, accurate, and easy quantitative analysis of low-volatility substances, particularly simple quantitative analysis of residues of low-volatility substances, and is therefore extremely useful in the food industry, other environmental industries, the chemical industry, and the transportation industry, and is suitable for use in these industries.

Claims

[Claim 1] A low-volatility substance detector for quantifying low-volatility substances using a chemiluminescence method, comprising: a heating unit exposed to the outside of the low-volatility substance detector for heating the low-volatility substance; and a collection paper holder for installing collection paper for supplying the substance to be measured to the low-volatility substance detector, with the collection paper holder having an installation opening for installing the collection paper facing the heating unit, and a ventilation opening in the portion facing the heating unit. [Claim 2] The low-volatility substance detector according to claim 1, characterized in that the area of ​​the ventilation opening is 30% or more of the area of ​​the heating plate exposed to the outside that constitutes the heating section. [Claim 3] The low-volatility substance detector according to claim 1 or 2, characterized in that a support beam is provided in the ventilation opening. [Claim 4] The low-volatility substance detector according to claim 3, characterized in that the strut is provided in the portion of the ventilation opening opposite the sample inlet that protrudes from the heating section. [Claim 5] The low-volatility substance detector according to claim 1 or 2, characterized in that the paper collection holder is detachably installed on the low-volatility substance detector. [Claim 6] The low-volatility substance detector according to claim 3, characterized in that the paper collection holder is detachably installed on the low-volatility substance detector. [Claim 7] A low-volatility substance detector for quantifying low-volatility substances using the chemiluminescence method, comprising a heating unit exposed to the outside of the low-volatility substance detector for heating the low-volatility substance, and a collection paper holder for setting collection paper facing the heating unit to supply the substance to be measured to the low-volatility substance detector, wherein the collection paper holder has an installation opening for setting the collection paper facing the heating unit and a ventilation opening in the part facing the heating unit, and a low-volatility substance detector, wherein the collection paper is set in the collection paper holder, the collection paper is set facing the heating unit, the collection paper is heated, and the low-volatility substance adhering to the collection paper is heated and vaporized. [Claim 8] The method for quantifying a low-volatility substance according to claim 7, characterized in that, in the previous quantification, after the vaporized low-volatility substance is discharged from the ventilation port, a new collection paper is placed in the collection paper holder. [Claim 9] The method for quantifying a low-volatility substance according to claim 7 or 8, characterized in that the area of ​​the ventilation opening is 30% or more of the area of ​​the heating plate exposed to the outside that constitutes the heating section. [Claim 10] The method for quantifying low-volatile substances according to claim 7 or 8, characterized in that a low-volatile substance detector with a support bar in the ventilation opening is used. [Claim 11] The method for quantifying low-volatile substances according to claim 9, characterized in that a low-volatile substance detector with a support bar in the ventilation opening is used. [Claim 12] The method for quantifying low-volatile substances according to claim 7 or 8, characterized in that the sampling paper is high-quality paper with a thickness of 25 to 95 μm. [Claim 13] The method for quantifying low-volatile substances according to claim 10, characterized in that the sampling paper is high-quality paper with a thickness of 25 to 95 μm. [Claim 14] The method for quantifying a low-volatility substance according to claim 7 or 8, characterized in that the collection paper has markings on the area where the substance to be measured should be attached. [Claim 15] The method for quantifying a low-volatility substance according to claim 12, characterized in that the collection paper has markings on the area where the substance to be measured should be attached. [Claim 16] The method for quantifying a low-volatile substance according to claim 7 or 8, characterized in that a process is performed to reduce the amount of blank paper in the collection paper before the collection paper is placed in the collection paper holder. [Claim 17] The method for quantifying a low-volatile substance according to claim 12, characterized in that a process is performed to reduce the amount of blank paper in the collection paper before the collection paper is placed in the collection paper holder. [Claim 18] The method for quantifying low-volatility substances according to claim 17, characterized in that the process for reducing the blank amount of the sample paper is one or more processes selected from drying, reducing pressure, drying under reduced pressure, heating and drying under reduced pressure, or including an adsorbent that adsorbs airborne impurities in the storage container. [Claim 19] The method for quantifying low-volatility substances according to claim 7 or 8, characterized in that the collection paper is stored in a sealed container before use. [Claim 20] The method for quantifying a low-volatility substance according to claim 19, characterized in that the sealed container is an aluminum bag with a zipper. [Claim 21] The method for quantifying low-volatile substances according to claim 7 or 8, characterized in that the sampling paper is a sampling paper that has undergone a blank test in which the blank amount was measured in advance using chromatography. [Claim 22] The method for quantifying low-volatile substances according to claim 12, characterized in that the sampling paper is a sampling paper that has undergone a blank test in which the blank amount was measured in advance using chromatography. [Claim 23] A method for quantifying a low-volatility substance according to claim 7 or 8, characterized in that a storage device is a container for storing a marker sample solution containing the substance to be measured, and a storage and transfer device is used to absorb and retain the marker sample solution stored in the storage device and transfer it to the collection paper, thereby transferring the low-volatility substance to the collection paper. [Claim 24] The method for quantifying a low-volatility substance according to claim 23, characterized in that the storage and transfer device is an ink-embedded pen, a liquid ink-filled pen, or a cotton swab. [Claim 25] The method for measuring explosive substances according to claim 24, characterized in that a low-volatility substance is transferred to the collection paper by tracing a mark on the collection paper using the liquid ink filling pen. [Claim 26] The method for quantifying a low-volatility substance according to claim 7 or 8, characterized in that the low-volatility substance is a nitro compound or an organic peroxide that is an explosive substance. [Claim 27] A method for determining a low-volatility substance according to claim 7 or 8, characterized in that the low-volatility substance in a marker sample solution containing the low-volatility substance is transferred to the collection paper, quantified, and the operation of the low-volatility substance detector is confirmed.

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