JP2012194088A - Gas sampling and measuring apparatus and gas sampling and measuring method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an apparatus for very easily sampling and measuring gas discharged from the surface of a sample without burdening any load on the sample.SOLUTION: An apparatus for measuring a concentration of a measuring object component contained in gas discharged from a sample to the gas comprises: a container covering a part of the sample; a flow channel for supplying a carrier gas which contains or does not contain a marker component of a prescribed concentration and in which concentrations of contained components are known; means for supplying the carrier gas of a prescribed supply volume; concentration measuring means for measuring the concentration of the measuring object component to a mixed gas of the carrier gas in the container and the gas discharged from the sample and the concentration of the marker component; and concentration calculation means for calculating the concentration of the measuring object component from the value of the supply volume of the carrier gas, the concentration of the measuring object component in the carrier gas and the concentration of the marker component, and measured concentration values of the measuring object component in the container and the marker component measured by the concentration measuring means.

Description

  The present invention relates to a gas sampling measurement device and a gas sampling measurement method for collecting gas released from a sample and measuring components contained in the collected gas. In particular, the present invention collects gas released from the surface of a living body for the purpose of clinical application, and measures a component that is an indicator of the physiological state and health state of the living body contained in the collected gas. The present invention relates to an apparatus and a method.

  Collecting and measuring the gas released from the sample is important for understanding the state of the sample and the effect of the sample on the surrounding environment.

  Of the gases released from the sample, the measurement of the gas released from the surface of the biological sample, for example, the gas released from the human skin surface (skin gas) has recently attracted attention. Since skin gas is thought to reflect blood components, it has been found that measuring the components contained in skin gas can help you understand the physiological and health status of people. Yes. If the physiological state and health state can be understood using skin gas, it is possible to carry out a very simple non-invasive clinical test that does not place a burden on the human body. For this reason, skin gas is attracting attention as a specimen that realizes the next generation non-invasive examination.

  When collecting a gas released from the surface of a biological sample such as skin gas, it is difficult to completely prevent the contamination of the atmosphere that causes measurement errors by putting the entire sample in a sealed container. Therefore, there is a need for a technique for collecting and measuring the gas released from the sample surface in a simple and accurate manner while suppressing air contamination while only a part of the sample is placed in the collection container.

  In Patent Document 1, only a part of a sample is put in a collection container, and a member of a sample insertion port in the collection container is pressurized to block a gap between the member and the sample, thereby preventing air from being mixed in. Attempts have been made. However, this technique requires pressure sensing and control in order to avoid excessive pressurization of the sample, and there is a problem to be solved that the apparatus becomes complicated and expensive.

  Further, when the collection gas is extracted from the collection container, for example, to analyze the collection gas with a measuring device, the collection container becomes a negative pressure, and air is mixed into the collection container. For this reason, there was a problem to be solved that sampling and measurement with high accuracy were not possible.

  Further, the volume of gas released from the sample is not constant due to individual differences and daily fluctuations, particularly when the sample is a living body. Therefore, if the concentration of the measurement target component in the collection container is not measured after measuring the volume of the gas released from the sample for each measurement, the measurement target component contained in the gas released from the sample is measured accurately. It is not possible to obtain a correct concentration. However, since the apparatus disclosed in Patent Document 1 does not include a means for measuring the volume of gas released from a sample, there is a problem to be solved that high-precision measurement cannot be performed.

JP 2007-155385 A

  The present invention overcomes the above-described problems, and provides a gas sampling measurement device and a gas sampling measurement method that easily and accurately collect and measure gas without imposing a burden on a sample.

A gas sampling and measuring apparatus of the present invention for carrying out a gas sampling and measuring method that solves the above problems is a measuring apparatus that measures the concentration of a measurement target component contained in a gas released from a sample with respect to the gas,
A container covering a portion of the sample;
A flow path for supplying a carrier gas with or without a predetermined concentration of a marker component and having a known concentration of the included component to the container;
Means for supplying the carrier gas of a predetermined supply volume;
A concentration measuring means for measuring a concentration of the measurement target component and a concentration of the marker component with respect to a mixed gas of the carrier gas and the gas released from the sample in the container;
Measurement of the supply volume value of the carrier gas, the concentration of the measurement target component and the concentration of the marker component in the carrier gas, and the concentration of the measurement target component and the marker component in the container measured by the concentration measuring means And a concentration calculating means for calculating the concentration of the measurement target component from the value.

  According to the gas sampling and measuring apparatus and gas sampling and measuring method of the present invention, the gas released from the sample is collected while preventing the air from being mixed, without requiring excessive pressurization or an expensive pressure control device to the sample. It is possible. In addition, the gas released from the sample can be measured with high accuracy, and a carrier gas having a wide range of compositions can be used.

It is a figure explaining the gas sampling measuring device of this invention, and the gas sampling and measuring method using the same. It is a figure explaining the gas sampling measuring device which concerns on the 1st and 3rd Example of this invention, and the gas sampling and measuring method using the same. It is a figure explaining the gas sampling measuring apparatus which concerns on the 2nd and 5th Example of this invention, and the gas sampling and measuring method using the same. It is a figure explaining the gas sampling measuring device which concerns on the 4th Example of this invention, and the gas sampling and measuring method using the same.

  With reference to FIG. 1, a gas sampling measurement apparatus according to an embodiment of the present invention will be described. The gas sampling and measuring device according to the embodiment of the present invention is a device for collecting a gas released from a sample 109 and measuring the concentration of at least one target component contained in the gas. This gas sampling and measuring apparatus includes a sampling container 107, an injection means (flow rate control means) 104, a gas mixing means 108, a concentration measuring means (concentration measuring apparatus) 118, and a pressure detecting means (pressure gauge) 120. . The collection container 107 covers at least a part of the sample 109 and includes a collection port for collecting the gas in the collection container 107. The flow rate control means 104 is a means for supplying a predetermined supply volume of carrier gas to the collection container 107. The gas mixing means 108 mixes the carrier gas and the gas released from the sample 109 in the collection container 107. The concentration measuring device 118 measures the concentration of the component in the gas collected from the collection container 107. The pressure gauge 120 detects the pressure in the collection container 107. Based on the pressure detected by the pressure gauge 120, the flow rate control means 104 can change the flow rate of the carrier gas within a range where the pressure in the collection container 107 becomes positive.

  The carrier gas is supplied from the carrier gas supply source 101. Here, the carrier gas is harmless to the sample 109, and does not react with the sample 109, the gas used in the sampling and measurement of the gas, or the members constituting the gas sampling measuring apparatus of FIG. Use high gas. Examples of such a carrier gas include high purity inert gases such as nitrogen, helium, argon, krypton, and xenon. A gas cylinder is generally used as the carrier gas supply source 101, but it is also possible to produce and supply a carrier gas by chemical reaction, purification of the atmosphere, or the like.

  By using a carrier gas whose composition is known in advance, it is possible to easily collect and measure the gas. However, when the composition is unknown or when concentration control is performed more strictly, a means for measuring the concentration of a component contained in the carrier gas may be provided. For example, as shown in FIG. 1, the carrier gas is supplied to the concentration measuring device 118 that measures the concentration of the gas collected from the collection container 107 via the switching valve 102, the flow rate control means 103, and the switching valve 121. The source 101 may be connected. Thereby, a structure for introducing the carrier gas into the concentration measuring device 118 is obtained. Alternatively, a dedicated concentration measuring device may be attached to the carrier gas supply source 101. When the first component (target component) contained in the gas released from the sample surface is analyzed, the measurement of the carrier gas changes to the measurement environment such as temperature at the time of measurement compared to the carrier gas preparation. Even when this occurs, it is desirable because the concentration of the component contained in the carrier gas can be accurately known, and more accurate measurement can be performed.

  Furthermore, when the concentration of the component in the carrier gas does not reach the detection lower limit of the concentration measuring device, the concentration is measured after concentrating the component to be measured. Thereby, the concentration of the component in the carrier gas can be measured. Specifically, the concentrating means 105 is connected to the carrier gas supply source 101 via the switching valve 102, and a certain amount is passed through the concentrating means 105 by the sampling pump 106. Concentration means 105 includes, for example, a means for condensing a gas to be concentrated by cooling it with a coolant (liquefied gas such as liquid nitrogen, dry ice and methanol, etc.), or after concentrating and adsorbing the components in the carrier gas on the solid phase. Examples include a means for extraction with a solvent, a means for extraction by heating after concentration and adsorption on a solid phase, a means for extraction by heating after concentration and adsorption on a solid phase, and further recondensing by cooling.

  An appropriate solid phase for adsorbing the components may be selected according to the characteristics of the components. For example, porous resin such as 2,6-diphenyl-p-phenylene oxide resin, porous carbon such as activated carbon and carbon molecular sieve, nonporous carbon such as graphite carbon black, zeolite such as molecular sieve, alumina, silica gel, etc. Is mentioned. In addition, the solid phase, fused silica, diatomaceous earth, glass beads, crystal particles, fluororesin, terephthalic acid or the like as a carrier and a liquid phase coated on the surface can be used. When a carrier coated with a liquid phase is used as the solid phase, an appropriate one may be selected according to the characteristics of the target component. As the liquid phase used for coating, dimethylpolysiloxane, a mixture of diphenylpolysiloxane and dimethylpolysiloxane in any proportion, a mixture of cyanopropylphenylpolysiloxane and dimethylpolysiloxane in any proportion, Polyglycols such as polyethylene glycol, paraffinic hydrocarbons such as squalane, fluorine oil, esters such as dibutyl maleate, alcohols such as polyesters and undecanol, ethers such as polyphenyl ether, amides, and triethanol Liquid phase (fixed) used in gas chromatographs such as amine acids such as amines, nitriles, nitro compounds, silicones such as methyl silicone, sulfur compounds such as methyl sulfide, phosphate esters, etc. Used as) and the like as are. These solid phases may be used alone or in combination of two or more.

  The concentration measuring device 118 may be appropriately selected to be suitable for analysis according to the characteristics of the component to be measured. Examples of the concentration measuring device 118 include various mass spectrometers, devices combining gas chromatographs with various detectors, various spectroscopic measuring devices, various electrochemical measuring devices, crystal resonator microbalance measuring devices, and the like. Detectors used in combination with gas chromatographs include mass spectrometer, thermal conductivity detector, flame ionization detector, helium ionization detector, argon ionization detector, photoionization detector, atomic emission detector, electron capture type Examples include a detector, a flame photometric detector, a far ultraviolet absorption detector, a nitrogen phosphorus detector, an electrical conductivity detector, a surface ionization detector, an alkali thermal ionization detector, and a Fourier transform infrared spectrometer. The spectroscopic measurement device includes an absorption spectroscopic measurement device such as an ultraviolet-visible spectroscopic measurement device and an infrared spectroscopic measurement device, an emission spectroscopic measurement device such as a fluorescence spectroscopic measurement device and a phosphorescence spectroscopic measurement device, and light scattering such as a Raman scattering spectroscopic measurement device. Examples thereof include photothermal spectroscopic measurement devices such as spectroscopic measurement devices, photoacoustic spectroscopic measurement devices and thermal lens spectroscopic measurement devices.

  By operating the switching valve 102, the carrier gas flow path is switched to inject the carrier gas into the collection container 107. In order to inject a desired flow rate into the collection container 107, a flow rate control means 104 is provided between the switching valve 102 and the collection container 107.

  It is desirable that at least the inner wall surface of the collection container 107 is made of a material that does not release gas (outgas) and does not adsorb the gas released from the sample 109 or the carrier gas. Examples of such materials include metals such as stainless steel, titanium, and aluminum, glass, and resins such as silicon resin and fluororesin. Furthermore, in order to further suppress generation of outgas and adsorption of gas components to the inner wall surface, it is desirable to perform a surface treatment on the inner wall surface of the collection container 107. Such surface treatments include precision polishing processes such as electrolytic polishing, chemical polishing, and electrolytic composite polishing, and materials such as high-density fused silica and fluorine-based resins that generate less outgas and absorb gas components. A coating is mentioned.

  Not only the main body of the sampling container 107 but also the entire gas sampling and measuring apparatus, pipes, joints, etc., at least their inner wall surfaces are made of the same material, or similar surfaces to those inner wall surfaces It is desirable to perform processing.

  In the collection container 107, an insertion port 110 for inserting the sample 109 is formed. In order to easily maintain the inside of the collection container 107 at a positive pressure, it is preferable that the insertion port 110 has a structure in which the gap between the insertion port 110 and the sample 109 is as narrow as possible. In order to realize such a structure, for example, an exchangeable member having a different opening diameter according to the size of the sample 109 is prepared, or a member having a small opening and made of a material having flexibility and elasticity is used. What is necessary is just to provide in the insertion port 110. Examples of the material having flexibility and elasticity include rubbers, gels, elastomers, foams such as polyethylene and urethane, and the like based on silicon resin or fluororesin.

  In order to make the gas composition in the collection container 107 uniform, a gas mixing means 108 is provided. The gas mixing means 108 is provided in the collection container 107. As the gas mixing means 108, for example, means for stirring the gas, means for introducing the carrier gas into the collection container 107 using an injection tube having pores, and various kinds of the introduced carrier gas in the collection container 107 are used. For example, the sampling container 107 may be provided with a mechanism or structure for forming a turbulent gas flow by means such as providing a pore or a nozzle at the injection port so that the gas is jetted in any direction.

  In order to monitor the pressure in the collection container 107, a pressure gauge 120 may be attached to the collection container 107.

  When the inside of the collection container 107 is cleaned with gas, a discharge port 111 for discharging the used gas is attached to the collection container 107 via the switching valve 112.

  A concentration measuring device 118 is further attached to the switching valve 112 via a flow rate control means 114. Further, when the measurement target component does not reach the detection lower limit of the concentration measuring device 118, the flow rate control means is connected to the concentration means (collection pipe) 115 and the sampling pump 116 similar to the concentration of the carrier gas via the switching valve 113. Install in front of 114.

  Furthermore, the gas sampling and measuring apparatus according to the embodiment of the present invention may include a computing device 119. The arithmetic unit 119 inputs the volume of the carrier gas injected into the collection container 107, the concentration of the measurement target component in the carrier gas, and the concentration of the measurement target component contained in the gas in the collection container 107, and the sample The volume of the gas released from the gas and the concentration of the target gas are calculated. Input of each value to the arithmetic device 119 may be performed by an operator of this device, and each device is electrically connected so that an output signal from the flow rate control means 104 or the concentration measuring device 118 is directly input to the arithmetic device 119. May be connected. The arithmetic device 119 may be a dedicated electric circuit or a personal computer.

Now, it is assumed that the gas to be measured and the marker component are included in the carrier gas used. The predetermined concentration of the marker component in the carrier gas is [C _mc ], the concentration of the marker component in the gas released from the sample 109 is [C _ms ], and the carrier gas supplied into the collection container 107 at a desired flow rate. Is a predetermined supply volume of V _c , and the marker component concentration in the collection container 107 at this time is [C _m ], the volume V _s of the gas released from the sample 109 is described by Equation 1.

Since the gas concentration in the collection container is uniform, the marker gas concentration in the gas V ₃ taken out from the container (or the gas V ₄ leaking out from the container) is equal to the marker component concentration in the collection container.

であるから、試料１０９から放出されるガスの体積V_sは（２）式で表わされる。

Now, the marker component contained in the carrier gas is a component that is not contained in the gas released from the sample 109 or contained in a very small amount (for example, at a ppt level, or a concentration below the detection lower limit of the measuring device used). If there is

Therefore, the volume V _s of the gas released from the sample 109 is expressed by equation (2).

  In the carrier gas, if the marker component is not contained in the gas released from the sample 109 or contained in a very small amount (for example, the ppt level or the concentration below the detection limit of the measuring device used), Even if it is a component, the component contained in the gas discharge | released from the sample 109 may be included. However, when the concentration of the target component contained in the carrier gas is one digit or more higher than the concentration of the target component released from the sample 109, it is preferable to remove or dilute the target component in advance. In particular, when the concentration of the target component released from the sample 109 is low (for example, ppb level), the target component concentration in the carrier gas is desirably equal to or less than the concentration of the target component released from the sample 109. . In addition, the marker component contained in the carrier gas is harmless to the sample, and does not react with the sample or the component released from the sample surface, and can be analyzed with a stable measurement device that does not cause a decomposition reaction. It is necessary to select components appropriately. As such marker components, components that do not exist in nature (such as various stable isotope gases, various stable isotope compounds, and perfluoromethylcyclohexane and perfluoromethylcyclopentane which are alternative tracer gases for fluorocarbon gases) are used. Also good. Stable isotope gases include isotopes of rare gases such as helium, argon, krypton and xenon, nitrogen, carbon dioxide, carbon monoxide, oxygen, methane, ethane, ethylene, propane, propene, butane, and 2-methylpropane. Gas isotopes. Examples of stable isotope compounds include isotopes such as acetaldehyde, acetone, ethanol, isopropyl alcohol. The carrier gas may be prepared and used in advance with a marker gas added, or may be prepared and used by a gas mixing device or manual operation. However, if the concentration range of the target component contained in the gas released from the sample varies depending on the sample, or if the concentration range of the target component is not known in advance, a carrier gas containing an arbitrary concentration of the marker component is prepared. Is preferable. Normally, the measuring device is adjusted so that the sensitivity is the best in the concentration range of the target component. Therefore, by preparing and using a carrier gas in which the concentration of the marker component is adjusted to the same concentration range as the target component, In addition, the marker component can be measured with higher accuracy.

By putting the value of the volume V _s of the gas released from the sample 109 obtained by using the above equation (2) into the equation (3), the target component contained in the gas released from the sample 109 is calculated. The concentration [C _s ] can be determined. However, in the formula (3), the concentration of the target component in the carrier gas is [C _tc ], and the concentration of the target component in the gas in the collection container is [C _t ].

  As described above, the marker component contained in the carrier gas is a component that is not contained in the gas released from the sample 109 or contained in a very small amount (for example, a ppt level or a concentration lower than the detection lower limit of the measurement apparatus to be used). The gas sampling and measuring apparatus of the present invention has been described with reference to certain cases. The gas sampling and measuring apparatus of the present invention is not limited to this, and the marker component contained in the carrier gas may be contained in the gas released from the sample 109. Moreover, even if it is a target component, the component contained in the gas discharge | released from the sample 109 may be contained in carrier gas. However, when the concentration of the target component contained in the carrier gas is one digit or more higher than the concentration of the target component released from the sample 109, it is preferable to remove or dilute the target component in advance. In particular, when the concentration of the target component released from the sample 109 is low (for example, ppb level), the concentration of the target component in the carrier gas may be equal to or less than the concentration of the target component released from the sample 109. desirable.

In the following, when the marker component contained in the carrier gas is also contained in the gas released from the sample 109, it is obtained by changing the supply amount of the carrier gas into the collection container. In this case, the volume V _s of the gas released from the sample 109 is expressed by Expression (4).

However, in the above equation (4), the concentration of the marker component contained in the gas in the container measured when the supply amount of the carrier gas is changed is [C _m2 ], and the supply amount (volume) of the carrier gas at that time V _c2 . The volume V _s of the gas released from the sample 109 is also expressed by equation (5), focusing on the target component.

In Equation (5), the concentration of the marker component contained in the gas in the container measured when the supply amount of the carrier gas is changed is defined as [C _t2 ]. Further, the concentration [C _s ] of the target component released from the sample 109 is expressed by Expression (6).

Further, the concentration [C _s ] of the target component released from the sample 109 is also expressed by Expression (7), paying attention only to the concentration of the target component.

  Furthermore, even when the marker component is not included in the carrier gas, it is possible to calculate the concentration of the target component released from the sample 109, that is, the marker component is also released from the sample 109 into the carrier gas. When it exists also in gas, it is equivalent to paying attention only to the target component. Therefore, the concentration of the target component in this case is expressed by Equation (7).

  Next, a gas sampling and measurement method using the gas sampling and measuring apparatus shown in FIG. 1 will be described below.

  After inserting the sample 109 into the collection container 107, carrier gas is introduced into the collection container 107 from the carrier gas supply source 101, and gas cleaning in the collection container 107 is performed. At this time, the switching valve 112 is operated so that the gas in the collection container 107 is discharged out of the collection container 107 from the discharge port 111. By this gas cleaning process, the gas remaining in the collection container 107, such as the atmosphere, that may affect the quantitative accuracy of the gas concentration is excluded out of the collection container 107.

After the gas cleaning, the flow rate control means 104 adjusts the introduction amount of the carrier gas into the collection container 107 to a desired flow rate, and obtains the supply volume V _c of the carrier gas supplied to the collection container 107. However, this flow rate is adjusted so that the pressure in the collection container 107 becomes a positive pressure. When it is difficult for the carrier gas and the gas released from the sample 109 to be mixed, the gas mixing means 108 mixes the carrier gas and the gas released from the sample 109 to form a mixed gas having a uniform composition in the collection container 107. The concentration can be quantified more accurately.

The switching valve 112 is operated so that the gas in the collection container 107 is introduced into the concentration measuring device 118 through the flow rate control means 114. The concentration [C _m ] of the marker component and the concentration [C _t ] of the target component contained in the gas injected into the concentration measuring device 118 are measured. When the marker component and the measurement target component are different components, the concentration of the target component is not necessarily measured at this time, and may be measured in a later process.

In the case where the marker component is contained only in the carrier gas and not contained in the gas released from the sample 109 or contained in a very small amount, the above measurement result is used to calculate from the sample 109 from the equation (2). The concentration [C _s ] of the target component contained in the gas released from the sample 109 is calculated from the volume V _s of the released gas and the equation (3).

Not marker component only carrier gas, if also contained in the gas emitted from the sample 109, by injecting carrier gas V _c to collection container 107, the gas in the collection container 107 by the gas mixing means 108 After uniforming and measuring the component concentration of the gas contained in the gas in the collection container 107 with the concentration measuring device 118, the flow rate of the carrier gas is then changed within a range where the pressure in the collection container 107 becomes positive. . The carrier gas injection volume V _{c2 at} this time and the concentration [C _m2 ] of the marker component contained in the gas in the collection container 107 are obtained. If the concentration of the target component contained in the gas in the collection container 107 is not measured before the flow rate of the carrier gas injected into the collection container 107 is changed, the concentration [C _t ] is determined at this time. Keep measuring. However, the target component may be used as the marker component. That is, the target component and the marker component may be the same component. In this case, there is an advantage that the measurement process is simplified.

Using the above measurement results, the volume V _{s of} the gas released from the sample 109 from the equation (4) or (5), and further the gas released from the sample 109 from the equation (6) or (7). The concentration [C _s ] of the target component contained therein is calculated.

  The above calculation may be performed manually or automatically using a density calculation means such as the arithmetic circuit 119.

  The sample 109 used in the present invention emits gas, and is used for daily use products including animals such as humans, livestock or pets, biological samples such as plants, buildings, automobiles, etc. or products used daily. Examples include materials such as wood, metal and resin that are used.

  The gas to be measured by the gas sampling and measuring apparatus of the present invention is not particularly limited as long as it does not corrode the gas sampling and measuring apparatus. However, for example, when the sample is a living body, it reflects the physiological state and health state of the living body. Ingredients. Ingredients that reflect the physiological and health conditions of the living body include, for example, acetone, which is suggested to be an indicator of diabetes, etc. in skin gas released from the human skin surface, kidney disease, liver disease, etc. It is expected to be an indicator of ammonia, hypoxia, nitric oxide, which is suggested to be an indicator of hypertension, hyperlipidemia, etc. Expected to be an indicator of isoprene, intestinal condition, etc. Hydrogen, short-chain alkanes (methane, ethane, propane, butane, pentane), dinitrogen monoxide, colon cancer and rectal cancer Fingers such as ethane, styrene, octane, heptane, benzene, toluene, lung cancer, which are expected to be indicators such as methane, lung cancer and oxidative stress Butane, which is expected to become an indicator, pentane, which is expected to be an indicator of schizophrenia and fat peroxidation, etc. It is expected to be an indicator of ethanol, alcohol consumption, acetaldehyde, which is expected to be an indicator of liver disease, lung cancer, etc., hepatic encephalopathy and information on bacteria in the oral cavity Indices such as methyl mercaptan, lung cancer, liver disease, hydrogen sulfide, which is expected to be an indicator of bacteria in the oral cavity, trimethylamine, which is expected to be an indicator of kidney disease, oxidative stress, etc. Examples thereof include carbon monoxide, superoxide, and methanol that are expected to serve as indicators of neurological diseases.

  If the sample is a material such as wood, metal, or resin used in everyday products, the components contained in the gas released from the material will give to the person and environment used in the usage environment. A concentration measurement is performed to confirm the effect. Examples of such components include formaldehyde, acetaldehyde, toluene, xylene, and ethylbenzene generated from adhesives, paints, preservatives, and the like used in materials when the sample is a material used in buildings or automobiles. Volatile organic compounds such as styrene, paradichlorobenzene, chloropyrifos, tetradecane, di-n-butyl phthalate, di-2-ethylhexyl phthalate, diazinon, and fenocarb.

Hereinafter, the present invention will be described in more detail with reference to examples.
Example 1
FIG. 2 shows an apparatus configuration example in the case where acetone contained in the gas released from the skin of the hand 209 as the gas released from the sample surface is analyzed by the gas sampling measuring apparatus of the present invention. An example of a gas sampling measurement method using the above will be described.

。また、キャリアガスには高純度ヘリウムガスにエタン−d₆を添加したものを用いているため、キャリアガスの中に含まれるアセトン濃度[C_tc]は無視できる程度である。 Those ethane -d ₆ is a stable isotope gas as a marker component in high purity helium gas was any concentration added is used as a carrier gas 201. Since ethane-d ₆ is not produced in the living body and its abundance in nature is negligible, it is not released from the skin of the hand 209 (

. Further, since the carrier gas is a high purity helium gas added with ethane-d ₆ , the acetone concentration [C _tc ] contained in the carrier gas is negligible.

In order to measure the concentration of ethane-d ₆ contained in the carrier gas 201, the flow rate switching valve 202 passes through the mass flow controller 203 to the gas chromatograph-mass spectrometer (GC-MS) 218 which is a concentration measuring device. Introduce carrier gas. A desired amount of the carrier gas is introduced into the GC-MS 218 by the mass flow controller 203, and the concentration [C _mc ] of ethane-d ₆ contained in the carrier gas is measured.

  The flow path is switched by the switching valve 202 and the carrier gas is introduced into the collection container 207. The collection container 207 is made of stainless steel whose inner wall is subjected to electrolytic composite polishing. The sample insertion port 210 is made of a perfluoroelastomer with very little outgas and has a structure that can be changed depending on the wrist size.

  The amount introduced into the collection container 207 is defined by the mass flow controller 204. The carrier gas introduced into the collection container 207 is uniformly mixed with the gas released from the hand 209 by the gas stirring fan 208. While the carrier gas is passed through the collection container 207, the overflow gas is discharged from the discharge port 211, and the gas in the collection container 207 is replaced.

After the gas replacement is completed, a predetermined amount V ₁ of carrier gas is introduced into the collection container 207 by the mass flow controller 204. However, the flow rate of the carrier gas is adjusted so that the pressure in the collection container 207 becomes a positive pressure. At this time, the switching valve 212 switches the flow path to a line connected to the mass flow controller 214. A predetermined amount of the gas in the collection vessel 207 is introduced into the GC-MS 218 by the mass flow controller 214, and the concentration [C _t ] of acetone and the concentration [C _m ] of ethane-d _{6 in} the collection vessel 207 are obtained. Measured.

The value Vs _s emitted from the hand 209 is calculated by substituting the value obtained as described above into the equation (2). Further, the calculated volume V _s and the value obtained as described above are substituted into the equation (3), and the concentration [C _s ] of acetone contained in the gas released from the hand 209 is calculated.

(Example 2)
FIG. 3 shows an apparatus configuration example in which isoprene contained in the gas released from the skin of the hand 309 as the gas released from the sample surface is analyzed by the gas sampling measuring apparatus of the present invention. An example of a gas sampling measurement method using the above will be described.

As in Example 1, used as the ethane -d ₆ is a stable isotope gas as a marker component was any concentration added to the high purity helium gas as a carrier gas 301. The gas sampling measurement apparatus of FIG. 3 is implemented except that the GC-MS 318 is not directly connected to the sampling container 307 or the like and the gas collected by the collection tubes 305 and 315 is introduced into the GC-MS 318. A configuration similar to that of Example 1 is provided.

Since the carrier gas is a high-purity helium gas to which ethane-d ₆ is added, the amount of isoprene contained in the carrier gas is very small (for example, on the order of sub ppb). However, since the amount of isoprene contained in the gas released from the hand 309 is also very small, the concentration of isoprene in the carrier gas cannot be ignored in order to perform quantification with high accuracy. Therefore, the concentration is determined by concentrating isoprene contained in the carrier gas as described below.

  In order to measure the concentration of isoprene contained in the carrier gas, first, the carrier gas is sucked by the sampling pump 306 to introduce an arbitrary amount of carrier gas into the collection tube 305 via the switching valve 302. . Then, isoprene in the carrier gas is concentrated and adsorbed on the collection tube 305. As the collection tube 305, a glass tube filled with two layers of 2,6-diphenyl-p-phenylene oxide resin and graphite carbon black is used. The collection tube 305 having adsorbed isoprene is removed, and the collection tube 305 is set in the GC-MS 318 to which the heat desorption device 317 is connected for analysis.

Thereafter, similarly to the procedure described in the first embodiment, gas cleaning (replacement of gas in the collection container 307) and introduction of a predetermined amount V ₁ of carrier gas into the collection container 307 are performed. The measurement of the isoprene concentration [C _t ] contained in the gas in the collection container 307 is also performed after the concentration by the collection tube 315. A predetermined amount of gas in the collection container 307 is not directly introduced into the GC-MS 318, but is introduced into the collection tube 315 by the sampling pump 316 to concentrate isoprene. The collection tube 315 is the same as that used for measuring the concentration of isoprene contained in the carrier gas. The collection tube 315 having adsorbed isoprene is removed, and the collection tube 315 is set in the GC-MS 318 to which the heating / desorption device 317 is connected for analysis. The concentration [C _m ] of ethane-d ₆ contained in the gas in the collection container 307 is directly introduced into the GC-MS 318 by the mass flow controller 314 in the same manner as described in Example 1. And measure.

From the values obtained as described above, the volume V _{s of the} gas released from the hand 309 and the concentration [C _s ] of isoprene are calculated in the same manner as in Example 1.

(Example 3)
Another example of the gas sampling measurement method in the case of analyzing acetone contained in the gas released from the skin of the hand 209 using an apparatus having the same configuration as the gas sampling measurement apparatus used in Example 1 is shown in FIG. Will be described. A gas containing methane as a marker component in compressed air is used as the carrier gas 201. The gas sampling measurement method in the present embodiment is implemented in that methane contained in the gas released from the skin of the hand 209 is used as a marker component, and that the target component acetone is also contained in the carrier gas. Different from Example 1.

In order to measure the concentration of acetone and methane contained in the carrier gas 201, the carrier is transferred to the gas chromatograph-mass spectrometer (GC-MS) 218, which is a concentration measuring device, by the flow path switching valve 202 via the mass flow controller 203. Introduce gas. A desired amount of the carrier gas is introduced into the GC-MS 218 by the mass flow controller 203, and the acetone concentration [C _tc ] and the methane concentration [C _mc ] contained in the carrier gas are measured.

Similar to the procedure described in Example 1, measurement gas cleaning (replacement of gas in the collection container 307), introduction of a predetermined amount of _Vc carrier gas into the collection container 307, and acetone in the collection container 207 The concentration [C _t ] and the methane concentration [C _m ] are measured.

The carrier gas introduction amount is changed from V _c to V _c2, and the methane concentration [C _m2 ] contained in the gas in the collection container 207 is measured in the same manner as described above. At this time, the concentration of acetone [C _t2 ] may be measured.

The value Vs _s emitted from the hand 209 is calculated by substituting the value obtained as described above into the equation (4). Further, the value obtained as described above is substituted into the equation (6) or (7), and the concentration [C _s ] of acetone contained in the gas released from the hand 209 is calculated.

Example 4
FIG. 4 shows an apparatus configuration example in the case where acetone contained in the gas released from the skin of the hand 409 as the gas released from the sample is analyzed by the gas sampling measuring apparatus of the present invention. An example of a gas sampling measurement method using the above will be described. High purity helium gas is used as a carrier gas, and the marker component is acetone, which is the same as the target component. Therefore, the concentration of the target component (marker component) contained in the carrier gas is negligible.

  The gas sampling and measuring apparatus used in the present embodiment has the same configuration as the gas sampling and measuring apparatus of FIG. 2 except for the following points. That is, the gas sampling and measuring apparatus in FIG. 4 does not have a mechanism for directly sending the carrier gas to the GC-MS 418.

First, after the inside of the collection container 407 is cleaned with high-purity helium gas, which is a carrier gas, as in Example 1, the amount of carrier gas introduced into the collection container 407 is changed as in Example 3. Then, acetone concentrations [C _t ] and [C _t2 ] in the collection container 407 are obtained. The carrier gas volumes V _c and V _c2 and the measured acetone concentrations [C _t ] and [C _t2 ] are input to the personal computer 419. Then, calculation is performed according to the equations (5) and (7), and the volume V _{s of the} gas released from the hand 409 and the concentration [C _s ] of acetone contained therein are calculated.

(Example 5)
Another example of the gas sampling measurement method in the case of analyzing acetone contained in the gas released from the skin of the hand 309 using an apparatus having the same configuration as the gas sampling measurement apparatus used in Example 2 is shown in FIG. Will be described. Example 2 differs from Example 2 in that high-purity helium gas is used as the carrier gas, as in Example 4, and the marker component is the same isoprene as the target component.

The concentration [C _tc ] of isoprene contained in the carrier gas is measured in the same manner as in Example 2 after being concentrated by the collection tube 315. Thereafter, similarly to the procedure described in Example 1, to implement the introduction of the carrier gas at a predetermined amount V _c to the gas washing in (gas substitution in the collection container 307) and collection container 307. In the same manner as in Example 2, the concentration of isoprene [C _t ] contained in the gas in the collection container 307 is measured after being concentrated by the collection tube 315. The carrier gas introduction amount is changed from V _c to V _c2, and the isoprene concentration [C _t2 ] contained in the gas in the collection container 307 is measured in the same manner as described above.

From the values obtained as described above, the volume V _{s of the} gas released from the hand 309 and the concentration [C _s ] of isoprene are calculated in the same manner as in Example 4.

  The present invention relates to an apparatus and method for collecting a gas released from the surface of a living body for clinical application and measuring a component that is an indicator of the physiological state or health state of the living body contained in the collected gas. Can be used.

101. Carrier gas supply source 102. Switching valve 103. Flow rate control means 104. Flow rate control means 105. Collection tube 106. Sampling pump 107. Collection container 108. Gas mixing means 109. Sample 110. Sample insertion port 111. Discharge port 112. Switching valve 113. Switching valve 114. Flow rate control means 115. Collection tube 116. Sampling pump 117. Thermal desorption device 118. Concentration measuring device 119. Arithmetic device 120. Pressure gauge 121. Switching valve

Claims (8)

A measuring device for measuring a concentration of a measurement target component contained in a gas released from a sample with respect to the gas,
A container covering a portion of the sample;
A flow path for supplying a carrier gas with or without a predetermined concentration of a marker component and having a known concentration of the included component to the container;
Means for supplying the carrier gas of a predetermined supply volume;
A concentration measuring means for measuring a concentration of the measurement target component and a concentration of the marker component with respect to a mixed gas of the carrier gas and the gas released from the sample in the container;
Measurement of the supply volume value of the carrier gas, the concentration of the measurement target component and the concentration of the marker component in the carrier gas, and the concentration of the measurement target component and the marker component in the container measured by the concentration measuring means And a concentration calculating means for calculating the concentration of the measurement target component from the value.   The measuring apparatus according to claim 1, wherein the container includes a gas mixing unit that mixes the carrier gas and a gas released from the sample.   The marker component contained in the carrier gas is not contained in the gas released from the sample or contained in a very small amount, and the concentration of the measurement target component and the concentration of the marker component in the carrier gas, and the concentration 3. The concentration calculation unit calculates the concentration of the measurement target component from the measured values of the concentration of the measurement target component and the marker component in the container measured by the measurement unit. The measuring device described in 1. The concentration of the component to be measured in the carrier gas is [C _tc ],
The concentration of the marker component in the carrier gas is [C _mc ],
The concentration of the measurement target component in the container is [C _t ],
When the concentration of the marker component in the container is [C _m ],
The measurement apparatus according to claim 3, wherein the concentration calculation unit calculates the concentration [C _s ] of the measurement target component with respect to the gas released from the sample by the equation (1).

The marker component contained in the carrier gas is also contained in the gas released from the sample,
A measured value of the concentration of the measurement target component and the marker component in the container measured by the concentration measuring means when the supply amount of the carrier gas into the container is a predetermined supply volume;
A predetermined supply volume value into the carrier gas container;
A measured value of the concentration of the measurement target component and the marker component in the container measured by the concentration measuring means when the supply amount of the carrier gas into the container is changed from the predetermined supply volume;
A changed supply volume value into the container of the carrier gas, and
From the concentration of the component to be measured and the concentration of the marker component in the carrier gas,
The measurement apparatus according to claim 1, wherein the concentration calculation unit calculates the concentration of the measurement target component. V _c , the supply volume of the carrier gas into the container
The concentration of the component to be measured in the container when the carrier gas supply volume is V _c is [C _t ],
The concentration of the marker component in the container is [C _m ] _,
V _c2 when the supply volume of the carrier gas into the container is changed,
When the carrier gas supply volume is V _c2 , the concentration of the component to be measured in the container is [C _t2 ],
The concentration of the marker component in the container is [C _m2 ] _,
The concentration of the component to be measured in the carrier gas is [C _tc ],
When the concentration of the marker component in the carrier gas is [C _mc ],
6. The measuring apparatus according to claim 5, wherein the concentration calculating means calculates the concentration [C _s ] of the measurement target component with respect to the gas released from the sample by the equation (2).

The carrier gas contains the component to be measured, but does not contain the marker component.
When the supply amount of the carrier gas into the container is a predetermined supply volume, the measured value of the concentration of the measurement target component in the container measured by the concentration measuring means and the predetermined supply of the carrier gas into the container Volume value,
A measured value of the concentration of the measurement target component in the container measured by the concentration measuring means when the supply amount of the carrier gas into the container is changed from the predetermined supply volume;
A changed supply volume value into the container of the carrier gas, and
From the concentration of the component to be measured in the carrier gas,
The measurement apparatus according to claim 1, wherein the concentration calculation unit calculates a concentration of the measurement target component. V _c , the supply volume of the carrier gas into the container
The concentration of the component to be measured in the container when the carrier gas supply volume is V _c is [C _t ],
V _c2 when the supply volume of the carrier gas into the container is changed,
The concentration of the component to be measured in the container when the carrier gas supply volume is V _c2 is [C _t2 ],
When the concentration of the component to be measured in the carrier gas is [C _tc ],
The measurement apparatus according to claim 7, wherein the concentration calculation means calculates the concentration [C _s ] of the measurement target component with respect to the gas released from the sample by the equation (3).

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