JP2011137740A - Sampling method using plasma, and sampling device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a sampling method using plasma, and a sampling device, capable of collecting and directly introducing a sample into an analyzer without destroying an analysis object, and of enhancing analytical accuracy. <P>SOLUTION: The sampling method includes the steps of emitting the plasma to a surface of the analytical object housed in a closed space; producing a sample gas, by making a surface layer part thereof guide into a gas phase; and introducing the sample gas into the analyzer through an introduction means from the closed space by a gas flow. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a sampling method and a sampling apparatus for collecting a sample from an analysis object and introducing the sample into an analysis apparatus when performing analysis using a general analysis apparatus.

  Many conventional analyzers require a sample in a liquid state or a gas state to be introduced into the analyzer. Therefore, when analyzing a solid bulk using such an analyzer, a part of it is physically broken and collected, and pulverized with a ball mill or mortar to form particles, and then an acid or alkali solvent. Pretreatment such as dissolving in solution to form a solution is performed.

  However, since the solution sample contains a solvent component, the analysis target component is hindered or contaminated by chemicals or instruments to be used, so that the analysis accuracy is lowered. There was a problem. In addition, since the original analyte is destroyed, for example, for those that are not allowed to be damaged such as valuables, paintings, criminal samples, living organisms, etc. In some cases. Furthermore, since the pretreatment requires a large number of chemical steps, it takes time to collect an analysis object and introduce it into the analyzer, and there is a problem that rapid analysis cannot be performed.

  As a method for simplifying the pretreatment, the surface of the analyte is evaporated or finely divided by irradiating with a powerful laser beam and locally raising the surface temperature, and the vapor or fine particles are collected. Alternatively, there is a laser ablation method in which the gas flow is introduced directly into the analyzer.

  However, in this method, not only the surface layer portion of the analysis object but also the analysis object inside the surface layer portion is evaporated or micronized by laser irradiation. Will remain. Therefore, as described above, there is a problem that this method cannot be used for things that are not allowed to be damaged, such as valuables, paintings, criminal samples, and living organisms. Further, in this method, in order to change the degree of sample collection, only the laser power, the laser irradiation time, and the focus stop can be adjusted as parameters, and there is a disadvantage that the controllability is poor.

  On the other hand, in recent years, particularly in the field of crime analysis, a method for collecting and analyzing a sample from a solid analysis object using plasma has been developed (for example, see Non-Patent Documents 1 and 2).

Development of a direct current gas sampling glow discharge ionization source for the time-of flight mass spectrometer, John P. Guzowski, Jr., Jose AC Broekaert, Steven J. Ray and Gary M. Hieftje, J. Anal. At. Spectrom. , 1999, 14, 1121-1127 Characterization of Direct-Current Atmospheric-Pressure Discharges Useful for Ambient Desorption / Ionization Mass Spectrometry, acob T. Shelley, Joshua S. Wiley, George CY Chan, Gregory D. Schilling, Steven J. Ray, and Gary M. Hieftje, J Am Soc Mass Spectrom 2009, 20, 837-844

  However, in the methods disclosed in Non-Patent Documents 1 and 2, because of the structure of the plasma source, the needle electrode dissolves in the plasma, so that detection of the metal element is difficult and the purity of the plasma is low. There is a problem that high analysis accuracy cannot be obtained. In addition, this method has drawbacks such that it can be used only for analysis using a time-of-flight mass spectrometer (TOF-MS), and only helium gas can be used as a plasma gas.

  The present invention has been made in view of these points, and it is possible to collect a sample without destroying an analysis object and directly introduce the sample into an analyzer, and to improve analysis accuracy. An object of the present invention is to provide a sampling method and a sampling apparatus using plasma.

  In order to achieve the above object, the sampling method using the plasma of the present invention releases the plasma to the surface of the analyte contained in the closed space and scatters the surface layer portion into the gas phase to obtain the sample gas. The sample gas is introduced into the analyzer through the introduction means from the closed space by a gas flow.

  In addition, the sampling apparatus using plasma according to the present invention includes a plasma source for generating plasma, an open part for accommodating an analysis object or its surface inside, and an introduction for introducing plasma generated by the plasma source. A sampling chamber formed with an outlet and an outlet for discharging the sample gas, the surface of which is discharged into the gas phase by discharging the plasma to the surface of the sample, and the gas flow from the sampling chamber And introducing means for introducing the sample gas flowing out into the analyzer.

  The plasma source includes a dielectric tube made of a dielectric material into which plasma gas is introduced, and a first electrode tube made of one or more conductors arranged on the outer side in the thickness direction of the dielectric tube; A second electrode tube made of one or more conductors spaced from the first electrode tube on the inner side in the thickness direction of the dielectric tube or on the outer side in the thickness direction of the dielectric tube; It is characterized by having.

  The dielectric tube is connected to the sampling chamber, and the sample gas flows out of the sampling chamber by the gas flow of the plasma gas or carrier gas introduced inside the dielectric tube, and the analyzer It is introduced in.

  The plasma source applies direct current power or alternating current power and pulse power having any frequency included in a range from a low frequency to a high frequency microwave region between the first electrode tube and the second electrode tube. It has the power supply.

  In addition, the first electrode tube and the second electrode tube are either platinum rhodium, platinum, molybdenum, tungsten, thorium tungsten alloy, lanthanum tungsten alloy, selenium tungsten alloy, or any one of which americium or thorium is attached to any of these. It is characterized by comprising.

  Further, the plasma is jet-like.

  According to the present invention, without destroying the analysis object, only a small part of the surface layer portion is scattered to obtain the sample gas, and the sample gas can be directly introduced into the analyzer by the gas flow. Therefore, since it is not necessary to perform complicated preprocessing as in the prior art, it is possible to perform rapid analysis with high analysis accuracy. In addition, it is possible to perform analysis using a highly sensitive analyzer even for an analysis object that could not be analyzed because damage is not allowed.

(A) is the schematic which shows the sampling apparatus which concerns on embodiment of this invention, (b) is AA sectional drawing of the plasma source shown to (a). Schematic which shows one Example of the sampling apparatus of this embodiment The graph which shows the time-dependent change of the signal strength of each element in IPC-MS using the sample which made molybdenum paste adhere to the base material of a copper plate. The graph which shows the time-dependent change of the signal intensity | strength of each element in IPC-MS using the sample which made aluminum composite grease adhere to the base material of a copper plate.

  Hereinafter, a sampling apparatus for performing a sampling method using plasma of the present invention will be described with reference to embodiments shown in the drawings.

  The sample that can be sampled according to the present invention can be solid, liquid, gas, or gel. Further, the present invention can be used not only when sampling a part of the surface layer portion from a bulk analysis object, but also when sampling a sample adhering to the surface of the analysis object. It is also possible to sample a sample attached to the surface from the living body itself.

  Samples sampled by the sampling apparatus of the present invention include, for example, ICP-MS (inductively coupled plasma mass spectrometer), ICP-OES (inductively coupled plasma emission spectrometer), MS (mass spectrometer), GC (gas chromatograph). It can be introduced into various analyzers such as TOF-MS (time-of-flight mass spectrometer) and matrix-assisted laser desorption / ionization (MALDI) to perform analytical measurement.

  FIG. 1 is a schematic diagram illustrating a sampling device according to an embodiment of the present invention.

  The sampling apparatus 1 of the present embodiment introduces a plasma source 2 that generates plasma P, an open portion 3a for accommodating an analysis object or its surface inside, and plasma P generated by the plasma source 2 A sampling chamber 3 formed with an inlet 3b, an outlet 3c for discharging the plasma P to the surface of the sample and discharging a sample gas whose surface layer is scattered in the gas phase; and the sampling And introducing means 4 for introducing the sample gas flowing out of the chamber 3 by the gas flow into the analyzer.

  For example, as shown in FIG. 1, the sampling chamber 3 has a hemispherical shape in which a part (a lower part in FIG. 1) is opened as an open part 3a. The shape of the sampling chamber 3 and the relative size with respect to the plasma source can be changed. In addition, the inlet 3b and the outlet 3c are formed in the outer peripheral portion of the sampling chamber 3 so as to be separated from each other. In addition, it is desirable to adjust the formation positions of the inlet 3b and the outlet 3c according to the incident angle of the plasma.

  In addition, a close contact member such as a suction cup 5 or an O-ring is attached to the open edge portion forming the open portion 3a of the sampling chamber 3, and when the solid bulk is analyzed, the open portion 3a. The suction chamber 5 can be adsorbed to the surface of the sample S or the mounting table in a state in which is directed toward the analysis object, and the sampling chamber 3 can be sealed.

  The plasma source 2 includes a dielectric tube 2a made of a dielectric material such as glass or ceramic, a first electrode tube 2b and a second electrode tube 2c made of a conductor disposed on the dielectric tube 2a, and the like. And a power source (not shown) for applying power between the electrodes.

  Specifically, at the center in the length direction of the dielectric tube 2a, as shown in FIG. 1B, the first electrode tube 2b is sandwiched between the dielectric tube 2a on the outer side and the inner side in the thickness direction, respectively. And the 2nd electrode tube 2c is arrange | positioned.

  As materials for the first electrode tube 2b and the second electrode tube 2c, metals such as platinum rhodium, platinum, molybdenum and tungsten are preferable because of their high melting points. However, when importance is attached to the ease of discharge and stability. Alternatively, a thorium tungsten alloy, a lanthanum tungsten alloy, a selenium tungsten alloy, or the like containing a small amount of a radioactive substance may be used. Alternatively, americium or thorium may be attached to any of these by a small amount of coating, sputtering, plating, embedding treatment, or the like. By using these materials, the stability of plasma discharge can be improved. Further, in the case where the analysis object is a substance exhibiting electrical conductivity, it may be structured to act as one electrode. Moreover, when an analysis object is an insulator, it is good also as a structure which acts as the dielectric tube 2a.

  Note that neither the first electrode tube 2b nor the second electrode tube 2c is in contact with the plasma, and a structure for supplying power to the plasma via the dielectric tube 2a is desirable. However, the first electrode tube 2b and the second electrode tube A structure in which at least one of the tubes 2c directly contacts the plasma may be used. In that case, it is desirable to use the material of the first electrode tube 2b and the second electrode tube 2c that does not contain the substance to be analyzed or does not interfere with the analysis by reacting with the substance to be analyzed. .

  Further, the arrangement and number of the first electrode tubes 2b and the second electrode tubes 2c can be changed. For example, the first electrode tube 2b may be disposed outside the dielectric tube 2a in the thickness direction, and the second electrode tube 2c may be disposed outside the first electrode tube 2b at an interval.

  As the power source, a DC power source or a power source that applies AC power and pulse power having any frequency included in a range from a low frequency to a high frequency microwave region can be used.

  Further, in the present embodiment, one end portion (lower end portion in FIG. 1) from which the plasma P of the dielectric tube 2a is emitted is incorporated into the sampling chamber 3 from the introduction port 3b.

  For example, the introduction means 4 includes a tube 8 having one end connected to the inlet of the sample S collected by the analyzer and the other end attached to the outlet 3c. Further, as shown in FIG. 1A, a pump 9 is connected to an intermediate position of the tube 8, and a valve 10 such as an electric or manual check valve is attached to the outlet 3c of the sampling chamber 3. preferable. Since the valve 10 is opened only when the pressure in the sampling chamber 3 rises while the sampling chamber 3 is sealed, the backflow of the sample gas can be prevented. Furthermore, an outlet and a valve for degassing the internal gas may be separately provided on the outer peripheral portion of the sampling chamber 3. In this case, the valve 10 on the outlet 3c side is preferably electrically operated. The pump 9 is not necessarily connected.

  When performing sampling using such a sampling device 1, first, the open portion 3a of the sampling chamber 3 is directed to the surface side of the analysis object, and the portion of the analysis object to be sampled is placed inside the open portion 3a. The suction cup 5 is adsorbed on the surface and sealed. And plasma gas (for example, helium gas) is introduce | transduced inside the dielectric material tube 2a, and electric power is applied between the 1st electrode tube 2b and the 2nd electrode tube 2c from the said power supply. As a result, the plasma gas is turned into plasma by the dielectric barrier discharge, and the plasma P is emitted from one end portion (the lower portion in FIG. 1) of the dielectric tube 2a to the surface of the analysis object in the sampling chamber 3.

  When the plasma P is emitted to the surface of the analysis object, the surface layer of the analysis object is peeled off, evaporated, excited, or ionized by high energy particles (ions, radicals, electrons, etc.) contained in a large amount in the plasma. It receives the process by the seed | species or some combination, becomes a vapor | steam and particle | grains, and is scattered as sampling gas in a gaseous phase. This sampling gas is transported through the tube 8 extended from the outlet 3c by the gas flow of the plasma gas introduced into the dielectric tube 2a, and is introduced into the inlet of the analyzer.

  Note that before the plasma P is emitted to the surface of the analysis target, the inside of the sampling chamber 3 may be previously evacuated to a vacuum state, and then the plasma P may be irradiated. Thereby, contamination from the gas remaining in the sampling chamber 3 can be prevented, and furthermore, the atmospheric pressure in the sampling chamber 3 is lowered and the atmospheric pressure in the plasma source 2 is also lowered. Even so, it can be easily converted into plasma. In addition, after the plasma P is released to the surface of the analysis object for a certain period of time in the sampling chamber 3, the sampling chamber 3 is filled with the sample gas, and then the valve 10 is opened to be introduced into the analyzer at once. Good. Thereby, analysis sensitivity can be improved by shortening the time for which the analysis object is introduced into the analyzer.

  In the present embodiment, the sample gas is conveyed by the gas flow of the plasma gas introduced from one end of the dielectric tube 2a. However, the dielectric tube 2a is formed into a double tube together with the sample gas, and a separate carrier gas is used. The sample gas may be conveyed by the gas flow of the carrier gas.

  The structure of the plasma source 2, the type of plasma gas, and the like are preferably selected according to the characteristics of the analysis object, for example, the degree of damage to the hardness and temperature. For example, by using helium gas as the plasma gas, it is possible to specifically scatter the analysis sample S containing chlorine or fluorine that is difficult to ionize into the gas. Moreover, the substance which is easy to oxidize by using oxygen gas can be specifically scattered in gas.

  Here, when a rare gas is used as the plasma gas, non-reactive plasma is generated, so that a physical reaction (sputtering) occurs in the surface layer portion of the analysis target, and sampling is performed. . In this case, the sampling rate (amount) is proportional to the plasma density × flow rate. On the other hand, when a molecular gas is mixed with the plasma gas, active radicals (for example, O radicals and OH radicals) are generated, so that a chemical reaction occurs in the surface layer portion of the analysis target, thereby sampling. Done. Therefore, by changing the type of gas used for the plasma gas, the type of radical generated is changed, so that the substance to be sampled and the sampling rate can be selectively changed.

The combination of the analyte and plasma is preferably selected depending on the compatibility. For example, for an organic compound, oxygen-mixed plasma or N ₂ O plasma is preferred because it can react with oxygen radicals and peel the surface sample on the same principle as hydrophilization. For some oxides, hydrogen plasma that can release a surface sample by a reduction reaction is preferable. Further, for a glass sample, fluorine-based gas mixed plasma is preferable because the sample tends to be released when fluorine attacks the glass. In addition, Ar plasma is preferable for a metal because a physical reaction (sputtering) easily occurs.

  In addition to the dielectric barrier discharge described above, the plasma P discharge method includes, for example, inductively coupled plasma discharge (ICP), capacitively coupled plasma discharge (CCP), hollow cathode discharge, corona discharge, streamer discharge, glow discharge, Any of arc discharge may be used.

  In addition, when it is desired to prevent damage to the analyte by the plasma P as much as possible, it can be generated by a predetermined discharge method, and the plasma temperature is low (for example, even if the living body is irradiated with plasma, the living body is not damaged). It is preferable to use so-called damage-free plasma P that is not damaged by discharge at a temperature of about 37 ° C., specifically, is neither hot nor touched. Further, by changing the concentration of plasma P (the concentration of ions and electrons in plasma P), it is also possible to obtain analysis information in the depth direction of the analysis object.

  According to this embodiment, without destroying the analysis object, only a part of the surface layer portion is scattered to obtain the sample gas, and the sample gas can be directly introduced into the analyzer by the gas flow. Therefore, since it is not necessary to perform complicated preprocessing as in the prior art, it is possible to perform rapid analysis with high analysis accuracy. In addition, it is possible to perform analysis using a highly sensitive analyzer even for an analysis object that could not be analyzed because damage is not allowed.

  According to the present embodiment, since the sample gas introduced into the analyzer from the sampling chamber is dispersed in the gas phase, the amount of moisture is extremely small compared to a sample obtained by conventional pretreatment or laser ablation. Further, the particle size of the particles contained in the sample gas is small and extremely small. Therefore, analysis by the so-called matrix effect, etc. that occurs when the analysis sensitivity decreases due to moisture contained in the sample, or when the sample has a large particle size or a large amount of use is introduced into the analyzer. There are effects such as being able to eliminate the influence on.

[First embodiment]
Next, the results of specific analysis using ICP-MS (Inductively Coupled Plasma Mass Spectrometer) (Agilent technologies HP4500) will be described.

  As shown in FIG. 2, the sampling apparatus 1 used in the first embodiment uses a quartz tube 6 bent at 90 degrees, the corner portion of which is the sampling chamber 3, an L-shaped side (the left side in FIG. 2). The side) is a dielectric tube 2a.

  An open portion 3 a is formed on the peripheral side surface of the corner portion of the quartz tube 6, and when performing analysis, the sample S is placed inside the open portion 3 a, so that the analysis object is placed in the sampling chamber 3. It can accommodate things.

  In addition, at the center on one side of the L-shaped quartz tube 6 (left side in FIG. 2), the first electrode tube 2b and the second electrode tube 2c as described above are respectively provided on the inner side and the outer side in the thickness direction. Is arranged. A high voltage power source of 9 kV is connected to the first electrode tube 2b and the second electrode tube 2c as a power source. Further, plasma gas can be introduced from one end (upper end in FIG. 2) on one side (left side in FIG. 2) of the L-shaped quartz tube 6, and a voltage is applied between the pair of electrodes. As a result, a plasma P which is long in the axial direction of one side (left side in FIG. 2) of the L-shaped quartz tube 6 is generated by the dielectric barrier discharge, and jet plasma P is applied to the sample S in the sampling chamber 3. Is to be injected.

  In this example, the sample S can be irradiated with the high-density plasma P by arranging the position where the pair of electrodes face each other at a position close to the position of the sample S. In addition, the temperature of the plasma P generated in the present embodiment is a low temperature of about 40 ° C., and the temperature of the plasma P is a low temperature, so that there is no discharge damage, so-called damage free plasma.

  Further, the upper end portion on the other side (the right side in FIG. 2) of the L-shaped quartz tube 6 is an outlet through which the plasma P is jetted onto the sample S and the sample gas scattered in the gas phase can flow out. 3c. By attaching a tube connected to the analyzer to the outlet 3c, the sample gas flows out from the outlet 3c by the gas flow of the plasma gas introduced inside the dielectric tube 3, and the analyzer is passed through the tube. To be introduced. That is, in this embodiment, the plasma gas also acts as a carrier gas for introducing the sample gas into the analyzer.

  Next, using the sampling device 1 described above, an analysis experiment by IPC-MS was performed. In this experiment, the analytical sample S was collected without destroying the copper plate of the base material 7 and it was confirmed whether or not the element to be detected could actually be detected.

  First, assuming that it is not dispersed in the gas phase by the gas flow of helium gas, molybdenum grease adhering to the copper plate of the substrate 7 is used as the sample S, helium gas is used as the plasma gas, the flow rate is 1 L / min, and the ICP Analytical experiment was conducted by -MS.

  Here, plasma P was sprayed onto the copper plate, which is the base material 7 on which the sample S was previously attached, and it was confirmed whether there was any damage due to the plasma P. Specifically, the molybdenum grease on the copper plate is placed in the open portion 3a by using the sampling device 1 described above, so that the molybden grease is accommodated in the sampling chamber 3, and then the power is turned on, Plasma P was emitted on the surface for 5 minutes. As a result, no trace of damage due to plasma P was observed on the surface of the copper plate of the base material 7.

  Next, the gas inlet 3b of the sampling device 1 and a cylinder of helium gas are connected by a tube (not shown), the plasma torch built in the ICP-MS, and the sampling device 1 described above The sample outlet 3c was connected with the tube, and the sampling apparatus 1 was turned on to perform analytical measurement.

  FIG. 3 is a graph showing the change over time of the detection signal for each element. In this analytical measurement, the sampling apparatus 1 is turned on 75 seconds after the start of measurement (monitoring) in ICP-MS, the power is turned off after 125 seconds, and the detection signals of Mo with mass numbers 95, 96, and 98 are monitored. did. Simultaneously, ArO + having a mass number of 56 and Na having a mass number of 23 other than the elements constituting the sample S were also monitored.

  As shown in FIG. 3, the peak of the Mo detection signal was confirmed after about 100 seconds within the time when the power of the sampling device 1 was turned on (from 75 seconds to 125 seconds after the start of measurement). Further, since no change can be confirmed in the ArO + and Na detection signals monitored at the same time, it is considered that the increase is not an accidental signal due to electrical noise or ICP-MS instability.

  From the above, by using the sampling device 1 described above, the molybdenum as the sample S is collected by the discharge of the plasma P and is detected by ICP-MS without damaging the base material 7 of the copper plate of the analysis object. It was confirmed that

[Second Embodiment]
In the second embodiment, the same sampling apparatus 1 as in the first embodiment is used, and as the sample S that is not dispersed by helium gas, aluminum composite grease adhered on the copper plate of the substrate 7 is used as the sample S. Analytical measurement by ICP-MS was performed.

  FIG. 4 is a graph showing the change over time of the detection signal for each element. In this analytical measurement, the sampling apparatus 1 was turned on 50 seconds after the start of measurement (monitoring) in ICP-MS, the power was turned off after 250 seconds, and measurement was performed for a total of 300 seconds. Further, the mass signal of Al having a mass number of 27 is monitored by ICP-MS, and at the same time, ArO + having a mass number of 56 other than the elements constituting the sample S, and the mass element having a mass number of 63, which is a constituent element of the base material 7 that is a copper plate. Cu was also monitored.

  As shown in FIG. 4, within the time when the power of the sampling apparatus 1 is turned on (between 50 seconds and 250 seconds after the start of measurement), the increase in the detection signal of Al having a mass number of 27 is about 60 seconds About 150 seconds later. In addition, since it is not possible to confirm a change in the ArO + detection signal monitored at the same time, it is considered that this is not an accidental increase in signal due to electrical noise or ICP-MS instability.

  Further, since no increase in the signal of Cu having a mass number of 63, which is a constituent element of the base material 7, was confirmed, it was confirmed that the base material 7 was not damaged by releasing the plasma P to the analysis target. It was.

  From the above, by using the sampling apparatus 1 described above, the aluminum as the sample S is collected by the discharge of the plasma P and is detected by ICP-MS without damaging the base material 7 of the copper plate of the analysis object. It was confirmed that

  In addition, this invention is not limited to said embodiment, It can change as needed.

  For example, when the plasma P is released to the object to be analyzed, the sample S is scattered by generating a gaseous hydride in the sampling chamber 3 using the hydride generation method and introducing the gas into the plasma P. You may make it easy to do.

DESCRIPTION OF SYMBOLS 1 Sampling apparatus 2 Plasma source 2a Dielectric tube 2b 1st electrode tube 2c 2nd electrode tube 3 Sampling chamber 3a Opening part 3b Inlet 3c Outlet 4 Introducing means 7 Base material 8 Tube 9 Pump 10 Valve P Plasma S Sample

Claims (7)

  Plasma is emitted to the surface of the analysis object stored in the closed space, and the surface layer portion is scattered into the gas phase to form a sample gas. The sample gas is sent from the closed space to the analyzer through the introduction means by the gas flow. A sampling method using plasma, characterized in that it is introduced. A plasma source for generating plasma;
An open part for accommodating the analysis object or its surface inside, an inlet for introducing plasma generated by the plasma source, and the plasma is emitted to the surface of the sample, and the surface layer part is in a gas phase A sampling chamber in which an outlet for discharging the sample gas scattered therein is formed;
Introducing means for introducing the sample gas flowing out of the sampling chamber by a gas flow into the analyzer;
A sampling apparatus using plasma, comprising:   The plasma source includes a dielectric tube made of a dielectric material into which plasma gas is introduced, and a first electrode tube made of one or more conductors arranged on the outer side in the thickness direction of the dielectric tube; A second electrode tube made of one or more conductors spaced from the first electrode tube on the inner side in the thickness direction of the dielectric tube or on the outer side in the thickness direction of the dielectric tube; The sampling apparatus using plasma according to claim 2, wherein:   The dielectric tube is connected to the sampling chamber, and the sample gas flows out of the sampling chamber by the gas flow of the plasma gas or carrier gas introduced inside the dielectric tube, and the analyzer The sampling apparatus using plasma according to claim 2 or 3, wherein the sampling apparatus is introduced into the apparatus.   The plasma source applies direct current power or alternating current power and pulse power having any frequency included in a range from a low frequency to a high frequency microwave region between the first electrode tube and the second electrode tube. The sampling apparatus using plasma according to claim 3 or 4, further comprising a power source.   The first electrode tube and the second electrode tube are made of any one of platinum rhodium, platinum, molybdenum, tungsten, thorium tungsten alloy, lanthanum tungsten alloy, selenium tungsten alloy, and a material in which americium or thorium is attached to any of these. A sampling apparatus using plasma according to any one of claims 3 to 5.   The sampling apparatus using plasma according to any one of claims 2 to 6, wherein the plasma is in a jet form.

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