JP3540756B2 - Organic trace component detector - Google Patents

Description

[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to an apparatus for detecting organic trace components such as PCBs and dioxins in a processing facility or environment.
[0002]
[Background Art]
In recent years, the production and import of PCB (Polychlorinated biphenyl, a general term for chlorinated isomers of biphenyl) has been prohibited because of its strong toxicity. Although production of this PCB began in Japan around 1954, the adverse effects on living organisms and the environment became apparent in the wake of the Kanemi Yusho incident. There was a background.
[0003]
PCB is a biphenyl skeleton in which 1 to 10 chlorine atoms are substituted. There are theoretically 209 types of isomers depending on the number and positions of the substituted chlorine atoms. The body has been identified. In addition, the physical and chemical properties, in vivo stability, and environmental dynamics of these isomers are diverse, and the current situation is that the chemical analysis of PCBs and the manner of environmental pollution are complicated. Furthermore, PCB is one of the persistent organic pollutants, and has properties that it is not easily decomposed in the environment, is fat-soluble, has a high bioconcentration rate, is semi-volatile, and can be moved through the atmosphere. In addition, it is reported that it remains widely in the environment such as water and living things.
As a result, since PCB is extremely stable in the body, it is accumulated in the body and causes chronic poisoning (skin damage, liver damage, etc.), and carcinogenicity and reproductive / developmental toxicity are recognized.
[0004]
Since PCB has been widely used as insulating oil for transformers and capacitors, it is necessary to treat the PCB. The applicant has previously proposed a hydrothermal decomposition apparatus for detoxifying the PCB. (See JP-A-11-253796, JP-A-2000-126588 and others). FIG. 5 shows an example of the outline of this hydrothermal decomposition apparatus.
[0005]
As shown in FIG. 7, the hydrothermal decomposition apparatus 120 includes a cylindrical primary reactor 122 provided with a cyclone separator 121, a pressurizing pump 124 for pressurizing a treatment liquid 123 of PCB, H ₂ O, and NaOH, It is provided with a preheater 125 for preheating the mixed solution, a secondary reactor 126 having a configuration wound with piping, a cooler 127 and a pressure reducing valve 128. Downstream of the pressure reducing valve 127, a gas-liquid separator 129 and an activated carbon tank 130 are arranged. Exhaust gas (CO ₂ ) 131 is discharged from a chimney 132 to the outside, and waste water (H ₂ O, NaCl) 133 is discharged. Separately, wastewater treatment is performed as needed.
In addition, H ₂ O and NaOH are introduced into the piping 134 of the PCB that becomes the processing liquid 123. The oxygen pipe 135 is directly connected to the primary reactor 125.
[0006]
In the above apparatus, the pressure inside the primary reactor 122 is increased to 26 MPa by pressurization by the pressurizing pump 124. Further, the preheater 125 preheats the mixed solution 123 of PCB, H ₂ O and NaOH to about 300 ° C. Further, oxygen is spouted into the primary reactor 122, and the temperature rises to 380 ° C to 400 ° C due to the internal reaction heat. The cyclone separator 121 separates large Na ₂ CO ₃ crystal particles precipitated in the primary reactor 122 and sends Na ₂ CO ₃ fine particles to the secondary reactor 126. The operation of the cyclone separator 121 prevents the secondary reactor 126 from being blocked. By this stage, the PCB has undergone a dechlorination reaction and an oxidative decomposition reaction, and has been decomposed into NaCl, CO ₂ and H ₂ O. Next, in the cooler 127, the fluid from the secondary reactor 126 is cooled to about 100 ° C., and the pressure is reduced to the atmospheric pressure by the pressure reducing valve 128 in the subsequent stage. Then, CO ₂ and steam are separated from the treated water by the gas-liquid separator 129, and the CO ₂ and steam are discharged into the environment through the activated carbon tank 130.
[0007]
By treating a PCB-containing container (for example, a transformer or a condenser) or the like using such a processing device, complete harmlessness is achieved, but it is also important to quickly monitor the PCB concentration in the facility. Conventionally, a method has been adopted in which the PCB is concentrated into a liquid by gas sampling and the concentrated liquid is analyzed. However, since this measurement requires several hours to several tens of hours, rapid monitoring was not possible.
[0008]
However, as a method of measuring a trace amount of PCB in a gas for monitoring, a mass spectrum analyzer combining a multiphoton ionization detector and a time of flight mass spectroscopy (TOFMAS) has been proposed. I have.
The outline of this conventional analyzer will be described with reference to FIG.
[0009]
As shown in FIG. 8, a sample gas 1 is supplied from a pulse nozzle 2 into a vacuum chamber 3 as a supersonic free jet, and the free jet is cooled by adiabatic expansion. Due to such cooling, a gas whose vibration / rotation level is biased toward the low energy side and whose wavelength selectivity is increased has its ionization efficiency, which efficiently absorbs resonant multiphotons such as the laser 4, increased. The molecules in the ionized gas are accelerated by the accelerating electrode 5, are given an acceleration inversely proportional to the mass, fly in the flight tube 6, are reflected by the reflectron 7, and enter the detector 8. By measuring the time of flight in the flight tube 6, the mass of the molecule or atomic particle can be obtained by calculation, and the PCB concentration of the measurement object can be obtained from the comparison of the signal intensity of the detector 8.
[0010]
Such an apparatus is excellent in principle in that a trace substance can be detected, but has a problem that the detection sensitivity is low because a laser pulse time width uses a nanosecond laser.
Therefore, it is desired to efficiently concentrate the sample gas 1.
[0011]
Further, when the amount of moisture in the sample gas 1 is large, the detector 8 detects a large amount of noise as noise. Therefore, when measuring the concentration of PCB in the wastewater, it is desirable to remove it in advance.
[0012]
In addition, in recent years, measurement of environmental hormones in exhaust gas or wastewater discharged from combustion facilities such as various incinerators or boilers has a very small amount of measurement target, and thus the appearance of a high-performance detection device is desired. .
[0013]
In view of the above problems, an object of the present invention is to provide an apparatus for detecting an organic trace component that can perform a quick and highly sensitive analysis when monitoring the concentration of a trace component such as PCB.
[0014]
[Means for Solving the Problems]
Molecular first invention comprises a sample introduction means for continuously introducing a collected sample into a vacuum chamber, the laser is irradiated to the introduced sample, a laser irradiation unit for laser ionization was laser ionization to solve the problem Comprising: a convergence unit for converging the convergence, an ion trap for selectively concentrating the converged molecules, and a time-of-flight mass spectrometer including an ion detector for detecting ions emitted at a constant period. Wherein at least one gas replacement means for removing moisture in the sample and replacing the sample with a replacement gas having a small molecular weight is provided on the collection line of the sample, and separating light molecules in the sample by a difference in mass. A high-molecular separator for concentrating into heavy molecules by interposing the gas replacement means on the downstream side of the gas replacement means in the sampling line. A vacuum pump to remove moisture in the harvested sample by vacuum degree so as not to vaporize the target object sample taken in a sample introduced within the replacement gas introducing means for supplying a replacement gas after water removal, body after gas replacement And a high temperature means for discharging the replacement gas together with the collected sample, and the high-mass molecular separator is provided with a vacuum pump for keeping the inside vacuum, and a sample introduction thin tube is provided in the separator main body. And a sample discharge thin tube are provided to face each other at a predetermined interval, and further comprising a cleaning liquid supply means for supplying a cleaning liquid to the inside of the main body of the gas replacement means.
[ 0015 ]
A second invention is characterized in that, in the first invention, the replacement gas is H ₂ or He.
[ 0016 ]
A third invention is characterized in that, in the first invention, the sample introduction means is a capillary column, and the tip of the capillary column faces the ion focusing section.
[ 0017 ]
In a fourth aspect based on the first aspect , the pulse wavelength of the laser is 280 nm or less.
[ 0018 ]
In a fifth aspect based on the first aspect , the pulse time width of the laser is 500 picoseconds or less.
[0019]
A sixth invention is characterized in that, in the first invention, the collected sample is water discharged from the inside of a processing facility that has undergone PCB decomposition processing.
[0020]
A seventh invention, in the first invention, characterized in that the sample taken is environmental hormones wastewater in discharged from the combustion equipment.
[ 0021 ]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, embodiments of the present invention will be described, but the present invention is not limited thereto.
[ 0022 ]
[First Embodiment]
FIG. 1 is a schematic diagram of an apparatus for detecting an organic trace component according to the present embodiment. As shown in FIG. 1, an organic trace component detection device 50 according to the present embodiment is a detector that detects the concentration of an organic trace component in wastewater or gas, and is provided in a sample collection line 70. Capillary column 54, which is a sample introduction means for continuously leaking sampled sample 51 passing through gas replacement means 71 into vacuum chamber 52 and introducing it as molecular beam 53, and irradiating laser beam 55 to said leaked molecular beam 53. A laser irradiation means 56 for laser ionization, a converging section 56 composed of a plurality of ion electrodes for converging laser-ionized molecules, an ion trap 57 for selectively concentrating the converged molecules, and A time-of-flight mass spectrometer 60 provided with an ion detector 59 for detecting ions reflected by the reflectron 58 and detecting the reflected ions. Than it is.
Then, from the comparison of the signal intensities detected by the detector 59, the PCB concentration of the measurement target can be obtained.
The measured PCB concentration may be sent to the monitoring command room, and may be disclosed to the outside by, for example, a monitor device (not shown).
[ 0023 ]
The gas replacement means 71 includes a gas replacement means main body 73 formed by introducing a sample 51 from a pipe 72 to a sample collection line 70, a vacuum pump 74 for removing moisture in the sample 51 introduced into the body 73. A replacement gas introducing means 76 for supplying a replacement gas 75 after removing water, and a temperature adjusting means (not shown) for raising the temperature of the main body 73 after the gas replacement and discharging the replacement gas 75 together with the sample 51. It becomes.
In the figure, reference numeral 78 indicates a switching valve, and 79 indicates a pump.
[ 0024 ]
The collected sample 51 is introduced into the gas replacement means main body 73 from the pipe 72 by the pump 79. Next, the water inside is evaporated by the vacuum pump 74. At this time, the degree of vacuum is set so that the sample to be measured does not vaporize.
Next, He or H ₂ is introduced as a replacement gas from the replacement gas introduction unit 76.
Then, (about 200 to 300 [° C. For example, if the PCB) inside the sample is allowed to warm to a temperature that evaporates by the temperature adjusting means, for introducing a collected sample 51 into the capillary column 54. Note that the temperature raising temperature may be a temperature corresponding to the component to be analyzed. For example, when measuring only PCBs of 2 chlorines, the temperature can be set lower than that of PCBs of 3 chlorines.
[ 0025 ]
After the sample is discharged, the inside of the main body 73 is cleaned with a cleaning liquid (eg, alcohol or the like) 81 supplied from the cleaning liquid supply unit 80 so as to clean the inside. Thereafter, the cleaning liquid is discharged 82, and the temperature is returned to a temperature at which the evaporation of the object to be measured can be ignored, to prepare for the next measurement. In this case, if necessary, the temperature may be actively cooled (room temperature to 30 to 40 ° C.) by the temperature adjusting means.
[ 0026 ]
Further, as shown in FIG. 2, a plurality of gas replacement means (71A to 71D) may be provided in parallel to measure continuously. Thus, while the means for which gas replacement has already been completed is cooled, gas replacement can be performed by another replacement means, and measurement efficiency is improved.
[ 0027 ]
By providing the above gas replacement means, the sample becomes a sample 51 entrained by He or H ₂ , so that introduction of water vapor into the time-of-flight mass spectrometer 60 is eliminated and the life of the apparatus can be extended. .
Further, the amount of noise spectrum due to water molecules is significantly reduced, and a spectrum of only the spectrum to be analyzed can be detected.
[ 0028 ]
It is preferable that the capillary column 54 for introducing the gas-replaced collected sample 51 has its tip facing the ion focusing section 56. Specifically, the capillary column among the electrodes constituting the ion focusing section 56 is most suitable. It is preferable that the electrode 54 is flush with the electrode on the column 54 side or protrudes toward the ion trap 57 from the electrode.
[ 0029 ]
The material of the capillary column is preferably quartz or stainless steel. In the case of stainless steel, control can be performed by applying an electric field by the ion focusing section 56.
[ 0030 ]
The capillary column 54 has a hole diameter of 1 mm or less, preferably about 3 mm for a laser. Further, the shorter the distance from the outlet of the capillary column 54 to the irradiation position of the laser beam 55, the better. However, even if it is too close, the tip is damaged by the laser beam 55. It is preferable to improve the ionization efficiency.
[ 0031 ]
Pulse wavelength of the laser beam 55 emitted from the laser irradiation means 56, as shown in Examples you later, 300 nm or less, preferably 280nm or less, more preferably to be about 266 ± 10 nm. This is because if it exceeds 300 nm, ionization of the organic trace component to be measured is not performed well.
[ 0032 ]
The pulse time width of the laser light 55 emitted from the laser irradiation means 56 is preferably a pulse laser of 500 picoseconds (10-12) seconds or less, more preferably 200 picoseconds or less. This is because a laser having a pulse time width of nanoseconds (10-9) has low detection sensitivity and is not preferable.
[ 0033 ]
The pulse repetition frequency of the laser light 55 emitted from the laser irradiation means 56 is preferably 10 MHz or more, and particularly preferably 76 MHz.
This is because the ionization efficiency is continuously improved by increasing the pulse repetition frequency.
[ 0034 ]
As described above, by shortening the pulse time width of the laser light 55 to 500 picoseconds (10 −12) or less, decomposition of the PCB by the laser light 55 can be suppressed, and the detection sensitivity can be improved.
[ 0035 ]
FIGS. 3A and 3B show signals from the ion detector 59 that has detected PCB. Here, the horizontal axis is the flight time (second), and the vertical axis is the ion signal intensity (V). FIG. 2B is an enlarged view of FIG. 3A for the 4-chlorine PCB.
[ 0036 ]
Using the above measuring device, for example, the concentration of PCB in the wastewater discharged from the PCB decomposition treatment equipment can be measured quickly and accurately, and the treatment can be monitored based on the measurement result.
[ 0037 ]
In the present embodiment, a liquid has been described as an example of the collected sample 51 , but the present invention is not limited to this, and a gas may be used instead of the liquid. In this case, the sampled gas is introduced into the gas replacement means main body 73 at a supersonic speed to bring the measurement target into a liquid state, and then the replacement gas 75 is introduced and the temperature is increased, so that the organic matter such as PCB in the gas is removed. Halides can also be measured.
[ 0038 ]
[Second embodiment]
FIG. 4 is a schematic diagram of an apparatus for detecting an organic trace component according to the present embodiment. FIG. 5 is a schematic diagram of a high-mass molecular separator.
As shown in FIG. 4, in the present embodiment, in the device of the first embodiment, the light in the sample is reduced due to the difference in mass on the downstream side of the gas replacement means 71 interposed in the sampling line 70. It is provided with a high-molecular separator 90 for separating molecules and concentrating them into heavy molecules. The same members as those in the first embodiment are denoted by the same reference numerals, and description thereof will be omitted.
[ 0039 ]
As shown in FIG. 5, the high-mass molecular separator 90 is provided with a vacuum pump 92 for keeping the inside of the separator main body 91 at a vacuum, and a sample introduction thin tube 93 and a sample discharge thin tube 94 are provided in the separator main body 91 at a predetermined interval. It is provided facing each other with d.
[ 0040 ]
When the sample 51 gas-replaced by the gas replacement means 71 is introduced into the separator 90, the mass of the sample diffused toward the opposed sample discharge pipe 94 is reduced by the degree of vacuum of the vacuum pump 92. Molecule 95 spreads outward and a heavy molecule 96 remains at the center with a large inertia force, so that it is introduced into the opposite discharge capillary tube 94 side, and as a result, the measurement target in the collected sample is concentrated. . Thus, for example, when the PCB concentration in the sample introduction capillary 93 is 1 ppm, the concentration on the sample discharge capillary 94 side is 10 ppm, which is about 10 times.
As a result, the measurement sensitivity of a PCB or the like is improved.
[ 004 1 ]
The diameters of the sample introduction thin tube 93 and the discharge thin tube 94, the distance d therebetween, and the degree of vacuum may be appropriately set in consideration of the mass of the object to be measured.
For the capillary column 54 into which the molecular beam 53 is continuously leaked and introduced into the vacuum chamber 52, the diameter of the discharge thin tube 94 is reduced so that the leaked molecular beam can be well leaked.
[ 0042 ]
In the embodiment described above, the PCB as an object to be measured is taken as an example of an organic trace component. However, the present invention is not limited to this. The present invention can also be applied to measurement of exhaust gas discharged from combustion facilities such as incinerators and boilers or environmental hormones in wastewater.
[ 0043 ]
[Third Embodiment]
FIG. 6 illustrates a monitoring system in gas in a PCB detoxification processing facility using the above-described measuring device.
As shown in FIG. 6, the PCB detoxification processing system is a harmful substance processing system for detoxifying an object to which PCB, which is a harmful substance, is adhered, contained, or stored. One or both of the separating means 1004 for separating the harmful substance 1002 from the container 1003 for storing the substance (for example, PCB) 1002 and the disassembling means 1005 for disassembling the constituent materials 1001a, b,. A pretreatment means 1006, a core separation means 1007 for separating a core 1001a, which is a constituent material of an object processed in the pretreatment means 1006, into a coil 1001b and an iron core 1001c, and the separated coil 1001b Coil separating means 1008 for separating wire 1001d and paper / tree 1001e, iron core 1001c separated by core separating means 1008 and metal container (container body and lid etc.) 1003 separated by dismantling means 1005 and coil Separation means 1 Cleaning means 1011 for cleaning the copper wire 1001d separated in 008 with the cleaning liquid 1010, and harmful substance decomposition processing for decomposing one or both of the cleaning waste liquid 1012 after cleaning and the harmful substance 1002 separated by the pretreatment means Means 1013.
[ 0044 ]
Here, as the harmful substance to be detoxified in the present invention, besides PCB, for example, vinyl chloride sheet, hazardous waste paint, waste fuel, toxic chemical, waste resin, untreated explosive, etc. can be mentioned. It is not limited to these as long as they are harmful substances caused by contamination.
[ 0045 ]
Examples of the object to be treated in the present invention include, but are not limited to, transformers and capacitors using PCB as an insulating oil, and storage containers storing paints that are harmful substances. Not something.
[ 0046 ]
Also, in the ballast for fluorescent lamps, PCB has been conventionally used, so that it is necessary to perform detoxification treatment. In this case, since the capacity is small, it is necessary to directly feed into the separation means 1009 without pretreatment. Can be detoxified.
[ 0047 ]
When the harmful substance is a liquid or the like, the harmful substance is detoxified by directly charging the harmful substance decomposition processing means 1013, and the stored container can be processed by the detoxification processing of the constituent materials. It is necessary to confirm that the liquid after the treatment is 3 ppb or less, which is the PCB discharge standard.
Since the configuration of the harmful substance processing means 1013 is the same as that shown in FIG. 7, the same components are denoted by the same reference numerals and description thereof will be omitted.
[ 0048 ]
The measurement system 61 of the present invention monitors the PCB concentration in the wastewater 133 separated by the gas-liquid separator 129 after decomposing the PCB in the harmful substance treatment means 1013 by using the above-mentioned trace measuring device.
By providing this measurement system, the PCB concentration can be monitored quickly and efficiently. As a result, the decomposition process can be performed while always monitoring whether the PCB process is being performed appropriately, and environmentally friendly measures can be taken.
[ 0049 ]
Further, the measurement system 62 of the present invention monitors the PCB concentration in the environment in the pre-processing means 1006 by using the above-mentioned trace measuring device.
Further, the measuring system 63 of the present invention monitors the PCB concentration in the exhaust gas 131 that has been purified from the processing means 1013 through an activation tank (not shown).
By providing these measurement systems, the PCB concentration can be monitored quickly and efficiently. As a result, the decomposition process can be performed while constantly monitoring whether or not the work process is being performed appropriately, and environmentally friendly measures can be taken.
[ 0050 ]
Therefore, by using this measuring device, it is possible to analyze at predetermined time intervals and constantly monitor whether or not predetermined standards such as drainage, exhaust gas, and working environment are satisfied. If the standard is exceeded, the exhaust gas can be further purified, for example, through an activation tank, and only the work procedures can be modified to prevent external environmental pollution.
[0051]
【The invention's effect】
As described above, according to the first aspect of the present invention, a sample introducing means for continuously introducing a collected sample into a vacuum chamber, a laser irradiating means for irradiating the introduced sample with a laser and performing laser ionization, A converging section for converging the ionized molecules, an ion trap for selectively concentrating the converged molecules, and a time-of-flight mass spectrometer equipped with an ion detector for detecting ions emitted at a constant period A detection device comprising: at least one gas replacement means for removing moisture in a sample and replacing the sample with a replacement gas having a small molecular weight in a collection line of the sample; A high-mass molecular separator for separating molecules and concentrating them into heavy molecules is provided on the downstream side of the gas replacement means in the sampling line. A vacuum pump to remove moisture in the harvested sample by vacuum degree so as not to vaporize the target object sample taken in a sample introduced into device main body, and the replacement gas introducing means for supplying a replacement gas after water removal, the gas replacement The temperature of the main body is later raised, and a temperature raising means for discharging the replacement gas together with the collected sample is provided.The high-mass molecular separator is provided with a vacuum pump for keeping the inside vacuum, and the sample is contained in the separator main body. The introduction thin tube and the sample discharge thin tube are provided facing each other at a predetermined interval, and further provided with a cleaning liquid supply means for supplying a cleaning liquid to the inside of the main body of the gas replacement means. H ₂ ) can be used as a collected sample, and the introduction of water vapor into the time-of-flight mass spectrometer is eliminated, so that the life of the apparatus can be extended. In addition, the accuracy of trace analysis is improved. Further, the gas can be efficiently replaced and the sample can be discharged after the replacement. In addition, the concentration rate of the sample is improved.
[ 0052 ]
According to a second aspect of the present invention, in the first aspect , since the replacement gas is H ₂ or He, the life of the time-of-flight mass spectrometer can be extended.
[ 0053 ]
In a third aspect based on the first aspect , the sample introduction means is a capillary column, and the tip of the capillary column faces the ion converging section, so that ionization efficiency is improved.
[ 0054 ]
In a fourth aspect based on the first aspect, since the pulse wavelength of the laser irradiated from the laser irradiation means is 300 nm or less, the ionization of the organic halide is favorably performed.
[ 0055 ]
In a fifth aspect based on the first aspect, the detection sensitivity is improved because the pulse time width of the laser irradiated from the laser irradiation means is 500 picoseconds or less.
[0056]
According to a sixth aspect, in the first aspect, since the collected sample is the effluent from the inside of the processing facility that has undergone the PCB decomposition treatment, the PCB concentration in the wastewater or gas can be analyzed quickly and accurately.
[0057]
A seventh invention, in the first invention, since an environment hormones in waste water the collected sample is discharged from the combustion equipment, it is possible to high-sensitivity analysis.
[Brief description of the drawings]
FIG. 1 is a schematic diagram of an apparatus for detecting an organic trace component according to a first embodiment.
FIG. 2 is a schematic diagram in which a plurality of gas replacement means are arranged in parallel.
FIG. 3 is a diagram showing measurement results of low chlorine PCB.
FIG. 4 is a schematic view of an apparatus for detecting an organic trace component according to a second embodiment.
FIG. 5 is a schematic view of a separator.
FIG. 6 is a schematic diagram of a PCB detoxification processing system according to a third embodiment.
FIG. 7 is a schematic diagram of a hydrothermal decomposition apparatus.
FIG. 8 is a schematic diagram of a laser measurement device according to the related art.
[Explanation of symbols]
Reference Signs List 50 Organic halide detector 51 Sampling sample 52 Vacuum chamber 53 Leakage molecular beam 54 Capillary column 55 Laser beam 56 Converging section 57 Ion trap 58 Reflectron 59 Ion detector 60 Time-of-flight mass spectrometer 61, 62, 63 Measurement System 70 Sampling line 71 Gas replacement means 72 Pipe 73 Gas replacement means main body 74 Vacuum pump 75 Replacement gas 76 Replacement gas introduction means 78 Switching valve 79 Pump 80 Cleaning liquid supply means 81 Cleaning liquid 90 High-molecular-weight molecular separator 91 Separator main body 92 Vacuum pump 93 Sample introduction tube 94 Sample discharge tube

Claims (7)

Sample introduction means for continuously introducing the collected sample into the vacuum chamber,
Laser irradiation means for irradiating the introduced sample with laser and laser ionizing,
A converging section for converging the laser ionized molecules,
An ion trap for selectively concentrating the converged molecules;
A time-of-flight mass spectrometer provided with an ion detector for detecting ions emitted at a constant period,
At least one gas replacement means for removing water in the sample and replacing it with a replacement gas having a small molecular weight is provided on the collection line of the sample, and
A high-mass molecular separator that separates light molecules in the sample with a difference in mass and concentrates them into heavy molecules is interposed on the downstream side of the gas replacement means of the sampling line,
The gas replacement means,
A vacuum pump that removes moisture in the collected sample by a degree of vacuum that does not vaporize the sample to be measured in the collected sample introduced into the gas replacement means main body;
Replacement gas introduction means for supplying a replacement gas after removing water,
Temperature rising means for raising the temperature of the main body after the gas replacement and discharging the replacement gas together with the collected sample,
The high-mass molecular separator,
With a vacuum pump that keeps the inside vacuum,
A sample introduction thin tube and a sample discharge thin tube are provided facing each other at a predetermined interval in the separator body,
The apparatus for detecting a trace organic component further includes a cleaning liquid supply unit that supplies a cleaning liquid to the inside of the main body of the gas replacement unit. In claim 1,
An apparatus for detecting an organic trace component, wherein the replacement gas is H ₂ or He. In claim 1,
An apparatus for detecting an organic trace component, wherein the sample introduction means is a capillary column, and the tip of the sample introduction means faces an ion focusing part. In claim 1,
An apparatus for detecting an organic trace component, wherein a pulse wavelength of the laser is 280 nm or less. In claim 1,
An apparatus for detecting an organic trace component, wherein a pulse time width of the laser is 500 picoseconds or less. In claim 1,
An apparatus for detecting an organic trace component, wherein the collected sample is effluent from processing equipment subjected to PCB decomposition processing. In claim 1,
Detector of organic trace component, wherein the sample taken is environmental hormones in waste water discharged from the combustion equipment.

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