JP2000310596A - Element analyzer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an element analyzer capable of detecting many kinds of elements on-line for a real time regardless of a solid, liquid or gaseous sample form without requiring a complicated pretreatment process to determine them. SOLUTION: An element analyzer is equipped with a control device l outputting a control signal optimally holding the wavelength and output of laser beam and laser beam irradiating timing, a plurality of pulse laser devices 3a, 3b, 3c,...3n oscillating laser pulses corresponding to a given command, a synthesizer 4 for synthesizing laser beams for irradiating a sample, an analytical cell 6 having a laser condensing lens 5 for condensing laser beam to irradiate the sample and a fluorescence condensing lens 7 condensing the emitted light from plasma and a fluorometric device 8 for detecting the light having an inherent wavelength of an element to be measured.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an elemental analyzer and, more particularly, to an elemental analyzer for quantifying a specific element contained in a sample by measuring fluorescence from plasma generated by laser irradiation on the sample.

[0002]

2. Description of the Related Art Techniques for detecting and quantifying various elements contained in a sample are being used in various fields today.
The intended purpose has been achieved. Examples include exhaust gas from industrial plants, analysis of harmful substances contained in wastewater, analysis of impurity elements in cooling water and components in exhaust gas in the fields of thermal power generation and nuclear power generation. The analysis of various elements is mainly performed off-line by analyzing and quantifying the troubles of many specialized technicians and workers.

For example, taking a nuclear power plant as an example, a conventional elemental analysis operation includes a concentration operation by trapping an element to be analyzed on a filter, a filter pretreatment operation according to various analyzers, and an actual analysis operation. It consists of three stages, work. In such elemental analysis, highly accurate measurement conforming to strict water quality management standards specific to nuclear power plants is required.

[0004]

In the above-described elemental analysis, it is necessary to go through three steps for detecting and quantifying the target element. All work must be done carefully because the sample being handled is radioactive, and technicians and workers are constantly strained during the work.

In addition, many steps must be processed according to a carefully determined procedure, and it takes a long time until the analysis result is found, and it is not possible to provide analysis data in a timely manner.

In addition, it is necessary to handle complicated judgment equipment, and the prolonged work increases the risk of exposure, and the daily radiation exposure of workers is restricted by legal regulations. In addition, the same worker cannot engage in the same work for a long time, and cannot work efficiently.
Further, waste such as a filter used for concentration is generated, and it often becomes difficult to treat a large amount of waste.

An object of the present invention is to detect and quantify various types of elements on-line and in real time, irrespective of the form of a sample such as a solid, a liquid, and a gas, and without requiring a complicated pretreatment step. It is an object of the present invention to provide an elemental analyzer capable of performing the above.

[0008]

In order to achieve the above object, the invention according to claim 1 comprises a device for outputting a control signal for keeping the wavelength and output of laser light to be irradiated on a sample and the irradiation timing of laser light optimal. A plurality of pulse laser devices that oscillate laser pulses in accordance with a given command, a synthesizing device that synthesizes a given sample irradiation laser beam, and irradiate a sample focused on the laser beam and introduced into the vessel. An analysis cell having a laser condensing lens and a fluorescent condensing lens for condensing emitted light from plasma generated in a sample irradiated with laser light, of the light condensed by the fluorescent condensing lens,
A fluorescence measuring device for detecting light having a specific wavelength of the element to be measured.

In the element analyzer having the above-described structure, a plurality of laser pulse devices are used to oscillate laser light suitable for the optical characteristics of the element to be measured, and irradiate the sample in the analysis cell. At this time, the sample is decomposed and ionized, and the generated plasma emits fluorescence unique to the element. The emitted light from the plasma is spectrally analyzed by a fluorescence measuring device. The element can be identified by spectroscopic analysis using this fluorescence measuring device, and can be further quantified.

Depending on the element to be measured, laser pulses are continuously emitted at appropriate intervals. According to this method, the amount of fluorescence is greatly increased, and it is possible to maintain good analysis sensitivity. For example, in the case of boron (B), oxygen (O), etc., it has been experimentally confirmed that when the second pulse is irradiated with a delay of about 20 μs following the first pulse, the emitted light increases and the sensitivity improves. . If the amount of fluorescence obtained by one pulse irradiation is small, a plurality of times of fluorescence may be integrated. Thus, the S / N ratio (the ratio of the noise signal N to the target signal S) can be improved.

Further, the invention according to claim 2 is characterized in that a sample concentration adjusting device is provided so as to maintain the sample concentration in a sensitivity range where the analysis cell can be detected.

In the element analyzer having the above structure, when the fluid sample concentration increases during the elemental analysis and exceeds the measurement range, the sample concentration is adjusted by the sample concentration adjusting device to a certain value which can be spectrally analyzed by laser light irradiation. Down to By lowering the sample concentration, it is possible to always maintain the sensitivity in a detectable range.

[0013] The invention according to claim 3 is characterized in that the analysis cell is provided with a thin film generating apparatus for maintaining a thin film state of the sample in an atmosphere or a rare gas atmosphere.

In the elemental analyzer having the above structure, when the absorption of laser light or fluorescence is large due to the properties of the fluid sample to be analyzed and the spectral analysis is difficult, the sample is held in a thin film state by the liquid thin film generator. By keeping the sample in a thin film state, the plasma generation efficiency is increased, the loss of fluorescence is reduced, and good detection sensitivity can be maintained.

Further, the invention according to claim 4 is characterized in that a mist generating device for maintaining the mist state of the sample in the atmosphere or a rare gas atmosphere is provided instead of the thin film generating means.

In the elemental analyzer having the above configuration, when the absorption of laser light or fluorescence is large due to the properties of the fluid sample to be analyzed and the spectral analysis is difficult, the sample is held in a mist state by the mist generator. By maintaining the sample in the mist state, the plasma generation efficiency increases,
Further, the loss of fluorescence is reduced, and the detection sensitivity can be kept good.

According to a fifth aspect of the present invention, there is provided a spectroscope for spectrally separating light having a specific wavelength of an element to be measured, out of irradiation light from plasma generated by irradiation of laser light by a fluorescence measuring apparatus, and the spectroscope. And a photomultiplier tube for detecting light from the light source.

In the elemental analyzer having the above-described configuration, the detection sensitivity of the spectroscopic analysis can be kept good by a simple combination of the spectroscope and the photomultiplier.

The invention according to claim 6 is characterized in that the spectroscope is provided with a prism, a diffraction grating or an interference filter corresponding to the wavelength of the element to be measured.

In the element analyzer having the above structure, the detection sensitivity of the spectroscopic analysis can be kept good by a simple combination of a prism, a diffraction grating or an interference filter and a photomultiplier.

Further, the invention according to claim 7 is characterized in that a hand-pass filter is provided instead of the spectroscope.

In the element analyzer having the above structure, the detection sensitivity of the spectroscopic analysis can be kept good by a simple combination of the band-pass filter and the photomultiplier tube.

Further, the invention according to claim 8 is characterized in that a photomultiplier tube, a phototransistor array or a charge-coupled device is provided in place of the photomultiplier tube.

In the element analyzer having the above structure, the detection sensitivity of the spectroscopic analysis can be kept good by a simple combination of the spectroscope and the photodiode array or the phototransistor array or the charge-coupled device.

Further, the invention according to claim 9 further comprises an optical fiber for transmitting laser light in an optical transmission path from the synthesizing device to the laser condensing lens of the analysis cell, and further comprises a light condensing lens of the analysis cell. An optical fiber for fluorescence transmission is provided in an optical transmission path leading to the fluorescence measurement device, so that work associated with elemental analysis is performed by remote control.

In the element analyzer having the above configuration, by transmitting the laser light for irradiating the sample and the light emitted from the plasma through the optical fiber, many operations associated with the element analysis can be performed by remote control. This makes it possible to completely isolate the place where the sample to be measured is handled from the analysis room, and to avoid putting the human body at risk even when handling samples that are harmful to the human body. it can.

Further, the invention according to claim 10 is characterized in that a multi-bundle optical fiber is provided instead of the optical fiber for transmitting laser light and the optical fiber for transmitting fluorescence.

In the element analyzer having the above configuration, the optical transmission line for transmitting the laser light for irradiating the sample and the radiation light from the plasma is constituted by a multi-bundle optical fiber. The optical transmission path can be simplified as compared with the configuration using the optical transmission line. Further, the size of the entire elemental analyzer can be reduced.

According to the eleventh aspect of the present invention, instead of the laser focusing lens and the fluorescence focusing lens of the analysis cell, the laser light for irradiating the sample is focused and the radiated light from the plasma generated in the sample is collected. A condensing lens that emits light is provided, and an optical transmission line for laser light from the synthesizing device to the condensing lens and an optical transmission line for fluorescence from the condensing lens to the synthesizing device are configured by a single optical fiber. Are transmitted through a single optical fiber.

In the element analyzer having the above structure, the optical transmission line for laser light from the synthesizer to the condenser and the optical transmission line for fluorescence from the condenser to the synthesizer are constituted by a single optical fiber. The optical transmission path can be simplified as compared with the case where the optical transmission paths for transmitting the sample irradiation laser light and the radiation light from the plasma are formed using dedicated optical fibers. Also,
It is possible to reduce the size of the entire element analyzer.

Furthermore, the invention according to claim 12 is characterized in that the pulse laser device has one or more laser light sources carried from the following group.

Pulsed Nd: YAG laser (fundamental wave and harmonic wave), excimer laser, OPO laser, dye laser, semiconductor laser, copper vapor laser, carbon gas laser, nitrogen gas laser In this analysis, a pulse laser having a wide range of wavelengths and outputs can be oscillated.

[0033]

DESCRIPTION OF THE PREFERRED EMBODIMENTS (First Embodiment) A first embodiment of the present invention will be described with reference to FIG. This elemental analysis device includes a control device 1, a timing control device 2, pulse laser devices 3a, 3b, 3c... 3n, a synthesis device 4, a laser condensing lens 5, an analysis cell 6, a fluorescent condensing lens 7, a fluorescent measuring device 8, It comprises a display device 9, an optical fiber 10, and cables 11a, 11b, 11c.

The control device 1 selects the irradiation method and the pulse laser devices 3a, 3b, 3c... 3n according to the element to be measured. Also, it controls the pulse timing, sample concentration, and fluorescence measurement timing. Further, the control device 1 receives an output signal from the fluorescence measurement device 8, calculates the concentration with a built-in computer, and displays the obtained result on the display device 9.

The timing control device 2 controls the pulse laser device 3a according to the irradiation method and the pulse timing signal.
The laser emission signals are output to 3b, 3c... 3n. Also,
A fluorescence measurement timing signal synchronized with the pulse timing signal is output.

The pulse laser devices 3a, 3b, 3c... 3n
Oscillates different laser pulses from short wavelength to long wavelength, respectively. Also, the laser output differs between the pulse laser devices 3a, 3b, 3c... 3n. Further, the pulse laser devices 3a, 3b, 3c... 3n preferably have a pulsed Nd: YAG laser (a fundamental wave and a harmonic) as a laser light source. An excimer laser (XeC) is a desirable laser light source instead of the YAG laser.
l, KrF, rare gas halides such as ArF), OPO lasers, dye lasers, semiconductor lasers, copper vapor lasers, carbon dioxide lasers, and pulsed lasers such as nitrogen gas lasers.

The synthesizing device 4 is a pulse laser device 3
a, 3b, 3c... 3n are combined. The laser collective lens 5 condenses laser light and irradiates the fluid sample to be introduced into the analysis cell 6. The fluorescent light condensing lens 7 condenses the radiated light from the plasma generated by the irradiation of the laser light and guides the radiated light to the fluorescence measuring device 8. Further, the fluorescence measurement device 8 includes a spectroscope and a photomultiplier tube, and among the emission light from the plasma, only the wavelength specific to the element to be measured is separated by the spectroscope,
Detect with a photomultiplier tube. The display device 9 displays the measurement data that has been display-processed by the computer of the control device 1.

In the analysis cell 6, if the fluid sample concentration is always stable and does not affect the spectroscopic analysis, it is not necessary to provide a sample concentration adjusting device described later. However, if the fluid sample to be collected is expected to constantly vary in concentration, it is desirable to provide some means for adjusting the sample concentration.

In this embodiment, the irradiation method is selected in the control device 1 according to the element to be measured, and any one of the pulse laser devices 3a, 3b, 3c.
An oscillation command is given to n. For example, when detection by double pulse irradiation is desired, if an oscillation command is given to the pulse laser devices 3a and 3b, laser pulses are emitted from the pulse laser devices 3a and 3b at intervals. This laser light is synthesized in the synthesizing device 4, further transmitted through the optical fiber 10, and irradiated on the fluid sample which has been condensed by the laser condensing lens 5 and has flowed into the analysis cell 6.

At this time, plasma is generated in the cell 15 by the irradiation of the laser beam. Light emitted from the plasma is collected by the fluorescent light collecting lens 7 and transmitted to the fluorescence measuring device 8. Since this light contains light of various wavelengths, only light having a wavelength specific to the element to be measured is separated by a spectroscope. Subsequently, light having a wavelength unique to the element extracted by the spectroscopy irradiates the photocathode of the photomultiplier tube, a current is generated according to the amount of photoelectrons emitted at this time, and an output signal according to the amount of photoelectrons is generated. can get. This output signal is given to the computer of the control device 1.

Reference data is stored in a built-in database in the computer.
The density is calculated based on the D-converted value. Further, processing for display is performed in the computer, and the result is displayed on the display device 9. If it is determined that the fluid sample can be irradiated with laser light by the concentration check and spectroscopic analysis is possible, element analysis is started in the next step.

In the present embodiment, it is possible to detect various types of elements online and in real time while introducing the sample into the analysis cell 6 communicating with the sampling location of the sample to be measured.

Further, since the elemental analysis can be performed on-line, the operation can be greatly simplified as compared with the off-line type, and the amount of generated waste can be significantly reduced. Become.

Further, since the elemental analysis can be performed in real time, the time required for obtaining the analysis result is shortened, and the analysis data can be provided in a timely manner.

Further, many operations associated with elemental analysis can be performed by remote control. This makes it possible to completely isolate the place where the sample to be measured is handled from the analysis room.For example, when handling a sample that causes fatal harm to the human body, the human body is not put at risk. It becomes possible to avoid.

The fluorescence measuring device 8 of the present embodiment may use a band pass filter instead of the spectroscope. Further, a photodiode array, a phototransistor array, or a charge-coupled device (CCD) can be used as a photoelectron detector instead of the photomultiplier tube.

In the spectroscope of the fluorescence measuring device 8, the dispersive element corresponding to the wavelength of the element is used for the incident light to reduce the total interference effect of the element. Desirable dispersion elements are prisms, diffraction gratings, interference filters and the like.

The light emitted from the plasma may be condensed by using an integrating sphere or a multiple reflecting mirror, and may be efficiently collected by a photoelectron detector such as a photomultiplier.

Further, if necessary, the irradiated laser beam may be condensed by using a multiple reflection mirror, and may be again irradiated on the sample to heat it efficiently.

According to the present embodiment, it is possible to detect and quantify various types of elements online and in real time without requiring a complicated pretreatment step.

Further, since the elemental analysis can be performed on-line, the operation can be greatly simplified as compared with the on-line type, and the amount of generated waste can be significantly reduced. . Further, analysis data can be provided in a timely manner.

(Second Embodiment) Further, a second embodiment of the present invention will be described with reference to FIGS.
In FIG. 2, the main configuration of this embodiment is the same as that of the first embodiment except for the sample concentration adjusting device provided in the analysis cell 6. The sample concentration adjusting device includes a sample tank 13 for guiding a fluid sample through a sample sampling line 12.
A pure water tank 14 for storing pure water for dilution; a cell 15 for receiving a mixed fluid of a fluid sample and pure water;
The pump is provided with a pump 16 for pumping the mixed fluid therein and discharging the drain, and a drain line 17 for guiding the drain to a pit or a collection container (not shown). The cell 15 is provided with a laser focusing lens 5 for focusing laser light and a fluorescence focusing lens 7 for focusing fluorescence.

The present embodiment has the above configuration, and adjusts the concentration of the fluid sample when the concentration of the fluid sample rises, for example, during elemental analysis and goes out of the measurement range. This adjustment of the sample concentration is performed by a method of diluting with pure water from a pure water tank 14 leading to the analysis cell 6.

The procedure for determining the density includes the following steps. In FIG. 3, first, the amount of fluorescence is measured (step 10).
1). Next, a comparison is made with a reference calibration curve (step 102). Next, it is determined whether calibration is possible (step 103). Next, when the result of the determination indicates that calibration is possible, the sample is diluted 10-fold (step 104). The number of dilutions is stored (step 105), and the process returns to step 101. If the result of determination is that calibration is impossible, the measured concentration is read (step 106), and then the concentration is calibrated with the dilution amount (step 107), and the concentration is determined (step 108).

In the present embodiment, during the elemental analysis, when the fluid sample concentration becomes high for some reason and exceeds the measurement range, the sample concentration can be analyzed by irradiating the sample concentration with laser light by the sample concentration adjusting device. Down to the value. This makes it possible to always maintain the sample concentration in a detectable sensitivity range.

According to the present embodiment, especially when the concentration of the fluid sample to be introduced into the analysis cell 6 is high, the sensitivity can be adjusted to a detectable range. Further, the measurement dynamic range can be made wider.

(Third Embodiment) Further, a third embodiment of the present invention will be described with reference to FIGS.
In FIG. 4, the main configuration of the elemental analyzer is the same as that of the first embodiment. However, in this embodiment, instead of the above-described analysis cell, a fluid that maintains a good S / N ratio in detection is used. The difference is that an analysis cell 18 equipped with a thin film generator is used. An optical transmission path between the fluorescence condenser lens 7 and the fluorescence measurement device 8 is constituted by an optical fiber 19.

FIG. 5 shows the details of the analysis cell 18 provided with the above-mentioned liquid thin film generating apparatus for a fluid sample. The analysis cell 18 includes a nozzle 20 for blowing a fluid so as to generate a thin film F of a sample, a sample tank 21 for collecting the fluid sample blown from the nozzle 20, and a pump 22 for pumping the sample.
And a circulation line 23 for circulating the sample over the measurement point, and a controller 24 for controlling the thin film formation. The analysis cell 18 is provided with a laser condenser lens 5 for irradiating the thin film F with laser light to generate plasma P and a fluorescent condenser lens 7 for condensing light emitted from the plasma P.

In this embodiment, the sample is irradiated from the laser condenser lens 5 with a laser pulser emitted from any of the pulse laser devices 3a, 3b,... 3n. Here, the sample is, for example, an aqueous solution of ferric chloride, and Fe contained in the sample is analyzed. F
It has been experimentally confirmed that when e is analyzed, the fluorescence of Fe cannot be detected by directly condensing the laser light into the sample solution. When the upper surface of the solution is irradiated with laser light, fluorescence can be detected, but the plasma is not stable due to the wave of the solution, and the lower limit of detection is 100,000 p.
p. m. Therefore, the sample is circulated at a high speed to form a thin film, and the laser light is focused on the thin film surface.

The sample blown out from the nozzle 20 flows downward as a thin film F. A laser condensing lens 5 is provided on the thin film F.
The laser beam condensed at is irradiated, and plasma P is generated. This plasma P is generated stably by thinning the sample. The emitted light is collected by the fluorescent light condensing lens 7 and transmitted to the fluorescence measuring device 8 through the optical fiber 19. The method of detecting the elements in the fluorescence measuring device 8 is basically the same as that described in the first embodiment.

Thus, it is possible to stably generate plasma using the liquid thin film generating apparatus for a fluid sample, and the lower limit of detection is significantly smaller than 3 p. p. m.

In this embodiment, in particular, the absorption of laser light and fluorescence by the solution is drastically reduced as compared with the method in which the sample is blown out at a high speed to form a thin film and the free surface is irradiated with a laser to condense it in the solution. As a result, the plasma generation efficiency is significantly increased. In addition, the loss of fluorescence is reduced, and the detection sensitivity can be kept good.

Further, since the laser light for irradiating the sample and the light emitted from the plasma are transmitted by the optical fibers 10 and 19, many operations involved in elemental analysis can be performed by remote control. This makes it possible to completely isolate the place where the sample to be measured is handled from the analysis room, and to avoid putting the human body at risk, for example, when handling a sample that causes fatal harm to the human body. It becomes possible to do.

Further, a large number of samples can be analyzed simultaneously at many measurement places by remote control.

In this embodiment, a rare gas may be supplied as an atmospheric gas into the analysis cell 25 so that the plasma generation is more effectively performed.

According to the present embodiment, even when analyzing a fluid sample having a large absorption of laser light or fluorescence, the sample can be kept in a thin film state by the liquid thin film generating apparatus. As a result, the plasma generation efficiency is increased, the loss of fluorescence is reduced, and the detection sensitivity can be kept good.

(Fourth Embodiment) Further, a fourth embodiment of the present invention will be described with reference to FIG. The element analyzer of the present embodiment includes an analysis cell 25 having a mist generator different from the analysis cell of the third embodiment in order to maintain a good S / N ratio. Except for the analysis cell 25, the other configuration is the same as that of the first embodiment. The mist generating device includes a nozzle 26 for blowing out a mist M of a sample, and a sample tank 27 for collecting a fluid blown out from the nozzle 26.
And a circulating line 29 that circulates the sample over the measurement point. Further, the analysis cell 25 is provided with a laser condenser lens 5 that irradiates the mist M with laser light to generate plasma P and a fluorescent condenser lens 7 that collects radiated light of the plasma P.

This embodiment has the above structure, and can obtain the same function as that of the third embodiment. That is, instead of forming a thin film of the fluid sample, the fluid sample is held in a mist state for analyzing Fe contained in the aqueous ferric chloride solution. When the ultrasonic transducer 28 operates, the fluid sample in the sample tank 27 becomes fine mist and reaches the nozzle 26 through the circulation line 29. Next, the mist blows downward from the nozzle 26.
When the laser light is applied to the fine mist M, plasma P is generated. This plasma P is generated stably by the mist of the sample. Light emitted from the plasma P is condensed by the fluorescence condenser lens 7 and transmitted to the fluorescence measurement device 8 through the optical fiber 19.

In the present embodiment, particularly, the sample is in a mist state, reaches the measurement point, and plasma is generated by the laser beam irradiated thereon, so that the free surface area is increased by the mist-formed sample. This allows
As compared with the method of condensing laser light in a solution, the absorption of laser light and fluorescence by the solution is drastically reduced, and the plasma generation efficiency is significantly increased. In addition, the loss of fluorescence is reduced, and the detection sensitivity can be kept good.

According to the present embodiment, the sample can be kept in the mist state by the mist generating device even when analyzing a fluid sample having a large absorption of laser light or fluorescence. As a result, the plasma generation efficiency is increased, the loss of fluorescence is reduced, and the detection sensitivity can be kept good.

(Fifth Embodiment) Further, a fifth embodiment of the present invention will be described with reference to FIG. The optical transmission path of this element analyzer is constituted by a multi-bundle optical fiber 30. This is used in place of the optical fiber 10 for transmitting laser light and the optical fiber 19 for transmitting fluorescence described above.

In the elemental analyzer having such a configuration, since the optical transmission lines for guiding the sample irradiation laser light and the radiation light from the plasma are constituted by the multi-bundle optical fiber 30, each optical transmission line is dedicated. The optical transmission path can be simplified as compared with a configuration using optical fibers. In addition, it is possible to reduce the size of the entire element analyzer.

According to the present embodiment, since the optical transmission line for transmitting the laser light for irradiating the sample and the radiation light from the plasma is constituted by the multi-bundle optical fiber 30, the optical transmission line can be simplified. In addition, it is possible to reduce the size of the entire element analyzer.

(Sixth Embodiment) Further, a sixth embodiment of the present invention will be described with reference to FIG. This elemental analyzer is connected to an optical fiber 10 for transmitting laser light and an optical fiber 19 for transmitting fluorescence, and is provided with a synthesizing device 31 for synthesizing laser light, and a condensing device provided in the analysis cell 8 for condensing laser light and fluorescence. A lens 32 and an optical fiber 33 constituting an optical transmission path between the synthesizing device 31 and the condenser lens 32 are provided.

In the element analyzer having such a structure, laser beam synthesis can be achieved by the synthesizer 31 and laser light and fluorescence can be focused by the single focusing lens 32, respectively. For this reason, the optical transmission path can be constituted by only one optical fiber 33. Therefore, the optical transmission path can be simplified as compared with the case where the optical transmission paths for transmitting the laser light for irradiating the sample and the radiation light from the plasma are formed using dedicated optical fibers. In addition, it is possible to reduce the size of the entire element analyzer.

According to the present embodiment, since the optical transmission line for laser light and the optical transmission line for fluorescence are constituted by a single optical fiber 33, the optical transmission line can be simplified.
In addition, it is possible to reduce the size of the entire element analyzer.

[0077]

According to the present invention, many kinds of elements can be detected online and in real time without a complicated pretreatment step. In addition, quantification is possible.

Further, elemental analysis can be performed on-line, the operation can be greatly simplified, and the amount of waste generated can be significantly reduced.

Further, analysis data can be provided in a timely manner.

[Brief description of the drawings]

FIG. 1 is a configuration diagram showing a first embodiment of an element analyzer according to the present invention.

FIG. 2 is a configuration diagram showing a second embodiment of the elemental analyzer according to the present invention.

FIG. 3 is a flowchart illustrating an example of a sample concentration determination method according to the present invention.

FIG. 4 is a configuration diagram showing a third embodiment of the elemental analyzer according to the present invention.

FIG. 5 is a configuration diagram showing details of a liquid thin film generation device of the present invention.

FIG. 6 is a configuration diagram showing a fourth embodiment of the elemental analyzer according to the present invention.

FIG. 7 is a configuration diagram showing a fifth embodiment of the elemental analyzer according to the present invention.

FIG. 8 is a configuration diagram showing a sixth embodiment of the elemental analyzer according to the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Control device 3a, 3b, 3c ... 3n Pulse laser device 4 Synthesizing device 5 Laser condensing lens 6, 18, 25 Analysis cell 7 Fluorescent condensing lens 8 Fluorescence measuring device 10, 33 Optical fiber 19 Fluorescent transmission optical fiber 30 Many Bundle optical fiber 34 condenser lens

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2G043 AA01 CA01 CA02 CA07 DA01 DA02 DA05 EA01 GA07 GB01 GB09 GB21 HA01 HA05 JA03 JA05 KA08 KA09 LA02 LA03 NA04 NA06 NA11 NA13

Claims (12)

[Claims] 1. A device for outputting a control signal for keeping a wavelength and an output of a laser beam to be irradiated on a sample and an irradiation timing of the laser beam optimally, and a plurality of pulse laser devices for oscillating a laser pulse in accordance with a given command And a synthesis device for synthesizing a given sample irradiation laser beam, a laser focusing lens for focusing the laser beam and irradiating the sample introduced into the vessel, and a plasma generated from the sample irradiated with the laser beam. An analysis cell having a fluorescence condensing lens for condensing emitted light, and a fluorescence measurement device for detecting light having a unique wavelength of the element to be measured among the light condensed by the fluorescence condensing lens. Element analyzer. 2. The element analyzer according to claim 1, further comprising a sample concentration adjusting device for maintaining the sample concentration in a sensitivity range where the analysis cell can detect. 3. The element analyzer according to claim 1, wherein the analysis cell includes a thin film generator for maintaining a thin film state of the sample in an atmosphere or a rare gas atmosphere. 4. The elemental analyzer according to claim 3, wherein a mist generator for maintaining a mist state of the sample in an atmosphere or a rare gas atmosphere is provided instead of the thin film generator. 5. A spectroscope for spectrally separating light having a specific wavelength of an element to be measured, from among irradiation light from plasma generated by irradiation of laser light, and detecting the light from the spectrometer. The element analyzer according to claim 1, further comprising a photomultiplier tube. 6. The element analyzer according to claim 5, wherein the spectroscope includes a prism, a diffraction grating, or an interference filter corresponding to the wavelength of the element to be measured. 7. The element analyzer according to claim 5, wherein a hand-pass filter is provided instead of the spectroscope. 8. The elemental analyzer according to claim 5, wherein a photo diode array, a photo transistor array, or a charge-coupled device is provided instead of the photomultiplier tube. 9. An optical transmission path from the synthesizing apparatus to the laser condensing lens of the analysis cell, comprising an optical fiber for transmitting laser light, and measuring the fluorescence from the fluorescence condensing lens of the analysis cell. 2. The elemental analyzer according to claim 1, wherein an optical fiber for fluorescence transmission is provided in an optical transmission path leading to the device, and an operation associated with the elemental analysis is performed by remote control. 10. The elemental analyzer according to claim 9, wherein a multi-bundle optical fiber is provided in place of the optical fiber for transmitting laser light and the optical fiber for transmitting fluorescence. 11. A condenser for condensing laser light for irradiating a sample and condensing radiated light from plasma generated in the sample instead of the laser condenser lens and the fluorescence condenser lens of the analysis cell. A lens, and an optical transmission path for laser light from the synthesizing device to the condensing lens and an optical transmission line for fluorescence from the condensing lens to the synthesizing device are constituted by a single optical fiber; 2. The elemental analyzer according to claim 1, wherein both are transmitted through said single optical fiber. 12. The elemental analyzer according to claim 1, wherein said pulsed laser apparatus has one or more laser light sources carried from the following groups. Pulsed Nd: YAG laser (fundamental and harmonic), excimer laser, OPO laser, dye laser, semiconductor laser, copper vapor laser, carbon dioxide laser, nitrogen gas laser