JPH0457990B2 - - Google Patents
Info
- Publication number
- JPH0457990B2 JPH0457990B2 JP10363583A JP10363583A JPH0457990B2 JP H0457990 B2 JPH0457990 B2 JP H0457990B2 JP 10363583 A JP10363583 A JP 10363583A JP 10363583 A JP10363583 A JP 10363583A JP H0457990 B2 JPH0457990 B2 JP H0457990B2
- Authority
- JP
- Japan
- Prior art keywords
- sample
- radiation
- measurement
- container
- measurement container
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 238000005259 measurement Methods 0.000 claims description 89
- 230000005855 radiation Effects 0.000 claims description 74
- 239000007788 liquid Substances 0.000 claims description 50
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 49
- 239000000941 radioactive substance Substances 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 34
- 238000004811 liquid chromatography Methods 0.000 claims description 11
- 239000011230 binding agent Substances 0.000 claims description 9
- 229910052693 Europium Inorganic materials 0.000 claims description 7
- 239000003463 adsorbent Substances 0.000 claims description 5
- 239000004033 plastic Substances 0.000 claims description 4
- 229920003023 plastic Polymers 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 2
- 239000010453 quartz Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims 1
- 239000000523 sample Substances 0.000 description 82
- 239000002904 solvent Substances 0.000 description 18
- 229910052794 bromium Inorganic materials 0.000 description 14
- 239000000460 chlorine Substances 0.000 description 14
- 229910052801 chlorine Inorganic materials 0.000 description 13
- 238000004020 luminiscence type Methods 0.000 description 12
- 229910052740 iodine Inorganic materials 0.000 description 11
- 230000005284 excitation Effects 0.000 description 10
- 239000011575 calcium Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 229910052791 calcium Inorganic materials 0.000 description 8
- 239000011777 magnesium Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 229910052712 strontium Inorganic materials 0.000 description 8
- -1 hexafluoro compound Chemical class 0.000 description 7
- 229910052771 Terbium Inorganic materials 0.000 description 6
- 229910052793 cadmium Inorganic materials 0.000 description 6
- 229910052736 halogen Inorganic materials 0.000 description 6
- 150000002367 halogens Chemical class 0.000 description 6
- 229910052749 magnesium Inorganic materials 0.000 description 6
- 230000000171 quenching effect Effects 0.000 description 6
- 229910052725 zinc Inorganic materials 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- 229910052772 Samarium Inorganic materials 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 230000002285 radioactive effect Effects 0.000 description 5
- 229910052684 Cerium Inorganic materials 0.000 description 4
- 229910052691 Erbium Inorganic materials 0.000 description 4
- 229910052689 Holmium Inorganic materials 0.000 description 4
- 229910052779 Neodymium Inorganic materials 0.000 description 4
- 229910052769 Ytterbium Inorganic materials 0.000 description 4
- 238000009825 accumulation Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000010791 quenching Methods 0.000 description 4
- 239000012488 sample solution Substances 0.000 description 4
- 241001473992 Abax Species 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 229910052775 Thulium Inorganic materials 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 229910052788 barium Inorganic materials 0.000 description 3
- 229910052790 beryllium Inorganic materials 0.000 description 3
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 229910052746 lanthanum Inorganic materials 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 3
- 229910052716 thallium Inorganic materials 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 229910052692 Dysprosium Inorganic materials 0.000 description 2
- 229910052688 Gadolinium Inorganic materials 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052792 caesium Inorganic materials 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 229910052701 rubidium Inorganic materials 0.000 description 2
- 229910052706 scandium Inorganic materials 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910005793 GeO 2 Inorganic materials 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012857 radioactive material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005464 sample preparation method Methods 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- DXIGZHYPWYIZLM-UHFFFAOYSA-J tetrafluorozirconium;dihydrofluoride Chemical compound F.F.F[Zr](F)(F)F DXIGZHYPWYIZLM-UHFFFAOYSA-J 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01T—MEASUREMENT OF NUCLEAR OR X-RADIATION
- G01T7/00—Details of radiation-measuring instruments
- G01T7/02—Collecting means for receiving or storing samples to be investigated and possibly directly transporting the samples to the measuring arrangement; particularly for investigating radioactive fluids
- G01T7/04—Collecting means for receiving or storing samples to be investigated and possibly directly transporting the samples to the measuring arrangement; particularly for investigating radioactive fluids by filtration
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01T—MEASUREMENT OF NUCLEAR OR X-RADIATION
- G01T1/00—Measuring X-radiation, gamma radiation, corpuscular radiation, or cosmic radiation
- G01T1/16—Measuring radiation intensity
- G01T1/20—Measuring radiation intensity with scintillation detectors
- G01T1/2012—Measuring radiation intensity with scintillation detectors using stimulable phosphors, e.g. stimulable phosphor sheets
Landscapes
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Physics & Mathematics (AREA)
- High Energy & Nuclear Physics (AREA)
- Molecular Biology (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Measurement Of Radiation (AREA)
Description
ãçºæã®è©³çްãªèª¬æã
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ããDETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for detecting radioactive substances in a liquid sample using liquid chromatography. More specifically, the present invention relates to a method for detecting radioactive substances using a stimulable phosphor.
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è¡ãªãããŠããã One method of separation analysis is to inject a sample solution into a packed tower (column) packed with an adsorbent, then inject an appropriate solvent to develop the sample, and then collect the sample components as they flow out of the column. Liquid chromatography is known. This liquid chromatography is also used to separate samples containing radioactive substances (substances containing radioactive isotopes), and is used to measure the radiation emitted from the eluate separated by liquid chromatography. The separation and identification of radioactive substances in samples is carried out using this method.
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æ§ç©è³ªã®æŸå°èœã枬å®ããæ¹æ³ã§ããã Traditionally, a method for measuring the radiation emitted from a liquid sample containing radioactive substances is to add a liquid scintillator, which is made by dissolving a solute (fluorescent agent) in an organic solvent, to the sample. Liquid scintillation methods, which involve detecting radiation as fluorescence, are widely used. In this method, a part of the radiation energy emitted from a radioactive substance in a sample is absorbed by a scintillator, and the radioactivity of the radioactive substance is measured by detecting the fluorescence (instantaneous luminescence) emitted from the scintillator. It is.
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ãã The liquid scintillation method described above is also applied to liquid chromatography of samples containing radioactive substances, and by separating a certain amount of the liquid sample flowing out of the column and adding a liquid scintillator, radiation from the sample is removed. measurements are being carried out.
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ã€ãŠããã That is, after a sample containing radioactive substances separated and developed by liquid chromatography is fractionated using a fraction collector, a liquid scintillator is added to each fraction, and the fluorescence emitted from the liquid scintillator is collected using a photomultiplier tube. By detecting and counting as electrical pulses, the radiation dose of each fraction is measured, and the radioactive substances in the sample are separated and identified.
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ãæž¬å®ããããã®æçšãªææ®µãšãªã€ãŠããã In this way, the liquid scintillation method has the advantage of being able to detect radioactivity even when the radiation emitted from radioactive substances is weak radiation such as α-rays and β-rays. It has become a useful means for measuring radioactivity.
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ãšã«ãã€ãŠãè¡ãªãããã In the liquid scintillation method, the scintillator's light emission is caused by the energy of the radiation emitted from the radioactive substance in the liquid sample, which first excites the solvent molecules formed by dissolving the solute (fluorescent agent), and then excites them. It occurs when solute molecules are excited due to collisions between solvent molecules and solute molecules (scintillator). In addition to this process in which radiation energy is transferred from solvent molecules to solute molecules, energy is transferred between solvent molecules due to interactions between solvent molecules in an excited state and solvent molecules in a ground state. This also includes the case where the scintillator is excited after energy is transferred to another solute molecule due to the interaction between the excited solvent molecule and the solute molecule of an object other than the scintillator. In addition, this energy transfer occurs not only through interactions between molecules such as collisions, but also when the sitillator absorbs fluorescence emitted from excited solvent molecules or other solute molecules.
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çŸè±¡ãåæã«çããã However, during this energy transfer process, the excitation energy is absorbed by some solvent molecules or other solute molecules and converted into heat, or the fluorescence generated by the scintillator is absorbed into the sample. A quenching phenomenon such as absorption by a light-absorbing substance also occurs at the same time.
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ãã The liquid scintillator essential in the liquid scintillation method is expensive and requires separation and purification before reuse. Furthermore, since it is difficult to recover scintillators with high purity, they are not often reused, and this also makes it difficult to reduce measurement costs. Furthermore, there are some problems in the handling of used scintillators containing radioisotopes, such as the difficulty in disposing of them.
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When the sample is poorly soluble, it is difficult to make the sample solution into a homogeneous phase, while when the sample solution is in a heterogeneous phase, there are problems such as internal absorption of radiation emitted from the sample. Therefore, it is necessary to correct for the quenching caused by the various causes mentioned above to accurately determine the sample counting efficiency, which makes the measurement operation complicated.
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In addition, pretreatment of the sample is required to remove the above-mentioned contaminants.
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That is, after adding a scintillator to a liquid sample, it is necessary to continuously measure light emitted from the scintillator for a certain period of time (for example, several minutes to several tens of minutes). In this measurement, when the intensity of radiation is low, the measurement time (measurement time) is long, and it cannot be said that the efficiency of measurement and the operating rate of the measuring device are sufficiently high.
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ãèŠæ±ããçµæãšãªãã Therefore, when the sample consists of a large number of samples as described above, there is a problem that it is difficult to process a large number of samples because the waiting time becomes long.
Another problem is that it takes time to obtain results. In particular, it is difficult to measure radiation when the radioactive isotope in the sample has a short half-life, and even more difficult when the intensity of the radiation is weak. This also means that the equipment used must be stable for long periods of time (e.g. against dark current drift in photomultiplier tubes), and in order to prevent this This results in either requiring expensive equipment or requiring experience and skill in adjusting the equipment.
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ãã The present inventor has conducted extensive research with the aim of solving the above-mentioned problems associated with the conventional liquid scintillation method used in liquid chromatography of samples containing radioactive materials. By sequentially supplying a plurality of radiation measurement containers containing an exhaustible phosphor to a sample supply device, a liquid sample is continuously or intermittently introduced into these measurement containers, and then the liquid sample is absorbed into the measurement containers. The inventors have discovered that the above-mentioned problems can be solved or the drawbacks reduced by utilizing a method of measuring radiation energy, and have arrived at the present invention.
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æäžã®æŸå°æ§ç©è³ªã®æ€åºæ¹æ³ã«ããã That is, the present invention provides the following features: (1) A plurality of radiation measurement containers each containing a photostimulable phosphor are installed under a column filled with an adsorbent so as to receive and hold a liquid sample that has passed through the column. A step of introducing the liquid sample into each measurement container by sequentially supplying the liquid sample; (2) By leaving the plurality of measurement containers for a certain period of time, the radiation energy emitted from the radioactive substance in the liquid sample is (3) emitting the radiation energy stored in the plurality of measurement containers as photostimulated light and photoelectrically reading the photostimulated light; A method for detecting radioactive substances in a liquid sample using liquid chromatography, including the steps of: continuously measuring radioactivity in the liquid sample;
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ããšãã§ããã After absorbing radiation, the stimulable phosphor used in the present invention emits light (stimulated luminescence) when irradiated with electromagnetic waves (excitation light) such as visible light and infrared rays.
It has the property of showing. Therefore, by introducing a liquid sample containing a radioactive substance into a radiation measurement container containing a stimulable phosphor, the radiation emitted from the radioactive stool in the sample is absorbed into the measurement container, and then this measurement is performed. By irradiating a container with electromagnetic waves (excitation light) such as visible light and infrared rays, accumulated energy proportional to the radiation dose is released as fluorescence (stimulated luminescence). By photoelectrically reading this fluorescence and converting it into an electrical signal, the radiation emitted from the sample can be measured.
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ãããšãã§ãããã®ã§ããã Furthermore, according to the present invention, by accumulating radiation energy from a sample in a radiation measurement container and then removing the sample, it is also possible to perform the accumulation operation and readout operation completely separately. Therefore, a plurality of measurement containers can be subjected to a readout operation at once. In this respect as well, the time required for conventional measurement can be shortened and the measurement operation can be simplified.
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枬å®å¹çãåŸããããã®ã§ããã Therefore, the operating rate of the measuring device can be increased and the number of measurements can be increased. Furthermore, this means that
This means that even when using a radioactive isotope with a short half-life and low radiation intensity, measurements can be made with high accuracy under the same conditions. Furthermore, according to the present invention, even if only one measuring device is used, by preparing a plurality of measuring containers, it is possible to obtain the same measurement efficiency as using multiple measuring devices at the same time in the conventional method. It is something that can be done.
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There is no need to mix (dissolve or suspend) the scintillator solution and sample in a container as in the liquid scintillation method, and the liquid sample containing the radioactive substance is simply placed in the measurement container containing the stimulable phosphor. Since measurement can be performed by introducing the sample, there is no need to separate and purify the sample after use.
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æã«è¡ãªãããšãã§ããã Therefore, since there is no particular need to remove impurities contained in the sample, there is no need for conventional sample pretreatment, and a high degree of skill and care based on experience is required when preparing the sample. It's something you don't do. In this respect as well, radiation measurement of the sample can be easily performed.
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æããã Below, a radiation measurement container suitably used in the radioactive substance detection method of the present invention will be described.
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ãããã The radiation measurement container used in the present invention usually consists of a sample storage part and a lid part. The lid part is not always necessary, and is used depending on the form of the measurement container, the type of sample, measurement conditions, etc.
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ãªãããã«ããæž¬å®å®¹åšã奜ãŸããã The stimulable phosphor contained in the measurement container does not need to be contained throughout the measurement container, and may be contained only in a portion of the container. However, by increasing the surface area of the part containing the stimulable phosphor, the ability to capture radiation emitted from the sample is increased, improving the accuracy of measurement values and reducing the amount of radioactivity present in trace amounts in the sample. It becomes possible to detect substances or substances with weak radiation intensity. On the other hand, from the point of view of radiation energy readout operations, it is preferable that the stimulable phosphor is partially incorporated in the measurement container, and in this case, it is desirable that the stimulable phosphor be incorporated in the portion that comes into contact with the sample. In addition, from the viewpoint of the range of radiation emitted from the sample, the measurement container should be designed so that the distance between the built-in part of the stimulable phosphor and the radioactive substance (radiation source) in the sample is as small as possible. preferable.
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ãªã©ãæããããšãã§ããã The stimulable phosphor used in the present invention is a phosphor that exhibits stimulated luminescence when irradiated with excitation light after absorbing radiation as described above. The phosphor is preferably a phosphor that exhibits stimulated luminescence in the wavelength range of 300 to 500 nm when excited by excitation light in the wavelength range of 800 nm. Examples of such stimulable phosphors include those described in U.S. Pat. No. 3,859,527.
Phosphors expressed by composition formulas such as SrS:Ce, Sm, SrS:Eu, Sm, ThO 2 :Er, and La 2 O 2 S:Eu, Sm, as described in JP-A-55-12142.
ZnS: Cu, Pb, BaOã»xAl 2 O 3 : Eu [However, 0.8
âŠxâŠ10], and M 2+ Oã»xSiO 2 :A [however,
M 2+ is Mg, Ca, Sr, Zn, Cd, or Ba, A is Ce, Tb, Eu, Tm, Pb, Tl, Bi, or Mn, and x is 0.5âŠxâŠ2.5. A phosphor expressed by a composition formula such as (Ba 1-xy , Mg x , Ca y )FX: aEu 2+ [where
is at least one of Cl and Br,
A phosphor represented by the composition formula: x and y are 0<x+yâŠ0.6 and xyâ 0, and a is 10 -6 âŠaâŠ5Ã10 -2 JP-A-12144-1987 stated in the issue
LnOX: xA [However, Ln is La, Y, Gd, and
At least one of Lu, X is at least one of Cl and Br, A is at least one of Ce and Tb, and x is 0<x<0.1
A phosphor expressed by the composition formula of (Ba 1-x , Mã x )FX:yA [where Mã is Mg,
at least one of Ca, Sr, Zn, and Cd, X is at least one of Cl, Br, and I, A is Eu, Tb, Ce, Tm, Dy, Pr, Ho,
At least one of Nd, Yb, and Er, x is 0âŠxâŠ0.6, and y is 0âŠyâŠ0.2] JP-A-55-160078 stated in the official bulletin,
MãFXã»xA:yLn [However, Mã is Ba, Ca, Sr,
At least one of Mg, Zn, and Cd, A
are BeO, MgO, CaO, SrO, BaO, ZnO,
Al 2 O 3 , Y 2 O 3 , La 2 O 3 , In 2 O 3 , SiO 2 , TiO 2 ,
ZrO 2 , GeO 2 , SnO 2 , Nb 2 O 5 , Ta 2 O 5 , and
At least one of ThO 2 , Ln is Eu, Tb,
Ce, Tm, Dy, Pr, Ho, Nd, Yb, Er, Sm,
and at least one of Gd, X is Cl,
At least one of Br, and I,
x and y are respectively 5Ã10 -5 âŠxâŠ0.5 and 0<yâŠ0.2] A phosphor is described in JP-A-56-116777 (Ba 1- x , Mã x )F 2ã»aBaX 2 :yEu, zA [However,
Mã is beryllium, magnesium, calcium,
at least one of strontium, zinc, and cadmium; X is at least one of chlorine, bromine, and iodine; A is at least one of zirconium and scandium;
a, x, y, and z are each 0.5âŠaâŠ1.25,
0âŠxâŠ1, 10 -6 âŠyâŠ2Ã10 -1 , and 0<z
âŠ10 -2 ], described in Japanese Patent Application Laid-Open No. 57-23673, (Ba 1-x , Mã x )F 2ã»aBaX 2 :yEu, zB ,
Mã is beryllium, magnesium, calcium,
at least one of strontium, zinc, and cadmium;
10 -6 âŠyâŠ2Ã10 -1 and 0<zâŠ10 -1 ] A phosphor is described in JP-A-57-23675 (Ba 1-x , Mã x )F 2ã»aBaX 2 :yEu, zA [However,
Mã is beryllium, magnesium, calcium,
at least one of strontium, zinc, and cadmium; X is at least one of chlorine, bromine, and iodine; A is at least one of arsenic and silicon; a, x, y, and z are each 0.5 âŠaâŠ1.25, 0âŠxâŠ1, 10 -6
âŠyâŠ2Ã10 -1 and 0<zâŠ10 -1 ], MãOX described in Japanese Patent Application No. 167498/1983 filed by the present applicant. :xCe[However, Mã is Pr,
Nd, Pm, Sm, Eu, Tb, Dy, Ho, Er, Tm,
is at least one trivalent metal selected from the group consisting of Yb, and Bi, X is one or both of Cl and Br, and x is 0<x<0.1]. The expressed phosphor is Ba 1-x M x/2 L x/2 FX:yEu +2 [However,
M represents at least one alkali metal selected from the group consisting of Li, Na, K, Rb, and Cs; L represents Sc, Y, La, Ce, Pr, Nd, Pm,
Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu,
represents at least one trivalent metal selected from the group consisting of Al, Ga, In, and Tl; X is Cl,
represents at least one halogen selected from the group consisting of Br, and I; and x is 10 -2 âŠ
xâŠ0.5, y is 0<yâŠ0.1] BaFX xA:yEu +2 [However, ,X is
is at least one halogen selected from the group consisting of Cl, Br, and I; A is a fired product of a tetrafluoroboric acid compound; and x is
10 -6 âŠxâŠ0.1, y is 0<yâŠ0.1] BaFX xA: yEu described in Japanese Patent Application No. 158048/1983 filed by the present applicant +2 [However, X is
at least one halogen selected from the group consisting of Cl, Br, and I; A is a hexafluoro compound consisting of a monovalent or divalent metal salt of hexafluorosilicic acid, exafluorotitanic acid, and hexafluorozirconic acid; and x is 10 -6 âŠxâŠ0.1, and y is 0<yâŠ0.1. BaFXã»xNaXâ²: aEu 2+ described in Application No. 166320/1987 [However,
X and X' are each at least one of Cl, Br, and I, x and a are each 0<xâŠ2, and a is 0<aâŠ0.2]
A phosphor having the composition formula MãFXã»xNaXâ²:yEu 2+ :zA [where Mã is Ba, Sr, and at least one alkaline earth metal selected from the group consisting of Ca; X and X' are Cl, Br, and I, respectively;
at least one halogen selected from the group consisting of; A is at least one transition metal selected from V, Cr, Mn, Fe, Co, and Ni; and x is 0<xâŠ2, y is 0<yâŠ
0.2, and z is 0<zâŠ10 -2 ], MãFXã»aMãXâ² described in the specification of Japanese Patent Application No. 184455/1983 filed by the present applicant.ã»bMâ²ãXâ³ 2ã»cMã
X 3ã»xA:yEu 2+ [However, Mã is at least one kind of alkaline earth metal selected from the group consisting of Ba, Sr, and Ca; Mã is Li, Na, K,
is at least one alkali metal selected from the group consisting of Rb, and Cs; Mâ²ã is Be and
is at least one divalent metal selected from the group consisting of Mg; M is at least one trivalent metal selected from the group consisting of Al, Ga, In, and Tl; A is a metal oxide; X is Cl, Br,
and at least one kind of halogen selected from the group consisting of I; Xâ², Xâ³, and X are F,
at least one halogen selected from the group consisting of Cl, Br, and I; and a is 0âŠ
aâŠ2, b is 0âŠbâŠ10 -2 , c is 0âŠcâŠ10 -2 ,
and a+b+câ§10 -6 ; x is 0<xâŠ0.5,
y is 0<yâŠ0.2], and the like.
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ããã However, the stimulable phosphor used in the present invention is not limited to the above-mentioned phosphors, and any phosphor that exhibits stimulated luminescence when irradiated with excitation light after absorbing radiation can be used. It can be something.
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ããã¯ç©è³ªãæããããšãã§ããã Examples of materials for the radiation measurement container used in the present invention include glass; quartz; polyethylene;
Plastic materials such as polypropylene, nylon, Teflon, etc. may be mentioned.
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ã«å¿ããŠèšå®ããããšãã§ããã A radiation measurement container can be obtained by incorporating a photostimulable phosphor into the above-mentioned material to form a container. Measurement container size, thickness, shape,
The amount and area of the built-in stimulable phosphor can be set depending on the amount of sample to be measured, measurement conditions, etc.
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èµãããŠããŠãããã The above-mentioned stimulable phosphor may also be incorporated into the measurement container in a state of being dispersed in a binder.
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çµåå€ãæããããšãã§ããã Examples of binders include binders typified by proteins such as gelatin, synthetic polymeric substances such as polyvinyl acetate, nitrocellulose, polyurethane, polyvinyl alcohol, linear polyester, and the like.
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æããããšãã§ããã Examples of the solvent for dispersing the stimulable phosphor particles in the binder include lower alcohols, chlorine atom-containing hydrocarbons, ketones, esters, and ethers.
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ä¹è³ïŒïŒ40ïŒé鿝ïŒã®ç¯å²ããéžã°ããã The mixing ratio of the binder and the stimulable phosphor particles in the above dispersion varies depending on the shape of the intended measurement container, the type of phosphor particles, etc., but is usually 1:8.
The ratio is selected from the range of 1:40 to 1:40 (weight ratio).
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ãããŠããŠãããã Note that the dispersion liquid contains a dispersant for improving the dispersibility of the phosphor particles in the dispersion liquid, and
Various additives such as a plasticizer may be mixed to improve the bonding strength between the binder and the phosphor particles after molding.
枬å®å®¹åšã¯ãŸããããšãã°ãããªãšãã¬ã³ãã¬
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ãã The measurement container also has a layered structure consisting of a support made of a plastic material such as polyethylene terephthalate and a layer made of a binder in which the above-mentioned stimulable phosphor is dispersed (phosphor layer). You can leave it there. That is, the container may be formed by deforming a sheet consisting of a support and a phosphor layer by heat treatment or the like.
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ããŠããã®ã奜ãŸããã Alternatively, the measuring container of the present invention may have a form in which a molded article made of a binder in which a stimulable phosphor is dispersed is fitted into a part of the measuring container made of the above-mentioned material. In this case, the removable molded article is preferably coated with a transparent polymeric material such as polyethylene or polyethylene terephthalate in order to physically and chemically protect the stimulable phosphor.
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¥ããŠæž¬å®ã«ãããããšãã§ããã In the present invention, it is not necessary to introduce the sample directly into the measurement container, but it is also possible to place another suitable container inside the radiation measurement container and introduce the liquid sample into the sample container for measurement. .
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ãã説æããã Next, the method for detecting radioactive substances of the present invention will be explained with reference to the schematic diagram shown in FIG. 1 of the accompanying drawings.
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ããã Figure 1 shows that in liquid chromatography,
FIG. 2 is a schematic illustration of a method for detecting radioactive substances contained in a liquid sample that is continuously dropped.
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ã§ãããŸããªãããŸãã¯çè²ãããŠããŠãããã The sample to be measured in the present invention, ie, the liquid sample containing a radioactive substance, may be a solution or a suspension, or may be colored.
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èœã§ããã Furthermore, any type of radiation emitted from the radioactive substance in the sample can be measured, such as α rays, β rays, γ rays, proton rays, neutron rays, light rays, meson rays, and cosmic rays. That is, radiation from any radionuclide can be measured.
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¥ãããã First, a liquid sample 4 is dropped from the bottom of a column 3 filled with an adsorbent in a sample introduction section 2 into a radiation measurement container 1 containing a photostimulable phosphor 1a, and a certain amount of the liquid sample is introduced. be done.
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ãèŠããã Next, in the radiation energy storage section 5,
At least a portion of the energy of the radiation emitted by the radioactive substance in the sample is absorbed by the stimulable phosphor in the measurement container 1 and accumulated. The accumulation time of this radiation energy (exposure time) varies depending on the intensity of radiation emitted from the radioactive substance contained in the sample, the amount and concentration of the substance, the shape of the measurement container, the intensity of stimulated luminescence, etc. , which usually takes about 1 second to 1 minute.
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¥åãããã Next, in the stored energy readout section 6, the excitation light 8 emitted from the light source 7 enters the measurement container 1.
is irradiated. When the stimulable phosphor in the measurement container 1 is irradiated with excitation light, it emits stimulated luminescence with an amount of light proportional to the accumulated radiation energy, and this light enters a photodetector 9 such as a photomultiplier tube. do. The photodetector 9 has a filter attached thereto that transmits only light in the wavelength region of stimulated luminescence and cuts out light in the wavelength region of excitation light, so that only stimulated luminescence can be detected. is used. Photodetector 9
The detected stimulated luminescence is converted into an electrical signal, and after being amplified to an appropriate level electrical signal in an amplifier 10, it is input to a recording device 11.
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眮ãçšããããšãã§ããã In the recording device 11, the level of an electrical signal corresponding to the radiation dose absorbed by the measuring container 1, for example, the count value of electrical pulses, is displayed as a digital value. As the recording device 11, for example, one that scans the photosensitive measurement container with a laser beam or the like to record optically, one that displays electronically on a CRT, etc.
Recording devices based on various principles can be used, such as those that record radiation images displayed on a video printer or the like, and those that record on a heat-sensitive recording material using heat rays.
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èœã§ããã In addition, by providing a data processing circuit in the recording device 11, the radioactivity intensity can be calculated from the obtained digital value according to the readout efficiency (luminous efficiency of stimulated luminescence) and the accumulation time of radiation energy, which are input in advance. By calculating and further inputting the radioactivity intensity per molecule of the target radioactive substance, it is also possible to calculate the amount or concentration of radioactive substance per measurement container, and then display and record the obtained data. .
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ãããšãåœç¶å¯èœã§ããã In addition, in the present invention, as a method for reading the radiation energy of the sample accumulated in the radiation measurement container, it is of course possible to use methods other than those exemplified above.
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ããããšãå¯èœã§ããã Furthermore, the operations according to the method for detecting radioactive substances of the present invention are not limited to the above-mentioned operations. It is also possible to efficiently separate radioactive substances. Furthermore, it is also possible to automate the entire measurement operation by continuously performing the operation of introducing a liquid sample into the radiation measurement container, the operation of accumulating radiation energy in the measurement container, and the operation of reading out the measurement container.
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ãŠãé£ç¶å䜿çšãå¯èœãšãªãã A used measurement container can be reused by cleaning it with an appropriate solvent or the like and then erasing the energy remaining in the measurement container by irradiating it with light or the like. Therefore, by reading out the measurement container without collecting the measurement container, and automating the operation of cleaning the used measurement container and erasing the remaining energy into the measurement process, it is possible to continuously reuse the container. becomes possible.
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é¢ãåå®ããããšãå¯èœãšãªããã®ã§ããã The method of detecting radioactive substances using liquid chromatography of the present invention can be suitably used when a large amount of liquid sample is used. Continuously and efficiently removes the radioactive substances contained in the
and can be detected quickly. Furthermore, it becomes possible to separate and identify radioactive substances in the separated and expanded liquid sample with high precision.
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Figure 1 shows that in liquid chromatography,
1 shows a schematic explanatory diagram of a method for detecting radioactive substances contained in a liquid sample that is continuously dropped. 1: Radiation measurement container, 1a: Stimulable phosphor,
2: Sample introduction section, 3: Column filled with adsorbent, 4: Liquid sample, 5: Accumulation section, 6: Reading section,
7: light source, 8: excitation light, 9: photodetector, 10: amplifier, 11: recording device.
Claims (1)
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è³ªã®æ€åºæ¹æ³ã[Scope of Claims] 1 (1) A radiation measurement container containing a stimulable phosphor is provided under a column filled with an adsorbent so as to receive and hold a liquid sample that has passed through the column. Step of introducing the liquid sample into each measurement container by sequentially supplying a plurality of liquid samples; (2) By leaving the plurality of measurement containers for a certain period of time, radiation energy emitted from the radioactive substance in the liquid sample is released. (3) emitting the radiation energy stored in the plurality of measurement containers as photostimulated light, and photoelectrically reading the photostimulated light; A method for detecting a radioactive substance in a liquid sample using liquid chromatography, comprising: continuously measuring radioactivity in the liquid sample. 2. The method for detecting a radioactive substance according to claim 1, wherein the radiation measurement container contains a binder containing and supporting the stimulable phosphor in a dispersed state. 3. The method for detecting a radioactive substance according to claim 1 or 2, wherein the radiation measurement container is a plastic container containing a photostimulable phosphor. 4. The method for detecting radioactive substances according to claim 1 or 2, wherein the radiation measurement container is a container made of glass or quartz containing a photostimulable phosphor. 5. The method for detecting a radioactive substance according to claim 1 or 2, wherein the stimulable phosphor is a divalent europium-activated alkaline earth metal fluorohalide phosphor.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10363583A JPS59228182A (en) | 1983-06-10 | 1983-06-10 | Detection of radioactive substance |
| FI842107A FI842107A7 (en) | 1983-05-27 | 1984-05-25 | FOERFARANDE FOER DETEKTERING AV RADIOAKTIV SUSBTANS. |
| DE8484106077T DE3478350D1 (en) | 1983-05-27 | 1984-05-28 | Method of detecting radioactive substance |
| CA000455306A CA1226977A (en) | 1983-05-27 | 1984-05-28 | Method of detecting radioactive substance |
| EP84106077A EP0127866B1 (en) | 1983-05-27 | 1984-05-28 | Method of detecting radioactive substance |
| US07/006,925 US4956559A (en) | 1983-05-27 | 1987-01-27 | Method of detecting radioactive substance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10363583A JPS59228182A (en) | 1983-06-10 | 1983-06-10 | Detection of radioactive substance |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59228182A JPS59228182A (en) | 1984-12-21 |
| JPH0457990B2 true JPH0457990B2 (en) | 1992-09-16 |
Family
ID=14359226
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10363583A Granted JPS59228182A (en) | 1983-05-27 | 1983-06-10 | Detection of radioactive substance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59228182A (en) |
-
1983
- 1983-06-10 JP JP10363583A patent/JPS59228182A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59228182A (en) | 1984-12-21 |
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