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JPH0457990B2 - - Google Patents
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JPH0457990B2 - - Google Patents

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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
Application number
JP10363583A
Other languages
Japanese (ja)
Other versions
JPS59228182A (en
Inventor
Hisashi Shiraishi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujifilm Holdings Corp
Original Assignee
Fuji Photo Film Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Fuji Photo Film Co Ltd filed Critical Fuji Photo Film Co Ltd
Priority to JP10363583A priority Critical patent/JPS59228182A/en
Priority to FI842107A priority patent/FI842107A7/en
Priority to DE8484106077T priority patent/DE3478350D1/en
Priority to CA000455306A priority patent/CA1226977A/en
Priority to EP84106077A priority patent/EP0127866B1/en
Publication of JPS59228182A publication Critical patent/JPS59228182A/en
Priority to US07/006,925 priority patent/US4956559A/en
Publication of JPH0457990B2 publication Critical patent/JPH0457990B2/ja
Granted legal-status Critical Current

Links

Classifications

    • GPHYSICS
    • G01MEASURING; TESTING
    • G01TMEASUREMENT OF NUCLEAR OR X-RADIATION
    • G01T7/00Details of radiation-measuring instruments
    • G01T7/02Collecting means for receiving or storing samples to be investigated and possibly directly transporting the samples to the measuring arrangement; particularly for investigating radioactive fluids
    • G01T7/04Collecting 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
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01TMEASUREMENT OF NUCLEAR OR X-RADIATION
    • G01T1/00Measuring X-radiation, gamma radiation, corpuscular radiation, or cosmic radiation
    • G01T1/16Measuring radiation intensity
    • G01T1/20Measuring radiation intensity with scintillation detectors
    • G01T1/2012Measuring 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

【発明の詳现な説明】 本発明は、液䜓クロマトグラフむヌを利甚する
液䜓詊料通の攟射性物質の怜出方法に関するもの
である。さらに詳しくは本発明は、茝尜性蛍光䜓
を甚いた攟射性物質の怜出方法に関するものであ
る。
DETAILED 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.

分離分析の䞀方法ずしお、吞着剀が充填された
充填塔カラムに詊料溶液を泚入した埌、適圓
な溶媒を泚入しお詊料を展開させ、そしお詊料成
分をカラムから流出分取するこずからなる液䜓ク
ロマトグラフむヌが知られおいる。この液䜓クロ
マトグラフむヌは攟射性物質攟射性同䜍元玠を
含有する物質を含む詊料の分離に぀いおも利甚
されおおり、液䜓クロマトグラフむヌ操䜜により
分取された溶出液から攟射される攟射線を枬定す
るこずにより詊料䞭の攟射性物質の分離、同定が
行なわれおいる。
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.

埓来より、攟射性物質をむ液䜓詊料から攟出さ
れる攟射線を枬定する方法ずしおは、たずえば有
機溶媒に溶質蛍光剀を溶解しおなる液䜓シン
チレヌタヌを詊料に添加するこずにより、詊料か
ら攟出される攟射線を蛍光ずしお怜出するこずか
らなる液䜓シンチレヌシペン法が広く利甚されお
いる。この方法は、詊料䞭の攟射性物質から攟出
される攟射線゚ネルギヌの䞀郚をシンチレヌタヌ
に吞収させ、このシンチレヌタヌから発せられる
蛍光瞬時発光を怜出するこずにより、該攟射
性物質の攟射胜を枬定する方法である。
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.

䞊蚘液䜓シンチレヌシペン法は、攟射性物質を
含む詊料の液䜓クロマトグラフむヌにも適甚され
おおり、カラムから流出する液䜓詊料の䞀定量を
分取したのち液䜓シンチレヌタヌを添加するこず
により、詊料からの攟射線の枬定が行なわれおい
る。
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.

すなわち、液䜓クロマトグラフむヌにより分離
展開された攟射性物質を含有する詊料をフラクシ
ペンコレクタヌによ぀お分取したのち、各フラク
シペンごずに液䜓シンチレヌタヌを添加し、液䜓
シンチレヌタヌから発せられる蛍光を光電子倍増
管により怜出しお電気的パルスずしお蚈数するこ
ずにより、各フラクシペンごずにその攟射線量を
枬定し、詊料䞭の攟射性物質の分離、同定を行な
぀おいる。
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.

このように液䜓シンチレヌシペン法は、攟射性
物質から攟出される攟射線がα線、β線等の匱い
攟射線である堎合にもその攟射胜を怜出するこず
ができるなどの長所を有しおおり、詊料の攟射胜
を枬定するための有甚な手段ずな぀おいる。
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.

液䜓シンチレヌシペン法においおは、シンチレ
ヌタヌの発光は液䜓詊料䞭の攟射性物質から攟出
される攟射線の゚ネルギヌによ぀お、溶質蛍光
剀を溶解しおなる溶媒分子がたず励起されたの
ち、励起された溶媒分子ず溶質分子シンチレヌ
タヌずの衝突などにより溶質分子が励起される
こずにより生じおいる。この攟射線゚ネルギヌが
溶媒分子から溶質分子ぞ移行する過皋においお
は、このほかに、励起状態にある溶媒分子ず基底
状態にある溶媒分子ずの間の盞互䜜甚によ぀お溶
媒分子間を゚ネルギヌが移行したり、あるいは励
起された溶媒分子ずシンチレヌタヌ以倖の物の溶
質分子ずの間の盞互䜜甚によ぀お別の溶質分子に
゚ネルギヌが移行したのちに、シンチレヌタヌが
励起される堎合も含たれる。たた、この゚ネルギ
ヌの移行は、衝突などの分子間の盞互䜜甚だけで
なく、励起された溶媒分子あるいは別の溶質分子
から発せられる蛍光をシチレヌタヌが吞収するこ
ずによ぀おも行なわれる。
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.

しかしながら、この゚ネルギヌの移行過皋にお
いおは䞀郚の溶媒分子あるいは別の溶質分子によ
぀お励起゚ネルギヌが吞収されたのち熱などに倉
換されおした぀たり、あるいはシンチレヌタヌか
ら発生せられる蛍光が詊料䞭の吞光性物質によ぀
お吞収されるずい぀た消光珟象も同時に生じる。
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.

䞊蚘液䜓シンチレヌシペン法においお䞍可欠な
液䜓シンチレヌタヌは高䟡なものであり、か぀再
䜿甚するためには分離粟補を必芁ずする。たた通
垞は、シンチレヌタヌを高玔床で回収するこずが
困難であるため、その再䜿甚はあたり行なわれ
ず、このこずによ぀おも枬定コストの䜎枛が困難
である。たたさらに、䜿甚枈みの攟射性同䜍元玠
を含むシンチレヌタヌの廃棄が容易ではないな
ど、その取扱いにおいおもいく぀かの問題があ
る。
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.

たた、液䜓シンチレヌシペン法においお甚いら
れる蛍光剀は有機物であるため、甚いうる溶媒は
殆どの堎合、有機溶媒に限られおいる。このた
め、攟射性の詊料が必ずしも溶媒に溶解するずは
限らず、詊料が溶媒に難溶性である堎合には適圓
な溶媒を遞択するか、あるいは乳化懞濁させるな
ど詊料の調補方法に工倫を必芁ずする。
Further, since the fluorescent agent used in the liquid scintillation method is an organic substance, the solvents that can be used are limited to organic solvents in most cases. Therefore, radioactive samples do not necessarily dissolve in solvents, and if the sample is poorly soluble in the solvent, it is necessary to select an appropriate solvent or devise a sample preparation method such as emulsifying and suspending the sample. do.

そしお、䞊蚘のように液䜓シンチレヌタヌでは
その発光機構が耇雑であるため、混入した䞍玔物
や詊料自身による消光䜜甚によ぀お蚈数効率は䜎
䞋するすなわち、怜出される攟射胜匷床が䜎䞋
する傟向にある。たずえば、シンチレヌタヌか
ら発せられる蛍光はシンチレヌタヌ䞭に溶存する
酞玠によ぀お消光されやすく、あるいは詊料溶液
が有色である堎合には、その着色物質によ぀おも
蛍光の吞収すなわち、消光が生じる。たた、
詊料が難溶性である堎合には、詊料溶液を均䞀盞
ずするこずが難しく、䞀方、䞍均䞀盞の詊料溶液
では、詊料から攟射される攟射線の内郚吞収が生
じるなどの問題がある。埓぀お、䞊蚘のような
皮々の原因によ぀お生じる消光に察しお補正を行
な぀お詊料の蚈数効率を厳密に求める必芁があ
り、枬定操䜜が煩雑なものずなる。
As mentioned above, liquid scintillators have a complex light emitting mechanism, so the counting efficiency tends to decrease (that is, the detected radioactivity intensity decreases) due to the quenching effect of mixed impurities and the sample itself. be. For example, fluorescence emitted from a scintillator is easily quenched by oxygen dissolved in the scintillator, or if the sample solution is colored, the colored substance also absorbs (ie, quenches) the fluorescence. Also,
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.

さらに、詊料䞭に混入した䞍玔物、借雑物、有
色物などの消光䜜甚による蚈数効率の䜎䞋を防ぐ
ためには、詊料の調補には现心の泚意が必芁ずさ
れ、枬定者には高床の熟緎ず経隓が芁求される。
たた、䞊蚘のような混入物を陀去するための詊料
の前凊理が必芁ずなる。
Furthermore, in order to prevent a decrease in counting efficiency due to the quenching effect of impurities, contaminants, and colored substances mixed in the sample, careful preparation of the sample is required, and the measurer must have a high degree of skill and experience. is required.
In addition, pretreatment of the sample is required to remove the above-mentioned contaminants.

さらにたた、液䜓シンチレヌシペン法においお
は詊料の攟射線枬定は実時間で行なわれおいる。
すなわち、液䜓詊料にシンチレヌタヌを加えたの
ち䞀定の時間たずえば、数分〜数十分間継続
的にシンチレヌタヌからの発光を枬定する必芁が
ある。この枬定においお、攟射線の匷床が匱い堎
合には枬定時間蚈枬時間は長時間に及び、枬
定の効率および枬定装眮の皌働率が充分高いずは
蚀えない。
Furthermore, in the liquid scintillation method, radiation measurements of a sample are performed in real time.
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.

埓぀お、詊料が䞊蚘のように倚数のサンプルか
らなる堎合には、埅ち時間が長くな぀おしたうた
めに、倚数のサンプルを凊理しがたいずの問題、
たた結果が埗られるたでに時間がかかるずいう問
題が生じおいる。特に、詊料䞭の攟射性同䜍元玠
が半枛期の短いものである堎合には攟射線枬定が
難しく、さらにその攟射線匷床が匱い堎合には䞀
局枬定が困難ずなるものである。このこずは、た
た、䜿甚する装眮が長時間の間安定しおいなけれ
ばならないたずえば、光電子増倍管の暗電流ド
リフトなどに察しおこずを意味するものであ
り、このこずを防止するためには高䟡な装眮を必
芁ずするか、あるいは装眮の調敎に経隓ず熟緎ず
を芁求する結果ずなる。
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.

本発明者は、攟射性物質を含む詊料の液䜓クロ
マトグラフむヌにおいお、埓来より利甚されおい
る液䜓シンチレヌシペン法に附随する䞊蚘のよう
な問題点の解決を目的ずしお鋭意研究を行な぀た
結果、茝尜性蛍光䜓が内蔵された耇数個の攟射線
枬定容噚を詊料䟛絊装眮に順次䟛絊するこずによ
り、液䜓詊料を連続的もしくは断続的にこれらの
枬定容噚内に導入し、次いで該枬定容噚に吞収さ
れた攟射線゚ネルギヌを枬定する方法を利甚する
こずによ぀お、前蚘の問題点の解決あるいは欠点
の䜎枛が実珟するこず芋出し、本発明に到達し
た。
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.

すなわち、本発明は、 (1) 吞着剀が充填されたカラムの䞋に、該カラム
内を通過した液䜓詊料を受け取り、保持するよ
うに、茝尜性蛍光䜓が内蔵された攟射線枬定容
噚を耇数個順次䟛絊するこずにより、該液䜓詊
料をそれぞれの枬定容噚に導入する工皋 (2) 該耇数個の枬定容噚を䞀定時間眮くこずによ
り、該液䜓詊料䞭の攟射性物質から攟出される
攟射線゚ネルギヌの少なくずも䞀郚を該枬定容
噚に吞収させる工皋 (3) 該耇数個の枬定容噚に蓄積されおいる攟射線
゚ネルギヌを茝尜光ずしお攟出させ、そしおそ
の茝尜光を光電的に読み取るこずにより、該液
䜓詊料䞭の攟射胜を連続的に枬定する工皋 を含む液䜓クロマトグラフむヌを利甚する液䜓詊
料䞭の攟射性物質の怜出方法にある。
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;

本発明に甚いられる茝尜性蛍光䜓は、攟射線を
吞収したのち、可芖光線および赀倖線などの電磁
波励起光の照射を受けるず発光茝尜発光
を瀺す性質を有するものである。埓぀お、攟射性
物質を含む液䜓詊料を茝尜性蛍光䜓を内蔵しおな
る攟射線枬定容噚に導入するこずにより、詊料䞭
の攟射性䟿質から攟出される攟射線を枬定容噚に
吞収させ、次いでこの枬定容噚に可芖光線および
赀倖線などの電磁波励起光を照射するこずに
より、その攟射線量に比䟋した蓄積゚ネルギヌを
蛍光茝尜発光ずしお攟出させる。そしおこの
蛍光を光電的に読み取぀お電気信号に倉換するこ
ずにより、詊料から攟出される攟射線を枬定する
こずができる。
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.

本発明においお、攟射線枬定容噚に内蔵された
蛍光䜓からの茝尜光の発光時間は瞬時であり、詊
料の攟射線匷床ずは無関係に茝尜光の枬光時間を
蚭定するこずができるため、液䜓詊料を枬定容噚
に導入しお、詊料からの攟射線゚ネルギヌを枬定
容噚に蓄積させたのちの読出し操䜜はたずえば数
十秒間以内で枈み、枬定時間を短瞮するこずがで
きる。
In the present invention, the emission time of the photostimulated light from the phosphor built into the radiation measurement container is instantaneous, and the photometric time of the stimulated light can be set regardless of the radiation intensity of the sample. The reading operation after introducing the sample into the measurement container and accumulating the radiation energy from the sample in the measurement container can be completed within several tens of seconds, thereby reducing the measurement time.

たた、本発明によれば、詊料からの攟射線゚ネ
ルギヌを攟射線枬定容噚に蓄積させたのち詊料の
陀去などを行なうこずにより、この蓄積操䜜ず読
出し操䜜ずを完党に分離しお行なうこずも可胜で
あるため、耇数の枬定容噚をたずめお読出し操䜜
にかけるこずができる。この点でも、埓来の枬定
に芁した時間を短瞮し、その枬定操䜜を簡略化す
るこずができるものである。
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.

埓぀お、枬定装眮の皌働率を高め、枬定回数を
増倧させるこずができる。さらに、このこずは、
半枛期が短く、か぀攟射線匷床の匱い攟射線同䜍
元玠を甚いた堎合でも、同䞀条件で粟床高く枬定
できるこずを意味する。たた、本発明によれば䜿
甚する枬定装眮が䞀぀であ぀おも、枬定容噚を耇
数個甚意するこずにより、結果ずしお埓来法にお
いお耇数の枬定装眮を同時に䜿甚するのず同等の
枬定効率が埗られるものである。
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.

さらに、本発明においおは、茝尜性蛍光䜓を内
蔵しおなる枬定容噚の移動䟛絊操䜜および該枬定
容噚ぞの詊料の導入操䜜を自動化するこずができ
るだけではなく、詊料から発せられる攟射線の該
枬定容噚ぞの吞収蓄積操䜜および該枬定容噚に蓄
積された攟射線゚ネルギヌの読出し操䜜をも自動
化するこずが可胜であり、このこずによ぀おより
䞀局その䜜業性を向䞊させるこずができるもので
ある。
Furthermore, in the present invention, it is possible not only to automate the operation of moving and supplying a measurement container containing a stimulable phosphor and the operation of introducing a sample into the measurement container, but also to automate the measurement of radiation emitted from the sample. It is also possible to automate the operation of absorbing and accumulating radiation energy into the container and the operation of reading out the radiation energy accumulated in the measurement container, thereby further improving the workability.

たた、本発明に甚いられる攟射線枬定容噚は埓
来のシンチレヌタヌを必芁ずしないものであり、
液䜓シンチレヌシペン法におけるように容噚䞭で
シンチレヌタヌ溶液ず詊料ずを混合し溶解もし
くは懞濁する必芁がなく、茝尜性蛍光䜓が内蔵
された枬定容噚に攟射性物質を含有する液䜓詊料
を単に導入するこずにより枬定するこずができる
ため、䜿甚埌詊料の分離粟補を行なう必芁がな
い。
Furthermore, the radiation measurement container used in the present invention does not require a conventional scintillator,
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.

埓぀お、本発明に甚いられる攟射線枬定容噚は
繰り返し䜿甚するこずができ、䞀回圓たりの枬定
のコストを䞋げるこずができる。たた、この枬定
容噚はプラスチツク物質などからなるため、取扱
いが非垞に容易なものである。
Therefore, the radiation measurement container used in the present invention can be used repeatedly, and the cost per measurement can be reduced. Furthermore, since this measuring container is made of plastic material, it is very easy to handle.

さらに、攟射線枬定においお䞊蚘攟射線枬定容
噚を甚いれば、埓来の液䜓シンチレヌシペン法ず
は異な぀お溶媒を必芁ずしない。埓぀お、液䜓シ
ンチレヌタヌにおけるような溶媒の遞択、詊料の
調補を特には行なう必芁がない。そしお、本発明
においおは前蚘のような消光珟象、特に蛍光に䜓
する消光珟象は起こりえない。埓぀お、詊料の攟
射胜枬定のための耇雑な消光補正蚈数効率の決
定を行なう必芁がなく、この点においおも枬定
操䜜が簡略化されるものである。
Furthermore, if the radiation measurement container described above is used in radiation measurement, unlike the conventional liquid scintillation method, no solvent is required. Therefore, there is no need to particularly select a solvent or prepare a sample as in a liquid scintillator. In the present invention, the above-mentioned quenching phenomenon, especially the quenching phenomenon associated with fluorescence, does not occur. Therefore, there is no need to perform complicated extinction correction (determination of counting efficiency) for measuring the radioactivity of a sample, and the measurement operation is simplified in this respect as well.

埓぀お、詊料に含たれる䞍玔物などを陀去する
必芁は特にはないため、埓来のような詊料の前凊
理を必芁ずせず、たた詊料の調補時においお経隓
に基づいた高床な熟緎および泚意を必芁ずしない
ものである。この点でも、詊料の攟射線枬定を容
易に行なうこずができる。
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.

以䞋に、本発明の攟射性物質の怜出方法におい
お、奜適に䜿甚される攟射線枬定容噚に぀いお説
明する。
Below, a radiation measurement container suitably used in the radioactive substance detection method of the present invention will be described.

本発明に甚いられる攟射線枬定容噚は通垞で
は、詊料の収玍郚分ず蓋郚分ずからなる。蓋郚分
は必ずしも必芁なものではなく、枬定容噚の圢
態、詊料の皮類および枬定条件などに応じお甚い
られる。
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.

枬定容噚に内蔵される茝尜性蛍光䜓は、枬定容
噚党䜓にわた぀お含有されおいる必芁はなく、容
噚の䞀郚分にのみ内蔵されおいおもよい。ただ
し、茝尜性蛍光䜓が内蔵されおいる郚分の衚面積
を倧きくするこずにより、詊料から攟出される攟
射線の捕促性が高められ、枬定倀の粟床の向䞊お
よび詊料䞭に埮量に存圚する攟射性物質の怜出あ
るいは攟射線匷床の匱い物質の怜出が可胜ずな
る。䞀方、攟射線゚ネルギヌの読出し操䜜の点か
らは、茝尜性蛍光䜓が枬定容噚に郚分的に内蔵さ
れた圢態の方が奜たしく、この堎合には詊料ず接
する郚分に内蔵されるのが望たしい。たた、詊料
から攟出される攟射線の飛皋距離の点から、枬定
容噚における茝尜性蛍光䜓の内蔵郚䜍ず詊料䞭の
攟射性物質線源ずの距離ができるだけ小さく
なるようにした枬定容噚が奜たしい。
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.

埓぀お、本発明においお枬定容噚の圢態は、目
的ずする詊料の量、攟射線匷床および枬定条件に
応じお遞ぶこずが望たしい。
Therefore, in the present invention, it is desirable that the shape of the measurement container be selected depending on the target sample amount, radiation intensity, and measurement conditions.

本発明においお䜿甚する茝尜性蛍光䜓は、先に
述べたように攟射線を吞収した埌、励起光を照射
されるず茝尜発光を瀺す蛍光䜓であるが、実甚的
な面からは400〜800nの波長範囲にある励起光
によ぀お300〜500nの波長範囲の茝尜発光を瀺
す蛍光䜓であるこずが望たしい。そのような茝尜
性蛍光䜓の䟋ずしおは、 米囜特蚱第3859527号明现曞に蚘茉されおいる
SrSCe、Sm、SrSEu、Sm、ThO2Er、お
よびLa2O2SEu、Smなどの組成匏で衚わされ
る蛍光䜓、 特開昭55−12142号公報に蚘茉されおいる
ZnSCu、Pb、BaO・xAl2O3Euただし、0.8
≊≊10、および、M2+O・xSiO2ただし、
M2+はMg、Ca、Sr、Zn、Cd、たたははBaであ
り、はCe、Tb、Eu、Tm、Pb、Tl、Bi、たた
はMnであり、は、0.5≊≊2.5であるなど
の組成匏で衚わされる蛍光䜓、 特開昭55−12143号公報に蚘茉されおいる
Ba1-x-y、Mgx、CayFXaEu2+ただし、
はClおよびBrのうちの少なくずも䞀぀であり、
およびは、≊0.6、か぀xy≠で
あり、は、10-6≊≊×10-2であるの組成
匏で衚わされる蛍光䜓、 特開昭55−12144号公報に蚘茉されおいる
LnOXxAただし、LnはLa、、Gd、および
Luのうちの少なくずも䞀぀、はClおよびBrの
うちの少なくずも䞀぀、はCeおよびTbのうち
の少なくずも䞀぀、そしお、は、0.1
であるの組成匏で衚わされる蛍光䜓、 特開昭55−12145号公報に蚘茉されおいる
Ba1-x、M〓xFXyAただし、M〓はMg、
Ca、Sr、Zn、およびCdのうちの少なくずも䞀぀
の、はCl、Br、およびのうちの少なくずも
䞀぀、はEu、Tb、Ce、Tm、Dy、Pr、Ho、
Nd、Yb、およびErのうちの少なくずも䞀぀、そ
しおは、≊≊0.6、は、≊≊0.2であ
るの組成匏で衚わされる蛍光䜓、 特開昭55−160078号公報に蚘茉されおいる、
M〓FX・xAyLnただし、M〓はBa、Ca、Sr、
Mg、Zn、およびCdのうちの少なくずも䞀皮、
はBeO、MgO、CaO、SrO、BaO、ZnO、
Al2O3、Y2O3、La2O3、In2O3、SiO2、TiO2、
ZrO2、GeO2、SnO2、Nb2O5、Ta2O5、および
ThO2のうちの少なくずも䞀皮、LnはEu、Tb、
Ce、Tm、Dy、Pr、Ho、Nd、Yb、Er、Sm、
およびGdのうちの少なくずも䞀皮、はCl、
Br、およびのうちの少なくずも䞀皮であり、
およびはそれぞれ×10-5≊≊0.5、およ
び≊0.2であるの組成匏で衚わされる蛍
光䜓、 特開昭56−116777号公報に蚘茉されおいる
Ba1-x、M〓xF2・aBaX2yEu、zAただし、
M〓はベリリりム、マグネシりム、カルシりム、
ストロンチりム、亜鉛、およびカドミりムのうち
の少なくずも䞀皮、は塩玠、臭玠、および沃玠
のうちの少なくずも䞀皮、はゞルコニりムおよ
びスカンゞりムのうちの少なくずも䞀皮であり、
、、、およびはそれぞれ0.5≊≊1.25、
≊≊、10-6≊≊×10-1、および
≩10-2であるの組成匏で衚わされる蛍光䜓、 特開昭57−23673号公報に蚘茉されおいる
Ba1-x、M〓xF2・aBaX2yEu、zBただし、
M〓はベリリりム、マグネシりム、カルシりム、
ストロンチりム、亜鉛、およびカドミりムのうち
の少なくずも䞀皮、は塩玠、臭玠、および沃玠
のうちの少なくずも䞀皮であり、、、、お
よびはそれぞれ0.5≊≊1.25、≊≊、
10-6≊≊×10-1、および≊10-1であ
るの組成匏で衚わされる蛍光䜓、 特開昭57−23675号公報に蚘茉されおいる
Ba1-x、M〓xF2・aBaX2yEu、zAただし、
M〓はベリリりム、マグネシりム、カルシりム、
ストロンチりム、亜鉛、およびカドミりムのうち
の少なくずも䞀皮、は塩玠、臭玠、および沃玠
のうちの少なくずも䞀皮、は砒玠および硅玠の
うちの少なくずも䞀皮であり、、、、およ
びはそれぞれ0.5≊≊1.25、≊≊、10-6
≊≊×10-1、および≊10-1であるの
組成匏で衚わされる蛍光䜓、 本出願人による特願昭57−167498号明现曞に蚘
茉されおいるM〓OXxCeただし、M〓はPr、
Nd、Pm、Sm、Eu、Tb、Dy、Ho、Er、Tm、
Yb、およびBiからなる矀より遞ばれる少なくず
も䞀皮の䞉䟡金属であり、はClおよびBrのう
ちのいずれか䞀方あるいはその䞡方であり、は
0.1であるの組成匏で衚わされる蛍光
䜓、 本出願人による特願昭57−89875号明现曞に蚘
茉されおいるBa1-xMx/2Lx/2FXyEu+2ただし、
は、Li、Na、、Rb、およびCsからなる矀よ
り遞ばれる少なくずも䞀皮のアルカリ金属を衚わ
しは、Sc、、La、Ce、Pr、Nd、Pm、
Sm、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu、
Al、Ga、In、およびTlからなる矀より遞ばれる
少なくずも䞀皮の䞉䟡金属を衚わしは、Cl、
Br、およびからなる矀より遞ばれる少なくず
も䞀皮のハロゲンを衚わしそしお、は10-2≩
≊0.5、は≊0.1であるの組成匏で衚
わされる蛍光䜓、 本出願人による特願昭57−137374号明现曞に蚘
茉されおいるBaFX・xAyEu+2ただし、は、
Cl、Br、およびからなる矀より遞ばれる少な
くずも䞀皮のハロゲンでありは、テトラフル
オロホり酞化合物の焌成物でありそしお、は
10-6≊≊0.1、は≊0.1であるの組成
匏で衚わされる蛍光䜓、 本出願人による特願昭57−158048号明现曞に蚘
茉されおいるBaFX・xAyEu+2ただし、は、
Cl、Br、およびからなる矀より遞ばれる少な
くずも䞀皮のハロゲンでありは、ヘキサフル
オロケむ酞、゚キサフルオロチタン酞およびヘキ
サフルオロゞルコニりム酞の䞀䟡もしくは二䟡金
属の塩からなるヘキサフルオロ化合物矀より遞ば
れる少なくずも䞀皮の化合物の焌成物でありそ
しお、は10-6≊≊0.1、は≊0.1であ
るの組成匏を衚わされる蛍光䜓、 本出願人による特願昭57−166320号明现曞に蚘
茉されおいるBaFX・xNaX′aEu2+ただし、
およびX′は、それぞれCl、Br、およびのう
ちの少なくずも䞀皮であり、およびはそれぞ
れは≊、およびは≊0.2である
の組成匏を衚わされる蛍光䜓、 本出願人による特願昭57−166696号明现曞に蚘
茉されおいるM〓FX・xNaX′yEu2+zAただ
し、M〓は、Ba、Sr、およびCaからなる矀より
遞ばれる少なくずも䞀皮のアルカリ土類金属であ
りおよびX′は、それぞれCl、Br、および
からなる矀より遞ばれる少なくずも䞀皮のハロゲ
ンでありは、、Cr、Mn、Fe、Co、およ
びNiより遞ばれる少なくずも䞀皮の遷移金属で
ありそしお、は≊、は≊
0.2、およびは≊10-2であるの組成匏
で衚わされる蛍光䜓、 本出願人による特願昭57−184455号明现曞に蚘
茉されおいるM〓FX・aM〓X′・bM′〓X″2・cM〓
3・xAyEu2+ただし、M〓は、Ba、Sr、お
よびCaからなる矀より遞ばれる少なくずも䞀皮
のアルカリ土類金属でありM〓はLi、Na、、
Rb、およびCsからなる矀より遞ばれる少なくず
も䞀皮のアルカリ金属でありM′〓はBeおよび
Mgからなる矀より遞ばれる少なくずも䞀皮の二
䟡金属でありM〓はAl、Ga、In、およびTlか
らなる矀より遞ばれる少なくずも䞀皮の䞉䟡金属
でありは金属酞化物でありはCl、Br、
およびからなる矀より遞ばれる少なくずも䞀皮
のハロゲンでありX′、X″、およびは、、
Cl、Br、およびからなる矀より遞ばれる少な
くずも䞀皮のハロゲンでありそしお、は≊
≊、は≊≊10-2、は≊≊10-2、
か぀≧10-6でありは≊0.5、
は≊0.2であるの組成匏で衚わされる
蛍光䜓、 などを挙げるこずができる。
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, BaO・xAl 2 O 3 : Eu [However, 0.8
≩x≩10], and M 2+ O・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 0.5≩x≩2.5. 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+y≩0.6 and xy≠0, and a is 10 -6 ≩a≩5×10 -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 , M〓 x )FX:yA [where M〓 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 0≩x≩0.6, and y is 0≩y≩0.2] JP-A-55-160078 stated in the official bulletin,
M〓FX・xA:yLn [However, M〓 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 5×10 -5 ≩x≩0.5 and 0<y≩0.2] A phosphor is described in JP-A-56-116777 (Ba 1- x , M〓 x )F 2・aBaX 2 :yEu, zA [However,
M〓 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 0.5≩a≩1.25,
0≩x≩1, 10 -6 ≩y≩2×10 -1 , and 0<z
≩10 -2 ], described in Japanese Patent Application Laid-Open No. 57-23673, (Ba 1-x , M〓 x )F 2・aBaX 2 :yEu, zB ,
M〓 is beryllium, magnesium, calcium,
at least one of strontium, zinc, and cadmium;
10 -6 ≩y≩2×10 -1 and 0<z≩10 -1 ] A phosphor is described in JP-A-57-23675 (Ba 1-x , M〓 x )F 2・aBaX 2 :yEu, zA [However,
M〓 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 ≩a≩1.25, 0≩x≩1, 10 -6
≩y≩2×10 -1 and 0<z≩10 -1 ], M〓OX described in Japanese Patent Application No. 167498/1983 filed by the present applicant. :xCe[However, M〓 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 ≩
x≩0.5, y is 0<y≩0.1] 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 ≩x≩0.1, y is 0<y≩0.1] 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 ≩x≩0.1, and y is 0<y≩0.1. BaFX・xNaX′: 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<x≩2, and a is 0<a≩0.2]
A phosphor having the composition formula M〓FX・xNaX′:yEu 2+ :zA [where M〓 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<x≩2, y is 0<y≩
0.2, and z is 0<z≩10 -2 ], M〓FX・aM〓X′ described in the specification of Japanese Patent Application No. 184455/1983 filed by the present applicant.・bM′〓X″ 2・cM〓
X 3・xA:yEu 2+ [However, M〓 is at least one kind of alkaline earth metal selected from the group consisting of Ba, Sr, and Ca; M〓 is Li, Na, K,
is at least one alkali metal selected from the group consisting of Rb, and Cs; M′〓 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; X′, X″, and X are F,
at least one halogen selected from the group consisting of Cl, Br, and I; and a is 0≩
a≩2, b is 0≩b≩10 -2 , c is 0≩c≩10 -2 ,
and a+b+c≧10 -6 ; x is 0<x≩0.5,
y is 0<y≩0.2], and the like.

ただし、本発明に甚いられる茝尜性蛍光䜓は䞊
述の蛍光䜓に限られるものではなく、攟射線を吞
収したのちに励起光が照射された堎合に、茝尜発
光を瀺す蛍光䜓であればいかなるものであ぀おも
よい。
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.

本発明に甚いられる攟射線枬定容噚の材料ずし
おは、たずえば、ガラス石英ポリ゚チレン、
ポリプロピレン、ナむロン、テフロン等のプラス
チツク物質を挙げるこずができる。
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.

攟射線枬定容噚は、茝尜性蛍光䜓を䞊蚘のよう
な材料の内に内蔵させお、容噚を圢成するこずに
より埗られる。枬定容噚の倧きさ、厚み、圢状、
内蔵される茝尜性蛍光䜓の量および面積などに぀
いおは、枬定察象ずする詊料の量、枬定条件など
に応じお蚭定するこずができる。
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.

䞊蚘茝尜性蛍光䜓はたた、結合剀䞭に分散され
た状態で枬定容噚に内蔵されおいおもよい。
The above-mentioned stimulable phosphor may also be incorporated into the measurement container in a state of being dispersed in a binder.

結合剀の䟋ずしおは、れラチン等の蛋癜質、ポ
リ酢酞ビニル、ニトロセルロヌス、ポリりレタ
ン、ポリビニルアルコヌル、線状ポリ゚ステルな
どのような合成高分子物質などにより代衚される
結合剀を挙げるこずができる。
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.

茝尜性蛍光䜓粒子を結合剀䞭に分散させるため
の溶剀の䟋ずしおは、䜎玚アルコヌル、塩玠原子
含有炭化氎玠、ケトン、゚ステル、゚ヌテル類を
挙げるこずができる。
Examples of the solvent for dispersing the stimulable phosphor particles in the binder include lower alcohols, chlorine atom-containing hydrocarbons, ketones, esters, and ethers.

䞊蚘分散液における結合剀ず茝尜性蛍光䜓粒子
ずの混合比は、目的ずする枬定容噚の圢状、蛍光
䜓粒子の皮類などによ぀お異なるが、通垞
乃至40重量比の範囲から遞ばれる。
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).

なお、分散液には、該分散液䞭における蛍光䜓
粒子の分散性を向䞊させるための分散剀、たた、
成圢埌の結合剀ず蛍光䜓粒子ずの間の結合力を向
䞊させるための可塑剀などの皮々の添加剀が混合
されおいおもよい。
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.

枬定容噚はたた、たずえば、ポリ゚チレンテレ
フタレヌト等のプラスチツク物質からなる支持䜓
ず䞊蚘茝尜性蛍光䜓が分散された結合剀からなる
局蛍光䜓局ずから構成されるような局構成を
有しおいおもよい。すなわち、支持䜓ず蛍光䜓局
ずからなるシヌトを熱凊理などによ぀お倉圢する
こずにより、容噚の圢態ずしたものであ぀おもよ
い。
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.

あるいは、本発明の枬定容噚は䞊蚘の材料から
なる枬定容噚の䞀郚に、茝尜性蛍光䜓が分散され
た結合剀からなる成圢物がはめ蟌たれた圢態を有
しおいおもよい。この堎合に、取倖し可胜な䞊蚘
成圢物は、茝尜性蛍光䜓を物理的および化孊的に
保護するために、ポリ゚チレン、ポリ゚チレンテ
レフタレヌト等の透明高分子物質によ぀お被芆さ
れおいるのが奜たしい。
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.

なお本発明においお、詊料は䞊蚘枬定容噚に盎
接導入する必芁はなく、攟射線枬定容噚の内偎に
別の適圓な容噚を入れおおき、その詊料容噚に液
䜓詊料を導入しお枬定にかけるこずもできる。
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. .

次に、本発明の攟射性物質の怜出方法に぀い
お、添付図面の第図に瀺した抂略図を参照しな
がら説明する。
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.

第図は、液䜓クロマトグラフむヌにおいお、
連続的に滎䞋される液䜓詊料に含たれおいる攟射
性物質を怜出するための方法の抂略的な説明図で
ある。
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.

本発明においお枬定察象ずされる詊料、すなわ
ち攟射性物質を含む液䜓詊料は、溶液でも懞濁液
でもかたわなく、たたは着色されおいおもよい。
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.

たた、詊料䞭の攟射性物質から攟出される攟射
線ずしおは、α線、β線、γ線、陜子線、䞭性子
線、光線、䞭間子線、宇宙線などいかなる皮類の
攟射線でも枬定するこずができる。すなわち、い
かなる攟射性栞皮からの攟射線であ぀おも枬定可
胜である。
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.

たず、茝尜性蛍光䜓が内蔵された攟射線枬
定容噚には詊料の導入郚においお、吞着剀が
充填されたカラムの䞋郚から液䜓詊料が滎䞋
され、䞀定量の液䜓詊料が導入される。
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.

次に、攟射線゚ネルギヌの蓄積郚においお、
詊料䞭の攟射性物質か攟出される攟射線の゚ネル
ギヌの少なくずも䞀郚が枬定容噚の茝尜性蛍光
䜓に吞収されお蓄積される。この攟射線゚ネルギ
ヌの蓄積時間被曝時間は、詊料に含たれる攟
射性物質から攟出される攟射線の匷さ、該物質の
量、濃床、䞊蚘枬定容噚の圢状および茝尜発光の
匷床などにより倉動するが、通垞は玄秒〜分
を芁する。
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.

次いで、蓄積゚ネルギヌの読出し郚におい
お、光源から発せられた励起光が枬定容噚
に照射される。枬定容噚の茝尜性蛍光䜓は、励
起光の照射を受けるず蓄積されおいる攟射線゚ネ
ルギヌに比䟋する光量の茝尜発光を発し、この光
は光電子増倍管などの光怜出噚に入射する。光
怜出噚ずしおは、茝尜発光の波長領域の光のみ
を透過し、励起光の波長領域の光をカツトするフ
むルタヌが貌着され、茝尜発光のみを怜出しうる
ようにされおいるものが甚いられる。光怜出噚
により怜出された茝尜発光は電気信号に倉換さ
れ、増幅噚においお適正レベルの電気信号に
増幅されたのち、蚘録装眮に入力される。
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.

蚘録装眮では、枬定容噚に吞収された攟
射線量に盞圓する電気信号のレベル、たずえば電
気的パルスの蚈数倀がデゞタル倀ずしお衚瀺され
る。蚘録装眮ずしおは、たずえば、感光枬定
容噚䞊をレヌザヌ光等で走査しお光孊的に蚘録す
るもの、CRT等に電子的に衚瀺するもの、CRT
等に衚瀺された攟射線画像をビデオ・プリンタヌ
等に蚘録するもの、熱線を甚いお感熱蚘録材料䞊
に蚘録するものなど皮々の原理に基づいた蚘録装
眮を甚いるこずができる。
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.

たた、蚘録装眮内にデヌタ凊理回路を蚭け
るこずにより、埗られたデゞタル倀から予め入力
しおおいた読出し効率茝尜発光の発光効率お
よび攟射線゚ネルギヌの蓄積時間に埓぀お攟射胜
匷床を蚈算し、さらに目的ずする攟射性物質䞀分
子圓りの攟射胜匷床を入力するこずにより、枬定
容噚圓りの攟射性物質の量あるいは濃床を蚈算し
たのち、埗られたデヌタを衚瀺蚘録するこずも可
胜である。
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. .

なお、本発明においお攟射線枬定容噚に蓄積さ
れた詊料の攟射線゚ネルギヌを読み出すための方
法ずしおは、䞊蚘に䟋瀺した以倖の方法を利甚す
るこずも圓然可胜である。
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.

たた、本発明の攟射性物質の怜出方法に埓う操
䜜は䞊述の操䜜に限られるものではなく、たずえ
ば、さらに埗られたデヌタに基づいお攟射性物質
の怜出された枬定容噚のみに぀いお詊料を収集
し、目的ずする攟射性物質を効率良く分離するこ
ずも可胜である。たた、攟射線枬定容噚ぞの液䜓
詊料の導入操䜜、攟射線゚ネルギヌの該枬定容噚
ぞの蓄積操䜜および該枬定容噚の読出し操䜜を連
続的に行なうこずにより、枬定操䜜党䜓を自動化
するこずも可胜である。
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.

䜿甚枈の枬定容噚は、適圓な溶媒などで掗浄し
たのち、光を照射するなどにより枬定容噚䞭に残
存する゚ネルギヌを消去するこずにより、再䜿甚
するずができる。埓぀お、䞊蚘枬定容噚を回収し
ないで、該枬定容噚を読み出したのち、䜿甚枈の
枬定容噚の掗浄および残存゚ネルギヌの消去操䜜
をも枬定工皋に組蟌んで自動化するこずによ぀
お、連続再䜿甚が可胜ずなる。
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.

本発明の液䜓クロマトグラフむヌを利甚した攟
射性物質の怜出方法は、液䜓詊料が倧量である堎
合に奜適に利甚するこずができるものであり、耇
数個の枬定容噚を䜿甚するこずにより、詊料䞭に
含有されおいる攟射性物質を連続的に効率良く、
か぀迅速に怜出するこずができる。そしお、分離
展開された液䜓詊料䞭の攟射性物質を高粟床に分
離、同定するこずが可胜ずなるものである。
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.

【図面の簡単な説明】[Brief explanation of the drawing]

第図は、液䜓クロマトグラフむヌにおいお、
連続的に滎䞋される液䜓詊料に含たれる攟射性物
質を怜出するための方法の抂略説明図を瀺すもの
である。 攟射線枬定容噚、茝尜性蛍光䜓、
詊料の導入郚、吞着剀が充填されたカラ
ム、液䜓詊料、蓄積郚、読出し郚、
光源、励起光、光怜出噚、増
幅噚、蚘録装眮。
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)

【特蚱請求の範囲】  (1) 吞着剀が充填されたカラムの䞋に、該カ
ラム内を通過した液䜓詊料を受け取り、保持す
るように、茝尜性蛍光䜓が内蔵された攟射線枬
定容噚を耇数個順次䟛絊するこずにより、該液
䜓詊料をそれぞれの枬定容噚に導入する工皋 (2) 該耇数個の枬定容噚を䞀定時間眮くこずによ
り、該液䜓詊料䞭の攟射性物質から攟出される
攟射線゚ネルギヌの少なくずも䞀郚を該枬定容
噚に吞収させる工皋 (3) 該耇数個の枬定容噚に蓄積されおいる攟射線
゚ネルギヌを茝尜光ずしお攟出させ、そしおそ
の茝尜光を光電的に読み取るこずにより、該液
䜓詊料䞭の攟射胜を連続的に枬定する工皋 を含む液䜓クロマトグラフむヌを利甚する液䜓詊
料䞭の攟射性物質の怜出方法。  䞊蚘攟射線枬定容噚が、茝尜性蛍光䜓を分散
状態で含有支持する結合剀を内蔵しおいる請求項
第項蚘茉の攟射性物質の怜出方法。  䞊蚘攟射線枬定容噚が、茝尜性蛍光䜓が内蔵
されたプラスチツク容噚である請求項第項もし
くは第項蚘茉の攟射性物質の怜出方法。  䞊蚘攟射線枬定容噚が、茝尜性蛍光䜓が内蔵
されたガラスもしくは石英補の容噚である請求項
第項もしくは第項蚘茉の攟射性物質の怜出方
法。  䞊蚘茝尜性蛍光䜓が、二䟡のナヌロピりム賊
掻アルカリ土類金属北化ハロゲン化物系蛍光䜓で
ある請求項第項もしくは第項蚘茉の攟射性物
質の怜出方法。
[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.
JP10363583A 1983-05-27 1983-06-10 Detection of radioactive substance Granted JPS59228182A (en)

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)

Also Published As

Publication number Publication date
JPS59228182A (en) 1984-12-21

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