JP6534985B2 - Hydrogen stable isotope ratio analysis method and system - Google Patents

Hydrogen stable isotope ratio analysis method and system Download PDF

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JP6534985B2
JP6534985B2 JP2016225706A JP2016225706A JP6534985B2 JP 6534985 B2 JP6534985 B2 JP 6534985B2 JP 2016225706 A JP2016225706 A JP 2016225706A JP 2016225706 A JP2016225706 A JP 2016225706A JP 6534985 B2 JP6534985 B2 JP 6534985B2
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isotope ratio
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孝子 保井
孝子 保井
吉村　了行
了行 吉村
界　義久
義久 界
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Nippon Telegraph and Telephone Corp
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Description

本発明は、食品の産地等の物質の起源に関する起源情報を分析するために用いられる水素安定同位体比分析技術に関する。   The present invention relates to a hydrogen stable isotope ratio analysis technique used to analyze source information on the origin of a substance such as a food production center.

一般に、食品の産地は、流通過程において文書管理されており、食品の産地偽装が疑われた場合のみ、分析機関等で科学的な裏付け調査が行われている。近年、産地表示の義務化の対象となる食品の種類が増えてきており、産地表示に対する関心が高まっている。一方、産地偽装問題は増加の傾向にあり、このような産地偽装を抑止するには、流通過程で産地情報に関する文書の管理に加えて、科学的な根拠に基づく産地判定を行うことが有効とされている。   In general, food production areas are under document control in the distribution process, and scientific supportive investigations are conducted by analytical institutions etc. only when there is a suspicion that food production areas are suspected. In recent years, the types of food that are subject to the obligatory labeling of production areas are increasing, and interest in the production area labeling is increasing. On the other hand, there is a tendency for the problem of production falsification to increase, and in order to deter such production falsification, in addition to the management of documents concerning production region information in the distribution process, it is effective to determine production based on scientific evidence. It is done.

従来より、食品に含まれる酸素や水素の安定同位体比は、産地推定の手がかりになることが報告されている（非特許文献１）。このような水素安定同位体比分析を行う場合、安定同位体比質量分析法（ＩＲＭＳ：Isotope Ratio Mass Spectrometry）や核磁気共鳴分光法（ＮＭＲ：Nuclear Magnetic Resonance Spectroscopy）を用いた、操作が複雑となる高価で大型の分析装置が必要となる。このため、分析に時間とコストがかかるという問題があり、これが普及を妨げる一つの要因となっていた。   Heretofore, stable isotope ratios of oxygen and hydrogen contained in food have been reported to be clues for estimating the production area (Non-patent Document 1). When performing such hydrogen stable isotope ratio analysis, operation is complicated using stable isotope ratio mass spectrometry (IRMS: Isotope Ratio Mass Spectrometry) or nuclear magnetic resonance spectroscopy (NMR: Nuclear magnetic resonance spectroscopy). Expensive and large analyzers are needed. For this reason, there is a problem that analysis takes time and cost, which has been one factor that hinders the spread.

近年、レーザ分光法における高感度化技術の進歩により、安定同位体比分析に利用できる高感度なレーザ分光装置が開発され注目されている。これを利用すると、安定同位体比分析を簡単に行うことができ、産地判別への応用も期待される（非特許文献２）。   In recent years, with the progress of high sensitivity technology in laser spectroscopy, a highly sensitive laser spectrometer that can be used for stable isotope ratio analysis has been developed and is attracting attention. If this is utilized, stable isotope ratio analysis can be easily performed, and application to production area determination is also expected (Non-Patent Document 2).

なかでも、Ｐｉｃａｒｒｏ社のＢ２２２１−ｉ（非特許文献３）は、サンプルを燃焼することにより、二酸化炭素と水蒸気を発生させる燃焼装置と、発生させた二酸化炭素と水蒸気の光吸収をＣＲＤＳ法により測定し、炭素または水素、またはその両方の安定同位体比を分析するレーザ分光式安定同位体比分析装置とからなる分析システムであり、炭素や水素の安定同位体比分析を容易に行うことができる。このため、食品等の産地、製法、成分など、物質の起源に関する起源情報を判別・推定するのに有効な手段であると考えられ、注目されている。特に、Ｂ２２２１−ｉは、有機物中の水素安定同位体比を容易に測定できるため、米、麦、蜂蜜など様々な食品などの産地を推定するのに有用である。   Among them, B2221-i of Picarro (Non-patent Document 3) measures the light absorption of generated carbon dioxide and water vapor by the CRDS method, by generating a carbon dioxide and water vapor by burning a sample. Analysis system that consists of a laser spectroscopic stable isotope ratio analyzer that analyzes the stable isotope ratio of carbon and / or hydrogen, or both, and can easily perform stable isotope ratio analysis of carbon and hydrogen. . For this reason, it is considered to be an effective means for discriminating and estimating the origin information on the origin of the substance, such as the origin of the food, the manufacturing method, and the components, and is attracting attention. In particular, B2221-i is useful for estimating production areas of various foods such as rice, wheat, honey and the like because it can easily measure the hydrogen stable isotope ratio in organic matter.

特開２０１０−２７６４６６号公報JP, 2010-276466, A

鈴木・中下・伊永，"安定同位体比分析による国内産米の産地及び有機栽培判別の可能性"，分析化学，Vol.58，No.12，pp.1053-1058，2009Suzuki, Nakashita, Inaga, "Possibility of determining the origin and organic cultivation of domestically produced rice by stable isotope ratio analysis", Analytical Chemistry, Vol. 58, No. 12, pp. 1053-1058, 2009 吉村・神徳・藤井・阪本・界，"高感度レーザガスセンシング技術と安定同位体比分析応用"，NTT技術ジャーナル，Vol.26，No.2，pp.27-30，2014Yoshimura, Shintoku, Fujii, Sakamoto, "The high sensitivity laser gas sensing technology and stable isotope ratio analysis application", NTT Technical Journal, Vol. 26, No. 2, pp. 27-30, 2014 B2221-iデータシート，Picarro社B2221-i data sheet, Picarro

しかしながら、物質中のヒドロキシル基（−ＯＨ）、カルボキシル基（−ＣＯＯＨ）、アミノ基（−ＮＨ２）などの基に含まれる水素原子は、交換性を有することが知られており（特許文献１）。これらの基を含む物質では、これら基の交換性水素と保管や輸送の間に周囲の環境中に含まれている水素原子との交換が生じ、水素安定同位体比が経時変化を起こすことになる。したがって、産地偽装の対象となりやすい、コメ、麦、蜂蜜など多くの食品類は、これらの基を含むため、分析対象となるサンプルによって保管や輸送の違いにより、交換性水素による水素安定同位体比の経時変化にばらつきが生じ、水素安定同位体比の比較による産地等の推定精度が低下するという問題点があった。   However, hydrogen atoms contained in groups such as hydroxyl group (-OH), carboxyl group (-COOH) and amino group (-NH2) in substances are known to have exchangeability (Patent Document 1). . In materials containing these groups, exchange of the exchangeable hydrogen of these groups with hydrogen atoms contained in the surrounding environment occurs during storage and transport, and the hydrogen stable isotope ratio changes with time. Become. Therefore, many foods such as rice, wheat, honey, etc., which are easily targeted for disguising areas, contain these groups, so the hydrogen stable isotope ratio due to exchangeable hydrogen is different depending on the storage and transport depending on the sample to be analyzed. There is a problem that the variation with time of variation occurs, and the estimation accuracy of the production area and the like by comparison of hydrogen stable isotope ratios decreases.

本発明はこのような課題を解決するためのものであり、水素安定同位体比の経時変化に起因する産地等の推定誤差を低減できる安定同位体比分析技術を提供することを目的としている。   The present invention is intended to solve such problems, and an object thereof is to provide a stable isotope ratio analysis technique capable of reducing an estimation error of a production area or the like caused by a temporal change in hydrogen stable isotope ratio.

このような目的を達成するために、本発明にかかる水素安定同位体比分析方法は、分析対象となる複数のサンプルに含まれる水素の安定同位体比を分析する水素安定同位体比分析方法であって、前記複数のサンプルのそれぞれを、空気中の水素安定同位体比が所定の標準比にある環境下で所定期間にわたり保管することにより、前記サンプルの交換性水素を前記空気中の水素と置換する水素置換ステップと、前記水素置換ステップで水素置換した前記複数のサンプルのそれぞれの水素安定同位体比を分析する安定同位体比分析ステップとを備えている。   In order to achieve such an object, the hydrogen stable isotope ratio analysis method according to the present invention is a hydrogen stable isotope ratio analysis method for analyzing the stable isotope ratio of hydrogen contained in a plurality of samples to be analyzed. The exchangeable hydrogen of the sample may be replaced with the hydrogen in the air by storing each of the plurality of samples for a predetermined period in an environment in which the hydrogen stable isotope ratio in air is at a predetermined standard ratio. And a stable isotope ratio analysis step of analyzing a hydrogen stable isotope ratio of each of the plurality of samples hydrogen-substituted in the hydrogen substitution step.

また、本発明にかかる上記水素安定同位体比分析方法の一構成例は、前記水素置換ステップが、前記複数のサンプルのそれぞれを、水素安定同位体比が前記標準比である標準水から発生させた水蒸気で満たした水素置換容器内で、前記所定期間にわたり保管するステップからなるものである。   In one configuration example of the above hydrogen stable isotope ratio analysis method according to the present invention, the hydrogen substitution step generates each of the plurality of samples from standard water whose hydrogen stable isotope ratio is the standard ratio. And storing in the hydrogen-replacement vessel filled with steam for the predetermined period.

また、本発明にかかる上記水素安定同位体比分析方法の一構成例は、前記安定同位体比分析ステップが、前記複数のサンプルのそれぞれを燃焼させることにより二酸化炭素および水蒸気を発生させる燃焼ステップと、前記燃焼ステップで発生させた二酸化炭素および水蒸気に対してレーザ光を照射してレーザ分光することにより、前記サンプルに含まれる水素の安定同位体比を前記複数のサンプルごとに測定するレーザ分光式安定同位体比測定ステップとからなるものである。   In one configuration example of the above hydrogen stable isotope ratio analysis method according to the present invention, the stable isotope ratio analysis step generates carbon dioxide and water vapor by burning each of the plurality of samples. Laser spectroscopy for measuring the stable isotope ratio of hydrogen contained in the sample for each of the plurality of samples by irradiating laser light to carbon dioxide and water vapor generated in the combustion step and performing laser spectroscopy And stable isotope ratio measurement step.

また、本発明にかかる水素安定同位体比分析システムは、分析対象となる複数のサンプルに含まれる水素の安定同位体比を分析する水素安定同位体比分析システムであって、前記サンプルのそれぞれを、空気中の水素安定同位体比が所定の標準比にある環境下で所定期間にわたり保管することにより、前記サンプルの交換性水素を前記空気中の水素と置換する水素置換容器と、前記水素置換容器で水素置換した前記複数のサンプルのそれぞれの水素安定同位体比を分析する安定同位体比分析装置とを備えている。   Further, a hydrogen stable isotope ratio analysis system according to the present invention is a hydrogen stable isotope ratio analysis system for analyzing stable isotope ratios of hydrogen contained in a plurality of samples to be analyzed, each of the samples being A hydrogen-replacement container for replacing exchangeable hydrogen of the sample with hydrogen in the air by storing the hydrogen stable isotope ratio in air in an environment in which the hydrogen stable isotope ratio in the air is at a predetermined standard ratio for a predetermined period; And a stable isotope ratio analyzer for analyzing the hydrogen stable isotope ratio of each of the plurality of hydrogen-replaced samples in a container.

本発明によれば、保管や輸送により、サンプルのうち空気中の水素原子と交換された交換性水素に関する水素安定同位体比が、サンプル間で一律に標準比に近づけられることになる。このため、サンプル間における保管や輸送の違いの影響を受けた交換性水素に関する水素安定同位体比が、ほぼ標準比となるため、同一産地のサンプルであれば、ほぼ同じ水素安定同位体比を示すことになる。したがって、水素安定同位体比の経時変化に起因する産地等の推定誤差を低減することができ、食品の産地等の物質の起源に関する起源情報を正確に分析することが可能となる。   According to the present invention, the hydrogen stable isotope ratio of exchangeable hydrogen exchanged with hydrogen atoms in air among the samples can be uniformly brought close to the standard ratio among the samples by storage and transport. For this reason, the hydrogen stable isotope ratio of exchangeable hydrogen affected by the difference in storage and transport among the samples is approximately the standard ratio, so in the case of a sample of the same production area, the hydrogen stable isotope ratio is approximately the same. It will be shown. Therefore, it is possible to reduce the estimation error of the production area and the like due to the temporal change of the hydrogen stable isotope ratio, and to accurately analyze the origin information on the origin of the substance such as the food production area.

水素安定同位体比分析システムを示す説明図である。It is an explanatory view showing a hydrogen stable isotope ratio analysis system. 水素安定同位体比の変化を示すグラフである。It is a graph which shows the change of hydrogen stable isotope ratio. 水素置換による水素安定同位体比の時間依存性を示すグラフである。It is a graph which shows the time dependence of the hydrogen stable isotope ratio by hydrogen substitution.

次に、本発明の一実施の形態について図面を参照して説明する。
［水素安定同位体比分析システム］
まず、図１を参照して、本発明の一実施の形態にかかる水素安定同位体比分析システム１について説明する。図１は、水素安定同位体比分析システムを示す説明図である。 Next, an embodiment of the present invention will be described with reference to the drawings.
Hydrogen stable isotope ratio analysis system
First, a hydrogen stable isotope ratio analysis system 1 according to an embodiment of the present invention will be described with reference to FIG. FIG. 1 is an explanatory view showing a hydrogen stable isotope ratio analysis system.

この水素安定同位体比分析システム１は、食品の産地等の物質の起源に関する起源情報を分析する際に用いられて、サンプルに含まれる水素安定同位体の比率を測定して分析するシステムである。
図１に示すように、水素安定同位体比分析システム１は、主な構成として、水素置換容器１０と安定同位体比分析装置２０とを備えている。 This hydrogen stable isotope ratio analysis system 1 is a system that is used when analyzing source information regarding the origin of a substance such as a food production area, and measures and analyzes the ratio of hydrogen stable isotopes contained in a sample .
As shown in FIG. 1, the hydrogen stable isotope ratio analysis system 1 mainly includes a hydrogen substitution container 10 and a stable isotope ratio analyzer 20.

水素置換容器１０は、ガラス瓶などの密封容器からなる。サンプルＳを水素置換容器１０で保管する場合には、水素置換容器１０内に、袋１３に入れたサンプルＳと、水素安定同位体比が標準比である標準水１１と、サンプルＳが標準水１１に直接濡れないように施した試料台１２とを入れた後、蓋１４を閉めて密封する。   The hydrogen displacement container 10 is a sealed container such as a glass bottle. When the sample S is stored in the hydrogen-replacement container 10, the sample S placed in the bag 13 in the hydrogen-replacement container 10, standard water 11 having a hydrogen stable isotope ratio as a standard ratio, and sample S as standard water 11. After placing the sample table 12 so as not to be directly wetted with 11, the lid 14 is closed and sealed.

安定同位体比分析装置２０は、例えばＰｉｃａｒｒｏ社のＢ２２２１−ｉなど、一般的なレーザ分光式安定同位体比分析装置からなり、燃焼部２１、レーザ光源２２、ガスセル２３、光検出器２４、および安定同位体比測定部２５が設けられている。   The stable isotope ratio analyzer 20 comprises a general laser spectroscopic stable isotope ratio analyzer such as B2221-i of Picarro, for example, and includes a combustion unit 21, a laser light source 22, a gas cell 23, a photodetector 24, and A stable isotope ratio measurement unit 25 is provided.

燃焼部２１は、水素置換容器１０で水素置換されたサンプルＳを粉末化したものを燃焼し、発生した水蒸気さらには二酸化炭素をガスセル２３へ供給する機能を有している。
レーザ光源２２は、可変波長のレーザ光Ｌをパルス状に出射する機能を有している。 The combustion unit 21 has a function of burning the powdered sample S hydrogen-replaced in the hydrogen displacement container 10 and supplying generated water vapor and carbon dioxide to the gas cell 23.
The laser light source 22 has a function of emitting laser light L of variable wavelength in a pulse shape.

ガスセル２３は、内部に複数のミラーが設けられており、レーザ光源２２からのレーザ光Ｌをこれらミラーで繰り返し反射させて燃焼部２１から供給された水蒸気さらには二酸化炭素に照射することにより、光学キャビティを形成する機能と、水蒸気さらには二酸化炭素を通過したレーザ光Ｌ’を外部に出力する機能とを有している。   The gas cell 23 is internally provided with a plurality of mirrors, and the laser light L from the laser light source 22 is repeatedly reflected by these mirrors, and the water vapor and further the carbon dioxide supplied from the combustion unit 21 are irradiated to obtain optical It has a function of forming a cavity, and a function of outputting laser light L 'that has passed through water vapor and carbon dioxide to the outside.

光検出器２４は、フォトダイオードからなり、ガスセル２３から出力されたレーザ光Ｌ’の光強度を検出する機能を有している。
安定同位体比測定部２５は、光検出器２４で検出された光強度に基づいて、レーザ光Ｌのパルス終端時に測定した減衰時間から吸収率を計算する機能と、得られた吸収率がピークとなる光吸収スペクトルに応じて、水蒸気さらには二酸化炭素に含まれる同位体の種別と濃度を特定する機能と、これら計測結果から安定同位体比を分析する機能とを有している。
なお、具体的な安定同位体比計測方法については、前述したキャビティリングダウン分光法（ＣＲＤＳ：Cavity Ring-Down Spectroscopy）以外の公知の手法を用いてもよい。 The light detector 24 is made of a photodiode and has a function of detecting the light intensity of the laser light L ′ output from the gas cell 23.
The stable isotope ratio measurement unit 25 has a function of calculating the absorptivity from the decay time measured at the pulse end of the laser light L based on the light intensity detected by the light detector 24, and the obtained absorptivity is a peak. It has a function to specify the type and concentration of isotope contained in water vapor and carbon dioxide according to the light absorption spectrum, and a function to analyze a stable isotope ratio from these measurement results.
In addition, as a specific stable isotope ratio measuring method, you may use well-known methods other than the cavity ring down spectroscopy (CRDS: Cavity Ring-Down Spectroscopy) mentioned above.

［発明の原理］
次に、本発明の原理について説明する。
前述したように、コメ、麦、蜂蜜など多くの食品類は、ヒドロキシル基（−ＯＨ）、カルボキシル基（−ＣＯＯＨ）、アミノ基（−ＮＨ２）など、水素原子を持つ基を多く含んでいる。食品の産地等の物質の起源に関する起源情報を分析する場合には、これらの基に含まれる水素原子の安定同位体比を分析することになる。 [Principle of the invention]
Next, the principle of the present invention will be described.
As described above, many food products such as rice, wheat and honey contain many groups having a hydrogen atom, such as hydroxyl group (-OH), carboxyl group (-COOH) and amino group (-NH2). When analyzing the origin information regarding the origin of a substance such as a food production area, the stable isotope ratio of hydrogen atoms contained in these groups is analyzed.

ここで、これらの基に含まれる水素原子は、交換性を有する交換性水素であるため、これら交換性水素と、収穫されてから保管や輸送の間に、周囲の環境中に含まれている水素原子との交換が生じ、交換性水素が持つ元の安定同位体比が経時変化することになる。これにより、サンプルによって保管や輸送の状況が異なるため、同一種であっても、サンプル間で安定同位体比の経時変化にばらつきが生じ、結果として、水素安定同位体比の比較による産地推定精度が低下することになる。   Here, since the hydrogen atoms contained in these groups are exchangeable hydrogen having exchangeability, they are contained in the surrounding environment between these exchangeable hydrogens and after being harvested and then stored and transported. Exchange with a hydrogen atom occurs, and the original stable isotope ratio of exchangeable hydrogen changes with time. As a result, since the conditions of storage and transport differ depending on the sample, even with the same species, variation in stable isotope ratio with time occurs among the samples, and as a result, the origin estimation accuracy by comparison of hydrogen stable isotope ratios Will be reduced.

ここで、このような保管や輸送の間に発生する交換性水素の交換は、サンプル全体で発生するのではなく、空気に晒されるサンプルの表面に近い部分で発生しやすいと考えられる。このため、サンプル内部における水素安定同位体比は保管や輸送においてあまり変化せず、サンプル表面における水素安定同位体比が変化しやすいものと推定される。したがって、サンプル表面における水素安定同位体比の変化が、サンプル間における安定同位体比の経時変化のばらつきの主たる原因であると考えられる。   Here, it is considered that exchange of exchangeable hydrogen generated during storage and transportation does not occur in the entire sample but is likely to occur in a portion close to the surface of the sample exposed to air. Therefore, it is presumed that the hydrogen stable isotope ratio inside the sample does not change much during storage and transport, and the hydrogen stable isotope ratio on the sample surface is likely to change. Therefore, the change of stable hydrogen isotope ratio at the sample surface is considered to be the main cause of the time-dependent variation of stable isotope ratio among samples.

本発明は、このようなサンプルにおける交換性水素の交換メカニズムに着目し、水素安定同位体比測定の前処理として、空気中の水素安定同位体比が所定の標準比にある環境下で、サンプルを所定期間にわたり保管することにより、サンプルの交換性水素を標準比に近づくよう強制的に置換するようにしたものである。
これにより、保管や輸送において変化したサンプル表面における水素安定同位体比を、各サンプル間で一律に標準比近くまで強制的に変化させることができる。 The present invention focuses on the exchange mechanism of exchangeable hydrogen in such a sample, and as a pretreatment for hydrogen stable isotope ratio measurement, the sample in an environment where the hydrogen stable isotope ratio in air is at a predetermined standard ratio. Is stored for a predetermined period of time, thereby forcing exchangeable hydrogen of the sample to be displaced to a standard ratio.
As a result, the hydrogen stable isotope ratio at the sample surface changed in storage and transport can be forcibly changed uniformly to near the standard ratio among the samples.

例えば、ある産地のコメＸの収穫時におけるコメ表面およびコメ内部の水素安定同位体比が等しくδＤX1であるとし、コメ表面およびコメ内部の水素安定同位体比の全体に対する寄与率が仮に規定できるものとしてＰI，ＰSとすると、収穫時におけるコメ全体の水素安定同位体比δＤXは、δＤX＝δＤX1×ＰI＋δＤX1×ＰSで求められる。
一方、このコメＸを保管・輸送したことにより、コメ内部の水素安定同位体比はほぼδＤX1であるが、コメ表面の水素安定同位体比はδＤX2に変化したものとすると、保管・輸送後のコメ全体の水素安定同位体比δＤX’は、δＤX’＝δＤX1×ＰI＋δＤX2×ＰSで求められる。 For example, assuming that the hydrogen stable isotope ratio of the rice surface and the inside of the rice at the time of harvest of rice X at a certain production area is equal to δD X1 , the contribution ratio to the whole of the hydrogen stable isotope ratio of the rice surface and the inside of rice can be tentatively specified. Assuming that P 1 and P 2 S are used, the hydrogen stable isotope ratio δD X of the whole rice at harvest time can be obtained by δD X = δD X1 × P I + δD X1 × P S.
On the other hand, although the stable isotope ratio of hydrogen inside rice is approximately δD X1 by storing and transporting this rice X, if the stable hydrogen isotope ratio of hydrogen on the surface of rice is changed to δD X2 , storage and transportation The hydrogen stable isotope ratio δD X ′ of the whole rice is determined by δD X ′ = δD X1 × P I + δD X2 × P S.

ここで、コメ表面の水素安定同位体比δＤX2は、保管・輸送の過程が異なるコメＸのサンプル間でばらつくことになり、実際にはδＤX21，δＤX22，δＤX23，…となるため、各サンプルの保管・輸送後の水素安定同位体比δＤ’も、δＤX1’，δＤX2’，δＤX3’，…となる。これがサンプル間における安定同位体比の経時変化のばらつきの主たる原因となる。 Here, the hydrogen stable isotope ratio δD X2 on the rice surface will vary between samples of rice X in which storage and transport processes differ, and in fact, δD X21 , δD X22 , δD X23,. The stable hydrogen isotope ratio δD ′ after storage and transportation of each sample is also δD X1 ′, δD X2 ′, δD X3 ′,. This is the main cause of the variation of stable isotope ratio with time among samples.

本発明によれば、水素安定同位体比測定の前処理として、空気中の水素安定同位体比が所定の標準比δＤ0にある環境下で、コメＸの各サンプルが保管されるため、コメ表面の水素安定同位体比δＤX21，δＤX22，δＤX23…は、サンプル間で一律にδＤ0近くまで強制的に変化することになる。このため、水素置換後のコメ全体の水素安定同位体比δＤX”は、サンプル間で共通してほぼδＤX”＝δＤX1×ＰI＋δＤ0×ＰSとなる。
これにより、収穫時におけるコメ全体の水素安定同位体比δＤXとは異なるものの、水素置換後のコメ全体の水素安定同位体比は、保管・輸送の過程が異なるサンプルであっても、コメＸであれば共通してδＤX”となる。 According to the present invention, each sample of rice X is stored under the environment where the hydrogen stable isotope ratio in air is at the predetermined standard ratio δD 0 as the pretreatment for the hydrogen stable isotope ratio measurement. The hydrogen stable isotope ratios δD X21 , δD X22 , δD X23 ... Of the surface will be forcibly changed to near δD 0 uniformly among the samples. Therefore, the hydrogen stable isotope ratio δD X ′ ′ of the whole rice after hydrogen substitution is approximately δD X ′ ′ = δD X 1 × P 1 + δD 0 × P S in common among the samples.
As a result, although the hydrogen stable isotope ratio δD X of the whole rice at harvest time is different, the hydrogen stable isotope ratio of the whole rice after the hydrogen substitution is the rice X even if the storage and transport processes are different. In this case, δD X ′ ′ is commonly used.

このことは、産地の異なるコメＹでも同様であり、収穫時におけるコメ表面およびコメ内部の水素安定同位体比がδＤy1であるとし、ＰI，ＰSがコメＹでも同程度であるとすると、水素置換後のコメＹ全体の水素安定同位体比δＤY”は、δＤY”＝δＤy1×ＰI＋δＤ0×ＰSとなる。
したがって、産地の異なるコメＸ，Ｙの水素置換後の水素安定同位体比δＤＸ”，δＤY”には、収穫時における水素安定同位体比δＤＸ1，δＤy1による差異が含まれており、これら差異により産地を判定することができる。 The same is true for rice Y from different production areas, and it is assumed that the hydrogen stable isotope ratio of the surface and inside of rice at harvest time is δD y1 , and P I and P S are the same for rice Y. The hydrogen stable isotope ratio δD Y ′ ′ of the whole rice Y after hydrogen substitution is δD Y ′ ′ = δD y1 × P I + δD 0 × P S.
Therefore, different rice X of origin, Y hydrogen stable isotopes DerutaDX after hydrogen substituted ", [delta] D Y", the hydrogen isotopic composition DerutaDX 1 during harvest, contains differences due to [delta] D y1, these The difference can be used to determine the production area.

なお、本発明において測定する水素の安定同位体比は、水素の天然に存在する非放射性同位体についての比を用いればよく、水素安定同位体比としては1ＨとＤ（2Ｈ）の比を用いればよい。この安定同位体比は、通常、絶対比ではなく、標準試料の同位体比からの千分偏差としてそれぞれ以下の式（１）で示されるδ値で表現される。なお、式中、ＳＡＭＰは試料における同位体比を示し、ＳＴＤは標準試料における同位体比を示す。 The stable isotope ratio of hydrogen measured in the present invention may be the ratio of hydrogen with respect to naturally occurring non-radioactive isotopes, and the hydrogen stable isotope ratio is the ratio of 1 H to D ( 2 H) Should be used. This stable isotope ratio is usually expressed not by an absolute ratio but by a δ value represented by the following equation (1) as a thousand deviation from the isotope ratio of a standard sample. In the formula, SAMP indicates the isotope ratio in the sample, and STD indicates the isotope ratio in the standard sample.

Figure 0006534985
水素安定同位体比の標準試料は、通常、標準平均海水（Vienna Standard Mean Ocean Water：ＶＳＭＯＷ）を用いて表記される。
Figure 0006534985
 A standard sample of hydrogen stable isotope ratio is usually expressed using standard mean sea water (Venna Standard Mean Ocean Water: VSMOW).

［測定例］
次に、図２を参照して、本実施の形態にかかる水素安定同位体比分析システム１の測定例について説明する。図２は、水素安定同位体比の変化を示すグラフである。 [Measurement example]
Next, with reference to FIG. 2, a measurement example of the hydrogen stable isotope ratio analysis system 1 according to the present embodiment will be described. FIG. 2 is a graph showing changes in hydrogen stable isotope ratio.

この測定例では、国内産のコメＸと外国産のコメＹを準備し、これらコメＸ，Ｙをそれぞれ２つのグループに分けて４種類のサンプルＳX1，ＳX2，ＳY1，ＳY2とし、それぞれ異なる環境で約１年間保管することにより、交換性水素による水素安定同位体比の経時変化にばらつきを生じさせた。
このようにして１年間保管した４種類のサンプルＳX1，ＳX2，ＳY1，ＳY2を、まずは、水素置換せずにミルで粉末化して凍結乾燥した後、Ｐｉｃａｒｒｏ社Ｂ２２２１−ｉを用いて水素安定同位体比δＤVSMOWを測定した。これにより、図２の水素置換前ＴＡにプロットされているような次の測定結果が得られた。 In this measurement example, domestic rice X and foreign rice Y are prepared, and these rice X and Y are divided into two groups to obtain four types of samples S X1 , S X2 , S Y1 and S Y2 , Storage for about 1 year in different environments caused variations in hydrogen stable isotope ratio over time due to exchangeable hydrogen.
The four kinds of samples S X1 , S X2 , S Y1 and S Y2 stored for one year in this way are first powdered in a mill without hydrogen substitution and freeze-dried, and then using Picarro B2221-i The hydrogen stable isotope ratio δD VSMOW was measured. Thereby, the following measurement results as plotted in the pre-hydrogen substitution TA in FIG. 2 were obtained.

国内産コメＸのサンプルＳX1：−３７．８‰
国内産コメＸのサンプルＳX2：−２６．５‰
外国産コメＹのサンプルＳY1：−７２．５‰
外国産コメＹのサンプルＳY2：−６１．３‰
これら測定結果から分かるように、産地が同一のコメＸ（Ｙ）であっても保管状態が異なるサンプルＳX1，ＳX2（ＳY1，ＳY2）間では、水素安定同位体比の測定誤差εAX（εAY）が１０‰以上あり、水素安定同位体比を用いて産地等を推定する際の推定精度が低下する要因になることが分かる。 Sample S X1 of domestic rice X: 37.8 ‰
Sample S X2 of domestic rice X: 26.5 ‰
Foreign rice Y sample S Y1 : -72.5 ‰
Sample S Y2 of foreign rice Y: -61.3 ‰
As can be seen from these measurement results, the measurement error ε of the hydrogen stable isotope ratio between the samples S X1 and S X2 (S Y1 and S Y2 ) which are different in storage condition even if rice X (Y) in the same place of production is the same It can be seen that AX (ε AY ) is 10 ‰ or more, which is a factor that reduces the estimation accuracy when estimating the production area using the hydrogen stable isotope ratio.

次に、本発明にかかる水素置換を適用して、交換性水素による影響を補償した場合について説明する。
まず、水素安定同位体比測定の前処理として、図１に示したように、水素置換容器１０に標準水１１を入れ、サンプルＳが標準水１１に直接濡れないように試料台１２を設け、その上に袋１３に入れたサンプルＳを置いた。ここでは、標準水１１として、標準比とする水素安定同位体比δＤVSMOW＝−７４．４‰の水を用いた。 Next, the case where the hydrogen substitution according to the present invention is applied to compensate for the influence of exchangeable hydrogen will be described.
First, as pretreatment for hydrogen stable isotope ratio measurement, as shown in FIG. 1, the standard water 11 is put in the hydrogen displacement vessel 10, and the sample stage 12 is provided so that the sample S does not get wet directly to the standard water 11. The sample S placed in the bag 13 was placed thereon. Here, as the standard water 11, water having a hydrogen stable isotope ratio δD VSMOW = -74.4% as a standard ratio was used.

次に、この水素置換容器１０を、温度５０℃に設定した恒温槽に入れて約１分間放置し、容器内部を標準水１１の蒸気で満たした後、蓋１４を閉めて密封し、サンプルＳを水素置換容器１０内で約１０時間にわたり、水素安定同位体比が標準比にある蒸気中に保管することにより、サンプルＳの交換性水素を標準比に近づくよう強制的に置換した。この水素置換は、サンプルＳX1，ＳX2，ＳY1，ＳY2ごとに、個別の水素置換容器１０を用意して行った。 Next, the hydrogen displacement vessel 10 is placed in a thermostatic bath set at a temperature of 50 ° C. and left for about 1 minute, the inside of the vessel is filled with the vapor of standard water 11, the lid 14 is closed and sealed, The exchangeable hydrogen of the sample S was forcibly displaced to approach the standard ratio by storing the following in the hydrogen substitution container 10 for about 10 hours in a vapor having a hydrogen stable isotope ratio at the standard ratio. This hydrogen substitution was performed by preparing individual hydrogen substitution containers 10 for each of the samples S X1 , S X2 , S Y1 and S Y2 .

このようにして、水素置換を行った後、前回と同様に４種類のサンプルＳX1，ＳX2，ＳY1，ＳY2を、水素置換せずにミルで粉末化して凍結乾燥した後、Ｐｉｃａｒｒｏ社Ｂ２２２１−ｉを用いて水素安定同位体比δＤVSMOWを測定した。これにより、図２の水素置換後ＴＢにプロットされているような次の測定結果が得られた。 After hydrogen substitution, the four samples S X1 , S X2 , S Y1 and S Y2 are powdered in a mill without hydrogen substitution and lyophilized in the same manner as in the previous step. Hydrogen stable isotope ratio δD VSMOW was measured using B2221-i. Thereby, the following measurement results as plotted in TB after hydrogen substitution of FIG. 2 were obtained.

国内産コメＸのサンプルＳX1：−４２．５‰
国内産コメＸのサンプルＳX2：−３９．５‰
外国産コメＹのサンプルＳY1：−７３．５‰
外国産コメＹのサンプルＳY2：−７１．１‰
これら測定結果から分かるように、本発明による水素置換を前処理として実施することにより、産地が同一のコメＸ（Ｙ）であれば保管状態が異なるサンプルＳX1，ＳX2（ＳY1，ＳY2）間であっても、水素安定同位体比の測定誤差εBX（εBY）が５‰以内となった。 Sample S X1 of domestically produced rice X: -42.5%
Sample S X2 of domestic rice X: 39.5 ‰
Foreign rice Y sample S Y1 : -73.5 ‰
Sample S Y2 of foreign rice Y: 71.1 ‰
As can be understood from these measurement results, samples S X1 and S X2 (S Y1 and S Y2 ) having different storage states if rice X (Y) having the same origin is produced by performing hydrogen substitution according to the present invention as pretreatment. Even in the interval), the measurement error ε BX (ε BY ) of the hydrogen stable isotope ratio was within 5 ‰.

これは、前述したように、これらサンプルＳX1，ＳX2，ＳY1，ＳY2のヒドロキシル基（−ＯＨ）、カルボキシル基（−ＣＯＯＨ）、アミノ基（−ＮＨ２）などの基に含まれる水素原子が、前処理である水素置換処理により、水素安定同位体比が標準比にある水蒸気に晒されたため、サンプルＳX1，ＳX2，ＳY1，ＳY2のうち交換性水素に関する水素安定同位体比が、強制的に標準比に近づけられたためと考えられる。 This is, as described above, hydrogen atoms contained in groups such as hydroxyl group (-OH), carboxyl group (-COOH) and amino group (-NH2) of these samples S X1 , S X2 , S Y1 and S Y2 However, since the hydrogen substitution processing as pretreatment results in exposure to water vapor having a hydrogen stable isotope ratio at a standard ratio, the hydrogen stable isotope ratio of exchangeable hydrogen among the samples S X1 , S X2 , S Y1 , S Y2 However, it is considered that it was because it was forced to approach the standard ratio.

図３は、水素置換による水素安定同位体比の時間依存性を示すグラフである。ここでは、コメＸのサンプルＳX1，ＳX2について、水素置換の時間長を変えて水素安定同位体比を測定したものである。このグラフから分かるように、５時間程度の水素置換で、交換性水素の置換量が飽和しており、コメの場合には、５時間の放置で十分効果が得られることが分かった。なお、物質によって水素置換時間が多少変化することも考えられるため、分析対象とする物質について予め交換性水素の置換量が飽和する時間を確認し、十分な水素置換時間を設定するようにしてもよい。 FIG. 3 is a graph showing the time dependency of the hydrogen stable isotope ratio by hydrogen substitution. Here, with respect to the samples S X1 and S X2 of rice X, the hydrogen stable isotope ratio is measured by changing the time length of hydrogen substitution. As can be seen from this graph, it was found that the substitution amount of exchangeable hydrogen is saturated by hydrogen substitution for about 5 hours, and in the case of rice, sufficient effects can be obtained by leaving for 5 hours. Since the hydrogen substitution time may change somewhat depending on the substance, it is possible to confirm in advance the saturation time of the exchangeable hydrogen substitution amount for the substance to be analyzed, and set a sufficient hydrogen substitution time. Good.

［本実施の形態の効果］
このように、本実施の形態は、サンプルＳのそれぞれを、空気中の水素安定同位体比が所定の標準比にある環境下で所定期間にわたり保管することにより、サンプルＳの交換性水素を標準比に近づくよう強制的に置換した後、これらサンプルＳのそれぞれについて、安定同位体比分析装置２０により水素安定同位体比を分析するようにしたものである。より具体的には、サンプルＳのそれぞれを、水素安定同位体比が標準比である標準水１１から発生させた水蒸気で満たした水素置換容器１０内で、所定期間にわたり保管することにより、水素置換を行うようにしたものである。 [Effect of this embodiment]
Thus, according to the present embodiment, the exchangeable hydrogen of sample S is standardized by storing each of sample S under the environment where the stable hydrogen isotope ratio in air is in the predetermined standard ratio for a predetermined period. After forced substitution so as to approach the ratio, the stable isotope ratio analyzer 20 analyzes the hydrogen stable isotope ratio of each of the samples S. More specifically, hydrogen substitution is carried out by storing each of the samples S for a predetermined period in a hydrogen substitution container 10 filled with water vapor generated from standard water 11 having a standard hydrogen stable isotope ratio. It is intended to

これにより、保管や輸送により、サンプルのうち空気中の水素原子と交換された交換性水素に関する水素安定同位体比が、サンプル間で一律に標準比に近づけられることになる。このため、サンプル間における保管や輸送の違いの影響を受けた交換性水素に関する水素安定同位体比が、ほぼ標準比となるため、同一産地のサンプルであれば、ほぼ同じ水素安定同位体比を示すことになる。したがって、水素安定同位体比の経時変化に起因する産地等の推定誤差を低減することができ、食品の産地等の物質の起源に関する起源情報を正確に分析することが可能となる。   As a result, due to storage and transportation, the hydrogen stable isotope ratio of exchangeable hydrogen exchanged with hydrogen atoms in air among the samples can be uniformly brought close to the standard ratio among the samples. For this reason, the hydrogen stable isotope ratio of exchangeable hydrogen affected by the difference in storage and transport among the samples is approximately the standard ratio, so in the case of a sample of the same production area, the hydrogen stable isotope ratio is approximately the same. It will be shown. Therefore, it is possible to reduce the estimation error of the production area and the like due to the temporal change of the hydrogen stable isotope ratio, and to accurately analyze the origin information on the origin of the substance such as the food production area.

［実施の形態の拡張］
以上、実施形態を参照して本発明を説明したが、本発明は上記実施形態に限定されるものではない。本発明の構成や詳細には、本発明のスコープ内で当業者が理解しうる様々な変更をすることができる。 [Extension of the embodiment]
As mentioned above, although this invention was demonstrated with reference to embodiment, this invention is not limited to the said embodiment. Various changes that can be understood by those skilled in the art can be made to the configuration and details of the present invention within the scope of the present invention.

１…水素安定同位体比分析システム、１０…水素置換容器、１１…標準水、１２…試料台、１３…袋、１４…蓋、２０…安定同位体比分析装置、２１…燃焼部、２２…レーザ光源、２３…ガスセル、２４…光検出器、２５…安定同位体比測定部、Ｓ…サンプル。   DESCRIPTION OF SYMBOLS 1 ... Hydrogen stable isotope ratio analysis system, 10 ... Hydrogen substitution container, 11 ... Standard water, 12 ... Sample stand, 13 ... Bag, 14 ... Lid, 20 ... Stable isotope ratio analyzer, 21 ... Combustion part, 22 ... Laser light source, 23: gas cell, 24: light detector, 25: stable isotope ratio measuring unit, S: sample.

Claims (4)

分析対象となるサンプルに含まれる水素の安定同位体比を分析する水素安定同位体比分析方法であって、
前記サンプルを空気中の水素安定同位体比が所定の標準比にある環境下で所定期間にわたり保管することにより、前記サンプルの交換性水素を前記空気中の水素と置換する水素置換ステップと、
前記水素置換ステップで水素置換した前記サンプルの水素安定同位体比を分析する安定同位体比分析ステップと
を備えることを特徴とする水素安定同位体比分析方法。 A hydrogen stable isotope ratio analysis method for analyzing the stable isotope ratio of hydrogen contained in a sample to be analyzed, comprising:
Hydrogen substitution step of replacing exchangeable hydrogen of the sample with hydrogen in the air by storing the sample for a predetermined period in an environment where the hydrogen stable isotope ratio in air is at a predetermined standard ratio;
A stable isotope ratio analysis step of analyzing a hydrogen stable isotope ratio of the sample hydrogen-substituted in the hydrogen substitution step; and a hydrogen stable isotope ratio analysis method. 請求項１に記載の水素安定同位体比分析方法において、
前記水素置換ステップは、前記サンプルを、水素安定同位体比が前記標準比である標準水から発生させた水蒸気で満たした水素置換容器内で、前記所定期間にわたり保管するステップからなることを特徴とする水素安定同位体比分析方法。 In the hydrogen stable isotope ratio analysis method according to claim 1,
The hydrogen substitution step comprises the step of storing the sample over the predetermined period in a hydrogen substitution container filled with water vapor generated from standard water whose hydrogen stable isotope ratio is the standard ratio. Hydrogen stable isotope ratio analysis method. 請求項１または請求項２に記載の水素安定同位体比分析方法において、
前記安定同位体比分析ステップは、
前記サンプルを燃焼させることにより二酸化炭素および水蒸気を発生させる燃焼ステップと、
前記燃焼ステップで発生させた二酸化炭素および水蒸気に対してレーザ光を照射してレーザ分光することにより、前記サンプルに含まれる水素の安定同位体比を測定するレーザ分光式安定同位体比測定ステップと
を含むことを特徴とする水素安定同位体比分析方法。 In the hydrogen stable isotope ratio analysis method according to claim 1 or 2,
The stable isotope ratio analysis step is
Burning the sample to generate carbon dioxide and water vapor;
A laser spectroscopic stable isotope ratio measuring step of measuring a stable isotope ratio of hydrogen contained in the sample by irradiating laser light to carbon dioxide and water vapor generated in the combustion step and performing laser spectroscopy; and A hydrogen stable isotope ratio analysis method characterized by comprising: 分析対象となるサンプルに含まれる水素の安定同位体比を分析する水素安定同位体比分析システムであって、
前記サンプルを空気中の水素安定同位体比が所定の標準比にある環境下で所定期間にわたり保管することにより、前記サンプルの交換性水素を前記空気中の水素と置換する水素置換容器と、
前記水素置換容器で水素置換した前記サンプルの水素安定同位体比を分析する安定同位体比分析装置と
を備えることを特徴とする水素安定同位体比分析システム。 A hydrogen stable isotope ratio analysis system for analyzing the stable isotope ratio of hydrogen contained in a sample to be analyzed, comprising:
A hydrogen-replacement vessel for replacing exchangeable hydrogen of the sample with hydrogen in the air by storing the sample for a predetermined period in an environment where the hydrogen stable isotope ratio in air is at a predetermined standard ratio;
A stable isotope ratio analyzer for analyzing a hydrogen stable isotope ratio of the sample hydrogen-replaced in the hydrogen-replacement container; and a hydrogen stable isotope ratio analysis system.
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