JP5757476B2 - How to determine the origin of distilled liquors - Google Patents
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本発明は、蒸留酒類に含まれる安定同位体の比率を測定して、蒸留酒類の産地又は種類を判別する方法に関する。 The present invention relates to a method for determining the production area or type of distilled alcoholic beverages by measuring the ratio of stable isotopes contained in the distilled alcoholic beverages.
近年、食品は、加工・流通技術の進歩によって広域流通するものとなっており、生産地から多くの事業者を経て消費者に届けられている。一般に加工食品は外見から原材料や生産地を見分けることは困難であるため、国際的な課題となっている原材料・産地偽装問題への対策として、種々の原材料・生産地判別技術が開発・利用されている。原材料・生産地判別技術としては、Ａｌ、Ｆｅ、Ｎｉ、Ｍｎ等の無機元素の組成を測定する無機元素組成分析やアミノ酸等の有機酸、糖等の組成を測定する有機成分組成分析による方法がある。特に、無機元素組成分析による判別方法は、原材料となる起源生物が生育した土壌等の生育環境を判別するために広く用いられているが、環境条件によって測定値に幅を生じることがあるため判別の指標となる基準値には信頼性が求められる方法である。また、ＤＮＡ型鑑定等のＤＮＡ分析、タンパク質の検出等による生化学的方法等がある。この方法は、比較的正確な判別を可能としているが、起源生物が同種である場合に判別が困難であり、同種の起源生物が群を形成している場合の産地判別には適さない方法である。物理化学的方法として、安定同位体比分析による方法等も利用されている。安定同位体比分析による判別は、起源生物を構成する炭素、窒素、酸素、水素等の安定同位体比が生育した環境・栄養源を反映していることを利用した判別方法であり、目的に応じて、元素を選択・組み合わせて判別が行われている。 In recent years, food has been distributed widely due to advances in processing and distribution technology, and has been delivered to consumers through many businesses from production areas. In general, it is difficult to distinguish raw materials and production areas from the appearance of processed foods, so various raw material / production area discrimination technologies have been developed and used as countermeasures against the problem of disguising raw materials and production areas, which is an international issue. ing. As a raw material / production area discriminating technique, there are methods based on an inorganic element composition analysis for measuring the composition of inorganic elements such as Al, Fe, Ni and Mn and an organic component composition analysis for measuring the composition of organic acids such as amino acids and sugars. is there. In particular, the discriminating method based on the analysis of inorganic element composition is widely used to discriminate the growth environment such as the soil where the source organism as the raw material has grown. However, the discriminating method may vary depending on the environmental conditions. This is a method for which reliability is required for the reference value that is an index of. In addition, there are biochemical methods such as DNA analysis such as DNA type identification, protein detection, and the like. Although this method enables relatively accurate discrimination, it is difficult to discriminate when the origin organisms are of the same species, and is not suitable for discriminating localities when the same species of origin organisms form a group. is there. As a physicochemical method, a method using stable isotope ratio analysis is also used. Discrimination by stable isotope ratio analysis is a discriminating method that utilizes the stable isotope ratio of carbon, nitrogen, oxygen, hydrogen, etc. that constitutes the source organism to reflect the growing environment and nutrient sources. Accordingly, discrimination is performed by selecting and combining elements.
農水産物を対象とした安定同位体比分析による原材料・生産地判別技術の分野には種々の核種の安定同位体比を測定し比較することによる判別方法があり、食品の原料を、試料食品中の炭素を封管燃焼法によって炭酸ガスとし測定した炭素安定同位体比に基づいて確認・特定する方法（特許文献１参照）や、茶葉等の農産物の栽培国・地域を、硫黄安定同位体比に基づいて又は硫黄安定同位体比と炭素若しくは窒素若しくは酸素安定同位体比の組み合せに基づいて判定する方法（特許文献２参照）や、農産物の産地を、アミノ酸の窒素安定同位体比の比較により判別する方法やウナギの産地、養殖ウナギと天然ウナギをアミノ酸の窒素、炭素安定同位体比の比較により判別する方法（特許文献３参照）が知られている。また、米の産地を米試料から抽出した脂肪酸成分をメチル化した脂肪酸誘導体の水素安定同位体比に基づいて判別する方法（特許文献４参照）が知られている。 In the field of raw material and production area discrimination technology by stable isotope ratio analysis for agricultural and marine products, there is a discrimination method by measuring and comparing the stable isotope ratios of various nuclides. For confirming and identifying the carbon of this plant as carbon dioxide by the sealed-tube combustion method based on the stable carbon isotope ratio (see Patent Document 1) Or based on a combination of stable sulfur isotope ratio and carbon or nitrogen or oxygen stable isotope ratio (see Patent Document 2), or by comparing the nitrogen stable isotope ratio of amino acids There are known a method for discriminating and a method for discriminating eel production areas, cultured eels and natural eels by comparing nitrogen and carbon stable isotope ratios of amino acids (see Patent Document 3). In addition, a method for discriminating rice production regions based on hydrogen stable isotope ratios of fatty acid derivatives obtained by methylating fatty acid components extracted from rice samples is known (see Patent Document 4).
特に、酸素、水素安定同位体比の測定を利用した判別方法として、バイオマスの可食部と非食部を有機成分の水素、酸素、炭素安定同位体比に基づいて判別する方法（特許文献４参照）や、農産物を使用した食品などの加工品の原料の植物種・植物栽培地域を、有機成分の炭素、水素、酸素、窒素、硫黄等の安定同位体比を分析することにより特定する方法（特許文献５参照）が知られている。また、米の生産地を、米を圧縮して抽出した水分の水素、酸素安定同位体比と米の生産地域における天水の水素、酸素安定同位体比を比較して特定する方法が知られている（特許文献６参照）。 In particular, as a discrimination method using measurement of oxygen and hydrogen stable isotope ratios, a method of discriminating edible parts and non-eating parts of biomass based on organic component hydrogen, oxygen, and carbon stable isotope ratios (Patent Document 4) And the plant species and plant cultivation areas of raw materials for processed products such as foods using agricultural products by analyzing stable isotope ratios of organic components such as carbon, hydrogen, oxygen, nitrogen, and sulfur. (See Patent Document 5). Also known is a method for identifying rice production sites by comparing the hydrogen and oxygen stable isotope ratios of water extracted by compressing rice with the hydrogen and oxygen stable isotope ratios of rainwater in the rice production areas. (See Patent Document 6).
このように酸素、水素安定同位体比は、水の起源を解析するために測定が行われており、市場で入手できるミネラル水、炭酸飲料、ビールの水素安定同位体比（δ２Ｈ）及び酸素安定同位体比（δ１８Ｏ）は、天水線に適合し、その販売地域の水道水のδ２Ｈ及びδ１８Ｏに相関があるという報告もなされている（J. Agric. Food Chem. (2010) 58, 7311-7316.参照）。 Thus, oxygen and hydrogen stable isotope ratios are measured to analyze the origin of water, and commercially available mineral water, carbonated beverages, hydrogen stable isotope ratios (δ 2 H) of beer and beer and It has also been reported that the oxygen stable isotope ratio (δ 18 O) is compatible with the rainwater line and correlates with δ 2 H and δ 18 O in the sales area (J. Agric. Food Chem. (2010) 58, 7311-7316.).
加工食品については、「加工食品品質表示基準」により、原材料の名称、主な原材料の原産地の表示について表示義務が定められており、ＰＣＲ法を用いたＤＮＡ分析により、原材料の品種と産地を判別する技術が汎用されている。しかしながら、酒類のような発酵食品を対象とした原材料・生産地判別においては、発酵に用いる微生物のＤＮＡが混入する、原材料のＤＮＡが発酵により分解される等の問題があることからＤＮＡ分析が容易でなく、欧州のワイン産地判別においてもみられるように、無機元素組成分析、安定同位体比分析を中心に土壌の特徴を判別する方法が主として採られている。無機元素組成分析については、起源生物が生育する土壌の組成等が局所的に特徴を有する場合に判別が容易でなく、指標とする基準値は判別の信頼性確保のために多数必要となる等の難点があることから、安定同位体比分析による判別が検討されている。 For processed foods, the “Processed Food Quality Labeling Standards” stipulates the labeling requirements for the names of raw materials and the origins of the main raw materials. The DNA analysis using the PCR method identifies the type and origin of the raw materials. The technology to do is widely used. However, in the determination of raw materials and production areas for fermented foods such as liquors, DNA analysis is easy due to problems such as contamination of microorganism DNA used for fermentation and decomposition of raw material DNA by fermentation. In addition, as seen in the determination of wine regions in Europe, methods for determining soil characteristics are mainly employed, focusing on inorganic element composition analysis and stable isotope ratio analysis. For inorganic elemental composition analysis, it is not easy to discriminate when the composition of the soil where the source organism grows has local characteristics, and a large number of reference values are required to ensure the reliability of discrimination, etc. Discrimination by stable isotope ratio analysis is being studied.
従来、食品の原材料又は産地判別のために酸素又は水素安定同位体比の測定が行われている。蒸留酒類は、その醸造の際に、蒸留の工程を含んでおり酸素及び水素の同位体分別が起こることから、酸素又は水素安定同位体比に基づく産地の判別が容易でないという問題がある。本発明の課題は、安定同位体比の測定に基づく、蒸留酒類の産地を判別する方法又は蒸留酒類の種類を判別する方法を提供することにある。 Conventionally, oxygen or hydrogen stable isotope ratios have been measured for discrimination of food raw materials or production areas. Distilled liquors have a problem in that it is not easy to determine the production area based on the stable isotope ratio of oxygen or hydrogen because the distillation process includes a distillation process and the isotopic fractionation of oxygen and hydrogen occurs. The subject of this invention is providing the method of discriminating the origin of distilled liquor based on the measurement of stable isotope ratio, or the method of discriminating the kind of distilled liquor.
本発明者は、醸造の過程で蒸留が行われ、酸素及び水素の同位体分別が起こる蒸留酒類において、蒸留酒中の水の酸素安定同位体比、水素安定同位体比を産地が既知の蒸留酒の数値と比較すること、及び、蒸留酒中のエタノールの炭素安定同位体比を種類が既知の蒸留酒の数値と比較することにより種類の判別が可能であることを見いだし、本発明を完成するに至った。 The present inventor is a distilled liquor in which distillation is performed in the brewing process and oxygen and hydrogen isotope fractionation are performed. Completion of the present invention was found by comparing with the value of liquor and comparing the carbon stable isotope ratio of ethanol in distilled liquor with the value of distilled liquor of known types. It came to do.
すなわち本発明は、
（１）試料である蒸留酒類における水の酸素安定同位体比又は水素安定同位体比を測定する工程、測定した試料における安定同位体比を産地が既知である蒸留酒類における安定同位体比と比較する工程を含むことを特徴とし、かつ蒸留酒類のアルコール分が３０度以下であることを特徴とする蒸留酒類の産地の判別方法や、
（２）試料である蒸留酒類における水の酸素安定同位体比若しくは水素安定同位体比、及びエタノールの炭素安定同位体比を測定する工程、測定した試料における安定同位体比を種類が既知である蒸留酒類における安定同位体比と比較する工程を含むことを特徴とする蒸留酒類の種類の判別方法や、
（３）蒸留酒類が、焼酎であることを特徴とする上記（１）又は（２）に記載の方法や、（４）判別される蒸留酒類の種類が、沖縄県を産地とする泡盛、鹿児島県奄美市若しくは大島郡を産地とする黒糖焼酎、又は北海道若しくは東北地方若しくは長野県を産地とする焼酎であることを特徴とする上記（２）に記載の方法に関する。
That is, the present invention
(1) The process of measuring the oxygen stable isotope ratio or hydrogen stable isotope ratio of water in a sample of distilled liquor, and comparing the stable isotope ratio of the measured sample with the stable isotope ratio of a distilled liquor whose origin is known A process for determining the production area of distilled alcoholic beverages, wherein the alcohol content of distilled alcoholic beverages is 30 degrees or less ,
(2) oxygen isotopic composition of water in the distillation liquor is specimen or hydrogen stable isotopes, and measuring the carbon isotope ratio of the ethanol, a stable isotope ratio in the measured sample type is known A method for discriminating the type of distilled liquor, comprising a step of comparing the stable isotope ratio in a certain distilled liquor,
( 3 ) The method according to (1) or ( 2) above, wherein the distilled liquor is shochu, and (4 ) the type of distilled liquor to be identified is Awamori, Kagoshima, whose origin is Okinawa Prefecture It relates to the method according to ( 2) above, characterized in that it is a brown sugar shochu produced in Amami-shi or Oshima-gun, or a shochu produced in Hokkaido, Tohoku or Nagano.
本発明は、蒸留酒類における酸素安定同位体比又は水素安定同位体比に基づいて、蒸留酒類の産地を簡便且つ的確に判別することを可能とする。また、蒸留酒類中の水の酸素安定同位体比若しくは水素安定同位体比とエタノールの炭素安定同位体比に基づいて、蒸留酒類の産地又は種類を簡便且つ的確に判別することを可能とする。 The present invention makes it possible to easily and accurately determine the production area of distilled alcoholic beverages based on the oxygen stable isotope ratio or hydrogen stable isotope ratio of distilled alcoholic beverages. In addition, based on the oxygen stable isotope ratio or hydrogen stable isotope ratio of water in distilled liquor and the carbon stable isotope ratio of ethanol, it is possible to easily and accurately discriminate the origin or type of distilled liquor.
本発明は、蒸留酒類における安定同位体比に基づいて、蒸留酒類の産地又は種類を判別する方法に関する。原子番号が等しく、質量数が異なる核種を互いに同位体の関係にあるといい、同位体には放射壊変を起こす放射性同位体とそれ以外の安定同位体がある。安定同位体は、自然界に略一定の比で存在しており、例えば、酸素安定同位体としては１６Ｏ、１７Ｏ、１８Ｏ、水素安定同位体としては１Ｈ、２Ｈ、炭素安定同位体としては１２Ｃ、１３Ｃがある。安定同位体比は自然界で略一様であり、これらの存在比（同位体存在度）は、１６Ｏ（９９．７６３％）、１７Ｏ（０．０３７％）、１８Ｏ（０．２００％）、１Ｈ（９９．９８４％）、２Ｈ（０．０１６％）、１２Ｃ（９８．８８９％）、１３Ｃ（１．１１１％）に近い値をとることが知られている。しかし、質量の違いから同位体間で物理的・化学的性質に差が生じる同位体効果により自然界における反応・相転移等の過程で同位体分別が起こるため、安定同位体が存在する環境・履歴により安定同位体間の存在比（安定同位体比）が変動する。このような変動を検出することにより安定同位体の起源を辿ることができることから、安定同位体比の測定は、農水産物の産地判別、食品等の原材料・生産地判別のために利用されている。例えば、炭素安定同位体比は、主として、起源の植物に固有であり食物連鎖の履歴を反映しており、糖源の判別に用いられることが多い。植物には、大気中のＣＯ２を直接還元的にペントースリン酸回路に取り込み光合成を行うＣ３植物と、ジカルボン酸経路を有するＣ４植物があるが、炭素安定同位体比は、大部分の植物が属するＣ３植物とサトウキビ、とうもろこし等のイネ科に多いＣ４植物との間で特徴的である。窒素安定同位体比は、食物連鎖の履歴を反映しており、主として起源の植物が生育した土壌の判別等に用いられている。酸素・水素安定同位体比は、主として生物が摂取した水の起源を反映しており、蒸発・凝縮を伴う水の循環による同位体分別効果により温度・緯度・標高・降雨量等の影響を受けて地理的に固有な特徴を示している。例えば、天水（河川、湖、氷河、地下の岩層に染み込み岩石圏の様々な深度においてみられる地下水を含む陸上表面のすべての水。）の酸素及び水素安定同位体比は、地域により異なる値となり、低緯度から高緯度に移るに従い値が減少していく傾向を示すことが知られている。本発明は、特に蒸留酒類における酸素、水素、炭素安定同位体比を蒸留酒類の産地又は種類の判別に利用するものである。 The present invention relates to a method for discriminating the origin or type of distilled alcoholic beverages based on the stable isotope ratio in distilled alcoholic beverages. It is said that nuclides with the same atomic number and different mass numbers are in an isotope relationship, and there are radioisotopes that cause radiation decay and other stable isotopes. Stable isotopes exist in nature at a substantially constant ratio, for example, 16 O, 17 O, 18 O as oxygen stable isotopes, 1 H, 2 H as hydrogen stable isotopes, and carbon stable isotopes. There are 12 C and 13 C. The stable isotope ratio is substantially uniform in nature, and the abundance ratio (isotope abundance) is 16 O (99.763%), 17 O (0.037%), 18 O (0.200%). ), 1 H (99.984%), 2 H (0.016%), 12 C (98.889%), and 13 C (1.111%). However, the isotope effect that causes differences in physical and chemical properties between isotopes due to the difference in mass causes isotope fractionation in the process of natural reactions and phase transitions. The abundance ratio between stable isotopes (stable isotope ratio) varies. Since the origin of stable isotopes can be traced by detecting such fluctuations, the measurement of stable isotope ratios is used for determining the origin of agricultural and marine products and for determining raw materials and production areas of foods, etc. . For example, the carbon stable isotope ratio is mainly unique to the plant of origin and reflects the history of the food chain, and is often used for discrimination of sugar sources. The plant, a C 3 plants performing photosynthesis uptake directly reductively pentose phosphate cycle of CO 2 in the atmosphere, there is a C 4 plants having a dicarboxylic acid pathway, carbon isotope ratios, most plants C 3 plants and sugarcane belongs, it is characteristic with the high C 4 plants Gramineae such as maize. The nitrogen stable isotope ratio reflects the history of the food chain and is mainly used for discrimination of soil where the plant of origin grew. The stable isotope ratio of oxygen and hydrogen mainly reflects the origin of water ingested by living organisms, and is affected by temperature, latitude, altitude, rainfall, etc. due to the isotope fractionation effect due to the circulation of water accompanied by evaporation and condensation. Show geographically unique features. For example, the oxygen and hydrogen stable isotope ratios of rainwater (rivers, lakes, glaciers, all water on the surface of the land including groundwater in various depths of the lithosphere infiltrating underground rock formations) vary from region to region. It is known that the value tends to decrease as it moves from low latitude to high latitude. In the present invention, oxygen, hydrogen, and carbon stable isotope ratios in distilled liquors are particularly used to determine the origin or type of distilled liquors.
本発明において、蒸留酒類とは、醸造の過程で蒸留される酒類であって、アルコール分１度以上の飲料を指す。蒸留酒類は、連続式蒸留焼酎、単式蒸留焼酎、ウイスキー、ブランデー、原料用アルコール、スピリッツのいずれでもよく、発泡性のものであってもよい。蒸留酒類の原料は、水の他、穀類、果実のいずれでもよく、米、米こうじ、麦、蕎麦、とうもろこし、サトウキビ、さつまいも、じゃがいも、ヤシ、乳、ブドウ、リンゴ、レモン、ハーブ等のいずれを原料とするものも用いることができる。蒸留酒類の形態は、原酒、あるいは製造段階で割水（加水ないし和水）がなされたもののいずれでもよく、蒸留酒類のアルコール分は１度以上である限り特に制限されないが、蒸留後の割水（加水）の量が多いほど蒸留による同位体分別の影響が小さくなることから、１度以上４５度以下であることが好ましく、１度以上３０度以下であることが特に好ましい。アルコール分とは、温度１５度の時において原容量１００分中に含有するエタノールの容量をいう。 In the present invention, distilled alcoholic beverages are alcoholic beverages distilled during the brewing process, and refer to beverages having an alcohol content of 1 degree or more. The distilled liquor may be any of continuous distillation shochu, single distillation shochu, whiskey, brandy, raw alcohol, and spirits, and may be foaming. The raw materials for distilled liquor may be cereals and fruits, as well as water. What is used as a raw material can also be used. The form of distilled liquor may be either raw liquor or water split (hydrolyzed or hydrated) at the production stage, and the alcohol content of the distilled liquor is not particularly limited as long as it is 1 degree or more. Since the influence of isotope fractionation by distillation decreases as the amount of (hydro) increases, it is preferably 1 degree or more and 45 degrees or less, and particularly preferably 1 degree or more and 30 degrees or less. The alcohol content refers to the volume of ethanol contained in the original volume of 100 minutes at a temperature of 15 degrees.
本発明において、蒸留酒類の産地とは、その酒類の醸造、割水が行われる地域、製造地のことをいう。判別の対象とする産地としては、日本国内、日本国外のいずれでもよく、製造地の水を使用しているといった産地と関連性を有する蒸留酒類が醸造されている地域であって、比較に用いるための産地が既知の試料が取得可能な地域であれば特に制限されない。日本国内の産地としては、「地理的表示に関する表示基準」において国税庁長官が指定する地域、壱岐（長崎県壱岐市）、球磨（熊本県球磨郡・人吉市）、琉球（沖縄県）、薩摩（鹿児島県（奄美市及び大島郡を除く。））、白山（石川県白山市）、の他、北海道、秋田県、岩手県、長野県、福岡県、熊本県等の都道府県を製造地域とする場合や、東北地方、九州地方等の地方を製造地域とする場合でもよい。 In the present invention, the production area of distilled liquor refers to the area where the brewing and splitting of the liquor is performed and the production area. The production area to be discriminated may be either in Japan or outside of Japan, and it is an area where distilled liquor that is related to the production area, such as using water from the production area, is brewed and used for comparison. There is no particular limitation as long as the production area is a region where a known sample can be obtained. Production areas in Japan include areas designated by the Commissioner of the National Tax Agency in the “Display Standards for Geographical Labeling”, Iki (Iki City, Nagasaki Prefecture), Kuma (Kumamoto Prefecture Kuma County, Hitoyoshi City), Ryukyu (Okinawa Prefecture), Satsuma ( In addition to Kagoshima Prefecture (excluding Amami City and Oshima-gun)), Hakusan (Hakusan City, Ishikawa Prefecture), Hokkaido, Akita Prefecture, Iwate Prefecture, Nagano Prefecture, Fukuoka Prefecture, Kumamoto Prefecture, and other prefectures are the manufacturing regions. In other cases, the manufacturing region may be the Tohoku region, the Kyushu region, or the like.
本発明において、蒸留酒類の種類とは、蒸留酒類の産地及び原料により特定される種類のことをいう。 In the present invention, the type of distilled liquor refers to the type specified by the origin and raw materials of the distilled liquor.
本発明の蒸留酒類の産地の判別方法は、試料である蒸留酒類における酸素安定同位体比又は水素安定同位体比を測定する工程、測定した試料の安定同位体比を産地が既知である蒸留酒類における安定同位体比と比較する工程、を含む方法であれば特に制限されるものではない。本発明では、産地の判別を行う試料蒸留酒類における、又は試料蒸留酒類の成分における、酸素安定同位体比又は水素安定同位体比を測定し、産地が既知である対照の蒸留酒類について測定された同成分且つ同元素の安定同位体比との比較を行う。試料における安定同位体比が、産地が既知である蒸留酒類における安定同位体比と近似している場合は、その試料蒸留酒類の産地が、対照の蒸留酒類の産地と同一であると判断される。 The method for discriminating the origin of distilled liquor according to the present invention includes a step of measuring an oxygen stable isotope ratio or a hydrogen stable isotope ratio in a sample of distilled liquor, and a distilled liquor whose origin is known for the measured stable isotope ratio of the sample. If it is a method including the process compared with the stable isotope ratio in, it will not restrict | limit in particular. In the present invention, the oxygen stable isotope ratio or the hydrogen stable isotope ratio in the sample distilled liquor or the sample distilled liquor for discriminating the production area was measured, and the measurement was performed for the control distilled liquor whose production area is known. Comparison is made with the stable isotope ratio of the same component and the same element. If the stable isotope ratio in the sample is similar to the stable isotope ratio in a distilled liquor whose origin is known, the locality of the sample distilled liquor is judged to be the same as that of the control distilled liquor. .
蒸留酒類の産地の判別方法における安定同位体比を測定する工程は、蒸留酒類における酸素安定同位体比又は水素安定同位体比のいずれかを測定して行うことができる。また、蒸留酒類における酸素安定同位体比及び水素安定同位体の両方を測定して行うこともできる。判別を的確に行う観点からは、蒸留酒類における酸素安定同位体比及び水素安定同位体比の両方を測定することが好ましい。あるいは、蒸留酒類に含まれる特定の成分について安定同位体比を測定して行うことができ、蒸留酒類の成分における酸素安定同位体比若しくは水素安定同位体比のいずれか、又は蒸留酒類の成分における酸素安定同位体比及び水素安定同位体比の両方を測定して行うこともできる。蒸留酒類の産地の判別方法において安定同位体比を測定する蒸留酒類の成分としては、水、エタノール、高級アルコール及びそのエステル、有機酸等の蒸留酒類を構成する物質であって元素として酸素又は水素を含む物質であればいずれでもよいが、判別を的確に行う観点から、水について測定を行うことが好ましい。 The step of measuring the stable isotope ratio in the method for discriminating the production area of distilled liquor can be performed by measuring either the oxygen stable isotope ratio or the hydrogen stable isotope ratio in distilled liquor. It can also be carried out by measuring both the oxygen stable isotope ratio and the hydrogen stable isotope in distilled liquors. From the viewpoint of accurately discriminating, it is preferable to measure both the oxygen stable isotope ratio and the hydrogen stable isotope ratio in distilled liquors. Alternatively, the stable isotope ratio can be measured for a specific component contained in the distilled liquor, either the oxygen stable isotope ratio or the hydrogen stable isotope ratio in the distilled liquor component, or in the distilled liquor component. It can also be carried out by measuring both oxygen stable isotope ratio and hydrogen stable isotope ratio. Components of distilled liquor for measuring the stable isotope ratio in the method for discriminating the origin of distilled liquor include substances that constitute distilled liquor such as water, ethanol, higher alcohols and esters thereof, and organic acids, and oxygen or hydrogen as an element. Any substance may be used as long as it contains water, but it is preferable to measure water from the viewpoint of accurately discriminating.
本発明の蒸留酒類の種類の判別方法は、試料である蒸留酒類における酸素安定同位体比若しくは水素安定同位体比、及び試料である蒸留酒類における炭素安定同位体比を測定する工程、測定した試料の安定同位体比を種類が既知である蒸留酒類における安定同位体比と比較する工程、を含む方法である。本発明では、種類の判別を行う試料蒸留酒類における、又は試料蒸留酒類の成分における、酸素安定同位体比若しくは水素安定同位体比、及び炭素安定同位体比を測定し、種類が既知である対照の蒸留酒類について測定された同成分且つ同元素の安定同位体比との比較を行う。試料における安定同位体比が、種類が既知である蒸留酒類における安定同位体比と近似している場合は、その試料蒸留酒類の種類が、対照の蒸留酒類の種類と同一であると判断される。 The method for discriminating the type of distilled liquor of the present invention includes a step of measuring an oxygen stable isotope ratio or a hydrogen stable isotope ratio in a sample distilled liquor, and a carbon stable isotope ratio in a sample distilled liquor, and a measured sample A step of comparing the stable isotope ratio with a stable isotope ratio in a distilled liquor of a known type. In the present invention, the oxygen stable isotope ratio or the hydrogen stable isotope ratio and the carbon stable isotope ratio in the sample distilled liquor for determining the type or in the component of the sample distilled liquor are measured, and the type is known. Comparison with the stable isotope ratio of the same component and the same element measured for the distilled alcoholic beverages of If the stable isotope ratio in the sample is close to the stable isotope ratio in a distilled liquor of a known type, it is determined that the type of the sample distilled liquor is the same as the type of the control distilled liquor .
蒸留酒類の種類の判別方法における安定同位体比を測定する工程は、蒸留酒類における水素安定同位体比又は酸素安定同位体比のいずれかと炭素安定同位体比とを測定して行うことができる。また、蒸留酒類における水素安定同位体比及び酸素安定同位体比の両方と炭素安定同位体比とを測定して行うことができる。判別を的確に行う観点からは、蒸留酒類における水素安定同位体比及び酸素安定同位体比及び炭素安定同位体比を測定して行うことが好ましい。あるいは、蒸留酒類に含まれる特定の成分について安定同位体比を測定して行うことができ、蒸留酒類の成分における水素安定同位体比若しくは酸素安定同位体比のいずれか、及び蒸留酒類の成分における炭素安定同位体比を測定して行う、又は、蒸留酒類の成分における水素安定同位体比及び酸素安定同位体比、及び蒸留酒類の他の成分における炭素安定同位体比を測定して行うこともできる。蒸留酒類の種類の判別方法において安定同位体比を測定する蒸留酒類の成分としては、水、エタノール、高級アルコール及びそのエステル、有機酸等の蒸留酒類を構成する物質であって元素として酸素又は水素又は炭素を含む物質であればいずれでもよいが、判別を的確に行う観点から、水とエタノールについて測定を行うことが好ましく、水における水素安定同位体比及び酸素安定同位体比を測定し、エタノールにおける炭素安定同位体比を測定して行うことが好ましい。 The step of measuring the stable isotope ratio in the method for discriminating the type of distilled liquor can be performed by measuring either the hydrogen stable isotope ratio or the oxygen stable isotope ratio and the carbon stable isotope ratio in the distilled liquor. Moreover, it can carry out by measuring both the hydrogen stable isotope ratio and the oxygen stable isotope ratio and the carbon stable isotope ratio in distilled liquors. From the viewpoint of accurately discriminating, it is preferable to measure hydrogen stable isotope ratio, oxygen stable isotope ratio and carbon stable isotope ratio in distilled liquors. Alternatively, the stable isotope ratio can be measured for a specific component contained in the distilled liquor, either the hydrogen stable isotope ratio or the oxygen stable isotope ratio in the distilled liquor component, and the distilled liquor component. This can be done by measuring the carbon stable isotope ratio, or by measuring the hydrogen stable isotope ratio and oxygen stable isotope ratio in the components of distilled liquor, and the carbon stable isotope ratio in other components of distilled liquor. it can. Components of distilled liquor for measuring the stable isotope ratio in the method for discriminating the type of distilled liquor include substances constituting distilled liquor such as water, ethanol, higher alcohols and esters thereof, organic acids, etc., and oxygen or hydrogen as an element. Alternatively, any substance containing carbon may be used, but from the viewpoint of accurately discriminating, it is preferable to measure water and ethanol, and the hydrogen stable isotope ratio and oxygen stable isotope ratio in water are measured. It is preferable to carry out by measuring the carbon stable isotope ratio.
本発明において測定する安定同位体比は、酸素、水素、炭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、常法に従い、酸素安定同位体比としては１６Ｏと１8Ｏの比を用いればよく、水素安定同位体比としては１Ｈと２Ｈの比を用いればよく、炭素安定同位体比としては１２Ｃと１３Ｃの比を用いればよい。これらの安定同位体比は、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数式で示されるδ値で表現される。
酸素安定同位体比は、次の数式（Ｉ）で示すことができる。
The oxygen stable isotope ratio can be expressed by the following formula (I).
安定同位体比の標準試料は、酸素・水素安定同位体比の標準試料としては、常用されている標準平均海水（Standard Mean Ocean Water（ＳＭＯＷ））や、米国南カロライナ州ピーディー層産箭石（Belemnites from PeeDeeFormation（ＰＤＢ））を用いればよく、炭素安定同位体比の標準試料としては、ＰＤＢを用いることができるが、本発明の安定同位体比の測定においては安定同位体比の比較が行えるものであればよく、ＳＭＯＷ、ＰＤＢ等の世界標準試料に換算可能な参照標準試料を使用することができる。 Standard samples for stable isotope ratios include standard mean ocean water (SMOW) and meteorites from the Peady Formation, South Carolina, USA. Belemnites from PeeDeeFormation (PDB) may be used, and PDB can be used as a standard sample of carbon stable isotope ratio, but stable isotope ratio can be compared in the measurement of stable isotope ratio of the present invention. Any reference standard sample that can be converted into a world standard sample such as SMOW or PDB can be used.
安定同位体比の測定は、公知の同位体比分析方法を用いることができ、常法に従い、質量分析計を用いて質量電荷比に応じた分離・検出を行い、各同位体の存在量を計測して行うことができる。質量分離の方法は、測定する試料に応じて、磁場型、四重極型、飛行時間型、イオントラップ型等のいずれの方法か選択でき、イオン化の方法は、電子イオン化法、化学イオン化法、脱離電子イオン化法、脱離化学イオン化法、高速原子衝撃法、エレクトロスプレーイオン化法、マトリックス支援レーザー脱離イオン化法等の公知の方法を用いることができる。安定同位体比を測定する試料の蒸留酒類は、液体の蒸留酒類を封管法等により試料を燃焼、熱分解する公知の手段を用いてガス化して質量分析に供することができるが、ガスクロマトグラフや液体クロマトグラフ等の精製装置、燃焼炉や熱分解炉や還元炉等の処理装置を組み合せた質量分析装置を用いて行うこともできる。また、蒸留酒類に含まれる炭素安定同位体比を測定する場合等は、試料の炭素をガス化して測定する有機元素分析計を質量分析装置の前段に接続した装置を用いて測定することもできる。このような、装置は、例えばガスクロマトグラフ／同位体比質量分析計（ＧＣ／ＩＲＭＳ）、元素分析／同位体比質量分析計（ＥＡ／ＩＲＭＳ）として、オンラインで測定する分析システムとして入手できる。 For the measurement of stable isotope ratio, a known isotope ratio analysis method can be used. According to a conventional method, a mass spectrometer is used for separation and detection according to the mass to charge ratio, and the abundance of each isotope is determined. Can be measured. The method of mass separation can be selected from magnetic field type, quadrupole type, time-of-flight type, ion trap type, etc., depending on the sample to be measured, and the ionization method can be selected from electron ionization method, chemical ionization method, Known methods such as a desorption electron ionization method, a desorption chemical ionization method, a fast atom bombardment method, an electrospray ionization method, and a matrix-assisted laser desorption ionization method can be used. Samples for measuring stable isotope ratios can be used for mass spectrometry by gasifying liquid distilled liquor using a known means for burning and pyrolyzing samples by a sealed tube method, etc. It is also possible to use a mass spectrometer that combines a purification apparatus such as a liquid chromatograph or a processing apparatus such as a combustion furnace, a pyrolysis furnace, or a reduction furnace. In addition, when measuring the carbon stable isotope ratio contained in distilled liquor, it can also be measured using an apparatus connected to the preceding stage of the mass spectrometer with an organic element analyzer that gasifies and measures the carbon of the sample. . Such an apparatus is available as an analysis system for measuring on-line, for example, as a gas chromatograph / isotope ratio mass spectrometer (GC / IRMS) or elemental analysis / isotope ratio mass spectrometer (EA / IRMS).
測定した試料における安定同位体比を、産地が既知である蒸留酒類又は種類が既知である蒸留酒類における安定同位体比と比較する工程は、測定した試料と産地又は種類が既知である蒸留酒類との安定同位体比の照合、又は測定した試料における安定同位体比について産地又は種類が既知である蒸留酒類における安定同位体比に対する統計学的判別により行うことができる。 The step of comparing the stable isotope ratio in the measured sample with the stable isotope ratio in a distilled liquor with a known place of origin or a known type of distilled liquor is the same as that of a distilled liquor with a known place of origin or type. The stable isotope ratio can be verified, or the stable isotope ratio in the measured sample can be determined by statistical discrimination with respect to the stable isotope ratio in distilled liquors whose origin or type is known.
産地が既知である蒸留酒類又は種類が既知である蒸留酒類における安定同位体比は、試料である蒸留酒類における安定同位体比を測定する工程と同様の工程を、産地又は種類が確認されている蒸留酒類について行うことにより測定することができる他、予め測定されている安定同位体比のデータベース等の数値情報を用いることができる。これらの産地又は種類が既知である蒸留酒類における安定同位体比は、判別しようとする産地毎又は種類毎に複数の試料について測定されていることが好ましく、平均値、中央値等の代表値を用いることができる。また、予め測定されている安定同位体比のデータベースは、安定同位体核種毎に、複数の判別しようとする産地・種類の群に分類されデータベース化されていることが好ましい。そのようなデータベースにおいては、判別しようとする産地・種類の各群間の安定同位体比同士が有意差を有していることを予め確認しておくことが好ましく、確認にはｔ検定や分散分析（analysis of variance，ＡＮＯＶＡ）を用いることができ、最小有意差法、Turkey法、Bonferroni法等の周知の多重比較方法のいずれかにより行うことができる。 The stable isotope ratio of distilled liquors with known origins or types of distilled liquors with known types is the same as the process for measuring stable isotope ratios with distilled alcoholic beverages as samples. In addition to being able to measure by performing on distilled liquors, numerical information such as a database of stable isotope ratios measured in advance can be used. It is preferable that the stable isotope ratio in distilled alcoholic beverages whose production area or type is known is measured for a plurality of samples for each production area or type to be discriminated, and representative values such as an average value and a median value are used. Can be used. Further, the database of stable isotope ratios measured in advance is preferably classified into a plurality of groups of production areas / types to be discriminated for each stable isotope nuclide. In such a database, it is preferable to confirm in advance that the stable isotope ratios between the groups of the production area / type to be identified have a significant difference. An analysis (analysis of variance, ANOVA) can be used, and can be performed by any of the well-known multiple comparison methods such as the least significant difference method, the Turkey method, and the Bonferroni method.
安定同位体比の比較は、例えば、産地の判別を行う場合は、複数試料の安定同位体比を測定し、産地の判別を行う試料蒸留酒類における安定同位体比と、産地が既知である蒸留酒類における安定同位体比の測定結果について照合し、有意差が認められない場合に、産地の判別を行う試料蒸留酒類と産地が既知である蒸留酒類の産地が同一であると判断することができる。種類の判別を行う場合も前記産地の判別を行う場合と同様に行うことができる。または、産地又は種類の判別を行う試料蒸留酒類が、産地又は種類が既知である蒸留酒類の産地又は種類毎に分類された各群に属するか否かを安定同位体比の類似度により統計学的に判別することにより行うことができる。統計学的な判別手法は、公知の手法から適切なものを用いればよく、Ｋ近傍法（K Nearest Neighbor，ＫＮＮ）によりユークリッド距離等の距離関数を選択して判別を行う、あるいは、データベースに基づいて判別関数を作成し、１〜３次元の散布図中に基準線又は面を設定することにより線形判別分析又は非線形判別分析を行うこともできる。このような判別手法としては、Fisherの線形判別関数を用いる方法、マハラノビスの汎距離に基づく非線形判別関数を用いる方法等がある。特に、試料蒸留酒類が複数の産地・複数の種類のいずれに属するかの判別を行う場合は、正準判別分析、ベイズ判別、ミニマックス基準による判別、ＳＩＭＣＡ（Soft Independent Modeling of Class Analogy）等により行うことができる。これらの方法は、適切に判別できるものを単独で用いてよいが、複数の方法で判別を行い得られた判別結果を組み合わせて照合してもよく、いずれの方法でも産地又は種類が同一であると判別された場合に産地又は種類が同一であると判断することができる。 For comparison of stable isotope ratios, for example, when discriminating the production area, measure the stable isotope ratio of multiple samples and determine the production area. Compared to the measurement results of stable isotope ratios in liquors, if there is no significant difference, it can be determined that the sample liquor used to determine the production area is the same as the production area of the distilled liquor whose production area is known . The determination of the type can be performed in the same manner as the determination of the production area. Alternatively, whether the sample distilled liquor for determining the production area or type belongs to each group classified by the production area or type of the distilled liquor whose production area or type is known is statistically determined based on the similarity of the stable isotope ratio. This can be done by discriminating automatically. As a statistical discrimination method, an appropriate one from known methods may be used, and discrimination is performed by selecting a distance function such as a Euclidean distance by the K Nearest Neighbor (KNN), or based on a database. A discriminant function can be created, and a linear discriminant analysis or a nonlinear discriminant analysis can be performed by setting a reference line or a surface in a 1 to 3 dimensional scatter diagram. As such discriminating methods, there are a method using Fisher's linear discriminant function, a method using a nonlinear discriminant function based on Mahalanobis' general distance, and the like. In particular, when discriminating whether sample distilled liquor belongs to multiple production areas or multiple types, canonical discriminant analysis, Bayes discrimination, discrimination based on minimax criteria, SIMCA (Soft Independent Modeling of Class Analogy), etc. It can be carried out. Any of these methods may be used alone, but may be collated by combining the discrimination results obtained by discriminating by a plurality of methods, and any method has the same place of origin or type. It can be determined that the production area or type is the same.
測定した試料における安定同位体比を、産地又は種類が既知である蒸留酒類における安定同位体比と比較する工程は、例えば、日本国内を産地とすることが既知である焼酎については、δ１８Ｏが−１５〜−１２の値であり且つδ１３Ｃが−２８〜−２５の値である場合に北海道又は東北地方又は長野県産の焼酎であると判別でき、δ１８Ｏが−９〜−６の値であり且つδ１３Ｃが−２９〜−２８の値である場合に沖縄県産の泡盛を含む焼酎であると判別でき、δ１８Ｏが−９〜−６の値であり且つδ１３Ｃが−２０〜−１６の値である場合に鹿児島県奄美市又は大島郡産の黒糖焼酎であると判別できる。 The step of comparing the stable isotope ratio in the measured sample with the stable isotope ratio in distilled liquors of known origin or type is, for example, δ 18 O for shochu that is known to originate in Japan. Is a value of −15 to −12 and δ 13 C is a value of −28 to −25, it can be determined that the shochu is produced in Hokkaido, Tohoku region or Nagano prefecture, and δ 18 O is −9 to − When the value is 6 and δ 13 C is a value of −29 to −28, it can be determined that the shochu contains Awamori produced in Okinawa Prefecture, δ 18 O is a value of −9 to −6, and δ When 13 C is a value of −20 to −16, it can be determined that it is brown sugar shochu produced in Amami City, Kagoshima Prefecture or Oshima-gun.
以下、実施例により本発明をより具体的に説明するが、本発明の技術的範囲はこれらの例示に限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, the technical scope of this invention is not limited to these illustrations.
１．蒸留酒類における割水と水の酸素安定同位体比との相関
蒸留酒への割水の酸素安定同位体比への影響を、米焼酎もろみを試料として安定同位体比質量分析計により測定した。常法に従って製造した米焼酎もろみを常圧蒸留し、その初留部分のみを採取し、アルコール分が５９．２％の原酒を得た。得られた原酒にアルコール分が、それぞれ５５％、４５％、３５％、２５％となるよう割水（加水）し、安定同位体比質量分析計を用いて水のδ１８Ｏを測定した。同様に、割水に使用した水のδ１８Ｏも測定した。その測定結果を図１に示す。図１に示されるとおり、蒸留酒への割水が多くアルコール分が低下するほど、δ１８Ｏの値が上昇し、割水に使用した水のδ１８Ｏに近づくことが確認された。
1. Correlation between split water and oxygen stable isotope ratio of water in distilled liquors The effect of split water on oxygen stable isotope ratio of distilled liquor was measured with a stable isotope ratio mass spectrometer using rice shochu moromi. Rice shochu moromi produced according to a conventional method was distilled at atmospheric pressure, and only the first fraction was collected to obtain a raw liquor having an alcohol content of 59.2%. The obtained raw liquor was split (hydrated) so that the alcohol content was 55%, 45%, 35%, and 25%, respectively, and δ 18 O of water was measured using a stable isotope ratio mass spectrometer. Similarly, δ 18 O of water used for water splitting was also measured. The measurement results are shown in FIG. As shown in FIG. 1, it was confirmed that the value of δ 18 O increased as the amount of water split into distilled liquor increased and the alcohol content decreased, approaching δ 18 O of water used for water splitting.
２．複数の産地・種類の蒸留酒類の安定同位体比
日本国内で製造された、産地が既知の蒸留酒を試料として、蒸留酒中の水の酸素安定同位体比、及びエタノールの炭素安定同対比を測定した。試料の蒸留酒は、アルコール分３０度以下のものを選択し、沖縄県産の泡盛を含む焼酎を１０種類、鹿児島県奄美市又は大島郡産の黒糖焼酎を５種類、北海道又は東北地方又は長野県産の焼酎を９種類含む、複数の産地の試料計８４種類について以下の測定に供した。
2. Stable isotope ratios of distilled liquors of multiple origins and types Using distilled liquors with known origins in Japan, the oxygen stable isotope ratios of water in distilled liquors and the carbon stable contrast of ethanol It was measured. Samples of distilled liquor are those with an alcohol content of 30 degrees or less, 10 types of shochu containing Awamori from Okinawa Prefecture, 5 types of brown sugar shochu from Amami City or Oshima-gun, Kagoshima Prefecture, Hokkaido or Tohoku Region or Nagano A total of 84 samples from a plurality of production areas, including 9 types of shochu produced in the prefecture, were subjected to the following measurements.
２−１．酸素安定同位体比の測定
蒸留酒試料の水の酸素安定同位体比を安定同位体比質量分析計により測定した。複数の産地の試料それぞれについて、試料瓶に試料蒸留酒３ｍＬと疎水性白金触媒（Hokko Beads）を入れ排気した後、密閉容器内でＣＯ２ガスとの間で１８℃で１２時間反応させて同位体交換を行った。次に、反応させたＣＯ２ガスにおける酸素安定同位体比（１８Ｏ／１６Ｏ）を安定同位体比質量分析計「ＤＥＬＴＡ ｐｌｕｓ ＸＬ」（Thermo Fisher Scientific社製）を用いて測定した。続いて安定同位体比質量分析計のDual Inletの片側にリファレンスガスを導入し、その反対側に反応させた試料ＣＯ２ガスをプログラムにより自動的に導入して質量分析を行った。質量分析は、リファレンスガスと試料ＣＯ２ガスを交互に６回測定した。得られた測定値に基づきδ１８Ｏを算出し、その平均値を試料の酸素安定同位体比（１８Ｏ／１６Ｏ）の値とした。この方法による測定誤差は、±０．０５‰であった。
2-1. Measurement of oxygen stable isotope ratio The oxygen stable isotope ratio of water of distilled liquor samples was measured with a stable isotope ratio mass spectrometer. For each sample from multiple localities, 3 mL of sample distilled liquor and hydrophobic platinum catalyst (Hokko Beads) were placed in a sample bottle and evacuated. Then, the sample was reacted with CO 2 gas at 18 ° C. for 12 hours in an airtight container. I changed my body. Next, the oxygen stable isotope ratio ( 18 O / 16 O) in the reacted CO 2 gas was measured using a stable isotope ratio mass spectrometer “DELTA plus XL” (manufactured by Thermo Fisher Scientific). Subsequently, a reference gas was introduced into one side of the Dual Inlet of the stable isotope ratio mass spectrometer, and a sample CO 2 gas reacted on the opposite side was automatically introduced by a program for mass analysis. In the mass spectrometry, the reference gas and the sample CO 2 gas were alternately measured 6 times. Based on the obtained measurement value, δ 18 O was calculated, and the average value was taken as the value of the oxygen stable isotope ratio ( 18 O / 16 O) of the sample. The measurement error by this method was ± 0.05 ‰.
２−２．炭素安定同位体比の測定
前記蒸留酒試料のエタノールの炭素安定同位体比を安定同位体比質量分析計により測定した。複数の産地の試料それぞれについて、錫コンテナに試料蒸留酒を封入し、燃焼型元素分析計「Flash 2000」（Thermo Fisher Scientific社製）の燃焼炉に落下させた。試料は、燃焼型元素分析計内の燃焼炉で、超高純度酸素雰囲気のもと錫の酸化熱を利用して温度１０００℃で燃焼・ガス化し、酸化触媒で完全に酸化させた。次に、生成したガスを６８０℃の条件で還元炉に導入し、余分なＯ２を除去した。続いて、生成したＨ２Ｏを過塩素酸マグネシウムで除去し、４５℃の条件で分離カラムでＣＯ２を分離した。分離したＣＯ２は、キャリアガスと共にインターフェースを通じて安定同位体質量分析計「ＤＥＬＴＡ Ｖ」（Thermo Fisher Scientific社製）に導入して質量分析を行い、炭素安定同位体比（１３Ｃ／１２Ｃ）を算出した。トレーサーで確認される測定誤差は測定値の０．３％であった。
2-2. Measurement of carbon stable isotope ratio The carbon stable isotope ratio of ethanol in the distilled liquor sample was measured by a stable isotope ratio mass spectrometer. For each sample from a plurality of production areas, sample distilled liquor was sealed in a tin container and dropped into a combustion furnace of a combustion element analyzer “Flash 2000” (manufactured by Thermo Fisher Scientific). The sample was combusted and gasified at a temperature of 1000 ° C. using an oxidation heat of tin in an ultrahigh purity oxygen atmosphere in a combustion furnace in a combustion element analyzer, and completely oxidized with an oxidation catalyst. Then, the generated gas was introduced into the reducing furnace under the condition of 680 ° C., to remove excess O 2. Subsequently, the produced H 2 O was removed with magnesium perchlorate, and CO 2 was separated with a separation column at 45 ° C. The separated CO 2 is introduced into a stable isotope mass spectrometer “DELTA V” (manufactured by Thermo Fisher Scientific) through an interface together with a carrier gas, mass analysis is performed, and a carbon stable isotope ratio ( 13 C / 12 C) is calculated. Calculated. The measurement error confirmed by the tracer was 0.3% of the measured value.
２−３．安定同位体比の測定結果
測定した複数の産地の試料蒸留酒の酸素安定同位体比（１８Ｏ／１６Ｏ）と炭素安定同位体比（１３Ｃ／１２Ｃ）のそれぞれから、前記数式に基づいてδ１８Ｏとδ１３Ｃを算出した。北海道又は東北地方又は長野県産の焼酎は、δ１８Ｏは−１５〜−１２の値を示したのに対し、沖縄県産の泡盛を含む焼酎、並びに鹿児島県奄美市又は大島郡産の黒糖焼酎は、δ１８Ｏは−９〜−６の値を示した。また、北海道又は東北地方又は長野県産の焼酎は、δ１３Ｃは−２８〜−２５の値を示し、沖縄県産の泡盛を含む焼酎は、δ１３Ｃは−２９〜−２８の値を示し、鹿児島県奄美市又は大島郡産の黒糖焼酎は、δ１３Ｃは−２０〜−１６の値を示した。測定した各試料のδ値についてδ１３Ｃを縦軸、δ１８Ｏを横軸としてプロットした散布図を図２に示す。図２に示されるとおり、各試料は産地毎に異なる分布を示し、さらに原料植物がＣ３植物であるかＣ４植物であるかによって明瞭な分布の差異を生じており、北海道又は東北地方又は長野県産の焼酎、沖縄県産の泡盛を含む焼酎、鹿児島県奄美市又は大島郡産の黒糖焼酎の間で、酸素・炭素安定同位体比の値に有意差が認められたことから、これらの蒸留酒類の産地・種類の判別が安定同位体比に基づいて行えることが確認された。
2-3. From each of the oxygen isotopic composition of the sample liquor of a plurality of origin measured results of measurement of
Claims (4)
The type of distilled alcoholic beverages to be identified is Awamori, which is the origin of Okinawa Prefecture, brown sugar shochu that is produced in Amami City, Kagoshima Prefecture or Oshima-gun, or shochu that is produced in Hokkaido, Tohoku, or Nagano Prefecture The method according to claim 2 .
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| JP5907521B2 (en) * | 2011-12-26 | 2016-04-26 | 独立行政法人酒類総合研究所 | Raw water source judgment method and raw water source judgment system |
| CN102967668B (en) * | 2012-11-20 | 2014-04-09 | 中国食品发酵工业研究院 | Method for identifying wine producing area based on stable isotope ratio |
| JP6176708B2 (en) * | 2013-05-15 | 2017-08-09 | 独立行政法人酒類総合研究所 | Method for determining the presence or absence of alcohol addition in alcoholic beverages |
| CN103675083B (en) * | 2013-11-12 | 2016-04-13 | 上海交通大学 | Stable isotope ratio is utilized to judge the method in the Chinese medicine Chinese bulbul place of production |
| JP6209133B2 (en) * | 2014-05-26 | 2017-10-04 | 日本電信電話株式会社 | Isotope ratio analysis system and analysis method |
| CN105067786B (en) * | 2014-11-03 | 2018-02-06 | 中国食品发酵工业研究院 | A kind of discrimination method of non-regenerative fruit juice |
| JP6557894B2 (en) * | 2015-01-28 | 2019-08-14 | 新潟県 | Sake identity identification method and sake identification method |
| JP6617880B2 (en) * | 2016-01-27 | 2019-12-11 | 独立行政法人酒類総合研究所 | Method for determining the presence or absence of citric acid addition in alcoholic beverages |
| JP7287502B2 (en) * | 2019-12-20 | 2023-06-06 | 日本電信電話株式会社 | Judgment system, collation device, and judgment method |
| CN111257403A (en) * | 2020-02-06 | 2020-06-09 | 中国食品发酵工业研究院有限公司 | Method for measuring stable hydrogen isotope ratio of pure acetic acid methyl site |
| CN111175368B (en) * | 2020-02-06 | 2023-10-31 | 中国食品发酵工业研究院有限公司 | Method for identifying addition of synthetic acetic acid in brewed vinegar |
| CN111257402A (en) * | 2020-02-06 | 2020-06-09 | 中国食品发酵工业研究院有限公司 | Method for identifying synthetic acetic acid in food additive glacial acetic acid |
| CN111505170A (en) * | 2020-06-04 | 2020-08-07 | 程铁辕 | Method for identifying authenticity of five-grain strong aromatic Chinese spirits |
| CN114689742A (en) * | 2022-03-05 | 2022-07-01 | 深圳职业技术学院 | Coffee bean stable isotope fractionation method and method for simultaneously identifying origin places of roasted and green coffee beans |
| CN115980167B (en) * | 2023-01-09 | 2023-12-01 | 广东省农业科学院农业质量标准与监测技术研究所 | Method for discriminating duck feces fragrance single-cluster tea harvesting season by stable isotope analysis technology and application |
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