TWI702396B - Method for rapid determination of fruit juice authenticity - Google Patents

Method for rapid determination of fruit juice authenticity Download PDF

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TWI702396B
TWI702396B TW106137674A TW106137674A TWI702396B TW I702396 B TWI702396 B TW I702396B TW 106137674 A TW106137674 A TW 106137674A TW 106137674 A TW106137674 A TW 106137674A TW I702396 B TWI702396 B TW I702396B
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juice
potassium
radioactivity
drink
fruit juice
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TW106137674A
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TW201918708A (en
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闕麗卿
林澤揚
崔秀煒
張源鑫
林旭陽
趙君行
黃蜂運
陳惠芳
吳秀梅
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衛生福利部食品藥物管理署
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Abstract

The invention provides a method for rapid determination of fruit juice authenticity. The method comprises the step of determining certain isotope in the juice. In some embodiments, the certain isotope is potassium-40 (K40 ). In some embodiments, the method further comprises the step of using certain species of juice standard as comparison.

Description

果汁真偽之快速鑑別方法Quick identification method of juice authenticity

本發明係關於鑑別果汁飲品真偽的領域。特定言之,本發明係關於一種利用偵測特定元素之同位素來鑑別果汁飲品真實性(Authenticity)或定量果汁飲品中天然果汁所佔含量的方法。The invention relates to the field of authenticating fruit juice drinks. In particular, the present invention relates to a method for identifying the authenticity of fruit juice drinks or quantifying the content of natural juice in fruit juice drinks by detecting isotopes of specific elements.

食品摻偽(Adulteration)事件近年來為國內及國際間備受重視的議題。據美國藥典(USP)食品摻偽資料庫的統計,在近年來的食品摻偽事件中,最常發生的項目包含橄欖油、牛奶、蜂蜜、番紅花、柳橙汁、咖啡與蘋果汁,上述項目佔總摻偽項目的50%以上。食品及飲品之摻偽以及如何確認食品的真實性已成為目前需因應解決的問題。 就定義而言,摻偽係指販售者為了經濟收益,在購買者不知情之狀況下,以不誠實之手段「添加(Addition)」非本質之成分,或「移除(Removal)」或「取代(Replacement)」原本食品/飲品內含之成分物質。摻偽的行為不僅違反法律關於食品標示的規定,也潛藏未經檢驗的替代摻偽物質造成大眾健康危害的疑慮。 隨著果汁飲品需求量的增加,果汁摻偽事件層出不窮,針對果汁摻偽的鑒別檢測技術成為飲料業及食品安全領域待解決的重要議題。常見的果汁摻偽方式包含加水稀釋、加糖、加酸、混摻低價水果果汁、混摻不同產地水果之果汁等。 目前在食品或飲品摻偽鑑別判定的常見檢測技術包含光譜法(Spectroscopy)、層析法(Chromatography)、同位素分析法(Isotopic analysis)、聚合酶鏈鎖反應法(Polymerase chain reaction;PCR)等。同位素分析主要是應用氫(H)、碳(C)、氮(N)、氧(O)等四個在生物體中最常見的元素皆有一對同位素如H2 /H1 、C13 /C12 、N15 /N14 及O18 /O16 ,這四組同位素的比值,可被運用作為食品/飲品摻假判別之依據。然而;特定同位素可用與其對應之摻偽方式之判定仍需諸多實驗與嘗試始能確定。 例如,對鮮乳及還原乳而言,從鮮乳中所純化的水之H2 /H1 與O18 /O16 的兩組比值相較於還原乳對照組的數值有統計上較高的趨勢;此外,甘蔗之蔗糖與玉米之果糖分子中的C13 同位素含量會較其他植物所合成糖之C13 同位素含量為高,可用以判定蜂蜜是否摻有蔗糖或玉米果糖。中華民國專利證書號I315742提及,可利用O18 /O16 之比值來判定果汁於製造時是否另外添加水,可用於辨別天然果汁及還原果汁,但I315742專利亦提及,使用此一技術進行鑑定時仍可能出現與實際情況不符的誤差。另一方面,若欲測定果汁的O18 /O16 比值,需要經過多種耗時的步驟(包含分離果汁中之水分、使經分離之水與二氧化碳進行長時間平衡、使用穩定同位素質譜儀測定平衡完成之二氧化碳等步驟),測定期間亦須考慮環境中的氧分子的影響;此外,H2 /H1 雖亦可用於鑑別果汁是否額外添加水,然而此測定方式則必須包含萃取的前處理步驟,以將樣品中之水份完全與其他成分諸如糖、酸、脂質及酒精等的有機物完全分離,始能進行測定(Giovanni Calderone and Claude Guillou; Food Chemistry, 106 (2008) 1399-1405)。I315742專利亦發展出使用聚合酶鏈鎖反應針對特定水果之目標基因進行檢測的方法;然而,該方法在加熱處理過程中,因多數果汁具有酸性,可能造成DNA的降解而不利於此偵測方式。 綜上所述,仍迫切需要建立步驟簡便、快速、準確且有效的針對果汁飲品摻偽檢測方法或是確認果汁飲品真實性的方法。Food adulteration incidents have been a topic of great concern both domestically and internationally in recent years. According to the statistics of the United States Pharmacopoeia (USP) Food Adulteration Database, in recent food adulteration incidents, the most frequently occurring items include olive oil, milk, honey, saffron, orange juice, coffee and apple juice. It accounts for more than 50% of the total adulteration items. The adulteration of food and beverages and how to confirm the authenticity of food has become a problem that needs to be resolved. As far as definition is concerned, adulteration means that the seller uses dishonest means to "add" non-essential ingredients, or "removal" or "removal" without the buyer's knowledge for economic gain. "Replacement" the ingredients contained in the original food/drink. The act of adulteration not only violates the law on food labeling, but also hides the doubt that uninspected alternative adulterated substances may cause harm to public health. With the increase in the demand for fruit juice drinks, fruit juice adulteration incidents have emerged one after another. The identification and detection technology for fruit juice adulteration has become an important issue to be resolved in the beverage industry and food safety fields. Common fruit juice adulteration methods include dilution with water, sugar, acid, low-priced fruit juice, and fruit juice from different origins. At present, common detection techniques used to identify adulteration in food or beverages include spectroscopy, chromatography, isotope analysis, and polymerase chain reaction (PCR). Isotope analysis mainly uses hydrogen (H), carbon (C), nitrogen (N), oxygen (O) and other four most common elements in organisms. There are a pair of isotopes such as H 2 /H 1 , C 13 /C 12 , N 15 /N 14 and O 18 /O 16 , the ratios of these four groups of isotopes can be used as the basis for judging food/drink adulteration. However, the determination of the specific isotope available and its corresponding adulteration method still requires many experiments and attempts to determine. For example, for fresh milk and reduced milk, the ratio of H 2 /H 1 and O 18 /O 16 of the purified water from fresh milk is statistically higher than that of the reduced milk control group. Trend; In addition, the C 13 isotope content in the sucrose of sugarcane and the fructose molecule of corn will be higher than the C 13 isotope content of sugar synthesized by other plants, which can be used to determine whether honey is mixed with sucrose or corn fructose. The Republic of China Patent Certificate No. I315742 mentions that the ratio of O 18 /O 16 can be used to determine whether the juice is made with additional water, which can be used to identify natural juices and reduce juices. However, the I315742 patent also mentions that this technology is used for Errors inconsistent with the actual situation may still occur during identification. On the other hand, if you want to determine the O 18 /O 16 ratio of fruit juice, you need to go through a variety of time-consuming steps (including separating the water in the juice, allowing the separated water and carbon dioxide to balance for a long time, and using a stable isotope mass spectrometer to determine the balance. To complete the carbon dioxide and other steps), the influence of oxygen molecules in the environment must also be considered during the measurement; in addition, although H 2 /H 1 can also be used to identify whether the juice is added with water, this measurement method must include the extraction pretreatment step , In order to completely separate the moisture in the sample from other organic substances such as sugar, acid, lipid and alcohol, the measurement can be performed (Giovanni Calderone and Claude Guillou; Food Chemistry, 106 (2008) 1399-1405). The I315742 patent also developed a method for detecting the target gene of a specific fruit using polymerase chain reaction; however, this method is not conducive to this detection method due to the acidity of most juices during the heating process. . In summary, there is still an urgent need to establish a simple, fast, accurate and effective method for detecting adulteration of fruit juice drinks or methods for confirming the authenticity of fruit juice drinks.

本文所揭示之內容係關於一種使用特定元素之同位素來鑑別果汁飲品真偽或真實性或定量果汁飲品中天然果汁所佔含量的方法。在一些態樣中,所述特定元素之同位素為鉀-40。 據此,本發明提供一種鑑別果汁飲品標示之真實性的方法,該方法包含使用天然放射性核種鉀-40放射活度以測定果汁飲品樣品中純果汁的純度,藉此判斷果汁飲品標示的真實性。本發明中所述鑑別果汁飲品真偽的方法可用於確認果汁飲品產品所標示的天然果汁含量百分比是否與真實狀況符合。其中所述果汁飲品真實性係指果汁飲品所標示的天然果汁含量百分比是否與其真實狀況符合。 本發明亦提供一種定量果汁飲品中天然果汁所佔含量的方法,該方法包含利用天然放射性核種鉀-40放射活度以測定果汁飲品樣品中純果汁所佔含量百分比。 本發明特定態樣中,前述方法中的果汁飲品包含天然果汁、天然蔬菜汁、濃縮果汁、濃縮蔬菜汁、還原果汁及還原蔬菜汁。在特定態樣中,所述果汁飲品為還原果汁或還原蔬菜汁。 本發明特定態樣中,前述鑑別果汁飲品真偽的方法或定量果汁飲品中天然果汁所佔含量的方法不需對果汁飲品進行樣品前處理之步驟。在一些態樣中,所述鑑別果汁飲品真偽或定量果汁飲品中天然果汁所佔含量的方法包含直接測定天然放射性核種鉀-40放射活度之步驟。 本發明特定態樣中,所述鑑別果汁飲品真偽的方法包含以下步驟:(a)測定果汁飲品樣品中天然放射性核種鉀-40放射活度,及(b)將(a)的結果與具對應純度之果汁飲品之標準品中之鉀-40放射活度進行比較;當(a)的結果在標準品範圍內則判斷為標示具真實性。 本發明特定態樣中,所述定量果汁飲品中天然果汁所佔含量的方法包含以下步驟:(a)測定果汁飲品樣品中天然放射性核種鉀-40放射活度,及(b)將(a)的結果與多個經不同倍率稀釋的果汁飲品之標準品之鉀-40放射活度比較,藉以定量該未知果汁飲品樣品中純果汁所佔含量百分比。 在特定態樣中,天然100%柳橙(丁)汁的鉀-40放射活度標準為約47 Bq/kg至約58 Bq/kg;在特定態樣中,天然100%柳橙(丁)汁的鉀-40放射活度標準為約53.5 Bq/kg。在特定態樣中,天然100%蘋果汁的鉀-40放射活度標準為約26 Bq/kg至約34 Bq/kg;在特定態樣中,天然100%蘋果汁的鉀-40放射活度標準為約26.3 Bq/kg。 在特定態樣中,前述標準品為一或多個經不同稀釋倍率稀釋的純果汁。在特定態樣中,前述標準品為一個純果汁標準品或一個經特定稀釋的果汁標準品。在特定態樣中,前述標準品為多個,其包含純果汁標準品及/或經特定稀釋的果汁標準品。 在特定態樣中,所述鑑別果汁飲品真偽或定量果汁飲品中天然果汁所佔含量的方法包含測定特性加馬射線(1461 keV)之量之步驟。 在特定態樣中,前述測定特性加馬射線之量之步驟的測定時間為約5,000秒至約100,000秒。 在特定態樣中,果汁飲品為柳橙(丁)汁且測定時間為約5,000秒至約100,000秒,或視情況為更長計測時間以達所需定量值之準確性參考。在特定態樣中,果汁飲品為蘋果汁且測定時間為約5,000秒至約100,000秒,或視情況為更長計測時間以達所需定量值之準確性參考。The content disclosed in this article is about a method of using isotopes of specific elements to identify the authenticity or authenticity of fruit juice drinks or to quantify the content of natural juice in fruit juice drinks. In some aspects, the isotope of the specific element is potassium-40. Accordingly, the present invention provides a method for identifying the authenticity of a juice drink label. The method includes using the natural radionuclide potassium-40 radioactivity to determine the purity of the pure juice in a juice drink sample, thereby judging the authenticity of the juice drink label . The method for identifying the authenticity of fruit juice drinks in the present invention can be used to confirm whether the percentage of the natural fruit juice content indicated on the fruit juice drinks product is consistent with the real situation. The authenticity of the juice drink refers to whether the percentage of the natural juice content indicated in the juice drink is consistent with its true condition. The present invention also provides a method for quantifying the content of natural fruit juice in a fruit juice beverage. The method comprises using the radioactivity of the natural radionuclide potassium-40 to determine the percentage of pure fruit juice in a fruit juice beverage sample. In a specific aspect of the present invention, the fruit juice drink in the aforementioned method includes natural fruit juice, natural vegetable juice, concentrated fruit juice, concentrated vegetable juice, reduced fruit juice, and reduced vegetable juice. In a specific aspect, the fruit juice drink is reduced fruit juice or reduced vegetable juice. In a specific aspect of the present invention, the aforementioned method for identifying the authenticity of a fruit juice beverage or a method for quantifying the content of natural fruit juice in a fruit juice beverage does not require the step of sample pre-processing on the fruit juice beverage. In some aspects, the method for identifying the authenticity of fruit juice drinks or quantifying the content of natural fruit juice in fruit juice drinks includes the step of directly determining the radioactivity of the natural radionuclide potassium-40. In a specific aspect of the present invention, the method for identifying the authenticity of fruit juice drinks includes the following steps: (a) determining the radioactivity of the natural radionuclide potassium-40 in the fruit juice drink sample, and (b) combining the result of (a) with Compare the potassium-40 radioactivity in the standard product of the juice drink with the corresponding purity; when the result of (a) is within the standard product range, the label is judged to be authentic. In a specific aspect of the present invention, the method for quantifying the content of natural fruit juice in a fruit juice beverage includes the following steps: (a) determining the radioactivity of the natural radionuclide potassium-40 in a fruit juice beverage sample, and (b) adding (a) The result is compared with the potassium-40 radioactivity of multiple standard juice drinks diluted with different magnifications to quantify the percentage of pure juice in the unknown juice drink sample. In a specific aspect, the potassium-40 radioactivity standard of natural 100% orange (diced) juice is about 47 Bq/kg to about 58 Bq/kg; in a specific aspect, natural 100% orange (diced) The potassium-40 radioactivity standard of juice is about 53.5 Bq/kg. In a specific aspect, the potassium-40 radioactivity standard of natural 100% apple juice is about 26 Bq/kg to about 34 Bq/kg; in a specific aspect, the potassium-40 radioactivity of natural 100% apple juice The standard is about 26.3 Bq/kg. In a specific aspect, the aforementioned standard product is one or more pure juices diluted with different dilution ratios. In a specific aspect, the aforementioned standard product is a pure juice standard product or a specific diluted juice standard product. In a specific aspect, there are a plurality of the aforementioned standard products, which include a pure fruit juice standard product and/or a specifically diluted fruit juice standard product. In a specific aspect, the method for identifying the authenticity of the juice drink or quantifying the content of the natural juice in the juice drink includes the step of determining the amount of characteristic plus horse radiation (1461 keV). In a specific aspect, the measurement time of the step of determining the amount of characteristic gamma rays is about 5,000 seconds to about 100,000 seconds. In a specific aspect, the fruit juice drink is orange (diced) juice and the measurement time is about 5,000 seconds to about 100,000 seconds, or a longer measurement time as the case may be, in order to achieve the accuracy reference of the required quantitative value. In a specific aspect, the fruit juice drink is apple juice and the measurement time is about 5,000 seconds to about 100,000 seconds, or as the case may be, the measurement time is longer to achieve the accuracy reference of the required quantitative value.

下文呈現本發明之簡單概述,提供對本發明基本的理解。此發明內容並非本發明之詳盡論述,且其並非意欲限制本發明之關鍵元素或描述本發明之範圍。除非另有定義,否則本文所用之所有技術及科學術語均具有與本發明所屬技術領域中具有通常知識者所瞭解相同之含義。應瞭解,以上一般描述及以下詳細描述僅為例示性及解釋性的且不限制所主張之任何主題。 在本文中,除非另外明確陳述,否則單數之使用包括複數。除非上下文另外清楚指定,否則如本說明書及隨附申請專利範圍中所使用之單數形式「一(a)」、「一(an)」及「該」亦包括複數個指示物。在本申請案中,除非另外陳述,否則「或」之使用意謂「及/或」。 本文所用之章節標題僅係為便於組織編排,不應理解為限制所述主題。出於任何目的,本申請案中所引用之所有文獻或部分文獻包括但不限於,專利、專利申請案、文章、書籍、手冊及論文,其以全文引用的方式併入本文中。 本文所用之術語「約」當用在數值前時指示該值可在合理範圍內變化,諸如所述值之±20%、±15%、±10%、±5%、±4%、±3%、±2%或±1%內。技藝人士當能夠瞭解此變化僅係合理反映誤差存在之真實情況。 如本文所用,術語「包含」或其語法變體意指本文中所描述的態樣包括所述要素,但不排除其他。「基本上由……組成」或其語法變體在用於界定本文中所描述的態樣時,不排除實質上不影響該態樣(諸如本發明的方法)之特徵的要素。「由……組成」或其語法變體意指排除未特別敍述之要素。上述用語的轉換所衍生的所有態樣皆在本發明之範疇內。舉例而言,當本發明所描述的方法包含步驟A、B及C時,「基本上由步驟A、B及C組成之方法」及「由A、B及C組成之方法」亦獨立地在被涵蓋在本發明之範疇內。 本文中所描述之方法主要係為提供一步驟簡便、快速、準確且有效的鑑別果汁飲品真實性或定量果汁飲品中天然果汁所佔含量的方法。現今技術雖可使用穩定同位素的比值對果汁飲品進行鑑定(例如依據O18 /O16 或H2 /H1 之比值確認樣品為天然果汁或還原果汁);然而上述方法仍有不適用於鑑定濃縮還原果汁之標示濃度是否與其實際狀況符合的問題。另一方面,前述穩定同位素方法皆係測定穩定同位素之比值,並未有利用單一同位素即可瞭解食品真實性的方法。相較之下,本發明提供利用鉀-40放射活度來鑑定食品的真實性的方法,並驚訝地發現鉀-40放射活度的參數確實可用於果汁飲品真實性之鑑定,且此方法並不需要測定使鉀-40與其他同位素的比值即可鑑定果汁飲品的真實性;且更發現此方法並不需繁複的樣品前處理步驟,且出乎意料之外的可用於經濃縮還原的果汁飲品真實性的鑑定。 本文所用之術語「果汁飲品」,係指由成熟果實直接榨出未經稀釋或發酵之純果汁飲品(亦稱為「天然果汁」)或是添加果汁成分之其他種類的飲品(例如:含有果汁成分的水、酒、風味水、氣泡飲料,或額外添加諸如糖或香料等其他成分之果汁),且該果汁添加量的多寡並未限制,亦可包含僅有水果風味但不含天然果汁成分的飲品。本文中所用之術語「果汁飲品」也包括由蔬菜經壓榨(或先經蒸、煮等過程再壓榨)且未經稀釋之純蔬菜汁(亦稱「天然蔬菜汁」),或添加天然蔬菜汁之如上述的其他種類的飲品。依據加工方式,本文所用使用的果汁飲品所含之果汁或蔬菜汁,可包含但不限於濃縮果汁、濃縮蔬菜汁、還原果汁、還原蔬菜汁、非還原果汁及非還原蔬菜汁。 本文所用之術語「100%果汁」或「純果汁」係指果汁飲品的可溶固型物成分完全來自於天然水果;水果濃縮汁經還原後的果汁在本文中亦可被稱為100%果汁或純果汁。 本文所用之術語「100%蔬菜汁」或「純蔬菜汁」係指蔬菜汁飲品的可溶固型物的成分完全來自於天然蔬菜;蔬菜濃縮汁經還原後的蔬菜汁在本文中亦可被稱為100%蔬菜汁或純蔬菜汁。 本文所用之術語「濃縮果汁」,是指由天然果汁經濃縮之濃縮汁,其可溶性固形物含量較天然果汁為高;通常不供為直接飲用。 本文所用之術語「濃縮蔬菜汁」,是指由天然蔬菜汁經濃縮之濃縮汁,其可溶性固形物含量較天然蔬菜汁為高;通常不供為直接飲用。 本文所用之術語「還原果汁」,是指將濃縮果汁稀釋還原,通常以其所含可溶性固形物來確認還原果汁產品的標準。還原果汁亦包含在還原過程中額外添加其他成分(例如維生素C等營養成分)的營養強化還原果汁。 本文所用之術語「還原蔬菜汁」,是指將濃縮蔬菜汁稀釋還原,通常以其所含可溶性固形物來確認還原蔬菜汁產品的標準。還原蔬菜汁亦包含在還原過程中額外添加其他成分(例如維生素C等營養成分)的營養強化還原蔬菜汁。 本文中所用之術語「直接測定」係指在針對果汁飲品試樣進行特定性質或參數的測試實驗時,不需要對果汁飲品樣品進行額外的樣品前處理的步驟。在一些態樣中,本發明之方法包含直接測定果汁飲品試樣中的天然放射性核種鉀-40放射活度的步驟。 本文中所用之術語「樣品前處理」係指在針對果汁飲品進行特定性質或參數的測試實驗前,為符合實驗原理或步驟的要求,須先針對樣品進行額外的處理;例如,萃取樣品中之水分、分離樣品中之固型物或雜質、分離樣品中的特定成分、對樣品進行熱處理、對樣品進行特定化學反應、對樣品進行純化等步驟。 本文中所用之術語「對應果汁飲品之標準品」係指若欲測定特定果汁飲品試樣的放射性同位素活度時,所需對應選擇的已知放射活度之標準品。例如,待測果汁飲品為蘋果汁時,對應果汁飲品的標準品可為已知特定同位素放射活度之蘋果汁或經不同倍率稀釋的蘋果汁。 本文所用之術語「經不同倍率稀釋」的果汁飲品標準品係指經適當稀釋的果汁飲品,可包含(但不限於)100%、95%、90%、85%、80%、75%、70%、65%、60%、55%、50%、45%、40%、35%、30%、25%、20%、15%、10%及5%等的果汁飲品。 本文中所用之「其他鑑別果汁飲品真偽的方法」之術語係指其他習知之可用於鑑別果汁飲品真偽的方法;例如:測定果汁飲品中之諸如O18 /O16 及/或H2 /H1 之穩定同位素之比值;傳統PCR或即時定量PCR(Real-time PCR);諸如紅外線光譜(IR)、紫外光光譜等的光譜技術;測定還原糖;液相層析串聯質譜儀;氣相層析串聯質譜儀等方法。 本文中所用之放射活度之「最小可偵測量」(Minimum Detectable Amount;MDA)係指依據檢體及計測條件之差異,儀器可測得的放射活度數值之下限;例如,在一般情況下,對於果汁飲品而言,MDA可小於5 貝克/公斤(Bq/kg)。在本文中,若未檢出特定核種之放射活度(例如鉀-40的放射活度),則在數據中會以「-」表示,即代表果汁飲品試樣的放射活度低於MDA。在本文中,檢體試樣之放射性分析加馬能譜分析之MDA依據下式進行評估:

Figure 02_image001
單位:活度/體積或活度/質量(Bq/L或Bq/kg) T:適當之空白試樣計數時間(分) B:適當之空白試樣的計數值,適宜空白試樣含合適物質與雜質(或干擾物質);化學處理程序、計測方法、計測時間及幾何形狀均與待分析之試樣相同。 E:待測核種的計數效率。 R:化學回收率。 V:試樣量,以體積或質量為單位表示。 在一方面,本發明提供一種鑑別果汁飲品標示之真實性的方法,該方法包含使用天然放射性核種鉀-40放射活度以測定果汁飲品樣品中純果汁的純度,藉此判斷果汁飲品標示的真實性。 在一些態樣中,所述鑑別果汁飲品真偽的方法可用於確認果汁飲品產品所標示的天然果汁含量百分比是否與真實狀況符合。其中所述果汁飲品真實性係指果汁飲品所標示的天然果汁含量百分比是否與其真實狀況符合。 在一些態樣中,所述測定果汁飲品中天然果汁所佔含量的方法可用於定量未知果汁飲品樣中天然果汁所佔含量百分比。 在一些態樣中,前述標方法中的果汁飲品包含天然果汁、天然蔬菜汁、濃縮果汁、濃縮蔬菜汁、還原果汁及還原蔬菜汁。在特定態樣中,所述果汁飲品為還原果汁或還原蔬菜汁。 本文中果汁飲品中所使用的蔬果的種類可包含但不限於水果類(諸如蕃茄、蘋果、葡萄柚、奇異果、芒果、鳳梨、西瓜、紅葡萄、白葡萄、蔓越莓、藍莓、黑覆盆子、紅覆盆子、楊梅(Babysberry)、柳橙(丁)(亦稱甜橙,包含椪柑、桶柑、蜜柑)、椰子、檸檬、哈蜜瓜、草莓、木瓜、釋迦、葡萄、榴槤、水梨、荔枝、龍眼、柚子、葡萄柚、橘子、金桔(柑)(Kumquat)、酪梨、桑椹、櫻桃、柿子、枇杷、香瓜、無花果、桃、李、番石榴、火龍果、萊姆、杏(apricot)、梅(Japanse apricot)、香蕉、楊桃、石榴、甘蔗);蔬菜類(諸如芹菜、蘆筍、小黃瓜、大黃瓜、南瓜、玉米、秋葵);豆類(諸如豌豆、菜豆、四季豆、大豆、毛豆、紅豆、綠豆);食用菌類(松茸菇草菇、秀珍菇、蘑菇、香菇、猴頭蘑、黑木耳、金針菇、杏鮑菇、口蘑、銀耳);在一些態樣中,所述蔬果的種類為柑橘類(Citrus)的水果(例如:柚、柑、橘、橙、檸檬、金桔)或是蘋果類的水果(例如:富士蘋果、青森蘋果、台灣蘋果、蜜蘋果、王林蘋果、青龍蘋果、華盛頓蘋果(五爪蘋果)、德國蘋果、煙台蘋果及英國蘋果)。 在一些態樣中,所述鑑別果汁飲品真偽或測定果汁飲品中天然果汁所佔含量的方法不包含或不需要對果汁飲品進行樣品前處理之步驟。 在一些態樣中,所述鑑別果汁飲品真偽或測定果汁飲品中天然果汁所佔含量可視情況包含對果汁飲品進行離心之步驟。在一些態樣中,該離心之步驟並不會顯著影響鉀-40放射活度的測定結果。 在一些態樣中,所述鑑別果汁飲品真偽的方法包含直接測定天然放射性核種鉀-40放射活度之步驟。 在一些態樣中,所述鑑別果汁飲品真偽的方法包含以下步驟:(a)測定果汁飲品樣品中天然放射性核種鉀-40放射活度,及(b)將(a)的結果與具對應純度之果汁飲品之標準品中之鉀-40放射活度進行比較;當(a)的結果在標準品範圍內則判斷為標示具真實性。 在一些態樣中,所述測定果汁飲品中天然果汁所佔含量的方法包含以下步驟:(a)測定果汁飲品樣品中天然放射性核種鉀-40放射活度,及(b)將(a)的結果與多個經不同倍率稀釋的果汁飲品之標準品之鉀-40放射活度比較,藉以定量該未知果汁飲品樣品中天然果汁所佔含量百分比。在一些態樣中,該(b)步驟包含任何諸如內插法、外插法、檢量線或標準曲線製作等習知用於定量方法中的步驟。 在特定態樣中,100%柳橙(丁)汁的鉀-40放射活度標準為約47 Bq/kg至約58 Bq/kg;在特定態樣中,100%柳橙(丁)汁的鉀-40放射活度標準為約53.5 Bq/kg。在特定態樣中,100%蘋果汁的鉀-40放射活度標準為約26 Bq/kg至約34 Bq/kg;在特定態樣中,100%蘋果汁的鉀-40放射活度標準為約26.3 Bq/kg。 在一些態樣中,前述標準品為一或多個經不同稀釋倍率稀釋的天然果汁。在一些態樣中,前述標準品為一個天然果汁標準品或一個經特定稀釋的果汁標準品。在一些態樣中,前述標準品為多個,其包含純果汁標準品及/或經特定稀釋的果汁標準品。在一些態樣中,前述「多個」標準品係指3、4、5、6、7、8、9或10個或更多個標準品。 在一些態樣中,所述鑑別果汁飲品真偽或測定果汁飲品中天然果汁所佔含量的方法包含測定特性加馬射線(1461 keV)之量之步驟。在特定態樣中,該測定包含透過高純鍺加馬偵檢儀之定量分析。 在一些態樣中,前述測定特性加馬射線之量之步驟的測定時間為約5,000秒至約100,000秒,或視情況調整該測定時間(例如:調整為更短或更長計測時間,較佳為更長計測時間)以達所需定量值之準確性參考。在一些態樣中,該測定時間為約6,000至約30,000秒、約7,000至約30,000秒、約8,000至約30,000秒、約9,000至約30,000秒、約10,000至約30,000秒、約11,000至約30,000秒、約12,000至約30,000秒、約13,000至約30,000秒、約14,000至約30,000秒、約15,000至約30,000秒、約16,000至約30,000秒、約17,000至約30,000秒、約18,000至約30,000秒、約19,000至約30,000秒、約20,000至約30,000秒、約20,000至約60,000秒、約21,000至約60,000秒、約22,000至約60,000秒、約23,000至約60,000秒、約24,000至約60,000秒、約25,000至約60,000秒、約26,000至約60,000秒、約27,000至約60,000秒、約28,000至約60,000秒、約29,000至約60,000、約10,000至約40,000秒、約10,000至約50,000秒、約10,000至約60,000秒、約10,000至約70,000秒、約10,000至約80,000秒、約10,000至約90,000秒或約10,000至約100,000秒。較佳地,該測定時間為約10,000至約30,000秒。 在一些態樣中,前述測定時間長短設定主要與試樣中鉀-40活度含量及欲得到定量值活度之不確定度(activity uncertainty)大小有關。例如,試樣中鉀-40活度越高,所需測定時間越短;測定時間越長,則可得到較低之不確定度。一般而言,不確定度為測得活度值之20%以內為可以接受;例如,以100%蘋果汁(如本文實例表6例示,其鉀-40活度值為約26-34 Bq/kg)為特定態樣進行鉀-40定量分析,其測定時間10,000秒可得到之不確定度皆為測得活度值之10%以內。若鉀-40活度小於10 Bq/kg時(例如果汁飲品為稀釋果汁態樣等),則視情況需拉長測定時間至30,000秒(此時,不確定度仍可維持在測得活度值之20%以內),或更長計測時間以達所需定量值之準確性參考。故在一些態樣中,本發明之方法包含視情況調整前述測定時間從而使不確定性落於可接受之範圍內。 在一些態樣中,其中果汁飲品為柳橙(丁)汁且測定時間為約5,000秒至約100,000秒,或更長計測時間以達所需定量值之準確性參考。在一些態樣中,果汁飲品為蘋果汁且測定時間為約5,000秒至約100,000秒,或更長計測時間以達所需定量值之準確性參考。 在一些態樣中,所述鑑別果汁飲品真偽或測定果汁飲品中天然果汁所佔含量的方法包含測定適當的空白組試樣作為背景值;在特定態樣中,所述適當的空白組試樣含有雜質或干擾物質,且其化學處理程序、計測方法、計測時間及幾何形狀均與待分析之果汁飲品試樣相同。 在一些態樣中,所述鑑別果汁飲品真偽或測定果汁飲品中天然果汁所佔含量的方法包含依據果汁飲品的體積及型態,選擇適當大小的幾何馬林計測容器(Marinelli beaker)或可適當盛裝及包覆果汁飲品試樣的容器;在特定態樣中,所述馬林計測容器的體積為1公升及125毫升、或其它所需介於前述二者體積之計測容器。在一些態樣中,所述馬林計測容器的體積為125毫升、150毫升、175毫升、200毫升、250毫升、300毫升、400毫升、500毫升、600毫升、700毫升、800毫升或900毫升。在一些態樣中,所述鑑別果汁飲品真偽或測定果汁飲品中天然果汁所佔含量的方法包含對置於容器中的果汁飲品試樣秤重的步驟。 在一些態樣中,所述鑑別果汁飲品真偽或測定果汁飲品中天然果汁所佔含量的方法包含使用加馬計測系統偵測放射性核種的放射活度;在特定態樣中,所述加馬計測系統包含高純鍺偵檢器(High Purity Germanium Detector)、多頻道分析儀(Multi-channel Pulse-height Analyzer)及諸如類比數位轉換器、分析軟體及個人電腦的電子裝置。 在一些態樣中,果汁飲品試樣經由加馬計測系統進行分析的分析時間需視純鍺偵檢器相對效率、檢體重量等而訂,且可依據試樣的組成成份及特性進行調整。 在一些態樣中,本文所描述的鑑別果汁飲品真偽或測定果汁飲品中天然果汁所佔含量的方法的步驟,可額外包含參考或比較一或多種其他鑑別果汁飲品真偽或測定果汁飲品成分含量的方法的結果的步驟。實例 實例 1 鉀-40的檢測方法 本文中之實例之測定方法係參照下述檢測方法進行: 測試檢體:果汁飲品(天然果汁或人工合成果汁)。 測試儀器:加馬計測系統,其包含高純鍺偵檢器(HPGe;Model GC3020 and GC4020,Canberra,美國)、多頻道脈高分析儀(System 35 Plus,Canberra,美國)及電子裝置。 分析軟體:Genie 2000加馬能譜分析軟體(Canberra,美國) 計測方式:依果汁飲品檢體不同之體積及形態,選擇合適大小之幾何馬林計測容器(1公升或125毫升),將果汁飲品檢體盛裝或經適當包覆並進行秤重,再置於加馬計測系統中,以多頻道脈高分析儀計測,計測時間依純鍺偵檢器相對效率、檢體重量等而訂,另依據檢體組成成份及特性等做計測時間之調整。天然放射性核種鉀-40放射活度,可依其釋出之特性加馬射線(1461 keV)而定量。 計測結果:可定量測得檢體中鉀-40之放射活度值(貝克/公斤;Bq/kg),該值常以「平均值±標準差」表示。若未檢出鉀-40活度,則報告數據以「-」表示,代表該檢體之鉀-40放射活度低於MDA(對於果汁飲品,MDA一般可小於5 Bq/kg),但仍視檢體及計測條件不同略有差異。實例 2 鮮榨柳橙(丁)汁的鉀-40的活度分析 自包含傳統市場、超級市場及大賣場(通化市場、信義市場、昆陽街騎樓攤販、家樂福、永春市場、信義市場、頂好及大潤發)等的不同來源取得不同產地(台灣及美國)的新鮮柳橙(丁)。將新鮮柳橙以壓榨柳橙果肉的方式取得新鮮柳橙原汁。每種柳橙至少取得1公升的新鮮柳橙原汁。依照實例1所述的方法,將不同來源及品種的1公斤新鮮柳橙原汁(檢體編號O1至O9)置於1公升馬林計測容器中,再置於加馬計測系統中,以多頻道脈高分析儀計測,計測時間為10,000秒,以測定鉀-40活度(Bq/kg)。結果列如下表1。由實驗結果可知,檢體編號O1至O9鮮榨柳橙(丁)汁之鉀-40活度落於相近的數值範圍內。
Figure 106137674-A0304-0001
實例 3 經不同稀釋倍率進行稀釋的鮮榨柳橙(丁)汁的鉀-40的活度分析 將購自永春愛買超市之柳橙經榨汁離心處理後以阻抗為18.2MΩ.cm之超純水進行不同倍率的稀釋,得到100%(未稀釋)、50%、25%、10%及5%濃度的經稀釋柳橙(丁)汁。依照實例2所述的方法,測定經不同稀釋倍率稀釋的柳橙(丁)汁(檢體編號O10至O14)的鉀-40活度(Bq/kg)。結果列如下表2。由實驗結果可知,檢體編號O10至O14的經不同稀釋倍率稀釋的柳橙(丁)汁的鉀-40活度係對應與稀釋倍率變化;且經稀釋後的柳橙(丁)汁檢體的鉀-40活度較低。此實驗結果顯示鉀-40活度可有效地用於鑑別果汁飲品(例如柳橙汁)的真偽或測定果汁飲品中天然果汁所佔含量,並且可利用此方法確認果汁飲品產品的標示與其實質內容物是否相符。
Figure 106137674-A0304-0002
實例 4 市售柳橙(丁)汁的鉀-40的活度分析 自不同來源取得市售果汁飲品,包含標示為100%之純柳橙汁(鮮榨或還原果汁)(檢體編號O15至O23)、標示含有10-20%柳橙原汁之柳橙汁飲品(檢體編號O24至O30)及標示不含柳橙原汁(即,0%)的柳橙風味飲品(檢體編號O31及O32)。依據前述實驗方式,取不同來源的1公斤市售柳橙汁飲品,測定其鉀-40活度(Bq/kg)。結果列如下表3。本結果之解讀並不欲受任何理論的限制。其中參照O15至O23的標示為100%之純柳橙汁的實驗結果,發明人驚訝的發現,加工過程為濃縮還原或鮮榨方式,並未顯著影響鉀-40的活度。此外,實質上不含有柳橙(丁)成分之汽水或氣泡水並未被偵測到鉀-40的活度(參照檢體O31及32),此結果相較於現有檢測方式(例如:測定O18 /O16 或H2 /H1 )確實產生未預期的有利的效果。
Figure 106137674-A0304-0003
註:符號「-」代表該放射活度小於最小可偵測量(MDA)。實例 5 鮮榨蘋果汁的鉀-40的活度分析 取得不同產地(日本、法國、智利、美國及紐西蘭)的新鮮蘋果。將新鮮蘋果以壓榨蘋果果肉的方式取得新鮮蘋果原汁。每種蘋果至少取得1公升的新鮮蘋果原汁。依照實例1所述的方法,將不同來源及品種的1公斤新鮮蘋果原汁(檢體編號A1至A5)置於1公升馬林計測容器中,再置於加馬計測系統中,以多頻道脈高分析儀計測,計測時間為10,000秒,以測定鉀-40活度(Bq/kg)。結果列如下表4。由實驗結果可知,檢體編號A1至A5鮮榨蘋果汁之鉀-40活度落於相近的數值範圍內。
Figure 106137674-A0304-0004
實例 6 經不同稀釋倍率進行稀釋的鮮榨蘋果汁的鉀-40的活度分析 承實例5,將檢體編號為A5(紐西蘭富士蘋果)的鮮榨蘋果汁以阻抗為18.2MΩ.cm之超純水進行不同倍率的稀釋,得到100%(未稀釋)、50%、25%、10%及5%濃度的經稀釋蘋果汁。依照實例2所述的方法,測定經不同稀釋倍率稀釋的蘋果汁(檢體編號A5至A9)的鉀-40活度(Bq/kg)。結果列如下表5。由實驗結果可知,檢體編號A5至A9的經不同稀釋倍率稀釋的蘋果汁的鉀-40活度係對應與稀釋倍率變化;且經稀釋後的蘋果汁檢體的鉀-40活度較低。此實驗結果顯示鉀-40活度可有效地用於鑑別果汁飲品(例如蘋果汁)的真偽或測定果汁飲品中天然果汁所佔含量,並且可利用此方法確認果汁飲品產品的標示與其實質內容物是否相符。 表5:鮮榨蘋果不同稀釋濃度鉀40活度分析
Figure 106137674-A0304-0005
實例 7 市售蘋果汁的鉀-40的活度分析 自不同來源取得市售果汁飲品,包含標示為100%之純蘋果汁(標示還原者表示還原果汁)(檢體編號A10至A17)、標示含有10-20%蘋果原汁之蘋果汁飲品(檢體編號A18及A19)及標示蘋果原汁含量小於10%的蘋果西打(檢體編號A20)。依據前述實驗方式,取不同來源的1公斤市售蘋果汁飲品,測定其鉀-40活度(Bq/kg)。結果列如下表6。本結果之解讀並不欲受任何理論的限制。其中參照A10至A17的標示為100%之純蘋果汁的實驗結果,發明人驚訝的發現,加工過程為濃縮還原或鮮榨方式,並未顯著影響鉀-40的活度。此外,標示蘋果原汁含量小於10%的蘋果西打並未被偵測到鉀-40的活度(參照檢體A20),此結果相較於現有檢測方式(例如:測定O18 /O16 或H2 /H1 )確實產生未預期的有利的效果。 表6:市售蘋果汁之鉀-40活度分析
Figure 106137674-A0304-0006
註:符號“-”代表該放射活度小於最小可偵測量(MDA)。The following presents a brief summary of the present invention to provide a basic understanding of the present invention. This summary is not an exhaustive discussion of the invention, and it is not intended to limit the key elements of the invention or describe the scope of the invention. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as understood by those with ordinary knowledge in the technical field to which the present invention belongs. It should be understood that the above general description and the following detailed description are only illustrative and explanatory and do not limit any claimed subject matter. In this article, unless expressly stated otherwise, the use of the singular includes the plural. Unless the context clearly dictates otherwise, the singular forms "一(a)", "一(an)" and "the" used in the scope of this specification and the appended application also include plural indicators. In this application, unless stated otherwise, the use of "or" means "and/or". The chapter headings used in this article are only for the convenience of organization and should not be construed as limiting the subject matter. For any purpose, all or part of the documents cited in this application include, but are not limited to, patents, patent applications, articles, books, manuals, and theses, which are incorporated herein by reference in their entirety. As used herein, the term "about" when used in front of a value indicates that the value can vary within a reasonable range, such as ±20%, ±15%, ±10%, ±5%, ±4%, ±3 of the stated value %, ±2% or within ±1%. The artisan should be able to understand that this change is only a reasonable reflection of the true situation of the error. As used herein, the term "comprises" or its grammatical variants means that the aspects described herein include the elements, but do not exclude others. When "essentially composed of" or its grammatical variants are used to define the aspect described herein, it does not exclude elements that do not substantially affect the characteristics of the aspect (such as the method of the present invention). "Consisting of" or its grammatical variants means excluding elements that are not specifically stated. All aspects derived from the conversion of the above terms are within the scope of the present invention. For example, when the method described in the present invention includes steps A, B and C, the "method consisting essentially of steps A, B and C" and "the method consisting of A, B and C" are also independently It is covered within the scope of the present invention. The method described in this article is mainly to provide a simple, fast, accurate and effective method for identifying the authenticity of fruit juice drinks or quantifying the content of natural juice in fruit juice drinks. Although the current technology can use the ratio of stable isotope to identify juice drinks (for example, confirm the sample is natural juice or reduced juice based on the ratio of O 18 /O 16 or H 2 /H 1 ); however, the above method is still not suitable for identification of concentrated juice. Restore the problem of whether the labeled concentration of juice is consistent with the actual situation. On the other hand, the aforementioned stable isotope methods all measure the ratio of stable isotope, and there is no method that uses a single isotope to understand the authenticity of food. In contrast, the present invention provides a method of using potassium-40 radioactivity to identify the authenticity of foods, and surprisingly found that the parameters of potassium-40 radioactivity can indeed be used to identify the authenticity of juice drinks, and this method does not It is not necessary to determine the ratio of potassium-40 to other isotopes to identify the authenticity of fruit juice drinks; and it is found that this method does not require complicated sample pretreatment steps, and unexpectedly can be used for concentrated and reduced fruit juices Identification of the authenticity of the drink. As used herein, the term "juice drink" refers to a pure juice drink (also known as "natural juice") that is directly squeezed from mature fruits without dilution or fermentation (also called "natural juice") or other types of drinks with added juice ingredients (for example: containing juice Ingredients of water, wine, flavored water, sparkling beverages, or juice with additional ingredients such as sugar or spices), and the amount of the juice added is not limited, and it may contain only fruit flavors but no natural juice ingredients Drinks. The term "juice drink" used in this article also includes pure vegetable juice (also known as "natural vegetable juice") that has been squeezed (or steamed, boiled, etc.) and undiluted, or added with natural vegetable juice The same as the other types of drinks mentioned above. According to the processing method, the fruit juice or vegetable juice contained in the fruit juice drink used herein may include, but is not limited to, concentrated fruit juice, concentrated vegetable juice, reduced fruit juice, reduced vegetable juice, non-reduced fruit juice and non-reduced vegetable juice. The term "100% juice" or "pure juice" as used herein means that the soluble solids of fruit juice drinks are entirely derived from natural fruits; the reduced fruit juice concentrate can also be referred to as 100% juice in this article Or pure juice. As used herein, the term "100% vegetable juice" or "pure vegetable juice" means that the soluble solids of the vegetable juice drink are entirely derived from natural vegetables; the vegetable juice after reduction of the vegetable concentrate can also be used in this article. It is called 100% vegetable juice or pure vegetable juice. The term "concentrated fruit juice" as used herein refers to a concentrated juice that is concentrated from natural fruit juice, and its soluble solid content is higher than that of natural fruit juice; it is usually not for direct drinking. The term "concentrated vegetable juice" as used herein refers to a concentrated juice that is concentrated from natural vegetable juice, and its soluble solid content is higher than that of natural vegetable juice; it is usually not for direct drinking. The term "reduced fruit juice" as used herein refers to the dilution and reduction of concentrated fruit juice, and the soluble solids contained in it are usually used to confirm the standard of reduced fruit juice products. Reduced fruit juice also includes nutritionally fortified reduced fruit juice with additional ingredients (such as vitamin C and other nutrients) added during the reduction process. The term "reduced vegetable juice" as used herein refers to the dilution and reduction of concentrated vegetable juice, and the soluble solid content is usually used to confirm the standard of reduced vegetable juice products. Reduced vegetable juice also includes nutritionally fortified reduced vegetable juice with additional ingredients (such as vitamin C and other nutrients) added during the reduction process. The term "direct determination" as used herein refers to a step that does not require additional sample pretreatment for juice drink samples when testing specific properties or parameters for juice drink samples. In some aspects, the method of the present invention includes the step of directly determining the radioactivity of the natural radionuclide potassium-40 in the juice drink sample. The term "sample pretreatment" as used in this article refers to the need to perform additional treatment on the sample before the test experiment of specific properties or parameters is carried out on the juice beverage, in order to meet the requirements of the experimental principle or procedure; for example, the extraction of the sample Moisture, separation of solids or impurities in the sample, separation of specific components in the sample, heat treatment of the sample, specific chemical reaction of the sample, and purification of the sample. The term "corresponding to fruit juice drink standard" as used herein refers to the selected standard with known radioactivity that needs to be selected when the radioisotope activity of a specific juice drink sample is to be determined. For example, when the juice drink to be tested is apple juice, the standard product corresponding to the juice drink can be apple juice with known radioactivity of a specific isotope or apple juice diluted with different magnifications. As used herein, the term "diluted at different times" refers to the juice drink standard product that has been properly diluted, which can include (but is not limited to) 100%, 95%, 90%, 85%, 80%, 75%, 70 %, 65%, 60%, 55%, 50%, 45%, 40%, 35%, 30%, 25%, 20%, 15%, 10% and 5% juice drinks. The term "other methods for authenticating juice drinks" as used herein refers to other conventional methods that can be used to identify the authenticity of juice drinks; for example, the determination of O 18 /O 16 and/or H 2 / in juice drinks The ratio of stable isotopes of H 1 ; traditional PCR or real-time PCR; spectroscopic techniques such as infrared spectroscopy (IR) and ultraviolet spectroscopy; determination of reducing sugars; liquid chromatography tandem mass spectrometer; gas phase Chromatography tandem mass spectrometer and other methods. The "Minimum Detectable Amount" (MDA) of radioactivity used in this article refers to the lower limit of the radioactivity value that can be measured by the instrument based on the difference between the specimen and measurement conditions; for example, in general For fruit juice drinks, MDA can be less than 5 Bq/kg (Bq/kg). In this article, if the radioactivity of a specific nucleus is not detected (for example, the radioactivity of potassium-40), it will be indicated by "-" in the data, which means that the radioactivity of the juice drink sample is lower than MDA. In this article, the radioactivity analysis of the specimen sample and the MDA of the horse energy spectrum analysis are evaluated according to the following formula:
Figure 02_image001
Unit: activity/volume or activity/mass (Bq/L or Bq/kg) T: appropriate count time of blank sample (minutes) B: appropriate count value of blank sample, suitable blank sample contains appropriate substance And impurities (or interfering substances); chemical treatment procedures, measurement methods, measurement time and geometry are the same as the samples to be analyzed. E: The counting efficiency of the nucleus to be tested. R: Chemical recovery rate. V: Sample size, expressed in units of volume or mass. In one aspect, the present invention provides a method for identifying the authenticity of a juice drink label, the method comprising using the natural radionuclide potassium-40 radioactivity to determine the purity of pure juice in a juice drink sample, thereby determining the authenticity of the juice drink label Sex. In some aspects, the method for identifying the authenticity of a fruit juice drink can be used to confirm whether the percentage of the natural juice content indicated on the fruit juice drink product is consistent with the real situation. The authenticity of the juice drink refers to whether the percentage of the natural juice content indicated in the juice drink is consistent with its true condition. In some aspects, the method for determining the content of natural juice in a fruit juice drink can be used to quantify the percentage of natural juice in an unknown juice drink sample. In some aspects, the fruit juice drink in the aforementioned labeling method includes natural fruit juice, natural vegetable juice, concentrated fruit juice, concentrated vegetable juice, reduced fruit juice, and reduced vegetable juice. In a specific aspect, the fruit juice drink is reduced fruit juice or reduced vegetable juice. The types of fruits and vegetables used in the juice drinks herein can include, but are not limited to, fruits (such as tomatoes, apples, grapefruit, kiwi, mango, pineapple, watermelon, red grapes, white grapes, cranberries, blueberries, blackberries). Pot, red raspberry, bayberry (Babysberry), orange (diced) (also known as sweet orange, including ponkan, barrel mandarin, tangerine), coconut, lemon, cantaloupe, strawberry, papaya, custard apple, grape, durian, Pear, lychee, longan, grapefruit, grapefruit, orange, kumquat (Kumquat), avocado, mulberry, cherry, persimmon, loquat, cantaloupe, fig, peach, plum, guava, dragon fruit, lime, Apricot (apricot), plum (Japanse apricot), banana, star fruit, pomegranate, sugar cane); vegetables (such as celery, asparagus, cucumber, cucumber, pumpkin, corn, okra); beans (such as peas, kidney beans, four seasons) Beans, soybeans, edamame, red beans, mung beans); edible fungi (matsutake mushrooms, straw mushrooms, mushrooms, shiitake mushrooms, hericium erinaceus, black fungus, enoki mushroom, eryngii mushroom, tricholoma, white fungus); in some forms, The types of fruits and vegetables are Citrus fruits (for example: pomelo, tangerine, tangerine, orange, lemon, kumquat) or apple fruits (for example: Fuji apple, Aomori apple, Taiwan apple, honey apple, king Lin apple, Qinglong apple, Washington apple (five-claw apple), German apple, Yantai apple and British apple). In some aspects, the method for identifying the authenticity of the juice drink or determining the content of the natural juice in the juice drink does not include or does not require the step of pre-processing the juice drink. In some aspects, identifying the authenticity of the juice drink or determining the content of natural juice in the juice drink may include the step of centrifuging the juice drink. In some aspects, the centrifugation step does not significantly affect the measurement results of potassium-40 radioactivity. In some aspects, the method for identifying the authenticity of fruit juice drinks includes the step of directly determining the radioactivity of the natural radioactive species potassium-40. In some aspects, the method for identifying the authenticity of fruit juice drinks includes the following steps: (a) determining the radioactivity of the natural radionuclide potassium-40 in the fruit juice drink sample, and (b) comparing the result of (a) with the corresponding Compare the potassium-40 radioactivity in the standard product of the pure juice drink; when the result of (a) is within the range of the standard product, the label is judged to be authentic. In some aspects, the method for determining the content of natural fruit juice in a fruit juice drink includes the following steps: (a) determining the radioactivity of the natural radionuclide potassium-40 in a fruit juice drink sample, and (b) combining (a) The result is compared with the potassium-40 radioactivity of multiple standard juice drinks diluted with different magnifications to quantify the percentage of natural juice in the unknown juice drink sample. In some aspects, the step (b) includes any steps conventionally used in quantitative methods such as interpolation, extrapolation, calibration curve or standard curve preparation. In a specific aspect, the potassium-40 radioactivity standard of 100% orange (diced) juice is about 47 Bq/kg to about 58 Bq/kg; in a specific aspect, the standard of 100% orange (diced) juice The standard of potassium-40 radioactivity is about 53.5 Bq/kg. In a specific aspect, the potassium-40 radioactivity standard of 100% apple juice is about 26 Bq/kg to about 34 Bq/kg; in a specific aspect, the potassium-40 radioactivity standard of 100% apple juice is About 26.3 Bq/kg. In some aspects, the aforementioned standard product is one or more natural juices diluted with different dilution ratios. In some aspects, the aforementioned standard is a natural fruit juice standard or a specially diluted fruit juice standard. In some aspects, there are a plurality of the aforementioned standard products, which include a pure fruit juice standard product and/or a specific diluted fruit juice standard product. In some aspects, the aforementioned "multiple" standard products refer to 3, 4, 5, 6, 7, 8, 9, or 10 or more standard products. In some aspects, the method for identifying the authenticity of the juice drink or determining the content of natural juice in the juice drink includes the step of determining the amount of characteristic plus horse radiation (1461 keV). In a specific aspect, the measurement includes a quantitative analysis by a high-purity germanium gama detector. In some aspects, the measurement time of the step of determining the amount of characteristic gamma rays is about 5,000 seconds to about 100,000 seconds, or the measurement time may be adjusted as appropriate (for example, adjusted to a shorter or longer measurement time, preferably For longer measurement time) in order to achieve the accuracy of the required quantitative value. In some aspects, the measurement time is about 6,000 to about 30,000 seconds, about 7,000 to about 30,000 seconds, about 8,000 to about 30,000 seconds, about 9,000 to about 30,000 seconds, about 10,000 to about 30,000 seconds, about 11,000 to about 30,000 Seconds, about 12,000 to about 30,000 seconds, about 13,000 to about 30,000 seconds, about 14,000 to about 30,000 seconds, about 15,000 to about 30,000 seconds, about 16,000 to about 30,000 seconds, about 17,000 to about 30,000 seconds, about 18,000 to about 30,000 seconds , About 19,000 to about 30,000 seconds, about 20,000 to about 30,000 seconds, about 20,000 to about 60,000 seconds, about 21,000 to about 60,000 seconds, about 22,000 to about 60,000 seconds, about 23,000 to about 60,000 seconds, about 24,000 to about 60,000 seconds, About 25,000 to about 60,000 seconds, about 26,000 to about 60,000 seconds, about 27,000 to about 60,000 seconds, about 28,000 to about 60,000 seconds, about 29,000 to about 60,000, about 10,000 to about 40,000 seconds, about 10,000 to about 50,000 seconds, about 10,000 To about 60,000 seconds, about 10,000 to about 70,000 seconds, about 10,000 to about 80,000 seconds, about 10,000 to about 90,000 seconds, or about 10,000 to about 100,000 seconds. Preferably, the measurement time is about 10,000 to about 30,000 seconds. In some aspects, the aforementioned determination time length setting is mainly related to the activity content of potassium-40 in the sample and the activity uncertainty of the desired quantitative value. For example, the higher the activity of potassium-40 in the sample, the shorter the required measurement time; the longer the measurement time, the lower the uncertainty can be obtained. Generally speaking, it is acceptable for the uncertainty to be within 20% of the measured activity value; for example, with 100% apple juice (as shown in Table 6 of the example herein, the potassium-40 activity value is about 26-34 Bq/ kg) is the quantitative analysis of potassium-40 for a specific sample, and the uncertainty that can be obtained at a measurement time of 10,000 seconds is within 10% of the measured activity value. If the potassium-40 activity is less than 10 Bq/kg (for example, the juice drink is a diluted juice state, etc.), the measurement time must be extended to 30,000 seconds depending on the situation (at this time, the uncertainty can still be maintained at the measured activity Within 20% of the value), or longer measurement time to achieve the accuracy reference of the required quantitative value. Therefore, in some aspects, the method of the present invention includes adjusting the aforementioned measurement time as appropriate so that the uncertainty falls within an acceptable range. In some aspects, the fruit juice drink is orange (diced) juice and the measurement time is about 5,000 seconds to about 100,000 seconds, or a longer measurement time to achieve the accuracy reference of the required quantitative value. In some aspects, the fruit juice drink is apple juice and the measurement time is about 5,000 seconds to about 100,000 seconds, or a longer measurement time to achieve the required quantitative value accuracy reference. In some aspects, the method for identifying the authenticity of the juice drink or determining the content of natural juice in the juice drink includes determining an appropriate blank group sample as a background value; in a specific aspect, the appropriate blank group test The sample contains impurities or interfering substances, and its chemical processing procedure, measurement method, measurement time and geometry are the same as the juice drink sample to be analyzed. In some aspects, the method for identifying the authenticity of the juice drink or determining the content of the natural juice in the juice drink includes selecting an appropriate size geometric Marin measuring container (Marinelli beaker) or a suitable size according to the volume and type of the juice drink. Suitable containers for holding and covering fruit juice beverage samples; in a specific aspect, the volume of the Marlin measuring container is 1 liter and 125 milliliters, or other measuring containers that require a volume between the two. In some aspects, the volume of the Marin measurement container is 125 ml, 150 ml, 175 ml, 200 ml, 250 ml, 300 ml, 400 ml, 500 ml, 600 ml, 700 ml, 800 ml or 900 ml. . In some aspects, the method for identifying the authenticity of a juice drink or determining the content of natural juice in the juice drink includes the step of weighing a juice drink sample placed in a container. In some aspects, the method for identifying the authenticity of fruit juice drinks or determining the content of natural juice in the fruit juice drinks includes detecting the radioactivity of radionuclides using a gamma measurement system; in a specific aspect, the gamma The measurement system includes a High Purity Germanium Detector, a Multi-channel Pulse-height Analyzer, and electronic devices such as analog-to-digital converters, analysis software, and personal computers. In some aspects, the analysis time of the juice drink sample analyzed by the Gamma measurement system depends on the relative efficiency of the pure germanium detector, the weight of the sample, etc., and can be adjusted according to the composition and characteristics of the sample. In some aspects, the steps of the method for identifying the authenticity of fruit juice drinks or determining the content of natural juice in the fruit juice drinks described herein may additionally include reference or comparison with one or more other authenticity of the fruit juice drinks or determination of the components of the juice drink The result of the content method. Examples Example 1 Detection Method of Potassium-40 The determination method of the example in this article is carried out with reference to the following detection method: Test sample: fruit juice drink (natural fruit juice or synthetic fruit juice). Test instrument: Gama measurement system, which includes high purity germanium detector (HPGe; Model GC3020 and GC4020, Canberra, USA), multi-channel pulse height analyzer (System 35 Plus, Canberra, USA) and electronic devices. Analysis software: Genie 2000 plus horse energy spectrum analysis software (Canberra, USA) Measurement method: According to the different volume and shape of the juice drink sample, choose the appropriate size geometrical marin measurement container (1 liter or 125 ml), and mix the juice drink The sample is packed or properly wrapped and weighed, and then placed in the Gama measurement system, measured with a multi-channel pulse height analyzer. The measurement time is based on the relative efficiency of the pure germanium detector and the weight of the sample. Adjust the measurement time based on the composition and characteristics of the sample. The radioactivity of the natural radionuclide potassium-40 can be quantified based on the characteristics of its release plus horse radiation (1461 keV). Measurement result: The radioactivity value (Beck/kg; Bq/kg) of potassium-40 in the sample can be quantitatively measured, and this value is often expressed as "average value ± standard deviation". If potassium-40 activity is not detected, the report data is indicated by "-", which means that the potassium-40 activity of the sample is lower than MDA (for juice drinks, MDA can generally be less than 5 Bq/kg), but still There are slight differences depending on the specimen and measurement conditions. Example 2 Activity analysis of potassium-40 in freshly squeezed orange (diced) juice Self-contained traditional markets, supermarkets and hypermarkets (Tonghua Market, Xinyi Market, Kunyang Street Arcade Vendor, Carrefour, Yongchun Market, Xinyi Market, Dinghao Fresh oranges (diced) from different origins (Taiwan and the United States) are obtained from different sources such as RT-Mart. The fresh orange juice is obtained by pressing the orange pulp. At least 1 liter of fresh orange juice is obtained for each type of orange. According to the method described in Example 1, 1 kg of fresh orange juice (sample numbers O1 to O9) of different sources and varieties was placed in a 1 liter of Marlin measurement container, and then placed in the Gama measurement system to perform multi-channel pulse The measurement time is 10,000 seconds to measure the potassium-40 activity (Bq/kg). The results are listed in Table 1 below. From the experimental results, it can be seen that the potassium-40 activity of the freshly squeezed orange (diced) juice of the specimen numbers O1 to O9 falls within a similar numerical range.
Figure 106137674-A0304-0001
Example 3 Activity analysis of potassium-40 in freshly squeezed orange juice diluted by different dilution ratios. Oranges purchased from Yongchun Aimai Supermarket were centrifuged and the impedance was 18.2MΩ. The ultrapure water of cm is diluted with different magnifications to obtain 100% (undiluted), 50%, 25%, 10%, and 5% diluted orange juice. According to the method described in Example 2, the potassium-40 activity (Bq/kg) of orange juice (sample number O10 to O14) diluted with different dilution ratios was measured. The results are listed in Table 2 below. It can be seen from the experimental results that the potassium-40 activity of the orange juice diluted with different dilution ratios of specimen numbers O10 to O14 corresponds to the change of the dilution ratio; and the diluted orange juice specimens The potassium-40 has a lower activity. The results of this experiment show that potassium-40 activity can be effectively used to identify the authenticity of fruit juice drinks (such as orange juice) or determine the content of natural juice in fruit juice drinks, and this method can be used to confirm the labeling of fruit juice drinks and their substance Whether the objects match.
Figure 106137674-A0304-0002
Example 4 Activity analysis of potassium-40 in commercially available orange (diced) juice. Commercially available juice drinks were obtained from different sources, including pure orange juice (freshly squeezed or reduced juice) labeled as 100% (sample numbers O15 to O23) ), orange juice beverages that contain 10-20% orange juice (sample numbers O24 to O30) and orange-flavored beverages that contain no orange juice (ie, 0%) (sample numbers O31 and O32). According to the aforementioned experimental method, 1 kg of commercially available orange juice drinks from different sources were taken to determine the potassium-40 activity (Bq/kg). The results are listed in Table 3 below. The interpretation of this result is not intended to be limited by any theory. With reference to the experimental results of O15 to O23 marked as 100% pure orange juice, the inventor was surprised to find that the processing process is concentrated reduction or fresh squeezing, which did not significantly affect the activity of potassium-40. In addition, the activity of potassium-40 was not detected in soda or sparkling water that does not substantially contain orange (D) components (refer to samples O31 and 32). This result is compared with existing detection methods (e.g., determination O 18 /O 16 or H 2 /H 1 ) does produce unexpected advantageous effects.
Figure 106137674-A0304-0003
Note: The symbol "-" means that the radioactivity is less than the minimum detectable amount (MDA). Example 5 The activity analysis of potassium-40 in freshly squeezed apple juice obtained fresh apples from different origins (Japan, France, Chile, the United States and New Zealand). Fresh apple juice is obtained by pressing the apple pulp. Obtain at least 1 liter of fresh apple juice for each type of apple. According to the method described in Example 1, 1 kg of fresh apple juice (sample numbers A1 to A5) of different sources and varieties are placed in a 1 liter of Marlin measurement container, and then placed in the Gama measurement system with multi-channel Pulse height analyzer measurement, measurement time is 10,000 seconds to determine potassium-40 activity (Bq/kg). The results are listed in Table 4 below. It can be seen from the experimental results that the potassium-40 activity of the freshly squeezed apple juice of specimens No. A1 to A5 falls within a similar numerical range.
Figure 106137674-A0304-0004
Example 6 The activity analysis of potassium-40 in freshly squeezed apple juice diluted by different dilution ratios. Following Example 5, the freshly squeezed apple juice with the specimen number A5 (New Zealand Fuji apple) was used with an impedance of 18.2MΩ. The ultrapure water of cm is diluted with different magnifications to obtain 100% (undiluted), 50%, 25%, 10% and 5% diluted apple juice. According to the method described in Example 2, the potassium-40 activity (Bq/kg) of apple juice (sample numbers A5 to A9) diluted with different dilution ratios was measured. The results are listed in Table 5 below. From the experimental results, it can be seen that the potassium-40 activity of apple juice diluted with different dilution ratios of specimen numbers A5 to A9 corresponds to the change of the dilution ratio; and the potassium-40 activity of the diluted apple juice specimens is lower . The results of this experiment show that potassium-40 activity can be effectively used to identify the authenticity of fruit juice drinks (such as apple juice) or determine the content of natural juice in fruit juice drinks, and this method can be used to confirm the labeling of fruit juice drinks and their substance Whether the objects match. Table 5: Analysis of Potassium 40 Activity in Different Dilution Concentrations of Freshly Squeezed Apples
Figure 106137674-A0304-0005
Example 7 Activity analysis of potassium-40 in commercially available apple juice Commercially available juice drinks were obtained from different sources, including pure apple juice labeled as 100% (reduced ones indicate reduced juice) (sample numbers A10 to A17), labeled Apple juice drinks containing 10-20% apple juice (sample numbers A18 and A19) and apple custard (sample number A20) with an apple juice content of less than 10%. According to the aforementioned experimental method, 1 kg of commercially available apple juice drinks from different sources were taken to determine the potassium-40 activity (Bq/kg). The results are listed in Table 6 below. The interpretation of this result is not intended to be limited by any theory. With reference to the experimental results of A10 to A17 marked as 100% pure apple juice, the inventor was surprised to find that the processing process is concentrated reduction or fresh squeezing, and the activity of potassium-40 is not significantly affected. In addition, the activity of potassium-40 was not detected in apple custard with an apple juice content of less than 10% (refer to sample A20). This result is compared with the existing detection methods (for example: measuring O 18 /O 16 Or H 2 /H 1 ) does produce unexpected advantageous effects. Table 6: Potassium-40 activity analysis of commercially available apple juice
Figure 106137674-A0304-0006
Note: The symbol "-" means that the radioactivity is less than the minimum detectable amount (MDA).

Claims (15)

一種鑑別果汁飲品標示之真實性的方法,該方法包含使用天然放射性核種鉀-40放射活度以測定果汁飲品樣品中純果汁的純度,藉此判斷果汁飲品標示的真實性。A method for identifying the authenticity of the label of a juice drink, the method includes using the radioactivity of the natural radionuclide potassium-40 to determine the purity of the pure juice in a juice drink sample, thereby determining the authenticity of the label of the juice drink. 如請求項1之方法,該方法包含以下步驟: (a)測定果汁飲品樣品中天然放射性核種鉀-40放射活度,及 (b)將(a)的結果與具對應純度之果汁飲品之標準品中之鉀-40放射活度進行比較;當(a)的結果在標準品範圍內則判斷為標示具真實性。Such as the method of claim 1, the method includes the following steps: (a) determining the radioactivity of the natural radionuclide potassium-40 in the juice drink sample, and (b) comparing the result of (a) with the standard of the juice drink with corresponding purity The potassium-40 radioactivity in the product is compared; when the result of (a) is within the range of the standard product, the label is judged to be authentic. 一種測定果汁飲品中天然果汁所佔含量的方法,該方法包含利用天然放射性核種鉀-40放射活度以測定果汁飲品樣品中純果汁所佔含量百分比。A method for determining the content of natural juice in a fruit juice drink, the method comprising using the radioactivity of the natural radionuclide potassium-40 to determine the percentage of the content of pure juice in a juice drink sample. 如請求項3之方法,該方法包含以下步驟: (a)測定果汁飲品樣品中天然放射性核種鉀-40放射活度,及 (b)將(a)的結果與多個經不同倍率稀釋的果汁飲品之標準品之鉀-40放射活度比較,藉以定量該未知果汁飲品樣品中純果汁所佔含量百分比。Such as the method of claim 3, the method includes the following steps: (a) determining the radioactivity of the natural radionuclide potassium-40 in a juice drink sample, and (b) comparing the result of (a) with multiple juices diluted with different magnifications Comparing the potassium-40 radioactivity of standard beverages to quantify the percentage of pure juice in the unknown juice beverage sample. 如請求項2之方法,其中所述果汁飲品之標準品可經稀釋或不經稀釋。The method according to claim 2, wherein the standard product of the fruit juice drink can be diluted or undiluted. 如請求項1或3之方法,所述果汁飲品包含天然果汁、天然蔬菜汁、濃縮果汁、濃縮蔬菜汁、還原果汁及還原蔬菜汁。According to the method of claim 1 or 3, the fruit juice drink includes natural fruit juice, natural vegetable juice, concentrated fruit juice, concentrated vegetable juice, reduced fruit juice, and reduced vegetable juice. 如請求項1或3之方法,該方法不需對果汁飲品進行樣品前處理之步驟。If the method of item 1 or 3 is requested, the method does not require the step of sample pre-processing on the juice beverage. 如請求項1或3之方法,其中該果汁飲品之標準品為純柳橙(丁)汁且其鉀-40放射活度標準為約47 Bq/kg至約58 Bq/kg;或該果汁飲品之標準品為純蘋果汁且其鉀-40放射活度標準為約26 Bq/kg至約34 Bq/kg。Such as the method of claim 1 or 3, wherein the standard product of the juice drink is pure orange (diced) juice and its potassium-40 radioactivity standard is about 47 Bq/kg to about 58 Bq/kg; or the juice drink The standard product is pure apple juice and its potassium-40 radioactivity standard is about 26 Bq/kg to about 34 Bq/kg. 如請求項1或3之方法,測定所述天然放射性核種鉀-40之放射活度之步驟包含測定特性加馬射線(1461 keV)之量之步驟。According to the method of claim 1 or 3, the step of measuring the radioactivity of the natural radionuclide potassium-40 includes the step of measuring the amount of characteristic gamma radiation (1461 keV). 如請求項9之方法,所述測定特性加馬射線之量之步驟的測定時間為約5,000秒至約100,000秒。According to the method of claim 9, the measurement time of the step of determining the amount of characteristic gamma rays is about 5,000 seconds to about 100,000 seconds. 如請求項1或3之方法,該方法包含測定適當的空白組試樣作為背景值的步驟。Such as the method of claim 1 or 3, the method includes the step of determining an appropriate blank group sample as a background value. 如請求項1或3之方法,該方法包含選擇體積為1公升及125毫升、或其它介於前述二者體積間的幾何馬林計測容器(Marinelli beaker)。Such as the method of claim 1 or 3, the method includes selecting a Marinelli beaker with a volume of 1 liter and 125 ml, or other volumes between the two volumes. 如請求項1或3之方法,測定所述天然放射性核種鉀-40之放射活度之步驟係利用加馬計測系統偵測放射性核種的放射活度;其中所述加馬計測系統包含高純鍺偵檢器(High Purity Germanium Detector)、多頻道分析儀(Multi-channel Pulse-height Analyzer)及電子裝置。According to the method of claim 1 or 3, the step of measuring the radioactivity of the natural radionuclide potassium-40 is to use the gamma measurement system to detect the radioactivity of the radionuclides; wherein the gamma measurement system contains high purity germanium Detector (High Purity Germanium Detector), Multi-channel Pulse-height Analyzer and electronic device. 如請求項10之方法,其中果汁飲品為柳橙(丁)汁且測定時間為約5,000秒至約100,000秒;或果汁飲品為蘋果汁且測定時間為約5,000秒至約100,000秒。The method of claim 10, wherein the fruit juice drink is orange (diced) juice and the measurement time is about 5,000 seconds to about 100,000 seconds; or the fruit juice drink is apple juice and the measurement time is about 5,000 seconds to about 100,000 seconds. 如請求項1或3之方法,該方法可進一步包含參考或比較一或多種其他鑑別果汁飲品真偽或測定果汁飲品成分含量的方法的結果的步驟。Such as the method of claim 1 or 3, the method may further include the step of referring to or comparing the results of one or more other methods for authenticating fruit juice drinks or determining the content of fruit juice drinks.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0994351A1 (en) * 1998-10-13 2000-04-19 Flotech 2000 Method for detecting adulteration of concentrated fruit juice with exogenous sugar sirop
TW200521241A (en) * 2003-12-19 2005-07-01 Yuan-Tay Shyu Authenticity detection of fresh squeezed orange juice by PCR
CN105606726A (en) * 2015-12-23 2016-05-25 陕西海升果业发展股份有限公司 Detection method for distinguishing authenticity of fruit juice
CN107003416A (en) * 2014-12-15 2017-08-01 韩国水力原子力株式会社 Light salt working year evaluation method based on the measurement of concetrations of K 40

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0994351A1 (en) * 1998-10-13 2000-04-19 Flotech 2000 Method for detecting adulteration of concentrated fruit juice with exogenous sugar sirop
TW200521241A (en) * 2003-12-19 2005-07-01 Yuan-Tay Shyu Authenticity detection of fresh squeezed orange juice by PCR
CN107003416A (en) * 2014-12-15 2017-08-01 韩国水力原子力株式会社 Light salt working year evaluation method based on the measurement of concetrations of K 40
CN105606726A (en) * 2015-12-23 2016-05-25 陕西海升果业发展股份有限公司 Detection method for distinguishing authenticity of fruit juice

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