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標題: 以微量元素與氫、氧、碳、氮同位素區分大蒜地理來源
Use of chemical profiling and stable isotopes of hydrogen, carbon, oxygen and nitrogen to differentiate geographical origins of garlic
作者: 林振男
Jhen-Nan Lin
關鍵字: 同位素;微量元素;大蒜;產地鑑定;主成分分析;判別分析;Isotopes;trace elements;garlic;origin identification;principal component analysis;discriminant analysis
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大蒜為國際市場上主要流通的香料作物之一,台灣加入世界貿易組織(WTO)後,為了維護國內大蒜市場價格,政府對不同來源國的大蒜設定關稅配額及進口限制,且伴隨著消費者對食安觀念的提升及為了達到防止非法進口與產地標示不實的大蒜,以科學的方式區分大蒜產地來源為不可或缺之技術。本研究擬分析大蒜之氫、氧、碳及氮同位素及22種微量元素,結合主成分分析(Principal Component Analysis, PCA)及判別分析(Discriminant Analysis, DA)進行數據統計,區分大蒜產地來源。研究收集來自台灣、阿根廷、韓國、中國及越南之大蒜進行分析,其中包括標示產地來源為台灣及中國的檢核樣品(AM-T及AM-C)。同位素分析結果顯示,以δ2H及δ18O能清楚區分阿根廷(南美洲)及亞洲地區的大蒜樣品,阿根廷大蒜之 2H及 18O皆明顯較亞洲大蒜為低。進一步利用主成分分析結果顯示其可對大蒜樣品產地進行區分,並能歸納出具有區分產地能力之特徵因子。接續,利用主成分分析歸納出之特徵因子進行判別分析,在經驗樣本充足的條件下,判別分析能建立有效分類大蒜產地的判別及分類函數,其判別率可達98%,經交叉驗證後則為95%。此外,本研究使用的檢核樣品AM-T及AM-C,可幫助了解主成分分析及判別分析在分類產地來源不明樣品時的可行性,檢核樣品於兩種分析方法中的分類結果皆相同,如AM-T之產地來源歸類為台灣,而AM-C之產地來源歸類為中國福建地區,此結果符合檢核樣品標示的產地來源。本次研究結果證實,透過分析大蒜樣品之氫、氧、碳及氮同位素及22種微量元素組成,結合主成分分析及判別分析之統計方法能有效區分大蒜樣品的產地來源,並確認其可信度及應用性,此研究技術將有助於其他農產品的產地鑑定。

Garlic is one of the primary spice crops circulating in the international market. After joining the World Trade Organization, the Taiwanese government developed tariff-rate quotas and import restrictions on garlic from different countries to maintain the market price of domestic garlic. In addition to an improvement in consumer awareness of food safety, to prevent garlic from being illegally imported from misidentified origins, a scientific technology was necessary for identifying the origin of garlic. This study identified the origin of garlic by combining laboratory analysis and statistical approaches. Data of laboratory analysis include results of 22 trace elements and stable isotopic compositions of hydrogen, oxygen, carbon and nitrogen. And the chemical and isotopic data were performed by statistical principal component analysis (PCA), and discriminant analysis (DA). Garlic samples were collected from Taiwan, Argentina, South Korea, China, and Vietnam. These samples included audit samples from Taiwan and China (AM-T and AM-C). The results of isotope analysis indicated that δ2H and δ18O could identify samples from Argentina (South America) and Asia. Argentinian garlic exhibited lower δ2H and δ18O ratios than Asian garlic did. The origins of garlic were identified in the plot of results from the PCA. The plot further indicated the characteristics of different origins. With the sufficient empirical data, classification functions for garlic from different origins were derived from DA based on the characteristics found in the plot of the PCA. The classification functions were applied to identify the origins of the garlic samples, and the identification rate was 98%. After cross-validation, the identification rate was 95%. In addition, the audit samples were useful in investigating the feasibility of using PCA and DA to identify the origin of unknown samples. The results of using the two methods to identify the two audit samples were consistent. The origin of sample AM-T was Taiwan, and the origin of sample AM-C was identified as Fujian, China. These results were in line with the origins of the audit samples, and the origins of these samples were not falsified. This study analyzed isotope ratios of hydrogen, oxygen, carbon, and nitrogen and compositions of 22 trace elements in garlic samples. Combining these analytical results with the PCA and DA, the origins of garlic samples were successfully identified. The technology used in this study is expected to be applied to techniques for identifying origins of other agricultural products in the future.
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