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Characterization and Classification of Wines from Grape Varieties Grown in Turkey

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Characterization and Classification of Wines from Grape Varieties Grown in Turkey CHARACTERIZATION AND CLASSIFICATION OF WINES FROM GRAPE VARIETIES GROWN IN TURKEY A Thesis Submitted to the Graduate School of Engineering and Sciences of İzmir Institute of Technology in Partial Fulfillment of the Requirements for the Degree of DOCTOR OF PHILOSOPHY in Food Engineering by İlknur ŞEN July 2014 İZMİR We approve the thesis of İlknur ŞEN Examining Committee Members: _________________________ Prof. Dr. Figen TOKATLI Department of Food Engineering, İzmir Institute of Technology ___________________________ Prof. Dr. Durmuş ÖZDEMİR Department of Chemistry, İzmir Institute of Technology ___________________________ Assoc. Prof. Dr. Banu ÖZEN Department of Food Engineering, İzmir Institute of Technology _________________________ Prof. Dr. Yeşim ELMACI Department of Food Engineering, Ege University _________________________________ Prof. Dr. Ahmet YEMENİCİOĞLU Department of Food Engineering, İzmir Institute of Technology 11 July 2014 _________________________ Prof. Dr. Figen TOKATLI Supervisor, Department of Food Engineering İzmir Institute of Technology _________________________________ ___________________________ Prof. Dr. Ahmet YEMENİCİOĞLU Prof. Dr. R. Tuğrul SENGER Head of the Department of Dean of the Graduate School of Food Engineering Engineering and Sciences ACKNOWLEDGEMENTS I would like to thank to my supervisor Prof. Dr. Figen TOKATLI for her guidance and support throughout the thesis study. I also would like to express my thanks to the committee members, Prof. Dr. Durmuş ÖZDEMİR and Assoc. Prof. F. Banu ÖZEN for their valuable comments and advices. I would like to thank to the research centers; Biotechnology and Bioengineering Research Center and Environmental Reference Research and Development Center for providing the HPLC and ICP-MS instruments. I also would like to thank to IYTE Scientific Research Projects Commission for funding my thesis with the projects 2008- IYTE-18 and 2010-IYTE-07. Finally, I would like to thank to my family for their support, encouragement, love and patience. ABSTRACT CHARACTERIZATION AND CLASSIFICATION OF WINES FROM GRAPE VARIETIES GROWN IN TURKEY The wines of Turkish grapes from four vintages (2006-2009) were classified according to variety, geographical origin and vintage based on their chemical composition (element, polyphenol, color, acid, sugar, alcohol, pH, total phenol and brix) by using multivariate statistical techniques. In the varietal classification of red wines, the partial least square-discriminant analysis (PLS-DA) demonstrated the discrimination of Boğazkere-Öküzgözü, Kalecik Karası, Syrah and Cabernet Sauvignon varieties from each other as the significant element, polyphenol, organic acid, sugar and alcohol parameters were combined in the model. Boğazkere and Öküzgözü wines of East Anatolia were characterized with their high coumaroylated anthocyanin derivatives, while Syrah wines of West Anatolia were rich in anthocyanins and flavonols. Kalecik Karası wines were the poorest in terms of total phenol content. In the classification of white wines, Emir wines of Kapadokya region were characterized with their high Li, Sr and resveratrol contents. Sultaniye wines were the lowest in polyphenol content and Muscat wines were the richest in hydroxycinnamic acids. The regional discrimination of red and white wines was achieved with the significant element and polyphenol compositions. The western region wines were characterized with their higher Pb content which may be due to the industrialization of West Anatolia. Moreover, red wines of Tekirdağ region were recognized with their low flavonol-glycoside contents. 2009 vintage red wines were characterized with their high anthocyanin and flavonol contents. In the same way, 2009 vintage white wines had higher flavonols, flavonol-glycosides, phenolic acids and flavan-3-ols. iv ÖZET TÜRKİYE’DE YETİŞTİRİLEN ÜZÜM ÇEŞİTLERİNDEN ÜRETİLEN ŞARAPLARIN KARAKTERİZASYONU VE SINIFLANDIRILMASI Türk üzümlerinden elde edilmiş, dört hasat yılına ait (2006-2009) şaraplar kimyasal içeriklerine (element, polifenol, renk, asit, şeker, alkol, pH, toplam fenol ve brix) dayanarak çoklu değişkenli istatistiksel yöntemler kullanılarak çeşide, coğrafi bölgeye ve hasat yılına göre sınıflandırılmıştır. Kırmızı şarapların varyeteye göre ayrımında, kısmi en küçük kareler- diskriminant analizi (PLS-DA), önemli element, polifenol, renk, organik asit, şeker ve alkol parametreleri modelde birleştirildiğinde, Boğazkere-Öküzgözü, Kalecik Karası, Şiraz ve Cabernet Sauvignon varyetelerinin birbirinden ayrımını göstermiştir. Batı Anadolu’nun Şiraz şarapları antosiyaninler ve flavonollerce zenginken, Doğu Anadolu’nun Boğazkere ve Öküzgözü şarapları içerdikleri yüksek kumaril antosiyanin türevleri ile karakterize edilmişlerdir. Kalecik Karası şarapları toplam fenol içeriği açısından en fakirdir. Beyaz şarapların sınıflandırılmasında, Kapadokya yöresinin Emir şarapları yüksek Li, Sr ve resveratrol içerikleri ile karakterize edilmişlerdir. Sultaniye şarapları polifenol içeriğinde en fakir ve Misket şarapları hidroksisinnamik asitlerce en zengindir. Kırmızı ve beyaz şarapların bölgesel ayrımı önemli element ve polifenol içerikleri ile sağlanmıştır. Batı bölgelerinin şarapları yüksek Pb içerikleri ile karakterize edilmiştir ki, bu Batı Anadolu’nun sanayileşmesinden dolayı olabilir. Ayrıca, Tekirdağ bölgesinin kırmızı şarapları düşük flavonol-glikozit içerikleri ile dikkat çekmişlerdir. 2009 mahsulü kırmızı şaraplar yüksek antosiyanin ve flavonol içerikleri ile karakterize edilmişlerdir. Benzer şekilde, 2009 mahsulü beyaz şaraplar yüksek flavonol, flavonol- glikozit, fenolik asit ve flavan-3-ol içermektedirler. v TABLE OF CONTENTS LIST OF FIGURES ........................................................................................................ ix LIST OF TABLES ...................................................................................................... xiii LIST OF ABBREVIATIONS ......................................................................................... xv CHAPTER 1. INTRODUCTION ..................................................................................... 1 CHAPTER 2. WINE ......................................................................................................... 3 2.1. History of Winemaking ........................................................................... 3 2.2. Quality of Wine ....................................................................................... 4 2.3. The Necessity of Wine Characterization ................................................ 6 2.4. Wine Types ............................................................................................. 9 2.5. Grape Varieties and Viticulture Regions in Turkey and in the World. .................................................................................................. 12 2.6. The Economy of Wine in Turkey and in the World ............................. 16 2.7. Wine Chemistry .................................................................................... 18 2.7.1. Minerals .......................................................................................... 18 2.7.2. Phenolic Compounds ..................................................................... 21 2.7.3. Color ............................................................................................... 32 2.7.4. Organic Acids, Sugars and Alcohols ............................................. 34 2.7.5. Nitrogen Containing and Aroma Compounds ................................ 39 2.8. Principles of Winemaking Process ....................................................... 40 2.9. Health Related Aspects of Wine ........................................................... 46 2.10. The Effect of Terroir on Wine Chemistry .......................................... 48 2.11. Principles of Wine Instrumental Analysis .......................................... 53 2.11.1. Inductively Coupled Plasma-Mass Spectroscopy (ICP-MS) and Optic Emission Spectroscopy ............................................... 53 2.11.2. High Pressure Liquid Chromatography (HPLC) .......................... 55 vi CHAPTER 3. MULTIVARIATE STATISTICAL TECHNIQUES ............................... 58 3.1. Unsupervised Statistical Techniques .................................................... 58 3.1.1. Principal Component Analysis (PCA) ........................................... 59 3.1.2. Hierarchical Cluster Analysis (HCA) ............................................ 62 3.2. Supervised Statistical Techniques ......................................................... 64 3.2.1. Partial Least Squares-Discriminant Analysis (PLS-DA) ............... 65 3.2.2. Soft Independent Modeling of Class Analogy (SIMCA) ............... 68 CHAPTER 4. MATERIALS AND METHODS ............................................................ 70 4.1. Sample Treatment Schedule ................................................................. 70 4.2. Wine Samples ....................................................................................... 70 4.3. ICP Analysis ......................................................................................... 73 4.3.1. Reagents ......................................................................................... 73 4.3.2. Instrumentation .............................................................................. 74 4.3.3. Standards and Spikes...................................................................... 76 4.3.4. Sample Treatment .........................................................................
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