The Pennsylvania State University the Graduate School College Of
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The Pennsylvania State University The Graduate School College of Agricultural Sciences NOVEL VINIFICATION TECHNIQUES TO IMPROVE PENNSYLVANIA WINE QUALITY A Thesis in Food Science by Laurel A. Vernarelli Submitted in Partial Fulfillment of the Requirements for the Degree of Master of Science August 2018 The thesis of Laurel A. Vernarelli was reviewed and approved* by the following: Ryan J. Elias Associate Professor of Food Science Thesis Advisor Joshua D. Lambert Associate Professor of Food Science Helene Hopfer Assistant Professor of Food Science Robert F. Roberts Head of the Department of Food Science *Signatures are on file in the Graduate School II Abstract Laurel A. Vernarelli, Food Science, The Pennsylvania State University Abstract of Masters Thesis, Submitted July 1, 2018 Novel Vinification Techniques to Improve Pennsylvania Wine Quality The Commonwealth of Pennsylvania is the fifth largest producer of grapes in the United States of America and was recently ranked as the tenth largest wine producing state. Wine is an important agricultural commodity to the Commonwealth, with $2 billion dollars in economic impact per year. Due to the cooler and more humid climate of the Northeastern United States, the challenges that Pennsylvania winemakers face differ from those of other wine-grape growing regions. Across the U.S. and globally, winemakers employ many vinification techniques and post-fermentation practices in order to contribute to wine quality and ensure a desirable product. Because wine quality and salability are correlated with freshness and maintenance of desirable sensory attributes, the success of these techniques is essential to the continued growth of the wine industry. The investigation of techniques which enhance or maintain quality, and that result in extended shelf stability of regional wines are of significant interest to the Pennsylvania winemaker. Novel processing methods for increased quality and shelf stability of wines were investigated. The overall aim of this thesis is to evaluate novel vinification techniques that can improve wine quality with respect to overall oxidative stability. Interspecific hybrid grapes (Vitis ssp.) are of particular interest to the Pennsylvania wine industry, as these extremely productive and disease-resistant varieties produce high quality wines and are suitable for growth in Northeastern climates. Hybrid grapes differ from traditional European wine grape Vitis vinifera in several significant ways, many of which impact the quality of finished wine. Unlike vinifera, hybrids have not been subjected to a thorough investigation of III the factors affecting wine quality and increased shelf stability. An improved understanding of the parameters affecting the production of high quality hybrid wines is extremely valuable to the Pennsylvania wine industry. Maceration is an important vinification technique known to improve quality and shelf stability of wines due to the increased eXtraction of phenolic compounds and other beneficial, redoX-active grape constituents. The versatile interspecific white-fleshed hybrid varieties Cayuga and Traminette were chosen to evaluate two novel maceration techniques, cryogenic maceration and extended skin contact, on the resulting phenolic content, antioxidant capacity, glutathione concentration, redox status of wine, CIE-LAB color values and conventional juice and wine parameters, in order to evaluate quantitative measures of overall quality and stability. In Cayuga and Traminette wines, both the cryogenic maceration and extended skin contact treatments resulted in significantly increased Folin-Ciocalteu total phenolic content over control wines. Antioxidant capacity, as measured by DPPH radical scavenging assay, was significantly increased in extended skin contact over control wines. However, eXtended skin contact resulted in significant decreases in glutathione concentration and lower Fe (II) content for both Cayuga and Traminette wines. CIE-LAB color values indicated that Cayuga extended skin contact wine was significantly darker and more orange in color compared to the cryogenic maceration and control wines. Overall, the quality parameters and shelf stability of the cryogenically treated wines were maintained or increased compared to the control, indicating these maceration techniques may provide a viable and novel technique for the production of high quality, white hybrid wine. Volatile sulfidic containing compounds (VSCs) have significant impacts on the sensory attributes of wine. Due to exceedingly low detection thresholds, VSCs are easily perceived by the consumer. Volatile sulfidic compounds such as H2S, methanthiol and ethanethiol are reminiscent of rotten eggs, cooked vegetables and sewage. The presence of these “reductive” aromas in wine is considered to be a quality defect. The removal of these off-aromas is typically IV achieved by the method of copper fining, where copper in the form of Cu(II) is added directly to the wine. Increasing evidence implicates Cu(II) as playing a significant role in the chemical reactions and pathways governing the loss and formation of sulfhydryls during wine storage. Several recent studies have shown that under reductive and anaerobic conditions, the reappearance of H2S and methanethiol has been observed post-bottling. Additionally, it has been reported that thiols are able to form compleXes with Cu(II), and that the bound forms are reversible. These findings are significant, and together indicate that Cu(II) is a participant in troublesome reactions that liberate or regenerate H2S and thiols post-bottling. Because Cu(II) clearly plays a role in the manifestation of this common wine fault, its direct addition to wine must be avoided or minimized. Therefore, novel techniques that allow for H2S and thiol removal without the inadvertent introduction of Cu(II) that can remain in wine have been investigated. Alternative fining techniques, such as the use of animal and plant-based proteins have been evaluated for Cu(II) removal post-copper fining. Proteins such as isinglass, gelatin, albumin, casein, and other plant-based proteins were assessed for their efficacy of Cu(II) concentration reduction under model wine conditions. The most substantial decrease in Cu concentration after 5 days was observed among the albumin and potato protein treatments, resulting in a 23 – 25% reduction in Cu concentration. The use of immobilized or bound forms of Cu(II), in which Cu(II) is adsorbed onto an inert substrate have been investigated as a replacement for traditional copper fining methods. Two bound Cu(II) forms, CuO- Alumina and Cu(NO3)2-Celite, were investigated for their ability to remove hydrogen sulfide (H2S), L-cysteine (Cys) and 3- sulfanylhexan-1-ol (3SH) under anaerobic model wine conditions over 4 hour and 24 hour time studies. The Cu concentration resulting from the presence of bound Cu(II) treatments in model wine solutions, Riesling and Lemberger over 24 hours was determined. The maceration techniques of cryogenic maceration and extended skin contact resulted in chemical composition changes in Traminette and Cayuga wines that would provide benefits V for the production of high quality, shelf stable white hybrid wines. Alternatives to traditional copper fining methods were investigated, including the use of proteins and bound Cu(II) substrates. Alternative fining methods using proteins were proven to be effective at Cu removal in model wine. Two bound Cu(II) substances, CuO-Alumina and Cu(NO3)2-Celite, were shown to successfully decrease the concentrations of H2S, Cys and 3SH under anaerobic model wine conditions over 4-hour and 24-hour time periods, and provide a simple and effective method for H2S and thiol removal in wine. These novel processing techniques have the potential to provide considerable benefits to the Pennsylvania wine industry. VI Contents List of Figures .................................................................................................................. XII List of Tables .................................................................................................................. XVII List of Abbreviations ...................................................................................................... XIX Dedication ........................................................................................................................... XX Acknowledgements ........................................................................................................ XXI Chapter 1 Literature Review ....................................................................................... 1 1.1 Introduction ............................................................................................................ 1 1.1.1 Winemaking in Pennsylvania.............................................................................. 2 1.2 Maceration Techniques.......................................................................................... 3 1.2.1 Extended Skin Contact ....................................................................................... 3 1.2.2 Cryogenic Maceration ........................................................................................ 4 1.3 Introduction to Oxidation Reactions in Wine........................................................... 5 1.4 Glutathione ............................................................................................................ 9 1.4.1 Role in Wine Oxidation ....................................................................................