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Macadamia Integrifolia) INVESTIGATING THE EFFECT OF THERMAL PROCESSING ON BIOCHEMICAL COMPOSITION AND KERNEL SHELF-LIFE OF MACADAMIA (MACADAMIA INTEGRIFOLIA) By Nana Millicent Duduzile Buthelezi (216053657) Submitted in fulfilment of the academic requirements for the degree of Doctor of Philosophy in Agriculture (Horticultural Science) Supervisor (s): Dr LS Magwaza Dr SZ Tesfay Discipline of Horticultural Sciences School of Agricultural, Earth and Environmental Sciences College of Agriculture, Engineering and Science Pietermaritzburg Campus December 2018 DECLARATION I, Nana Millicent Duduzile Buthelezi (Student No. 216053657), declare that the research reported in this thesis, except where otherwise indicated, is my original work. This thesis has not been submitted for any degree or examination at any other university. Student signature: …………………………………………. Date: 07/12/18 Nana Millicent Duduzile Buthelezi Supervisor signature: ………………………………………….. Date: 07/12/18 Dr L.S. Magwaza Supervisor signature: ………………………………………….. Date: 07/12/18 Dr S.Z. Tesfay i SUMMARY The aim of this study was to evaluate and compare quality parameters of raw and roasted macadamia kernels and the impact of different roasting temperatures and cultivars on biochemical composition and shelf life of macadamia nuts. Another objective was to develop visible to near infrared (Vis/NIR) spectroscopy (Vis/NIRS) calibration models that could be used by the macadamia industry to predict rancidity. A critical review of literature identified biochemical markers associated with quality loss in macadamia nuts and the importance of thermal processing on macadamia kernel quality and shelf life. The prospects for the use of Vis/NIRS as a non-destructive technology to predict rancidity on macadamia kernels was also reviewed. Initial studies were conducted to determine the effect of roasting, roasting temperatures and cultivar on chemical and sensory quality of macadamia nuts. It was found that roasted kernels of ‘A4’ and ‘Beaumont’ cultivars had good quality during the accelerated storage of 70 days, indicated by lower peroxide value (PV), high concentration of flavonoids, phenols and antioxidants, confirming the vital role of antioxidant activity in delaying lipid oxidation or rancidity. According to sensory panelists, roasted kernels had enhanced crispy texture, aroma, flavour, appearance and good marketability during storage compared to raw kernels. The study suggested that roasting enhanced quality and shelf life of macadamia nuts. The study on the effect of drying temperatures on postharvest quality of macadamia nuts showed that ‘A4’ and ‘Beaumont’ kernels roasted at 125 °C had lower PV, higher concentration of phenols and antioxidants and enhanced sensory quality; crispy texture, brown colour and nutty taste compared to the quality of kernels roasted at 50 °C, 75 °C, 100 °C and 150 °C. Kernels roasted at 50 °C, 75 °C and 100 °C were more prone to deterioration as indicated by high PV and poor sensory quality; hard texture, light colour and slightly nutty taste whereas kernels roasted at 150 °C had high levels of rancidity, lower concentration of flavonoids, phenols, antioxidants, excessive crispy texture, dark brown colour and bitter taste. The study on the effect of cultivar on kernel quality and shelf life of roasted macadamia nuts showed that the ‘Beaumont’ cultivar had lower PV, acid value (AV), high phenols and antioxidants and good sensory quality; nutty taste with no noticeable rancid taste during the accelerated storage of 18 weeks compared to ‘A4’ cultivar which had poor quality during storage due to higher PV and AV, lower concentration of phenols and antioxidants and poor sensory quality; poor nutty taste and rancid taste. The studies in this thesis suggested that roasting macadamia nuts at 125 °C significantly enhanced kernel quality and storability of macadamia nuts by inactivating ii oxidative enzyme system such as lipoxygenic and lipolytic enzymes associated with deteriorative reactions such as oxidative and hydrolytic rancidity. Roasting also leads to denaturation of several enzymes such as peroxidase and polyphenol oxidase, which are responsible for the development of off-flavours and darkening reactions through the development of browning pigments. The inactivation of these enzymes led to low levels of rancidity indicated by lower PV and AV in roasted kernels which in turn might have contributed to high concentration of flavonoids, phenols and antioxidants observed in roasted kernels during storage. This could be due to the release of some bound antioxidant phenolic compounds acting as free radical scavengers from the cell matrix and increase phenolic extractability upon roasting. According to the panelists, kernels roasted at 125 °C had crispy texture, good flavour, taste, aroma, overall appearance and were marketable during storage. Another study in this thesis showed that the ‘Beaumont’ cultivar had good quality, indicated by lower PV, AV, high concentration of phenols and antioxidants and good sensory quality during the accelerated storage of 18 weeks compared to ‘A4’ cultivar which had poor quality, indicated by higher PV and AV, lower concentration of phenols and antioxidants and poor sensory quality during storage. These findings suggested that ‘Beaumont’ cultivar could be preferable for long term storage. The partial least square (PLS) regression models developed in this study to predict peroxide value demonstrated the potential of Vis/NIRS as a non- destructive tool for prediction of rancidity on intact kernels of ‘A4’, ‘Beaumont’, roasted and raw macadamia nuts. The high prediction accuracy recorded when models developed to predict rancidity on macadamia kernels demonstrated robustness of PLS models. Where speed and accuracy are required for evaluating the degree of rancidity on individual intact macadamia kernels, Vis/NIRS and models developed in this study are recommended. iii ACKNOWLEDGEMENTS I would like to express my profound gratitude and appreciation to the following people: • Dr L.S. Magwaza (Supervisor), thank you for the invaluable guidance during this study, without your advice it would have been extremely difficult to complete my PhD study. Words fail me, but my gratitude is immeasurable, I have grown both as a scientist and an author. • Dr S.Z. Tesfay (Supervisor), thank you for your immense knowledge, patience, motivation, invaluable guidance from the beginning to the end of my PhD study. • Khayelihle Ncama, thank you for your contribution towards the completion of this study. • My siblings, thank you for the support and courage you always give me. • National Research Foundation (NRF), thank you for financial support which made it possible to undertake the study. iv PUBLICATIONS AND CONFERENCE PRESENTATIONS All chapters of this work, except chapter 1 and 7, were intended for publication, and as a result, are written in the form of manuscripts. Due to the time limit, only chapter 2 is currently accepted for publication and other chapters are currently under review while others are or will be submitted to relevant journals. Published papers Buthelezi, N. M. D., Tesfay, S. Z., Ncama, K., and Magwaza, L. S. (2019). Destructive and non-destructive techniques used for quality evaluation of nuts: A review. Scientia Horticulturae 247, 138-146. Conferences Buthelezi, N.M.D., Magwaza, L.S., Tesfay, S.Z., 2018. The effect of processing conditions on the quality attributes of ‘A4’ and ‘Beaumont’ macadamia (Macadamia intergrifolia). College of Agriculture, Engineering and Science Postgraduate Research and Innovation Symposium, University of KwaZulu-Natal, Westville Campus, Durban, 25 October, 2018. (Oral). v PREFACE This thesis is a compilation of manuscripts where individual chapter is an independent article introduced disjointedly. Hence, some repetition between individual chapters has been inevitable. vi TABLE OF CONTENTS Declaration……………………………………………….…………………….……….. i Summary…………………………………………………………………..…………… ii Acknowledgements……………….………………………………..…………………… iv Publications and conference presentations…………………………………………… v Preface……………………………………………………………………………..….… vi CHAPTER 1: GENERAL INTRODUCTION…….……………………….………… 1 1. Introduction…………………………………………………………………………… 1 2.Research hypothesis…………………………………………………………………… 7 3. Research aim……………………………………………………………………….…. 8 4. Research objectives…………………………………………………………………… 8 References……………………………………………………………………………….. 8 CHAPTER 2a: LITERATURE REVIEW: THE EFFECT OF THERMAL PROCESSING ON NUTRITIONAL QUALITY AND KERNEL SHELF LIFE OF MACADAMIA NUTS…………………………………..………………………….….. 13 Abstract………………………………………………………………..………………… 13 1. Introduction…………………………………………………………………………… 14 2. Thermal processing…………………………………………………………………… 17 3. Rancidity……………………………………………………………………………… 19 3.1. Oxidation…………………………………………………………………………… 20 3.1.1. Fatty acid composition…………………………………….……………………… 23 3.2. Hydrolysis………………………………………………………………..…….…… 24 3.3. Measurements of rancidity…………….…………………………………………… 26 4. Non-destructive methods…………..………………………………………………… 28 4.1. Application of visible to near infrared spectroscopy……………………………….. 28 4.1.1. Basic concepts…………………………………………………………………….. 29 4.2. Potential use of NIRS to predict internal quality of macadamia nuts……………….. 31 5. Conclusion…………………………………………………………………………….. 32 References……………………………………………………………………………….. 33 CHAPTER 2b: DESTRUCTIVE AND NON-DESTRUCTIVE TECHNIQUES USED FOR QUALITY EVALUATION OF NUTS: A REVIEW………………..…. 41 Abstract………………………………………………………………………………….. 41 vii 1. Introduction………………………………………………………………..……….…
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