Evaluation of Peanut Roasting Using Oven and Microwave Technologies on the Development of Color, Flavor, and Lipid Oxidation THESIS Presented in Partial Fulfillment of the Requirements for the Degree Master of Science in the Graduate School of The Ohio State University By Alicia LouAnn Smith, B.S. Graduate Program in Food Science and Technology The Ohio State University 2014 Master's Examination Committee: Professor Dr. Sheryl Barringer, Advisor Professor Dr. Luis Rodriguez-Saona Professor Dr. Ahmed Yousef Copyright by Alicia LouAnn Smith 2014 Abstract Roasted peanut color, flavor, and lipid oxidation values were evaluated for different time and temperature combinations using oven, microwave, and combination roasting technologies. Raw peanuts were oven roasted at 135 °C, 163 °C, 177 °C, and 204 °C, microwave roasted for 1-3 min, or combination roasted by microwave and oven roasting for various times and temperatures. Roasted peanut color, volatiles, odor activity values (OAVs), free fatty acid, peroxide values, and sensory attribute values based on descriptive sensory panel analysis were determined. Two commercial peanut butter samples were analyzed for color and volatile comparison. L* values were used to categorize peanuts into under roasted, ideally roasted, and over roasted. Raw peanuts were roasted by different methods to produce equivalent, commercially ideal L* roast color. Volatiles were measured using selected ion flow tube mass spectrometry (SIFTMS). OAVs were calculated based on volatile levels quantified with SIFT-MS and known odor thresholds. The total roasting time in order to achieve ideal color was not shortened by most of the combination treatments compared to their oven roasted equivalents. Oven before microwave roasting compared to the reverse was found to significantly increase the L* value likely due to the increase in the dielectric loss factor. Peanuts with ideal color had L* values that were not significantly different, but the ii volatile levels were different. Hexanal concentrations in all peanuts decreased then increased with roasting, but were below the level previously found to be unacceptable to consumers. Ethanol to methanol ratios in roasted peanuts were all below the level found in raw peanuts. Pyrazine levels increased as roasting time increased, although oven at 177 °C treatments had the highest and microwave treatments had the lowest levels. Volatile levels generally increased as roasting time or temperature increased with raw peanuts having the lowest levels and over roasted peanuts having the highest volatile levels. Oven 177 °C for 15 min generally had the highest level of volatiles among the roasting treatments tested. Based on the OAVs that were greater than one, roasted peanut samples had similar volatiles important for flavor compared to the commercial samples. Lipid oxidation values were not significantly different between the roasted peanut samples, displaying no evidence to support that roasting time or temperature affected lipid oxidation, when ideal color was produced. Sensory attribute values showed no significant difference between oven, microwave, or combination roasting for most of the peanut flavor descriptors. Microwave and microwave combination roasting produced similar color, flavor, lipid oxidation, and sensory attribute values compared to oven roasting treatments. Soft independent modeling of class analogies based on volatile levels showed that raw peanuts were the most different, commercial samples were the most similar to each other, and oven, microwave, and combination roasting were all similar in volatile profile. iii Dedicated to my family and friends iv Acknowledgements I would first like to thank my advisor Dr. Sheryl Barringer. She has been a wonderful professional role model for me since I first had her as an instructor. She has challenged me both scientifically and professionally to do my best and inspired me to be passionate about my work and field. Her efforts throughout my academic career have made me a better food scientist and for that, I am thankful. I would also like to thank my committee members Dr. Ahmed Yousef and Dr. Luis Rodriguez-Saona for supporting me throughout my research project. Dr. Jennifer Perry and Dr. Julie Marshall provided additional laboratory support in completing this project and I am grateful for their assistance and collaboration efforts. Secondly, I would like to thank Dr. Valente Alvarez, who believed in me as an undergraduate student. I would not be where I am today without his help and advice. It has also been great working with his past and present staff at the Food Industries Center. I am grateful for all the help and experience everyone gave me at the Food Industries Center. I also appreciate the help and support from the faculty, staff, and students in the Department Food Science & Technology at Ohio State. I also appreciate the advice and friendship of my lab mates. It was truly a great experience working with all of them. My family and friends have also been a huge support group and I love them all very much. Last, but not least, I would like to thank v The J.M. Smucker Company and employees that provided me with the opportunity to complete this research. It has been a wonderful experience working with them during my Master’s degree and I appreciate the support and guidance. vi Vita B.S. Food Science, The Ohio State University………………..………………………2012 Fields of Study Major Field: Food Science and Technology vii Table of Contents Abstract ............................................................................................................................... ii Acknowledgements ..............................................................................................................v Vita.................................................................................................................................... vii List of Tables .......................................................................................................................x List of Figures .................................................................................................................... xi Chapter 1: Literature Review ...............................................................................................1 1.1 Peanut Color ...............................................................................................................1 1.2 Peanut Flavor..............................................................................................................2 1.2.1 SIFT-MS ..............................................................................................................5 1.2.2 Raw Peanut Volatiles...........................................................................................6 1.2.3 Maillard Browning Volatiles ...............................................................................7 1.2.4 Lipid Oxidation Volatiles ..................................................................................10 1.3 Lipid Oxidation ........................................................................................................10 1.4 Microwave Processing .............................................................................................11 Chapter 2: Comparison of Peanut Roasting Using Oven and Microwave Technologies on the Development of Color, Flavor, and Lipid Oxidation ...................................................13 2.1 Abstract ....................................................................................................................13 2.2 Practical Application ................................................................................................14 2.3 Introduction ..............................................................................................................14 2.4 Methods ....................................................................................................................16 2.4.1 Peanut Roasting .................................................................................................16 2.4.2 SIFT-MS ............................................................................................................18 2.4.3 Color ..................................................................................................................22 2.4.4 Peanut Oil Analysis ...........................................................................................23 viii 2.4.5 Sensory ..............................................................................................................24 2.4.6 Statistical Analysis ............................................................................................25 2.5 Results and Discussion .............................................................................................25 2.5.1 Color ..................................................................................................................25 2.5.2 Volatiles .............................................................................................................26 2.5.3 Lipid Oxidation..................................................................................................32 2.5.4 Sensory ..............................................................................................................34 2.6 Conclusion................................................................................................................38 2.7 References ................................................................................................................38 Chapter 3: Color and Volatile Analysis of Peanuts Roasted Using Oven and Microwave Technologies ......................................................................................................................43 3.1 Abstract ....................................................................................................................43 3.2 Practical Application ................................................................................................44 3.3 Introduction ..............................................................................................................44 3.4 Methods ....................................................................................................................46 3.4.1 Peanut Roasting .................................................................................................46 3.4.2 SIFT-MS ............................................................................................................47 3.4.3 Color ..................................................................................................................51 3.4.4 Statistical Analysis ............................................................................................52 3.5 Results and Discussion .............................................................................................52 3.5.1 Color ..................................................................................................................52 3.5.2 Volatile Levels in Raw Peanuts .........................................................................56 3.5.3 Volatile Levels in Ideally and Over Roasted Peanuts .......................................66 3.5.4 Soft Independent Modeling of Class Analogy ..................................................71 3.6 Conclusions ..............................................................................................................74 3.7 References ................................................................................................................74 References ..........................................................................................................................79 Appendix: Odor Thresholds ...............................................................................................87 ix List of Tables Table 1.1. Odors of selected volatiles in peanuts................................................................ 2 Table 2.1. Kinetics of volatile compounds in peanuts for SIFT-MS analysis .................. 19 Table 2.2. Average odor activity values (OAVs) from ideally roasted peanuts and commercial peanut butter samples. OAVs less than one are indicated with white boxes. 29 Table 2.3. Sensory attribute values determined by a descriptive sensory panel for different peanut roasting treatments*................................................................................ 37 Table 3.1. Kinetics of volatile compounds in peanuts for SIFT-MS analysis .................. 49 Table 3.2. Volatile levels (ppb) of raw and under roasted peanuts ................................... 58 Table 3.3. Volatile levels (ppb) of ideally roasted peanuts............................................... 60 Table 3.4. Volatile levels (ppb) of over roasted peanuts .................................................. 64 Table 3.5. Soft independent modeling of class analogy (SIMCA) interclass distances comparing oven, microwave (MW), and combination roasting treatment volatile concentrations (ppb).......................................................................................................... 73 Table A1. Odor thresholds of volatiles in air .................................................................... 87 x List of Figures Figure 1.1. Schematic of selected ion flow tube mass spectrometer (SIFT-MS) (Smith and Spanel 2005) ....................................................................................................................... 6 Figure 1.2. Maillard browning reaction flow chart based on Hodge 1953 and Nursten 2005..................................................................................................................................... 9 Figure 2.1. Percent free fatty acid in treatments with no significant difference in L* value with raw peanuts as the control ......................................................................................... 33 Figure 2.2. Peroxide values (MEQ/1000 g sample) of treatments with no significant difference in L* value with raw peanuts as the control .................................................... 34 Figure 3.1. L* values of oven, microwave (MW), and combination roasting treatments, ideal L* values range from 56-61 ..................................................................................... 54 Figure 3.2. Volatile levels of pyrazines as roasting time increases for Oven at 177 °C, Oven at 204 °C, and Microwave roasting treatments ....................................................... 70 xi Chapter 1: Literature Review 1.1 Peanut Color Raw peanut seeds lack chromoplasts and other coloring agents, which results in a white seed color (Abegaz and Kerr 2006). Roasting peanuts promotes the formation of melanoidin pigments formed from amino acids reacting with reducing sugars, which gives peanut butter its distinct color (Abegaz and Kerr 2006). Pigments formed during roasting absorb in the blue-violet spectrum resulting in the perceived brown color of peanut paste (Abegaz and Kerr 2006). Roasted peanut color is used as a quality assurance parameter for peanut butter producers (Pattee and others 1991). Hunter L or CIELAB L* values can be used to determine the ideal roasted peanut color. Hunter L values of 51-52 or CIELAB L* values of 58-59 are the optimum values when roasted peanut attribute is the main focus (Pattee and others 1991). Pattee and others (1991) found that deviations less than 2 units away from the ideal CIELAB L* values were difficult for an eight member trained roasted peanut flavor profile panel to detect differences in roasted peanut intensity. Moisture also plays an important role in peanut butter color. Felland and Koehler (1997) found that peanut butter color became darker (lower Hunter L values) as 2.5% and 5.0% water was added. Abegaz and Kerr (2006) found that adding 2% or 5% moisture to peanut paste produced darker samples over a storage period of 52 weeks with the 5% 1 added water having the darker color. Abegaz and Kerr (2006) also established that adding 180 ppm of tertiary butylhydroquinone (TBHQ) and 4% sucrose to peanut paste did not have a significant effect on color. 1.2 Peanut Flavor The Maillard reaction, Strecker degradation, caramelization of sugars, and lipid oxidation are responsible for the volatiles in roasted peanuts (Neta and others 2010). Pyrazines formed from Maillard browning reactions are responsible for the roasted nutty flavor in peanuts (Buckholz and others 1980; Mason and others 1966). Carbonyls are produced by oxidation and Strecker degradation (Buckholz and others 1980) and provide a harsh green note found in roasted peanuts (Buckholz and Daun 1981). Peanut flavor is complex and each volatile has a distinct odor that is perceived by humans (Table 1.1). Table 1.1. Odors of selected volatiles in peanuts. Volatile (E)-2-heptenal (E)-2-nonenal (E)-2-octenal (E)-2-pentenal (E,E)-2,4-decadienal 1-decene 1-octanol 1-octen-3-ol 1-pentanol 1-penten-3-one 2,3-butanedione 2,3-diethyl-5methylpyrazine Odor Reference fatty, green fatty, green fatty, deep fried green, painty fatty, deep fried strong, cardboard citrus, fatty, woody, waxy mushroom sweet, alcohol solvent buttery Matsui and others 1998 Matsui and others 1998 Matsui and others 1998 Brown and others 1973 Matsui and others 1998 MacLeod and Coppock 1976 SAFC 2011 Ba and others 2012 Ruth 1986 Matsui and others 1998 Matsui and others 1998 roasty Matsui and others 1998 continued 2 Table 1.1. Continued 2,5-dimethylpyrazine 2,6-dimethylpyrazine 2,6-nonadienal 2-butenal 2-decanone 2-heptanol 2-hexanone 2-methyl-3ethylpyrazine 2-methylbutanal 2-methylpropanal 2-methylpyrazine 2-nonanone 2-octanone 2-pentanone 2-undecanone 3-methylbutanal 3-methyl-2-butanone 3-methylbutanoic acid 4-vinylguaiacol 5-methylfurfural acetaldehyde acetic acid acetoin acetone alpha-pinene ammonia benzaldehyde benzene butanal butanone decanal decane dimethyl disulfide dimethyl sulfide malty, chocolate nutty, earthy cucumber-like pungent, suffocating fresh, nutty oily, earthy floral, apple Braddock and others 1995 Schirack and others 2006a Matsui and others 1998 Ruth 1986 Lei and Boatright 2001 SAFC 2011 Flores and others 1997 roasty Matsui and others 1998 green malty chocolate, nutty, meaty, green hot milk, soap, green, fruity, floral floral orange peel fruity Matsui and others 1998 Matsui and others 1998 SAFC 2011 Ba and others 2012 camphor Lei and Boatright 2001 Arora and others 1995 Ba and others 2012 Matsui and others 1998/ Flores and others 1997 Singh and others 2003 sweaty Matsui and others 1998 spicy, phenolic sweet, spicy, caramel, bitter almond green, sweet, fruity bread dough, yeasty buttery, cream minty chemical, sweet weak pine pungent, irritating pleasant, bitter sweet, solventy smoky, fish, amylic, aldehydeenal or dienal butterscotch fresh, floral fatty, waxy onion like decayed cabbage Matsui and others 1998 malty/ cheesy-green Vazquez-Araujo and others 2009 Ruth 1986 Braddock and others 1995 Ruiz and others 2010 Ruth 1986 Jiang and Kubota 2004 Ruth 1986 Ruth 1986 Ruth 1986 Ba and others 2012 Arora and others 1995 Olafsdottir and others 2005 Buckholz and Daun 1981 Olafsdottir and others 2005 Ruth 1986 continued 3 Table 1.1. Continued dimethyl trisulfide ethanol ethyl 2methylbutanoate ethyl acetate furfural sulfurous sweet, alcoholic Matsui and others 1998 Ruth 1986 fruity Matsui and others 1998 fruity, pleasant almonds gasoline-like solventy, green gasoline-like Ruth 1986 Ruth 1986 Niu and others 2011/ Matsui and others 1998 Olafsdottir and others 2005 Ruth 1986 Matsui and others 1998/ Lei and Boatright 2001 Flores and others 1997 Matsui and others 1998 Schirack and others 2006a Ruth 1986 Ruiz and others 2010 Ruth 1986 Ruth 1986 Ruth 1986 Ruth 1986 Flores and others 1997 Matsui and others 1998/ Lei and Boatright 2001 Ruth 1986 Neta and others 2010 Ruth 1986 cheese, sweaty Niu and others 2011 sweet, honey-like/ floral, sweet, caramel honey, floral, green, sweet caramel, sweet, alcoholic, cooked, broth, spicy sour lemon-like mild sweet ether-like sweet, chemical earthy vanilla-like Matsui and others 1998/ Braddock and others 1995 SAFC 2011 guaiacol smokey/ burnt heptanal heptane earthy, boiled potato gasoline-like hexanal green/ oxidized, nutty hexane hexanoic acid hexenal hydrogen sulfide isobutanoic acid methanol methyl acetate methyl mercaptan methyl methanoate nonanal octanal octane pentanal pentane pentanoic acid (valeric acid) phenylacetaldehyde phenylacetic acid propanal propanoic acid R-limonene terpinolene tetrahydrofuran toluene trimethylpyrazine vanillin green-mold sweaty fruity rotten eggs rancid butter sweet fragrant, fruity sulfidy pleasant green fatty/ fresh leave 4 Ba and others 2012 Ruth 1986 Matsui and others 1998 Jiang and Kubota 2004 Ruth 1986 Schirack and others 2006a Frauendorfer and Schieberle 2006 Matsui and others 1998 1.2.1 SIFT-MS Selected ion flow tube mass spectrometry (SIFT-MS) is a quantitative mass spectrometric method that utilizes chemical ionization to accurately quantify trace gases in real time (Figure 1.1) (Smith and Spanel 2005). Volatile organic compounds (VOCs) can be identified and quantified with SIFT-MS from whole-gas samples (Harper and others 2011). Positive ions are created and filtered through a quadrupole mass filter to obtain ions with the desired mass-to-charge ratio (Smith and Spanel 2005). H3O+, NO+, and O2+ are the ions normally desired because they do not react with bulk components of air (Harper and others 2011). The ions are injected into the carrier gas (helium) and pushed along the flow tube to maintain the same temperature of the carrier gas (Smith and Spanel 2005). At the downstream end of the flow tube, ions are sampled into a differentially pumped quadrupole mass spectrometer and detected by a channeltron multiplier/pulse counting system (Smith and Spanel 2005). The reactant gas and injected ions are introduced into the carrier gas in measurable amounts through an entry port (Smith and Spanel 2005). Primary ion current decay and growth of the product ion count rates are observed with the downstream mass spectrometer/detection system taking into account the reactant gas flow rate (Smith and Spanel 2005). This allows the rate coefficient and ion products to be determined (Smith and Spanel 2005). The count of product ions divided by the count of reagent ions determines the concentration of a compound in real time (Harper and others 2011). Selected ion mode (SIM) provides direct quantification of specific target compounds which increases the sensitivity and precision of the analysis (Harper and others 2011). 5 SIFT-MS has a variety of applications for use in environmental science, medicine, food science, cell biology, and agriculture (Smith and Spanel 2005). SIFT-MS has been used to evaluate the volatile profile of roasted cashews (Agila and Barringer 2011) and almonds (Agila and Barringer 2012). Figure 1.1. Schematic of selected ion flow tube mass spectrometer (SIFT-MS) (Smith and Spanel 2005) 1.2.2 Raw Peanut Volatiles Acetone, acetaldehyde, ethanol, hexanal, methanol, octane, pentanal, pentane, and 2-butanone were identified in raw peanuts (Pattee and others 1969). Hexanal was 6 suggested to be a main contributor to raw peanut aroma based on this research; however, other volatiles may also be important (Pattee and others 1969). Hexanal and possibly pentanal, octanal, nonanal, and decanal are responsible for the “green or beany” flavor of raw peanuts based on the flavor thresholds (Brown and others 1972). Methanol, ethanol, pentane, acetone, dimethyl sulfide, methyl acetate, 2-methylpropanal, 2-methylbutanal, 3methylbutanal, pentanal, dimethyl disulfide, and hexanal were identified in raw peanuts (Young and Hovis 1990). The enzymes alcohol dehydrogenase and lipoxygenase may also be responsible for volatile production. Acetaldehyde, methanol, pentane, ethanol, and hexanal were shown to be related to alcohol dehydrogenase and lipoxygenase activity during peanut maturation (Patte and others 1970). Patte and others (1970) also detected trace amounts of acetone and pentanal in peanuts. 1.2.3 Maillard Browning Volatiles Maillard browning is a non-enzymatic reaction that takes place between reducing sugars and amino acids in the presence of heat. Peanuts contain amino acids including alanine, arginine, aspartic acid, cystine, glutamic acid, glycine, histidine, hydroxylysine, isoleucine, leucine, lysine, methionine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, and valine (Hoffpauir 1953), which can participate in Maillard browning. The main sugar source in peanuts is sucrose, which converts to glucose and fructose during roasting and are the main contributors in the browning reactions (Mason and others 1969). Maillard reactions produce pyrazines, pyrroles, furans, and low molecular weight compounds (Schirack and others 2006a). 7 The parts of the Maillard reaction include the initial stage, intermediate stage and final stage. During the initial stage, the products created are colorless and do not absorb in the ultraviolet spectrum (Hodge 1953; Nursten 2005). This stage includes sugar-amine condensation and Amadori rearrangement, which are reactions A and B, respectively (Figure 1.2) (Nursten 2005). The intermediate stage produces products that are colorless or yellow and absorb in the ultraviolet spectrum (Hodge 1953; Nursten 2005). Sugar dehydration, sugar fragmentation, and amino acid degradation, also known as Strecker degradation, make up the intermediate stage, which are reactions C, D, and E, respectively (Firgure 1.2) (Hodge 1953; Nursten 2005). Highly colored products are produced during the final stage and include aldol condensation (reaction F) and aldehydeamine condensation and formation of heterocyclic nitrogen compounds (reaction G) (Figure 1.2) (Nursten 2005). Free-radical breakdown of Maillard intermediates is represented by reaction H (Figure 1.2) (Nursten 2005). 8 + amino compound N-SUBSTITUTED GLYCOSYLAMINE ALDOSE SUGAR + H2O A B H C 1-AMINO-1-DEOXY-2-KETOSE - 3 H2O D C - 2 H 2O + α-amino acid SCHIFF BASE OF HMF OR FURFURAL REDUCTONES +2 H -2 H - amino compound + H2O HMF OR FURFURAL FISSION PRODUCTS + α-amino acid DEHYDROREDUCTONES E with or without amino compound + α-amino acid G E E F + amino compound ALDIMINES G F F G ALDOLS AND N-FREE POLYMERS + amino compound G CO2 + ALDEHYDE + amino compound ALDIMINES OR KETIMINES + amino compound ALDIMINES G MELANOIDINS (BROWN NITROGENOUS POLYMERS AND COPOLYMERS) Figure 1.2. Maillard browning reaction flow chart based on Hodge 1953 and Nursten 2005. 9 G G 1.2.4 Lipid Oxidation Volatiles Alcohols, alkanes, ketones, and aldehydes are the source of off-flavors in peanuts formed from the breakdown of hydroperoxides during lipid oxidation (Schirack and others 2006a). Oxidative rancid flavors or cardboard flavors are associated with low molecular weight aldehydes such as pentanal, hexanal, octanal, and nonanal, which are lipid oxidation products produced in peanuts (Warner and others 1996). Off-flavors such as painty and cardboardy were determined to be associated with lipid oxidation in peanuts (Braddock and others 1995). 1.3 Lipid Oxidation Peanut kernels contain about 50% oil on a dry basis (Hoffpauir 1953). Peanut oil contains several long-chain fatty acids including oleic, linoleic, palmitic, stearic, arachidic, behenic, and lignoceric acids (Hoffpauir 1953). Oleic and linoleic acids make up 48% and 31% of the fatty acids present in peanuts, respectively (Bett and Boylston 1992). Since peanuts contain a high amount of unsaturated fats, they are susceptible to lipid oxidation. Free fatty acid (FFA) and peroxide value tests can be performed on peanut oil to determine the extent of primary oxidation. A Runner peanut crop in 1942 was found to have 0.65% FFA on a moisture free basis (Hoffpauir 1953), although peanut oil should have low levels of FFA ranging from 0.8% in immature seed to 0.05% in mature seed (Sanders 2002). Peroxide values for peanut oil should have a maximum of 10 meq peroxides oxygen/kg oil in order to maintain acceptable flavor (Sanders 2002). Flavor and oxidative stability were tested of peanuts that had high amounts of oleic acid and lower amounts of linoleic acid (Braddock and others 1995). The 10 researchers found that the peanuts with higher amounts of oleic acid had a more desirable flavor during storage and the shelf life was almost two times longer compared to normal peanuts (Braddock and others 1995). Bolton and Sanders (2002) studied the stability of oil roasting high-oleic peanuts in high-oleic peanut oil and found that shelf life decreased when the high-oleic peanut oil was not used. 1.4 Microwave Processing Peanuts are traditionally dry roasted commercially for peanut butter applications and oil and/or dry roasted for other applications such as candy and snack peanuts (Young and others 1974). In hot air (oven) heating, energy is conducted into the food matrix from the surface of the product, which is a slower heating method (Datta and Rakesh 2013). Factors that affect hot air heating are air temperature, air velocity, food thermal conductivity, food density, and specific heat (Datta and Rakesh 2013). For microwave heating, energy is absorbed in the volume of the food product resulting in fast internal heating (Datta and Rakesh 2013). Power level, food size, food shape, and dielectric properties of the food are all factors that affect microwave heating (Datta and Rakesh 2013). Microwave energy has benefits including reduced product cost by increased production, improved quality, and fewer heating problems (Decareau 1985). Microwaves save energy by having instantaneous start-up and fast heating, which increases production (Decareau 1985). Microwave heating allows internal evaporation to take place inside the food, which enhances the moisture loss during heating (Datta and Rakesh 2013). The heating is selective in that moist areas will heat more than dry areas and the heating is not 11 as uniform as conventional heating (Datta and Rakesh 2013). With shelled and in-shell peanuts, dielectric properties were only measured up to 50 °C, but increasing temperature decreased the dielectric loss factor (Boldor and others 2004). Young and others (1974) compared dry, oil, and microwave roasting methods on the flavor and composition of peanut butter. Although there were differences among panelists, dry roasted peanuts scored lower in flavor compared to microwave roasted peanuts with a trained taste panel (Young and others 1974). Microwave blanching peanuts has also been explored as an alternative to traditional techniques (Schirack and others 2006b). Schirack and others (2006b) found that microwave blanching could be utilized without producing microwave-associated off-flavor. The objectives of this research were to determine differences in color, volatile levels, sensory characteristics, and lipid oxidation results between oven, microwave, and combination roasting treatments. 12 Chapter 2: Comparison of Peanut Roasting Using Oven and Microwave Technologies on the Development of Color, Flavor, and Lipid Oxidation 2.1 Abstract Roasted peanut quality was evaluated using oven, microwave, and combination roasting technologies. Raw peanuts were roasted by different methods to produce equivalent, commercially ideal L* roast color. Raw peanuts were oven roasted at 163 °C, 177 °C, and 204 °C, microwave roasted, or combination roasted using oven and microwave technologies at different times and temperatures. Roasted peanut color, volatiles, free fatty acid, peroxide values, and sensory attribute values based on descriptive sensory panel analysis were determined. Two commercial peanut butter samples were analyzed for color and volatile comparison. Odor activity values (OAVs) were calculated based on volatile levels quantified with selected ion flow tube mass spectrometry and known odor thresholds. Based on the OAVs that were greater than one, roasted peanut samples had similar volatiles important for flavor compared to the commercial samples. Lipid oxidation values were not significantly different between the roasted peanut samples, displaying no evidence to support that roasting time or temperature affected lipid oxidation, when ideal color was produced. Sensory attribute values showed no significant difference between oven, microwave, or combination roasting for most of the peanut flavor descriptors. Microwave and microwave 13 combination roasting produced similar color, flavor, lipid oxidation, and sensory attribute values compared to oven roasting treatments. 2.2 Practical Application Roasted peanut color, flavor, lipid oxidation, and sensory attributes are important quality parameters used to evaluate roasted peanuts. Oven and microwave roasting technologies that were roasted to the same peanut color had similar volatiles responsible for flavor as commercial peanut butter samples. Based on the evaluated quality parameters, microwave or combination roasting technologies may be used as alternative roasting methods to produce peanut butter. 2.3 Introduction Peanuts are produced in Alabama, Florida, Georgia, Mississippi, New Mexico, North Carolina, Oklahoma, South Carolina, Texas, and Virginia in the United States (USDA 2013b). In 2012, there were 6.74 billion pounds of peanuts produced in the United States, which was a record high (USDA 2013b). Drought and other weather conditions can affect yields and production of crops (USDA 2013b). There are several peanut products produced from peanuts including snack peanuts, peanut butter, and peanut candy (USDA 2012). Out of those peanut products, peanut butter was the primary product consumed between 1967 and 2010 (USDA 2012). Runner peanuts have increased in price from $344.35 per ton on January 4, 2006 (USDA 2006), to $499.65 per ton on January 2, 2013 (USDA 2013a). Alternative roasting technology may help reduce production costs associated with peanut butter manufacturing. Microwave energy has benefits including reduced product 14 cost by increased production, improved quality, and fewer heating problems (Decareau 1985). Microwaves save energy by having instantaneous start-up and fast heating, which increases production (Decareau 1985). Microwave heating allows internal evaporation to take place inside the food, which enhances the moisture loss during heating (Datta and Rakesh 2013). Melanoidin pigments form during peanut roasting giving peanut butter a distinct color (Abegaz and Kerr 2006). Roast color is used as a control parameter for peanuts commercially because of the relationship it has with flavor development (Smyth and others 1998). The ideal CIELAB L* value for roasted peanuts ranges from 58-59 ± 2 (Pattee and others 1991). Different time and temperature combinations during peanut roasting have been shown to produce equivalent surface color (McDaniel and others 2012). Similar quality can be achieved with different roasting conditions and roasting technologies. Equivalent external surface color for almonds was achieved with oven, microwave, and oil roasting (Agila and Barringer 2012). Microwave roasted almonds were found to have higher volatile levels with selected ion flow tube mass spectrometry and better flavor in sensory testing compared to oven and oil roasting methods (Agila and Barringer 2012). Dry, oil, and microwave roasted peanuts were evaluated for flavor and it was found that dry roasted peanuts scored lower in flavor than microwave roasted peanuts, while oil roasted peanuts had the highest flavor scores (Young and others 1974). Microwave blanched peanuts and the associated off-flavors have been studied with sensory panels and instrumentally (Schirack and others 2006a, Schirack and others 2006b). 15 Lipid oxidation in roasted peanuts also affects quality. High free fatty acid values can indicate improper handling, moisture, or fungal growth, while peroxide values are used as an indicator of lipid oxidation (Sanders 2002). The objectives of this study were to determine which technology or combination treatment roasted to equivalent ideal color provided ideal flavor, the lowest free fatty acid and peroxide values, and acceptable sensory characteristics. 2.4 Methods 2.4.1 Peanut Roasting Raw peanuts (Medium Runner, Birdsong Peanuts, Sylvester, GA, U.S.A.) with the shells removed were stored for less than 10 mo in sealed containers under refrigeration conditions (4 °C) to minimize lipid oxidation. Raw peanut samples (60 ± 0.1 g) were roasted with the skins intact. Oven roasting was performed using a bench top roaster oven (Nesco Jet-Steam Oven, American Harvest, Two Rivers, WI, U.S.A.). The bottom pan in the roaster oven was fitted with a 30.48 cm by 5.08 cm round baking pan (Wilton Industries, Woodridge, IL, U.S.A.). Aluminum foil was fitted around the exterior of the baking pan, which extended to the top of the roaster oven to prevent peanuts from escaping. Oven roasting was performed with the fan speed on high to allow the peanuts to freely circulate in the modified roaster. Microwave roasting was performed in an 1100 W microwave oven (Panasonic, Matsushita Home Appliance Corporation of America, Danville, KY, U.S.A.) on high power with the peanuts (60 ± 0.1 g) in a single layer in a glass dish. Combination treatments were performed by first oven roasting or microwave 16 roasting and then peanuts were immediately transferred to the other respective roasting treatment in less than 1 min. After roasting, the peanuts were cooled for 10 min at ambient temperature in a single layer and the skins were removed with gloved hands using a stainless steel mesh colander to rub off the skins. Samples were ground in an electric blender (Magic Bullet Express, Homeland Housewares, New York, NY, U.S.A.) with a stainless steel cross blade and short cup for 30 sec. Roasting conditions were chosen to produce equivalent, ideal color. Oven roasting was carried out at 177 °C for 10 min, at 204 °C for 7 min, and at 163 °C for 20 min. Microwave roasting was carried out for 2 min 30 sec. Combination roasting treatments included microwave roasting for 1 min then oven roasting at 204 °C for 6 min, microwave roasting for 2 min then oven roasting at 177 °C for 8 min, and oven roasting at 204 °C for 6 min then microwave roasting for 1 min. Two commercial peanut butter samples manufactured by The J.M. Smucker Company were purchased from a local market. These samples were selected due to project sponsorship, and have not been associated with any previous microbiological product or process issues. Commercial sample #1 was a stabilized peanut butter (Jif ® Creamy Peanut Butter, The J.M. Smucker Company, Orrville, OH, U.S.A.). Commercial sample #2 was a natural peanut butter sample that only contained peanuts (Smucker’s ® Natural Peanut Butter Creamy No Salt Added, The J.M. Smucker Company, Orrville, OH, U.S.A.). Commercial sample #2 was emptied into a glass beaker and thoroughly mixed before flavor and color analysis. 17 2.4.2 SIFT-MS Ground peanut samples and commercial peanut butter samples (50 ± 0.1 g) were placed into a 500 mL Pyrex bottle and capped with open top caps fitted with polytetrafluoroethylene (PTFE)-faced silicone septa. Bottled samples were stored under refrigeration conditions and were allowed to equilibrate at ambient temperature for 2 h before being placed in the water bath. The sample bottles were placed in a 50 ± 3 oC water bath (Precision Scientific, Jouan Inc., Winchester, VA, U.S.A.) for 60 min before the volatiles were measured. Five replicates of every roasting treatment and the commercial peanut butter samples were analyzed. Selected ion flow tube-mass spectrometry (SIFT-MS) (SYFT Voice 200, Syft Technologies Ltd., Christchurch, New Zealand) was used to detect and quantify peanut volatiles. A selected ion mode (SIM) method was developed using H3O+, NO+, or O2+ as precursor ions; refer to Smith and Spanel (2005) for more information on SIFT-MS. The method developed was based on known volatiles present in raw and roasted peanuts (Matsui and others 1998; Young and Hovis 1990; Coleman and others 1994; Brown and others 1973; Mexis and Kontominas 2009; Smyth and others 1998; Braddock and others 1995; Buckholz and Daun 1981; Singleton and Pattee 1991; Pattee and Singleton 1981; Ku and others 1998; Shu and Waller 1971). Volatile kinetics are shown in Table 2.1. Headspace of the Pyrex bottles was measured by piercing the septa with a stainless steel passivated sampling needle (18 gauge x 1.9 cm length), which was attached to the inlet of the SIFT-MS. A second stainless steel needle (14 gauge x 15 cm length) also pierced the septa to maintain atmospheric pressure in the bottle. The 18 headspace of each bottle was scanned for 2 min. A blank water sample was the first sample tested and was run after each peanut sample to ensure the needle was clear of lingering volatiles. Roasting treatment replicates were analyzed in a random order to account for variation in the roasting method. Validations were passed daily on the SIFTMS before volatiles were analyzed. The flow tube pressure during the SIFT-MS run was 0.086 ± 0.005 Torr. Mixtures were reported for compounds that had mass conflicts. In this study, 2,3diethyl-5-methylpyrazine is a mixture of 4-vinylguaiacol and 2,3-diethyl-5methylpyrazine; 2-pentanone is a mixture of 3-methyl-2-butanone and 2-pentanone; 3methylbutanoic acid is a mixture of pentanoic acid and 3-methylbutanoic acid; butanal is a mixture of acetaldehyde, butanal and pentanal; hexane is a mixture of 2-methylbutanal and hexane; methyl methanoate is a mixture of acetic acid and methyl methanoate; pentane is a mixture of tetrahydrofuran and pentane; 2,6 nonadienal is a mixture of (E,E)2,6-nonadienal and (E,Z)-2,6-nonadienal; hexenal is a mixture of (E)-2-hexenal and (Z)3-hexenal; dimethylpyrazine is a mixture of 2,3-dimethylpyrazine, 2,5-dimethylpyrazine, and 2,6-dimethylpyrazine; terpenes are a mixture of R-limonene, alpha-pinene, phenylacetic acid, and terpinolene. Table 2.1. Kinetics of volatile compounds in peanuts for SIFT-MS analysis Compound (E)-2-heptenal (E)-2-nonenal Formula Precursor ion Product ion k (10-9 cm3/s) m/z Ref C7H12O C9H16O NO+ NO+ C7H11O+ C9H15O+ 3.9 3.8 111 139 5 5 19 continued Table 2.1. Continued (E)-2-octenal (E)-2-pentenal (E,E)-2,4decadienal 1-decene 1-octanol 1-octen-3-ol 1-pentanol 1-penten-3-one 2,3-butanedione 2,3-diethyl-5methylpyrazine dimethylpyrazine 2,6-nonadienal 2-butenal 2-decanone 2-heptanol 2-hexanone 2-methyl-3ethylpyrazine 2-methylpropanal 2-methylpyrazine 2-nonanone 2-octanone 2-pentanone 2-undecanone 3-methylbutanal 3-methylbutanoic acid 5-methylfurfural acetoin acetone ammonia benzaldehyde benzene butanal butanone decanal decane C8H14O C5H8O NO+ NO+ C8H13O+ C5H7O+ 4.1 4.0 125 83 5 5 C10H16O NO+ C10H15O+ 4.2 151 5 C10H2O C8H18O C8H16O C5H12O C5H8O C4H6O2 NO+ NO+ H3O+ NO+ NO+ NO+ C10H20.NO+ C8H17O+ C8H15+ C5H11O+ C5H8O.NO+ C4H6O2+ 2.1 2.3 3.1 2.5 2.5 1.3 170 129 111 87 114 86 2 C9H14N2 O2+ C9H14N2+ 2.5 150 8 C6H8N2 C9H14O C4H6O C10H20O C7H16O C6H12O NO+ NO+ NO+ NO+ NO+ NO+ C6N2H8+ C9H14O.NO+ C4H5O+ C10H20O.NO+ C7H15O+ NO+.C6H12O 2.8 2.5 4.1 2.5 2.4 3.6 108 168 69 186 115 130 8 8 5 8 10 4 C7H10N2 NO+ C7H10N2.NO+ 2.5 152 8 C4H8O C5H6N2 C9H18O C8H16O C5H10O C11H22O C5H10O O2+ NO+ NO+ NO+ NO+ NO+ H3O+ C4H8O+ C5H6N2+ C9H18O.NO+ C8H16O.NO+ NO+.C5H10O C11H22O.NO+ C5H6+ 3.0 2.8 2.7 3.3 3.1 3.4 3.6 72 94 172 158 116 200 66 5 8 3 3 4 3 5 C5H10O2 NO+ C5H10O2.NO+ 2.5 132 8 C6H6O2 C4H8O2 C3H6O NH3 C7H6O C6H6 C4H8O C4H8O C10H20O C10H22 NO+ NO+ NO+ O2+ NO+ O2+ O2+ NO+ NO+ O2+ C6H6O2+ C4H8O2.NO+ NO+.C3H6O NH3+ C7H5O+ C6H6+ C2H4O+ NO+.C4H8O C10H19O+ C10H22+ 3.1 2.5 1.2 2.6 2.8 1.6 3.5 2.8 3.3 2.0 110 118 88 17 105 78 44 102 155 142 10 8 4 7 4 7 4 4 5 7 6 8 4 8 4 continued 20 Table 2.1. Continued dimethyl disulfide dimethyl sulfide dimethyl trisulfide C2H6S2 C2H6S C2H6S3 O2+ NO+ O2+ ethanol C2H6O NO+ C7H14O2 ethyl 2methylbutanoate furfural guaiacol heptanal heptane hexanal hexane hexanoic acid hexenal hydrogen sulfide isobutanoic acid methanol methyl acetate methyl mercaptan methyl methanoate nonanal octanal octane pentane phenylacetaldehyde propanal propanoic acid pyrazine terpenes toluene trimethylpyrazine vanillin (CH3)2S2+ (CH3)2S+ C2H6S3+ C2H5O+, C2H5O+.H2O, C2H5O+.2H2O 2.3 2.2 2.2 NO+ C7H14O2.NO+ C5H4O2 C7H8O2 C7H14O C7H16 C6H12O C6H14 C6H12O2 C6H10O H2S C4H8O2 NO+ NO+ NO+ H3O+ H3O+ O2+ NO+ NO+ O2+ O2+ CH4O H3O+ C3H6O2 NO+ CH4S H3O+ C2H4O2 C9H18O C8H16O C8H18 C5H12 C8H8O C3H6O C3H6O2 C4H4N2 C10H16 C7H8 C7H10N2 C8H8O3 NO+ NO+ NO+ O2+ O2+ NO+ NO+ O2+ NO+ NO+ NO+ O2+ O2+ C5H4O2+ C7H8O2+ C7H13O+ H3O+.C7H16 C6H11+ C6H14+ C6H12O2.NO+ C6H9O+ H2S+ (CH3)2CHCOOH+ CH5O+, CH3OH2+.H2O, CH3OH.H+.(H2O)2 NO+.CH3COOCH3 CH4S.H+, CH4S.H+.H2O NO+.HCOOCH3 C9H17O+ C8H15O+ C8H18+ C3H6+ C8H8O+ C3H5O+ C2H5COOH+ C4H4N2+ C10H16+ C7H8+ C7H10N2+ C8H8O3+ 94 62 126 45, 63, 81 7 7 10 2.4 160 8 3.2 2.5 3.3 2.6 3.7 1.7 2.5 3.8 1.4 2.5 96 124 113 119 83 86 146 97 34 88 33, 51, 69 104 49, 67 90 141 127 114 42 120 57 74 80 136 92 122 152 10 8 5 1 4 7 8 4 11 7 1.2 2.7 1.6 1.8 5.0 2.7 3.0 1.9 1.6 2.5 2.5 2.2 2.8 2.2 1.7 2.5 2.8 6 6 7 11 7 8 5 7 7 8 4 7 8 8, 9 7 8 8 [1] Arnold and others 1998, [2] Diskin and others 2002, [3] Smith and others 2003, [4] Spanel and others 1997, [5] Spanel and others 2002, [6] Spanel and Smith 1997, [7] 21 Spanel and Smith 1998, [8] Syft Technologies, Inc. 2011, [9] Wang and others 2003, [10] Wang and others 2004, [11] Williams and others 1998 Odor activity values (OAVs) were calculated based on known odor thresholds of volatiles in air (Table A1, Appendix). Odor thresholds were converted to ppm based on 25 °C and 1 atm of pressure. The smallest odor thresholds reported in literature were used to make the OAVs conservative. Some odor thresholds were not found in literature. OAVs were calculated by dividing the volatile concentration by the odor thresholds found in literature. Average OAVs were determined for all roasting treatments and commercial samples. 2.4.3 Color Peanut samples were blended for 20 sec in an electric blender (Magic Bullet Express, Homeland Housewares, New York, NY, U.S.A.) with a stainless steel cross blade and short cup. The paste was pressed into the bottom of an Optilux Petri Dish (BD Biosciences, San Jose, CA, U.S.A.). Commercial peanut butter samples were spread on the bottom of an Optilux Petri Dish (BD Biosciences, San Jose, CA, U.S.A.). Each petri dish was completely filled before analysis. Color measurements were performed at ambient temperature using a Color Quest XE colorimeter (Hunter Associate Laboratory, Inc., Reston, VA, U.S.A.). A reflectance specular included method was used with illuminant D65, 10° standard observer angle, and a 2.54 cm area view. The CIELAB L*a*b* values were collected. Individual samples were measured in triplicate and roasting treatments were analyzed in triplicate to obtain the averages. 22 2.4.4 Peanut Oil Analysis Ground peanut samples were wrapped in two layers of cheesecloth. Oil was extracted from the cheesecloth at ambient temperature using a Carver press Model C 3851-0 (Carver, Inc., Wabash, IN, U.S.A.). Samples were placed in a large stainless steel cylinder pellet mold with a stainless steel pan on the bottom to collect the peanut oil. The press was subjected to 9072 kg of clamping force then allowed to drop to 6804 kg. The clamping force was increased again to 9072 kg and allowed to drop to 6804 kg. Finally, the press was increased to 9072 kg of clamping force and allowed to drop for 3 min before the sample was removed and oil was collected for analysis. Oil was extracted from six replicates per roasting treatment to be able to perform triplicates on the free fatty acid and peroxide value tests. 2.4.4.1 Free Fatty Acid Free fatty acid values were determined with the AOCS Official Method Ab 5-49 (AOCS 1998a). Extracted oil (7.05 ± 0.05 g) was placed in a flask. Neutralized alcohol (50 mL) and phenolphthalein indicator (1 mL) were added to the flask. The solution was titrated with 0.25 N NaOH with constant stirring until a faint pink color was obtained for at least 1 min. The percentage of free fatty acid (oleic acid) was calculated using the following formula (AOCS 1998a), where mL was the amount of NaOH required: % FFA = 23 2.4.4.2 Peroxide Value Peroxide values were determined with the AOCS Official Method Cd 8-53 (AOCS 1998b). Extracted oil (5.00 ± 0.05 g) was placed into a 250-mL Erlenmeyer flask. Acetic acid-chloroform 3:2 (v/v) solution (30 mL) was added to the flask to dissolve the sample. Saturated KI solution (0.5 mL) was added to the flask. The solution was allowed to stand for 1 min then distilled water (30 mL) was added to the flask. The solution was titrated with 0.1 N sodium thiosulfate with constant stirring until the yellow iodine color almost disappeared. Starch indicator solution (2.0 mL) was added to the flask and titration continued until the blue color disappeared. A blank titration was conducted daily using the reagents. The peroxide value was calculated using the following formula (AOCS 1998b), where B was the volume of titrant (mL of blank), S was the volume of titrant (mL of sample), and N was the normality of sodium thiosulfate solution: Peroxide value (milliequivalents peroxide/1000g sample) = ( ) ( ) 2.4.5 Sensory Peanuts were roasted at The Ohio State University (Columbus, OH, U.S.A.), vacuum sealed, and frozen. The sensory analysis was performed at Lubbock Christian University (Lubbock, TX, U.S.A.). Peanuts were shipped and stored frozen until they were processed. Peanut samples were ground into a paste before analysis. Seven trained panelists completed the descriptive sensory analysis on the roasted peanuts. A peanut lexicon based on Johnsen and others (1988) was used, which included roasted peanut, sweet, salty, bitter, raw beany green, dark roast, woody hulls skins, sweet aromatic, astringent, fruity fermented sour over ripe, cardboard oxidized, and painty oxidized oil as 24 flavor descriptors. An abbreviated 1-10 scale was used to rate the intensity of the sensory attributes based on Johnsen and others (1988). The averages of the seven panelists’ scores were reported for each sensory attribute. 2.4.6 Statistical Analysis One-way analysis of variance (ANOVA) and Tukey’s post hoc test was performed on the data using Minitab 16 (Minitab Inc., State College, PA, U.S.A.). For the one-way ANOVA α = 0.05 and a Tukey’s family error rate of 5 was used. 2.5 Results and Discussion 2.5.1 Color In commercial roasting, roast color is primarily used as a control parameter because of the relationship it has with flavor development (Smyth and others 1998). Hunter color-difference values are commonly used for quality assurance with commercial peanut butter producers (Pattee and others 1991). CIELAB L* values of 58-59 are the optimum values when the peanut sensory attribute ‘roasted peanut’ is the main focus (Pattee and others 1991). In one study it was difficult for an eight member trained roasted peanut flavor profile panel to detect differences in roasted peanut intensity with deviations less than 2 units away from the ideal L* value (Pattee and others 1991). All roasting treatments and one commercial sample fell within the desired L* range of 58-59 ± 2. Commercial #1 fell within the ideal L* range, while commercial #2 (L* = 54.56 ± 0.28) was darker in color compared to most of the other samples. A darker roast color was expected because “natural” peanut butter is roasted for a longer time (Elder 2013). 25 2.5.2 Volatiles Volatiles in roasted peanuts are mainly due to the Maillard reaction, which produces pyrazines, Strecker degradation, caramelization of sugars, and lipid oxidation (Neta and others 2010, Warner and others 1996). Maillard reactions produce pyrazines, pyrroles, furans, and low molecular weight compounds (Schirack and others 2006a). Pyrazines are responsible for the roasted flavor in peanuts (Buckholz and others 1980). Carbonyls are produced by oxidation and Strecker degradation in peanuts, although some can be lost during roasting because of the volatility of the compounds (Buckholz and others 1980). Oxidative rancid flavors or cardboard flavors are associated with low molecular weight aldehydes such as pentanal, hexanal, octanal, and nonanal, which are lipid oxidation products produced in peanuts (Warner and others 1996). Volatiles in all seven roasting treatments and two commercial samples had odor activity values (OAVs) that were generally greater than one indicating the volatiles were detectable to the consumer and were likely important to peanut flavor (Table 2.2). OAVs greater than one are indicated by the gray boxes in Table 2.2. All roasting treatments and commercial samples generally followed the same trend, in that for all treatments, the volatile always had an OAV greater than one or always had an OAV less than one. This indicated that the same volatiles are contributing to peanut flavor in samples that had equivalent roast color. Methyl mercaptan had the greatest OAVs among the volatiles, at 9.45 x 1010 to 8.86 x 1012, which indicated that this volatile should have a strong impact on aroma in roasted peanuts (Table 2.2). Methyl mercaptan has a sulfidy aroma (Ruth 1986), and is likely derived from methionine during Maillard browning (Nursten 2005). Vanillin, 2,326 butanedione, butanal, and hydrogen sulfide had OAVs greater than one thousand for all roasting treatments and commercial samples indicating these volatiles were also very important to peanut flavor. The aroma of vanillin, 2,3-butanedione, butanal, and hydrogen sulfide are vanilla-like (Matsui and others 1998), buttery (Matsui and others 1998), smoky/fish/amylic/aldehyde-enal or dienal (Ba and others 2012), and rotten eggs (Ruth 1986), respectively. These volatiles are formed during Maillard browning or are a product of lipid oxidation, with the exception of vanillin. Vanillin was found to be a product of peanut hull lignin hydrolysis in boiled peanuts (Sobolev 2001), although peanut hulls were not used in the present study. The mechanism for vanillin formation in roasted peanuts is not certain. Not every volatile had an OAV greater than one (Table 2.2). The volatiles with OAVs less than one are not detectable by the human nose and are indicated by the white boxes in Table 2.2. Volatiles that had OAVs that were less than one for all samples included (E)-2-pentenal, 1-decene, 2-octanone, 2-pentanone, 2-undecanone, benzene, decane, octane, and toluene. Thus, these volatiles were probably not important to peanut flavor based on this study. Except for toluene, these volatiles have not been shown to have an aroma impact with roasted peanuts. Toluene was found to be a high impact aroma-active compound in peanuts as determined by aroma extract dilution analysis (AEDA) and based on dilution factors (Schirack and others 2006a), which does not support the current study. However, the AEDA technique has flaws because it cannot determine if compounds exist in concentrations above sensory thresholds and does not take into account the volatile perception in the food matrix (Schirack and others 2006a). 27 Odor thresholds were not based on the food matrix or determined in this research; therefore, OAV determinations also have flaws. Almonds that were microwave roasted had higher levels of volatiles compared to oven and oil roasted treatments (Agila and Barringer 2012), which did not occur in the present research with peanuts. In this study, oven roasted treatments had higher OAVs or were not significantly different from microwave or combination treatments (Table 2.2). Microwave blanching of peanuts has been associated with stale/floral and ashy offflavors related to an increase in guaiacol, phenylacetaldehyde, and 2,6-dimethylpyrazine concentrations (Schirack and others 2006a). Microwave roasted treatments had OAVs that were lower or not significantly different from the oven roasted treatments and not different from the microwave combination treatments for these three volatiles (Table 2.2). Therefore, microwave roasted treatments did not have higher concentrations of the volatiles known to be associated with microwave blanched off-flavors. Commercial #1 and #2 had lower volatile levels compared to the roasting treatments tested in this study (Table 2.2). Commercial #1 contained ingredients other than peanuts, which may contribute to the lower OAVs. Commercial #1 was produced less than two months before the flavor analysis and commercial #2 was produced less than three months before the flavor analysis, which may also contribute to the differences in OAVs compared to the freshly roasted peanuts. 28 Table 2.2. Average odor activity values (OAVs) from ideally roasted peanuts and commercial peanut butter samples. OAVs less than one are indicated with white boxes. Oven 163 °C for 20 min Oven 177 °C for 10 min Oven 204 °C for 7 min Microwave 2 min 30 sec Microwave 2 min then Oven 177 °C for 8 min Microwave 1 min then Oven 204 °C for 6 min Oven 204 °C for 6 min then Microwave 1 min Commercial #1 Commercial #2 Volatile (E)-2-heptenal 1.17cd 2.29a 1.61b 1.29bcd 1.52bc 1.09de 1.07def 0.66f 0.69ef (E)-2-nonenal 22.24c 43.88a 32.31b 22.89c 24.34c 20.95cd 19.58cde 13.18e 14.40de (E)-2-octenal 9.05c 17.21a 13.57b 10.16c 10.45c 8.19cd 7.87cde 5.37de 5.20e (E)-2-pentenal (E,E)-2,4decadienal 1-decene 0.02b 0.05a 0.03b 0.03b 0.03b 0.02b 0.02b 0.01c 0.01c 174.10c 340.21a 255.00b 205.37bcd 192.51c 162.88c 161.60c 103.82d 95.76d <0.01ab <0.01ab <0.01a <0.01ab <0.01ab <0.01ab <0.01ab <0.01ab <0.01b cd a ab cd bc cd cd d 7.24d 29 1-octanol 1-octen-3-ol 1-pentanol 1-penten-3-one 2,3-butanedione 2,3-diethyl-5methylpyrazine dimethylpyrazine 2,6-nonadienal 2-butenal 12.99 30.28 22.29 12.82 17.64 13.50 13.23 8.48 25.34bcd 48.05a 34.32b 27.05bcd 32.82bc 22.73cd 24.75bcd 17.99d 18.23d 15.72bc 29.21a 19.38b 14.74c 14.52c 13.83c 12.53c 4.02d 3.16d 539.66bc 1038.71a 714.90b 619.11bc 694.11b 488.24cd 470.54cd 299.85d 310.90d 47706.23c 84187.95a 65917.72b 46825.81c 50695.69bc 48136.10c 45746.19c 15834.28d 12283.00d 2008.52cd 4704.82a 3259.53b 1757.31cde 2460.81bc 1985.31cd 1660.38cde 1207.72de 872.13e 2.09cde 5.25a 3.51b 2.18cde 2.79bc 2.29cd 2.02cde 1.31e 1.60de 312.00bc 541.56a 403.81b 309.47bc 393.17b 275.02cd 272.55cd 183.42d 212.38cd c a b c c c c d 0.09d 0.85 1.47 1.16 0.76 0.85 0.81 0.75 0.11 2-decanone 8.76abc 8.97abc 9.57abc 9.70ab 10.38a 8.47abc 8.99abc 5.82c 6.26bc 2-heptanol 1.56bc 3.71a 2.47b 1.59bc 1.79b 1.53bc 1.47bc 0.51c 0.51c 2-hexanone 1.09bc 1.52a 1.24b 1.03cd 1.00cd 0.89cd 0.82d 0.47e 0.40e 4059.75bc 6804.55a 5362.73ab 3380.47c 4687.77bc 3975.61bc 3671.40bc 834.72d 705.77d 2-methylpropanal continued 29 Table 2.2. Continued 2-nonanone 0.91abc 1.07a 1.16a 1.07a 0.98ab 1.01ab 1.02ab 0.73bc 0.65c 2-octanone 0.50cd 0.72a 0.69ab 0.57abcd 0.66abc 0.54bcd 0.57abcd 0.46d 0.44d 2-pentanone 0.15bc 0.27a 0.19b 0.16bc 0.16bc 0.14c 0.13c 0.07d 0.05d 2-undecanone 0.41abc 0.50abc 0.57ab 0.59a 0.50abc 0.48abc 0.50abc 0.32c 0.35bc b a c de d de de de 119.46e 3-methylbutanal 3-methylbutanoic acid acetone 587.92 1300.28 419.64 188.00 262.24 193.81 216.81 189.75 1121.33c 2769.33a 1582.60b 952.97c 1134.50c 932.83c 890.78c 541.52d 401.87d 2.61bc 4.66a 3.16b 3.43b 3.13b 2.48bc 2.15c 0.86d 0.66d ammonia 35.37bc 47.36a 38.60b 24.91d 38.71b 29.97cd 27.34d 13.65e 16.75e benzaldehyde 304.68b 477.91a 312.87b 275.80bc 262.73bc 226.83c 221.31c 125.81d 99.64d 0.06b 0.11a 0.07b 0.07b 0.07b 0.05b 0.05b 0.02c 0.02c 6320.12bc 9451.42a 7816.66ab 5447.14c 5742.78c 5773.39c 5790.90c 1423.35d 1141.18d 1.36bc 2.56a 1.67b 1.42b 1.56b 1.18bcd 1.10bcd 0.59d 0.74cd cde a b cd bc cde def ef 31.89f benzene butanal 30 butanone decanal 53.03 105.31 79.90 57.71 67.30 51.24 49.07 36.47 0.02cd 0.03a 0.02abc 0.02bcd 0.03ab 0.02bcd 0.02bcd 0.01d 0.01d 3903.36bc 9364.97a 5276.60b 4655.40b 5034.02b 3499.90bcd 3185.69bcd 1514.41d 1917.97cd dimethyl sulfide 243.39a 243.98a 187.11b 142.52c 171.51bc 143.41c 140.15c 91.72d 56.26e dimethyl trisulfide 16.42bc 27.12a 21.98ab 14.90c 17.67bc 14.39c 14.85c 7.15d 7.66d 10.69c 47.30a 16.54b 10.69c 11.27c 9.03cd 9.23cd 7.07de 5.93e 1991.99bc 3642.13a 2360.13b 1942.10bc 1845.34bc 1612.34c 1747.58c 966.09d 905.60d 5.70bc 10.42a 6.64b 5.82bc 5.73bc 4.56bcd 4.37cd 2.43de 2.07e bcd a b bc bc bcd cd d 481.59d decane dimethyl disulfide ethanol ethyl 2methylbutanoate furfural guaiacol 711.46 1879.70 1149.02 1037.23 1053.39 738.99 667.57 410.67 heptanal 64.98bc 86.46a 69.62b 62.01bcd 62.69bcd 51.16cde 49.24de 38.30ef 33.73f heptane 5.38b 10.55a 5.00b 2.32cd 4.08bc 2.95c 3.05c 0.79d 0.66d hexanal 77.63b 119.80a 69.63bc 70.74b 61.96bcd 54.15cd 52.31d 32.04e 22.54e continued 30 Table 2.2. Continued hexane hexanoic acid hexenal hydrogen sulfide isobutanoic acid 236.19bc 419.45a 317.17b 247.45bc 241.24bc 230.97c 221.07c 63.29d 49.12d 18.80cd 71.47a 31.08b 22.87bc 21.46cd 18.10cd 18.73cd 13.41cd 12.12d 64.08bcd 147.94a 89.12b 71.83bcd 87.85bc 60.53cd 54.21d 23.30e 22.84e 2498.07c 3622.24a 3750.18a 3195.16abc 3242.36abc 3308.68ab 2820.86bc 1503.23d 1480.73d bc a b c bc c c d 18.97d 117.54 273.73 157.54 87.89 113.26 98.68 90.24 23.22 methanol 5.46a 5.42a 4.10b 2.70d 4.10b 3.26cd 3.43c 1.92e 1.72e methyl acetate 4.94b 7.39a 4.25bc 2.72d 4.88b 3.11cd 2.75d 0.89e 0.89e 7.15E+12ab 8.86E+12a 7.34E+12ab 4.30E+12c 6.70E+12b 5.69E+12bc 4.78E+12c 1.71E+11d 9.45E+10d 833.10b 1158.49a 808.07bc 578.67de 648.27cd 548.81de 609.32de 480.92ef 319.58f 155.13bc 230.84a 178.60b 137.24bcd 159.59bc 131.12cd 127.91cd 118.37cd 109.74d octanal 900.65bc 1420.68a 1306.81a 801.94c 1196.47ab 793.24c 938.15bc 943.41bc 852.77c octane pentane 0.03b 0.04a 0.03ab 0.03b 0.03ab 0.02b 0.03b 0.01c 0.01c a ab bc a d cd d e 4.02e methyl mercaptan methyl methanoate nonanal 31 13.15 12.10 11.15 12.81 9.23 9.61 9.27 2.52 phenylacetaldehy de propanal 311.31b 429.51a 441.00a 336.80b 268.37b 318.66b 316.27b 143.04c 93.65c 608.89c 1267.47a 882.67b 523.64c 606.63c 600.56c 513.97c 133.99d 123.56d propanoic acid 300.82bc 462.94a 268.20bcd 148.05ef 318.60b 201.08cde 170.13de 33.99g 42.30fg toluene 0.66cd 0.99a 0.75b 0.72bc 0.59de 0.61de 0.54e 0.17f 0.20f trimethylpyrazine 3.76cd 9.60a 6.59b 4.08cd 4.94bc 4.20cd 3.62cd 2.47d 3.16cd 80561.71bcd 3.07E+05a 1.49E+05b 83600.36bcd 1.33E+05bc 85073.32bcd 63193.59cd 30581.22d 25760.96d vanillin a-g Samples with different letters for the same volatile are significantly different 31 2.5.3 Lipid Oxidation No significant difference was found in percent free fatty acid (FFA) values when comparing the roasting treatments with ideal L* values to the raw peanuts as the control (Figure 2.1). FFA values ranged from 2.1 – 4.4% for the different roasting treatments. The average free fatty acid percentage on a moisture-free basis from a Runner peanut crop in 1942 was 0.65% (Hoffpauir 1953). Peanut oil has low levels of FFA ranging from 0.8% with immature seed to 0.05 % in mature seed (Sanders 2002). FFA values can increase from improper handling, moisture, fungal growth, or other factors (Sanders 2002). The reported literature values were lower than the average free fatty acid values determined in this study, indicating the peanuts may have been exposed to moisture, fungal growth, or improper handling. The raw peanut FFA value was not significantly different from the roasted peanut values, which indicated that when peanuts were roasted to ideal color the FFA values were not affected. No significant difference was found in peroxide values comparing the seven roasting treatments with ideal L* values with raw peanuts as the control (Figure 2.2). Peroxide value is used as an indicator of peanut quality with high values indicating that lipid oxidation has taken place (Sanders 2002). The maximum peroxide value for peanut oil is 10 meq peroxides oxygen/kg oil to maintain acceptable flavor (Sanders 2002). All samples tested in this study were below 10 meq/kg oil indicating that the peanut oil had low levels of lipid oxidation. The raw peanut peroxide value was not significantly different from the roasted peanut values indicating that roasting treatment did not affect the peroxide values. 32 4.0 a Free fatty acid (%) 3.5 3.0 a a a a a a a 2.5 2.0 1.5 1.0 0.5 Oven 204 °C for 6 min then Microwave 1 min Microwave 1 min then Oven 204 °C for 6 min Microwave 2 min then Oven 177 °C for 8 min Microwave 2 min 30 sec Oven 204 °C for 7 min Oven 177 °C for 10 min Oven 163 °C for 20 min Raw 0.0 Roasting Treatment Figure 2.1. Percent free fatty acid in treatments with no significant difference in L* value with raw peanuts as the control a Samples with different letters are significantly different 33 Peroxide value (MEQ/1000g sample) 2.0 1.8 a 1.6 a 1.4 1.2 1.0 a a a a a a 0.8 0.6 0.4 0.2 Oven 204 °C for 6 min then Microwave 1 min Microwave 1 min then Oven 204 °C for 6 min Microwave 2 min then Oven 177 °C for 8 min Microwave 2 min 30 sec Oven 204 °C for 7 min Oven 177 °C for 10 min Oven 163 °C for 20 min Raw 0.0 Roasting Treatment Figure 2.2. Peroxide values (MEQ/1000 g sample) of treatments with no significant difference in L* value with raw peanuts as the control a Samples with different letters are significantly different 2.5.4 Sensory No differences were observed between any of the roasting treatments for woody hulls skins, sweet aromatic, astringent, or salty sensory attributes (Table 2.3). None of the 34 roasting treatments contained fruity fermented sour over ripe, cardboard oxidized, or painty oxidized oil sensory attributes. The panelists noted a musty/smoky aftertaste with the oven 177 °C for 10 min treatment and microwave for 2 min then oven 177 °C for 8 min treatment. Significant differences were observed with roasted peanut, sweet, dark roast, bitter, and raw beany green sensory attributes (Table 2.3). In a previous study, roast peanutty, sweet aromatic, and sweet taste attributes were positively correlated with each other and negatively correlated with bitter, ashy, and total offnote attributes based on descriptive sensory analysis performed with microwave blanched peanuts (Schirack and others 2006b). In our study, the bitter attribute was found to be negatively correlated with the roasted peanut attribute. Higher values were found with the lowest oven roasting temperature and decreased as the oven temperature increased for the bitter attribute. Higher oven roasting temperatures and combination treatments with higher oven temperatures gave higher roasted peanut, sweet, and raw beany green sensory attribute values. Dark roast has been positively correlated with bitter and negatively correlated with the raw beany attribute for microwave blanched peanuts (Schirack and others 2006b). A similar trend was observed in this study with dark roast being negatively correlated to the raw beany green attribute. The microwave and lowest temperature oven roast had the highest level of dark roast attribute, which may be explained by the unevenness of the microwave roasting and long roasting time in the oven, respectively. Roasting treatments that had the highest sensory scores for the roasted peanut and sweet attributes were oven 177 °C for 10 min, oven 204 °C for 7 min, and the combination 35 treatment microwave 1 min then oven 204 °C for 6 min. Most of the flavor descriptor values were not significantly different between the oven, microwave, and combination treatments. 36 Table 2.3. Sensory attribute values determined by a descriptive sensory panel for different peanut roasting treatments*. Oven 163 Oven 177 Oven 204 °C for 20 °C for 10 °C for 7 min min min 37 Sensory Attribute Roasted Peanut 5.00 6.00 6.00 Sweet 2.00 3.00 3.00 Dark Roast 3.67 2.67 3.33 Bitter 3.67 3.00 2.67 Raw Beany Green 0.67 2.00 1.67 Woody Hulls Skins 2.33 2.00 2.00 Sweet Aromatic 2.00 2.00 2.33 Astringent 3.33 3.00 3.33 Salty 0.67 0.67 0.67 Fruity Fermented Sour Over Ripe 0.00 0.00 0.00 Cardboard Oxidized 0.00 0.00 0.00 Painty Oxidized Oil 0.00 0.00 0.00 * Numbers are statistically significant if they are greater than ± 0.50 37 Microwave 2 min 30 sec 5.33 3.00 4.00 3.00 0.67 2.33 2.00 3.33 0.67 0.00 0.00 0.00 Microwave 2 min then Oven 177 °C for 8 min 5.67 2.00 3.33 3.00 1.33 2.00 2.00 3.00 0.67 0.00 0.00 0.00 Microwave 1 min then Oven 204 °C for 6 min 6.33 2.67 3.00 2.67 2.00 2.00 2.33 3.00 0.67 0.00 0.00 0.00 Oven 204 °C for 6 min then Microwave 1 min 6.00 2.00 3.00 3.00 1.33 2.00 2.33 3.33 0.67 0.00 0.00 0.00 2.6 Conclusion Oven, microwave, and combination technologies produced equivalent L* color values and similar flavor quality based on the OAVs and sensory results. No significant differences were found in free fatty acid or peroxide values between the raw and roasted samples, which indicated that lipid oxidation was not affected by the roasting treatments tested. Microwave technology can shorten the roasting time, which may decrease processing costs, while still producing similar OAVs compared to the oven roasting and commercial peanut butter samples. Microwave combination treatments can also produce similar flavor quality based on OAVs and sensory results and could be considered as a commercial processing option. 2.7 References Abegaz EG, Kerr WL. 2006. Effect of Moisture, Sugar and Tertiary Butylhydroquinone on Color, Texture and Microstructure of Peanut Paste. J Food Quality 29(6):643-657. Agila A, Barringer S. 2012. Effect of Roasting Conditions on Color and Volatile Profile Including HMF Level in Sweet Almonds (Prunus dulcis). J Food Sci 77(4):C461-C468. AOCS. 1998a. AOCS Official Method Ab 5-49 Free Fatty Acids. In: Firestone D, editor. 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Compositional and Mechanical Properties of Peanuts Roasted to Equivalent Colors using Different Time/Temperature Combinations. J Food Sci 77(12):C1292-C1298. Mexis SF, Kontominas MG. 2009. Effect of gamma irradiation on the physic-chemical and sensory properties of raw shelled peanuts (Arachis hypogaea L.) and pistachio nuts (Pistacia vera L.). J Sci Food Agri. 89(5):867-875. Neta ER, Sanders T, Drake MA. 2010. Understanding Peanut Flavor: A Current Review. In: Hui YH, editor. Handbook of Fruit and Vegetable Flavors. New Jersey: John Wiley & Sons, Inc. p 985-1022. Nursten H. 2005. The Maillard Reaction Chemistry, Biochemistry, and Implications. Reading, UK: The Royal Society of Chemistry. 83 p. Pattee HE, Giesbrecht FG, Young CT. 1991. Comparison of Peanut Butter Color Determination by CIELAB L*a*b* and Hunter Color-Difference Methods and the Relationships of Roasted Peanut Color to Roasted Peanut Flavor Response. J Agric Food Chem 39(3):519-523. Pattee HE, Singleton JA. 1981. Peanut Quality: Its Relationship to Volatile CompoundsA review. In: Teranishi R, Barrera-Benitez B, editors. Quality of Selected Fruits and Vegetables of North America. Washington DC: American Chemical Society. p 147-161. Ruth JH. 1986. Odor Thresholds and Irritation Levels of Several Chemical Substances: A Review. Am Ind Hyg Assoc J 47(3):A142-A151. Sanders TH. 2002. Groundnut (peanut) oil. In: Gunstone FD, editor. Vegetable Oils In Food Technology: Composition, Properties and Uses. Florida: CRC Press LLC. p 231243. Schirack AV, Drake M, Sanders TH, Sandeep KP. 2006a. Characterization of AromaActive Compounds in Microwave Blanched Peanuts. J Food Sci 71(9):C513-C520. Schirack AV, Drake M, Sanders TH, Sandeep KP. 2006b. Impact of Microwave Blanching on the Flavor of Roasted Peanuts. J Sens Stud 21(4):428-440. Shu CK, Waller GR. 1971. Volatile Components of Roasted Peanuts: Comparative Analysis of the Basic Fraction. J Food Sci 36(4):579-583. Singleton JA, Pattee HE. 1991. 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Spanel P, Van Doren JM, Smith D. 2002. A selected ion flow tube study of the reactions of H3O+, NO+, and O2+ with saturated and unsaturated aldehydes and subsequent hydration of the products. Int J Mass Spectrom 213(2-3):163-176. Spanel P, Yufeng J, Smith D. 1997. SIFT studies of the reactions of H3O+, NO+ and O2+ with a series of aldehydes and ketones. Int J Mass Spectrom 165/166:25-37. Syft Technologies, Inc. 2011. Kinetics library database. Christchurch, New Zealand: Syft Technologies Inc. [USDA] United States Department of Agriculture, Economic Research Service. 2012. USDA ERS – Food Availability (Per Capita) Data System. USDA. Available from: http://www.ers.usda.gov/data-products/food-availability-(per-capita)-data-system.aspx. Accessed Jan 30, 2013. [USDA] United States Department of Agriculture, Farm Service Agency. 2006. Peanut Reports. Washington, D.C.: USDA. Available from: http://www.fsa.usda.gov/FSA/epasReports?area=home&subject=ecpa&topic=ftapn&summaryYear=2006&x=14&y=13. Accessed Jan 30, 2012. [USDA] United States Department of Agriculture, Farm Service Agency. 2013a. Peanut Reports. Washington, D.C.: USDA. Available from: http://www.fsa.usda.gov/FSA/epasReports?area=home&subject=ecpa&topic=fta-pn . Accessed Jan 30, 2012. 41 [USDA] United States Department of Agriculture, National Agricultural Statistics Service. 2013b. Crop Production 2012 Summary. USDA. ISSN: 1057-7823. Available from: USDA; 1, 95. van Gemert LJ. 2011. Odour Thresholds. Compilations of odour threshold values in air, water and other media. The Netherlands: Oliemans Punter & Partners BV. P 11-180. Wang T, Spanel P, Smith D. 2003. Selected ion flow tub, SIFT, studies of the reactions of H3O+, NO+ and O2+ with eleven C10H16 monoterpenes. Int J Mass Spectrom 228(1):117126. Wang T, Spanel P, Smith D. 2004. A selected ion flow tube, SIFT, study of the reactions of H3O+, NO+ and O2•+ ions with several N- and O-containing heterocyclic compounds in support of SIFT-MS. Int J Mass Spectrom 237(2-3):167-174. Warner KJH, Dimick PS, Ziegler GR, Mumma RO, Hollender R. 1996. ‘Flavor-fade’ and Off-Flavors in Ground Roasted Peanuts As Related to Selected Pyrazines and Aldehydes. J Food Sci 61(2):469-472. Williams TL, Adams NG, Babcock LM. 1998. Selected ion flow tube studies of H3O+(H2O)0,1 reactions with sulfides and thiols. Int J Mass Spectrom 172(1-2):149-159. Young CT, Hovis AR. 1990. A Method for the Rapid Analysis of Headspace Volatiles of Raw and Roasted Peanuts. J Food Sci 55(1):279-280. Young CT, Young TG, Cherry JP. 1974. The Effect of Roasting Methods on the Flavor and Composition of Peanut Butter. Proc Am Peanut Res Educ Assoc 6(1):8-16. 42 Chapter 3: Color and Volatile Analysis of Peanuts Roasted Using Oven and Microwave Technologies 3.1 Abstract Roasted peanut color and flavor was evaluated for different time and temperature combinations of roasting. Raw peanuts were oven roasted at 135 °C, 163 °C, 177 °C, and 204 °C, microwave roasted for 1-3 min, or combination roasted by microwave and oven roasting for various times and temperatures. Volatiles were measured using selected ion flow tube mass spectrometry (SIFT-MS). L* values were used to categorize peanuts into under roasted, ideally roasted, and over roasted. The total roasting time in order to achieve ideal color was not shortened by most of the combination treatments compared to their oven roasted equivalents. Oven before microwave roasting compared to the reverse was found to significantly increase the L* value likely due to the increase in the dielectric loss factor. Peanuts with ideal color had L* values that were not significantly different, but the volatile levels were different. Hexanal concentrations in all peanuts decreased then increased with roasting, but were below the level previously found to be unacceptable to consumers. Ethanol to methanol ratios in roasted peanuts were all below the level found in raw peanuts. Pyrazine levels increased as roasting time increased, although oven at 177 °C treatments had the highest and microwave treatments had the lowest levels. Volatile levels generally increased as roasting time or temperature increased with raw peanuts having the lowest levels and over roasted peanuts having the 43 highest volatile levels. Oven 177 °C for 15 min generally had the highest level of volatiles among the roasting treatments tested. Soft independent modeling of class analogies based on volatile levels showed that raw peanuts were the most different, commercial samples were the most similar to each other, and oven, microwave, and combination roasting were all similar in volatile profile. 3.2 Practical Application Peanuts can be roasted to equivalent colors and have similar volatile levels by different roasting methods. Oven and microwave roasting technologies produced the same roasted peanut color and had similar volatile trends as roasting time increased. Combination roasting also produced ideal color and similar volatile levels indicating that microwave technology may be used to roast peanuts on a commercial level. 3.3 Introduction Peanuts are roasted to achieve desirable color and flavor characteristics in peanut products, especially peanut butter. Similar quality can be achieved with different roasting conditions and roasting technologies, so it is important to understand the quality differences between roasting techniques. Roast color has a relationship with flavor development and therefore color is used as a control parameter for commercially roasted peanuts (Smyth and others 1998). The ideal CIELAB L* value for roasted peanuts ranges from 58-59 ± 2 (Pattee and others 1991). In roasted peanuts, the Maillard reaction, Strecker degradation, caramelization of sugars, and lipid oxidation are responsible for volatile formation (Neta and others 2010). 44 Selected ion flow tube mass spectrometry (SIFT-MS) can identify and quantify volatile organic compounds from whole-gas samples (Harper and others 2011). SIFT-MS was used to measure Maillard reaction and lipid oxidation volatiles in almonds roasted from oven, microwave, and oil roasting techniques and microwave roasting was found to produce the highest volatile levels (Agila and Barringer 2012). Maillard reaction, sugar degradation, and lipid oxidation volatiles were also measured during cashew roasting using SIFT-MS and it was found that volatiles increased during roasting (Agila and Barringer 2011). Raw almonds and cashews were found to have lower volatile levels than roasted almonds or cashews (Agila and Barringer 2011, 2012). Cocoa volatiles including alkylpyrazines and Strecker aldehydes were measured using SIFT-MS and found to increase with increased roasting temperature from 120 to 170 °C (Huang and Barringer 2011). As roasting time or temperature increases, the brown melanin color intensifies in peanuts (Pattee and others 1991). Oven, microwave, and oil roasted almonds were able to produce color equivalent to commercial almond samples (Agila and Barringer 2012). Hexanal, ethanol, and methanol have been identified in raw peanuts (Pattee and others 1969, Brown and others 1972, Young and Hovis 1990) and negatively affect raw peanut flavor (Brown and others 1977). Pyrazines, which are responsible for the roasted nutty aroma of roasted peanuts (Mason and others 1966), increase as roasting time increases (Buckholz and Daun 1981). Carbonyls provide a harsh green note found in roasted peanuts (Buckholz and Daun 1981) and are produced by oxidation and Strecker degradation (Buckholz and others 1980). Oven, microwave, or combination roasting techniques could be used to produce similar color and volatile levels. The objectives of 45 this study were to determine the color and volatile differences of peanuts roasted with oven, microwave, and combination roasting technologies. The effect that under, ideal, and over roasted peanuts had on volatile levels was also determined. 3.4 Methods 3.4.1 Peanut Roasting Raw peanuts (Medium Runner, Birdsong Peanuts, Sylvester, GA, U.S.A.) with the shells removed were stored for less than 10 mo in sealed containers under refrigeration conditions (4 °C) to minimize lipid oxidation. Raw peanut samples (60 ± 0.1 g) were roasted with the skins intact. Oven roasting was performed using a bench top roaster oven (Nesco Jet-Steam Oven, American Harvest, Two Rivers, WI, U.S.A.). The bottom pan in the roaster oven was fitted with a 30.48 cm by 5.08 cm round baking pan (Wilton Industries, Woodridge IL, U.S.A.). Aluminum foil was fitted around the exterior of the baking pan, which extended to the top of the roaster oven to prevent peanuts from escaping. Oven roasting was performed with the fan speed on high to allow the peanuts to freely circulate in the modified roaster. Microwave roasting was performed in an 1100 W microwave oven (Panasonic, Matsushita Home Appliance Corporation of America, Danville, KY, U.S.A.) on high power with the peanuts (60 ± 0.1 g) in a single layer in a glass dish. Combination treatments were performed by first oven roasting or microwave roasting and then peanuts were immediately transferred to the other respective roasting treatment in less than 1 min. After roasting, the peanuts were cooled for 10 min at ambient temperature in a single layer and skins were removed with gloved hands using a stainless steel mesh colander to rub off the skins. Samples were ground in an electric 46 blender (Magic Bullet Express, Homeland Housewares, New York, NY, U.S.A.) with a stainless steel cross blade and short cup for 30 sec. Oven roasting was carried out at 135 °C, 163 °C, 177 °C, and 204 °C for 5-20 min. Microwave roasting was carried out from 1 to 3 min. Combination roasting treatments included microwave roasting then oven roasting and oven roasting then microwave roasting at 163-204 °C for 5-15 min and microwaving 1-2 min. 3.4.2 SIFT-MS Ground peanut samples (50 ± 0.1 g) were placed into a 500 mL Pyrex bottle and capped with open top caps fitted with polytetrafluoroethylene (PTFE)-faced silicone septa. Bottled samples were stored under refrigeration conditions and were allowed to equilibrate at ambient temperature for 2 h before being placed in the water bath. The sample bottles were placed in a 50 ± 3 oC water bath (Precision Scientific, Jouan Inc., Winchester, VA, U.S.A.) for 60 min before the volatiles were measured. Five replicates of every roasting treatment were analyzed. Selected ion flow tube-mass spectrometry (SIFT-MS) (SYFT Voice 200, Syft Technologies Ltd., Christchurch, New Zealand) was used to detect and quantify peanut volatiles. A selected ion mode (SIM) method was developed using H3O+, NO+, or O2+ as precursor ions; refer to Smith and Spanel (2005) for more information on SIFT-MS. The method developed was based on known volatiles present in raw and roasted peanuts (Matsui and others 1998; Young and Hovis 1990; Coleman and others 1994; Brown and others 1973; Mexis and Kontominas 2009; Smyth and others 1998; Braddock and others 47 1995; Buckholz and Daun 1981; Singleton and Pattee 1991; Pattee and Singleton 1981; Ku and others 1998; Shu and Waller 1971). Volatile kinetics are shown in Table 3.1. Headspace of the Pyrex bottles was measured by piercing the septa with a stainless steel passivated sampling needle (18 gauge x 1.9 cm length), which was attached to the inlet of the SIFT-MS. A second stainless steel needle (14 gauge x 15 cm length) also pierced the septa to maintain atmospheric pressure in the bottle. The headspace of each bottle was scanned for 2 min. A blank water sample was the first sample tested and was run after each peanut sample to ensure the needle was clear of lingering volatiles. Roasting treatment replicates were analyzed in a random order to account for variation in the roasting method. Validations were passed daily on the SIFTMS before volatiles were analyzed. The flow tube pressure during the SIFT-MS run was 0.088 ± 0.005 Torr. Mixtures were reported for compounds that had mass conflicts. In this study, 2,3diethyl-5-methylpyrazine is a mixture of 4-vinylguaiacol and 2,3-diethyl-5methylpyrazine; 2-pentanone is a mixture of 3-methyl-2-butanone and 2-pentanone; 3methylbutanoic acid is a mixture of pentanoic acid and 3-methylbutanoic acid; butanal is a mixture of acetaldehyde, butanal and pentanal; hexane is a mixture of 2-methylbutanal and hexane; methyl methanoate is a mixture of acetic acid and methyl methanoate; pentane is a mixture of tetrahydrofuran and pentane; 2,6 nonadienal is a mixture of (E,E)2,6-nonadienal and (E,Z)-2,6-nonadienal; hexenal is a mixture of (E)-2-hexenal and (Z)3-hexenal; dimethylpyrazine is a mixture of 2,3-dimethylpyrazine, 2,5-dimethylpyrazine, 48 and 2,6-dimethylpyrazine; terpenes are a mixture of R-limonene, alpha-pinene, phenylacetic acid, and terpinolene. Table 3.1. Kinetics of volatile compounds in peanuts for SIFT-MS analysis Compound (E)-2-heptenal (E)-2-nonenal (E)-2-octenal (E)-2-pentenal (E,E)-2,4-decadienal 1-decene 1-octanol 1-octen-3-ol 1-pentanol 1-penten-3-one 2,3-butanedione 2,3-diethyl-5methylpyrazine dimethylpyrazine 2,6-nonadienal 2-butenal 2-decanone 2-heptanol 2-hexanone 2-methyl-3ethylpyrazine 2-methylpropanal 2-methylpyrazine 2-nonanone 2-octanone 2-pentanone 2-undecanone 3-methylbutanal 3-methylbutanoic acid Formula Precursor ion Product ion k (10-9 cm3/s) m/z Ref C7H12O C9H16O C8H14O C5H8O C10H16O C10H2O C8H18O C8H16O C5H12O C5H8O C4H6O2 NO+ NO+ NO+ NO+ NO+ NO+ NO+ H3O+ NO+ NO+ NO+ C7H11O+ C9H15O+ C8H13O+ C5H7O+ C10H15O+ C10H20.NO+ C8H17O+ C8H15+ C5H11O+ C5H8O.NO+ C4H6O2+ 3.9 3.8 4.1 4.0 4.2 2.1 2.3 3.1 2.5 2.5 1.3 111 139 125 83 151 170 129 111 87 114 86 5 5 5 5 5 2 C9H14N2 O2+ C9H14N2+ 2.5 150 8 C6H8N2 C9H14O C4H6O C10H20O C7H16O C6H12O NO+ NO+ NO+ NO+ NO+ NO+ C6N2H8+ C9H14O.NO+ C4H5O+ C10H20O.NO+ C7H15O+ NO+.C6H12O 2.8 2.5 4.1 2.5 2.4 3.6 108 168 69 186 115 130 8 8 5 8 10 4 C7H10N2 NO+ C7H10N2.NO+ 2.5 152 8 C4H8O C5H6N2 C9H18O C8H16O C5H10O C11H22O C5H10O O2+ NO+ NO+ NO+ NO+ NO+ H3O+ C4H8O+ C5H6N2+ C9H18O.NO+ C8H16O.NO+ NO+.C5H10O C11H22O.NO+ C5H6+ 3.0 2.8 2.7 3.3 3.1 3.4 3.6 72 94 172 158 116 200 66 5 8 3 3 4 3 5 C5H10O2 NO+ C5H10O2.NO+ 2.5 132 8 6 8 4 8 4 continued 49 Table 3.1. Continued C6H6O2+ C4H8O2.NO+ NO+.C3H6O NH3+ C7H5O+ C6H6+ C2H4O+ NO+.C4H8O C10H19O+ C10H22+ (CH3)2S2+ (CH3)2S+ C2H6S3+ C2H5O+, C2H5O+.H2O, C2H5O+.2H2O 3.1 2.5 1.2 2.6 2.8 1.6 3.5 2.8 3.3 2.0 2.3 2.2 2.2 NO+ C7H14O2.NO+ C5H4O2 C7H8O2 C7H14O C7H16 C6H12O C6H14 C6H12O2 C6H10O H2S C4H8O2 NO+ NO+ NO+ H3O+ H3O+ O2+ NO+ NO+ O2+ O2+ CH4O H3O+ C3H6O2 NO+ methyl mercaptan CH4S H3O+ methyl methanoate nonanal octanal octane pentane C2H4O2 C9H18O C8H16O C8H18 C5H12 NO+ NO+ NO+ O2+ O2+ C5H4O2+ C7H8O2+ C7H13O+ H3O+.C7H16 C6H11+ C6H14+ C6H12O2.NO+ C6H9O+ H2S+ (CH3)2CHCOOH+ CH5O+, CH3OH2+.H2O, CH3OH.H+.(H2O)2 NO+.CH3COOCH3 CH4S.H+, CH4S.H+.H2O NO+.HCOOCH3 C9H17O+ C8H15O+ C8H18+ C3H6+ 5-methylfurfural acetoin acetone ammonia benzaldehyde benzene butanal butanone decanal decane dimethyl disulfide dimethyl sulfide dimethyl trisulfide ethanol ethyl 2methylbutanoate furfural guaiacol heptanal heptane hexanal hexane hexanoic acid hexenal hydrogen sulfide isobutanoic acid methanol methyl acetate C6H6O2 C4H8O2 C3H6O NH3 C7H6O C6H6 C4H8O C4H8O C10H20O C10H22 C2H6S2 C2H6S C2H6S3 NO+ NO+ NO+ O2+ NO+ O2+ O2+ NO+ NO+ O2+ O2+ NO+ O2+ C2H6O NO+ C7H14O2 110 118 88 17 105 78 44 102 155 142 94 62 126 45, 63, 81 10 8 4 7 4 7 4 4 5 7 7 7 10 2.4 160 8 3.2 2.5 3.3 2.6 3.7 1.7 2.5 3.8 1.4 2.5 96 124 113 119 83 86 146 97 34 88 33, 51, 69 104 49, 67 90 141 127 114 42 10 8 5 1 4 7 8 4 11 7 1.2 2.7 1.6 1.8 5.0 2.7 3.0 1.9 1.6 6 6 7 11 7 8 5 7 7 continued 50 Table 3.1. Continued phenylacetaldehyde propanal propanoic acid pyrazine terpenes toluene trimethylpyrazine vanillin C8H8O C3H6O C3H6O2 C4H4N2 C10H16 C7H8 C7H10N2 C8H8O3 NO+ NO+ O2+ NO+ NO+ NO+ O2+ O2+ C8H8O+ C3H5O+ C2H5COOH+ C4H4N2+ C10H16+ C7H8+ C7H10N2+ C8H8O3+ 2.5 2.5 2.2 2.8 2.2 1.7 2.5 2.8 120 57 74 80 136 92 122 152 8 4 7 8 8, 9 7 8 8 [1] Arnold and others 1998, [2] Diskin and others 2002, [3] Smith and others 2003, [4] Spanel and others 1997, [5] Spanel and others 2002, [6] Spanel and Smith 1997, [7] Spanel and Smith 1998, [8] Syft Technologies, Inc. 2011, [9] Wang and others 2003, [10] Wang and others 2004, [11] Williams and others 1998 3.4.3 Color Peanut samples were blended for 20 sec in an electric blender (Magic Bullet Express, Homeland Housewares, New York, NY, U.S.A.) with a stainless steel cross blade and short cup. The paste was pressed into the bottom of an Optilux Petri Dish (BD Biosciences, San Jose, CA, U.S.A.). Each petri dish was completely filled before analysis totaling 50 g or more of sample. Color measurements were performed at ambient temperature using a Color Quest XE colorimeter (Hunter Associate Laboratory, Inc., Reston, VA, U.S.A.). A reflectance specular included method was used with illuminant D65, 10° standard observer angle, and a 2.54 cm area view. The CIELAB L*a*b* values were collected. Individual samples were measured in triplicate and roasting treatments were analyzed in triplicate to obtain the averages. 51 3.4.4 Statistical Analysis One-way analysis of variance (ANOVA) and Tukey’s post hoc test was performed on the data using Minitab 16 (Minitab Inc., State College, PA, U.S.A.). For the one-way ANOVA α = 0.05 and a Tukey’s family error rate of 5 was used. Soft independent modeling of class analogies (SIMCA) was performed on the volatile concentration data using Pirouette version 3.11 (Infometrix Inc., Bothell WA, U.S.A.). Mean-center was selected for the processing, the probability threshold was 0.95, the scope was local, and the maximum factor was three. A standard normal variate (SNV) transformation was performed on the data in the statistical program before running the SIMCA. 3.5 Results and Discussion 3.5.1 Color Roasting peanuts promotes the formation of melanoidin pigments formed from amino acids reacting with reducing sugars, which gives peanut butter its distinct color (Abegaz and Kerr 2006). In commercial roasting, roast color is used as a primary control parameter because of the relationship it has with flavor development (Smyth and others 1998). Hunter color-difference values are commonly used for quality assurance with commercial peanut butter producers (Pattee and others 1991). CIELAB L* values of 5859 are the optimum values when the peanut sensory attribute ‘roasted peanut’ is the main focus (Pattee and others 1991). When color was less than 2 units away from the ideal L* value, it was difficult for an eight member trained roasted peanut flavor profile panel to detect differences in roasted peanut intensity (Pattee and others 1991). 52 Ranges of time and temperature conditions were used to roast peanuts in oven and microwave technologies. Nine roasting treatments fell within the desired L* range (Figure 3.1). These treatments included three oven treatments, one microwave treatment, and five combination treatments. Nine treatments were under roasted including raw, three oven treatments, two microwave treatments, and three combination treatments. Five treatments were over roasted including three oven treatments, one microwave treatment, and one combination treatment. Raw peanuts and certain under, ideal, and over roasted peanut treatments were selected to be evaluated for volatile levels. 53 80 70 ab abc * bcd * f 60 L* value ab a * hi hi abc * gh hi de * ef f fg 50 abc cd * f f * * * ef ef ef i 40 30 20 Oven 204 °C 6 min then MW 1 min MW 1 min then Oven 204 °C 6 min MW 2 min then Oven 204 °C 5 min MW 1 min then Oven 204 °C 5 min Oven 177 °C 8 min then MW 2 min MW 2 min then Oven 177 °C 8 min MW 2 min then Oven 177 °C 5 min Roasting Treatments MW 1 min then Oven 177 °C 5 min MW 3 min MW 2 min 30 sec MW 2 min MW 1 min Oven 204 °C 10 min Oven 204 °C 7 min Oven 204 °C 5 min Oven 177 °C 20 min Oven 177 °C 15 min Oven 177 °C 10 min Oven 177 °C 5 min Oven 163 °C 20 min Oven 135 °C 20 min Raw 0 MW 2 min then Oven 163 °C 15… 10 Figure 3.1. L* values of oven, microwave (MW), and combination roasting treatments, ideal L* values range from 56-61 a-i Samples with different letters are significantly different * Samples with stars are within the ideal L* range As roasting time or temperature increases, the brown melanin color also intensifies (Pattee and others 1991). With increased roasting time, for a given treatment type at the same temperature, L* values decreased (Figure 3.1). Lower L* values indicate a darker roast color, while higher values indicate a lighter roast color. Similarly, the color became darker with increased roasting temperature for the same roasting time. 54 Most combination treatments produced no statistically significant difference in color compared to the oven roasting treatments with equivalent total roasting time (Figure 3.1). Microwave 2 min then oven at 177 °C for 8 min had a total roasting time of 10 min and there was no significant difference in L* value compared to the oven at 177 °C for 10 min treatment. Similarly, microwave 1 min then oven at 204 °C for 6 min and its reverse treatment had a total roasting time of 7 min with no significant difference in L* value compared to the oven at 204 °C for 7 min treatment. In order to produce ideal color, microwave roasting alone saved time compared to oven roasting; however, the combination treatments tested did not shorten the total roasting time. Reversing the order of combination treatments sometimes changed the L* value (Figure 3.1). Microwave 2 min then oven at 177 °C for 8 min was significantly lighter in color compared to its reverse treatment. In other words, oven before microwave had a darker color than the reverse. This difference may be due to the effect of temperature on the dielectric properties. Dielectric loss factor relates to the ability of a food to dissipate electrical energy, so the higher the value the more energy a food absorbs (Fellows 2009). With selected fruits and vegetables, as the temperature increases, the dielectric loss factor first decreases, then above 34 °C increases as temperature increases up to 130 °C (Sipahioglu and Barringer 2003). In ground almond shells, at a similar moisture content to peanuts (6 %), the dielectric loss factor increased with increased temperature to at least 90 °C (Gao and others 2012). None of these studies perfectly matched the moisture content of peanuts or the temperatures analyzed in this research (163 °C to 204 °C), but it is hypothesized that dielectric loss factor values increase with increasing temperatures up 55 to 204 °C with low moisture content peanut samples. Oven roasting before microwave roasting would increase the temperature of the peanuts before microwaving. The increased temperature before microwaving would increase the dielectric loss factor of the peanuts and provide more electrical energy dissipation in the same time period resulting in a darker roast color. This theory may explain why the oven before microwave treatment had a darker color than the reverse treatment. It is expected that oven roasting before microwave roasting would be more efficient than the reverse. 3.5.2 Volatile Levels in Raw Peanuts Raw and under roasted peanuts (L* value > 61) had L* values that were not significantly different; however, the volatile levels were significantly different for many volatiles (Figure 3.1 and Table 3.2). The volatile levels of the roasting treatments are ordered based on L* value from highest to lowest in Tables 3.2, 3.3, and 3.4. Compared to other methods, measuring the brown color is not sensitive in evaluating the degree of the Maillard reaction (O’Brien and others 1989). Volatile levels created by the Maillard browning reaction were more sensitive to roasting treatments than the L* values. Hexanal is a main contributor to the aroma of raw peanuts (Pattee and others 1969; Brown and others 1972) and is connected with off-flavor in peanut butter (Brown and others 1977). Hexanal is associated with alcohol dehydrogenase and lipoxygenase activity during peanut maturation (Pattee and others 1970). Levels were the highest in the raw and the most under roasted sample and concentrations decreased when the peanuts were roasted to ideal color (Tables 3.2, 3.3, and 3.4). Aldehydes, such as hexanal, are formed during storage from lipid oxidation (Bett and Boylston 1992; Reed and others 56 2002) and levels in roasted peanuts have been shown to increase during storage (Bett and Boylston 1992; Grosso and Resurreccion 2002; Warner and others 1996). From ideally roasted to over roasted peanuts, the hexanal levels increased, likely due to lipid oxidation, since hexanal is a secondary oxidation product of linoleic acid (Frankel 1985). In roasted peanuts, a hexanal content higher than 7.40 µg/g (7400 ppb) was found to be unacceptable to consumers based on overall acceptance scores (Grosso and Resurreccion 2002). All peanut samples had hexanal levels well below the concentration found in previous research to be unacceptable by consumers. Ethanol and methanol are present in raw peanuts (Pattee and others 1969; Young and Hovis 1990) and have been shown to negatively affect raw peanut flavor (Brown and others 1977). Ethanol and methanol are related to alcohol dehydrogenase and lipoxygenase activity during peanut maturation (Patte and others 1970). Ethanol is at the highest levels in raw peanut samples and was determined to be the most important volatile component for raw peanut flavor (Brown and others 1977). Cler scores, which indicated better flavor, increased as ethanol levels decreased in raw peanut samples (Brown and others 1977). As roasting time increased, there was no evident trend with ethanol or methanol levels (Tables 3.2, 3.3, and 3.4). A decrease in ethanol to methanol ratios was correlated with an increase in flavor scores of raw peanut samples (Brown and others 1977). Raw peanuts had the highest ethanol to methanol ratio (1.13) (Table 3.2). Ethanol to methanol ratios of roasted peanut samples (0.06 – 0.26) were all lower than raw peanuts. There was no distinct trend with the ratios as roasting time increased. 57 Table 3.2. Volatile levels (ppb) of raw and under roasted peanuts Oven 177 Microwave °C for 5 2 min min 6.84efg 6.81fg f 1.47 1.43f 3.21fg 3.72efg 5.83d 6.67d 1.47bcde 0.92ef 8.09c 8.86bc 10.89de 12.06de 10.51e 9.44e 74.66cd 68.44d ef 9.56 11.52def 205.82fg 362.40def 1.79ef 1.53ef 9.81g 33.43fg 2.20f 2.85ef 9.73hi 13.04gh 3.81a 4.50a 6.90e 8.36de def 23.95 20.15ef 2.88f 3.61f 280.95g 525.03efg 6.84de 19.07de 4.73b 5.02b 5.41f 6.38def 28.71ef 30.28e 2.00ab 2.27ab a 164.59 31.03fg 36.99def 21.29fg 2.42d 3.62d 40.87fg 38.77g 975.56d 938.15d 769.23hi 674.08i 61.13b 53.72bc 32.14cd 28.69d ef 256.48 362.44de Raw Volatile (E)-2-heptenal (E)-2-nonenal (E)-2-octenal (E)-2-pentenal (E,E)-2,4-decadienal 1-decene 1-octanol 1-octen-3-ol 1-pentanol 1-penten-3-one 2,3-butanedione 2,3-diethyl-5-methylpyrazine 2,5-dimethylpyrazine 2,6-nonadienal 2-butenal 2-decanone 2-heptanol 2-hexanone 2-methyl-3-ethylpyrazine 2-methylpropanal 2-methylpyrazine 2-nonanone 2-octanone 2-pentanone 2-undecanone 3-methylbutanal 3-methylbutanoic acid 5-methylfurfural acetoin acetone ammonia benzaldehyde benzene butanal 3.63g 1.21f 1.80g 4.09d 0.46f 10.66abc 10.54de 8.46e 20.22e 5.32f 15.45g 0.89f 1.24g 2.37ef 1.95i 5.19a 5.26e 8.34g 1.32f 43.94g 1.00e 6.02ab 7.12bcdef 6.94f 2.56ab 95.97c 13.22g 1.39d 12.36h 34.18e 82.95j 21.88d 13.20e 28.57f 58 Oven 204 °C for 5 min 6.17fg 1.44f 3.61fg 5.58d 1.19def 8.05c 10.23e 9.70e 66.85d 10.01def 335.13efg 1.80ef 28.10fg 2.75ef 12.43gh 4.00a 8.03de 23.13def 4.11f 467.84fg 14.16de 5.21b 6.55cdef 29.73e 2.02ab 79.21cd 28.65efg 2.84d 45.11efg 788.10d 829.56ghi 50.07bc 23.97de 350.11de continued Table 3.2. Continued butanone 7.24h 30.96gh 52.00efgh 39.99fgh decanal 1.30g 1.68fg 1.94efg 1.66fg decane 10.82de 9.02e 10.74de 9.31e d d d dimethyl disulfide 2.90 16.77 37.32 28.41d dimethyl sulfide 35.25g 302.48a 168.74cdef 196.18bcd dimethyl trisulfide 11.88f 15.98def 14.67ef 17.43def ethanol 2254.34c 3199.10b 954.33gh 1920.98cd ethyl 2-methylbutanoate 16.44e 20.20de 17.60e 19.50de furfural 2.46e 6.78e 6.78e 7.37e guaiacol 4.49e 4.16e 9.09e 6.27e heptanal 5.43f 10.52de 10.10de 10.17de g efg fg heptane 57.92 951.01 930.60 1137.78efg hexanal 326.31ab 406.45a 149.83efg 187.67cdefg hexane 73.14e 256.20e 364.21de 359.67de hexanoic acid 9.24g 20.90bcd 9.54g 16.13cdefg hexenal 1.29f 2.80ef 3.95def 2.99ef hydrogen sulfide 803.71i 956.96hi 1091.00ghi 1052.74ghi isobutanoic acid 25.28f 76.58ef 69.75ef 81.11ef methanol 2003.26g 14523.52bc 7939.86f 10935.45de g fg methyl acetate 15.95 241.46 243.31fg 296.94fg methyl mercaptan 15.73j 978.14ij 1040.22ij 1462.23hi methyl methanoate 124.39e 315.08d 239.94de 243.16de nonanal 5.30g 6.14fg 6.47efg 6.55efg octanal 9.97def 9.91def 10.95cdef 9.94def octane 29.90f 38.72ef 41.66def 38.82ef pentane 334.09f 984.02bcd 637.90e 898.20cd phenylacetaldehyde 23.51e 56.25d 54.73d 67.54cd h h gh propanal 8.70 144.02 278.77 254.22gh propanoic acid 10.40g 48.53fg 61.91fg 68.82fg pyrazine 0.27e 2.74de 2.58de 2.60de terpenes 3.67f 4.92f 5.17f 4.64f toluene 22.78cdef 25.09bcde 20.69def 20.42def trimethylpyrazine 1.93i 5.40hi 11.54fghi 9.66ghi vanillin 1.09c 1.91c 1.64c 1.84c a-j Samples with different letters for the same volatile in Tables 3.2, 3.3, and 3.4 are significantly different. Statistical analysis was performed comparing all roasting treatments in Tables 3.2, 3.3 and 3.4. 59 Table 3.3. Volatile levels (ppb) of ideally roasted peanuts 60 Volatile (E)-2-heptenal (E)-2-nonenal (E)-2-octenal (E)-2-pentenal (E,E)-2,4-decadienal 1-decene 1-octanol 1-octen-3-ol 1-pentanol 1-penten-3-one 2,3-butanedione 2,3-diethyl-5methylpyrazine 2,5-dimethylpyrazine 2,6-nonadienal 2-butenal 2-decanone 2-heptanol 2-hexanone Oven 204 °C for 6 min Microwave 1 min Microwave 2 min 30 sec Microwave 1 min Oven 204 °C for 6 min Microwave 2 min Oven 177 °C for 8 min 7.92fg 1.71ef 4.11efg 8.37d 1.04def 8.66bc 12.42de 11.13e 69.50d 13.67def 649.61cde 9.55ef 2.00def 5.31def 12.02d 1.32cde 8.74bc 12.03de 12.17de 81.73cd 17.99de 664.94cde 8.06fg 1.83def 4.28efg 9.43d 1.05def 7.50c 12.67de 10.23e 76.71cd 14.19def 683.54cd 11.28def 2.12cdef 5.47def 12.49cd 1.24cdef 9.55abc 16.55de 14.77cde 80.52cd 20.17cde 719.89c 8.64fg 1.94def 4.73defg 9.94d 1.12def 7.42c 12.19de 11.40e 87.20bcd 15.68def 677.44cd 11.94cdef 2.82bcde 7.10cde 12.51cd 1.64bcde 10.23abc 20.92bcd 15.44cde 107.47bc 20.78cd 936.05bc 16.98bcd 3.82b 9.00bc 20.98bc 2.19b 9.66abc 28.41bc 21.62bcd 161.99a 30.19bc 1195.49ab 2.43def 2.57def 2.91def 3.60cde 2.94def 4.77bcd 6.89b 77.48ef 2.89ef 17.41fgh 4.22a 12.66cde 19.67f 83.75def 3.28def 17.66fgh 4.55a 13.67cde 24.59cdef 88.13def 2.92ef 19.02efg 3.97a 13.20cde 21.21def 107.26de 4.17bcdef 19.78defg 4.87a 15.43cde 24.03def 80.18ef 3.31def 19.89defg 4.11a 13.45cde 26.03cdef 134.88cde 4.29bcde 27.03bcde 4.49a 21.28bcd 29.69bcd 201.90b 5.75bc 34.41ab 4.21a 31.97b 36.39b continued 60 Oven 163 °C for 20 min Oven 204 °C for 7 min Oven 177 °C for 10 min 61 Table 3.3. Continued 2-methyl-3-ethylpyrazine 2-methylpropanal 2-methylpyrazine 2-nonanone 2-octanone 2-pentanone 2-undecanone 3-methylbutanal 3-methylbutanoic acid 5-methylfurfural acetoin acetone ammonia benzaldehyde benzene butanal butanone decanal decane dimethyl disulfide dimethyl sulfide dimethyl trisulfide ethanol ethyl 2-methylbutanoate 5.45ef 1244.67def 41.84de 5.40b 6.52cdef 35.37de 2.16ab 21.54fg 31.98def 4.85d 61.56cdef 848.87d 1044.14efgh 40.79c 24.67de 642.70c 78.29efgh 1.92efg 11.75de 82.68d 137.84f 17.83def 832.59h 19.69de 8.20def 1146.04def 60.10cde 5.65b 6.57cdef 44.42cde 2.55ab 18.67g 34.21def 9.65cd 52.73defg 1355.17cd 951.47fghi 50.83bc 32.29cd 604.55cd 100.89efg 2.26efg 12.23de 120.82cd 140.17f 17.89def 964.31gh 21.88cde 7.74ef 1347.80d 46.04de 5.32b 6.22def 38.04cde 2.09ab 19.25g 33.49def 5.27d 60.49cdef 981.61d 1144.61efg 41.81c 25.42de 640.76c 84.32efg 2.00efg 11.47de 90.83d 141.04ef 17.27def 814.34h 18.17de 61 12.30cdef 1589.24cd 64.88cd 5.19b 7.52bcdef 43.87cde 2.17ab 26.05fg 40.73cde 7.32d 65.65cde 1240.28cd 1478.37bcd 48.42bc 30.95cd 637.36c 110.72def 2.63def 16.57bcde 130.65cd 168.68cdef 21.21cdef 1016.48fgh 20.79de 8.00def 1376.33d 51.22de 4.80b 5.67ef 42.91cde 1.78b 58.40de 40.26cde 5.23d 68.95cd 1032.49d 1350.64cde 56.15bc 27.79de 701.44c 96.99efg 2.07efg 9.76e 101.30d 239.37b 19.71def 964.61gh 22.44bcde 12.41cdef 1818.06bcd 69.63cd 6.14ab 7.85bcde 53.59bcd 2.45ab 41.68ef 56.82bc 8.00d 93.75b 1250.20cd 1474.23bcd 57.66bc 33.19cd 867.53bc 119.14cde 3.12bcde 15.45cde 136.94cd 184.03cdef 26.38cd 1491.64def 26.59bcd 24.10bcd 2306.87bc 118.08bc 5.63b 8.23bcd 76.03b 2.16ab 129.16b 99.43a 12.19cd 122.58a 1843.65bc 1808.60a 88.08a 52.32ab 1048.97ab 182.24bcd 4.12bc 20.32bcd 243.05bc 239.96b 32.55bc 4266.36a 41.03a continued 62 Table 3.3. Continued furfural guaiacol heptanal heptane hexanal hexane hexanoic acid hexenal hydrogen sulfide isobutanoic acid methanol methyl acetate methyl mercaptan methyl methanoate nonanal octanal octane pentane phenylacetaldehyde propanal propanoic acid pyrazine terpenes toluene 8.89de 13.15e 8.96ef 2005.57def 104.69g 627.84cd 11.43efg 5.40def 1416.64efg 125.21def 10451.99def 453.27ef 2427.94fgh 248.09de 6.59efg 9.30ef 44.64cdef 848.81de 64.35cd 519.19fg 168.46defg 4.09cde 13.61de 17.27f 11.84cde 20.43de 11.28cde 1528.96efg 141.56fg 702.76cd 13.96cdefg 7.16cde 1604.61def 121.94def 8238.48ef 449.64ef 2183.31ghi 235.61de 7.08defg 7.95f 44.18cdef 1172.65ab 68.53bcd 528.95efg 146.60efg 5.18cde 9.31ef 23.01cdef 9.29de 14.55e 9.31ef 1943.27def 108.37g 655.97cd 11.04fg 6.03def 1661.62cdef 136.92def 9951.82def 513.09def 2892.27efg 223.45de 6.76efg 7.86f 41.25ef 879.70cde 64.84cd 606.66def 199.10def 4.77cde 8.38ef 19.42def 62 11.67cde 20.75cde 11.41cde 2687.31cde 124.01g 685.11cd 13.10defg 8.75cd 1628.32def 157.15de 12516.11cd 805.84de 3403.07defg 263.95de 8.23cdef 11.86bcdef 53.33cdef 844.41de 54.61d 612.79def 315.46cd 5.58cde 12.99de 18.92ef 11.61cde 14.01e 11.83bcde 3544.30bcd 155.37efg 670.79cd 11.47efg 6.38def 1254.53fgh 163.08de 16667.74b 815.13de 3635.91cdef 339.21cd 8.00defg 8.93ef 45.53cdef 1203.19ab 63.35cd 615.08def 297.86cde 5.73cd 8.30ef 21.04def 13.52cde 22.63cde 12.67bcde 3295.45bcd 139.35fg 900.76bc 18.97bcdef 8.88cd 1883.34cd 218.58cd 12526.33cd 701.99de 3732.09bcde 329.02cd 9.21bcde 12.96bcde 53.45cdef 1020.16bcd 89.73a 891.64cd 265.55de 6.71cd 14.19cde 24.02cdef 21.21bcd 37.02bcd 15.73ab 6945.89a 239.76bcde 1191.23ab 43.62a 14.74b 1819.09cde 379.80ab 16531.80b 1219.30bc 4500.73bcd 471.69bc 11.90b 14.08abcd 66.61abcd 1107.97bc 87.40ab 1280.35ab 458.38bc 8.67bc 22.68b 31.37ab continued Table 3.3. Continued trimethylpyrazine 23.89efgh 26.93defg 27.76defg 32.63def 24.84defgh 43.53cde 63.39bc vanillin 2.03c 2.69c 2.73c 4.27bc 2.59c 4.80bc 9.86b a-i Samples with different letters for the same volatile in Tables 3.2, 3.3, and 3.4 are significantly different. Statistical analysis was performed comparing all roasting treatments in Tables 3.2, 3.3 and 3.4. 63 63 Table 3.4. Volatile levels (ppb) of over roasted peanuts Volatile (E)-2-heptenal (E)-2-nonenal (E)-2-octenal (E)-2-pentenal (E,E)-2,4-decadienal 1-decene 1-octanol 1-octen-3-ol 1-pentanol 1-penten-3-one 2,3-butanedione 2,3-diethyl-5-methylpyrazine 2,5-dimethylpyrazine 2,6-nonadienal 2-butenal 2-decanone 2-heptanol 2-hexanone 2-methyl-3-ethylpyrazine 2-methylpropanal 2-methylpyrazine 2-nonanone 2-octanone 2-pentanone 2-undecanone 3-methylbutanal 3-methylbutanoic acid 5-methylfurfural acetoin acetone Microwave 3 min Oven 177 °C for 15 min 14.74bcde 2.93bcd 8.03bcd 22.61b 1.78bcd 9.53abc 17.93cde 23.27bc 87.12bcd 29.55bc 880.83bc 4.57bcd 147.10bcd 3.92cdef 23.14cdef 4.10a 22.89bc 25.08cdef 21.12bcde 1610.42cd 153.76ab 4.99b 6.29def 60.55bc 2.14ab 17.14g 47.06cd 30.83ab 60.00cdef 2413.23ab 24.95a 5.40a 13.31a 34.00a 3.33a 12.79a 40.96a 33.19a 169.19a 48.73a 1454.24a 10.03a 309.08a 7.96a 40.88a 5.54a 51.41a 47.50a 52.67a 3248.94a 215.55a 7.77a 10.97a 107.82a 3.03a 87.61c 107.14a 22.76bc 118.81a 2710.00a 64 Oven 204 °C for 10 min 17.40bc 3.42b 9.20bc 21.91b 2.01bc 9.64abc 28.72b 21.71bcd 116.79b 32.70b 1165.97ab 6.71b 207.76b 5.92b 31.24bc 5.11a 32.61b 33.54bc 26.55bc 2487.97bc 134.48b 6.29ab 8.91abc 74.19b 2.50ab 38.45efg 69.27b 14.11cd 93.18b 1858.37bc Oven 177 °C for 8 min Microwave 2 min 17.89b 3.17bc 10.66ab 25.15b 2.22b 11.44ab 28.36bc 31.16ab 97.13bcd 37.45b 1155.85ab 6.13bc 182.74bc 5.26bcd 28.26bcd 5.40a 34.81b 29.34bcde 29.08b 2222.80bc 213.49a 6.39ab 9.47ab 75.80b 2.63ab 30.24fg 66.47b 38.08a 79.29bc 2548.04a continued Table 3.4. Continued ammonia benzaldehyde benzene butanal butanone decanal decane dimethyl disulfide dimethyl sulfide dimethyl trisulfide ethanol ethyl 2-methylbutanoate furfural guaiacol heptanal heptane hexanal hexane hexanoic acid hexenal hydrogen sulfide isobutanoic acid methanol methyl acetate methyl mercaptan methyl methanoate nonanal octanal octane pentane phenylacetaldehyde propanal propanoic acid pyrazine terpenes toluene 1273.36def 49.68bc 49.88ab 805.32bc 188.01bc 2.85cdef 16.39bcde 322.34ab 155.32def 24.33cde 1494.93def 22.73bcde 27.61ab 50.06ab 11.38cde 2188.25def 228.29cdef 906.30bc 19.36bcde 12.20bc 2360.51ab 209.07cd 9924.67def 896.35cd 3922.45bcde 339.88cd 7.89defg 11.00cdef 59.94bcde 946.44bcd 63.74cd 831.46cde 323.59cd 14.08a 14.21cde 29.57bc 65 1787.54ab 102.56a 56.83ab 1251.04a 277.93a 6.74a 33.27a 458.13a 299.71a 53.66a 2970.57b 48.46a 37.35a 70.65a 19.76a 8668.87a 282.85bc 1521.33a 39.10a 22.77a 1938.89bcd 489.98a 20922.75a 2176.47a 6073.56a 740.08a 14.71a 17.87a 89.29a 1368.71a 89.27a 1498.95a 878.06a 12.45ab 30.89a 37.59a 1623.45abc 66.54b 44.05bc 1015.53ab 189.39bc 4.18b 22.13bc 278.41b 210.12bc 31.74bc 1394.66efg 30.31bc 23.18bc 42.42bc 14.91bc 4689.33b 182.06defg 1156.82b 21.41bc 15.41b 2088.81abc 316.97bc 15175.35bc 1241.17bc 4790.00bc 474.72bc 10.93bc 14.70abc 67.71abc 1072.99bcd 76.93abc 1129.90bc 500.03b 8.69bc 19.17bcd 26.10bcd 1474.03bcd 61.27b 59.97a 1072.36ab 240.98ab 3.65bcd 25.53ab 455.19a 193.63bcde 38.15b 1574.81de 30.57b 38.42a 69.77a 13.70bcd 4410.31bc 263.14bcd 1240.83ab 25.32b 15.72b 2405.11a 323.83bc 14093.60bc 1377.66b 4973.78ab 560.36b 9.74bcd 16.17ab 84.82ab 1181.44ab 63.51cd 961.23c 523.95b 17.09a 20.70bc 29.19bc continued Table 3.4. Continued trimethylpyrazine 46.27bcd 101.25a 65.82b 57.37bc vanillin 6.72bc 20.14a 9.70b 10.02b a-g Samples with different letters for the same volatile in Tables 3.2, 3.3, and 3.4 are significantly different. Statistical analysis was performed comparing all roasting treatments in Tables 3.2, 3.3 and 3.4. 3.5.3 Volatile Levels in Ideally and Over Roasted Peanuts Ideally roasted peanuts had L* values that were not significantly different and within the desired range (58-59 ± 2); however, the volatile levels were significantly different for almost all of the volatiles (Table 3.3). Only 1-decene, 2-decanone, 2nonanone, 2-undecanone, and 5-methylfurfural did not have significantly different levels within the ideally roasted samples. Comparing raw peanuts and all roasting treatments, as roasting time increased, the volatile levels generally increased. The general trend was that raw peanuts had the lowest level of all volatiles followed by the under roasted peanuts, ideally roasted peanuts, and over roasted peanuts had the highest level of volatiles. Pyrazines are responsible for the roasted nutty aroma of roasted peanuts (Mason and others 1966). Pyrazines including 2,3-diethyl-5-methylpyrazine, dimethylpyrazine, 2methyl-3-ethylpyrazine, pyrazine, and trimethylpyrazine increased as roasting time increased for a given temperature (Figure 3.2). As roasting time increases, pyrazine levels have been shown to increase (Buckholz and Daun 1981, Leunissen and others 1996). Although pyrazines followed the same trend as roasting time increased for the treatments oven at 177 °C, oven at 204 °C and microwave roasting, the pyrazine levels were not equivalent for each roasting treatment. Generally, oven at 177 °C treatments had the 66 highest levels of pyrazines and microwave treatments had the lowest levels of pyrazines (Figure 3.2). Although pyrazines are associated with roasted flavor, as pyrazine levels increase the bitter flavors also increase (Leunissen and others 1996, Vercellotti and others 1992). Oven at 177 °C treatments generally had the highest levels of pyrazines, although the higher levels may not be desirable for flavor. Carbonyls are associated with the harsh green notes found in roasted peanuts (Buckholz and Daun 1981). Strecker degradation is also a source of carbonyl formation including acetaldehyde, 2-methylbutanal, 3-methylbutanal, and phenylacetaldehyde (Mason and others 1967). The amino acids that form these compounds have been found in raw peanuts and are destroyed during roasting (Mason and others 1969) due to the conversion into carbonyls. Roasted peanuts were found to contain greater carbonyl concentrations compared to raw peanuts, likely due to lipid oxidation at higher roasting temperatures with the Maillard reaction and Strecker degradation being secondary causes of the carbonyl increase (Brown and others 1972). More than 30 carbonyls were analyzed with SIFT-MS in this research. Generally, the carbonyl levels increased with increased roasting time (Tables 3.2, 3.3, and 3.4), which supported previous research. Previous literature has reported ideal temperatures and roasting conditions needed to achieve ideal roasted peanut flavor. Temperatures above 150 °C are used for roasting peanuts in order to produce roasted peanut flavors and start chemical reactions (Davidson and others 1999). In this study, roasting temperatures ranged from 135 °C to 204 °C. The treatment roasted at 135 °C did not produce ideal color even after 20 min of roasting, while the treatments above 150 °C were able to produce ideal color in 7-20 min. In one 67 study, certain peanut genotypes were roasted at 175 °C for 15 min and gave the highest levels of pyrazines (except for 2-methoxy-3-methylpyrazine) and highest sensory scores for roasted peanut flavor and aroma compared to other roasting temperatures (Baker and others 2003). However, in this study peanuts roasted at 177 °C for 15 min were considered over roasted in color, although the roasting treatment produced the highest levels of pyrazines (Figure 3.2). Variables such as peanut size, temperature fluctuations among roasters (Davidson and others 1999), peanut roasting sample size, and peanut variety differences make it difficult to determine the ideal roasting conditions to achieve the best roasted peanut volatile levels. While pyrazines are generally associated with positive flavors produced from the Maillard reaction, lipid oxidation products are not desirable. Therefore, higher volatile concentrations are not always an indication of better roasted peanut flavor. Over roasted peanuts had L* values < 56. Oven at 177 °C for 15 min generally produced the highest levels of volatiles among all of the roasting treatments (Tables 3.2, 3.3, and 3.4). Lipid oxidation and Maillard reaction volatiles were generally higher in the over roasted treatments compared to the under and ideally roasted samples. 3-Methylbutanal did not peak in the over roasted peanuts and generally decreased as roasting time increased for the oven roasting treatments (Tables 3.2, 3.3, and 3.4). 3Methylbutanal is formed during Strecker degradation (Mason and others 1967) from the amino acid leucine (Brown and others 1972). At low moisture contents, the amount of free leucine in peanuts decreased as roasting time increased (Chiou and others 1991). In a model system, 3-methylbutanal formation increased as temperature increased (Arnoldi 68 and others 1987). Strecker aldehydes, such as 3-methylbutanal, are not end products and can react to form other compounds (Balagiannis and others 2009) therefore, it was expected that 3-methylbutanal levels would decrease with increased roasting time. This trend was observed with the oven roasted treatments although this volatile was not significantly different between any of the microwave or combination treatments. 69 Raw Oven 177 °C for 5 min Oven 177 °C for 10 min Oven 177 °C for 15 min a 300 a 250 b 200 b 150 100 50 0 a a c c b a c c c c b b a d c b c c 300 a 200 a b 150 100 50 0 c c Raw Oven 204 °C for 5 min Oven 204 °C for 7 min Oven 204 °C for 10 min 250 a b b b a a c c b c bc a b c c b b a a 350 250 a 200 c c Raw Microwave 2 min Microwave 2 min 30 sec Microwave 3 min 300 a 150 b c a b b b c bc 2-methylpyrazine d 2-methyl-3-ethylpyrazine 0 c c b a dimethylpyrazine 50 b c a bc b d c b a trimethylpyrazine 100 2,3-diethyl-5-methylpyrazine Volatile concentration (ppb) Volatile concentration (ppb) 350 pyrazine Volatile concentration (ppb) 350 Volatile Figure 3.2. Volatile levels of pyrazines as roasting time increases for Oven at 177 °C, Oven at 204 °C, and Microwave roasting treatments a-d Different letters for a single volatile within a graph are significantly different. 70 3.5.4 Soft Independent Modeling of Class Analogy Interclass distances are based on factor loadings and show the distance between samples (Grasso and others 2009). Smaller interclass distances show more similarity between volatile concentrations of roasting treatments, whereas larger interclass distances indicate more differences between volatile concentrations. Soft independent modeling of class analogies (SIMCA) using interclass distances and based on volatile concentrations showed that some samples had a similar volatile profile (Table 3.5). Commercial sample volatile results were obtained from Chapter 2 in the thesis. Raw peanuts were the most different from all of the roasted samples having interclass distances 53 or greater compared to roasted peanuts, so the data was removed in order to see differences between the remaining samples. The commercial samples had a volatile profile more similar to each other than to any of the roasted samples tested in this study. The greatest numbers of high interclass distances were between the roasted and commercial samples. This was likely due to the commercial samples having additional ingredients and longer storage time compared to the freshly roasted peanuts in this study. Oven 177 °C for 15 min, microwave 2 min 30 sec, and microwave 3 min treatments were the most similar to the commercial samples. Two of those treatments were over roasted in color and the oven 177 °C for 15 min treatment generally had the highest volatile levels. Oven 177 °C for 5 min had a large number of high interclass distances, which indicated that this sample was also very different from the other roasted samples (Table 3.5). This treatment was the lightest color and thus was the most under roasted of the treatments tested. The smallest interclass distance was between two microwave roasted treatments, indicating those treatments produced the most similar volatile profile. Many 71 of the interclass distances were less than 11, indicating oven, microwave, and combination treatments had similarities between the volatile profiles. 72 Table 3.5. Soft independent modeling of class analogy (SIMCA) interclass distances comparing oven, microwave (MW), and combination roasting treatment volatile concentrations (ppb) Oven 177 °C for 5 min MW 2 min Oven 204 °C for 5 min Roasting Treatment MW 2 min Oven 204 °C for 5 min Oven 204 °C for 6 min MW 1 min Oven 204 °C for 6 min MW 1 min MW 2 min 30 sec MW 1 min Oven 204 °C for 6 min MW 2 min Oven 177 °C for 8 min Oven 163 °C for 20 min Oven 204 °C for 7 min Oven 177 °C for 10 min Commercial #1 Commercial #2 MW 3 min Oven 177 °C for 15 min 47 10 21 37 16 19 22 11 14 9 28 16 15 4 8 33 17 18 6 11 8 63 37 28 13 16 11 14 42 24 19 10 11 8 8 21 34 37 31 37 19 26 23 45 29 Commercial #1 41 33 31 38 24 37 39 56 52 60 Commercial #2 37 31 29 36 24 37 36 49 49 54 9 MW 3 min 22 15 15 10 3 8 11 15 8 13 25 26 16 11 15 12 11 10 6 10 7 7 25 25 10 24 13 16 8 10 5 4 9 5 14 32 32 9 4 37 22 25 11 9 10 7 17 8 16 40 40 6 5 MW 2 min 30 sec 73 MW 1 min Oven 204 °C for 6 min MW 2 min Oven 177 °C for 8 min Oven 163 °C for 20 min Oven 204 °C for 7 min Oven 177 °C for 10 min Oven 177 °C for 15 min Oven 204 °C for 10 min Oven 177 °C for 8 min MW 2 min Oven 204 °C for 10 min 73 5 3.6 Conclusions Peanuts were oven, microwave, or combination roasted to produce color that was not significantly different between the roasting methods within each peanut color classification of under, ideal, or over roasted. 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Analysis of volatile sulfur compounds in Swiss cheese using selected ion flow tube mass spectrometry (SIFT-MS). In: Qian MC, Fan X, Mahattanatawee K, editors. Volatile Sulfur Compounds in Food. Washington, DC: American Chemical Society. p 153-181. Huang Y. Barringer SA. 2011. Monitoring of Cocoa Volatiles Produced during Roasting by Selected Ion Flow Tube-Mass Spectrometry (SIFT-MS). J Food Sci 76(2):C279-C286. Ku KL, Lee RS, Young CT, Chiou RYY. 1998. Roasted Peanut Flavor and Related Compositional Characteristics of Peanut Kernels of Spring and Fall Crops Grown in Taiwan. J Agric Food Chem. 46(8)3220-3224. Leunissen M, Davidson VJ, Kakuda Y. 1996. Analysis of Volatile Flavor Components in Roasted Peanuts Using Supercritical Fluid Extraction and Gas Chromatography-Mass Spectrometry. J Agric Food Chem 44(9):2694-2699. Mason ME, Johnson B, Hamming M. 1966. Flavor Components of Roasted Peanuts. Some Low Molecular Weight Pyrazines and a Pyrrole. J Agric Food Chem 14(5):454460. Mason ME, Johnson B, Hamming MC. 1967. Volatile Components of Roasted Peanuts. The Major Monocarbonyls and Some Noncarbonyl Components. J Agric Food Chem 15(1):66-73. Mason ME, Newell JA, Johnson BR, Koehler PE, Waller GR. 1969. Nonvolatile Flavor Components of Peanuts. J Agric Food Chem 17(4):728-732. Matsui T, Guth H, Grosch W. 1998. A comparative study of potent odorants in peanut, hazelnut, and pumpkin seed oils on the basis of aroma extract dilution analysis (AEDA) and gas chromatography-olfactometry of headspace samples (GCOH). Eur J Lipid Sci. Technol. 100(2):51-56. Mexis SF, Kontominas MG. 2009. Effect of gamma irradiation on the physic-chemical and sensory properties of raw shelled peanuts (Arachis hypogaea L.) and pistachio nuts (Pistacia vera L.). J Sci Food Agri. 89(5):867-875. Neta ER, Sanders T, Drake MA. 2010. Understanding Peanut Flavor: A Current Review. In: Hui YH, editor. Handbook of Fruit and Vegetable Flavors. New Jersey: John Wiley & Sons, Inc. p 985-1022. 76 O’Brien J, Morrissey PA, Ames JM. 1989. Nutritional and toxicological aspects of the Maillard browning reaction in foods. Crit Rev Food Sci 28(3):211-248. Pattee HE, Giesbrecht FG, Young CT. 1991. Comparison of Peanut Butter Color Determination by CIELAB L*a*b* and Hunter Color-Difference Methods and the Relationships of Roasted Peanut Color to Roasted Peanut Flavor Response. J Agric Food Chem 39(3):519-523. Pattee HE, Singleton JA. 1981. Peanut Quality: Its Relationship to Volatile CompoundsA review. In: Teranishi R, Barrera-Benitez B, editors. Quality of Selected Fruits and Vegetables of North America. Washington DC: American Chemical Society. p 147-161. Pattee HE, Singleton JA, Cobb WY. 1969. Volatile Components of Raw Peanuts: Analysis by Gas-Liquid Chromatography and Mass Spectrometry. J Food Sci 34(6):625627. Pattee HE, Singleton JA, Johns EB, Mullin BC. 1970. 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J Food Sci 56(2):579-581. Sipahioglu O, Barringer SA. 2003. Dielectric Properties of Vegetables and Fruits as a Function of Temperature, Ash, and Moisutre Content. J Food Sci 68(1):234-239. Smith D, Spanel P. 2005. Selected Ion Flow Tube Mass Spectrometry (SIFT-MS) for online Trace Gas Analysis. Mass Spectrom Rev 24(5):661-700. Smith D, Wang T, Spanel P. 2003. Analysis of ketones by selected ion flow tube mass spectrometry. Rapid Commun Mass Sp 17(23):2655-2660. 84 Smyth DA, Macku C, Holloway OE, Deming DM, Slade L, Levine H. 1998. Evaluation of Analytical Methods for Optimizing Peanut Roasting for Snack Foods. Pean Sci 25(2):70-76. Sobolev VS. 2001. Vanillin Content in Boiled Peanuts. J Agric Food Chem 49(8):37253727. Spanel P, Smith D. 1997. SIFT studies of the reactions of H3O+, NO+ and O2+ with a series of alcohols. Int J Mass Spectrom 167/168:375-388. Spanel P, Smith D. 1998. SIFT studies of the reactions of H3O+, NO+ and O2+ with a series of volatile carboxylic acids and esters. 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Defining Roasted Peanut Flavor Quality. Part 1. Correlation of GC Volatiles with Roast Color as an Estimate of Quality. In: Charalambous G, editor. Food Science and Human Nutrition. The Netherlands: Elsevier Science Publishers B.V. p 183-209. Wang T, Spanel P, Smith D. 2003. Selected ion flow tub, SIFT, studies of the reactions of H3O+, NO+ and O2+ with eleven C10H16 monoterpenes. Int J Mass Spectrom 228(1):117126. Wang T, Spanel P, Smith D. 2004. A selected ion flow tube, SIFT, study of the reactions of H3O+, NO+ and O2•+ ions with several N- and O-containing heterocyclic compounds in support of SIFT-MS. Int J Mass Spectrom 237(2-3):167-174. Warner KJH, Dimick PS, Ziegler GR, Mumma RO, Hollender R. 1996. ‘Flavor-fade’ and Off-Flavors in Ground Roasted Peanuts As Related to Selected Pyrazines and Aldehydes. J Food Sci 61(2):469-472. Williams TL, Adams NG, Babcock LM. 1998. Selected ion flow tube studies of H3O+(H2O)0,1 reactions with sulfides and thiols. Int J Mass Spectrom 172(1-2):149-159. Young CT, Hovis AR. 1990. A Method for the Rapid Analysis of Headspace Volatiles of Raw and Roasted Peanuts. J Food Sci 55(1):279-280. Young CT, Young TG, Cherry JP. 1974. The Effect of Roasting Methods on the Flavor and Composition of Peanut Butter. Proc Am Peanut Res Educ Assoc 6(1):8-16. 86 Appendix: Odor Thresholds Table A1. Odor thresholds of volatiles in air Volatile (E)-2-heptenal (E)-2-nonenal (E)-2-octenal (E)-2-pentenal (E,E)-2,4-decadienal 1-decene 1-octanol 1-octen-3-ol 1-pentanol 1-penten-3-one 2,3-butanedione 2,3-diethyl-5-methylpyrazine 2,5-dimethylpyrazine 2,6-nonadienal 2-butenal 2-decanone 2-heptanol 2-hexanone 2-methylpropanal 2-nonanone 2-octanone 2-pentanone 2-undecanone 3-methylbutanal 3-methylbutanoic acid acetone ammonia benzaldehyde benzene butanal butanone Odor Threshold (mg/m3) in air 0.034 0.0005 0.0027 1.4 0.00004 37 0.005 0.00236 0.02 0.0001 0.00005 0.000009 0.17 0.00006 0.067 0.003 0.041 0.098 0.001 0.032 0.06 0.098 0.03 0.00035 0.00015 0.94 0.0266 0.0008 1.5 0.0002 0.21 87 Reference van Gemert 2011 van Gemert 2011 van Gemert 2011 van Gemert 2011 van Gemert 2011 van Gemert 2011 van Gemert 2011 van Gemert 2011 van Gemert 2011 van Gemert 2011 van Gemert 2011 van Gemert 2011 van Gemert 2011 van Gemert 2011 van Gemert 2011 van Gemert 2011 van Gemert 2011 van Gemert 2011 van Gemert 2011 van Gemert 2011 van Gemert 2011 van Gemert 2011 van Gemert 2011 van Gemert 2011 van Gemert 2011 van Gemert 2011 Ruth 1986 Ruth 1986 van Gemert 2011 van Gemert 2011 van Gemert 2011 continued Table A1. Continued decanal decane dimethyl disulfide dimethyl sulfide dimethyl trisulfide ethanol ethyl 2-methylbutanoate furfural guaiacol heptanal heptane hexanal hexane hexanoic acid hexenal hydrogen sulfide isobutanoic acid methanol methyl acetate methyl mercaptan methyl methanoate nonanal octanal octane pentane phenylacetaldehyde propanal propanoic acid toluene trimethylpyrazine vanillin 0.00025 3.6 0.0001 0.0025 0.0062 0.17 0.00006 0.008 0.0001 0.00085 2.7 0.0082 0.01 0.0029 0.0004 0.0007 0.005 4 0.5 1E-12 0.001 0.0003 0.000052 8 0.27 0.001 0.0024 0.003 0.12 0.033 0.0000002 88 van Gemert 2011 van Gemert 2011 Ruth 1986 Ruth 1986 Ruth 1986 van Gemert 2011 van Gemert 2011 van Gemert 2011 van Gemert 2011 van Gemert 2011 van Gemert 2011 van Gemert 2011 van Gemert 2011 van Gemert 2011 van Gemert 2011 van Gemert 2011 van Gemert 2011 van Gemert 2011 van Gemert 2011 van Gemert 2011 van Gemert 2011 van Gemert 2011 van Gemert 2011 van Gemert 2011 van Gemert 2011 Ruth 1986 van Gemert 2011 van Gemert 2011 van Gemert 2011 van Gemert 2011 Ruth 1986
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