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<strong>Abstract</strong><br />

<strong>SCHIRACK</strong>, <strong>ANDRIANA</strong> <strong>VAIS</strong>. <strong>The</strong> <strong>Effect</strong> <strong>of</strong> <strong>Microwave</strong> Blanching on the Flavor<br />

Attributes <strong>of</strong> Peanuts. (Under the direction <strong>of</strong> K.P. Sandeep.)<br />

<strong>The</strong> use <strong>of</strong> microwave technology as an alternative blanching method for<br />

peanuts could potentially reduce energy costs and processing time, and lead to<br />

products with better nutrient retention. However, an <strong>of</strong>f-flavor was found in peanuts<br />

which were microwave-blanched at high temperatures. As a result, the objective <strong>of</strong><br />

this research has been to determine the impact <strong>of</strong> different microwave blanching<br />

parameters on the properties <strong>of</strong> roasted peanuts, and to characterize the <strong>of</strong>f-flavor<br />

observed during high-temperature microwave blanching using a descriptive sensory<br />

panel and analysis <strong>of</strong> volatile flavor compounds. <strong>The</strong> processing parameters best<br />

suited for microwave blanching <strong>of</strong> peanuts were determined based on energy<br />

absorbed during processing, internal and surface temperatures, loss in moisture<br />

content, and blanchability. <strong>The</strong> best blanchability resulted from higher process<br />

temperatures and lower final moisture content. However, peanuts which reached<br />

the highest internal temperatures during blanching also developed an <strong>of</strong>f-flavor,<br />

which was characterized by increased intensities <strong>of</strong> stale/floral and burnt/ashy notes.<br />

Solvent extraction / solvent assisted flavor evaporation (SAFE), gas<br />

chromatography-olfactometry (GC/O), gas chromatography-mass spectrometry<br />

(GC/MS), aroma extract dilution analysis (AEDA), threshold testing, and model<br />

systems were used to examine the chemical compounds which may be responsible<br />

for this microwave-related <strong>of</strong>f-flavor. Analysis revealed an increased formation <strong>of</strong><br />

guaiacol, phenylacetaldehyde, and 2,6-dimethylpyrazine in the <strong>of</strong>f-flavored peanuts<br />

as compared to a process control, which led to the burnt and stale/floral


characteristics noted by descriptive sensory panel. <strong>The</strong>se compounds were only a<br />

small fraction <strong>of</strong> over 200 aroma-active compounds which were found to contribute<br />

to roasted peanut flavor using GC/O. This research illustrates the importance <strong>of</strong> the<br />

relative concentrations <strong>of</strong> the many aroma-active compounds found in peanuts.<br />

<strong>The</strong>se findings could aid in training sensory panels to evaluate processing-related<br />

<strong>of</strong>f-flavors, because guaiacol and phenylacetaldehyde could be used as chemical<br />

standards to define the burnt/ashy and stale/floral <strong>of</strong>f-flavors which can occur during<br />

high temperature processing. Through this project, it was determined that it is<br />

possible to achieve acceptable blanchability in peanuts using microwave blanching<br />

while minimizing the possibility <strong>of</strong> an <strong>of</strong>f-flavor.


THE EFFEGT OF MICROWAVE BLANCHING ON THE FLAVOR ATTRIBUTES OF<br />

PEANUTS<br />

By<br />

Andriana Vais Schirack<br />

A dissertation submitted to the Graduate Faculty <strong>of</strong> North Carolina State University<br />

in partial fulfillment <strong>of</strong> the requirements for the degree <strong>of</strong> Doctor <strong>of</strong> Philosophy.<br />

Dr. K.P. Sandeep<br />

Chair <strong>of</strong> Advisory Committee<br />

Dr. Timothy Sanders<br />

FOOD SCIENCE<br />

Raleigh<br />

2006<br />

Approved by:<br />

Di. MaryAnne Drake<br />

Dr. Donn Ward


Dedicated to my husband, Pete<br />

ii


BIOGRAPHY<br />

Andriana Schirack is originally from Columbus, Ohio, where she attended<br />

Ohio State University as an OSU Medalist Scholar and National Merit Scholar.<br />

Andriana graduated with a B.S. in Food Science in December, 1997 after completing<br />

an internship in product development <strong>of</strong> infant formula with Ross Laboratories. In<br />

2000, Andriana completed a master’s program in Food Science at North Carolina<br />

State University with a minor in statistics. During this time, she was also employed<br />

as an aseptic processing technician in the dairy plant. From 2000 to 2003, Andriana<br />

was an Assistant Food Scientist at Jim Beam Brands in Clermont, Kentucky, where<br />

she was trained in analytical chemistry for technical problem solving and developed<br />

new beverages for global launch as part <strong>of</strong> the product development team. She<br />

began her Ph.D. program in the summer <strong>of</strong> 2003 under the direction <strong>of</strong> Dr. K.P.<br />

Sandeep, and has been very active in the national IFT Student Association and the<br />

NCSU Food Science Club. Andriana and her husband, Pete, will move to<br />

Minneapolis, MN where she will begin work at General Mills as an R&D Scientist.<br />

iii


ACKNOWLEDGMENTS<br />

Thanks to my advisor, Dr. K.P. Sandeep, and my committee members, Dr.<br />

MaryAnne Drake, Dr. Tim Sanders, and Dr. Donn Ward for their guidance. Also,<br />

thanks to the many family and friends who have supported me in the past several<br />

years. Most <strong>of</strong> all, a huge thanks to my husband, Pete – for making this possible.<br />

iv


TABLE OF CONTENTS<br />

v<br />

Page<br />

List <strong>of</strong> Tables ......................................................................................................viii<br />

List <strong>of</strong> Figures ....................................................................................................... x<br />

Chapter 1. Introduction ........................................................................................1<br />

References....................................................................................................7<br />

Chapter 2. Literature Review .............................................................................10<br />

Composition <strong>of</strong> Peanuts..............................................................................11<br />

Overview <strong>of</strong> Peanut Production...................................................................12<br />

Harvesting...................................................................................................13<br />

Curing .........................................................................................................14<br />

<strong>Effect</strong> <strong>of</strong> Peanut Immaturity.........................................................................18<br />

Storage .....................................................................................................20<br />

Blanching ....................................................................................................21<br />

Roasting......................................................................................................26<br />

<strong>Microwave</strong> Processing ................................................................................28<br />

Mechanisms <strong>of</strong> Action.................................................................................30<br />

Dielectric Properties....................................................................................32<br />

<strong>Microwave</strong> Blanching <strong>of</strong> Peanuts ................................................................35<br />

Flavor Chemistry <strong>of</strong> Peanuts.......................................................................36<br />

Flavor Production During Roasting .............................................................37<br />

Roasting Parameters <strong>Effect</strong> on Flavor ........................................................43<br />

Flavor Research in Other Nuts....................................................................45<br />

Precursors to Roasted Notes......................................................................46<br />

Off-flavors in Peanuts .................................................................................47<br />

Flavors Due to Lipid Oxidation....................................................................48<br />

Off-flavors Due to Anaerobic Respiration....................................................52<br />

Fruity Fermented Off-flavor.........................................................................55<br />

Off-flavors Due to External Contamination..................................................57<br />

Dark Soured Aromatic Off-flavor .................................................................57<br />

Methods <strong>of</strong> Flavor Analysis.........................................................................58<br />

Gas Chromatography-Mass Spectrometry (GC-MS) ..................................64<br />

Correlation to Quality and Sensory .............................................................65<br />

Gas Chromatography – Olfactometry (GC-O).............................................66<br />

GC-O Applications ......................................................................................69<br />

Sensory Evaluation .....................................................................................70<br />

Descriptive Sensory Analysis......................................................................74<br />

Project Objectives .......................................................................................76<br />

Abbreviations ..............................................................................................78<br />

Symbols ......................................................................................................80


References..................................................................................................81<br />

Chapter 3. <strong>Effect</strong> <strong>of</strong> Processing Parameters on the Temperature and<br />

Moisture Content <strong>of</strong> <strong>Microwave</strong>-Blanched Peanuts ............................................90<br />

<strong>Abstract</strong>.......................................................................................................91<br />

Introduction ................................................................................................91<br />

Materials and Methods................................................................................94<br />

Results and Discussion...............................................................................97<br />

Energy Absorption ..................................................................................97<br />

Peanut Temperature ...............................................................................98<br />

Change in Moisture Content .................................................................101<br />

Blanchability..........................................................................................102<br />

Conclusions ..............................................................................................104<br />

Acknowledgments.....................................................................................105<br />

Abbreviations ............................................................................................106<br />

References................................................................................................107<br />

Tables and Figures ...................................................................................109<br />

Chapter 4. Impact <strong>of</strong> <strong>Microwave</strong> Blanching on the Flavor <strong>of</strong> Roasted<br />

Peanuts.............................................................................................................118<br />

<strong>Abstract</strong>.....................................................................................................119<br />

Introduction ...............................................................................................120<br />

Materials and Methods..............................................................................123<br />

Peanuts.................................................................................................123<br />

Processing Experiments .......................................................................123<br />

Temperature Measurement During Blanching ......................................124<br />

Moisture Content Analysis ....................................................................125<br />

Sensory Evaluation ...............................................................................125<br />

Data Analysis ........................................................................................126<br />

Results and Discussion.............................................................................127<br />

Sensory Analysis ..................................................................................127<br />

Temperature Pr<strong>of</strong>iles and Change in Moisture Content .......................128<br />

Conclusions ..............................................................................................130<br />

Abbreviations ............................................................................................130<br />

Acknowledgments.....................................................................................131<br />

References................................................................................................132<br />

Table Legends ..........................................................................................135<br />

Chapter 5. Characterization <strong>of</strong> Aroma-Active Compounds in <strong>Microwave</strong><br />

Blanched Peanuts.............................................................................................141<br />

<strong>Abstract</strong>.....................................................................................................142<br />

Introduction ...............................................................................................143<br />

vi


Materials and Methods..............................................................................145<br />

Peanuts.................................................................................................145<br />

Chemicals .............................................................................................147<br />

Static Headspace Gas Chromatography...............................................147<br />

Solvent Extraction with Solvent Assisted Flavor Evaporation (SAFE)...148<br />

Gas Chromatography/Olfactometry (GC/O)..........................................149<br />

Gas Chromatography/Mass Spectrometry (GC/MS).............................150<br />

Identification <strong>of</strong> Odorants ......................................................................151<br />

Quantification <strong>of</strong> Odorants ....................................................................151<br />

Threshold Testing .................................................................................152<br />

Sensory Evaluation <strong>of</strong> Peanut Models ..................................................153<br />

Results and Discussion.............................................................................154<br />

Sensory analysis...................................................................................154<br />

Static Headspace Analysis....................................................................155<br />

Gas Chromatography-Olfactometry ......................................................156<br />

Quantification ........................................................................................159<br />

Threshold Determination.......................................................................160<br />

Model Systems .....................................................................................163<br />

Conclusion ................................................................................................165<br />

Acknowledgments.....................................................................................165<br />

References................................................................................................167<br />

Chapter 6. Conclusions and Future Work ........................................................178<br />

Conclusions ..............................................................................................179<br />

Future Work ..............................................................................................182<br />

References................................................................................................184<br />

Appendices .......................................................................................................185<br />

Appendix 1: Analysis <strong>of</strong> Peanut Volatiles by Solvent Extraction, SAFE,<br />

GC-O, and GC-MS....................................................................................186<br />

Appendix 2: Quantification <strong>of</strong> Peanut Volatiles ........................................192<br />

Appendix 3: Summary <strong>of</strong> Aroma-Active Compounds Found in<br />

Peanut Samples Using Aroma Extract Dilution Analysis (AEDA)..............194<br />

vii


Chapter 2<br />

LIST OF TABLES<br />

Table 1 Peanut Volatile Analysis by Gas Chromatography..........................63<br />

Table 2 Lexicon <strong>of</strong> Peanut Flavor Descriptors (Johnsen et al., 1988) ..........72<br />

Chapter 3<br />

Table 1 Processing Parameters During <strong>Microwave</strong> Blanching <strong>of</strong><br />

Peanuts .......................................................................................109<br />

Table 2 Means by Treatment <strong>of</strong> Internal Temperatures <strong>of</strong> Peanuts<br />

During <strong>Microwave</strong> Blanching .......................................................109<br />

Table 3 Maximum Internal Temperatures <strong>of</strong> Peanuts by Treatment<br />

During <strong>Microwave</strong> Blanching .......................................................110<br />

Chapter 4<br />

Table 1 <strong>Microwave</strong> Application Parameters and Resulting Blanching<br />

Efficiency.......................................................................................136<br />

Table 2 Lexicon <strong>of</strong> Peanut Flavor Descriptors (Modified From Johnsen<br />

et al., 1988; and Sanders et al., 1989) ..........................................137<br />

Table 3 Means Separation <strong>of</strong> Blanching Treatments by Sensory<br />

Attribute.........................................................................................138<br />

Table 4 Correlations Between Peanut Flavor Attributes.............................139<br />

Table 5 Maximum Internal Temperature in Peanuts by Treatment ............140<br />

Table 6 Moisture Content <strong>of</strong> Peanuts After Blanching................................140<br />

Chapter 5<br />

Table 1 <strong>Effect</strong> <strong>of</strong> High Temperature <strong>Microwave</strong> Blanching on Sensory<br />

Attributes .....................................................................................172<br />

Table 2 Model System Concentrations in Reference Peanut Paste……...173<br />

viii


Table 3 High Impact Aroma-Active Compounds in Peanuts as<br />

Determined by AEDA ..................................................................174<br />

Table 4 Relative Abundance <strong>of</strong> Selected High Aroma Impact<br />

Compounds in Peanuts ...............................................................176<br />

Table 5 Quantification, Sensory Orthonasal Threshold Values, and Odor<br />

Activity Values <strong>of</strong> Selected Compounds in Peanuts ....................177<br />

Appendices<br />

Table 1 Aroma Active Compounds in Reference Peanuts Detected by<br />

Gas Chromatography-Olfactometry.............................................194<br />

Table 2 Aroma-Active Compounds in <strong>Microwave</strong>-Blanched Peanuts<br />

Detected by Gas Chromatography-Olfactometry.........................201<br />

ix


Chapter 3<br />

LIST OF FIGURES<br />

x<br />

Page<br />

Figure 1 Mean Energy Absorbed by Peanuts Per Treatment for All<br />

Replicates During <strong>Microwave</strong> Heating for 4, 5, 8, or 11<br />

Minutes (Set 1) ............................................................................111<br />

Figure 2 Internal and Surface Temperatures <strong>of</strong> Peanuts During<br />

<strong>Microwave</strong> Blanching for 11 Minutes With and Without Using<br />

Fan (Set 1) ..................................................................................112<br />

Figure 3 Internal and Surface Temperatures <strong>of</strong> Peanuts <strong>of</strong> 5 and 11%<br />

Initial Moisture Content (MC) During <strong>Microwave</strong> Blanching for<br />

11 Minutes Without Using a Fan (Set 2)......................................113<br />

Figure 4 Relationship Between Maximum Internal Temperature and Final<br />

Moisture Content <strong>of</strong> Peanuts After <strong>Microwave</strong> Blanching<br />

(Correlation R 2 = 0.87). F= Fan Used During Blanching,<br />

NF = No Fan Used, MC = Moisture Content...............................114<br />

Figure 5 Mean <strong>of</strong> Blanchability Results Per Treatment for All Replicates<br />

During <strong>Microwave</strong> Blanching <strong>of</strong> Peanuts for 4, 5, 8, or 11<br />

Minutes (Set 1) ............................................................................115<br />

Figure 6 Mean <strong>of</strong> Blanchability Results Per Treatment for All Replicates<br />

During <strong>Microwave</strong> Blanching <strong>of</strong> Peanuts for 11 Minutes<br />

Without Using a Fan (Set 2) ........................................................116<br />

Figure 7 Relationship Between Maximum Internal Temperature and<br />

Blanchability <strong>of</strong> Peanuts After <strong>Microwave</strong> Blanching<br />

(Correlation R 2 = 0.81). <strong>The</strong> Average Final Moisture Content<br />

(MC) <strong>of</strong> Each Treatment is Noted................................................117


CHAPTER 1: INTRODUCTION<br />

1


Peanuts are a valuable agricultural crop in the United States, specifically in<br />

Virginia, the Carolinas, and in the Southeast and Southwest regions. <strong>The</strong> annual<br />

production <strong>of</strong> peanuts in the United States reached 4.2 billion pounds in 2004<br />

(NASS, 2005). Peanuts are valuable nutritionally due to their high protein content<br />

and the amount <strong>of</strong> unsaturated fats. <strong>The</strong> most common use <strong>of</strong> peanuts worldwide is<br />

crushing for oil and meal. <strong>The</strong> oil is used for cooking and as a salad oil, while the<br />

defatted meal is processed into protein concentrates and isolates. In the United<br />

States, a majority <strong>of</strong> the domestic peanut crop is used for products such as peanut<br />

butter, and it also serves as a versatile ingredient in confections.<br />

When peanuts are roasted, they obtain a unique flavor which drives product<br />

marketing in the peanut industry. This flavor is the result <strong>of</strong> genetics, handling,<br />

storage, and processing factors (Sanders et al., 1995). As a result, there is an<br />

interest in the effects <strong>of</strong> harvesting and processing techniques on peanut flavor<br />

(Singleton and Pattee, 1991; Singleton and Pattee, 1992; Osborn et al., 1996; Baker<br />

et al., 2003; Didzbalis et al., 2004).<br />

<strong>The</strong> processing <strong>of</strong> peanuts includes several steps from harvesting to final<br />

product. Handling <strong>of</strong> the peanut crop starts with digging, shaking <strong>of</strong>f soil and debris,<br />

drying the peanuts from 35 - 40% moisture content to 15 - 20%, combining to<br />

separate the pods from the plants, transport to storage facilities, removing the hulls,<br />

and blanching to remove the seed coat from the kernels (Ory et al., 1992). After<br />

blanching, most <strong>of</strong> the peanuts are roasted for use in peanut butter, confections, or<br />

other snack foods.<br />

2


<strong>The</strong> processing parameters used during blanching can have significant<br />

impacts on the final product quality. <strong>The</strong> process <strong>of</strong> peanut blanching consists <strong>of</strong> an<br />

application <strong>of</strong> heat followed by abrasive removal <strong>of</strong> the seed coat. This step is done<br />

for several reasons. Blanching results in the removal <strong>of</strong> the seed coat which contains<br />

tannins that contribute <strong>of</strong>f-flavors and <strong>of</strong>f-colors. Blanching is also used to remove<br />

foreign material and dust (St. Angelo et al., 1977). It also reduces enzyme activity<br />

and moisture content, which are factors impacting subsequent quality (Adelsberg<br />

and Sanders, 1997). Furthermore, blanching aids in the electronic color-sorter<br />

removal <strong>of</strong> damaged or discolored seeds, which are associated with aflatoxin<br />

contamination (Sanders et al., 1999).<br />

Several methods are used for blanching: dry-blanching, spin-blanching,<br />

water-blanching, alkali-blanching, and hydrogen peroxide-blanching. In general, the<br />

most common method in industrial processing is dry-blanching. In this process,<br />

peanuts are placed on conveyor belts and moved through large hot-air ovens in<br />

which the direction <strong>of</strong> airflow is alternated in successive zones (Adelsberg and<br />

Sanders, 1997). <strong>The</strong> peanuts are heated in sequential zones from 30 °C to 90 °C,<br />

with a total processing time <strong>of</strong> approximately 45 minutes. During this time, moisture<br />

is removed from the peanuts, the seed coat is loosened, and after cooling, the seed<br />

coats are mechanically removed (Sanders et al., 1999). Paulsen and Brusewitz<br />

(1976) suggested that the mechanism <strong>of</strong> blanching is due to differences in thermal<br />

expansion and subsequent contraction <strong>of</strong> the seed and seed coat, resulting in a<br />

loosening <strong>of</strong> the seed coat.<br />

3


<strong>Microwave</strong> processing has been investigated as an alternative to traditional<br />

processing methods due to the speed <strong>of</strong> operation, energy savings, and efficient<br />

process control (Giese, 1992). Since heating takes place only in the food material<br />

and not in the surrounding medium, microwave processing can reduce energy costs.<br />

Shorter heating times also lead to greater nutrient retention, better quality<br />

characteristics such as texture and flavor, as well as increased production (Giese,<br />

1992). <strong>The</strong> use <strong>of</strong> a continuous microwave system for blanching has been proposed<br />

as a means <strong>of</strong> reducing production time and energy costs during peanut processing.<br />

Previous studies at North Carolina State University have shown promise for the use<br />

<strong>of</strong> an industrial microwave system. Peanuts were effectively blanched by the<br />

microwave when the peanuts reached temperatures over 85 °C and final moisture<br />

contents <strong>of</strong> 6% or lower. In a study using a series <strong>of</strong> individual trays <strong>of</strong> peanuts<br />

passing through the microwave field, Rausch et al. (2005) examined the potential<br />

use <strong>of</strong> microwaves for peanut blanching. In the current study, refinement <strong>of</strong> the<br />

microwave applicator has allowed a solid bed <strong>of</strong> peanuts to be exposed to<br />

microwave energy in a continuous process, using a processing technique similar to<br />

that <strong>of</strong> Boldor et al. (2005).<br />

<strong>The</strong> best blanching efficiencies result from peanuts which are subjected to the<br />

highest temperatures during blanching and lose the most moisture. Moisture<br />

content affects blanchability as well as stability and flavor quality <strong>of</strong> peanuts<br />

(Adelsberg and Sanders, 1997; Katz, 2002). However, high temperature processing<br />

has been tied to the formation <strong>of</strong> <strong>of</strong>f-flavors. For example, elevated temperatures are<br />

used during curing, in which the moisture content <strong>of</strong> the peanuts after digging is<br />

4


educed from 35-40% moisture to 8-10% to prevent quality losses before further<br />

processing. It has been documented that curing peanuts at temperatures above<br />

35 °C is related to the formation <strong>of</strong> anaerobic by-products which produce an <strong>of</strong>f-<br />

flavor. Also, with increased curing temperatures above 35 °C, positive attributes<br />

such as roasted peanutty decrease while <strong>of</strong>f-flavors such as fruity/fermented<br />

increase in intensity (Sanders et al., 1990). This decrease in positive flavor attribute<br />

intensity with increase in temperature has also been observed in dry-blanching<br />

(Sanders et al., 1999).<br />

Such changes in the quality and flavor <strong>of</strong> peanuts have been described<br />

previously using descriptive sensory analysis. Peanuts were first evaluated using a<br />

method called the Critical Laboratory Evaluation <strong>of</strong> Roasted Peanuts, or CLER<br />

(Holaday, 1971). Later, sensory lexicons for peanuts and peanut products were<br />

constructed by Oupadissakoon and Young (1984) and Syarief et al. (1985). A<br />

standardized lexicon was subsequently developed to address deficiencies in earlier<br />

models such as lack <strong>of</strong> differentiation <strong>of</strong> oxidized <strong>of</strong>f-flavors and lack <strong>of</strong><br />

sweet/caramel descriptors (Johnsen et al., 1988). <strong>The</strong> lexicon used in this research<br />

incorporates a ten point scale to rate intensity <strong>of</strong> flavor attributes using commercially<br />

available products as references (Sanders et al., 1989).<br />

Using descriptive sensory analysis, a processing-related <strong>of</strong>f-flavor has been<br />

noted in peanuts undergoing high-temperature microwave blanching (Katz, 2002).<br />

<strong>The</strong> chemical cause <strong>of</strong> this <strong>of</strong>f-flavor is not yet known. In other studies, specific<br />

volatile compounds identified by GC-mass spectrometry have been linked to sensory<br />

attributes in peanuts (Young and Hovis, 1990; Vercellotti et al., 1992). Instrumental<br />

5


techniques can be used to analyze the volatile compounds which affect peanut<br />

flavor, although these compounds are present at very low concentrations and can<br />

interact with other components <strong>of</strong> the food matrix, leading to difficulties in their<br />

extraction (Reineccius, 2002). A variety <strong>of</strong> extraction and isolation techniques have<br />

been applied in peanut flavor research, including solvent extraction and high vacuum<br />

distillation (Didzbalis et al., 2004), static headspace (Young and Hovis, 1990), and<br />

dynamic headspace (Crippen et al, 1992). Other <strong>of</strong>f-flavors which have been<br />

documented in peanuts, such as fruity fermented, have been linked to their<br />

causative chemical compounds (Didzbalis et al., 2004). By identifying the<br />

compounds responsible for an <strong>of</strong>f-flavor, the possible causes, such as anaerobic<br />

respiration, lipid oxidation, or enzymatic activity, may be determined and the <strong>of</strong>f-<br />

flavor itself can possibly be prevented.<br />

<strong>The</strong> use <strong>of</strong> microwave technology for blanching peanuts can result in a large<br />

reduction in processing time, subsequent cost savings, and better product quality.<br />

<strong>The</strong> objective <strong>of</strong> this study was to characterize the impact <strong>of</strong> different microwave<br />

blanching parameters on the quality and flavor <strong>of</strong> roasted peanuts, and to identify<br />

the chemical components responsible for the <strong>of</strong>f-flavor caused by high-temperature<br />

microwave blanching. <strong>Microwave</strong> blanching is an alternative processing method<br />

which holds the promise <strong>of</strong> better product quality and more efficient process control,<br />

if properly implemented. However, the occurrence <strong>of</strong> an <strong>of</strong>f-flavor in the final product<br />

may be problematic in the adoption <strong>of</strong> this method. <strong>The</strong> identification <strong>of</strong> the<br />

chemical compounds causing this <strong>of</strong>f-flavor could ultimately aid in the development<br />

<strong>of</strong> an alternative blanching method for peanuts using microwave technology.<br />

6


REFERENCES<br />

Adelsberg GD, Sanders TH. 1997. <strong>Effect</strong> <strong>of</strong> peanut blanching protocols on bed<br />

and seed temperatures, seed moisture, and blanchability. Peanut Science 24:<br />

42-46.<br />

Baker GL, Cornell JA, Gorbet DW, O'Keefe SF, Sims CA, Talcott ST. 2003.<br />

Determination <strong>of</strong> pyrazine and flavor variations in peanut genotypes during<br />

roasting. J. Food Sci. 68(1): 394-400.<br />

Boldor D, Sanders TH, Swartzel KR, Farkas, BE. 2005. A model for<br />

temperature and moisture distribution during continuous microwave drying.<br />

Journal <strong>of</strong> Food Process Engineering 28(1): 68-87.<br />

Crippen KL, Vercellotti JR, Lovegren NV, Sanders TH. 1992. Defining roasted<br />

peanut flavor quality. Part 2. Correlation <strong>of</strong> GC volatiles and sensory flavor<br />

attributes. In: Charalambous G, editor. Food Science and Human Nutrition.<br />

New York: Elsevier Science Publishers. p 211-227.<br />

Didzbalis J, Ritter KA, Trail, AC, Plog FJ. 2004. Identification <strong>of</strong> fruity/fermented<br />

odorants in high temperature cured roasted peanuts. J. Agric. Food Chem. 52:<br />

4828-4833.<br />

Giese J. 1992. Advances in microwave food processing. Food Technology<br />

46(9): 118-123.<br />

Holaday CE. 1971. Report <strong>of</strong> the peanut quality committee. Journal <strong>of</strong><br />

American Peanut Research and Education Association 3: 238-241.<br />

Johnsen PB, Civille GV, Vercellotti JR, Sanders TH, Dus CA. 1988.<br />

Development <strong>of</strong> a lexicon for the description <strong>of</strong> peanut flavor. Journal <strong>of</strong><br />

Sensory Studies 3: 9-17.<br />

Katz TA. 2002. <strong>The</strong> effect <strong>of</strong> microwave energy on roast quality <strong>of</strong> microwave<br />

blanched peanuts. Master's <strong>The</strong>sis, North Carolina State University, Raleigh,<br />

NC.<br />

NASS. 2005. USDA crop production 2004 summary. Washington, DC:<br />

National Agriculture Statistics Service.<br />

Ory RL, Crippen KL, Lovegren NV. 1992. Off-flavors in peanuts and peanut<br />

products. In: Charalambous G, editor. Developments in Food Science v. 29:<br />

Off-Flavors in Foods and Beverages. Amsterdam, <strong>The</strong> Netherlands: Elsevier<br />

Science Publishers. p 57-75.<br />

Osborn GS, Young JH, Singleton JA. 1996. Measuring the kinetics <strong>of</strong><br />

7


acetaldehyde, ethanol, and ethyl acetate within peanut kernels during high<br />

temperature drying. Transactions <strong>of</strong> the ASAE 39(3): 1039-1045.<br />

Oupadissakoon C, Young CT. 1984. Modeling <strong>of</strong> roasted peanut flavor for some<br />

Virginia type peanuts from amino acid and sugar contents. J. Food Sci. 49: 52-<br />

58.<br />

Paulsen MR, Brusewitz GH. 1976. Coefficient <strong>of</strong> cubical thermal expansion for<br />

Spanish peanut kernels and skins. Transactions <strong>of</strong> the ASAE 19(3): 592-595,<br />

600.<br />

Rausch TD, Sanders TH, Hendrix KW, Drozd JM. 2005. <strong>Effect</strong> <strong>of</strong> microwave<br />

energy on blanchability and shelf life <strong>of</strong> peanuts. J. Agric. Food Chem.,<br />

submitted.<br />

Reineccius, G. 2002. Instrumental methods <strong>of</strong> analysis. In: Taylor AJ, editor.<br />

Food Flavor Technology. Sheffield, England: Sheffield Academic Press. p<br />

210-251.<br />

St. Angelo AJ, Kuck JC, Hensarling TP, Ory RL. 1977. <strong>Effect</strong>s <strong>of</strong> water and spin<br />

blanching on oxidative stability <strong>of</strong> peanuts. Journal <strong>of</strong> Food Processing and<br />

Preservation 1: 249-260.<br />

Sanders TH, Adelsberg GD, Hendrix KW, McMichael Jr. RW. 1999. <strong>Effect</strong> <strong>of</strong><br />

blanching on peanut shelf-life. Peanut Science 26: 8-13.<br />

Sanders TH, Blankenship PD, Vercellotti JR, Crippen KL. 1990. Interaction <strong>of</strong><br />

curing temperature and inherent maturity distributions on descriptive flavor <strong>of</strong><br />

commercial grade sizes <strong>of</strong> Florunner peanuts. Peanut Science 17: 85-89.<br />

Sanders TH, Pattee HE, Vercellotti JR, Bett KL. 1995. Advances in peanut flavor<br />

quality. In: Pattee HE, Stalker HT, editors. Advances in Peanut Science.<br />

Stilwater, OK: American Peanut Research and Education Society, Inc. p 528-<br />

553.<br />

Sanders TH, Vercellotti JR, Blankenship PD, Crippen KL, Civille GV. 1989.<br />

Interaction <strong>of</strong> maturity and curing temperature on descriptive flavor <strong>of</strong> peanuts.<br />

J. Food Sci. 54(4): 1066-1069.<br />

Singleton JA, Pattee HE. 1991. Peanut moisture/size, relation to freeze damage<br />

and effect <strong>of</strong> drying temperature on volatiles. J. Food Sci. 56(2): 579-581.<br />

Singleton JA, Pattee HE. 1992. Maturity and storage affect freeze damage in<br />

peanuts. J. Food Sci. 57(6): 1382-1384.<br />

Syarief H, Hamann DD, Giesbrecht FG, Young CT, Monroe RJ. 1985.<br />

8


Interdependency and underlying dimensions <strong>of</strong> sensory flavor <strong>of</strong> selected<br />

foods. J. Food Sci. 50: 631-638.<br />

Vercellotti JR, Crippen KL, Lovegren NV, Sanders TH. 1992. Defining roasted<br />

peanut flavor quality. Part 1. Correlation <strong>of</strong> GC volatiles with roast color as an<br />

estimate <strong>of</strong> quality. In: Charalambous G, editor. Developments in Food<br />

Science v. 29: Food Science and Human Nutrition. Amsterdam, <strong>The</strong><br />

Netherlands: Elsevier Science Publishers. p 183-206.<br />

9


CHAPTER 2:<br />

LITERATURE REVIEW<br />

10


Composition <strong>of</strong> Peanuts<br />

<strong>The</strong> structure <strong>of</strong> a peanut seed consists <strong>of</strong> two cotyledons and a germ, which<br />

is enveloped in a thin skin called the testa. <strong>The</strong> peanut heart contains bitter material<br />

and as a result is <strong>of</strong>ten removed during processing, while the testa is removed<br />

during blanching. <strong>The</strong> testa contains mainly protein, fiber and carbohydrates, as<br />

well as tannins which give the skin a bitter flavor (H<strong>of</strong>fpauir, 1953).<br />

Within each year, the composition and quality <strong>of</strong> the peanut crop changes due<br />

to climatic variations as well as different harvesting and handling techniques (Pattee<br />

et al., 1990). Peanut seeds consist <strong>of</strong> approximately 50% fat and 30% protein<br />

(H<strong>of</strong>fpauir, 1953). <strong>The</strong> main fatty acids found in peanuts include palmitic, oleic, and<br />

linoleic acids. Up to 6% <strong>of</strong> peanut oil consists <strong>of</strong> long chain saturated fatty acids<br />

such as arachidic acid (20:0), behenic acid (22:0), lignoceric acid (24:0), oleic acid<br />

(18:1), and linoleic acid --18:2 (Chung et al., 1993). A large percentage <strong>of</strong> peanut oil<br />

consists <strong>of</strong> polyunsaturated fatty acids, which are a substrate for oxidation by<br />

lipoxygenase (Ory et al., 1992, St. Angelo, 1996). Ahmed and Young (1982)<br />

indicated that the oleic/linoleic acid ratios in the peanut varied with cultivar, growing<br />

location, maturity, as well as temperatures during the last few weeks <strong>of</strong> harvest.<br />

This oleic/linoleic acid ratio has been positively correlated to oil stability.<br />

<strong>The</strong> protein in peanuts includes albumins, and two globulins, arachin and<br />

conarachin. <strong>The</strong> total protein has a high digestibility coefficient and has significant<br />

amounts <strong>of</strong> 10 essential amino acids (H<strong>of</strong>fpauir, 1953). <strong>The</strong> specific amino acid<br />

content <strong>of</strong> peanuts varies depending on the type <strong>of</strong> peanut, cultivar, location, and<br />

11


maturity, because the concentrations <strong>of</strong> free amino acids decrease as the peanut<br />

matures (Basha and Young, 1996; Ahmed and Young, 1982).<br />

While in general, plants possess naturally occurring antioxidants such as<br />

superoxide dismutase, tocopherols, carotenes, and ascorbic acid, oilseeds are<br />

specifically identified with peroxidases and catalase. Peroxidase and catalase<br />

function by aiding the conversion <strong>of</strong> hydrogen peroxide to water and oxygen, and<br />

thereby help eliminate this precursor to free radical species (Sanders et al., 1993).<br />

Peanut oil also contains antioxidants such as α, γ, and δ tocopherols (H<strong>of</strong>fpauir,<br />

1953).<br />

<strong>The</strong> other components in peanuts include carbohydrates such as starch,<br />

sucrose, pectins, and cellulose (H<strong>of</strong>fpauir, 1953). Sucrose is the main carbohydrate<br />

in peanuts. In processing, there are slight losses in sucrose during roasting,<br />

although glucose and fructose decrease to a greater extent. Peanuts also contain<br />

high levels <strong>of</strong> potassium, phosphorus, and magnesium, although the amounts<br />

change with cultivar (Ahmed and Young, 1982).<br />

Overview <strong>of</strong> Peanut Production<br />

In the early 1990’s, China, the U.S., and Argentina were the most important<br />

peanut exporting countries, and the primary importers were the European<br />

Community, Japan, and Canada. However, imports to the European Community<br />

have dropped due to a policy shift encouraging the use <strong>of</strong> rapeseed or sunflower<br />

seed oil instead <strong>of</strong> importing peanut oil. Most <strong>of</strong> the increases in peanut production<br />

since the 1970’s have occurred in Asian countries such as India, China, Indonesia<br />

12


and Burma. <strong>The</strong> peanut prices in the Rotterdam market have been recognized as<br />

the world reference price, and this has been tied to monthly estimates <strong>of</strong> peanut<br />

production in America’s Southeast (Carley and Fletcher, 1995).<br />

<strong>The</strong> United States produces approximately 10% <strong>of</strong> the world’s peanuts<br />

(Sanders et al., 1993). Each year in the U.S., 700,000 hectares <strong>of</strong> peanuts are<br />

harvested, with each hectare producing approximately 2.8 tons (Smith et al., 1995).<br />

<strong>The</strong> U.S. peanut industry relies on an extensive price support and production quota<br />

system (Carley and Fletcher, 1995). Peanuts are grown in the Southeast (Alabama,<br />

Florida, Georgia), Southwest (Oklahoma, Texas, and New Mexico), as well as in<br />

Virginia and North Carolina (Smith et al., 1995). <strong>The</strong>re are four major market types<br />

<strong>of</strong> peanuts in the U.S.: runner, virginia, valencia, and spanish (Sanders et al., 1993).<br />

<strong>The</strong> most important use <strong>of</strong> world peanut production remains the crushing <strong>of</strong><br />

peanuts for oil and meal (Carley and Fletcher, 1995). <strong>The</strong> oil is used for cooking<br />

and as a salad oil, while the defatted meal is processed into high protein<br />

concentrates and isolates. In comparison, a large percentage <strong>of</strong> peanuts in the<br />

United States is used for peanut butter and in confections. Alternative uses for<br />

peanut protein have been explored for applications such as fermented milk and<br />

yogurt systems, soup bases, nonfermented cheese analogs, meat product<br />

ingredients, breads and snack products, and the replacement <strong>of</strong> casein in extended<br />

milk products (McWatters and Cherry, 1982).<br />

Harvesting<br />

Harvesting includes the removal <strong>of</strong> peanuts from the ground, and separating<br />

the nuts from soil and vines. Further steps include drying the peanuts from 35-40%<br />

13


moisture content to 15-20%, combining to separate the pods from the plants,<br />

transport to storage facilities, removing the hulls, and blanching to remove the testa<br />

from the seeds (Ory et al., 1992). Peanuts are separated from accompanying<br />

materials during harvest by vibrating, perforated screens or by a belt screen which<br />

uses multiple parallel belts rotating continuously around sheaves (Smith et al.,<br />

1995). <strong>The</strong>re is a potential for <strong>of</strong>f-flavor development if the peanuts are damaged<br />

during handling, because lipoxygenase, which is usually separated from the oil by<br />

cell compartmentalization, can then oxidize the oil and create <strong>of</strong>f-flavors (Ory et al.,<br />

1992).<br />

<strong>The</strong> harvest is set at a time to maximize the number <strong>of</strong> mature pods.<br />

However, immature pods are usually present in every lot, especially during<br />

abnormally cool or hot harvesting weather, and are difficult to separate from mature<br />

pods. <strong>The</strong> percent <strong>of</strong> immature pods in a lot depends on the peanut variety, weather<br />

conditions during growth and development, as well as harvest date (Osborn et al.,<br />

2001).<br />

Curing<br />

Curing is the process <strong>of</strong> reducing the moisture content <strong>of</strong> peanuts to a level<br />

maintaining safety and quality (Young et al., 1982). Curing is needed before<br />

combining because when the peanuts contain 35-40% moisture, they are s<strong>of</strong>t and<br />

susceptible to damage by the combine (Ory et al., 1992). Curing dries the peanuts<br />

either completely, or to 20-25% wet basis (w.b.) moisture in the field, with a final<br />

artificial drying in wagons to 8-10%. If the peanuts are not dried to less than 10%<br />

14


(w.b.) within 3 days, large quality losses result from biological activity (Young et al.,<br />

1982). Fungus growth due to high moisture content can lead to high free fatty acid<br />

concentrations, caused by fungal lipase activity (Sanders et al., 1993).<br />

In wagon drying, a balance is needed in air flow, air humidity, and drying time<br />

so that the bottom layers <strong>of</strong> peanuts are not over-dried, but the top layer <strong>of</strong> peanuts<br />

will not spoil before drying is completed (Young et al., 1982). Deep-bed drying <strong>of</strong><br />

peanuts can be envisioned as the drying <strong>of</strong> successive single layers. For each<br />

layer, the temperature and humidity <strong>of</strong> the air is changed as it passes through the<br />

peanuts (Troeger, 1982).<br />

<strong>The</strong> rate <strong>of</strong> moisture removal during peanut drying is proportional to the<br />

difference in vapor pressure <strong>of</strong> the peanut interior and that <strong>of</strong> the surrounding air. As<br />

the moisture content <strong>of</strong> the peanut decreases, the time needed to remove a certain<br />

amount <strong>of</strong> moisture increases because the vapor pressure difference is not as great.<br />

When the humidity <strong>of</strong> the air becomes equal to that <strong>of</strong> the peanuts, drying ceases<br />

(Troeger, 1982).<br />

<strong>The</strong> heat used for drying also promotes reactions <strong>of</strong> the concentrated peanut<br />

components (Sanders et al., 1993). <strong>The</strong> step <strong>of</strong> curing in peanut processing initiates<br />

catabolic processes, such as degradation <strong>of</strong> carotenoids. Enzymatic and<br />

nonenzymatic reactions also occur, which have been only minimally investigated<br />

(Sanders et al., 1995).<br />

Troeger (1982) conducted drying simulations to determine effects <strong>of</strong> varying<br />

parameters on drying time and energy use. Simulations showed that drying peanuts<br />

with a higher airflow rate (4.72 m 3 /s versus 3.05 m 3 /s) decreased drying time about<br />

15


6%, while energy use increased 45% as a result. Too low <strong>of</strong> airflow resulted in a<br />

greater difference in moisture content in peanuts between the top and bottom layers<br />

<strong>of</strong> the dryer, and the initial moisture content <strong>of</strong> the peanuts also had a significant<br />

effect on the variation between peanut layers. Allowing the drying air to rise 15 °C<br />

reduced drying time by 36%, while energy consumption increased 14%. However,<br />

this higher temperature rise also reduced the relative humidity to an unacceptable<br />

range to maintain product quality (Troeger, 1982).<br />

Delwiche et al. (1986) examined the use <strong>of</strong> microwaves for peanut curing in<br />

comparison to traditional methods. Because peanuts must be dried at temperatures<br />

lower than 35 °C and humidity greater than 60% to maintain quality, drying times<br />

exceed 30 hours for peanuts which are dried in standard wagons. Due to faster<br />

processing times, the energy requirement for microwave vacuum drying was found<br />

to be less than for traditionally dried peanuts. However, high moisture shelling<br />

followed by microwave drying led to elevated levels <strong>of</strong> Aspergillus flavus growth on<br />

the seeds. In addition, as microwave process rate and temperatures increased,<br />

seed germination potential decreased and the seeds were more susceptible to<br />

abrasion and impact. During these experiments, Delwiche et al. (1986) adjusted<br />

microwave power levels depending on the initial temperature and moisture content<br />

<strong>of</strong> the peanuts, using the following equation:<br />

Q = γdry cdry (Tf-Ti) + γdry cw [mci / (1-mci)] (Tf-Ti) + hlg γdry [(mci / 1-mci) – (mcf/1-mcf)]<br />

Where:<br />

Q = Energy per unit volume (kJ/m 3 )<br />

γdry = Bulk density <strong>of</strong> dry seeds (kg/m 3 )<br />

16


cdry = Specific heat <strong>of</strong> dry seeds (1.880 kJ / (kg °C))<br />

Tf and Ti = Final and initial temperature <strong>of</strong> seeds (°C)<br />

mci and mcf = Initial and final seed moisture content (wb)<br />

cw = Specific heat <strong>of</strong> water (4.187 kJ/(kg °C))<br />

hlg = Heat <strong>of</strong> vaporization <strong>of</strong> water (2.418 x 104 kJ/kg at 35 °C)<br />

<strong>The</strong> curing <strong>of</strong> peanuts at temperatures above 35 °C has been associated with<br />

anaerobic by-products which produce an <strong>of</strong>f-flavor (Whitaker et al., 1974). An<br />

increase in the concentration <strong>of</strong> alcohols, aldehydes and esters, especially ethanol,<br />

ethyl acetate, and acetaldehyde, is thought to be tied to this change in respiration<br />

from aerobic to anaerobic (Pattee et al., 1990). At the high rates <strong>of</strong> respiration<br />

occurring at high curing temperatures, oxygen cannot diffuse into the seed at a<br />

sufficient rate, causing anaerobic respiration to take place. This was shown in an<br />

experiment by Whitaker et al. (1974), in which a significant depression in oxygen<br />

partial pressure was found inside peanuts cured at 52 °C compared to those cured<br />

at 24 °C.<br />

With increasing curing temperature, positive attributes such as roasted<br />

peanutty decreased and fruity fermented intensity increased (Sanders et al., 1990).<br />

Volatiles such as mercaptans, carbon dioxide, and carbonyls also increased during<br />

roasting after high temperature curing (Young, 1973). Drying temperatures above<br />

35 °C are avoided to prevent <strong>of</strong>f-flavor formation (Troeger, 1982).<br />

17


<strong>Effect</strong> <strong>of</strong> Peanut Immaturity<br />

Peanut quality is affected by the degree <strong>of</strong> maturity at harvest, which reflects<br />

the extent <strong>of</strong> interaction <strong>of</strong> genetic, physiological and biochemical processes<br />

(Sanders et al., 1995). Maturity in peanuts is achieved more quickly at higher soil<br />

temperatures, while irrigation practices and harvest date also affect peanut maturity<br />

class (Sanders, 1989). Peanuts are a botanically indeterminate plant, which flower<br />

and initiate peanut development over an extended period <strong>of</strong> time. Although in<br />

general, a larger seed is related to greater degree <strong>of</strong> maturity, in commercial peanut<br />

lots <strong>of</strong> any specific size, a range <strong>of</strong> maturities is found. In fact, not all mature<br />

peanuts are large and not all immature peanuts are small (Sanders et al., 1995).<br />

Quality characteristics such as roast color, flavor, and storability are variable within<br />

peanut lots <strong>of</strong> the same commercial size, and this may be the result <strong>of</strong> a distribution<br />

<strong>of</strong> maturities (Sanders, 1989).<br />

Differences in maturity will affect the carbohydrate and amino acid<br />

composition, as well as the moisture content <strong>of</strong> the peanuts. As the peanuts mature,<br />

the moisture content decreases, although a range <strong>of</strong> moisture contents are present<br />

at harvest <strong>of</strong> 20-70%. As a result <strong>of</strong> this and the related biochemical and physical<br />

development <strong>of</strong> the peanuts during processing and shelf life, quality differences can<br />

occur (Sanders et al., 1993). For example, during maturation and processing steps<br />

such as curing, the precursors for Maillard reaction reach optimum levels (Sanders<br />

et al., 1995). Also, as peanuts mature, there is an increase in total oil,<br />

triacylglycerol, and the oleic to linoleic acid ratio. At the same time, free fatty acids,<br />

mono- and diacylglycerols, and polar lipids decrease in concentration. Although<br />

18


there is no direct correlation published between amount <strong>of</strong> oil and shelf life, a<br />

significant correlation has been shown between oil content with maturity, which itself<br />

is related to flavor and shelf life potential (Sanders et al., 1993).<br />

<strong>The</strong> compositional and structural differences in the proteins and sugars <strong>of</strong><br />

immature peanuts suggest that these components will react differently to processes<br />

in manufacture (Sanders, 1989). Vercellotti et al. (1994) formulated a biochemical<br />

model <strong>of</strong> carbohydrate turnover during peanut curing. Immature peanuts had more<br />

low molecular weight reducing substances and oligosaccharides than the mature<br />

peanuts at all stages during curing. In addition, during maturation, many enzyme-<br />

catalyzed reactions occur by way <strong>of</strong> proteases, lipases, glycosidases, and<br />

phosphatases to make flavor intermediates. This dependence on timing may<br />

change the flavor compounds present in the final product (Sanders et al., 1993). As<br />

a result <strong>of</strong> these compositional differences, the type <strong>of</strong> response to conditions such<br />

as high temperature curing or freeze damage will also vary based on maturity<br />

(Sanders et al., 1995).<br />

<strong>The</strong> degree <strong>of</strong> maturity will also affect color development <strong>of</strong> the peanuts<br />

during roasting. Immature peanuts brown at a lower temperature and more rapidly<br />

than mature peanuts. Consequently, close control <strong>of</strong> roasting is needed to reach the<br />

optimum Hunter L value <strong>of</strong> 50 ± 1 (Ory et al., 1992).<br />

Immature peanuts also vary in their flavor pr<strong>of</strong>iles. In general, immature<br />

peanuts are more susceptible to <strong>of</strong>f-flavor formation than mature peanuts (Osborn et<br />

al., 2001), and at a given temperature, immature peanut seeds have a higher level <strong>of</strong><br />

<strong>of</strong>f-flavor production than mature seeds (Pattee et al., 1965). Immature peanuts<br />

19


have significantly lower intensities <strong>of</strong> positive notes such as roasted peanutty flavor<br />

after roasting, and a higher intensity <strong>of</strong> <strong>of</strong>f-flavors such as painty, cardboardy, and<br />

fruity-fermented (Sanders, 1989; Pattee et al., 1990; McNeill and Sanders, 1998). In<br />

addition, sour and bitter notes were higher in immature peanuts, and increased in<br />

intensity with increasing curing temperature (Sanders et al., 1989). Sanders et al.<br />

(1989, 1989b) determined that the flavor potential <strong>of</strong> any peanut lot is related to its<br />

percentage <strong>of</strong> immature peanuts and the methods <strong>of</strong> curing and handling applied.<br />

Storage<br />

After curing, peanuts can be stored before further processing, and the storage<br />

conditions will affect the final product quality. When peanuts are stored after harvest,<br />

storage time and seed size will affect carbohydrate and amino acid composition,<br />

volatiles, and roast seed blanchability (Pattee et al., 1982). Raw peanuts are subject<br />

to loss in quality during storage due to insect, bird, and rodent infestation, microbial<br />

activity, mechanical damage, physical changes such as weight loss or shrinkage,<br />

biochemical changes in flavor, and absorption <strong>of</strong> odors (Smith et al., 1995). Farmers<br />

stock peanuts, or peanuts which have only been picked and threshed, are stored<br />

anywhere from one week to as long as 10 months (Smith et al., 1995).<br />

Decreasing the moisture and temperature in a storage facility will decrease<br />

quality loss during storage. Generally, the best storage conditions for farmer stock<br />

peanuts are approximately 10 °C and 7.5% moisture content wet basis (Smith et al.,<br />

1995). However, if the storage conditions drop below 7% moisture or 7 °C, high<br />

losses in milling quality result when the peanuts are shelled (Smith et al., 1995).<br />

20


Peanuts are commonly stored in flat-storage warehouses, including the<br />

conventional form, the conventional with doghouse, and the muscogee with<br />

doghouse type warehouses. Large crops <strong>of</strong> peanuts can also be stored in circular<br />

tanks or silos such as those used in the grain industry. For adequate air circulation<br />

through the peanut mass, there is a minimum distance which should be maintained<br />

between the peanut mass and the warehouse ro<strong>of</strong> at the eaves. Peanuts are loaded<br />

into a warehouse using a hydraulic lift or hoist to empty peanuts from the drying<br />

trailer into a dump pit. A bucket elevator then transports the peanuts to a horizontal<br />

belt conveyor with a mobile tripper which distributes the peanuts in the storage<br />

space below. Farmer stock peanuts can be damaged when handled by a bucket<br />

elevator at belt speeds greater than 61 m/min, by crushing during loading and<br />

unloading, or by the drop from the tripper to the warehouse floor (Smith et al., 1995).<br />

After storage, peanuts are cleaned, shelled and undergo gravity or density<br />

separation. Damaged and split seeds are removed during processing using<br />

bichromatic machines, cameras, or electronic sorting machines (Smith et al., 1995).<br />

Blanching<br />

<strong>The</strong> next steps in peanut processing include blanching and roasting. <strong>The</strong><br />

process <strong>of</strong> peanut blanching consists <strong>of</strong> an application <strong>of</strong> heat followed by abrasive<br />

removal <strong>of</strong> the seed coat. This step is done for several reasons. Blanching results in<br />

the removal <strong>of</strong> the seed coat which contains tannins that contribute <strong>of</strong>f-flavors and<br />

<strong>of</strong>f-colors (St. Angelo et al., 1977). Blanching also reduces enzyme activity and<br />

moisture content, which are factors impacting subsequent quality (Adelsberg and<br />

21


Sanders, 1997). For example, in a study <strong>of</strong> lipoxygenase activity in blanched<br />

peanuts, the enzyme activity significantly decreased with increasing heating time<br />

and temperature. Furthermore, blanching aids in the removal <strong>of</strong> damaged or<br />

discolored seeds, which are associated with aflatoxin contamination (Sanders et al.,<br />

1999). After the seed coats are removed during blanching, electronic color sorters<br />

are used to detect the damaged seed, effectively reducing aflatoxin in contaminated<br />

lots (Whitaker, 1997).<br />

Several methods are used for blanching: spin-blanching, water-blanching,<br />

dry-blanching, alkali-blanching, and hydrogen peroxide blanching. In spin blanching,<br />

peanuts are passed through a skin cutter, dried to lower the moisture to 5%, and<br />

then the skins are loosened and removed using a spin-blancher. Water-blanched<br />

peanut seeds are slit and treated with 86 °C water for 90 seconds, dried to bring the<br />

moisture to 5%, and the skins are then removed mechanically (St. Angelo et al.,<br />

1977).<br />

In general, the most common method in industrial processing is dry<br />

blanching. To dry the peanuts, they are placed on conveyor belts and moved<br />

through large hot-air ovens in which the direction <strong>of</strong> air flow is alternated in<br />

successive zones (Adelsberg and Sanders, 1997). <strong>The</strong> peanuts are treated to<br />

increasing temperatures in subsequent zones from 30 °C to 90 °C, with a total time<br />

<strong>of</strong> approximately 45 minutes. During this time, moisture is removed from the<br />

peanuts and the seed coat is loosened, and after cooling, the seed coats are<br />

mechanically removed (Sanders et al., 1999). Specific information on industrial<br />

blanching protocols is hard to obtain due to proprietary issues. However, industrial<br />

22


lanching has been imitated using a Proctor and Schwartzingle chamber. This is a<br />

flame-heated oven with airflow control, which can be alternated at timed intervals<br />

while gradually increasing oven temperatures (Adelsberg and Sanders, 1997).<br />

It has been suggested that the mechanism <strong>of</strong> blanching is due to differences<br />

in thermal expansion and subsequent contraction <strong>of</strong> the seed and seed coat,<br />

resulting in a loosening <strong>of</strong> the seed coat. In an experiment by Paulsen and<br />

Brusewitz (1976), the coefficient <strong>of</strong> cubical thermal expansion <strong>of</strong> seeds (50 – 60.5 x<br />

10 -5 / °C) was significantly different than that for peanut skins (26.5 – 55 x 10 -5 / °C),<br />

and as drying continued, the coefficient for cubical thermal expansion for skins<br />

decreased due to moisture loss. This trend led to an increased stress and rupturing<br />

<strong>of</strong> the skins as the seeds expanded at an increased rate (Paulsen and Brusewitz,<br />

1976).<br />

<strong>The</strong> efficiency <strong>of</strong> blanching has been correlated to the genetic makeup <strong>of</strong> the<br />

plant, with the selection <strong>of</strong> certain parents resulting in improved blanchability<br />

(Cruickshank et al., 2003). However, processing parameters during blanching have<br />

a significant impact as well. Adelsberg and Sanders (1997) studied the effects <strong>of</strong><br />

varying parameters on peanut temperature distributions and blanching efficiency.<br />

<strong>The</strong> magnitude <strong>of</strong> peanut bed temperature variation during blanching was related to<br />

final oven set point temperature and to dwell time at each temperature setting. <strong>The</strong><br />

temperature variation <strong>of</strong> individual seeds was up to 5 °C between the seed surface<br />

and a set distance (3 mm) inside the seed. This difference was thought to be due to<br />

the high oil content in peanuts, which leads to low thermal conductivity values<br />

(Adelsberg and Sanders, 1997). Individual seed variation in temperature may affect<br />

23


degree <strong>of</strong> enzyme inactivation, moisture loss, blanchability, and storage stability<br />

(Adelsberg and Sanders, 1997). In addition, an increase in the range <strong>of</strong> exit surface<br />

temperatures <strong>of</strong> the peanuts was correlated to non-uniform drying, which causes a<br />

large variation in single seed moisture distribution (Vilayannur, 1998; Rausch, 2002).<br />

<strong>The</strong> effects <strong>of</strong> moisture content and time-temperature parameters were also<br />

evaluated in terms <strong>of</strong> blanching efficiency. In general, with increasing temperatures<br />

and increasing moisture loss, blanching becomes more efficient (Paulsen and<br />

Brusewitz, 1976; Katz, 2002). Blanchability was correlated with the final oven set<br />

point temperature and negatively correlated with the final moisture content when<br />

above 3.8% (Adelsberg and Sanders, 1997). <strong>The</strong> specific parameters giving the best<br />

blanching efficiencies are still being debated. Adelsberg and Sanders (1997)<br />

reported that reduction <strong>of</strong> peanut moisture content from 5.5 to < 4 % using<br />

temperatures <strong>of</strong> 87.7 °C for 45 and 60 minutes and 98 °C for 30, 45, and 60 minutes<br />

resulted in blanchability above 75%. However, Katz (2002) found that blanching<br />

treatments in which peanut temperatures exceeded 96.7 °C and moisture content<br />

was lower than 6.0%, showed blanching efficiencies greater than 84.5%.<br />

<strong>The</strong> perception in the peanut industry is that blanching reduces shelf life<br />

(Sanders et al., 1999). For example, blanching has been tied to an increase in lipid<br />

oxidation in raw peanuts (Ory et al., 1992). Pattee and Singleton (1971) suggested<br />

that blanching may increase production <strong>of</strong> <strong>of</strong>f-flavors in peanuts during storage<br />

compared to raw peanuts, because although methanol and acetaldehyde<br />

concentrations decreased during blanching, pentane increased over storage as a<br />

result <strong>of</strong> enzyme reactions or lipid oxidation. However, in a study by Sanders et al.<br />

24


(1999), no detrimental effects <strong>of</strong> blanching on oxidative stability were found.<br />

Although blanched and nonblanched peanuts were different in peroxide value and<br />

OSI value, all values were within acceptable ranges, indicating no meaningful shelf<br />

life differences over storage (Sanders et al., 1999).<br />

<strong>The</strong> quality and oxidative stability <strong>of</strong> the peanuts may depend on temperature<br />

and time parameters used during blanching. In a study by Rausch (2002), peanuts<br />

were stable to lipid oxidation after microwave blanching, as determined by peroxide<br />

value, oxidative stability index, hexanal and pentanal concentrations, when treated<br />

with specific power and exposure time conditions. However, peanut batches which<br />

reached surface temperatures above 100 °C declined rapidly in quality over the 28-<br />

week storage period (Rausch, 2002). Blanching temperature has also been<br />

correlated with other flavor effects. Positive attributes such as roasted peanutty had<br />

a weak negative relationship with final blanching temperature in peanuts blanched to<br />

high temperatures (98.9 °C) and for longer times (Sanders et al., 1999).<br />

It has also been reported that different types <strong>of</strong> blanching appear to have<br />

varying effects on shelf life stability. Unblanched peanuts were the least and water-<br />

blanched were the most stable <strong>of</strong> roasted peanuts (St. Angelo et al., 1977).<br />

However, it has been reported that in unroasted peanuts, water-blanched peanuts<br />

have the shortest shelf life, while spin-blanched peanuts and unblanched raw<br />

peanuts were more stable. It has been suggested that water-blanched peanuts gain<br />

a glaze <strong>of</strong> protein and lipids washed from the insides <strong>of</strong> slits made during blanching.<br />

This glaze oxidizes and shortens shelf life <strong>of</strong> the peanuts as compared to spin-<br />

blanched nuts and unblanched nuts which are not roasted (St. Angelo et al., 1978).<br />

25


Additional detrimental effects occur in peanuts which are blanched to reduce<br />

aflatoxin levels. In this case, blanching may result in a more rapid deterioration <strong>of</strong><br />

already inferior quality peanuts (Sanders et al., 1999).<br />

Moisture content has been shown to affect the stability and flavor quality <strong>of</strong><br />

the peanuts (Pattee et al., 1982; Sanders, 1998; Katz, 2002). <strong>The</strong> best blanching<br />

efficiencies result from peanuts which are subjected to the highest temperatures<br />

during blanching and lose the most moisture. In addition, a uniform moisture<br />

distribution in the peanut batch after blanching allows for a more uniform roast and<br />

overall better quality <strong>of</strong> the final product (Rausch, 2002). Moisture content also has<br />

an effect on formation <strong>of</strong> flavor precursors during storage before final processing.<br />

Peanuts which were stored at a higher moisture content (8.7-9.2% versus 6%) had<br />

more hydrolysis <strong>of</strong> sugars and proteins, as well as a greater deterioration <strong>of</strong> quality<br />

(Pattee et al., 1982). Furthermore, higher moisture peanuts had lower roasted<br />

peanutty intensity and pyrazine concentrations, and had higher intensities <strong>of</strong> sensory<br />

notes related to lipid oxidation, such as painty and cardboard (Abegaz et al., 2004).<br />

Roasting<br />

After blanching, many <strong>of</strong> the peanuts will be roasted for use in peanut butter,<br />

confections, or other snack foods. During processing in a continuous roaster, the<br />

product is metered onto the roaster bed which is an oscillating pan or a fixed-pitch<br />

belt. Hot air is generated in the upper chamber by using either electricity or fuel<br />

sources. This heated air is then distributed from above or below to make a fluidized<br />

bed. Mixing is induced in the peanut bed by bubbling air from below or jet shearing<br />

26


when the air is distributed from above (Cammarn et al., 1990). A recirculation fan is<br />

used to remove exhaust gas. Peanuts are roasted at an internal temperature <strong>of</strong> 265<br />

to 300 °F, and the moisture content is lowered from 4-6% moisture to 1% moisture<br />

(H<strong>of</strong>fpauir, 1953). As a result, reactions such as the Maillard reaction occur which<br />

are key to the formation <strong>of</strong> typical roasted peanut flavor and color.<br />

<strong>The</strong> predominant reactions occurring during roasting include the Maillard<br />

reaction, Strecker degradation, and sugar caramelization. <strong>The</strong> Maillard reaction<br />

involves a reducing sugar, such as glucose from the hydrolysis <strong>of</strong> sucrose, and an<br />

amino acid under specific conditions <strong>of</strong> pH, water activity, and temperature. <strong>The</strong><br />

reaction intermediate loses a water molecule to form glycosylamine. After the<br />

subsequent Amadori rearrangement, an amino keto sugar is formed, which can lead<br />

to further decomposition products (Cammarn et al., 1990).<br />

<strong>The</strong> Strecker degradation involves the decomposition <strong>of</strong> glucose to a dione,<br />

which reacts with an amino acid and loses water molecule, and eventually<br />

polymerizes to form pyrazines or other products. At high temperatures,<br />

caramelization <strong>of</strong> sugars can also occur. Caramelization involves the dehydration<br />

and decomposition <strong>of</strong> sugar molecules to form a variety <strong>of</strong> products such as<br />

aldehydes, ketones, sugar fragments, and unsaturated rings. <strong>The</strong>se unsaturated<br />

molecules can absorb light to make brown pigments (Cammarn et al., 1990).<br />

In addition to protein and carbohydrate reactions, after the peanuts are<br />

roasted, the oil is more susceptible to oxidation. This occurs despite the fact that<br />

lipoxygenase and polyphenoloxidase have been denatured, because <strong>of</strong> the<br />

presence <strong>of</strong> nonenzymatic catalysts (Ory et al., 1992).<br />

27


<strong>Microwave</strong> Processing<br />

<strong>Microwave</strong> processing has been explored as an alternative to traditional<br />

processing methods, due to its speed <strong>of</strong> operation, energy savings and efficient<br />

process control. Because heating takes place only in the food material and not the<br />

surrounding medium, microwave processing can reduce energy costs. Shorter<br />

heating times lead to greater nutrient retention, better quality characteristics such as<br />

texture and flavor, as well as increased production (Giese, 1992).<br />

<strong>The</strong> development <strong>of</strong> the continuous conveyor microwave oven in the 1960’s<br />

greatly aided the industrial use <strong>of</strong> microwaves for food processing, due to a more<br />

uniform distribution <strong>of</strong> microwave energy. Conveyor systems include resonant-<br />

cavity systems and waveguide systems. A conveyor passes through a microwave<br />

field in a resonant cavity system, while the product conveyor in a waveguide system<br />

runs through a slot perpendicular to the waveguide (Giese, 1992).<br />

<strong>The</strong>re are not many large-scale industrial microwave applications currently,<br />

with less than 500 worldwide (Giese, 1992). <strong>The</strong> exceptions include the use <strong>of</strong><br />

microwaves for tempering <strong>of</strong> frozen foods, precooking <strong>of</strong> poultry and pork products,<br />

and drying <strong>of</strong> pasta and onions. Tempering using microwaves can be completed in<br />

minutes, compared to the 2-5 day period needed for traditional thawing techniques,<br />

and there is less microbial growth, little weight loss, increased juice and flavor<br />

retention, and less space required. <strong>Microwave</strong> cooking has been increasingly<br />

successful for precooking bacon, meat patties, and poultry, due to increased yields,<br />

shorter preparation times, and increased product quality (Mudgett, 1989). <strong>The</strong><br />

cooking <strong>of</strong> bacon by microwave processing also yields high quality rendered fat as a<br />

28


y-product (Giese, 1992). Drying is conducted with combination <strong>of</strong> conventional<br />

heating and microwaves for pasta, which utilizes less energy and less case<br />

hardening (Mudgett, 1989). In addition, many industrial processes combine<br />

conventional and microwave heating to raise the surface temperature and improve<br />

browning and crisping, to accelerate drying rates, or to reduce microbial counts<br />

(Mudgett, 1989).<br />

Other applications are still being explored for microwave processing.<br />

<strong>Microwave</strong>s are commonly used for drying cookies and biscuits, but are not used for<br />

commercial bread baking despite energy savings reported. <strong>Microwave</strong> sterilization<br />

is currently conducted at 110-130 °C under pressure, although problems are still<br />

being addressed such as development <strong>of</strong> proper packaging materials, excessive<br />

surface heating, and cooling after sterilization (Giese, 1992). <strong>Microwave</strong> processes<br />

with potential include vacuum and freeze drying, fat rendering, roasting, and<br />

pasteurization (Mudgett, 1989). In the drying <strong>of</strong> mushrooms, combined microwave<br />

and hot air drying allowed a shorter heat treatment; as a result, the mushrooms had<br />

a higher aroma retention and preservation <strong>of</strong> the volatile ratios which are significant<br />

to mushroom flavor (DiCesare et al., 1992). <strong>Microwave</strong>s have also been<br />

investigated as an alternative method to blanch vegetables (Sevirini et al., 2003),<br />

and this method has shown advantages in vitamin C and carotenoid retention in<br />

microwave-blanched carrots, spinach and bell peppers (Ramesh et al., 2002)<br />

In peanut processing, microwave vacuum drying has been researched as a<br />

method for curing (Delwiche, 1986). <strong>Microwave</strong>s have also been investigated as an<br />

alternative method to roast peanuts (Megahed, 2001). However, Megahed (2001)<br />

29


concluded that in comparison to conventional roasting methods, the use <strong>of</strong><br />

microwave technology resulted in the increase <strong>of</strong> conjugated dienes and trienes,<br />

epoxy and hydroperoxide formation, oil darkening, and the general formation <strong>of</strong><br />

undesirable and possibly harmful oxidation products and pigments. Likewise,<br />

Yoshida et al. (2005) found that following microwave roasting, the lipid pr<strong>of</strong>ile <strong>of</strong><br />

peanuts changed unfavorably, as free fatty acids and diacylglycerols increased<br />

significantly, although the unsaturated fatty acids which were located in the second<br />

position on the triacylglycerol were protected from oxidation.<br />

Mechanisms <strong>of</strong> Action<br />

<strong>Microwave</strong>s are electromagnetic waves which are between radio and infrared<br />

wavelengths on the electromagnetic spectrum. High frequency energy is emitted by<br />

the magnetron, and includes poles <strong>of</strong> positive and negative charge changing<br />

direction billions <strong>of</strong> times each second. As a result, water, salts, and other polar<br />

molecules line up according to charge in the microwave electric field (Giese, 1992).<br />

In orientation polarization, dipoles such as water attempt to follow the rapidly<br />

changing electrical field, and energy is lost due to random thermal motion <strong>of</strong> water;<br />

this type <strong>of</strong> polarization is highly temperature dependent (Ryynanen, 1995).<br />

Hydrated ions in a food also try to move in the direction <strong>of</strong> the changing electrical<br />

field, and transfer energy as a result (Ryynanen, 1995).<br />

<strong>Microwave</strong> energy heats foods instantaneously, unlike conventional heating<br />

methods, which transfer thermal energy from product surfaces inward 10-20 times<br />

more slowly (Mudgett, 1989). Heating using microwaves is based on the ability <strong>of</strong><br />

30


the material to absorb electromagnetic radiation and convert it into heat. <strong>The</strong><br />

magnetic field interactions in food are negligible, due to only trace amounts <strong>of</strong><br />

magnetic materials present such as nickel, cobalt, or iron. As a result, only the<br />

electric field has an effect (Ryynanen, 1995; Mudgett, 1989). <strong>The</strong> overall heating<br />

rate in microwave processing is dependent on dielectric constant and dielectric loss,<br />

specific heat, and density. <strong>Microwave</strong> energy inactivates microorganisms by thermal<br />

denaturation <strong>of</strong> proteins and nucleic acids, just like conventional thermal processing,<br />

and depends on the same time/temperature relationships (Mudgett, 1989).<br />

<strong>The</strong> transmission properties <strong>of</strong> the electromagnetic waves are related to the<br />

dielectric and thermal properties <strong>of</strong> the food, and also determine the distribution <strong>of</strong><br />

energy (Ryynanen, 1995). Packaging also has an effect, as microwaves are<br />

transmitted through ceramic, plastics, paper, and glass, but metals such as<br />

aluminum foil reflect microwaves (Giese, 1992). Energy reflected from the surface<br />

causes standing wave patterns <strong>of</strong> nodes and antinodes, which result in uneven<br />

energy distribution at product surfaces and hot and cold spots within the product<br />

(Mudgett, 1989).<br />

<strong>The</strong> microwave penetration depth and overall heating rate will be determined<br />

by the specific heat, density, surface to volume ratio, thermal conductivity,<br />

evaporative cooling <strong>of</strong> the food, as well as the shape <strong>of</strong> the food. <strong>The</strong> sphere and<br />

cylinder are the best shapes for microwave heating, because microwaves can<br />

penetrate the food from all sides. In general, foods which have a high surface-to-<br />

volume ratio will cook more rapidly (Giese, 1992). Products heated in a continuous<br />

microwave with slab geometry, such as trays <strong>of</strong> peanuts in microwave blanching,<br />

31


experience more heating on the surface than in the middle <strong>of</strong> the product, which<br />

exposes a limitation <strong>of</strong> infrared thermometry for process measurements (Rausch,<br />

2002)<br />

<strong>The</strong> moisture content and temperature <strong>of</strong> the product affect rates <strong>of</strong> internal<br />

conduction and surface convection. <strong>The</strong>se are determined by thermal diffusivity,<br />

and are also affected by heat loss from surface cooling by moisture evaporation<br />

(Mudgett, 1989). <strong>The</strong> electric field inside the load is affected by the dielectric<br />

properties, geometry <strong>of</strong> the load, and the oven configuration (Ryynanen, 1995).<br />

For practical purposes, penetration depth is calculated, which is the depth<br />

below a plane surface at which the power density <strong>of</strong> the electromagnetic wave has<br />

decayed by 1/e (~37%) <strong>of</strong> its surface value (Ryynanen, 1995). Foods which contain<br />

more moisture and salt content will exhibit less penetration depth by the<br />

microwaves, and subsequently have less uniform heating (Mudgett, 1989; Giese,<br />

1992).<br />

Dielectric Properties<br />

<strong>The</strong> permittivity describes the ability <strong>of</strong> a material to absorb, transmit, and<br />

reflect electromagnetic energy. Permittivity has two parts: the real permittivity or<br />

dielectric constant, ε', and the imaginary component or dielectric loss, ε".<br />

Permittivity is described by the equation (Ryynanen, 1995):<br />

Where:<br />

ε = ε' - j ε"<br />

ε = Relative complex permittivity<br />

32


ε' = Relative real permittivity (dielectric constant)<br />

ε" = Relative dielectric loss factor<br />

j = Imaginary unit<br />

<strong>The</strong> dielectric constant relates the ability <strong>of</strong> the material to absorb energy,<br />

while the dielectric loss factor is related to various mechanisms <strong>of</strong> energy<br />

dissipation. <strong>The</strong> dielectric loss is always positive and usually smaller than the<br />

dielectric constant (Ryynanen, 1995). <strong>The</strong> dielectric constant decreases with<br />

increasing temperature, while temperature has a variable effect on dielectric loss,<br />

depending on the product. A large dielectric loss will translate into shorter heating<br />

times (Giese, 1992).<br />

Dielectric properties are most commonly measured in one <strong>of</strong> three ways: by<br />

open-ended coaxial probe, transmission line, or by resonant cavity. In all <strong>of</strong> these<br />

methods, a microwave signal is generated at a certain frequency and is directed at<br />

or through the material being tested. By observing the changes in signal caused by<br />

the material, the dielectric properties are calculated (Engelder and Buffler, 1991).<br />

In general, food products have a loss factor <strong>of</strong> 25 or less, and exhibit a<br />

penetration depth <strong>of</strong> 0.6-1.0 cm. However, dielectric properties change with the<br />

composition <strong>of</strong> the food and with frequency. Both ε' and ε" are affected by the<br />

moisture content, concentration <strong>of</strong> salt, frequency <strong>of</strong> electromagnetic field, and the<br />

temperature. Dielectric properties are also affected by the physical state <strong>of</strong> the food.<br />

For example, as the temperature <strong>of</strong> frozen goods rises through thawing, both ε' and<br />

33


ε" increase greatly, but then decrease after thawing with rising temperature<br />

(Ryynanen, 1995).<br />

Water is the main component <strong>of</strong> most foods, and as a result, its<br />

concentration will also determine its dielectric properties. Dielectric properties have<br />

been <strong>of</strong> interest in agricultural products for use in determining moisture content. In<br />

agricultural products, the dielectric properties vary widely among different kinds <strong>of</strong><br />

grain, crop and weed seed, although in general both ε' and ε" are greater in samples<br />

<strong>of</strong> higher bulk densities and higher equilibrium moisture content. For example, the<br />

dielectric properties at microwave frequencies have been used to nondestructively<br />

estimate the moisture content <strong>of</strong> shelled peanuts (Trabelsi and Nelson, 2006).<br />

<strong>The</strong> salt in foods binds the free water molecules, and acts as a conductor in<br />

an electromagnetic field. As a result, salt depresses the permittivity and elevates the<br />

dielectric loss factor when compared to pure water, because it adds charge carriers<br />

to the matrix. However, while ε' increases with water content, low or moderate salt<br />

content does not affect this value much (Ryynanen, 1995). For salty foods at lower<br />

frequencies, ε' decreases sharply with a rise in temperature. In pure water, ε'<br />

increases slightly with decreasing frequency. <strong>The</strong> degree <strong>of</strong> influence <strong>of</strong> water and<br />

salt content in a food depends on the amount to which they are bound or restricted<br />

in movement by other food components (Ryynanen, 1995). Likewise, the effect <strong>of</strong><br />

colloidal organic solids is to depress the permittivity (dielectric constant) by excluding<br />

more dielectrically active materials such as water from the volume. <strong>The</strong> exclusion <strong>of</strong><br />

water by carbohydrates affects dielectric properties, as carbohydrates do not show<br />

much dipole polarization at microwave frequencies (Ryynanen, 1995). For fats and<br />

34


oils, both ε' and ε" are low and relatively independent <strong>of</strong> frequency and temperature<br />

(Ryynanen, 1995).<br />

<strong>The</strong> dielectric properties <strong>of</strong> shelled and unshelled peanuts have been<br />

measured in bulk samples (Trabelsi and Nelson, 2004). Shelled peanuts have<br />

much higher densities than unshelled peanuts, and the corresponding difference in<br />

dielectric properties relates to the amount <strong>of</strong> water interacting with the electric field,<br />

as well as proportions <strong>of</strong> air and dry matter in the peanuts. Trabelsi and Nelson<br />

(2004) also found that in peanuts, the dielectric constant and dielectric loss both<br />

increase with increasing moisture content <strong>of</strong> the peanuts, while as microwave<br />

frequency increases, the dielectric loss increases but there is little change in the<br />

dielectric constant. A range <strong>of</strong> dielectric properties at frequencies between 6 and 18<br />

GHz was tabulated (Trabelsi and Nelson, 2004). Likewise, in a study by Boldor et<br />

al. (2004), the dielectric properties <strong>of</strong> peanut pods and kernels were reported at a<br />

range <strong>of</strong> temperatures (23-50 °C) and moisture contents (18-39%).<br />

<strong>Microwave</strong> Blanching <strong>of</strong> Peanuts<br />

<strong>The</strong> advantages <strong>of</strong> using microwaves for blanching include reduced<br />

processing times, increases in shelf stability, and increase in nutrient retention. In a<br />

study using a series <strong>of</strong> individual trays <strong>of</strong> peanuts passing through a microwave<br />

applicator, Rausch et al. (2005) examined the potential use <strong>of</strong> microwaves for<br />

peanut blanching. Reducing the moisture content <strong>of</strong> the peanuts to 6% using<br />

microwave blanching required 6 minutes compared to 60 minutes using traditional<br />

forced heated air (Rausch et al., 2005). Later refinement <strong>of</strong> the microwave<br />

35


applicator allowed a solid bed <strong>of</strong> peanuts to be exposed to microwave energy in a<br />

continuous process. This eliminated the heat reflection and focusing effect observed<br />

by Rausch et al. (2005) and prevented the subsequent wide variation in peanut bed<br />

surface temperatures (Boldor et al., 2005).<br />

Several studies have examined the effects <strong>of</strong> processing parameters on<br />

blanching efficiency in peanuts. In a study by Rausch et al. (2005), the microwave<br />

treatments in which the peanuts reached the highest surface temperature (>85 °C)<br />

and resulted in low moisture contents (6%) resulted in high blanching efficiencies<br />

over 85%. <strong>The</strong>se treatments resulting in 4.8-6.0% final moisture content also<br />

provided the longest shelf life as determined by PV, OSI, and hexanal and pentanal<br />

content (Rausch et al., 2005). Similarly, all microwave-blanched peanuts were more<br />

oxidation stable than oven-blanched peanuts in a study by Katz (2002). In<br />

microwave blanching <strong>of</strong> peanuts, increased heat treatment to 110 °C surface<br />

temperature <strong>of</strong> the peanuts improved oil stability as evident by the lower peroxide<br />

value and higher oxidative stability index (Katz, 2002). However, the mildest<br />

microwave blanching treatment (4.7 kW for 2.85 min) was <strong>of</strong>ten indistinguishable<br />

from unblanched and oven-blanched peanuts in oxidative stability (Katz, 2002).<br />

Flavor Chemistry <strong>of</strong> Peanuts<br />

Raw peanuts contain volatiles characteristic <strong>of</strong> lipid oxidation that arise<br />

through natural enzymatic processes or by degradation <strong>of</strong> damaged seeds (Waltking<br />

and Goetz, 1983). <strong>The</strong> volatile components <strong>of</strong> raw peanuts associated with<br />

lipoxygenase activity include: ethanol, pentane, pentanal, and hexanal (Pattee et al.,<br />

36


1969). <strong>The</strong> flavor characteristics <strong>of</strong> major headspace volatiles in raw peanuts were<br />

identified as musty aftertaste, fruity, and musty (Young and Hovis, 1990). A<br />

combination <strong>of</strong> γ-butyrolactone, benzaldehyde, indene, 2-methoxy-3-<br />

isopropylpyrazine, nonanal, benzyl alcohol, and alkyl-substituted benzenes have<br />

also been associated with the legume-like flavor (Fischer and Grosch, 1981). In<br />

addition, high amounts <strong>of</strong> raw/beany flavor in the raw peanuts have been correlated<br />

with methanol and ethanol concentrations (Crippen et al., 1992).<br />

Flavor Production During Roasting<br />

<strong>The</strong> unique flavor <strong>of</strong> roasted peanuts drives product marketing in the peanut<br />

industry. This flavor is the result <strong>of</strong> genetics, production and handling, storage, and<br />

processing factors (Sanders et al., 1995). <strong>The</strong> basic characteristics <strong>of</strong> roasted<br />

peanut flavor have been described as nutty, stemming from the presence <strong>of</strong><br />

methylpyrazine, 2,6-dimethylpyrazine, and 2-methyl-5-ethylpyrazine; cheesy, from<br />

isobutyric and valeric acids; and garlic, from sulphides present in the peanuts (Lee,<br />

1980). <strong>The</strong> thermal products <strong>of</strong> the roasting process contribute to the unique peanut<br />

flavor, and are affected by environment during storage and the initial mix <strong>of</strong> flavor<br />

precursors (Vercellotti et al., 1994). Non-enzymatic carbonyl-amine browning and<br />

lipid oxidation reactions are the sources <strong>of</strong> volatile flavor compounds in peanuts, and<br />

include interactions between peanut components as well as thermal decomposition<br />

products and loss <strong>of</strong> volatiles (H<strong>of</strong>fpauir, 1953; Warner et al., 1996).<br />

Maillard reactions are primarily responsible for browning reactions in roasted<br />

peanuts, although caramelization <strong>of</strong> sugars plays a minor role. <strong>The</strong> products <strong>of</strong><br />

37


owning reactions include pyrazines, pyrroles, furans, and other low molecular<br />

weight compounds (Ahmed and Young, 1982). However, although many<br />

compounds have been found in roasted peanuts which also contribute nutty or<br />

roasted character to other roasted foods, such as potato chips, c<strong>of</strong>fee beans, and<br />

cocoa (Mason et al., 1969; Waltking and Goetz, 1983), the characteristic roasted<br />

peanutty component remains elusive.<br />

<strong>The</strong> concentration <strong>of</strong> carbohydrates and other carbonyls impacts peanut<br />

flavor through the Maillard reaction during roasting. During roasting, moisture and<br />

volatiles are driven <strong>of</strong>f, while proteins are denatured and are involved in Maillard<br />

reactions (H<strong>of</strong>fpauir, 1953). Reducing sugars are liberated from sucrose and free<br />

amino acids are liberated from large peptides during roasting to form Maillard<br />

reaction products. <strong>The</strong> heating process destroys the integrity <strong>of</strong> the membranes<br />

separating starch, oil, and storage proteins in the peanuts, resulting in reaction rates<br />

approximating the Arrhenius model (Mason et al., 1969).<br />

In order to react with amino acids, the carbohydrate must be a reducing<br />

sugar, polyhydroxycarbonyl compound or a breakdown product such as that which<br />

results from the hydrolysis <strong>of</strong> sucrose into fructose and glucose. <strong>The</strong>se<br />

carbohydrates can then form a Schiff base with amino acids, which undergo<br />

reactions to become reductones, and then in turn are formed into any <strong>of</strong> a series <strong>of</strong><br />

flavor compounds through condensation and ring closure reactions. For example,<br />

imidazoles and pyrazines are formed which can condense into colored polymers<br />

(Sanders et al., 1995). In addition to Maillard products, carbonyls are produced by<br />

Strecker degradation and oxidation, but then may be lost by volatilization (Buckholz<br />

38


et al., 1980). Likewise, sugars present can undergo caramelization or can be<br />

degraded (H<strong>of</strong>fpauir, 1953).<br />

<strong>The</strong> volatiles produced by roasting have been classified into three groups<br />

(Ory et al., 1992): those which increase in production rate over a wide range <strong>of</strong><br />

temperatures (such as methanol, acetaldehyde, 3-methylbutanal, N-methylpyrrole,<br />

and 3- carbon substituted pyrazines), those produced at low concentrations at<br />

temperatures below 142 °C (2-methylpropanal, dimethylpyrazine, 4-carbon<br />

substituted pyrazines, benzene acetaldehyde), and a third group which is little<br />

affected by an increase in roasting temperature (ethanol and lipid oxidation<br />

products).<br />

Pyrazines, which are volatile heterocyclic nitrogen-containing compounds, are<br />

the major flavor compounds impacting roasted peanut flavor (Warner et al., 1996;<br />

Baker et al., 2003). Pyrazines and a pyrrole were first identified in roasted peanuts<br />

by Mason and Johnson (1966) by making aqueous condensates <strong>of</strong> stripped volatiles<br />

<strong>of</strong> Spanish peanuts, and subsequent analysis by gas chromatography-mass<br />

spectrometry (GC-MS). Nuclear magnetic resonance, ultraviolet detection and mass<br />

spectrometry were used to identify methylpyrazine, 2, 5-dimethylpyrazine,<br />

trimethylpyrazine, ethylmethylpyrazine, dimethylethylpyrazine, and N-methylpyrrole<br />

in roasted Spanish peanuts (Mason and Johnson, 1966). Through vacuum<br />

degassing <strong>of</strong> pressed, roasted peanuts followed by GC-MS, IR and UV identification,<br />

Johnson et al. (1971) first identified 19 alkylpyrazines present in the basic fraction <strong>of</strong><br />

roasted peanuts. Most <strong>of</strong> the alkyl pyrazines reported were attributed to browning<br />

reactions. However, the formation <strong>of</strong> 2-phenyl-2-alkenal was attributed to aldol<br />

39


condensations between phenylacetaldehyde and aliphatic aldehydes, acetaldehyde,<br />

isobutyraldehyde, or isovaleraldehyde, with the next step being dehydration.<br />

Likewise, the headspace volatiles <strong>of</strong> roasted peanuts held in storage showed 2-<br />

methyl pyrazine and 2,6-dimethyl pyrazine in the highest concentrations, <strong>of</strong> 11.19-<br />

25.82 ng/mL headspace gas/10g peanuts (Warner et al., 1996).<br />

Several pathways have been suggested for the formation <strong>of</strong> pyrazines,<br />

including the reaction <strong>of</strong> sugars with amino acids, condensation and eventual<br />

cleavage to form alkylpyrazines. Alternatively, at high temperatures, sugars may<br />

first rearrange and cleave into smaller fragments, which then condense with amino<br />

acids to form alkylpyrazines, and this latter is the more likely route in roasted foods<br />

(Koehler and Odell, 1970).<br />

However, pyrazines are not the only compounds which have been detected in<br />

peanuts. In a study <strong>of</strong> roasted peanut volatiles, Mason et al. (1967) found<br />

acetaldehyde, isobutyraldehyde, benzaldehyde, phenylacetaldehyde, as well as<br />

tentative identification <strong>of</strong> 2-methylbutanal, 3-methylbutanal, and 3-methyl-2-<br />

butanone using 2,4-dinitrophenylhydrazone derivatives. <strong>The</strong>se aldehydes were<br />

thought to arise by Strecker degradation <strong>of</strong> the corresponding amino acid. Ethyl<br />

acetate, toluene, and N,N-dimethylformamide were also identified (Mason et al.,<br />

1967). Other heterocyclic and sulfur compounds, such as phenols, ketones, esters,<br />

alcohols, and hydrocarbons were found among the volatile components <strong>of</strong> roasted<br />

peanuts by Walradt et al. (1971). Basha and Young (1996) separated peanut seed<br />

proteins into fractions by gel filtration, heated these fractions, and tested the<br />

resulting headspace gasses for flavor volatiles present in roasted peanuts, such as<br />

40


n-methylpyrrole. Walradt et al. (1971) also identified 5, 6, 7, 8-tetrahydroquinoxaline<br />

and methyl- and ethyl acetylpyrazine as occurring in roasted peanuts for the first<br />

time. Johnson et al. (1971b) identified 24 compounds including seven furans, six<br />

pyrroles, three 2-phenyl-2-alkenals, and two thiophenes in the neutral fraction <strong>of</strong><br />

roasted peanuts, specifically: toluene, methyl disulfide, n-hexanal,<br />

2-methyltetrahydr<strong>of</strong>uran-3-one, furfural, 5-methylfurfural, furfuryl alcohol,<br />

naphthalene, acetyl-2-thiophene, N-(2-furfuryl)-pyrrole, phenyl-3-furan, 2-phenyl-2-<br />

butenal, 2-acetylpyrrole, pyrrole-2-carboxaldehyde, and 5-methyl-2-hexenal.<br />

<strong>The</strong> compounds isobutyraldehyde, isovaleraldehyde, 2-methylbutanal, 1-<br />

methylpyrrole, 2-methylpyrazine, and 2,5-dimethylpyrazine were identified by<br />

polymer adsorption method and subsequent mass spectrometry in roasted peanuts<br />

(Buckholz, Jr. et al., 1980b). Ho et al. (1981) reported many flavor components for<br />

the first time using nitrogen gas to remove volatile components <strong>of</strong> roasted peanuts<br />

and subsequent condensation and ether extraction, including lactones, pyrazines,<br />

pyrroles, pyridines, sulfides, thiophenes, and furanoids. Hexanal, 1-methylpyrrole,<br />

cyclobutanol, 4-ethyl-2, 5-dimethylsoxazolidine, 2, 6-dimethylpyrazine, 1-hexanol,<br />

and acetic acid were detected in raw, roasted, and fried Runner peanuts (Burroni et<br />

al., 1997). In fact, when Pattee and Singleton (1981) reviewed volatiles in roasted<br />

peanuts, they found a total <strong>of</strong> 223 compounds.<br />

<strong>The</strong> sensory analysis <strong>of</strong> roasted peanut flavor has been correlated to pyrazine<br />

levels (Maga, 1982). Specifically, 2-ethyl-3-methylpyrazine as well as 2-nonenal has<br />

been associated with the peanutty sensory characteristic (Clark and Nursten, 1977).<br />

An increase in pyrazine compounds was related to a transition between weak and<br />

41


strong roasted flavor in peanuts (Leunissen et al., 1996; Buckholtz et al., 1980).<br />

Methylpropanal, methylbutanal, dimethylpyrazine, and methylethylpyrazine have<br />

been related to dark roasted flavor in peanuts (R> 0.84) using both a dynamic<br />

headspace technique and direct GC (Crippen et al., 1992). Pyrazine<br />

measurements, rather than Hunter LAB value, have also been used with increased<br />

accuracy in relating peanut aroma and flavor in industrial processing, where a mix <strong>of</strong><br />

genotypes may be used (Baker et al., 2003).<br />

Several efforts have been made to tie specific pyrazines to the sensory<br />

“roasted peanutty” characteristic. Mason and Johnson (1966) suggested that<br />

trimethylpyrazine or 2-methyl-5-ethylpyrazine might be responsible for the<br />

characteristic roasted note in peanuts. 2, 3, 5-trimethylpyrazine appears also to be a<br />

good indicator <strong>of</strong> roasted peanut flavor especially in Florida MDR 98 peanuts (Baker<br />

et al., 2003). However, in peanuts roasted above 150 °C, 2,5-dimethylpyrazine had<br />

a high correlation with roasted peanut flavor and aroma, as compared to L-values,<br />

for all genotypes <strong>of</strong> peanuts tested (Baker et al., 2003). Methylpyrazine is<br />

associated with the sensory characteristic <strong>of</strong> "roasted" and is desirable at low<br />

concentrations; however, at higher concentrations <strong>of</strong> methylpyrazines as well as<br />

other pyrazines, the flavor becomes more bitter (Leunissen et al., 1996).<br />

<strong>The</strong> peanuts used for roasting are a mix <strong>of</strong> genotypes, seed sizes, maturities,<br />

and seed composition, so establishing the relationship between volatile compounds<br />

and roasted peanut flavor would allow for roasting optimization (Baker et al., 2003).<br />

However, not only are pyrazines the most substantial compound tied to positive<br />

characteristics in roasted peanuts, they also function to obscure some <strong>of</strong>f-flavors. In<br />

42


fact, Ory et al. (1992) suggested that the quality <strong>of</strong> volatiles in peanuts is easier to<br />

determine in raw peanuts, because volatiles formed during roasting may obscure<br />

smaller peaks.<br />

Roasted peanuts are susceptible to eventual fade in the flavor pr<strong>of</strong>ile, which<br />

may be due to lipid oxidation. Flavor-fade seems to be associated with the masking<br />

<strong>of</strong> pyrazines and other "roasted peanut" flavor compounds by large quantities <strong>of</strong> low-<br />

molecular weight aldehydes produced during lipid oxidation, such as hexanal,<br />

heptanal, octanal, and nonanal (Dimick, 1994). Eliminating or decreasing the rate <strong>of</strong><br />

flavor-fade requires understanding the relationships between carbonyl-amine and<br />

lipid oxidation reactions, as well as degradation and polymerization reactions <strong>of</strong><br />

heterocyclic nitrogen compounds (Warner et al., 1996).<br />

<strong>The</strong> proteins in peanuts may also be involved in <strong>of</strong>f-flavor formation. Basha<br />

et al. (1998) isolated a high molecular weight protein fraction from peanut seed<br />

which was involved in <strong>of</strong>f-flavor production during the roasting <strong>of</strong> peanuts. <strong>The</strong><br />

Maillard reactions <strong>of</strong> sulfur amino acids with carbohydrates can also cause sulfide or<br />

sulfur heterocyclic <strong>of</strong>f-flavors, although small amounts <strong>of</strong> these compounds can add<br />

positively to overall flavor (Sanders et al., 1995).<br />

Roasting Parameters <strong>Effect</strong> on Flavor<br />

Although current quality standards for roasted peanut flavor are based on<br />

seed color and changes in moisture content after roasting, other factors such as<br />

peanut genotype, harvest maturity, planting date, and improper curing and drying<br />

also affect roasted flavor (Baker et al., 2003). Pyrazine formation is increased by<br />

43


asic pH, and higher concentrations <strong>of</strong> certain sugars such as fructose. <strong>The</strong> specific<br />

type <strong>of</strong> pyrazine formed is influenced by the nitrogen source (Koehler and Odell,<br />

1970).<br />

Time and temperature conditions <strong>of</strong> roasting have perhaps the most<br />

significant impact on compound formation. Leunissen et al. (1996) found that the<br />

concentrations <strong>of</strong> pyrazine compounds and hexanol, hexanal, and methylpyrrole<br />

were related to the severity <strong>of</strong> the roasting conditions. In a model system study,<br />

Koehler and Odell (1970) found that no pyrazine compounds were formed at<br />

temperatures less than 100 °C, but above this temperature pyrazine yield rapidly<br />

increased. Roasting at temperatures above 120 °C produces a wide range <strong>of</strong><br />

compounds in peanuts due to Maillard reactions (Leunissen et al., 1996). In the<br />

early stages <strong>of</strong> a heating reaction at 120 °C, methylpyrazine was the major product,<br />

while the ratio <strong>of</strong> dimethylpyrazine to methylpyrazine steadily increased thereafter.<br />

At temperatures above 150 °C, some pyrazine degradation may occur (Koehler and<br />

Odell, 1970). By direct chromatography, Vercellotti et al. (1992) found<br />

methylpropanal, methylbutanal, methylbutanol, methylpyrazine, dimethylpyrazine,<br />

methylethylpyrazine, and vinylphenol to vary with degree <strong>of</strong> roast. Other factors will<br />

affect roasting temperature, as seen in Chiou et al. (1991), where the internal<br />

temperature <strong>of</strong> low-moisture seeds (3.4%) was higher than high moisture seeds<br />

(10.4%).<br />

44


Flavor Research in Other Nuts<br />

Several studies have been conducted on the flavor pr<strong>of</strong>iles <strong>of</strong> other types <strong>of</strong><br />

nuts, and compounds such as pyrazines and pyrroles have been found in common<br />

with peanuts. Nutty notes in roasted pecans were attributed to alkyl pyrazines and<br />

pyridine by Wang and Odell (1972). In these experiments, the authors characterized<br />

the volatile compounds <strong>of</strong> roasted pecans using GC-MS and DNPH derivatives.<br />

Nineteen carbonyl compounds were identified, <strong>of</strong> which 17 were found in pecan oil<br />

extracted from raw and heated pecans, suggesting that the majority <strong>of</strong> the<br />

compounds arose from the lipid fraction <strong>of</strong> the nuts. Wang and Odell (1972)<br />

identified the burned notes in roasted pecans as being associated with furfural, 2,3-<br />

pentadione, pyruvaldehyde, and glyoxal, and some <strong>of</strong> these compounds were<br />

thought to arise from triacylglycerol breakdown during roasting.<br />

Pyrazines and pyrroles have also been found in roasted filberts. Sheldon et<br />

al. (1972) identified volatiles in roasted filberts, including pyrazines, pyrroles,<br />

carbonyls, furans, and two sulfur-containing compounds by GC-MS. <strong>The</strong><br />

development <strong>of</strong> roasted filbert flavor appeared to parallel the development <strong>of</strong> 2-<br />

methylbutanal, 3-methylbutanal, and dimethyl sulfide during roasting.<br />

Likewise, Takei and Yamanishi (1974) studied roasted almond volatiles by<br />

separating compounds into nonbasic, basic carbonyl, and basic noncarbonyl<br />

fractions. Using GC-MS, pyrazines, aldehydes, ketones, and furanoic compounds<br />

were identified, and several new components were found using a methanol extract.<br />

In this extract, 2,5-dimethyl-4-hydroxy-3(2H)-furanone was identified as important to<br />

the flavor <strong>of</strong> roasted almond (Takei and Yamanishi, 1974).<br />

45


Precursors to Roasted Notes<br />

Initial attempts to identify precursors <strong>of</strong> roasted peanut flavor led to the<br />

conclusion that roasted flavor arose from low molecular weight compounds such as<br />

aleurone grains and protein bodies in the peanut (Mason and Waller, 1964).<br />

Flavor precursors were believed to form flavors through intracompartmental<br />

pyrrolysis and degradation <strong>of</strong> the precursors at temperatures exceeding 132 °C<br />

(Mason and Waller, 1964). <strong>The</strong>n Mason et al. (1969) found that raw defatted<br />

peanuts would develop typical roasted peanut aroma, no matter if heated in peanut<br />

oil or oil from another source. Flavor development has been shown to be sensitive to<br />

peanut maturity, and Mason et al. (1969) correlated the concentration increase <strong>of</strong> a<br />

specific peptide to increase in maturity, suggesting that this peptide is a<br />

characteristic precursor <strong>of</strong> typical roasted peanut flavor. Newell et al. (1967) also<br />

postulated a mechanism for the conversion <strong>of</strong> amino acids and sugars into volatile<br />

flavor compounds, with the ultimate product <strong>of</strong> 2,5-dimethylpyrazine. <strong>The</strong> same<br />

group found that aspartic acid, glutamic acid, glutamine, asparagine, histidine, and<br />

phenylalanine were associated with the production <strong>of</strong> typical peanut flavor. <strong>The</strong>se<br />

amino acid concentrations initially represent a majority <strong>of</strong> free amino acids present,<br />

and decrease as they are degraded during roasting (Newell et al., 1967).<br />

Moisture content also plays a part in flavor development. During roasting,<br />

hydrolysis can occur in higher moisture peanuts, increasing the amounts <strong>of</strong> free<br />

amino acids and monosaccharides, and as a result, the original content <strong>of</strong> flavor<br />

precursors in raw peanuts may not be a final indicator <strong>of</strong> flavor quality (Chiou et al.,<br />

1991). In fact, Chiou et al. (1991) found that the amino acid content <strong>of</strong> peanuts<br />

46


changed with time <strong>of</strong> roasting and initial moisture content. <strong>The</strong> higher the moisture<br />

content <strong>of</strong> the peanuts, the more labile the proteins were to heat denaturation,<br />

indicating that the moisture content may affect the balance <strong>of</strong> flavor precursors<br />

(Chiou et al., 1991).<br />

By identifying the compounds that contribute to a flavor, the precursor<br />

compounds and path <strong>of</strong> development may also be eventually identified (Crippen et<br />

al., 1992). Consequently, appropriate pretreatment <strong>of</strong> raw peanuts could be applied,<br />

such as adjustment <strong>of</strong> moisture content to release precursors and therefore enhance<br />

formation <strong>of</strong> roasted peanutty flavor (Chiou et al., 1991). Alternatively, those<br />

precursor concentrations in plants could be increased using genetic engineering to<br />

produce food with more flavor (Teranishi, 1998).<br />

Off-flavors in Peanuts<br />

<strong>The</strong> <strong>of</strong>f-flavors affecting the sensory pr<strong>of</strong>ile <strong>of</strong> a food can be caused by a<br />

variety <strong>of</strong> sources. Foods can contain <strong>of</strong>f-flavors either by airborne or waterborne<br />

contamination, through packaging, oxidation, nonenzymatic browning, enzymatic<br />

reactions, biochemical reactions, microbial contamination, or light-induced reactions<br />

(Reineccius, 1991). In non-preserved foods, the most common source <strong>of</strong> <strong>of</strong>f-flavors<br />

is microbial activity, due to production <strong>of</strong> undesirable primary metabolites, chemical<br />

conversion <strong>of</strong> certain food constituents, or through residual enzyme activity after cell<br />

death (Reineccius, 1991).<br />

In peanuts, the causes <strong>of</strong> <strong>of</strong>f-flavors can be divided into three groups: <strong>of</strong>f-<br />

flavors caused by lipid oxidation, <strong>of</strong>f-flavors which are caused by excessive amounts<br />

47


<strong>of</strong> ethanol (with possible accompaniment <strong>of</strong> methylbutanol and 2,3-butanediol), and<br />

those <strong>of</strong>f-flavors caused by external contamination such as limonene, antioxidants,<br />

or insecticides (Ory et al., 1992). <strong>The</strong> main sources <strong>of</strong> <strong>of</strong>f-flavors in peanuts may be<br />

lipid oxidation and anaerobic respiration due to temperature abuse.<br />

Flavors Due to Lipid Oxidation<br />

Lipid oxidation is one <strong>of</strong> the leading causes <strong>of</strong> <strong>of</strong>f-flavors in raw and roasted<br />

peanuts, due to a high content <strong>of</strong> peanut lipids that contain unsaturated fatty acids<br />

(Warner et al., 1996; Lee et al., 2002). Oxidation <strong>of</strong> the fatty acids in peanut oil can<br />

be caused by light, heat, air, metal contamination, or microorganisms (Ory et al.,<br />

1992). Oil composition is crucial to oxidation rates and by-product formation. When<br />

evaluating fatty acid composition on product quality, a higher percentage <strong>of</strong> oleic<br />

acid, low percentage <strong>of</strong> linoleic acid, a high oleic/linoleic acid ratio, and low iodine<br />

value are associated with better oil stability and longer shelf-life <strong>of</strong> peanuts<br />

(Jambunathan et al., 1993). In a study examining peanuts from US, China, and<br />

Argentina, Sanders et al. (1992) found that US peanuts had consistently higher<br />

tocopherol content, lower free fatty acids and peroxide value, as well as lower<br />

copper and iron content. In addition, US peanuts had higher oleic:linoleic acid<br />

ratios, showing the influence <strong>of</strong> these factors on oxidative reactions and shelf life.<br />

Lipid oxidation has been correlated with factors such as water activity, relative<br />

humidity, and especially oxygen concentration in the environment (Labuza, 1971).<br />

However, the chief causes <strong>of</strong> lipid oxidation are enzymes such as<br />

lipoxygenase or lipase (Sanders et al., 1993). Lipoxygenase is specific for<br />

48


polyunsaturated acids that have a cis-cis 1, 4 pentadiene structure such as linoleic<br />

and linolenic acids (Ory et al., 1992). Lipoxygenases activate oxygen to produce<br />

hydroperoxides at the allylic carbon in polyunsaturated fatty acids, and conjugated<br />

dienes can be subsequently made by rearrangement. Hydroperoxides subsequently<br />

break down into alcohols, alkanes, ketones and aldehydes which can be the source<br />

<strong>of</strong> <strong>of</strong>f-flavors in the peanut. Oxidation by enzymes such as lipoxygenase is likely at<br />

locations <strong>of</strong> cell membrane disruption, as reactants previously separated become<br />

mixed and available for reaction (Ory et al., 1992).<br />

When these enzymes are inactivated by high temperatures during roasting,<br />

autoxidation becomes the principle source <strong>of</strong> lipid breakdown (Lee et al., 2002).<br />

Although all enzymes are denatured during roasting, some enzymes such as<br />

peroxidase, which contains iron, and polyphenoloxidase, which contains copper, can<br />

become pro-oxidants after denaturation (Ory et al., 1992). Transition metals such as<br />

iron and copper can promote lipid oxidation in peanuts by abstracting hydrogen from<br />

unsaturated fatty acid to make a radical, or by indirectly generating reactive oxygen<br />

species (Sanders et al., 1995).<br />

Lipid oxidation can be identified using chromatographic analysis <strong>of</strong> the<br />

samples. Regular lipid oxidation in raw or roasted peanuts is indicated by hexanal<br />

and/or hexanol in high concentrations, and when present at levels greater than 2<br />

ppm, these can be detected by taste panelists (Ory et al., 1992). <strong>The</strong><br />

monohydroperoxides that are formed from linoleate oxidation are precursors for<br />

volatile decomposition products such as nonanal, octanal, decanal, and hexanal,<br />

and the most predominant <strong>of</strong> these is hexanal (Min et al., 1989). Both the quality<br />

49


and quantity <strong>of</strong> volatiles formed in heat-treated lipids are governed by the type <strong>of</strong><br />

hydroperoxide precursors in the sample (Ulberth and Roubicek, 1993). Volatiles<br />

such as ethanol, pentane, and pentanal have also have been associated with lipid<br />

oxidation (Brown et al., 1977). Furthermore, lipid oxidation products can be linked<br />

through glycosidic linkages or hemiacetal and ketal links to polysaccharides, which<br />

are then released during the roasting process (Vercellotti et al., 1994).<br />

Lipid oxidation can also be identified in a chromatogram by a general rise in<br />

the base line volatiles beyond hexanal, due to the appearance <strong>of</strong> oxidation by-<br />

products such as aldehydes, ketones, and hydrocarbons. Most <strong>of</strong> the compounds<br />

with retention times less than hexanal are lost during the roasting process (Ory et<br />

al., 1992). Volatile pr<strong>of</strong>iles <strong>of</strong> roasted peanuts both with and without lipid oxidation<br />

were analyzed using direct GC and an external closed inlet device and<br />

“aromagrams” for different quality peanuts were generated (Vercellotti et al., 1992).<br />

Vercellotti et al. (1992) also published pr<strong>of</strong>iles matching flavor peaks identified with<br />

GC-O to retention time, enumerating lipid degradation compounds found in the<br />

rancid peanuts.<br />

Although the flavor and aroma <strong>of</strong> high quality roasted peanuts is in part due to<br />

oxidized compounds generated during storage (Ahmed and Young, 1982), these<br />

compounds can also have a negative impact at higher concentrations. Oxidation<br />

reactions can result in decrease <strong>of</strong> desirable peanut flavor by loss <strong>of</strong> low molecular<br />

weight flavor compounds and generation <strong>of</strong> undesirable volatile carbonyls such as<br />

nonanal, decadienals, or heptadienals (Sanders et al., 1993). Vercellotti et al.<br />

(1992) found that during lipid oxidation, <strong>of</strong>f-flavor producing volatiles such as<br />

50


hexanal are intensified to the high ppm range, while positive olfactory attributes<br />

become imperceptible as heterocycles and thio-derivatives disappear at high<br />

oxidation levels. Low molecular weight aldehydes such as pentanal, hexanal,<br />

heptanal, octanal, and nonanal can also create a cardboard or oxidative rancid flavor<br />

(Warner et al., 1996). St. Angelo et al. (1984) found that when the presence <strong>of</strong><br />

hexanal, hexanol and pentane exceeded concentrations <strong>of</strong> 2-3 ppm in GC<br />

chromatograms, the peanuts were judged as rancid by the sensory panel.<br />

Because <strong>of</strong>f-flavors caused by oxidation have been closely correlated to the<br />

differences in lipid pr<strong>of</strong>iles in peanuts, researchers have isolated the peanut oil in<br />

flavor experiments. Chung et al. (1993) studied the differences in the headspace<br />

volatile production from peanut oil heated under a broad range <strong>of</strong> temperatures from<br />

50-200 °C simulating mild frying, deep-frying, and near-pyrrolysis conditions, and<br />

they identified hydrocarbons as the most abundant class, followed by aldehydes.<br />

During heating, free fatty acids were formed from the hydrolysis <strong>of</strong> triacylglycerols,<br />

and these were transformed to γ-hydroxy fatty acids by oxidative attack <strong>of</strong> hydroxy<br />

radicals, followed by transformation to lactones by cyclization. <strong>The</strong>se lactones may<br />

be responsible for the formation <strong>of</strong> fruitlike aromas in the peanuts, as γ-octalactone<br />

and γ-nonalactone were found in the peanut oil. Formation <strong>of</strong> fatty and rancid <strong>of</strong>f-<br />

flavors in peanut oil during heating was attributed to the formation <strong>of</strong> carbonyl<br />

compounds. <strong>The</strong>se low molecular weight carbonyls could be isolated only by<br />

derivatization to thiazolidine compounds (Chung et al., 1993).<br />

Lipid oxidation reactions are strongly influenced by storage conditions, and as<br />

a result, <strong>of</strong>f-flavors can develop during this time. In a study by Warner et al. (1996),<br />

51


headspace concentrations <strong>of</strong> hexanal, heptanal, octanal, and nonanal increased<br />

during storage, with hexanal being the major aldehyde at concentrations <strong>of</strong> 187-865<br />

ng/mL headspace gas/10g peanuts after 26 days. In combination with this, higher<br />

TBA values and oxidative rancid flavor scores were seen, indicating that <strong>of</strong>f-flavor<br />

production was in part due to production <strong>of</strong> low-molecular weight aldehydes from<br />

lipid oxidation.<br />

Peanuts naturally contain antioxidants which can slow or prevent lipid<br />

oxidation reactions. For example, it has been noted that peanuts contain alpha-<br />

tocopherol and carotenoids (Sanders et al., 1995). In addition, some products <strong>of</strong><br />

reducing sugar reactions and Maillard browning such as reductones are free radical<br />

scavengers, which protect peanuts from oxidative damage to proteins,<br />

phospholipids, nucleic acids, and polysaccharides (Sanders et al., 1993).<br />

Off-flavors Due to Anaerobic Respiration<br />

When peanuts are subjected to cold or heat stress, the respiration process<br />

changes from aerobic to anaerobic (Singleton and Pattee, 1992, Osborn et al.,<br />

1996). Anaerobic respiration is initiated by an insufficient supply <strong>of</strong> oxygen diffusing<br />

into the seed for the increased respiratory need at higher temperatures.<br />

Temperature stress in peanut seeds can occur at any temperature greater than<br />

35 °C or less than 4 °C, for example during an abusive curing process. In addition,<br />

when cells are exposed to heat or cold stress, membrane damage occurs and<br />

cellular components can leak, disrupting metabolic processes (Singleton and Pattee,<br />

1997).<br />

52


<strong>The</strong> results <strong>of</strong> temperature stress include an increased concentration <strong>of</strong><br />

acetaldehyde and ethanol, which have been linked to <strong>of</strong>f-flavor formation (Singleton<br />

and Pattee, 1992). Pattee et al. (1965) reported compounds from high temperature<br />

cured peanuts for the first time, including: formaldehyde, acetaldehyde, ethanol,<br />

acetone, isobutyraldehyde, ethyl acetate, butyraldehyde, isovaleraldehyde, 2-methyl<br />

valeraldehyde, methylbutylketone, and hexaldehyde. Although some <strong>of</strong> these<br />

compounds were found in control peanuts as well, quantitative differences existed;<br />

in fact, comparison <strong>of</strong> the concentrations <strong>of</strong> acetaldehyde and ethyl acetate<br />

suggested that <strong>of</strong>f-flavors may result from increased concentration in the peanuts<br />

(Pattee et al., 1965). Ethyl acetate concentrations increase when ethanol produced<br />

by anaerobic respiration reacts with carboxylic acids in the plant cells to produce<br />

esters. <strong>The</strong>se esters have been commonly associated with flavor production<br />

(Osborn et al., 1996). High temperature cured peanuts were also found to have<br />

increased concentrations <strong>of</strong> mercaptans, carbon dioxide, basic compounds, and<br />

carbonyls as temperature increased (Young, 1973).<br />

Other changes in the cell can also be used to index quality damage in<br />

peanuts due to temperature abuse. Peanut seed exposed to cold or heat stress<br />

exhibits an increased efflux <strong>of</strong> potassium and acetic acid, resulting in an increase <strong>of</strong><br />

conductivity <strong>of</strong> the leachate. In addition, photomicrographs <strong>of</strong> tissue from stressed<br />

peanuts shows that cells take on an irregular shape, because cellular constituents<br />

expand in heat-stressed seed (Singleton and Pattee, 1997).<br />

<strong>The</strong> levels <strong>of</strong> these marker compounds and amounts <strong>of</strong> <strong>of</strong>f-flavor production<br />

are affected by environmental and processing parameters. Specifically, moisture<br />

53


content has a significant effect. In a study by Singleton and Pattee (1991), as the<br />

moisture level <strong>of</strong> peanuts exposed to freezing temperatures was increased from 6 to<br />

40%, acetaldehyde and ethanol increased in concentration, to up to 27 times the<br />

control concentration. <strong>The</strong> high moisture peanuts were more susceptible not only to<br />

freeze damage, but also to heat stress, and also had increased rates <strong>of</strong> hydrolytic<br />

reactions. Even peanuts at 25% moisture were more susceptible to freeze damage,<br />

and subsequent elevated drying temperatures accentuated the damage (Singleton<br />

and Pattee, 1991). In a study by Osborn et al. (1996), seed moisture content as well<br />

as peanut maturity appeared to influence production rates <strong>of</strong> acetaldehyde, ethanol,<br />

and ethyl acetate, although ethyl acetate production rate appeared to be proportional<br />

to amounts <strong>of</strong> ethanol produced.<br />

Time and temperature protocols during processing also have an effect.<br />

During drying <strong>of</strong> peanuts, formation <strong>of</strong> acetaldehyde, ethanol, and ethyl acetate did<br />

not begin right away. Instead, volatiles increased after 5-15 hours <strong>of</strong> processing,<br />

while ethanol concentrations began to decrease after 30-40 hours (Osborn et al.,<br />

1996). Procedures for detection <strong>of</strong> high temperature <strong>of</strong>f-flavors must take into<br />

account that volatiles diffuse from peanuts during drying. <strong>The</strong> concentrations <strong>of</strong><br />

these volatiles after processing depends on the rate <strong>of</strong> both formation and diffusion<br />

rates <strong>of</strong> each volatile, which are affected by seed temperature during drying. Seed<br />

temperature has been related to amount <strong>of</strong> <strong>of</strong>f-flavor produced in the peanuts as<br />

well. Likewise, the ratio <strong>of</strong> acetaldehyde to ethanol to ethyl acetate during the drying<br />

process was also related to drying air temperature (Osborn et al., 1996).<br />

54


Brown et al. (1977) found that the GC peak area ratios <strong>of</strong> ethanol/methanol<br />

and ethanol/total volatiles were correlated to taste panel flavor scores, and there<br />

was a negative correlation between ethanol and roasted flavor (Brown et al., 1977).<br />

Ethanol, ethyl acetate, and acetaldehyde contribute to an <strong>of</strong>f-flavor in raw peanuts<br />

which is described as a fermented odor and taste, and this process can be<br />

monitored using headspace analysis and GLC (Singleton and Pattee, 1992).<br />

Conversely, the absence <strong>of</strong> acetaldehyde, ethyl acetate, and ethanol is connected to<br />

the absence <strong>of</strong> <strong>of</strong>f-flavor when peanuts are dried under conditions in which<br />

anaerobic respiration does not develop (Osborn et al., 1996). In a study by Young<br />

and Hovis (1990), the descriptive term <strong>of</strong> abusive drying was correlated to ethanol,<br />

and "aging" was correlated to 2-methylbutanal and 3-methylbutanal.<br />

Fruity Fermented Off-flavor<br />

Exposure to high temperatures, such as during the curing process, has also<br />

been correlated to the development <strong>of</strong> the fruity fermented <strong>of</strong>f-flavor. Reducing<br />

substances have been shown to contribute fruity fermented <strong>of</strong>f-flavors, and are also<br />

principle fruit flavors in themselves, such as hydroxyfuranones which contribute to<br />

pineapple, strawberry and apricot flavors (Vercellotti et al., 1994). <strong>The</strong> fruity<br />

fermented <strong>of</strong>f-flavor has been found to increase with a concurrent increase in<br />

ethanol concentration (Sanders et al., 1989).<br />

<strong>The</strong> specific compounds causing the fruity fermented <strong>of</strong>f-flavor were<br />

investigated by Didzbalis et al. (2004). Using gas chromatography-olfactometry<br />

(GC-O) and solvent assisted flavor evaporation (SAFE), fruit esters such as ethyl 3-<br />

55


methylpropanoate, ethyl 2-methylbutanoate and ethyl 3-methylbutanoate as well as<br />

increased levels <strong>of</strong> short chain organic acids such as butanoic acid, hexanoic acid,<br />

and 3-methylbutanoic acid were found in immature peanuts cured at high<br />

temperatures, which had the fruity fermented <strong>of</strong>f-flavor. By adding these compounds<br />

back to a model system, the short chain organic acids were shown to be responsible<br />

for the cheesy fermented aroma, while the esters added fruity, apple-like aromas.<br />

Subsequent processing, such as roasting, increased the levels <strong>of</strong> short chain<br />

organic acids by 10- to 40-fold in fruity fermented peanuts (Didzbalis et al., 2004).<br />

In addition to the <strong>of</strong>f-flavor, fruity fermented peanuts have been associated<br />

with lower levels <strong>of</strong> the desirable roasted peanutty flavor and sweet aromatic notes.<br />

Pattee et al. (1989) first noted the impact <strong>of</strong> the fruity character in suppressing<br />

roasted peanut flavor. An inverse linear relationship was found between roasted<br />

peanut flavor and fruity <strong>of</strong>f-flavor in roasted peanut paste, with a 1:2 decrease /<br />

increase ratio, respectively. <strong>The</strong> fruity <strong>of</strong>f-flavor in peanuts may suppress roasted<br />

peanut flavor perception, or production <strong>of</strong> the roasted peanut attribute may be<br />

reduced due to high-temperature curing (Pattee et al., 1990).<br />

Immature peanuts may be more susceptible to fruity fermented <strong>of</strong>f-flavor<br />

formation due to the incomplete biosynthesis <strong>of</strong> primary metabolites. Furthermore,<br />

these metabolites will mix and react during cell damage caused by temperature<br />

stress (Didzbalis et al., 2004). Threonine, tyrosine, and lysine have been found in<br />

high concentrations in immature peanuts with high levels <strong>of</strong> <strong>of</strong>f-flavors, and as a<br />

result were associated with the production <strong>of</strong> atypical flavors (Newell et al., 1967).<br />

Didzbalis et al. (2004) found that while immature peanuts cured at high temperatures<br />

56


exhibited the fruity fermented <strong>of</strong>f-flavor, both mature peanuts cured at high<br />

temperature and immature peanuts cured at low temperatures were free <strong>of</strong> the <strong>of</strong>f-<br />

flavor, and had higher roasted peanutty scores as well.<br />

Off-flavors Due to External Contamination<br />

Off-flavors can occur due to outside contamination from many sources, such<br />

as chlorophenols from the reaction <strong>of</strong> phenol and chlorine in the water supply or<br />

from algaecides and fungicides; production <strong>of</strong> chloroanisoles by microbial activity;<br />

airborne contaminants due to emissions from nearby industry; contaminated plant<br />

water used to wash, heat or for reconstitution; pesticides, disinfectants or detergents<br />

used in proximity <strong>of</strong> the foodstuff; or from minor constituents <strong>of</strong> food packaging such<br />

as closures, can coatings, or lubricants (Reineccius, 1991). In peanuts, external<br />

contamination can occur if the peanuts are stored with citrus products (limonene<br />

contamination), antioxidants are applied (propylene glycol or ethyl hexanoate<br />

contamination), or insecticides are applied, because these compounds can be<br />

absorbed by the peanuts (Ory et al., 1992).<br />

Dark Soured Aromatic Off-flavor<br />

<strong>The</strong> dark soured aromatic <strong>of</strong>f-flavor (DSA) was described by Katz (2002) as a<br />

new flavor descriptor for an <strong>of</strong>f-flavor formed in peanuts treated at high temperatures<br />

during microwave blanching. This DSA flavor may be unique to microwave-treated<br />

peanuts. However, initial results were inconclusive, as sensory panelists found DSA<br />

in raw and oven-treated control peanuts as well, possibly due to the panelists’<br />

57


confusion with painty notes developing during lipid oxidation over storage.<br />

Development <strong>of</strong> DSA appears also to be related to temperature. Treatments<br />

resulting in highest temperatures (4.7kW for 5.77 min, and 7.3 kW for 2.85 min) had<br />

significantly more DSA detected in the samples by sensory panel (Katz, 2002).<br />

Methods <strong>of</strong> Flavor Analysis<br />

<strong>The</strong> separation <strong>of</strong> volatile aroma compounds from non-volatile food matrices<br />

has been a subject <strong>of</strong> much research. Great care must be taken during the isolation<br />

<strong>of</strong> flavor compounds not only to ensure that the isolates have the sensory properties<br />

<strong>of</strong> the foods being studied, but also that heat labile compounds are not destroyed,<br />

highly volatile compounds are not lost during distillation, or low solubility compounds<br />

are not lost in extractions (Teranishi, 1998). Vercellotti et al. (1992) recommended<br />

using temperatures no higher than 130 °C for half an hour during analysis to prevent<br />

the production <strong>of</strong> additional peanut volatiles. Unfortunately, aroma-active<br />

compounds in foods have a wide range <strong>of</strong> chemical properties, such as polarity,<br />

volatility, and solubility, so it is difficult to choose the best extraction method. In<br />

addition, aroma compounds can be present at very low concentrations, even<br />

femtogram levels, and extractions can be complicated by interference from other<br />

components <strong>of</strong> the food matrix (Reineccius, 2002).<br />

<strong>The</strong> majority <strong>of</strong> past methods used to quantify peanut volatiles have involved<br />

heating large sample sizes and using distillation to separate the volatile compounds<br />

<strong>of</strong> the peanut, which caused changes in volatile compound levels, thermal<br />

conversion <strong>of</strong> volatiles to other isomers, or loss <strong>of</strong> volatile compounds during transfer<br />

58


(Pawliszyn, 2000). Also, the elevated temperatures used during distillation can<br />

cause the formation <strong>of</strong> artifacts, such as Maillard or Strecker compounds when<br />

sugars and free amino acids are present. While distillation utilizes differences in<br />

vapor pressure, solvent extractions and chromatography utilize differences <strong>of</strong><br />

distribution equilibria (Teranishi, 1998). After Dupuy et al. (1971) developed a direct<br />

GC method to analyze peanut flavor, a database was then developed to establish a<br />

"normal" peanut volatiles pr<strong>of</strong>ile <strong>of</strong> good quality raw peanuts which have few<br />

breakdown products <strong>of</strong> lipid peroxidation. Since the 1950’s, the number <strong>of</strong><br />

compounds characterized for their flavor properties has grown from 500 to 15,000,<br />

due to the advent <strong>of</strong> gas and liquid chromatography, infrared, nuclear magnetic<br />

resonance, and mass spectrometry (Teranishi, 1998).<br />

Direct sample introduction methods in GC have generally employed<br />

headspace sampling, in which gas samples at ambient or elevated temperatures are<br />

drawn <strong>of</strong>f from the headspace <strong>of</strong> a sample in a gas-tight syringe and injected directly<br />

into the GC (Waltking and Goetz, 1983). Headspace techniques target very volatile<br />

and abundant compounds, which can otherwise be lost during extraction, and these<br />

techniques can be conducted at very low temperatures to prevent artifact formation<br />

(Reineccius, 2002). Headspace techniques can also be beneficial due to speed <strong>of</strong><br />

operation; for example, Young and Hovis (1990) developed a rapid headspace<br />

method to determine objectionable flavor defects in peanut samples at the rate <strong>of</strong><br />

four per hour.<br />

Sample sensitivity in headspace analysis has been enhanced using dynamic<br />

headspace or purging techniques (Waltking and Goetz, 1983). Purge and trap<br />

59


techniques enable the efficient stripping <strong>of</strong> compound with a high boiling point, and<br />

reflect the flavor <strong>of</strong> oil samples to a greater degree than static headspace techniques<br />

(Ulberth and Roubicek, 1993). A neutral, nonreactive gas is used to purge the<br />

sample, and the volatiles are trapped using porous polymer, charcoal, liquid<br />

nitrogen, or sub-ambient cooling (Waltking and Goetz, 1983). In a study by<br />

Vercellotti et al. (1992), a sparging device combined with FID and FPD allowed<br />

simultaneous detection <strong>of</strong> 18 typical active flavor compounds and 14 sulfur-<br />

containing compounds in peanuts. A polymer adsorption method involving nitrogen<br />

flow over peanut samples in a jacketed glass column to a series <strong>of</strong> Tenax traps was<br />

used by Buckholz, Jr. et al. (1980b) to collect and quantitate headspace volatiles<br />

from freshly roasted peanuts. <strong>The</strong> results approximated the same ratio <strong>of</strong> volatiles<br />

perceived by human senses in the peanut samples. Although this method reduced<br />

sample handling and allowed both a larger sample size and shorter extraction time<br />

(4 hours), the method also resulted in partial loss <strong>of</strong> some <strong>of</strong> highly volatile<br />

compounds. This was corrected by using three traps in a series (Buckholz Jr. et al.,<br />

1980b).<br />

An alternative to purge and trap is SPME (solid phase microextraction), which<br />

is a volatile extraction method using no organic solvents and relatively low<br />

temperatures via substituted siloxane coatings attached to a plastic fiber. <strong>The</strong> fiber<br />

partitions molecules in liquid and air matrices (Pawliszyn, 2000). Modified SPME<br />

methods have been used to analyze volatiles in microwave processing. For<br />

example, Roberts and Pollien (1998) designed a method to quantitate aroma<br />

60


compounds eluting from microwave-heated spaghetti, which incorporated a trap and<br />

condenser to capture volatiles.<br />

Solvent extraction is a technique used to capture higher molecular weight<br />

compounds than is possible with headspace analyses. Because water can also be<br />

co-extracted with the aroma compounds, an additional distillation step is <strong>of</strong>ten<br />

necessary. <strong>The</strong> high vacuum transfer (HVT) method is based on the concept <strong>of</strong><br />

transferring volatiles under vacuum between two vessels based on a large<br />

temperature differential (Engel et al., 1999). A specialized version <strong>of</strong> this is the<br />

solvent assisted flavor evaporation method, or SAFE. Engel et al. (1999) developed<br />

the SAFE, which in connection with solvent extraction and a high vacuum pump<br />

(5x10 -3 Pa) allows the isolation <strong>of</strong> volatiles from solvent extracts, food suspensions<br />

such as fruit pulp, matrices with a high fat content, and aqueous foods such as milk<br />

or beer. Engel et al. (1999) developed SAFE to avoid some <strong>of</strong> the drawbacks <strong>of</strong><br />

HVT, such as: condensation <strong>of</strong> aroma volatiles with higher boiling points inside<br />

transfer tubing, limitation to only diethyl ether and dichloromethane extracts due to<br />

their freezing point, blockage <strong>of</strong> samples high in fat in the stopcock <strong>of</strong> the sample<br />

funnel, as well as the fragility <strong>of</strong> the system. Using SAFE, higher boiling point<br />

alkanes as well as more <strong>of</strong> the polar odorants such as vanillin, sotolon and 3-<br />

methylbutanoic acid were isolated when compared to HVT. Furthermore, the use <strong>of</strong><br />

SAFE resulted in higher yields from fatty matrices <strong>of</strong> 50% fat, compared to high<br />

vacuum transfer (Engel et al., 1999). Solvent assisted flavor evaporation has been<br />

used in several applications, including the analysis <strong>of</strong> volatile compounds in fresh<br />

milk (Bendall, 2001).<br />

61


Selective detectors can be used in GC analysis to enhance sensitivity. Sulfur<br />

volatiles such as hydrogen sulfide, carbonyl sulfide, methanethiol, dimethylsulfide,<br />

carbon disulfide, propanethiol, diethylsulfide, and dimethyl disulfide were identified in<br />

peanuts by sulfur specific flame photometric detection (Vercellotti et al., 1992). This<br />

is significant because many sulfur-containing compounds have low thresholds <strong>of</strong><br />

1ppb or less, enabling these compounds to have significant impact on flavor<br />

perception even at low concentrations (Sanders et al., 1995).<br />

Alternative techniques have also been employed besides traditional<br />

chromatographic analysis. Pattee et al. (1990) surveyed the quality <strong>of</strong> the 1987<br />

Georgia peanut crop using a headspace volatile concentration (HSVC) test, which<br />

allows detection <strong>of</strong> high-temperature <strong>of</strong>f-flavor in wagon lots being graded for<br />

marketing. Off-flavor volatiles in peanuts have also been measured using the<br />

organic volatiles meter -- OVM (Osborn et al., 2001). <strong>The</strong> OVM uses a tin-oxide<br />

meter to measure total organic volatiles in the sample headspace by change in<br />

sensor conductivity, with the main volatiles being ethanol, acetaldehyde and ethyl<br />

acetate (Osborn et al., 2001). Alternatively, electronic nose technology has been<br />

used to detect <strong>of</strong>f-flavors in peanuts and could differentiate <strong>of</strong>f-flavored, high-<br />

temperature cured and regular ground, unroasted peanut seeds Osborn, et al.<br />

(2001).<br />

(Table 1):<br />

Current methods in the literature for analyzing peanut volatiles were surveyed<br />

62


Table 1: Peanut Volatile Analysis by Gas Chromatography<br />

Method Sample preparation Standard Detector Tinitial Tfinal Reference<br />

Static<br />

Headspace<br />

SPME<br />

Purge and<br />

Trap<br />

30 s grind in c<strong>of</strong>fee mill, 1.5 g in<br />

10 mL vial, block heated 30 min at<br />

150 °C.<br />

45-60 s grind in 1s pulses. Heated<br />

145 °C, 20 min in headspace<br />

sampler. 1mL headspace gas<br />

injected.<br />

1g oil sample heated 60 min at<br />

60 °C, 1.25 mL HS c injected.<br />

1 min grind in c<strong>of</strong>fee mill. Heated<br />

120 °C for 30 min. 1 mL HS<br />

injected.<br />

60 g ground in c<strong>of</strong>fee grinder.<br />

Heated at 140 °C, 30 min.<br />

5 g ground for 8 s, heated at 60 °C<br />

for 15 min.<br />

0.5 g protein. Heated at 150 °C for<br />

12 min. 2 mL HS gas injected.<br />

5 g ground in food processor to 1-2<br />

mm diameter. Heated in 60 °C<br />

waterbath for 30 min. Fiber<br />

exposed for 15 min.<br />

1g ground peanut placed between<br />

glass wool into inlet <strong>of</strong> GC.<br />

Heated at 130 °C, and stripped<br />

with nitrogen for 24 min.<br />

external<br />

standard -<br />

acetone in water<br />

external<br />

standard -<br />

pyrazines<br />

external<br />

standard with<br />

pentane,<br />

hexanal,<br />

2-heptanal<br />

63<br />

FID a 120 °C<br />

MS b 35 °C<br />

FID 38 °C<br />

N/A MS 50 °C<br />

3-heptanone<br />

(2.0mL <strong>of</strong><br />

0.1mg / mL)<br />

standard<br />

hexanal solution<br />

in water added<br />

to peanuts<br />

peaks confirmed<br />

with standards<br />

external<br />

standard -<br />

pyrazines in<br />

water<br />

peaks compared<br />

to known<br />

standards<br />

FID 35 °C<br />

200 °C at 20 °C /<br />

min heating rate,<br />

Tf for 3 min<br />

200 °C at 10 °C /<br />

min heating rate,<br />

splitless<br />

170 °C at 6 °C /<br />

min heating rate,<br />

1:15 split ratio<br />

220 °C at 30 °C /<br />

min heating rate<br />

300 °C at 15 °C /<br />

min heating rate<br />

Young and<br />

Hovis, 1990<br />

Warner et al.,<br />

1996<br />

Ulberth and<br />

Roubicek, 1992<br />

Burroni et al.,<br />

1997<br />

Rausch, 2002<br />

N/A 65 °C N/A Lee et al., 2002<br />

FID 120 °C<br />

FID<br />

FID<br />

60 °C, 3<br />

min<br />

50 °C, 2<br />

min<br />

200 °C at 20 °C /<br />

min heating rate<br />

80 °C, 2 °C / min<br />

heating rate<br />

225 °C, 3 °C /<br />

min heating rate,<br />

then held at Tf<br />

until 85 min<br />

Basha et al.,<br />

1998<br />

Baker et al.,<br />

2003<br />

Lovegren et al.,<br />

1982


Table 1 (continued)<br />

Method Sample preparation Standard Detector Tinitial Tfinal Reference<br />

Purge and<br />

Trap<br />

DNPH<br />

derivative<br />

0.5 g peanut, volatiles purged at<br />

127 °C.<br />

100g sample mixed with 300 mL<br />

deionized water for 1 min.<br />

Desorbed in trap at 200 °C.<br />

2.5 g sample, ground for 30s.<br />

0.5 g sample placed into inlet <strong>of</strong><br />

GC, stripped with nitrogen at<br />

130 °C for 24 min.<br />

1.25 g peanut paste purged for<br />

30 min. Heated at 60 °C with<br />

nitrogen, then concentrated in<br />

closed loop.<br />

Ground with glycerol and water,<br />

extracted with methylene<br />

chloride, evaporated, made into<br />

2,4-dinitrophenylhydrazone<br />

derivatives, and carbonyls<br />

regenerated.<br />

a FID = flame ionization detector<br />

b MS = mass spectrometer detector<br />

c HS = headspace<br />

d FPD = flame photometric detector<br />

N/A FID N/A N/A<br />

2-propanol N/A 100 °C<br />

external<br />

standards<br />

64<br />

FID 50 °C<br />

200 °C at 2 °C<br />

/ min heating<br />

rate<br />

225 °C at 3 °C<br />

/ min heating<br />

rate<br />

N/A FPD d N/A N/A<br />

butanal<br />

internal<br />

standard<br />

Gas Chromatography-Mass Spectrometry (GC-MS)<br />

FID 100 °C<br />

200 °C, 6 °C /<br />

min heating<br />

rate<br />

Crippen et al.,<br />

1992<br />

Singleton and<br />

Pattee, 1992<br />

Muego et al.,<br />

1990<br />

Crippen et al.,<br />

1992<br />

Mason et al.,<br />

1967<br />

After separation by GC methods, identification <strong>of</strong> flavor compounds can be<br />

accomplished using several methods. Tentative identifications can be made using<br />

the retention index and flavor character as noted through GC-O. To further aid in


the identification <strong>of</strong> volatile compounds, gas chromatography-mass spectrometry<br />

(GC-MS) has been frequently used in flavor chemistry. In GC-MS, after the sample<br />

is volatilized and separated in the GC column, fragments <strong>of</strong> specific mass and<br />

charge are created by either electron or chemical ionization techniques. <strong>The</strong>se ions<br />

are accelerated and directed to a mass analyzer, where they are separated based<br />

on their mass/charge ratio. Each molecule will yield a characteristic fragmentation<br />

pattern used to identify the molecule, because the concentration <strong>of</strong> different ions<br />

formed depends on their stability and bond energies. Analysis using the MS can<br />

yield structural information about the molecule, the molecular weight, as well as the<br />

chemical formula, depending on the type <strong>of</strong> MS technique used (Ravindranath,<br />

1989).<br />

Correlation to Quality and Sensory<br />

Flavor volatiles which have been identified in the peanut pr<strong>of</strong>ile have been<br />

linked to the positive characteristics as well as the <strong>of</strong>f-flavors found in peanut<br />

products. Lovegren et al. (1982) found a good quality peanut to have the following<br />

volatile pr<strong>of</strong>ile: free methanol (2 ppm), methanol produced + acetaldehyde (1.5<br />

ppm), ethanol (1.3 ppm), acetone (0.25 ppm), N-methylpyrrole (0.25 ppm), hexanal<br />

(0.10 ppm), nonanal (0.10 ppm), total volatiles pr<strong>of</strong>ile (8 ppm). Although the color <strong>of</strong><br />

roasted peanuts can be predicted using GC pr<strong>of</strong>iles, the characteristic roasted<br />

peanut flavor note remains unpredictable by instrumental analysis (Ory et al., 1992).<br />

Poor peanut sensory quality has been correlated to a high concentration <strong>of</strong><br />

certain volatiles. <strong>The</strong> harsh, green notes <strong>of</strong> pentanal were shown to have a negative<br />

65


correlation with sensory preference (Buckholz et al., 1980). Young and Hovis (1990)<br />

related compounds identified by GC-MS to flavor pr<strong>of</strong>iles in roasted peanuts: N-<br />

methyl pyrrole was correlated with a musty <strong>of</strong>f-flavor; pentane, acetone, and<br />

dimethyl sulfide with a musty aftertaste; 2-methylpropanol with fruity; 2-butanone<br />

with degree <strong>of</strong> roast; pentanal with tongue or throat burn; and hexanal with beany<br />

flavor. Likewise, Vercellotti et al. (1992) monitored sulfur compounds such as<br />

hydrogen sulfide ("rotten eggs" <strong>of</strong>f-flavor), methyl sulfide (burnt cabbage), dibutyl<br />

sulfide (rotten onion), dimethyl sulfide (cooked cabbage), dimethyl trisulfide (burnt<br />

cabbage or onion), allyl sulfide (garlic-like) using FPD detection. <strong>The</strong>se compounds<br />

are detectable at thresholds less than 1 ppb, and add positively to the overall<br />

bouquet at very low concentrations.<br />

Gas Chromatography – Olfactometry (GC-O)<br />

Although traditional GC techniques will determine volatile compounds present<br />

in a sample, only a small percentage <strong>of</strong> these will be odor-active. Furthermore, the<br />

relative amount <strong>of</strong> a compound in a food does not necessarily equal its sensory<br />

impact. This can be due to matrix effects through which the compounds are<br />

suppressed, but also depends on human thresholds for the compound. As a result,<br />

GC-Olfactometry techniques have been used to bridge the gap between analytical<br />

chemistry and sensory analysis.<br />

<strong>The</strong> use <strong>of</strong> GC-Olfactometry was explored in the 1970's (Acree et al., 1976).<br />

<strong>The</strong> GC-O technique follows volatile extraction from the product and allows a portion<br />

<strong>of</strong> the column effluent to reach a "sniffing" port, while the other portion is routed to<br />

66


the detector. <strong>The</strong> compounds can then be identified by aroma descriptors in<br />

combination with retention indices and identification by GC-MS. <strong>The</strong> main purpose <strong>of</strong><br />

GC-O is to order the aroma volatiles in a food matrix according to their potential<br />

importance (Ferreira et al., 2002). Although it is possible that a flavor may result<br />

from a single chemical compound, it is more commonly found that the perceived<br />

flavor is a result <strong>of</strong> the interaction <strong>of</strong> several compounds. For example, Bendall<br />

(2001) discovered differences in milk flavor caused by concentration differences in a<br />

set <strong>of</strong> flavor compounds held in common by the two treatments, rather than selective<br />

occurrence <strong>of</strong> compounds uniquely associated with a particular treatment.<br />

<strong>The</strong> volatiles with the most impact on flavor have been identified using a<br />

determination <strong>of</strong> threshold (CHARM or AEDA), measuring the frequency <strong>of</strong> citations<br />

and by assessing intensity (OSME), and by cross modality matching (Ferreira et al.,<br />

2002). Both Charm Analysis and AEDA are based on dilution <strong>of</strong> samples until an<br />

odor is no longer detectable (Drake and Civille, 2002). <strong>The</strong> highest dilution at which<br />

the odor is still detected is converted to a flavor dilution value (FD) in AEDA, or to a<br />

Charm value. <strong>The</strong> charm algorithm gives an estimate <strong>of</strong> sensory intensity apart from<br />

the complexities caused by psychological estimation <strong>of</strong> stimulus intensity (Acree et<br />

al., 1984). However, these techniques require a large number <strong>of</strong> samples and<br />

panelists, making the method time-consuming (Drake and Civille, 2002).<br />

In AEDA (aroma extract dilution analysis), the flavor extract is sequentially<br />

diluted at a certain rate (usually 2-, 3-, 5-, or 10-fold) and each dilution is analyzed<br />

by GC-O by a number <strong>of</strong> judges. A dilution rate <strong>of</strong> 10 was shown to be the best by<br />

simulations although lower dilution rates were advantageous if the compound had a<br />

67


very narrow threshold distribution (Ferreira et al., 2002). Those compounds with a<br />

higher odor activity value (OAV), which is the ratio <strong>of</strong> compound concentration to<br />

threshold value, tend to be more influential in the aroma pr<strong>of</strong>ile, although some<br />

compounds can be suppressed by the food matrix (Grosch, 2001). <strong>The</strong> FD factor is<br />

proportional to the OAV <strong>of</strong> the compound in air. However, although the FD factor<br />

and OAV are relative to the concentration <strong>of</strong> the compound in the extract, they are<br />

not measures for perceived odor intensity (Grosch, 2001).<br />

OSME is another GC-O method which is commonly used. Instead <strong>of</strong><br />

dilutions, in OSME, three or more panelists evaluate not only the aroma character,<br />

but also the aroma intensity over time. Another technique, which does not involve<br />

dilutions, is posterior intensity technique. Two or more trained panelists note aroma<br />

character as well as maximum perceived intensity (Drake and Civille, 2002).<br />

Additional olfactometry techniques include the NIF/SNIF (nasal impact<br />

frequency/surface <strong>of</strong> nasal impact frequency) method. This method is based on the<br />

frequency <strong>of</strong> detection <strong>of</strong> a compound by untrained panelists. Only undiluted flavor<br />

extract is evaluated, so that the method requires fewer GC injections (Drake and<br />

Civille, 2002). However, this method does not differentiate between compounds<br />

which are far above threshold levels from those barely detectable, but instead<br />

assigns importance to a compound based on the proportion <strong>of</strong> panelists which can<br />

detect it. Although all GC-O methods have their weaknesses, they perform the<br />

same general function to select key odorants which may have the most impact on<br />

the flavor pr<strong>of</strong>ile (Noble, 2002).<br />

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GC-O Applications<br />

High vacuum distillation (HVT), GC-O, and AEDA were used to evaluate the<br />

volatile components <strong>of</strong> nonfat dry milks subjected to varying heat treatments<br />

(Karagul-Yuceer et al., 2001). HVT, GC-O, and AEDA were also used to evaluate<br />

the typical aroma components <strong>of</strong> British Farmhouse Cheddar cheese (Suriyaphan et<br />

al., 2001). Aroma extract dilution analysis and GC-O were used to analyze volatiles<br />

created during c<strong>of</strong>fee roasting (Czerny and Grosch, 2000). In peanut research, GC-<br />

O was used to generate "aromagrams" correlating odors and peak identities from<br />

GC analysis <strong>of</strong> roasted peanuts (Vercellotti et al., 1992b). Likewise, Matsui et al.<br />

(1998) used AEDA through GC-O on headspace samples to identify 2-ethyl-3,5-<br />

dimethylpyrazine, 2,3-diethyl-5-methylpyrazine and 1-penten-3-one to have the<br />

highest flavor dilution factors in commercially processed peanut oil.<br />

After linking analytical data with sensory data through GC-Olfactometry<br />

techniques, threshold analysis can be conducted to gauge human perception <strong>of</strong><br />

these compounds. To correlate with sensory, compounds found by chromatographic<br />

analysis must exceed human thresholds. For example, the compounds<br />

methylpropanal, methylbutanal, N-methylpyrrole, hexanal, hexanol, 2-pentylfuran,<br />

vinylphenol, and decadienal were determined to have thresholds below the levels<br />

found by FID in roasted peanuts, and therefore will have an effect on the flavor<br />

(Vercellotti et al., 1992).<br />

A final step might include the addition <strong>of</strong> specific compounds into a<br />

deodorized model system, to analyze creation <strong>of</strong> the flavor note. A model is created<br />

that matches the original sample aroma, and this can be the starting material for<br />

69


omission experiments to further define the compounds which contribute to the flavor<br />

pr<strong>of</strong>ile (Grosch, 2001). <strong>The</strong>re are many reasons why a model may not accurately<br />

represent the sample, including the omission <strong>of</strong> odorants which are only detectable<br />

in the food by GC-O but not by other GC detectors, or incorrect quantitative data<br />

(Grosch, 2001).<br />

In recent years, the shift <strong>of</strong> emphasis in flavor chemistry has been to the<br />

correlation <strong>of</strong> chemical structures to sensory characteristics, and to the study <strong>of</strong> the<br />

biological activities <strong>of</strong> the compounds (Teranishi, 1998). As a result, if the chemical<br />

causes <strong>of</strong> positive flavors as well as <strong>of</strong>f-flavors can be identified, they can also<br />

potentially be controlled.<br />

Sensory Evaluation<br />

<strong>The</strong> perception <strong>of</strong> peanut flavors involves the gustatory system to detect basic<br />

tastes <strong>of</strong> sweet, salty, sour, and bitter stimuli which react with taste receptors in the<br />

taste buds; the olfactory system to perceive volatiles which access receptors in the<br />

ro<strong>of</strong> <strong>of</strong> the nasal cavity; and the trigeminal system, which responds to stimuli <strong>of</strong> heat,<br />

astringency, acridness, and pungency (Sanders et al., 1993). While the range <strong>of</strong><br />

concentrations perceived in tasting is typically less than 10 4 , volatiles can be<br />

detected by the olfactory system in a range <strong>of</strong> concentration <strong>of</strong> 10 12 (Sanders et al.,<br />

1993).<br />

<strong>The</strong> first sensory method accepted for quality evaluation <strong>of</strong> peanuts was the<br />

Critical Laboratory Evaluation <strong>of</strong> Roasted Peanuts (CLER) method (Holaday, 1971).<br />

In the CLER method, 20 halves <strong>of</strong> peanuts were selected from a 300g sample, and<br />

70


each half was allocated into one <strong>of</strong> four categories: badly <strong>of</strong>f-flavor, low level <strong>of</strong>f-<br />

flavor, low peanut flavor, or good peanut flavor. <strong>The</strong> CLER score was found by<br />

calculating the number <strong>of</strong> peanuts in each category (St. Angelo, 1996). This method<br />

has been criticized for using a single continuum for quality and hedonic responses<br />

(Sanders et al., 1995). As a result, the CLER score only indirectly reflects the<br />

roasted flavor <strong>of</strong> a sample as it mixed hedonic ratings with roast level (Johnsen et<br />

al., 1988).<br />

A lexicon for roasted peanut flavor was developed by Oupadissakoon and<br />

Young (1984). A lexicon is a set <strong>of</strong> words used to describe the flavor <strong>of</strong> a product<br />

(Drake and Civille, 2003). Lexicons are used to provide a means <strong>of</strong> communication<br />

within an industry. Researchers use the lexicon to associate flavors with treatment<br />

variables, growers and processors use the lexicon to communicate quality issues,<br />

and manufacturers can use the lexicon to communicate with suppliers and the<br />

consumer (Johnsen et al., 1988). Lexicons can be used to correlate instrumental<br />

data, product development, shelf life, quality control and basic research. A well-<br />

developed lexicon will be discriminatory, representative <strong>of</strong> a wide range <strong>of</strong> samples,<br />

defined and unambiguous, composed <strong>of</strong> nonredundant terms, can be related to<br />

instrumental data and consumer perceptions, and contains references for all terms<br />

(Drake and Civille, 2003).<br />

It was suggested that the lexicon by Oupadissakoon and Young (1984)<br />

lacked terms to separate the different degrees <strong>of</strong> roast in peanuts <strong>of</strong>ten present in a<br />

lot (Johnsen et al., 1988). In 1985, Syarief et al. also developed a lexicon for<br />

roasted peanuts as well as peanut butter, using "oxidized", "mold", "earthy", and<br />

71


"petroleum'" as terminology for <strong>of</strong>f-flavors. A lexicon was later developed to address<br />

deficiencies in earlier attempts such as lack <strong>of</strong> differentiation in oxidized <strong>of</strong>f-flavors<br />

and lack <strong>of</strong> sweet/caramel descriptors (Johnsen et al., 1988).<br />

<strong>The</strong> lexicon <strong>of</strong> peanut flavor descriptors that was developed by Johnsen et al.<br />

(1988) can be found in Table 2. A ten point scale was established to rate intensity <strong>of</strong><br />

flavor, using flavor intensities <strong>of</strong> commercially available products. For example, on a<br />

scale <strong>of</strong> 0-10, the sodium carbonate in saltine crackers was rated an intensity <strong>of</strong> 2,<br />

the apple flavor in Motts apple juice was an intensity <strong>of</strong> 4, orange in Minute Maid<br />

orange juice was an intensity <strong>of</strong> 6, grape in Welch's grape juice was an intensity <strong>of</strong> 8,<br />

and cinnamon in Big Red gum was an intensity <strong>of</strong> 10 (Johnsen et al., 1988). <strong>The</strong><br />

terminology has been modified and improved over the years, including the addition<br />

<strong>of</strong> a "fruity" descriptor associated with high temperature curing (Sanders et al.,<br />

1989).<br />

Table 2: Lexicon <strong>of</strong> Peanut Flavor Descriptors (Johnsen et al., 1988).<br />

Aromatics Roasted Peanutty<br />

Raw Bean / Peanutty<br />

Dark Roasted Peanut<br />

Sweet Aromatic<br />

<strong>The</strong> aromatic associated with medium-roast peanuts<br />

(about 3-4 on USDA color chips) and having fragrant<br />

character such as methyl pyrazine<br />

<strong>The</strong> aromatic associated with light-roast peanuts<br />

(about 1-2 on USDA color chips) and having legumelike<br />

character (specify bean or pea if possible)<br />

<strong>The</strong> aromatic associated with dark roasted peanuts (4+<br />

on USDA color chips) and having very browned or<br />

toasted character<br />

<strong>The</strong> aromatics associated with sweet material such as<br />

caramel, vanilla, molasses, fruit (specify type)<br />

72


Woody/Hulls/Skins<br />

Cardboard<br />

Table 2 (continued)<br />

<strong>The</strong> aromatics associated with base peanut character<br />

(absence <strong>of</strong> fragrant top notes) and related to dry wood,<br />

peanut hulls, and skins<br />

<strong>The</strong> aromatic associated with somewhat oxidized fats and<br />

oils and reminiscent <strong>of</strong> cardboard<br />

Painty <strong>The</strong> aromatic associated with linseed oil, or oil based paint<br />

Burnt<br />

Green<br />

<strong>The</strong> aromatic associated with very dark roast, burnt<br />

starches, and carbohydrates (burnt toast or espresso<br />

c<strong>of</strong>fee)<br />

<strong>The</strong> aromatic associated with uncooked vegetables/grass<br />

twigs, cis-3-hexanal<br />

Earthy <strong>The</strong> aromatic associated with wet dirt and mulch<br />

Grainy<br />

Fishy<br />

<strong>The</strong> aromatic associated with raw grain (bran, starch, corn,<br />

sorghum)<br />

<strong>The</strong> aromatic associated with trimethylamine, cod liver oil,<br />

or old fish<br />

Chemical/Plastic <strong>The</strong> aromatic associated with plastic and burnt plastics<br />

Skunky/Mercaptan<br />

<strong>The</strong> aromatic associated with sulfur compounds, such as<br />

mercaptan, which exhibit skunk-like character<br />

Tastes Sweet <strong>The</strong> taste on the tongue associated with sugars<br />

Chemical<br />

Feeling<br />

Factors<br />

Sour <strong>The</strong> taste on the tongue associated with acids<br />

Salty <strong>The</strong> taste on the tongue associated with sodium ions<br />

Bitter<br />

Astringent<br />

Metallic<br />

<strong>The</strong> taste on the tongue associated with bitter agents such<br />

as caffeine or quinine<br />

<strong>The</strong> chemical feeling factor on the tongue, described as<br />

puckering/dry and associated with tannins or alum<br />

<strong>The</strong> chemical feeling factor on the tongue described as flat,<br />

metallic and associated with iron and copper<br />

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Descriptive Sensory Analysis<br />

Evaluating flavor by descriptive analysis separates the overall flavor character<br />

<strong>of</strong> a product into its components. <strong>The</strong>se components are precisely defined and<br />

referenced during training <strong>of</strong> the panelists (Lawless and Heymann, 1999). <strong>The</strong><br />

panelists evaluate the impact <strong>of</strong> each flavor component using a defined scale, on<br />

which they have been trained to distinguish the range <strong>of</strong> intensities (Lawless and<br />

Heymann, 1999).<br />

To develop the descriptors for the food product, a trained panel leader<br />

presents a range <strong>of</strong> samples that includes typical flavors and <strong>of</strong>f-flavored samples.<br />

Discussion among the panelists is guided to develop descriptive terms. Definitions<br />

and references are defined for all terms, and subsequent analyses are used to<br />

eliminate redundant terms and to further develop the final list which will be used for<br />

sample analysis (Drake and Civille, 2003).<br />

<strong>The</strong> first trained descriptive analysis panel for roasted peanut flavor was<br />

established at North Carolina’s Tate University in 1975. <strong>The</strong> panel used 14<br />

character notes and three categories including aroma, flavor-by-mouth, and<br />

aftertaste (Sanders et al., 1995). However, the development <strong>of</strong> descriptive sensory<br />

analysis began much earlier. <strong>The</strong> Flavor Pr<strong>of</strong>ile Method was developed in the<br />

1950's by Arthur D. Little. This method involved a small panel <strong>of</strong> highly trained<br />

experts which evaluated samples as a group using a four point scale. Although this<br />

method was very sensitive, the technical language used was difficult at times to<br />

interpret. In the 1960's, General Foods developed the Texture Pr<strong>of</strong>ile Method, which<br />

involved at least ten panelists and a scale anchored with specific food references.<br />

74


Givaudan-Roure developed Quantitative Flavour Pr<strong>of</strong>iling in the 1990's. <strong>The</strong> method<br />

is distinguished by its extensive use <strong>of</strong> references, making the results easier to<br />

compare between labs and over time. A panel <strong>of</strong> experts is utilized to characterize<br />

flavors, using nonambiguous technical language (Murray et al., 2001).<br />

One <strong>of</strong> the most common techniques in descriptive sensory analysis used<br />

today is QDA, or Quantitative Descriptive Analysis. QDA involves a panel <strong>of</strong> 10-12<br />

people, and a panel leader which is not actively involved in the evaluation. In QDA,<br />

the subject marks a line scale at the perceived intensity. <strong>The</strong> line scale is anchored<br />

on each end but has no interval numbers or labels, with the possible exception <strong>of</strong> the<br />

reference. It is not essential that each judge uses the same segment <strong>of</strong> the scale,<br />

but rather that performance is consistent (Stone et al., 1974). Although the data<br />

must be measured by hand, this type <strong>of</strong> scale may eliminate central tendency in the<br />

subjects. QDA is usually linked to product-specific scaling, in which scoring is<br />

relative to other samples. Although the panelist training does not need to be as<br />

extensive as in other methods <strong>of</strong> descriptive analysis, the product-specific scaling<br />

makes comparisons with other panels difficult. <strong>The</strong> key elements <strong>of</strong> the QDA<br />

technique include: formal statistical testing for reliability, development <strong>of</strong> a language<br />

by the group under a panel administrator’s leadership, subject selection based on<br />

performance, repeated judgements to monitor panel performance, relatively short<br />

subject training time, data collection using coded samples, and the use <strong>of</strong> analysis <strong>of</strong><br />

variance and principle component analysis to evaluate data (Stone et al., 1974).<br />

<strong>The</strong> Spectrum technique, developed by Gail Civille in 1970s, is also<br />

commonly used today. <strong>The</strong> Spectrum technique is based on a complete and<br />

75


detailed description <strong>of</strong> the sensory characteristics <strong>of</strong> a sample both in qualitative and<br />

quantitative aspects, by a panel consisting <strong>of</strong> 12-15 members. <strong>The</strong> trained panel<br />

uses a 15-point category scale, which is marked at regular intervals with numbers or<br />

words. More extensive training is needed to train the panel in the use <strong>of</strong> a category<br />

scale, but it is a universal scaling technique which can be easily applied to other<br />

products. This method is also differentiated by its extensive use <strong>of</strong> references<br />

(Drake and Civille, 2003).<br />

A final technique that is also used is Free Choice Pr<strong>of</strong>iling. In this method,<br />

consumers generate their own terms to describe samples. Although it may be<br />

harder to interpret data as a result, the consumers may find novel ways to<br />

differentiate products, and the data will also reflect consumers' perception <strong>of</strong> the<br />

product (Murray et al., 2001).<br />

Project Objectives<br />

Using these techniques <strong>of</strong> descriptive sensory analysis and chemical<br />

techniques such as GC-O and GC-MS, the flavor pr<strong>of</strong>ile <strong>of</strong> peanuts can be<br />

characterized. Specifically, the <strong>of</strong>f-flavors which may form during high temperature<br />

microwave blanching can be linked to their causative chemical compounds. <strong>The</strong><br />

objectives <strong>of</strong> this study were to characterize the processing parameters best suited<br />

for the microwave blanching <strong>of</strong> peanuts, to identify the conditions under which the<br />

<strong>of</strong>f-flavor occurs, and to analyze this <strong>of</strong>f-flavor using descriptive sensory analysis<br />

and chemical analysis. Through this project, the causes <strong>of</strong> the <strong>of</strong>f-flavor formed<br />

76


during high temperature microwave blanching could be determined and thereby<br />

possibly prevented, allowing the adoption <strong>of</strong> this alternative blanching process.<br />

77


Abbreviations<br />

AEDA Aroma extract dilution analysis<br />

CLER Critical laboratory evaluation <strong>of</strong> roasted peanuts<br />

DNPH 2, 4-dinitrophenylhydrazine<br />

DSA Dark soured aromatic<br />

FD Flavor dilution factor<br />

FID Flame ionization detector<br />

FPD Flame photometric detector<br />

g Gram<br />

GLC Gas liquid chromatography<br />

GC Gas chromatography<br />

GC-MS Gas chromatography-mass spectrometry<br />

GC-O Gas chromatography-olfactometry<br />

HSVC Headspace volatile concentration test<br />

HVT High vacuum transfer<br />

IR Infrared spectroscopy<br />

L Liter<br />

m Meter<br />

min Minute<br />

MS Mass spectrometry<br />

NIF Nasal impact frequency<br />

OSI Oxidative stability index<br />

78


OVM Organic volatiles meter<br />

Pa Pascal<br />

ppb Parts per billion<br />

ppm Parts per million<br />

PV Peroxide value<br />

QDA Quantitative descriptive analysis<br />

s Second<br />

SAFE Solvent assisted flavor evaporation<br />

SNIF Surface <strong>of</strong> nasal impact frequency<br />

SPME Solid phase microextraction<br />

TBA Thiobarbituric acid analysis<br />

US United States<br />

USDA United States department <strong>of</strong> agriculture<br />

UV Ultraviolet spectroscopy<br />

w.b. Wet basis<br />

79


ε Relative complex permittivity<br />

Symbols<br />

ε' Relative real permittivity (dielectric constant)<br />

ε" Relative dielectric loss factor<br />

cdry Specific heat <strong>of</strong> dry seeds (1.880 kJ / (kg °C))<br />

cw Specific heat <strong>of</strong> water (4.187 kJ/(kg °C))<br />

γdry Bulk density <strong>of</strong> dry seeds (kg/m 3 )<br />

hlg Heat <strong>of</strong> vaporization <strong>of</strong> water (2.418 x 104 kJ/kg at 35°C)<br />

j Imaginary unit<br />

mcf Final seed moisture content (w.b.)<br />

mci Initial seed moisture content (w.b.)<br />

Q Energy per unit volume (kJ/m 3 )<br />

Ti Initial temperature (°C)<br />

Tf Final temperature (°C)<br />

80


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analysis <strong>of</strong> gas chromatographic effluents. Food Chemistry 14: 273-286.<br />

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gas chromatographic effluents. Analytical Chemistry 48(12): 1821-1822.<br />

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89


CHAPTER 3:<br />

EFFECT OF PROCESSING PARAMETERS ON THE TEMPERATURE AND<br />

MOISTURE CONTENT OF MICROWAVE-BLANCHED PEANUTS<br />

A.V. Schirack 1 , T.H. Sanders 2 , K.P. Sandeep 1*<br />

1 Department <strong>of</strong> Food Science<br />

North Carolina State University, Raleigh, North Carolina 27695-7624<br />

2 USDA-ARS, Market Quality and Handling Research Unit<br />

North Carolina State University, Raleigh, North Carolina 27695-7624<br />

Submitted for publication in Journal <strong>of</strong> Food Process Engineering.<br />

M.E. Castell-Perez, and R. Moreira, eds. Blackwell Publishing, Malden, MA.<br />

90


ABSTRACT<br />

Peanut blanching consists <strong>of</strong> heat application followed by abrasive removal <strong>of</strong><br />

the seed coat. <strong>The</strong> use <strong>of</strong> a continuous microwave system for the blanching <strong>of</strong><br />

peanuts has been proposed as a means <strong>of</strong> reducing processing time and energy<br />

costs compared to the traditional hot air, multi-zone oven. <strong>The</strong> purpose <strong>of</strong> this<br />

research was to characterize effective processing parameters for microwave<br />

blanching. <strong>The</strong> factors examined were the time <strong>of</strong> exposure in the microwave, use<br />

<strong>of</strong> increased airflow in the microwave applicator during processing, and the initial<br />

moisture content <strong>of</strong> the peanuts. Processing treatments were differentiated by<br />

energy absorbed during processing, average and maximum internal temperatures,<br />

loss in moisture content, and blanchability. High blanchability resulted from higher<br />

process temperatures and greater loss in moisture content. Treatments exceeding<br />

110 °C resulting in a final moisture content <strong>of</strong> 5.5 % or below yielded blanchability<br />

percentages greater than the 85 % industry standard. <strong>The</strong> time required to generate<br />

sufficient heat to dry peanuts for acceptable blanchability is greatly reduced by the<br />

use <strong>of</strong> microwave technology.<br />

INTRODUCTION<br />

Peanut blanching consists <strong>of</strong> heat application followed by abrasive removal <strong>of</strong><br />

the seed coat. Removal <strong>of</strong> the seed coat prepares peanuts for further processing<br />

into specific products, and the heating step reduces enzyme activity and moisture<br />

91


content, which are factors impacting subsequent quality (Adelsberg and Sanders,<br />

1997). Blanching allows for electronic color-sorter removal <strong>of</strong> damaged or discolored<br />

seed, which are associated with aflatoxin contamination (Sanders et al., 1999).<br />

Several methods are used for blanching: dry-blanching, spin-blanching,<br />

water-blanching, alkali-blanching, and hydrogen peroxide blanching. In general, the<br />

most common method in industrial processing is dry-blanching. In this process,<br />

peanuts are placed on conveyor belts and moved through large ovens in which the<br />

direction <strong>of</strong> airflow is alternated in successive zones (Adelsberg and Sanders, 1997).<br />

<strong>The</strong> peanuts are heated in sequential zones from 30 °C to 90 °C, with a total normal<br />

processing time <strong>of</strong> approximately 45 minutes. During this time, moisture is removed<br />

from the peanuts, the seed coat is loosened, and after cooling, the seed coats are<br />

mechanically removed (Sanders et al., 1999). Paulsen and Brusewitz (1976)<br />

suggested that the mechanism <strong>of</strong> blanching is due to differences in thermal<br />

expansion and subsequent contraction <strong>of</strong> the seed and seed coat, resulting in a<br />

loosening <strong>of</strong> the seed coat.<br />

Adelsberg and Sanders (1997) studied the effects <strong>of</strong> varying parameters on<br />

peanut temperature distributions and blanchability using a lab-scale simulation <strong>of</strong><br />

conventional blanching methods. <strong>The</strong> magnitude <strong>of</strong> temperature variation in the<br />

peanut bed during blanching was related to the final set point temperature <strong>of</strong> the<br />

oven and to the dwell time at each temperature setting. In general, with increased<br />

temperatures and increased moisture loss, blanching percentage increased<br />

(Paulsen and Brusewitz, 1976; Katz, 2002). Adelsberg and Sanders (1997)<br />

provided specific detail <strong>of</strong> that information when they reported that reduction <strong>of</strong><br />

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peanut moisture content from 5.5 to < 4 % using temperatures <strong>of</strong> 87.7 °C for 45 and<br />

60 minutes and 98 °C for 30, 45, and 60 minutes resulted in maximum blanchability.<br />

Moisture content affects blanchability as well as stability and flavor quality <strong>of</strong> peanuts<br />

(Adelsberg and Sanders, 1997; Katz, 2002).<br />

<strong>Microwave</strong> processing has been explored as an alternative to traditional<br />

blanching methods due to speed <strong>of</strong> operation, energy savings, and efficiency <strong>of</strong><br />

process control. Shorter heating times during processing lead to greater nutrient<br />

retention, better quality characteristics such as texture and flavor, as well as<br />

increased production (Giese, 1992). <strong>The</strong> use <strong>of</strong> vacuum drying and microwaves for<br />

peanut processing has been studied in comparison to traditional methods (Delwiche<br />

et al., 1986). In a study using a series <strong>of</strong> individual trays <strong>of</strong> peanuts passing through<br />

a linear applicator, Rausch et al. (2005) examined the potential use <strong>of</strong> microwaves<br />

for peanut blanching. In the current study, refinement <strong>of</strong> the microwave applicator<br />

has allowed a solid bed <strong>of</strong> peanuts to be exposed to microwave energy in a<br />

continuous process, using a processing technique similar to Boldor et al. (2005).<br />

Processing a continuous bed <strong>of</strong> peanuts eliminated the heat reflection and focusing<br />

effect observed by Rausch et al. (2005) and prevented wide variation in peanut bed<br />

surface temperatures.<br />

<strong>The</strong> use <strong>of</strong> microwave technology for blanching peanuts can result in large<br />

decreases in processing time and subsequent cost savings. <strong>The</strong> purpose <strong>of</strong> this<br />

research was to characterize effective processing parameters for microwave<br />

blanching, using a range <strong>of</strong> factors including exposure time, use <strong>of</strong> increased air flow<br />

in the applicator, and initial moisture content <strong>of</strong> the peanuts. Relationships between<br />

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moisture content, energy absorbed by the peanuts, internal and surface temperature<br />

pr<strong>of</strong>iles, and blanchability were evaluated in response to variations in processing<br />

parameters.<br />

MATERIALS AND METHODS<br />

Medium-grade size, runner-type peanuts (Arachis hypogaea L., variety<br />

Georgia Green) at an average moisture content <strong>of</strong> 7 % (wet basis) were obtained<br />

from a single harvested lot from USDA, ARS, National Peanut Research Laboratory<br />

(Dawson, Georgia). <strong>The</strong> peanuts were harvested, cured, shelled, sized, and stored<br />

according to normal practices prior to delivery to Raleigh, NC. A second lot <strong>of</strong><br />

peanuts at 11% moisture content were received from USDA, ARS, National Peanut<br />

Research Laboratory (Dawson, Georgia). <strong>The</strong> second lot was divided into 150<br />

pound samples which were dried to 5 %, 7 %, and 9 % moisture content with forced<br />

ambient air, and one lot was maintained at 11 % moisture content. All peanuts were<br />

bagged, placed in opaque tubs and stored in a cooler at 6 °C and 60 % relative<br />

humidity before use in experiments one week later. Before use, peanuts were<br />

tempered overnight to room temperature.<br />

Peanuts were heated using a 5 kW, 915 MHz microwave unit (Industrial<br />

<strong>Microwave</strong> Systems, Morrisville, NC) with a 2.74 m belt conveyor for sample<br />

delivery. <strong>The</strong> conveyor tunnel was equipped with an electric fan and heater, which<br />

was set to deliver 25 °C air into the system. <strong>The</strong> microwave generator was<br />

controlled by a data acquisition and control unit (HP34970A, Agilent, Palo Alto, CA).<br />

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<strong>The</strong> computer monitored power output, reflected power, and power at the exit <strong>of</strong> the<br />

microwave tunnel through power diodes (JWF 50D-030+, JFW Industries, Inc.,<br />

Indianapolis, IN). Immediately after blanching, peanuts were cooled to room<br />

temperature using forced ambient air. Samples were taken for moisture content and<br />

blanchability analysis. <strong>The</strong> remainder <strong>of</strong> each sample was sealed in plastic bags<br />

and stored in opaque plastic tubs.<br />

A random complete block design was used to evaluate the effect <strong>of</strong><br />

processing factors during microwave blanching. <strong>The</strong> experiments were split into two<br />

sets (Table 1). Set 1 consisted <strong>of</strong> 7% moisture content peanuts heated using<br />

varying microwave exposure times and both with (F) and without (NF) the use <strong>of</strong><br />

circulated 25 °C air in the conveyor tunnel. <strong>The</strong>se peanuts were exposed to<br />

microwave energy for 4, 5, 8, or 11 minutes. <strong>The</strong> control sample for this set was<br />

peanuts undergoing the same storage procedures but which were not treated with<br />

microwave energy. Peanuts in Set 2 had initial moisture contents <strong>of</strong> 5, 7, 9 and<br />

11 % and were processed for the same exposure time (11 minutes, 5 kW) without<br />

the use <strong>of</strong> a fan. <strong>The</strong> treatments in Set 2 were replicated three times, while<br />

treatments in Set 1 were replicated four times.<br />

<strong>The</strong> surface temperatures <strong>of</strong> the peanuts during processing were measured<br />

using infrared probes installed along the length <strong>of</strong> the conveyor tunnel (model OS36-<br />

T, OMEGA Engineering, Inc., Stamford, CN). Internal peanut temperatures were<br />

measured using four fiber optic probes (FOT- L/10M, Fiso Technologies, Inc.,<br />

Quebec, Canada) inserted into the center <strong>of</strong> individual peanuts which traveled the<br />

length <strong>of</strong> the conveyor. <strong>The</strong> probes were connected to a multi-channel fiber optic<br />

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signal conditioner (Model UMI 4, Fiso Technologies, Inc., Quebec, Canada) which<br />

was controlled using FISO Commander s<strong>of</strong>tware (Fiso Technologies, Inc., Quebec,<br />

Canada) on a laptop computer (Dell Inspiron 8500, Dell Computer Corporation,<br />

Round Rock, TX). Data collection was started simultaneously for the infrared probes<br />

and fiber optic probe systems to coordinate internal and external temperature<br />

measurements during processing.<br />

<strong>The</strong> energy absorbed by the peanuts during treatment was calculated using<br />

the forward power from the generator and subtracting energy lost in reflection and at<br />

the end <strong>of</strong> the conveyor tunnel. <strong>The</strong> exposure time <strong>of</strong> the treatment was also used<br />

to calculate an average total absorption <strong>of</strong> energy during each treatment.<br />

After the seed coats were removed, moisture content was measured using a<br />

forced convection oven (Despatch LXD Series, Despatch Industries, Minneapolis,<br />

MN); 25 gram samples were dried at 130 °C for 11 hours, and weight change was<br />

used to calculate moisture content. Analyses were conducted in triplicate.<br />

For seed coat removal, 350 grams <strong>of</strong> peanuts were exposed to counter-<br />

rotating grit rollers for two minutes on a laboratory scale blancher (Model EX Ashton,<br />

Ashton Food Machinery Company, Inc., Newark, NJ). Blanchability was determined<br />

by visual inspection <strong>of</strong> a subsample <strong>of</strong> 100 peanuts. Peanuts with any portion <strong>of</strong><br />

skin attached were categorized as unblanched. Analyses were conducted in<br />

triplicate for each treatment. All statistical analysis including analysis <strong>of</strong> variance<br />

was conducted using SAS s<strong>of</strong>tware (Version 9.1, SAS Institute Inc., Cary, NC).<br />

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RESULTS AND DISCUSSION<br />

Energy Absorption. <strong>Microwave</strong> blanching involves the generation <strong>of</strong> heat by<br />

the selective absorption <strong>of</strong> electromagnetic energy by water molecules and ionic<br />

materials, as reflected in the dielectric properties <strong>of</strong> the material. In this study, all<br />

treatments were statistically different in the amount <strong>of</strong> energy absorbed during<br />

microwave blanching (p < 0.0001), although a significant effect occurred within<br />

replicates in Set 1 only. Peanuts in the 11 minute exposure treatment absorbed the<br />

most energy overall (Fig. 1). All other exposure times were significantly different (p<br />

< 0.05) from each other, and the use <strong>of</strong> a fan made no difference. <strong>The</strong> amount <strong>of</strong><br />

power absorbed depends on the intensity <strong>of</strong> the electric field, as well as the dielectric<br />

properties <strong>of</strong> the material. This is <strong>of</strong>ten expressed by the equation:<br />

P=2Πfε0E 2 ε”<br />

where f is frequency (Hz), E is electric field intensity (v/m), ε” is the dielectric loss<br />

and ε0 is the dielectric constant <strong>of</strong> free space (8.854 farad/m). Although the<br />

dielectric properties <strong>of</strong> shelled peanuts at these experimental conditions are not<br />

found in the literature, Trabelsi and Nelson (2004) found that at frequencies <strong>of</strong> 12 to<br />

18 GHz, shelled peanuts at 5.1% moisture content had a dielectric constant (ε’) <strong>of</strong><br />

2.1 and dielectric loss (ε”) <strong>of</strong> 0.11. Boldor et al.(2004) found a range <strong>of</strong> dielectric<br />

constants <strong>of</strong> 4.5-10 and dielectric loss values from 1.25-2.75 in peanuts at 18-33%<br />

moisture content (dry basis), respectively. Although the dielectric properties will<br />

decrease with frequency and increase with higher moisture content, these studies<br />

give a general range <strong>of</strong> values for the conditions in this study. <strong>The</strong>se values for<br />

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dielectric constant and dielectric loss in peanuts are relatively low compared to other<br />

foods on a dielectric properties map (Ryynanen, 1995), although this would be<br />

expected because <strong>of</strong> the high content <strong>of</strong> oil in the peanuts.<br />

In Set 2, 11 % moisture content peanuts absorbed more energy than the 5 %<br />

moisture content peanuts in each replicate, but the remaining treatments were not<br />

different (data not shown). In peanuts, water dominates the effect on dielectric<br />

properties (Trabelsi and Nelson, 2004). In fact, in many materials, the change in<br />

dielectric constant and dielectric loss with moisture content is so pronounced, it has<br />

been used to develop methods <strong>of</strong> measuring moisture content using microwave<br />

technology (Engelder and Buffler 1991). <strong>The</strong>se differences in energy absorption<br />

with moisture content agree with the literature (Trabelsi and Nelson, 2004), as a<br />

significant decrease in dielectric constant and dielectric loss was seen in shelled<br />

peanuts as moisture content decreased from 18 to 7%.<br />

Peanut Temperature. As microwave energy is absorbed by the peanuts, the<br />

rate <strong>of</strong> temperature increase will depend on the power (P), mass (M), and specific<br />

heat (Cp), as in the following equation (Metaxas and Meredith, 1983):<br />

P = M Cp (T-T0) / t<br />

During microwave heating, both internal (Table 2) and surface temperatures <strong>of</strong> the<br />

peanuts were monitored. A comparison <strong>of</strong> internal and surface temperature pr<strong>of</strong>iles<br />

for select treatments can be seen in Fig. 2 and 3. <strong>The</strong> average internal temperature<br />

pr<strong>of</strong>iles <strong>of</strong> the treatments (Table 2) from both sets were significantly different from<br />

each other (p < 0.0001). In Set 1, peanuts from treatment 11NF had the highest<br />

internal temperatures, followed by 8NF.<br />

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All treatments using the fan (F) had consistently lower temperatures than the NF<br />

treatment <strong>of</strong> the same time, due to surface cooling <strong>of</strong> the peanuts (Table 2). Fans<br />

are commonly used in the curing (drying) <strong>of</strong> peanuts (Troeger 1982; Young, 1982).<br />

Since one <strong>of</strong> the objectives <strong>of</strong> blanching is to reduce moisture, the use <strong>of</strong> a fan was<br />

included in these experiments. During microwave heating, some heat will be lost<br />

from the material due to radiation and also by convection, which is affected by the<br />

difference in the temperatures between the material (T) and its surroundings (Tinf),<br />

the surface area (A), and h, the heat transfer coefficient (Metaxas and Meredith,<br />

1983):<br />

Qconv = h A (T – Tinf)<br />

Convection is also affected by the velocity <strong>of</strong> the surrounding air; as a result, a fan<br />

will increase surface cooling. Evaporation at the surface <strong>of</strong> the material will also<br />

increase, as a fan will remove moisture from the system quickly and speed moisture<br />

diffusion. This will result in lower temperatures due to increased evaporative<br />

cooling, and temperature gradients can be formed. Furthermore, Datta and Liu<br />

(1992) found that during microwave processing <strong>of</strong> solids, heat is generated at<br />

increasing rates at the surface, and the difference between surface and center<br />

temperature continue to increase with time <strong>of</strong> processing. As a result, cooling the<br />

surface <strong>of</strong> the peanuts by using a fan during blanching has a large effect on internal<br />

temperatures, and did not enhance blanching as might be expected.<br />

<strong>The</strong> effect <strong>of</strong> increased airflow via a fan during blanching has been studied<br />

previously. In their research on conventional oven blanching, Adelsberg and<br />

Sanders (1997) found that increased airflow caused the portion <strong>of</strong> the peanut bed<br />

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exposed to the fan to be approximately 10 °C lower than the rest <strong>of</strong> the peanuts.<br />

This temperature difference was greater in treatments conducted at higher<br />

temperatures, reaching a 17 °C difference in treatments conducted at 98.9 °C<br />

(Adelsberg and Sanders 1997). <strong>The</strong> difference in the temperatures between the<br />

longer treatments in this study conducted with and without a fan were somewhat<br />

larger, but they were also conducted at much higher temperatures used in<br />

microwave blanching.<br />

In Set 2, the lowest moisture peanuts reached the highest temperatures (Table 2,<br />

Fig. 3). Although all treatments in Set 2 exceeded 100 °C, peanuts in the 5 % MC<br />

treatment had the highest internal temperature (139 °C), followed by 7 %, 9 %, and<br />

11 % MC treatments. <strong>The</strong> typical temperature pr<strong>of</strong>ile which is seen in materials<br />

dried using microwave technology has three separate regions: an initial heating<br />

region in which the temperature <strong>of</strong> the material reaches the wet bulb temperature; a<br />

constant temperature drying region, in which most <strong>of</strong> the liquid is vaporized and<br />

moves through the sample; and a third region in which the temperature increases<br />

without any further removal <strong>of</strong> liquid (Metaxa and Meredith 1983). Peanuts with<br />

lower initial moisture contents (5% and 7%) did not absorb as much energy during<br />

processing, because <strong>of</strong> the relatively lower amounts <strong>of</strong> polar components in the<br />

sample. However, these low moisture peanuts may be progressing through this<br />

drying curve more quickly as they soon reach an equilibrium moisture content during<br />

the constant drying region. As a result, they spend more <strong>of</strong> the processing time in<br />

the third region <strong>of</strong> the curve, increasing in temperature.<br />

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Treatments 11NF, 8NF, and 5NF also had the highest surface temperatures,<br />

which exceeded 100 °C, and lower moisture peanuts (5 % and 7 % MC) had higher<br />

surface temperatures in Set 2. Boldor et al. (2005) found that more convective<br />

cooling will occur at the surface <strong>of</strong> peanuts during drying when more water is being<br />

evaporated, thus treatments with the most moisture loss will have a greater cooling<br />

effect at the surface. This agrees with the trend seen in the peanuts in Set 2, in<br />

which all peanuts were treated for the same period <strong>of</strong> time, but the higher moisture<br />

content peanuts had lower surface temperatures. Surface temperatures have been<br />

previously correlated to internal temperatures in microwave processing <strong>of</strong> peanuts<br />

(Boldor et al., 2005).<br />

Change in moisture content. <strong>The</strong> final moisture content <strong>of</strong> the peanuts was<br />

significantly affected by treatment (p < 0.0001), although replicate effects were<br />

significant in Set 1 only (p = 0.02). In Set 1, as processing times increased, internal<br />

peanut temperatures increased, and more moisture was lost (Fig. 4). Treatments<br />

8NF and 11NF had significantly lower final moisture content (approximately 4.0 - 5.5<br />

%) than other treatments (p < 0.05). Unlike conventional heating, microwave energy<br />

is absorbed throughout the volume <strong>of</strong> the wet solid, and the temperature <strong>of</strong> the solid<br />

can reach the boiling point <strong>of</strong> the liquid component. As the moisture evaporates, a<br />

pressure gradient is formed from the vapors and will drive the moisture from the<br />

interior <strong>of</strong> the solid (Metaxas and Meredith, 1983).<br />

Despite the variations in initial moisture contents and energy absorption, all<br />

peanuts in Set 2 reached a similar moisture content <strong>of</strong> approximately 4.1 % (Fig. 4).<br />

This moisture content appears to be the final equilibrium point at which the peanuts<br />

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finish the constant drying region <strong>of</strong> the temperature pr<strong>of</strong>ile. Since the lower moisture<br />

peanuts reached this point more quickly, they entered the third phase in the<br />

temperature pr<strong>of</strong>ile, and reached higher temperatures during processing than the<br />

9% and 11% peanuts (Table 2, Fig. 3). It has been noted that it is difficult to remove<br />

tightly bound water using microwaves, because <strong>of</strong> the low absorption <strong>of</strong> energy by<br />

the residual liquid (Metaxas and Meredith, 1983). As a result, the 4% moisture level<br />

may be at a transition between free and bound water in the peanuts, which would<br />

impede further moisture loss during processing at the conditions studied.<br />

Blanchability. Treatments had a significant effect on blanchability<br />

(p < 0.0001). Individually, the treatments <strong>of</strong> 8NF, 11F, and 11NF were not<br />

significantly different from each other (Fig. 5) but were more blanchable than the<br />

other treatments (p < 0.05). Only 8NF and 11NF consistently exceeded the industry<br />

standard <strong>of</strong> 85 % blanchability in Set 1, and all variable moisture content peanut<br />

samples in Set 2 exceeded the standard (Fig. 6). In addition, the peanuts with initial<br />

moisture content <strong>of</strong> 5 % were significantly higher in blanchability (average = 93 %)<br />

than the other 3 lots for each replicate. To ensure that the initial ambient air drying<br />

step for peanuts in Set 2 did not affect blanchability, controls for each moisture<br />

content were also examined, and blanchability was found to average 1 %.<br />

High blanchability resulted from higher process temperatures and lower final<br />

moisture content, with those treatments exceeding 110 °C and reaching a final<br />

moisture content <strong>of</strong> 5.5 % or below yielding blanchability greater than 85 % (Fig. 7).<br />

Similarly, Rausch et al. (2005), when blanching individual trays <strong>of</strong> peanuts, found<br />

that microwave treatments resulting in 0.5 – 1.0 % moisture loss provided better<br />

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lanchabilities as well as a longer raw peanut shelf life. It has been suggested that<br />

the mechanism <strong>of</strong> blanching is due to differences in thermal expansion and<br />

subsequent contraction <strong>of</strong> the seed and seed coat, resulting in a loosening <strong>of</strong> the<br />

seed coat. In an experiment by Paulsen and Brusewitz (1976), the difference<br />

between the coefficients <strong>of</strong> cubical thermal expansion <strong>of</strong> seeds (50 – 60.5 x 10 -5 /°C)<br />

and that for peanut skins (26.5 – 55 x 10 -5 /°C) grew larger at lower moisture<br />

contents. As a result, this explains why peanuts which reached the lowest moisture<br />

content were the most effective treatments for blanchability. In fact, in another<br />

study, Paulsen and Brusewitz (1976b) determined that the effectiveness <strong>of</strong><br />

blanching was dependent mainly on the degree <strong>of</strong> moisture removal, although<br />

Adelsberg and Sanders (1997) did not see an increase in blanchability at moisture<br />

contents below 3.8%. Instead, Adelsberg and Sanders (1997) determined that<br />

differences in blanchability may be affected by thermal expansion or variations in<br />

moisture loss, or possibly a combination <strong>of</strong> factors. This study was also not able to<br />

separate these factors <strong>of</strong> temperature and final moisture content, although initial<br />

moisture content does not appear to have much effect on blanchability.<br />

An interplay <strong>of</strong> temperature and moisture loss must be responsible for the high<br />

rates <strong>of</strong> blanchability seen in the 8NF treatment. Although this treatment absorbed<br />

significantly less energy and reached lower temperatures than the 11NF treatment<br />

and the peanuts in Set 2, it reached a level <strong>of</strong> blanchability above the 85% standard.<br />

In order to investigate this, the maximum internal temperatures during processing<br />

were also evaluated, and were found significantly different (p < 0.0001) for each<br />

treatment (Table 3). In this comparison, the maximum temperature <strong>of</strong> the 8NF<br />

103


treatment was over 100 °C, similar to the 11NF treatment and the peanuts in Set 2<br />

which ranged from 119 – 139 °C. In temperatures under 100 °C, Datta and Liu<br />

(1992) found that temperature pr<strong>of</strong>iles became increasingly non-uniform over longer<br />

heating times during microwave processing. However, Ni et al. (1999) found that the<br />

non-uniformity in temperatures is lessened when the food temperature reaches the<br />

boiling point <strong>of</strong> water. <strong>The</strong> same study (Ni et al, 1999) also found that the key<br />

variable which controls moisture loss during the microwave heating <strong>of</strong> solid foods<br />

was achieving an average temperature uniformly. By evaluating the maximum<br />

temperatures reached during processing, it was seen that the internal temperatures<br />

during the 8NF treatment exceeded 100 °C, and perhaps reached a more uniform<br />

temperature pr<strong>of</strong>ile, leading to greater moisture loss and acceptable blanchability.<br />

CONCLUSIONS<br />

<strong>The</strong> use <strong>of</strong> microwave technology for peanut blanching provides a significant<br />

decrease in processing time and can result in cost savings. In this study, the<br />

relationships between temperature, moisture content, and blanchability using a<br />

continuous belt processing method have been demonstrated. <strong>Effect</strong>ive blanchability<br />

was correlated to high process temperatures and corresponding low moisture<br />

content. All peanuts with internal temperatures exceeding 110 °C and reaching a<br />

final moisture content <strong>of</strong> 5.5 % or below yielded acceptable blanchability. Even<br />

peanuts varying in initial moisture content resulted in a low final moisture content<br />

and acceptable blanchability. This study demonstrated that peanuts heated by<br />

104


microwave attain much higher temperatures than conventional multizone oven<br />

heated peanuts. <strong>The</strong> time required to generate sufficient heat to dry peanuts for<br />

acceptable blanchability is greatly reduced by the use <strong>of</strong> microwave technology.<br />

ACKNOWLEDGMENTS<br />

Funded in part by the North Carolina Agricultural Research Service. Paper<br />

no. --- <strong>of</strong> the Journal Series <strong>of</strong> the Dept. Food Science, North Carolina State<br />

University, Raleigh, NC 27695. <strong>The</strong> assistance <strong>of</strong> Keith Hendrix and Jim Schaefer is<br />

gratefully acknowledged. <strong>The</strong> authors would also like to thank Marshall Lamb and<br />

Bobby Tennille <strong>of</strong> USDA, ARS, National Peanut Laboratory (Dawson, Georgia) for<br />

supplying the peanuts used in this study. <strong>The</strong> use <strong>of</strong> trade names in this publication<br />

does not imply endorsement by the North Carolina State University or USDA, ARS<br />

<strong>of</strong> the products named nor criticism <strong>of</strong> similar ones not mentioned.<br />

105


ABBREVIATIONS<br />

ARS - Agricultural Research Service<br />

F - Fan used during processing<br />

MC - Moisture content (wet basis)<br />

NF - No fan used during processing<br />

OSI - Oxidative stability index<br />

PV - Peroxide value<br />

USDA - United States Department <strong>of</strong> Agriculture<br />

106


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SANDERS, T.H., ADELSBERG, G.D., HENDRIX, K.W. and MCMICHAEL, R.W.<br />

JR. 1999. <strong>Effect</strong> <strong>of</strong> blanching on peanut shelf-life. Peanut Science 26, 8-13.<br />

TRABELSI, S. and NELSON, S.O. 2004. <strong>Microwave</strong> dielectric properties <strong>of</strong> shelled<br />

and unshelled peanuts. Transactions <strong>of</strong> the ASAE 47(4), 1215-1222.<br />

TROEGER, J.M. 1982. Peanut drying energy consumption - a simulation analysis.<br />

Peanut Science 9, 40-44.<br />

YOUNG, J.H., PERSON, N.K., DONALD, J.O., and MAYFIELD, W.D. 1982.<br />

Harvesting, curing, and energy utilization. In Peanut Science and Technology.<br />

Edited by Pattee, H.E. and Young, C.T. Amer. Peanut REs. Educ. Soc., Inc.,<br />

Yoakum, TX.<br />

108


TABLES AND FIGURES<br />

Table 1: Processing parameters during microwave blanching<br />

<strong>of</strong> peanuts<br />

Treatment Initial moisture content <strong>of</strong> peanuts<br />

Set 1 4 min., Fan 7 %<br />

4 min., No fan 7 %<br />

5 min., Fan 7 %<br />

5 min., No fan 7 %<br />

8 min., Fan 7 %<br />

8 min., No fan 7 %<br />

11 min., Fan 7 %<br />

11 min., No fan 7 %<br />

Set 2 11 min., No fan 5 %<br />

11 min., No fan 7 %<br />

11 min., No fan 9 %<br />

11 min., No fan 11 %<br />

Table 2: Means by treatment <strong>of</strong> internal temperatures <strong>of</strong> peanuts<br />

during microwave blanching<br />

Treatment Mean temperature (°C)<br />

Set 1 4 min., Fan 38.4j 1<br />

5 min., Fan 54.7i<br />

8 min., Fan 57.4h<br />

11 min., Fan 62.7g<br />

4 min., No fan 71.0e<br />

5 min., No fan 63.9f<br />

8 min., No fan 85.7d<br />

11 min., No fan 103.3b<br />

Set 2 5 % Moisture content 102.9b<br />

7 % Moisture content 104.9a<br />

9 % Moisture content 98.6c<br />

11 % Moisture content 98.1c<br />

1 Values followed by the same letter are not significantly different (LSD = 0.91)<br />

109


Table 3: Maximum internal temperatures <strong>of</strong> peanuts by treatment<br />

during microwave blanching<br />

Treatment Maximum temperature (°C)<br />

Set 1 4 min., Fan 69.3h 1<br />

5 min., Fan 77.0gh<br />

8 min., Fan 84.4fg<br />

11 min., Fan 90.6ef<br />

4 min., No fan 92.0ef<br />

5 min., No fan 94.6e<br />

8 min., No fan 112.8d<br />

11 min., No fan 128.0bc<br />

Set 2 5 % Moisture content 138.8a<br />

7 % Moisture content 132.5ab<br />

9 % Moisture content 122.2cd<br />

11 % Moisture content 119.1cd<br />

1 Values followed by the same letter are not significantly different (LSD = 9.8)<br />

110


Energy absorbed (kJ)<br />

3000<br />

2500<br />

2000<br />

1500<br />

1000<br />

500<br />

0<br />

4 min., Fan 4 min., No fan<br />

5 min., Fan 5 min., No fan<br />

8 min., Fan 8 min., No fan<br />

11 min., Fan 11 min., No fan<br />

Samples<br />

Fig. 1: Mean energy absorbed by peanuts per treatment for all replicates during microwave heating<br />

for 4, 5, 8, or 11 minutes (Set 1)<br />

111


Temperature <strong>of</strong> peanuts (°C)<br />

160<br />

140<br />

120<br />

100<br />

80<br />

60<br />

40<br />

20<br />

0<br />

0 2 4 6 8 10 12<br />

Time <strong>of</strong> microwave exposure (min)<br />

Figure 2: Internal and surface temperatures <strong>of</strong> peanuts during microwave blanching for 11 minutes<br />

with and without using fan (Set 1)<br />

112<br />

11 min with fan (internal)<br />

11 min with fan (surface)<br />

11 min without fan (internal)<br />

11 min without fan (surface)


Temperature <strong>of</strong> peanuts (°C)<br />

160<br />

140<br />

120<br />

100<br />

80<br />

60<br />

40<br />

20<br />

0<br />

0 2 4 6 8 10 12<br />

Time <strong>of</strong> microwave exposure (min)<br />

Figure 3: Internal and surface temperatures <strong>of</strong> peanuts <strong>of</strong> 5 and 11% initial moisture content (MC)<br />

during microwave blanching for 11 minutes without using a fan (Set 2)<br />

113<br />

5% MC peanuts (internal)<br />

11% MC peanuts (internal)<br />

5% MC peanuts (surface)<br />

11% MC peanuts (surface)


Internal temperature (°C)<br />

140<br />

130<br />

120<br />

110<br />

100<br />

90<br />

80<br />

70<br />

60<br />

9% MC (Set 2)<br />

11% MC (Set 2)<br />

5% MC (Set 2)<br />

7% MC (Set 2)<br />

11NF<br />

8NF<br />

3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5<br />

Moisture content (% wb)<br />

Fig 4. Relationship between maximum internal temperature and final moisture content <strong>of</strong> peanuts<br />

after microwave blanching (correlation r 2 = 0.87). F= fan used during blanching, NF = no fan used,<br />

MC = moisture content<br />

114<br />

11F<br />

8F<br />

5NF<br />

4F<br />

5F<br />

4NF


Percent blanchability<br />

100<br />

90<br />

80<br />

70<br />

60<br />

50<br />

40<br />

30<br />

20<br />

10<br />

0<br />

Samples<br />

Figure 5: Mean <strong>of</strong> blanchability results per treatment for all replicates during microwave blanching <strong>of</strong><br />

peanuts for 4, 5, 8, or 11 minutes (Set 1)<br />

115<br />

4 min., Fan<br />

4 min., No fan<br />

5 min., Fan<br />

5 min., No fan<br />

8 min., Fan<br />

8 min., No fan<br />

11 min., Fan<br />

11 min., No fan


Percent blanchability<br />

100<br />

95<br />

90<br />

85<br />

80<br />

75<br />

Samples<br />

Figure 6: Mean <strong>of</strong> blanchability results per treatment for all replicates during microwave blanching <strong>of</strong><br />

peanuts for 11 minutes without using a fan (Set 2)<br />

116<br />

5% <strong>Microwave</strong><br />

7% <strong>Microwave</strong><br />

9% <strong>Microwave</strong><br />

11% <strong>Microwave</strong>


Maximum internal temperature (°C)<br />

140<br />

130<br />

120<br />

110<br />

100<br />

90<br />

80<br />

70<br />

60<br />

7.30% MC<br />

7.78% MC<br />

7.54% MC<br />

7.19% MC<br />

40 50 60 70 80 90 100<br />

Blanchability (%)<br />

Figure 7: Relationship between maximum internal temperature and blanchability <strong>of</strong> peanuts after<br />

microwave blanching (correlation r 2 = 0.81). <strong>The</strong> average final moisture content (MC) <strong>of</strong> each<br />

treatment is noted.<br />

117<br />

4.20% MC<br />

7.36% MC<br />

6.92% MC<br />

4.28% MC<br />

4.14% MC<br />

4.06% MC<br />

4.49% MC<br />

5.51% MC


CHAPTER 4:<br />

IMPACT OF MICROWAVE BLANCHING ON THE FLAVOR OF<br />

ROASTED PEANUTS<br />

Andriana V. Schirack 1 , MaryAnne Drake 1* , Timothy H. Sanders 2 , K.P. Sandeep 1<br />

1 Department <strong>of</strong> Food Science<br />

North Carolina State University, Raleigh, North Carolina 27695-7624<br />

2 USDA-ARS, Market Quality and Handling Research Unit<br />

North Carolina State University, Raleigh, North Carolina 27695-7624<br />

*Corresponding author:<br />

mdrake@unity.ncsu.edu<br />

Department <strong>of</strong> Food Science, Box 7624,<br />

North Carolina State University, Raleigh, North Carolina 27695-7624<br />

Running title: Impact <strong>of</strong> microwave blanching on peanut flavor<br />

Accepted for publication in Journal <strong>of</strong> Sensory Studies.<br />

M.Gacula, Jr., ed. Blackwell Publishing, Malden, MA.<br />

118


ABSTRACT<br />

<strong>Microwave</strong> blanching <strong>of</strong> peanuts has been proposed as an attractive<br />

alternative to traditional techniques <strong>of</strong> blanching, due to energy and time savings.<br />

However, the occurrence <strong>of</strong> a processing-related <strong>of</strong>f-flavor has been reported. This<br />

study examined the effect <strong>of</strong> processing factors during microwave blanching on the<br />

moisture content and sensory characteristics <strong>of</strong> the peanuts. Peanuts reached a<br />

range <strong>of</strong> internal temperatures during microwave blanching treatments between 4<br />

and 11 minutes. A total <strong>of</strong>fnote attribute was introduced to the peanut lexicon and<br />

was used successfully to differentiate the effects <strong>of</strong> microwave treatments. <strong>The</strong><br />

microwave-associated <strong>of</strong>f-flavor was related (but not identical) to cardboardy/stale<br />

flavor, and was related inversely to the positive flavor attributes roasted peanutty,<br />

sweet aromatic, and sweet taste. Peanuts reaching the highest internal<br />

temperatures and greatest moisture losses during blanching exhibited the most total<br />

<strong>of</strong>fnote flavor; however, temperatures as high as 113 °C did not produce significantly<br />

increased total <strong>of</strong>fnote intensity.<br />

Key Words: microwave, blanching, peanuts, sensory, <strong>of</strong>f-flavor, moisture<br />

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INTRODUCTION<br />

Peanuts are an important crop in the United States, with an annual production<br />

<strong>of</strong> 4.26 billion pounds in 2004 (NASS, 2005). <strong>The</strong> most common use <strong>of</strong> peanuts is<br />

crushing for oil and meal. <strong>The</strong> oil can be used for cooking and as a salad oil, while<br />

the defatted meal can be processed into protein concentrates and isolates. In the<br />

United States, a large percentage <strong>of</strong> peanuts is used for manufacturing peanut<br />

butter and confections. <strong>The</strong> unique flavor <strong>of</strong> roasted peanuts drives product<br />

marketing in the peanut industry. This flavor is the result <strong>of</strong> genetics, handling,<br />

storage, and processing factors (Sanders et al., 1995). As a result, there is an<br />

interest in the effects <strong>of</strong> production techniques on peanut flavor (Baker et al., 2003;<br />

Singleton and Pattee, 1992; Singleton and Pattee, 1991; Osborn et al., 1996;<br />

Didzbalis et al., 2004).<br />

A peanut seed consists <strong>of</strong> two cotyledons and the germ, and is enveloped in<br />

a seed coat, or testa. <strong>The</strong> blanching <strong>of</strong> peanuts, or removal <strong>of</strong> the testa, is done for<br />

several reasons. Blanching removes the seed coat, which may interfere with further<br />

processing into specific products, and reduces enzyme activity and moisture<br />

content, which are factors impacting subsequent quality (Adelsberg and Sanders,<br />

1997). Blanching aids in the electronic color-sorting removal <strong>of</strong> damaged or<br />

discolored seeds, which are associated with aflatoxin contamination (Sanders et al.,<br />

1999). Blanching also is used to remove foreign material and dust (St. Angelo et al.,<br />

1977).<br />

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Several methods are used for blanching: dry-blanching, spin-blanching,<br />

water-blanching, alkali-blanching, and hydrogen peroxide-blanching. <strong>Microwave</strong><br />

blanching has been explored as an attractive alternative to traditional processing<br />

methods due to its speed <strong>of</strong> operation, energy savings, and efficient process control<br />

(Giese, 1992). Since heating takes place only in the food material and not in the<br />

surrounding medium, microwave processing can reduce energy costs. Shorter<br />

heating times also lead to greater nutrient retention, better quality characteristics<br />

such as texture and flavor, as well as increased production (Giese, 1992).<br />

<strong>The</strong> best blanching efficiencies result from peanuts which are subjected to the<br />

highest temperatures during blanching and lose the most moisture. However, high<br />

temperature processing has been tied to the formation <strong>of</strong> <strong>of</strong>f-flavors. Curing peanuts<br />

(in order to remove moisture before storage) at temperatures above 35 °C has been<br />

related to the formation <strong>of</strong> anaerobic by-products which produce an <strong>of</strong>f-flavor. With<br />

increasing curing temperature, positive attributes such as roasted peanutty decrease<br />

while <strong>of</strong>f-flavors such as fruity/fermented increase in intensity (Sanders et al., 1990).<br />

This decrease in positive flavor attribute intensity with increase in temperature also<br />

has been observed in blanching with traditional techniques (Sanders et al., 1999).<br />

In addition, blanching has been studied in relation to rates <strong>of</strong> lipid oxidation in<br />

raw peanuts. Lipid oxidation is one <strong>of</strong> the leading causes <strong>of</strong> <strong>of</strong>f-flavors in raw and<br />

roasted peanuts, due to a high content <strong>of</strong> peanut lipids that contain unsaturated fatty<br />

acids (Warner et al., 1996; Lee et al., 2002). Oxidation reactions also can result in<br />

the decrease <strong>of</strong> desirable peanut flavor by loss <strong>of</strong> low molecular weight flavor<br />

compounds or the generation <strong>of</strong> volatile carbonyls which can create a cardboard or<br />

121


oxidative rancid flavor (Sanders et al., 1993; Warner et al., 1996). <strong>The</strong> effect <strong>of</strong><br />

blanching on lipid oxidation is not yet known, as some studies have shown an<br />

increase in lipid oxidation after blanching (Ory et al., 1992), while a study by Sanders<br />

et al. (1999) showed no practical detrimental effects <strong>of</strong> blanching on oxidative<br />

stability.<br />

<strong>The</strong> quality and flavor <strong>of</strong> peanuts were evaluated first using a method called<br />

the Critical Laboratory Evaluation <strong>of</strong> Roasted Peanuts, or CLER (Holaday, 1971).<br />

Later, sensory lexicons for peanuts and peanut products were constructed by<br />

Oupadissakoon and Young (1984) and Syarief et al. (1985). A standardized lexicon<br />

subsequently was developed to address deficiencies in earlier models such as lack<br />

<strong>of</strong> differentiation in oxidized <strong>of</strong>f-flavors and lack <strong>of</strong> sweet/caramel descriptors<br />

(Johnsen et al., 1988). In this lexicon, a ten point scale is used to rate intensity <strong>of</strong><br />

flavor, using commercially available products as references. This terminology<br />

subsequently was modified and improved, including the addition <strong>of</strong> a "fruity"<br />

descriptor associated with high temperature curing (Sanders et al., 1989).<br />

Using descriptive sensory analysis, a processing-related <strong>of</strong>f-flavor has been<br />

noted in peanuts undergoing microwave blanching. <strong>The</strong> <strong>of</strong>f-flavor has been<br />

described as having “stale” and “sour” notes (Katz, 2002). <strong>The</strong> cause <strong>of</strong> this <strong>of</strong>f-<br />

flavor is not known. <strong>The</strong> objective <strong>of</strong> this study was to characterize the impact <strong>of</strong><br />

different microwave blanching parameters on the sensory attributes <strong>of</strong> roasted<br />

peanuts. <strong>The</strong> effects <strong>of</strong> the moisture content <strong>of</strong> the peanuts and internal temperature<br />

pr<strong>of</strong>iles were studied in relation to sensory characteristics determined by a<br />

descriptive panel.<br />

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Peanuts<br />

MATERIALS AND METHODS<br />

Medium sized Runner peanuts (Arachis hypogaea L., variety Georgia Green)<br />

at an average <strong>of</strong> 7% moisture were obtained from a single lot from the USDA-ARS-<br />

National Peanut Research Laboratory (Dawson, Georgia). Although different peanut<br />

varieties may have different flavor properties, Georgia Green peanuts were chosen<br />

for the experiments because this variety represents the largest proportion <strong>of</strong> peanuts<br />

on the U.S. commercial market. <strong>The</strong> peanuts were harvested, cured, shelled, sized,<br />

and stored according to normal practices prior to delivery to Raleigh, NC. All<br />

peanuts were bagged and stored in opaque plastic containers in a cooler at 6 °C and<br />

60% relative humidity before use. Before blanching, peanuts were allowed to warm<br />

to room temperature overnight in opaque containers.<br />

Processing Experiments<br />

Peanuts were blanched using a 5 kW, 915 MHz microwave unit (Industrial<br />

<strong>Microwave</strong> Systems, Morrisville, NC) with a 2.74 m conveyor for sample delivery.<br />

<strong>The</strong> conveyor tunnel was equipped with an electric fan and a heater, which was set<br />

to deliver 25 °C air. <strong>The</strong> microwave generator was controlled by a data acquisition<br />

and control unit (HP34970A, Agilent, Palo Alto, CA). <strong>The</strong> computer monitored power<br />

output, reflected power, and power at the exit <strong>of</strong> the microwave tunnel through<br />

power diodes (JWF 50D-030+, JFW Industries, Inc., Indianapolis, IN). A randomized<br />

complete block design was used to evaluate the effect <strong>of</strong> processing factors during<br />

123


microwave blanching (Table 1). A filled conveyor <strong>of</strong> peanuts (approximately 6 kg)<br />

was exposed to the microwave field for 4, 5, 8, or 11 minutes in a continuous<br />

process. <strong>The</strong> variation in microwave exposure times allowed for a range <strong>of</strong> internal<br />

temperatures to be reached in the peanuts during heating. This translated into<br />

peanuts which ranged from minimally blanched to those exhibiting high blanching<br />

efficiency, as determined by the percentage <strong>of</strong> seeds with complete removal <strong>of</strong> the<br />

testa (Table 1). Each <strong>of</strong> these treatments was processed both with (“F”) and without<br />

a fan (“NF”). <strong>The</strong> use <strong>of</strong> a fan was explored due to the effect on temperature and<br />

moisture content in the peanuts during heating. <strong>The</strong> control for these treatments<br />

was a batch <strong>of</strong> peanuts which went through the same processing procedures but did<br />

not receive microwave heating.<br />

<strong>The</strong> treatments were replicated four times. Immediately after blanching,<br />

peanuts were cooled to room temperature using forced ambient air. <strong>The</strong>y then were<br />

sealed in plastic bags, and stored in opaque containers in a cooler at 6 °C and 60%<br />

relative humidity. <strong>The</strong> peanuts were processed into paste for sensory analysis<br />

within 2 days <strong>of</strong> blanching.<br />

Temperature Measurement During Blanching<br />

Internal temperatures <strong>of</strong> the peanuts during blanching were measured using<br />

four fiber optic probes (FOT- L/10M, Fiso Technologies, Inc., Quebec, Canada)<br />

inserted into the center <strong>of</strong> individual peanuts as they traveled the length <strong>of</strong> the<br />

conveyor. <strong>The</strong> probes were connected to a multi-channel fiber optic signal<br />

conditioner (Model UMI 4, Fiso Technologies, Inc., Quebec, Canada) which was<br />

controlled using FISO Commander s<strong>of</strong>tware (Fiso Technologies, Inc., Quebec,<br />

124


Canada) on a laptop computer (Dell Inspiron 8500, Dell Computer Corporation,<br />

Round Rock, TX).<br />

Moisture Content Analysis<br />

After the peanuts were blanched, moisture content was measured using a<br />

forced convection oven (Despatch LXD Series, Despatch Industries, Minneapolis,<br />

MN). Twenty five gram samples were dried at 130 °C for 11 hrs, and weight change<br />

was used to calculate moisture content (wet basis). <strong>The</strong> analysis was conducted in<br />

triplicate.<br />

Sensory Evaluation<br />

An 800 g sample from each replicate was roasted and processed into paste<br />

for sensory analysis. A thermostat-controlled Aeroglide Roaster was used<br />

(Aeroglide Corporation, Raleigh, NC) to roast samples at 177 °C for the time needed<br />

to achieve L values in the range <strong>of</strong> 48-52 (Vercellotti et al., 1992) using a colorimeter<br />

(Hunter LAB DP-9000, Hunter Associates Laboratory, Reston, VA). Samples were<br />

ground into paste for sensory evaluation using a food processor (Cuisinart Little Pro<br />

Plus, Cuisinart Corporation, East Windsor, NJ). A grind / cool protocol was used to<br />

prevent overheating <strong>of</strong> the paste, as discussed by Sanders et al. (1989). Samples<br />

were kept frozen at -20 °C in glass jars until evaluation.<br />

For descriptive sensory analysis, samples were coded with three digit random<br />

codes, and evaluated against controls for each processing replication. <strong>The</strong> sensory<br />

panel consisted <strong>of</strong> 10 panelists, each with at least 3 months training in peanut<br />

sensory evaluation. Panelists were trained with the Spectrum TM Descriptive Analysis<br />

125


method using a 15 point intensity scale (Meilgaard et al., 1999), and samples were<br />

described using the peanut lexicon developed by Johnsen et al. (1988) and Sanders<br />

et al. (1989), with the addition <strong>of</strong> some attributes specifically for this study (Table 2).<br />

Each sample was evaluated in duplicate by each panelist.<br />

<strong>The</strong> microwave-related <strong>of</strong>f-flavor first noted by Katz (2002) was described as<br />

Dark Soured Aromatic (DSA). However, no standardized references were available<br />

for this attribute. Throughout panel training and calibration discussions for the<br />

present study, the term DSA was discarded and the term ashy, as defined by the<br />

aroma <strong>of</strong> cigarette ash, was added. Discussion <strong>of</strong> the initial analysis <strong>of</strong> microwave-<br />

blanched samples revealed some difficulty in agreement on the exact nature <strong>of</strong> <strong>of</strong>f-<br />

flavors detected. As a result, the total <strong>of</strong>fnote term, which encompassed all negative<br />

attributes which were unique from the control, was used and proved effective in<br />

differentiating the samples.<br />

Data Analysis<br />

<strong>The</strong> results were analyzed using the general linear model procedure in SAS<br />

(Version 9.1, SAS Institute Inc., Cary, NC), with Fisher’s least significant difference<br />

used as a post-hoc test. Correlation analysis was used to describe relationships<br />

amongst the variables and samples.<br />

126


Sensory Analysis<br />

RESULTS AND DISCUSSION<br />

<strong>Microwave</strong> exposure time and use <strong>of</strong> air circulation had a significant effect<br />

on peanut flavor attributes (Table 3) such as roasted peanutty, sweet aromatic, dark<br />

roast, raw beany, woody, bitter, ashy, and sweet (p < 0.0001), as well as on<br />

cardboardy/stale (p < 0.001). Although these attributes were statistically significant,<br />

some <strong>of</strong> the differences between treatments for attributes such as roast peanutty or<br />

sweet aromatic were not likely to be meaningful in practical terms due to the small<br />

range in average score. In the range <strong>of</strong> processing parameters examined, treatment<br />

11NF was the most different, because it was significantly higher in total <strong>of</strong>fnote<br />

(Table 3). <strong>The</strong> 11NF treatment was characterized by higher cardboardy/stale, bitter,<br />

dark roast and ashy attribute intensities, while being characterized less by the raw<br />

beany attribute.<br />

<strong>The</strong> attribute, total <strong>of</strong>fnote, was incorporated into the lexicon as an additional<br />

tool to differentiate the processing treatments. <strong>The</strong> total <strong>of</strong>fnote term does not<br />

describe the specific attributes <strong>of</strong> the sample, so future work should characterize this<br />

<strong>of</strong>fnote using a descriptive panel. However, treatments were differentiated based on<br />

total <strong>of</strong>fnote (p < 0.0001), indicating that this term was effective in a basic<br />

categorization <strong>of</strong> processing effects.<br />

Several <strong>of</strong> the sample attributes were correlated to each other (Table 4).<br />

Desirable attributes such as roast peanutty, sweet aromatic, and sweet taste<br />

positively correlated with each other, and negatively correlated with bitter, ashy, and<br />

127


total <strong>of</strong>fnote. Also, dark roast was correlated positively with bitter, woody/hulls/skins,<br />

ashy, and total <strong>of</strong>fnote, and negatively correlated with raw beany and sweet taste.<br />

Total <strong>of</strong>fnote, which was the attribute primarily used to differentiate the processing<br />

treatments, was correlated to dark roast, woody/hulls/skins, cardboardy/stale, bitter,<br />

and ashy and was related inversely to the positive attributes <strong>of</strong> roasted peanutty,<br />

sweet aromatic, and sweet (p < 0.05). It is notable that although total <strong>of</strong>fnote was<br />

correlated to attributes commonly linked to over-roasting, all treatments were<br />

roasted to the same endpoint based on color, implying that this <strong>of</strong>f-flavor was not<br />

related to actual roasting differences.<br />

A progression <strong>of</strong> changes in sensory attributes can be observed with longer<br />

microwave exposure times during blanching. As exposure times increased to 11<br />

minutes and air was not circulated in the conveyor, the treatments were<br />

characterized by high intensities <strong>of</strong> total <strong>of</strong>fnote attribute. <strong>The</strong> use <strong>of</strong> increased<br />

airflow during processing affected <strong>of</strong>f-flavor formation, as 11F was more similar to<br />

treatments with shorter exposure times in the microwave.<br />

Temperature pr<strong>of</strong>iles and change in moisture content<br />

<strong>The</strong> maximum internal temperature reached in these treatments was<br />

compared (Table 5), and treatments were significantly different (p < 0.0001). As the<br />

amount <strong>of</strong> energy absorbed and internal temperatures increased, peanuts lost more<br />

moisture during heating. <strong>The</strong> final moisture content <strong>of</strong> the peanuts was affected<br />

significantly by treatment (p < 0.0001), and the treatments <strong>of</strong> 8NF and 11NF had<br />

128


significantly lower final moisture content (Table 6) than the other treatments. <strong>The</strong><br />

peanuts which lost the most moisture also exhibited the highest total <strong>of</strong>f-flavor.<br />

Moisture content has been shown to have a significant effect in peanut flavor<br />

development and quality, both by affecting the concentrations <strong>of</strong> precursors<br />

available for flavor formation, and by changing the susceptibility to quality loss due to<br />

the environment. For example, hydrolysis can occur during roasting in peanuts with<br />

higher moisture contents, which increases the amounts <strong>of</strong> free amino acids and<br />

monosaccharides that serve as precursors for flavor development (Chiou et al.,<br />

1991). This indicates that the changes in moisture content during blanching may<br />

affect final peanut flavor. In past studies, lower moisture content after blanching<br />

appeared more conducive to higher blanching efficiency. However, this loss in<br />

moisture also may lead to the creation <strong>of</strong> <strong>of</strong>f-flavors.<br />

Ongoing volatile analysis may help identify the causes <strong>of</strong> microwave-<br />

associated <strong>of</strong>f-flavor. Specific compounds identified by GC-MS have been linked to<br />

sensory attributes in peanuts (Young and Hovis, 1990; Vercellotti et al., 1992;<br />

Didzbalis et al., 2004). By identifying the compounds responsible for the total<br />

<strong>of</strong>fnote perception, a chemical anchor for clarification <strong>of</strong> this flavor can be identified.<br />

As a result, the metabolic cause may be determined and the <strong>of</strong>f-flavor itself possibly<br />

can be prevented if microwave blanching is adopted as an industry practice.<br />

129


CONCLUSIONS<br />

<strong>Microwave</strong> exposure time and amount <strong>of</strong> air circulation during processing had<br />

a small, but significant effect on peanut flavor attributes. Total <strong>of</strong>fnote was related to<br />

other <strong>of</strong>f-flavors such as cardboardy, ashy, and bitter, and was related inversely to<br />

positive attributes such as roast peanutty and sweet aromatic. <strong>The</strong> treatment <strong>of</strong> 11<br />

minutes without air circulation was the most different because it scored the highest<br />

in total <strong>of</strong>fnote and reached temperatures <strong>of</strong> 128 °C or higher. A short duration<br />

treatment, in which the internal temperature <strong>of</strong> the peanuts does not exceed a<br />

maximum <strong>of</strong> 110 °C, appears to be acceptable for heating for seed coat removal. It<br />

is possible to achieve efficient blanchability in peanuts while preventing microwave-<br />

associated <strong>of</strong>f-flavor. Further research is needed to determine the compounds<br />

responsible for and the possible causes <strong>of</strong> microwave-blanching related <strong>of</strong>f-flavor.<br />

F - Fan used<br />

MC - Moisture content (wet basis)<br />

NF - No fan used<br />

W.B. - Wet basis<br />

ABBREVIATIONS<br />

130


ACKNOWLEDGMENTS<br />

Funded in part by the North Carolina Agricultural Research Service. Paper<br />

no. --- <strong>of</strong> the Journal Series <strong>of</strong> the Dept. Food Science, North Carolina State<br />

University, Raleigh, NC 27695. <strong>The</strong> use <strong>of</strong> trade names in this publication does not<br />

imply endorsement by North Carolina Agricultural Research Service or USDA, ARS<br />

<strong>of</strong> the products named nor criticism <strong>of</strong> similar ones not mentioned.<br />

131


REFERENCES<br />

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Peanut Science 24, 42-46.<br />

BAKER, G.L., CORNELL, J.A., GORBET, D.W., O’KEEFE, S.F., SIMS, C.A., and<br />

TALCOTT, S.T. 2003. Determination <strong>of</strong> pyrazine and flavor variations in<br />

peanut genotypes during roasting. J. Food Sci. 68(1), 394-400.<br />

CHIOU, R.Y.-Y., CHANG, Y.-S., TSAI, T.-T., and HO, S. 1991. Variation <strong>of</strong><br />

flavor-related characteristics <strong>of</strong> peanuts during roasting as affected by initial<br />

moisture contents. J. Agric. Food Chem. 39, 1155-1158.<br />

DIDZBALIS, J., RITTER, K.A., TRAIL, A.C., and PLOG, F.J. 2004. Identification<br />

<strong>of</strong> fruity/fermented odorants in high temperature cured roasted peanuts.<br />

J. Agric. Food Chem. 52, 4828-4833.<br />

GIESE, J. 1992. Advances in microwave food processing. Food Technology<br />

46(9), 118-123.<br />

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American Peanut Research and Education Association 3, 238-241.<br />

JOHNSEN, P.B., CIVILLE, G.V., VERCELLOTTI, J.R., SANDERS, T.H., and<br />

DUS, C.A. 1988. Development <strong>of</strong> a lexicon for the description <strong>of</strong> peanut flavor.<br />

J. Sensory Studies 3, 9-17.<br />

KATZ, T.A. 2002. <strong>The</strong> effect <strong>of</strong> microwave energy on roast quality <strong>of</strong> microwave<br />

blanched peanuts. MSc <strong>The</strong>sis, pp. 87-88, North Carolina State University,<br />

Raleigh, NC.<br />

LEE, S.-Y., TREZZA, T.A., GUINARD, J.-X., and KROCHTA, J.M. 2002. Whey-<br />

protein-coated peanuts assessed by sensory evaluation and static headspace<br />

gas chromatography. J. Food Sci. 67(3), 1212-1218.<br />

MEILGAARD, M.M. G.V. and CIVILLE, B.T. Carr. 1999. Selection and training <strong>of</strong><br />

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Statistics Service, Washington, DC.<br />

ORY, R.L., CRIPPEN, K.L. and LOVEGREN, N.V. 1992. Off-flavors in peanuts<br />

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Foods and Beverages, Vol. 29, (G. Charalambous, ed.) pp. 57-75, Elsevier<br />

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OSBORN, G.S., YOUNG, J.H., and SINGLETON, J.A. 1996. Measuring the<br />

kinetics <strong>of</strong> acetaldehyde, ethanol, and ethyl acetate within peanut kernels<br />

during high temperature drying. Transactions <strong>of</strong> the ASAE 39(3), 1039-1045.<br />

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flavor for some Virginia type peanuts from amino acid and sugar contents.<br />

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SANDERS, T.H., ADELSBERG, G.D., HENDRIX, K.W. and MCMICHAEL, R.W.<br />

1999. <strong>Effect</strong> <strong>of</strong> blanching on peanut shelf-life. Peanut Science 26, 8-13.<br />

SANDERS, T.H., BLANKENSHIP, P.D., VERCELLOTTI, J.R., and CRIPPEN,<br />

K.L. 1990. Interaction <strong>of</strong> curing temperature and inherent maturity distributions<br />

on descriptive flavor <strong>of</strong> commercial grade sizes <strong>of</strong> Florunner peanuts. Peanut<br />

Science 17, 85-89.<br />

SANDERS, T.H., PATTEE, H.E., VERCELLOTTI, J.R. and BETT, K.L. 1995.<br />

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and H.T. Stalker, eds.) pp. 528-553, American Peanut Research and Education<br />

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SANDERS, T.H., VERCELLOTTI, J.R., BLANKENSHIP, P.D., CRIPPEN, K.L.,<br />

and CIVILLE, G.V. 1989. Interaction <strong>of</strong> maturity and curing temperature on<br />

descriptive flavor <strong>of</strong> peanuts. J. Food Sci. 54(4), 1066-1069.<br />

SANDERS, T.H., VERCELLOTTI, J.R., and GRIMM, D.T. 1993. Shelf life <strong>of</strong><br />

peanuts and peanut products. In: Shelf Life Studies <strong>of</strong> Foods and<br />

Beverages. (G. Charalambous, ed.) pp. 289-309, Elsevier Science Publishers,<br />

Amsterdam, <strong>The</strong> Netherlands:<br />

SINGLETON, J.A. and PATTEE, H.E. 1991. Peanut moisture/size, relation to<br />

freeze damage and effect <strong>of</strong> drying temperature on volatiles. J. Food<br />

Sci. 56(2), 579-581.<br />

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damage in peanuts. J. Food Sci. 57(6), 1382-1384.<br />

ST. ANGELO, A.J., KUCK, J.C., HENSARLING, T.P. and ORY, R.L. 1977.<br />

<strong>Effect</strong>s <strong>of</strong> water and spin blanching on oxidative stability <strong>of</strong> peanuts. J.<br />

Food Processing and Preservation 1, 249-260.<br />

SYARIEF, H., HAMANN, D.D., GIESBRECHT, F.G., YOUNG, C.T. and<br />

MONROE, R.J. 1985. Interdependency and underlying dimensions <strong>of</strong> sensory<br />

133


flavor <strong>of</strong> selected foods. J. Food Sci. 50, 631-638.<br />

VERCELLOTTI, J.R., CRIPPEN, K.L., LOVEGREN, N.V., and SANDERS, T.H.<br />

1992. Defining roasted peanut flavor quality. Part 1. Correlation <strong>of</strong> GC volatiles<br />

with roast color as an estimate <strong>of</strong> quality. In: Developments in Food Science:<br />

Food Science and Human Nutrition, Vol. 29, (G. Charalambous, ed.) pp. 183-<br />

206, Elsevier Science Publishers, Amsterdam, <strong>The</strong> Netherlands.<br />

WARNER, K.J.H., DIMICK, P.S., ZIEGLER, G.R., MUMMA, R.O., and<br />

HOLLENDER, R. 1996. "Flavor-fade" and <strong>of</strong>f-flavors in ground roasted<br />

peanuts as related to selected pyrazines and aldehydes. J. Food Sci.<br />

61(2), 469-472.<br />

YOUNG, C.T., and HOVIS, A.R. 1990. A method for the rapid analysis <strong>of</strong><br />

headspace volatiles <strong>of</strong> raw and roasted peanuts. J. Food Sci. 55(1), 279-280.<br />

134


TABLE LEGENDS<br />

Table 1. <strong>Microwave</strong> application parameters and resulting blanching efficiency<br />

Table 2. Lexicon <strong>of</strong> peanut flavor descriptors (modified from Johnsen et al., 1988;<br />

and Sanders et al., 1989)<br />

Table 3. Means separation <strong>of</strong> blanching treatments by sensory attribute<br />

Table 4. Correlations between peanut flavor attributes<br />

Table 5. Maximum internal temperature in peanuts by treatment<br />

Table 6. Moisture content <strong>of</strong> peanuts after blanching<br />

135


TABLE 1.<br />

MICROWAVE APPLICATION PARAMETERS AND RESULTING BLANCHING<br />

EFFICIENCY<br />

Treatment Airflow during processing<br />

Average Blanching<br />

Efficiency (%)<br />

4 minutes With fan 42.2<br />

4 minutes Without fan 59.1<br />

5 minutes With fan 52.8<br />

5 minutes Without fan 77.8<br />

8 minutes With fan 66.7<br />

8 minutes Without fan 90.0<br />

11 minutes With fan 77.7<br />

11 minutes Without fan 90.3<br />

136


TABLE 2.<br />

LEXICON OF PEANUT FLAVOR DESCRIPTORS<br />

(MODIFIED FROM JOHNSEN ET AL., 1988; AND SANDERS ET AL., 1989)<br />

Roast Peanutty<br />

Sweet Aromatic<br />

<strong>The</strong> aromatic associated with medium-roast peanuts (about 3-4 on USDA<br />

color chips) and having fragrant character such as methyl pyrazine<br />

<strong>The</strong> aromatics associated with sweet material such as caramel, vanilla,<br />

molasses<br />

Other Aromatics Other aromatics detected in the sample<br />

Dark Roast<br />

<strong>The</strong> aromatic associated with dark roasted peanuts (4+ on USDA color<br />

chips) and having very browned or toasted character<br />

Raw/Beany <strong>The</strong> aromatics associated with under-roasted peanuts or beans<br />

Woody/Hulls/Skins<br />

Cardboardy/Stale<br />

<strong>The</strong> aromatics associated with base peanut character (absence <strong>of</strong> fragrant<br />

top notes) and related to dry wood, peanut hulls, and skins<br />

<strong>The</strong> aromatic associated with somewhat oxidized fats and oils and<br />

reminiscent <strong>of</strong> cardboard<br />

Earthy/Musty/Wet Dirt <strong>The</strong> aromatic associated with wet dirt and mulch<br />

Painty/Old Oil <strong>The</strong> aromatic associated with linseed oil, oil based paint<br />

Plastic/Chemical <strong>The</strong> aromatic associated with plastic and burnt plastics<br />

Fruity/Fermented <strong>The</strong> aromatic associated with fruity or fermented foods<br />

Ashy <strong>The</strong> aromatic associated with cigarette ash<br />

Sweet <strong>The</strong> taste on the tongue associated with sugars<br />

Sour <strong>The</strong> taste on the tongue associated with acids<br />

Bitter<br />

Astringency<br />

Tongue and<br />

Throat Burn<br />

Metallic<br />

Total Off-note<br />

<strong>The</strong> taste on the tongue associated with bitter agents such as caffeine or<br />

quinine<br />

A chemical feeling factor on the tongue and oral tissues, described as<br />

puckering/dry and associated with tannins or alum<br />

A chemical feeling factor described as a burning sensation on the tongue or<br />

throat<br />

A chemical feeling factor on the tongue described as flat, metallic and<br />

associated with iron and copper<br />

A term summarizing the overall degree to which a sample exhibits <strong>of</strong>fflavors,<br />

as compared to the reference<br />

137


Treatment Control<br />

TABLE 3.<br />

MEANS SEPARATION OF BLANCHING TREATMENTS BY SENSORY ATTRIBUTE<br />

4 min,<br />

Fan<br />

4 min,<br />

w/o Fan<br />

5 min,<br />

Fan<br />

138<br />

5 min,<br />

w/o Fan<br />

8 min,<br />

Fan<br />

8 min,<br />

w/o Fan<br />

11 min,<br />

Fan<br />

11 min,<br />

w/o Fan LSD a<br />

Roast Peanutty 4.33 b 4.36 4.55 4.65 4.40 4.33 4.45 4.40 4.28 0.13<br />

Sweet Aromatic 2.89 2.90 3.04 2.90 2.94 2.88 2.88 2.88 2.81 0.11<br />

Dark Roast 3.02 2.82 2.92 3.00 2.75 2.87 3.03 2.97 3.26 0.14<br />

Raw Beany 2.05 2.30 2.23 2.18 2.45 2.28 2.12 2.23 1.90 0.16<br />

Woody/Hull/Skins 3.09 3.06 3.06 3.08 3.04 3.02 3.04 3.08 3.11 0.09<br />

Cardboardy/Stale 0.61 0.95 0.92 0.99 0.88 1.06 0.81 1.06 1.16 0.28<br />

Sweet Taste 2.54 2.65 2.62 2.54 2.63 2.61 2.57 2.54 2.49 0.11<br />

Bitter 3.27 3.27 3.22 3.30 3.28 3.26 3.28 3.29 3.38 0.10<br />

Astringency 1.02 1.04 1.01 1.02 1.01 1.01 1.00 1.03 1.01 0.04<br />

Ashy 0.54 0.38 0.38 0.51 0.47 0.49 0.62 0.55 0.82 0.22<br />

Total Offnote 1.19 1.32 1.24 1.56 1.40 1.56 1.28 1.61 2.25 0.33<br />

a LSD = Least Significant Difference<br />

b Attribute intensities were scored using the 15-point Spectrum TM universal intensity scale (Meilgaard et al., 1999).


Sweet<br />

Aromatic<br />

TABLE 4.<br />

CORRELATIONS BETWEEN PEANUT FLAVOR ATTRIBUTES<br />

Dark<br />

Roast<br />

Raw<br />

Beany<br />

Woody /<br />

Hull/Skins<br />

Cardboardy<br />

/Stale<br />

139<br />

Sweet<br />

Taste<br />

Bitter Astringency Ashy<br />

Total<br />

Offnote<br />

Roast Peanutty 0.77 a -0.35 0.48 -0.46 -0.41 0.57 -0.67 -0.13 -0.55 -0.76<br />

Sweet Aromatic -0.53 0.59 -0.52 -0.37 0.81 -0.81 -0.17 -0.76 -0.79<br />

Dark Roast -0.96 0.78 -0.05 -0.79 0.79 -0.01 0.89 0.71<br />

Raw Beany -0.79 0.08 0.77 -0.85 -0.01 -0.88 -0.72<br />

Woody/Hull/Skins -0.20 -0.66 0.79 0.25 0.81 0.63<br />

Cardboardy/Stale -0.31 0.11 -0.26 0.08 0.50<br />

Sweet Taste -0.85 -0.08 -0.86 -0.83<br />

Bitter 0.04 0.89 0.82<br />

Astringency -0.05 -0.12<br />

Ashy 0.86<br />

a Numbers in bold represent significant correlations (p < 0.05)


TABLE 5.<br />

MAXIMUM INTERNAL TEMPERATURE IN PEANUTS BY TREATMENT<br />

Treatment Mean temperature (°C)<br />

4 min., Fan 69.3 g 1<br />

5 min., Fan 77.0 fg<br />

8 min., Fan 84.4 ef<br />

11 min., Fan 90.6 de<br />

4 min., No fan 92.0 de<br />

5 min., No fan 94.6 d<br />

8 min., No fan 112.8 c<br />

11 min., No fan 128.0 ab<br />

1 Values followed by the same letter are not significantly<br />

different (LSD = 9.8)<br />

TABLE 6.<br />

MOISTURE CONTENT OF PEANUTS AFTER BLANCHING<br />

Treatment<br />

Moisture content after<br />

blanching (w.b.)<br />

Control 7.92 a 1<br />

4 min., Fan 7.30 abc<br />

5 min., Fan 7.54 ab<br />

8 min., Fan 7.19 bc<br />

11 min., Fan 6.92 c<br />

4 min., No fan 7.78 a<br />

5 min., No fan 7.36 abc<br />

8 min., No fan 5.51 d<br />

11 min., No fan 4.49 e<br />

1 Values followed by the same letter are not significantly different (LSD = 0.61)<br />

140


CHAPTER 5:<br />

CHARACTERIZATION OF AROMA-ACTIVE COMPOUNDS IN MICROWAVE<br />

BLANCHED PEANUTS<br />

Andriana V. Schirack 1 , MaryAnne Drake 1* , Timothy H. Sanders 2 , K.P. Sandeep 1<br />

1 Department <strong>of</strong> Food Science<br />

North Carolina State University, Raleigh, North Carolina 27695-7624<br />

2 USDA-ARS, Market Quality and Handling Research Unit<br />

North Carolina State University, Raleigh, North Carolina 27695-7624<br />

*Corresponding author:<br />

mdrake@unity.ncsu.edu<br />

Department <strong>of</strong> Food Science, Box 7624,<br />

North Carolina State University, Raleigh, North Carolina 27695-7624<br />

Running title: Aroma compounds in blanched peanuts…<br />

Submitted for publication in Journal <strong>of</strong> Food Science.<br />

D. B. Lund, ed. Institute <strong>of</strong> Food Technologists, Chicago, IL.<br />

141


<strong>Abstract</strong><br />

<strong>Microwave</strong> blanching <strong>of</strong> peanuts has been explored as an alternative to conventional<br />

oven methods based on its speed <strong>of</strong> operation, energy savings, and efficiency <strong>of</strong><br />

process control. Although processing times can be greatly reduced, the occurrence<br />

<strong>of</strong> stale/floral and ashy <strong>of</strong>f-flavors have been reported at high process temperatures.<br />

This study examined the chemical compounds responsible for this <strong>of</strong>f-flavor using<br />

solvent extraction / solvent assisted flavor evaporation (SAFE), gas<br />

chromatography-olfactometry (GC/O), gas chromatography-mass spectrometry<br />

(GC/MS), and aroma extract dilution analysis (AEDA). Select compounds were<br />

quantified based on AEDA results using SAFE and GC/MS. Quantification,<br />

threshold testing, and analysis <strong>of</strong> model systems revealed increased formation <strong>of</strong><br />

guaiacol and phenylacetaldehyde in the <strong>of</strong>f-flavored peanuts which resulted in the<br />

burnt and stale/floral flavors noted by a trained panel.<br />

Key Words: microwave, peanut, <strong>of</strong>f-flavor, gas chromatography-olfactometry,<br />

threshold<br />

142


Introduction<br />

<strong>The</strong> most common use <strong>of</strong> world peanut production remains the crushing <strong>of</strong><br />

peanuts for oil and meal. However, the proportion <strong>of</strong> peanuts used for other food<br />

products has steadily increased (Revoredo and Fletcher 2002). <strong>The</strong> unique flavor <strong>of</strong><br />

roasted peanuts drives product marketing for products such as peanut butter and<br />

confections. This flavor is the result <strong>of</strong> genetics, production, handling, storage, and<br />

processing factors (Sanders and others 1995).<br />

<strong>The</strong> main sources <strong>of</strong> volatile flavor compounds in peanuts are non-enzymatic<br />

carbonyl-amine browning and lipid oxidation reactions, and include interactions<br />

between peanut components as well as thermal decomposition products and loss <strong>of</strong><br />

volatiles (H<strong>of</strong>fpauir 1953; Warner and others 1996). Maillard reactions are primarily<br />

responsible for browning reactions in roasted peanuts, and produce pyrazines,<br />

pyrroles, furans, and other low molecular weight compounds. In addition to Maillard<br />

products, carbonyls are produced by Strecker degradation and oxidation, but can<br />

then be lost by volatilization (Buckholz and others 1980). Pyrazines, which are<br />

volatile heterocyclic nitrogen-containing compounds, are thought to be the major<br />

flavor compounds impacting roasted peanut flavor (Warner and others 1996).<br />

<strong>The</strong> causes <strong>of</strong> <strong>of</strong>f-flavors in peanuts include lipid oxidation, induction <strong>of</strong><br />

anaerobic respiration, and external contamination with compounds such as<br />

limonene, antioxidants, or insecticides (Ory and others 1992). Lipid oxidation is one<br />

<strong>of</strong> the leading causes <strong>of</strong> <strong>of</strong>f-flavors in raw and roasted peanuts, due to a high content<br />

<strong>of</strong> unsaturated fatty acids (Warner and others 1996; Lee and others 2002).<br />

Oxidation <strong>of</strong> the fatty acids in peanut oil can be caused by light, heat, air, metal<br />

143


contamination, microorganisms or enzymatic activity (Ory and others 1992; Sanders<br />

and others 1993). Hydroperoxides formed during lipid oxidation subsequently break<br />

down into alcohols, alkanes, ketones and aldehydes which can be the source <strong>of</strong> <strong>of</strong>f-<br />

flavors in the peanut. Exposure to high temperatures, such as during the curing<br />

process, has also been correlated to the development <strong>of</strong> <strong>of</strong>f-flavors (Whitaker and<br />

others 1974). High concentrations <strong>of</strong> certain compounds such as ethanol, ethyl<br />

acetate, and acetaldehyde were found in high temperature cured peanuts (Pattee<br />

and others 1965). In addition, fruity fermented <strong>of</strong>f-flavor has been shown to occur<br />

predominantly in immature peanuts undergoing high temperature curing (Sanders<br />

and others 1989; Didzbalis and others 2004).<br />

Most previous studies examining the effects <strong>of</strong> processing techniques on<br />

peanut flavor have concentrated on high temperature curing. However, new<br />

processing technologies have been developed which can improve production<br />

efficiency but can also impact flavor quality. For example, microwave technology<br />

has been investigated as an alternative method for the drying (Delwiche 1986) and<br />

roasting <strong>of</strong> peanuts (Megahed 2001; Yoshida and others 2005). Although<br />

microwave roasting led to formation <strong>of</strong> undesirable lipid oxidation products, the use<br />

<strong>of</strong> microwaves for blanching has potential as an alternative to traditional blanching<br />

methods due to the speed <strong>of</strong> operation, energy savings, and efficiency <strong>of</strong> process<br />

control. However, during high temperature microwave treatments, an <strong>of</strong>f-flavor has<br />

been observed which was related to other <strong>of</strong>f-flavors such as cardboardy, ashy, and<br />

bitter, and was related inversely to positive attributes such as roast peanutty and<br />

sweet aromatic (Schirack and others 2006).<br />

144


<strong>The</strong> objective <strong>of</strong> this study was to investigate the <strong>of</strong>f-flavor formed in peanuts<br />

during the high temperature heating step <strong>of</strong> microwave blanching through<br />

instrumental volatile analysis and model systems. <strong>The</strong> identification <strong>of</strong> the<br />

compounds responsible for the <strong>of</strong>f-flavor could enable better quality control and may<br />

ultimately aid in the adoption <strong>of</strong> alternative blanching methods in peanut processing.<br />

Peanuts<br />

Materials and Methods<br />

Medium-grade size, runner-type peanuts (Arachis hypogaea L., variety<br />

Georgia Green) at an average moisture content <strong>of</strong> 7 % (wet basis) were obtained<br />

from a single harvested lot from USDA, ARS, National Peanut Research Laboratory<br />

(Dawson, Georgia). <strong>The</strong> peanuts were harvested, cured, shelled, sized, and stored<br />

according to normal practices prior to delivery to Raleigh, NC. Peanuts were heated<br />

as part <strong>of</strong> the blanching process using a 5 kW, 915 MHz microwave unit (Industrial<br />

<strong>Microwave</strong> Systems, Morrisville, NC) using the equipment and methods detailed<br />

previously in Schirack and others (2006). A filled conveyor <strong>of</strong> peanuts<br />

(approximately 6 kg) was exposed to the microwave field for 11 minutes in a<br />

continuous process, in which internal peanut temperatures were as high as 128 °C.<br />

Immediately after heating, peanuts were cooled to room temperature using forced<br />

ambient air. <strong>The</strong> control sample was peanuts undergoing the same preparation and<br />

storage procedures but which were not treated with microwave energy. <strong>The</strong> peanuts<br />

were roasted before descriptive sensory and instrumental analysis, in order to<br />

approximate the impact <strong>of</strong> the <strong>of</strong>f-flavor on commercial products, such as<br />

145


confections and peanut butter. <strong>The</strong> peanuts were also roasted to avoid interference<br />

<strong>of</strong> the strong raw/beany note <strong>of</strong> unroasted peanuts with <strong>of</strong>f-flavor detection<br />

(Didzbalis and others 2004).<br />

An 800 g sample for each replicate was roasted and processed into paste for<br />

sensory and instrumental analysis. A thermostat-controlled Aeroglide Roaster was<br />

used (Aeroglide Corporation, Raleigh, NC) to roast samples at 177 °C for the time<br />

needed to achieve L values in the range <strong>of</strong> 48-52 (Vercellotti and others 1992) using<br />

a Hunter LAB DP-9000 colorimeter (Hunter Associates Laboratory, Reston, VA).<br />

Samples were ground into paste using a food processor (Cuisinart Little Pro Plus,<br />

Cuisinart Corporation, East Windsor, NJ). A grind / cool protocol was used to<br />

prevent overheating <strong>of</strong> the paste, as discussed by Sanders and others (1989).<br />

Samples were kept frozen at -20 °C in glass jars until evaluation.<br />

<strong>The</strong> peanut samples evaluated by instrumental analysis were selected based<br />

on sensory analysis results. For descriptive sensory analysis, samples were coded<br />

with three digit random codes, and evaluated against controls for each <strong>of</strong> four<br />

processing replications. <strong>The</strong> sensory panel consisted <strong>of</strong> 10 panelists, each with at<br />

least 40 h training in peanut sensory evaluation. Panelists were trained with the<br />

Spectrum TM Descriptive Analysis method using a 15 point intensity scale (Meilgaard<br />

and others 1999). Each sample was evaluated in duplicate by each panelist.<br />

Samples were described using the peanut lexicon developed by Johnsen and others<br />

(1988) and Sanders and others (1989), with the addition <strong>of</strong> some attributes identified<br />

by the trained panel for these samples, such as ashy, as defined by the aroma <strong>of</strong><br />

cigarette ash; and total <strong>of</strong>fnote, an attribute which encompassed all negative<br />

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attributes which were different from the control. <strong>The</strong> 11-minute blanching treatment<br />

was described by the panel (Table 1) as high in total <strong>of</strong>fnote, cardboardy, and ashy<br />

(Schirack and others 2006). As a result, the 11-minute blanching treatment sample<br />

and its process control were selected for instrumental volatile analyses.<br />

Chemicals<br />

Ethyl ether (anhydrous, 99.8 %), sodium chloride (99 %), sodium sulfate<br />

(99 %), 2-methyl-3-heptanone (internal standard for the neutral/basic fraction), and<br />

2-methylvaleric acid (internal standard for the acidic fraction) were obtained from<br />

Sigma-Aldrich Corporation (St. Louis, MO). <strong>The</strong> standards for the aroma<br />

compounds listed in Table 3 were provided by the Sigma-Aldrich Corporation (St.<br />

Louis, MO) with the exception <strong>of</strong> tetradecanal (VWR, West Chester, PA).<br />

Static headspace gas chromatography<br />

Static headspace chromatography was conducted to screen the most volatile<br />

flavor compounds in the sample as possible contributors to the microwave-related<br />

<strong>of</strong>f-flavor. Peanut samples were analyzed using 1g <strong>of</strong> peanut paste in a 10 mL<br />

crimp-top vial. An external standard <strong>of</strong> hexanal diluted in acetone at 104 ppm was<br />

used. <strong>The</strong> sample was heated for 30 minutes at 150 °C with a carrier gas flow <strong>of</strong><br />

17 mL/minute. <strong>The</strong> headspace was sampled for 0.5 minutes using a Turbomatrix 40<br />

Headspace Sampler (Perkin Elmer Life and Analytical Sciences, Inc., Wellesley,<br />

MA). For separation and identification <strong>of</strong> headspace volatiles, a Perkin Elmer<br />

Autosystem XL gas chromatograph (GC) was coupled to a Perkin Elmer Turbomass<br />

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Gold mass spectrometer (MS; Perkin Elmer Life and Analytical Sciences, Inc.,<br />

Wellesley, MA). <strong>The</strong> injector temperature was maintained at 150 °C. Separations<br />

were performed on a fused silica capillary column (ZB-5, 30 m x 0.25 mm i.d., 1.0<br />

µm df,; Phenomenex, Torrance, CA). <strong>The</strong> GC oven temperature was programmed to<br />

increase from 35 °C to 300 °C at a rate <strong>of</strong> 15 °C/minute with an initial and final hold<br />

time <strong>of</strong> 1 minute each. <strong>The</strong> carrier gas was helium with a flow rate <strong>of</strong> 0.83<br />

mL/minute, and the flow was split at a 20 to 1 ratio. Mass spectrometer conditions<br />

were as follows: capillary direct interface temperature, 270 o C; ionization energy, 70<br />

eV; mass range, 50-300 a.m.u; EM voltage (Atune+306 V); scan rate, 0.5 scans/s.<br />

Each sample was evaluated in duplicate.<br />

Solvent extraction with solvent assisted flavor evaporation (SAFE)<br />

Compounds <strong>of</strong> a higher molecular weight were screened using a solvent<br />

extraction/SAFE technique to determine if they contribute to the microwave-related<br />

<strong>of</strong>f-flavor. One hundred grams <strong>of</strong> peanut paste was weighed and placed in Teflon<br />

bottles. <strong>The</strong>n, 100 mL <strong>of</strong> ethyl ether, 100 mL saturated sodium chloride solution, and<br />

2.45 ppm <strong>of</strong> internal standard (comprised <strong>of</strong> 2-methyl-3-heptanone and 2-methyl<br />

pentanoic acid in methanol) were added. <strong>The</strong> mixtures were shaken for 30 minutes<br />

on a Roto mix (Type 50800; <strong>The</strong>rmolyne Dubuque, IA) at high speed. <strong>The</strong> bottles<br />

were then centrifuged at 3000 rpm for 15 min in order to separate the solvent phase<br />

from the mixture, which was subsequently transferred to a glass jar. <strong>The</strong> procedure<br />

was repeated twice with the addition <strong>of</strong> 100 mL <strong>of</strong> ethyl ether to the sample each<br />

time.<br />

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Volatile compounds from the solvent extract were collected using solvent<br />

assisted flavor evaporation (SAFE). <strong>The</strong> assembly used was similar to that<br />

described by Engel and others (1999). Distillation was carried out for 2 h under<br />

vacuum (ca. 10 -4 Torr). <strong>The</strong> sample was loaded into the top <strong>of</strong> the SAFE apparatus,<br />

and released into the vacuum dropwise. <strong>The</strong> SAFE apparatus was maintained at 50<br />

o C with a circulating water bath. After distillation, the distillate was concentrated to<br />

20 mL under a gentle stream <strong>of</strong> nitrogen gas.<br />

<strong>The</strong> concentrated distillate was washed twice with 3 mL sodium bicarbonate<br />

(0.5M) and vigorously shaken. It was then washed three times with 2 mL saturated<br />

sodium chloride solution. <strong>The</strong> ether layer containing the neutral/basic fraction was<br />

collected, dried over anhydrous sodium sulfate, and concentrated to 0.5 mL under a<br />

gentle stream <strong>of</strong> nitrogen gas. Acidic volatiles were recovered by acidifying the<br />

aqueous phase with hydrochloric acid (18% w/v) to a pH <strong>of</strong> 2.0 and extracting the<br />

sample three times with 5 mL ethyl ether. <strong>The</strong> sample was dried over anhydrous<br />

sodium sulfate before being concentrated to 0.5 mL under a nitrogen gas stream.<br />

Gas chromatography/olfactometry (GC/O)<br />

For GC/O analysis, an HP5890 series II gas chromatograph (Hewlett-Packard<br />

Co., Palo Alto, CA) equipped with a flame ionization detector (FID), sniffing port, and<br />

a splitless injector was utilized. Both the neutral/basic and acidic fractions were<br />

analyzed from each extraction. Two microliters were injected onto a polar capillary<br />

column (DB-WAX, 30 m length x 0.25 mm i.d. x 0.25 μm film thickness <strong>of</strong> stationary<br />

phase (df); J. & W. Scientific, Folsom, CA) and a nonpolar column (DB-5MS, 30 m<br />

149


length x 0.25 mm i.d. x 0.25 μm df; J & W Scientific, Folsom, CA). Column effluent<br />

was split 1:1 between the FID and sniffing port using deactivated fused silica<br />

capillaries (1 m length x 0.25 mm i.d.). <strong>The</strong> GC oven temperature was programmed<br />

to increase from 40 o C to 200 o C at a rate <strong>of</strong> 8 o C/min with an initial hold for 3 min<br />

and a final hold <strong>of</strong> 20 min. <strong>The</strong> FID and sniffing port were maintained at a<br />

temperature <strong>of</strong> 250 o C. <strong>The</strong> sniffing port was supplied with humidified air at<br />

30 mL/min.<br />

Both post peak intensity and aroma extract dilution analysis (AEDA) were<br />

used to characterize the aroma properties and perceived intensities <strong>of</strong> the aroma-<br />

active compounds in the solvent extracts (Van Ruth 2001; Grosch 1993). Four<br />

experienced panelists with at least 40 hours <strong>of</strong> training sniffed the neutral/basic and<br />

acidic fractions <strong>of</strong> the solvent extracts on the two different columns. For post peak<br />

intensity analysis, panelists described the odor and scored the intensity <strong>of</strong> odorants<br />

in the extracts using a 5-point numerical intensity scale (Van Ruth 2001). For<br />

AEDA, the solvent fractions were serially diluted at a ratio <strong>of</strong> 1:3 (v/v) with diethyl<br />

ether and sniffed (using a DB-WAX column for acidic fractions, and a DB-5MS<br />

column for neutral basic fractions) until no odorants were detected by the panelists.<br />

Gas chromatography/mass spectrometry (GC/MS)<br />

For GC/MS analysis <strong>of</strong> the solvent extracts, a 6890N GC/5973 mass selective<br />

detector (Agilent Technologies, Inc., Palo Alto, CA) was used. Separations were<br />

performed on a fused silica capillary column (DB-5MS, 30 m length x 0.25 mm i.d. x<br />

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0.25 μm df; J & W Scientific, Folsom, CA). Helium gas was used as a carrier at a<br />

constant flow <strong>of</strong> 1 mL/min. Oven temperature was programmed to increase from<br />

40 o C to 200 o C at a rate <strong>of</strong> 2 o C/min with initial and final hold times <strong>of</strong> 5 and 30 min,<br />

respectively. Mass selective detector conditions were as follows: capillary direct<br />

interface temperature, 250 o C; ionization energy, 70 eV; mass range, 50-300 a.m.u;<br />

EM voltage (Atune+200 V); scan rate, 2.94 scans/s. Each extract (1 μL) was<br />

injected in duplicate in the splitless mode.<br />

Identification <strong>of</strong> odorants<br />

Retention indices (RI) were calculated using an n-alkane series (Van den<br />

Dool and Kratz 1963). For positive identifications, RI, mass spectra, and odor<br />

properties <strong>of</strong> unknowns were compared with those <strong>of</strong> standard compounds analyzed<br />

under identical conditions. Tentative identifications were based on comparing mass<br />

spectra <strong>of</strong> unknown compounds with those in the mass spectral database <strong>of</strong> the<br />

National Institute <strong>of</strong> Standards and Technology (1992) and by matching the RI<br />

values and odor properties <strong>of</strong> unknowns against published values in the Kovacs<br />

retention indices located at http://www.flavornet.org.<br />

Quantification <strong>of</strong> odorants<br />

Relative abundance <strong>of</strong> compounds was calculated relative to the peak areas<br />

<strong>of</strong> 2-methyl-3-heptanone (for the neutral/basic fraction) or 2-methylvaleric acid (for<br />

the acidic fraction). In the cases when target flavor compounds coeluted with other<br />

peanut volatiles, an extracted ion search was used for quantification. For guaiacol<br />

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(m/z 124 and 109), toluene (m/z 91), heptanal (m/z 96 and 114), tetradecanal (m/z<br />

96 and 194), 2-phenylethylalcohol (m/z 91), 2-methylbutanal (m/z 86 and 56), 1,4-<br />

butanediol (m/z 71 and 57), the specific ions in parenthesis were monitored during<br />

analysis. <strong>The</strong> response factors <strong>of</strong> selected compounds were determined by direct<br />

addition <strong>of</strong> known amounts <strong>of</strong> standards to odor-free water prior to solvent extraction<br />

and SAFE. Response factors for the compounds were calculated using a five-point<br />

standard curve on a DB-5 column (DB-5MS, 30 m length x 0.25 mm i.d. x 0.25 μm<br />

df; J & W Scientific, Folsom, CA) using GC/MS (6890N GC/5973 MSD; Agilent<br />

Technologies, Inc., Palo Alto, CA). <strong>The</strong> selected compounds were then quantified<br />

using the response factor and the peak area ratio <strong>of</strong> the compound to the internal<br />

standard.<br />

Threshold testing<br />

Orthonasal detection thresholds <strong>of</strong> acetophenone, phenylacetaldehyde, and<br />

2,6-dimethylpyrazine (in oil) and toluene, acetophenone and 2,6-dimethylpyrazine (in<br />

water) were determined using the forced choice ascending concentration series<br />

method <strong>of</strong> limits (ASTM practice E 679-91). Compounds were diluted in methanol<br />

(for the water threshold) or in vegetable oil (oil threshold) before addition to the<br />

matrix <strong>of</strong> either deodorized water or vegetable oil. Deodorized water was prepared<br />

by boiling deionized water to two-thirds <strong>of</strong> its volume. <strong>The</strong> vegetable oil (Wesson,<br />

ConAgra Foods, Omaha, NE) was obtained at a local grocery store. <strong>The</strong> compound<br />

concentrations were serially diluted by a factor <strong>of</strong> three for each level in the<br />

threshold test, and a seven level series was used. Blank samples in each set were<br />

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adjusted with the same concentration <strong>of</strong> methanol to eliminate any bias due to the<br />

solvent used. Each 2-ounce sample cup (Sweetheart Cup Company, Inc., Owings<br />

Mills, MD) was filled to 20 mL and allowed to equilibrate for one hour before testing.<br />

All sample preparation and testing was done with the lights <strong>of</strong>f to minimize<br />

compound degradation during this time. Each level in the series was presented in a<br />

randomized order.<br />

Panelists were asked to choose the different sample out <strong>of</strong> a set <strong>of</strong> three, and<br />

to indicate whether they were guessing. <strong>The</strong> individual best estimate threshold was<br />

calculated by taking the geometric mean <strong>of</strong> the last concentration which was<br />

incorrect, and the first concentration which was correct with no further samples<br />

missed. <strong>The</strong> group threshold was calculated as the geometric mean <strong>of</strong> the individual<br />

best estimate thresholds. Thirty five panelists were used. <strong>The</strong> panelist’s degree <strong>of</strong><br />

certainty was used to adjust the best estimate threshold according to the method in<br />

Lawless and others (2000).<br />

Sensory evaluation <strong>of</strong> peanut models<br />

Sensory analysis <strong>of</strong> model systems was conducted to further investigate the<br />

compounds responsible for the <strong>of</strong>f-flavor caused by high temperature microwave<br />

blanching in peanuts. Flavor models were prepared from peanut paste which was<br />

chosen based on absence <strong>of</strong> <strong>of</strong>f-flavor. <strong>The</strong> peanut paste was divided into 15 g<br />

portions, and the compounds were introduced by a disposable pipet. After addition<br />

<strong>of</strong> the chemicals, the peanut paste was stirred for 30 s and then equilibrated for 2 h<br />

prior to sensory analysis.<br />

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Phenylacetaldehyde, guaiacol, and 2,6-dimethylpyrazine were prepared in<br />

methanol for aroma evaluation or in 95 % ethanol for flavor evaluation across the<br />

concentration range found in the peanut samples by quantification (Table 2). <strong>The</strong><br />

peanut models were evaluated in duplicate for aroma or flavor by 6 highly trained<br />

panelists, each with > 150 h <strong>of</strong> training in the sensory evaluation <strong>of</strong> peanuts.<br />

Sensory analysis<br />

Results and Discussion<br />

<strong>The</strong> sensory attributes <strong>of</strong> high-temperature microwave-blanched peanuts<br />

were described previously (Table 1) by a descriptive sensory panel (Schirack and<br />

others 2006). Peanuts which had been microwave blanched were significantly<br />

higher (P < 0.05) in total <strong>of</strong>fnote, which is a term encompassing all negative aspects<br />

<strong>of</strong> the sample which are different from a reference. <strong>The</strong> total <strong>of</strong>fnote term was<br />

introduced to the current peanut lexicon (Johnsen and others 1988; Sanders and<br />

others 1989) for this study, because the descriptive panel had some difficulty in<br />

agreeing to the exact nature <strong>of</strong> the <strong>of</strong>f-flavor. Based on the other attribute scores<br />

which were significantly higher (P < 0.05) than the process control, the microwave<br />

blanched peanuts also displayed higher intensities <strong>of</strong> dark/ashy, bitter, and<br />

cardboardy/stale notes, which also may contribute in part to the total <strong>of</strong>fnote score.<br />

Further descriptive panels were conducted with experienced panelists to<br />

more fully describe the nature <strong>of</strong> the <strong>of</strong>f-flavor. Over the course <strong>of</strong> five sessions, the<br />

panelists agreed that the distinct <strong>of</strong>f-flavor <strong>of</strong> microwave blanched peanuts (which<br />

had an average total <strong>of</strong>fnote score <strong>of</strong> 2.0 on a 15 point intensity scale) was best<br />

154


characterized by the attributes <strong>of</strong> stale/floral, cardboardy, and burnt/ashy. Product<br />

references such as cigarette ash for the burnt/ashy attribute were very useful,<br />

although the development <strong>of</strong> clear chemical anchors would be even more beneficial<br />

in further clarifying this total <strong>of</strong>fnote attribute to panelists.<br />

Static headspace analysis<br />

Static headspace analysis was conducted as the first step to screen the<br />

samples for compounds contributing to the microwave-related <strong>of</strong>f-flavor. In this<br />

analysis, no unique volatile compounds were found in the <strong>of</strong>f-flavored sample which<br />

were not present in the process control (data not shown). This technique did isolate<br />

compounds which have been previously identified with flavor deterioration in high<br />

temperature-cured peanuts such as hexanal, 3-methylbutanal, and 2-methylpentanal<br />

(Pattee and others 1965). However, the compound concentrations in the control and<br />

<strong>of</strong>f-flavored samples were not significantly different (P < 0.05). Most compounds<br />

which are similar in volatility to hexanal can be lost during roasting (Ory and others<br />

1992). In addition, this extraction technique isolates only the most volatile and<br />

lowest molecular weight flavor compounds. This could explain why flavor<br />

differences detected in roasted peanuts by the sensory panel were not reflected in<br />

static headspace results. As a result, the static headspace method was deemed not<br />

suitable in differentiating the microwave blanched samples from the control peanuts<br />

and was not investigated further.<br />

155


Gas Chromatography-Olfactometry<br />

Over 200 aroma-active compounds were detected through gas<br />

chromatography-olfactometry (GC/O) in the peanut samples, which is consistent<br />

with reviews <strong>of</strong> the flavor compounds in peanuts in the literature (Pattee and<br />

Singleton 1981). Although many flavor compounds have been documented in<br />

peanuts, systematic studies <strong>of</strong> the relative importance and balance <strong>of</strong> the flavor<br />

compounds in peanuts are lacking. In this study, aroma extract dilution analysis<br />

(AEDA) was used to narrow the list <strong>of</strong> compounds which may have the most impact<br />

on the flavor. In AEDA, solvent extracts were serially diluted by a factor <strong>of</strong> 3 until no<br />

odorants were detected by the panelists. <strong>The</strong> compounds with dilution factors (FD)<br />

greater than 5 for the process control and the <strong>of</strong>f-flavored peanuts are shown for<br />

both the neutral/basic and acidic fractions (Table 3). Of the 38 compounds with the<br />

highest FD values, 26 were positively identified using odor properties, retention<br />

indices, and mass spectra; 10 were tentatively identified using odor properties and<br />

retention indices in comparison to standards; and two compounds remained<br />

unidentified.<br />

Maillard reaction products and lipid oxidation products are known to affect<br />

peanut flavor. <strong>The</strong> impact <strong>of</strong> pyrazines, which have long been associated with the<br />

characteristic flavors <strong>of</strong> peanuts (Mason and Johnson 1966; Johnson and others<br />

1971) was both increased and lessened in the microwave blanched samples. For<br />

example, the FD factor <strong>of</strong> 2,5-dimethyl-3-ethylpyrazine (brothy) was lower in the <strong>of</strong>f-<br />

flavored samples, while 2,6-dimethylpyrazine (nutty/earthy) and 2-ethyl-5-<br />

methylpyrazine (fruity) FD factors were higher. Lipid oxidation compounds, such as<br />

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(E,E)-2,4-decadienal (fried/oxidized), (E,Z)-2,4-heptadienal (fatty), nonanal<br />

(green/floral), decanal (fried), and heptanal (fatty) were found in both the control and<br />

<strong>of</strong>f-flavored peanuts. Products such as nonanal and decanal are formed from<br />

monohydroperoxide precursors during linoleate oxidation (Min and others 1989).<br />

While some <strong>of</strong> these compounds such as heptanal are associated with cardboard or<br />

rancid <strong>of</strong>f-flavors (Warner and others 1996), other lipid oxidation compounds such as<br />

hexanal and 2,4-decadienal have been documented in good quality peanuts<br />

(Vercellotti and others 1992b). Based on AEDA results, the role <strong>of</strong> lipid oxidation<br />

compounds in microwave-related <strong>of</strong>f-flavor was not clear.<br />

GC/O results correlate with quantitative differences best when olfactometry<br />

differences between samples are high (Cullere and others 2004). Seventeen<br />

compounds had the largest differences in AEDA results between the process control<br />

and microwave-blanched peanuts (i.e., differences in FD factors <strong>of</strong> 3 or more).<br />

<strong>The</strong>se compounds included floral compounds such as phenylacetaldehyde (rosy)<br />

and geranyl buyrate (rosy); fatty compounds such as (E,E)-2,4-decadienal<br />

(fried/oxidized), (E,Z)-2,4-heptadienal (fatty), and (E)-2-hexenoic acid (fatty); sweet<br />

or fruity compounds such as 4-ethylbenzaldehyde (burnt sugar), benzaldehyde<br />

(sweet/malty), toluene (sweet/chemical), 2,3-butanediol (fruity), tetradecanal<br />

(honey/hay), methyl cinnamate (strawberry), 2-methylbutanal (chocolate/malty), and<br />

2-ethyl-5-methylpyrazine (sweet/fruity); savory compounds such as 2,6-<br />

dimethylpyrazine (nutty/earthy) and 2,5-dimethyl-3-ethylpyrazine (brothy ); and<br />

others such as guaiacol (burnt/smoky), and delta-elemene (wood). Many <strong>of</strong> these<br />

compounds have been reported previously in peanuts (Mason and others 1967;<br />

157


Johnson and others 1971; Clark and Nursten 1977; Ho and others 1981; Vercellotti<br />

and others 1992). Specifically, several <strong>of</strong> these compounds have been associated<br />

with <strong>of</strong>f-flavors in peanuts, such as 2,3-butanediol (Ory and others 1992), and 2-<br />

methylbutanal, which has been correlated to an “aging” <strong>of</strong>f-flavor (Young and Hovis<br />

1990). In addition, 2,6-dimethylpyrazine, 2-ethyl-5-methylpyrazine, 2-ethyl-3,5-<br />

dimethylpyrazine, phenylacetaldehyde, and guaiacol (2-methoxyphenol) were<br />

identified in high temperature cured peanuts by Didzbalis and others (2004).<br />

It is important to note that AEDA is only a semi-quantitative technique, and it<br />

does not establish that compounds are present in concentrations above sensory<br />

threshold. AEDA also does not reflect the impact <strong>of</strong> the food matrix on the<br />

perception and odor properties <strong>of</strong> a compound. In fact, although the FD factors are<br />

relative to the compounds’ concentration in the extract, they are not measures for<br />

perceived odor intensity (Grosch 1993). No compound in the AEDA results by itself<br />

gave the exact odor noted in microwave-blanched peanuts. This indicated that the<br />

microwave-related <strong>of</strong>f-flavor may be influenced by the other compounds in the food<br />

matrix or caused by a combination <strong>of</strong> compounds that are present in both samples,<br />

but at different concentration levels.<br />

In order to compare volatile concentrations across samples, the relative<br />

abundances <strong>of</strong> compounds identified by GC/O were calculated using relative<br />

abundance: {(peak area <strong>of</strong> internal standard/concentration <strong>of</strong> internal standard) =<br />

(peak area <strong>of</strong> compound/concentration <strong>of</strong> compound)}. <strong>The</strong> relative abundance<br />

values for compounds which were not further quantified are seen in Table 4. Many<br />

<strong>of</strong> the compounds in the acid fractions <strong>of</strong> the solvent extract were not different in<br />

158


flavor dilution factors, nor did they possess a unique character that could potentially<br />

contribute to the microwave-related <strong>of</strong>f-flavor. Many <strong>of</strong> these compounds had a<br />

sweet or burnt sugar odor which can be expected from Maillard reaction products.<br />

An examination <strong>of</strong> the relative abundances revealed compounds which were below<br />

reported thresholds or which had no consistent differences between samples for this<br />

set <strong>of</strong> compounds.<br />

Quantification<br />

Select compounds were quantified by analysis <strong>of</strong> standards in deodorized<br />

water using solvent extraction, SAFE, and GC-MS analysis. Compounds were<br />

chosen for further quantification if they had large differences in AEDA results<br />

between the <strong>of</strong>f-flavored peanuts and the control, or if they had been tied to <strong>of</strong>f-<br />

flavors in the peanut literature (i.e., lipid oxidation compounds). A selection <strong>of</strong><br />

pyrazines was also quantified to determine whether these decreased in<br />

concentration in the <strong>of</strong>f-flavored peanuts, because coincident decreases in the<br />

roasted peanutty attribute have been documented with other <strong>of</strong>f-flavors in peanuts<br />

(Sanders and others 1989; Didzbalis and others 2004). <strong>The</strong> nine compounds<br />

selected for quantification included: one compound possibly contributing to the burnt<br />

note in the <strong>of</strong>f-flavored peanuts (guaiacol), a compound possibly adding the<br />

stale/floral attribute noted by the sensory panel (phenylacetaldehyde), two pyrazines<br />

(2,6-dimethylpyrazine, and 2,3-diethyl-5-methylpyrazine), two compounds with sweet<br />

odors (acetophenone, toluene), and three lipid oxidation compounds (nonanal,<br />

159


decanal, 2,4-decadienal). A five point standard curve was used, and for all<br />

compounds, the linear fit had an R 2 ≥ 92%.<br />

<strong>The</strong> results <strong>of</strong> quantification (Table 5) support the descriptive panel comments<br />

used to describe the <strong>of</strong>f-flavor. <strong>The</strong> microwave-blanched peanuts were described as<br />

being more burnt/ashy, which could be due to an increase in guaiacol, and more<br />

stale/floral, which could be due to the increase in phenylacetaldehyde. <strong>The</strong> samples<br />

were not differentiated in levels <strong>of</strong> acetophenone or nonanal. Although large FD<br />

differences were seen between the samples for toluene, quantification results did not<br />

support these differences, but the AEDA differences may have been complicated<br />

due to coelution with the solvent peak during GC/O.<br />

Threshold determination<br />

In order to clarify quantification results, threshold analyses were conducted to<br />

gauge human perception <strong>of</strong> these compounds. Detection threshold values for the<br />

quantified compounds which were not available in the literature were determined<br />

experimentally using the ASTM ascending forced choice method <strong>of</strong> limits procedure<br />

(Table 5). Because peanuts are composed <strong>of</strong> approximately 50% fat (H<strong>of</strong>fpauir<br />

1953), both the water and oil thresholds were evaluated. Based on these threshold<br />

values, guaiacol, phenylacetaldehyde, 2,6-dimethylpyrazine, and 2,3-diethyl-5-<br />

methylpyrazine had the most impact on the flavor <strong>of</strong> these samples.<br />

Phenylacetaldehyde, 2,6-dimethylpyrazine, and 2,3-diethyl-5-methylpyrazine<br />

concentrations in both control and <strong>of</strong>f-flavored samples were above the threshold<br />

values. Not only were guaiacol concentrations in the <strong>of</strong>f-flavored peanuts double<br />

160


that <strong>of</strong> the control, but only in the <strong>of</strong>f-flavored peanuts did the concentrations exceed<br />

the compound’s threshold in oil. Toluene, acetophenone, nonanal, decanal, and<br />

(E,E)-2,4-decadienal values were below the threshold values, either in the oil matrix<br />

or in both matrices.<br />

After threshold testing, the odor activity value (OAV) <strong>of</strong> each compound in<br />

different matrices was determined in the control and microwave-blanched peanuts<br />

(Table 5). <strong>The</strong> OAV is the ratio <strong>of</strong> the compound concentration in a food to its<br />

sensory threshold. <strong>The</strong> OAV can further identify those compounds having the most<br />

flavor impact (Guth and Grosch 1994). In Emmentaler cheese, a high fat food, the<br />

oil threshold value was chosen to calculate OAV for evaluation <strong>of</strong> key compounds<br />

because the lipid phase predominated in the samples (Preininger and Grosch 1994).<br />

Similarly in this study, the OAVs in oil were compared due to the high lipid content <strong>of</strong><br />

peanuts. Phenylacetaldehyde, 2,6-dimethylpyrazine, 2,3-diethyl-5-methylpyrazine,<br />

and guaiacol had the highest OAV in oil <strong>of</strong> the compounds quantified. <strong>The</strong> OAV<br />

values <strong>of</strong> phenylacetaldehyde, 2,6-dimethylpyrazine, and guaiacol were the highest<br />

in the <strong>of</strong>f-flavored samples and were also approximately twice their OAV values in<br />

the control, which further supported the role <strong>of</strong> these compounds in the flavor pr<strong>of</strong>ile<br />

<strong>of</strong> microwave-blanched peanuts.<br />

Phenylacetaldehyde has been previously found in peanuts (Mason and<br />

others, 1967), in lavender honey (Bouseta and others 1996), and in other foods such<br />

as chocolate (Schieberle and Pfnuer 1999). Phenylacetaldehyde has also been<br />

linked to <strong>of</strong>f-flavors, such as aroma deterioration in beer (Soares da Costa and<br />

others 2004) and rosy <strong>of</strong>f-flavor in Cheddar cheese (Carunchia Whetstine and others<br />

161


2005). Phenylacetaldehyde is known to be generated in peanuts from phenylalanine<br />

through Strecker degradation (Mason and others 1967). Phenylalanine is typically<br />

present as a flavor precursor in peanuts and makes up a significant portion <strong>of</strong> the<br />

free amino acids present (Newell and others 1967). Guaiacol is found in strongly<br />

flavored cheeses (Suriyaphan and others 2001), and affected the sensory<br />

differences in Spanish aged wines (Cullere and others 2004). This phenolic<br />

compound has also caused medicinal or antiseptic <strong>of</strong>f-flavors in apple juice (Orr and<br />

others 2000). 2,3-diethyl-5-methylpyrazine and 2,6-dimethylpyrazine have been<br />

correlated to peanut flavor (Mason and Johnson 1966; Maga 1982), and 2,3-diethyl-<br />

5-methylpyrazine is a key odorant in bitter chocolate (Schieberle and Pfnuer 1999).<br />

Among these four key compounds, phenylacetaldehyde, guaiacol, and 2,6-<br />

dimethylpyrazine were present at significantly different (P < 0.1) levels in the <strong>of</strong>f-<br />

flavored samples, and as a result were pursued as the possible source <strong>of</strong> the<br />

microwave-related <strong>of</strong>f-flavor. <strong>The</strong>se three compounds are affected by increased<br />

temperatures. Pyrazine formation begins above 100 °C, and yield increases as the<br />

temperature increases (Koehler and Odell 1970). Although guaiacol can be<br />

produced by Alicyclobacillus spoilage (Orr and others 2000) and has been<br />

associated with the maturation <strong>of</strong> wine in oak barrels (Pollnitz and others 2004),<br />

most pertinently to peanut production, guaiacol is also a thermal degradation product<br />

<strong>of</strong> ferulic acid during the roasting process (Holscher and Steinhart 1994). Likewise,<br />

the kinetic rate <strong>of</strong> phenylacetaldehyde formation was significantly increased with<br />

increasing temperatures (Soares da Costa and others 2004). During peanut<br />

blanching, the microwave process temperatures reached up to 128 °C, which may<br />

162


e high enough for pyrazine formation, and could explain the increased formation <strong>of</strong><br />

phenylacetaldehyde and guaiacol.<br />

Interestingly, lipid oxidation compounds did not appear to have a role in<br />

microwave-related <strong>of</strong>f-flavor. This is consistent with the literature, as Katz (2002)<br />

found that microwave-blanched peanuts were more oxidation stable than oven-<br />

blanched peanuts as evident by lower peroxide values and higher oxidative stability<br />

index. In addition, Maillard reaction products in peanuts such as reductones are free<br />

radical scavengers which could further prevent formation <strong>of</strong> oxidation products<br />

(Sanders and others 1993).<br />

Model systems<br />

In order to examine the effects <strong>of</strong> these compounds at their relative<br />

concentrations in a food matrix, phenylacetaldehyde, guaiacol, and 2,6-<br />

dimethylpyrazine were added singly and in combination to a freshly roasted peanut<br />

paste free <strong>of</strong> <strong>of</strong>f-flavors (Table 2). Although these compounds individually had<br />

distinct aromas during GC/O <strong>of</strong> rosy (phenylacetaldehyde), smoky/burnt (guaiacol),<br />

and nutty/earthy (2,6-dimethylpyrazine), the flavor pr<strong>of</strong>ile <strong>of</strong> the reference paste<br />

changed in different ways upon compound addition, emphasizing the effect <strong>of</strong><br />

compound concentration and the effect <strong>of</strong> other components in the matrix.<br />

In aroma evaluation, 6 out <strong>of</strong> 6 panelists agreed that the addition <strong>of</strong><br />

phenylacetaldehyde, guaiacol, and 2,6-dimethylpyrazine singly at the average<br />

concentrations found during quantification, created notable and negative differences<br />

from the control. In each <strong>of</strong> these models, a decrease in roasted peanutty aroma<br />

163


was also observed. <strong>The</strong> addition <strong>of</strong> phenylacetaldehyde caused a green/plant-like<br />

note, while the addition <strong>of</strong> guaiacol gave a darker roast character to the model as<br />

compared to the control. 2,6-dimethylpyrazine, although adding a sweet, caramel<br />

note at lower concentrations, became perceived as a sweet and rotten aroma at<br />

higher concentrations. In the tasting models, phenylacetaldehyde added a<br />

green/plant-like note at low concentrations, but created a stale/cardboardy character<br />

at higher concentrations. Guaiacol added astringency, bitterness, and more ashy<br />

and woody character to the flavor. 2,6-dimethylpyrazine added rotten notes to the<br />

flavor, and also contributed to the perception <strong>of</strong> dark roast flavor. A combination <strong>of</strong><br />

these three compounds at their respective concentrations found in microwave<br />

blanched peanuts created an aroma pr<strong>of</strong>ile high in dark roast character, with more<br />

astringency and tongue and throat burn, and less impact <strong>of</strong> positive characteristics<br />

such as roasted peanutty attribute. <strong>The</strong> panel agreed that the combination <strong>of</strong><br />

phenylacetaldehyde, guaiacol, and 2,6-dimethylpyrazine each at a concentration <strong>of</strong><br />

one standard deviation above the average concentration found in the microwave-<br />

blanched samples appeared to most closely mimic the <strong>of</strong>f-flavor in microwave-<br />

blanched peanuts.<br />

<strong>The</strong> unique characters <strong>of</strong> these three compounds combine to form an <strong>of</strong>f-<br />

flavor which is difficult to define. Further work must be conducted to clarify the role<br />

<strong>of</strong> 2,6-dimethylpyrazine. However, it appears that guaiacol contributes to the dark<br />

roast/burnt flavor perceived in the microwave samples, and phenylacetaldehyde is<br />

responsible for a green and cardboardy note which could be perceived as<br />

stale/floral. In the future, these compounds could be used as chemical anchors for<br />

164


sensory panelists analyzing process samples and would aid in the identification <strong>of</strong><br />

process-related <strong>of</strong>f-flavors.<br />

Conclusion<br />

More than 200 aroma-active compounds contributed to the flavor <strong>of</strong> roasted<br />

peanuts. Maillard reaction, lipid oxidation, and thermal degradation products<br />

dominated the flavor pr<strong>of</strong>iles. Isolation <strong>of</strong> the compounds causing a microwave-<br />

related <strong>of</strong>f-flavor in peanuts was possible through solvent extraction/SAFE, GC/O,<br />

GC/MS, threshold testing and model systems analysis. <strong>The</strong> stale/floral and ashy <strong>of</strong>f-<br />

flavor in microwave-blanched peanuts was related to increased concentrations <strong>of</strong><br />

phenylacetaldehyde, guaiacol, and 2,6-dimethylpyrazine. Increased and<br />

unfavorable levels <strong>of</strong> these compounds may have been formed through Maillard<br />

reactions and thermal degradation during the high temperatures attained during<br />

microwave blanching. <strong>The</strong>se findings are important because they further explore the<br />

relative balance <strong>of</strong> the many aroma-active compounds which have been<br />

documented in peanuts, and could possibly aid in enhancing quality control for<br />

alternative processing techniques in peanut production.<br />

Acknowledgments<br />

This research was funded in part by the North Carolina Agricultural Research<br />

Service. This is paper no. --- <strong>of</strong> the Journal Series <strong>of</strong> the Dept. Food Science, North<br />

Carolina State University, Raleigh, NC 27695. <strong>The</strong> assistance <strong>of</strong> Mary Carunchia<br />

Whetstine, Lisa Oerhl Dean, Evan Miracle and Joy Wright is gratefully<br />

165


acknowledged. <strong>The</strong> use <strong>of</strong> trade names in this publication does not imply<br />

endorsement by North Carolina Agricultural Research Service or USDA, ARS <strong>of</strong> the<br />

products named nor criticism <strong>of</strong> similar ones not mentioned.<br />

166


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Table 1- <strong>Effect</strong> <strong>of</strong> high temperature microwave blanching on<br />

sensory attributes<br />

Attribute<br />

Process<br />

Control<br />

172<br />

<strong>Microwave</strong><br />

Blanched<br />

Peanuts<br />

Roast Peanutty 4.33a a 4.28a<br />

Sweet Aromatic 2.89a 2.81a<br />

Dark Roast 3.02a 3.26b b<br />

Raw Beany 2.05a 1.90a<br />

Woody/Hull/Skins 3.09a 3.11a<br />

Cardboardy/Stale 0.61a 1.16b<br />

Sweet Taste 2.54a 2.49a<br />

Bitter 3.27a 3.38b<br />

Astringency 1.02a 1.01a<br />

Ashy 0.54a 0.82b<br />

Total Offnote 1.19a 2.25b<br />

a Attribute intensities were scored using the 15-point Spectrum TM<br />

universal intensity scale (Meilgaard et al., 1999)<br />

b Means followed by different letters are significantly different<br />

between treatments (p < 0.05)


Table 2- Model system concentrations in reference peanut paste<br />

Model Compound Added<br />

Concentration<br />

(ppb) a<br />

Reference -- --<br />

1 2,6-dimethylpyrazine 16401<br />

2 2,6-dimethylpyrazine 17698<br />

3 2,6-dimethylpyrazine 18996<br />

4 Guaiacol 13.62<br />

5 Guaiacol 18.33<br />

6 Guaiacol 23.04<br />

7 Phenylacetaldehyde 3236<br />

8 Phenylacetaldehyde 3915<br />

9 Phenylacetaldehyde 4594<br />

10 2,6-dimethylpyrazine 16401<br />

Guaiacol 13.62<br />

Phenylacetaldehyde 3236<br />

11 2,6-dimethylpyrazine 17698<br />

Guaiacol 18.33<br />

Phenylacetaldehyde 3915<br />

12 2,6-dimethylpyrazine 18996<br />

Guaiacol 23.04<br />

Phenylacetaldehyde 4594<br />

a<br />

Concentrations calculated based on average, average +σ, average<br />

+ 2σ as determined in quantification results<br />

173


Table 3 - High impact aroma-active compounds in peanuts as determined by AEDA<br />

RI b Log3 FD Factors c<br />

No. Compound Fraction Odor a<br />

DB-5MS DB-WAX Control Off- Method <strong>of</strong><br />

flavor Identification<br />

1 2-methylbutanal NB Chocolate/malty 653 907 6 9 RI, odor, MS d<br />

2 Toluene NB Sweet/chemical 756 1027 5 11 RI, odor, MS<br />

3 2,3-butanediol NB Fruity 803 1554 3 9 RI, odor e<br />

4 Furfural AC Sweet 821 1468 5 7 RI, odor, MS<br />

5 (E)-2-hexenal AC Fruity 844 1188 3 5 RI, odor, MS<br />

6 Ethyl valerate AC Fruity 915 1116 6 6 RI, odor e<br />

7 2,6-dimethylpyrazine NB Nutty/earthy 934 1314 6 9 RI, odor, MS<br />

8 Heptanal NB Fatty 937 1163 5 7 RI, odor, MS<br />

9 (E,Z)-2,4-heptadienal NB Fatty 968 1399


28 4-acetoxy-2,5-dimethyl-<br />

3(2H)-furanone<br />

AC Burnt sugar 1386 1981 7 6 RI, odor<br />

29 Delta-decalactone AC Sweet/ fruity 1471 2209 5 7 RI, odor<br />

30 Geranyl butyrate NB Rosy 1544 1888 3 8 RI, odor<br />

31 Tetradecanal NB Honey/hay 1618 1931 6 2 RI, odor, MS<br />

32 (E)-2-hexenoic acid NB Fatty 1632 1938 6 10 RI, odor<br />

33 Pantolactone AC Burnt sugar 1689 1998 6 5 RI, odor, MS<br />

34 Unknown AC Sweet N/A 352 5 6 Odor<br />

35 Unknown AC Sweet/malty N/A 707 6 7 Odor<br />

36 Benzaldehyde AC Sweet/malty ND 1500 6 2 RI, odor, MS<br />

37 Methyl cinnamate AC Strawberry ND 2045 7 ND RI, odor<br />

38 3-methoxy-2,5dimethylpyrazine<br />

AC Spicy/pepper ND 1385 4 5 RI, odor<br />

a<br />

Odor description by GC/O<br />

b<br />

Retention indices (RI) were calculated from GC/O data<br />

c<br />

Flavor dilution factors were determined on a DB-5MS column for neutral and basic compounds, and on a DB-WAX column for acidic<br />

compounds<br />

d<br />

Compound identified by RI, MS data and odor character in comparison with the standard<br />

e<br />

Compound tentatively identified using RI data and odor character in comparison with standard<br />

f ND: not detected<br />

175


Table 4 - Relative abundance <strong>of</strong> selected high aroma impact compounds in peanuts<br />

Compound RI on<br />

DB-5MS a<br />

Concentration in<br />

control (ppb) b<br />

176<br />

Concentration in<br />

<strong>of</strong>f-flavored peanuts<br />

(ppb)<br />

Threshold in water<br />

(ppb)<br />

Threshold in oil<br />

(ppb)<br />

Decanoic acid 1357 25.7 ± 18.6 48.2 ± 61.3 10000 d<br />

Not reported<br />

2-methylbutanal 653 2613 ± 856 4024 ± 789 1 d<br />

2.2 d<br />

Heptanal 937 0.41 ± 0.03 0.14 ± 0.04 3 d<br />

250 d<br />

(E,Z)-2,4-heptadienal 968 ND e<br />

0.29 ± 0.05 Not reported 4000 d<br />

2-ethyl-3,5-dimethylpyrazine 1095 5534 ±3117 6961 ± 495 0.04 d<br />

2.2 d<br />

3-ethylphenol 1176 14.9 ±4.5 16.5 ± 3.1 0.05 f<br />

Not reported<br />

3,5-diethyl-2-methylpyrazine 1184 554 ± 410 572 ± 28 Not reported Not reported<br />

Tetradecanal 1618 3.05 ± 1.98 0.63 ± 0.18 Not reported Not reported<br />

Compound RI on<br />

DB-Wax c<br />

Concentration in<br />

control (ppb)<br />

Concentration in<br />

<strong>of</strong>f-flavored peanuts<br />

(ppb)<br />

Threshold in water<br />

(ppb)<br />

Threshold in oil<br />

(ppb)<br />

Methyl hexanoate 1142 486 ± 471 72 ± 67 50 d<br />

Not reported<br />

(E)-2-hexenal 1188 77 ± 48 15 ± 11 17 d<br />

424 d<br />

2-ethyl-5-methylpyrazine 1323 3441 ± 1937 498 ± 149 100 h Not reported<br />

2,5-dimethyl-3-ethylpyrazine 1416 352 ± 163 1239 ± 806 0.4 d<br />

24 d<br />

Furfural 1468 941 ± 514 536 ± 370 3000 d<br />

Not reported<br />

Benzaldehyde 1500 506 ± 250 328 ± 285 Not reported Not reported<br />

Maltol (hydroxymethylpyrone) 1936 303 ± 92 71 ± 59 210 g<br />

Not reported<br />

Pantolactone 1998 133 ± 44 126 ± 106 Not reported Not reported<br />

2051 59 ± 52 17 ± 13 0.6 d<br />

25 d<br />

Furaneol TM<br />

a Retention indices (RI) were calculated from mass spectrometry results on a DB-5MS column<br />

b Average concentration ± standard deviation<br />

c RI calculated from flame ionization results on a DB-WAX column<br />

d Orthonasal threshold reported by Rychlik and others (1998)<br />

e ND - not detected<br />

f Retronasal threshold reported by Rychlik and others (1998)<br />

g Orthonasal threshold reported by Karagul-Yuceer and others (2004)<br />

h Orthonasal threshold reported by Maga (1977)


Table 5 - Quantification, sensory orthonasal threshold values, and odor activity values <strong>of</strong> selected compounds in peanuts<br />

Nr. Compounds RI on<br />

DB-5MS<br />

column a<br />

Concentration<br />

in control<br />

(ppb)<br />

Concentration<br />

in <strong>of</strong>f-flavored<br />

peanuts (ppb)<br />

177<br />

Threshold<br />

in water<br />

(ppb)<br />

1 Toluene 756 104 ± 30 114 ± 23 527 ± 4 c<br />

2 2,6-dimethylpyrazine 944 15234 ± 2594 40009 ± 2773 g<br />

718 ± 5 c<br />

3 Phenylacetaldehyde 1058 4447 ± 1894 8266 ± 1505 f<br />

2 d<br />

4 Acetophenone 1080 3.60 ± 0.16 3.2 ± 3.2 245 ± 6 c<br />

5 Guaiacol 1089 13.7 ± 0.6 29 ± 5 f<br />

2.5 e<br />

6 2,3-diethyl-5methylpyrazine<br />

1148 2.2 ± 0.5 1.6 ± 0.3 0.09 e<br />

7 Nonanal 1159 121 ± 79 168 ± 42 1 e<br />

8 Decanal 1231 3.7 ± 0.7 5.9 ± 0.5 0.1 e<br />

9 (E,E)-2,4-decadienal 1343 135 ± 85 28.9 ± 4.5 0.07 e<br />

Threshold<br />

in oil<br />

(ppb)<br />

94660 c<br />

1021 ± 3 c<br />

154 ± 4 c<br />

5629 ± 6 c<br />

16 e<br />

0.5 e<br />

1000 e<br />

6700 e<br />

180 e<br />

a Retention indices calculated from mass spectrometry results on a DB-5MS column<br />

b <strong>The</strong> odor activity value (OAV) is the ratio <strong>of</strong> the concentration to the threshold value <strong>of</strong> the compound<br />

c Orthonasal threshold experimentally determined from 35 panelists<br />

d Orthonasal threshold reported by Carunchia Whetstine and others (2005)<br />

e Orthonasal threshold reported by Rychlik and others (1998)<br />

f Concentration is significantly different from the control at p < 0.05<br />

g Concentration is significantly different from the control at p < 0.1<br />

OAV <strong>of</strong><br />

control<br />

in<br />

water b<br />

OAV <strong>of</strong><br />

control<br />

in oil<br />

OAV <strong>of</strong><br />

<strong>of</strong>fflavored<br />

peanuts<br />

in water<br />

OAV <strong>of</strong><br />

<strong>of</strong>fflavored<br />

peanuts<br />

in oil<br />

0.2 0.001 0.2 0.001<br />

21 15 56 39<br />

2224 29 4133 54<br />

0.015 0.001 0.01 0.0006<br />

5.5 0.9 12 1.81<br />

24 4 18 3.2<br />

121 0.1 168 0.17<br />

37 0.001 59 0.001<br />

1929 0.8 413 0.16


CHAPTER 6:<br />

CONCLUSIONS AND FUTURE WORK<br />

178


Conclusions<br />

This research investigated the impact <strong>of</strong> different microwave blanching<br />

parameters on the properties <strong>of</strong> roasted peanuts, and characterized the changes in<br />

flavor which occur in peanuts during microwave blanching at high temperatures.<br />

<strong>The</strong> microwave processing parameters best suited for blanching peanuts were first<br />

identified. Processing treatments were differentiated by energy absorbed during<br />

processing, average and maximum internal temperatures, loss in moisture content,<br />

and blanchability. <strong>The</strong> best blanchability resulted from higher process temperatures<br />

and greater loss in moisture content. Treatments exceeding 110 °C resulting in a<br />

final moisture content <strong>of</strong> 5.5 % or less yielded blanchability values greater than the<br />

85 % industry standard.<br />

<strong>The</strong> effect <strong>of</strong> this alternative blanching technique on flavor was evaluated<br />

using descriptive sensory analysis. A sensory panel determined that peanuts<br />

reaching the highest internal temperatures (~ 128 °C) and resulting in the lowest<br />

moisture content (4.5%) during blanching had the most total <strong>of</strong>fnote flavor.<br />

However, temperatures as high as 113 °C did not produce significant <strong>of</strong>f-flavor. <strong>The</strong><br />

microwave-associated <strong>of</strong>f-flavor was related to stale/floral and burnt/ashy flavors,<br />

and was related inversely to positive flavor attributes such as roasted peanutty,<br />

sweet aromatic, and sweet taste.<br />

Analysis <strong>of</strong> the peanut flavor volatiles using GC/O, GC/MS, and threshold<br />

testing revealed an increased formation <strong>of</strong> guaiacol, phenylacetaldehyde, and 2,6-<br />

dimethylpyrazine in the <strong>of</strong>f-flavored peanuts compared to that in a process control.<br />

Model system work confirmed that increased concentrations <strong>of</strong> these compounds<br />

179


caused the increased intensity <strong>of</strong> burnt and stale/floral characteristics noted by the<br />

descriptive sensory panel. <strong>The</strong>se compounds were only a small fraction <strong>of</strong> over 200<br />

aroma-active compounds which were found to contribute to roasted peanut flavor<br />

using GC/O. Increased and unfavorable levels <strong>of</strong> these compounds may have been<br />

formed through Maillard reactions and thermal degradation during the high<br />

temperatures reached in microwave blanching. This research also confirmed the<br />

importance <strong>of</strong> Maillard reaction and lipid oxidation compounds in the peanut flavor<br />

pr<strong>of</strong>ile. However, as the results show, even increased concentrations <strong>of</strong> compounds<br />

which are commonly found in good quality peanuts can lead to an imbalance in the<br />

flavor pr<strong>of</strong>ile and cause the perception <strong>of</strong> an <strong>of</strong>f-flavor.<br />

This research has helped improve the peanut lexicon, and has further<br />

characterized the extraction techniques best suited for the volatile analysis <strong>of</strong><br />

peanuts. <strong>The</strong> analysis <strong>of</strong> an <strong>of</strong>f-flavor that was difficult to define was made possible<br />

through the introduction <strong>of</strong> the total <strong>of</strong>fnote term to the peanut lexicon, which was<br />

used successfully to differentiate the effects <strong>of</strong> microwave treatments. Further<br />

additions were made to the lexicon, such as the attribute “ashy”, which was<br />

referenced by the aroma <strong>of</strong> cigarette ash. In instrumental analysis, solvent<br />

extraction and SAFE were deemed more suitable than static headspace methods for<br />

analysis <strong>of</strong> aroma-active peanut compounds generated during the high temperatures<br />

in microwave blanching, indicating that compounds <strong>of</strong> higher molecular weight and<br />

moderate volatility had the highest impact on flavor.<br />

This research is important because it illustrates the importance <strong>of</strong> the relative<br />

concentrations <strong>of</strong> the many aroma-active compounds found in peanuts. Although<br />

180


microwave technology may provide many advantages during blanching, its effects<br />

on the formation <strong>of</strong> flavor compounds must be considered. This research could aid<br />

in training sensory panels to evaluate processing-related <strong>of</strong>f-flavors, because<br />

guaiacol and phenylacetaldehyde could be used as chemical standards to define the<br />

burnt/ashy and stale/floral <strong>of</strong>f-flavors which can occur during high temperature<br />

processing. Through this project, it was determined that it is possible to achieve<br />

acceptable blanchability in peanuts using microwave blanching while minimizing the<br />

possibility <strong>of</strong> an <strong>of</strong>f-flavor.<br />

181


Future Work<br />

In future work, analysis <strong>of</strong> peanut flavor compounds before roasting may<br />

further illuminate the chemical changes caused by microwave blanching. During<br />

roasting, many flavors originating from the raw product might be obscured, as was<br />

seen in green c<strong>of</strong>fee beans (Yeretzian and others 2002). In addition, more chemical<br />

anchors (standards) could be assigned to the attributes in the peanut lexicon. Just<br />

as certain fruity esters and short chain organic acids have been associated with the<br />

fruity/fermented <strong>of</strong>f-flavor (Didzbalis and others 2004), and guaiacol can be used to<br />

demonstrate the attribute <strong>of</strong> ashy, other chemical standards could be established.<br />

This would help in the training <strong>of</strong> panelists and could provide a basis to further<br />

instrumentally classify differences between peanut varieties as well as peanuts from<br />

different geographical locations, which have been shown to vary in flavor (Sanders<br />

and others 1992). This research demonstrated that we do not fully understand the<br />

importance <strong>of</strong> the relative concentrations <strong>of</strong> aroma compounds needed to achieve<br />

good quality peanut flavor. To aid this understanding, omission experiments (in<br />

which one or more compounds are omitted from an aroma model) could be<br />

conducted to pinpoint those compounds key to peanut flavor, as for example has<br />

been done in c<strong>of</strong>fee (Grosch 2001; Czerny and others 1999).<br />

Peanuts are not only valuable for their flavor attributes, but also for their<br />

nutritional benefits, some <strong>of</strong> which may not be known to the average consumer.<br />

Peanuts are a good source <strong>of</strong> mono- and polyunsaturated fats (H<strong>of</strong>fpauir 1953),<br />

which have been connected to better heart health in nutritional literature (Kris-<br />

Etherton and others 2001), and phytosterols such as beta-sitosterol, which may<br />

182


protect against colon, prostate, and breast cancers (Awad and others 2000). Also,<br />

like red wine and grapes, peanuts are a good source <strong>of</strong> resveratrol, which has been<br />

associated with reduced cardiovascular disease and anticarcinogenic properties<br />

(Sanders and others 2000). Furthermore, peanuts contain significant amounts <strong>of</strong> B<br />

vitamins and tocopherol (H<strong>of</strong>fpauir 1953), which play important roles in heart and<br />

nervous system health. Although these nutritional benefits will make peanuts more<br />

marketable to consumers, some <strong>of</strong> these components are also heat and process-<br />

sensitive. Polyunsaturated fats are several times more prone to oxidation (Min and<br />

others 1989), and vitamins are well known to degrade at high processing<br />

temperatures (Lund 1982). <strong>The</strong> effect <strong>of</strong> microwave blanching and microwave<br />

roasting on components such as vitamins, polyunsaturated fatty acids, resveratrol,<br />

and beta-sitosterol could be assessed. If significant losses <strong>of</strong> these compounds<br />

could be prevented using microwave blanching or microwave roasting, it would<br />

further increase the value <strong>of</strong> this product.<br />

183


References<br />

Awad AB, Chan KC, Downie AC, Fink CS. 2000. Peanuts as a source <strong>of</strong> beta-<br />

sitosterol, a sterol with anticancer properties. Nutrition and Cancer 36(2):238-<br />

241.<br />

Czerny M, Mayer F, Grosch W. 1999. Sensory study on the character impact<br />

odorants <strong>of</strong> roasted Arabica c<strong>of</strong>fee. J Agric Food Chem 47:695-699.<br />

Didzbalis J, Ritter KA, Trail AC, Pflog FJ. 2004. Identification <strong>of</strong> fruity/fermented<br />

odorants in high temperature cured roasted peanuts. J Agric Food Chem 52:<br />

4828-4833.<br />

Grosch W. 2001. Evaluation <strong>of</strong> the key odorants <strong>of</strong> foods by dilution<br />

experiments, aroma models, and omission. Chemical Senses 26(5): 533-545.<br />

H<strong>of</strong>fpauir CL. 1953. Peanut composition: relation to processing and utilization.<br />

Agricultural and Food Chemistry 1:668-671.<br />

Kris-Etherton PM, Zhao G, Binkoski AE, Coval SM, Etherton TD. 2001. <strong>The</strong><br />

effects <strong>of</strong> nuts on coronary heart disease risk. Nutrition Reviews 59(4):103-<br />

111.<br />

Lund DB. 1982. Influence <strong>of</strong> processing on nutrients in foods. Journal <strong>of</strong> Food<br />

Protection 45(4):367-373.<br />

Min DB, Lee, SH, Lee EC. 1989. Singlet oxygen oxidation <strong>of</strong> vegetable oils. In:<br />

Min DB, Smouse TH, editors. Flavor chemistry <strong>of</strong> lipid foods. Champaign, IL:<br />

American Oil Chemists' Society. p 57-97.<br />

Sanders TH, McMichael RW Jr, Hendrix KW. 2000. Occurrence <strong>of</strong> resveratrol in<br />

edible peanuts. J Agric Food Chem 48:1243-1246.<br />

Sanders TH, Vercellotti JR, Crippen KL, Hinsch RT, Rasmussen GK, Edwards<br />

JH. 1992. Quality factors in exported peanuts from Argentina, China, and the<br />

United States. JAOCS 69(10): 1032-1035.<br />

Yeretzian C, Jordan A, Badoud R, Lindinger W. 2002. From the green bean to<br />

the cup <strong>of</strong> c<strong>of</strong>fee: investigating c<strong>of</strong>fee roasting by on-line monitoring <strong>of</strong><br />

volatiles. European Food Research Technology 214:92-104.<br />

184


APPENDICES<br />

185


Appendix 1:<br />

Analysis <strong>of</strong> Peanut Volatiles by Solvent Extraction, SAFE, GC-O, and GC-MS<br />

Extraction (1 day)<br />

Standard Operating Procedure<br />

1. Make saturated salt solution: 50g NaCl to 300mL dI water. Add salt until some<br />

precipitates out.<br />

2. Weigh out sample: 2x50g for rep 1, 2x50g for rep 2. Weigh directly into plastic<br />

extraction bottles.<br />

3. Make up internal standard with concentration <strong>of</strong> 50μL 2-methyl-3-heptanone,<br />

50μL 2-methyl valeric in 5 mL methanol. In sample, use 15μL istd per bottle<br />

x2bottles ( = 30μL per rep).<br />

4. Add 50 mL <strong>of</strong> NaCl solution to each bottle.<br />

5. Add 50 mL ethyl ether anhydrous per bottle (HPLC or spectral grade).<br />

6. Make sure cap is tight, place on shaker and shake for 30 minutes at speed 8.<br />

7. Centrifuge bottles - make sure centrifuge is balanced. Angular velocity = 3x1000.<br />

Be sure to screw on both lids <strong>of</strong> the centrifuge. Set timer for 15 minutes and<br />

start.<br />

8. Pull <strong>of</strong>f top layer <strong>of</strong> ether and put in mason jar. Put jar in freezer between<br />

shaking/centrifuging. Use 1 jar per replicate = 2 jars total.<br />

9. Repeat three times, only adding ether for subsequent repetitions. This will result<br />

in 300mL per rep (50mL x 2 bottles/rep x 3 extractions).<br />

186


SAFE (3 SAFE's can be done in 1 day)<br />

(If the sample was in the freezer overnight, allow it to warm up early at RT)<br />

1. Make sure blue ball valve on vacuum system is closed (nearest to pump).<br />

2. Turn on the rough pump to achieve 10 -2 Torr (turn on gauge), and plug in the fan.<br />

3. Fill waterbath with 40-50°C water and plug in so it can warm up.<br />

4. Assemble the SAFE apparatus:<br />

Put Teflon threaded pieces and associated o-ring on any glass part without<br />

threads. Also, a sample stopper and stopcock are needed.<br />

<strong>The</strong>re are 4 parts to the SAFE: a round bottom flask, elbow, trap, and the<br />

main unit.<br />

Connect elbow and trap, and clamp into place.<br />

Attach this to the second trap (leave in dewar). Put traps as deep as possible<br />

into dewars.<br />

Make sure configuration is completely horizontal, and then loosely attach<br />

SAFE apparatus to ring stand. Fit nose <strong>of</strong> SAFE into neck <strong>of</strong> trap.<br />

5. Open blue valve slowly to 1/2 way, and wait to stabilize. <strong>The</strong>n connect SAFE – if<br />

it’s not going in easily, change angle <strong>of</strong> the SAFE apparatus. Use the vacuum to<br />

pull the SAFE into place. Avoid applying torque while attaching SAFE to trap -<br />

screw in and back <strong>of</strong>f as necessary. Tighten as much as you can by hand (use<br />

gloves).<br />

6. Wait until pressures stabilize to 10 -2 Torr, then turn on the small diffusion pump<br />

(small metal switch).<br />

187


7. If target pressures are not reached in 15 minutes, check for leaks. When open<br />

fully, should get to 10 -3 and 10 -4 before proceeding.<br />

8. Fill up dewars with liquid nitrogen.<br />

9. Attach 2 sets <strong>of</strong> heating tape - tie to sample chamber, wrap to right <strong>of</strong> stopcock<br />

and over neck <strong>of</strong> first trap, and use the second tape to cover the neck <strong>of</strong> the<br />

round bottom flask. Leave access to all threads.<br />

10. Attach water hoses – allow for a slow stream on exit to the sink.<br />

11. Plug in heating tape and turn on.<br />

12. Make sure all fittings tight, and make sure stopcock is closed.<br />

13. Add sample to top chamber, then slowly open stopcock to let drops <strong>of</strong> extract into<br />

round bottom flask.<br />

14. After all <strong>of</strong> the extract is introduced, pour ether in as wash (~30mL). Rinse both<br />

the glassware used, and inside <strong>of</strong> chamber.<br />

15. Let SAFE distillation run approximately 2 hours. It is done when you can no<br />

longer see boiling in round bottom flask.<br />

16. Refill liquid nitrogen in dewars and cover (aluminum foil); make sure nitrogen<br />

levels are full during entire run and periodically check waterbath temperature.<br />

17. NOTE: Make sure the sample does not freeze during the SAFE procedure –<br />

apply heating tape far down the neck <strong>of</strong> the round bottom flask, and make sure<br />

water levels in the bath are sufficiently high enough.<br />

When SAFE is completed:<br />

1. Close blue valve.<br />

188


2. Turn <strong>of</strong>f waterbath.<br />

3. Turn <strong>of</strong>f circulating water and heating tape.<br />

4. Turn <strong>of</strong>f fine pump, then rough pump. Allow 20 minutes to cool.<br />

5. Release vacuum (loosen stopcock). Detach SAFE from trap.<br />

6. After fan cools <strong>of</strong>f, unplug it.<br />

7. Put frozen trap into dewar with room temperature water in the hood, and allow to<br />

defrost.<br />

8. Transfer sample into small jar, and wash elbow with ether for remaining sample.<br />

9. Label this with 1) date 2) experimenter’s name and 3) extraction step using<br />

colored lab tape and sharpie.<br />

10. Clean SAFE with hot soapy water and in base bath, then bake dry in oven.<br />

11. Put extract under nitrogen to evaporate to 20 mL. This will take about 30<br />

minutes – do not allow to go to dryness! It is easier to transfer extract to test<br />

tube for evaporation <strong>of</strong> last few milliliters.<br />

Phase Separation (1 day)<br />

1. Wash concentrate with 3mL <strong>of</strong> 0.5M Na2CO3. Shake for 10s, and take <strong>of</strong>f water<br />

layer (water is on bottom, use long pipette).<br />

2. Repeat for 2 washes total.<br />

3. Wash with 2mL saturated NaCl, and take <strong>of</strong>f water layer.<br />

4. Repeat this twice for 3 washes total.<br />

5. <strong>The</strong> ether phase at this point is the Neutral Basic fraction. Label this as “Stock<br />

NB1”.<br />

189


Aqueous Phase<br />

1. Use fresh pipettes for the next segment.<br />

2. Lower pH to 2.0 with 18% HCl w/v. Initial pH is ~11, and this usually requires 2<br />

pipettes’ full <strong>of</strong> acid.<br />

3. Re-extract with 5 mL ether. Take <strong>of</strong>f ether layer (top), and leave ~1mm above<br />

meniscus. If water gets into sample, freeze overnight and separate.<br />

4. Repeat for 3 washes total.<br />

5. This ether layer is the Acid fraction.<br />

Filtering with Sodium Sulfate<br />

Make sodium sulfate columns<br />

1. Fill MonStr pipettes partway with glass wool, pack wool towards bottom.<br />

2. Fill pipette halfway with sodium sulfate (anhydrous, reagent grade) which has<br />

been baked in the oven (deodorized).<br />

Filtration<br />

1. Tape 2 sodium sulfate columns together, and shake columns to loosen powder.<br />

2. Filter samples through columns into a new, smaller test tube. Don’t let columns<br />

go dry.<br />

3. Dry down sample to less than 2mL under nitrogen.<br />

4. Label GC vials for the fractions: each fraction (NB, Acid) has 2 GC vials (one<br />

with insert, one without). For one sample that includes 2 replicates, you will have<br />

8 vials total.<br />

190


5. Filter through a third sodium sulfate column into a GC vial without insert.<br />

6. Dry to 0.5 mL under nitrogen.<br />

7. Transfer 200 μL to second GC vial with insert, and save remaining 300 μL in<br />

freezer.<br />

8. Blow down sample in insert to 50 μL immediately before starting GC analysis.<br />

GC-O Analysis<br />

1. Use HP 5890 with FID and sniffing port.<br />

2. Both the neutral/basic and acidic fractions are analyzed from every extraction.<br />

3. Two μL are injected using the sandwich technique into a polar capillary column<br />

(DB-WAX) and into a nonpolar column (DB-5). For injection, 2 µL ether, 1 µL air,<br />

and then 2 µL <strong>of</strong> sample are drawn into a 10 µL injection syringe.<br />

4. Three experienced panelists will sniff the neutral/basic and acidic fractions <strong>of</strong><br />

peanut paste extracts on two different columns. <strong>The</strong> samples will be described<br />

and scored using a 5-point scale.<br />

GC-MS Analysis<br />

1. Use 6890N GC / 5973 MSD and DB-5MS column.<br />

2. Each extract (1 μL) is injected in the splitless mode.<br />

3. Duplicate analyses are performed on each sample.<br />

191


Appendix 2: Quantification <strong>of</strong> Peanut Volatiles<br />

First, identify the target compounds in the project by GC/MS and GC/FID<br />

based on the retention index, odor property, and mass spectra as compared to<br />

standards. Calculate relative abundance for a general idea <strong>of</strong> the compound<br />

concentration, and then quantify to find absolute abundance.<br />

exceptions:<br />

To quantify compounds, follow the procedure in Appendix 1, with the following<br />

1. Before beginning, calculate the stock solutions <strong>of</strong> the compound standards.<br />

Make the highest concentration first, and dilute accordingly to make 5 levels<br />

<strong>of</strong> standards. Convert all concentrations to a weight per volume basis, using<br />

the compound density. Be sure not to add more than 500 μL or less than<br />

2 μL <strong>of</strong> the standard to any sample.<br />

2. Make a table to carefully detail the amount <strong>of</strong> standard added to each<br />

concentration level. Don’t forget the internal standard.<br />

3. Make the stock solutions in methanol, and add these to 100 mL <strong>of</strong> deodorized<br />

deionized water at the calculated concentrations. All standards can be<br />

extracted at once, unless there are co-eluting peaks.<br />

4. Add 50 mL <strong>of</strong> ether to each sample, and continue with the procedure in<br />

Appendix 1 from this point on.<br />

5. For GC/MS analysis, inject each <strong>of</strong> the 5 levels <strong>of</strong> standard at least 3 times.<br />

Inject each NB fraction on the GC/MS and each acid fraction on the DB-WAX.<br />

Consider using a dedicated syringe for these standards to avoid<br />

192


contamination, and run a blank on the GC/MS to be certain that the syringe is<br />

clean.<br />

6. Record the ratio <strong>of</strong> the peak area <strong>of</strong> each compound to the peak area <strong>of</strong> the<br />

internal standard, and construct a standard curve. This standard curve must<br />

be linear, and should have an R 2 greater than 0.85. Place the concentration<br />

ratio on the x axis (concentration <strong>of</strong> the compound / concentration <strong>of</strong> internal<br />

standard). Place the area ratio on the y axis (peak area <strong>of</strong> the compound /<br />

peak area <strong>of</strong> the internal standard). <strong>The</strong> response factor is calculated as the<br />

inverse <strong>of</strong> the slope <strong>of</strong> this line.<br />

7. To calculate the absolute abundance <strong>of</strong> the compound:<br />

Conc. <strong>of</strong> cmpd = response factor * (area <strong>of</strong> cmpd/area <strong>of</strong> istd) * (conc. cmpd / conc. <strong>of</strong> istd)<br />

193


Appendix 3: Summary <strong>of</strong> Aroma-Active Compounds Found in<br />

Peanut Samples Using Aroma Extract Dilution Analysis (AEDA)<br />

Table 1: Aroma Active Compounds in Reference Peanuts Detected by<br />

Gas Chromatography-Olfactometry<br />

Fraction a<br />

DB-5 DB-<br />

WAX<br />

AC sweet e<br />

352 1.5<br />

AC burnt 628 1.5<br />

NB chocolate/malty 653 2.5<br />

AC fruity 667 1.5<br />

NB sweet/malty 678 2.0<br />

AC vinegar 691 1.8<br />

NB garlic/onion 700 1.5<br />

NB malty 702 1.5<br />

AC sweet/malty 707 1.7<br />

NB fatty 710 1.5<br />

AC lemony 714 2.0<br />

NB nutty/malty 747 1.5<br />

AC plastic/chemical 752 1.5<br />

NB sweet/acrid/chemical 760 2.0<br />

AC chocolate/sweet 763 1.8<br />

AC onion 772 1.5<br />

AC malty 783 2.0<br />

NB sweet/chocolate/malty 809 3.5<br />

NB malty/fruity 810 1.5<br />

NB corn chip/smoky 814 1.5<br />

AC sweet 821 1.0<br />

AC chemical/rubber 833 2.0<br />

AC fruity 840 1.5<br />

NB onion/brothy 860 1.4<br />

NB sweet/fruity 886 2.0<br />

NB grape 886 2.0<br />

AC malty/chocolate 898 2.5<br />

NB burnt sugar 906 2.0<br />

NB chocolate 907 2.5<br />

NB sweaty 910 3.5<br />

AC dried apricots/cheesy 929 3.5<br />

NB peanutty/earthy 930 3.8<br />

NB corn chip/fatty 931 4.0<br />

NB onion 947 2.2<br />

NB potato/brothy 965 3.3<br />

NB sweet 972 1.5<br />

Odor b<br />

194<br />

RI c<br />

Intensity d


AC nutty/burnt 975 1.5<br />

NB cabbage/garbage 977 3.3<br />

NB fried 977 3.0<br />

AC sweet 980 1.5<br />

NB metallic/mushroom 986 2.5<br />

NB potato 992 1.5<br />

NB roasted/nut 998 2.5<br />

AC sweaty 999 2.0<br />

AC burnt/cabbage 1001 1.5<br />

NB fruity/sweet 1003 2.3<br />

NB popcorn/musty 1004 4.5<br />

NB fruity/citrus 1006 3.0<br />

AC bubble gum 1008 2.0<br />

AC sour/burnt 1010 2.0<br />

NB peanutty 1021 2.0<br />

NB nutty/corn chip 1023 2.0<br />

NB green/spicy 1025 1.8<br />

NB fruity/chemical 1026 3.2<br />

NB green 1031 2.0<br />

AC sweaty/musty 1036 2.0<br />

NB brothy/nutty 1037 3.0<br />

AC fruity/burnt sugar 1043 2.0<br />

NB plastic bottle 1047 2.0<br />

NB skunk 1052 2.7<br />

AC nutty/roasted 1054 1.5<br />

NB burnt/burnt sugar 1058 5.1<br />

NB rosy 1060 2.8<br />

NB dirty/floral/fatty 1068 3.0<br />

AC chemical 1071 2.0<br />

NB sweet/nutty 1081 1.5<br />

NB dirty 1082 1.5<br />

NB fruity/sweet 1087 1.5<br />

AC sweet 1090 1.5<br />

NB burnt 1091 3.8<br />

NB chemical/fruity 1092 3.0<br />

NB nutty 1093 2.8<br />

NB popcorn 1093 1.5<br />

NB burnt/brothy 1100 4.0<br />

AC chemical/ammonia 1105 2.0<br />

AC green peanuts 1106 3.0<br />

NB fruity 1107 3.0<br />

NB dusty/rubber 1111 2.5<br />

AC sugary/ stale 1112 3.5<br />

NB citrus 1113 1.8<br />

NB animal/brothy 1113 3.0<br />

AC fruity 1116 2.5<br />

195


NB roasted/nutty 1130 2.4<br />

AC burnt/dusty/sweet 1130 2.0<br />

NB bubble gum/fruity 1136 2.8<br />

NB popcorn 1137 1.5<br />

AC burnt, sweet 1143 2.0<br />

NB rubber/sulfur 1144 2.0<br />

NB nutty 1148 3.0<br />

NB pine/spicy 1158 2.0<br />

NB green/floral 1159 3.0<br />

AC nutty/chemical 1159 2.8<br />

AC sweet/fruity 1163 1.5<br />

NB burnt/roasted nuts 1165 4.0<br />

AC chemical/sweet 1166 2.5<br />

AC maple syrup 1169 3.7<br />

NB old books 1176 3.5<br />

NB burnt sugar 1183 2.0<br />

NB fried/popcorn 1183 1.5<br />

NB roasted 1185 2.8<br />

NB dusty/foul/green 1187 4.0<br />

NB sweet/chemical 1192 3.3<br />

AC burnt sugar 1196 2.3<br />

AC sweet/fruity 1198 1.5<br />

NB spicy 1205 2.0<br />

NB roasted/burnt 1208 2.0<br />

NB garlic 1211 2.0<br />

AC sweet/fruity 1212 2.5<br />

NB nutty/green/plastic 1215 3.5<br />

NB pungent/frier oil 1216 3.2<br />

NB rosy/floral 1218 2.8<br />

AC musty/urine 1222 3.6<br />

NB cheesy 1226 2.0<br />

NB fried 1231 2.2<br />

NB fruity 1233 2.7<br />

NB spicy/green 1237 3.0<br />

AC floral/spicy/sweaty 1241 3.0<br />

NB metallic/mushroom 1248 4.0<br />

NB potato/green 1249 4.0<br />

AC spicy/garlic 1251 2.5<br />

AC burnt sugar 1254 2.3<br />

NB cuke/floral 1255 1.8<br />

NB burnt/roasted nuts 1260 3.0<br />

AC chemical 1262 2.0<br />

NB roasted/sweet 1265 1.5<br />

NB oxidized/nutty 1267 2.3<br />

NB popcorn 1277 4.5<br />

NB sweet 1282 1.5<br />

196


AC oxidized 1289 1.5<br />

NB dusty/nutty/popcorn 1290 3.5<br />

NB burnt/nutty 1291 2.5<br />

NB catty 1299 3.5<br />

AC popcorn 1300 3.5<br />

NB fruity 1304 3.5<br />

NB nutty/roasted/earthy 1308 2.0<br />

AC sweaty/cheesy 1310 2.0<br />

NB fatty/stale 1313 3.5<br />

NB dusty/catty/chemical 1317 5.0<br />

AC sweaty 1318 2.0<br />

NB floral 1319 2.8<br />

NB cabbage 1322 3.7<br />

AC bubble gum/fruity 1323 2.3<br />

NB burnt 1328 2.0<br />

NB fruity 1328 3.0<br />

NB solvent 1335 3.0<br />

NB burnt/roasted 1336 3.5<br />

NB parmesan cheese 1339 4.0<br />

NB fried/oxidized 1343 4.0<br />

NB glue/solvent 1343 3.0<br />

NB sweet/green/peanuts 1345 3.5<br />

NB fake peanut butter 1346 2.5<br />

NB coconut 1349 2.0<br />

NB bready 1351 3.0<br />

AC fruity 1354 3.0<br />

NB fatty/licorice/oxidized 1355 2.7<br />

AC catty 1358 1.5<br />

NB wood/campfire 1361 3.5<br />

NB popcorn/corn chip 1364 3.5<br />

AC vinegar/cabbage 1365 3.5<br />

NB floral/musty 1368 3.5<br />

NB spicy/skunk 1368 3.0<br />

NB nutty 1377 5.0<br />

NB green/geranium 1381 4.0<br />

NB burnt/smoke 1381 4.0<br />

AC sugary 1386 2.5<br />

NB stale/fatty 1389 4.0<br />

AC spicy 1395 4.0<br />

NB potato 1398 3.7<br />

NB chemical/nutty 1401 5.5<br />

AC burnt/chocolate 1401 3.3<br />

NB hay/sweet/licorice 1405 3.3<br />

NB parmesan/nutty 1411 3.0<br />

NB chemical/marker 1414 3.8<br />

AC brothy 1416 3.5<br />

197


NB burnt potatoes 1428 4.0<br />

NB grainy/metallic 1436 2.5<br />

AC chocolate/dark roast 1437 2.8<br />

AC burnt/bell pepper 1440 2.8<br />

NB fried/nutty 1442 2.5<br />

NB oxidized 1454 3.5<br />

AC glue/sweet 1456 2.0<br />

AC citrus 1458 2.5<br />

AC sweet 1468 2.0<br />

NB nutty 1469 3.5<br />

AC burnt sugar 1470 2.0<br />

NB brothy 1473 1.5<br />

AC sweet and mossy 1477 2.0<br />

NB bell pepper/oxidized 1481 3.5<br />

NB carpet 1483 2.0<br />

AC sour/vinegar 1484 2.0<br />

AC rosy 1485 2.0<br />

AC fatty 1487 1.5<br />

NB metallic 1489 3.0<br />

AC sweaty 1494 2.0<br />

AC sweet/vanilla/floral 1498 2.8<br />

AC burnt 1498 1.5<br />

AC sweet/malty 1500 2.0<br />

NB nutty/chemical 1503 3.4<br />

NB nutty 1504 2.5<br />

NB hay/fatty 1509 2.8<br />

AC plastic/chemical 1527 2.0<br />

AC malty/sweaty 1528 2.0<br />

NB solvent/nutty 1535 3.0<br />

AC vinegar/vegetable 1540 2.0<br />

AC rosy 1547 2.5<br />

AC cheesy/sweet 1549 4.0<br />

NB peanut butter 1553 3.3<br />

NB nutty/roasted 1556 1.5<br />

NB burnt/sour 1565 3.0<br />

AC sour/stinky 1567 2.0<br />

NB rosy 1553 2.1<br />

NB rosy 1572 5.6<br />

AC cheese popcorn 1572 3.5<br />

NB floral/nutty 1577 4.0<br />

AC vanilla 1582 2.0<br />

AC sweaty/malty 1592 4.3<br />

AC rosy 1594 1.8<br />

AC rosy 1606 5.0<br />

AC cheesy/sweaty 1606 3.0<br />

NB roasted/sweet 1609 3.0<br />

198


NB brothy 1612 3.5<br />

NB honey/hay 1618 2.0<br />

NB woody/smoky 1625 1.5<br />

NB fatty 1632 2.0<br />

NB floral 1633 2.5<br />

NB fruity/Juicy Fruit 1638 2.0<br />

AC brothy/sweaty 1645 5.0<br />

NB stale/cucumber 1651 4.0<br />

NB brothy 1654 2.0<br />

NB woody/smoky/sweet 1658 2.0<br />

AC orange/citrus 1666 2.5<br />

NB nutty/burnt 1677 3.0<br />

AC sweet/solvent 1680 1.8<br />

AC sweaty/swiss cheese 1680 4.0<br />

NB fatty 1693 2.3<br />

NB popcorn 1697 1.5<br />

NB brine/broth/roasted 1710 1.0<br />

AC chemical/sulfur 1728 1.8<br />

AC dirty/sweaty animal 1734 4.5<br />

AC burnt sugar 1735 2.8<br />

NB garlic 1750 1.5<br />

NB oxidized 1759 3.5<br />

AC solvent/spicy/floral 1760 1.5<br />

AC burnt sugar 1763 1.5<br />

NB rosy 1763 2.5<br />

NB grainy 1770 2.0<br />

AC minty/tobacco/hay 1784 3.3<br />

NB meaty/smoky 1787 3.5<br />

NB oxidized 1793 3.5<br />

AC burnt sugar 1801 2.0<br />

AC floral/pungent 1813 2.0<br />

AC sugary 1825 2.0<br />

NB sweet/spicy/stale 1827 3.0<br />

NB peanut butter 1855 2.0<br />

NB brothy/oxidized 1886 2.8<br />

AC hay 1888 1.5<br />

AC sweet/strawberry 1895 2.0<br />

NB nutty 1903 1.5<br />

AC burnt sugar/ cotton<br />

1913 2.5<br />

candy<br />

AC menthol 1933 2.0<br />

AC burnt sugar 1937 2.0<br />

AC toast 1939 3.0<br />

NB oniony/nutty 1945 2.5<br />

AC burnt toast/burnt<br />

sugar<br />

1987 3.0<br />

199


AC burnt sugar 1988 3.3<br />

NB peanut butter 1992 2.5<br />

AC toasted marshmallow 2008 3.0<br />

AC smoky 2016 2.5<br />

NB brothy/meaty 2017 3.0<br />

NB sweet/papery 2023 2.3<br />

NB solvent/spicy 2025 2.0<br />

NB metallic/papery 2049 2.5<br />

AC burnt sugar 2051 3.0<br />

AC fake strawberry 2059 3.5<br />

AC burnt/sulfur 2061 2.0<br />

NB meaty/nutty 2070 2.5<br />

NB sweaty/nutty 2085 1.8<br />

AC sweet/hay 2089 1.5<br />

NB oxidized 2091 1.5<br />

NB toast 2099 3.0<br />

NB fruity 2109 1.5<br />

AC sweet/strawberry 2120 2.5<br />

NB sweet/grainy 2128 2.0<br />

AC maple/cotton candy 2158 2.0<br />

NB spicy/cinnamon/pumpkin spice 2163 2.5<br />

NB burnt/nutty 2180 2.0<br />

AC burnt<br />

2198 2.3<br />

sugar/strawberry<br />

NB grainy/sweet 2223 2.0<br />

AC tealeaves/smoky 2239 2.5<br />

NB sweet/spicy 2262 2.0<br />

AC brothy/meaty/smoked 2330 3.0<br />

a<br />

Fraction in which odor was detected, AC = acid, NB = neutral/basic<br />

b<br />

Odor description by GC/O<br />

c<br />

Retention indices (RI) calculated from GC/O data<br />

d<br />

Odor intensity for each compound averaged from panelist data<br />

e<br />

Compounds in bold were determined to have high impact on flavor<br />

through subsequent AEDA analysis (Schirack et al., 2006).<br />

AEDA was conducted on the DB-5 column for NB compounds,<br />

and on the DB-WAX column for AC compounds.<br />

200


Table 2: Aroma-Active Compounds in <strong>Microwave</strong>-Blanched<br />

Peanuts Detected by Gas Chromatography-Olfactometry<br />

Fraction a<br />

Odor b<br />

201<br />

RI c<br />

DB-5 DB-WAX Intensity d<br />

NB sweet e<br />

355 1.5<br />

NB fruity 556 1.5<br />

NB painty 594 1.5<br />

NB chocolate/malty 636 2.7<br />

AC vinegar 666 3.5<br />

NB onion 678 2.0<br />

NB chocolate 693 2.0<br />

AC sweet 699 1.5<br />

NB sweet/malty 702 2.5<br />

AC rubber 739 1.5<br />

NB sweet 743 1.5<br />

NB burnt/roasted 747 2.0<br />

NB plastic/sweet 780 2.0<br />

NB fruity 803 2.0<br />

AC sweet/fruity 807 1.5<br />

NB malty/chocolate 807 2.0<br />

AC grassy/hay 809 1.5<br />

AC sweaty 815 2.0<br />

NB ammonia 820 2.0<br />

NB sweaty 822 2.5<br />

NB onion 823 1.8<br />

NB malty/chocolate 839 3.2<br />

AC burnt sugar/fruity 844 1.5<br />

AC grainy 851 1.5<br />

AC green 853 1.5<br />

AC popcorn 858 1.5<br />

AC butyric/cheesy 868 2.5<br />

NB beany 876 1.5<br />

NB garlic 882 2.5<br />

NB roasted/potato/bread 890 1.8<br />

AC buttery 906 3.0<br />

NB caramel/malty 908 2.5<br />

AC sweaty 909 3.6<br />

NB fishy/oxidized 909 2.5<br />

NB plastic 910 2.5<br />

NB buttery 912 3.0<br />

AC dried apricots/fruity 922 3.8


NB fatty/potato 930 3.3<br />

AC nutty/sweet/roasted 937 1.5<br />

NB potato/fatty 937 3.3<br />

NB onion 939 2.5<br />

AC barnyard 940 3.5<br />

AC malty 943 2.0<br />

NB nutty/earthy 944 4.3<br />

AC bo/sweaty 965 3.0<br />

NB buttery potato/fatty 968 2.0<br />

NB cheesy 969 2.0<br />

NB spicy 970 2.0<br />

NB plastic bottle 975 2.0<br />

AC citrus 979 1.8<br />

AC sweet/fruity 981 2.0<br />

NB baked potato 988 2.0<br />

NB onion 989 2.5<br />

NB onion 992 3.0<br />

NB burnt 994 2.0<br />

NB sweet/fruity 995 1.5<br />

NB corn chip 1002 3.5<br />

NB t<strong>of</strong>fee 1002 2.0<br />

NB metallic/mushroom 1002 3.5<br />

NB fruity/citrus 1010 2.4<br />

NB peanut candy 1011 3.0<br />

NB solvent 1012 2.5<br />

NB old books 1012 1.5<br />

AC sweet 1015 1.5<br />

NB malty/buttery 1024 2.5<br />

NB sweet/chemical 1027 2.0<br />

AC citrus/orange 1034 2.0<br />

AC geranium 1036 3.0<br />

NB nutty 1039 2.4<br />

NB green 1046 2.3<br />

AC sweet/burnt sugar 1047 2.5<br />

AC vinegar 1049 1.3<br />

NB plastic/rubber/chemical 1050 2.8<br />

NB roasted 1057 1.5<br />

NB rosy/green 1058 4.8<br />

NB popcorn 1063 2.0<br />

NB nutty/cheesy 1064 2.5<br />

NB burnt plastic/weeds 1071 2.8<br />

NB oxidized 1071 3.0<br />

NB brothy/potato 1074 2.5<br />

NB fruity 1080 2.9<br />

202


AC cedar 1081 3.0<br />

AC burnt sugar/nutty 1086 1.8<br />

NB popcorn 1087 2.5<br />

NB burnt 1089 3.0<br />

NB dusty/rubber 1094 3.0<br />

AC charred/brothy 1095 3.3<br />

NB peanuts 1095 2.5<br />

NB sweet/fruity 1095 2.8<br />

NB chemical/cabbage 1101 2.5<br />

AC cotton candy 1102 4.1<br />

NB minty 1109 3.0<br />

NB fried 1112 3.5<br />

AC geranium/nutty/roasted 1113 3.5<br />

AC fruity 1120 2.3<br />

NB green 1122 2.0<br />

NB ammonia/brothy 1128 3.5<br />

NB popcorn 1139 2.8<br />

NB green/floral 1142 2.3<br />

NB minty 1142 3.0<br />

AC burnt sugar/dusty 1145 2.3<br />

NB burnt 1151 4.0<br />

NB sweet/roasted 1153 2.0<br />

AC burnt sugar 1154 2.0<br />

NB smoky/dirty 1155 3.8<br />

NB cucumber/floral 1159 3.5<br />

NB nutty 1159 2.5<br />

NB paremsan/fatty 1163 2.5<br />

AC burnt sugar 1163 4.3<br />

NB cabbage 1168 2.0<br />

NB carpet 1171 4.3<br />

NB metallic 1172 2.5<br />

NB green/weedy 1172 2.0<br />

NB old books 1176 3.0<br />

NB solvent 1182 1.5<br />

NB sweaty 1182 3.0<br />

NB roasted/popcorn 1184 3.8<br />

NB oregano 1184 2.0<br />

AC caramel 1185 2.8<br />

NB bell pepper 1186 3.0<br />

AC fruity 1188 1.8<br />

NB wine 1188 3.5<br />

NB sour 1196 2.3<br />

NB burnt 1197 2.0<br />

NB sulfur/fatty 1201 3.0<br />

203


NB rosy 1202 2.8<br />

NB malty 1205 2.0<br />

NB potato/fatty 1211 3.8<br />

NB plastic bottle 1218 1.5<br />

NB licorice 1220 4.2<br />

AC sulfur/rubber/exhaust 1223 4.2<br />

NB fried/oxidized 1231 4.0<br />

NB dish soap 1232 2.0<br />

NB garlic 1232 2.3<br />

AC sweet/burnt sugar 1236 1.8<br />

NB citrus/green 1239 3.0<br />

AC burnt sugar 1240 2.3<br />

NB catty/weeds 1243 3.3<br />

AC fruity 1246 2.0<br />

NB smoke/burnt 1257 3.0<br />

NB solvent/sweet 1257 1.5<br />

NB sweat 1257 2.0<br />

NB citrus 1263 2.8<br />

NB sweet/spicy 1264 3.0<br />

NB floral/cucumber 1267 3.0<br />

NB mushroom/metallic 1270 3.3<br />

NB burnt rubber 1275 3.5<br />

NB nutty 1277 3.5<br />

NB popcorn 1278 3.5<br />

AC sweet/fruity 1281 2.3<br />

NB vegetable/green 1286 3.0<br />

AC waxy 1292 2.0<br />

NB fecal/mothball 1294 3.5<br />

NB spicy 1295 3.0<br />

NB nutty 1303 4.5<br />

NB oxidized/licorice 1309 3.5<br />

NB wine/alcohol 1318 2.5<br />

AC roasted 1319 1.5<br />

NB rosy 1322 3.0<br />

AC bubble gum/fruity 1323 2.0<br />

NB bell pepper 1330 3.0<br />

NB catty 1334 4.9<br />

NB vinegar 1334 3.8<br />

AC burnt sugar 1335 3.0<br />

NB spicy 1337 3.0<br />

NB rubber/sulfur 1338 3.0<br />

NB fried/oxidized 1343 3.8<br />

NB citrus 1349 3.5<br />

NB minty/spicy 1349 4.0<br />

204


AC brothy 1350 2.0<br />

NB garlic 1352 5.0<br />

AC burnt 1352 2.0<br />

NB corn chip 1355 3.0<br />

NB sweet/hay/oxidized 1357 3.7<br />

NB malty/grainy 1361 4.0<br />

NB peanut butter 1363 3.0<br />

AC vinegar 1368 3.5<br />

AC sweet 1369 1.5<br />

NB burnt corn chip 1372 3.5<br />

AC spicy/pepper 1374 3.0<br />

AC sweet/burnt sugar 1376 3.0<br />

NB charcoal/smoky/wood 1378 2.5<br />

NB green/fresh 1381 2.5<br />

NB potato 1386 4.5<br />

NB dusty/cheesy 1387 2.0<br />

AC fatty 1387 2.0<br />

AC mushroom 1387 2.0<br />

NB sulfur 1388 4.0<br />

NB popcorn 1391 3.2<br />

NB burnt toast 1399 4.0<br />

NB frier oil 1399 4.0<br />

NB sweet/cloying/hay 1404 2.3<br />

NB green peanuts 1405 4.5<br />

AC burnt/charred 1409 3.5<br />

NB grainy/smoky 1411 3.0<br />

NB plastic 1411 4.0<br />

AC potato/brothy 1416 3.5<br />

NB oxidized 1417 3.3<br />

AC vinegar 1420 3.3<br />

NB stale 1424 2.0<br />

NB smoked meat 1425 2.5<br />

NB garlic 1436 3.0<br />

NB burnt/nutty 1437 3.0<br />

AC spicy 1439 1.5<br />

NB spicy 1440 3.0<br />

NB parmesan cheese 1442 3.5<br />

AC carpet/dusty 1445 2.5<br />

NB green/floral 1445 3.0<br />

NB plastic/sweet/burnt 1448 3.0<br />

NB licorice 1450 1.5<br />

NB fried/garlic 1462 1.5<br />

NB wood/sweet 1464 3.0<br />

AC sweet/fruity 1467 2.3<br />

205


AC sweet/fruity 1471 2.5<br />

NB rosy 1472 3.0<br />

NB nutty 1476 2.0<br />

NB sweet/hay 1478 2.0<br />

NB sweet/alcoholic 1481 3.0<br />

AC vanilla 1482 2.9<br />

NB barn/fecal 1483 2.3<br />

NB green 1484 3.0<br />

NB smoke/chemical 1485 4.5<br />

NB oxidized 1490 3.0<br />

AC old books 1495 2.5<br />

NB smoked/peanut 1498 3.0<br />

NB nutty/roasted 1504 2.5<br />

AC fruity/sugary 1509 3.0<br />

NB sweet/bell pepper 1513 3.5<br />

NB floral/cucumber 1514 3.0<br />

AC acidic 1523 2.5<br />

AC cheesy 1538 2.5<br />

NB peanut candy 1539 3.0<br />

NB popcorn 1543 3.5<br />

NB rosy 1544 2.8<br />

NB fruity 1554 2.0<br />

NB spicy 1555 3.0<br />

AC sweet/solventy 1560 2.3<br />

AC popcorn 1560 2.0<br />

NB stale/malty 1565 3.5<br />

NB rosy 1571 5.5<br />

NB floral/hay 1572 2.8<br />

NB oxidized/butyric acid 1577 3.0<br />

AC nutty 1578 2.0<br />

AC vanilla/waxy 1584 3.0<br />

AC cheesy 1587 3.8<br />

AC sweaty 1592 3.5<br />

NB rosy 1605 4.2<br />

NB honey/hay 1618 2.0<br />

AC burnt/cheesy 1628 5.0<br />

NB fatty 1632 1.8<br />

NB roasted 1636 2.3<br />

AC waxy 1636 3.5<br />

NB fruity 1638 2.5<br />

NB brothy 1648 3.3<br />

AC sweet/honey 1655 1.5<br />

NB plastic bottle 1660 2.5<br />

NB bell pepper 1662 2.0<br />

206


NB fruity/floral 1670 3.0<br />

NB rosy 1671 2.0<br />

NB oxidized/fried 1678 2.3<br />

AC sweaty 1681 1.5<br />

AC sweet 1689 2.3<br />

NB popcorn/nutty 1689 3.8<br />

NB fried/fatty 1696 2.0<br />

AC sweet/fruity 1710 1.5<br />

AC burnt toast 1721 2.0<br />

NB popcorn 1728 2.5<br />

AC burnt sugar 1730 2.0<br />

AC strawberry/burnt sugar 1738 2.0<br />

NB hay/oxidized 1740 1.5<br />

NB peanut butter 1746 3.0<br />

NB burnt oil/fatty/oxidized 1751 3.5<br />

AC sour/fruity 1760 1.8<br />

NB cheesy 1763 3.5<br />

NB sweet/burnt 1775 2.5<br />

AC sweaty/dirty 1775 3.0<br />

NB fatty/spicy corn chip 1786 3.5<br />

AC maple syrup 1789 3.5<br />

NB grainy/cheesy 1799 3.5<br />

AC fatty/sweet/coconut 1807 3.5<br />

AC hay/sweet 1813 2.8<br />

NB burnt 1813 2.0<br />

NB minty/tobacco 1822 3.0<br />

NB chemical/burnt 1825 3.0<br />

NB grainy/nutty 1830 3.3<br />

NB onion/brothy 1842 2.5<br />

AC hay/licorice 1850 1.5<br />

NB nutty 1858 3.5<br />

NB oxidized 1863 4.0<br />

AC burnt sugar 1880 2.0<br />

NB floral 1888 2.5<br />

AC burnt/waxy 1913 1.5<br />

NB burnt/sulfur 1917 2.0<br />

AC bready 1925 2.5<br />

AC cotton candy 1936 3.0<br />

NB brothy/fatty 1938 1.5<br />

AC fruity 1940 2.0<br />

NB sweet 1945 1.8<br />

NB peanut butter 1959 3.0<br />

AC sour 1971 2.0<br />

AC burnt sugar 1981 3.3<br />

207


AC sour 1982 1.5<br />

AC green/hay/fatty 1989 2.0<br />

AC burnt sugar/fruity 1998 1.5<br />

NB burnt toast 2008 2.5<br />

AC burnt sugar 2022 2.8<br />

AC burnt 2039 1.5<br />

NB floral 2049 2.0<br />

AC fruity 2052 2.0<br />

NB nutty/green 2059 2.0<br />

NB fecal/stale/burnt 2068 2.5<br />

NB burnt nutty 2089 2.3<br />

NB fruity 2104 1.5<br />

AC hay/licorice 2111 2.5<br />

AC burnt sugar 2124 2.0<br />

NB beany 2133 2.3<br />

AC maple syrup 2171 2.3<br />

NB sweet/citrus 2177 2.5<br />

AC burnt/sweaty 2187 2.0<br />

NB sweet/pumpkin spice 2203 2.0<br />

AC sweet/fruity 2209 2.5<br />

NB brothy/smoky 2228 2.3<br />

NB corn chips 2237 3.0<br />

AC burnt sugar 2237 1.5<br />

NB burnt corn 2284 2.3<br />

AC sweet/floral 2321 2.0<br />

AC sweet/burnt 2319 1.8<br />

a<br />

Fraction in which odor was detected, AC = acid, NB = neutral/basic<br />

b<br />

Odor description by GC/O<br />

c<br />

Retention indices (RI) calculated from GC/O data<br />

d<br />

Odor intensity for each compound averaged from panelist data<br />

e<br />

Compounds in bold were determined to have high impact on flavor<br />

through subsequent AEDA analysis (Schirack et al., 2006).<br />

AEDA was conducted on the DB-5 column for NB compounds,<br />

and on the DB-WAX column for AC compounds.<br />

208

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