EFFECT OF DRYING TEMPERATURE ON THE ...

EFFECT OF DRYING TEMPERATURE ON THE

COMPOSITION OF HYDRO DISTILLED CINNAMON

BARK OIL

N.D.I. Kumarage

(09/8959)

Degree of Master of Science in Sustainable Process Development

Department of Chemical and Process Engineering

University of Moratuwa

Sri Lanka

August 2013

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EFFECT OF DRYING TEMPERATURE ON THE

COMPOSITION OF HYDRO DISTILLED CINNAMON

BARK OIL

Nawammalie Dushyantha Iroshini Kumarage

(09/8959)

Thesis submitted in partial fulfillment of the requirements for the degree Master of

Science in Sustainable Process Development

Department of Chemical and Process Engineering

University of Moratuwa

Sri Lanka

August 2013

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i

DECLARATION OF THE CANDIDATE AND SUPERVISOR

“I declare that this is my own work and this thesis does not incorporate without

acknowledgement any material previously submitted for a Degree or Diploma in any

University or other institute of higher learning and to the best of my knowledge and

belief it does not contain any material previously published or written by another

person except where the acknowledgement is made in the text”

……………………..

Candidate : N.D.I. Kumarage Date : 08th November 2013

I endorse the declaration by the candidate.

………………………..

Supervisor : Dr. A.D.U. Shantha Amarasinghe Date : 08th November 2013

Copyright Statement

“I hereby grant the University of Moratuwa the right to archive and to make

available my thesis or dissertation in whole or part in the University Libraries in all

forms of media, subject to the provisions of the current copyright act of Sri Lanka. I

retrain all proprietary rights, such as patent rights. I also retain the right to use in

future works (such as articles or books) all or part of this thesis or dissertation”.

……………………..

Candidate : N.D.I. Kumarage Date : 08th November 2013

“I have supervised and accepted this thesis/dissertation for the award of the degree”

………………………..

Supervisor : Dr. A.D.U. Shantha Amarasinghe Date : 08th November 2013

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Abstract

Cinnamon (Cinnamomum Zeylanicum) is an endemic plant popularly known as “Kurundu”in Sri Lanka. Cinnamon yields mainly cinnamon leaf oil and cinnamon bark oil. Cinnamonbark oil produces by processing dried cinnamon chips. Composition of cinnamon bark oilvaries due to many factors including the type and quality of cinnamon chips. Good qualitycinnamon chips can be produced by uniform drying. Present study examines the effect of airdrying temperature during pre processing of cinnamon chips on the volatile organiccompounds of cinnamon bark oil extracted by the method of hydro-distillation of cinnamonchips. Laboratory scale tunnel dryer fitted with an electrical heater was used to dry cinnamonchips at five different air drying temperatures; ambient temperature, 35 °C, 40 °C, 45 °C and50 °C. The extracted cinnamon bark oil was analysed by gas chromatography-massspectrometry (GC-MS). A total of 16 compounds were identified, cinnamaldehyde-E,cinnamyl acetate, linalool and eugenol, in that order, being the main volatile organiccompounds. Results indicated that air drying temperature of cinnamon chips significantlyaltered the composition of cinnamon bark oil. Percentage of Cinnamaldehyde-E increasedwith the increase in drying temperature. High percentage of monoterpenes, cinnamaldehydeand cinnamaldehyde derivatives such as cinnamyl acetate, and 2-methoxy-cinnamaldehydewas observed at low temperature drying. Increase in drying temperature resulted insubstantial losses in certain oxygenated terpenes and sesquiterpene. The percentage ofcinnamaldehyde-E could be substantially increased by hot air drying but at the expense of oilyield.

Keywords: Bark oil, air drying, volatile organic compounds, cinnamon chips

ABSTRACT

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DEDICATION

This thesis is dedicated to my beloved PARENTS, HUSBAND and SON

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ACKNOWLEDGEMENT

I take this opportunity to acknowledge to people who has done an immense support

to enable my thesis work a success from its start to the end. First of all my sincere

thanks goes to my supervisor Dr. A.D.U.S. Amarasinghe, Senior Lecturer,

Department of Chemical & Process Engineering, University of Moratuwa for his

continuous in depth guidance throughout my research. My gratitude also goes to the

Post Graduate Division and NORAD fund of Telemark University, Norway.

My special thanks to Mr. Prasanna Welahetti and Mr. Sujeewa Buddhasiri for giving

their valuable support. All the staff members in the Dept. of Chemical & Process

Engineering, specially, Indika Athukorala, Lalith Fernando, Shantha Peris, Ranjith

Abeywardhane, Jayweera Wijesinghe, Nihal Perera, Ranjith Maskorala, and

Sajeewani Silva are gratefully acknowledged for their support in various occasions.

Cooperation given by staff members at Cinnamon Research Institute, Thihagoda is

appreciated specially in the stages of literature survey in this research. I would like to

extend my sincere appreciation to Dr. M.A.B. Prashantha in the Dept. of Chemistry

of university of Jayawardanapura for their support for doing Gas chromatography

analysis.

I sincerely thank my beloved parents and husband for providing continued support

and encouragement during my research work.

Finally, I would like to express my thankfulness for many individuals especially

Amila Chandra, Janitha Bandara & Gagani Nandadewa and friends who have not

been mentioned here personally and helped me by thought word or deeds in making

this research a success.

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v

TABLE OF CONTENTSDeclaration of the Candidate and Supervisor ........................................................ i

Abstract .................................................................................................................. ii

Dedication ............................................................................................................. iii

Acknowledgement ................................................................................................. iv

List of Figures ..................................................................................................... viii

List of Tables ......................................................................................................... ix

List of Abbreviations ..............................................................................................x

List of Appendices ................................................................................................. xi

1 INTRODUCTION ...........................................................................................1

1.1 Background .................................................................................................1

1.2 Drying of Cinnamon Chips ..........................................................................1

1.3 Justification of Research ..............................................................................2

1.4 Objectives of the Research ...........................................................................3

1.5 Outline of the Thesis ....................................................................................4

2 LITERATURE REVIEW ................................................................................5

2.1 Cinnamon Products ......................................................................................5

2.1.1 Quills .................................................................................................6

2.1.2 Quillings ............................................................................................7

2.1.3 Featherings ........................................................................................7

2.1.4 Chips .................................................................................................7

2.1.5 Cinnamon oil .....................................................................................7

2.1.5.1 Leaf Oil......................................................................................8

2.1.5.2 Bark Oil .....................................................................................8

2.1.5.3 Properties of cinnamon oil..........................................................8

2.1.5.4 Chemical composition ................................................................9

2.2 Processing of Cinnamon Chips .................................................................. 10

2.2.1 Cinnamon process flow .................................................................... 10

2.2.2 Types of “katta-chips” ..................................................................... 11

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2.2.3 Cinnamon “katta-Chips” peeling process ......................................... 11

2.2.4 Drying and storage ........................................................................... 12

2.2.5 Cinnamon oil extraction methods ..................................................... 13

2.2.5.1 Steam distillation ..................................................................... 13

2.2.5.2 Hydro distillation ..................................................................... 14

2.2.5.3 Solvent extraction .................................................................... 14

2.2.5.4 Super critical CO2 extraction .................................................... 14

2.3 Essential Oil Analysis ................................................................................ 14

2.3.1 Methods of oil analysis .................................................................... 15

2.3.2 Volatile organic compounds of cinnamon oil ................................... 16

2.3.3 Effect of the drying on the volatile organic compounds of essential oil

19

2.4 Statistical Analysis of the Effect of the Drying Using SPSS ....................... 22

3 MATERIALS AND METHODOLOGY ....................................................... 24

3.1 Materials & Equipments ............................................................................ 24

3.2 Drying of Cinnamon Chips ........................................................................ 26

3.3 Extraction of Cinnamon Bark Oil ............................................................... 28

3.4 Identification of Volatile Organic Compounds ........................................... 29

4 DATA ANAYSIS ........................................................................................... 30

4.1 Calculation of Moisture Content ................................................................ 30

4.2 Gas Chromatography and Mass Spectrometer Analysis .............................. 31

4.3 Statistical Analysis ..................................................................................... 33

4.3.1 One way ANOVA............................................................................ 33

4.3.1.1 Performing the ANOVA with SPSS ......................................... 33

4.3.2 Principal component analysis (PCA) ................................................ 36

5 RESULTS AND DISCUSSION ..................................................................... 38

5.1 Drying characteristics of Cinnamon chips .................................................. 38

5.2 Gas Chromatography Analysis ................................................................... 40

5.3 Statistical Analysis ..................................................................................... 42

5.3.1 Mean comparison by ANOVA ......................................................... 42

5.3.1.1 Verification for the validity of assumption ............................... 42

5.3.1.2 One way ANOVA descriptives................................................. 44

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5.3.1.3 Mean comparison using Student-Newman-Keuls (SNK) test .... 45

5.3.2 Principal component analysis (PCA) ................................................ 47

6 CONCLUSIONS AND RECOMMENDATIONS ........................................ 52

Reference List ...................................................................................................... 54

Appendices ............................................................................................................ 61

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viii

LIST OF FIGURES

Figure 2.1: (a) cinnamon quills, (b) cinnamon featherings, (c) cinnamon chips, (d)

cinnamon bark oil, (e) cinnamon leaf oil ..................................................6

Figure 2.2: Flow diagram of cinnamon processing .................................................. 11

Figure 2.3: (a) Collected cinnamon tree parts, (b) Katta peeling process, (c) Peeled

Katta ...................................................................................................... 12

Figure 3.1: (a) Weighing balance, (b) Moisture balance .......................................... 24

Figure 3.2: Fixed bed dryer with component ........................................................... 25

Figure 3.3: (a) Thermocouple, (b) Anemometer ...................................................... 26

Figure 3.4: GC-MS-7890A gas chromatograph equipped with a 5975C plus mass

spectrometer (Agilent, American) .......................................................... 26

Figure 3.5: Cinnamon chips sampling method ......................................................... 27

Figure 3.6: Cinnamon oil extraction apparatus ........................................................ 28

Figure 3.7: Cinnamon oil separation apparatus ........................................................ 29

Figure 4.1: Chromatogram of cinnamon bark oil (35 °C temperature -Trial 1) ......... 32

Figure 4.2: Flow chart of ANOVA procedure in SPSS software .............................. 35

Figure 5.1: Variation of moisture content with time for different air drying

temperatures ......................................................................................... 39

Figure 5.2: Variation of drying rate with moisture content for different air drying

temperatures……………………………………………………………39

Figure 5.3: Normal Q-Q plot of cinnamaldehyde-E at ambient temperature............. 43

Figure 5.4: Principal component plot (PC2 vs PC1). ambient temperature dried (�),

air dried at 35 °C (*), air dried at 40 °C (Í), air dried at 45 °C (Æ), air

dried at 50 °C (∆) ................................................................................. 50


air dried at 35 °C (*), air dried at 40 °C (Í), air dried at 45 °C (Æ), air

dried at 50 °C (∆) ................................................................................. 51

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ix

LIST OF TABLES

Table 2.1: Physico-chemical properties of cinnamon oil ............................................9

Table 2.2: Properties of selected volatile organic compounds of cinnamon bark oil . 10

Table 5.1: Moisture content on dry basis and drying time for different drying

temperatures .......................................................................................... 38

Table 5.2: Gas chromatography analysis for cinnamon oil dried at different

temperatures .......................................................................................... 41

Table 5.3: Levene's test of homogeneity of variances for cinnamaldehyde-E ........... 42

Table 5.4: Welch test of equality of means .............................................................. 42

Table 5.5: Shapiro-Wilk tests of normality for cinnamaldehyde-E ........................... 43

Table 5.6: Descriptive table of cinnamaldehyde-E at different temperatures ............ 44

Table 5.7: ANOVA table of cinnamaldehyde-E ...................................................... 44

Table 5.8: Mean comparisons of cinnamaldehyde-E................................................ 45

Table 5.9: Concentration of volatile compounds (relative content %) in hydro

distilled cinnamon bark .......................................................................... 46

Table 5.10: Correlations between volatile organic compounds and principal

components (PC) ................................................................................... 48

Table 5.11: Correlation coefficient values for the volatile organic compounds against

principal component 1 ,2 and 3 ............................................................. 49

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x

LIST OF ABBREVIATIONS

Abbreviation Description

R&D Research & Deveopment

SNK Student Newman Keuls

PCA Principal Component Analysis

SCF Super Critical Fluids

GLC Gas Liquid Chromatography

GC Gas Chromatography

MS Mass Spectrometry

IR Infrared

HPLC High Performance Liquid Chromatography

TTE 1,1,2-trichloro- 1,2,2-trifluoroethane

SDE Simultaneous distillation extraction

LSD Least Significant Difference

ANOVA Analysis of Variance

MST Mean Square Treatment

MSE Mean Square Error

PC Principal Component

DF Degrees of Freedom

RSD Relative standard deviation

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xi

LIST OF APPENDICES

Appendix A: Gas chromatograms of hydro distilled cinnamon oil at different drying

temperatures ...................................................................................... 61

Appendix B: Standard & obtained mass spectra of different volatile organic

compounds of cinnamon bark oil ........................................................ 66

Appendix C: Gas chromatogram data sheets of hydro distilled cinnamon oil at

different drying temperatures .............................................................. 70

Appendix D: One-Way ANOVA and principal components analysis (PCA) steps in

IBM SPSS statistics 19 ....................................................................... 75

Appendix E: Matlab code for plotting the drying curves .......................................... 78

Appendix F: SPSS Output of the One-Way ANOVA .............................................. 80

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xii

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1 INTRODUCTION

1.1 Background

Cinnamon (Cinnamomum Zeylanicum) is an endemic plant popularly known as

“Kurundu” in Sri Lanka. Cinnamon is mostly used in cooking and baking and can be

added to any food item such as salads, confectionaries, beverages, soups, stews and

sauces. Cinnamon yields mainly cinnamon leaf oil and cinnamon bark oil. Cinnamon bark

oil which has a light yellow colour is used in food and pharmaceutical industries.

Cinnamon leaf oil is cheaper than bark oil and is used in the flavor industry.

Cinnamon bark oil is produced by processing dry cinnamon chips.

1.2 Drying of Cinnamon Chips

Fresh cinnamon chips contain very high amount of moisture; up to about 60% (w/w

wet basis). Drying is the most common and fundamental method for post-harvest

preservation of medicinal plants, vegetables and spices to inhibit microorganism

growth and prevent degradation due to biochemical reactions. Nevertheless, a series

of physical and chemical alterations that may have an adverse effect on quality may

take place during drying. Such alterations include changes in appearance, as well as

in aroma, caused by the loss of volatile organic compounds or the formation of other,

new components as a consequence of oxidation reactions, esterification reactions,

etc. (Diaz-Maroto, et al.,2002c). Traditional drying methods (e.g. sun and solar

drying) have many drawbacks due to the inability to handle the large throughput of

mechanical harvesters and to achieve the high-quality standards required for

medicinal plants. High ambient air temperature and relative humidity during the

harvesting and drying season promote the insect and mould development in

harvested crops. Furthermore, the intensive solar radiation causes several quality

reductions like vitamin losses or color changes in dried crops. Thus, the traditional

natural drying in the shade does not meet the particular requirements of the related

standards. To overcome these problems, producers mostly adopt the heated-air batch

dryers or continuous conveyor dryers (Oztekin et al., 1999).

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General to the Sri Lankan spice industry, improper drying has been identified as the

main reason for losses such as presence of high moisture content, semi-dry and

mould developed conditions. A study done by Economics Research Unit of

Department of Export Agriculture, reports that around 70% of the producers use sun

drying on home yard having no brick or cemented floor which has a high potential to

moisture retention and microbial contamination. More than 69% of the producers

who had been interviewed in this study claimed that their drying process was

disturbed by occasional rain.

1.3 Justification of Research

Sri Lanka is the major cinnamon producing, country in the world and it controls over

60% of the world cinnamon trade. Sri Lanka produces the best quality cinnamon

bark, mainly as quills, while quilling, featherings, chips, ground cinnamon,

cinnamon powder, leaf oil and bark oil are the other products. It also produces

annually around 120 T leaf oil and 4–5 MT bark oil. Cinnamon bark oil is very high

value oil due to the presence of high amount of cinnamaldehyde and other valuable

aromatic compounds and Sri Lanka is the main supplier of this commodity

(Parthasarathy, et al., 2008). World trade in Sri Lankan cinnamon is centered on

London and Dutch ports of Amsterdam and Rotterdam, which are the main

transshipment points for the leading buyers such as Mexico, US, UK, Germany,

Holland, Colombia, etc.

A growing demand for cinnamon in future can be expected with the increasing of

concern on health hazards associated with synthetic flavoring agents used in food

industry and increasing preference for natural flavors all over the world. As a

pioneering cinnamon supplier to the international market, Sri Lanka holds a major

responsibility in developing methods to increase the cinnamon harvest and extract

more oil yield per hectare by minimizing the pre and post harvesting losses along the

cinnamon supply chain while conserving its existing quality.

Due to the increasing demand for cinnamon oil in global market, there is an urgent

need for increased investment in research and product development for value

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addition in cinnamon. Investigation of the current supply chain of cinnamon oil

production, identification of the drawbacks and adapting necessary technological

input has been a timely need which results in value adding to the industry. This

research is an effort of exploring of such a value adding technological contribution

which can be practically substituted to the current oil production process.

Cinnamon has a vast research area to explore. Only limited numbers of R&D efforts

have contributed to the progress of cinnamon research and most of them were

initiated from Sri Lanka. Publications by Ceylon Institute of Scientific and Industrial

Research and by the Department of Export Agriculture hold some of these research

efforts and they were mainly concentrated on cinnamon chemistry, quality

assessment, developing agro-technology for cultivation and post-harvest processing.

Thihagoda, Sri Lanka is the only dedicated cinnamon research station in the world

which also works for dissemination of R&D results to farmers, interested institutions

and industries. In addition to Sri Lanka, Research Station at Calicut, Kozhikode

under the Central Plantation Crops Research Institute, Kerala in India has done some

R&D efforts on cinnamon tree spices.

Various studies have been performed on the effect of drying on the volatile organic

compounds of different spices. However no studies have been performed to

investigate the effect of drying on the volatile organic compounds of cinnamon bark

and leaf oil.

Considering the observations made with respect to cinnamon bark oil production

industry, the need for optimization of drying temperature has been identified as the

most affecting parameter for the cinnamon bark oil production in this research.

1.4 Objectives of the Research

Composition of cinnamon bark oil varies due to many factors including the type and

quality of cinnamon chips. Good quality cinnamon chips can be produced by uniform

drying. Present study has examined the influence of five different air drying

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temperatures, ambient temperature, 35 °C, 40 °C, 45 °C and 50 °C on the volatile

compounds in cinnamon bark.

1.5 Outline of the Thesis

This thesis is consisted with five chapters. In the first chapter, research objectives are

mentioned and justified with the introduction to the research area. A literature review

on cinnamon bark and available extraction methods of cinnamon bark oil, methods of

oil analysis and effect of drying on volatile organic compounds of essential oil has

been presented in the second chapter. In the third chapter, all the materials used to

conduct the study and the methodology followed to fulfil the research objectives are

described. Data analysis using IBM SPSS Statistics 19 are mentioned in fourth

chapter. The results obtained during the present study are presented and discussed in

the fifth chapter. The last and sixth chapter contains the conclusion of the study.

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2 2 LITERATURE REVIEW

In the first section of the literature review, information has been given on various

cinnamon bark types and how they can be graded. After that major cinnamon oil

types are discussed with their physical and chemical properties. Cinnamon bark oil

production process is described starting from plantation to oil production. Oil

extraction methods, essential oil analysis methods, and the physico chemical analysis

of volatile organic compounds of cinnamon oil are discussed in the next sections.

Since drying is the main preprocessing step recognized in this research, the effect of

the drying on volatile organic compounds of cinnamon oil and methods of statistical

analysis are presented finally.

2.1 Cinnamon Products

About 24,000 ha are under cinnamon cultivation in Sri Lanka and cinnamon groves

are located in the western and south-western regions of the island such as Negambo,

Kaluthara, Ambalangoda, Matara and Rathnapura (Ravindran et al., 2004). The

tropical sunshine and abundant rain in many parts of Sri Lanka provide the ideal

habitat for the growth of cinnamon. Cinnamon is a moderate sized plant grown up to

16 m height and 60 cm breast diameter. It has a smooth bark having light pinkish

brown, grown up to 10 mm thick which gives a strong pleasant spicy and burning

taste. It has oval or elliptical leaves bearing pale yellowish green flowers,

ellipsoidical dark purple fruits.

The most commonly produced product is cinnamon quills. There are several other

by-products generated during the processing of quills. They are classified into five

major commercial groups as quillings, featherings, chips, bark oil and leaf oil which

are shown in Figure 2.1. The major export product out of them is always quills that

accounts for about 90% of the whole industry.

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(a) (b)

(c) (d) (e)

Figure 2.1: (a) cinnamon quills, (b) cinnamon featherings, (c) cinnamon chips, (d)

cinnamon bark oil, (e) cinnamon leaf oil

2.1.1 Quills

The cinnamon is marketed mainly as quills. Scraped peel of the inner bark of mature

cinnamon stems first dried in the sun (not direct sun) to curl and join together by

overlaps, the hollow of which has been filled with small pieces of peeled cinnamon

to form length of 106.7 cm (42 in) and thereafter allow for air curing. Different

cinnamon grades are available in market such as Continental, Mexican, Hamburg and

etc. The desired colour of the quills is light brown and reddish brown patches

(foxing) can be also seen due to the quality defects arising from drying conditions.

The value of quills gets depreciated depending on the amount of foxing. Names of

“Superficial” (Malkorahedi) and “Heavy” (Korahedi) are given according to the

depth of the patches.

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http://www.google.lk/imgres?q=cinnamon+chips&hl=en&tbo=d&biw=1786&bih=849&tbm=isch&tbnid=I-bv0NOYdaVrCM:&imgrefurl=http://phoenixherb.com/products-page/culinary-herbs-and-spices/cinnamon-chips-cinnamomum-burmannii/&docid=BgGYXXykBT3mxM&imgurl=http://phoenixherb.com/wp-content/uploads/2012/02/cinnamon-chips-1024x768.jpg&w=1024&h=768&ei=RbfJUNKvFcieiQea9YHgAg&zoom=1&iact=hc&vpx=371&vpy=485&dur=2380&hovh=194&hovw=259&tx=108&ty=98&sig=108408357086983289307&page=2&tbnh=140&tbnw=192&start=46&ndsp=54&ved=1t:429,r:75,s:0,i:306



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2.1.2 Quillings

Quillings are marketed as medium quality cinnamon but their aroma and taste are

similar to those of quills. Quillings can be separated from quills due to their shape

and size which is done prior to the sun drying process. Another type called

featherings can be contained with quillings up to 3% by mass.

2.1.3 Featherings

Featherings are pieces of inner bark, obtained by peeling and/ or scraping the bark of

small twigs and stalks of cinnamon shoots, which may include a quantity of chips as

specified.

2.1.4 Chips

Chips are inferior quality cinnamon and the raw materials which were used in this

research. Chips scraped off from the greenish brown, mature thick pieces of bark.

Also the outer bark, which is obtained by beating or scraping the shoots, is also

considered to be chips. Chips are graded into two categories as;

Grade 1- Those containing small featherings obtained by scraping very small twigs.

They contain a small amount of the outer bark material and, which are inferior

quality cinnamon.

Grade 2- Those containing inner and outer bark and pieces of wood.

2.1.5 Cinnamon oil

Cinnamon leaf and bark are sources of cinnamon oil, which are named as leaf oil and

bark oil. Cinnamon oil has been mostly focused on the biologic effects in human

beings and animals, such as antifungal activities (Guynot, et al., 2003; Suhr and

Nielsen, 2003), antibacterial activities (Kalemba and Kunicka, 2003) and anti-

diabetic activities (Bailey and Day, 1989; Qin, et al., 2003; Mang, et al., 2006).

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2.1.5.1 Leaf Oil

Cinnamon leaves are obtained as a by-product in the cinnamon industry and they are

steam distilled in large vessels to produce leaf oil. Normally before distilling, leaves

are left in fields for 3 to 4 days. Since leaf oil is heavier than water, oil collects at the

bottom of the separation vessel. Yield is normally 1% oil based on dry weight basis.

The amount of eugenol content determines the grading of leaf oil. In the local

market, leaf oil directly goes from the distillers to the local merchants. Major buying

countries of cinnamon leaf oil from Sri Lanka are US ( 57 %), and European market

UK ( 14.4 %), Germany ( 6.07 % ), France (4.40%), Spain (4.83 %), Italy (3.3 %)

and India (4.12 %) (Ravindran et al., 2004). The issue with the leaf oil production is

that the amount of leaves available for distillation varies with the season and labour

(Ravindran et al., 2004).

2.1.5.2 Bark Oil

Cinnamon bark oil is one of the expensive essential oils in the world market. The

price or value of bark oils, largely depend on the material used to distill the oil.

Similar apparatus and techniques to leaf oil production, are used for bark oil

production and hydro distillation is also used by some manufacturers.

Cinnamaldehyde content determines the quality of cinnamon bark oil. The lowest

quality bark oil which is called “katta thel” is produced from rough bark (“katta-

chips”). When high quality bark oil is required, quills, qullings and featherings are

used (Ravindran et al., 2004).

2.1.5.3 Properties of cinnamon oil

There is no international standard for cinnamon bark oil properties. Higher the

cinnamaldehyde percentage is the higher market price. In the United States, EOA

standard specifies an aldehyde content of 55-78%. However, in the case of leaf oil,

international standards do exist. In this case, a phenol content of 75–85% has been

specified for oil of Sri Lankan origin. Cinnamaldehyde is another constituent of leaf

essential oil, contributing to the total flavor, and the specification limits its content to

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5%. In the USA, the FMA (Fragrance Materials Association) specifies the eugenol

content (80–88%) in cinnamon leaf oil in terms of its solubility in KOH. The

physico-chemical properties of cinnamon oil are given in Table 2.1 (Parthasarathy et

al., 2008).

Table 2.1: Physico-chemical properties of cinnamon oil

Bark oil Leaf oilSpecific gravity 1.021–1.070 (at 20 °C) 1.044–1.062 (at 30 °C)

Refractive index 1.567–1.614 (at 20 °C) 1.522–1.530 (at 30 °C)Optical rotation (°) −1°–0° (at 20 °C) 3.60° (at 30 °C)Eugenol content (%) – 65–87.2

2.1.5.4 Chemical composition

Volatile organic compounds are contained in other parts, including root bark, fruits,

flowers, twigs and branches. A systematic study of the chemical composition of Sri

Lankan produced spice oils and essential oils was carried out by Paranagama

(Paranagama, M.Phil. thesis, 1991). In this study GC-MS technique with capillary

columns was used to investigate the essential oil composition of cinnamon (leaf oil,

bark oil and root bark oil).

Volatile oils are very complex mixtures of compounds. The constituents of the oils

are mainly monoterpenes and sesquiterpines, which are hydrocarbons with the

general formula (C5H8)n. Oxygenated compounds derived from these hydrocarbons

include alcohols, aldehydes, esters, ethers, ketones, phenols and oxides. It is

estimated that there are more than 1000 monoterpenes and 3000 sesquiterpines

structures. Other compounds include phenyl propenes and specific compounds

containing sulphur or nitrogen (Maheshwari et al., 2010).

Molar mass, density and boiling point of selected volatile constituents are given in

Table 2.2. Process parameters used in the cinnamon bark oil extraction process is

heavily dependent on these properties.

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Table 2.2: Properties of selected volatile organic compounds of cinnamon bark oil

Source: http://www.lookchem.com, Visited, 15th January 2013

2.2 Processing of Cinnamon Chips

2.2.1 Cinnamon process flow

An overview of cinnamon processing steps is given in Figure 2.2 (Ravindran et al.,

2004). The term quills is defined as scrapped peel of the inner bark of mature

cinnamon shoots, joined together by overlapping tubes, the hollow of which has been

filled with smaller pieces of cinnamon peels which is thereafter dried first in the sun

and thereafter in shade for a certain length of time. Quillings are broken pieces and

splits of all grades of cinnamon quills. The feather like pieces of inner bark

consisting of shavings and small pieces of bark left over from the quill-making

process are called featherings. Cinnamon chips are obtained from rough unpeelable

Component Molecularformula

Molarmassg/mol

Densityg/ml

Boilingpoint oC

1 1,4-dimethyl benzene(p-xylene) C8H10 106.18 0.87 139.61

2 Styrene C8H8 104.15 0.903 145.1593 benzene, 1,2,3-trimethyl C9H12 120.194 0.891 176.124 α-phellandrene C10H16 136.26 0.835 171.5

5 benzene,1-methyl-4-(1-methylethyl)(p-cymene) C10H14 134.24 0.861 173.9

6 β-phellandrene C10H16 136.26 0.82 175

7 1,6-octadiene-3-ol,3,7-dimethyl(linalool) C10H18O 154.25 0.859 198.5

8 benzenepropanal C9H10O 134.18 - -

9 3-cyclohexene-1-ol,4-methyl-1-(1-methylethyl) (terpinen-4-ol) C10H18O 154.25 0.933 208.999

10 2-Propenal,3-phenyl(cinnamaldehyde) C9H8O 132.16 1.034 246.8

11 cinnamaldehyde-E C9H8O 132.16 1.05 246.84112 eugenol C10H12O2 164.22 1.067 25513 caryophyllene C15H24 204.35 0.894 268.3614 2-propen-1-ol-3-phenyl-, acetate

(cinnamyl acetate) C11H12O2 176.2 1.054 265

15 2-Propenal,3-(2-methoxyphenyl)-(2-methoxy-cinnamaldehyde) C10H10O2 162.19 1.068 334.8

16 benzyl benzoate C14H12O2 212.248 1.128 324.1

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bark scraped off from thicker stems. The stems of the cinnamon produce mainly

“katta-Chips” or quills. Other by products are firewood, quillings and featherings.

Cinnamon leaf and bark oils are obtained by distilling the leaf and bark separately.

Figure 2.2: Flow diagram of cinnamon processing

2.2.2 Types of “katta-chips”

There are mainly two types of “katta-chips” available in the market called “mas

katta” and “wal katta”. wal katta is obtained from twigs and immature branches by

beating these parts and is greenish rather than brownish. mas katta is obtained from

unpeelable cinnamon tree parts and matured branches. According to market detail

mas katta has higher demand than wal katta but wal katta is commonly found

compared to the mas katta.

2.2.3 Cinnamon “katta-Chips” peeling process

Cinnamon plants are grown as bushes. When plants are two years of age, they are

ready for harvesting. The peelers can identify the cinnamon tree parts which cannot

be used to make cinnamon quills by their experience. Peeler selects main tree stem

for cinnamon quill preparation and rest of the tree parts such as twigs, leaves and

unpeelable cinnamon tree parts are left at the cinnamon yards. After that “katta-

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chips” peelers come to plantation and collect cinnamon tree parts (see Figure 2.3a)

which can be used to make “katta-chips”. Usually old people and school children get

involved in “katta-chips” peeling process (Figure 2.3b,c). The price range for “katta-

chips” in the local market is very low although the peeling process is time

consuming.

(a) (b)

(c)

Figure 2.3: (a) Collected cinnamon tree parts, (b) Katta peeling process, (c) Peeled

Katta

2.2.4 Drying and storage

Water content of peeled “katta-chips” is more than half of its weight. Since price of

the cinnamon “katta-chips” mainly depends on the weight and availability of small

particles, the usual habit of “katta-chips” peelers is to store “katta-chips” in poly sack

immediately after peeling instead of drying them as village “katta-chips” collectors

deduct weight for water composition without investigating whether “katta-chips”

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peelers have dried them or not. Therefore peeled “katta-chips” remain in poly sacks

until village “katta-chips” collector come to peeler’s houses for buying. Therefore

storage time in poly sack at peeler’s house depend on the frequency of collecting by

village “katta-chips” collector. It may be one day or one week. The frequency of

collection varies due to many factors including the season of the year. During the

main season, collection is very frequent due to the availability.

Village “katta-chips” collectors examine the wetness of “katta-chips” by touching

and visual examination and dry them if they are not at the required dryness as

requested by the “katta-chips” traders. Cinnamon traders in towns, remove

unnecessary parts such as cinnamon leaves, wood pieces and sieve to remove dust.

Cleaned “katta-chips” are packed in poly sacks until they are sent to the cinnamon oil

producers for distillation.

2.2.5 Cinnamon oil extraction methods

This section describes main methods of cinnamon oil extraction and their

fundamental concepts. The choice of each extraction method lies on, sensitivity of

the essential oils to the action of heat and water, volatility of the essential oil and

water solubility of the essential oil (Ravindran et al., 2004).

2.2.5.1 Steam distillation

Dried cinnamon bark is placed in still and the steam is allowed to pass through the

cinnamon bark under pressure which softens the cells and allows the bark oil to

escape in vapour form. The vapour produced is passed into a condenser and then it is

cooled. The mixture of water and cinnamon bark oil is left from the condenser and

separated into two layers in a separator. Proper temperature must be maintained

throughout the distillation process, and pressure, length of time, equipment, and

batch size are strictly monitored.

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2.2.5.2 Hydro distillation

Water or hydro distillation is one of the oldest and easiest methods being used for the

extraction of essential oils. In this method, the material is completely immersed in

water, which is boiled by applying heat using direct fire, steam jacket, closed steam

jacket, closed steam coil or open steam coil. One of the drawbacks of hydro

distillation is esterification due to the prolong action of hot water.

2.2.5.3 Solvent extraction

The dried cinnamon bark gets contacted with a solvent like ether, petroleum, hexane

or acetone and the soluble volatile organic compounds of the cinnamon bark dissolve

in the solvent. This is not considered the best method for extraction as the solvents

can leave a small amount of residue behind which could cause allergies and effect

the immune system.

2.2.5.4 Super critical CO2 extraction

This method can be introduced as a tool to overcome disadvantages of the traditional

essential oil extraction processes such and also can be used for applications where

high purity is required. CO2 is the most common super critical fluid (SCF). In the

process of cinnamon bark oil production, super critical CO2 at 300-600 bar are used.

This method gives a higher yield (1.4%) than conventional distillation yield (0.5-

0.8%). However this method is more costly, due to high capital investment and

operational costs.

2.3 Essential Oil Analysis

Aromatic plants are generally referred to as essential oil yielding plants and have

volatile, odoriferous oils in special cells, glands or ducts located in different parts of

a plant, such as the leaves, barks, roots, flowers and fruits and sometimes in just one

or two parts. The oils are usually present in very small amounts and comprise only a

tiny fraction of the entire plant material. The oils are produced during some

metabolic processes of the plant and are secreted or excreted as odoriferous by-

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products. The fragrant oils may not necessarily be present as such in the living plants

but may occur as odourless compounds called glycosides. When the plant tissues are

macerated, an enzyme reaction occurs, these causes the glycosides to undergo a

chemical change. This action in turn liberates the distinctive essential oil

(Vishwambhar, 2013).

Essential oil can be analyzed in both qualitatively and quantitatively. The

information given by such analyses are very useful in research to evaluate the

performance and in economy it is the factor which determines the price of the

commodity.

2.3.1 Methods of oil analysis

The easiest and quickest way of qualitative analysis is the sensory evaluation, such as

the viscosity, colour, clarity and odour. Sensory evaluation can also be used as the

first identification of oil adulteration. Testing of physical parameters such as specific

gravity, optical rotation and refractive index can be used to reveal any adulteration

with a foreign substance in an oil sample. Apart from these basic methods, with the

introduction of new technologies of instrumentation, gas liquid chromatography

(GLC) has come to play a big role as it can be used to detect relatively minor

compounds in essential oil which cannot be detected from the classical methods such

as titration. By combining infrared (IR) spectroscopy and mass spectroscopy (MS) to

GLC more positive identification of compounds can be obtained (Ravindran et al.,

2004). GC could detect the major volatile organic compounds, but it is difficult to

detect the minor volatile organic compounds of the extracts that are present at low

levels. There are also limitations associated with mass spectrometry, including an

inability to distinguish closely related isomers due to very similar mass spectra,

compounds to be investigated are not present in spectra library and the computer

incorrectly choosing a compound based on a similar mass (Cai et al., 2006).

Moreover, a singular analytic method gives little information, and thus, the analysis

for herbal medicines does not completely reflect the quality of herbal medicines (Liu

et al., 2010). GC–MS has been proven to be a powerful and suitable tool for the

determination of volatile compounds because of its high separation efficiency and

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sensitive detection (Kopka, 2006). However, the essential oils are complex systems

with varying compositions, and the peaks are often overlapping or embedded, even

when the chromatographic/spectral conditions are optimized (Wang et al., 2010). As

in other studies, the essential oils of cinnamon were analyzed using high performance

liquid chromatography (HPLC), gas chromatography (GC) and gas chromatography–

mass spectrometry (GC–MS) (Jayaprakasha et al., 2002; Wang et al., 2005; Ding et

al., 2011; Geng et al., 2011).

2.3.2 Volatile organic compounds of cinnamon oil

Cinnamon yields mainly leaf and bark oils, which are used in perfumery and

flavouring. The major component of leaf oil is eugenol, while that of bark oil is

cinnamaldehyde. Volatile organic compounds do occur in other parts, including root

bark, fruits, flowers, twigs and branches. The volatile oil content in cinnamon bark

varies from 0.4 to 2.8% and leaves from 0.24–3.0%, depending on the location and

method of distillation (Angmor et al., 1972; Wijesekera, 1978; Rao et al., 1988

Krishnamoorthy et al., 1996; Raina et al., 2001).

The chemical composition of the essential oils in cinnamon has been studied by

different researchers. Analysis of cinnamon bark and leaf oils has been done by high-

pressure liquid chromatography (HPLC) and most important distinguishing feature is

the cinnamaldehyde (55-75%) and eugenol(5-18%) content in cinnamon bark oil

(Ross, 1976). Similarly, Senanayake, (1978) reported that the oil from the stem bark

of a commercial sample contained 75% cinnamaldehdyde, 5% cinnamyl acetate,

3.3% caryophyllene, 2.4% linalool and 2.2% eugenol, while camphor (56%) was the

major component of root bark oil with cineole, cu-terpineol, α-pinene, and limonene

also of importance. The principal component of leaf oil, namely, eugenol, varies

from 65 to 92%. Cinnamaldehyde is the major component in all the cases and is the

character-impact component in cinnamon bark, followed by cinnamyl acetate,

eugenol and 2-methoxy-cinnamaldehyde (Archer, 1988). Another analysis of

cinnamon bark volatile oil claimed the presence of 13 volatile organic compounds

accounting for 100% of the total amount and (E)-cinnamaldehyde was found as the

major component along with δ-cadinene (0.9%) (Singh, et al., 2007). The volatile

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compounds of cinnamon barks extracted using hydro distillation from three species

and seven habitats, were detected and identified by GC–MS and indicated that the

main compound in the volatile oils of nine samples was trans-cinnamaldehyde

(66.28–81.97%) (Li, et al., 2013).

Krishnamoorthy et al., (1988) observed variation in the bark oil content in plants

with purple leaf flushes (1.84%) and those with green flushes (1.43%). Various

researches have been carries out to investigate the chemical composition of the oil

obtained from cinnamon leaf (Singh, et al., 2007), buds (Jayaprakasha, 2002) and

stem (Senanayake, et al., 1978). The volatile oil from the stem bark of Madagascan

origin was rich in eugenol (Medici et al., 1992). Krishnamoorthy et al., (1996)

reported 2.7–2.8% volatile oil was contained with 58-68% cinnamaldehyde content

in the bark and 75-78% eugenol in the leaves of the cinnamon varieties Navashree

and Nithyasree. Several chemotypes of C. zeylanicum have been reported, based on

the chemical composition of leaf oil. Guenther, (1953) and Rao et al., (1988)

reported two chemical races of C. zeylanicum from Bubhaneshwar, India, one rich in

eugenol (83.1-88.6%) and the other dominated by benzyl benzoate (63.6-66.0%).

Another chemotype with 85.7% linalool in leaf oil was reported by Jirovetz et al.,

(2001). Nath et al., (1996) recorded a chemotype of C. verum with 84.7% benzyl

benzoate in bark oil and 65.4% benzyl benzoate in leaf oil from the Brahmaputra

Valley, India. Two chemotypes of C. verum from Brazil were reported by Koketsu et

al., (1997); one rich in eugenol (94.14-95.09%) and the other predominated by

eugenol and safrole (with 55.08-58.66% eugenol and 29.57-39.52% safrole,

respectively). According to Variyar and Bandyopadhyay, (1989), eugenol type is the

most commonly occurring chemical race of C. verum. Higher oil content was

reported in cinnamon leaf from Hyderabad (4.7%) compared with that from

Bangalore (1.8%) (Mallavarapu et al., 1995). The two oils were of eugenol type and

differed with respect to the relative amounts of linalool, cinnamaldehyde, cinnamyl

alcohol, cinnamyl acetate and benzyl benzoate. The essential oil of the leaves of C.

zeylanicum from Cameroon contained eugenol (85.2%), (E)-cinnamaldehyde (4.9%),

linalool (2.8%) and b-caryophyllene (1.8%) (Jirovetz et al., 1998). The oils from the

leaves and bark of C. zeylanicum from Madagascar contained cinnamaldehyde and

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camphor as the major volatile organic compounds (Chalchat and Valade, 2000). The

leaf oil from Little Andaman Island contained 47 detectable constituents,

representing 99.96% of the oil. The main constituents were eugenol (76.60%),

linalool (8.5%), piperitone (3.31%), eugenyl acetate (2.74%) and cinnamyl acetate

(2.59%) (Raina et al., 2001). The leaves harvested in summer gave the highest oil

recovery (1.84%) and eugenol content (83%), whereas in the rainy season, the

concentration of esters, namely, eugenyl acetate and benzyl benzoate, were

comparatively higher (Kaul et al., 1996). Cinnamon leaves affected by leaf spot

disease yielded less oil (1.2%), but the eugenol content was unaffected (Kaul et al.,

1998). Rao et al., 2006 reported that the essential oil content (1.9–2.2%) and the

chemical composition of C. verum leaves were not affected by storage up to a period

of 15 months.

Kaul et al., (2003) analysed essential oil profiles of various parts of cinnamon. The

oil yields of different plant parts were: 0.40% in tender twigs; 0.36% in the pedicels

of buds and flowers; 0.04% in buds and flowers; 0.33% in the pedicels of fruits; and

0.32% in fruits. The tender twig oil was richer in α-phellandrene (3.4%), limonene

(1.6%) and (E)-cinnamaldehyde (4%). The volatile oils from pedicels were richer in

(E)-cinnamyl acetate (58.1–64.5%), β-caryophyllene (9.6–11.1%) and neryl acetate

(1.4–2.0%). Higher amounts of (Z)- cinnamyl acetate (6.1%), α-humulene (2.2%),δ-

cadinene (2.2%), humulene epoxide I (5%), α-muurolol (4.9%) and α-cadinol (2.4%)

were observed in the oil of buds and flowers. However, all the oils contained linalool

(3.6–27.4%), (E)-cinnamyl acetate (22.0–64.5%) and β-caryophyllene (6.9–11.1%)

as their major compounds.

Bernard et al., (1989) studied the composition of volatiles from C. zeylanicum bark

by two methods, namely, direct distillation and extraction using TTE (1,1,2-

trichloro- 1,2,2-trifluoroethane) followed by hydro distillation. Both methods were

comparable, yielding 0.98–1.1% volatile oil. However, compositional differences

were observed in both the oils. The TTE extract had a higher cinnamaldehyde

content (84.1%) compared with the direct hydro distilled oil (75%). α-Pinene, 1,8-

cineole and p-cymene, which were present in minor amounts in the hydro distilled

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oil, were absent in the TTE product. There was less linalool, β-caryophyllene and

cinnamyl acetate in the oil obtained by the TTE method compared with the direct

distillation method.

2.3.3 Effect of the drying on the volatile organic compounds of essential oil

Drying is commonly employed in preparing spices for market, as some spices can

contain up to 75-80% water, and water levels need to be lowered to less than 15%. In

the countryside, the household method of drying in the shade, or in well-ventilated

rooms is still in use today, but industrial-scale drying is carried out in convection

ovens. Drying of spices inhibits microorganism growth and forestalls certain

biochemical changes; but at the same time it can give rise to other alterations that

affect spice quality, such as changes in appearance and alterations in aroma caused

by losses in volatiles or the formation of new volatiles as a result of oxidation

reactions, esterification reactions, etc (Diaz-Maroto, et al.,2002c).

Changes taking place in the volatile compounds present in spices and other plants

have been studied by different workers who have shown that the changes depend on

several factors: primarily the drying method and the biological characteristics of the

plant concerned. Reductions in the total quantities of essential oils have been

reported, amounting to 36-45% in sweet basil, 23-33% in marjoram, and 6-17% in

oregano during drying at ambient temperature (Nykanen and Nykanen, 1987).

Conventionally, low drying temperatures between 30 °C and 50 °C are recommended

to protect sensitive active ingredients for drying of medicinal plants, but the

decelerated drying process causes a low capacity of drying installations (Muller and

Heindl, 2006).

Drying in a convection oven also produces losses in volatiles, with the losses varying

according to the drying temperature and drying time employed (Raghavan, et al.,

1994a; Venskutonis, 1997). Increases in the quantities of certain compounds

normally present in the spice (Baritaux, et al., 1992; Yousif, et al., 1999; Bartley &

Jacobs, 2000) or formation of new compounds have in some cases been observed

after drying, probably as a consequence of oxidation reactions, hydrolysis of

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glycosylated forms, or the release of substances following the rupture of cell walls

(Huopalahti, et al., 1985).

Accordingly, processing (grinding, drying, etc.) not only brings about a reduction in

overall spice aroma but may also result in qualitative changes by giving rise to a

secondary aroma in addition to the original aroma of the fresh plant.

Prematilake, et al., (1997) has studied the effect of the drying time of fillings on the

quality of cinnamon quills. High quality quills and the bark oils extracted from them

with more aroma and flavor constituents can be prepared by making the quills with

4-5 day dried fillings.

The effect of the drying methods: oven-drying at 45°C, air-drying at ambient

temperature, and freeze-drying on the volatile compounds was evaluated for Bay

Leaf (Laurus nobilis L.) (Diaz-Moroto, et al., 2002a); Spearmint (Mentha spicata L.)

(Diaz-Moroto, et al., 2002b); and parsley (Petroselinum crispum L.) (Diaz-Moroto, et

al., 2002c). Air drying at ambient temperature resulted in few losses in volatile

compounds compared with the fresh herb, whereas oven drying at 45 °C and freeze-

drying caused a decrease in the concentrations of the majority of the volatile organic

compounds.

Using freeze-drying as the drying treatment has been reported to result in changes

that are less pronounced, and the spice has been observed to retain features that are

closer to the characteristic appearance and aroma of the fresh plant (Raghavan, et al.,

1994a; Paakkonen, et al., 1989; Venskutonis, et al., 1996).

The effect of a particular drying method on the release or retention of volatile

compounds is not predictable and depends on the compound and the spice concerned.

Oven-drying and freeze-drying of dill herbs lead to decrease in most of the volatile

compounds compared with the levels in the fresh spice (Huopalahti, et al., 1985;

Raghavan, et al., 1994a). The same occurs in parsley (Diaz-Moroto, et al., 2002c). In

contrast, the effect of oven drying at 30 °C and freeze-drying on the volatile

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compounds in thyme and sage has been minor, whereas losses at 60 °C were 43% in

thyme and 31% in sage (Venskutonis, 1997).

Microwave-drying produced greater losses in volatile compounds than oven-drying

in rosemary, although it did preserve the spice’s characteristic green color

(Jaganmohan, et al., 1998). Likewise, freeze-drying preserves the characteristic

appearance of the fresh product (Yousif, et al., 2000), although causing substantial

losses to certain volatiles in the cases of parsley and bay leaf (Diaz-Moroto, et al.,

2002a; Diaz-Moroto, et al., 2002c), whereas shade-drying of spearmint leaves has

resulted in a product with a good green color and few losses of volatiles (Raghavan,

et al., 1994b).

On the other hand, certain compounds normally present have been observed to

increase in different spices after drying, for example, eugenol in bay leaf (Diaz-

Moroto, et al., 2002a), thymol in thyme (Venskutonis, 1997), and some

sesquiterpenes in different spices (Baritaux, et al., 1992; Raghavan, et al., 1994a;

Yousif, et al., 1999; Bartley & Jacobs, 2000; Jerkovic, et al., 2001).

The method used to extract and analyze the volatiles can also influence the results.

The traditional method of extracting essential oils from plants, steam distillation,

primarily collects the most volatile organic compounds, whereas solvent-based

extraction methods are capable of extracting substances spanning a broader range of

volatilities, depending on the solvent employed.

Simultaneous distillation extraction (SDE) has been widely used in analyzing the

volatiles of herbs and plants. Supercritical fluid extraction (SFE) offers an advantage

over SDE, in that the substances extracted can be altered by making minor variations

in the pressure and temperature conditions of the extraction fluid (Reverchon, 1997).

In owers of Roman chamomile (Chamaemelum nobile L. All. var. ora plena), it

was found that drying methods had no effect on the number of chemical components

of the essential oil, but had a signicant effect on the proportion of the various

components in sun-drying, shade-drying and oven-drying at 40 °C (Omidbaigi, et al.,

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2004). However, in Felicia muricata leaves, chemical composition in leaves were

affected by the drying method and total of 38,40,33 and 30 volatile organic

compounds has been identified in the oils of fresh, air dried, sun dried and oven dried

samples (Ashafa and Grierson, 2008). Drying at 45ºC was found as the best

condition based on the changes of essential oil and color during drying and storage

for tarragon (Artemisia dracunculusL.) (Hosseini, et al., 2011).

There were significant chemical alterations in the major volatile organic compounds

of the essential oils obtained from Helichrysumodoratissimum plant using different

methods of drying (Asekun, et al., 2007).

Studies conducted to investigate the effect of different temperatures in the oils of

sweet wormwood (Artemisia annuaL.) indicate that the drying temperature has a

significant effect on volatile organic compounds, as when the temperature was

increased, the monoterpenes content was gradually decreased and vice versa for

sesquiterpenes. (Khangholi and Rezaeinodehi, 2008).

2.4 Statistical Analysis of the Effect of the Drying Using SPSS

Statistics is a mathematical tool for quantitative analysis of data and it has been used

by different researchers for analyzing the data to find out the effect of the drying for

volatile compounds present in spices and other plants.

Powerful statistical software (Minitab, SAS, STAT, IBM SPSS Statistics, Stata,

STATISTICA and etc.) has been developed that allows for thorough calculations on

large data sets that would be impossible to perform manually. Some of the available

methods are complex and difficult to apply, while others can easily and successfully

be employed by researchers without a strong statistical background (Ho, 2006).

Ruse, et al., (2007) reported that the effect of pre-treatment methods (perforation,

halving and steam-blanching) and drying conditions on the composition of volatile

compounds in cranberries. A three-way ANOVA analysis using IBM SPSS 20.0 was

selected to investigate factor effects (volatile compound, cultivar and drying method)

and interactions among them.

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Li, et al., (2013) showed that the nine samples of cinnamon bark can be effectively

identified and evaluated using principal component analysis. Load factor analysis

revealed that the differences in the volatile compounds of the nine samples were

mainly reflected in the aldehyde, alcohol, alkane and eugenol contents.

Principal component analysis (PCA) and the Student-Newman-Keuls test (SPSS,

Program 2000) were used to assess the significance of the differences among the

various drying methods for Bay Leaf (Laurus nobilis L.) (Diaz-Moroto, et al.,

2002a); Spearmint (Mentha spicata L.) (Diaz-Moroto, et al., 2002b); and parsley

(Petroselinum crispum L.) (Diaz-Moroto, et al., 2002c). Oven drying at 45 °C and

air-drying at ambient temperature produced quite similar results and caused hardly

any loss in volatiles as compared to the fresh herb, whereas freezing and freeze-

drying brought about substantial losses.

The leaves of lemongrass (Cymbopogon citratus) were dried using three different

drying methods and statistical analysis was carried out using the Least Significant

Difference (LSD) test at 0.05%. Oven drying at 45 °C gave the highest essential oil

percentage (2.45%) compared to shade-drying (2.12%) and sun-drying methods

(2.10%) (Hanna, et al., 2007).

Mercer, 2012 investigated and compared the kinetics of mango drying using three

elevated temperatures in an Armfield Model UOP8 laboratory-scale tray dryer.

Analysis of variance (ANOVA) and Duncan test using SPSS 19.0.0 (IBM SPSS

Statistics, Chicago, Illinois, USA) was performed to determine the differences in

temperatures. Even though the curves at 44 °C and 50 °C were not statistically

different (p = 0.05), a significant difference (at p=0.05) was observed between the

curves at 50 °C and 60 °C.

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3 3 MATERIALS AND METHODOLOGY

After selecting a suitable cinnamon type, experimental setup was equipped for

carrying out the research. Fixed bed tunnel dryer was used for drying cinnamon at

different drying temperatures. Cinnamon bark oil was extracted by hydro distilling

the dried sample. Finally the composition analysis was carried out for each cinnamon

bark oil sample.

3.1 Materials & Equipments

Cinnamon chips were collected from a cinnamon plantation at Gonapinuwala area in

Galle district, southern province of Sri Lanka during the month of August. These

cinnamon chips were of the type "mas-katta".

Mettler PM4000 (0-4000 grams) electronic balance was used for weighing the

cinnamon chips (Figure 3.1a). Laboratory moisture balance (Citizen-MB 200X) was

used to determine the initial moisture content of samples (Figure 3.1b).

(a) (b)

Figure 3.1: (a) Weighing balance, (b) Moisture balance

Laboratory tunnel dryer fitted with an electrical heater was used to uniformly dry

cinnamon chips on a fixed bed (Figure 3.2) of the dimensions 30.5 x 30.5 x 5 cm3.

The dryer was consisted of a centrifugal blower which was used to blow air over an

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electrical heater (rating 0.9kW) to the base of the drying chamber. Hot air was blown

upwards through a vertical duct which was consisted with an air flow stabilization

unit. The drying chamber was fitted at the upper end of the duct. The inlet dry bulb

temperature was monitored by a thermostat and a relay was used to control the

heater. A thermometer was inserted at inlet to measure the incoming air temperature

to the drying chamber (Figure 3.3a) and air flow rate was measured at dryer outlet

using an anemometer (TECPEL 712) (Figure 3.3b).

Figure 3.2: Fixed bed dryer with component

(a) (b)

Inclined manometer Switch boxHeating unit

Centrifugal blower

Drying chamber

Thermometer

cinnamon chips

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Figure 3.3: (a) Thermocouple, (b) Anemometer

Inlet air temperature was controlled with an accuracy of ± 1 °C. A constant air flow

rate of 0.023 m3/s (this is the maximum air flow rate of the unit) was maintained

throughout the experiment. The oil samples were analysed using gas chromatography

mass spectrometer (Agilent, American 7890A/5975C GC-MS system) (Figure 3.4).

Figure 3.4: GC-MS-7890A gas chromatograph equipped with a 5975C plus mass

spectrometer (Agilent, American)

3.2 Drying of Cinnamon Chips

A bulk of 30 kg of cinnamon chips of the type “mas katta” was selected for the

experiments. Cinnamon chips were kept in sealed poly sack bags to avoid loss of

moisture. The sampling method indicated in Figure 3.5 was used to maintain the

uniformity between experiments. Cinnamon chips of weight 30 kg was divided into 5

lots containing 6 kg each for air drying at temperatures of ambient, 35 °C, 40 °C, 45

°C and 50 °C. Initial moisture content (M0) of cinnamon chips (w/w wet basis) was

measured using moisture balance for randomly selected 5 samples from each Lot and

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average initial moisture content was calculated. Four samples of 500 grams each was

randomly selected from Lot 1 for drying at ambient temperature. The first sample

was loaded to the drying chamber. The bed dimensions were 30.5 x 30.5 x 5 cm3.

The vanes were fully opened to give maximum air flow rate and the blower was

switched on. Temperature readings and the loss of weight of sample were recorded at

10 min time intervals. Drying and weighing were continued until the final moisture

content of 24% (w/w dry basis) was achieved for all of four samples.

Figure 3.5: Cinnamon chips sampling method

Lot 1 sample 1randomly selected

sample of 500g


sample of 500g


sample of 500g


sample of 500g

Dried, using air blown atambient temperature. Loss of

weight was recorded at 10 minintervals

Dried, using airblown atambient

temperature.


temperature.


temperature.

Drying of cinnamon chips was continued using air blown at ambient temperature untilthe final moisture content of 24%

Bulk ofcinnamonchips 30kg

Lot 16 kg

Lot 26 kg

Lot 36 kg

Lot 46 kg

Lot 56 kg

Initial moisture content(M0) was measured for

randomly selected 5samples of 10g each

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The final moisture content of 24 % was selected based on the average moisture

content of cinnamon chips available in the market. The moisture content (on dry

basis) at any instant was calculated using the equations given in section 4.1. Frequent

mixing of cinnamon chips was done to achieve uniform drying. Dried samples were

packed in poly sack bags and stored in a dry place before hydro distilled.

For temperatures above ambient, the loading of cinnamon chips was done after the

blowing air reached the required set temperature for drying. All the other

experimental procedures were carried out as similar to ambient temperature (Lot 1)

for air drying at temperatures of 35 °C (Lot 2), 40 °C (Lot 3), 45 °C (Lot 4) and 50

°C (Lot 5).

3.3 Extraction of Cinnamon Bark Oil

The volatile organic compounds of cinnamon bark were obtained by traditional

hydro-distillation (HD) method using cinnamon oil extraction apparatus as shown in

Figure 3.6. The four replicate samples dried at a particular temperature were mixed

together to achieve uniformity before the hydro distillation process.

Figure 3.6: Cinnamon oil extraction apparatus

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Four samples of 250 grams each were randomly selected. Each sample of dried

cinnamon bark was distilled using 850 ml of water for about 90 min. Cinnamon bark

oil was separated from water in the distillate using a separating funnel (Figure 3.7)

and the separated sample was stored in a dark place until the GC analysis was carried

out. As in the case of drying, four replicate experiments were performed for hydro

distillation of cinnamon chips dried at a particular temperature.

Figure 3.7: Cinnamon oil separation apparatus

3.4 Identification of Volatile Organic Compounds

The oil samples were analysed using GC-MS and a 5% phenyl / 95% dimethyl

polysiloxane capillary column (30 m × 0.5 mm i.d., film thickness 0.25μm) was used

for the separation. The injector temperature was 25 °C, and the oscillatory

temperature was 100 °C. A 2μl of extract was injected in split mode (split ratio of

1:100) to the column. The initial temperature was kept at 70 °C for 2 min, and the

temperature was gradually increased to 270 °C at a rate of 5 °C/min. Mass detector

conditions were as follows: FID mode; source temperature, 250 °C; scanning rate

100 scan/min; quadropole temperature, 150 °C.

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4 4 DATA ANAYSIS4.1 Calculation of Moisture Content

The moisture content (w/w wet basis) was calculated using the equation 4.1.

4.1

Where,

The wet basis moisture content was converted to dry basis using the equation 4.2.

4.2

Where,

The average initial moisture content was found to be 0.5844 (w/w wet basis) and

calculated dry basis moisture contents of cinnamon chips at different temperatures

are mentioned in Table 5.1.

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The rate of drying was calculated using the equation 4.3.

4.3

Where,

4.2 Gas Chromatography and Mass Spectrometer Analysis

The extracted cinnamon bark oil samples were analysed to identify the volatile

organic compounds by the method of Gas-Chromatography and Mass-Spectrometer

(GC-MS) analysis. Figure 4.1 depicts the chromatogram of the cinnamon bark oil

hydro distilled from cinnamon chips which were dried using air at 35 °C condition

(Trial 1). Gas chromatograms of cinnamon oil at different drying temperatures are

shown in Appendix A. The volatile organic compounds which were indicated as a

peak in gas chromatograms were identified by matching with the recorded mass

spectra from the National Institute of Standards and Technology (NIST08. LIB)

libraries data provided by the software of the GC-MS systems, whose spectra most

closely resemble with the submitted component spectrum. Li, et al., (2013) identified

the volatile organic compounds using the libraries of National Institute of Standards

and Technology (NIST05. LIB), provided by the software of the GC-MS systems.

The submitted spectrum is commonly originated from a GC/MS data file, where it

can be a single mass spectral scan or an average.

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Appendix B represents the comparison of the standard and mass spectra of different

volatile organic compounds in cinnamon bark oil obtained in the current study. Each

search produces a “hit list” of library spectra, which was ordered by similarity to the

target spectrum according to a computed “match factor”. Ideally, this quantity should

reflect the likelihood that the user and reference spectrum arose from the same

compound. Quantitative analyses of each essential oil component were carried out by

a peak area normalization measurement. Relative content percentage was calculated

as the area corresponding to each component with regards to the total area of the

chromatogram. Gas chromatogram data sheets at different drying temperatures are

represented in Appendix C. Table 5.2 summarizes the relative content (%) of volatile

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Retention time(min)

Volatile organic compounds incinnamon bark oil

3.115 p-xylene

3.409 styrene

5.257 Benzene,1,2,3-trimethyl

5.487 α-phellandrene

5.93 p-cymene

6.049 β-phellandrene

7.718 linalool

9.372 benzenepropanal

9.78 terpinen-4-ol

10.888 cinnamaldehyde

12.234 cinnamaldehyde-E

14.478 eugenol

16.098 caryophyllene

16.667 cinnamyl acetate

18.747 2-methoxy- cinnamaldehyde

23.987 benzyl benzoate

Figure 4.1: Chromatogram of cinnamon bark oil (35 °C temperature -Trial 1)

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organic compounds of cinnamon bark oil at five air drying temperatures (ambient, 35

°C, 40 °C, 45 °C and 50 °C).

4.3 Statistical Analysis

Statistics is a mathematical tool for quantitative analysis of data, and as such it serves

as the means by which we extract useful information from data. Statistical analyses

are a critical component of research.

One way - analysis of variance (ANOVA) test and principal component analysis

(PCA) test in IBM SPSS statistics 19 statistical software were used to assess the

significance of the differences among the samples dried at different air drying

temperatures.

4.3.1 One way ANOVA

Analysis of variance (ANOVA) is a statistical test for detecting differences in group

means when there is one parametric dependent variable and one or more independent

variables. The ANOVA procedure can be used correctly if the following conditions

are satisfied. The dependent variable should be of the type either interval data or ratio

data. Interval data type means, the differences of two scale of measured variable are

same. Ratio data type means, size of one scale of measured variable has half, twice or

three times than other scale. The populations should be approximately normally

distributed. The population variances should be equal (homogeneity of variances) and

the observations are all independent of one another. Post-Hoc multiple comparison

procedures (eg: Student-Newman-Keuls (SNK) and etc.) are used to determine which

means are significantly different, if there are more than two treatments (Gaur & Gaur,

2009).

4.3.1.1 Performing the ANOVA with SPSS

One way ANOVA was used to compare the group means of five dying temperatures.

By referring Table 5.2, temperature intervals (ambient, 35 °C, 40 °C, 45 °C and 50

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°C) and 16 volatile organic compounds of cinnamon bark oil were considered as

independent variable and dependent variables respectively. Null Hypothesis (H0:

μambient= μ35= μ40= μ45= μ50, μ represents mean temperature), alternative hypothesis

(H1: not H0) and α level (α = 0.05) were defined.

An assessment of the normality and homogeneity of data was a prerequisite for one

way ANOVA test. The significance value (Sig.) in Levene’s F test, greater than 0.05

means that homogeneity of variances (variances of each independent group are

similar) can be achieved. If the Levene's F statistic is less than 0.05 (significant), the

variances of each independent group are not similar and the significant differences

between groups are determined using Welch test instead of ANOVA table. If the

significance value is less than 0.05, then there are statistically significant differences

between groups. There are two main methods of assessing the normality; graphically

and numerically. Shapiro-Wilk test was applied for verifying the normality of data set.

It is more appropriate for small sample sizes (< 50 samples) but can also handle

sample sizes as large as 2000. If the Significance value of the Shapiro-Wilk test is

greater than 0.05 then the data is normal and if not, then the data significantly deviate

from a normal distribution. In order to determine normality graphically, output of a

normal Q-Q (quantile-quantile) plot can be used. This plot compares each point in

data set to where those points would be in an idealized (calculate expected normal

values), perfectly normal distribution with the same mean and standard deviation as

data set. If the data are normally distributed then the data points will be close to the

diagonal line. If the data points stray from the line in an obvious non-linear fashion

then the data are not normally distributed (Ho, 2006).

One way ANOVA in IBM SPSS statistics 19 was applied for analyzing the effect of

drying temperatures (ambient, 35 °C, 40 °C, 45 °C and 50 °C) on these 16 volatile

organic compounds of cinnamon bark oil separately (Refer Appendix D-Figure D.1 &

D.2). Mean, standard deviation and average standard error were calculated for five

drying temperatures of volatile organic compounds of cinnamon bark oil, using one

way ANOVA. Range of minimum and maximum values were obtained to provide an

overall indication of the level of variations manifested by the drying temperatures.

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Verification of homogeneity and normality for data set was achieved. The flow chart

for applying ANOVA using SPSS software is given in Figure 4.2.

Figure 4.2: Flow chart of ANOVA procedure in SPSS software

Relative content % of cinnamonbark oil components

at different drying temperatures

Define null hypothesis,alternative hypothesis & α level

Identify independent & dependentvariables

Do ANOVA tocheck significance of

group means

Do Welch test tocheck significance of

group means

Yes

Do Levene’s Ftest to checkhomogeneity

Do Shapiro-Wilktest to check

normality

Yes NoIsSig > 0.05

Yes

IsSig > 0.05

IsSig < 0.05

Yes

IsSig < 0.05

Do ANOVA with SNK testto compare means

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In ANOVA table, F-ratio is MST/MSE and Sig. is the significance level for the F-

ratio. If the significance value less than 0.0005 means that F-ratio is highly significant.

In SPSS software, this significance value is mentioned to three digits as 0.000 and it is

not actually zero. The mean square for between groups gives the mean square of each

source of variance, is often called “Mean Square Treatment”, or MST. The mean

square for within groups is often called “Mean Square Error”, or MSE. Each mean

square is the relevant sum of squares divided by its degrees of freedom (df).

Student-Newman-Keuls (SNK) test was used to compare means of drying

temperatures (ambient, 35 °C, 40 °C, 45 °C and 50 °C). The means of temperature

groups were divided into homogeneous subsets that were statistically significantly

different from each other. If two groups appear in the same column, then those groups

are not significantly different.

The coefficients of variation (RSD or %RSD) for these five drying temperatures were

determined by the ratio of standard deviation to the mean.

4.3.2 Principal component analysis (PCA)

The central idea of principal component analysis (PCA) is to reduce the

dimensionality of a data set consisting of a large number of interrelated variables,

while retaining as much as possible of the variation present in the data set. The goals

of PCA are to (a) extract the most important information from the data table, (b)

compress the size of the data set by keeping only this important information, (c)

simplify the description of the data set, and (d) analyze the structure of the

observations and the variables. In order to achieve these goals, PCA computes new

variables called principal components which are obtained as linear combinations of

the original variables. The assumptions underlying PCA can be classified as statistical

(normality and linearity) and conceptual (homogeneity) (Jolliffe, 2002).

The complete set of data in Table 5.2 was subjected to principal component analysis

(PCA) using the varimax rotation method (Refer Appendix D- Figure D.3). This

analysis was done for identifying the interrelated variables. Correlations between

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http://en.wikipedia.org/wiki/Coefficient_of_variation



37

volatile organic compounds of cinnamon bark oil & principal components (PCs) and

explained variance % & cumulative variance % of principal components were

calculated. Explained variance % of principal components was the percentage

variance of each and every PC divided by total variance. For a good principal

component solution, a particular volatile organic compound should load high

correlation value on one principal component and low correlation values on all other

principal components in the rotated component matrix. In case if a volatile organic

compound has high correlation on more than one principal component, it may be

wanted to drop from the analyses. Correlation value > 0.6 was considered as relevant

for that principal component and the value may be positively or negatively signed.

The Principal component plots were plotted using principal component scores for four

replicates of each drying temperatures.

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5 5 RESULTS AND DISCUSSION5.1 Drying characteristics of Cinnamon chips

The results of the variation of moisture content of cinnamon chips dried at different

temperatures are summarized in Table 5.1.

Table 5.1: Moisture content on dry basis and drying time for different drying

temperatures

Moisture content on dry basis (kgH2O/kg dry solid)

Drying Temperature (°C) 30±2 35±1 40±1 45±1 50±1

Time (minutes)0.000 1.406 1.406 1.406 1.406 1.406

10 1.344 1.216 - - -

15 - - 0.917 0.831 0.831

20 1.227 1.093 0.848 0.756 -

30 1.122 0.981 0.710 0.605 0.568

40 1.017 0.869 0.631 0.501 -

45 - - - - 0.367

50 0.917 0.793 0.552 0.404 -

55 - - - - 0.246

60 0.817 0.717 0.473 0.311 -

70 0.766 0.649 0.412 0.221 -

80 0.717 0.581 0.356 - -

90 0.664 0.513 0.29 - -

100 0.612 0.462 0.245 - -

110 0.555 0.414 - - -

120 0.502 0.367 - - -

130 0.455 0.318 - - -

140 0.432 0.268 - - -

150 0.408 0.234 - - -

160 0.384 - - - -

170 0.361 - - - -

180 0.337 - - - -

190 0.313 - - - -

200 0.288 - - - -

210 0.266 - - - -

220 0.248 - - - -

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Cinnamon chips achieved the required final moisture content of 24% (w/w dry basis)

within 220, 147, 100, 68 and 55 minutes for the air drying temperatures of ambient, 35

°C, 40 °C, 45 °C and 50 °C respectively. Moisture content on dry basis against the

drying time and drying rate against moisture content on dry basis for different drying

temperatures were plotted using MATLAB R2007b (Appendix E) and it is illustrated

in Figure 5.1 and Figure 5.2 respectively.

0 5 0 1 0 0 1 5 0 2 0 00 .2

0 .4

0 .6

0 .8

1

1 .2

1 .4

1 .6

tim e (m inute s)

moi

stur

e co

nten

t-dry

bas

is (k

gH2O

/Kg

dry

solid

)

Am bie nt te m perature3 5 °C4 0 °C4 5 °C5 0 °C

Figure 5.1: Variation of moisture content with time for different air drying

temperatures

0 .2 0 .4 0 .6 0 .8 1 1 .2 1 .40

0 .5

1

1 .5

2

2 .5

3

m o i s tur e c o n te n t -d ry bas is (k gH 2 O /K g dr y s o l id )

dryi

ng ra

te (k

gH2O

/m2.

hr)

Am bie nt3 5 ° C4 0 ° C4 5 ° C5 0 ° C

Figure 5.2: Variation of drying rate with moisture content for different air drying

temperatures

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The result, clearly indicates a falling rate drying period, which is corresponded to

internal migration of moisture from inner layers to the surface. The reduction in

drying rate may due to the shrinkage of the cell structure and the reduction in water

concentration of cinnamon chips which result in a lower diffusion coefficient.

5.2 Gas Chromatography Analysis

The results of gas chromatography analysis are given in this section and it describes

how the volatile organic compounds in cinnamon bark oil behaves with respect to five

air drying temperatures (ambient, 35 °C, 40 °C, 45 °C and 50 °C). Relative content %

for 16 identified volatile organic compounds of cinnamon bark oil at different drying

temperatures are summarized in Table 5.2.

Quantitatively, cinnamaldehyde-E was the most abundant aromatic compound in

cinnamon bark oil, followed by cinnamyl acetate, linalool and eugenol in all the

samples. Similar results were obtained by other workers using steam distillation of

cinnamon stem bark of commercial samples (Senanayake, et al., 1978) and hydro

distillation of air dried cinnamon stem bark samples (Paranagama, et al., 2001) in Sri

Lanka.

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Table 5.2: Gas chromatography analysis for cinnamon oil dried at different temperatures

No Volatile organicCompounds

Relative content % (in different drying temperature)

Temperature (°C) Ambient 35 40 45 50

No of Trials 1 2 3 4 1 2 3 4 1 2 3 4 1 2 3 4 1 2 3 4

1 1,4-dimethyl benzene (p-xylene) 0.972 0.957 0.948 0.927 0.827 0.897 0.871 0.886 0.795 0.813 0.848 0.823 0.871 0.903 0.859 0.894 0.656 0.679 0.671 0.652

2 styrene 0.1 0.109 0.099 0.16 0.17 0.165 0.182 0.199 0.138 0.142 0.136 0.147 0.205 0.198 0.189 0.225 0.137 0.167 0.158 0.146

3 benzene,1,2,3-trimethyl 0.202 0.184 0.172 0.218 0.132 0.147 0.168 0.175 0.204 0.21 0.215 0.208 0.215 0.195 0.204 0.174 0.275 0.223 0.204 0.249

4 α-phellandrene 0.662 0.736 0.747 0.877 0.891 0.837 0.976 1.063 0.492 0.498 0.504 0.523 0.254 0.265 0.282 0.257 0.146 0.184 0.183 0.135

5 benzene,1-methyl-4-(1-methylethyl)(p-cymene) 1.463 1.473 1.555 1.474 1.807 1.782 1.797 1.769 0.751 0.728 0.743 0.731 0.58 0.562 0.619 0.611 0.533 0.507 0.527 0.541

6 β-phellandrene 1.876 1.522 1.717 1.539 2.681 2.393 2.389 2.748 1.255 1.269 1.243 1.214 0.977 0.918 0.994 0.99 0.519 0.512 0.607 0.543

7 1,6-octadiene-3-ol,3,7-dimethyl (linalool) 4.23 4.894 4.301 4.649 5.082 5.25 5.213 5.15 4.141 4.139 4.161 4.155 4.657 4.511 4.345 4.878 3.785 3.701 3.713 3.588

8 benzenepropanal 0.332 0.326 0.32 0.358 0.441 0.459 0.482 0.485 0.46 0.475 0.473 0.456 0.426 0.418 0.491 0.45 0.399 0.343 0.375 0.371

93-cyclohexene-1-ol,4-methyl-1-(1-methylethyl)(terpinen-4-ol)

0.463 0.477 0.496 0.533 0.421 0.473 0.471 0.481 0.425 0.459 0.438 0.442 0.459 0.476 0.499 0.461 0.421 0.368 0.379 0.397

10 2-propenal,3-phenyl(cinnamaldehyde) 0.688 0.69 0.617 0.671 0.542 0.569 0.585 0.547 0.487 0.494 0.52 0.506 0.627 0.655 0.612 0.611 0.527 0.536 0.558 0.507

11 cinnamaldehyde-E 63.352 63.977 63.762 63.91 66.585 67.287 67.374 67.437 73.122 73.34 73.302 73.581 76.37 76.194 76.226 76.322 78.611 78.42 78.896 78.648

12 eugenol 4.216 4.546 4.477 4.169 3.807 3.688 3.699 3.635 3.349 3.33 3.334 3.325 3.42 3.444 3.599 3.572 2.221 2.168 2.291 2.271

13 caryophyllene 1.715 1.618 1.681 1.701 1.394 1.391 1.377 1.373 0.998 1.079 1.125 0.995 0.767 0.768 0.756 0.743 0.648 0.639 0.628 0.657

14 2-propen-1-ol 3-phenylacetate (cinnamyl acetate) 14.199 14.025 14.656 14.49 10.371 10.45 10.223 9.952 8.318 7.913 8.532 8.263 5.738 6.016 5.748 6.044 8.206 8.145 7.976 7.93

152-propenal,3-(2-methoxyphenyl) (2-methoxy-cinnamaldehyde)

0.914 0.929 0.896 0.951 0.261 0.291 0.283 0.301 0.218 0.212 0.225 0.208 0.269 0.262 0.275 0.283 0.239 0.267 0.243 0.235

16 benzyl Benzoate 2.273 2.138 2.028 2.152 1.047 1.076 0.813 0.989 0.773 0.766 0.75 0.743 0.686 0.657 0.659 0.668 0.743 0.737 0.724 0.728

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5.3 Statistical Analysis

5.3.1 Mean comparison by ANOVA

5.3.1.1 Verification for the validity of assumption

One of the assumptions of the one-way ANOVA is that the variances between the

independent groups are similar (homogeneity of variances). Table 5.3 indicates the

result of Levene's test of homogeneity of variance for cinnamaldehyde-E among

different temperature groups.

Table 5.3: Levene's test of homogeneity of variances for cinnamaldehyde-E

Component Significance

cinnamaldehyde-E 0.251

The significance value, greater than 0.05 means that homogeneity of variances can

be achieved. For cinnamaldehyde-E, Levene's F Statistic has a significance value of

0.251. Therefore, the assumption of homogeneity of variance (similar variance) is

met for cinnamaldehyde-E. By referring Appendix F.1 significance values of other

volatile organic compounds of cinnamon bark oil except β-phellandrene, linalool,

eugenol and caryophyllene are greater than 0.05 and their group variances are equal.

Welch test was performed to examine the statistical significance of these four

components (β-phellandrene, linalool, eugenol and caryophyllene) and the results are

given in Table 5.4. Results indicate that the significance values are less than 0.05 and

hence the group means are statistically significant.

Table 5.4: Welch test of equality of means

Component Significance

β-phellandrene 0.000

linalool 0.000

eugenol 0.000

caryophyllene 0.000

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The assumption of normality in one-way ANOVA is used to determine whether a

data set is well-modelled by a normal distribution or not. Table 5.5 represents the

results of Shapiro-Wilk test (verifying the normality) for cinnamaldehyde-E at five

air drying temperatures (ambient, 35 °C, 40 °C, 45 °C and 50 °C). The significance

values for these temperature groups are greater than 0.05 and hence data set of

cinnamaldehyde-E are normally distributed. Test of normality for other 15 volatile

organic compounds of cinnamon bark oil has mentioned in Appendix F.2 and

normality condition was achieved.

Table 5.5: Shapiro-Wilk tests of normality for cinnamaldehyde-E

Temperature (°C) Significance

Ambient 0.318

35 0.056

40 0.827

45 0.594

50 0.828

In Figure 5.3 the normal Q-Q plot of cinnamaldehyde-E at ambient temperature

indicates that the data points are close to the diagonal line. This is a clear evidence

that the data is normally distributed.

Figure 5.3: Normal Q-Q plot of cinnamaldehyde-E at ambient temperature

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5.3.1.2 One way ANOVA descriptives

The results of descriptive statistics and the ANOVA analysis of cinnamaldehyde-E

for the samples dried at different temperatures are given in Table 5.6 and Table 5.7

respectively.

Table 5.6: Descriptive table of cinnamaldehyde-E at different temperatures

Temperature

°CMean

Std.

Deviation

Std.

Error

95% Confidence

Interval for MeanMinimum Maximum

Lower

Bound

Upper

Bound

Ambient 63.75025 0.280284 0.140142 63.30426 64.19624 63.352 63.977

35 67.17075 .395313 .197656 66.54172 67.79978 66.585 67.437

40 73.33625 .188850 .094425 73.03575 73.63675 73.122 73.581

45 76.27800 .081976 .040988 76.14756 76.40844 76.194 76.370

50 78.64375 .195606 .097803 78.33250 78.95500 78.420 78.896

Total 71.83580 5.725439 1.280247 69.15621 74.51539 63.352 78.896

The F-value is 2464.07 and the corresponding p-value is given as <0.000. Therefore,

the null hypothesis (H0) can be safely rejected with the conclusion that the mean

temperature of cinnamaldehyde-E is not the same among the five drying

temperatures (ambient, 35 °C, 40 °C, 45 °C and 50 °C). Similar analysis was carried

out for all the other volatile compounds and the results are summarized in Appendix

F.3 and Appendix F.4 respectively.

Table 5.7: ANOVA table of cinnamaldehyde-E

Sum of

Squaresdf

Mean

SquareF Sig.

Between Groups 621.886 4 155.471 2464.070 0.000

Within Groups 0.946 15 0.063

Total 622.832 19

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The results of all the volatile organic compounds of cinnamon bark oil under

investigation clearly indicate that null hypothesis (H0) can be safely rejected.

5.3.1.3 Mean comparison using Student-Newman-Keuls (SNK) test

Table 5.8 is the mean comparison table which contains the results of Student-

Newman-Keuls (SNK) test for cinnamaldehyde-E. This method, gives an idea of

which groups differ from each other.

Table 5.8: Mean comparisons of cinnamaldehyde-E

Temperature NSubset for alpha = 0.05

1 2 3 4 5

Ambient 4 63.75025

35 4 67.17075

40 4 73.33625

45 4 76.27800

50 4 78.64375

Sig. 1.000 1.000 1.000 1.000 1.000

The first column contains the list of temperature groups in order from lowest to

highest mean. The second column of the table identifies the number of replicate

experiments in each and every temperature group. The remaining columns identify

the five homogeneous subsets of temperature groups that are statistically

significantly different from each other. The results of Student-Newman-Keuls (SNK)

test for all the other volatile organic compounds are given in Appendix F.5. The

homogeneous subsets which are formed including more than one temperature groups

indicate that mean of such temperature groups are not differed significantly at the

α=0.05 significance level.

The peak area of volatile organic compounds in gas chromatogram was chosen as the

analytical signal for the relative content, and the identified volatile organic

compounds are given in Table 5.9 with mean and relative standard deviation (RSD)

values based on quadruplicated experiments carried out to find the compositions

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relevant to different air drying temperatures (ambient, 35 °C, 40 °C, 45 °C and 50

°C). Table 5.9 also summarizes the results of the Student-Newman-Keuls test for

comparison of mean values by using letters a, b, c, d and e.

Table 5.9: Concentration of volatile compounds (relative content %) in hydro

distilled cinnamon bark

aDifferent letters (a,b,c,d,e) in the same row indicate statistical difference at the α=0.05 level according to the Student-Newman-Keuls test.

The RSD values for most of the volatile organic compounds were found to be less

than 10% for 4 replicated experiments. This result indicates that the method of

drying and hydro-distillation carried out in the present study were reasonably

uniform. On the other hand, cinnamon chips used in the present study were from the

same batch and hence the variations due to pre-processing (method of removal from

stems), type of cinnamon chips (mas katta, wal katta etc.) and regional variations

(due to acclimatization) were minimised.

Compound ambienttemperature

35°C 40°C 45°C 50°C

mean(n=4)

RSD(%)

mean(n=4)

RSD(%)

mean(n=4)

RSD(%)

mean(n=4)

RSD(%)

mean(n=4)

RSD(%)

p-xylene 0.95d 1.98 0.87c 3.53 0.82b 2.70 0.88c 2.30 0.66a 1.91styrene 0.12a 3.33 0.18c 8.45 0.14ab 3.45 0.20c 7.49 0.15b 8.68Benzene,1,2,3-trimethyl 0.19b 10.41 0.16a 12.65 0.21bc 2.19 0.20b 8.82 0.24c 13.01

α-phellandrene 0.76d 2.60 0.94e 10.52 0.50c 2.66 0.26b 4.75 0.16a 15.58p-cymene 1.49d 0.49 1.79e 0.93 0.74c 1.45 0.59b 4.49 0.53a 2.75β-phellandrene 1.66d 3.45 2.55e 7.39 1.25c 1.88 0.97b 3.64 0.55a 7.93linalool 4.52c 11.70 5.17d 1.43 4.15b 0.26 4.60c 4.92 3.70a 2.20benzenepropanal 0.33a 15.58 0.47c 4.44 0.47c 2.02 0.45c 7.35 0.37b 6.17terpinen-4-ol 0.49c 2.75 0.46bc 5.92 0.44b 3.18 0.47bc 3.90 0.39a 5.92cinnamaldehyde 0.67d 7.93 0.56b 3.56 0.50a 2.89 0.63c 3.28 0.53ab 3.98cinnamaldehyde-E 63.75a 2.20 67.17b 0.59 73.34c 0.26 76.28d 0.11 78.64e 0.25eugenol 4.35e 6.17 3.71d 1.95 3.33b 0.31 3.51c 2.56 2.24a 2.46caryophyllene 1.68e 5.92 1.38d 0.74 1.05c 6.08 0.76b 1.54 0.64a 1.93cinnamyl acetate 14.34d 3.98 10.25c 2.14 8.26b 3.11 5.89a 2.82 8.06b 1.642-methoxy-cinnamaldehyde 0.92d 0.25 0.28c 5.99 0.22a 3.43 0.27c 3.28 0.25b 5.84

benzyl benzoate 2.15c 2.46 0.98b 12.01 0.76a 1.83 0.67a 1.98 0.73a 1.17

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Increase in air drying temperature above 35 °C resulted in the reduction of quality

and yield of cinnamon bark oil (Chandra et al., 2011). Since essential oils have

highly volatile aromatic compounds, they may escape during the drying operation.

Increasing the temperature can damage the cell membranes of cinnamon. Rupturing

of cell walls and tissues where cinnamon oil is accumulated could be the main reason

for the reduction in oil yield and concentration of most of the volatile organic

compounds listed in Table 5.9.

The results of Student-Newman-Keuls test indicate significant difference at α =0.05

level (as marked with letters a,b,c,d and e) among the composition of cinnamon bark

oils which were extracted from cinnamon chips dried at different temperatures. Air

drying at high temperatures resulted in substantial losses in concentrations of

monoterpenes (α-phellandrene, β-phellandrene and p-cymene), cinnamaldehyde and

cinnamaldehyde derivatives such as cinnamyl acetate, and 2-methoxy-

cinnamaldehyde. Increase in air drying temperature also resulted in substantial losses

in certain oxygenated terpenes (linalool, terpinen-4-ol and eugenol) and

sesquiterpene (caryophyllene). The only component to have an increase in

concentration with the increase in air drying temperature was found to be

cinnamaldehyde-E which is also a highly volatile component. However it represents

a significantly higher concentration (about 60%) than the other volatile organic

compounds in cinnamon bark oil and it may probably have high affinity to the bark

resulting in high internal mass transfer resistance during air drying.

5.3.2 Principal component analysis (PCA)

Principal components analysis (PCA) was carried out on the relative percentages of

16 volatile organic compounds of cinnamon bark oil to compare the possible

differences among different air drying temperatures (ambient, 35 °C, 40 °C, 45 °C

and 50 °C). The results are presented in Table 5.10, Figure 5.4 and Figure 5.5. Since

PCA looks for groups of correlated variables along which the variance is maximized,

each principal component (PC) is interpreted as a group of correlated variables. The

correlated volatile organic compounds which are important to attribute a meaning to

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each component are highlighted in Table 5.10 and are displayed in Figure 5.4 and

Figure 5.5 at the edges of the respective PC axes.

Table 5.10: Correlations between volatile organic compounds and principal

components (PC)

Compound PC1 PC2 PC3

β-phellandrene 0.978 0.019 0.113

α-phellandrene 0.941 0.206 0.169

p-cymene 0.906 0.292 0.190

Benzene,1,2,3-trimethyl -0.789 0.186 -0.234

linalool 0.775 -0.308 0.469

cinnamaldehyde-E -0.770 -0.511 -0.377

caryophyllene 0.741 0.556 0.350

styrene -0.030 -0.881 0.205

cinnamyl acetate 0.490 0.832 0.220

benzenepropanal 0.332 -0.825 -0.168

benzyl benzoate 0.296 0.821 0.474

2-methoxy- cinnamaldehyde 0.159 0.790 0.580

cinnamaldehyde -0.001 0.282 0.899

terpinen-4-ol 0.387 0.019 0.795

p-xylene 0.517 0.109 0.795

eugenol 0.606 0.249 0.694

Correlations presented in bold are important for the attribution of ameaning to components

The explained variance % and the cumulative variance % of principal components

PC1, PC2 and PC3 are given in Table 5.11. The results suggest that the components

in PC1 have the highest contribution to the variance with an explained variance

percentage of 39.2% while volatile organic compounds in PC2 and PC3 having

explained variance percentage of 27.7% and 24.1% respectively. The volatile organic

compounds selected in the principal components attribute a variance contribution

ratio of 91% and only 9% of the information is lost. This indicates that the three

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principal components express 91% of the all information. Hence, the three principal

components can reflect the vast majority of cinnamon oil composition. All of the

samples in the space of the principal components had relatively independent

positions and were effectively distinguished.

Table 5.11: Correlation coefficient values for the volatile organic compounds against

principal component 1 ,2 and 3

PC volatile compound loading%

explainedvariance

%cumulative

variance1 β-phellandrene 0.978 39.227 39.227α-phellandrene 0.941p-cymene 0.906benzene,1,2,3-trimethyl -0.789linalool 0.775cinnamaldehyde-E -0.770caryophyllene 0.741

2 styrene -0.881 27.691 66.918cinnamyl acetate 0.832benzenepropanal -0.825benzyl benzoate 0.8212-methoxycinnamaldehyde 0.790

3 cinnamaldehyde 0.899 24.070 90.988terpinen-4-ol 0.795p-xylene 0.795eugenol 0.694

Figure 5.4 and Figure 5.5 depict the planes of principal components 1 vs 2 and 1 vs 3

respectively. PC1 is mainly separating the samples of cinnamon chips which were

dried using hot air at 35 °C (loaded on the positive, right side of PC1) and 50 °C

(loaded on the negative, left side of PC1). Hot air at 35 °C is characterized by high

amounts of monoterpenes (α-phellandrene, β-phellandrene and p-cymene),

oxygenated terpene (linalool) and sesquirtepene (caryophyllene) and 50 °C is

characterized by high amounts of benzene,1,2,3-trimethyl and cinnamaldehyde-E .

PC2 is mainly separating the ambient air temperature (displaced towards the positive,

upper side of PC2), and hot air at 45 °C (displaced towards the negative, lower side

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of PC2). Results suggest that ambient air temperature having higher amounts of

cinnamyl acetate, benzyl benzoate and 2-methoxy-cinnamaldehyde, and hot air at 45

°C having higher amounts of styrene and benzenepropanal.


air dried at 35 °C (*), air dried at 40 °C (Í), air dried at 45 °C (Æ), air dried at 50

°C (∆)

PC3 separates the ambient air and hot air at 45 °C temperatures (loaded on the

positive, upper side of PC3) from hot air at 40 °C (loaded on the negative, lower side

of PC3) indicating higher amounts of cinnamaldehyde, terpinen-4-ol, p-xylene and

eugenol in 45 °C and ambient and lower amounts of those volatile organic

compounds in 40 °C.

β-phellandreneα-phellandrenep-cymenelinaloolcaryophyllene

benzene,1,2,3-trimethylcinnamaldehyde-E

cinnamyl acetatebenzyl benzoate2-methoxy-cinnamaldehyde

styrenebenzenepropanal

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air dried at 35 °C (*), air dried at 40 °C (Í), air dried at 45 °C (Æ), air dried at 50

°C (∆)

cinnamaldehydeterpinen-4-olp-xylene eugenol

β-phellandreneα-phellandrenep-cymenelinaloolcaryophyllene

benzene,1,2,3-trimethylcinnamaldehyde-E

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6 6 CONCLUSIONS AND RECOMMENDATIONS

The use of GC-MS to analyze the volatile oil compounds of cinnamon chips can

effectively identify the 16 volatile organic compounds. Quantitatively,

cinnamaldehyde-E was the most abundant aromatic compound in cinnamon bark oil

extracted from chips, followed by cinnamyl acetate, linalool and eugenol in all the

samples. Statistical analysis using Student-Newman-Keuls (SNK) test and principal

component analysis (PCA) reveals the effect of air drying temperatures for varying

the chemical composition of cinnamon bark.

Effect of drying cinnamon chips at high temperatures on the composition of

cinnamon bark oil was found to be significant (at a=0.05). Substantial reduction in

concentrations of monoterpenes, oxygenated terpenes and sesquiterpenes was

observed with the increase in air drying temperature. However the concentration of

cinnamaldehyde-E has increased significantly from 63.75% for drying at ambient

tempearture to 78.64% for drying at 50 °C.

The results obtained in the study of principal component analysis can provide a

comprehensive evaluation of the air drying temperature on cinnamon quality. The

highest amounts of monoterpenes, oxygenated terpenes, sesquirtepene and

cinnamaldehyde and its derivatives were observed in the composition of bark oil

extracted from cinnamon chips which was died using ambient air. Because drying at

ambient temperature takes longer and the drying conditions are difficult to control,

air drying at 35 °C would seem to be more advisable, in that this drying treatment is

fast, simple, and easy to control.

In a previous study, the oil yield was found to be significantly reduced due to hot air

drying, specifically above 35 °C (Chandra et al., 2011). Therefore even if high

percentage of cinnamaldehyde-E is preferred in cinnamon bark oil, increase of

drying temperature may not be the best option due to reduction in oil yield. Results

of statistical analysis confirmed the selection of 35 °C as the maximum hot air

temperature for drying cinnamon chips without affecting the quality of bark oil.

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GC-MS and statistical analysis can be used to carry out the studies of determining

the quality of cinnamon bark oil & cinnamon leaf oil according to the maturity level

of cinnamon tree, variations of type of katta, and climate & region variations of

cinnamon cultivating.

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61

APPENDICES

Appendix A: Gas chromatograms of hydro distilled cinnamon oil at different

drying temperatures

(a) (b)

(c) (d)

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Figure A.1: Air drying at ambient temperature (a) Trial 1, (b) Trial 2, (c) Trial 3 and

(d) Trial 4

(a) (b)

(c) (d)

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Figure A.2: Air drying at 35 °C temperature (a) Trial 1, (b) Trial 2, (c) Trial 3 and (d)

Trial 4

(a) (b)

(c) (d)

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Trial 4

(a) (b)

(c) (d)

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Trial 4

(a) (b)

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(c) (d)


Trial 4

Appendix B: Standard & obtained mass spectra of different volatile organic

compounds of cinnamon bark oil

Source: National Institute of Standards and Technology (NIST08. LIB)

(a) (b)

(c) (d)

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Figure B.1: Mass spectra for (a) 1, 4-dimethyl benzene (p-xylene), (b) styrene, (c)

benzene, 1, 2, 3-trimethyl and (d) α-phellandrene

(a) (b)

(c) (d)

Figure B.2: Mass spectra for (a) benzene,1-methyl-4-(1-methylethyl) (p-cymene), (b)

β-phellandrene, (c) 1,6-octadiene-3-ol,3,7-dimethyl-(linalool) and (d)

benzenepropanal

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(a) (b)

(c) (d)

Figure B.3: Mass spectra for (a) 3-cyclohexene-1-ol,4-methyl-1-(1-methylethyl)

(terpinen -4-ol), (b) 2-propenal,3-phenyl (cinnamldehyde), (c) cinnamaldehyde-E

and (d) eugenol

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(a) (b)

(c) (d)

Figure B.4: Mass spectra for (a) caryophyllene, (b) 2-propen-1-ol 3-phenyl acetate

(cinnamyl acetate), (c) 2-Propenal,3-(2-methoxyphenyl)- (2-methoxy-

cinnamadehyde) and (d) benzyl benzoate

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Appendix C: Gas chromatogram data sheets of hydro distilled cinnamon oil at

different drying temperatures

(a) (b)

(c) (d)

Figure C.1: Air drying at ambient temperature (a) Trial 1, (b) Trial 2, (c) Trial

3 and (d) Trial 4

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(a) (b)

(c) (d)

Figure C.2: Air drying at 35 °C temperature (a) Trial 1, (b) Trial 2, (c) Trial 3

and (d) Trial 4

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(a) (b)

(c) (d)


and (d) Trial 4

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(a) (b)

(c) (d)


and (d) Trial 4

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(a) (b)

(c) (d)


and (d) Trial 4

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Appendix D: One-Way ANOVA and principal components analysis (PCA) steps

in IBM SPSS statistics 19

(a) (b)

(c) (d)

Figure D.1: (a) Calculating one way ANOVA, (b) One-way ANOVA

window, (c) Post Hoc Multiple Comparisons window and (d) Options window

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(a) (b)

(c) (d)

Figure D.2: (a) Testing the normality, (b) Statistics window, (c) Explore

window and (d) Plots window

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(a) (b)

(c) (d)

(e)

Figure D.3: (a) Factor Anaysis window, (b) Descriptive window, (c)

Extraction window, (d) Rotation window and (e) Option window

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Appendix E: Matlab code for plotting the drying curves

Appendix E.1: Matlab code for plotting moisture content on dry basis against time

function drying=drying_data()

%Importing data from excel file into defined arrays

time1=[xlsread('Drying curve graph.xlsx',1,'A4:A31')]';

moisture_dry_basis1=[xlsread('Drying curve graph.xlsx',1,'B4:B31')]';


moisture_dry_basis2=[xlsread('Drying curve graph.xlsx',1,'C4:C23')]';


moisture_dry_basis3=[xlsread('Drying curve graph.xlsx',1,'D4:D18')]';


moisture_dry_basis4=[xlsread('Drying curve graph.xlsx',1,'E4:E14')]';


moisture_dry_basis5=[xlsread('Drying curve graph.xlsx',1,'F4:F12')]';

%Plot the curves in same figures

f1=figure(1);

plot(time1,moisture_dry_basis1,'kx',time2,moisture_dry_basis2,'k.',time3,moisture_d

ry_basis3,'k^',time4,moisture_dry_basis4,'k+',time5,moisture_dry_basis5,'k*');

xlabel('time(hr)');ylabel('moisture content-dry basis (kgH2O/Kg dry solid)')...

;title('Dry basis moisture content Vs time');grid on;

End

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Appendix E.2: Matlab code for plotting drying rate against moisture content on dry

basis

function drying=drying_data()

%Importing data from excel file into defined arrays


moisture_dry_basis1=[xlsread('Drying curve graph.xlsx',1,'B4:B29')]';


moisture_dry_basis2=[xlsread('Drying curve graph.xlsx',1,'C4:C22')]';


moisture_dry_basis3=[xlsread('Drying curve graph.xlsx',1,'D4:D17')]';


moisture_dry_basis4=[xlsread('Drying curve graph.xlsx',1,'E4:E14')]';


moisture_dry_basis5=[xlsread('Drying curve graph.xlsx',1,'F4:F12')]';

%Plot the curves in same figures

f1=figure(1);

plot(time1,moisture_dry_basis1,'kx',time2,moisture_dry_basis2,'k.',time3,moisture_d

ry_basis3,'k^',time4,moisture_dry_basis4,'k+',time5,moisture_dry_basis5,'k*');

xlabel('time(minutes)');ylabel('moisture content-dry basis (kgH2O/Kg dry solid)')...

;title('Dry basis moisture content Vs time');grid on;

end

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Appendix F: SPSS Output of the One-Way ANOVA

Table F.1: Test of homogeneity of variances

LeveneStatistic df1 df2 Sig.

p-xylene .531 4 15 .715styrene 2.071 4 15 .136benzene, 1,2,3-trimethyl 2.983 4 15 .054α-phellandrene 4.047 4 15 .020p-cymene 2.793 4 15 .065β-phellandrene 15.185 4 15 .000linalool 7.340 4 15 .002benzenepropanal 1.102 4 15 .391terpinen-4-ol .707 4 15 .600cinnamaldehyde .710 4 15 .598cinnamaldehyde-E 1.502 4 15 .251eugenol 17.042 4 15 .000caryophyllene 7.397 4 15 .002cinnamyl acetate .760 4 15 .5672-methoxy-cinnamaldehyde 1.367 4 15 .292benzyl benzoate 2.939 4 15 .056

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Table F.2: Tests of Normality

Temperature Kolmogorov-Smirnova Shapiro-WilkStatistic df Sig. Statistic df Sig.

p-xylene Ambient .187 4 . .990 4 .95735 .260 4 . .903 4 .44840 .192 4 . .989 4 .95345 .227 4 . .940 4 .65350 .249 4 . .921 4 .544

styrene Ambient .359 4 . .746 4 .03635 .224 4 . .938 4 .64140 .214 4 . .956 4 .75545 .230 4 . .955 4 .74750 .175 4 . .980 4 .900

benzene, 1,2,3-trimethyl

Ambient .190 4 . .979 4 .89335 .237 4 . .941 4 .65840 .185 4 . .993 4 .97145 .204 4 . .972 4 .85450 .183 4 . .983 4 .919

α-phellandrene Ambient .288 4 . .934 4 .61935 .196 4 . .976 4 .87840 .257 4 . .920 4 .53645 .234 4 . .895 4 .40650 .297 4 . .831 4 .169

p-cymene Ambient .407 4 . .732 4 .02635 .189 4 . .978 4 .89240 .251 4 . .925 4 .56445 .250 4 . .923 4 .55250 .250 4 . .939 4 .650

β-phellandrene Ambient .272 4 . .891 4 .39035 .301 4 . .812 4 .12640 .212 4 . .965 4 .81245 .331 4 . .793 4 .09150 .271 4 . .855 4 .243

linalool Ambient .258 4 . .916 4 .51735 .203 4 . .971 4 .84740 .272 4 . .885 4 .36145 .149 4 . .994 4 .97850 .271 4 . .949 4 .708

Benzenepropanal Ambient .298 4 . .875 4 .31935 .269 4 . .900 4 .43340 .271 4 . .871 4 .30145 .232 4 . .910 4 .48150 .233 4 . .970 4 .843

terpinen-4-ol Ambient .201 4 . .951 4 .72535 .386 4 . .770 4 .05940 .222 4 . .979 4 .89645 .255 4 . .879 4 .33550 .202 4 . .966 4 .816

cinnamaldehyde Ambient .303 4 . .806 4 .11335 .254 4 . .922 4 .54640 .204 4 . .968 4 .83245 .256 4 . .849 4 .22250 .175 4 . .995 4 .983

cinnamaldehyde-E Ambient .267 4 . .875 4 .318

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35 .366 4 . .768 4 .05640 .242 4 . .968 4 .82745 .237 4 . .930 4 .59450 .241 4 . .968 4 .828

eugenol Ambient .266 4 . .870 4 .29635 .296 4 . .923 4 .55540 .269 4 . .917 4 .52245 .264 4 . .860 4 .26050 .227 4 . .949 4 .708

caryophyllene Ambient .271 4 . .890 4 .38335 .259 4 . .881 4 .34540 .289 4 . .867 4 .28645 .267 4 . .884 4 .35550 .156 4 . .994 4 .976

cinnamyl acetate Ambient .198 4 . .963 4 .79535 .211 4 . .934 4 .61640 .260 4 . .955 4 .74845 .298 4 . .784 4 .07750 .248 4 . .905 4 .455

2-methoxy-cinnamaldehyde

Ambient .142 4 . .997 4 .98935 .227 4 . .957 4 .76040 .194 4 . .976 4 .87945 .142 4 . .997 4 .99150 .333 4 . .828 4 .163

benzyl benzoate Ambient .233 4 . .967 4 .82235 .276 4 . .870 4 .29840 .218 4 . .938 4 .64045 .240 4 . .875 4 .31650 .219 4 . .954 4 .743

a. Lilliefors Significance Correction

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Table F.3: Descriptives table

N Mean Std.Deviation Std. Error

95% ConfidenceInterval for Mean Minimum MaximumLowerBound

UpperBound

p-xylene ambient 4 .95100 .018815 .009407 .92106 .98094 .927 .97235 4 .87025 .030739 .015370 .82134 .91916 .827 .89740 4 .81975 .022111 .011056 .78457 .85493 .795 .84845 4 .88175 .020288 .010144 .84947 .91403 .859 .90350 4 .66450 .012662 .006331 .64435 .68465 .652 .679

Total 20 .83745 .100448 .022461 .79044 .88446 .652 .972styrene ambient 4 .11700 .029017 .014509 .07083 .16317 .099 .160

35 4 .17900 .015122 .007561 .15494 .20306 .165 .19940 4 .14075 .004856 .002428 .13302 .14848 .136 .14745 4 .20425 .015305 .007653 .17990 .22860 .189 .22550 4 .15200 .013191 .006595 .13101 .17299 .137 .167

Total 20 .15860 .034701 .007759 .14236 .17484 .099 .225benzene, 1,2,3-trimethyl

ambient 4 .19400 .020199 .010100 .16186 .22614 .172 .21835 4 .15550 .019672 .009836 .12420 .18680 .132 .17540 4 .20925 .004573 .002287 .20197 .21653 .204 .21545 4 .19700 .017378 .008689 .16935 .22465 .174 .21550 4 .23775 .030934 .015467 .18853 .28697 .204 .275

Total 20 .19870 .032714 .007315 .18339 .21401 .132 .275α-phellandrene ambient 4 .75550 .089363 .044681 .61330 .89770 .662 .877

35 4 .94175 .099033 .049517 .78417 1.09933 .837 1.06340 4 .50425 .013426 .006713 .48289 .52561 .492 .52345 4 .26450 .012557 .006278 .24452 .28448 .254 .28250 4 .16200 .025232 .012616 .12185 .20215 .135 .184

Total 20 .52560 .304681 .068129 .38300 .66820 .135 1.063p-cymene ambient 4 1.49125 .042789 .021395 1.42316 1.55934 1.463 1.555

35 4 1.78875 .016701 .008350 1.76218 1.81532 1.769 1.80740 4 .73825 .010689 .005344 .72124 .75526 .728 .75145 4 .59300 .026646 .013323 .55060 .63540 .562 .61950 4 .52700 .014514 .007257 .50390 .55010 .507 .541

Total 20 1.02765 .527133 .117871 .78094 1.27436 .507 1.807β-phellandrene ambient 4 1.66350 .166874 .083437 1.39797 1.92903 1.522 1.876

35 4 2.55275 .188772 .094386 2.25237 2.85313 2.389 2.74840 4 1.24525 .023386 .011693 1.20804 1.28246 1.214 1.26945 4 .96975 .035255 .017628 .91365 1.02585 .918 .99450 4 .54525 .043254 .021627 .47642 .61408 .512 .607

Total 20 1.39530 .709065 .158552 1.06345 1.72715 .512 2.748linalool ambient 4 4.51850 .310145 .155072 4.02499 5.01201 4.230 4.894

35 4 5.17375 .073794 .036897 5.05633 5.29117 5.082 5.25040 4 4.14900 .010708 .005354 4.13196 4.16604 4.139 4.16145 4 4.59775 .226170 .113085 4.23786 4.95764 4.345 4.87850 4 3.69675 .081439 .040719 3.56716 3.82634 3.588 3.785

Total 20 4.42715 .528227 .118115 4.17993 4.67437 3.588 5.250Benzenepropanal ambient 4 .33400 .016733 .008367 .30737 .36063 .320 .358

35 4 .46675 .020726 .010363 .43377 .49973 .441 .48540 4 .46600 .009416 .004708 .45102 .48098 .456 .47545 4 .44625 .032786 .016393 .39408 .49842 .418 .49150 4 .37200 .022949 .011475 .33548 .40852 .343 .399

Total 20 .41700 .058841 .013157 .38946 .44454 .320 .491terpinen-4-ol ambient 4 .49225 .030347 .015173 .44396 .54054 .463 .533

35 4 .46150 .027343 .013672 .41799 .50501 .421 .481

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40 4 .44100 .014024 .007012 .41869 .46331 .425 .45945 4 .47375 .018464 .009232 .44437 .50313 .459 .49950 4 .39125 .023157 .011579 .35440 .42810 .368 .421

Total 20 .45195 .041172 .009206 .43268 .47122 .368 .533cinnamaldehyde ambient 4 .66650 .034083 .017042 .61227 .72073 .617 .690

35 4 .56075 .019973 .009986 .52897 .59253 .542 .58540 4 .50175 .014477 .007238 .47871 .52479 .487 .52045 4 .62625 .020516 .010258 .59360 .65890 .611 .65550 4 .53200 .021150 .010575 .49835 .56565 .507 .558

Total 20 .57745 .065478 .014641 .54681 .60809 .487 .690Cinnamaldehyde-E ambient 4 63.75025 .280284 .140142 63.30426 64.19624 63.352 63.977

35 4 67.17075 .395313 .197656 66.54172 67.79978 66.585 67.43740 4 73.33625 .188850 .094425 73.03575 73.63675 73.122 73.58145 4 76.27800 .081976 .040988 76.14756 76.40844 76.194 76.37050 4 78.64375 .195606 .097803 78.33250 78.95500 78.420 78.896

Total 20 71.83580 5.725439 1.280247 69.15621 74.51539 63.352 78.896eugenol ambient 4 4.35200 .187302 .093651 4.05396 4.65004 4.169 4.546

35 4 3.70725 .072131 .036066 3.59247 3.82203 3.635 3.80740 4 3.33450 .010344 .005172 3.31804 3.35096 3.325 3.34945 4 3.50875 .089842 .044921 3.36579 3.65171 3.420 3.59950 4 2.23775 .055036 .027518 2.15018 2.32532 2.168 2.291

Total 20 3.42805 .711164 .159021 3.09521 3.76089 2.168 4.546caryophyllene ambient 4 1.67875 .042836 .021418 1.61059 1.74691 1.618 1.715

35 4 1.38375 .010308 .005154 1.36735 1.40015 1.373 1.39440 4 1.04925 .063751 .031876 .94781 1.15069 .995 1.12545 4 .75850 .011676 .005838 .73992 .77708 .743 .76850 4 .64300 .012410 .006205 .62325 .66275 .628 .657

Total 20 1.10265 .396882 .088746 .91690 1.28840 .628 1.715cinnamyl acetate ambient 4 14.34250 .283688 .141844 13.89109 14.79391 14.025 14.656

35 4 10.24900 .219218 .109609 9.90017 10.59783 9.952 10.45040 4 8.25650 .256721 .128360 7.84800 8.66500 7.913 8.53245 4 5.88650 .166144 .083072 5.62213 6.15087 5.738 6.04450 4 8.06425 .132193 .066096 7.85390 8.27460 7.930 8.206

Total 20 9.35975 2.929241 .654998 7.98882 10.73068 5.738 14.6562-methoxy-cinnamaldehyde

ambient 4 .92250 .023302 .011651 .88542 .95958 .896 .95135 4 .28400 .017010 .008505 .25693 .31107 .261 .30140 4 .21575 .007411 .003705 .20396 .22754 .208 .22545 4 .27225 .008921 .004460 .25805 .28645 .262 .28350 4 .24600 .014376 .007188 .22312 .26888 .235 .267

Total 20 .38810 .275535 .061612 .25915 .51705 .208 .951benzyl benzoate ambient 4 2.14775 .100234 .050117 1.98825 2.30725 2.028 2.273

35 4 .98125 .117854 .058927 .79372 1.16878 .813 1.07640 4 .75800 .013880 .006940 .73591 .78009 .743 .77345 4 .66750 .013229 .006614 .64645 .68855 .657 .68650 4 .73300 .008602 .004301 .71931 .74669 .724 .743

Total 20 1.05750 .573052 .128138 .78930 1.32570 .657 2.273

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Table F.4: ANOVA table

Sum ofSquares df Mean Square F Sig.

p-xylene Between Groups .185 4 .046 97.800 .000Within Groups .007 15 .000Total .192 19

styrene Between Groups .018 4 .005 15.284 .000Within Groups .005 15 .000Total .023 19

benzene, 1,2,3-trimethyl

Between Groups .014 4 .004 8.501 .001Within Groups .006 15 .000Total .020 19

α-phellandrene Between Groups 1.707 4 .427 113.724 .000Within Groups .056 15 .004Total 1.764 19

p-cymene Between Groups 5.270 4 1.318 2094.795 .000Within Groups .009 15 .001Total 5.280 19

β-phellandrene Between Groups 9.351 4 2.338 174.093 .000Within Groups .201 15 .013Total 9.553 19

linalool Between Groups 4.823 4 1.206 37.788 .000Within Groups .479 15 .032Total 5.301 19

benzenepropanal Between Groups .059 4 .015 30.514 .000Within Groups .007 15 .000Total .066 19

terpinen-4-ol Between Groups .024 4 .006 10.930 .000Within Groups .008 15 .001Total .032 19

cinnamaldehyde Between Groups .074 4 .018 34.844 .000Within Groups .008 15 .001Total .081 19

cinnamaldehyde-E Between Groups 621.886 4 155.471 2464.070 .000Within Groups .946 15 .063Total 622.832 19

eugenol Between Groups 9.455 4 2.364 229.521 .000Within Groups .154 15 .010Total 9.609 19

caryophyllene Between Groups 2.974 4 .743 590.460 .000Within Groups .019 15 .001Total 2.993 19

cinnamyl acetate Between Groups 162.310 4 40.578 847.059 .000Within Groups .719 15 .048Total 163.029 19

2-methoxy-cinnamaldehyde

Between Groups 1.439 4 .360 1532.758 .000Within Groups .004 15 .000Total 1.442 19

benzyl benzoate Between Groups 6.166 4 1.542 316.176 .000Within Groups .073 15 .005Total 6.239 19

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F.5: Post hoc test

Student-Newman-Keuls (SNK) -Uses Harmonic Mean Sample Size = 4.000

Means for groups in homogeneous subsets are displayed.

Table F.5.1: Multiple comparisons of p-xylene

Temperature N Subset for alpha = 0.051 2 3 4

50 4 .6645040 4 .8197535 4 .8702545 4 .88175

Ambient 4 .95100Sig. 1.000 1.000 .466 1.000

Table F.5.2: Multiple comparisons of styrene

Temperature N Subset for alpha = 0.051 2 3

Ambient 4 .1170040 4 .14075 .1407550 4 .1520035 4 .1790045 4 .20425

Sig. .072 .373 .057

Table F.5.3: Multiple comparisons of benzene, 1,2,3-trimethyl


35 4 .15550Ambient 4 .19400

45 4 .1970040 4 .20925 .2092550 4 .23775

Sig. 1.000 .553 .067

Table F.5.4: Multiple comparisons of α-phellandrene

Temperature N Subset for alpha = 0.051 2 3 4 5

50 4 .1620045 4 .2645040 4 .50425

Ambient 4 .7555035 4 .94175

Sig. 1.000 1.000 1.000 1.000 1.000

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Table F.5.5: Multiple comparisons of p-cymene


50 4 .5270045 4 .5930040 4 .73825

Ambient 4 1.4912535 4 1.78875

Sig. 1.000 1.000 1.000 1.000 1.000

Table F.5.6: Multiple comparisons of β-phellandrene


50 4 .54525

45 4 .96975

40 4 1.24525Ambient 4 1.66350

35 4 2.55275

Sig. 1.000 1.000 1.000 1.000 1.000

Table F.5.7: Multiple comparisons of linalool


50 4 3.6967540 4 4.14900

Ambient 4 4.5185045 4 4.5977535 4 5.17375

Sig. 1.000 1.000 .540 1.000

Table F.5.8: Multiple comparisons of benzene-propanal


Ambient 4 .3340050 4 .3720045 4 .4462540 4 .4660035 4 .46675

Sig. 1.000 1.000 .405

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Table F.5.9: Multiple comparisons of terpinen-4-ol


50 4 .3912540 4 .4410035 4 .46150 .4615045 4 .47375 .47375

Ambient 4 .49225Sig. 1.000 .152 .185

Table F.5.10: Multiple comparisons of cinnamaldehyde


40 4 .5017550 4 .53200 .5320035 4 .5607545 4 .62625

Ambient 4 .66650Sig. .082 .097 1.000 1.000

Table F.5.11: Multiple comparisons of cinnamaldehyde-E


Ambient 4 63.7502535 4 67.1707540 4 73.3362545 4 76.2780050 4 78.64375

Sig. 1.000 1.000 1.000 1.000 1.000

Table F.5.12: Multiple comparisons of eugenol


50 4 2.2377540 4 3.3345045 4 3.5087535 4 3.70725

Ambient 4 4.35200SiH. 1.000 1.000 1.000 1.000 1.000

Table F.5.13: Multiple comparisons of caryophyllene


50 4 .6430045 4 .7585040 4 1.0492535 4 1.38375

Ambient 4 1.67875Sig. 1.000 1.000 1.000 1.000 1.000

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Table F.5.14: Multiple comparisons of cinnamyl acetate


45 4 5.8865050 4 8.0642540 4 8.2565035 4 10.24900

Ambient 4 14.34250Sig. 1.000 .233 1.000 1.000

Table F.5.15: Multiple comparisons of 2-methoxy-cinnamaldehyde


40 4 .2157550 4 .2460045 4 .2722535 4 .28400

Ambient 4 .92250Sig. 1.000 1.000 .295 1.000

Table F.5.16: Multiple comparisons of benzyl Benzoate


45 4 .6675050 4 .7330040 4 .7580035 4 .98125

Ambient 4 2.14775Sig. .193 1.000 1.000

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