Chemistry of Spices 177407205X, 9781774072059

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CHEMISTRY OF SPICES

CHEMISTRY OF SPICES

Levitah Castil Mapatac

ARCLER

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www.arclerpress.com

Chemistry of Spices Levitah Castil Mapatac

Arcler Press 2010 Winston Park Drive, 2nd Floor Oakville, ON L6H 5R7 Canada www.arclerpress.com Tel: 001-289-291-7705 001-905-616-2116 Fax: 001-289-291-7601 Email: [email protected] e-book Edition 2020 ISBN: 978-1-77407-387-2 (e-book) This book contains information obtained from highly regarded resources. Reprinted material sources are indicated and copyright remains with the original owners. Copyright for images and other graphics remains with the original owners as indicated. A Wide variety of references are listed. Reasonable efforts have been made to publish reliable data. Authors or Editors or Publishers are not responsible for the accuracy of the information in the published chapters or consequences of their use. The publisher assumes no responsibility for any damage or grievance to the persons or property arising out of the use of any materials, instructions, methods or thoughts in the book. The authors or editors and the publisher have attempted to trace the copyright holders of all material reproduced in this publication and apologize to copyright holders if permission has not been obtained. If any copyright holder has not been acknowledged, please write to us so we may rectify.

Notice: Registered trademark of products or corporate names are used only for explanation and identification without intent of infringement. © 2020 Arcler Press ISBN: 978-1-77407-205-9 (Hardcover) Arcler Press publishes wide variety of books and eBooks. For more information about Arcler Press and its products, visit our website at www.arclerpress.com

ABOUT THE AUTHOR

Levitah C. Mapatac is an Associate Professor, researcher, writer and a PhD holder from the University in Science and Technology of Southern Philippines. Her interest varies from different chemistry concepts and applications and currently doing research in traditional medicines, water waste pollution and environmental chemistry in the aspect of contamination pathways, profilling and rehabilatation of mining waste.

TABLE OF CONTENTS

List of Figures ........................................................................................................xi List of Tables ........................................................................................................xv List of Abbreviations .......................................................................................... xvii Preface........................................................................ ................................... ....xix Chapter 1

Introduction to Chemistry of Spices .......................................................... 1 1.1. A Brief Overview ................................................................................ 2 1.2. Background ........................................................................................ 6 1.3. Chemistry of Spices .......................................................................... 10 1.4. Value of Spices ................................................................................. 13 1.5. Conclusion ....................................................................................... 14 References ............................................................................................... 16

Chapter 2

Spices Around the World ........................................................................ 17 2.1. Introduction ...................................................................................... 18 2.2. Top 10 Most Popular In The World of Spices ..................................... 18 2.3. Spices Color and Chemistry .............................................................. 22 2.4. Contamination of Spices With Chemicals at Production Stage .......... 29 2.5. Countries Having Most Spices .......................................................... 39 2.6. Export of Spices ................................................................................ 42 2.7. Spice Blends ..................................................................................... 43 2.8. Conclusion ....................................................................................... 47 References ............................................................................................... 49

Chapter 3

Chemical Composition of Major Spices................................................... 51 3.1. Introduction ...................................................................................... 52 3.2. Major Compounds in Spices ............................................................. 55 3.3. Spices and Their Composition ........................................................... 58 3.4. Distinct Properties of Spices.............................................................. 75

3.5. Conclusion ....................................................................................... 81 References ............................................................................................... 82 Chapter 4

Processing of Spices and Process Required for Quality Check ................ 83 4.1. Introduction ...................................................................................... 84 4.2. Pre-Treatment Methods ..................................................................... 87 4.3. Small-Scale Spice Processing ............................................................ 90 4.4. Cultivation of Various Spices ............................................................. 97 4.5. Measure The Quality of Spices: Maintaining Color Control With Spectrophotometers ....................................... 103 4.6. Process Involved For Preserving Spices ........................................... 104 4.7. Constraints In Spice Production In Asia ........................................... 105 4.8. Processing, Storage Methods, and Quality Attributes of Spices and Aromatic Herbs ...................................................... 107 4.9. Conclusion ..................................................................................... 112 4.10. Case Study: Pathogens And Spices ................................................ 113 References ............................................................................................. 121

Chapter 5

Spices and Its Medicinal Properties ....................................................... 123 5.1. Introduction .................................................................................... 124 5.2. Alligator Pepper, Grains of Paradise, Guinea Grains, and Melegueta Pepper.................................................................. 126 5.3. Black Amomum (Guinea Grains) .................................................... 127 5.4. Bermuda Onion, Onion, And Shallot (Figure 5.1) ........................... 128 5.5. Ajo, Garlic, Rocambole, And Serpent Garlic (Figure 5.2) ................ 131 5.6. Galangal, Greater Galangal, Languas Cha, And Siamese Ginger (Figure 5.3) ....................................................................... 135 5.7. Bengal Cardamom, Black Cardamom, Brown Cardamom, Greater Cardamom, Indian Cardamom, Jalpaiguri Cardamom, And Nepalese Cardamom (Figure 5.4) .......................................... 138 5.8. Celery (Figure 5.5) .......................................................................... 141 5.9. Saffron (Figure 5.6) ......................................................................... 143 5.10. Indian Saffron, Turmeric (Figure 5.7) ............................................. 146 5.11. Conclusion ................................................................................... 150 References ............................................................................................. 151

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Chapter 6

Chemical Hazards in Spices .................................................................. 153 6.1. Introduction .................................................................................... 154 6.2. Chemical Hazards .......................................................................... 155 6.3. Potential Food Hazards in Spices .................................................... 157 6.4. Chemical Contaminants in Household Spices ................................. 159 6.5. Spice Contamination: Hold Bacteria and Harmful Chemicals ......... 160 6.6. Hazard Analysis and Controls To Address The Hazards (Figure 6.3)................................................................................... 166 6.7. Potential Process-Related Biological and Chemical Hazards In Spices......................................................................... 168 6.8. The Microbiology of Herbs And Spices ........................................... 168 6.9. Control of Chemicals Hazards In Spices ......................................... 170 6.10. Prioritization of Chemical Hazards In Spices and Herbs ............... 175 References ............................................................................................. 177

Chapter 7

Impact of Spices: Chemical and Medicinal ............................................ 179 7.1. Introduction .................................................................................... 180 7.2. Chemical Composition of Spices and Their Antioxidant Activity...... 182 7.3. Effect of Spices on Human Health and Other Applications.............. 188 7.4. Potential Health Benefits of Major Seed Spices ............................... 195 7.5. Cumin (Cuminum Cyminum L.) ...................................................... 196 7.6. Medicinal and Pharmacological Properties ..................................... 198 7.7. Coriander (Coriandrum Sativum L.) ................................................ 200 7.8. Medicinal and Pharmacological Properties of Coriander................. 202 7.9. Fennel (Foeniculum Vulgare Mill.) .................................................. 204 7.10. Medicinal and Pharmacological Properties of Fennel .................... 208 7.11. Medicinal and Pharmacological Properties of Fenugreek .............. 211 7.12. Conclusion ................................................................................... 214 References ............................................................................................. 216

Chapter 8

Innovations in the Spices Industry......................................................... 219 8.1. Introduction .................................................................................... 220 8.2. Innovation ...................................................................................... 223 8.3. Spice Trade ..................................................................................... 228 8.4. Black Pepper................................................................................... 230 8.5. Ginger ............................................................................................ 235 ix

8.6. Coffee ............................................................................................. 238 8.7. An Innovative Method For Cultivation Of Turmeric (Figure 8.10) ..... 240 8.8. On-Farm Assessment of Technological Innovation of Fennel Cultivation .................................................................... 241 8.9. Case Study: Grenada Nutmeg Sector Development Strategy ........... 243 8.10. Conclusion ................................................................................... 253 References ............................................................................................. 254 Index ..................................................................................................... 257

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LIST OF FIGURES Figure 1.1. Variety of spices at a central market in Agadir, Morocco Figure 1.2. Distinction between herbs and spices Figure 1.3. Unripe drupes – fleshy fruit of the plant from which black pepper is made Figure 1.4. Indian spices Figure 1.5. Usage of spices in Ancient Greece Figure 1.6. Allspice that has the aroma of a combination of spices, especially cinnamon, cloves, ginger, and nutmeg Figure 1.7. Curcumin, major constituent of turmeric Figure 1.8. Bay Leaves and its major constituent (1,8-cineole) Figure 1.9. Piperine—the main constituent of black pepper Figure 1.10. Cinnamaldehyde Figure 1.11. Carvacrol from which the characteristic flavor of oregano comes Figure 1.12. Saffron’s constituent crocin that gives yellow color to it Figure 1.13. A Spice market in Dubai Figure 1.14. Red ginger Figure 2.1. Basil Figure 2.2. Marjoram Figure 2.3. Cinnamon sticks, dried flowers, and cinnamon in powdered form Figure 2.4. Syzygium aromaticum, the plant from which cloves are obtained Figure 2.5. The turmeric plant Figure 2.6. Nutmeg Figure 2.7. Saffron Figure 2.8. Scoville scale board on display at a spice market in Hoston Figure 2.9. Ancho chilies from Mexico Figure 2.10. Habanero Chilies from Mexico Figure 2.11. A traditional style of making Mitmita xi

Figure 3.1. Chemical structure of curcumin Figure 3.2. Chemical composition of C. sativum Figure 3.3. Major constituent of fennel Figure 3.4. Bioactive compounds of garlic Figure 3.5. Major constituent of clove Figure 3.6. Cumin-aldehyde Figure 3.7. Ginger rhizomes and its components Figure 4.1. Variety of spices Figure 4.2. Processing steps of spices Figure 4.3. Solar dryer Figure 4.4. Flow chart of spice processing Figure 4.5. Spice plantation of Kerala, India Figure 4.6. Constraints in spice production Figure 5.1. White Bermuda Figure 5.2. Growing garlic Figure 5.3. Galangal Figure 5.4. Nepalese cardamom Figure 5.5. Celery Figure 5.6. Saffron Figure 5.7. Turmeric Figure 6.1. Health risks in spices Figure 6.2. Pathogen testing for spices Ingredients Figure 6.3. Spice testing Figure 6.4. Microbiology of herbs and spices Figure 7.1. Cumin seed Figure 7.2. Apigenin structure Figure 7.3. Luteolin structure Figure 7.4. Coriander seeds Figure 7.5. Fennel seeds Figure 7.6. Fenugreek Figure 8.1. Spices

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Figure 8.2. Innovation in the spice industry Figure 8.3. The stages of the process of adopting innovation Figure 8.4. History of spice trade Figure 8.5. Growing black pepper Figure 8.6. Structural design of three cultivation methods Figure 8.7. Ginger Figure 8.8. Model of ginger sowing machine Figure 8.9. Coffee Figure 8.10. Cultivation of turmeric Figure 8.11. Fennel cultivation

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LIST OF TABLES Table 1.1. Equivalents of spices Table 2.1. Spices found in Africa with their flavor and ingredients Table 2.2. Spices found in Asia with their flavors and ingredients Table 2.3. Spices found in Latin America and the Caribbean Table 2.4. Spices found in Europe and their flavor and ingredients Table 2.5. Spices found in Middle East and their flavor and ingredients Table 2.6. Spices found in Indian subcontinent and their flavor and ingredients Table 2.7. Spices found in North America and their flavor and ingredients Table 3.1. Chemical category of fresh fennel Table 4.1. Spice moisture content Table 5.1. Different indications of saffron Table 5.2. Saffron and some of its medicinal applications and agents Table 5.3. Saffron and its application in case of infection Table 5.4. Various indications of turmeric Table 5.5. Turmeric and its application in case of cancer Table 5.6. Turmeric and its application in case of infection Table 7.1. Chemical composition of spices (seasonings) and culinary herbs Table 7.2. Flavonoid content in spices from the USDA (U.S. Department of Agriculture) database on flavonoids content of selected foods Table 7.3. The major biologically active compounds found in spices and herbs Table 7.4. Reported therapeutic effects of spices in different diseases Table 7.5. Spices against cancer Table 7.6. Major bioactive compounds of spices with potential beneficial effects for the management of CVD (Cardiovascular disease) Table 7.7. Spices that have anti-cancer activity Table 8.1. Distribution of world supplies in 2006 and Grenadian supplies in 2006 and 2008 Table 8.2. Global nutmeg supply

LIST OF ABBREVIATIONS

AAACP

ACP Agriculture Commodities Programme

BHA

butylated hydroxyanisole

BHT

butylated hydroxytoluene

CCPs

critical control points

CDC’s FDOSS

Centers for Disease Control and Prevention’s Foodborne Disease Outbreak Surveillance System

CFIA

Canadian Food Inspection Agency

CFR

code of federal regulations

CFTRI

Central Food Technological Research Institute

COX

cyclooxygenase enzyme

DADS

diallyl disulfide

DATS

diallyl tri-sulfide

FAO

Food and Agriculture Organization

FDA

Food and Drug Administration

HACCP

hazard analysis and critical control points

ISO

International Standards Organization

ITC

International Trade Centre

LMFs

low-moisture foods

LPO

lipid peroxidation

MDGs

millennium development goals

MRPs

processes for microbial reduction

PAIFOD

Publically Available International Foodborne Outbreak database

PHAC

Public Health Agency of Canada

PHO

Public Health Ontario

RASFF

rapid alert system for food and feed

ROI

return on investment

SAC

S-allylcysteine

SAH

spices and aromatic herbs

US

United States

VBNC

viable but non-culturable

VTEC

verotoxigenic E. coli

WHO

World Health Organization

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PREFACE

As the human civilizations across different parts of the world evolved, they brought along new discoveries and new inventions. Simultaneously, Science began to research, define, and explain the discoveries. Spices were one such discovery that impacted the food culture everywhere, locally, and globally. Spices were amongst the first precious items in human history that were valued so much that they were used in trade. The modern man has come very far since that initial phase. Today, there are much more costly trade items than spices, but the bounty nature is so vast that humans have not yet been able to crack the chemistry of all the plants although the existence is so old. Research is always on the go and with every discovery; there comes the possibilities of further research. The same is true for the chemistry of spices. As one studies the subject, one finds that the usual concepts have a lot of hidden knowledge behind them and the breadth of the subject is very large. In this book, an effort has been made to educate the reader from an expert point of view in a manner that is easily understandable by a beginner as well. •

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•

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It begins with the history of the spices trade, the basic chemistry of spices and the value of spices. The properties of the spices are explored in the way they are useful in the real life and how chemistry plays an important role in the utility of spices for various purposes. Next, the spices diversity across the world is explored in detail. It includes statistics like countries having most spices and the spices that are most used in the world. The major compounds in common spices are explored next along with the functions of the chemical constituents. The processing of spices and Quality check procedures are also given. The medicinal properties of the spices are given in detail with a description about the chemical compounds that make them useful. Chemical hazards of spices are another important section that is described in an elaborative manner.

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The beneficial properties of the spices are covered next. The book concludes with a section describing the innovations in the spices industry.

Chapter

1

Introduction to Chemistry of Spices

CONTENTS 1.1. A Brief Overview ................................................................................ 2 1.2. Background ........................................................................................ 6 1.3. Chemistry of Spices .......................................................................... 10 1.4. Value of Spices ................................................................................. 13 1.5. Conclusion ....................................................................................... 14 References ............................................................................................... 16

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Chemistry of Spices

Spices are made of components whose chemical composition and behavior mechanisms make up their true essence. Various types of substances can be derived from spices that have been found to have useful properties like being anti-oxidant, chemopreventive, and so on. The discussion of the chemical aspects of the spices throws light on their composition, uses, properties, and other relevant characteristics that lend them their peculiar nature. It is interesting to discover how each region in the world have their types of spices, and the study of the factors of such origination is also vital to get through with the chemistry of spice. Exploring the potential of spices as a health and a food product is based on the deep study of their constituents. This book encompasses all that is described above in an elaborate manner.

1.1. A BRIEF OVERVIEW Around the world, there would hardly be any household that does not use spices. Every day, spices are used a couple of times in the preparation of meals. The variety in spices is so diverse that even after centuries of human evolution, the research on spices still continues. It has been said by Charlemagne, Eighth Century King, Conqueror, and is considered to be a Spice Lover that, “Spices are the friend of physicians and the pride of cooks.”

Figure 1.1: Variety of spices at a central market in Agadir, Morocco.

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Source: https://en.wikipedia.org/wiki/Spice

Let us begin to know spices from a literal sense of what they are in the scientific terms. It is important to know that spice is actually a product. Spices are the substances derived from plants, and they can be a seed or in powder form. Usually, the spices are used to add flavor to the food and food products. However, spices are also used as coloring and preserving agents for food (Figure 1.1). Often, people do not know the difference between a spice and a herb, but their distinction is important to know from technical perspective. Simply put, herbs are the leaves of a plant. A few examples of herbs are oregano, cilantro, and rosemary. On the other hand, spices are the products that are derived from the non-leafy parts of the plant. Leaves of Cilantro are the herbs, while coriander, which is the seed, is a spice (Figure 1.2).

Figure 1.2: Distinction between herbs and spices. Source: http://www.onthegreenfarms.com/wp-content/uploads/2011/03/Saving-seeds.jpg

The special character of every spice is attributed to the chemical reactions and interaction of its constituents. A spice is characterized by three major things: taste, aroma, and color. Spices are further specified as aromatic products. The source of spice can be a bud, fruit, stem, root or flower of a plant. Figure 1.3 shows an

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Chemistry of Spices

unripe drupe of the Piper nigrum plant from which black pepper is made. Drupe is the term used for the fleshy fruit on the plant that has a thin skin and a stone in the center containing the seed.

Figure 1.3: Unripe drupes – fleshy fruit of the plant from which black pepper is made. Source: https://upload.wikimedia.org/wikipedia/commons/3/31/Black_ Pepper_%28Piper_nigrum%29_fruits.jpg

Black pepper is also the spice that is consumed the most all over the world followed by turmeric and cinnamon. On average, every person consumes about 10 to 20 grams of spice on a daily basis. A research study in Norway indicated that people consume 3 grams per day whereas, in a country like India that is known for spices, the average consumption is 14 to 20 grams per individual in a single day (Figure 1.4).

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Figure 1.4: Indian spices. Source: https://commons.wikimedia.org/wiki/File:Indian_Spices.jpg

In the US, paprika, and chili peppers are the most consumed spices after black pepper and cinnamon. Controversies over spices have made headlines time and again. These revolve around the issues of contamination, adulteration, and counterfeit products. Such debates have drawn attention to a lot of research in the field of chemistry of spices, and more vigilant regulations have been introduced to keep the misuses in check. When we talk about the chemistry of spices, the key areas of study include the areas of use, the compounds that enable the specific use and flavor, and the production of spices along with the adulteration prospects. Close examination of the methods through which spices can be counterfeited or contaminated reveals that the value for the customer id decreased although it brings profits for the manufacturer. The peculiar nature of every spice is the result of its constituents which are complex compounds. No spice is made of one single constituent, and it is always a mix of organic compounds. Cuminaldehyde is one of the natural organic compounds found in cumin seeds. In each spice, there is a constituent that is the major contributor to the uniqueness of that specific spice. The major contributor will either add the specific odor, taste or the color to the spice. In the chapters that follow, the major contributors will be studied in detail.

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Chemistry of Spices

The primary usage of spice is as a seasoning, but there are others like beverages, medicines, and colorants.

1.2. BACKGROUND When we trace the history of spices, it was first used as currency and for health benefits. The oldest records of written evidence of spices come from the cultures of Egypt, China, and India. History has it that in the ancient times, the hunters used to cover the meat using leaves of the bushes. Accidentally, they found that some leaves changed the taste of the meat. Such kind of discoveries led to first utilization of the spices to preserve food and to cover up the unpleasant tastes. Previously, there also used to be no distinction between spices used for flavoring and as medicine. The trend was that whichever leaf, gum, seed or root of a plant was found to have some unique fragrance or aroma, it was high in demand and thus became a condiment in that culture where it was discovered. In the ancient Egypt, spices were used for cooking purposes as early as 1555 BC. These included juniper, fennel, garlic, and cumin. In China, the first journal on spices was composed around 2700 BC. It was called “Pen Ts’ao Ching” or “The Classic Herbal.” It contained a list of more than hundreds of plants having medicinal value including a spice known as “kwei,” similar to cinnamon. Historical evidence supports that cloves and nutmeg were brought to China from the region of Moluccas, Indonesia. In the period of 3rd century BC, the Chinese attendants would put cloves in their mouth when they had to address the king or the queen because it made their breath smell nice. On the long voyages of Sea between Southeast Asia and China, it was a common practice to carry ginger plants in pots as a means of providing fresh food and preventing diseases like scurvy. Records from Mesopotamian civilization indicate that various types of aromatic plants were famous in the fertile valleys of Tigris and Euphrates. Aromatic plants like coriander, cinnamon, saffron, myrrh, and cardamom have been mentioned in the scrolls from Mesopotamian Civilization. History indicates that there was a king called King Merodach-Baladan II in the Mesopotamian times who was very fond of growing different plants. His garden has 64 varieties of plants. He is also said to have make journals on the cultivation of many spices. In the region of Babylonia, some herbs were revered so much that the religion had an ancient medical god of the moon. It

Introduction to Chemistry of Spices

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was a tradition to harvest some parts of the herbs only in the moonlight. In India, a big number of indigenous spices have been in use for health benefits and in cooking. Cardamom and turmeric are the two spices that were the first to be cultivated in India around 8th century BC. Aromatic plants like mustard were used to keep distance from evil elements. Many spices like black pepper, cardamom, and ginger were used for their medicinal values. Cloves were chewed after eating meals for improving digestion and the flow of saliva. In Greece, the import of eastern spices was very common, and their usage was very prominent in the region. Figure 1.5 summarizes the usage of some of those spices that were used by the Ancient Greeks:

Figure 1.5: Usage of spices in Ancient Greece. Source: http://www.mccormickscienceinstitute.com/resources/history-of-spices

Hippocrates, the Greek physician who was known as the father of medicine, mentioned many spices like thyme, mint, cinnamon, and marjoram in his writings. He asserted that each type of herb required a very careful method of preparation. Many remedies founded by him are in use even today. As history progresses, more organized accounts of spices and herbs were brought forth by the physicians of those times. Like Greeks, the Roman people were also engaged in the extensive use of spices in their cuisine. The Romanians used spices to add flavor to the wines and for making scented balms and oils. In ancient times, as the trades began between the Arabian and Roman Empire, spices were being used as the primary sources of trading. The source of the spices was not revealed to retain the value of the

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Chemistry of Spices

products as a monopoly. For many years, the origins of spices were kept secret, but at one point, some experts began noticing the connection between the stories told by the Arabians and the hike in the prices of spices. The followers of Mohammed, who established the principles of the Islam religion, were leading scientists of their time, as Mohamed himself had owned a shop that kept a stock of Asian spices, frankincense, and myrrh. The Arabians invented many good methods of extracting scents from plants and their flowers. The physicians in the country used spices in the making of syrups and as flavoring agents. In Europe, when the Asian spices were first introduced, they were very expensive. Table 1.1 illustrates the equivalents of some portions of spices from those times. Table 1.1: Equivalents of Spices Spices A Pound of Saffron A pound of ginger 2 Pounds of mace A pound of nutmeg

Equivalents A horse A sheep A cow 7 fat oxen

Records indicate that the price of gaining access to trade with the merchants from London was fixed at 10 pounds of pepper. Peppercorns were widely used as currency for rent purposes, taxes, and tolls. Brides of rich families would receive pepper as dowry. The era of Crusades brought forth the international exchange of products. This led to a decrease in the cost of Asian spices which were otherwise very expensive. The medical teachings from Arabian played an important role in the utilization of spices across the world. Charlemagne, the King of France and an Emperor, had a big contribution to the development of local herbs. He was the first one to bring about the cultivation of herbs like fennel, sage, fenugreek, and parsley on a large scale. In Europe, spices were increasingly used by the Church in preparation of feasts and all. The practice of tying the herbs in a bundle and using them to ward off the witches was also known. The first grocery store of the classic style was established by King Henry II, and it was an association of merchants. It was called as the Guild of the pepperers. The association engaged in the making and the cleaning process of the spices.

Introduction to Chemistry of Spices

9

Most of the members of the Guild began practicing medicine because of their experience at the Guild. Under the guidance of the Guild, these were some of the practices followed by the members to heal patients: • Using juniper wine as it was good for health; • Garlic soup served as healthy meal; • Placing clove extracts under the noses of the patients; • Sterilization of rooms using sage smoke. The period from 1300 to 1500 can be termed as the age of spice discovery. During this time, Marco Polo, the Italian merchant was very active in his travels. In his journal, he mentioned how he had known the flavor of the sesame oil in Afghanistan and the plants of ginger in Kain-du that was known for wines flavored by rice and spices. Here’s a list of more accounts of usage of spice by him: •

Pepper, ginger, and cinnamon were found in abundance in the Malabar Coast of India. • Pepper was imported in vast quantities to Hanchow in East China. • Many valuable spices were grown in Java islands and in the Islands in the Sea of China. Historical Evidence suggests that Polo’s discoveries and their reporting lead to an increase in International Trade. Columbus brought a Spanish medicinal practitioner after his second voyage in 1493, and that physician invented spices like capsaicin and allspice (Figure 1.6).

Figure 1.6: Allspice that has the aroma of a combination of spices, especially cinnamon, cloves, ginger, and nutmeg.

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Chemistry of Spices

Source: https://pixabay.com/en/allspice-piment-spice-spice-grain-686859/

Around the 15th century, trade routes were established to India via Sea and the spices from India began to be exported to other countries. These included ginger, nutmeg, mace, pepper, and cloves. King Manuel was the creator of many new markets of spices across Europe. Pepper trade was monopolized by the Portuguese, and the cost of the pepper was used as the measure in European business. In the period from 1600 to 1861, plant-based medicines became common in the United States (US). Drinks flavored with various types of leaves began to be used as beverages. By the beginning of the nineteenth century, American commerce was no longer hindered by the British taxes and his trade of products like butter, cheese, soap, and flour for spices became common. Today, the distribution of spices from one world to the other is highly commercialized. Research in spices is also rising as more and evidence is found which affirms the writings of the ancestors about the spices.

1.3. CHEMISTRY OF SPICES As stated previously, every spice has a major organic compound that lends it some unique flavor or aroma. In this section, we will look at some of the major constituents in a few spices.

1.3.1. Turmeric The major constituent in Turmeric is the curcuminoids that give it its yellow color (Figure 1.7).

Figure 1.7: Circumin, major constituent of turmeric. Source: https://commons.wikimedia.org/wiki/File:Curcumin_structure_(keto). svg

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1.3.2. Bay Leaves The major constituent in Bay leaves is the 1,8-cineole (Figure 1.8).

Figure 1.8: Bay Leaves and its major constituent (1,8-cineole). Sources: https://commons.wikimedia.org/wiki/File:1,8-Cineol2.svg, https:// en.wikipedia.org/wiki/File:BayLeaves.jpg

1.3.3. Black Pepper The major constituent in Black pepper is piperine because of which it is pungent (Figure 1.9).

Figure 1.9: Piperine—the main constituent of black pepper. Source: http://www.epharmacognosy.com/2012/07/piperine-biological-sourceit-is.html

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Chemistry of Spices

1.3.4. Cinnamon Cinnamon gets its flavor from cinnamaldehyde (Figure 1.10).

Figure 1.10: Cinnamaldehyde. Source: https://commons.wikimedia.org/wiki/File:Cis-Cinnamaldehyde.svg

1.3.5. Oregano Oregano has a constituent called carvacrol because it has its characteristic odor (Figure 1.11).

Figure 1.11: Carvacrol from which the characteristic flavor of oregano comes. Source: https://commons.wikimedia.org/wiki/File:Carvacrol_acsv.svg

1.3.6. Coriander Leaves In the coriander leaves, the two main chemical components include 2-decanoic acid and many aldehydes that have 9–10 carbons.

1.3.7. Saffron Saffron gets its color from a chemical compound called the crocin (Figure 1.12).

Introduction to Chemistry of Spices

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Figure 1.12: Saffron’s constituent crocin that gives a yellow color to it. Source: https://commons.wikimedia.org/wiki/File:Crocin.png

1.4. VALUE OF SPICES As we have seen in the history behind spices, they had a very high value, and it remains high even today although the ways in which they are valued have changed. Common spices are not very cheap, and some like cardamom have quite a high cost. A pound of saffron today costs as much as almost 7,000 dollars (Figures 1.13 and 1.14).

Figure 1.13: A Spice market in Dubai.

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Chemistry of Spices

Source: https://pixabay.com/en/spices-spice-market-market-dubai-1321120/

Figure 1.14: Red ginger. Source: https://pixabay.com/en/viet-nam-spices-red-ginger-market-1093014/

1.5. CONCLUSION The spices tend to yield a great as well as varied variety of the organic amalgamations, within which, most of these compounds generally averse being a participant directly in the process of evolution as well as progress. All these pertaining amalgamates were conventionally being known as the secondary metabolites, having an assumption or prediction of the prodigious consideration. Though, much have been considered regarding the criticality of the chemical structures along with their trails belonging to the biosynthesis, all the natural products, be it the turbulent ones or the non- turbulent ones, have been often apprehended as irrelevant in terms of biology. Various secondary metabolites that are being present within spices are being considered as an area of fertility in order to have assessment of the chemicals since few decades, striving for having evolution of the novel reactions of the synthetic along with its methodologies as well as the analytical chemistry. In the current years, many of the researchers have witnessed the presence of great prominence on the secondary metabolites in comparison to that of

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the various other dietary elements or the components that might be having a hold of the dramatic effect or influence on the pertaining health of the human beings. In here, most of the present spices, as well as herbs, tend to make up or create certain essential secondary metabolites, which are considered to be bioactive, and that have flexible properties of medicine along with the pharmacology. The persistence of the relationship of the structure-activity form of all these presents amalgamates has been acknowledged as an ecstatic, wherein the nanotechnology, as well as the molecular biology, would certainly be presenting with an interdependent part to play.

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REFERENCES 1.

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Compound Interest, (2014). Chemical Compounds in Herbs & Spices. Compound Interest. [online] Available at: https://www.compoundchem. com/2014/03/13/chemical-compounds-in-herbs-spices/ (Accessed on 9 March 2019). Institute, M., (n.d.). History of Spices. McCormick Science Institute. [online] McCormick Science Institute. Available at: http://www. mccormickscienceinstitute.com/resources/history-of-spices (Accessed on 9 March 2019). Research Gate, (2003). [online] Available at: https://www.researchgate. net/publication/275771715_Case_Study_-_THE_NUTMEG_AND_ SPICE_INDUSTRY_IN_GRENADA_Singh_R_Sankat_CK_and_ Mujaffar_S (Accessed on 9 March 2019). Spexcertiprep.com (2018). Webinar. The Chemistry of Spices. SPEX CertiPrep. [online] Available at: https://www.spexcertiprep.com/ webinar/the-chemistry-of-spices (Accessed on 9 March 2019).

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CONTENTS 2.1. Introduction ...................................................................................... 18 2.2. Top 10 Most Popular In The World of Spices ..................................... 18 2.3. Spices Color and Chemistry .............................................................. 22 2.4. Contamination of Spices With Chemicals at Production Stage .......... 29 2.5. Countries Having Most Spices .......................................................... 39 2.6. Export of Spices ................................................................................ 42 2.7. Spice Blends ..................................................................................... 43 2.8. Conclusion ....................................................................................... 47 References ............................................................................................... 49

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Spice trade opened trade routes in many countries, and since then they became an important commodity that is used in foods. Each part of the world has some unique spices associated with it. Spice can add any flavor to the food, be it acidic, spicy, sour or sweet. The in-depth analysis of the constituents of spices while exploring their unique characteristics and regions of origin offers a very vast subject that is very interesting to explore.

2.1. INTRODUCTION This chapter covers the spices that are most commonly used in the world. The usage of each in the relevant cuisine and the place of origin are also introduced. Next section is the one covering the most important aspect of the spices, i.e., their chemistry. Many aspects related to spice composition; spice flavor, spice fragrance, spice production, spice contamination, and spice quality are covered in detail. Countries having a larger number of spices are covered next followed by a continent wise list of spice blends found across the world.

2.2. TOP 10 MOST POPULAR IN THE WORLD OF SPICES In this section, we are going to discuss the most famous spices across the world. The most common spice in the world is Basil. Although Basil is a herb, it is used in many combinations with the spices. It has a taste that a mix of sweet and sour. The main value of basil is in its characteristic fragrance that can be destroyed by heat. So, it is mostly added to the cooked dishes to get the perfect aroma (Figure 2.1).

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Figure 2.1: Basil. Source: https://pixabay.com/en/basil-herbs-food-fresh-cooking-932079/

The second most used is the Marjoram. The primary use of Marjoram is as a seasoning in every meal. Spicy mixtures of marjoram with tarragon, basil, rosemary, and thyme are very common in many world famous cuisines. Essentially, Marjoram itself is also an herb, but its flower and the leaves are used to make the spice (Figure 2.2).

Figure 2.2: Marjoram. Source: https://pixabay.com/en/marjoram-cooking-2370814/

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The third most used spice in the world is Cinnamon. It is very common in Eastern countries. It is used as a seasoning, in pastries, hot chocolate, and coffee. The flavor of cinnamon is used widely in drinks, muffins, pickles, biscuits, fruit salads, vegetable salads, and so on (Figure 2.3).

Figure 2.3: Cinnamon sticks, dried flowers, and cinnamon in powdered form. Source: https://en.wikipedia.org/wiki/Cinnamon

The fourth most common spice is the Cloves. Cloves are actually the aromatic flower buds of a tree that is known as the Syzygium aromaticum belonging to the family of Myrtaceae. The tree is native to Indonesia. Cloves are used to cook a variety of dishes like meat, pork, and vegetables. Clove is also widely used in making desserts like puddings, pastries, and compotes to give a unique flavor to the sweet dishes (Figure 2.4).

Figure 2.4: Syzygium aromaticum, the plant from which cloves are obtained.

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Source: https://oddstuffmagazine.com/top-10-popular-world-spices.html

The fifth most widely used spice is the Mustard. Mostly, it is used to grill meat, eggs, and sausages. In Russia, the mustard dressing is a must in many dishes. Many flavors of mustard are used in Russia and other countries. It serves as an important addition to the sauces, mayonnaise. Using mustard coating with fish protects the meat juice from being leaked and also adds a very good aroma to the dish. The sixth most used spice is the Allspice. As noted previously, allspice has a unique taste of its own. It is not a mixture of some spices as the name suggests but an individual spice. It is often used as s substituent to black pepper because it is similar in taste to black pepper. When used with any non-vegetarian dish, it tastes perfect. Allspice is not only used in food dishes, but also used in the preparation of confectioneries and liqueurs The seventh most used spice is Ginger. It is one of the fragrant spices. It is used in the manufacture of sweets. It is used in all dishes like vegetables, meat, desserts, rice, and the dishes involving egg. Ginger is also an important ingredient for some soft drinks and beer. In some cuisines like Japanese, ginger is served as a side dish like sushi. Sometimes, the ginger is also eaten raw after marinating it. The health benefits of ginger include improved metabolism, and it also helps in weight loss.

Figure 2.5: The turmeric plant.

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Source: https://commons.wikimedia.org/wiki/File:Turmeric_plant.jpg

The eighth most widely used spice is the Turmeric. It is famous in the east and in Europe. The taste of turmeric complements fish recipes, egg recipes, beans, cheese, rice, and salad recipes. Turmeric is one of the most important ingredients of the local cuisines in all parts of India. Indian taste cannot be complete without turmeric. It is also used to preserve pickles as it keeps them fresh. Turmeric is considered as one of the most favorite spices in the East (Figure 2.5). The ninth most used spice is the Bay leaf. Its most common use is to pickle the vegetables, and it is also used to prepare many meat dishes. It is also an important ingredient for soup and sauces. The tenth place in the most used spices is occupied by Nutmeg. It is used in the preparation of meat dishes and vegetable dishes. Other uses of nutmeg are confectionery, pasta, and eggs. Seafood and pastries are also complemented with the use of nutmeg in many cuisines across the world (Figure 2.6).

Figure 2.6: Nutmeg. Source: https://en.wikipedia.org/wiki/Nutmeg

2.3. SPICES COLOR AND CHEMISTRY When we talk about any chemical that acts as a colorant for any spice, there are two possibilities: either the color is a dye, or it is pigment. The difference between them is that the pigments will not get dissolved in water but the dyes will.

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The color of any spice means the visible light. Visible colors are the colors that fall in the spectrum from 400 to 700 nanometers. If any plant absorbs the light between this visible range, its color to the visible eye is yellowish green. There is a particular atom or a group of atoms in a functional group that gives the color to a substance. And that atom or the functional group is called chromophore. The functional group can be a conjugated pi-bond, combinations of alternating single and double bonds. An example is a carotene which is a terpenoid hydrocarbon with several isomers. Carotene lends orange or red color to the substance in which it is present. Another example is chlorophyll which is a pigment that lends green color because it contains magnesium. There is another group of atoms called the auxochrome due to which the ability of the chromophore to absorb the light is affected. Auxochrome is said to help in the perception of a color to the eye. Examples include carbonyls, amino groups, carboxylic acids, and hydroxyl groups.

Figure 2.7: Saffron. Source: https://pixabay.com/en/saffron-spice-taste-color-cook-2119547/

When we study the chemistry of plants, we find that the primary color in all plants is green due to the presence of the pigment chlorophyll. It is the magnesium in all the compounds that cause the color to be displayed.

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Another compound called the Anthracene is also a conjugated complex that is aromatic. A carotenoid is a compound that will absorb the light that lies between 400 and 500; that is the blue light will be absorbed, and the red, yellow, and orange colors will come out. Saffron, the most expensive spice, has a component called the crocin which is responsible for the orange color of the saffron (Figure 2.7). In the flower marigold, it is the xanthophyll compound that produces the yellow color. Out of all the natural color compounds, the flavonoid is the biggest group. They are defined as the plant chemicals present in almost every fruit or vegetable which are responsible for their beautiful colors. Flavonoids not only add color but they also have benefits for the immune system as they are anti-inflammatory. These flavonoids are usually composed of fifteen carbon backbone structures that have two phenol groups, a heterocyclic ring, and the pattern is usually C6-C3-C6. All of them contain a ketone group as well. The flavonoids are divided into three categories as given below: • Isoflavonoids; • Neoflavonoids; and • Bioflavonoids. All compounds or functional groups that are responsible for the color of a compound or its flavor have antioxidants in them. Terpenes are one such group. In the last few years, it has become a common practice to discuss the antioxidants to be present in polyphenols and anthocyanins. It is due to the health benefits associated with the functional groups adding color that fruits like blueberries and grapes are considered a plus for a healthy lifestyle. If we look at the medicines, most of them are derived from plants. About 80% of the primary healthcare methods are derived from herbs. There is a reason why so many herbs and spices are used for medicinal purposes in healthcare. These plants have such chemical compounds in them which make them antioxidant and antimicrobial. A very simple example is this regard is capsaicin and mint. These are used to bring relief from pain and are derived from plants itself. Let us understand how capsaicin helps to fight pain. It is basically a process of fighting pain with pain. Whenever pain occurs in the body, neuropeptides are released by the nervous system. It is released as a response to the pain

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caused by inflammation. A neuropeptide is a compound that is not only a neurotransmitter, but it acts as a neuromodulator as well. When we apply the capsaicin to the body, the neuropeptides are demolished, and this reduces the pain. Capsaicin also inhibits the activity of the c-nerve fibers. C-nerve fibers are the ones that cause throbbing pain. Now let us look at the ointments like camphor and mint that have the cooling effect. An opposed to capsaicin, these pain relievers give a cooling effect. The process is the same: forbidding the activity of the c-fibers causing the throbbing pain and causing a simulation of some nerve fibers. This sensation in the body is called chemesthesis. Chemesthesis are the type of sensations which activate the receptors of senses different from the ones like taste. These sensations are the ones that create perceptions of cold, heat, and pain. The ointments like mint infuse coolness in the body by activating the trigeminal nerve sensors that send the signals to the brain for sensing cold. These chemicals activate the ion channels of the nerve cells, and this is how the feeling of the coolness is preserved. For the spices, the TRP1 and TRPA2 receptors of the nerves are activated that cause the sensations of extreme pain. This is the reason why it is advised to not touch one’s extremely sensitive parts like nose or eyes while cutting the peppers or while handling the hot sauces. When you are touching these hot spices, it is not the taste response that will cause the extreme sensation but the pain response. Wherever there is a mucous membrane, the action will be there, and it will result in pain. Now you know that it is the compounds like capsaicin and piperine in spices like pepper that cause the pain.

2.3.1. Scoville Scoville is basically a scale to measure the spiciness or the pungency of spicy foods like peppers. The capsaicin compound in itself has about sixteen million Scoville units which comes equal to about 70% of the compounds generating heat in a pepper (Figure 2.8).

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Figure 2.8: Scoville scale board on display at a spice market in Hoston. Source: https://commons.wikimedia.org/wiki/File:PepperswithscovilleCentral MarketHoustonTX.JPG

The use of the Scoville scale was invented by Wilbur Scoville. Wilbur was an American pharmacist, and he invented the use of this scale in 1912. Let us now look at the process of how the Scoville scale is determined. The first step is to take an extraction of a dry pepper which is then immersed in alcohol. The second step is to dilute the extract immersed in alcohol. This is done through multi-point dilutions using the sugar water. The third step is the empirical testing in which a panel of experts tastes the hot peppers or the hot sauces. This test is like a sensory test. Different concentrations of hot sauce or the pepper are given to the panel for testing. The panel usually has five experts. If three experts report the heat in a single concentration level, it implies that the test has yielded a positive result. According to the level of the dilution, the Scoville units are calculated. A habanero pepper has about a hundred thousand Scoville heat units. Carolina pepper is the one having the highest level of Scoville units, and the figure is two million Scoville units. You might have come across pepper spray that is uses as a safety measure by women and for other relevant security purposes. This pepper spray usually has about four to five million

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Scoville units. This is the reason why these pepper sprays are used for the security purpose. One might have seen many videos where people take up the challenges of having the hottest sauces. Over the time, any person eating a hot sauce gets acclimated to that taste, and with more chances of experiencing that taste, more heat is actually required to activate the pain reaction. This is why anybody who likes spicy food looks for more spicy food each time he eats one. There is a city called Irvin dale in California where a controversy of shutting down the Sriracha factory came out in 2014. As a response to the ongoing debate, the public started storing stock of the hot sauces made by the factory. The reason of shutting down was the offensive odor. A solution was then found to get rid of the bad odor, and the hot sauce was brought back to the market. The base ingredient for all the hot sauces is the chili pepper which was discovered in America itself. However, today the primary producer of the chili peppers is India. There are many varieties of chili pepper. Some of them are given below: • Bell peppers; • Cayenne peppers; • Frutescens; • Scotch bonnets; • Carolina reper; • Rocoto; • Aji. Over the years, studies have found out the presence of some metals in the spices. Traces of heavy metals have been found in the common hot sauces. A Chinese hot sauce packet was found to have twenty-one parts per million of lead which is 30% of the permissible intake per day. Now let us look at some of the compounds that give flavor to the most common spices. Carbohydrates like Sugars, ethyl maltol and glucose give a taste of cotton candy in some spices. The carbonyls found in the ketones are responsible for the berry-like taste found in raspberry, apple, and bitter almonds. The organic acid compounds are responsible for giving the flavor of a pear. The salty taste can be attributed to the ionic salts.

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Monosodium glutamate called as the MSG gives the savory flavor in noodles and cooked meat. In beer, the flavor compounds give a feeling of a hop due to the compounds called like the esters. The compounds that can give the natural flavor are very expensive. An example of this is the raspberry ketone whose extract costs about 10,000 dollars per pound. The perception of any taste is based on the part of the tongue that tastes the flavor. The sweet taste is done by the front part of the tongue, and this comes from proteins and carbohydrates. The G-protein receptors present in the taste buds are the ones responsible for tasting the sweetness. The perception of the salty taste is done by a blue part near the front of the tongue. This area has ion routes which are taking the metals like sodium and potassium. The perception of the sour taste is due to the acids, and this is received by the side portions of the tongue. The bitter taste is perceived due to the presence of the compounds called the phenols and the catechins. This bitter taste is detected by the nerves called as the type-2 taste receptors. The reception of taste offers interesting studies about the food product being tasted. Let us take the example of cilantro. The seeds are called coriander and cilantro is the name used when the leaves are used. Many people around the world do not like the fragrance of cilantro. They feel it tastes like soap. In a survey at the University of Toronto, a set of people were asked about their country of origin and their views about the taste of cilantro. About 20% of the people agreed that it does taste like soap. In another survey, 70% of the people from Europe also feel the same about cilantro. There is a reason why cilantro actually feels like it is soaps. There is a good percentage of the aldehydes in the cilantro which are also present in soaps. One aldehyde has a unique odor which is also found in soaps. In Cilantro, there are three types of aldehydes, and this is the reason why it tastes different to some people. It is advised that the cilantro must be crushed and then left to oxidize, this will change the bad scent into a pleasant one and hence the pleasant taste. Let us now look at another interesting fact about the nerve receptors. The dislike of cilantro has a genetic aspect associated with it as well. A particular type of nerve receptors cannot process the unsaturated aldehydes and convert them into pleasant compounds. These receptors are not present in the taste buds, but they are a part of the olfactory system. This seems true because almost 80% of the taste perception comes due to the odor. This is also the reason why one cannot taste food when one has caught cold.

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This brings us to the discussion of how we perceive the fragrance of different spices. The part of the sensory system that is used for smelling is called the olfactory system. In humans, this system functions like as a chemoreception system. Any chemical has certain odor to it. This odor enters through the nasal passage, is diffused by the medium of mucus and then olfactory nerves get activated. The olfactory system is the only sensory system which has a direct connection the forebrain. All the other senses are first processed by the central brain, but the sense of smell is directly sent to the forebrain. The natural components carrying the fragrance are mostly the flowers. The fragrance is due to the volatile chemicals having mass less than even hundred units. You might have heard or seen the natural air pollution in which portions of haze hang around the sky and cause the blurring of the vision. This is actually the Volatile chemical pollution or the off-gas from plants. This smoke kind of cloud is a cloud of compounds like isopropene units, terpenoids, terpenes, and terpenols. When it comes to fragrance, terpenes are a very important compound. Most of the compounds get their natural smell from these terpenes present in them. For example, the limonene that gives the citrus scent in the lemons or other citrus fruits.

2.4. CONTAMINATION OF SPICES WITH CHEMICALS AT PRODUCTION STAGE If we consider the regions of the world where the spices are grown, we find that about 60% of the spices are grown in India and smaller percentage is grown in countries like Bangladesh, Turkey, and China. In all the production areas, the environment is not the same, and some regions have sanitation issues. This first came into the limelight after the issue of salmonella poisoning in Mexico. The studies conducted to analyze the situation revealed that in typical Mexican grocery stores, the level of salmonella contamination was found to be equivalent or higher than those of the intestine fecal sample of the local animals. This case and a few similar ones brought attention to the fact that the quality was being compromised of spices and this practice was going unnoticed. The storage conditions had to be questioned, and the purity issues came up as to whether any type of dirt or sand was being added. This led the researchers and experts to look at all the stages of rice processing and look at

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the points where there were the chances of contamination to occur. There are many points in the processing stage of the spices where contamination can occur. The first stage is the storage of spices in big stocks as the spices are received in bulk quantities. Quality checks and proper inspection is crucial at this very first stage to prevent the contamination. The quality check must establish whether the form of spices that they are getting is an original one that is expected to be there or whether they are getting a modified or replaced version. Here is a complete list of questions that must be addressed to make sure that the spices are contaminated in any way. • •

Is there an adequate identification process in place? Are the hazards associated with the spices being identified and addressed? • In what conditions is the stock of the spices stored? • Are the stocks kept for years so that the required production can be met? • Is the climate of the place where spices are stored suitable for the purpose? • Is the location of the storage of spices free of pests? A good practice that can be followed to keep the spices safe is to fumigate the raw material in order to protect it from pests and rodents. It should also be checked whether the materials being used to fumigate are legal or not. In the initial processing stage, it must be noted what kind of sorting is done and the medium through which it is done. Is it mechanical or physical? Another step that must be adopted is to make sure that the cleaning is done. In the cleaning process, following points must be noted: • • • • • •

Are some chemicals used for cleaning? Are those chemical filtered from the spices after cleaning and how it is done? Are residual solvents being used to get rid of the cleaning chemicals? Is the raw material being dried after cleaning? What are the conditions under which the material is being dried, it is being dried in a kiln or in open air? What is the procedure of the processing of the spices?

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•

What is the procedure of the roasting of the spices if that is being done? Spices contain many volatile compounds as their constituents. The boiling points of most of them fall under the mark of 250°C. In the process of roasting, the temperature could be raised to a higher level than this temperature of 250°C that could have an impact in some way or the other. Grinding is a must in every production of spices; therefore it must be checked whether there is a dedicated grinder for the same. If the same grinder is being used for some other purposes as well, the chance of contamination rises by manifold. In spices, the cross-contamination of nut allergens can be problematic. The age of the equipment being used for spice processing also needs to be taken care of. The worn out metals can contaminate the spices. At the final stage of packaging, there is a big chance of the spice material getting contaminated with the packaging materials. This must be checked so that no unidentified ingredients get mixed with the spices. The most common form of contamination is with the microorganisms which include viruses and bacteria. A report by the Food and Drug Administration (FDA) suggests that 7% of the spice products are contaminated by salmonella infection which is a bacterial disease that affects the intestinal tract. It has also been discovered that spices are more likely to be contaminated as compared to other food products. There is also a risk of contamination from molds. A mold is type of fungus that grows in the shape of multicellular filaments. Improper methods of storage can definitely result in an increase of mold growth. This can also occur to the increased levels of moisture. Then there is the filth like the insects, dirt or other unwanted particles. It has been found that almost 12% of the imported spices get infected with filth and this causes the rejection of the shipments as well. There may also be a cross-contamination by other spices, food products or nuts. Severe contamination can result due to the use of excessive amount of pesticides or using the illegal pesticides. Other issues may rise due to use of solvents in manufacturing or the use of heavy metals. Chemicals like unapproved additives and preservatives can also cause serious contamination. The underreporting of additives can also occurs that may be a cause of concern. It is also important what additives can be considered as nutrients and which will contaminate.

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The levels of the toxic metals need to be monitored as these can cause severe problems. Some metals that are particularly toxic are mercury, cadmium, and arsenic. Their high concentration is particularly hazardous. Metals like zinc, chromium, magnesium, and lead are also on the watch list as their contamination with the spices can occur in any way like nutrients, preservatives, additives, or as part of worn-out machinery. Wear metals that can cause the contamination are the iron, chromium, aluminum, iron, and copper. The United States (US) Department of Agriculture keeps a database in which the nutrient content is reported. You must be wondering now how can a person tell if the spice has excess of the nutrients or the additives. For this, one needs to cross verify whether the spices are coming under the permissible levels of the distribution of the spice products. The spice products that can be used for checking include condiments, sauces, teas, salt, and black pepper. The varieties of the whole form and the ground form can also be checked. Comparison between brands in terms of organic produce can also be made. On a general level, following scenarios can be studied to ensure the purity of the spices: •

Determine the level of contamination by additives and the nutrients. • Determine the concentration levels of the toxic metals. • Check if there are any metals which the spices may have come in contact with unexpectedly and the same were either not reported or under-reported. • Try to identify the patterns of adulteration. Let us look at an example of performing an analysis of a spice for adulteration and contamination of any kind. In a particular study, the experts choose to find out the adulteration in a very common spice called the chili powder. The first thing that he did was to buy the chili powder from different outlets as follows: • • • • •

Chain store of Walmart; Solar store; Retail shops; Any supermarket; Organic brand;

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• Order online. These were the results found when the level of toxic metals was noted in all of them: • •

Chain store of Walmart – Unreported salt; Solar store – 1.2 ppm cadmium, 0.4 ppm arsenic, 7.1 ppm chromium; • Retail shops; • Any supermarket; • Organic brand – 2 ppm of lead, unreported salt mix having an average of 2% Sodium; • Order online. Other metal constituents in spices like cinnamon and turmeric for the same study are given below: • ppm of lead in cinnamon; • 2.2 of lead in red pepper. There is a reason why heavy rate of sodium is found as an additive, but it is not reported. It is because of the money. Adulteration brings money for the producers and for the manufacturers, but the value for the customer decreases. If we talk about the US, then the food products in which adulteration is most common are as follows: Juices, olive oil, spices, honey, and milk. The canola oil is just about 25 dollars per hundred pounds whereas olive oil is 115 dollars per hundred pounds. This is the reason why canola oil is the most common adulterant for olive oil. Milk is usually adulterated with urea and water as real milk costs about 100 dollars per hundred pounds. Juices are also very expensive in the states, same as honey and these are most frequently adulterating with corn syrup. Another study at New York revealed that almost 80% of the spices imported to New York have the similar levels of adulteration as stated above. The FDA of US defines the adulteration as the not permitted level of any component in a food product that will cause harm. A food product whose quality is compromised means the substitution of a constituent to it or the addition of another. This can result in an inferior or damaged product. Let us understand what a damaged spice product would mean. Suppose we take garlic as an example. Now a plant of garlic will have its leaves, roots, stem, and flowers it is the little buds on the plant that

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is going to be of use. If we get any other part of garlic plant, and not those buds, it means we are getting a damaged or an inferior product. Grinding the leaves and the stem will not give the product so it will be considered as an inferior product. Any product that has been kept in storage for a long time and a growth of mold has formed on it is a damaged product as well. Intentional adulterations can also be used that compromises the original product. This might be done for benefits listed as follows: • Altering the weight of the product; • Altering the strength of the product; • Altering the quality of the product. The most common intentional adulterations for spices are materials like sawdust or bran powder, silica or sand, starch or flower, salts like sodium, like sodium chloride, chalk or talcum powder, charcoal. It’s interesting with charcoal, and there was an adulterant or counterfeit for cumin seeds where you take grass seeds, and you call them charcoal, so you make them look like cumin seeds, but they are actually grass seeds. Brick powder is often substituted for things like chili powder or cumin powder. Then you have your illegal dyes; things like your lead chromate dyes, your azodyes, your metanil yellow; these are meant to take a product that may be lost some of its color that would be natural for that spice and basically dye it back to make it look more appealing or more like the spice they are trying to pass it for. Then there are illegal preservatives, preservatives that are not approved, and maybe they have an old product that they want to make sure that it lasts in the warehouses or in their processing facilities for a year or more so they’ll add illegal preservatives or illegal pesticides, either illegal amounts of pesticides or totally illegal pesticides. So how do we find out if a sample is adulterated or counterfeited? Well, you can build a spice profile. For that, you need reliable sources of valid data for real products which can be very difficult to come by. Here in the US, the USDA actually does provide spice profiles or food profiles. If you go to their national nutrition database, they will give you what a typical spice or food product would look like in terms of all the nutritional information. And sometimes they also have a lot of statistics that go along with it. This one happens to be for caraway seed.

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One can also do journal searches for marker compounds. So, there are things like the capsaicin which are indicative to hot peppers so that could be an organic marker compound if you are trying to test the validity or the actual product to see if it is counterfeit or not. You can examine your chemical data for your targets, do you see heavy metals, do you see wear metals, do you see unreported additives? And you compare your data against your profiles. Black pepper is the king of spices, it is 20% of the spice market, and it is the un-ripened cooked fruit of the flowering vine Piper nigrum, and the fruit is called the peppercorn. The largest producers of black pepper in the world are Vietnam and India, and they’re harvested from May to August, and each vine will yield about 10 kilograms of peppercorn a season. It takes 12 years for a vine to mature enough to actually produce a harvest. There are technically three colors of black peppers, but we know four (excuse me, or peppercorns), black pepper which is 75% of the peppercorns sold, white peppercorn which is 25% sold, now some people think white peppercorns are actually different than black peppercorn, it is the same peppercorn. What happens is they take those peppercorn, and they soak them in running water, like a stream, to rot over the course of several weeks, that outer layer rots off and separates and you’re left with the white layer underneath. You also have your green peppercorns, which are pickled usually and they are a specialty food item. Then you have red and pink. These are not actually from the Piper nigrum plant; they are from a different species altogether. So the active compounds that you could build a profile around, the organic compounds for your flavor, is piperine, it’s 5 to 10% by mass, and it is the outside layer of the plant so that blackened or that green layer is where that piperine compound comes from. So, if you’re going to have a white peppercorn, you actually lost that outer layer. Now that compound actually is very reactive to light and will change very quickly, that is why they say you shouldn’t really buy ground pepper that is more than a few weeks or a few months old because it very quickly loses that flavor compound. Now if you’ve ever tasted real black pepper, freshly ground and then tried what most Americans grew up with as black pepper that stuff that sits in the shaker for years, there is a very big difference. There is a different quality to the taste, there’s a different quality to the smell, and that is mostly because these volatile compounds very quickly change to other things or volatilize off the pepper, so you are better off getting a whole peppercorn in

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order to get that fruity fragrance and flavor. Now the peppercorn, if they’re being ground, you have to be concerned about what temperature is it being ground at or roasted at because the melting point for the piperine is 130°C. The scent compounds for pepper, which makes that spicy floral scent, is caryophyllene and pinene and they are both terpenes. When we looked for contamination and additives, we found lead and chromium mostly in our dollar store brand at about one point two (1.2) ppm. So, we did find some lead contamination. We used the USDA database for black pepper, and they did have quite a few data points, they were able to give us statistics, and from those statistics, we calculate three standard deviations, and we were able to build a profile for black pepper, what would be a normal distribution for black pepper. Now there were two elements that we were interested in, the silica and aluminum, and we could not find USDA data for, but we did find references in the literature for silica being at 20 micrograms per gram in seeds and between 100–200 micrograms per gram for fruit and grain. For aluminum, we found references for teas at 100 micrograms per gram and for a baking mix where aluminum is added that was about 800 micrograms per gram. When we took our data and compared it to the USDA, one product clearly fell out of distribution, the dollar ground E. The darker the purple compound, the farther away from three standard deviations, so it was purple it fell outside three standard deviations. And you can see out dollar ground E for every single compound fell out of three standard deviations. We also had magnesium and aluminum and silica fall out of three standard deviations for what normal black pepper should look like. In particular, what we found was that there were toxic metals, of course, the lead and we saw large amounts of additive metals that were not reported or under-reported. If we look at the retail whole black pepper, that’s the very last black pepper, and you can see that the silica level for whole black pepper from a reliable retailer, with 300 micrograms per gram. But, in our dollar store, in our dollar store ground E and something like our Farmers ground, it was close to 1,000 micrograms per gram, if not over 1,000 micrograms per gram, so clearly silica was added to this. When we look at the sodium level, the sodium levels for most of our reliable black peppers were the 100, 150, and 200 ranges. But the dollar ground E was closer to 300 as well as the farmers ground, closer to 300 micrograms per gram. We also found patterns that suggested adulteration, it was the dollar store brands that we saw the high metals in, and it was the dollar store brands

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that fell out of distribution. So, our cheap spices were the ones that tend to be out of range. And we happened to read about a solvent test, test for the counterfeiting of black pepper. A popular process for counterfeiting black pepper, especially whole black pepper, is to take papaya seeds and dry them, they look very, very similar to black pepper, whole black pepper, and then you can substitute out all or part of the whole black pepper for these dried papaya seeds. The dried papaya seeds, however, will float in a solvent where real black pepper seeds will actually fall to the bottom. So, hearing about this little experiment, we decided we would try it on our two whole black pepper samples, our whole dollar store, and our whole retail, our whole retail is on the left, it fell to the bottom, but our whole dollar store floated to the top, so we did have what we believed to be a counterfeited whole black pepper. Our second profile is cinnamon. For cinnamon, you are actually consuming the inner layer of the bark, and the largest producers in the world are Indonesia and China. And there are many varieties; they’re all based on different sizes, bark thicknesses, they have slightly different flavors and fragrances. What we think of as cinnamon or most of us is cassia. It’s the most common; it’s also called the Chinese cinnamon. There are other types of cinnamon that are more expensive, the Vietnamese cinnamon and things like that. Cinnamon is a tree that’s grown for two years, and then it is cut down to ground level. That will force the tree to send up much thinner shoots and then those are cut down to quills and graded for size. For our samples, we looked at seven spice samples; they ranged between one dollar and twenty-nine dollars for 100 grams. We had an organic sample, two whole samples of cinnamon and different cinnamon products; a cinnamon tea, which was a mix of three cinnamons and a supplement, which was the Loureiroi cinnamon. When we built our profile, the flavor and fragrance compounds marker would be cinnamaldehyde, and it’s up to 1% for the mass of the bark, and it’s in the essential oil. Ninety percent of the essential oil is the compound cinnamaldehyde, and it has a boiling point of 248°C. So, if it’s being roasted or dried in any in a kiln, it could be driving off some of this volatile compound. When we looked for our heavy metals, we did find all of our heavy metals in our cinnamon compound and the worst offenders were all of the metals for the cheaper brands, with the exception of, unfortunately, our

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organic brand again, seemed to have some lad at almost three ppm. You can see mercury in our three cheaper brands, the dollar E, the dollar 5 and the farmers. We found cadmium at 0.6 or 0.9% of the daily allowable daily allowance. So, there was quite a bit of metals in our cinnamon, again we went to the USDA, and we found our cinnamon distribution, found all of our different nutrient metals, and we calculated our three standard deviations. For this, we have several products that seemed to be questionable. Our supplements and our tea did fall out of distribution, and now this might be because they are products and not “quote/un-quote” spices, or it might be that something has been done to those supplements and teas that do not characterize them as cinnamon anymore. Our dollar store E clearly fell out of distribution, and then there were some wear metals or other compounds that were questionable. What are very surprising though are things like our silica. On our supplements, silica was not listed on the supplements ingredients list, but we found it 10 times higher than some of our other samples, our retail sample at 100 micrograms per gram and here the supplement was 10 times that amount at over 1,000 micrograms per gram. Also, surprising, the tea, which is considered to be a supplement or food product, had sodium in it that was not reported on the label. If you look at the sodium for retail, you’re looking at between 50 and maybe 150 micrograms per gram but for the supplement, it’s over 200, and for the tea, it’s over 600 micrograms per gram. So, did we find any toxic metals for our cinnamon? Yes. Were their large amounts of additive metals not reported or under-reported? Yes, especially the products were not in range, and some of our cheaper spices were out of range. So, what does that mean? That means there is an obvious cost when it came to the heavy metals. The cheaper samples, the dollar store samples, where more than 50% of the samples were high metals, particularly our dollar SI brand. This one brand did come up over and over again, or our dollar eat 31 and 23% of the highest heavy metals that we found. Most of our cheaper samples were about 77% of all of the high levels including our dollars and our chain stores, and it does show that there is economic motivation for adulterating or allowing increasing contamination into these samples. We will give you a little summary of some of our spice findings.

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Did we find toxic metals? Yes, mostly lead, then cadmium, some arsenic, a lot of chromium, but it was total chrome and not designated as chrome six or isolated as chrome six. Some of the levels, especially in the hot sauce, were of levels of concern. Where there are large amounts of under-reported or non-reported wear metals or additives? Yes, mostly sodium, silica, magnesium, and iron. Were there patterns of adulteration? Yes. There were some suspicious colors and consistencies of these spices. Some of the black pepper spices, especially the one that fell out of distribution, had a very uniform gray color, it did not actually look like black pepper, and it looked more like charcoal. I didn’t have the characteristic flex that you would expect in black pepper. Some of our spice mixes, our chili mixes, and chili powder mixes, had an odd color to them, very unrealistic looking colors and consistency. There were also products and spices that did not fall with what would be considered normal distribution with our USDA range, especially in the cheaper brands of spices, the dollar brands. And there were some clearly counterfeited or adulterated spices.

2.5. COUNTRIES HAVING MOST SPICES The craving for a spicy dish is a one which we are all familiar with. Across the whole world, every region has developed its cuisine on the basis of spices that originated in that country. In this section, we will look upon a list of the countries where spices are used to the maximum extent (Figure 2.9).

Figure 2.9: Ancho chilies from Mexico.

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Source: https://commons.wikimedia.org/wiki/File:Chile_Ancho_seco.JPG

The first in the list is Mexico. Here, you will not come across any dish that does not have any chilies in it. Most of the chilies like Jalapeno, Habanero, Ancho, Serrano, and all are grown at home. Mexico is a city that can properly test how much of chilies will you be able to tolerate (Figure 2.10).

Figure 2.10: Habanero Chilies from Mexico. Source: https://pixabay.com/en/habanero-chilli-peppers-habanero-2804/

Some common dishes that are relished because of the spices are Pozole and Tacos. A traditional Mexican Taco will have a portion of spicy meat mix with beans and salsa that will be spread on white tortilla bread which is soft and flat. Next country where spices are widely used is Thailand. Street food is quite common here where you will find many options having stir-fried and spicy dishes. Their range of soup is also very good, and each stall will have a different taste. In Thai cuisine, spices are not the only ingredients used to make good recipes. Instead, they use a combination of herbs and vegetables along with spices to create their authentic flavors.

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Thai cuisine is quite famous all over the world. A soup called the Tom Yum soup is made from a perfect blend of sour and spicy flavors, all in one bowl. Kaffir limes, galangal, and lemongrass are used to give the sour taste. Next in the list is India and here every dish has a lot of spices in it. The main ones that are added to every dish are pepper, coriander, garlic, chilies, and cardamom. India is known for its extraordinary taste of its dishes that is not found anywhere in the world. Combinations of garlic, cinnamon, Kashmiri chilies, cloves, and vinegar are used to cook dishes that form the authentic taste of the region. Chinese cuisine also owes its characteristic flavor to the spices. An area of China called the Sichuan province has the food recipes which are the spiciest in the entire country. In the southwest region, a blend of oil, Sichuan peppercorn, and dried chilies is used to add the peculiar taste to the cuisine. This mixture is the one that attracts most of the food lovers here. In Jamaica, hot spices are very common like Scotch Bonnet pepper. This hot spice is the one that gives flavor to the Caribbean dishes. Here, it is a common practice to add coconut milk or potatoes to lessen the heat from spices. Korea is yet again another country in which spicy food is eaten to a large extent. Here, the local recipes usually mix spices with simple vegetables. The best example of this is kimchi in which the cabbage is mixed with hot chilies. It is said that the hotness of the spices in the Korean food may cause you to cry and yet make you addictive of the taste. Malaysia also has many exotic tastes in its cuisine. The taste of Malaysian cuisine is the taste of a thousand chilies all at once in your mouth. There is a dish called Otak that has dried chilies which are mixed with fish, and this is then steamed in a banana leaf. Ethiopia has another great cuisine of spicy food. There are particular restaurants which specifically made their dishes according to the spices well, and you can select one of your own choices. One good example of a spices mix used here is the ‘Mitmita’ that has cinnamon, cloves, salt, piri, and cumin. Mitmita has a characteristic orange color (Figure 2.11).

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Figure 2.11: A traditional style of making Mitmita. Source: https://commons.wikimedia.org/wiki/File:Mitmita_being_made_in_ mortar_and_pestle.jpg

Sri Lanka was once the most active route in the spice trade. Its cuisine has many recipes that use several blends of spices. A good example is the coconut sambal that is a mix of dried fish, ground coconut, chili paste, and lime juice. In the authentic taste, chili, and curry powder are added along with green chilies, and curry leaves to give the extra taste. In Bhutan, green chilies are as common as any other normal vegetable. Almost all the dishes contain green chilies. Jalapeno type peppers are used in many dishes.

2.6. EXPORT OF SPICES In the year 2017–2018, from India alone, a total of about one billion kilograms of spices were exported, and the value of the same in USD was 3.11 Billion USD. The main spices that were exported are given as follows: • • •

Fenugreek; Celery; Ginger;

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• • • • • • • • • •

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Coriander; Cumin; Chili; Turmeric; Fennel; Ajwain; Garlic; Tamarind; Nutmeg; Pepper.

2.7. SPICE BLENDS A spice blend is defined as a spice mix. Common examples of spice blends include curry powder, garlic salt, chili powder, and other salts. Following is the list of ingredients of the ‘mixed spice’ blend: • Allspice; • Cloves; • Mace; • Coriander; • Nutmeg; • Cinnamon; • Ginger. Mixed spice is also known by the name of pudding spice. Overall, it is a blend of spices that are sweet. The top note flavor in this mix is the cinnamon, followed by allspice and nutmeg. The primary use of this blend is in baking, with fruits and in combination with other sweet foods. Quite often, people get confused between allspice and mixed spice. In literal sense, both of the terms sound similar. However, there is a big difference. Allspice is an individual spice that is obtained by drying the unripe berries from a tropical evergreen tree called the Pimenta dioica. This tree is locally found in the Central American region and the Caribbean. On the other hand, mixed spice is the name given to the blend of many spices like cloves, coriander, caraway, and cinnamon. Another very common spice blend is the five spices. This is also confused with the allspice, but of course, it is different. Five spices is a mixture of particular five spices in which the

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most top note is that of the star anise. It is interesting to know that the blend of spices offers some unique flavors that appeal really well to the senses and that are the reason they are being widely used. The blend called mixed spice offers the fragrance of cinnamon that feels warm, coriander which lends its unique fragrance, ginger that adds a tinge of its uniqueness and the same for cloves. Whenever mixed spice is added to any food dish, it lends it a warm tone that is basically sweet but feels really savory. As an alternative to five spices, one can also use a mixture of anise seeds, cloves, cinnamon, and ginger. Often, the experts come across new flavors when they experiment with various spices. The substitutes for one type of spice are also a common practice to lend some very unique flavors to the foods. For example, cinnamon is used with many other spices in various recipes, and those are used as substituents whenever cinnamon is not available. Also, the berries of the allspice plant are similar in taste to a combination of cinnamon, nutmeg, and cloves. Coriander and cumin powder are also quite similar in their tastes when they are added to the food recipes. The grounded coriander acts as a perfect substitute for the cumin powder. In some recipes, the flavor may be altered altogether; therefore the usage must be done with care. Coriander has the lemony and earthy flavor of cumin, and this is the reason why it acts as the substituent. One blend that is particularly used on a very large scale in India is the Tikka masala. Typically, it consists of the following Indian spices: • • • • • • • • • • •

Cardamom; Cinnamon; Coriander; Paprika; Garlic; Pepper; Mint; Clove; Nutmeg; Chili; Ginger.

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Some herbs are also used in spices mixture across the world in many cuisines. Here is a country-wise list of blends that are famous in some major parts of the world. Africa (Table 2.1) Table 2.1: Spices Found in Africa with their Flavor and Ingredients Name of spice/ spice blend Ras sl Haneout Dukkah

Harissa Berbere

Flavor/Ingredient

Country where used

Mix of coriander, cumin, red pepper Mix of roasted hazelnut, coriander, cumin, and sesame seeds Made by smoking red peppers A blend of sweet, spicy, and bitter spices

Used in North Africa, particularly Morocco Egypt

North Africa and Tunisia Somalia, Djibouti, Ethiopia, and Eritrea

Asia (Table 2.2) Table 2.2: Spices Found in Asia with their Flavors and Ingredients Name of spice/spice Flavor/Ingredient blend Chinese Five Spice Star anise, cinnamon, fennel, cloves, and Szechwan. Gomasio Made from unhulled sesame seeds Togarashi Poppy seeds, orange peel, Korean chile, ginger, and seaweed.

Country where used China and Taiwan Japan Japan

Latin America and the Caribbean (Table 2.3) Table 2.3: Spices Found in Latin America and the Caribbean Name of spice/spice blend Adobo

Flavor/Ingredient

Country where used

Pepper, garlic, and oregano

Philippines.

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Chili Powder

A mix of paprika, Mexican oregano, and cumin. Thyme, black pepper, allspice, and cinnamon

Jerk Spice

Whole of America. Jamaica

Europe (Table 2.4) Table 2.4. Spices Found in Europe and their Flavor and Ingredients Name of spice/ spice blend Fines Herbs Herbs de Provence

Khmeli Suneli Quatre Epices

Flavor/Ingredient

Country where used

Mix of coriander, cumin, red pepper Mix of roasted hazelnut, coriander, cumin, and sesame seeds Made by smoking red peppers A blend of sweet, spicy, and bitter spices

Used in North Africa, particularly Morocco Egypt

North Africa and Tunisia Somalia, Djibouti, Ethiopia, and Eritrea

Middle East (Table 2.5) Table 2.5: Spices Found in Middle East and their Flavor and Ingredients Name of spice/ spice blend Advieh Baharat Za’atar

Flavor/Ingredient

Country where used

Mix of cumin, coriander, nutmeg, cardamom, and cloves. Cumin, cloves, cinnamon, and black pepper Sumac, thyme seeds, and sesame seeds

Iran North Africa Turkey, Egypt, Algeria, Lebanon, Morocco, Palestine, Saudi Arabia

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Indian Subcontinent (Table 2.6) Table 2.6: Spices Found in Indian Subcontinent and their Flavor and Ingredients Name of spice/spice Flavor/Ingredient blend Chaat Masala Chili pepper, black salt, dried mango powder, and asafetida Curry Powder Coriander, fenugreek, cumin, red pepper, turmeric Garam Masala Cloves, cumin, cardamom, coriander, cinnamon, and nutmeg Panch Phoron A mix of nigells, fennel seeds, fenugreek, cumin, and black mustard

Country where used North India North India Countrywide

Bengal

North America (Table 2.7) Table 2.7: Spices Found in North America and their Flavor and Ingredients Name of spice/spice blend Poultry Spice

Pickling Spice

Pumpkin Pie Spice

Dry Rub

Flavor/Ingredient

Country where used

Thyme, rosemary, nutmeg, black pepper and marjoram Mix of mustard seeds, peppercorns, whole coriander, red pepper A mix of Ginger, Cinnamon, nutmeg, and allspice Salt, brown sugar, garlic powder, paprika, and black pepper

Used in North Africa, particularly Morocco Whole of America

North America

Whole of America

2.8. CONCLUSION Since many decades, spices are being utilized in order to provide flavor to their respective food products as well as making up the rare distinguishing

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flavors of the varied pertaining distinctive cuisines, all across the globe. Predominantly, spices have been stemmed in the various tropical regions of the world, though, the US has lately begin with the process of stemming or originating varied distinct spices so that they could be able to supply the requirement of all the people pertaining in that respective country. The consumption or the utilization of spices has been on a considerable increment since the previous few years that are still known to be due within the pan in accordance with the higher level of enticement in the various distinct forms of food products, which tend to make an apt utilization of the great assortment of the provided spices. The potentiality possessed by the spices of behaving as an antioxidant, being an addition to the capability of providing flavor to the respective food products, often tends to attract the attention of majority. Thus, much has been provided regarding pertinence of spices across the world and the parts wherein it has been widely consumed and originated or stemmed.

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REFERENCES 1.

2.

3.

4.

Kitchn., (n.d.). 25 Spice Mixes from Around the World. [online] Available at: https://www.thekitchn.com/spice-mixes–189368 (Accessed on 9 March 2019). Oddstuffmagazine.com (n.d.). Top 10 Most Popular in the World of Spices. [online] Available at: https://oddstuffmagazine.com/top–10popular-world-spices.html (Accessed on 9 March 2019). Skyscanner India, (n.d.). 10 Incredible Destinations for Spicy Food Lovers - Skyscanner India. [online] Available at: https://www. skyscanner.co.in/news/tips/10-countries-to-visit-if-you-love-spicyfood (Accessed on 9 March 2019). Spexcertiprep.com (2018). Webinar. The Chemistry of Spices. SPEX CertiPrep. [online] Available at: https://www.spexcertiprep.com/ webinar/the-chemistry-of-spices (Accessed on 9 March 2019).

Chapter

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Chemical Composition of Major Spices

CONTENTS 3.1. Introduction ...................................................................................... 52 3.2. Major Compounds in Spices ............................................................. 55 3.3. Spices and Their Composition ........................................................... 58 3.4. Distinct Properties of Spices.............................................................. 75 3.5. Conclusion ....................................................................................... 81 References ............................................................................................... 82

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The spices are used for their preservative, flavoring, and health-promoting properties since ancient times. Early records show that spices were used for preservation of food in ancient Roma and Greece and also in medicines in ancient Egypt and Assyria. Spices are usually known as the aromatic plants. They are an important collection of agricultural commodities which are being utilized by various civilizations around the world to add taste, flavor, and nutritional values. It is also used to increase the shelf life of food. Though spices are characterized by a peculiar quail-quantitative configuration for its essential oil and all of these essential oils, comprise compounds with established biological activity. Therefore, the aim of this chapter is to describe the major compounds present in the spices and their effective biological activities such as chemical, nutritional, and microbiological characteristics for essential oils present in the spices.

3.1. INTRODUCTION The International Standards Organization (ISO) which is based at Geneva defines spices and condiments as “Vegetable products or mixtures thereof, free from extraneous matter, used for flavoring, seasoning, and imparting aroma in foods.” Spices are used to impart color, aroma, and taste to various food preparations. The volatile oil present in the spices are the main reason behind the aroma and oleoresins are behind the taste. The interest is regularly growing in the practical and theoretical aspects of the biosynthetic mechanism involved in spices. The relationship between the chemical structure and biological activity is also being studied these days on a large scale. The antioxidant properties of spices and are of particular interest in regards to the impact of oxidative modification of low-density lipoprotein cholesterol in the development of atherosclerosis. According to Webster spices are defined as “Any of various aromatic vegetable productions as pepper, cinnamon, nutmeg, mace, allspice, ginger, cloves, etc., used in cookery to season and to flavor sauces, pickles, etc.; a vegetable condiment or relish, usually in the form of a powder; also, as condiments collectively.” The application of spices and herbs in preservation, flavoring, and health promotion has been known since ancient times. Records show that earlier these spices were majorly used as medicinal in ancient Assyria and Egypt and

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as food preservatives in Greece and Rome. Spices and herbs are generally known as aromatic plants. They are an essential group of agricultural commodities. They are being used to add taste, flavor, and nutritional values by various civilizations around the globe. They are also used to increase the shelf life of food and to heal different mental, physical, and emotional problems (Bhat et al., 2014). However, spices are characterized by a strange quail-quantitative composition for their essential oil. This essential oil contains different compounds with established biological activity (Stefanini et al., 2006). Turmeric belongs to the ginger family, Zingiberaceae. The scientific name of turmeric is Curcuma longa L. it is native to India. Turmeric with its rhizomes is a source of a bright yellow spice. It is cultivated in gardens of homes in Africa and used to be sold in several markets (Jansen, 2005). Coriander belongs to the family of Apiaceae. It is among several of the aromatic plants which are actually gathered after completion of flowering, with the leaves being denoted to as an herb, and the dried seeds as a spice (Shahwar et al., 2012). These plants can be grown all around the year. Processing of coriander is done to increase its profitability, palatability, and to enable international trade also. Processing of leaves and fruits of coriander plant is the best method to preserve this herb (Bhat et al., 2014). Fennel is a well-known culinary herb. In ancient times, Romans used to cultivate fennel for its succulent edible shoots and aromatic fruit. Former to the Norman Conquest, it was listed in the Anglo-Saxon medical recipes and cookery. In ancient times, fennel, along with the St John’s wort and other herbs, used to hung over doors on Midsummer’s Eve to ward off evil spirits. In the same way, it was used as a condiment for the salt fish consumed during Lent. Fenugreek belongs to the family of Fabaceae. It is one of the plants which is used both as a spice and an herb. The seed of the plant is used as a spice whereas the leaves are used as an herb. This plant is cultivated around the globe as a semi-arid crop, but it is native to India and southern Europe. The dried leaves usually have a bitter taste and a strong characteristic smell. They are used as a flavoring agent in making several dishes, particularly in curry. Syzygium aromaticum is the scientific name of clove. Clove is among the most valuable spice. Since ancient times, it is being used as a food

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preservative and also for medical purposes. Indonesia is the major clove production country. Nowadays, it is being cultured in various other countries around the globe like Brazil. Clove is one of the richest sources of phenolic compounds like eugenol acetate, eugenol, and garlic acid. The clove plant possesses a great potential for cosmetic, pharmaceutical, food, and agricultural applications. Cumin belongs to the family of Umbelliferae. It is among the large number of spices which are used to flavor foods and beverages around the globe, majorly in India and Mediterranean regions, and occupies a place of importance (Milan et al., 2008). Cumin seeds have a spicy and bitter taste and an aromatic odor. It is majorly used in the Egyptian kitchen and is called as “Kammoun” locally (Hajlaoui et al., 2010). Black pepper is known as the king of Spices. It is an essential and widely used spice all over the globe. The black pepper is dried and mature fruit known as berry of the tropical, perennial climbing plant Piper nigrum L. It belongs to the family of Piperaceae. Curry leaf (Murraya koenigii (L.) Spreng., Rutaceae family, 2n = 18) is a semideciduous, ornamental, and evergreen tropical tree of around 4–6 cm height with various uses including medicinal purposes also. Ginger is a very well-known spice which is widely used as a flavoring agent and in many countries, in medicines also. This plant is cultivated on a large scale in Southeast Asia and China, India, and Africa. Ginger has the same characteristics as that of turmeric. Both of them have pale yellow flowers which are surrounded by the long lanceolate leaves. Cardamom is known as the Queen of Spices. It belongs to the family of Zingiberaceae. In India, it is very important plantation crop. The name cardamom is used for species within three genera in the Ginger family (Zingiberaceae). There are two kinds of cardamoms found in the spice world, one is true cardamom also known as small cardamom and another is large cardamom. After saffron and vanilla, cardamom is generally named as the third most expensive spice in the world. The high price of cardamom reflects the high status of this most pleasantly aromatic spice. These spices are majorly valued as medicinal plants. They have gained attention of various researchers around the globe to validate the pharmacological activities of spices experimentally. The main objective of

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this chapter is to provide the relevant information such as their origin, use, and mainly the composition of the major species available around the globe. Spices have been really very much important for the mankind from the start of history. Distinct number of mythological evidences comprising the “Bagvat Gita” and “Epic of Gilgamesh” recommends their utilization for a lot of purpose. Due to their strong quality of preservation, spices were majorly used for embalming. As per the Ayurveda, spices also help in maintaining the balance of body humors (Gupta et al., 2013). Apart from this, spices have also been utilized to change the appearance of any food. For example, turmeric, and pepper usually change the color, taste as well as appearance of the food along with various health-related benefits. Nutmeg, cinnamon, and ginger used to enhance the process of digestion, and they are considered beneficial for spleen as well as sore throats. But the beneficial properties of different spices are not yet clinically proven. Although, traditional practices underline the various health-related benefits. Recent studies and research have emphasized other biological functions of different spices comprising antioxidant, antimicrobial, anti-inflammatory, etc.

3.2. MAJOR COMPOUNDS IN SPICES Spices are used to impart color, taste, and aroma to various food items. Sometimes, unwanted odors get also imparted. The oleoresins present in spices impart the taste, and volatile oils impart the aroma to the food items. In the production of flavorants, aroma compounds play an important role. These flavorants are generally used in the food industries to improve and flavor the appeal of various products. They are usually categorized by presence of different functional groups such as alcohols, amines, aldehydes, esters, ketones, ethers, terpenes, thiols, and other miscellaneous compounds. The volatile oils constitute these components in spices (Zachariah, 1995; Menon, 2000). Caryophyllene-rich oils possess sweet floral odors in black pepper, while oil having high pinene content provides turpentine-like off-odors (Lewis et al., 1969). Fresh pepper contains few major compounds such as trans-linalool oxide and α-terpineol. While dry black pepper oil comprises α- and β-pinenes, β-caryophyllene, and d-limonene as major components. Cardamom oil contains very less amount of mono- or sesquiterpene

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hydrocarbons. This is particularly dominated by oxygenated compounds which are potential aroma compounds. Various identified compounds such as alcohol, aldehyde, and esters are generally found in different spice oils. But the dominance of the ether, α-terpinyl, linalyl acetates, and 1,8-cineole in the composition make the volatiles of cardamom a unique combination (Lewis et al., 1966; Salzer, 1975; Korikanthimath et al., 1997). The characteristic organoleptic properties of ginger consist of two classes of constituents like the odor and the flavor. The ginger flavor is determined by its steam volatile oil constituents whereas the pungency of ginger is determined by gingerols. Gingerols are defined as the non-steam volatile components. The steam volatile oil consists of oxygenated monoterpenes, monoterpene hydrocarbons and sesquiterpene hydrocarbons (Purseglove et al., 1981). The major contributors to the ginger aroma are the monoterpene constituents. These are present in ample amount in the natural oil of the green rhizome as compared to the essential oil which is distilled from dried ginger. Oxygenated sesquiterpenes are rather insignificant constituents of the volatile oil. It appears to be an important contributor to its flavor properties. The sesquiterpene hydrocarbon constituent of ginger oil is (-)-α-zingiberene. Ginger oil in Australia has a reputation of processing a lemony aroma because of high content of isomers, neral, and geranial, often together known as citral (Wohlmuth et al., 2006). Cinnamon has a delicate, spicy aroma which is ascribed to its volatile oil. Cinnamon and cassia contain volatile components in all parts. These volatile compounds are further classified broadly into monoterpenes, sesquiterpenes, and phenylpropenes (Senanayake, 1997). The oil extracted from the bark of the stem has 75% cinnamaldehyde and 5% cinnamyl acetate, which mainly contribute to the flavor (Angmor et al., 1972; Wijesekera, 1978; Krishnamoorthy et al., 1996). Methyl amyl ketone, methyl salicylate, etc. are the minor constituents which are mainly responsible for the typical pleasant odor of cloves. Eugenol (70–85%), eugenyl acetate (15%) and b-caryophyllene (5–12%) dominate the oil and they together make up 99% of the oil. In 1972, Walter reported that beta-Caryophyllene is a constituent of the bud oil. Earlier, beta-Caryophyllene was thought of as an artifact of distillation The volatile oil of nutmeg has different compounds namely, monoterpene hydrocarbons which are around 61–88%; oxygenated monoterpenes that is monoterpene alcohols, monoterpene esters; aromatic ethers; sesquiterpenes,

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alkenes, aromatic monoterpenes, organic acids, and miscellaneous compounds. Depending upon the type of compound present, the flavor varies from a sweet, spicy taste to a heavier one. The oil has a camphor-like aroma and a clove-like sweet, spicy, bitter taste with a terpeny. Among all the seed spices, cumin fruits have a characteristic bitter flavor and warm aroma because of huge oil content in them. Of all this, around 40–65% is cumin aldehyde (4-isopropyl benzaldehyde). The odor is defined as penetrating, fatty, and overpowering, irritating, curry-like, spicy, heavy, warm, and persistent, even after drying out (Weiss, 2002). The distinct flavor of cumin is particularly due to the presence of dihydrocuminaldehyde and monoterpenes. Around 95% of the essential oil is present in the mature fruit of fennel. Much greater amounts are found in the fully ripe fruit. Hydro-distillation produces around 1.5–3.5%. Usually, fenchone, and anethole are found more in the ripe and waxy fruits than in the leaves and stems (Akgül, 1986; Kruger and Hammer, 1999). Anethole has flavoring properties and is definitely sweet, as it is 13 times sweeter than sugar. As for coriander, in the unripe fruits and the vegetative parts of the plant, aliphatic aldehydes predominate in the steam- volatile oil and are responsible for the peculiar aroma. When fruits ripe, it acquires more sweet and pleasant odor. The main component of the volatile oil is the linalool, a monoterpene alcohol. Sotolon is a lactone and very powerful aromatic compound. It is the main flavor and aroma compound found in fenugreek seeds (Mazza et al., 2002). Sotolon is also referred to as sotolone, sugar lactone, caramel furanone, and fenugreek lactone. Among all the leafy spices present, around 45 aroma volatiles of desert parsley have been recognized, with the major ingredients as apiole, myristicin, b-phellandrene, 4-isopropenyl-1-methylbenzene, and p-mentha-1,3,8- triene (MacLeod et al., 1985). Particularly apiole has a necessary parsley odor character. The leaf stems of celery depict three major constituents of volatiles, for example, apiole (about 23%), 3-butylphthalide (about 22%) and sedanolide (about 24%). The last two have a strong characteristic celery aroma (MacLeod et al., 1988). Limonene (around 40.5%), β-selinene (around 16.3%), cis-ocimene (around 12.5%) and β-caryophyllene (around 10.5%)

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are few of the volatile oil constituents which are present in celery leaves from Nigeria (Ehiabhi et al., 2003). The curry leaf plant is extremely valued for its medicinal value and characteristic aroma (Philip, 1981). A number of leaf essential oil constituents and carbazole alkaloids have been extracted from the curry leaf plant (Mallavarapu et al., 1999). There are a great number of oxygenated monoterpenes and sesquiterpenes present, for example, cis-ocimene (34.1%), α-pinene (19.1%), γ-terpinene (6.7%) and β-caryophyllene (9.5%), which seems to be responsible for the intense odor linked with the stalk and flower parts of curry leaves (Onayade and Adebajo, 2000).

3.3. SPICES AND THEIR COMPOSITION 3.3.1. Turmeric Turmeric, also known as Curcuma long L., has been provided with the attribution of the numerable properties of the medicine within the system belonging to the medicine in the traditional manner for the purpose of providing with the treatment for the various usual illnesses. It generally belongs to the genus Curcuma that possesses the inclusion of the various species of the plants along with the roots as well as the rhizomes which have been undergrounded. Around 40 species belonging to the category of the genus are being acknowledged as indigenous in context of India, which indicates to the origin of the respective country. Earlier, it was being utilized for the purpose of the having an addition to the food so that they could be able to enhance or improve the palatability, conservation as well as preservation of the food and the storage. Generally, the spice is being considered to get propagated in the regions which are warm as well as rainy within the various countries including Indonesia, Peru, China, and Jamaica. In comparison to the other countries, India has stand out, being the major producer as well as exporter of various species but specifically turmeric, currently, even after the fact that the provided crop is generally being grown in various countries across the world including Japan, Sri Lanka, Thailand, Malaysia, Pakistan, and many more. Thus, it has been estimated on an official basis that around 80% of the production, occurring across the globe, of the turmeric is just coming out from India. The various essential states

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within this country, which tends to grow turmeric, are Karnataka, Assam, Tamil Nadu, Andhra Pradesh, West Bengal, Orissa, and Maharashtra. And in this series, Andhra Pradesh secures the 1st position taking into account the production as well as the productivity, which has been followed by Tamil Nadu. Turmeric is being acknowledged as an antioxidant phytochemicals, which is known as the polyphenol and thus, possesses the composition of the chemical which belongs to C21H20O6. It possesses an inclusion of the mixture of the compounds being phenolic in nature, also known as the curcumin of around 5%, along with the various compounds being related to it, which is also known as the curcuminoids. It also includes the volatile oil for of approximately 5% along with the zingiberene as well as the turmerone; protein, higher amounts of the vitamin A, cineole as well as various other monoterpenes and thus, several vitamins viz: Vitamin C, Vitamin E, various carotenoids and the curcumin (Figure 3.1).

Figure 3.1: Chemical structure of curcumin. Source: http://turmericworld.com/curcumin.php

Functions: • • •

Curcumin is also being considered as one of the provided antioxidants. Cineole tends to brace up the central nervous system and also act as an antiseptic. All the pertaining essential oils does possess the various bracing impacts on the gallbladder as well as revives the liver so that it can produce much of the bile and thus does the regulation of its viscosity.

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The existence or the pertinence of curcumin is in two forms, out of which, one is keto and the other one is enol. The form of the Keto is generally be preferred or prioritized in the phase of the solid, whereas the format of enol is present in the solution and is being recognized as the indicator of the PH value as it turns out be yellow when tested with the acidic solution and becomes bright red in case wherein the solution is basic.

3.3.2. Coriander Coriander, also known as Coriandrum sativum, which is an herbaceous as well as an annual plant, being related to the family of Apiaceae. It is also being considered as a culinary as well as the plant possessing medicinal properties. And this specific herb is being cultivated or propagated everywhere across the globe. These species, which are actually rich in the linalool properties, generally tend to possess the capability to get aptly utilized being an essential oil. It is also being utilized as an agent of analgesic, antispasmodic, digestive, carminative as well as the antirheumatic. The fruits it possesses, which are also known as the seeds, are being utilized for the purpose of providing flavors to the candies, within the cookery, in the industry of tobacco, in the perfumeries, beverages, etc. Coriander is one of the prime spices which were being in the process of utilization by the mankind. For the reasons of its medicinal properties as well as for the grounds of culinary, the coriander spice was being utilized in Egypt in the former times and thus, has been mentioned in the Ebers Papyrus. Within the products related to food, cosmetics as well as the perfumeries, coriander is being applied in the form of the agent providing flavors. It inhibits much of the medicinal properties which are essential for the various drugs to get prepared. The seeds which have been powered along with the dry extracts, decoration, tea, tincture or any of the infusion is being provided with the reference or recommendation for the various complaints related to the dyspeptic, the dropping of the appetite, issue of insomnia, anxiety or depression as well as the agitation. The essential oils along with the various other distinct extracts being made out of the coriander, I being shown so that they could be able to hold the various properties including antibacterial, antidiabetic, antioxidant,

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anticancerous, and thus the antimutagenic. Leaves along with the seeds might have an inclusion of, many of the required or essential turbulent oil which includes borneol, cymene, phellandrene, terpinolene, linalool, pinene, cineole, etc. thus, in addition to it, they are being acknowledged as quite rich in terms of the numerable flavonoids of polyphenolic being antioxidant in nature. For example, the rhamnetin, quercetin, epigenin as well as kaempferol. Therefore, generally, the fruits tend to possess the inclusion of approximately 0.2 to 2.6% of the turbulent oil (Figure 3.2).

Figure 3.2: Chemical composition of C. sativum. Source: https://www.sciencedirect.com/science/article/pii/S2221169115000647

The key or the essential element or the component being related to the oil is the d-linalool, also known as coriandrol, being in its existence in about 55–74%. Various other elements or the compounds which is being present within the oil generally tends to have an inclusion of the various chemicals including borneol, decyl aldehyde, anethole, geraniol, carvone, geranyl acetate, elemol, caryophyllene oxide as well as the various pertaining hydrocarbons. The several other constituents which are being existent within the fruits and tends to have an inclusion up to 26% of the fats which has been made of the glycerides, specifically of the oleic, the acids related to the linolenic as well as the petroselinic, of which a lesser or the small quantity of the unsaponifiable matter, proteins, having start of about 1.0% and 20% of the provided sugars, rutin, coumarins along with the flavonoid glycosides.

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The leaves tend to possess the inclusion of the less turbulent oil in comparison to that of the fuels; around fats possessing 5%, approximately 22% of the proteins, sugars, Vitamin C, coumarins as well as the flavonoids glycosides which are almost equivalent to those within the provided fruits, and various others. These turbulent or the volatile oils generally tend to contain majorly the decyl as well as the nonyl aldehydes, and also the linalool properties amongst the various other pertaining properties. This specific herb is quite a great source of having mineral viz the potassium, iron, manganese, and calcium. It is actually quite rich in terms of many if the provided essential vitamins having an inclusion of the folic acid, Vitamin A, niacin, beta carotene, and many others.

3.3.3. Fennel Fennel, also known as Foeniculum vulgare Mill, is related to the family of the Apiaceae which was earlier called the Umvelliferae. It is originally being propagated in the southern parts of the Europe as well as the Mediterranean region and is being produced in many of the countries across the world including Rumania, India, France, Germany, Russia, Argentina, the USA, Italy, and Japan. The exports of all over the world belonging to this spice have gradually improved in the recent years, and its importance has surged accordingly. Originally, the terminology of the Fennel has got emerged from the Middle English word fennel or fenny; the Anglo-Saxon word fenol and similar from the various other languages which possess the meaning hay which actually means happiness. At the times of the Ancient Greek, fennel was being acknowledged or recognized as the marathon. This is, thus, basically the emergence of the name of the respective place, which is the Marathon, possessing the meaning as the place of the fennel, as the site of the provided battle of the marathon. The mythology of the Greek has provided with the claim that Prometheus used to do the process of stalking of the plant belonging to the fennel seeds so that he could be able to steal them from the respective gods. In the times of the medieval period, the spice fennel was being utilized for the purpose of having a conjunction with the wort of many of the researchers so that they could be able to keep the witchcrafts away and including the various other evil things along with it.

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This may have got emerged or originated due to the fennel seeds which were being utilized in the form of the repellent of the insects. This is being considered as one of the nine herbs which has been declared as sacred by the Anglo- Saxons. The major components or the elements of the chemicals belonging to the spice fennel are generally the α-pinene, trans-anethole, methyl chavicol, anisic aldehyde, fenchone, 8-cineole, myrcene, and various others. All the fruits which tend to have an inclusion of approximately 1.5 to 8.6% of the turbulent or the volatile oil, 9 to 28% of the oil that has been fixed and is generally comprised or composed essentially of petroselinic acid, linoleic acid as well as the oleic acid along with the comparatively higher level of the concentration of the tocopherols, the various flavonoids, possession of the proteins, sugars, much of the vitamins, minerals, and various other essential nutrients (Figure 3.3).

Figure 3.3: Major constituent of fennel. Source: http://www.yourarticlelibrary.com/biology/plants/fennel-sources-cultivation-and-uses/49851

The lower level of the concentration of the polyacetylenes got lately detected within the roots. The propanoid being an antimicrobial phenyl has also got isolated from the provided stem. The turbulent or the volatile oil generally tend to have an inclusion of the mostly trans-anethole along with the various fewer amounts of the fenchone, limonene, α-pinene, estragole as well as camphene. Various other elements or the compounds generally tend to provide with the presentation having an inclusion of the hydrocarbons or the fenchyl alcohol. Approximately, four of the provided constituents were existent within the spice fennel seeds which tend to have a constitution of 97% of the entire components of the essential oil wherein the phenol ethers were considered

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to be the major category of the chemical and is being followed by the monoterpene hydrocarbons. The greatest constituents of the essential oils were the trans-anethole which has been followed by the isoanethole, α-pinene, α-phellandrene and fenchone (Table 3.1). Table 3.1: Chemical Category of Fresh Fennel Chemical Category Monoterpene: Hydrocarbons Ketones Esters Phenols & Phenol Ethers Sesquiterpene Hydrocarbons Unknown Total identified

Composition (%) 17.6 5.0 0.6 72.7 0.1 1.3 97.3

Source: http://epgp.inflibnet.ac.in/epgpdata/uploads/epgp_content/food_ technology/technology_of_spices_and_condiments/06.chemical_composition_of_spices_and__condiments/et/2875_et_m6.pdf

3.3.4. Fenugreek The fenugreek or the seeds of methi, also being known as the Trigonella foenumgraecum L is being related to the subfamily of the Papilionacae belonging to the family of Leguminosae that is a bean family. This specific plant is basically an aromatic herbaceous annual which tends to get propagated or cultivated in the countries belonging to Asia as well as Mediterranean. It is being believed that these have got emerged within the southern parts of the Europe or from the South- Western countries of Asia, which is also known as the self- dependent center or the emergence within Ethiopia. Within the country India, the process of the propagation or the cultivation is generally being focused or concentrated majorly in the areas of Rajasthan which tends to possess a contribution of approximately 80% of the entire area or the region along with the productivity or the production. Trigonella is basically a diminutive of the Latin word belonging to the Greek trigon on which means triangle and is generally composed of tries

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which in general means three as well as the gony possessing the meaning as knee or the angle. It usually provides with the reference to the triangular shape of the flowers. The region or the area, as well as the production belonging to the fenugreek within the various regions, have grown substantially in the recent times. It provides with the slightest of the increments within the region or the area under the process of civilization as well as the production of the spice fenugreek while this respective time- period, wherein the production of it got doubled and since then, declined. The Fenugreek tends to have an inclusion of the simplest of the alkaloids involving majorly the trigonelline, carpaine, choline as well as the gentianine. Thus, the provided constituents consist the following: • • •

•

The saponins which tends to yield on the hydrolysis steroid. The flavonoids having an inclusion of the vitexin. The oils, which have been fixed, that at the time of extraction along with the solvents of the fat, tend to yield the extract along with the robust odor or the smell. Possession of the considerate amount for the mucilage that tends to seems to be generally a galactomannan and is nearly being held responsible for the process of swelling up of the provide seeds within the water.

3.3.5. Garlic Garlic tend to have an inclusion of more than 200 compounds of the provide chemicals out of which, few plays an important role being the turbulent oil along with the compounds having or containing sulfur, protein, and the various other enzymes. Allicin is said to be the compound which helps in providing the garlic with all the properties of antibiotic and thus, is being responsible for the possession of the robust odor or the smell. Garlic also has the possession of the citral, linalool, A phellandrene and B phellandrene along with the geraniol. The various vitamins as well as the minerals content having an inclusion of the B-vitamins especially B1, ascorbic acid, selenium, potassium, magnesium, and various other nutrients required for it. Approximately seventeen of the provided amino acids are being identified within the garlic having an inclusion of the eight most required ones (Figure 3.4).

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Figure 3.4: Bioactive compounds of garlic. Source: https://www.sciencedirect.com/science/article/pii/S0308814616307099

3.3.6. Clove Clove, also known as Syzygium aromaticum (L.) Merril. & Perry, syn. Eugenia aromaticum or E. caryophyllata is being considered as one of the most former as well as the worthwhile spices in accordance with the Orient. It is being considered to be in relation with the member of the family, known as Myrtaceae. The clove belonging to the commerce is generally being the buds of the flower which has been dried as well as unopened. The terminology of the clove has got derived from either clavus, which is a Latin word, or clou which belongs to the French word providing with the meaning as nail. The buds tend to get resembled with the nails being irregular in its shape. The area or the region along with the production of the clove within many countries is being on its increment phase since few recent years.

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Thus, there possess a marginal increment within the area or the region which are under the process of propagation or cultivation and thus, the production is on its decrement rate within various countries across the globe. Lately, the production of the clove all over the world has got averaged near to 80,000 t per provided year. Indonesia is thus, being considered to be one of the largest producers of the clove ion comparison to all the other countries, across the world. It is basically being utilized for the process of preparing the cigarettes being kretek. Wherein Singapore has been considered as the entrepot for the process of trading of the clove. The major countries which are being acknowledged as the largest importers in the world are Saudi Arabia, India, France, and the USA (Figure 3.5).

Figure 3.5: Major constituent of clove. Source: http://www.poultrydvm.com/supplement/cloves

3.3.7. Cumin Cumin or jeera, also known as Cuminum cyminum, is being related to the family of the Apiaceae, and is being widely utilized as a spice as within the former times and belongs to the Eastern parts of the Mediterranean and thus, having an extension to the East India, the seeds of the Cumin are being utilized for the possession of the rare or the unique aroma and are quite known or popular for it in the various cuisines of the distinct countries. Cumin is said to be quite known or popular spice in the areas or the regions of the Westerns countries as well as the Central Asia, within the Central as well as the southern parts of the America, India, and Burma along with Indonesia. The seeds of cumin within India have identified the effective or the efficient utilization of this in the various foods, liquor, beverages, perfumeries,

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toiletries, and thus, it is being brown in the mildest of the climes within Gujarat, Uttar Pradesh as well as Rajasthan. The best of the seeds which tend to belong to the category of the black cumin generally comes from the country of Egypt, wherein they develop or grow within the utmost precise conditions in the oasis and thus, wherein these are being irrigated till the provided seeds tend to pod the form. The black cumin is being recognized as the fruit which belongs to the related plant which tends to develop or grow wild in the regions of Iran as well as the region of the north India, viz the Kashmir. The seeds of cumin within India have been exported with the various distinct formats, such as the seeds being natural, in the powdered form as well as in the form of essential oils. They are being exported to the USA, Japan, North Africa, Singapore, and various other countries across the world, wherein India is being considered to be one of the largest producers as well as the consumer of the seeds of cumin in the entire world, possessing an annual production which ranges between approximately 0.1 and 0.2 million t (Figure 3.6).

Figure 3.6: Cumin-aldehyde. Source: id=7660

http://www.rdchemicals.com/chemicals.php?mode=details&mol_

3.3.8. Pepper Black pepper belongs to the family of Piperaceae. The scientific name of black pepper is Piper nigrum. Pepper is basically cultivated for its fruit, which is further dried and used as spice and seasoning. This same fruit is used to produce green pepper and white pepper. In South India, black pepper is extensively grown. The fruit of pepper is known as peppercorn. When the fruit is dried, it becomes a dark red small drupe of 5 mm diameter when matured fully. It

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contains a single seed. One of the most common spices in European cuisine are dried, ground pepper, and its variants, having been known and prized since ancient times for both its use as a medicine and its flavor. The flavor of spiciness present in black pepper is mainly due to the piperine chemical. The ground black peppercorn is basically referred to as pepper. In few parts of the world, pepper may be easily found on the dinner table or usually alongside the table salt. Black pepper is also known as the king of spices and black gold. It the majorly consumed spice in the whole world. Completely dried black pepper contains around 8–10% of moisture content as compared to many other spices available. Dried black pepper can be stored in airtight containers for many years without losing its aroma and taste. The word ‘pepper’ is derived from the Sanskrit pippali, via the Latin piper and Old English pipor. The Latin word is also the source of German pfeffer, French poivre, Dutch pepper, and other similar forms. ‘Pepper’ was used in a symbolic sense, meaning ‘spirit’ or ‘energy,’ at least as far back as the 1840s. The major producing countries of black pepper is Brazil, India, Indonesia, Malaysia, Sri Lanka and Vietnam (Peter, 2000). The total average export from various countries producing black pepper is around 138,000 t. By monetary value, peppercorns are the most widely traded spice around the globe, which accounts for around 20% of all the spice imports. The pepper price can be volatile. This figure greatly varies year by year. The International Pepper Exchange is situated in Kochi, India. Vietnam has recently become the world’s largest producer and exporter of pepper (116,000 t in 2006). Vietnam rules the export market by exporting almost the entire production. Other major producers comprise Indonesia (67,000 t), India (65,000 t), Brazil (35,000 t), Malaysia (22,000 t), Sri Lanka (12,750 t), Thailand, and China. The International Trade Centre (ITC) which is located at Geneva put the latest trade in spices at 400,000–450,000 t, which are valued at US$1.5–2.5 billion per annum. Black pepper accounts for around 35% of the world trade in spices. The spicy heat of pepper is basically due to the presence of piperine compound. The piperine compound is found in the seed as well as in the outer fruit. The amount of piperine present in black pepper is around 4.6–

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9.7%, and in case of white pepper, it is quite more than that. Black pepper consists of 5–9% of piperine, 2–4% of volatile oil, piperettine, piperidine, and few alkaloids such as piperyline, piperolein A, piperolein B, piperanine, etc. The known pungent principles are piperine and piperanine. Black pepper oil has δ-Iimonene and β-caryophyllene, β and α pinenes as the main components. The component caryophyllene has sweet floral odors while oils having high content of pinene give turpentine-like off-odors. In fresh pepper, the major compounds are α-terpineol and trans – linalool oxide. It is also reported that black pepper contains flavanol glycosides mainly those of kaempferol, quercetin, and rhamnetin in substantial concentration, as well as sterols (stigmast-4-ene-3, 6-dione, and stigmastane-3, 6-dione) and polysaccharides. The chemical composition of black pepper is as follows: Terpenes: • α-thujone (0.22–3.59%); • α-pinene (1.11–16.20%); • β-pinene (4.92–14–33%); • β-phellandrene (0.46–27.37%); • camphene (0.23–1.44%); • sabinene (0.14–13.78%); • myrcene (1.66–2.53%); • δ- limonene (16.41–24.36%). Sesquiterpene: • α- terpinen-4-ol (0.01–0.18%); • β- caryophyllene (9.39–30.94%); • β-bisabolene (0.09–5.18%); • β-farnesene (0.03–3.26%); • trans- linalool (0.04–0.25%). White pepper has less volatile oil content but do have the same alkaloids and pungent principles as black pepper. Both, black pepper and white pepper contains around 65% carbohydrates, 11% protein, lipids, crude fiber, and others. Pepper oil has a complex mixture of monoterpenes, sesquiterpene, and various small amounts of oxygenated compounds, with no pungent principles present. Major monoterpenes include α-pinene, α-thujene, β-pinene, camphene, sabinene, βphellandrene, myrcene, 3-carene

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and limonene. Sesquiterpenes include β-caryophyllene which is a major component, α-cubebene, α-copaene, β-bisabolene, β-selinene, β-farnesene, humulene, curcumene, α-selinene and sesquisabinene. Oxygenated components include β-pinone, linalool, l-terpinen-4-ol, myristicin, etc.

3.3.9. Curry Leaf Murraya koenigii is a scientific term. It is commonly known as the curry leaf tree. Murraya koenigii is an innate of India, Sri Lanka, and other South Asian countries. Curry leaves are grown all over India, and they beautify every backyard, mainly in the southern states, where most cuisines are prepared with the delicate flavoring of this highly aromatic leafy spice. The curry leaves are used to add flavor to variety of dishes. They are typically fried in oil to impart flavor to every curry preparation (Choudhury and Garg, 2007). Fresh leaves produce a very strong aroma while cooling. This plant has also been utilized in traditional medicine systems to make variety of ailments. The oil extracted from these leaves are further used in soap and perfume industries (Shanthala and Prakash, 2005). The curry leaves are majorly valued for its medicinal value and characteristic aroma. Various number of alkaloids and essential oil constituents have been extracted from this plant. There are wide range of oxygenated mono and Sesquiterpene present in the plant of curry leaf, for example, cis-ocimene (34.1%), α-pinene (19.1%), βcaryophyllene (9.5%), δ-terpenene (6.7%) and β- phellandrene which seems to be responsible for the strong odor linked with the stalk and flower parts of curry leaves.

3.3.10. Ginger Ginger is the rhizome of Zingiber officinale Roscoe. It is one of the most widely used species of the family Zingiberaceae. It is a common condiment for various foods and beverages. Ginger has been used since ancient times for varied human ailments, to help in digestion and to treat stomach upset, nausea, etc. (Figure 3.7).

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Figure 3.7: Ginger rhizomes and its components. Source: https://www.sciencedirect.com/science/article/pii/S2213434416300676

The ginger plant has a perennial, tuberous root or rhizome, the stems are rigid, round, oblique, annual, and invested by smooth sheaths of leaves, around 1 m in height. Ginger rhizome is usually used up as a fresh paste, slices preserved in syrup, dried powder, and crystallized ginger or majorly for flavoring tea. In various countries like China and India, fresh ginger is used to make meat and vegetable dishes and also as a flavoring agent in different beverages (Shukla and Singh, 2006). Ginger is a kind of natural dietary component which has anticarcinogenic and antioxidant properties (Manju and Nalini, 2005). The characteristic organoleptic properties of ginger are majorly due to the two class of constituents. The aroma of ginger is mainly due to the elements of steam-volatile oil which are mostly Sesquiterpene hydrocarbons, oxygenated monoterpenes, and monoterpene hydrocarbons. Whereas the pungency is due to the presence of non-steam-volatile elements. These nonsteam-volatile elements are also known as the gingerols. The main Sesquiterpene hydrocarbon element of ginger oil is α-zingiberene. Various ginger oil has a status of producing a particular ‘lemony’ aroma, because of high amount of the isomers, neral, and geranial which is collectively known as citral. Polyphenols, β carotene, vitamin C, tannins, and flavonoids are the antioxidant components which are present in ginger.

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3.3.11. Cardamom Small cardamom is known as the ‘queen of spices.’ It belongs to the family of Zingiberaceae. Cardamom is a rich spice which is produced from the seeds of Elettaria cardamomum Maton, a perennial plant. After saffron and vanilla, cardamom is the third spice which is highly expensive. Cardamom crosses the sweet/savory boundary between main dishes and desserts. The real home of cardamom spice is the mountains of the southwestern parts of the Indian Peninsula. As early as the 4th century BC, cardamom was used as a medicinal herb in India and was an article of Greek and Roman trade. Until recently, India had a virtual monopoly of cardamom. In India, the cultivation of cardamom is majorly confined to three states that are Kerala, Karnataka, and Tamil Nadu (Korikanthimath et al., 2002). However, it is now cultivated in Sri Lanka, Guatemala, Thailand, Laos, Vietnam, Nepal, Costa Rica, Mexico, El Salvador and Tanzania (Mehra, 2001). In 2004, cardamom shared around 60% of the total import value of US$204 million. From US$6.64/kg in 2000 to US$4.30/kg in 2004, the world prices of cardamom fell by 10% around. Lower unit values were observed in the Arab countries due to oversupply of cardamom and its declined demand. Followed by Kuwait, Saudi Arabia is the major importer of cardamom. After Nepal, Guatemala was the main exporter of cardamom in the world in 2004, with an export value of US$80 million. Nepal exports black cardamom. India is the world’s main producer of cardamom, but the main quantity is used within the country, with limited exports (International Trade Centre, 2006). The chief exporters of cardamom spice are Guatemala, Costa Rica, Indonesia, Nigeria, India, Brazil, Thailand, South Africa, and Nicaragua. Alternatively, Saudi Arabia claims to be its single chief importer. After Saudi Arabia, Kuwaitis is at the second place in the importing list but is nowhere near the leader. The main importers of cardamom are Kuwait, Saudi Arabia, China, United Arab Emirates, Hong Kong, the Netherlands, Japan, the USA, and Singapore. The total production of cardamom in the world is approximately 30,000 MT. Nowadays, the major producer of cardamom is Guatemala. Its average annual production is 18,000–20,000 MT. The second largest producer of cardamom is India. The average production of cardamom in India is around 11,000–12,000 MT. In the

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international markets, the quality of Indian cardamom is considered as superior. The western Asian region countries like Saudi Arabia, India, and United Arab Emirates have maximum consumption of cardamom, and these countries share around 60% of the total world’s consumption. Whereas the Scandinavian countries like Finland, Denmark, Sweden, Iceland, and Norway have around 16% share in the world consumption. Rest of the European countries have only 14% share, Japan has 3% share, and the USA has 2.5% share in world consumption of cardamom. The global consumption of cardamom is estimated to be around 15,000–24,000 t whereas; the current demand of cardamom at domestic level has been estimated as 11,000 MT. The largest producer of cardamom is India (Amomum subulatum Roxburgh), with a yearly production of 4000 MT. Nepal (2500 MT) and Bhutan (1000 MT) comes at second and third position respectively (Berrig et al., 1993). In India, Sikkim is the main producer as it produces around 85% of total cardamom production of India. Around 4000 t of large cardamom which is valued at about Rs. 1.60 billion, is annually produced in Sikkim alone. It is also known as greater Nepal or Indian cardamom. It is native of the Eastern Himalayan region. Large cardamom is the most important perennial cash crop of the region and is widely cultivated with Himalayan alder (Alnus nepalensis) as a shade tree (Sharma et al., 2002). The crop of large cardamom is a kind of shadeloving crop. It cultivates under dense (60–70% of full daylight interception) to light shade (26% full daylight interception) conditions. For optimum growth of cardamom, the required daylight intensity is 5000–20,000 lux. Hence, it is required to clear the undergrowth in virgin forest. The regulation of overhead shade is also required in such a way that around 50% shades is there in the area. Around 30 species of trees are used to give shade to the plants of cardamom. The major chemical elements of cardamom oil are α-pinene, α-phellandrene, β pinene, myrcene, sabinene, limonene, trans-nerolidol, and methyl eugenol. It contains around 2.8–6.2% volatile oil, 10% protein, up to 50% starch, 1–10% fixed oil, manganese, and iron, among others. The volatile oil mainly consists of α-terpinyl acetate and 1,8-cineole. Both of them can be present at concentration of about 50%. The lesser

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components of volatile oil are limonene, linalool, sabinene, linalyl acetate, α-terpineol, α-pinene, camphene, 1,4-cineole, borneol, myrcene, etc. Acid constituents of the oil consist of acetic, butyric, citronellic, decanoic, dodecanoic, geranic, hexanoic, heptanoic, nerylic, and perillic acids. The fixed oil majorly includes waxes containing n-alkanes and sterols.

3.4. DISTINCT PROPERTIES OF SPICES 3.4.1. Flavoring and Coloring Properties Spices are in very high demand so as to meet the need and requirements of exotic flavors that are required for the purpose of cooking at home and also by food processors. The dried, as well as fresh forms, are easily available in the open markets or supermarkets. Generally, spices are utilized for flavoring either in their ground or whole form or as extractives. Spices such as sesame seeds, allspices, and bay leaves provide aroma and flavor along with the textural and visual effects that are not possible with extractives. However, ground spices may release the flavor present in them more readily as the flavor comprising cells have been damaged during the process of milling. On the other hand, whole spices release their flavors very slowly (Dziezak, 1989). In industrial use, the form of ground spices is generally used to provide physical appearance and, usually, they are supplemented with oleoresins or essential oils. Various spice extractives such as oleoresins and essential oil, serve as an alternative to ground as well as whole spices. They also provide stability which is required in the process of product formation. Essential oils are defined as the aromatic volatile components that are present in various spices. They are used to provide the characteristic flavor of spices. Basically, essential oils are the combination of oxygenated compounds (alcohol, esters, aldehydes) and hydrocarbons (terpenes). Spices are also used as the coloring material in some of the foods and also in the production of dyes such as turmeric. The value-added products of distinct spices can be utilized in freeze-dried or dehydrated forms, in canned or in brine forms like green and white pepper. As flavors, spices have the advantage of being natural as compared to the chemical flavors with persistent taste. They are very versatile to be used across a broad range of foods and also they can serve as beneficial alternatives to sugars, salts, and seasonings with chemical preservatives.

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They also add color to the food item and hence form a part of special culinary foods. It also has various applications in the cosmetic industry. Few of the spices such as saffron, turmeric, and annatto can also impart the desired.

3.4.2. Nutritional Properties Spices that are obtained from various seeds are very rich sources of fats, proteins, and carbohydrates. Spices play a major role in the nutrition being a good source of micro as well as macronutrients. Ogunka-Nnoka and Mepha (2008) performed research on the analysis of few Nigerian spices. The Nigerian spices were shown to be quite rich in micro and macronutrients. Various spices have rich sources of magnesium, calcium, phosphorus, and zinc. Functional foods or nutraceuticals are few substances that are considered as a food which eventually provides health or medicinal benefits. A food which has ingredients or components that provide a latent advantage to well-being, health, disease resistant or physical fitness beyond the advantages expected from its major nutritional components of lipids, carbohydrates, proteins, vitamins, and minerals which are referred to as the functional food. Spices are rich source of the phenolic compound along with the antioxidant property that impacts the nutrition by various ways.

3.4.3. Antioxidant Properties Rancidity is the hydrolytic or oxidative corrosion of fats that are responsible for the loss of texture, natural flavor, appearance, and nutritional value of fat also. Method of lipid oxidation consists of three chief steps. These steps are formation of free radicals, free-chain reaction or propagation of free radicals and the last, termination step in which non-radical products are formed. In the induction period or initiation phase, there is a huge loss of hydrogen on revelation of an unsaturated hydrocarbon to light or heat. The reaction further proceeds when the radical which is free of fat reacts with the oxygen so as to form peroxide radical. Then the peroxide radical extracts the hydrogen from different fat molecule which form a hydroperoxide and few other fats free radical. In the propagation step, to form a hydroperoxide and distinct fat-free radical the chain reaction remains to continue. Peroxy radicals, hydroperoxides, and new hydrocarbon radicals are also formed during the process of propagation.

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They crumble to form some extra radicals that add to chain reaction. When there occurs interaction between the two radicals, the process of termination takes place so as to form decompositional products (Nawar, 1985). Antioxidants are the substances which retard rancidity, deterioration, and discoloration because of the oxidation (Halliwell and Gutteridge, 1984). Food antioxidants can be characterized into two depending upon their action mechanism; primary or chain-breaking antioxidants and secondary antioxidants (Malhavi et al., 1996). Various spices work as the primary antioxidant. They inhibit or delay the initiation of the step of propagation by reacting with a proxy or fat-free radical. Also, they can terminate the chain reaction of free radicals by giving electrons or hydrogen to free radicals and then converting them into the stable compound that is they work as the acceptor of hydrogen donor free radical. Rosemary extract displayed antioxidant property in refrigerated turkey (Barbut et al., 1985) and also in soybean oil and lard respectively (Economou et al., 1991). Ginger rhizomes are used to prevent lipid oxidation in the animal fat (Lee et al., 1986). Sage, rosemary, bay, and thyme have been mostly utilized for baked products. Antioxidant characteristic of Aframomum danielli in reducing peroxidation rate in oils had also been reported (Fasoyiro et al., 2001). The phenolic structures of various spices permit them to work as primary antioxidants. These allow them to form energy free radicals by resonance hybrid (Smith, 1991). Few of the spices work as secondary antioxidants like synergists or chelators (Osawa et al., 1992). Few spices work better in the presence of synergists or chelators. As acid or metal chelators, spices work by binding the metalloproteins or metals which ultimately promotes the process of oxidation and hence permitting the primary antioxidants to do its function as well as capture free radicals. As synergists, spices work much better in the presence of antioxidants. Synergism is regarded as those instances when the integrated effect from various antioxidants is higher than the total of the individual effect acquired when used alone. Acid synergists enhance primary antioxidants by maintaining the acidic medium so as to enhance the antioxidants. They can regenerate antioxidants by chelating or deactivating pro-oxidant also. Various studies have shown

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that consumption of spices can donate to the overall consumption of plant antioxidants (Sharon, 2007). Skin exposure to extreme UV rays destroys the skin which leads to fine lines and wrinkles. Antioxidants like allicin present in garlic inhibit the activity of free radical. Spices such as garlic having the ability scavenge free radicals, and thus, they can be utilized to prevent pigmentation as well as inflammation problems of the skin.

3.4.4. Antimicrobial Properties The antimicrobial characteristics of spices can be categorized into bacteriostatic, bactericidal, fungistatic, and fungicidal properties. The volatile components present in cardamom have the inhibitory effect on the gram-negative bacteria (Isao et al., 1991). When ground rosemary is added to pork, it delays the listerial growth in the phase of refrigerated storage (Shelef and Pandit, 1994). The essential oils present in thyme and oregano inhibits the growth of mycelia of Aspergillus spp. (Pasteur et al., 1995). Essential oils of cinnamon, thyme, clove, bay, etc. are very much essential in terms of spices (Karapina, 1995). Nutmegs and almonds were very much efficient against 25 generals of bacteria inspected by Deans and Ritchie (1987). The extracts of onion exhibit distinct antimicrobial properties (Syed et al., 1996). Aframomum danielli has antimicrobial properties in contrast to a broad spectrum of microorganisms (Adegoke and Skura, 1994; Fasoyiro et al., 2001). Garlic is regarded as a natural antibiotic of which the main activity is completely devoted to the allicin. The activity of garlic has been demonstrated against Staphylococcus aureus and resistant enterococci.

3.4.4.1. Mode of Antimicrobial Action of Spices Though the antimicrobial properties of spices, as well as their derivatives, have been clearly examined against a broad variety of microorganisms over the past few years but their mode of action is yet not understood completely. Actually, spices along with their essential oils have various bioactive compounds available in variable amounts. Mostly, the bioactive compounds present in spices can be further divided into two compounds namely, volatile, and non-volatile compounds. The volatile compound is chiefly responsible for the property of antimicrobial activity of distinct spices. Further, they can be categorized into four main

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groups asterpenes, terpenoids, phenylpropenes, and other products of degradation (Hyldgaard et al., 2012). Terpenes are assessed as less active antimicrobial compounds among various other compounds. For example, the weak activity of ρ-cymene. It is one of the key components of thyme. ρ-cymene is basically related to its action as an impurity of substitutional membrane. It can also affect the potential of membrane as well as melting temperature, that in turn causes a decline in the cell mobility (Hyldgaard et al., 2012). Whereas, terpenoids like carvacrol and thymol have their antimicrobial activity because of their functional groups such as delocalized electrons and hydroxyl groups. For example, thymol can easily interact with the membrane with the polar head group region of the layer of lipid as well as with the proteins. Interaction with the polar head group affects the permeability of the membrane. On the other hand, interaction with proteins determines the accumulation of those structures that are misfolded (Hyldgaard et al., 2012; Marchese et al., 2016). These changes can ultimately lead to the cell leakages that can bring the cell to death (O’Bryan et al., 2015). Once it gets into the cell, thymol can also interrupt essential energy generating processes such as the synthesis of ATP and the citrate metabolic pathway (Hylgaard et al., 2012; O’Bryan et al., 2015). Carvacrol mainly acts at the membrane level as a transmembrane carrier of the monovalent cations, swapping K+ with H+ in the cytoplasm (O’Bryan et al., 2015). Various other organic compounds present in different spices are phenylpropenes, such as cinnamaldehyde and eugenol. The antimicrobial activity of eugenol is basically performed at the level of the membranes as well as proteins, comprising permeabilization along with the enzyme inactivation. On the other hand, cinnamaldehyde that is not as powerful as eugenol can easily react as well as cross-link with DNA and proteins in spite of just interacting with the cell membrane. Finally, distinct spices have various other degradation compounds that basically originate from lactones, terpenes, sulfur-, and nitrogen-containing molecules, glycosides, and unsaturated fatty acids. For example, the mode of action of AITC which is a nitrogen-containing compound is basically considered as a non-specific inhibition of periplasmic or intracellular targets. Actually, because of its highly electrophile central carbon atom, it can also restrict some enzymes and affect various proteins by oxidative cleavage

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of the disulfide bonds (Hyldgaard et al., 2012). AITC is the key component of the mustard essential oil. Clemente et al., (2016) further reported that the mustard essential oil-induced cell cycle capture that result in bacterial filamentation. In spite of the affecting membrane as well as intracellular stability, Szabo et al., (2010) reported that oregano, clove, rosemary, and lavender essential oils has an inhibitory activity of the quorum sensing. For example, molecules like furanones can be affected by the bacteria which is bound to the LuxR-type proteins and eventually destabilize them (Camilli and Bassler, 2006). By this approach, spices could immensely impact the swarming, motility, and biofilm production of the bacteria. In total, the antimicrobial activity of the spices cannot be assured depending upon the action of one compound only. The ultimate activity is a kind of synergistic effect of various components.

3.4.5. Preservative Properties Spices play a major role in the food safety by functioning as an antimicrobial agent in numerous foods. The antimicrobial properties of distinct species have been identified that totally depends on type, concentration, composition, storage condition, etc. (Shelef, 1980). Different kinds of spices are known today mainly for their preservative properties. This function of spices in assuring the food safety cannot be exaggerated. The preservative characteristic of various spices is because of the oleoresins and volatile oils present in them. Essential oils of oregano and thyme are the significant kinds fumigants against the fungi who attacks the stored grains (Pasteur et al., 1995). Essential oils of ginger, nutmeg, cloves are very much active against several insects that infest the maize in storage. Eugenol is a kind of an active ingredient in Ocimum spp. It is a latent repellant of maize weevil Sitophillus zeamais (Chogo and Frankel, 1981; Hassanali et al., 1990). Gould (1989) related the activities of different essential oils with impairment of a diversity of enzyme systems comprising those that are involved in energy production as well as structural component synthesis.

3.4.6. Insecticidal Properties Spices owns the potential to be further utilized in the pest management

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and also it has been recommended that the disagreeable odor of oleoresin and essential oils can provide protection against various insect attacks. The insect repelling assets of black peppercorns have been to provide protection against moth in clothing (CTA, 1993). The screened pepper fruit under the hermeneutic situations have been found to attack all the stages of life of Callotsobruchus maculatus in stored cowpea. Extracts of Ocimum spp has revealed potential insecticidal properties (Chogo and Frankel, 1981).

3.5. CONCLUSION Spices are natural products which are processed by using different techniques. They are very much essential in our daily nutrition. Along with imparting the taste and flavor to the food, it also encourages several beneficial physiological effects. The ideal consumption of different spices is proved as safe and effective. Various health benefits are there as a spiced diet is likely to make healthy life. All the above-discussed spices namely turmeric, coriander, fennel, fenugreek, garlic, clove, cumin, pepper, curry leaf, ginger, and cardamom are majorly used in several delicacies. An ordinary meal can be turned into an extraordinary one by the use of spices. They have a miscellaneous array of naturally occurring phytochemicals. These phytochemicals have overlapping and complementary actions. Various metabolic diseases and cardiovascular disorders are linked with the oxidative processes taking place in the body. Therefore, spices can also be used as a source of antioxidants to fight these reactions. Hence, spices and herbs are major part of our daily lives. Their composition matters a lot. Different compounds are present in different spices and have different functions. So, every spice has its own value.

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REFERENCES 1.

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Anandaraj, M., (n.d.). Perennial Spice Crops: Black Pepper, Cinnamon, Clove and Nutmeg. [eBook] Encyclopedia of life support systems. p. 8. Available at: https://www.eolss.net/sample-chapters/C10/E1– 05A–48–00.pdf (Accessed on 9 March 2019). Chemical Composition of Spices and Condiments, (n.d.). [eBook] p. 13. Available at: http://epgp.inflibnet.ac.in/epgpdata/uploads/epgp_ content/food_technology/technology_of_spices_and_condiments/06. chemical_composition_of_spices_and__condiments/et/2875_et_ m6.pdf (Accessed on 9 March 2019). Compound Interest, (n.d.). Chemical Compounds in Herbs & Spices. Compound Interest. [online] Available at: https://www.compoundchem. com/2014/03/13/chemical-compounds-in-herbs-spices/ (Accessed on 9 March 2019). Parthasarathy, V., Chempakam, B., & Zachariah, T., (2008). Chemistry of Spices. [eBook] p. 455. Available at: https://catbull.com/alamut/ Bibliothek/Chemistry_of_Spices.pdf (Accessed on 9 March 2019). Peter, K., (2001). Handbook of Herbs and Spices. [eBook] North and South America: Woodhead Publishing Limited, p. 332. Available at: https://www.researchgate.net/profile/Br_Rajeswara_Rao/post/ What_is_the_best_way_to_extract_the_active_ingredients_of_ medicinal_plants_And_how_are_they_to_know_the_active_ ingredient_in_the_medical_plant2/attachment/59d61de279197b807 797bc03/AS%3A273808903082002%401442292537638/download/ herbs+and+spices-Book.pdf (Accessed on 9 March 2019). Shaaban, H., & Moawad, S., (2017). Chemical Composition, Nutritional and Functional Properties of Some Herbs and Spices. [eBook] International Scientific Organization, p. 15. Available at: http://bosaljournals.com/csp/images/pdffiles/45CSP.pdf (Accessed on 9 March 2019).

Chapter

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Processing of Spices and Process Required for Quality Check

CONTENTS 4.1. Introduction ...................................................................................... 84 4.2. Pre-Treatment Methods ..................................................................... 87 4.3. Small-Scale Spice Processing ............................................................ 90 4.4. Cultivation of Various Spices ............................................................. 97 4.5. Measure The Quality of Spices: Maintaining Color Control With Spectrophotometers ....................................... 103 4.6. Process Involved For Preserving Spices ........................................... 104 4.7. Constraints In Spice Production In Asia ........................................... 105 4.8. Processing, Storage Methods, and Quality Attributes of Spices and Aromatic Herbs ...................................................... 107 4.9. Conclusion ..................................................................................... 112 4.10. Case Study: Pathogens And Spices ................................................ 113 References ............................................................................................. 121

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Spices are defined as a non-leafy part of plants that are used for adding seasoning or flavoring. In the whole world, Asia is known as the ‘Land of Spices’ as it is the place of origin, production, consumption, and export of most spices. Spices are majorly grown in tropical countries while the United States (US) has newly started growing a number of different spices to supply the domestic requirements. The use of spices has increased over the past few years, due in part to the high level of interest in different types of foods which uses a broad range of spices. The main objective of this chapter is to describe the steps which are involved in the processing of spices, pre-treatment methods and the cultivation of various spices. It also explains the quality check measures which are necessary to maintain the good quality of the product. In the end, various constraints are described that are involved in the production of spices.

4.1. INTRODUCTION Spices can be described as the non-leafy parts of the plant which are used for seasoning or flavoring purposes. They are used for adding flavors to various foods and beverages and also as herbal medicines. Asia is known as the ‘Land of Spices.’ Asia is the major place of origin, production, consumption, and export of a different variety of spices. Among the total world’s 70 plant species grown as spices, 13 are considered major spices which are produced in Asia. Piper nigrum which is known as black pepper, in general, is the whole dried fruit of a perennial climber. Indonesia and India together produce around half of the total world production of 180,000 t. Cardamom is a collection of herbaceous plants whose fruits are generally used as spices. They are of ginger family. The best quality of all is the small cardamom also known as Elettaria cardamomu, which is usually grown in India and Sri Lanka. Other types of cardamom include Bengal cardamom (A. aromaticum), large cardamom (Amomum subulatum), bastard cardamom (A. xanthioides) and Siam cardamom (A. krervanh). India and Sri Lanka are the major producers of cardamom. Cassia and cinnamon are the related plants of Cinnamomum genus whose bark is used as a spice. Essential spices comprise the true cinnamon (C. verum), Indonesian cassia (C. burmannii), cassia (C. cassia), Indian cassia (C. tamala) and Vietnamese cassia (C. loureirii).

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Chili pepper is another spice which is acquired from the dried fruit of C. frutescens and Capsicum annuum. C. frutescens is also known as bird pepper, and it is much pungent. It can be made into cayenne pepper to add flavor to spicy oriental hot foods. While C. annuum which is also known as the sweet pepper is less pungent. It is generally used to produce paprika pepper for coloring and flavoring western food items. Cloves are obtained from the closed flower buds of Syzygium aromaticum. In Asia India, Indonesia, Malaysia, and Sri Lanka usually produce clove. But large amounts of cloves are produced in other continents such as Tanzania, the West Indies, and Madagascar. The dried seed of Coriandrum sativum is known as coriander. Coriandrum sativum is an herbaceous plant. Coriander is majorly produced in India. Other producers of coriander are Thailand and Pakistan. Cuminum cyminum or cumin is an annual herb. The fruits of cumin are highly aromatic and pungent. India and China are the major producers of cumin. Garlic or Allium sativum is an annual herb. The underground herb of this herb is used as a spice.

Figure 4.1: Variety of spices. Source: https://eastsidefm.org/arts-wednesday-15-november-2017/spices-2/

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The major producing countries of garlic are India, Thailand, and Korea. Ginger or Zingiber officinale is a perennial herb. The underground rhizomes, young, and old, are used as a spice. Thailand and India are the major producers. Mace and nutmeg are two spices which are derived from Myristica fragrans, an evergreen tree. Three-quarters of the total world production is produced by Indonesia. The second major producer is Grenada. Turmeric is the underground rhizome of Curcuma longa which is used as a spice, herbal medicine, and natural colorant. The major producer and exporter of turmeric is India (Figure 4.1). Vanilla comes from a pod of an orchid plant scientifically known as Vanilla planifolium. The fragrance of which reveals itself after a sequence of consecutive treatments and fermentation in the sun. Madagascar is the largest producer in the world while Indonesia comes at second position. Spices are very delicate products which can be damaged by extreme processing and high temperature. Hence, much care is needed to ensure the better quality of the products. There are various chief quality control methods that the small-scale processors must be aware of. Processing methods that are involved for the production of herbs and spices consists of fumigation with ethylene oxide (EtO), irradiation, and vacuum-assisted steam. The process of fumigation with EtO has been shown to considerably decrease the microbial populations on spices (Leistritz, 1997), while some EtO-treated spices have been shown to undergo drastic changes in color and flavor (Vajdi and Pereira, 1973). When the spices are treated by EtO, the volatile contents present in them gets reduced to half or sometimes more than that also (Vajdi and Pereira, 1973). Volatile compounds are lost due to the low pressure required to remove EtO (Vajdi and Pereira, 1973; Almela et al., 2002). Spice crops are usually get contaminated by dirt, dust, insects, pesticides, variety of microbes and animal hairs and droppings. Hence, the crop is required to be cleaned before processing. The very first stage is to remove dirt and dust by using a winnowing basket. These baskets can be made by locally available bamboo, palm or other leaves. Small machines are also available for cleaning purposes, but they are no that cost effective. The crop must be washed in clean and potable water after the process of winnowing. This washing must be very quick so that the spice is not soaked in water. The soaking of spice will ultimately reduce

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the quality of them. The washing water should be transformed frequently to prevent recontamination of spices by dirty water. The major objective of this chapter is to analyze the different kinds of spices and aromatic herbs (SAH) which are being processed, commercialized, and consumed these days. Additionally, the socio-cultural features of actors, the processing and the preservation techniques used and hygiene practices, the definition of quality attributes of SAH according to the actors, and the main constraints faced by the actors were studied with the aim to enhance the processing, and the quality of SAH commercialized at regional and national levels.

4.2. PRE-TREATMENT METHODS 4.2.1. Washing Root and rhizome spices, for example, angelica, ginger, calamus, and turmeric that are dug out of the soil, requires good washing to eliminate the adhering mud and dirt. Wherever enough facilities are available, and the pressure-water washing may be possible to remove out the dirt. Decrease in the microbial load will also be influenced by the effectiveness of this operation.

4.2.2. Peeling Almost all the spices are dried whole that is without peeling, while ginger, onion, and garlic are the exceptions. The skin of the ginger rhizomes creates a barrier to evaporation or transportation of moisture from within, and therefore a precondition for effective drying of ginger is peeling. Hand peeling with special scraping knives is employed to dry out the ginger. Mechanical peeling of ginger has been tried with harsh machines for almost sixty seconds, which is correspondent to hand-scraping regarding the loss of volatile oil, peeling loss of 10 to 20 % and time of drying. The timing of harsh peeling is somewhat crucial, and care must be taken. Else, it results in major losses. This is another way of reducing the time of drying, but the conventional trade will have to be educated and certain about its economy and the insignificant chances of adulteration in the sliced and dried product (Kuppuswamy, 1974; Natarajan et al., 1972).

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4.2.3. Pricking Longitudinally pricking the skin of chilies helps to decrease the time of drying (Laul et al., 1970) and also helps in improved retention of color and overall quality.

4.2.4. Blanching Blanching is usually practiced in vegetable drying and dehydration around the globe. This is mainly used for the inactivation of enzymes. Blanching is not used for garlic, celery, parsley, and onion, as they add specific flavors to various food items and blanching damages those enzymes which are involved in generating the flavor. In ginger and chilies also, blanching is not desirable. However, blanching, also known as simmering is a commercial practice in the case of turmeric, mainly in the existence of small quantity of alkali (Desikachar, Srinivason and Subramanyam, 1959) as described under curing of turmeric (pora 2.6.4).

4.2.5. Chemical Treatments Different types of chemical treatments methods such as antioxidant treatment, alkali treatments, sulfuring by sulfur fumes, bleaching by liming treatment, and treatment with SO or hydrogen peroxide are used by the industries for different spice like liming or bleaching of ginger, alkali treatment for cardamom, bleaching of cardamom by sulfuring and curing of turmeric with appropriate chemical solutions.

4.2.6. Curing and Other Treatments Various spices, for example, garlic, cinnamon, and cassia, turmeric, and saffron are cured by different techniques so as to produce the characteristic aroma or flavor for which they are valued.

4.2.6.1. Smoke-Curing of Garlic The improved quality of smoked foods is due to • • • •

Integration of natural antioxidants; Partial dehydration; Impregnation of antiseptic constituents; Enhancement in organoleptic quality;

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• Result of heat on microorganisms. The profits of the smoking process of garlic and physicochemical changes during storage of smoke-cured garlic have also been reported.

4.2.6.2. Cinnamon and Cassia: Peeling and Curing The peeled slips that is bark from cinnamon and cassia branches are collected and packed one above the other with their convex and concave surfaces in juxtaposition until the packings measure about 20 to 30 cm wide and 30 to 45 cm long. These slips are loaded up within inclusions of sticks and are enfolded in mats. The packs are then kept overnight in that particular condition only. This is done to allow the process of fermentation. In fact, no fermentation process develops. A slight softening of the bark takes place, with the effect that the peels become flexible very easily. This flexible peel will help in the consequent piping operation or the elimination of the epidermis and the green cortex.

4.2.6.3. Curing of Turmeric Curing of raw turmeric fingers and rhizomes that are freshly dug out of the earth is very important for the development of its aroma and attractive yellow color due to curcumin. If curing of turmeric is not done, both color and aroma will not be there. After 3 or 4 days of turmeric harvesting, curing can begin. The mother rhizomes and fingers are detached by hand, if required, the rhizomes are kept for seed purposes, and the fingers are cured for marketing by the following techniques. •

Conventional Technique: The fingers and bulbs are boiled in water until a froth comes out and white fumes start to appear, giving the typical turmeric aroma. The fingers and bulbs become softer and yield when pressed between the lingers. At this stage, they are removed from the boiling water, drained properly, colored artificially if necessary and dried in the sun for 10 to 15days, after which they are polished to remove any adhering rootlets and scales. The quality of the final product, including its color and aroma depends largely on the correctness of curing, but according to another report, the curing quality of turmeric is mostly a varietal character, although other factors such as high moisture content, maturity, and seasonal conditions influence

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the percentage of recovery (the ratio of the cured and dried turmeric to raw turmeric) to some extent. •

Improved Scientific Method: At Central Food Technological Research Institute (CFTRI), a new scientific method of turmeric curing has been developed. According to this method, the washed row tubers are allowed to boil in dilute limewater, sodium carbonate, or sodium bicarbonate solution instead of boiling in water. For bringing the yellow color characteristic to the tubers, a solution comprising 20 g of Sodium bisulfate and 20 g of concentrated hydrochloric acid per 70kg of boiled tubers has been suggested (Desikachar, Srinivasan, and Subrahmanyam, 1959) instead of Chemichrome solution.

4.2.6.4. Curing of Saffron The worth of saffron majorly depends on the methods by which the stigmas are processed. In Spain, the process is known as ‘toasting,’ and the stigmas are placed in sieves in layers which are 2–3 cm thick. These sieves are located at 15 cm above an almost spent fire for drying. The product is dried carefully by changing their position or order and by stacking also. Excessive care must be taken that the stigmas are protected against dampness as well as light because light bleaches saffron to a paleyellow color. Drying in the sun also bleaches the saffron or changes its color (Katyal, 1967).

4.3. SMALL-SCALE SPICE PROCESSING The processing of spices has a very long and important history. Spices are defined to be a valuable product and have an efficient impact on the economy of various countries. Processing of spices can be done at different levels, but small-scale processing of spices is successful socially and viable economically. In terms of inducing food poisoning, the dried foods are relatively lowrisk and safe products. Therefore, they are sustainable to get produced at small-scale. But spices are a kind of exception to this. They generally have high level of microbes which are contaminated and usually cause food poisoning. Special care must be taken of the spices to assure the quality of them because they are delicate in nature and usually gets damaged by extreme

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processing and high temperature. There are various key quality control points which small-scale processors required to be aware of (Figure 4.2).

Figure 4.2: Processing steps of spices.

Source: http://nkworlds.com/Spices.php

4.3.1. Correct Harvesting Time By using inferior and low-quality input material, it is not really possible to produce spices of high quality. Therefore, good quality products should be used for the production of spices. The main key of producing good quality products is harvesting spices at the right point of its maturity. Generally, what is being done nowadays, immature spices are harvested, and many times their aroma and flavor compounds are not fully developed. Hence, low-quality products are produced. This consequent in the production of spices having inferior aroma and taste. The farmers do early harvest before the spices are fully matured. The reason behind this early harvesting is that there is a fear of crop being stolen from the land or sometimes the farmers require money immediately. Various efforts must be made to wait for the time until when the spices are matured fully before the process of harvesting.

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4.3.2. Cleaning Crops of spices are usually contaminated by dirt, dust, insects, and pesticides, variety of microbes and animal hair and droppings. So, before performing the process of harvesting, the crops should be cleaned. The process of cleaning crops involves various stages. The first stage involves the removal of dirt and dust by using a winnowing basket. These baskets can be made from palm, bamboo, and other leaves locally. A person who is used to do this work can easily remove the dirt, dust, and stones efficiently and rapidly. Different types of small machines are available for the cleaning process, but they are rarely found to be cost effective. After the process of winnowing, the crop must be washed in clean and potable water. This will remove the dirt if present after winnowing, completely. Washing can also reduce the quality of spices. Therefore, washing must be quickly done so that spices are not soaked in water. Washing process sometimes causes contamination also. Hence, to avoid recontamination of spices by dirty water which is the effluent of the washing process, the washing water should be changed regularly. As spices are not treated with heat during the processing, so it is mandatory to use clean water. Many bacteria are introduced by using dirty water which ultimately causes food poisoning.

4.3.3. Drying Drying is the most important part of spice processing to guarantee good quality of spices production. If the spices are dried inadequately, there will be growth of mold. The sale value of moldy spices can be less than 50% of the normal value. Additionally, the growth of bacteria having tendency of causing food poisoning, on few spices is a risk if adequate washing and drying is not done. Spices consist of volatile oils which are affected adversely by high temperatures. Hence, the temperature during the process of drying should be controlled tightly to assure a product of good quality. Small scale processors do the process of drying the spices, by putting them under the sun. Well, this is another chance of spice contamination. Various efforts must be made to dry the spices in a clean environment, far away from the insects, animals, and birds, as they can cause the contamination to the spices.

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4.3.3.1. Drying During the Dry Season Sun drying is generally adequate during the dry season to dry out the spices. This is the simple and cheap method of drying which involves laying the products on mats under the sun. Yet, there are various problems linked to this method of drying. Dirt and dusts are usually blown onto the crop and sometimes unexpected rainstorm may re-wet the products. The process causes contamination also. Drying the products in direct sunlight can unfavorably affect the color of few of the more sensitive spices. This issue can be resolved by using a solar dryer which reduces the chance of spoilage and contamination. The simplest form of solar dryer is the cabinets dryer which can be constructed by using locally available resources such as coir fiber, bamboo or nylon weave. For larger units of drying as over 30 kg per day, a Brace solar dryer can be used. The cost of construction required for this type of dryer is greater. A complete financial evaluation must be made to check if it economically viable or not (Figure 4.3).

Figure 4.3: Solar dryer. S o u r c e : h t t p s : / / w w w. s c i e n c e d i r e c t . c o m / s c i e n c e / a r t i c l e / p i i / S0038092X17304619

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4.3.3.2. Drying During the Wet Season During the wet season and high humidity, solar drying or sun drying cannot be used effectively. This season usually coincides with the spice harvesting. An artificial dryer who uses an inexpensive source of energy is mandatory. This may be a husk or wood burning dryer or a combined wood burning and solar dryer. It is essential to control the time and temperature of drying. For most spices, the maximum temperature of drying is 50°C. At higher temperature above this, the volatile compounds present in spices which are the main reason behind the aroma and flavor, are driven off. Spices must be quickly dried until they attain their final moisture content. They must not be overdried as this would be responsible for detrimental effect on the quality of the product.

4.3.4. Grading Spices can be graded by size, color, density, shape, and flavor. Machines are available for larger scale production units (Table 4.1). Table 4.1: Spice Moisture Content Spice Mace Nutmeg, cloves Turmeric, coriander Cinnamon Pepper, pimento, ginger Cardamom

Max. final moisture content (% wet basis) 6.0 8.0 9.0 11.0 12.0 13.0

Source: https://www.doc-developpement-durable.org/file/Culture-epices/ Spice%20Processing.pdf

4.3.5. Grinding Spices can be either in whole or ground into powder. The process of grinding adds value to the product. Sometimes, it also detracts the value of product. Various consumers are very conscious of having grounded spices as they get contaminated frequently. This contamination may cause many diseases.

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There is no method of identifying the ground spices that whether they are pure or adulterated. Generally, the ground spices are made by grinding broken and inferior spices. The shelf life of ground spices is much shorter than the shelf life of whole spices. Once the spices are grounded, the aroma and flavor deteriorate soon. For small scale processors, it is better to sell spices as a whole to get desired benefits. This will also remove the requirement of moisture proof material for packaging and sealing machines. Manual grinders are generally used for small scale production such as up to 100 kg per day. Small models which are designed for domestic grinding of spices are very suitable. To make the work easier, a bicycle or treadle can be attached to the machine. This will help in the grinding of spices. For large-scale production of grounded spices, a small and powered grinding mill is required. Various models are present which can grind the spices at the rate of 25 kg per hour. A grinding mill is required to be placed in a well-ventilated and separate room to avoid contamination by dust. Great care must be taken to assure uniform size of powder or pieces after the process of grinding, and to reduce spice heating during the process of grinding of spices.

4.3.6. Packaging and Storage After the completion of drying process, the products must be packed into a clean and heavy gauge polypropylene sack, quickly. It is done to avoid pick up of moisture by the products. The spices after grinding must be cooled first. Then they are packed into the sack. After packaging, they must be stored out of direct sunlight to avoid condensation forming on the inside of the sack. Workers must never handle the spices directly. They should always use scoops and clean gloves to handle them. Sacks must also be dated and labeled. The need of packaging totally depends upon: • The kind of spice; • Spices are grounded or intact; • The humidity of storage. If the humidity in the air is not too high, then most intact spices will store in sacks or boxes adequately. Ground spices can be stored without special packaging also, if the humidity level is low. This process for a long period of time can cause a loss of aroma and flavor. This can also cause spoilage and contamination of spices.

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Therefore, it is better to store the spices in a barrier film like polypropylene. It is essential in the areas where the humidity level is very high. It provides a good package and retains quality of spices also. Losses and contamination can also be prevented by using polypropylene. It is not available, and cellulose film can be used if it is sealable to heat. Polyethene is a poor material to be used for packaging. It can only be used for short duration as it allows the aroma and flavor of the spices to escape (Figure 4.4).

Figure 4.4: Flow chart of spice processing. Source: https://www.researchgate.net/figure/Flow-diagram-of-processing-ofspices-and-aromatic-herbs_fig1_308928923

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4.4. CULTIVATION OF VARIOUS SPICES 4.4.1. Cardamom Cardamom is usually known as the “queen of aromatic spices.” It is mainly used for flavoring, masticatory, and for medicines. In the climate of high heat, humidity with temperature ranging from 15°C to 32°C and equally distributed annual rainfall of 150–300 cm, the production of cardamom is very high. Different types of soils which can be used for good production of cardamom are deep red soil, well-drained forest loams and laterite soil having huge amount of humus and leaf mold. At an altitude of 800–1600 meters above the level of sea, tropical rain forests provide the most pleasant environment for the growth and production of cardamom. The plant is shade-loving and hence is grown under the shady trees. In the market of world, the demand of cardamom is immensely increasing day by day. To meet this demand, the production of cardamom has to be increased as compared to the present level. More than sixty countries buy cardamom from India. The main countries are Russia, Saudi Arabia, Sweden, Afghanistan, U.K., Finland, Germany, Bahrain, and Kuwait. Guatemala, a country in Central America is at the first position in the production of cardamom. Currently, Guatemala has developed as the toplevel producer and exporter of cardamom sharing around 90% of the world export of cardamom. After Guatemala, India is the main producer of cardamom. In India, whole production comes from three states, Karnataka, Kerala, and Tamil Nadu and contributes 53%, 42%, and 5% respectively, of the total production of India. As Guatemala stepped up its production from the mid-1980s, the shares of Indian have come down from 60% to 3% in the world market.

4.4.2. Pepper Among all the spices, black pepper is known as “the kind of spices.” It is very important dollar earning crop. It plays a decisive role in the state and national economies. It is very useful to flavor the foodstuffs. Pepper is a tropical plant and hence needs a minimum temperature of 10°C and maximum of 30°C temperature. A 200–300 cm well-distributed rainfall helps in the growth of pepper. The pepper plant grows as a vine and hence requires the support of some

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other tree for its growth. It blooms on deep, well-drained loamy soils, friable, covering the lateritic hilltops of Western Ghats; however, it can also be produced on red and laterite soils. It can be grown well from almost sea level to an altitude of 1,200 m. The coastal sandy plains do not suit its growth. Indonesia is the largest producer of pepper. In Indonesia, pepper has grown meanwhile the days before the colonial period. After European colonist came in Indonesia in early 1500 BC, it became a high-value product. Pepper is a kind of smallholder estate crop and labor-intensive product largely cultivated in Lampung for black, Bangka Belitung and Kalimantan for white pepper. Pepper is also cultivated in Java, Sulawesi, and other areas in Sumatera Island. Pepper plantation in Indonesia is currently around 120,000 hectares, which is gradually decreased from more than 150,000 hectares during the period of the 1990s including 500,000 farmers approximately. In the last decade, pepper production in Indonesia is rapidly increasing because of various numbers of constraints in cultivation which still have not been resolved like foot rot diseases, viral, and pest and climatic changes. After Indonesia, India is the second largest producer of pepper. The production has increased from 21,000 tons in the year 1950–51 to 64,000 tons in 2002–03. The distribution of pepper is majorly focused on Karnataka, Kerala, and Tamil Nadu. Around one-third of India’s total production of pepper is exported to approximately 80 foreign countries. The main consumers are the Russian Federation, Canada, the USA, East, and South European countries, Egypt, and Sudan. Though, the crop records a low productivity of 306 kg per ha as compared to other producing countries such as Thailand with a productivity of around 4,000 kg per ha. India’s hitherto unquestioned status all over the history as the chief producer and exporter of black pepper in the world is now under risk with primary forecast on production and export data from Vietnam. Post the period of WTO, the shares of Indian quantity, in world exports was nearly found halved from 27% in 1996 to 12.7% in 2000. Although the quantity of export listed a compound annual growth rate of 5.79% in the preWTO period, it was an upsetting (-) 5.73% in the post-WTO period.

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4.4.3. Chilies Chili is another essential spice. The production of chilly requires a temperature between 10° and 30°C, and moderate annual rainfall between 60 cm and 125 cm. Too scarce and too heavy rainfall, both are harmful for the production process of chilies. They can be produced on wide variety of soils comprising black cotton soil, and different types of loamy soils. Chilies can be grown up to 1,700 meters elevation. The production of chilies has increased from 351,000 tons to around 970 tons. All states of India produce some quantity of chilies. But Guntur, Warangal, Khammam, East, and West Godavari and Prakasam are the foremost chilly producing districts. Most of the chilies produced in India are consumed within the country, and only 5 to 7% are exported, mainly to Sri Lanka, the USA and Russia.

4.4.4. Ginger Ginger is used as a spice and for producing medicines. It is produced in tropical and sub-tropical climate and requires temperature between 10° to 25°C and rainfall of 125–250 cm. The soil which is best suited for the production of chilies are well-drained sandy, clayey or red loams, and laterites. It can be grown to an altitude of 1,300 m above the sea level. In the whole world, India is the largest producer of ginger. India produces around 80% of total world production of ginger. From 15,000 tons to 318,000 tons, the ginger production has increased 21 times. This crop production requires an area of around 90,000 hectares which results in yield of 35.1 quintals per hectare approximately. The main states of India which produces ginger are Kerala, Sikkim, Meghalaya, Orissa, West Bengal, and Mizoram, which accounts for around 84% of the total production of the country. Around 80 to 90% of the total ginger production is consumes in India only. Still, India is a chief exporter of ginger in the international market. Around 80% of the export of India goes to the West Asian countries.

4.4.5. Turmeric Turmeric is another spice which is inherent to the tropical lands of SouthEast Asia. It is generally used in dyes and medicines. The production of ginger requires tropical climate and well-drained clayey and sandy loams, medium black, alluvial or red soil for growth.

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The major producer of turmeric is India in the whole world. Its production noted more than fourfold increase from 152,000 tons into 658,000 tons in 2002–03 with a record production of 714,000 tons in 2001–02. Other major turmeric producing countries are Pakistan, Haiti, China, Jamaica, Taiwan, Peru, and Thailand. Asian countries consume much of their turmeric production. In India, Andhra Pradesh is the largest producer of turmeric. The neighboring state, Karnataka is the second largest producer, and it usually produces around 20% of the total production of India. Mysore and Belgaum are outstanding producers. About 90% of the total production is consumed within the country. Only 10% produced turmeric is exported to the USA, Russia, Japan, Sri Lanka, and Singapore.

4.4.6. Areca nut It is a tough nut which is cut into small pieces. It is used for chewing with betel leaves, catechu, and lime. The stem of areca nut is used for construction drives and leaves for thatching. Areca is a tropical tree which reaches at a height of 20–25 meters on maturity. It flourishes well in areas having 15°–35°C temperature and 200– 300 cm annual rainfall. It grows on a large variety of soils ranging fromwell-drained laterite, alluvial to red loamy soils. The cultivation of areca can be done from sea level to 1,000 meters. In the whole world, India is the largest producer of areca nut. In 2003–04, India produced around 4 lakh ton of areca nut from 3 lakh hectares of land. Around 40 lakh people who are involved in cultivating, curing, processing, and trading of areca nut are earning their livelihood from this nut. Kerala, Tripura, Karnataka, Assam, and Meghalaya are the major producing states of India. They account for about 90% of the total output of India. Among all, Kerala is the largest producer which accounts for 37% of the Indian production. Most of the areca nut produced in India is consumed within the country. Only a small amount is exported mainly to UAR, Nepal, Pakistan, Saudi Arabia, Kenya, and Singapore.

4.4.7. Coconut The coconut palm provides us with various useful products of our daily use.

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It is generally used for production of copra which ultimately provides us oil. This copra oil is used for cooking and various other purposes. The trunk of the coconut tree gives timber and shells of the nut are used as fuel. Further, the leaves of the coconut tree are used for different purposes for example making of baskets, mats, screens, and many times for roofing the huts. Sweet drink can be obtained from the juice of green nuts. This juice is collected from the spathe of coconut and sugar, vinegar, and toddy can be made by using this juice. The coconut oil cake is used as food and also fed to cattle. Coconut is a perennial crop and hence has discrete features such as long period of gestation of 5–7 years and long period of economic life span of around 60 years or more. The favorable temperature for the growth of coconut is between 25° and 30°C as it is a tropical crop. It requires well-distributed rainfall of 125 to 130 cm. Drought and frost are very dangerous for coconut. Frost and drought are very detrimental to coconut. It is mostly grown under the conditions of rainfed in many parts of India such as Kerala, Tamil Nadu, and Karnataka. In rest of the country, coconut can be grown under irrigated conditions. The best quality of soil which is used for the growth of coconut is well drained rich loamy soils. It also grows on sandy loams and in adjoining river valleys. The coconut is a species of tropical tree. It is majorly grown and harvested by the small-scale farmers. Production of coconuts is focused on coastal areas such as Samoa, Fiji, and island, as well as in the humid tropics such as Indonesia, the Philippines, and India. The leader of coconut production in the world is Indonesia. The majority of the coconut of Indonesia is produced in the province of North Sulawesi. More than half of the coconuts produced are exported to other countries of the world. Indonesia is one of the top producers of pineapples. The second largest producer of coconuts in the whole world is the Philippines. Previously, it was the world’s largest producer of coconut. Luzon, the Eastern Visayas and Southern Mindanao are some of the most prominent locations of the country for coconut production. It is predicted that almost one-quarter of total farmland is d to the production of coconut in the Philippines. The third largest producer of coconut is India in the whole world. In the year of 2016, India was responsible for the production of around 119

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million tons of coconut. For agriculture industry, coconut production is very essential in India, mainly in the rural areas of the country. In India, small, and marginal farmers with an average holding size of less than 0.20 ha in Kerala and 2 ha. in other three states dominate coconut production sector in the country. Production of coconut increased from 358,000 tons in 1950–51 to 12,822,000 tons in 2002–03. Kerala is the major producer accounting for half of the total production of India in 2002–03. The major production comes from Thrissur, Kollam, Ernakulam, Thiruvananthapuram, Kannur, Alappuzha, Kottayam, and Malappuram districts. These districts produce more than three-fourths of the total production of Kerala. Tamil Nadu making about one-fourth of the total production of India. However, every district of Tamil Nadu produces coconut, but over half the production of the state comes from Thanjavur, Salem, and Coimbatore districts. Karnataka is the third largest producer in India accounting for 12% of the total production of the country in 2002–03.

Figure 4.5: Spice plantation of Kerala, India. Source: https://www.visittnt.com/kerala-tours/spice-plantations-kerala.html

The export of coconut and its products shows that India has done well in coir and coir products, while in the export of other coconut-based products;

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its share is very insignificant as compared to other coconut growing countries of the world. Though, the export of coconut products exhibited significant increase from 1990–91 to 2003–04. The universal demand for coconuts and coconut products has increased significantly. It is estimated that 9% increase per annum for fresh coconuts, 45% for activated carbon, 45% increase for coconut milk, eight-fold increases for coir products and 100% increase in coir dust will be documented in the next 5 to 10 years (Figure 4.5).

4.5. MEASURE THE QUALITY OF SPICES: MAINTAINING COLOR CONTROL WITH SPECTROPHOTOMETERS 4.5.1. Spices and Color Spices are obtained from a variety of sources, and hence, the color of these spices varies in a dramatic way. There are many spices which are not only used as enhancers of the flavor, but they are also used to enhance the color of various dishes as well. This is the main reason of performing color control techniques in the processing and development stages of spices. This will impact on overall result of the product. The pigments which are present in raw spice products increases on maturity; hence the color control monitoring can specify when the base product is ripened perfectly, and it is further ready to process. Also, spices vary in color between their solid state and several degrees of crushing or grinding to make coarse or fine powders and even paste. Color measurement instrumentation should be capable of accounting for variations in texture color so as to quantify color accurately. Therefore, color control monitoring during these stages of processing is very important for making the anticipated aesthetic appeal and final product outcome.

4.5.2. Color Control Regulations Many spices depend upon the color control as a sign of quality of product. The ASTA (American Spice Trade Association) has gathered a list of standardizations for the analysis of spice using color control methods. For example, the color control of the extremely popular spice, paprika, uses ASTA “Color Units” as an international standard for measuring

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extractable color and it is determined by spectrophotometric method. The “Color Unit” score obtained is then used to specify the product quality and set the price accordingly. Monitoring of color control by using spectrophotometers plays a major role in meeting set standards for product purity and safety. If the spices get contaminated, it will result into a severe issue. Various government agencies, for example, the USDA (United States Department of Agriculture), the FDA (Food and Drug Administration), and the EPA (Environmental Protection Agency) have established few specific requirements of inspection for safety compliance. The American Spice Trade Association has created five key recommendation guidelines for the detection of pathogens in spices: • •

• • •

Reduce the risk for introduction of filth all over the supply chain; Avoid environmental contamination, post-processing contamination during processing and storage, and crosscontamination; Use microbial reduction techniques which are validated; Perform post-treatment testing to verify a safe product; and Test to validate a clean and wholesome manufacturing environment.

4.5.3. Using Spectrophotometers for Color Control Different spices have different texture, color, and consistency. They often share sufficient similarities which can be measured by using specific kind of instrumentation technique. While measuring the color control of the spices, the samples are generally opaque in nature. The sample is measured accurately by using directional 45°/0° reflectance geometry. Hunter-Lab provides different variety of spectrophotometers. These spectrophotometers are designed for precise measurement of color control in spices, including the Lab Scan XE, Color Flex EZ and the MiniScan EZ 4500. This instrument is very simple to use and provide exact data, providing users with the ability to measure up to government standards and quality expectations.

4.6. PROCESS INVOLVED FOR PRESERVING SPICES Spices and herbs are abundant in food systems. They are usually utilized

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for improving quality, adding culinary interest, extending the shelf life and preserving the food. Contamination of spices and herbs with pathogenic bacteria is very well known. The contamination can be result of growing conditions, hygiene, and sanitation practices and lack of good quality of manufacturing practices. Loads of bacteria on untreated spices are very high, readily within the range of 104 to 107 cfu/g (Buckenhuskes, 2001), presenting food safety and risks to fresh and managed prepared foods. Foodborne illness outbreaks associated with Salmonella and other bacterial pathogens has been accredited to spices (FDA, 2013). Processing of spices and herbs before their utilization in food systems provides a value for preserving safety and quality of food items, majorly related to ready to eat foods, which usually do not require any further processing (Little et al., 2003). But, providing this further food safety processing step can damage the quality of spice and herb by changing color, volatile, and flavor chemistry. While choosing any method of treatment, it is very much essential to verify whether the method is able to inactivate the target pathogen so as to deliver a safe product to the consumer. Safety is the paramount. The verified process should yield a product which matches the quality standards. The yielded product must also be competitive in price.

4.7. CONSTRAINTS IN SPICE PRODUCTION IN ASIA Asia is the major place of spice production. It is the main exporter and consumer of spices, but there are few constraints which are hampering the production or expansion of spice cultivation to meet the worldwide requirements of spices. These constraints are basically categorized into four such as biotic, abiotic, socio-economic, and technological which are briefly described in Figure 4.6:

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Figure 4.6: Constraints in spice production.

Biotic Constraints: They are basically caused due to biotic factors which includes pests and diseases, and mainly the lack of genetic variability. Among the producers of spices, different devastating diseases are very well known. There is disease of clove named as “Sumatra.” This disease wiped out overall production of clove in Indonesia. Footrot disease in black pepper has made severe harms to the Indian producers. Various crops of spice propagate vegetative, and therefore limits the genetic variability which is a kind of a prerequisite for crop breeding programs. The existence of two sexes on different plants in nutmeg makes it tough to get set of fruit without male trees, whose existence without any yield is a disadvantage in plantation. The requirement for artificial pollination in vanilla, a labor-intensive operation makes it uneconomic to yield this delicate spice in few countries where labor is a major issue. Abiotic Constraints: These are mainly caused due to different exogenous natural factors like flood, drought, fire, soil toxicity, storm, etc. These factors usually contaminate the production process of spices. Socio-economic Constraints: Marketing, competition with other economic crops or synthetics, quality control, lack of capital investment and labor, etc. are the major socio-economic constraints which hamper the processing of spices. Technological Constraints: The technological constraints arise due to lack of various technologies and technology transfer. This might hamper the production process of various spices. These technologies comprise the formation of superior varieties, enhanced culture practices, and technology involved in processing.

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4.8. PROCESSING, STORAGE METHODS, AND QUALITY ATTRIBUTES OF SPICES AND AROMATIC HERBS SAH or spices, as well as aromatic herbs, generally tends to form up an essential cluster of plants belonging to the biodiversity, having an inclusion of the Liliaceae, the Myrtaceae, the Solanaceae along with the Zingiberaceae. The distinct fragments of all these pertaining plants are as follows: the flora bud, the seed, the leaves, the fruit, the flowers, the seed, the rhizomes as well as the stems (De Vienne, 2007). These are being utilized for seasoning along with the savoring features (Tchiegang and Mbougueng, 2005; Chassaing, 2006) being the entire powder, record as well as the mixture of infinite number of spices and the pertaining aromatic herbs (Peter, 2006; Tchiegang and Mbougueng, 2005). They generally tend to possess the specificity to get gobbled within the provided food in petite quantity all across the globe (Betts, 2014). Certain spices along with the aromatic herbs have also been utilized for the certain sacramental purposes, for instance: for religious, medicinal or the cosmetic ones, in accordance with the report submitted by Thomas et al., (2012). The process of gobbling up of the various spices, as well as the aromatic herbs, usually relies on the certain clusters related to the socio-cultural ones, the pertinence of habits of the provided food along with their respective accessibility within the distinct regions of residing (Sossa, 2013). In accordance with the countries pertaining across the world, the spices as well as the aromatic herbs, being an addition to the role of culinary food, deliberated to the provided food products within which they were being established, in the form of the nutritive part for instance: having an involvement within the lipids, mineral, proteins along with the carbohydrates, certain properties related to its functionality as well as the virtues belonging to the pharmacology (Tchiegang and Mbougueng, 2005). It is true that the spices, as well as the aromatic herbs, generally tend to possess an inclusion of the notable quantity related to the vitamin B, C, A along with the pertinent mineral being sodium, iron, potassium, calcium, phosphorus, and many more (AlJasass and Al-Jasser, 2012). They too have a possession of the various uncontaminated properties in opposition to the varied gastroenteritis pathogenic bacteria, the Staphylococci, Escherichia coli along with the Listeria (Tchiegang and Mbougueng, 2005; El Kalamouni, 2010).

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Similar to what has been reported by Mah et al., (2009) the amalgamation of garlic and the various other distinct spices that has constrained the generation of the varied biogenic amine within Myeolchi-jeot, a product that is fermented anchovy, along with the Korean salted and thus, impose restrictions regarding the evolution or the growth of the variety of persistent microorganisms. Being an addition to it, the pertaining species along with the various aromatic herbs or plants tend to make up an essential source belonging to the varied natural uncontaminated compounds as well as antioxidants for the pertaining factories related to the process up of provided food (Abdou, 2009) by a version of the declination of all the pertaining free extremists (Popovici et al., 2009) along with the process of procrastinating of the oxidization of the provided lipids by providing them with a permit to have an extension of the conservation of the time period of food products (Nyegue, 2006; Popovici et al., 2009). But, the spices along with the aromatic herbs or plants can get extensively tainted or adulterated at the time of the storing, processing, or at the time of shifting them (Qaher, 2005). Thus, in accordance with this, the spices, as well as pertaining aromatic herbs, provides with a wide number of threats related to health that are needed in order to get explicit. In case identical to the various other distinct products related to agriculture, the pertinent spices along with the aromatic herbs are required to get tacit to a great degree of adulteration, be it in the form of biological as well as chemical one, at the time of post-harvest, possessing an inclusion of the certain levels belonging to the processing, distributing, storing, selling, and thus, making an opposite utilization of it (Hackl et al., 2013). The existence of the various other distinct bacterium microorganisms, for instance: Salmonella, which has also been provided in terms of the report by Eke et al., (2013). But, very a smaller number of probing or assessment have been executed based on the provided status of sanitary, the value or worth of the nutrition along with the probable properties that are antiseptic being present within an extensive assortment belonging to spices as well as aromatic herbs or plants within the respective country.

4.8.1. Sorting and Heating The process of sorting has been considered as the first and foremost step in the processing of the spices as well as the aromatic herbs or plants. At the

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time of this specific step, the varied spices along with the aromatic herbs have been quite sorted so that they could be able to remove or eliminate all the unwanted portions, i.e., the parts which are moldy as well as rotting. In accordance with the process of heating that is generally being applied in the case related to chili, wherein approximately 2 L of the provided water has been mixed along with the 25 kg of the presented product and thus, this respective amalgamation is being heated at a degree of 80–90 at the time of a regular timing of nearly 5 mins prior to the time wherein it becomes sundried. At the time of opting for the step of heating, the palm oil which is ½ L for the provided chili which is of 25 kg and is being mixed with the boiling water, which has been exercised by approximately 18% of the provided processors, so that they could be able to eliminate the characteristics belonging to the organoleptic in relation with the product, which is sun-dried.

4.8.2. Sun Drying of SAH The process of sun drying has been considered as one of the major steps that have been involved at the time of processing of the spices along with the aromatic herbs or plants, similar to that which has been reported by Dufresne (2008). In accordance with the Bonazzi and Dumoulin (2014), the technique related to sun drying have resulted in the reduction of the activity related to water within the Spices as well as Aromatic Herbs or plants, and subsequently tends to prevent the growth or evolution of belonging to the certain microorganisms, but it also tend to possess the reduction of weight of the provided Spices as well as Aromatic Herbs or plants and thus, would be generating unconducive results after the process of drying, which has been claimed by approximately 98% of processors that have been assessed till now. In accordance with the identical observations that have been provided with the report by Dufresne (2008). Regrettably, the technique related to the process of drying, which has been applied by the various pertaining processors have still being present even conventionally, wherein nearly 98% of the processors have been surveyed due to the restriction imposed to the process related to the sun drying, similar to what has been reported by Tunde-Akintunde (2010) whilst just probably 1.2% of them generally tend to make an apt utilization of the pertaining electric dryer. In consideration of the disparity to the practices r the procedures related to sun drying belonging to Spices as well as Aromatic Herbs or plants

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within various provided countries all across the globe, the process of drying having utilization of the varied advanced driers within various countries that have already been developed and thus, imposes limits or constraints on the pertaining threats of contamination. The other persistent issue or problem that has provided with an outcome from the process related to sun drying is that it would certainly be not conceivable for anyone to possess a determination of the provided time of drying as it has been believed that the intensity belonging to the sun has been considered as variable.

4.8.3. Packaging of SAH All the spices which have been originated from the ground are being packaged within various distinct forms of materials for instance: within petite plastic bottles (6%) or in case of the glass bottles (64.6%) whereas the pertaining bags of jute (19.3%), baskets or bowls (3.3%), varied plastic bag (6.7%) and thus, are being extensively utilized in the form of packaging of the provided materials for all the spices that have been considered as non-ground. In consideration of all the outcomes that have been generated, it was seeming that bottle of glass is the only packaging material that has been greatly or extensively utilized by many of the provided processors belonging to the pertaining spices. Therefore, in accordance with the assessment of the various processors, the glass bottles have been presented with the permit to possess a great presentation related to the specified product along with the extended preservation or maintenance of the period along with it. All such results are all according to the findings that has been discovered related to the certain provided authors who have provided with the report regarding the utilization of the certain materials that has been packaged, at times all the conventional similar to that of the boxes related to that of the paperboard, varied plastic sacks, paper bags which are multi-walled, that has presented with the deliberation of the spices as well as the aromatic herbs which are considered as a better conservation (Prashant, 2014). In accordance with all the processors that have been interviewed or assessed, certain limitations are still pertaining that have been associated or linked with the processing of the provided spices along with the aromatic herbs or the plants. The factors, which have greatly cited by all the provided actors, are as follows: the practice related to the process of sun drying due to the duration it possesses along with the risks associated with the climate (80%), the process of milling (70%) due to the persistence of the irritation

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caused by certain provided characters belonging to the spices.

4.8.4. Storage of Spices and Aromatic Herbs and Problems Associated with the Storage After the processing, spices, and aromatic herbs were instantly sold in the market. Sometimes, they are also stored for further use by using different techniques. For around 75% of the processors who were interviewed, the non-processed SAH are dried under the sun twice or thrice times a week. This would be very helpful for the long period conservation for almost two years. They can also be dried by using electric drier so as to avoid the attack by mold. The storage of fresh SAH such as ginger, chili, garlic, and anion by the cool is practiced by 5% of the processors. The extreme storage duration of the SAH kept in cool conditions is around 10 days as per the 80% of the processors who practiced this method. Hence, the level of moisture for most of the SAH must be decreased to below 11% so as to prevent the proliferation of microorganisms. As per the European Spice Association, the content of moisture in spices after the process of drying is very much conclusive for the proliferation of microorganisms (Yogendrarajah, 2014; Tulu et al., 2014). For 98% of processors, the salt which is added to SAH during the milling process allows to store them for at least a year. The spice and aromatic herbs in powder form already lost after almost three months few of their organoleptic properties such as the taste exposed by 9.9% for the aroma and 11.4% of the respondents.

4.8.5. Quality Attributes of SAH All the pertaining providers of responses be it the traders, processors or the consumers, which have been assessed that are entirely based on their respective perceptions or preferences based on criteria related to the quality, possessing an inclusion of the integrity of physicality belonging to the Spices along with the Aromatic Herbs or the plants being in the absence of the certain portions which are: rotting or moldy (48.4%), the nonappearance of all the elements that belongs to abroad (57.3%) along with the persistence of aroma, which means, the quality of attribute that has been considered as most important (45.5%). But, many of the provided practices related to the processing, which has been mentioned in the above paragraphs that might

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possess an impact related to the criteria of the pertaining quality. Rather, at the time of the drying step, approximately 13.4% belonging to all the provided processors, which has been spread across varied products based on the floor, whilst nearly 29.3% has been spread pertaining on the sidewalks that has been considered to be contrary on the part of hygiene in relation with the dried spices along with the plants which are aromatic (Codex, 2015).

4.9. CONCLUSION Many surveys have been conducted by various researchers so that they could be to have an identification or recognition of the pertinent spices as well as aromatic herbs that are being utilized in various countries across the world. Much of them have been imported from there, in the rest of the world and thus, are being consumed or utilized. These researches have also helped in providing with the information regarding the processing along with the process of commercialization of the species along with the aromatic herbs that have been executed by men as well as women, being a distinction to various other pertaining products, for instance: Afitin, as well as Lanhouin, are being utilized so that it could augment or enhance the respective flavor along with the taste in certain provided dishes within various parts of the world. Being an addition to it, much can be perceived or apprehended regarding the processing of spices as well as the aromatic herbs, for example: as it is being majorly executed in a condition which is extremely unhygienic that is actually conducive to the probable adulteration at the toxicological as well as the microbiological facet. The process of packaging the provided material has usually been made up of the containers, which are rudimentary, that can also become one of the major sources of the adulteration of such processed spices along with the aromatic herbs. Moreover, certain analysis have been done at the time of survey, which discovered that the utilization of spices, as well as the aromatic herbs, has been linked or connected with the various groups, being socio-cultural. On the basis of the observation of various practices related to the hygiene, the requirement for the characterization have been aroused and thus, having an enhancement in the practices concerned with the processing along with the pertaining final- goods, so that they could be able to demonstrate the persistent impact of such practices on the provided quality of all such final-

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goods that are being extensively utilized within certain rural as well as urban arenas in several countries across the globe. This will, thus, presents with an explicit or tacit guidelines for having enhancement within the practices related to the processing of the spices along with the aromatic herbs and accordingly, great progression or development in the quality, be it in the physicochemical, microbiological or the toxicological facet, belonging to the spices as well as aromatic herbs that have been commercialized in various parts of the world.

4.10. CASE STUDY: PATHOGENS AND SPICES 4.10.1. Background Spices and dried herbs are important food commodities; they are used all over the world in food preparation, usually in small amounts, to flavor foods. Spices and dried herbs are a group of agricultural commodities that can be fruit or seed-based (such as paprika), bark or flower based (such as cinnamon), root or rhizomes based (such as turmeric and ginger) and leaf based (such as oregano). Spices and dried herbs are classified as low-moisture foods (LMFs). LMFs are defined as food items that have water activity of less than 0.85. Generally, the minimum available water (aw) required to facilitate growth of most bacteria is 0.87; although under optimal conditions, bacteria such as Staphylococcus aureus can grow at aw of 0.83.

As LMFs are generally ambient-stable and assumed to be low-risk, they are considered to be an unlikely source to be implicated for foodborne illness. However, in recent years, there has been an increased number of recalls for dried herbs and spices due to contamination by pathogens.

Based on a review of documented recalls, Salmonella is the principal food pathogen associated with dried herbs and spices. Between 1970 and 2003, there were 21 recalls of 12 spice types in the US. Of the 21 recalls, Salmonella accounted for 95% (20/21) of documented US recalls. Between January 2008 and August 2011, the Rapid Alert System for Food and Feed (RASFF) (Food and Feed Safety Alerts) of the European Commission reported 22 alerts for herbs, spices, and pepper. Of the 22 alerts, Salmonella was identified in 21 alerts, and E. coli was identified in one alert. In Canada, the Canadian Food Inspection Agency (CFIA) recalled a number of spices and dried herb products in 2014. These included paprika

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powder, spice products, white pepper powder, black peppercorn, flax seed powder, carob powder, rosemary leaves, and dried oregano leaves. The pathogen involved in all of these recalls was Salmonella. As of June 2015, CFIA has recalled garlic powder, kalonji, and chicken broth powder due to contamination with Salmonella. This document will review the literature on the presence of pathogens in spices and dried herbs at the point-of-sale, the evidence of foodborne illness outbreaks associated with LMFs, the factors that contribute to contamination of these products, and the mechanisms of survival for microorganisms in these products. It will answer the following three questions: • •

•

What are the microbial qualities of spice/dried herbs products at point-of-sale? Have LMFs such as spices been associated with outbreaks of foodborne illnesses? What are the pathogens associated with these outbreaks? What are the contributing factors for contamination of LMFs (specifically spices and dried herbs), and how can microorganisms survive in low moisture foods?

4.10.2. Method A literature search was performed by Public Health Ontario’s (PHO) Library Services on March 31st, 2015 in the following databases: Ovid MEDLINE, and Embase, EBSCOhost Food Science, BIOSIS, and Scopus. Search results were limited to English language articles only published from January 1, 2005-March 31, 2015. Search terms included: “microbial growth, bacterial growth or development, microbial viability counts, spice, relevant spices, nuts or dried herbs, low moisture, low water activity, low Aw, relevant pathogens and foodborne disease, illness or poisoning outbreak.” Additional information was identified through cited reference searching of full-text articles. To review the evidence of outbreaks associated with low-moisture food (LMF), a search was conducted through Public Health Agency of Canada’s (PHAC) “Publically Available International Foodborne Outbreak database” (PAIFOD), between January 1, 2005 to April 1, 2015, on documented outbreaks associated with LMF.8 The information obtained was evaluated for relevance and 45 records were included in this report.

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4.10.3. Microbial Quality of Spices/Dried Herbs at Point-of-Sale Based on a review of the published literature, a number of studies were identified that examined the microbial quality of different spices and dried herbs at point-of-sale around the globe. Cronobacter species, an opportunistic pathogen, has been isolated from a number of LMFs and food ingredients including spices and dry herbs. Similarly, Verotoxigenic E. coli (VTEC), Salmonella, Staphylococcus, Bacillus cereus (spores), Clostridium botulinum and Clostridium perfringens (spores), and Listeria monocytogenes have also been isolated from a variety of LMFs. Spices and spice products that were sampled within these studies had varying degrees of contamination from pathogenic microorganisms. In a study conducted in the United Kingdom, 750 samples of spices and spice ingredients, as well as 1,946 samples of ready-to-eat foods where spice had been incorporated, were collected to test for a number of pathogens including Salmonella spp. B. cereus and Bacillus spp. Based on their results, ready-to-eat food samples tested positive for B. cereus (17%) and Bacillus spp. (17%), Enterobacteriaceae (11%), E. coli (4%). In addition, spices, and spice ingredients tested positive for B. cereus (19%), other Bacillus spp. (53%) and Salmonella (5x105 CFU/g), 23.4% for E. coli (>0.3MPN/g), and 21.9% for molds (>5x103 CFU/g). In addition, two studies conducted in Turkey had identified various pathogens (aerobic bacteria, S. aureus, B. cereus, E. coli, sulfate-reducing bacteria, molds/yeast, Salmonella spp. and E. coli 0157 H:7) in sampled spices and dried herbs. Donia et al., performed microbial and aflatoxin analysis on 303 samples of different spices and medicinal dried herbs in Egypt. From their analysis, aerobic bacterial count, spore-forming bacteria, coliform, E. coli, S. aureus, yeast, and mold were detected. Total viable counts of microorganisms were found in different spices at various levels. For example, E. coli was detected in all samples except for tea, black pepper, karakade, and saffron, while S. aureus was only detected in basil, peppermint, and spearmint. The highest and lowest mean counts were found in peppermint and black pepper respectively. All samples tested were free of aflatoxins (B1, B2, G1, and G2). Ahene et al., performed microbial analysis of aniseed, rosemary, and several spice products in Ghana. Microorganisms isolated from the spices varied depending on the product tested. For example, aniseed had the highest count of bacterial load, and Royco shrimp cube and Royco beef cube had the least. Aeromonas salmonicida, Enterobacter cloacae, Enterobacter amnigenus, Enterobacter agglomerans, Enterobacter Sakazakii, Flavobacterium spp, Chromobacterium violaceum, Pseudomonas putida, Pseudomonas aeruginosa, Acinetobacter spp, Pseudomonas cepacia, and Serratia plymuthica were detected in the tested samples. In Brazil, Moreira et al., analyzed different spices and dried herbs for the presence of mesophilic bacteria, thermotolerant coliforms, B. cereus, S. aureus, and Salmonella. Twenty-one percent of all samples tested positive for thermotolerant coliforms, while 5.6% were positive for Salmonella. Black pepper had the highest level of contamination; 18.2% of black pepper samples were positive for Salmonella spp. and 8.3% of dehydrated green onion samples tested positive for B. cereus. No pathogens were detected in samples of bay leaves. Turcovsky et al., tested 602 food items for the presence of Cronobacter spp. The highest contamination was

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observed in foods of plant origin (spices, teas, chocolate, nuts, pastries, and vegetables). Sixty-two percent (13/21) of spice samples tested were positive for Cronobacter spp. Based on FDA sampling and testing data between FY2007 and FY2009, Salmonella was detected in 6.6% of imported spices. This is 1.9 times more Salmonella contamination than all other imported FDA-regulated foods during this period of time. The 2014 systematic review by the Food and Agriculture Organization of the United Nations/World Health Organization (FAO/WHO) identified 77 studies investigating the prevalence and/or concentration of microbial hazards in spices. The report concluded that many spices can be contaminated with various microbial hazards. The evidence identified by this review suggests that spices and dried herbs available at point-of-sale can be contaminated with pathogens. A number of studies also concluded that spices and dried herbs may be high-risk products, and when contaminated, may pose a potential risk to consumers.

4.10.4. Foodborne Illnesses Outbreaks Associated with Spices and Dried Herbs This review identified reports of foodborne illness outbreaks associated with spices, dried herbs, and other LMFs. In Canada, a 1974 salmonellosis outbreak associated with black pepper resulted in 17 cases. In 1993, Germany experienced the largest spice-associated outbreak of foodborne illness to date. Potato chips, which were seasoned with contaminated paprika, were implicated as the cause of the outbreak, which resulted in 1,000 cases of Salmonella. The investigation revealed that paprika was added to the potato chips after the final pathogen reduction step of food manufacturing. A 2007 multistate salmonellosis outbreak in the U.S. resulted in 69 cases, where 93% of cases were children less than 3 years of age. Imported broccoli powder in spice mix used in Veggie Booty (a children’s snack) was implicated as the cause of this outbreak. Another multi-state salmonellosis outbreak, which occurred in 2009, resulted in 272 cases in 44 states. It was discovered that imported contaminated black and red pepper was added to ready-to-eat salami products. Between January 1, 2005, and April

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1, 2015, 23 foodborne outbreaks associated with spices and dried herbs were documented in the Publicly Available International Foodborne Outbreak Database (PAIFOD) of the PHAC. The PAIFOD contains information on approximately 9,000 foodborne outbreaks from Canadian and international sources. The information is obtained from peer-reviewed journals, newspapers, listserves, press releases, health units, and the National Laboratory and government websites. B. cereus, C. perfringens and Salmonella spp. were the pathogens most commonly associated with spice/herb-related outbreaks. Based on data from the PAIFOD, Salmonella spp. was the reported causative agent with all four spice-related outbreaks in the U.S. A preliminary report from FAO/WHO on foodborne pathogens of concern with spices and herbs also concluded that although various bacterial hazards have been identified in spices and herbs, only Salmonella spp., B. cereus, and C. perfringens have been reported to be associated with foodborne outbreaks.

4.10.5. Microbial Survival in Low-Moisture Food Some microorganisms can survive in LMFs for a prolonged period of time. Examples include survival of Cronobacter spp. in milk powder and Salmonella in chocolate, egg powder, animal feed, spices, nuts, and nut butters. Salmonella Enteritidis, E. coli and K. pneumonia have been shown to persist in milk powder for up to 15 months, while E. Sakazakii, E. vulneris, and K. oxytoca were still recoverable after two years. Salmonella can survive in LMFs for weeks, months, and even years. Long-term survival of different strains of Salmonella in peanut butter has been reported by many studies. Burnett et al., reported that if peanut butter is contaminated with Salmonella, it is likely to survive for the duration of its shelf life. In addition, peanut butter with lower aw can result in greater survival rates for S. Tennessee, S. Typhimurium and Enterococcus faecium. Day et al., demonstrated that Salmonella Typhi and Shigella dysenteries can survive in dry infant formula for an extended period of time. Furthermore, it was observed that the presence of nitrogen can enhance the survival of these pathogens. Survival among different Salmonella serotypes in LMFs may vary under different temperatures and aw. Temperature, aw, medium composition of food and serotype of bacteria all play an important

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role in the survival kinetics of Salmonella in LMFs.31, 32 Salmonella can survive the longest in seeds and nuts at temperatures of around 20°C. Different Salmonella strains that were inoculated in dried paper disks within the laboratory environment survived for up to 70 days at holding temperatures of 25°C–35°C, and up to 24 months at a holding temperature of 4°C.33 S. Tennessee is more persistent than S. Montevideo and Typhimurium at higher temperatures in low-moisture whey protein powder held at 36°C and 70°C. In comparison, S. Agona did not differ significantly in terms of persistence when compared to S. Tennessee under different temperatures The mechanism(s) by which the microorganisms are able to survive in LMF is not fully understood. Survival of microorganisms in dry processing environments and LMF depends on their ability to adapt to high osmotic potentials or dry conditions. Osmoregulation refers to the maintenance of an optimal constant osmotic pressure in the body of a living organism. In low-moisture environments/ foods, microorganisms adapt by balancing the osmolarity of their internal cell with that of the external environment to avoid water loss. This is done by a number of different cellular mechanisms that include an influx of K+, followed by a longer-term adaptation such as the uptake of electrically neutral, low molecular weight compatible solutes (e.g., proline, glycine betaine, and ectoine). In a study by Lehner et al., the following factors were identified in facilitating the survival of Cronobacter species in low-moisture environments: •

Their ability to form biofilms with the production of cellulose (in the extracellular matrix). • Adherence to hydrophilic and hydrophobic surfaces. • The production of extracellular polysaccharides along with cellto-cell signaling molecules. Kieboom et al., investigated the morphological changes in Salmonella Enteritidis after exposure to low-moisture environments. Exposure to low aw resulted in the formation of filaments and development of elongated S. enteritidis cells. When placed in more favorable conditions, these cells can split and form numerous single cells. Furthermore, cells exposed to low moisture

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environments demonstrated a tolerance to hypochlorite. Filamentation occurs when S. enteritidis is exposed to low aw and osmotic stress due to the production of inhibitors for cell division. It has been suggested that the production of filaments by microorganisms is to gain a further advantage for survival. The filamented cells can lead to increased desiccation tolerance in comparison to non-filamentous cells. Deng et al., demonstrated that Salmonella cells in peanut oil undergo a physiologically dormant state with